Advances in Rosin-Based Chemicals

molecules
Review
Advances in Rosin-Based Chemicals: The Latest
Recipes, Applications and Future Trends
Szymon Kugler 1, * , Paula Ossowicz 1 , Kornelia Malarczyk-Matusiak 1
and Ewa Wierzbicka 2
1 Faculty of Chemical Engineering, West Pomeranian University of Technology in Szczecin, Pulaskiego 10,
70-322 Szczecin, Poland; paula.ossowicz@zut.edu.pl (P.O.); kornelia.malarczyk@zut.edu.pl (K.M.-M.)
2 Industrial Chemistry Research Institute, Rydygiera 8, 01-793 Warsaw, Poland; ewa.wierzbicka@ichp.pl
* Correspondence: skugler@zut.edu.pl

Received: 22 March 2019; Accepted: 23 April 2019; Published: 26 April 2019
Abstract: A comprehensive review of the publications about rosin-based chemicals has been compiled.
Rosin, or colophony, is a natural, abundant, cheap and non-toxic raw material which can be easily
modified to obtain numerous useful products, which makes it an excellent subject of innovative
research, attracting growing interest in recent years. The last extensive review in this research area
was published in 2008, so the current article contains the most promising, repeatable achievements in
synthesis of rosin-derived chemicals, published in scientific literature from 2008 to 2018. The first
part of the review includes low/medium molecule weight compounds: Especially intermediates,
resins, monomers, curing agents, surfactants, medications and biocides. The second part is about
macromolecules: mainly elastomers, polymers for biomedical applications, coatings, adhesives,
surfactants, sorbents, organosilicons and polysaccharides. In conclusion, a critical evaluation of
the publications in terms of data completeness has been carried out with an indication of the most
promising directions of rosin-based chemicals development.
Keywords: rosin; curing agent; resin; surfactant; biocide; medicine; polymer
1. Introduction
The natural origin, low price, abundance and chemical modification potential of rosin make it a
valuable raw material in numerous applications [1–14]. Besides the mentioned advantages, rosin is
also safe for living organisms [15]. Its derivatives are claimed as non-toxic as well, despite their
allergenicity [16,17]. This unique set of beneficial properties of rosin determines it as an attractive
subject of innovative research characterized by a considerably growing interest in recent decades,
as can be seen in Figure 1.
Unfortunately, the awareness of the possibility of using rosin as a raw material for obtaining
valuable chemicals is generally unsatisfactory. There is a burning need to bring this topic to the
attention of a larger group of scientists. Furthermore, the growing number of publications causes
difficulties in keeping up with the latest research, as well as in selection of more promising discoveries.
Sadly, the last comprehensive review document dedicated exclusively to rosin and its modifications
was published in 2008 [1]. Since then, only fragmentary information on rosin has appeared in review
articles on bio-based polymers and resin systems [2–21], as well as in reviews on rosin derivatives in
catalysis [12], controlled drug-delivery systems [13] and small-molecule compounds [14].
In view of these facts, publication of a wide, comprehensive and critical review of achievements
since 2008 is an important solution to solve the problem of a severe lack of current review literature in
this field. The growing number of publications is not the only obstacle in creating a literature review
on rosin. No less important challenge is to collect information from existing literature. Quite often
Molecules 2019, 24, 1651; doi:10.3390/molecules24091651 www.mdpi.com/journal/molecules

Molecules 2019, 24, 1651 2 of 52
Molecules 2019, 24, x FOR PEER REVIEW 2 of 51

articles do not contain full information about a particular reaction, but refer to earlier articles, which,
in turn,often
mayarticles
refer todoeven
not contain
earlierfull information
articles, whichabout
mayanotparticular reaction,online,
be available but refer
ortomay
earlier
notarticles,
be in English.
which, in turn, may refer to even earlier articles, which may not be available online, or may not be in
The current article is a direct answer to the aforementioned issues. Its aims are: (I) to provide
English.
a precise review of the scientific literature from 2008 to 2018, (II) select promising studies with clear
The current article is a direct answer to the aforementioned issues. Its aims are: (I) to provide a
practicalprecise
application and
review of the(III) an overall
scientific assessment
literature from 2008 of
to the
2018,reviewed
(II) select achievements
promising studies in with
orderclear
to identify
the most perspective
practical development
application directions
and (III) an overall of rosin-based
assessment chemicals.
of the reviewed The review
achievements is identify
in order to presented in a
modern, thepleasant-to-browse
most perspective development directionswith
form, illustrated of rosin-based
patientlychemicals.
completed Thereaction
review is schemes.
presented inThea article
modern, pleasant-to-browse form, illustrated with patiently completed reaction
provides concise, but exhaustive information on the achievements in preparation of rosin-derived schemes. The article
provides concise, but exhaustive information on the achievements in preparation of rosin-derived
chemicals in the last decade. Its main idea is to inspire and encourage the world of science to actively
chemicals in the last decade. Its main idea is to inspire and encourage the world of science to actively
take interest in rosin and the possibilities of its modification.
take interest in rosin and the possibilities of its modification.
Figure 1. Number
Figure of scientific
1. Number articles
of scientific articlesand
andpatent documents
patent documents containing
containing the keyword
the keyword “rosin”“rosin”
in the in the
years 1990-2017.
years 1990–2017.
2. Basic2.Information
Basic Information
aboutabout Rosin
Rosin
Rosin, Rosin, or colophony, is a solid and brittle mixture of non-volatile conifer tree resin components.
or colophony, is a solid and brittle mixture of non-volatile conifer tree resin components.
It can display colors ranging from almost colorless, through shades of yellow and brown to black.
It can display colors ranging from almost colorless, through shades of yellow and brown to black.
Depending on the origin, two industrially important types of rosin can be distinguished, i.e. gum
Dependingrosinonandthe
tallorigin, two
oil rosin. Gum industrially
rosin is theimportant
non-volatiletypesresidueofremaining
rosin canafter
be distinguished,
distillation of treei.e., gum rosin
resin
and tallobtained
oil rosin.byGum
tappingrosin is thetrees.
of living non-volatile
Tall oil rosinresidue remaining
is a by-product after pulping
of wood distillation
in theofkraft
treeprocess.
resin obtained
Gumofrosin
by tapping livingaccounts
trees. for
Tallca.oil60% of world
rosin rosin production,
is a by-product of wood whereas tall in
pulping oil the
rosin is ca.process.
kraft 35%. In the
Gum rosin
past, rosin was widely obtained from the solvent extraction of harvested
accounts for ca. 60% of world rosin production, whereas tall oil rosin is ca. 35%. In the past, rosin was wood as so-called wood
rosin, but nowadays, this technology is of little importance [1,22]. The price of rosin in the first half
widely obtained from the solvent extraction of harvested wood as so-called wood rosin, but nowadays,
of 2018 ranged from 300 to 2750 USD/ton depending on its origin, supplier and color. Annual world
this technology is of little importance [1,22]. The price of rosin in the first half of 2018 ranged from 300
production of rosin is ca. 1.2 million tons and has remained stable in the last decades [1,2,22].
to 2750 USD/ton depending
Resin acids, with the ongeneral
its origin, supplier
formula and color.
C19H29COOH, Annual
constitute up world
to 95 wt.%production
of rosin, of rosin is ca.
while
1.2 million tons
neutral and has remained
compounds are present stable
in amountsin the of alast
fewdecades
percent. A [1,2,22].
number of resin acids based on a few
diterpene
Resin acids,carbon
with skeletons
the general wereformula
identifiedCso far29[1].
19 H The most
COOH, abundant
constitute upresin
to 95acids
wt.%are of
built on while
rosin,
neutral compounds are present in amounts of a few percent. A number of resin acids basedbeon a few
abietane and pimarane skeletons. Their structural formulas are shown in Figure 1. It should
emphasized, that abietane-structured acids are characterized by conjugated double bond systems,
diterpene carbon skeletons were identified so far [1]. The most abundant resin acids are built on abietane
which makes them particularly susceptible to chemical modifications. It is noteworthy, that abietane-
and pimarane
structuredskeletons. Their structural
acids isomerize at elevated formulas
temperature aretoshown in Figure
afford readily 2. It should
reactive levopimaricbe emphasized,
acid,
that abietane-structured
according to Scheme acids 1. On theareother
characterized by conjugated
hand, pimarane-type acids do double
not have bond systems,
conjugated doublewhich
bond makes
them particularly
systems, whichsusceptible to chemical
limits their chemical modifications.
processability. The It isdetailed
noteworthy,
chemicalthatcomposition
abietane-structured
of rosin acids
isomerize at elevated temperature to afford readily reactive levopimaric acid, accordingorigin
depends on its type (gum, tall oil or wood), thermal history, species of tree and geographical to Scheme 1.
On the [23,24]. Compositions of gum rosin from various sources are presented in Table 1, where it can be
other hand, pimarane-type acids do not have conjugated double bond systems, which limits
their chemical processability. The detailed chemical composition of rosin depends on its type (gum,
tall oil or wood), thermal history, species of tree and geographical origin [23,24]. Compositions of gum
rosin from various sources are presented in Table 1, where it can be seen that the content of abietane-
type acids may vary between 64 and 87 wt.%. Such detailed composition of a rosin can be determined,
e.g., by the capillary electrophoresis method [25].
Molecules that24,the
seen2019, 1651 3 of 52
content of abietane- type acids may vary between 64 and 87 wt.%. Such detailed
composition of a rosin can be determined, eg. by the capillary electrophoresis method [25].
COOH COOH COOH COOH
A) Abietic acid B) Levopimaric acid C) Palustric acid D) Neoabietic acid
included in the schemes. There are situations where some data simply has not been reported by
original authors, eg. product morphology or yield. Such missing data could not be presented in this
review. What
COOH
does the above mean?COOH
The more data provided,
COOH
the more advancedCOOHthe research on a
compound, and the more reliable the recipe. The lack of data should indicate that the research on a
E) Dehydroabietic F) Sandaracopimaric G) Isopimaric acid H) Pimaric acid
certain rosin derivative is probably
acid acid at an early, basic stage. It has to be underlined that reaction
schemes do not take into account advanced stereochemistry. Finally, almost all reactions were
Figure
conducted
Figure 1. Structural
under
2. Structural inertformulas
an formulas of theofmost
atmosphere: thenitrogen
most common
common or abietane-structured
argon, so reaction
abietane-structured (A–E)
schemes
(A–E) and
do notpimarane-
include this
and pimarane-structured
structured
information.
(F–H) (F–H) resin acids.
resin acids.
Table 1. Composition of resin acids in gum rosin from different sources [23].
Abietane-type Acids Content (wt.%) Other Acids

Species Origin HOOCPalustric/Levopimaric Neoabietic Dehydroabietic
Abietic (wt.%)
Rosin
Pinus massoniana China 39 25 16 7 13
Pinus elliotti Brazil 37 15 16 5 27
NH2
Pinus merkusii Indonesia 28 27 5 4 36
Pinus sylvestris Russia 35 23 15 10 17
Dehydro- HOOC
Pinus halepensisNH3 Greece 45 Abietic acid
23 13 5 14
abietylamine
>150°C France 35 Ni 20 180°C 15 9 21
200°C 3h
Portugal 34 21 19 9 17
Pinus pinaster
O Cl Spain 26 22 27 6 19
O
P USA 14 39 18 4 O 25 O
Cl Cl HOOC HOOC
Dehydroabietic acid
in CHCl3 O Levopimaric acid
OH for making films, coatings and O
In recent studies
65°C/3h
unmodified rosin was used adhesives [26–42],
O
biomedical applications [43–55], or in mining, metallurgy and construction [56–58] and for filler
230°C, 3h O
purposes [59–64]. However, chemical modification
COOH pTSA
of rosin gives many-fold greater possibilities of
in CH3COOH
using
O=C this raw material, which are described in the next, main section 120°C,
of this12h
article.
HOOC
Cl
Maleopimaric acid
3.Dehydroabietyl chloride
Rosin-based Chemicals Acrylpimaric acid
yield: 92%
(yield 93%) HOOC yield: 73- 93%
3.1. General Comments on the
Scheme Whole Review
Scheme 1.1.Synthesis
Synthesis of essential
of essential rosin-based
rosin-basedsubstrates/intermediates.
substrates/intermediates.
The review contains short, but exhaustive descriptions of rosin-derived compound syntheses
3.2. Small and Table 1. Composition of resin acids in gum rosin from different sources [23].
published in Medium Moleculeliterature
the scientific Compounds from the JCR list since 2008. It does not include older
achievements
This section in the field ofrosin-derived
describes rosin, that were widely described
small/medium
Abietane-type in
molecule
Acids previous
Content reviewwith
compounds
(wt.%) literature
strictly[1,65] and
defined
Species Origin Other Acids
commercialized
structures that do[66–80]. It includes
not contain the preparations
repeated
Abietic units of completely
typical for new chemicals,
macromolecules.
Palustric/Levopimaric Neoabietic as well
Dehydroabietic as new ways
(wt.%)
to synthesize already
Pinus massoniana China
known compounds.
39
Only
25
products with16
declared or7 obvious practical 13
applications
3.2.1. elliotti have been
PinusIntermediates Brazilchosen. The37 review is divided15 into two 16sections according
5 to the general
27
Pinus merkusii
molecular structure Indonesia
of the prepared 28 compounds,27 while each section5 is divided according
4 36
to practical
PinusIntermediates
sylvestris are the products of simple 23 rosin modifications, which are10necessary for17the
application and theRussia 35
structure similarity 15
of the compounds. The collected data are given in the article
preparation
Pinus halepensis of manyGreece
new compounds. 45 They can 23 be synthesized in13very simple, well5 described ways 14
text and in schemes. The following
France 35 information20are presented in 15the text: product
9 name, product
21
with high yields. The sustainability of these processes is high: They usually use a biobased main
morphology,
Pinus pinaster substrates name(s), 34
Portugal separation techniques
21 and practical
19 applications.9 On the other hand,17
substrate (rosin) in solvent-free
Spain processes.
26 Some drawback
22 can be 27
the separation processes,
6 that19
may
data such as reaction scheme, catalyst use, reaction media, temperature, pressure, time and yield are
not always be easy, USA because of the 14 high viscosity, 39 m.p. and stickiness
18 of products.
4 In view of25the
above, rosin-based intermediates have very high commercialization potential and some of them are
commercially available in certain regions of the world.
In recent studies unmodified rosin was used for making films, coatings and adhesives [26–42],
Maleopimaric acid is an off-white solid (m.p. 223 °C). It can be prepared from abietic acid and
biomedical applications [43–55], or in mining, metallurgy and construction [56–58] and for filler
maleic anhydride via a Diels-Alder reaction according to Scheme 1 [81], followed by recrystallization
[82]. Maleopimaric acid is one of the crucial products in rosin chemistry. It can be used directly as an
epoxy resin hardener, but its applications are much wider. They include preparation of epoxy resins
[83,84], acrylic resins [85–87], allyl resins [88–90], polyols [91], bio-based curing agents for synthetic
epoxy resins [92–98] or bio-based ones [99], surfactants [100–103], intermediates [104,105],
biologically active compounds [105–108], polyurethanes [109-112], chemicals for NMR techniques
[113] and photolitography [114], sorbents [115], organosilicon compounds [116], printing inks [117]
Molecules 2019, 24, 1651 4 of 52
purposes [59–64]. However, chemical modification of rosin gives many-fold greater possibilities of
using this raw material, which are described in the next, main section of this article.
3. Rosin-based Chemicals
3.1. General Comments on the Whole Review

The review contains short, but exhaustive descriptions of rosin-derived compound syntheses
published in the scientific literature from the JCR list since 2008. It does not include older
achievements in the field of rosin, that were widely described in previous review literature [1,65] and
commercialized [66–80]. It includes preparations of completely new chemicals, as well as new ways to
synthesize already known compounds. Only products with declared or obvious practical applications
have been chosen. The review is divided into two sections according to the general molecular structure
of the prepared compounds, while each section is divided according to practical application and the
structure similarity of the compounds. The collected data are given in the article text and in schemes.
The following information are presented in the text: product name, product morphology, substrates
name(s), separation techniques and practical applications. On the other hand, data such as reaction
scheme, catalyst use, reaction media, temperature, pressure, time and yield are included in the schemes.
There are situations where some data simply has not been reported by original authors, e.g., product
morphology or yield. Such missing data could not be presented in this review. What does the above
mean? The more data provided, the more advanced the research on a compound, and the more reliable
the recipe. The lack of data should indicate that the research on a certain rosin derivative is probably at
an early, basic stage. It has to be underlined that reaction schemes do not take into account advanced
stereochemistry. Finally, almost all reactions were conducted under an inert atmosphere: nitrogen or
argon, so reaction schemes do not include this information.
3.2. Small and Medium Molecule Compounds

This section describes rosin-derived small/medium molecule compounds with strictly defined
structures that do not contain the repeated units typical for macromolecules.
3.2.1. Intermediates
Intermediates are the products of simple rosin modifications, which are necessary for the
preparation of many new compounds. They can be synthesized in very simple, well described ways
with high yields. The sustainability of these processes is high: They usually use a biobased main
substrate (rosin) in solvent-free processes. Some drawback can be the separation processes, that may
not always be easy, because of the high viscosity, m.p. and stickiness of products. In view of the
above, rosin-based intermediates have very high commercialization potential and some of them are
commercially available in certain regions of the world.
Maleopimaric acid is an off-white solid (m.p. 223 ◦ C). It can be prepared from abietic acid and
maleic anhydride via a Diels-Alder reaction according to Scheme 1 [81], followed by recrystallization [82].
Maleopimaric acid is one of the crucial products in rosin chemistry. It can be used directly as an
epoxy resin hardener, but its applications are much wider. They include preparation of epoxy
resins [83,84], acrylic resins [85–87], allyl resins [88–90], polyols [91], bio-based curing agents for
synthetic epoxy resins [92–98] or bio-based ones [99], surfactants [100–103], intermediates [104,105],
biologically active compounds [105–108], polyurethanes [109–112], chemicals for NMR techniques [113]
and photolitography [114], sorbents [115], organosilicon compounds [116], printing inks [117] and
for the hydrophobization of wood surfaces [118–120]. It is noteworthy that the main degradation
products of maleopimaric acid are water, carbon dioxide, formamide and also aliphatic and aromatic
derivatives [121]. It is worth noting that fumaropimaric acid is an isomer of hydrated maleopimaric
acid, which can be synthesized in a similar way [122], but its importance to rosin chemistry is much
smaller: it can be used in synthesis of triglycidyl epoxy resin [122] and water-borne polyurethanes [109].
derivatives [121]. It is worth noting that fumaropimaric acid is an isomer of hydrated maleopimaric
acid, which
Molecules 2019, can be synthesized in a similar way [122], but its importance to rosin chemistry is much
24, 1651 5 of 52
smaller: it can be used in synthesis of triglycidyl epoxy resin [122] and water-borne polyurethanes
[109].
Acrylpimaric ◦ C). It can be prepared from abietic acid and acrylic
Acrylpimaricacid acidisisanan off-white
off-white solid (m.p.
solid 220220
(m.p. °C). It can be prepared from abietic acid and
acid according
acrylic to Scheme
acid according 1, followed
to Scheme by precipitation,
1, followed filtration,filtration,
by precipitation, washing washing
and recrystallization [123,124].
and recrystallization
It is noteworthy
[123,124]. that neat that
It is noteworthy rosinneat
canrosin
be acrylated as well [125].
can be acrylated as wellAs an important
[125]. As an importantmaterial in rosin
material in
chemistry, acrylpimaric acid can be used for preparation of diallyl
rosin chemistry, acrylpimaric acid can be used for preparation of diallyl acrylpimarate [123], acrylpimarate [123], polyesters of
acrylated
polyestersrosin and polyethylene
of acrylated rosin and glycols [125], epoxy
polyethylene resins[125],
glycols [126,127],
epoxy acrylpimaryl dichloride
resins [126,127], [128,129],
acrylpimaryl
acrylpimaric acid amides
dichloride [128,129], [130], cyclic
acrylpimaric aciddiamide
amides[131],
[130],quaternary
cyclic diamideammonium salts [132–136],
[131], quaternary calcium
ammonium
and
salts [132–136], calcium and zinc salts [137] as well as polyesters [138]. Moreover, it can becuring
zinc salts [137] as well as polyesters [138]. Moreover, it can be used directly as an epoxy used
agent [139].
directly as an epoxy curing agent [139].
Another
Another important
important compound
compound in in this
this subsection
subsection is is dehydroabietyl
dehydroabietyl chloride.
chloride. ItIt isis aa viscous,
viscous,
yellow, oily liquid [140,141]. It can be prepared using: (i) oxalyl chloride
yellow, oily liquid [140,141]. It can be prepared using: (i) oxalyl chloride according to Scheme 1 prior according to Scheme 1
prior to evaporation
to evaporation of unnecessary
of unnecessary substances
substances [142],
[142], (ii)(ii) phosphorustrichloride
phosphorus trichlorideinin chloroform
chloroform (yield
(yield
92.5%) [140] or (iii) thionyl chloride in presence of 4-dimethylaminopyridine
92.5%) [140] or (iii) thionyl chloride in presence of 4-dimethylaminopyridine [143]. It can [143]. It canbebe used
used as
as a substrate for the synthesis of macroinitiators for atom transfer
a substrate for the synthesis of macroinitiators for atom transfer radical polymerization (ATRP) radical polymerization (ATRP)
reactions [142], rosin
reactions [142], rosinphosphate
phosphateesters esters [140],
[140], N-hydroxyethylacrylamide
N-hydroxyethylacrylamide esterester of dehydroabietic
of dehydroabietic acid
acid [144], dehydroabietic ethyl methacrylate [145,146],
[144], dehydroabietic ethyl methacrylate [145,146], dehydroabietic propargyl ester dehydroabietic propargyl ester [147]
[147]
dehydroabietic
dehydroabietic hexyl hexylacrylate
acrylate [148],
[148], as well
as well as intermediates
as other other intermediates in synthesis
in synthesis of various of various
surfactants
surfactants [143,149] and medicines
[143,149] and medicines [141,150,151]. [141,150,151].
Dehydroabietylamine, also known
known as ◦ C). It is commercially
Dehydroabietylamine, also as leelamine,
leelamine, is is aa solid
solid (m.p. 44.5 °C).
(m.p. 44.5 It is commercially
available. Its application in antitumor therapies was investigated in recent
available. Its application in antitumor therapies was investigated in recent years [152–155]. Moreover,years [152–155]. Moreover,
it can be a substrate for preparation of epoxy resin [156], bio-based benzoxazines
it can be a substrate for preparation of epoxy resin [156], bio-based benzoxazines [157], quaternary [157], quaternary
ammonium surfactants [158,159],
ammonium surfactants [158,159], acrylic
acrylicmonomers:
monomers:glycidyl glycidyl methacrylate
methacrylate monomer
monomer [160][160]
or N-or
N-dehydroabietic acrylamide
dehydroabietic acrylamide [161]. [161].
3.2.2. Resins and Monomers

3.2.2. Resins and Monomers
Rosin-based resins and monomers are compounds which contain epoxy, acrylic, allyl, hydroxyl or
Rosin-based resins and monomers are compounds which contain epoxy, acrylic, allyl, hydroxyl
oxazine reactive groups, that enable cross-linking, polymerization or building in the polymer matrix.
or oxazine reactive groups, that enable cross-linking, polymerization or building in the polymer
Their preparations are usually well described and easy to perform. The syntheses are similar to
matrix. Their preparations are usually well described and easy to perform. The syntheses are similar
conventional resins/monomers preparations, however the necessity of using organic solvents in several
to conventional resins/monomers preparations, however the necessity of using organic solvents in
reactions is a disadvantage in the context of Green Chemistry rules. The high modification potential
several reactions is a disadvantage in the context of Green Chemistry rules. The high modification
of rosin derivatives allows one to prepare resins and monomers showing diverse and designable
potential of rosin derivatives allows one to prepare resins and monomers showing diverse and
properties. They can exhibit adjustable glass transition temperatures, low volume shrinkage, as well as
designable properties. They can exhibit adjustable glass transition temperatures, low volume
improve elastic modulus, Young’s modulus, shape-memory, flame retardancy, corrosion protection
shrinkage, as well as improve elastic modulus, Young's modulus, shape-memory, flame retardancy,
features of final casts/polymers in comparison with petroleum-based compounds. Therefore, the best
corrosion protection features of final casts/polymers in comparison with petroleum-based
described recipes show high commercialization potential in the segment of resins, adhesives and
compounds. Therefore, the best described recipes show high commercialization potential in the
paints, but in most cases, additional applied research should be performed to increase their technology
segment of resins, adhesives and paints, but in most cases, additional applied research should be
readiness level (TRL).
performed to increase their technology readiness level (TRL).
Triglycidyl ester of maleopimaric acid is a beige, viscous liquid. It can be prepared from
Triglycidyl ester of maleopimaric acid is a beige, viscous liquid. It can be prepared from
maleopimaric acid, epichlorohydrin and sodium hydroxide according to Scheme 2, followed by
maleopimaric acid, epichlorohydrin and sodium hydroxide according to Scheme 2, followed by
filtration, washing and evaporation [83]. It can be used in liquid epoxy resins [83], non-cytotoxic
filtration, washing and evaporation [83]. It can be used in liquid epoxy resins [83], non-cytotoxic bio-
bio-based epoxypolyurethanes [162] as well as synthesis of rosin-based cyclic carbonates [132]. Similar
based epoxypolyurethanes [162] as well as synthesis of rosin-based cyclic carbonates [132]. Similar
liquid resin can be synthesized from fumaropimaric acid [122].
liquid resin can be synthesized from fumaropimaric acid [122].
O Cl O O
1.
O
Maleopimaric O 2. NaOH
O
acid O
TBA Br Maleopimaric acid
O in H2O O
O triglycidyl ester
COOH 70-130°C, 10h COO yield: 75%
O
Scheme 2. Synthesis of triglycidyl ester of maleopimaric acid.

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Scheme
Scheme 2.
Scheme Synthesis
2. 2.
Synthesis of triglycidyl
ofof
Synthesis triglycidyl ester
ester
triglycidyl of maleopimaric
ofof
ester maleopimaric acid.
acid.
maleopimaric acid.
Diglycidyl acrylpimarateis
Diglycidylacrylpimarate yellowish
isisa ayellowish liquid.
liquid.It
yellowishliquid.
yellowish liquid. ItItItcan
canbe
can
can bebeprepared
be preparedfrom
prepared
prepared fromacrylpimaric
from acrylpimaricacid,
acrylpimaric acid,
acid,
epichlorohydrin
epichlorohydrinand and sodium hydroxide according to Scheme 3, prior
and sodium hydroxide according to Scheme 3, prior tofiltration, to filtration,
filtration, washing
washingand
filtration,washing and
drying
drying[126].
drying [126].It
[126].
[126]. can
It
It It
can
canbe
can
bebeused
be
used
usedin
ininepoxy
used in
epoxy
epoxy materials
epoxy
materials
materialsshowing
materials showing
showing
showing improved
improved
improved thermal,
improved mechanical
thermal,
thermal,
thermal, and
andshape-
mechanical
mechanical
mechanical and and
shape-
shape-
memory
memory
memory properties
shape-memory
properties
properties [126].
properties
[126].[126].
[126].
COOH
COOH Cl COO
COO
COOH Cl O COO
Acrylpimaric
Acrylpimaric acid
acid 1. 1. Cl O O
1.
Acrylpimaric acid
2. N
N aOH
2. 2. aOH
N aOH O
OO
TEBAC
TEBAC
TEBAC Diglycidyl
115-60°C,
115-60°C,
115-60°C,
5h
5h5h O
Diglycidyl acrylpimarate
Diglycidyl acrylpimarate
acrylpimarate
O O yield: 88%
COOH
COOH
COOH
COO
COO
COO yield:
yield:88%
88%
Scheme
Scheme 3. 3.
3.
Scheme Synthesis
Synthesis of
Synthesis diglycidyl
ofof
diglycidyl acrylpimarate.
acrylpimarate.
diglycidyl acrylpimarate.
Another
Another diglycidyl
diglycidyl derivative
derivative of acrylpimaric
ofof
acrylpimaric acid
acid and
and its siloxane modification
itsits
siloxane modification can
can be prepared
bebe
prepared
Another diglycidyl derivative acrylpimaric acid and siloxane modification can prepared
according to Scheme 4, prior to washing, filtration and vacuum evaporation [127]. Prepared epoxy
according
accordingtotoScheme priorto
Scheme4,4,prior washing,
toto washing,filtration
washing, filtrationand
filtration andvacuum
and vacuumevaporation
vacuum evaporation
evaporation[127].
[127].Prepared
Preparedepoxy
epoxy
resins
resins can
can improve
improve the
the
the thermal
thermal
thermal stability
stability
stability and
and
and flame
flame
flame retardancy
retardancy
retardancy of
of
of products
products
products [127].
[127].
[127].
resins can improve the thermal stability and flame retardancy of products [127].
COOH
COOH O CH
CHCH OCH
OCH CH3
COOH OO 33 3 3 3 CH
3
OCH CH
3 3
CH
CHCH
3
O
OO O
OO O O
OO
H CO
H33H
CO3
(
(
CO
Si
Si
( Si
O
O )
)
Om ( Si O )k( Si O)
m)m( Si Ok)k( SiO )On
( Si O ) ( Si
n)n
3 3
O
OO O
OO OO
Ph
PhPh OCH
OCH Ph
3 3 PhPh
3
OCH
O
OO
(C O
22H
(C(C ))33N
H255H N OO
TPT
5)3N TPT
TPT
110°C
110°C COO 120°C
110°C COO
COO 120°C
120°C CH ORO
COOH OH
CHCH3
3 3 OROORO CH CHCH
33 3
COOH
COOH OHOH O
OO ORO
ORO
ORO( Si O )
( Si( SiO )Om)(
( Si
(
Si O
O )
)k (
(
) Si
(
Si O ) RO
k k O )On n)RO
mm Si O Si nRO
Ph ORO
Acrylpimaric
Acrylpimaric HO PhPh OROORO Ph PhPh
Acrylpimaric HOHO
acid
acid
acid Siloxane
Siloxane modified
modified
Siloxane AP-EDGE
AP-EDGE
modified AP-EDGE
COO
COO yield: 81-89%
COO
R
COO
COO yield: 81-89%
yield: 81-89%
R==
R=
COO O
OO
Ethylene glycol diglycidyl EEW
EEW
EEW (experimental
(experimental
(experimental
Ethylene
Ethyleneglycol diglycidyl
glycol diglycidyl value) (g/mol) = 481,
ether
ether modified
modified acrylpimaric
acrylpimaric acid
acid
O
OO O
OO value) (g/mol)
value) ==
(g/mol) 481,
481,
ether modified acrylpimaric acid 645, 714, 952,
(AP-EDGE)
(AP-EDGE)
(AP-EDGE)
COO
COO
COO
O
OO
O
OO
O
OO 645, 714,
645, 714, 952,1190
952, 1190
1190
Scheme
Scheme
Scheme4. Preparation
4.4.
4. Preparation of
Preparation ethylene
ofof
Preparation ethylene glycol
ofethylene
ethylene
glycol diglycidyl
glycol
diglycidyl
glycol ether
diglycidyl
ether
diglycidyl modified
ether
modified
ether acrylpimaric
modified
acrylpimaric
modified acid
acid
acrylpimaric and
acrylpimaric
and
acid its
acid
and siloxane
and
itsits its
siloxane
siloxane
derivative.
siloxane derivative.
derivative.
derivative.
Dimaleopimaryl
Dimaleopimaryl isisaaa abrownish yellow solid. bebeprepared from levopimaric acid
Dimaleopimarylketone
Dimaleopimaryl ketoneis
ketone brownish
brownishyellow
brownish yellowsolid.
yellow solid.It
solid. It Itcan
cancanbe prepared
preparedfrom
prepared fromlevopimaric
from levopimaricacid
levopimaric acid
acid
and
and maleic anhydride according to Scheme 5, prior to washing
washing and recrystallization [163]. It can be
and maleic anhydride according to Scheme 5, prior to washing and recrystallization [163]. It canbebe
maleic anhydride according to Scheme 5, prior to washing and recrystallization [163]. It can
used directly as an epoxy resin hardener, as well as for the synthesis of bio-based epoxy resins, i.e.,
used
useddirectly
directlyasasananepoxy
epoxyresin hardener,as
resinhardener, well
asas wellas
well asas for
forthe
for thesynthesis
the synthesisof
synthesis bio-based
ofof bio-basedepoxy
bio-based epoxyresins,
epoxy resins,i.e.
resins, i.e.
i.e.
tetraglycidyl
tetraglycidyl dimaleopimaryl
dimaleopimaryl ketone,
ketone, according
according
according to
to
to Scheme
Scheme
Scheme 5
55 [163].
[163].
[163].
tetraglycidyl dimaleopimaryl ketone, according to Scheme 5 [163].
O
OO
O O
OO
OO
O
OO
O
OO O
OO
O O
OO
OO O
OO
pTSA
pTSA O O 1. NaOH
1. 1.
NaOH
in
pTSA OO OO O
OO NaOH
in toluene
toluene
in toluene O
OO 2.
Cl
Cl O
135-230°C
135-230°C O 2. 2. Cl O O
135-230°C OO O
OO
5h
5h 5h zinc acetate
zinc acetate
zinc acetate zinc acetate
in zinc acetate
in CH
CHCH33COOH
COOH in
zinc acetate
COOH
in
?°C,
3COOH
12h in DMF,
DMF,
in DMF,
?°C,
?°C, 6h
6h 6h
?°C,
COOH
COOH ?°C,
?°C,12h12h
O
O O
Levopimaric
Levopimaric
Levopimaric
O O
OO
OO
acid
acid
acid
O
OO O
OO
Dipimaryl
Dipimaryl
Dipimaryl ketone
ketone
ketone O
O
OO
OO
yield:
yield: 97%
97%
yield: 97%
O
OO
O
Dimaleopimaryl
Dimaleopimaryl
Dimaleopimarylketone
ketone
ketone
O O Tetraglycidyl
Tetraglycidyl
Tetraglycidyl
yield:
yield: 85%
85%
yield: 85% dimaleopimaryl
dimaleopimaryl ketone
ketone
dimaleopimaryl ketone
Scheme
Scheme 5. Synthesis
5. 5.
Scheme Synthesis of
of
Synthesis tetraglycidyl
dimaleopimaryl ketone.
ketone.
Scheme 5. Synthesis ofof tetraglycidyl
dimaleopimaryl ketone.
ketone.
Molecules 2019, 24, 1651 7 of 52
Molecules2019,
Molecules 2019,24,
24,xxFOR
FORPEER
PEERREVIEW
REVIEW 77 of
of 51
51
Rosin
Rosinpentaglycidyl
pentaglycidylether
etherisisaaasolid. It
solid. It can
It can
can bebe prepared
be prepared from
prepared from epoxidized
from epoxidized rosin, water,
epoxidized rosin,
rosin, potassium
water, potassium
potassium
Rosin pentaglycidyl ether is solid. water,
hydroxide
hydroxide and
and epichlorohydrin
epichlorohydrin according
accordingto Scheme
to 6,
Scheme and6, using
and such
using separation
such methods
separation as vacuum
methods as
hydroxide and epichlorohydrin according to Scheme 6, and using such separation methods as
drying, filtration,
vacuum drying, precipitation
drying, filtration, and washing
filtration, precipitation
precipitation and [164].
and washing It can
washing [164]. be used
[164]. ItIt can
can be as a
be usedcomponent
used as in
as aa component epoxy
component in resin
in epoxy
epoxy
vacuum
systems
resin showing
systems high glass
showing high transition
glass temperature
transition as wellasaswell
temperature elastic
as modulus
elastic [164]. [164].
modulus
resin systems showing high glass transition temperature as well as elastic modulus [164].
1. KOH
KOH O
O
3-chloro- 1.
3-chloro- O
O OH
OH O
OH O O O
O
peroxybenzoic
peroxybenzoic OH 2. O
acid O
HH22OO 2. Cl
Cl
O
O
acid O OH
OH OH
OH O O
O O
in CH Cl2 inCC2HH5OH
OHaqaq inCH Cl
CH2Cl O
O
in CH22Cl 2 in 2 5 in 2 22 O O
O
0°C, 6-8h O
0°C, 6-8h 90°C, 36h
90°C, 36h 80°C, 7h
80°C, 7h
COOH COOH COOH Rosin OO

COOH COOH COOH Rosin
Rosin
Rosin pentaglycidyl
pentaglycidyl CC
Epoxidized rosin
Epoxidized rosin Hydroxylated rosin
Hydroxylated rosin O
ether
ether O
Scheme 6.
Scheme
Scheme 6. Synthesis
6. of rosin
Synthesis of
of rosin pentaglycidyl
rosin pentaglycidyl ether.
pentaglycidyl ether.
ether.
Polygral
Polygral is
Polygral is
is aaa solid
solid byproduct
solid byproduct
byproduct of of the
of the paper
the paper
paper andand forestry
forestry industry,
forestry industry, containing
industry, containing rosin
containing rosin acids
rosin acids
acids andand their
and their
their
oligomers [165].
oligomers [165].
oligomers It can
[165]. It can be be epoxidized
be epoxidized
epoxidized to to prepare
to prepare bio-based
prepare bio-based epoxy
bio-based epoxy resins.
epoxy resins. Endocyclic
resins. Endocyclic epoxidized
Endocyclic epoxidized
epoxidized
polygral
polygral is
is a red brown solid,
solid, which
which can
can be
be prepared
prepared using
using 3-chloroperoxybenzoic
3-chloroperoxybenzoic
polygral is a red brown solid, which can be prepared using 3-chloroperoxybenzoic acid, according acid,
acid, according
according to
to
to Scheme
Scheme 7, 7,
priorprior to to
vacuumvacuum evaporation.
evaporation. On On
the the
other other
hand, hand, exocyclic
exocyclic epoxidized
epoxidized
Scheme 7, prior to vacuum evaporation. On the other hand, exocyclic epoxidized polygral is a viscous polygralpolygral
is a is
viscous a
viscous red brown liquid, that can be prepared in two ways, using oxalyl chloride or N,N 0 -diisopropyl
red brown
red brown liquid,
liquid, that that can
can bebe prepared
prepared in in two
two ways,
ways, using
using oxalyl
oxalyl chloride
chloride or N,N′-diisopropyl
N,N′-diisopropyl
carbodiimide
carbodiimide before
before addition
addition of glycidol,
of according
glycidol, accordingto Scheme
to 7
Scheme
carbodiimide before addition of glycidol, according to Scheme 7 prior to washing prior
7 to washing
prior to and
washing vacuum drying.
and vacuum
and vacuum
They
drying.can be
drying. They used
They cancan be for preparing
be used
used for bisphenol
for preparing A-free
preparing bisphenol epoxy
bisphenol A-free resins
A-free epoxy [165].
epoxy resins
resins [165].
[165].
O
O
3-chloro-
3-chloro- 1.NN CC NN
1. 2.
O peroxybenzoic
peroxybenzoic 2. O
OH O O
O OH O
acid
acid HOOC
HOOC HOOC O CC
O HOOC O
O inCH
in CH2ClCl pTSA/DMAP
pTSA/DMAP
2 22
-5°C, 10h
10h in CH
in CH2Cl
Cl
-5°C, COOH 2 22
COOH O
O COOH 0°C, 72h
72h COO
COOH 0°C, COO
Endocyclic
Endocyclic Cl
Cl O
O O
O
Polygral
Polygral Exocyclic
epoxidized
epoxidized Exocyclic
polygral
polygral O Cl O epoxidized
epoxidized
(C2HH5))3NN O Cl O
(C 2 5 3 Cl
Cl
polygral
polygral
in toluene
in toluene OH
OH
20°C, 24h
24h O CC
O (C2HH5))3NN
20°C, (C 2 5 3
intoluene
in toluene
0°C, ?h
0°C, ?h
COCl
COCl
Scheme 7.
Scheme 7. Preparation
Preparation of
of epoxidized
epoxidized rosin
rosin oligomers.
oligomers.
Diglycidyl
Diglycidyl dehydroabietylamine
Diglycidyl dehydroabietylamine is
dehydroabietylamine is
is aaa yellowish
yellowish sticky
yellowish sticky liquid.
sticky can be
liquid. ItIt can
liquid. be
be synthesized
synthesized from
synthesized from
from
dehydroabietylamine,
dehydroabietylamine, epichlorohydrin
epichlorohydrin and sodium
and hydroxide
sodium hydroxide according to
according
dehydroabietylamine, epichlorohydrin and sodium hydroxide according to Scheme 8, prior to Scheme
to 8, prior
Scheme to
8, filtration,
prior to
washing,
filtration, drying
washing, and vacuum
drying and distillation
vacuum [156]. It
distillation can be
[156]. Itapplied
can be in epoxy
applied inresins
filtration, washing, drying and vacuum distillation [156]. It can be applied in epoxy resins exhibitingepoxy exhibiting
resins better
exhibiting
thermal
better stabilitystability
better thermal
thermal and higher
stability andglass
and higher
highertransition
glass temperatures
glass transition
transition than petroleum-based
temperatures
temperatures than products [156].
than petroleum-based
petroleum-based products
products
[156].
[156]. Rosin maleimidodicarboxylic acid diglycidyl ether is a yellowish solid. It can be prepared from
Rosin maleimidodicarboxylic
epichlorohydrin and dicarboxylic acid diglycidyl
derivative of ether
maleimide is a yellowish
(described solid.
in more
Rosin maleimidodicarboxylic acid diglycidyl ether is a yellowish solid. It can be prepared fromIt can be
detail inprepared
Section from
3.2.3)
epichlorohydrin
according to Scheme
epichlorohydrin and9dicarboxylic
and dicarboxylic derivative
prior to filtration, washing,
derivative of maleimide
of maleimide (described
drying and(described in more
rotary evaporation
in more[84].
detail
detail in subsection
It in subsection
shows higher
3.2.3)
glass according
transition to Scheme
temperature, 9 prior
modulus to filtration,
and washing,
thermal drying
stability than and
its rotary
plant evaporation
oil counterparts
3.2.3) according to Scheme 9 prior to filtration, washing, drying and rotary evaporation [84]. It shows [84]. It
[84]. shows
higherglass
higher glasstransition
transitiontemperature,
temperature,modulus
modulusand andthermal
thermalstability
stabilitythan
thanitsitsplant
plantoil
oilcounterparts
counterparts[84]. [84].
Cl O
1.
2. NaOH
Dehydroabietylamine
Molecules 2019, 24, 1651 H2O ; TBA Br O
Diglycidyl 8 of 52
Molecules
Molecules 2019,
2019, 24,
24, xx FOR
FOR PEER
PEER REVIEW
REVIEW 45°C, 153h dehydroabietylamine
88 of
of 51
51
NH2 N O
yield: 90%
Cl
Cl O
O
Scheme 8. Synthesis of1.
1.diglycidyl dehydroabietylamine.
2.
2. NaOH
NaOH
O O
Dehydroabietylamine
Dehydroabietylamine
O O H
H22O
O ;; TBA Br
COOH
TBA Br
O
O Diglycidyl
Diglycidyl
N
O 45°C,
45°C, 153h
153h dehydroabietylamine
dehydroabietylamine
N COO
NH N
N O
O
NH22 O yield:
yield: 90%
90%
H2N COOH
Cl O O
Scheme 8.
8. Synthesis O
in DMF
Scheme Synthesis of
of diglycidyl
diglycidyl dehydroabietylamine.
dehydroabietylamine.
NaH COO O
160°C, 4h in DMF Rosin-maleimidodicarboxylic
O
O COOH 150°C, 5h O
acid
O diglycidyl ether
O
O O COOH
O COOH COOH
N
N yield: 47%
MaleopimaricO
O Rosin-maleimidodicarboxylic
O acid N
N
COO
COO
O
acid H yield: 87%
H22N
N COOH
COOH
Cl O
O O
Cl O O
O
Scheme
in DMF9. Preparation of rosin maleimidodicarboxylic
NaH acidCOO
diglycidylOether.
in DMF NaH COO O
160°C,
160°C, 4h
4h in
in DMF Rosin-maleimidodicarboxylic
COOH DMF
150°C,
Rosin-maleimidodicarboxylic
COOH
Triester of maleopimaric acid and 150°C, 5h
5h
trimethylolpropane is a dark yellow solid. acid
acidItdiglycidyl ether
can be prepared
diglycidyl ether
COOH
COOH
according to Scheme 10, prior to washing and vacuum distillation [98]. It can be used in yield:
yield: 47%
47%of
synthesis
Maleopimaric
Maleopimaric Rosin-maleimidodicarboxylic acid
rosin-based epoxy Rosin-maleimidodicarboxylic
resin [98]. acid
acid
acid yield:
yield: 87%
87%
Epoxy resin having EEW = 199.68 g/eq based on maleopimaric acid and trimethylolpropane ester
can be preparedScheme
Scheme 9.
9. Preparation
according to Scheme
Preparation of rosin
of 10,
rosin maleimidodicarboxylic
prior to extraction andacid
maleimidodicarboxylic diglycidyl
vacuum
acid ether.
distillation
diglycidyl ether. [98]. It can be
ether.
used directly as an epoxy compound, or transformed into acrylate resin [98].
Triester
Triester
Acrylateof
Triester of maleopimaric
maleopimaric
ofresin
maleopimaric acid
acid and
based on epoxidized and trimethylolpropane
trimethylolpropane is
is aa dark yellow
dark yellow
maleopimaric-trimethylolpropane yellow solid.
solid.
adduct It
It can
can bebe prepared
prepared
according to Scheme
according to Scheme 10, 10, prior to washing
priorIttocan
10 [98]. washing and
be usedand vacuum
as avacuum distillation
distillationby
resin crosslinked [98].
[98]. It can be used
It can methacrylated
styrene, in synthesis
be used in synthesiseugenol of
of
rosin-based
rosin-based epoxy
epoxy resin
resin
or methacrylated guaiacol [98].[98].
[98].
[98].
Epoxy
Epoxy resin
resin having
having EEW
EEW == 199.68
199.68 g/eq
g/eq based
based onon maleopimaric
maleopimaric acid acid and
and trimethylolpropane
trimethylolpropane ester ester
can beO prepared according
HO toOH Scheme 10,
OH prior to extraction and
can be prepared according to Scheme 10, prior to extraction and vacuum distillation vacuum distillation [98].
Crosslinked It can
resinbe
[98]. It can be
O
used
used directly
directly asas an
an epoxy
epoxy compound,
compound, or
or transformed
transformed into
into acrylate
acrylate resin
resin [98].
[98]. styrene
OH OH
Acrylate O or methacrylated eugenol
Acrylate resin
resin based
based
pTSA
on
on epoxidized
epoxidized
OH O
maleopimaric-trimethylolpropane
maleopimaric-trimethylolpropane adduct can
can be
adductguaiacol
or methacrylated be prepared
prepared
according to Scheme 10
according to Scheme 10in [98]. [98]. It can be used
xylene It can be used O as a resin crosslinked by styrene, methacrylated eugenol
as a resin crosslinked by styrene, methacrylated eugenol
O O OH O
or
or methacrylated
methacrylated guaiacol
guaiacol [98].
[98]. O
HO O
1. K OH/ O
O
O COOH HO
NaOH
HO OH
OH OH
OH OH Crosslinked
Crosslinked resin
resin
O
O O
Cl O styrene
2. OH OH O styrene
HO
OH OH
Maleopimaric O
O or
or methacrylated
methacrylated eugenol
eugenol
O O
pTSA O or methacrylated guaiacol
acid pTSA in DMSO OHOH O
O COO
OH or methacrylated guaiacol
in
in xylene
<24°C,18h
xylene O
O
O O
O O OH
OH O O O O
O
Maleopimaric acid OH O
O
HO HO
O
O HO O
O
1.
1. OK
K OH/
OH/ trimethylolpropane ester O O O
O O
O
COOH
COOH NaOH OH
O NaOH
O O yield:
OH 93%
O O
Cl
Cl O O
O O 2. O HO
2. O O
O HO
Maleopimaric
Maleopimaric O
OH
O
O O
in O O O
acid
acid
O in DMSO
DMSO COO
OH
OH
O O
O O <24°C,18h COO HO
<24°C,18h O
O OH
O O O
O
O Maleopimaric
Maleopimaric acid
acid OH
OH O
O O
HOO
O
O
O O HO
O O O trimethylolpropane
trimethylolpropane ester
PPh3
ester O O
O
O
O Maleopimaric acid
O O O
O
O
Maleopimaric
O acid
O
O O
O OO yield: 93%
HQ
yield: 93%
trimethylolpropane-based 85°C, 3.5h trimethylolpropane-based
OO
O O O
Oepoxy resin yield:
O O 85% epoxy acrylate resin
OH
OH yield: 95%
O O
O
O
O O O
O
O Scheme
OScheme 10.O
10. Preparation of maleopimaric acid-trimethylolpropane HO
ester-based
HO epoxy acrylate
O Preparation of maleopimaric acid-trimethylolpropane ester-based epoxy acrylate resin
OH O
O resin
O
O OH
crosslinked by
crosslinked by unsaturated
unsaturated monomers.
monomers.
OO O O
O
O O
O PPh
PPh33
Maleopimaric
Maleopimaric acid
acid Maleopimaric acid
O Maleopimaric acid
O resin having EEW = 199.68 g/eq based onHQ
EpoxyO O
maleopimaric acid and trimethylolpropane ester
trimethylolpropane-based HQ
trimethylolpropane-based trimethylolpropane-based
can be prepared according to
epoxy Scheme 10, prior to85°C,
85°C, 3.5h
3.5h
extraction and vacuumtrimethylolpropane-based
distillation [98]. It can be
epoxy resin
resin yield:
yield: 85%
85% epoxy
epoxy acrylate
acrylate resin
resin yield:
yield: 95%
95%
used directly as an epoxy compound, or transformed into acrylate resin [98].
Scheme
Scheme 10.
10. Preparation
Preparation of
of maleopimaric
maleopimaric acid-trimethylolpropane
acid-trimethylolpropane ester-based
ester-based epoxy
epoxy acrylate
acrylate resin
resin
crosslinked
crosslinked by
by unsaturated
unsaturated monomers.
monomers.
Molecules 2019, 24, 1651 9 of 52
Acrylate resin based on epoxidized maleopimaric-trimethylolpropane adduct can be prepared

according to Scheme 10 [98]. It can be used as a resin crosslinked by styrene, methacrylated eugenol or
Molecules 2019, 24, guaiacol
methacrylated x FOR PEER REVIEW
[98]. 9 of 51
Dehydroabietic ethyl methacrylate is a white powder. It can be prepared from dehydroabietyl

chloride and hydroxyethyl methacrylate according to Scheme 11, prior to neutralization, drying,
evaporation and chromatography O [146]. It can be widely used as 2a)2Omonomer in preparation of graft
HO(CH
O(CH
and block copolymers [146,166–170]. 2)2OH It is worth noting, that a similar O compound dehydroabietic
ethyl acrylate
O(CH2)2Ois a yellow, viscous
pyridine liquid, which can be prepared (CH3)from
3N hydroxyethylO(CHacrylate
2)2O
and
dehydroabietyl
O chloride
O priorinto
CHfiltration,
2Cl2 COCl
precipitation in CH
and vacuum 2Cl2
distillation [171].
O It can be used
O for
Dehydroabietic 50°C, 4h Dehydroabietyl 0-25°C, 48h Dehydroabietic
preparation of homopolymer with no declared application [171]. Moreover, rosin ethyl acrylate can be
ethylinacrylate chloride ethyl methacrylate
used
Molecules preparation
2019, 24, x FORof bio-based
PEER REVIEWgraft copolymers of chitosan for controlled release applications9[172]. of 51
Scheme 11. Synthesis of dehydroabietic ethyl acrylates.
Cl
O
HO(CH2)2O
O(CH2)2OH O O
HO(CH2)6OH
pyridine (CH3)3N(CH3)3N
O(CH
Molecules 2)2O
2019, 24, xDMAP
FOR PEER REVIEW HO O(CH2)2O 9 of 51
O O in CH2Cl2 COCl HQ in CH2Cl2
in THF O OO
50°C, 4h Dehydroabietyl in THF
0-25°C, 48h
Dehydroabietic
COCl 50°C, 12h O 25°C, 10h Dehydroabietic
O
ethyl acrylate chloride O
ethyl methacrylate
Dehydroabietyl O O Hydroxyhexyl O Dehydroabietic
HO(CH2)2O
chloride dehydroabietate
Scheme
O(CH 11.
) OHSynthesis ofyield: 72%
dehydroabietic ethyl hexyl
acrylates. acrylate yield: 41%
Scheme 11. Synthesis of dehydroabietic ethyl acrylates.
2 2
O
O(CH ) O pyridine
Scheme (CH3)3acrylate.
12. Synthesis of dehydroabietic hexyl N O(CH ) O
2 2 Cl 2 2
Dehydroabietic
O O
hexyl acrylate
in CH2Cl2is a solid. COCl
It can be synthesized
in CH2Cl2from dehydroabietyl
O O
chloride,
Dehydroabietic
hexanediol and acryloyl 50°C, 4h
chloride according Dehydroabietyl
to Scheme 12, 0-25°C,
and 48h separationDehydroabietic
using methods such as
Dehydroabietic ethyl methacrylate is a white powder. It Ocan be prepared from dehydroabietyl
chloride
ethyl acrylate
filtration, HO(CH2)6OH
precipitation, washing and vacuum drying [148]. Its application is a ethyl
soft methacrylate
acrylic monomer
(CH3)3N11, prior to neutralization, drying,
chloride and hydroxyethyl methacrylate according to Scheme
(glass transition DMAP
temperature of −23 ◦ C), whichHO can impart a flexibility to the integrated polymer [148].
evaporation and chromatography Scheme 11.[146]. It canofbe
Synthesis widely used
dehydroabietic HQ as aacrylates.
ethyl monomer in preparation of
O graft
in THF in THF
and block
COCl copolymers [146,166–170]. ItOis worth noting, that25°C,
50°C, 12h a similar
10h compound dehydroabietic ethyl O
Cl O
Dehydroabietyl
acrylate is a yellow, viscous liquid, which
O Hydroxyhexyl can be prepared from hydroxyethyl
O Dehydroabietic acrylate and
chloride
dehydroabietyl chloride prior dehydroabietate
to filtration, yield:
precipitation 72% and O
vacuum hexyl
distillation acrylate yield:
[171]. It can be41%used
HO(CH2)6OH
for preparation of homopolymer with no declared (CH3)3N[171]. Moreover, rosin ethyl acrylate
application
HO
DMAP Scheme 12. Synthesis of dehydroabietic HQhexyl acrylate.
can be used in preparation of bio-based graft copolymers O
in THF in THF of chitosan for controlled release
50°C, 12h 25°C, 10h O
applications
COCl [172].
Dehydroabietic ethyl methacrylate O
is a white powder. It can be preparedO from dehydroabietyl
Dehydroabietyl
Dehydroabietic hexyl acrylate OisHydroxyhexyl
a solid. It can to be Scheme
synthesized from to O Dehydroabieticchloride,
dehydroabietyl
chloride
chlorideand hydroxyethyl methacrylate according 11, prior neutralization, drying,
hexanediol and acryloyl dehydroabietate
chloride according toyield:
Scheme72% 12, and using hexyl
separation acrylate
methodsyield: 41%
such as
evaporation and chromatography [146]. It can be widely used as a monomer in preparation of graft
filtration, precipitation,
and block copolymers [146,166–170].washing
Scheme and
12. vacuum
Synthesis
It is worth
Scheme 12. Synthesis drying
of [148].
dehydroabietic
of noting, Its application
hexyl
that a similar
dehydroabietic acrylate. is a soft acrylic
compound dehydroabietic ethyl
hexyl acrylate. monomer
(glass
acrylate transition temperature
is a yellow, viscous of −23 °C), which
liquid, which can canimpart a flexibility
be prepared from to the integrated polymer
hydroxyethyl acrylate[148].and
Dehydroabietic ethyl
N-hydroxyethylacrylamide ester
N-hydroxyethylacrylamide methacrylate
ester of is a white
of dehydroabietic powder. It can
dehydroabietic acid is a viscous, be prepared
viscous, from dehydroabietyl
yellow liquid.
liquid. It can be
dehydroabietyl chloride prior to filtration, precipitation and vacuum distillation [171]. It can be used
chloridefrom
prepared and hydroxyethyl
dehydroabietyl methacrylate
chloride and according to Scheme 11, prior toaccording
N-hydroxyethylacrylamide
N-hydroxyethylacrylamide neutralization,
according drying,13,
to Scheme
to Scheme 13,
for preparation of homopolymer with no declared application [171]. Moreover, rosin ethyl acrylate
evaporation
prior to
to filtration,andwashing,
filtration, chromatography
washing, drying
drying [146].
and
and It canchromatography
column
column be widely used as[144].
chromatography a[144].
monomer
It It
cancan inbe
be preparation
used as as of graft in
a monomer
can be used in preparation of bio-based graft copolymers of chitosan forusedcontrolleda monomer
release
in and
thermoset block
thermoset copolymers
system
system with with[146,166–170].
soybean
soybean oil-basedIt is
oil-based worth
resin noting,
forfor
resin that
coating
coating a similar
andand adhesivecompound
adhesive dehydroabietic
applications
applications [144].ethyl
[144].
applications [172].
acrylate is a yellow, viscous liquid, which can be prepared from hydroxyethyl acrylate and
Dehydroabietic
dehydroabietyl hexylprior
chloride acrylate is a Osolid.
to filtration, It can beand
precipitation synthesized from dehydroabietyl
vacuum distillation [171]. It can be chloride,
used
hexanediol and acryloyl
forDehydroabietyl
preparation chloride with
of homopolymer according to Scheme
no declared 12, and
application using
[171]. separation
Moreover, rosinmethods
ethyl such as
acrylate
Dehydroabietic acid
filtration, chloride NH
can be precipitation,
used washingofand
in preparation vacuum
bio-based drying
graft [148]. Its application
copolymers of chitosanisfor a soft
N-hydroxyethylacrylamide acrylic ester
controlled monomer
release
(glass transition
applications [172]. temperature of −23 °C), which can impart a purity: 90%, yield: 80%
flexibility to the integrated polymer [148].
N-hydroxyethylacrylamide
Dehydroabietic hexyl acrylate OH
esteris of dehydroabietic
a solid. acid is a viscous,
It can be synthesized yellow liquid.chloride,
from dehydroabietyl It can be
N O
prepared
hexanediol from dehydroabietyl
and acryloyl chloride Etaccording
3N
chloride Scheme 12, H and using separation
and toN-hydroxyethylacrylamide according to
methods Scheme
such as13,
C O
COCl in CH2Cl2 ; 45°C/4h O
filtration, precipitation, washing and vacuum drying [148]. Its application
prior to filtration, washing, drying and column chromatography [144]. It can be used as a monomer is a soft acrylic monomer
in (glass transition
thermoset system
Schemetemperature
with of −23
soybean
13. Synthesis
Synthesis
°C), which
ofoil-based can for
resin impart
N-hydroxyethylacrylamide a flexibility
coating and of
ester to the integrated
adhesive applications
dehydroabietic polymer
acid. [144].[148].
N-hydroxyethylacrylamide ester of dehydroabietic acid is a viscous, yellow liquid. It can be
prepared
Rosin-based
Rosin-basedfrom high
dehydroabietyl
high adhesion chlorideO and N-hydroxyethylacrylamide
adhesion polyurethane
polyurethane acrylate is
acrylate is aa faint-yellow
faint-yellow solid. according
solid. cantobe
It can
It beScheme
synthesized
synthesized13,
Dehydroabietyl
prior to filtration, washing, drying and column chromatography Dehydroabietic
[144]. It can be acid
used as a monomer
from hydrogenated
from hydrogenated rosin,
rosin,isophorone
isophoronediisocyanate
diisocyanate
NH and
and 2-hydroxyethyl
2-hydroxyethyl acrylate
acrylate according
according to Scheme
to Scheme 14,
in thermoset chloride
system with soybean oil-based resin for coating andN-hydroxyethylacrylamide adhesive applications [144].ester
14, prior to precipitation, vacuum drying and column chromatography purity: 90%, [173].
yield:Its80%
application is an
adhesive having a high polymerizationOHrate, O low volume shrinkage and high adhesion [173].
N O
Dehydroabietyl Et3N
C O
H Dehydroabietic acid
chlorideCOCl NH
in CH2Cl2 ; 45°C/4h O N-hydroxyethylacrylamide ester
purity: 90%, yield: 80%
Molecules 2019, 24, 1651 10 of 52
NCO O Rosin-based O
HO
O O
high
NCOand column chromatography [173]. Its application
adhesion
prior to precipitation, vacuum drying O
is an adhesive
polyurethane
having a highNCO dibutyltin dilaurate
polymerization rate, low volume shrinkage and high adhesion [173]. acrylate
Molecules 2019, 24, x FORp-methoxyphenol
Isophorone PEER REVIEW HN O 10 of 51
40°C NH
diisocyanate O
NCO
NCO O
O O
O Rosin-based
O COOH O
HO
HO
O NCO O
high adhesion
O NCO MgCl2 in butyl acetate O
O
N
O
O N polyurethane
NCO dibutyltin dilaurate
NCO dibutyltin dilaurate H
O p-methoxyphenol O O acrylate
O
Isophorone p-methoxyphenol HN
HN O
O
40°C NH
NH 75-100°C O
diisocyanate O
N
H
O
O
O
O COOH
COOH O
O
Scheme 14. Synthesis of rosin-based high
MgCl2
2
adhesion
in butyl acetatepolyurethane acrylate.
N
N N
N
O
O dibutyltin dilaurate H
H
O
O O
O O
O
O
O p-methoxyphenol
Rosin-based glycidyl methacrylate monomers are viscous
liquids: brown rosin acid-glycidyl
75-100°C O
O
methacrylate and colorless dehydroabietylamine-glycidyl methacrylate. They can be N H
H
O
O
Nprepared from
glycidyl methacrylate and rosin or dehydroabietylamine according to Scheme 15, prior to the use of
Scheme 14. polyurethane acrylate.
such separation Scheme 14. Synthesis
techniques of rosin-based
as washing, highand
extraction adhesion polyurethane
evaporation acrylate.
[160,174]. They significantly
improve thermal
Rosin-based
and mechanical
glycidyl
properties
methacrylate
of
monomers
soybean
are
oil-based
viscous
thermosets
liquids: brown
[160]. Moreover,
rosin
they
acid-glycidyl
Rosin-based glycidyl methacrylate monomers are viscous liquids: brown rosin
can be used in copolymerization with other acrylate monomers [175], or as an advanced tackifier in acid-glycidyl
methacrylate
methacrylate and
and colorless
colorless dehydroabietylamine-glycidyl
dehydroabietylamine-glycidyl methacrylate. They can be prepared from
the UV-crosslinking pressure sensitive adhesives [174,176].methacrylate. They can be prepared from
glycidyl methacrylate and rosin or dehydroabietylamine
glycidyl methacrylate and rosin or dehydroabietylamine according accordingtotoScheme
Scheme 15,15, prior
prior to to
thethe
useuseof
of such separation techniques as
such separation techniques as washing, washing,
O
extraction and evaporation [160,174]. They significantly
extraction and evaporation [160,174]. They significantly
improveCOOH
improve thermal
thermaland
and
O
mechanical
mechanical properties
properties ofof
soybean
soybeanoil-based thermosets
oil-based thermosets[160]. Moreover,
[160]. O
Moreover,theythey
can
be O HO O
canused in copolymerization
be used in copolymerization
O
withwith
other acrylate
other monomers
acrylate monomers[175], or asoran
[175], asadvanced
an advanced tackifier in the
tackifier in
UV-crosslinking pressure
O sensitive adhesives
the UV-crosslinking pressure sensitive adhesives [174,176].
[174,176].
OH NH2 N
TBA Br O
in MEK O
O HO
O
COOH <80°C, 24h
COOH O O O
O
O
O
O
O
O HO
HO O
O
Rosin acid O
O
in ethanol
O
O
Rosin
acid-glycidyl 40-80°C, 60h
O
OH NH N
methacrylate monomerOH NH22 N
TBA Br Dehydro-
yield: 95% Dehydroabietylamine-glycidyl
O
O
in MEK
in MEK abietylamine HO
<80°C, 24h methacrylate
O
O
HO monomer
O
O O
O O
O yield: 89%
Rosin acid in ethanol

Rosin
Scheme acid-glycidyl
15. Synthesis of rosin-based glycidyl methacrylate monomers.
40-80°C, 60h
O
O
Dehydro-
Ethylene glycol maleic rosinate yield: 95%
(meth)acrylate can be preparedDehydroabietylamine-glycidyl
abietylamine from maleated rosin, ethylene
glycol and (meth)acrylic acid according to Scheme 16 [85]. It can be applied in styrene-acrylate
yield: 89%
copolymers increasing their thermal stability [86], as well as in preparation of moleculary imprinted
Scheme
polymers for stationary
Scheme 15. Synthesis
phases
15. used inof
Synthesis rosin-based
rosin-based glycidyl
ofhigh-performance methacrylate
glycidylliquid monomers.[85,87].
chromatography
methacrylate monomers.
Diallyl acrylpimarate is a yellow liquid [123]. It can be prepared from acrylpimaric acid and an
Ethylene
allyl Ethylene glycol
halide byglycol maleic
maleic
different rosinate
rosinate
methods, (meth)acrylate
(meth)acrylate
according to Schemecan be
can be prepared
17,prepared
and using from
from maleated
maleated
separation rosin, ethylene
rosin,
methods ethylene
such as
glycol and (meth)acrylic
glycol andwashing,
filtration, (meth)acrylic acid according
acid according
extraction to Scheme
to Scheme
and evaporation 16 [85].
16 [85]. It
[88,123,177]. It can
It can be
can be applied
be applied in
applied in styrene-acrylate
asstyrene-acrylate
a monomer in
copolymers
copolymers
polyester increasingresins
increasing
unsaturated their thermal
their thermal
from stabilityresources
stability
renewable [86], as
[86], as well
well as or
as
[123], in in
in preparation
preparation ofaminated
of
synthesis of moleculary
moleculary imprinted
imprinted
curing agent
polymers
polymers
for for
epoxy for stationary phases used in high-performance liquid chromatography
stationary phases used in high-performance liquid chromatography [85,87].
[178]. [85,87].
Diallyl acrylpimarate is a yellow liquid [123]. It can be prepared from acrylpimaric acid and an
allyl halide by differentO methods, according
HO to Scheme 17, and using O separation
O methods such as
R
filtration, washing, extraction and evaporation [88,123,177]. It can be applied O R as a monomer in
O O O
polyester unsaturated resins from renewable resources [123], or in synthesis of aminated curing
Ethylene agent
glycol
O
for epoxy [178]. O
O maleic rosinate
O
ZnO O O (meth)acrylate
HOOC Maleic rosin
O
O 200-220°C,
HO
HO
3h
O
R O
O O
O
R
R O O R
O
O R R R = H- or CH3-
O
O O
O O O
O
Ethylene glycol
O
O
O
Preparation
Scheme 16. Preparation of ethylene
of ethylene glycol O acrylate.
glycol maleic rosinate O
O
maleic rosinate
O
O
ZnO O O
O
(meth)acrylate
O
HOOC
HOOC Maleic rosin 200-220°C, 3h O
R
R
O
O
O O
O R
R R
R== H-
H- or
or CH
CH33--
O
O
Scheme 16. Preparation of ethylene glycol maleic rosinate acrylate.

Molecules 2019, 24, 1651 11 of 52

Diallyl acrylpimarate is a yellow liquid [123]. It can be prepared from acrylpimaric acid and
an allyl halide by
Aminated different
diallyl methods, according
acrylpimarate to Schemesolid.
is a yellow-brown 17, and using
It can be separation
synthesizedmethods such
from diallyl
as filtration, washing,
acrylpimarate extraction
and cysteamine and evaporation
hydrochloride [88,123,177].
according to SchemeIt can
17,be applied
prior as a monomer
to washing, in
extraction
polyester unsaturated resins from renewable resources [123], or in synthesis of aminated
and evaporation [178]. It can be applied as a resin or a curing agent for epoxy resins, giving them curing agent
for epoxy [178].
improved thermal and acrylpimarate
shape-memoryisproperties [178]. solid. It can be synthesized from diallyl
Aminated diallyl a yellow-brown
acrylpimarate and cysteamine hydrochloride according to Scheme 17, prior to washing, extraction
COOH COO
and evaporation [178]. It can be applied asCla resin or a curing agent for epoxy NH2
resins, giving them
HS COO
improved thermal and shape-memory COONa properties
HDMA Cl [178].
in DMF DMAP
NaOH in dioxane+ethanol
<60°C, <2h
COOH in ethanol COO UV 36W, 4h
microwaves 700W
Cl
25°C, 1h HS NH2 COO S
COOH COONa HDMA Cl COO S
in DMF Br DMAP
NaOH COO
<60°C, <2h Aminated di-allyl
in dioxane+ethanol
Acrylpimaricin ethanol K2CO 3 UV 36W, 4h acrylpimarate
microwaves 700W
acid Sodium
25°C, 1h Di-allyl
in acetone H2N
acrylpimarate
COONa
acrylpimarate
70°C, 12h yield: 58% NH2 S
COOH COO S
yield: 100% Br yield: 85-92%
COO
Aminated di-allyl
Acrylpimaric K2CO3
acrylpimarate
acid Sodium
Scheme 17.
Scheme 17. Synthesis of diallyl
in acetone Di-allyland
diallyl acrylpimarate
acrylpimarate and its
its aminated
aminated derivative.
derivative. H2N
acrylpimarate
COONa
70°C, 12h acrylpimarate yield: 58% NH2
Sodiumyield:
Aminated 100%acrylpimarate
diallyl
maleopimarate is a solid,iswhich yield:
a yellow-brown
can 85-92%
solid.from
be prepared It can be synthesized
maleopimaric acid from diallyl
according to
acrylpimarate
Scheme 18 prior and cysteamine
to drying hydrochloride
at 40 °C according
[89]. Its to Scheme
applications 17, prior
include to washing,
the
Scheme 17. Synthesis of diallyl acrylpimarate and its aminated derivative.
extraction
synthesis of and
triallyl
evaporation [178]. It can be applied as a resin or a curing agent for epoxy resins, giving them improved
maleopimarate.
thermal and shape-memory
Sodium maleopimarateproperties
is a solid, [178].
which can be prepared from maleopimaric acid according to
O O O
Scheme 18 prior to dryingis at
Sodium maleopimarate a solid,
40 °C which
[89].can
Itsbeapplications
preparedCl
from maleopimaric
include acid according
the synthesis of triallylto
◦ O Na O
Scheme 18 prior to drying at 40 C [89]. Its applications include the synthesis of triallyl maleopimarate.
maleopimarate. O HDMA Cl
NaOH in DMF, microwaves
O Na <60°C, <3.5h O
O O O
O in H2O O or: Cl O
O Na O
25°C, 1h Br
COOH O COO Na Sodium HDMA Cl C=O Tri-allyl
NaOH 2CO
Kin 3 p-benzoquinone
DMF, microwaves O
Maleopimaric acid maleopimarateO Na maleopimarate
O
<60°C, <3.5h
in acetone
O in H2O yield 100%
O or: 70°C, 12h yield:
O 91-93%
25°C, 1h Br
COOH COO Na
Scheme Sodiumof triallyl maleopimarate.
18. Synthesis C=O Tri-allyl
K CO p-benzoquinone O
Maleopimaric acid maleopimarate 2 3
maleopimarate
in acetone
yield 100% 70°C, 12h for use as nucleating yield:agents
91-93%for
In a similar way dehydroabietic acid salts can be synthesized
isotactic polypropylene in aScheme non-isothermal
18. Synthesiscrystallization process, improving the crystallization
Scheme 18. Synthesis ofof triallyl
triallyl maleopimarate.
maleopimarate.
temperature and accelerating the nucleation rate [179,180]. Triallyl maleopimarate is a white viscous
liquid,
In which
a similarcanway
be prepared from sodium
dehydroabietic maleopimarate
acid salts can be synthesizedand allylfor halide
use asaccording
nucleatingto Scheme 18,
agents for
prior to extraction,
isotactic polypropylene washing, filtration and vacuum
non-isothermal
in a non-isothermal distillation
crystallization
crystallization [88,89].improving
process, It can be used as a monomer
crystallization
the crystallization
in UV-cured polymer films and coatings, giving them improved adhesion
temperature and accelerating the nucleation rate [179,180]. Triallyl maleopimarate is a white and mechanical properties
viscous
[89], aswhich
liquid, well as in be
can thermally
prepared cured
fromfully
sodiumbio-based resin systems
maleopimarate exhibiting
and allyl halide satisfactory
according tothermal
Schemeand 18,
mechanical
prior to properties
extraction, [88].
washing, filtration and vacuum distillation [88,89]. It can
to extraction, washing, filtration and vacuum distillation [88,89]. It can be used as a monomer in be used as a monomer
Mono-allyl
in UV-cured
UV-cured polymer rosin
polymer films derivatives
films
andand have
coatings,
coatings, been also
giving
giving them themsynthesized
improved
improved inadhesion
adhesionrecent
andyears.
and Allyl rosinate
mechanical
mechanical can
properties
properties be
[89],
prepared
[89],
as well asininaqueous
as well asthermally [181]
in thermally orcured
cured ethanol [182]
fully
fully medium
bio-based
bio-based from
resin
resin rosin, exhibiting
systems
systems sodium hydroxide
exhibiting and thermal
satisfactory
satisfactory allyl chloride
thermal and
according to Scheme
mechanical properties [88]. 19, prior to filtration and distillation [181]. It can be potentially applied as an
unsaturated monomer in copolymerization reactions
Mono-allyl rosin derivatives have been also synthesized in recent [181] as well as in UV-cured
recent years. resins [182]. On
years. Allyl rosinate can be the
other hand,
prepared allyl maleopimarate
in aqueous [181] or ethanol can be prepared
[182] medium in THF
fromfrom
rosin,maleopimaric
sodium hydroxide acid, oxalyl chloride
and allyl and
chloride
allyl alcohol according to Scheme 19, and using
according to Scheme 19, prior to filtration and distillation distillation [181]. It can be potentially applied asand
such separation methods as vacuum distillation an
column chromatography
unsaturated [90]. It can be usedreactions
copolymerization
monomer in copolymerization in unsaturated
reactions [181] as
[181] asresins
well as
well andin epoxy
UV-cured
UV-curedresins as a [182].
resins
resins cross-linking
[182]. On the
agenthand,
other [90]. allyl maleopimarate can be prepared in THF from maleopimaric acid, oxalyl chloride and
allyl alcohol according to Scheme 19, and using such separation methods as vacuum distillation and
chromatography [90].
column chromatography [90]. It can be used in unsaturated resins and epoxy resins as a cross-linking
agent [90].
O O O O 1. O Cl O
O O
Molecules 2019, 24, 1651 12 of 52
OH O Na O O Cl O O
Cl
Molecules 2019, 24, x FOR PEER REVIEW 2. 12 of 51
NaOH OH
O O HDMA Cl O O 1. O(C H Cl O
in H2O O 2 5)3 O
O O in H2O O O 1. O Cl
p-benzoquinone O
25°C, 1h microwaves
O Na <700W O O OH
O O OO
OH Cl in THFO
OH O<65°C,
Na 0.5h
Cl Allyl rosinate
O OO 50-25°C,
Cl 16h
O OO
Sodium rosinate Cl 2.
Rosin NaOH yield 95% Maleopimaric OH
yield 92% HDMA Cl 2. (C H ) Allyl maleopimarate
inNaOH
H2O 2 5 3 OH
acid
in H2O
HDMA Cl OH p-benzoquinone
yield 62%
25°C,
in H O1h microwaves (C 2H5)3 O
2 in H2O<700W in THF
25°C, 1h <65°C, 0.5h
Scheme 19. Synthesis of mono-allyl rosin OH p-benzoquinone
derivatives.
microwaves <700WAllyl rosinate O 50-25°C, 16h
in THF O
O
Rosin Sodium rosinate
<65°C, 0.5h yield 95%
Allyl rosinate MaleopimaricO Allyl
50-25°C, 16hmaleopimarate
O
Rosin yield
Sodium 92%
arerosinate
Benzoxazines compounds yield consisting
95% of a bicyclic acid group with an oxazine
Maleopimaric yieldmoiety.
62%
yield 92% Allyl maleopimarate
Maleopimaric acid imidophenol is a white, crystal solid. It can acid be synthesized from maleopimaric
yield 62%
Scheme 19.Synthesis
Synthesis of mono-allyl rosin derivatives.
acid and 4-aminobenzoicScheme phenol19. according toofScheme
mono-allyl20, rosin
priorderivatives.
to precipitation and drying [96]. It
can be used in synthesis ofScheme 19. Synthesis
benzoxazine of mono-allyl
monomers [96]. rosin derivatives.
Benzoxazines
Benzoxazines are compounds consisting of a bicyclic group with anmoiety.
oxazine moiety.
Rosin-based benzoxazine monomers are orangegroup
are compounds consisting of a bicyclic solids. with an oxazine
They can be synthesizedMaleopimaric
from
acidMaleopimaric acid
Benzoxazinesis are
imidophenol imidophenol
compounds
a white, is a white,
crystal consisting
solid. crystal solid. It
of abebicyclic
It can can be
synthesized synthesized
groupfrom from maleopimaric
withmaleopimaric
an oxazine moiety.
acid20,and
maleopimaric acid, paraformaldehyde and aniline or 4-aminobenzoic acid, according to Scheme
acid and
Maleopimaric
4-aminobenzoic 4-aminobenzoic
acid
phenol phenol
imidophenol
according according
is a white,
to Scheme to Scheme
crystal
20, prior 20,
solid. prior
It can to
be
to precipitation precipitation
synthesized and
from
and drying [96].drying [96].
maleopimaric It
prior to filtration, washing and rotary evaporation [96]. They can be polymerized into It can be used
products of
can be
acid andused in synthesis ofphenol
4-aminobenzoic benzoxazine monomers
according to Scheme[96]. 20, prior to precipitation and drying [96]. It
in significant
synthesis of benzoxazine
thermal benzoxazinemonomers [96].
stability [96]. monomers are orange solids. They can be synthesized from
can beRosin-based
used in synthesis of benzoxazine monomers [96].
maleopimaric
Rosin-based acid, paraformaldehyde
benzoxazine monomers and aniline or 4-aminobenzoic
are orange solids. They acid, according
can to Schemefrom
be synthesized 20,
O OH O
maleopimaric acid, paraformaldehyde and aniline or 4-aminobenzoic acid, according to Scheme of
prior to filtration,
O washing and rotary evaporation [96]. They can be polymerized into products 20,
significant
prior thermal
O
to filtration, stability and
washing [96].rotary evaporation 1. H2N
[96]. TheyRcan be polymerized into N products O of
significant thermal 2. (CH2O)n

H2N stabilityOH [96]. N
O O OH O OO N
O in DMF
O in DMF OH 120°C, 5h COOH R=H O
or COOH
O 1. H2N R O
O 160°C, 4h N
COOH R
2. (CH2O)n
H
O2N OH 1. H2N R
O
N O Maleopimaric acid O N Rosin-based
NO
in DMF
Maleopimaric H2N in DMF OH
2. (CHimidophenol
COOH 2O)n
120°C, 5h COOH
benzoxazine
N O R=H or COOH N
O
yield: 88% O yield: 76-81%
acid 160°C, 4h in DMF
COOH R
in DMF 120°C, 5h COOH R = H or COOH
160°C, 4h Maleopimaric acid Rosin-based
COOH R
Maleopimaric Scheme
Scheme20. 20.Synthesis
Synthesisof
ofmaleopimaric
maleopimaric
COOH acid
acid imidophenoland
imidophenol
imidophenol anditsitsbenzoxazines.
benzoxazines.benzoxazine
acid Maleopimaric acid
yield: 88% Rosin-based
yield: 76-81%
Maleopimaric
Rosin-based benzoxazine monomers
Dehydroabietylamine-guaiacol are orange
(brown powder, imidophenol
COOHsolids. They
m.p. 104can be synthesized
°C) frombenzoxazine
maleopimaric
and dehydroabietylamine-4-
acid yield: 88% yield: 76-81%
acid, paraformaldehyde
methylumbelliferone and
Scheme(yellow aniline ormaleopimaric
spherical
20. Synthesis of 4-aminobenzoic
crystal solid, acid,
acid m.p. according
131
imidophenol °C)andareitsto Scheme
fully 20, prior
bio-based
benzoxazines. to filtration,
benzoxazines
washing and rotary
[157]. They can be evaporation
synthesized from[96]. dehydroabietylamine
They can be polymerized into products
via Mannich of significant
condensation, thermal
according to
Scheme 21. TheyScheme 20. Synthesis
can compound
Dehydroabietylamine-guaiacol of maleopimaric
resins with strong
(brown acid
powder, imidophenol
corrosion and and
protection
m.p. 104 °C) itsand
benzoxazines.
thermal stability [157].
dehydroabietylamine-4-
stability [96].
methylumbelliferone (yellow spherical
Dehydroabietylamine-guaiacol crystalpowder,
(brown solid, m.p. 131 °C)
m.p. 104are ◦ C)
fully
andbio-based benzoxazines
dehydroabietylamine-4-
Dehydroabietylamine-guaiacol (brown powder, m.p.◦ 104 °C)O andOHdehydroabietylamine-4-
[157]. They can be synthesized from dehydroabietylamine via Mannich
methylumbelliferone (yellow spherical crystal solid, m.p. 131 C) are fully bio-based condensation, according to
benzoxazines [157].
methylumbelliferone (yellow spherical crystal solid, m.p. 131 °C) are fully O
bio-based benzoxazines
TheyScheme
can be21. They can
synthesized compound
from resins with
dehydroabietylaminestrong corrosion
via Mannich protection and
NHcondensation,
2 thermal stability
according to [157]. 21.
Scheme
[157]. They can be synthesized from dehydroabietylamine via Mannich condensation, according to
They can compound
Scheme 21. They can resins
compound
HOstrong corrosion
with O O
resins with strong protection
corrosionand thermal
protectionO
stability O[157].
and
OH thermal stability [157].
N N
paraformaldehyde
paraformaldehyde
NH2 in dioxane O
in dioxane O 85°C, OH
O O O 20h
<90°C, 20h
HO O O OO
Dehydroabietylamine
Dehydroabietylamine Dehydroabietylamine
NH2 paraformaldehyde N
N
-4-methylumbelliferone paraformaldehyde -guaiacol benzoxazine
in dioxane O
benzoxazine
O yield:
O 70% HO O
in dioxane O
85°C, 20h yield: 64%
O N <90°C, 20h paraformaldehyde N
Dehydroabietylamine paraformaldehyde Dehydroabietylamine
Scheme 21. Dehydroabietylamine
Synthesis of in dioxane
fully bio-based benzoxazines.
in dioxane
O-4-methylumbelliferone
O O 85°C, 20h-guaiacol benzoxazine
<90°C, 20h
benzoxazine yield: 70%
Dehydroabietylamine yield: 64%
Dehydroabietylamine
3.2.3. Hardeners Dehydroabietylamine
-4-methylumbelliferone -guaiacol benzoxazine
Scheme 21. Synthesis of fully bio-based benzoxazines. yield: 64%or
benzoxazine yield:
Rosin-based 70%
hardeners, i.e. curing agents, are compounds containing anhydride, carboxyl
hydroxyl groups, which allows
3.2.3. Hardeners Scheme one21.to apply them
Synthesis in epoxy
of fully
fully or urethane resin systems. In comparison
bio-based
Scheme 21. Synthesis of bio-basedbenzoxazines.
benzoxazines.
with petroleum-based hardeners they bring improved endurance and thermal properties to resin
Rosin-based hardeners, i.e. curing agents, are compounds containing anhydride, carboxyl or
3.2.3. Hardeners
3.2.3. Hardeners
hydroxyl groups, which allows one to apply them in epoxy or urethane resin systems. In comparison
with Rosin-based
Rosin-based hardeners,
petroleum-based
hardeners, i.e. curing
hardeners
i.e., curing agents,
they bring are compounds
improved
agents, endurance
compounds containing anhydride,
and thermal
containing carboxyl
properties
anhydride, to resinor or
carboxyl
hydroxyl
hydroxyl groups,
groups, which
which allowsone
allows onetotoapply
applythem
them in in epoxy or
or urethane
urethaneresin
resinsystems.
systems.InIncomparison
comparison
with
with petroleum-basedhardeners
petroleum-based hardenersthey they bring
bring improved
improved endurance
enduranceand
andthermal
thermalproperties
properties to to
resin
resin
systems. Moreover, rosin-based anhydrides are non-toxic, as opposed to conventional anhydride

curing agents. Their preparation is simple and well described, and usually does not require the use
of solvents. These strengths cause the great interest in use of rosin based chemicals as hardeners of
conventional
Molecules and bio-based resins resulting in several commercializations of eg., maleated rosins. 13 of 52
2019, 24, 1651
Methyl maleopimarate is a white solid. It can be prepared from abietic acid, iodomethane and
maleic2019,
Molecules anhydride,
24, x FOR according
PEER REVIEW to Scheme 22, prior to recrystallization [82]. It can be used as bio-based 13 of 51
curing agent for epoxies [82,183], as well as in synthesis of binaphthyl-appended
systems. Moreover, rosin-based anhydrides are non-toxic, as opposed to conventional anhydride crown ethers
systems.
curingderived Moreover,
agents.from rosin
Their rosin-based
[184].
preparation isanhydrides
simple and are non-toxic,
well as opposed
described, to conventional
and usually anhydride
does not require the use
curing agents. Their preparation is simple and well described, and usually does not require the use
of solvents.
O
These strengths cause the great interest in use of rosin basedOchemicals O O
as hardeners of
of solvents. OThese O strengths
O O cause the great interest in use of rosin based chemicals asOhardeners
O of
conventional and bio-based resins resulting in several CH3I commercializations of e.g., maleated rosins.
conventional and O bio-based resins resulting in several commercializations of eg., maleated rosins. O
Methyl maleopimarate is a white 180°C solid. It can
K2CObe prepared180°Cfrom abieticpTSA
acid, iodomethane and
Methyl maleopimarate
pTSA is a white
3h solid. It can be prepared3hfrom abietic acid, iodomethane and
3
maleic anhydride,in according to Scheme 22, prior to recrystallization [82]. inItCH
in DMF 3COOH
can be used as bio-based
maleic anhydride, CHaccording
3COOH to Scheme 22, prior to 24h
25°C, recrystallization [82]. It can be12h
used as bio-based
120°C,
curing agent for epoxies [82,183],
120°C, 12h
curing agent for epoxies [82,183], as well
as as
wellin synthesis
as in of
synthesisbinaphthyl-appended
of binaphthyl-appended crown ethersethers
crown derived
COO COO COOH COOH
from rosin from
derived [184].
COOrosin [184]. COOH
Methyl abietate Abietic Levopimaric

Methyl maleopimarate yield: 81% Maleopimaric
O
O acid acid O O O O
O
yield 90% O O O acid yield: 92%
CH I
3 O
O
180°C of maleopimaric
Scheme 22. Synthesis K2CO3 acid and methyl
180°C maleopimarate.
pTSA
pTSA 3h 3h
in DMF in CH3COOH
in CH3COOH
Rosin-maleimidopolycarboxylic
120°C, 12h acids are25°C, 24h
white/yellowy or gray/brown 120°C, 12h They can be
powders.
prepared from maleopimaricCOO COO COOH
acid with aspartic or 4-aminobenzoic COOH
acid, or rosin with 1,1′-
COO COOH
(methylenedi-4,1-phenylene)bismaleimide, according to Scheme 23, before separation via such
methods as precipitation, filtration, Methyl abietate
washing, dryingAbietic Levopimaric [94,185]. They have a
Methyl maleopimarate yield: 81% Maleopimaric
potential to replace petroleum-based epoxy curing acid agents [94,185].
acid Furthermore, rosin-
yield 90% acid yield: 92%
maleimidodicarboxylic acid can be used for synthesis of rosin-based chain extender for
polyurethanesScheme Scheme
[186], 22.Synthesis
or22.
epoxySynthesis of maleopimaric
resins of maleopimaric acid
[84]. acidand
andmethyl
methylmaleopimarate.
maleopimarate.
Rosin-polycaprolactone flexible dianhydride are solids with a melting point depending on the
Rosin-maleimidopolycarboxylic
length of oligoester diol chain. They
Rosin-maleimidopolycarboxylic acids are
can are
acids white/yellowy
be synthesized
white/yellowy fromororrosin,
gray/brown powders.
oligocaprolactone
gray/brown powders. They
diolscan
They and be be
can
prepared
maleic from
anhydride maleopimaric
according toacid with
Scheme 24 aspartic
and usingor 4-aminobenzoic
vacuum evaporation acid,
as
prepared from maleopimaric acid with aspartic or 4-aminobenzoic acid, or rosin with 1,1 -(methylenedi- a or rosin
separation0 with
method 1,1′-
(methylenedi-4,1-phenylene)bismaleimide,
[97]. Their application is bio-based
4,1-phenylene)bismaleimide, according according
curingtoagent to resins
for epoxy
Scheme 23, Scheme
before [97].23, before separation
separation via such as
via such methods
methods Tall-oil based polyol can be prepared from diethanolamine and tall oil containing up to 20 have
as precipitation, filtration, washing, drying and recrystallization [94,185]. They wt.% a
precipitation, filtration, washing, drying and recrystallization [94,185]. They have a potential to
potential to replace
of rosin acids, according petroleum-based
to Scheme 25, prior epoxy curing
to vacuum agents of
evaporation [94,185]. Furthermore,
water [187]. It can be used rosin-
as
replace petroleum-based epoxy curing agents [94,185]. Furthermore, rosin-maleimidodicarboxylic acid
chain extenders in ureaurethane
maleimidodicarboxylic acid canelastomers,
be used improving their thermal
for synthesis resistance and
of rosin-based chainstorage modulsfor
extender
can be used for synthesis of rosin-based chain extender for polyurethanes [186], or epoxy resins [84].
[187].
polyurethanes [186], or epoxy resins [84].
length of H2Noligoester COOH
diol chain. They canCOOH be synthesized fromLevopimaric
rosin, oligocaprolactone diols and
O acid
maleic anhydride according to NScheme 24 and using vacuum evaporation as a separation method
in DMF HOOC
[97]. Their application
160°C, 4h is bio-based curingO agent for epoxyO resins [97]. O
O pTSA; in CH3COOH
Tall-oil O
based polyol can be prepared from diethanolamine and tall oil containing up to 20 wt.%
N N 120°C, 12h
of rosin acids, according to Scheme 25, prior to vacuum evaporation of water [187]. It can be used as
O
O O
chain extenders in ureaurethane elastomers, improving their thermal resistance and storage moduls
COOH
[187].
O O
N N
COOH acid yield: 87% Levopimaric O O
H2N COOH COOH
O acid
N
Maleopimaric
in DMFNH2 O HOOC
acid O
160°C, 4h HOOC O O
O pTSA; in CH3COOH
HOOC COOH N
O COOH N N 120°C, 12h
COOH COOH
in DMF
O O COOH
165-180°C O O
6.5h Rosin-maleimidotricarboxylic Dirosin-maleimidodicarboxylic
acid COOH
yield: 54% acid yield: 87%
O O
N N
Scheme 23. Synthesis of rosin-maleimidodicarboxylic acids.
COOH acid yield: 87% O O
Maleopimaric NH2 O
length
acidof oligoester diol chain. They canHOOC be synthesized from rosin, oligocaprolactone diols and
maleic anhydride
HOOC COOHaccording to Scheme 24
N and using vacuum evaporation as a separation method [97].
COOH COOH COOH
Their application
in DMF is bio-based curing agent for epoxy resins [97].
O COOH
165-180°C
Tall-oil based
6.5h
polyol can be prepared from diethanolamine and tall
Rosin-maleimidotricarboxylic oil containing up to 20 wt.% of
Dirosin-maleimidodicarboxylic
rosin acids, according to Schemeacid yield: 54%
25, prior to vacuum evaporation of water acid Ityield:
[187]. 87%
can be used as chain
extenders in ureaurethane elastomers, improving their thermal resistance and storage moduls [187].
Molecules 2019,
Molecules 2019, 24,
24, xx FOR
FOR PEER
PEER REVIEW
REVIEW 14 of
14 of 51
Molecules 2019, 24, x FOR PEER REVIEW 14 of 51 51
Molecules 2019, 24, 1651 14 of 52
Scheme
Scheme 23.
Scheme23. Synthesis
23.Synthesis of
Synthesis of rosin-maleimidodicarboxylic
of rosin-maleimidodicarboxylic acids.
acids.
rosin-maleimidodicarboxylic acids.
COOH
COOH OO OO O
OO O O O
O
COOH O RR O OO
R O
OO O
O O
HOHO
HO OO O
OO
RR O O
OO O
O O O
O O
HOHO R
HO
pTSA
pTSA O
OO
pTSA
(or(or
(or nano-ZnO)
nano-ZnO)
nano-ZnO) HH33PO
PO4 4
230-240°C, H3PO 4
230-240°C,
230-240°C, 5h5h
5h 180-190°C
180-190°C
180-190°C
4h
4h R R
4h
Abietic
Abietic R
Abietic OO O
O O O O O
acidacid
acid HOHO R =
HO R == H H O(CH
[ O(CH
O O O O
O OO
O
2)5 CC ]mO(CH
O(CH2)2O(CH2)2O [ C (CH2)5O ]n H
HOR H [ O(CH 2))5 C ]m O(CH 2))2O(CH
O(CH2))2O
O[C
C (CH2))5O
(CH O ]n H
H O
Rosin-polycaprolactone O
anhydride
HO
HO [ 2 5 ]m 2 2 2 2 [ 2 5 ]n
Rosin-polycaprolactone anhydride
Rosin-polycaprolactone
curing agent anhydride
yield: 76%
M = 530, 1000, 1250
n 530, 1000, 1250
Mn == curing agent yield: 76%
curing agent yield: 76%
Mn 530, 1000, 1250
Scheme 24.Synthesis
Synthesisof
ofrosin-polycaprolactone
rosin-polycaprolactone anhydride curing agent.
Scheme
Scheme 24.
24. Synthesis of rosin-polycaprolactone anhydride
of rosin-polycaprolactone anhydride curing
anhydride curing agent.
curing agent.
agent.
O OH
O OH R= CH3 (CH2)7 CH CH (CH2)7
O HO OH O N OH
N R O OH CH3 (CH
R= CH (CH2))7 CH
CH CH
CH (CH2))7
(CH
O HO H OH N R= 3 2 7 2 7
O HO N OH R O N OH
R OH N
H
140°C, 5h R O
O OH
H and
or R=
R
R OH
TallOH
oil 140°C, 5h
5h O and
140°C, R O and OH or R=
R=
or
Tall oil
Tall oil R
O NH OH
R OH
Tall oil-based
O
O polyol
NH
NH
Tall oil-based polyol
Tall
Scheme 25.oil-based
Synthesispolyol
of tall oil-based polyol.
Scheme 25.
Synthesis of
of tall
tall oil-based
oil-based polyol.
polyol.
3.2.4. Surfactants
3.2.4. Surfactants
3.2.4. Surfactants
3.2.4. Small/medium molecule rosin-based surfactants are ionic or non-ionic compounds that lower
surface tension between
Small/medium
Small/medium different
molecule
molecule substances.
rosin-based
rosin-based In comparison
surfactants with
are ionic
ionic orpetrochemical
or non-ionic
non-ionic compounds counterparts,
compounds thatthey
that lower
lower
Small/medium molecule rosin-based surfactants are ionic or non-ionic compounds that lower
are
surface
surface characterized
tension
tension by
between
between designable
different
different surface
substances.activity,
substances. In
Inaffinity to
comparison
comparison many chemicals
with
with (especially
petrochemical
petrochemical cycloaliphatic
counterparts,
counterparts, they
they
surface tension between different substances. In comparison with petrochemical counterparts, they
are and aromatic),
characterized
are characterized
characterized by non-toxicity,
by designable mild biocidal
surface
by designable surface activity, properties
activity, and
affinity
activity, affinity to
affinity toenhanced
many
to many thermal
chemicals
many chemicals stability.
(especially
chemicals (especially Unfortunately,
cycloaliphatic
(especially cycloaliphatic
cycloaliphatic
are their syntheses are designable
less wellmild
described than rosin-based resins and hardeners, eg. reaction yields are
and
and aromatic),
aromatic), non-toxicity,
non-toxicity, mild biocidal
biocidal properties
properties and enhanced thermal stability. Unfortunately,
andoften
aromatic), non-toxicity,
unavailable. mildthe
Moreover, biocidal
use of properties and enhanced
unsustainable chemicals thermal
in the stability.
mentioned Unfortunately,
reactions
their
their syntheses
syntheses are areless
lesswell
welldescribed
describedthan thanrosin-based
rosin-basedresinsresinsand
andhardeners,
hardeners,e.g., reaction
eg. reaction yields areare
their syntheses are less well described than rosin-based resins and hardeners,
noticeably decreases the “green” aspect of these rosin derivatives. Therefore, it is an urgent need eg. yields toare
often unavailable.
often unavailable. Moreover,
unavailable. Moreover, the the use of
the use ofunsustainable
of unsustainable chemicals
unsustainable chemicals in the
chemicals in mentioned
in the reactions
the mentioned noticeably
mentioned reactions
reactions
often
undertake appliedMoreover,
studies on theseuse compounds, as well as to find more sustainable preparation
decreases
noticeably the “green”the
decreases aspect of these
“green” aspectrosinof derivatives.
these rosin Therefore, it
derivatives. is an urgent
Therefore, it isneed
an to undertake
urgent need to
noticeably
processesdecreases
in order tothe “green”
increase TRL aspect
of this ofgroup
these of rosin
rosinderivatives.
derivatives.Therefore, it is an urgent need to
applied
undertake studies on these
applied compounds,
studies on these ascompounds,
well as to find as more
well sustainable
as to find preparation
more processes
sustainable in order
preparation
undertake applied studies
Dehydroabietyl on these
phosphate compounds,
diester is a yellow as well as toliquid.
viscous find more It can sustainable
be prepared preparation
from
to increase
processes TRL
in of
order this
to group
increase of rosin
TRL of derivatives.
this group of rosin derivatives.
processes in order chloride,
dehydroabietyl to increase TRL of this
decanediol, andgroup of rosin derivatives.
polyphosphorus acid according to Scheme 26, prior to
Dehydroabietyl
Dehydroabietyl phosphate
phosphate and diester
diester is
is a[140].
yellow viscous
be usedliquid. ItIt can
can be prepared from
washing, vacuum evaporation
Dehydroabietyl phosphate drying
diester is aa yellow
yellow
It can viscous
viscous liquid.
liquid. It can
as highly-active surfactant
be prepared from
[140],
from
dehydroabietyl
dehydroabietyl
phosphorus source chloride,
chloride, decanediol,
and crystal growthandand polyphosphorus
control agent in synthesisacid according to Scheme 26, prior
prior to
26, prior to
dehydroabietyl chloride, decanediol, polyphosphorus acidofaccording
hydroxyapatite [188]. 26,
to Scheme to
washing,
washing, vacuum
vacuum evaporation
evaporation and
and drying
drying [140].
[140]. It can be used as highly-active surfactant [140],
It
washing, vacuum evaporation and drying [140]. It can be used as highly-active surfactant [140],
phosphorus
phosphorus sourcesource andandcrystal
crystalgrowth
growth
O control
controlagent agentin insynthesis
synthesisof ofhydroxyapatite
hydroxyapatite[188]. [188].
phosphorus source and crystal growth control agent in synthesis of hydroxyapatite [188].
HO(CH2)10OH HO P O H
NaOH
in CHCl3 OH
OO n
<80°C;reflux
HO(CH2))105h
OH HOin P
CHCl
O H
HO(CH 2 10OH HO P O 3 H NaOH
reflux;6h NaOH
in CHCl3
COCl
in CHCl3 OHOH COO(CH2)10O O(CH2 )10OOC COO(CH2)10O O(CH2 )10OOC
<80°C;reflux COO nn
<80°C;reflux in CHCl
CHCl3 O P OH O P ONa
5h
Dehydroabietyl in
5h (CH2)103
reflux;6h
chloride
COCl reflux;6h Dehydroabietyl DDPD sodium salt
COCl COO(CH2))10OO O(CH
O(CH2))10OOC
OOC COO(CH2))10OO O(CH
O(CH2))10OOC
OOC
HO
COO phosphate
COO(CH 2 diester
10 (DDPD)
2 10 COO(CH 2 10 2 10
COO
Dehydroabietyl yield 90.2% yield
O 82.8%
O P OH
P
OH O
O P
P
ONa
ONa
Dehydroabietyl (CH2))10
(CH Dehydroabietyl DDPD sodium
sodium salt
salt
chloride
chloride Scheme 26. HO
2 10
Dehydroabietyl
Synthesis of phosphate
dehydroabietyl phosphate diester sodiumDDPD
salt.
HO diester
phosphate diester (DDPD)
(DDPD)
yield 90.2%
yield 90.2% yield 82.8%
yield 82.8%
Rosin-based chloride can be prepared from maleated rosin and phosphorus trichloride
Scheme
according to Scheme
Scheme
27, 26.
26. Synthesis
prior of dehydroabietyl
of dehydroabietyl
to evaporation phosphate
[101]. It can diester
be used as
phosphate sodium
a substrate
diester sodium salt.
for synthesis of rosin-
salt.
based ester amines [101].
Rosin-based
Rosin-basedchloride
Rosin-based chloridecan
chloride be prepared
can
can be prepared
be from from
prepared maleated rosin and
from maleated
maleated phosphorus
rosin
rosin trichloridetrichloride
and phosphorus
and phosphorus according
trichloride
to Scheme 27,
according to
according prior
to Scheme to
Scheme 27,evaporation
27, prior
prior to [101]. It
to evaporation can be
evaporation [101]. used
[101]. It as
It can a
can besubstrate
be used
used as for synthesis
as aa substrate
substrate forof rosin-based
for synthesis
synthesis of ester
of rosin-
rosin-
amines
based [101].
based ester
ester amines [101].
amines [101].
Rosin-based ester tertiary amine can be prepared from rosin chloride and N,N-dimethyl
ethanolamine according to Scheme 27, prior to washing, drying, extraction, evaporation and
recrystallization
Molecules [101].
2019, 24, x FOR Potential
PEER REVIEWapplications include drug carriers and surfactants. Its surface activity
15 of 51
Rosin-based ester tertiary amine can be prepared from rosin chloride and N,N-dimethyl
significantly increases in presence of rosin phosphate ester (Scheme 26) [101].
ethanolamine according to Scheme 27, prior to washing, drying, extraction, evaporation and
Rosin-based
recrystallization esterPotential
2019, 24, 1651[101].
tertiary applications
amine can include
be prepared from rosin chloride and N,N-dimethyl
Molecules O O drug carriers and surfactants. Its surface
O activity
15 of 52
ethanolamine according to
significantly increases in presence Scheme 27, prior to washing,
of rosin phosphate ester (Scheme drying, extraction, evaporation and
PCl3 N 26) [101].
recrystallization [101]. OH Potential applications includeCldrugHO N
carriers and surfactants. Its surface activity
significantly increases OOH ininpresence
CHCl3 O Cl ester (C
of rosin phosphate 2H5)3N
(Scheme 26) [101]. O N
55°C, in benzene
O OH PCl33h O Cl HO25°C, 3h
N
O N
O O O
OH Cl (C2H5)3NN N N
COOH in CHCl
PCl3 3 COCl COO
OH Cl HOin benzene N
Maleic rosin O
55°C, 3h Rosin-based chloride
O Rosin-based ester
O tertiary
OH
in CHCl3 Cl (C25°C,
H ) 3h
2 5 3N amine purity N
81.18%
in benzene N
COOH 55°C, 3h COCl COO
O O 25°C, 3h O
Maleic rosin Scheme 27. Synthesis of rosin-based ester
Rosin-based chloride tertiary amine. Rosin-based ester tertiary
N
COOH COCl COOamine purity 81.18%
Maleic
Solid rosin
N-dodecyl-maleimidepimaric Rosin-based chloride
acid (C12-MPA) can be prepared Rosin-based ester tertiary
from maleopimaric acid
Scheme27. 27. Synthesis
Synthesis of rosin-based ester ester tertiary
tertiary amine. amine purity 81.18%
and dodecylamine according Scheme to Scheme 28, prior to washing, drying,amine.
filtration, rotary evaporation
and purification via Scheme column chromatography [100]. Sodium N-dodecylmaleimidepimaric
Rosin-based ester tertiary 27.
Solid N-dodecyl-maleimidepimaric amineSynthesis
can
acidof
berosin-based
preparedester
(C12-MPA) from
can tertiary
be rosin amine.
prepared chloride and N,N-dimethyl
from maleopimaric acid
carboxylate is a product of C12-MPA neutralization using NaOH, prior to evaporation,
ethanolamine
and dodecylamine according
according to Scheme
to Scheme 27, 28,
prior
priorto towashing,
washing, drying, extraction,
drying, filtration, evaporation
rotary evaporationand
recrystallization and vacuum drying. It forms micellescan ofbevarious shapes, maleopimaric
depending onacid its
and Solid N-dodecyl-maleimidepimaric
recrystallization
purification [101].via Potential
column applications acid
chromatography (C12-MPA)
include drugSodium
[100]. prepared
carriers andfromsurfactants. Its surface
N-dodecylmaleimidepimaric
concentration
and dodecylamine [102]. It can be used in oil extraction, tocosmetics and industrial washing [100].
carboxylate
activity is a according
significantly product
increases of to presence
in Scheme
C12-MPA 28, prior washing,
neutralization
of rosin phosphate drying,
using
ester filtration,
NaOH,
(Scheme prior
26) rotary evaporation
to evaporation,
[101].
and Acrylpimaryl
purification dichloride
via columnis an orange,
chromatographysticky paste.
[100].It can be
Sodium prepared from acrylpimaric
N-dodecylmaleimidepimaric acid
recrystallization and vacuum drying.acid
Solid N-dodecyl-maleimidepimaric It forms
(C12-MPA) micelles
can be of prepared
various shapes, depending acid
from maleopimaric on and
its
according
carboxylate to Scheme 29, priorofto solvent evaporation [128]. Itusingcan beNaOH,used in synthesis ofevaporation,
surfactants
concentrationisaccording
dodecylamine
a product
[102]. It cantobe used
Scheme
C12-MPA
in28,
oilprior neutralization
extraction, cosmetics
to washing, and industrial
drying,
prior to[100].
filtration,washing
rotary evaporation and
[128], herbicides [129],
recrystallization and fungicidesdrying.
vacuum [189] and It insecticides
forms [190]of various shapes, depending on its
micelles
Acrylpimaryl
purification via column dichloride is an orange,
chromatography [100].sticky paste.
Sodium It can be prepared from acrylpimaric
N-dodecylmaleimidepimaric carboxylate acidis a
Acrylic
concentration rosin
[102].ester
It diethylamine
can be used in tertiary
oil amine
extraction, surfactant
cosmetics and is industrial
a sticky paste. It can
washing be prepared
[100].
according
product to Schemeneutralization
of C12-MPA 29, prior to solvent
usingevaporation
NaOH, prior [128]. It can be used
to evaporation, in synthesis of and
recrystallization surfactants
vacuum
fromAcrylpimaryl
acrylpimaryl chloride,
dichloride N,N-diethylethanolamine
is an[189]
orange, sticky paste.andIthydrochloric
can be prepared acid according to Scheme
from acrylpimaric 29
acid
[128], herbicides
drying. It forms [129],
micelles fungicides
of various shapes,anddepending
insecticides on[190]
its concentration [102]. It can be used
[128]. Thistoproduct,
according Scheme in
29,adiethylamine
mixture
prior with soapnut
to solvent evaporation saponin
[128].exhibits
It canisbe noteworthy
used inpaste. surfaceofactivity
synthesis andoil
in
surfactants
Acrylic
extraction, rosin
cosmetics ester
and industrial tertiary
washing amine surfactant
[100]. a sticky It can be prepared
emulsification
[128], herbicides ability
[129], tofungicides
apply in pharmacy, cosmetics and
[189] and insecticides [190]commodity chemicals [128].
from acrylpimaryl chloride, N,N-diethylethanolamine and hydrochloric acid according to Scheme 29
[128].Acrylic
This
O
rosin ester
product,
C12H25NH in2 diethylamine
a mixture C12Hwith
25
tertiary
soapnut amine surfactant
saponin exhibits is anoteworthy
sticky paste.surface
O
It can be prepared
activity and
from
O acrylpimaryl O chloride, N,N-diethylethanolamine and hydrochloric
emulsification ability to apply inNpharmacy, cosmetics and commodity chemicals [128]. acid according to Scheme 29
[128]. This product, in DMF in a mixture
O with O soapnut saponin exhibits noteworthy surface activity and
<165°C, 8h NaOH N
emulsification
O ability
C12H25NH to2 apply inCpharmacy,
12H25 cosmetics and commodityO chemicals [128].
O O in C2H5OH
N 70°C, 12h O
O Cin DMF
12H25NH2
O C12H25 O
NaOH ON
O O <165°C,
COOH 8h
N in C2H5OHSodium COO Na
in DMF O O COOH
<165°C, 8h N-dodecyl-maleimidepimaric
°C, 12h
70NaOH ON
MaleopimaricCOOH N-dodecyl- in C2H5OH carboxylate
acid maleimidepimaric acid 70°C, 12h 29% COO Na
yield Sodium
yield
O 76%
COOH
COOH N-dodecyl-maleimidepimaric
MaleopimaricScheme28.
Scheme 28. Synthesis COO Na carboxylate
Sodium
Synthesis of sodium N-dodecyl-maleimidepimaric
N-dodecyl- N-dodecyl-maleimidepimaric carboxylate.
carboxylate.
COOH
acid maleimidepimaric acid yield 29% yield 76%
N-dodecyl-maleimidepimaric
Maleopimaric dichloride
COOH
Acrylpimaryl N-dodecyl- COCl
is an orange, sticky paste. It can becarboxylate
prepared from acrylpimaric acid
acid SchemePCl3 28. Synthesis of sodium N-dodecyl-maleimidepimaric
OH Nyield 76%
carboxylate. H
maleimidepimaric acid yield
N 29% N
according to Scheme 29, prior to solvent evaporation [128]. It can be used in synthesis ofClsurfactants [128],
Cl
in CHCl3
herbicides
COOH [129], fungicides [189] and
55°C, 3h 28. Synthesis
Scheme insecticides [190]
COCl of sodium N-dodecyl-maleimidepimaric carboxylate.
COO HCl COO
PCl3 (C2H5)3NOH N H H
COOH COCl N N N
Cl N Cl
COOH in CHCl3 COCl in benzene
PCl3h
55°C, 3 25°C, 3h
OH N H
N COO HCl N
ClCOO H Cl
in CHCl3 (C2H5)3N
Acrylic rosin COOH Acrylic rosin
COCl N
COO N
55°C, 3h in benzene COO
chloride Acrylic
rosin
COO HCl COO
(C25°C,
H ) 3h
N H
COOH yield 96%COCl 2 5 3
N,N-diethyl N N
in benzene
Acrylic rosin Acrylic rosin ethanolamine
25°C, 3h diesterCOO Acrylic rosin ester
COO
chloride Acrylic
yield 87%rosin diethylamine tertiary amine
Acrylic rosin Acrylic rosin
yield 96% N,N-diethyl COO surfactant yield: 100%
COO
chloride Acrylic rosin diester
ethanolamine Acrylic rosin ester
yield
Scheme 29. Preparation of 96% N,N-diethyl
yielddiethylamine
acrylic rosin ester 87% tertiarydiethylamine
amine surfactant.
tertiary amine
ethanolamine diester Acrylicyield:
surfactant rosin 100%
ester
yield 87% diethylamine tertiary amine
Scheme 29. Preparation of acrylic rosin ester diethylamine tertiary amine surfactant.yield: 100%
surfactant
Scheme29.
Scheme 29.Preparation
Preparation of
of acrylic
acrylic rosin
rosin ester
ester diethylamine
diethylaminetertiary
tertiaryamine
aminesurfactant.
surfactant.
Acrylic rosin ester diethylamine tertiary amine surfactant is a sticky paste. It can be prepared from
acrylpimaryl chloride, N,N-diethylethanolamine and hydrochloric acid according to Scheme 29 [128].
Molecules 2019, 24, 1651 16 of 52
This product, in a mixture with soapnut saponin exhibits noteworthy surface activity and emulsification
ability to apply
Molecules 2019, 24,in pharmacy,
x FOR cosmetics and commodity chemicals [128].
PEER REVIEW 16 of 51
Quaternary
Quaternaryammoniumammonium saltssalts of
of rosin
rosin esters
esters are
are yellow
yellow solids. Theycan
solids. They canbe
beprepared
preparedfromfrom
Quaternary
maleopimaryl ammonium
chloride salts in
(described ofSection
rosin esters
3.2.5)are
and yellow solids. They can be prepared
N,N-diethylethanolamine with from
hexadecyl
maleopimaryl chloride (described in subsection 3.2.5) and N,N-diethylethanolamine with hexadecyl
maleopimaryl chloride (described
bromide, in subsection 3.2.5) and N,N-diethylethanolamine with hexadecyl
bromide,ororepichlorohydrin
epichlorohydrinwith withtriethylamine,
triethylamine, according
according toto Scheme
Scheme 30,30,and
andusing
usingsuch
suchseparation
separation
bromide, or epichlorohydrin with triethylamine, according to Scheme 30, and using such separation
methods
methodsasasvacuum
vacuumdistillation,
distillation,filtration,
filtration, washing, drying,
drying,extraction
extractionand
andrecrystallization
recrystallization[104,191].
[104,191].
methods as vacuum distillation, filtration, washing, drying, extraction and recrystallization [104,191].
O Cl
Maleopimaric O O Cl Maleopimaryl O Rosin
Maleopimaric
acid
O Maleopimaryl
chloride O Cl O
O Rosin
2-hydroxypropyl
acid Cl O chloride O Cl O 2-hydroxypropyl
O Cl O O chloride ester
O in toluene O chloride ester
in toluene O
95°C, 4h O
O 95°C, 4h Cl O
O Cl O
COOH O C
COOH O O C (C2H5)3N
COCl (C2H5)3N O O OH (C2H5)3N
COCl 2H5)3N
(Ctoluene O OH 50°C
in 50°C O
O in toluene 4h
98°C, 6h 4h O
O N 98°C, 6h
HO N O
O HO O O
O O
O CH3(CH2)15Br O
O CH3(CH2)15Br O O
N 90°C, 5h O
C N
COO N 90°C, 5h O N
COO Br O C Cl
(CH2)15CH3 N O O O Cl
Br (CH2)15CH3 COO N O OH
Diethylaminoethyl rosin ester COO OH
Diethylaminoethyl rosin ester Rosin 2-hydroxypropyl-triethyl
quaternary ammonium salt Rosin diethylaminoethyl Rosin 2-hydroxypropyl-triethyl
ammonium chloride yield: 72%
quaternary ammonium
yield: 85% salt Rosin diethylaminoethyl
ester yield: 80% ammonium chloride yield: 72%
yield: 85% ester yield: 80%
Scheme30.
30. Synthesis of
of quaternary ammonium salts
saltsof
ofrosin
rosinesters.
Scheme 30.Synthesis
Scheme Synthesis ofquaternary
quaternary ammonium
ammonium salts of rosin esters.
esters.
Their
Theirpotential
potentialapplications
applicationsinclude
include corrosion
corrosion inhibitiors [104,191,192]
[104,191,192]dispersants
dispersantsfor
formagnetite
magnetite
Their potential applications include corrosion inhibitiors [104,191,192] dispersants for magnetite
(Fe
(Fe 3O3O
4 )4)nanoparticles
nanoparticles[191,192]
[191,192] and
and inhibitors in protein
protein aggregation
aggregationprocesses
processes[193–195].
[193–195].InInaddition,
addition,
(Fe3O4) nanoparticles [191,192] and inhibitors in protein aggregation processes [193–195]. In addition,
a asimilar
similarrosinyl
rosinyltriquaternary
triquaternaryammonium
ammoniumsalt salt having
having antifungal
antifungal activity
activity was
was also
alsoreported
reported[196].
[196].
a similar rosinyl triquaternary ammonium salt having antifungal activity was also reported [196].
Anotherapproach
Another approach to to introduce
introduce quaternary
quaternary ammonium
ammonium moieties
moieties into
into rosin
rosinisispresented
presentedinin
Another approach to introduce quaternary ammonium moieties into rosin is presented in
Scheme3131[197].
Scheme [197].As
Asititcan
canbebeseen,
seen, rosin
rosin bisquaternary
bisquaternary ammonium
ammonium chloride
chloridecancanbebeprepared
preparedfrom
from
Scheme 31 [197]. As it can be seen, rosin bisquaternary ammonium chloride can be prepared from
rosin,
rosin, ethanol,
ethanol, fumaric
fumaric acid
acidacid and
and and epoxy
epoxy quaternary
quaternary ammonium
ammonium salt,
salt, and and using such separation
rosin, ethanol, fumaric epoxy quaternary ammonium salt,using
andsuch
usingseparation methods
such separation
asmethods
washing asand
washing
drying. and drying.
Thus Thusgemini
obtained obtained gemini surfactant
surfactant has good has good
surface
methods as washing and drying. Thus obtained gemini surfactant has good surface activity and
surfaceand
activity activity and
antifungal
antifungal
activity activity
against fungiagainst fungi responsible
responsible for wood decay for wood
[197].decay [197].
antifungal activity against fungi responsible for wood decay [197].
O O
HOOC OH Cl O
O OH Cl
HOOC COOH Cl Cl N Cl
COOH O OH Cl
OH p-hydroquinone O OH N OH
OH p-hydroquinone N
ZnO 230°C, 3h OH N
230°C, 3h N N
ZnO3.5h
180°C, O O OH
180°C, 3.5h O OH
82°C, 8.5h O
82°C, 8.5h O O
O O
COOH COO
COOH
Levopimaric Ethyl COO Ethyl
Levopimaric
acid Ethyl
levopimarate Ethyl
fumaropimarate COO
acid levopimarate fumaropimarate COO Rosin
Rosin
bisquaternary
bisquaternary
ammonium
salt ammonium
yield: 93% COO
salt yield: 93% COO
Scheme 31. Preparation of rosin bisquaternary ammonium salt.

Scheme31.
Preparationof
of rosin
rosin bisquaternary
bisquaternary ammonium
ammonium salt.
salt.
Dehydroabietyltrimethyl ammonium bromide is a yellow solid. It can be prepared from
Dehydroabietyltrimethyl
Dehydroabietyltrimethyl ammoniumammonium bromide
bromide is
is aa yellow
yellow solid.
solid. ItIt can
can be
be prepared
prepared from
from
dehydroabietylamine, formic acid and methyl bromide according to Scheme 32, and using such
dehydroabietylamine,formic
dehydroabietylamine, formic acid
acid and
and methyl
methyl bromide
bromide according
according to
to Scheme
Scheme 32,32, and
and using
usingsuch
such
separation techniques as washing, extraction and evaporation, drying, vacuum distillation and
separationtechniques
separation techniquesasaswashing,
washing, extraction
extraction and
and evaporation,
evaporation, drying,
drying, vacuum
vacuum distillation
distillationand
and
recrystallization [158]. Such surfactant can be used for preparation of ordered porous titania [159],
recrystallization[158].
recrystallization [158].Such
Suchsurfactant
surfactant can
can be used for preparation
preparation ofof ordered
orderedporous
poroustitania
titania[159],
[159],
zirconia [198] or silica [158] with potential applications in catalysis and separation.
zirconia
zirconia [198]ororsilica
[198] silica[158]
[158]with
withpotential
potentialapplications
applications in
in catalysis
catalysis and separation.
separation.
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51
HCOOH CH33Br
HCHO
HCHO in acetone
in ethanol/H
in O
ethanol/H22O 25°C, 4h
25°C, 4h
<80°C, 9h
<80°C, 9h Br
Br
NH222
NH N
N N
N
Dehydroabietylamine
Dehydroabietylamine N,N-dimethyl
N,N-dimethyl Dehydroabietyltrimethyl
Dehydroabietyltrimethyl
dehydroabietylamine
dehydroabietylamine ammonium bromide
ammonium bromide
Scheme 32.
Scheme 32. Synthesis of dehydroabietyltrimethyl
Synthesis of dehydroabietyltrimethyl ammonium
ammonium bromide.
bromide.
bromide.
Another
Anotherrosin-based
Another rosin-basedgemini
rosin-based gemini surfactants
gemini surfactants [143,199]
surfactants can
[143,199] can
[143,199] be
can be prepared
be prepared from
prepared from dehydroabietyl
from dehydroabietyl chloride,
dehydroabietyl chloride,
chloride,
3-(dimethylamino)-1-propylamine
3-(dimethylamino)-1-propylamine and and
and α,ω-dibromoalkanes
α,ω-dibromoalkanes according to
to
to Scheme
Scheme 33.
33. The
The product
product
separation
separation methods
separation methods include
methods include column
include column chromatography,
column chromatography, vacuum
chromatography, vacuum drying
vacuum drying and
drying and recrystallization
and recrystallization from
recrystallization from
from
ethanol/ethyl
ethanol/ethyl acetate
acetate [143]. They can
[143]. They can be used
used
used in
in
in preparation
preparation of
of three-dimensional
three-dimensional mesoporous
mesoporous
materials
materialsfor
materials forseparations,
for separations,catalysis
separations, catalysisand
catalysis anddrug
and drugdelivery
drug delivery[143].
delivery [143].
[143].
H222N
H N
Br
Br (( ))n-2 Br
n-2 Br
n={3,6,8,10}
n={3,6,8,10}
in C
in C22H
H55OH
OH
N
N 80°C,
80 °C, 36h
36h Br
Br Br
Br
0°C, 2h
C
C C
C C
C
COCl
COCl O N N O
O N
N N
N ( )n-2 N
n-2 N N
N O
O
O N N
H
H H
H H
H
Dehydroabietyl
Dehydroabietyl 3-(N,N-dimethyl)-propyl
3-(N,N-dimethyl)-propyl
chloride
chloride Rosin-based Gemini
Rosin-based Gemini surfactant
surfactant
dehydroabietamide
Scheme 33.
Synthesis of
of rosin-based
rosin-based gemini
gemini surfactant.
surfactant.
Rosin-based
Rosin-based cyclic tricarbonate
Rosin-based cyclic tricarbonate is
tricarbonate isisaaabrown
brownsolid.
brown solid.It
solid. It can
It can
can be prepared
be prepared
be prepared fromfrom
from maleopimaric
maleopimaric
maleopimaric acid
acid
acid triglycidyl
triglycidyl
triglycidyl ester ester
ester and and carbon
and carbon
carbon dioxide
dioxide
dioxide according
according according
to to Scheme
to Scheme
Scheme 34, to
34, prior
34, prior prior
to to washing
washing
washing and vacuum
and vacuum
and vacuum drying
drying
drying [132].
[132]. Its Its applications
applications includeinclude synthesis
synthesis of quaternary
of quaternary ammoniumammonium salt derivatives
salt derivatives [132] [132] and
and non-
non-isocyanate polyurethanes
isocyanate polyurethanes
isocyanate polyurethanes [200]. [200]. Rosin-based
[200]. Rosin-based carbamate
Rosin-based carbamate group-containing
carbamate group-containing quaternary
group-containing quaternary ammonium
quaternary ammonium
ammonium
salt
salt derivatives are
salt derivatives are brown
are brownsolids.
brown solids.They
solids. They
They cancan
can be prepared
be prepared
be prepared fromfrom
from rosin-based
rosin-based
rosin-based cycliccyclic
cyclic tricarbonate,
tricarbonate,
tricarbonate, N,N-
N,N-
N,N-dimethylaminopropylamine
dimethylaminopropylamine and alkyl and alkyl
bromidesbromides according
according to Scheme
to Scheme 34, and34, and vacuum
using using vacuum
drying
drying
and and recrystallization
recrystallization [132].exhibit
[132]. They
[132]. They They exhibit
exhibit strong antimicrobial
strong antimicrobial
strong antimicrobial properties
properties
properties [132]. [132].
[132].
Maleopimaric acid
Maleopimaric acid O
O CO22 O
O
O
O O
O O O
triglycidyl ester
triglycidyl ester O O
Rosin-based
LiBr/ethane-1,2-diol Rosin-based
O
O O
O
in NMP
in NMP
O
O cyclic carbonate
cyclic carbonate
O 110°C, 2MPa
2MPa O O
O O
O
110°C, yield: 89%
yield: 89%
O
O 7h
7h O
O O
O
O
O O
O
O
O
COO
COO N O
O O
O nn == 2,
2, or
or 5,
5, or
or 11
11
N COO
COO
in ethanol
in ethanol H
H
H
H H222N
H N R N
N N
N (CH222))nnnCH
(CH CH333
75°C, 2h
75°C, 2h R
R N
R N N
N Br
Br
O
O R N
N
O
O O
O O
O R N
N (CH222))nnnCH
(CH CH333
O
O R N
R N N
N H
H
H
H O
O
O
O O Br
Br
R=
R= O
OH O
O
O
O Rosin-base or:
OH Rosin-basedcarbamate
OH
OH
carbamate O
O group-containing quaternary
group-containing quaternary
R=
R=
yield: 92%
92% ammonium salt
ammonium salt derivative
derivative
yield: O
O
yield: 78%,
yield: 78%, or
or 85%,
85%, oror 80%
80%
Br(CH222))nnnCH
Br(CH CH333
R N
R N N
N COO R N
N N (CH222))nnnCH
CH333
H
H in ethanol; 70°C, 15h COO R N (CH
COO
COO H
H Br
Br
Scheme34.
Scheme
Scheme 34.Synthesis
34. Synthesis
Synthesis of rosin-based
of rosin-based
of rosin-based carbamate
carbamate
carbamate and carbamate
and carbamate
and carbamate group-containing
group-containing
group-containing quaternary
quaternary
quaternary ammonium
ammonium
ammonium
salt salt derivatives.
salt
derivatives. derivatives.
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51
Maleopimaric
Maleopimaric acid diethanolamide
Maleopimaric acid
acid diethanolamideis
diethanolamide isisaaasolid.
solid.It
solid. It can
It can
can be be synthesized
be synthesized
synthesized from
fromfrom maleopimaric
maleopimaric
maleopimaric acidacid
acid and
and
and Maleopimaric acid
diethanolamine diethanolamide
according to Schemeis a35solid.
[103].It It
can bebe
can synthesized
applied as from
a maleopimaric
dispersant and a acid and
viscosity
diethanolamine
diethanolamine according
according toto Scheme
Scheme 3535 [103].
[103]. It
It can
can bebe applied
applied as
as aa dispersant
dispersant and
and aa viscosity
viscosity
diethanolamine
depressant according to Scheme 35 [103]. It can be applied as a dispersant and a viscosity
depressant in
depressant in coal-water
in coal-water slurry
coal-water slurry [103].
slurry [103].
[103].
depressant in coal-water slurry [103].
O
O OH
OH OH
OH
O OH O
O OH
O OH
N
N OH
OH N
N OH
O N OH N OH
O
O
Maleopimaric
Maleopimaric KOH Maleopimaric
Maleopimaric acid
acid
Maleopimaric
acid
KOH
KOH 4h Maleopimaric acid
diethanolamide
acid O
O 160°C,
160°C, 4h N
N OH
OH diethanolamide
acid O 160°C, 4h OH
OH N OH diethanolamide
COOH
COOH OH OO
COOH O OH
OH
N
N OH
OH OH
O
O N OH
O
Scheme 35. Synthesis of
of maleopimaric
maleopimaric acid
acid diethanolamide.
diethanolamide.
Scheme 35. Synthesis of maleopimaric acid diethanolamide.
Acrylpiamric
Acrylpiamric acid
acid salts
salts of
of calcium
calcium and
and zinc
zinc are
are solids.
solids. They
They can
can be
be prepared
prepared from
from acrylpimaric
acrylpimaric
Acrylpiamric acid salts of calcium and zinc are solids. They can be prepared from acrylpimaric
acid,
acid, sodium
sodium hydroxide
hydroxide andand calcium
calcium chloride
chloride or
or zinc
zinc sulfate
sulfate according
according to
to Scheme
Scheme 36
36 and
and using
using such
such
acid, sodium hydroxide and calcium chloride or zinc sulfate according to Scheme 36 and using such
separation
separation methods as washing, filtration and drying [137]. They can be used as a stabilizer of
methods as washing, filtration and drying [137]. They
They can
can be
be used
used as a stabilizer of
separation methods as washing, filtration and drying [137]. They can be used as a stabilizer of
poly(vinyl
poly(vinyl chloride)
chloride) showing
showing better
showing betterthermal
better thermalstability
thermal stabilitythan
stability thancommercial
than commercialCa/Zn
commercial Ca/Znstearate
Ca/Zn stearate[137].
stearate [137].
[137].
poly(vinyl chloride) showing better thermal stability than commercial Ca/Zn stearate [137].
COO
COO COOH
COOH
COO COO
COO
COOH COO
ZnSO
ZnSO44** 7H
7H22O
O NaOH
NaOH NaOH
NaOH CaCl
CaCl22
ZnSO4* 7H2O NaOH NaOH CaCl2
22
in
in acetone/water
acetone/water in
in acetone/water
acetone/water
in water/ethanol
acetone/water in water/ethanol
acetone/water 22
Zn
Zn2 water/ethanol water/ethanol Ca
Ca2
COO
COO Zn water/ethanol
-15-50°C
-15-50°C COOH
COOH
water/ethanol
-15-50°C
-15-50°C
Ca
COO COO
COO
-15-50°C
27h COOH -15-50°C
27h
Zinc
Zinc acrylpimarate
acrylpimarate 27h
27h
Acrylpimaric
Acrylpimaric acid
acid 27h
27h
Calcium acrylpimarate
Calcium COO
acrylpimarate
Zinc acrylpimarate Acrylpimaric acid Calcium acrylpimarate
Scheme 36.
36. Synthesis
of acrylpimaric acid
acrylpimaric acid divalent
acid divalent metal
divalent metal salts.
metal salts.
salts.
Scheme Synthesis
Synthesis of
of acrylpimaric
acrylpimaric
Rosin-derived
Rosin-derived binapthyl-appended
Rosin-derivedbinapthyl-appended
binapthyl-appended 22-crown-6
22-crown-6
22-crown-6 ether
ether
ether can can
can be be synthesized
be synthesized synthesized from
from methyl
from methyl maleopimarate,methyl
Rosin-derived binapthyl-appended 22-crown-6 ether can be synthesized from methyl
maleopimarate,
maleopimarate,
sodium borate sodium
sodium
and sodium borate
borate
hydrideand
and sodium
sodiumto
according hydride
hydride
Scheme according
according
37 [184]. to
Itto Scheme
canScheme
be used37
37in[184].
[184].
highlyIt can
can bebe used
used in
Itenantioselective in
maleopimarate, sodium borate and sodium hydride according to Scheme 37 [184]. It can be used in
highly
highly enantioselective
enantioselective
reactions reactions
reactions
because of its amines because
because
enantiomericof
of its
its amines
amines enantiomeric
enantiomeric recognition
recognition ability
ability [184].
[184]. Very
Very
highly enantioselective reactions because of recognition ability [184]. Very
its amines enantiomeric similar compounds
recognition ability [184].can be
Very
similar
similar
also compounds
compounds
synthesized can
can be
directly be also
also
from synthesized
synthesizedor
maleopimaric directly
directly from
from maleopimaric
fumaropimaricmaleopimaric
acid [201]. or
or fumaropimaric
fumaropimaric acid acid [201].
[201].
similar compounds can be also synthesized directly from maleopimaric or fumaropimaric acid [201].
O
O
O O
O
OH
OH O
O OH O
O O
O
O O O
O NaBH OH
OH
NaBH44 OH NaH
NaH O O
NaBH4 NaH O O
dioxane in O O
O
O dioxane in THF
THF O
O
O dioxane
0.5h
0.5h in THF
50h
50h O
COO
COO COO
COO
0.5h COO 50h COO
COO COO
COO
Rosin-derived
Rosin-derived
Methyl
Methyl maleopimarate
maleopimarate Rosin-based Rosin-derived
Methyl maleopimarate Rosin-based diol
diol (yield:
(yield: 53%)
53%) binaphthyl-appended
binaphthyl-appended 22-crown-6
22-crown-6 ether
ether
Rosin-based diol (yield: 53%) binaphthyl-appended 22-crown-6 ether
Scheme
Scheme 37.
37. Synthesis
Synthesis of
of rosin-derived
rosin-derived binapthyl-appended
22-crown-6 ether.
ether.
Scheme
Scheme 37.
37. Synthesis
Synthesis of
of rosin-derived
rosin-derived binapthyl-appended
22-crown-6 ether.
ether.
3.2.5.
3.2.5. Biologically
3.2.5. Biologically Active
Biologically Active Compounds
Active Compounds
Compounds
Biologically Active Compounds
Pure abietic
Pure abietic
Pure
acid
abietic acid isolated
acid isolated
isolated from from rosin
from rosin
rosin andand its
and its derivatives
its derivatives exhibit
derivatives exhibit many
exhibit many potential
many potential activities
potential activities
activities ofof
of
interest to
interest to the
the pharmaceutical
pharmaceutical industry,
industry, for example,
for example, antitumor,
antitumor, anti-inflammatory,
anti-inflammatory, antimycotic
antimycotic and
and
interest tothe
to thepharmaceutical
pharmaceuticalindustry,industry,forfor example,
example, antitumor,
antitumor, anti-inflammatory,
anti-inflammatory, antimycotic
antimycotic and
anti-arteriosclerotic
anti-arteriosclerotic properties
properties and
and uses
uses in
in treating
treating digestive
digestive canal,
canal, acute
acute and
and chronic
chronic gastritis,
gastritis, and
and
and anti-arteriosclerotic
anti-arteriosclerotic properties
properties and uses
and uses in treating
in treating digestive
digestive canal,canal,
acuteacute and chronic
and chronic gastritis,
gastritis, and
erosive
erosive gastritis,
gastritis, allergy,
allergy, asthma,
asthma, arthritis
arthritis and
and psoriasis
psoriasis [202].
[202]. In
In this
this subsection
subsection rosin-based
rosin-based chemicals
chemicals
and erosive
erosive gastritis,
gastritis, allergy,
allergy, asthma, asthma, arthritis
arthritis and psoriasis
and psoriasis [202]. In[202]. In this subsection
this subsection rosin-based rosin-based
chemicals
with
with main
main applications
applications as
as biologically
biologically active
active compounds
compounds can
can be
be found.
found. They
They include
include both
both
chemicals
with mainwith main applications
applications as biologically
as biologically active active compounds
compounds can can
be be found.They
found. Theyinclude
include both
medications
medications and
and biocides.
biocides. Their
Their synthetic
synthetic routes
routes are
are usually
usually characterized
characterized in
in detail
detail and,
and, from
from the
the
medications and
medications and biocides.
biocides. Their
Their synthetic
synthetic routes
routes areare usually
usually characterized
characterized in in detail
detail and,
and, from the
chemical
chemical point
point of
of view,
view, their
their TRLs
TRLs are
are rather
rather high.
high. It
It is
is worth
worth noting,
noting, that
that although
although the
the sustainability
sustainability
chemical point of view, their TRLs are rather high. It is is worth
worth noting,
noting, that
that although
although the the sustainability
sustainability
of
of their
their syntheses
syntheses is is usually
usually worse
worse than
than for
for other
other rosin
rosin derivatives
derivatives (due
(due toto the
the necessity
necessity ofof using
using more
more
of their syntheses is usually worse than for other rosin derivatives (due to the necessity of using more
dangerous
dangerous chemicals),
chemicals), itit is
is still
still better
better than
than their
their petrochemical
petrochemical counterparts
counterparts (thanks
(thanks toto the
the use
use of
of bio-
bio-
dangerous chemicals), it is still better than their petrochemical counterparts (thanks to the use of bio-
based rosin as a main substrate).
Methyl dehydroabietate is a white solid. It can be prepared from dehydroabietyl chloride and
methanol according to Scheme 38, prior to vacuum evaporation and recrystallization [141]. It can be
used as a substrate in the synthesis of antimicrobial agents and medicines [141,150].
Methyl 7-oxodehydroabietate is a yellow oil. It can be prepared from methyl dehydroabietate
and chromium
Molecules trioxide according to Scheme 38, followed by extraction, drying and column
2019, 24, 1651 19 of 52
chromatography [141]. It can be used as a substrate in synthesis of antimicrobial agents and medicines
[141,150].
dangerous chemicals),acid
Dehydroabietic it isderivative
still better QC4
than can
theirbepetrochemicalfrom counterparts (thanks to the use of
Methyl dehydroabietate is a white solid. It can prepared
be prepared from methyl 7-oxodehydroabietate,
dehydroabietyl chloride and
bio-based rosin as a main substrate).
methanol according to Scheme 38, prior to vacuum evaporation and recrystallization [141].toItScheme
phenylhydrazine hydrochloride, 1,2-dibromoethane and N-methyl piperazine, according can be
Methyl dehydroabietate
38 [141,150]. It shows is a white
antimicrobial solid. It
properties canand,
[150] be prepared
moreover, from dehydroabietyl
induces chloride
gastric cancer and
cell death
used as a substrate in the synthesis of antimicrobial agents and medicines [141,150].
methanol
via oncosis according to Scheme 38, prior to vacuum evaporation and recrystallization [141].
to be ablebe
It can
Methyland apoptosis [151]. Another
7-oxodehydroabietate dehydroabietic
is a yellow oil. It canacid derivativefrom
be prepared QC2methyl
is reported
dehydroabietate to
used as
inhibit a substrate
skin cancer in the
cell synthesis
lines [203]. of antimicrobial agents and medicines [141,150].
and chromium trioxide according to Scheme 38, followed by extraction, drying and column
chromatography [141]. It can be used as a substrate in synthesis of antimicrobial agents and medicines
CrO3
Dehydroabietyl
[141,150]. HN NH2
COO
N
chloride
Dehydroabietic acid (CH 3COO)2O QC4 can be prepared from methyl 7-oxodehydroabietate,
derivative
CH3OH CH3COOH O
phenylhydrazine hydrochloride, 1,2-dibromoethane and N-methylBr(CH2piperazine,
)2Br N according to Scheme
25°C/12h H N
38 [141,150].2hIt shows antimicrobial properties [150] and, moreover, induces gastric cancer cell death
HCl TBAB K 2CO 3
via oncosis and apoptosis [151]. Another dehydroabietic acid derivative
in EtOH NaOH
QC2 KI is reported to be ableN
to
inhibit skin cancer cell lines COO [203]. COO 4h 25°C in CH3CN
Methyl Methyl 7-oxo- yield: yield: yield: N
COCl dehydroabietateCrO dehydroabietate 61% QC4
Dehydroabietyl yield: 92% 3 56% 18-67% COO
yield: 64% HN NH2
N
chloride (CH COO) O
3 2
CH3OH Scheme 38. Synthesis
CH3COOH
of dehydroabietic
dehydroabietic
O derivative QC4.
derivative QC4.
Br(CH2)2Br N
25°C/12h H N
2h
N-(2-methyl-naphthyl)maleopimaric
Methyl 7-oxodehydroabietate is a yellow acid diimides
oil. It can and
HCl be their methyl
prepared
TBAB
fromesters
K are white
methyl
2CO3
solids (m.p.
dehydroabietate
215-290°C).
and chromium They can beaccording
trioxide synthesizedto Scheme in
from maleopimaricEtOH
38, followed acid, NaOH
by KI
2-methyl-1-naphtylamine
extraction, drying and column N and
COO COO 4h 25°C in CH3CN
dimethyl sulfate according
Methyl It to
canScheme
be 39,
used and
as ausing
Methyl 7-oxo- separation
substrate in methods
synthesis ofsuch as extraction,
antimicrobial washing,
agents and
yield: yield: yield: N
drying, evaporation
medicines [141,150]. and
COCl dehydroabietate recrystallization [106,107].
dehydroabietate 61% They show significant antitumor QC4cytotoxicity
56% 18-67%
against
Dehydroabietic yield:acid
several human 92%
cancerderivative yield:
cell lines,
QC4 64%
especially
can beNCI cells andfrom
prepared MGC-803
methyl cells [106].
7-oxodehydroabietate,
Anticancer effects
phenylhydrazine of various rosin
hydrochloride, derivatives, especially
1,2-dibromoethane thioureas, were
and N-methyl also investigated;
piperazine, accordingtheyto
Scheme 38. Synthesis of dehydroabietic derivative QC4.
showed38
Scheme significantly
[141,150]. Itcytotoxicity toward diverse
shows antimicrobial human
properties [150] carcinoma cell lines
and, moreover, [108].gastric cancer cell
induces
deathN-(2-methyl-naphthyl)maleopimaric
via oncosis and apoptosis [151]. Another acid diimides and their methyl esters QC2
dehydroabietic acid derivative is reported
are white to be
solids (m.p.
O NH R R
able to inhibit skin cancer cell
2 lines [203].
215-290°C).O They can be synthesized from maleopimaric acid, 2-methyl-1-naphtylamine and
N-(2-methyl-naphthyl)maleopimaric N acid diimides and their N
methyl
dimethyl sulfateO according to Scheme O 39, and O using separation
(CH O
methods suchO esters are white
as extraction, solids
washing,
3)2SO4
(m.p. 215–290 ◦ C). They can be synthesized from maleopimaric acid, R=
2-methyl-1-naphtylamine or and
drying, evaporation and recrystallization [106,107]. They show significant antitumor cytotoxicity
K2CO3
dimethyl sulfate according
against several human (C2H 5)3N
cancer to Scheme 39, and using
cell lines, especially in separation
NCI methods such
cells and MGC-803 cells [106].as extraction, washing,
acetone
drying, hexamethyl
evaporation and disilazane
recrystallization [106,107]. They6h show significant
Anticancer effects reflux,
of various rosin derivatives, especially
in DMF
thioureas, wereantitumor cytotoxicity
also investigated; they
against several human
showed significantly
COOH
cancer
cytotoxicity
reflux, 4h cell lines, especially
toward diverse COOHNCI cells and MGC-803
human carcinoma cell lines [108]. cells
COO[106].
O NH2 R R
Maleopimaric
O (2-methyl-naphthy) (2-methyl-naphthy) methyl
acid O
N
maleopimaric acid
O diimides
(CH3)2SO4
N
maleopimaric
O Oacid diimides
O
yield: 30-41% yield: 46-53% R = or
K2CO3
(C2H39.
Scheme 5)3NSynthesis of N-(2-methyl-naphthyl)maleopimaric acid diimides.
in acetone
hexamethyl disilazane reflux, 6h
in DMF
Thiadiazole
COOH group-containing
reflux, 4h amides of dehydroabietic
COOH or acrylpimaric COO
acids can
be prepared
from adequate rosin acid, thiosemicarbazide and an acyl chloride according to Scheme 40, and using
such separation methods as filtration,
Maleopimaric vacuum drying, recrystallization
(2-methyl-naphthy) and column
(2-methyl-naphthy) chromatography
methyl
acid They can be potentiallymaleopimaric
[130]. applied as insecticides [130,190].
acid diimides maleopimaric acid diimides
yield: 30-41% yield: 46-53%
Scheme 39.
Synthesis of N-(2-methyl-naphthyl)maleopimaric acid
of N-(2-methyl-naphthyl)maleopimaric acid diimides.
diimides.
Thiadiazoleeffects
Anticancer group-containing amides
of various rosin of dehydroabietic
derivatives, especially or acrylpimaric
thioureas, acidsinvestigated;
were also can be prepared
they
from adequate
showed rosin acid,
significantly thiosemicarbazide
cytotoxicity and human
toward diverse an acyl carcinoma
chloride according
cell linesto Scheme 40, and using
[108].
suchThiadiazole
separation methods as filtration,
group-containing vacuum
amides drying, recrystallization
of dehydroabietic andacids
or acrylpimaric column chromatography
can be prepared from
[130]. They
adequate can acid,
rosin be potentially applied asand
thiosemicarbazide insecticides [130,190].
an acyl chloride according to Scheme 40, and using such
separation methods as filtration, vacuum drying, recrystallization and column chromatography [130].
They can be potentially applied as insecticides [130,190].
in POCl3 O O
(C2H5)3N NH R
H2N N O
reflux, 4h in CH2Cl2 H R Cl
S R
COOH 0°C, 12h in P OCl3 (C2H5)3N
N NH
N reflux, 4h in CH2Cl2 S
Dehydroabietic Dehydroabietic acid COOH
0°C, 12h
N
acid 2019, 24, 1651
Molecules amide with thiadiazole N
20 of 52
group yield:78-86% Acrylpimaric Acrylpimaric acid amide with
Molecules 2019, 24, x FOR PEER REVIEW acid thiadiazole groups yield:58-85%
20 of 51
S NH2 Scheme 40. Synthesis of rosinRacid amides

= {-CH with thiadiazole groups. N
3, -C6H11, -C6H5, -C6H5R' } N
O
R NH
H2N N COOH S
R Cl O
Acrylpimaric H
acid-based aromatic diacylthioureas can SbeNHprepared 2 from acrylpimaryl
in POCl3 O O
(C H )
2 5 3
dichloride, potassium thiocyanate N NH
and aromatic amines according to Scheme 41, prior to vacuum
R
H2N N O
reflux, 4h in CH2Cl2 H R Cl
evaporation and recrystallization [129].S They may be applied as botanical herbicides showingRhigher
COOH 0°C, 12h in P OCl 3 (C2H5)3N
N NH
activity than similar dicarboxamide, dihydrazone N and diimide compounds
reflux, 4h in CH2Cl[129].
2 Moreover, S
some
Dehydroabietic
acrylpimaryl Dehydroabietic
diimides possess antibacterialacidactivities against COOH
Gram-positive 0°C,Staphylococcus
12h aureus and
N
acid amide with thiadiazole
Gram-negative Escherichia coli [204]. Furthermore, some acrylpimaryl dicarboxamidesN show
group yield:78-86% Acrylpimaric Acrylpimaric acid amide with
antibacterial properties against E. coli, whereas their acid activity against Gram-positive
thiadiazole bacteria was
groups yield:58-85%
significantly lower [205].
Solid acrylpimaryl Scheme
Scheme 40.
40. Synthesis
quaternarySynthesis of
of rosin
ammonium rosin acid amides
salts
acid canwith
amides thiadiazole
thiadiazole groups.
be synthesized
with from acrylpimaryl acid,
groups.
oxalyl chloride, epichlorohydrin and volatile tertiary amines according to Scheme 41 and using such
Acrylpimaric
Acrylpimaric acid-basedaromatic
acid-based aromatic diacylthioureas
diacylthioureas becan
can and preparedbe prepared from acrylpimaryl
from acrylpimaryl dichloride,
separation methods as vacuum distillation, extraction recrystallization [189]. They show
dichloride,
potassium potassium thiocyanate
thiocyanate and aromatic and aromatic
amines aminestoaccording
according Scheme to prior
41, Scheme to 41, priorevaporation
vacuum to vacuum
fungicidal activity and can be applied in wood preservation [189]. Very similar acrylpimaryl
evaporation and recrystallization
and recrystallization [129]. They [129].
may beThey
applied mayasbe applied herbicides
botanical as botanical herbicides
showing showing
higher activityhigher
than
materials that can be applied as surfactants were also prepared [133]. Another fungicidal rosin-based
activity than similar
similar dicarboxamide, dicarboxamide,
dihydrazone dihydrazone
and diimide and diimide compounds [129]. Moreover, some
materials can be prepared in similar way fromcompounds [129]. Moreover,
rosin, epichlorohydrin and some
amines acrylpimaryl
[134–136].
acrylpimaryl
diimides diimides
possess possessactivities
antibacterial antibacterial
against activities against Gram-positive
Gram-positive Staphylococcus Staphylococcus
aureus and aureus and
Gram-negative
Maleopimaryl chloride is a yellowish solid. It can be prepared from maleopimaric acid and oxalyl (or
Gram-negative
Escherichia Escherichia
coli [204]. Furthermore,coli [204].
some30Furthermore,
acrylpimaryl some acrylpimaryl
dicarboxamides dicarboxamides show
show antibacterial
thionyl) chloride, according to Scheme or 42, prior to vacuum distillation and washingproperties
[104,105].
antibacterial
against E. properties
coli, whereas against
their E.
activity coli, whereas
against their
Gram-positive activity
bacteriaagainstwas Gram-positive
significantly bacteria
lower [205].was
It can be used as an intermediate in preparation of surfactants [104] or fungicides [105].
significantly lower [205].
Solid acrylpimaryl
Acrylpimaryl diacarboxamidequaternary ammonium salts can be synthesized
R = {-H, -CH3, -(CH3)2, -OCH3,
from acrylpimaryl
Acrylpimaryl diacylthioureaacid,
compound yield:58-85%
oxalyl chloride, epichlorohydrin and volatile
-CF 3, -F, tertiary
-Cl, -Br, amines
-OH, -NO 2 } according to compound yield:60-77%
Scheme 41 and using such
O
separation methods as vacuum distillation, extraction and recrystallization [189]. They show O S
C NH2 1. KSCN [189]. Very similar Cacrylpimaryl
fungicidal
HN activity and can be applied in wood preservation R N NH
H
materials that can be applied as surfactants were also prepared [133]. Another fungicidal rosin-based
R 2. H2N
materials can be prepared in similar way from rosin, epichlorohydrin and amines R[134–136].
COCl
Maleopimaryl chloride is a yellowish (C2H5)3Nsolid. It can be prepared from maleopimaric acid and oxalyl (or
in acetonitrile
R in CH Cl ; <5°C, 12h 25°C, 4h Cand H
NH washing
thionyl) chloride, N C according to 2Scheme 2 30 or 42, prior to vacuum distillation N [104,105].
R H O R
It can be used as an intermediate in preparation of surfactants 1.[104] or
NH3*H2O fungicides
O [105].
S
O 1. N2H4 2. LiAlH4
N 2. CHO 3. CHO
C
Acrylpimaryl diacarboxamide R = {-H, -CH3, -(CH3)2, -OCH3, Acrylpimaryl diacylthiourea
N
H N
compound yield:58-85% COCl
-CF3, -F, -Cl, -Br, -OH, -NO2 } compound yield:60-77%
O R R
Acrylpimaryl O S
R
C NH2 chloride 1. KSCN C
HN 1. in THF 1. in THFR R N NH
R H
2. in EtOH 2. in THF R
C N N
H 0-25°C, 17hR 2. H23.N in EtOH
R N
O 0-25°C, 17h
COCl
Acrylpimaryl dihydrazone (C2H5)3N in acetonitrile Acrylpimaryl diimide
R 25°C, 4h H
compound yield:45-60%
N C in CH2Cl2; <5°C, 12h compound
C NH
Nyield: 22-59%
R H O R
1. diacylthioureas,
NH3*H2O O S
Scheme 41.O Synthesis
Scheme 41. Synthesis ofof acrylpimaric
acrylpimaric
1. N2H4
acid-based
acid-based aromatic
aromatic diacylthioureas, dicarboxamides,
dicarboxamides,
2. LiAlH4
dihydrazones
dihydrazones and diimides.
N 2. CHO 3. CHO
C and diimides.
N
H COCl N
Solid acrylpimaryl quaternary ammonium R R
salts can be synthesized from acrylpimaryl acid,
R Acrylpimaryl
oxalyl chloride, epichlorohydrin and volatilechloride
tertiary amines according to Scheme 41 and using such
1. in THF 1. in THF R
R
separation methods as vacuum distillation, extraction and recrystallization [189]. They show fungicidal
2. in EtOH 2. in THF R
C N N
activity Hand can be applied in wood0-25°C, preservation
17h [189]. Very 3.similar
in EtOHacrylpimaryl materials that can
N
O 0-25°C, 17h
be applied as surfactants were also prepared [133]. Another fungicidal rosin-based materials can be
Acrylpimaryl dihydrazone Acrylpimaryl diimide
prepared
compound in similar way from rosin, epichlorohydrin and amines [134–136]. Maleopimaryl
yield:45-60% chloride
compound yield: 22-59%is a
yellowish solid. It can be prepared from maleopimaric acid and oxalyl (or thionyl) chloride, according
Scheme30 41.
to Scheme Synthesis
or Scheme 42,ofprior
acrylpimaric
to vacuumacid-based aromatic
distillation diacylthioureas,
and washing [104,105]. dicarboxamides,
It can be used as an
dihydrazones and diimides.
intermediate in preparation of surfactants [104] or fungicides [105].
Molecules 2019, 24, 1651 21 of 52
Molecules 2019,
Molecules 2019, 24,
24, xx FOR
FOR PEER
PEER REVIEW
REVIEW 21 of
21 of 51
51
R ==
R
R = CH
CH33 or
CH or CH
CH CHCH
COCl
COCl COO
COO 3 or CH222CH333 COO
COO
COO
COCl COO
OH
OH
OH OH
OH
OH
1.NaOH
1.
1. NaOH
NaOH R
R
R
2.
2. N
N
N
2. O
O Cl
Cl
Cl R
R R
R R
R N R
R N
N R
R
O Cl
Cl
Cl R R
OH
OH
OH OH
OH
OH R
R
in CH
in CH222Cl
Cl222 (C222H
H555))333N
N R
(C R
R
R
COCl
COCl
50°C, 4h
50°C, 4h COO
COO in alcohol
in alcohol COO
COO
COO
COCl COO Cl N
N
N
Cl
Cl 85°C, 3.5h
85°C, 3.5h Cl
Acrylpimaryl dichloride
Acrylpimaryl dichloride Cl
Cl
Cl R
R
R
R
R
R
Cl
Cl
Acrylpimaryl quaternary
Acrylpimaryl quaternary
ammonium salt
ammonium salt yield:
yield: 71-82%
71-82%
Scheme 42.
Synthesis of acrylpimaryl
Synthesis of
of acrylpimaryl quaternary
acrylpimaryl quaternary ammonium
quaternary ammonium salts.
salts.
Maleated rosin-based dithioureacompounds

compoundsareareyellow
yellowsolids
solids(m.p.
(m.p.162–216
162–216 ◦
Maleated rosin-based dithiourea
dithiourea compounds are yellow solids (m.p. 162–216 °C).C).
°C). They
They
They cancan
can be
be
be prepared
prepared from
prepared from maleated
from maleated rosin
maleated rosin acyl
rosin acyl chloride,
acyl chloride, hydrazine
chloride, hydrazine and
hydrazine and substituted
and substituted benzoyl
substituted benzoyl isothiocyanates,
benzoyl isothiocyanates,
according to
according to Scheme
Scheme 43,
43, and
and using
and using separation
using separation methods
separation methods such
methods such as
such as rotary
rotary evaporation,
as rotary recrystallization
evaporation, recrystallization
evaporation, recrystallization
and column
column chromatography
[105]. They can be potentially
potentially used
used as
as fungicides
fungicides
and column chromatography [105]. They can be potentially used as fungicides [105]. [105].
[105].
O
O
O O
O
O NH22
NH
NH R ==
R
R = {{{ H;
H; -CH
H; -CH33;;; -OCH
-CH -OCH ;; -Cl
-Cl }}
O 2 3 -OCH333; -Cl } R
R
R
O
O
O O
O
O O
O
N
N
N
O
O
O O
O
O NCS O
O
O
O O
O
O NCS
NCS O
O
O
O
O
O O
O
H
H
H
Cl S
Cl S Cl
Cl N22H
N
N H ** HHO O N
N
N NH
Cl S Cl 2H444* H222O R
R
R N
N
N NH
NH
in benzene
in benzene in CH
in CH222Cl
Cl222 S
S
S
<80°C, 5h
<80°C, 5h 0-25°C, 4h
0-25°C, 4h NH22
NH
NH O
2
in acetonitrile
acetonitrile O
O
in
COOH
COOH
COOH COCl
COCl
COCl NH
NH
NH reflux, 44hh H
H
H H
H
C reflux, C
C
C N
N H
C
C N N
N
N
N
N
N
O O
O
O H
H
H
O
O R
R
Maleated rosin
Maleated rosin Maleated rosin
Maleated rosin S
S
S O
O
O R
Maleated rosin
Maleated rosin Maleated rosin-based
Maleated rosin-based
acyl chloride
acyl chloride
hydrazide yield:
hydrazide yield: 75%
75% dithiourea
dithiourea
yield: 85%
yield: 85%
Scheme Synthesis of maleated
maleated rosin-based dithiourea
dithiourea compounds.
Scheme 43.
43. Synthesis of
of maleated rosin-based
rosin-based dithiourea compounds.
compounds.
Glucose
Glucose dehydroabietate
dehydroabietate can
can bebe prepared
prepared from
from dehydroabietic
dehydroabietic acid
acid and
and glucose
glucose according
according to to
Scheme 44
Scheme 44 prior
prior to
to vacuum
vacuum distillation,
distillation, filtration
filtration and
and washing
washing [206].
[206]. Its
Its potential
potential application is as
application is as aa
surfactant in
surfactant in food
food industry
industry [206].
[206].
OH
OH
OH
HO
HO
HO
OH
OH
OH
HO
HO
Dehydroabietic
Dehydroabietic HO Glucose dehydroabietate
Glucose dehydroabietate
acid
acid HO
HO
HO OH
OH
OH OH
OH
yield: 51%
yield: 51%
OH
KOH
KOH
COOH
COOH
COOH in propanediol
in propanediol COO
COO
COO
190°C, 6h
190°C, 6h OH
OH
OH OH
OH
OH
Scheme 44.
Scheme
44. Preparation of glucose
Preparation of
of glucose dehydroabietate.
glucose dehydroabietate.
dehydroabietate.
Acrylic rosin
Acrylic rosin cyclic
cyclic diamide
diamide is
is aa solid.
solid. It
It can
can be
be prepared
prepared from
from acrylpimaric
acrylpimaric acid
acid and
and diethylene
diethylene
triamine according to Scheme 45 prior
Scheme 45 prior
triamine according to Scheme prior toto washing
to washing and
washing and drying
and drying [131].
drying [131]. It can be used as a fungicide for
[131]. It can be used as a fungicide for
wood preservation
wood preservation [131].
preservation [131].
[131].
COOH
COOH
COOH C O
C
C O
O
NH
NH
NH
Acrylpimaric
Acrylpimaric H22N(CH
H
H N(CH )) NH(CH
NH(CH )) NH NH
2N(CH222)222NH(CH222)222NH222 Acrylic rosin
Acrylic rosin
acid
acid xylene
xylene cyclic diamide
cyclic diamide
<180°C, 8h
<180°C, 8h C NH NH
NH
NH
C
C NH
NH
COOH
COOH
COOH O
O
O
Scheme 45.
Scheme Preparation of
45. Preparation of acrylic
acrylic rosin
rosin cyclic
cyclic diamide.
diamide.
3.2.6. Other
3.2.6. Other Small/Medium
Small/Medium Molecule
Molecule Products
Products
Molecules 2019, 24, 1651 22 of 52

Hydroabietic acid can be prepared from rosin and hydrogen using palladium/SBA-15
mesoporous silica catalyst, according to Scheme 46 [207]. This catalyst is more efficient than others
[208,209]
Molecules
3.2.6. Its Small/Medium
2019,
Other applications
24, x FOR PEERinclude
REVIEW oxidation-resistant
Molecule Products solvent-borne tackifiers and coatings, a substrate22 of 51
for esterification with glycerol [210], additives for polyvinylidene difluoride binders for lithium
Hydroabietic
Hydroabietic
titanium oxide anodesacid
acidcan
[76]. beIt prepared
can be be
can from
prepared
used inrosin
fromand hydrogen
rosin
high-performance using epoxy
and liquid palladium/SBA-15
hydrogen using mesoporous
resinspalladium/SBA-15
[83], for synthesis
silica catalyst,
mesoporous
of high adhesion according
silicapolyurethane to Scheme
catalyst, according 46
acrylate [207].
to[173].
Scheme This catalyst
It is46noteworthy, is more
[207]. This catalyst efficient than others
is more efficient
that non-catalytic [208,209]
than
decarboxylation othersof
Its applications
[208,209] Its include
applications oxidation-resistant
include solvent-borne
oxidation-resistant tackifiers
solvent-borne and
tackifiers
rosin can take place at temperatures above 200 °C, and the main product of such decomposition is coatings,
and a
coatings, substrate
a for
substrate
esterification
for withwith
esterification
norabieta-8,11,13-trieneglycerol [210],[210],
glycerol
[211]. additives for polyvinylidene
additives difluoride
for polyvinylidene binders binders
difluoride for lithiumfortitanium
lithium
oxide anodes [76]. It can be used in high-performance liquid epoxy resins
titanium oxide anodes [76]. It can be used in high-performance liquid epoxy resins [83], for synthesis[83], for synthesis of
high
of adhesion
high adhesion polyurethane
polyurethane acrylate
acrylate[173].
[173].ItItisisnoteworthy,
noteworthy,that thatnon-catalytic
non-catalytic decarboxylation
decarboxylation of of
H2
rosin can take place at temperatures above 200 ◦ C, and the main product of such decomposition is
rosin can take place at temperatures above 200 °C, and the main product of such decomposition is
norabieta-8,11,13-triene Pd/SiO
[211].
2 > 200°C
norabieta-8,11,13-triene [211].
in ethanol Norabieta-
160°C,8MPa,4h Hydroabietic acid -8,11,13-triene
COOH Rosin H2 COOH yield: >97%
Pd/SiO
Scheme
2 > 200°C
46. Hydrogenation of rosin to hydroabietic acid.
in ethanol Norabieta-
160°C,8MPa,4h Hydroabietic acid
Rosin-based standard-quality biodiesel can be prepared in a catalyst-free process -8,11,13-triene
from dark-
COOH Rosin COOH yield: >97%
grade rosin, heavy turpentine and supercritical methanol in supercritical CO2 as a green medium.
Yields >93% were obtained after 46.
Scheme
Scheme 3 hHydrogenation
46. at 340 °C, under
Hydrogenation of a pressure
of rosin
rosin to of 11 MPa
to hydroabietic
hydroabietic [212]. Yield of >85% can be
acid.
acid.
achieved using Pt/mesoporous aluminosilicate catalyst after 4 h at 300–350 °C, 5 MPa [213]. A yield
>99%Rosin-based
can be achieved standard-quality
standard-quality
using Ni/layered biodiesel
biodiesel can
can
double be be prepared
prepared
hydroxide in aincatalyst-free
catalyst a after
catalyst-free
<2 hprocessprocess
at 190 °C, 5 from
from MPa dark-
dark-grade
[214].
grade
rosin, rosin,
heavy
Catalytic heavyofturpentine
turpentine
cracking and is
rosin and
supercritical
also supercritical
possiblemethanol
to carry methanol
inout usinginacid-activated
supercritical supercritical
CO2 as a greenCO as a green
2medium.
montmorillonite Yields >93%
medium.
[215].
Yields
were >93% were
obtained
Acrylpimaryl obtained
after 3 h at 340
nitrile can ◦ C,
afterbe3 h at 340a °C,
under
prepared underlevopimaric
pressure
from a pressure
of of
11 MPa [212]. 11 MPa
acid and of >85%
Yield[212]. Yieldcan
acrylonitrile ofaccording
>85% can be
be achieved to
achieved
using
Scheme using
47, Pt/mesoporous
Pt/mesoporous
prior aluminosilicate
aluminosilicate
to extraction, catalyst
filtration catalyst
and after 4 h atafter
precipitation300–350 ◦
4 h atC,300–350
[216,217]. can°C,
5ItMPa be 5used
[213].MPa
A yield >99%
in[213]. A yield
synthesis can
of
>99%
be can be using
achieved
diacrylpimaryl achieved using
Ni/layered
ketone Ni/layered double
double hydroxide
and acrylpimaryl amidoxime hydroxide
catalyst
[217].after <2 h after
catalyst at 190<2◦ C,
h at 190 °C,
5 MPa 5 MPa
[214]. [214].
Catalytic
Catalytic
cracking cracking
of rosin isof rosin
also is also
possible possible
to carry to
out carry
using out using
acid-activatedacid-activated montmorillonite
montmorillonite
Acrylpimaryl nitrile amidoximes can be prepared from adequate acrylpimaryl nitriles and [215]. [215].
Acrylpimaryl
Acrylpimaryl
hydroxylamine nitrile
nitrile can
according be prepared
to Scheme from
47, prior levopimaric acid
to precipitation, filtration andaccording
and acrylonitrile
washing, drying [217]to
Scheme 47, can
[218]. They priorbetoused
extraction,
to preparefiltration andthin
bioactive precipitation
films filled[216,217]. It
It can
by magnetite be
be used in synthesis
cannanoparticles of
for oil spill
diacrylpimaryl
collecting [217] ketone and acrylpimaryl
and thorium ions removal amidoxime
[218]. [217].
Acrylpimaryl nitrile amidoximes can be prepared from adequate acrylpimaryl nitriles and
hydroxylamine according to Scheme O 47, priorOto precipitation, washing, filtration O and drying [217]
[218]. They can be used

2. Triethylene- 4. NHto ( ) 3
2OHprepare bioactive thin films filled by magnetite nanoparticles for oil spill
N N
H H
collecting tetramine
[217] and thorium
70°C, 2h
ions removal [218].
in toluene
10°C, 24h O O O
1. Oxalyl 3.
2. Triethylene- 4.CN
NH2OH N( N )3
chloridetetramine H
OH H
HO H2N N OH HO N NH2
N N
in DMF70°C, 2h Diacrylpimaryl nitrile
in toluene 185°C, 12h H N NH
in toluene 2
Diacrylamidoxime 2 amidoxime ketone
50°C, 4h 10°C, 24h NH2OH 70°C, 4h
triethylenetetralevopimaramide
1. Oxalyl 3. CNN C O
chloride OH HO H2N N OH HO N NH2
N N sulfonic acid; in toluene
p-toluene
in DMF Diacrylpimaryl nitrile
in toluene 185°C, 12h H2N 235°C,
NH2 4h
Diacrylamidoxime amidoxime ketone
50°C, 4h CN NH2OH 70°C, 4h
triethylenetetralevopimaramide
185°C, 12h H2N
N C C O
NH2OH
p-toluene sulfonic acid; in toluene
HOOC 70°C N
OH 235°C, 4h COOH CN CN
4h
Levopimaric CNHOOC Acrylpimaryl
acid Acrylpimaryl nitrileH2N Diacrylpimaryl nitrile
185°C, 12h amidoxime
yield: 78%NH2OH C ketone yield: 80%
HOOC Scheme 47. 70°C of Nacrylpimaryl

47. Synthesis OH nitrile and
and acrylpimaryl amidoximes.
Scheme Synthesis of acrylpimaryl nitrile COOH
acrylpimaryl
CNamidoximes. CN
4h
Levopimaric HOOC Acrylpimaryl
acidAcrylpimarylAcrylpimaryl nitrilecan be Diacrylpimaryl nitrile
Rosin-oil dimernitrile
acids amidoximes
mixture amidoxime
canprepared from rosin
be prepared from and industrial
adequate fatty oils according
acrylpimaryl to
nitriles and
yield: 78% ketone yield: 80%
Scheme 48, prior
hydroxylamine to washing
according and rotary
to Scheme evaporation
47, prior [219]. It washing,
to precipitation, can be used for preparation
filtration and dryingof[217,218].
a liquid
Scheme 47. Synthesis of acrylpimaryl nitrile and acrylpimaryl amidoximes.
Rosin-oil dimer acids mixture can be prepared from rosin and industrial fatty oils according to
Scheme 48, prior to washing and rotary evaporation [219]. It can be used for preparation of a liquid
Molecules 2019, 24, 1651 23 of 52
They can be used to prepare bioactive thin films filled by magnetite nanoparticles for oil spill
collecting
Molecules
[217]
Molecules 2019,
2019, 24, xxand
24, FORthorium
FOR PEER
ions
PEER REVIEW
REVIEW removal [218]. 23 of
23 of 51
51
Rosin-oil dimer acids mixture can be prepared from rosin and industrial fatty oils according
thermal stabilizer [219]. It is noteworthy, that dimerized rosin is usually produced separately and can to
Scheme
thermal
thermal
be 48, prior
stabilizer
stabilizer
applied in to washing
[219].
[219].
acrylic It is
It
adhesives and[220,221]
rotary evaporation
is noteworthy,
noteworthy, that
that [219].
dimerized
dimerized
to improve rosin
their It
rosin can
is be used
is usually
usually
wetting, for preparation
produced
produced
adhesion of stability
separately
andseparately
thermal aand
andliquid
can
can
thermal stabilizer
be applied
be applied in
[220]. [219].
in acrylic It is
acrylic adhesives noteworthy,
adhesives [220,221] that
[220,221] to dimerized
to improve rosin
improve their is usually
their wetting, produced
wetting, adhesion
adhesion and separately
and thermal and
thermal stabilitycan
stability
be applied in acrylic adhesives [220,221] to improve their wetting, adhesion and thermal stability [220].
[220].
[220].
CH3(CH2)5 HOOC
(CH22))55
CH33(CH (CH2)7COOH HOOC
HOOC
CH
fatty acids (CH22))77COOH
(CH COOH
(CH2)7CH3
fatty acids
fatty acids
catalyst (CH22))77CH
(CH CH33
240°C,0.5MPa,5h COOH
catalyst
catalyst (CH2)7COOH COOH
240°C,0.5MPa,5h
240°C,0.5MPa,5h
COOH COOH
(CH22))77COOH
(CH COOH
COOH
COOH COOH
COOH
Rosin COOH
COOH
Mixture of rosin-oil dimer acids
COOH
COOH
Rosin
Rosin Mixture of
Mixture of rosin-oil
rosin-oil dimer
dimer acids
acids
Scheme 48. Preparation of rosin-oil dimer acids mixture.
Scheme 48.
Scheme
Preparation of
of rosin-oil
rosin-oil dimer
dimer acids
acids mixture.
mixture.
Solid rosin-based chain extender for polyurethanes can be synthesized from rosin-
Solid
Solid rosin-basedacid,
Solid rosin-based
rosin-based
maleimidodicarboxylic chain
chain
chain extender
extender
extender
thionyl chloridefor for
forand polyurethanes
polyurethanes
polyurethanes
ethylene can
can
glycol, can
be
according be synthesized
be synthesized
synthesized
to Scheme from
from
49, from
rosin-
and rosin-
using
rosin-maleimidodicarboxylic
maleimidodicarboxylic
maleimidodicarboxylic
such separation methods acid,
acid, acid, thionyl
thionyl
as thionyl
vacuum chloride
chloride chloride
and
distillation, and ethylene
and ethylene
ethylene
washing glycol,
glycol, glycol, according
according
according
and evaporation to
to Its to
Scheme
Scheme
[186]. 49,Scheme
49, and
application 49,
and using
using
in
and
such
such using such
shapeseparation separation
separation methods methods
as
methods as vacuum
memory polyurethanes as
vacuum vacuum
improves distillation,
distillation,
distillation, washing
washing
shape recovery washing
and and evaporation
evaporation
and evaporation
at >1000% strain up to [186].
[186].
[186]. Its
96%Its Its application
application
application in
[186]. in
in shape memory
shape memory
shape polyurethanes
memory polyurethanes improves
polyurethanes improves shape
improves shape recovery
shape recovery
recovery at at >1000%
at >1000% strain
>1000% strain up
strain up to
up to 96%
to 96% [186].
96% [186].
[186].
O O O
O
O Cl O
SO Cl HO OH O
O O
HO
HO
N COOH Cl
Cl SS Cl
Cl OH N O
O
C
DMF pyridine OH
NN COOH 85°C, 5h
COOH inpyridine
toluene NN C
C
O
DMF
DMF pyridine Rosin-based
O 85°C, 5h
5h 110°C,
in 5h
toluene O O
Rosin-maleimido-85°C, in toluene O chain
Rosin-based
Rosin-based
O 110°C, 5h
110°C, 5h O
COOH O
dicarboxylic acid
Rosin-maleimido-
Rosin-maleimido- COOH O HO extender
chain
chain
COOH
COOH dicarboxylic acid
dicarboxylic acid COOH
COOH HO
HO extender
extender
Scheme 49. Synthesis of rosin-based chain extender for polyurethanes.
Scheme 49.
Scheme
49. Synthesis of
Synthesis of rosin-based chain
of rosin-based
rosin-based chain extender
chain extender for
extender for polyurethanes.
for polyurethanes.
polyurethanes.
Chiral thioureas and thiouronium salts containing dehydroabietyl groups are well characterized
Chiral
whiteChiral thioureas
or thioureas and
yellow solids thiouronium
and thiouronium
thiouronium
[222]. They salts containing
salts containing
can dehydroabietyl
dehydroabietyl
dehydroabietyl
be prepared groups
from groupschiralareare well characterized
well
amines characterized
(including
white
white or yellow
or
or solids
yellow
yellow [222].
solids
solids They
[222].can
[222]. be
They
Theyprepared
can
can from
be
be chiral
prepared
prepared amines
dehydroabietylamine), carbon disulfide and butyl halides according to Scheme 50 and using (including
from
from chiral
chiral dehydroabietylamine),
amines
amines (including
(including
such
carbon disulfide
dehydroabietylamine),
dehydroabietylamine), and butyl
carbon halides
carbon disulfide
separation methods as filtration, according
disulfide
washing,and and to
butyl Scheme
halides
butyldrying,
vacuum 50 and using
according
halidesevaporation
according to tosuch
andScheme
Schemeseparation
column 50 and methods
using
50chromatography
and using such as
such
filtration,
separation
separation
[222]. They washing,
can bevacuum
methods
methods as
useful drying,
as filtration,
filtration,
for the evaporation
washing,
washing,
physical vacuum
vacuum anddrying,
separationcolumn
drying, chromatography
evaporation
evaporation
of racemic and
mixtures [222].
[222]. They
and column
column can be useful
chromatography
chromatography
Moreover, rosin-
for the
[222]. physical
derived thioureas can be used as enantioselective catalysts for many reactions [12]. In recent rosin-
[222]. They
They can
can separation
be
be useful
useful of
for
forracemic
the
the mixtures
physical
physical [222].
separation
separation Moreover,
of
of racemic
racemicrosin-derived
mixtures
mixtures thioureas
[222].
[222]. can
Moreover,
Moreover, be used as
rosin-
years
derived
derived
these were: thioureas
enantioselective
thioureas
Michaelcan
catalystsbe
canadditionused
for many
be used as as enantioselective
reactions [12].
enantioselective
[223,224], In catalysts
recent
tandem catalysts years for many
these reactions
were:
for many reactions
Michael/cyclization Michael
sequence[12].[12]. In
addition
[225], recent
In recent years
[223,224],
years
asymmetric
these were:
tandem
these were: Michael addition
Michael/cyclization
Michael
Michael/hemiketalization addition
[226], [223,224],
sequence [225],
[223,224],
asymmetric tandem
asymmetric
tandem Michael/cyclization
Michael/cyclization
aza-Henry reaction sequence [225],
Michael/hemiketalization
sequence
[227], asymmetric [225],
[226],
tandem asymmetric
asymmetric
reaction
aza-Henry reaction
[228], Mannich reaction [226], asymmetric
[227], asymmetric
[226],
[229,230], asymmetric aza-Henry
tandem aza-Henry
reaction
Friedel–Crafts reaction
[228], Mannich
reaction
alkylation [227],
[227],
[231], asymmetric
reaction
enantio- [229,230],
asymmetric tandem reaction
Friedel–Crafts
tandem
and diastereoselective reaction
[228], Mannich
[228], Mannich
alkylation
asymmetric [231], reaction
enantio-
reaction
addition [229,230],
[229,230],
[232], Friedel–Crafts
andasdiastereoselective
wellFriedel–Crafts alkylation
as synthesisasymmetric
alkylation
of [231], enantio-
addition
[231],
chiral amines enantio-
[232],
[233] and
as
or and welldiastereoselective
as synthesis
diastereoselective
N-protected β-amino of
asymmetric
chiral amines
asymmetric addition
[233]
additionor [232],
N-protected
[232], as
as well as
β-amino
well as synthesis
malonates
synthesis of
of chiral
[234].
chiral Inamines
recent
amines [233]
studies
[233]
malonates [234]. In recent studies rosin-derived thioureas are dominant majority of all investigated or
or N-protected
rosin-derived
N-protected β-amino
thioureas
β-amino
malonates
are dominant
malonates
rosin-derived [234].
[234]. In recent
In recent
majority
catalysts. ofTheystudies
all
studies rosin-derived
investigated
are rosin-derived
not explored thioureas
rosin-derived
thioureas
further in are
are dominant
catalysts.
thedominant
current majority
Theyarticle
are not
majority of all
all they
explored
of
because investigated
further
investigated in
are the
rosin-derived
the current
rosin-derived
subject catalysts.
article because
catalysts.
of a comprehensive They
They they are
are
review not
arenot explored
theexplored
subject [12].
publication further
offurther in the
the
a comprehensive
in
For now, current
reports review
current article because
publication
article
on another because
rosin-based theycatalysts
[12].
they arenow,
For
are the
the
subject
reports
subject of
on
of aa comprehensive
another rosin-based
comprehensive
are rare [235–237]. review
review publication
catalysts are
publication rare[12]. For
[235–237].
[12]. For now,
now, reports
reports on
on another
another rosin-based
rosin-based catalysts
catalysts
are rare
are rare [235–237].
[235–237].
R' CS2 R' R" NH2 S C4H9 X X = Cl or Br or I
C4H9
R'
R' CS22
CS
DCC R'
R' R" NH
R" NH22 R' SS R"CC44HH99 XX S X = Cl
X Cl or
or Br
Br or I
NH2 N C S in CH2Cl2 N N in C2H5OH CC44HH99 R'=and/or R" = or I
2H5)2O
in (CDCC <20°C, 12h R' H
R' R" 65-90°C, 24 h
H R" SS
NH22
NH DCC inCH
CH22Cl
Cl R' R" X
<20°C, NN CC SS in 22 NN NN inCC22HH55OH
in OH R' and/or R" =
R'
or and/or R" =
in
in (C HH )12h
(C ) OO
22 55 22 <20°C,12h
12h Chiral
HH HH
N N
<20°C, 65-90°C,24
65-90°C, 24hh R' H
R' H R" R" XX
<20°C,12h
<20°C, 12h NN NN or
or
thiourea
Chiral
Chiral HH HH
Chiral thiouronium salt
yield: 76-91%
thiourea
thiourea
yield:
Chiral
Chiral 83-99.5% salt
thiouronium
thiouronium salt
yield: 76-91%
yield: 76-91%
yield: 83-99.5%
yield: 83-99.5%
Synthesis of
of chiral
chiral thioureas
thioureas and their thiouronium salts.
Scheme 50.
Synthesis of
of chiral
chiral thioureas
thioureas and
and their
their thiouronium
thiouronium salts.
salts.
Optically pure rosin-based chiral alcohols and their phosphorus derivatizing agents are white
Optically
Optically
solids. They canpure
pure rosin-based chiral
rosin-based
be synthesized chiralmaleopimaric
from alcohols and
alcohols and their
theirin
acid phosphorus
phosphorus derivatizing
derivatizing
two main ways agents
agents
according are white
are white
to Scheme 51
solids.
solids.
and They
They
using canseparation
can
such be synthesized
be synthesized from
from
methods maleopimaric
asmaleopimaric acid in
acid
washing, filtration, in two main
two main
drying, ways according
ways according
evaporation, to Scheme
to Scheme 5151
and using
and using such
such separation
separation methods
methods as
as washing,
washing, filtration,
filtration, drying,
drying, evaporation,
evaporation, and
recrystallization
Molecules 2019, 24, 1651 24 of 52
Optically pure rosin-based chiral alcohols and their phosphorus derivatizing agents are white
MoleculesThey
solids. 2019, 24,
canx be
FOR PEER REVIEW
synthesized from maleopimaric acid in two main ways according to Scheme 24
51 of
and51
using such separation methods as washing, filtration, drying, evaporation, and recrystallization [113].
[113]. They can be 31 used in 31P-NMR-based determination of enantiomeric excess in solutions
They
[113]. can
Theybe can
usedbe in used
P-NMR-based
in 31amines determination
P-NMR-based of enantiomeric excess in solutions containing
containing chiral alcohols and [113]. determination of enantiomeric excess in solutions
chiral alcohols and amines [113].
containing chiral alcohols and amines [113].
O 1. PCl3 1. PCl3
O O
O 1. CH3OH
2. PCl O 2. PCl
1. CDCl3 3 / pyridine O
O O 3. LiAlH 3. CDCl
Chiral3 diol or acid
2. CH3OH 4 O 2. / pyridine O
4. LiAlH
3. PhCH(OCH
4 3)2 O 4. Chiral
3. S8 diol or acid O
4. PhCH(OCH3)2 O 4. S8 O
S
SP Y
CH2OH Y
COOH Y = O or N CH2O P Y
CH2OH chiral alcohols
Rosin-based Y = O or N CH2O
COOH Y
Rosin-based chiral phosphorus
Rosin-based
yield: chiral
53-65% alcohols Rosin-based chiral agens
phosphorus
yield: 53-65% derivatizing
Maleopimaric 1. PCl3
derivatizing agens
Maleopimaric
acid 1. SOCl2 / DMF OH
2. PCl
CDCl O
2. SOCl
Piperidine OH 1. 3 3 / pyridine
acid 1. 2 / DMF
LiAlH4 / THF
3. Piperidine OH 3. CDCl
2. Chiral3 single alcohol
/ pyridine O P Y
2. or monoamine O P
OH 3. Chiral single alcohol Y
3. LiAlH4 / THF 4. or
S8monoamine O R
4. S8 R
CH2
CH2 N CH2
N CH2 N
N
Scheme 51. Synthetic routes of rosin-based chiral alcohols and phosphorus derivatizing agents.
Scheme
Scheme 51.
51. Synthetic
Synthetic routes
routes of
of rosin-based
rosin-based chiral
chiral alcohols
alcohols and
and phosphorus derivatizing agents.
Rosin-based molecular glass photoresists can be prepared from maleopimaric acid,
Rosin-based molecular
molecular glass photoresists
glass can be prepared
photoresists be from
canchloride maleopimaric
prepared acid, hydroxylamine,
from maleopimaric acid,
hydroxylamine, 2-diazo-1-naphthoquinone-4-sulfonyl and unsaturated compounds: vinyl
2-diazo-1-naphthoquinone-4-sulfonyl
hydroxylamine, chloride and unsaturated
2-diazo-1-naphthoquinone-4-sulfonyl chloride compounds:
and unsaturated vinyl ethyl ether, or
compounds:
ethyl ether, or dihydropyran, or cyclohexyl vinyl ether, according to Scheme 52 and using vinyl
such
dihydropyran,
ethyl or cyclohexyl vinyl ether, according toether,
Scheme 52 and using such separation methods as
separation methods as filtration, washing and vacuum drying [114]. These materials canusing
ether, or dihydropyran, or cyclohexyl vinyl according to Scheme 52 and such
be applied
filtration,
separation washing and
methods as vacuum drying [114]. These materials can be applied in photolithography
filtration, washing and vacuum drying [114]. These materials can be applied [114].
in photolithography [114].
in photolithography [114].
O O N2 O N2
Maleopimaric O O N2
R=
N2
or: O
Maleopimaric
acid R=
O or: O
acid O
O
or: O
O
SO2 or:
O
O O SO SO2
N O 2 O O SO
O N2 2
COOH O O N O
N2 N O O
COOH O O N
in ethyl acetate O SO2Cl Unsaturated O O
HO NH2
25-45°C,3h
in ethyl acetate O SO2Cl compound
Unsaturated
HO NH2
25-45°C,3hO compound
in ethyl acetate
O in50-60°C, 3-4h
ethyl acetate
N OH (C2H5)3N COOH 50-60°C, 3-4h
COOR
N OH (C2acetone
in H5)3N COOH
COOR
O in25°C, 4h
acetone
O 25°C, 4h NHMPI 2-diazo-
COOH
NHMPI 2-diazo- Rosin-based molecular
N-hydroxymaleopimarimide
COOH 1-naphthoquinone- Rosin-based molecular
glass compound
N-hydroxymaleopimarimide 1-naphthoquinone-
4-sulfonate yield: 94% glass compound
(NHMPI) yield: 70% 4-sulfonate yield: 94% yield: 90%
(NHMPI) yield: 70% yield: 90%
Scheme 52.
Synthesis of
of rosin-based molecular glass
rosin-based molecular glass compound.
compound.
Scheme 52. Synthesis of rosin-based molecular glass compound.
3.3. Macromolecular Compounds
3.3. Macromolecular Compounds
This section
section describes
describesrosin-derived
rosin-derivedmacromolecular
macromolecularcompounds
compoundswith repeated
with repeated units typical
units of
typical
of This section describes
macromolecules.
macromolecules. It contains rosin-derived
It contains polymers,
polymers, macromolecular
oligomers, compounds with
oligomers,macroinitiators
macroinitiators and repeated
and polymer units
polymer typical of
functionalized
functionalized
macromolecules. It contains
materials. Additionally,
Additionally, some polymers,
small/medium oligomers,
molecule
molecule macroinitiators
compounds,
compounds, which and polymer
which functionalized
are not presented in the
materials.
previous Additionally,
previous section,
section,but some
butnecessary
necessary small/medium
to obtain
to obtain molecule
appropriate
appropriate compounds,
macromolecules,
macromolecules, which are not presented
are described
are described here. inNon-
the
here. Non-toxicity,
previous
natural section,
toxicity,origin,
naturallow but
origin,necessary
price, low to
rigidprice, obtain appropriate
rigidhydrophobicity,
structure, macromolecules,
structure, hydrophobicity, are
excellent
excellent thermal described
thermal
properties, here. Non-
properties,
anticorrosive
toxicity, natural
performance, origin,
anticorrosive performance, low
mild biocidalmild price, rigid
biocidaland
properties structure,
properties hydrophobicity,
andare
stickiness stickiness
the most excellent
areattractive thermal
the mostreasons
attractive properties,
to reasons to
use rosin
anticorrosive
derivatives inperformance,
use rosin derivatives in themild
the preparation biocidalof
preparation
of polymer properties
polymerA
materials. and stickiness
materials. are the most
A disadvantage
disadvantage of these attractive
of these
processes reasons to
in processes
comparison in
use rosin derivatives in the preparation of polymer materials. A disadvantage
comparison with petrochemical counterparts is the relatively lower reactivity of rosin derivatives of these processes in
comparison
resulting from with
thepetrochemical
steric hinderance counterparts is the relatively
of the diterpene skeleton andlower
thereactivity of rosin
usually lower purityderivatives
of rosin-
resulting from the steric hinderance of the diterpene skeleton and the usually
based intermediates, as discussed in subsection 3.2.1. As a result, rosin-based polymer materials lower purity of rosin-
are
based intermediates, as discussed in subsection 3.2.1. As a result, rosin-based
usually characterized by distinct polydispersity and molecular weights rather far from their polymer materials are
usually characterized by distinct polydispersity and molecular weights rather far from their
Molecules 2019, 24, 1651 25 of 52

with petrochemical counterparts is the relatively lower reactivity of rosin derivatives resulting from the
theoretical
steric hinderance values. Therefore,
of the diterpene their TRL and
skeleton is lower than for
the usually small/medium
lower molecule intermediates,
purity of rosin-based compounds of
rosin. It is noteworthy, that compared to non-renewable counterparts, the
as discussed in Section 3.2.1. As a result, rosin-based polymer materials are usually characterized use of rosin significantly
increases
by distinct
Molecules
the sustainability
2019,polydispersity
of preparation processes according to Green Chemistry
and molecular weights rather far from their theoretical values. Therefore,
24, x FOR PEER REVIEW
rules, so25there
of 51
is
stillTRL
their highisdemand
lower than forfor
basic and appliedmolecule
small/medium researchcompounds
in this field.of rosin. It is noteworthy, that compared
theoretical
to non-renewablevalues.counterparts,
Therefore, their TRL
the use of is lower
rosin than for increases
significantly small/medium molecule compounds
the sustainability of preparation of
3.3.1.ItPolymers
rosin.
processes is according for Biomedical
noteworthy, to that
Green Applications
compared
Chemistry to non-renewable
rules, so there is counterparts, the usefor
still high demand of rosin
basic significantly
and applied
increases
research the
in sustainability
this
Poly(ethylene field.glycol) of preparation
rosin esters areprocesses
oligomers,according
which cantobe Green Chemistry
prepared rules,polyethylene
from rosin, so there is
still highand
glycol demand
maleicfor basic and according
anhydride, applied research in this
to Scheme 53 field.
prior to drying at 40–70 °C [81,238]. Proposed
3.3.1. Polymers for Biomedical Applications
applications include shells for controlled drug delivery [238,239] and dental films for periodontitis
3.3.1. Polymers
treatment [240].
Poly(ethylene forMoreover,
Biomedical
glycol) rosin Applications
maleopimaric acid PEG which
esters are oligomers, esters can
can show carbon from
be prepared steel rosin,
corrosion protection
polyethylene
properties
glycol [241].
and maleic anhydride, according ◦
Poly(ethylene glycol) rosin esters aretooligomers,
Scheme 53which
priorcan
to drying at 40–70
be prepared fromCrosin,
[81,238]. Proposed
polyethylene
glycol Block
applications copolymer
and maleicinclude of dehydroabietyl
shells
anhydride, foraccording
controlled toethyl
drug
Schememethacrylate
delivery toand
[238,239]
53 prior ethylene glycol
andatdental
drying 40–70 °Cwith
films fordisulfide group
periodontitis
[81,238]. Proposed
can be
treatment prepared
[240]. via
Moreover, ATRP according
maleopimaric to
acid Scheme
PEG 54,
esters prior
can show to neutralization,
carbon steel
applications include shells for controlled drug delivery [238,239] and dental films for periodontitis evaporation
corrosion protection and
precipitation
properties
treatment [241].[168].
[240]. Potential
Moreover, applications
maleopimaric acidinclude drug-delivery
PEG esters nanocarriers
can show carbon for cancer
steel corrosion therapy
protection
[168].
properties [241].
O O O
Block copolymer of dehydroabietyl
O ethyl methacrylate and ethylene glycol with disulfide group
O
can be prepared via ATRP according O to Scheme 54, prior to neutralization, evaporation and
O O
precipitation [168]. Potential applications include drug-delivery nanocarriers for cancer therapy
[168]. 160°C, 2h
O
O O O
O COO [ (CH2)2O]9 H
O O[(CH2)2O]nH O COO[(CH2)2O]9 H
O Levopimaric Maleopimaric acid
O
O[(CH2)2O]nH O
COOH acid PEG 400 ester PEG 400 ester
O
Maleopimaric acid 2+ 160°C, 2h
HO(CH2CH2)9H Zn O
yield: 42% (PEG 400) 220°C, 5h
CH3O[CH2CH2O]nH O COO [ (CH2)2O]9 H
O O[(CH2)2O]nH 750)
COO[(CH2)2O]9 H
(PEG
pTSA Levopimaric
O
Maleopimaric acid
O[(CH2)2O]nH
200°C, ?h COOH acid
O PEG 400 ester CH3O[CH2CH2O]nH PEG 400 ester
O 180-220°C
Maleopimaric acid 4h 2+
(PEG 750)
HO(CH2CH2)9H Zn
COO [ (CH2)2O]n+1H yield: 42% (PEG 400) 220°C, 5h pTSA
CH3O[CH2CH2O]nH O COO [ (CH2)2O]n+1H
200°C, ?h
Maleopimaric
(PEG 750)acid
O COOH Levopimaric acid
PEG 750 ester pTSA Levopimaric acid PEG 750 ester
200°C, ?h O 3 2 2 n CH O[CH CH O] H
180-220°C
(PEG 750)
Scheme53.
Scheme 53.Synthesis
Synthesis
4h ofofpoly(ethylene
poly(ethyleneglycol)
glycol) rosinesters.
rosin esters.
COO [ (CH2)2O]n+1H pTSA
COO [ (CH2)2O]n+1H
200°C, ?h
Maleopimaric acid of dehydroabietyl ethyl methacrylate
Block copolymer COOH Levopimaric
and ethylene glycol acid
with disulfide
PEG
group can750
be ester
prepared via ATRP according toLevopimaric
Scheme acid
54, prior to neutralization, PEG 750 esterand
evaporation O
Poly(ethylene glycol) with O
(bromoisobutyryl)ethyl
precipitation disulfide
[168]. Potential
Scheme group include
applications
53. Synthesis drug-delivery nanocarriers for cancer therapy [168].
Oof poly(ethylene glycol) rosin esters. O
O O O S Br O
( O )113 S O O
O
O
O CuBr/PMDETA in anisole; 47°C, <2h
OO
Poly(ethylene glycol) with O
O
S O
(bromoisobutyryl)ethyl disulfide group O( )113 O O S (O )n Br
O O
O O O S Br O O
( O )113 Poly(dehydroabietic
S O ethyl methacrylate-b-ethylene
O
O
glycol) with disulfide group
O
O (PEG113-ss-PMrosin
CuBr/PMDETA 27) <2h
in anisole; 47°C,
O
O
O S O
O( )113 ethyl
Scheme 54. Preparation of block copolymer of dehydroabietyl O methacrylate
O ( glycol
S and ethylene )n Br
with disulfide group. O
Poly(dehydroabietic ethyl methacrylate-b-ethylene glycol) with disulfide group
(PEG113-ss-PMrosin27)methacrylate) can be prepared
The rosin derivative quaternized poly-(N,N-dimethylaminoethyl
via Scheme
“living” reversibleof
Preparation
54. Preparation
54. ofaddition-fragmentation
block copolymer
block copolymer of chain-transfer
of dehydroabietyl
dehydroabietyl polymerization
ethyl methacrylate
ethyl methacrylate (RAFT)
and ethylene
and ethylene glycol from
glycol
dehydroabietic acid, 3-chloropropanol, N,N-dimethylaminoethyl methacrylate and cumyl
with disulfide group.
dithiobenzoate as a RAFT transfer agent, according to Scheme 55, and using gel chromatography,
precipitation and vacuum
The rosin derivative drying as
quaternized separation techniques [242]. methacrylate)
poly-(N,N-dimethylaminoethyl It can be usedcan asbe
amphipathic
prepared
antibacterial
via “living” agent in a wide
reversible variety of biomedical and
addition-fragmentation general use polymerization
chain-transfer applications [242].(RAFT) from
dehydroabietic acid, 3-chloropropanol, N,N-dimethylaminoethyl methacrylate and cumyl
dithiobenzoate as a RAFT transfer agent, according to Scheme 55, and using gel chromatography,
precipitation and vacuum drying as separation techniques [242]. It can be used as amphipathic
Molecules 2019, 24, 1651 26 of 52
The rosin derivative quaternized poly-(N,N-dimethylaminoethyl methacrylate) can be prepared via

“living” reversible addition-fragmentation chain-transfer polymerization (RAFT) from dehydroabietic
acid, 3-chloropropanol, N,N-dimethylaminoethyl methacrylate and cumyl dithiobenzoate as a RAFT
transfer agent, according to Scheme 55, and using gel chromatography, precipitation and vacuum
drying as separation techniques [242]. It can be used as amphipathic antibacterial agent in a wide
variety of biomedical and general use applications [242].
Cl OH S SS
Cl OH (( ))m (( )n-m
) S n-m
m
oxalylchloride
oxalyl chloride O O
triethylamine O O
triethylamine O O
COOH in THF; 0°C, 15h COO Cl O O
COOH in THF; 0°C, 15h COO Cl Cl
Cl
Dehydroabieticacid
Dehydroabietic acid 3-chloropropyl
3-chloropropyl N
N
N
N
dehydroabietate yield: 65%
dehydroabietate yield: 65% in
in
acetonitrile
acetonitrile
80°C, 72h
S 80°C, 72h COO
S COO
S
O S ( )n SS S Rosin derivative
O ( )n S Rosin derivative
N quaternized
N O O quaternized
O O
O poly-DMAEMA
AIBN O poly-DMAEMA
N,N-dimethylaminoethyl AIBN 5h Mn=8300, 14400, 17600,
N,N-dimethylaminoethyl 60°C, Mn=8300, 14400, 17600,
methacrylate (DMAEMA) 60°C, 5h Poly-DMAEMA
N 19300, 19600, 59800
methacrylate (DMAEMA) Poly-DMAEMA
N 19300, 19600, 59800
Mn=5490, 7500, 1400 or 41000
Mn=5490, 7500, 1400 or 41000
Scheme 55. Preparation of the rosin derivative quaternized poly(dimethylaminoethyl methacrylate).
Scheme 55. Preparation of the rosin derivative quaternized
quaternized poly(dimethylaminoethyl
poly(dimethylaminoethyl methacrylate).
methacrylate).
3.3.2. Elastomers
3.3.2.
3.3.2. Elastomers
Elastomers
Poly(dehydroabietic ethyl
Poly(dehydroabietic methacrylate-β-n-butyl acrylate-β-dehydroabietic ethyl meth-
Poly(dehydroabieticethyl methacrylate-β-n-butyl
ethyl methacrylate-β-n-butyl acrylate-β-dehydroabietic ethyl meth-acrylate)
acrylate-β-dehydroabietic ethyl meth-
acrylate)
triblock triblock
copolymer copolymer can
can be prepared be prepared
in prepared in ATRP
ATRP polymerization polymerization from
from butyl acrylate, butyl acrylate,
dehydroabietic
acrylate) triblock
dehydroabietic
copolymer
hydroxyethyl
can be
acrylate and diethyl
in ATRP polymerization
meso-2,5-dibromoadipate
from
according
butyl
to
acrylate,
Scheme 56,
hydroxyethyl
dehydroabietic acrylate and diethyl
hydroxyethyl meso-2,5-dibromoadipate
acrylate and diethyl according to Scheme
meso-2,5-dibromoadipate 56, prior
according to to diluting,
Scheme 56,
prior to diluting,
neutralization, neutralization,
evaporation, evaporation,
precipitation and precipitation
vacuum and vacuum
drying [146]. drying
Its [146]. Its
application is application
sustainable
prior to diluting,
is sustainable neutralization,
thermoplastic evaporation,
elastomers [146]. precipitation and vacuum drying [146]. Its application
thermoplastic elastomers
is sustainable thermoplastic [146].
elastomers [146].
C4H9 O Br C4H9 Poly(dehydroabietic
C4H9 OO Br O Poly(dehydroabietic
O C4O
H9 O ethyl methacrylate-b-
O Br OO ethyl methacrylate-b-
O O O O O O -n-butyl acrylate-b-
NiBrBr2(PPh3)2O -n-butyl acrylate-b-
O O O Br O -dehydroabietic ethyl
NiBr2(PPh
85°C, 3)2
P, 17h Br (
)n ( )nBr
O
O C4H9 -dehydroabietic
methacrylate) yield: ethyl
36%
Butyl 85°C, P, 17h Br (
)n O
( )n O O CO methacrylate) yield: 36%
O 4H9 O
Butyl Poly(n-butyl acrylate)
acrylate O O O O O O O O
Poly(n-butyl acrylate)
macroinitiatior O O
acrylate O CO
4H9 O Cl
macroinitiatior
yield: 58% O
Cl (
O
)m( )n ( )n ( )m Cl
yield: 58% C4H9
Cl ( )m( )n O ( )nO ( )m
O
O O O O O O
O O9
C4H O
O C4H9O
O O
O O O
OO O
Mn=76kg/mol
O
CuCl/PMDETA
O in DMF; 90°C, 8h Mn=76kg/mol
CuCl/PMDETA in DMF; 90°C, 8h
Scheme 56. Synthesis of rosin-based triblock copolymer.
Scheme 56. Synthesis of rosin-based triblock copolymer.
copolymer.
Cellulose/rosin ATRP macroinitiators can be prepared from dehydroabietic acid, cellulose and
Cellulose/rosin
2-bromoisobutyryl ATRP
ATRP macroinitiators
Cellulose/rosin bromide, can
can be
according to Scheme
macroinitiators be prepared from
57, prior to
prepared dehydroabietic
drying
from acid,
at 40 °C [142].
dehydroabietic It iscellulose
acid, used for and
cellulose the
and
2-bromoisobutyryl bromide, according to Scheme 57, prior to drying at 40 ◦ C [142]. It is used for the
preparation of graftbromide,
2-bromoisobutyryl copolymers [142]. to Scheme 57, prior to drying at 40 °C [142]. It is used for the
according
preparation of
of graft
graft copolymers
Rosin-acid-modified
preparation ethyl [142].
copolymers cellulose/butyl
[142]. acrylate graft copolymer can be prepared in ATRP
reaction from dehydroabietic
Rosin-acid-modified acid, cellulose,acrylate
ethyl cellulose/butyl 2-bromoisobutyryl bromide
graft copolymer can beand butyl in
prepared acrylate
ATRP
accordingfrom
reaction to Scheme 57, prior to
dehydroabietic sorption
acid, of CuBr
cellulose, x and precipitationbromide
2-bromoisobutyryl in methanol.
and [142].
butylPotential
acrylate
applications
according include thermoplastic
to Scheme elastomers
57, prior to sorption and coatings
of CuBr with UV absorption
x and precipitation property
in methanol. [142].
[142]. Potential
applications include thermoplastic elastomers and coatings with UV absorption property [142].
Molecules 2019, 24, 1651 27 of 52
O
OR Mn=7750-17100 g/mol
RO R = H or Et
Bu C O
HO RO
O OR
Molecules 2019, 24, x FOR PEER REVIEW O RO O
27 of 51
O OH O
O O
O
Br O C
Br OR OR
OR Mn=7750-17100 g/mol RO O
2-bromoisobutyryl and Ethyl RO O OR
RO R = H or Et CuBr/PMDETA O
bromide cellulose (EC) O in THF/DMF
O Bu C O
HO RO
DMAP inOTHF; 25°C, 24h 70°C, 6h O OR
( )n
RO O O Bu RO
OR O
O OH O O
O O O
O Br
Br Br C
Br
OR EC-g-(DA)-Br
OR EC-g-(DA)-g-poly(butyl
RO O acrylate)
O
2-bromoisobutyryl and Ethylchloride RO OR
Cl Dehydroabietyl ATRP macroinitiator
O CuBr/PMDETA Oyield 76%
bromide cellulose (EC) O in THF/DMF
O
DMAP in57.
Scheme THF; 70°C, 6h
25°C, 24hof graft copolymer of rosin-modified ethyl
Synthesis O butyl acrylate.
of graft copolymer of rosin-modified ethylcellulose and
( )n
Scheme 57. Synthesis RO O cellulose and butyl acrylate. Bu
OR
O
Cellulose grafted byethyl
copolymer ofBrrosin acid ethyl methacrylate and alkyl O
Rosin-acid-modified cellulose/butyl acrylate graft copolymer can(meth)acrylate
be preparedcan
Br in be
ATRP
prepared via ATRP, according to Scheme EC-g-(DA)-Br
58, prior to sorption andEC-g-(DA)-g-poly(butyl
precipitation in methanol acrylate)
[166].
reaction
Cl
fromO dehydroabietic acid, cellulose, 2-bromoisobutyryl bromide and butyl acrylate according
Dehydroabietyl ATRP
chloride“green” macroinitiator yield 76%hydrophobic,
Potential applications include thermoplastic elastomers having significant
to Scheme 57, prior to sorption of CuBrx and precipitation in methanol. [142]. Potential applications
thermal and mechanical
Scheme features
57. Synthesis [166].
of graft
include thermoplastic elastomers andcopolymer
coatingsofwithrosin-modified ethyl cellulose
UV absorption propertyand[142].
butyl acrylate.
Cellulose grafted by copolymer OR of rosin acid ethyl methacrylate and alkyl (meth)acrylate can
Cellulose grafted by copolymer of ROrosin OH
acid ethyl methacrylate and alkyl (meth)acrylate can be
)m
be prepared via ATRP, according to Scheme 58, prior to sorption and precipitation in methanol [166].
prepared via ATRP, according
O
to Scheme
O 58, prior to sorption andO precipitation in O
methanol [166].
Potential applications include “green” thermoplastic elastomersOhaving
Potential applications include “green” thermoplastic elastomers havingsignificant
significant hydrophobic,
hydrophobic,
)n(
RO OH O(CH2)2O
thermal and mechanical features [166].
thermal and mechanical features [166]. OR l
O Br
Cellulose O
(
R = H or
macroinitiator
OR O
RO
(Cell) and OH
)m
O
butyl acrylate (BA) O instead of BA O RO
O O OH
O lauryl methacrylate
C4H9 O O
O also works O
)n(
RO OH O(CH2)2O l
O OR C12Hl25
RO OH
O
O Br O
Cellulose O
(
CuBr/PMDETA R =inHtoluene;
or 80-90°C, 24h O
macroinitiator O
O(CH2)2O (Cell) and
O O
(
O O butyl acrylate (BA) instead of BA

Cell-g-P(BA-co-DAEMA) RO OH
Dehydroabietic O lauryl methacrylate O C4H9
yield: 80%O O
)m(
C4H9 O also works

ethyl methacrylate C12H25
l
O
Mn = 27000, 28000, 31700, 49300, 40700, 54800,
(DAEMA) O RO OH
O
83300, 101100, 129900, 142800, 200100, 242600
)n
O(CH2)2O
CuBr/PMDETA in toluene; 80-90°C, 24h O
O O
O(CH2)2O
O
(
O O Cell-g-P(BA-co-DAEMA)
Scheme 58. Synthesis of graft copolymer of cellulose, rosin acid and butyl acrylate (or lauryl
Dehydroabietic yield: 80% O C4H9
)m(
methacrylate).
ethyl methacrylate
Mn = 27000, 28000, 31700, 49300, 40700, 54800,
(DAEMA)
83300, solids,
101100, 129900,
which142800,
can be200100, 242600in several
)n
Rosin alcohols are colorless prepared O(CH

ways2)2O according to Scheme
59, and using such separation methods like evaporation, extraction, washing and O O drying [243,244]
[245].
Scheme They
58. can
Scheme 58.
be used in graft
Synthesis preparation
Synthesisofofgraft copolymer of ofcross-linked
copolymer of cellulose, structures
rosin
cellulose, rosin acidand
acid
with
and butyl
butyl
acrylamide
acrylate
acrylate
and
(or (or
N,N′-
lauryl
lauryl
methylenebisacrylamide
methacrylate).
methacrylate).
[243,244], as well as norbornene-based monomers [245].
Rosin-norbornene monomers, i.e. dehydroabietanyl norborn-5-ene-2-carboxylate and 4-
((norborn-5-ene-2-carbonyl)oxy)butyl
RosinRosin alcoholsare
alcohols are colorless
colorlesssolids, dehydroabietate,
solids,which can becan
which are
be viscous
prepared oily in
in several
prepared liquids
ways [245].ways
according
several They can
to Schemebe
according
synthesized
59, and using
to Scheme from
59, and dehydroabietic
suchusing
separation
such methods acid
separation derivatives
like methods and
evaporation, norbornenecarboxylic
likeextraction,
evaporation,washing acid according
and drying
extraction, toand
[243,244]
washing
Scheme
[245]. 59, prior
They can to
beevaporation,
usedcanin be washing, drying
preparation and column
of cross-linked chromatography
structures [245]. Its application
with acrylamide and N,N′-and
drying [243,244] [245]. They used in preparation of cross-linked structures with acrylamide
is polymerization, or block
methylenebisacrylamide
0 copolymerization
[243,244], as well as with norbornene, via
norbornene-based “living” [245].
monomers ring-opening metathesis
N,N -methylenebisacrylamide [243,244], as well as norbornene-based monomers [245].
polymerization (ROMP) process
Rosin-norbornene monomers, [245,246].
i.e. dehydroabietanyl norborn-5-ene-2-carboxylate and 4-
Rosin-norbornene monomers, i.e., dehydroabietanyl norborn-5-ene-2-carboxylate and
Homopolymers of rosin-modifieddehydroabietate,
((norborn-5-ene-2-carbonyl)oxy)butyl norbornene can be synthesized
are viscous oily vialiquids
ROMP[245].process according
They can be
4-((norborn-5-ene-2-carbonyl)oxy)butyl
to dehydroabietate, are viscous oily liquids [245]. canThey can
synthesized from dehydroabietic acid derivatives and norbornenecarboxylic acid according be
Scheme 59 [246]. Moreover, triblock and pentablock copolymers with norbornene segments to
be synthesized from dehydroabietic acid derivatives and norbornenecarboxylic acid according to
Scheme 59, prior to evaporation, washing, drying and column chromatography [245]. Its application
Scheme 59, prior to evaporation,
is polymerization, washing, drying
or block copolymerization withand column chromatography
norbornene, [245]. Its
via “living” ring-opening application
metathesis
polymerization (ROMP) process [245,246].
Homopolymers of rosin-modified norbornene can be synthesized via ROMP process according
to Scheme 59 [246]. Moreover, triblock and pentablock copolymers with norbornene segments can be
Molecules 2019, 24, 1651 28 of 52
is polymerization, or block copolymerization with norbornene, via “living” ring-opening metathesis

prepared [246]. They can be applied as bio-based thermoplastic elastomers showing well-designed
polymerization (ROMP) process
architecture and high elastic [245,246].
recovery [245,246].
Dehydroabietic acid
O
SOCl2 HO(CH2)4OH OH
prepared [246]. They can be applied as bio-based
O thermoplastic
OH elastomers
O showing well-designed
in DMF (C2H5)3N (CH2)4
architecture and
0°C, 3h high elastic
in CH2Cl2 recovery [245,246].
trimethylacetic (CH )
O anhydride
2 4
Grubbs' cat.
0-40°C, 18h O (CH2)4
OH DMAP O in CH2Cl2
Dehydroabietic acid O in THF 0.75h
O
O
60°C, 24h O
O
4'-hydroxybutyl
OH
O O
SOCl2 HO(CH2)4OH
dehydroabietate
O OH 4-((norborn-5-ene-2-
O
in DMF (C2H5)3N yield: 73% 2)4
(CH
LiAlH4 in THF
0°C, 3h in CH2Cl2 trimethylacetic -carbonyl)oxy)butyl
(CH2)4 n
0°C, 13h O anhydride dehydroabietate
Grubbs' cat.
0-40°C, 18h Polymer
O (CH22)4
OH DMAP (Monomer 2) yield: O 82% in CH2Cl2 O
O in THF 0.75h O
4'-hydroxybutyl
O 60°C, 24h O
O O
O OH dehydroabietate 4-((norborn-5-ene-2- m n
OH
trimethylacetic yield: 73% Grubbs' cat.
O
LiAlH4 in THF -carbonyl)oxy)butyl O
n
0°C, 13h anhydride in CH2Cl2 dehydroabietate O
DMAP 0.75h O Polymer 2
(Monomer 2) yield: 82%
Dehydroabietane- in THF O
-18-ol yield: 84% 60°C Dehydroabietanyl
O
24h norborn-5-ene- 1h
OH O OH -2-carboxylate
O n
m
Copolymer 1 n
trimethylacetic (Monomer 1) yield: Polymer 1
Grubbs'85%
cat. O
Mn=114-187 kg/mol
anhydride in CH2Cl2 O
DMAP 0.75h O
Dehydroabietane-
Scheme
Scheme
in THF
59.59. Synthesisofofrosin-norbornene
Synthesis
O
rosin-norbornene monomers
monomers and
and polymerization
polymerizationofofthem.
them.
-18-ol yield: 84% 60°C Dehydroabietanyl
24h norborn-5-ene- 1h
Rosin-based waterborne
Homopolymers polyurethanes
-2-carboxylate
of rosin-modified norbornenecan can
be prepared from maleopimaric
be synthesized acid, according
via ROMPCopolymer
process diethylene
1 to
n
glycol,59polyether
Scheme [246]. Moreover, (Monomer
glycol, toluene
triblock and1) pentablock
diisocyanate, Polymer
yield: 85%dimethylol
copolymers 1with norbornene
propionic acid andMtrimethylamine
segments
=114-187 can
kg/mol be
n
according
prepared to They
[246]. Scheme can60, and using
be applied such separation
as bio-based methods
thermoplastic as vacuum
elastomers dryingwell-designed
showing and rotary
evaporation [111].
Scheme Such
59. polymers
Synthesis of can be also
rosin-norbornene
architecture and high elastic recovery [245,246]. synthesized
monomers using
and fumaropimaric
polymerization of rosin
them. instead of
maleopimaric acid [109]. These materials exhibit excellent mechanical properties,
Rosin-based waterborne polyurethanes can be prepared from maleopimaric acid, diethylene thermal stability,
waterRosin-based
resistance, antimicrobial properties against
waterborne polyurethanes Gram-negative
can be prepared from Escherichia coli andacid,
maleopimaric Gram-positive
diethylene
glycol, polyether glycol, toluene diisocyanate, dimethylol propionic acid and trimethylamine according
Staphylococcus
glycol, aureus
polyether [109,111]
glycol, and an
toluene affinity for cellulose
diisocyanate, dimethylolnanocrystals
propionic[112],
acidwhich allows to apply
and trimethylamine
to Scheme 60, and using such separation methods as vacuum drying and rotary evaporation [111].
them in various
according biomass-based
to Scheme 60, and polymer
using suchand composite
separationmaterials.
methods as vacuum drying and rotary
Such polymers can be also synthesized using fumaropimaric rosin instead of maleopimaric acid [109].
evaporation [111]. Such polymers can be also synthesized using fumaropimaric rosin instead of
These materials
O exhibit excellent mechanical OHproperties,
HO DEGthermal stability,
TDI PEG TDI water
DEG MPAresistance,
DEG TDI antimicrobial
maleopimaric O acidHO [109]. These OH materials exhibit excellent mechanical properties, thermal TEA stability,
H
properties against Gram-negativeO Escherichia
DEG coli and Gram-positive Staphylococcus aureus [109,111]
water resistance, antimicrobial properties against Gram-negative Escherichia coli and Gram-positive
DMPA
andStaphylococcus
an affinity for O (DEG) nanocrystals [112], which allows to apply them in various biomass-based
cellulose COO
aureus HO and
[109,111] DEG anMPAaffinity forHO
cellulose nanocrystals [112],MPA
which
120-240°C DEG TDI PEG TDI DEG DEGallows
TDI to apply
polymer
them inand composite
various 8hmaterials.
biomass-based HO polymer
OH Rosin-based waterborne polyurethane
and composite materials.
(PEG) 110-80°C
O 3hOH HO DEG TDI PEG TDI DEG MPA DEG
30°C TDI
O HO OH TEA H
COOH OCN
O NCO DEG N (TEA) 0.5h
DMPA
O (DEG) TDI DEG HO
COO
HO DEG MPA PEG
Maleopimaric acid120-240°C HO DEG TDI PEG TDI DEG MPA DEG TDI
HO OH
(MPA) 8h (TDI)
HO OH Rosin-based
TDI waterborne polyurethane
DEG MPA DEG TDI
COOH
TDI PEG TDI DEG
(PEG)
MPA DEG TDI 110-80°C(DMPA) DEG DMPA COOH
3h 60°C TDI DEG 30°CTDI
MPA DEG
OCN COOH OCN NCONCO 3h
N (TEA) 0.5h
PEG TDI DEG HO
PEG TDI DEG HO
Maleopimaric acid
(MPA) Scheme 60. Preparation ofHO
rosin-basedOHwaterborneTDI
polyurethane.
DEG MPA DEG TDI
(TDI) COOH
DMPA COOH
TDI PEG TDI DEG MPA DEG TDI (DMPA) DEG
3.3.3. Coatings and Adhesives
60°C TDI DEG MPA DEG TDI
OCN NCO
3h
PEG TDI DEG HO
Scheme60. Preparationof
ofrosin-based
rosin-based waterborne polyurethane.
waterborne polyurethane.
3.3.3. Coatings and Adhesives

Molecules 2019, 24, 1651 29 of 52
Rosin-modified poly(acrylic acid) is a solid. It can be prepared from poly(acrylic acid) and abietic
acid according to Scheme 61, prior to washing and vacuum drying [247]. It can be applied as an
3.3.3. Coatings
Molecules and
2019, 24,
24, Adhesives
excellent
Molecules binder
2019, xx FOR
FOR
for PEER REVIEW
REVIEW
silicon-graphite
PEER negative electrodes in lithium-ion batteries [247]. 29 of
29 of 51
51
Rosin-modified poly(acrylic acid) is a solid. It can be prepared from poly(acrylic acid) and abietic
Rosin-modified
Rosin-modified poly(acrylic acid)
acid) is
is aa solid.
solid. It
It can
can be
be prepared
prepared fromfrom poly(acrylic
poly(acrylic acid)
acid) and
and abietic
abietic
acid according to M n=? poly(acrylic
Scheme 61, prior to washing HO vacuum
and drying [247]. It
O can be applied as an
acid according
acid according
O OH to to Scheme
Scheme 61, 61, prior
prior toto washing
washing and vacuum
and vacuum drying
drying [247]. ItIt can
can bebe applied as an
in lithium-ion[247]. [247].applied as an
H
excellent binder for silicon-graphite
H 3O negative
O OH electrodes batteries
excellent binder for silicon-graphite negative electrodes
O in lithium-ion
excellent binder for silicon-graphite negative electrodes in lithium-ion batteries [247]. batteries
O [247].
( )n (acid-catalyzed
O
Poly(acrylic acid) Mn=?=? activation) ( )n (nucleophilic addition

M HO
(PAA)
O OH
n 25°C, 3h Activated PAA HO & elimination) ( )OnO PAA-Rosin
O OH H
H 100°C, 12h
H3OO O
O OH
OH O
H 3 O O
O
(( ))nn Scheme 61.
(acid-catalyzed
(acid-catalyzed Preparation of rosin-modified poly(acrylic O
acid).
O
Poly(acrylic acid)
Poly(acrylic acid) activation)
activation) (( ))nn (nucleophilic addition
(nucleophilic addition
(PAA)
N-dehydroabietic
(PAA)
25°C, 3h
25°C, 3h
acrylamide Activated
Activated
is a whitePAA
PAA & elimination)
&
solid. It can
elimination)
be 12h ((
synthesized from ))dehydroabietylamine
nn PAA-Rosin
PAA-Rosin
100°C,
100°C, 12h
and acryloyl chloride according to Scheme 62, prior to washing and vacuum distillation. It can be
Scheme61.
Scheme
61. Preparationof
Preparation of rosin-modified
of rosin-modified poly(acrylic
rosin-modified poly(acrylic
poly(acrylic acid).
acid). of rigid petroleum-
used as a bio-based acrylic monomer in compolymerization processes acid).
instead
based monomers [161].
N-dehydroabieticacrylamide
N-dehydroabietic
N-dehydroabietic acrylamideisis
acrylamide isaaawhite
whitesolid.
white solid. It
solid. It can
It can bebe synthesized
synthesizedfrom from dehydroabietylamine
fromdehydroabietylamine
dehydroabietylamine
Rosin and soybean oil-based acrylic copolymers cansynthesized
be prepared from N-dehydroabietic
and and acryloyl chloride according to Scheme 62, prior to washing and vacuum distillation. It can
can be
acrylamide and acrylated epoxidized soybean oil according to Scheme 62 [161].It They
andacryloyl
acryloylchloride
chloride according
according to Scheme
to Scheme 62, prior
62, priorto washing
to washing and vacuum
and vacuum distillation.
distillation. can
It beare
used
be
aused
used as aa bio-based
as characterized
bio-based
as bio-based
acrylic acrylic monomer
monomer
acrylic
by considerable
monomer in compolymerization
inhydrophobicity
in compolymerization
compolymerization and heat processesprocesses
instead
processes
resistivity
instead
ofalso
instead
and
of rigid
rigid
of rigid petroleum-
petroleum-based
other petroleum-
properties
based monomers
based monomers
monomers [161]. [161].
[161]. petroleum-based materials [161].
comparable with similar
Rosin and
Rosin and soybean
soybean oil-based
oil-based acrylicacrylic copolymers
copolymers can can be be prepared
prepared from from N-dehydroabietic
N-dehydroabietic
acrylamide
acrylamide and O and acrylated epoxidized
acrylated epoxidized O soybean oil
soybean oil according according to Scheme
to Scheme 62 [161].62 [161]. They
They areare
O
characterized
characterized by by considerable HN hydrophobicity and heat resistivity and also other properties
considerable hydrophobicity and heat resistivity and also other properties
Cl
comparable with with similar
similar petroleum-based
petroleum-based materials Triglyceride
materials [161]. O
comparable in CH2Cl2 [161]. 1-3
Acrylated epoxidized DHAAM
-5-23°C, 0.5h
O
O O
O
soybean oil (AESO)O
NH2 HN tert-butyl benzoilO peroxide ( AESO )m( DHAAM )n
HN
Cl Rosin and soybean oil-based
Cl N-dehydroabietic <170°C,
Triglyceride
Triglyceride O
O
9h
1-3
1-3
Dehydroabietylaminein CH
in CH2ClCl2 acrylamide (DHAAM) Acrylated epoxidized acrylic copolymer
2 2
-5-23°C, 0.5h
0.5h Acrylated epoxidized DHAAM
DHAAM
-5-23°C, soybean oil (AESO)
Scheme62. 62.Preparation
Preparationof of rosin andsoybean
rosin and oil (AESO)
plant oil-based acrylic
acryliccopolymers.
NH2 Scheme
NH 2
plant
tert-butyl
tert-butyl
oil-based
benzoil peroxide
benzoil peroxide (( AESO
AESO )m( DHAAM
copolymers. )m( DHAAM ))nn
N-dehydroabietic
N-dehydroabietic <170°C,
<170°C, 9h 9h Rosin and soybean
Rosin and soybean oil-basedoil-based
Rosin
Rosin and and
Dehydroabietylamine POSS-based
soybean oil-based non-isocyanate
acrylamide (DHAAM)
acrylic polyurethanes
copolymers can be can be prepared
prepared from from rosin-based
acrylic
N-dehydroabieticcopolymer cyclic
acrylamide
Dehydroabietylamine acrylamide (DHAAM) acrylic copolymer
carbonate, polyamine and cyclic carbonate-functionalized
and acrylated epoxidized soybean oil according to Scheme 62 [161]. They are characterized POSS according to Scheme 63 [200]. Theirby
Scheme 62.
Preparation of of rosin
rosin and
and plant
plant oil-based
oil-based acrylic
acrylic copolymers.
copolymers.
applications include coatings showing improved water tolerance,
considerable hydrophobicity and heat resistivity and also other properties comparable with similar hardness and thermal stability
[200].
petroleum-based
Rosin and
Rosin and materials
POSS-based
POSS-based
[161].
non-isocyanate polyurethanes
non-isocyanate polyurethanes can can bebe prepared
prepared from from rosin-based
rosin-based cyclic
cyclic
Rosin
carbonate, and POSS-based
polyamine
carbonate, polyamine and cyclic and non-isocyanate
cyclic polyurethanes
carbonate-functionalized
O carbonate-functionalized
can
POSS be prepared
according to from
Scheme rosin-based
63 [200]. cyclic
Their
1. H2N R' NH2 POSS according to (H) SchemeO63 [200]. Their
carbonate, polyamine
applications
Rosin-based
applications include and cyclic
coatings carbonate-functionalized
O
showing O improved
O water
O POSS
tolerance,
include coatings showing improved water tolerance, hardness and thermal stability according R
hardness to
N Scheme
R'
and NH 63
O
thermal [200]. Their
stability
O
cyclic
applications
[200].
[200]. carbonate
include coatings showing improved
O water tolerance, hardness
O and R N R'
thermal
(H)
NH O
stability [200].
O O O
O O O 2. O
O
O O
O O 1. H
1. H2N N R'
R' NH
NH2 O
(H)
(H) O
O O O in2 DMF 2
R N R' NH
N R' NH O
= cyclic carbonate
Rosin-based
Rosin-based C=O O O
O O
O O
O
100°C, 12h R O
functionalized POSS
O
cyclic carbonate
cyclic carbonate O O
O O
O
O R
R NN R' NH
(H) R' NH
O
O
O O O O (H)
O O O O O O O
O O O
OH O 2.
2. OO
OO
R= O or: O O OO R N R' NH O
O O
O O in DMF
in DMF COO (H)
OH
C=O
O O
100°C, 12h
12h == cyclic
cyclic carbonate
carbonate
C=O 100°C, functionalized POSS
functionalized POSS
OO O
O
R' = or: (CH2)2 or: or: ( N )2 Rosin & POSS-based
O OH H O
O
OO OH non-isocyanate polyurethane
O
R=
R= O or:
or: R N R'
R N R' NH
NH O
O
O COO (H)
OH O
O COO (H)
OH
Scheme 63. Preparation of rosin & POSS-based non-isocyanate polyurethane.
R' ==
R' or:
or:
(CH2))2 or:
(CH 2 2 or:
or: ((
or:
N ))2
N Rosin &
Rosin & POSS-based
POSS-based
H 2
H
Rosin can be introduced as a chain extender into polyurethanes non-isocyanate
non-isocyanate polyurethane
polyurethane
to obtain rosin-based urethane-
amide hard segments, according to Scheme 64 [248]. A potential application of the prepared materials
Scheme 63.
63. Preparation
Preparation of of rosin
rosin &
& POSS-based
POSS-based non-isocyanate
non-isocyanate polyurethane.
Scheme
is as sealants Scheme
for non-invasive disc regeneration
63. Preparation of rosin surgery [248].
& POSS-based Physicalpolyurethane.
non-isocyanate mixtures of rosin and 1,4-
polyurethane.
butanediol were also investigated for this use [249].
Rosincan
Rosin
Rosin canbe
can be introduced
be introduced
introducedas asas
aa chain
chain extender
extender
a chain into polyurethanes
into
extender polyurethanes to obtain
to obtain rosin-based
into polyurethanes rosin-based urethane-
urethane-
to obtain rosin-based
amide hard segments,
amide hard segments,
urethane-amide according
according
hard segments, to Scheme
to Scheme
according 64
to64 [248]. A potential
[248]. A64potential
Scheme application
[248]. Aapplication of the prepared
of the prepared
potential application materials
materials
of the prepared
is as
is as sealants
sealants for
for non-invasive
non-invasive disc disc regeneration
regeneration surgery
surgery [248].
[248]. Physical
Physical mixtures
mixtures of
of rosin
rosin and
and 1,4-
1,4-
butanediol were
butanediol were also
also investigated
investigated for for this
this use
use [249].
[249].
Molecules 2019, 24, 1651 30 of 52
materials is as sealants for non-invasive disc regeneration surgery [248]. Physical mixtures of rosin and
1,4-butanediol were also investigated for this use [249].
O
Molecules
OCN2019,Ur
24, xUrFORNCO
PEER REVIEW 30 of 51
O
OCN Ur Ur NCO
80°C,Ur0.1hUr NCO HN
OCN
80°C, 0.1h HN O
Ur OCN Ur Ur NCO
OCN Ur Ur NCO
Ur O
HN OCN Ur Ur NCO
80°C, 0.1h Ur O
Ur UrNCO
H
COOH HN N
Ur
NCO OCN Ur Ur N NO Ur Ur NCO
COOH OCN Ur Ur H O Ur Ur NCO
Rosin NCO N ON
Urethane-amide hard segment
Rosin COOH Ur Ur
Urethane-amide Ur Ur NCO
hard segment OCN
O
Rosin Scheme 64. Preparation Urethane-amide
segments.hard segment
Scheme 64. Preparation of
of rosin-modified urethane-amide
rosin-modified urethane-amide hard segments.
hard
Scheme 64. Preparation of rosin-modified urethane-amide hard segments.
Scheme 64. Preparation of rosin-modified urethane-amide hard segments.
Maleopimaric acid-modified polyester polyol aqueous dispersion can be prepared from
Maleopimaric acid-modified polyester polyol aqueous dispersion can be prepared from
maleopimaric acid, adipic
Maleopimaric acid, isophtalic
polyester acid, 5-sulfoisophtalic acid, neopentyl glycol and
maleopimaric acid, acid-modified
adipic acid, isophtalic polyol aqueous dispersion
acid, 5-sulfoisophtalic acid,canneopentyl
be prepared from
glycol and
trimethylolpropane,
maleopimaric acid,
trimethylolpropane,
according
according
totoScheme
adipic acid, 65,
isophtalic
Scheme
prior
acid,to
65, prior
dissolving/dispersing
to5-sulfoisophtalic
in water and
acid, neopentyl
dissolving/dispersing in water and
diethylene
glycol and
diethylene
glycol monoethyl ether
trimethylolpropane,
glycol monoethyl ether acetate
according as
acetate to a cosolvent
cosolvent
as Scheme [91].
[91].
65, prior
a cosolvent It
[91].to can be
be applied
applied in
in
It dissolving/dispersing two-component
two-component waterborne
waterborne
in water and diethylene
can be applied in two-component waterborne
polyurethane
polyurethane materials
materials
glycol monoethyl
polyurethane and
ether
materialsandcoatings
acetate
and as [110]
coatings showing
[110]
a cosolvent
coatings [110] improved
showing
[91].
showing be thermal
improved
It canimproved stability,
thermal
appliedthermal hardnesshardness
stability,
in two-component
stability, and resistances
hardness
waterborne and
and
to ethanol
resistances and
polyurethanewater
to to
resistances ethanol [91,110].
materials
and
ethanol and
andwater
watercoatings
[91,110].
[91,110].[110] showing improved thermal stability, hardness and
resistances to ethanol and water [91,110].
HOOC
HOOC COOH
COOH O
O O
O
HOHO OH
HO (( OO ))nn
HOOC COOH OH O O
HO OH HO O
O OH Hydrophilic
OH Hydrophilic polyester
polyester
( O )n OH Hydrophilic polyester
intermediate (HPI)
butyl
butyl stannoicacid
stannoic acid
HO O intermediate (HPI)
SOSO butyl stannoic acid
150-205°C intermediate (HPI)
3Na3Na 150-205°C
SO
SO33Na
SO3Na
5-sulfoisophtalic acid 150-205°C
5-sulfoisophtalic acid SO3Na
Na
5-sulfoisophtalic acid
OH O
O
OH O
OH
HO OH
HO OH butyl stannoic acid
OH HO OH butylstannoic
stannoic acid
HOHO OH Neopentyl O butyl acid
HO OHNeopentyl
Neopentyl OO in
in xylene
xylene Mn = 2422
HOOC COOH Trimethylol- glycol
glycol
in150-230°C,
xylene 3.5h Mn =M2422
n = 2422
HOOC COOH Trimethylol- glycol 150-230°C, 3.5h
HOOC COOH Trimethylol-
propane (TMP) (NPG) (NPG) O 150-230°C, 3.5h Maleopimaric
propane
propane (TMP)
(TMP) (NPG)
COOH OO Maleopimaric
Maleopimaric
HOOC COOH
COOH COOH acid-modified
Isophtalic acid HOOCHOOC Adipic acid COOH
COOH
Maleopimaric NPG MPA HPI IPA acid-modifiedacid-modified
Isophtalic
Isophtalic acidacid Adipic
Adipic acid
acid Maleopimaric
Maleopimaric NPG MPA
NPG polyester polyol
MPAHPIHPI IPAIPApolyester
(IPA) (AA) acid polyol
polyester polyol
(IPA)(IPA) (AA)(AA) acid
acid NPG ( IPA HPI MPA TMP AA HPI ) IPA NPG
(MPA) NPG( ( IPA
NPG HPI MPA
IPA HPI MPATMP AA AA )m m
HPI HPIIPA IPA
NPG NPG
(MPA)
(MPA) TMP )m
Scheme
Scheme 65.65.
Scheme Preparation
Preparation ofof hydrophilic
hydrophilic maleopimaricacid-modified
hydrophilic maleopimaric acid-modified
acid-modified poliester
poliesterpolyol.
polyol.
Scheme 65.65. Preparationof
Preparation ofhydrophilic maleopimaric
maleopimaric acid-modifiedpoliester polyol.
poliester polyol.
3.3.4. Surfactants
3.3.4.
3.3.4.Surfactants
Surfactants
3.3.4. Surfactants
Rosin-based
Rosin-based comb-like polymeric surfactants can bebe
prepared from rosin glycidyl methacrylate and
Rosin-basedcomb-like
comb-like polymeric surfactants
polymeric surfactants can
can prepared
be prepared from
from rosin
rosin glycidyl
glycidyl methacrylate
methacrylate
andRosin-based
methacrylate comb-like
polyethylene polymeric
glycol ester surfactants
according tocan be
Scheme prepared
66, priorfrom
to rosin
vacuum glycidyl
drying, methacrylate
precipitation,
and methacrylate
methacrylate polyethylene
polyethylene glycol ester according
glycol ester according toto Scheme
Scheme 66,
66,prior
priortotovacuum
vacuumdrying,
drying,
andprecipitation,
methacrylate
dialysis and freezingpolyethylene
[175].
dialysis and Their glycol
freezing
precipitation, dialysis and freezing [175].ester
application
Their according
include to Scheme
preparation
application include of 66, prior
pymetrozine
preparation of to vacuum
water drying,
suspension
pymetrozine
Their application include preparation of pymetrozine waterwater
precipitation,
concentrates
suspension dialysis
[175]. and
concentrates freezing
[175].
suspension concentrates [175]. [175]. Their application include preparation of pymetrozine water
suspension concentrates [175].
O
O O
(( )x)x( ( )y)y
O O O(CH CH22O)
O(CH22CH O)nnCH
CH33 OO
O
O Methacrylate polyethylene
Methacrylate polyethylene ( ) (
OO x
O)O
y
O(CH CH2O)nCH3 O
Rosinglycidyl
Rosin glycidyl O glycol ester 2(MAPEG)
(MAPEG) O
OHMethacrylate polyethylene
((
OH O HO
methacrylate
methacrylate AIBN (MAPEG) HO
Rosin glycidyl glycol ester
( ))n )n
(RGMA)
(RGMA) OH in ethanol
ethanol OO
HO
methacrylate AIBN 13h
<80°C, 13h
OO
n
OO
(RGMA) OO in ethanol O
O
<80°C, 13h MM
n==
6336, 7271,
6336, 7940,
7271, 7969
7940, 7969
O O n
Poly-(RGMA-co-MAPEG)
Mn = 6336, 7271, 7940, 7969
Poly-(RGMA-co-MAPEG)
Scheme66.
Scheme
66. Preparation
Preparation of
ofcomb-like
of surfactants. Poly-(RGMA-co-MAPEG)
comb-likesurfactants.
comb-like surfactants.
Polyesters ofacrylated
acrylatedScheme
rosin 66.
and Preparation
polyethyleneofglycols
comb-like besurfactants.
can be
Polyesters of acrylated
Polyesters of rosin andand
rosin polyethylene glycols
polyethylene glycolscancan beprepared
prepared
prepared according
according toto
according toScheme
Scheme 6767[125].
Scheme 67
[125].
They They
canThey
[125]. can
be used
can asbe used as surfactants
be surfactants in preparation
in preparation
used as surfactants of
of stable
in preparation stable emulsions
of emulsions [125].
[125]. [125].
stable emulsions
Polyesters of acrylated rosin and polyethylene glycols can be prepared according to Scheme 67
[125]. They can be used as surfactants in preparation of stable emulsions [125].
Molecules 2019, 24, 1651 31 of 52
O
COOH
O ( O
)
(( ))
COOH CO O x O
COOH HO-[(CH2)2O]x-H CO O x O
HO-[(CH C O
ZnO22))22O]
HO-[(CH
O]x-H O
x O
x-H
270°C,
ZnO6-8h
ZnO 6-8h
270°C,
COOH 270°C, 6-8h
COOH COOH HO
COOH HO Mn = 864-3082
COOH O n
Acrylated rosin
COOH HO Mn = 864-3082
Acrylated rosin Polyester
of acrylated rosin and
O
O
polyethylene glycol
n Mn = 864-3082
n
Acrylated rosin Polyester of acrylated rosin and polyethylene glycol
Polyester of acrylated
Scheme 67. Preparation of acrylated rosin/polyethylene rosin
glycol and polyethylene glycol
polyester.
Scheme 67. Preparation of acrylated rosin/polyethylene glycol polyester.
Rosinimide
Rosin imidepolyethers
polyethersare
arelight
light brown
brown solids.
solids. They
Theycan
canbe
beprepared
preparedfromfromrosin, poly(ethylene
rosin, poly(ethylene
Rosin
glycol) and imide polyethers
polyamines are light
according to brown solids.
Scheme 68, They
and cansuch
using be prepared from
separation rosin, poly(ethylene
methods as as
washing,
glycol) Rosin imide polyethers
and polyamines are light
according brown solids.
to Scheme They
68, and can be
using prepared
such from methods
separation rosin, poly(ethylene
washing,
glycol) precipitation
drying, and polyamines and according
filtration to SchemeThey
[250,251]. 68, and
can using
be such separation
applied as methods
petroleum crude as
oilwashing,
sludge
glycol)
drying, and polyamines
precipitation and according to Scheme 68, and using such separation methods as washing,
drying,
dispersantsprecipitation
[250]. andfiltration
filtration[250,251].
[250,251]. They
They can be applied
can be applied asas petroleum
petroleumcrude
crudeoiloilsludge
sludge
drying, precipitation
dispersants [250]. and filtration [250,251]. They can be applied as petroleum crude oil sludge
dispersants [250].
dispersants [250].
H O R NH2 R N H
O O H ( O )m H
)n)n )n
H O H R NH R N
HO O N R NH22
O O H ( O )mH
)n)n )n
O H NH2 O O NR N
O O
HO R NH N H O H O( O )m
O NH2 2 O N O HO H N H
( O )m H O
)n)n )n
O R NH2 O O H N O
)n)n )n
O inRDMF
NH2 HO HO O O H
HO ( O )mH
(( (
HO
HO O O O NH2 O in( DMF O )m
135°C
in DMF
(( (
HO
Zn O O O O 170°C, 5h
in DMF O
HO
140°C,
O O 1h O COO in135°C
DMF
2h in DMF5h
170°C,
O
240°C
Zn 140°C, 1h 135°C (( ( 170°C, 5h
COO 2h
(( (
Zn
240°C 140°C, 1h COO 2h COO
COOH COO
240°C PEG COO
COOH COO Mn = 2310-3610 g/mol COO
COOH maleopimarate PEG COO
Levopimaric PEG M = 2310-3610 g/mol
maleopimarate Rosin imide Mnn= 2310-3610
Levopimaric
acid R = -(CHmaleopimarate Rosin imide ether Rosing/mol
imide
Levopimaric 2)4- or -[(CH2)2]NH]2(CH2)2- yield:
Rosin85-95% Rosin
imide imide ether
acid R = -(CH2)4- or -[(CH2)2]NH]2(CH2)2- yield:imide
Rosin
yield: 85-95% 80-93%
ether
acid R = -(CH2)4- or -[(CH2)2]NH]2(CH2)2- yield: 85-95% yield: 80-93%
Scheme 68. Preparation of non-ionic rosin imide polyethers. yield: 80-93%
Preparation ofnon-ionic
non-ionic rosin
rosin imide
imide polyethers.
Scheme 68. Preparationof
Scheme68. of non-ionic rosin polyethers.
imide polyethers.
3.3.5. Sorbents
3.3.5.
3.3.5. Sorbents
Sorbents
3.3.5.Rosin-poly(acrylamide)
Sorbents star copolymers can be prepared according to Scheme 69, prior to
Rosin-poly(acrylamide)
Rosin-poly(acrylamide) star
star copolymers
copolymers can be prepared
can prepared according to Scheme 69, prior toto
Soxhlet extraction using acetone
Rosin-poly(acrylamide) and
star can be
drying [243,244,252].
copolymers according
They canaccording
be prepared to
be used forto Scheme69,
wastewater
Scheme 69,prior
priorto
treatment
Soxhlet
Soxhlet extraction
extraction
[243,244,252] and asusing
using acetone
acetone
a matrix and
for Fe anddrying [243,244,252].
drying
3Odrying
They
[243,244,252].
4 nanoparticles
can be
They
[253].They can used for
can for wastewater
bewastewater treatment
used for wastewater
Soxhlet extraction using acetone and [243,244,252]. be used treatment
[243,244,252]
treatment and as aand
[243,244,252] matrix
as for
a Fe3O4for
matrix nanoparticles
Fe O [253].
nanoparticles [253].
[243,244,252] and as a matrix for Fe3O4 nanoparticles
3 4 [253].
O
NaBH4 O
O NH
NaBH4 2
NaBH H H
in diethyl 4 O NHO2 NH2 H2N
NH2 H H
inether
diethyl O O NH2 NH NH H2N
in diethyl
25°C, 24h
ether ON N O NHO2 N N OH
2N
ether24h O ON ON O
25°C, N N O O
OH 25°C, 24h OH
HN HN
O
[ ]n O O
O
O
O
O[ ]n O
H in HHO
K2S2O O [ ]n [ ]n O
OH
C OH OH H8 H2 [ ]]nn [[ ]n]nO
OH K2S65°C,
2O8 in
2hH2O O [
C K2S2O8 in H2O
O [ ] O O [ ]
OC 65°C, 2h
65°C, 2h O [ ]nnO O O O [ ]nn OO
Rosin acid
O NO NO
O Rosin alcohol NH2 OO O
H2N
N N O
Rosin acid Rosin alcohol HN HN
Rosin acid Rosin alcohol NH2
NH2 H H
H2N
H2N
H H
Mn=??
M =??
Mnn=??
Scheme 69. Synthesis of rosin alcohol and rosin-poly(acrylamide) star copolymer.
Scheme 69. Synthesis of rosin alcohol and rosin-poly(acrylamide) star copolymer.
Scheme
Scheme 69.69.Synthesis
Synthesisofofrosin
rosinalcohol
alcohol and
and rosin-poly(acrylamide)
rosin-poly(acrylamide) star
starcopolymer.
copolymer.
Linear rosin-modified cationic poly(acrylamide) can be prepared from dehydroabietyl chloride,
Linear rosin-modified
bromopropan-1-ol, cationic poly(acrylamide)
methyldiallylamine, acrylamide and can be prepared from dehydroabietyl chloride,
Linear
Linear rosin-modified
rosin-modified cationicpoly(acrylamide)
cationic poly(acrylamide) candiallyl
be dimethyl
be prepared
prepared from
fromammonium chloride
dehydroabietyl
dehydroabietyl in a
chloride,
chloride,
bromopropan-1-ol,
few-step methyldiallylamine,
process, according acrylamide
to Scheme 70,acrylamide
followed byand and diallyl
operations dimethyl ammonium
such as filtration, chloride
washing, in a
drying
bromopropan-1-ol,
bromopropan-1-ol, methyldiallylamine,
methyldiallylamine, acrylamide and diallyl
diallyl dimethyl
dimethyl ammonium
ammonium chloride
chloridein in
a a
few-step
and process, according
recrystallization [149]. Its to Scheme
utilization 70,
mayfollowed
be in by operations
flocculation such
processes as filtration,
[149]. washing, drying
few-step process, according to Scheme 70, followed by operations such as filtration,
few-step process, according to Scheme 70, followed by operations such as filtration, washing, drying washing, drying
and recrystallization [149]. Its utilization may be in flocculation processes [149].
andand recrystallization
recrystallization [149].ItsItsutilization
[149]. utilizationmay
maybe be in
in flocculation
flocculation processes
processes[149].
[149].
Dehydroabietic acid O
Molecules 2019, 24, 1651 CH2 32 of 52
bromopropyl ester m NH2
Molecules 2019, 24, x FOR PEERNREVIEW O 32 of 51
yield: 67%
Cl p n NH2 m
N N
n NO
Dehydroabietic acid Br Cl
Dehydroabietic
bromopropyl esteracid in C2H5OH C
O CH2
bromopropyl ester 65°C,N48h O O N m AIBA NH2 Hydrophobically
CH2
m 50°C, 10h O
yield: 67% N
Br NH2 O O modifiedcationic
O
yield: 67%
C Diallylmethlyl Cl
N
C
p n NH2
N polyacrylamidem
O O Br n ClN p n NH2 m
dehydroabietic acid propyl NBr NCl
n N Br Cl
(C2H5)3N in C2H5OHester ammonium
C bromide
HO Br in THF in C2H5OH
65°C, 48hC O O N AIBA Hydrophobically
Mn=??
65°C, 48h O O NBr AIBA10h
50°C, O O
Hydrophobically
modifiedcationic
55°C, 8h 50°C, 10h C O
C Br
Diallylmethlyl O modifiedcationic
O C O Br Diallylmethlyl C polyacrylamide
O O Br dehydroabietic acid propyl polyacrylamide
(C2H5)3N dehydroabietic acid propyl
ester ammonium bromide Mn=??
HO Br (C H5)3N
in2THF ester ammonium bromide
Dehydroabietyl Mn=??
HO Br in THF
O C Cl 55°C, 8h
chloride
55°C, 8h
Scheme 70. Preparation of linear rosin-poly(acrylamide) copolymer.
Dehydroabietyl
Dehydroabietyl
chloride
C Cl tetraethylenepentamine
O Rosin amide is a solid. It can be prepared from maleopimaric acid and
O C Cl chloride
tetraethylenepentamine Scheme
according to
70.Preparation
Scheme
Preparationof
71, prior
oflinear
to precipitation, washing and lyophilization
linear rosin-poly(acrylamide)
rosin-poly(acrylamide) copolymer.
Scheme
Scheme 70.
70. Preparation of linear rosin-poly(acrylamide) copolymer.
copolymer.
[115]. It creates nano-micelles in aqueous solutions and can act as a sorbent and sinking agent in metal
ions removal
Rosin
Rosin [115].
tetraethylenepentamine amideisisaasolid.
tetraethylenepentamine solid. It
It can be prepared from maleopimaric acid and
Rosin tetraethylenepentamineamide amide is a solid. It preparedfrom
can be prepared frommaleopimaric
maleopimaric acid
acid andand
tetraethylenepentamine
tetraethylenepentamine according
according to to Scheme
Scheme 71, 71,
priorprior
to to precipitation,
precipitation, washing
washing and and lyophilization
lyophilization [115].
Maleopimaric O according to Scheme 71, prior to precipitation,COOH H2N washing and lyophilization
[115]. Itnano-micelles
creates nano-micelles in aqueous solutions and can act as a sorbent NH
and sinking agent in metal
It creates
acid in aqueous solutions and can act as a
[115]. It creates nano-micelles in aqueous solutions and can act as a sorbent andsorbent and sinking Rosin
agent
sinking in metal
agent in metalions
ions removal [115]. O O tetraethylenepentamine
removal [115].
ions removal [115]. H
H2N ( N )3 NH2 HN NH
amide
Maleopimaric OO
60°C, 12h COOH NH2N
H2N NH
Maleopimaric
acid COOH
O COOH COOH H
NH Rosin
acid O O Rosin
O H O tetraethylenepentamine
Scheme
H2N 71. (H N )3 NH2of rosin-tetraethylenepentamine
Preparation amide. amide
O H2N
( N )3 NH 2
HN
HN N
NH
NH
amide
O 60°C, 12h NH
60°C, 12h COOH H
COOH
3.3.6. Organosilicons COOH
COOH
Rosin glycidyl esterScheme is 71.

a Preparation
brown, viscousof rosin-tetraethylenepentamine
liquid. It can be synthesized amide. from rosin and
Scheme
Scheme71. 71.Preparation
Preparation of of rosin-tetraethylenepentamine
rosin-tetraethylenepentamine amide. amide.
epichlorohydrin according to Scheme 72 without further purification [254]. It can be used for
3.3.6.
3.3.6. Organosilicons
Organosilicons
preparation of cross-linking agent for silicone rubber [254].
3.3.6. Organosilicons
Rosin-modified
Rosin glycidyl room-temperature-vulcanized
ester is a brown, silicone
viscousIt liquid. It rubber
can be can be prepared
synthesized from from
rosinrosin
and
Rosin
Rosinglycidyl esterester
glycidyl is a brown, viscous viscous
is a brown, liquid. can be synthesized
liquid. from rosin and
It can be synthesized epichlorohydrin
from rosin and
glycidyl ester,
epichlorohydrin aminopropyltrietoxysilane,
according to Scheme 72 without tetraetoxysilane
further purificationand [254].hydroxyl-terminated
It can be used for
according to Schemeaccording
epichlorohydrin 72 without tofurther purification [254]. It can be used for[254].
preparationcan of
becross-linking
polydimetoxysilane according
preparation of cross-linking toScheme
agentScheme 72
72 without
for silicone[254]. further
Rosin-modified
rubber [254].
purification
silicones showsItsignificantly used for
better
agent for silicone
preparation
thermal and of rubber [254].
cross-linking
mechanical agent for
properties in silicone
comparison rubber
with[254].
unmodified silicone [254–256].
Rosin-modified room-temperature-vulcanized silicone rubber can be prepared from rosin
Rosin-modified room-temperature-vulcanized silicone rubber can be prepared from rosin
glycidyl ester, aminopropyltrietoxysilane, tetraetoxysilane and hydroxyl-terminated
glycidyl ester, O aminopropyltrietoxysilane, Otetraetoxysilane and( )hydroxyl-terminated
polydimetoxysilane
Cl H N
according to2Scheme 72 [254]. Rosin-modified silicones shows significantly better
polydimetoxysilane according to Scheme O72 [254]. Rosin-modified
Si O silicones
HO ( Si shows
O ) H significantly better
thermal and NaOH
mechanical propertiesOinSicomparison with unmodified silicone n
[254–256].
thermal and TEBAC
mechanical properties in comparison O
with unmodified silicone [254–256].
O
117-60°C O Y X Y X
5h O 80°C, 1h O ( )
Cl
Cl
O O H2N
H2N
NH O
OH
Si O
O Si O
( (X)
)
HO ( Si O ) H
X Y X
COOH NaOH C O Si O Si O C O O nH
HO ( Si )
NaOH
TEBAC
O Si O
O
O
OO
O
(Y) n Y X Y
TEBAC O O dibutyltin Y X Y X
Rosin 117-60°C
Rosin-modified
O
dilaurate
O Rosin
Y Xmodified
Y X
117-60°C
5h O 80°C, 1h
O (X)
O 80°C, 1haminopropyltrietoxysilane
NH O Si O X Y X
5h Rosin glycidyl ester 25°C,
O Si 0.25h silicone
X Yrubber
O
C
NH OH
OH O (X) X
COOH
COOH
yield: 92%
C yield: 100%
C O
(Y) O yield:Y 100%
X Y
O
O C O
(Y)
dibutyltin
Y X Y
Rosin Scheme 72. Preparation O
O of rosin-modifiedRosin-modified dibutyltin
room-temperature-vulcanized silicone
dilaurate Rosin
rubber. modified
RosinScheme 72. Preparation
O of rosin-modified room-temperature-vulcanized
Rosin-modified dilaurate
silicone rubber.
Rosin modified
RosinOglycidyl ester aminopropyltrietoxysilane 25°C,25°C, 0.25h silicone rubber
Rosinyield:
glycidyl
92% ester aminopropyltrietoxysilane 0.25h silicone rubber
Maleated rosin-modified
Rosin-modified vinyl fluorosiliconeyield:
room-temperature-vulcanized resin 100%
canrubber
silicone be prepared
can be from yield:rosin
maleopimaric
prepared from 100%
acid and
yield: 92% yield: 100% yield: 100%glycidyl
siloxanes according to Scheme
ester, aminopropyltrietoxysilane, 73 prior to vacuum
Scheme 72. Preparation of tetraetoxysilane
evaporation [116]. It can
and hydroxyl-terminated
rosin-modified room-temperature-vulcanized
be used in preparation
polydimetoxysilane
silicone rubber.
of
Scheme
fluorosilicone 72. Preparation
rubber, having of rosin-modified
improved room-temperature-vulcanized
mechanical and thermal properties silicone
in rubber.
comparison with
according to Scheme 72 [254]. Rosin-modified silicones shows significantly better thermal and
unmodified
Maleatedsample [116].
rosin-modified vinyl fluorosilicone resin can be prepared from maleopimaric acid and
mechanical properties
Maleated in comparison
rosin-modified with unmodified
vinyl fluorosilicone resin silicone [254–256].
can be prepared from maleopimaric acid and
siloxanes
Maleated according to
rosin-modifiedScheme 73
vinyl prior to vacuum
fluorosilicone evaporation [116]. It can be used in preparation of
siloxanes according to Scheme 73 prior to vacuumresin can be prepared
evaporation [116]. It can from maleopimaric
be used acidof
in preparation and
fluorosilicone
siloxanes accordingrubber,
to having
Scheme 73improved
prior to mechanical
vacuum and thermal
evaporation properties
[116]. It can bein comparison
used in with
preparation
fluorosilicone rubber, having improved mechanical and thermal properties in comparison with
unmodified sample
of unmodified
fluorosilicone rubber,[116].
having improved mechanical and thermal properties in comparison with
sample [116].
unmodified sample [116].
Molecules 2019, 24, 1651 33 of 52
Molecules2019,
Molecules 2019,24,
24,xxFOR
FORPEER
PEERREVIEW
REVIEW 3333of of
5151
H2N O Si
H2N F3C Si O O Si
F3C Si O
++HO (2 Si O ) H++ F3C OOSi OSi CF3+
Si O Si HN Si O Si O Si O
CF3+
Si O Si Si O Si
O Si O O
Si COOH
Si O Si +HO ( Si
Siloxane 1 Siloxane
O )n
nH
+ F3C Si O CF +
Si COOH
( Si O )n22H F3C
OSi OSi 3 O Si O Si
Siloxane 1 HOSiloxane COOH O
Siloxane 1 Siloxane 2 F3CSiloxaneSiloxane
Si O3 Si O 4
Siloxane O
3 Siloxane 4 O
Siloxane 3
KOH Siloxane 4 N
KOH O N
100°C, 12h
KOH 12h
100°C, O N CF3
HOOC O
O O CF3
H2N CF100°C, 12h
3
HOOC O O
CF3
H2N CF3 HOOC OO O
H2N CF3 O Si O ( Si O )a ( Si O )b ( Si O )c Si
O Si O ( Si O )a ( Si O )b ( Si O )c Si
Si O ( Si O)a ( Si O )b ( Si O )c Si 150°C, 4h Si O ( Si O )a ( Si O )b ( Si O )c Si
Si O ( Si O)a ( Si O )b ( Si O )c Si Maleated rosin-modified
150°C, 4h
Si OVinyl
( Si Ofluorosilicone
)a ( Si O )b ( Si resin
O )c Si Maleated
vinyl
150°C, 4h rosin-modified
fluorosilicone resin
Vinyl fluorosilicone resin Maleated
vinyl rosin-modified
fluorosilicone resin
Vinyl fluorosilicone
Scheme
Scheme 73.73. resin
Preparationof
Preparation ofmaleated
maleated rosin-modified
rosin-modifiedvinyl vinyl fluorosilicone
vinylfluorosilicone resin.
fluorosilicone resin. resin
Scheme 73. Preparation of maleated rosin-modified vinyl fluorosilicone resin.
Scheme 73. Preparation of maleated rosin-modified vinyl fluorosilicone resin.
3.3.7.
3.3.7. Polysaccharides
Polysaccharides
3.3.7. Polysaccharides
3.3.7. Superhydrophobicwood
Polysaccharides
Superhydrophobic woodcancan be
be prepared
prepared using
using maleated
maleatedrosin,
rosin,aluminum
aluminum chloride and and
chloride
Superhydrophobic
tetrabutyltitanate woodto can
according be prepared
Scheme 74 [119]. using
Such amaleated rosin,
hydrophobic aluminum
material is chloride and
appreciated in in
tetrabutyltitanate according
Superhydrophobic woodto Scheme 74 [119]. using
Such a hydrophobic material is chloride
appreciated
tetrabutyltitanate according
construction. Related to can
starch-rosin
be prepared
Scheme 74 have
materials [119].been
Such amaleated
also
rosin,material
hydrophobic
prepared [120].
aluminumis appreciatedandin
construction. Relatedaccording
tetrabutyltitanate starch-rosin materials
to Scheme 74have
[119].been also
Such prepared [120].
a prepared
hydrophobic material is appreciated in
construction. Related starch-rosin materials have been also [120].
construction.
OH
Related
OHstarch-rosin
OH OH materials
OH have been also prepared [120].
OH OH OH OH COOH
OH COOH
OH OH OH OH OH
Wood COOH
COOH
COOH
Wood COOH
Wood Maleated rosin COOH
AlCl
Maleated3rosin COOH
Ti(OC4H9)4 COOH O O O O
Maleated
AlCl3rosin
in H2O/NH 3/C O O
AlCl
Ti(OC 4H329H
)45OH O O O
O
O
25-180°C, 41h HO Ti
in H O/NH /C H)4OH
Ti(OC H
4 9 O AlO O
O O
2 3 2 5 O HO O O O
in H25-180°C,
2O/NH3/C241h
H5OH O O OO O
HO
Al OO Ti O
25-180°C, 41h O HO O HO Ti
O OAl O
O O HO Superhydrophobic-surface
O wood O
O O O O O
Superhydrophobic-surface
Scheme 74. Preparation of rosin-impregnated superhydrophobic wood. wood
Superhydrophobic-surface wood
Scheme74.
Preparation of
of rosin-impregnated
rosin-impregnated superhydrophobic
superhydrophobic wood.
wood.
Rosin-esterified starch
Scheme 74. biopolymer can
Preparation of be prepared according
rosin-impregnated to Schemewood.
superhydrophobic 75, prior to filtration,
precipitation, washing and
Rosin-esterifiedstarch drying [257,258].
starchbiopolymer
biopolymer can Rosin
can be decreases
be prepared solubility
prepared according and swelling of starch, which
Rosin-esterified accordingtotoScheme
Scheme75,75,prior to to
prior filtration,
filtration,
potentially allows tostarch
Rosin-esterified use this polymer incan
biopolymer foodbeand biomedical
prepared materials
according [257]. 75, prior to filtration,
to Scheme
precipitation,
washing anddrying
and drying[257,258].
[257,258]. Rosin
Rosin decreases
decreasessolubility
solubilityand
andswelling
swellingofof
starch, which
starch, which
precipitation,
potentially washing
allows to and
use drying
this [257,258].
polymer in foodRosin
and decreases solubility
biomedical materials and swelling of starch, which
[257].
potentially allows to use this polymer in food and biomedical materials [257].
potentially allows to use this polymer in food and biomedical materials [257].
OH
OH
OHOH HO O O O
OH
O lipase OH OH
OH in DMSO 40°C,HO1-4h O OH O
OH O OH O
OH n+m HO O O
O
Starch O lipase
Degree1-4h
of substitution:
OH OH
m
O
OH O lipase
in DMSO 40°C, OH
O OH
n+m in DMSO 40°C, 1-4h 0.031-0.092 OH
OH Rosin acid starch
O OH n
Starch n+m
Degree of substitution: OH
m
O
Starch Degree of substitution:
0.031-0.092 OH
m OH O
Scheme 75. Preparation Rosin
of rosin-esterified
0.031-0.092 acid starch
starch.
OH
n
Rosin acid starch n
Cellulose nanofibers and Scheme 75. Preparation
nanocrystals of rosin-esterified
surface-modified starch.
by rosin can be prepared according to
Scheme75. 75. Preparation of rosin-esterified
rosin-esterifiedstarch.
Scheme 76, prior to washing in ethanolPreparation
Scheme
[259,260]. They can be used as starch.
antibacterial reinforcements in
Cellulose
bio-based nanofibers
package and nanocrystals
films [260]. In similar way surface-modified
hemp fibers canby berosin can be
modified byprepared according
tall oil rosin acids into
Cellulose
Cellulose
Scheme 76, nanofibers
nanofibers
prior to washingand
and nanocrystals
in nanocrystals
ethanol surface-modified
surface-modified
[259,260]. They can be byrosin
by
used rosin
as canbebeprepared
can prepared
antibacterial according
according
reinforcements to to
in
order to improve the reinforcement adhesion to an epoxy matrix [261].
Scheme
Scheme 76, 76, prior
prior to to washing
washing inin ethanol
ethanol [259,260].
[259,260]. They can
can be
be used
used as
asantibacterial
antibacterial
bio-based package films [260]. In similar way hemp fibers can be modified by tall oil rosin acids in reinforcements
reinforcements in in
bio-based
bio-based package
order to package
improve the films
films [260]. In similar
[260]. In similar
reinforcement way hemp
waytohemp
adhesion fibers
fibers
an epoxy can be
can be
matrix modified by tall oil rosin acids
modified by tall oil rosin acids in
[261]. in
order
order to to improve
improve thethe reinforcementadhesion
reinforcement adhesionto toan
anepoxy
epoxy matrix
matrix [261].
[261].
Molecules 2019, 24, 1651 34 of 52
OH OH R = abietate
HO HO R or
= abietate
OH
OH
OH
Rosin OH
OH
OH pimarate
R = abietate
HO HO
OH OH or
R pimarate
O
OH HO
O HO OH Rosin
Rosin O
OH HO
OHO OH or =pimarate
abietate
O
O OH
in H2Rosin
O/HCl O
O OH Degreeorofpimarate
substitution:
O O Degree
O
OH O in H2O/HCl O
OH O 0.05 of
Degree
substitution:
of substitution:
HO
O in H2O/HCl
130°C, 24h OHO 0.05
Degree
HO OH
OH
OH
OH n in H2O/HCl
130°C, 24h HO OH
OH RO n O 0.05 of substitution:
HO
Cellulose nanofibers
OH n 130°C, 24h HO n 0.05
HO OH n HO OH R O n
Cellulose nanofibers
OH
Cellulose nanofibers n
130°C, 24h
Rosin modified cellulose
R O nanofibers
n
Cellulose nanofibers Rosin modified cellulose
Rosin modified cellulose nanofibers
R nanofibers
Scheme 76. Preparationof
76. Preparation Rosin modified
ofrosin-modified
rosin-modified cellulose
cellulose nanofibers
nanofibers.
Scheme Scheme
cellulose nanofibers.
Scheme 76.
76. Preparation
Preparation of
of rosin-modified
rosin-modified cellulose
cellulose nanofibers.
nanofibers.
Scheme 76. Preparation of rosin-modified cellulose nanofibers.
Chitosan grafted
Chitosan grafted by
by rosin
rosin acrylate
acrylate isis aa solid.
solid. ItIt can
can be
be prepared
prepared fromfrom chitosan
chitosan and
and rosin
rosin acid
acid
Chitosan
Chitosan grafted
grafted by
by rosin
rosin acrylate
acrylate is
is aa solid.
solid. It
It can
can be
be prepared
prepared from
from chitosan
chitosan and
and rosin
rosin acid
acid
hydroxyethyl
Chitosan
hydroxyethyl acrylate
acrylate according
grafted by rosintoacrylate
according Scheme
totoSchemeis77a77
prior
solid.toItprecipitation,
prior can
to filtration,
be prepared
from chitosan
filtration, and drying
and
washing rosin [172].
acid
and drying
hydroxyethyl
hydroxyethyl acrylate
acrylate according
according to Scheme
Scheme 77 prior
prior to to precipitation,
77applications precipitation, filtration,
filtration, washing
washing and
and drying
drying
It can
[172]. be potentially
hydroxyethyl
It can
[172].
used
acrylate
be potentially in controlled
according to release
Scheme
used inincontrolled 77 prior to [172].
precipitation,
release applications filtration,
[172]. washing and drying
[172]. It
It can
can be
be potentially
potentially used
used in controlled
controlled release
release applications
applications [172].
[172].
[172]. It can be potentially used in controlled release applications [172].
RR OH O
OO R OH RR
== O O O
O
OHOH O R R= O
OH OH R= O O
OH O OO O
O O
O
OO
O O
O O HO NH O
HO
O OO K2KS22SO K S OO HO NH nnChitosan graft
O O
O
288
2 2O 8 HO NH Chitosangraft
n Chitosan graft
HOHO
HO
NHNH 2
NH2
2 inin
H2H
in H
K2S2COOH
2O/CH
O/CH
O/CH
OCOOH
8
3 33COOH [[[ ]]m
m n Chitosan
rosin graft
rosinacrylate
acrylate Grafting
Graftingpercentage:
percentage:
NH2
HO Chitosan n in H 2O/CH COOH [O m
]m RR
R rosin acrylate Grafting percentage:
Chitosan
Chitosan n n60°C,
60°C,2h;
2h; microwaves
3
60°C,22h;microwaves
microwaves OO O
O R rosin acrylate
copolymer
copolymer 72.3%
Grafting percentage:
72.3%
72.3%
Chitosan n 60°C, 2h; microwaves
O copolymer 72.3%
O O copolymer
Scheme
Scheme
Scheme 77.
77.
77.
Scheme Preparation
Preparation
77.Preparation of
of
Preparationof chitosan
chitosan
ofchitosan graft
graftrosin
chitosan graft
graft rosinacrylate
rosin acrylatecopolymer.
acrylate
acrylate copolymer.
copolymer.
copolymer.
Scheme 77. Preparation of chitosan graft rosin acrylate copolymer.
3.3.8. Other
3.3.8. OtherMaterials
Materials
3.3.8.
3.3.8. Other
Other Materials
Materials
3.3.8. Other Materials
Dehydroabietic
Dehydroabietic
Dehydroabieticacid-glycerol
acid-glycerol carbonate
carbonate
acid-glycerolcarbonate product
product
carbonateproduct
product can canbe
can
can beprepared
be preparedfrom
prepared fromdehydroabietic
from dehydroabietic
dehydroabietic acid
acid
acid andand
and
Dehydroabietic
Dehydroabieticacid-glycerol
acid-glycerol carbonate product be
canbe preparedfrom
beapplied
prepared fromdehydroabietic
dehydroabieticacid
acid and
and
glycerin
glycerin
glycerincarbonates according
carbonates
carbonates according totoScheme
Scheme
according to Scheme78 78
78 [262].
[262]. It
It can
can
78 [262]. ItIt can be applied
can be applied in
in
applied in xerographic
xerographic
xerographic tonners
tonners
tonners [262].
[262].
[262].
glycerin
glycerincarbonates according
carbonates accordingtotoScheme
Scheme 78[262].
[262]. It can be inxerographic
be applied in xerographictonners
tonners[262].
[262].
O (1) O (2) O (3) O (4) O (5) O (6) DA R = H, or CH2OH
O (1) O (2) O (3) O (4) O (5) O (6) DA R = H, or CH2OH
O O (1)(1) O O DA (2)(2)O O DA (3) (3)OO (4)
DA(4) OO DA (5)
(5) O
O DA (6) DA
O O DA DA DA DA DA (6)
O DA RR= =H,H,
oror
CHCH 2OH
2OH
O
O
O
R O O O
O O DADA O DA DA O DA
DA O DA
DA O DA
DA OO O
R O O O O O DA =
O
O O O O OO O
O O
O DA =
R R
(C2H5)4N I ++ ++ ++ ++ HO ++ OO
DA= =
DA
(C2H5)4N I R
(C2150°C,
H
(C52)H
4N
150°C,
12hI
5)4IN
R
12hR R OH
++ OH
OH ++ ++ OH
OH + HO
HO ++ O
O
OO DA
OHOHOH O O O OH
OH
DA
150°C,
150°C, 12h 12h OH OH O O O O O O
COOH OHOH OHOH OO OO O O O O O O DA
DA
COOH Dehydroabietic
Dehydroabietic OO O O
O DA O
DA O OO OO
COOH
COOH OO DA
Dehydroabietic Dehydroabietic O
Dehydroabietic
acid-glycerin O
Dehydroabietic acid
DA DA
DA OO DA
acid acid-glycerin O DA
DA
O
DA
acid-glycerin
carbonate O
Dehydroabietic
Dehydroabietic acid carbonate product
acid acid-glycerinproduct yield:
yield: 99%
99% O DA
DA
carbonateproduct
carbonate product yield:
yield:99%
99%
Scheme 78.
Scheme78. Preparation
78.Preparation of
of rosin-glycerin
Preparation of rosin-glycerin carbonate
carbonate xerographic
xerographic toner.
Scheme
Scheme rosin-glycerin xerographictoner.
carbonatexerographic toner.
Scheme 78.78.Preparation
Preparationof
ofrosin-glycerin
rosin-glycerin carbonate
carbonate xerographictoner.
toner.
Rosin-polyphthalate resin
Rosin-polyphthalateresin
Rosin-polyphthalate resinisis
isaaaglossy
glossy light
light yellow
glossy light yellow solid.
yellow solid.It
solid. ItItcan
canbe
can beprepared
be preparedfrom
prepared from maleopimaric
frommaleopimaric
maleopimaric
acid, Rosin-polyphthalate
and phthalic resin is a glossy
anhydride-glycerol lightaccording
polyester yellow solid.
to It can be
Scheme 79 prepared
prior to from maleopimaric
vacuum
acid, Rosin-polyphthalate
acid, and
and phthalic
phthalic resin is a glossy
anhydride-glycerol
anhydride-glycerol light according
polyester
polyester yellow solid.
to
to It can 79
Scheme
Scheme be
79 prepared
prior
priortoto from drying
vacuum
vacuum drying [117].
maleopimaric
[117].
drying [117].
acid,
Its and phthalic
application is ananhydride-glycerol polyester
environmentally-friendly according to
phenol-free Scheme
printing ink79[117].
prior to vacuum drying [117].
acid,
Its
Its Itsand phthalic
application
application anhydride-glycerol
is
is is an polyester
environmentally-friendly
ananenvironmentally-friendly according
phenol-free to Scheme
printing ink79 prior
[117]. to vacuum drying [117].
application environmentally-friendlyphenol-free printing ink
phenol-free printing ink[117].
[117].
Its application is an environmentally-friendly phenol-free printing ink [117].
O O HO
O O R HO
O R R
R OH O R R R HO
O R OH R
O O R R R=
O O OH OH R= HO
O R OH
OH R OH
R OH
R R=
R O OH OH O
O R R OHOH O
R OH OO R=
OO R OH O OHOH
OH OH O O O
OH OH O O
O R R OHOH
O RO OH R
OH O O O
O R OH
260°C, 2h O R R
COOH 260°C, 2h O RO
R R
COOH O R OH2h
260°C, COO
OH OH ROHROHRosin-based
Rosin-based
O O
COOH OH OH
Maleopimaric acid 260°C, 2h COO OH OHO R R Rosin-based
R phenol-free
Maleopimaric
COOH acid COO R R R phenol-free
Maleopimaric acid R R R
OH R
OH Rosin-based
phenol-free
resin
COO R R resin
Maleopimaric acid R R R phenol-free
resin
Scheme
Scheme 79.
79. Preparation
Preparation of
of rosin-based
rosin-based phenol-free
phenol-free resin.
resin.resin
Scheme79. Preparation of rosin-based
rosin-basedphenol-free
phenol-freeresin.
resin.
Rosin propargyl Scheme
ester is aa79. Preparation
white, of rosin-based
transparent liquid. It phenol-free
can be resin.
synthesized from rosin chloride
Rosin
Rosin propargyl
propargyl ester
ester is iswhite,
a white, transparent
transparent liquid.
liquid. It It
can can
bebe synthesized
synthesized from
from rosin
rosin chloride
chloride and
and Rosin propargyl ester is a white, transparent liquid. It can be synthesized from rosin chloride
and propargyl alcohol according to Scheme 80, prior to washing and column chromatography [147].
propargyl alcohol according to Scheme 80, prior to washing and column chromatography [147].
propargyl
and
It Rosin alcohol
propargyl
propargylaccording
alcohol
ester istoa Scheme
according 80, prior
to Scheme
white, 80, to
transparent washing
prior Itand
to washing
liquid. cancolumn
and chromatography
column
be synthesized chromatography
from rosin [147]. It can
[147].
chloride
It can
can be
be used
used toto prepare
prepare caprolactone
caprolactone graft graft copolymers
copolymers [147].
[147].
be used
It can to
be
and propargyl
Rosinprepare
used to caprolactone
prepare graft
caprolactone
alcohol according copolymers
graft [147].
copolymers
to Scheme 80, prior to washing[147]. and column chromatography [147].
Rosin ester
ester containing
containing poly(α-azide-ε-caprolactone)
poly(α-azide-ε-caprolactone) can can bebe prepared
prepared from
from rosin
rosin propargyl
propargyl ester,
ester,
It can Rosin
Rosin
be used ester
ester
to containing
containing
prepare
α-chloro-ε-caprolactone poly(α-azide-ε-caprolactone)
poly(α-azide-ε-caprolactone)
caprolactone
and sodium graft
azide copolymers
according can
can
[147].
to be
beprepared
Scheme prepared
80, from
and fromrosin
usingrosinpropargyl
propargyl
such ester,
separation ester,
α-chloro-ε-caprolactone and sodium azide according to Scheme 80, and using such separation
α-chloro-ε-caprolactone
Rosin ester
methods as containing and
and sodium
sodium azideazide according
according
poly(α-azide-ε-caprolactone) to
to Scheme
can Scheme
be80, 80,using
and
prepared and using
such
from such separation
separation
rosin propargyl methods
ester,
methods as centrifugation
centrifugation and
and vacuum
vacuum drying
drying [147].
[147]. This
This biodegradable
biodegradable copolymer
copolymer shows
shows properties
properties
methods as centrifugation and vacuum drying [147]. This biodegradable
α-chloro-ε-caprolactone and sodium azide according to Scheme 80, and using such separation copolymer shows properties
methods as centrifugation and vacuum drying [147]. This biodegradable copolymer shows properties
similar to poly(methyl acrylate) [263]. Similar polymers with quaternary ammonium groups showing
antimicrobial properties can be also prepared [264].
Molecules 2019, 24, 1651
Acrylic rosin methacryl diester can be prepared from acrylic rosin and 2-hydroxyethyl35 of 52
methacrylate according to Scheme 81, prior to rotary evaporation and vacuum drying [124]. It can be
used as acrylic
Molecules monomer
2019, 24, orREVIEW
x FOR PEER resin [124]. 35 of 51
as centrifugation and vacuum drying
Poly(styrene-co-acrylic [147].
rosin ester) canThis biodegradable
be prepared copolymer
via suspension shows properties
polymerization of acrylicsimilar
to poly(methyl
rosinsimilar
methacryl acrylate)
to poly(methyl
ester and[263].
acrylate)Similar
styrene[263]. polymers
Similarto
according with
polymers
Schemewith quaternary
quaternary
81, prior ammonium
ammonium
to washing, groups
groups
filtration showing
and showing
vacuum
antimicrobial
drying properties
antimicrobial
[124]. can be
Its properties
application isalso
can be prepared
also prepared
microspheres [264].
[264].
[124].
Acrylic rosin methacryl diester can be prepared from acrylic rosin and 2-hydroxyethyl
methacrylate according to Scheme 81, prior to rotary evaporation and vacuum drying [124]. It can be
Dehydroabietyl
Molecules 2019, 24,chloride Dehydroabietic propargyl ester
)n
x FOR PEER REVIEW 35 of 51
used as acrylic monomer or resin [124]. O
Poly(styrene-co-acrylic OH ester) can be prepared via suspension polymerization of acrylic
rosin
similar to poly(methyl acrylate) [263]. Similar polymers with quaternary ammonium groups showing
rosin methacryl
antimicrobial ester and
properties styrene
(Ccan
2H5)be
according to Scheme 81, prior to washing, filtration and vacuum
3N also prepared [264].
CuI
COCl [124]. Its application
drying in CH2is
Clmicrospheres [124].
Acrylic rosin methacryl 2diester
O can be DBU acrylic rosinO andO 2-hydroxyethyl
prepared from
22°C, 24h O
in THF
methacrylate according to Scheme 81, prior to rotary evaporation
35°C, 12h
and vacuum drying [124]. ItNcan be
N
Dehydroabietyl chloride or resinDehydroabietic propargyl ester O
)n
used as acrylic monomer [124]. N3 N
(
O
Cl Poly(styrene-co-acrylic rosin OH ester)
( O can be prepared Rosin ester containing
)n via suspension polymerization of acrylic
rosin methacryl ester and styrene according to Scheme
Poly(α-azide- poly(α-azide-ε-caprolactone)
O 81, prior to washing, filtration and vacuum
(C2H5)3N
CuI
drying [124]. Its application
O COCl
O in CH Cl2 -ε-caprolactone)
is2microspheres [124].
O M = 10400, 11000, 12200
DBU nO
O
22°C, 24h O in THF
2-hydroxyethyl- in DMF N
NaN3 25°C, 12h 35°C, 12h N
2-bromoisobutyrate
Dehydroabietyl chloride Dehydroabietic propargyl
Cl ester
( )n
N O
α-chloro-ε-caprolactone N3
Sn(II) 2-ethylhexanoate O
Cl in toluene OH ( (O ))n
n
Poly(α-chloro-ε-caprolactone)
Rosin ester containing
O
120°C, 12h O poly(α-azide-ε-caprolactone)
(C2H5)3N Poly(α-azide- O
CuI
O
COCl O in CH2Cl2 -ε-caprolactone) DBU M = 10400, 11000, 12200
Scheme
Scheme Preparation
80. 80. Preparation O rosin
of
of rosin ester
ester containing
containing O n O
poly(α-azide-ε-caprolactone).
2-hydroxyethyl- 22°C, 24h Oin DMF in THF
NaN3 25°C, 12h N
2-bromoisobutyrate Cl 35°C, 12h N
N O
Acrylic rosinSn(II) 2-ethylhexanoate
methacryl diester can be prepared N3
from acrylic rosin and 2-hydroxyethyl PDI=1.17-1.36
methacrylate
(
COOH
in toluene (O COO )n Poly(α-chloro-ε-caprolactone)
COO
Cl O (O )n Rosin ester containing
according to Scheme120°C,81, prior
12h to rotary evaporation and O vacuum drying [124]. It can be used as acrylic
Poly(α-azide-
O O poly(α-azide-ε-caprolactone)
O
O
monomer orO resin
O
[124].
HO -ε-caprolactone)
O O
Mn = 10400,
Scheme 80. Preparation of rosin ester containing poly(α-azide-ε-caprolactone). 11000, 12200
ZnO, HQ AIBN
2-hydroxyethyl- in DMF
O O ( )n( )m
200-230°C NaN3 25°C, 12h Cl gelatin
2-bromoisobutyrate PDI=1.17-1.36
COOH 3.5h COO COO in H 2 O COO COO
Sn(II)COOH
2-ethylhexanoate
Acrylic rosin in toluene O (O O )n Poly(α-chloro-ε-caprolactone)
<90°C, 5h O
( )n( )m
120°C, 12hAcrylic
O rosin ethyl methacrylO O O
HO O
diester yield: 92% Poly(styrene-co-O
AIBN
ZnO,
Scheme HQ
80. Preparation of rosin ester containing
O -acrylic rosin ester)
gelatin O ( )n( )m
200-230°C
COOH COO
3.5h 81. Preparation
Scheme in H2O rosin ester
of Ostyrene and acrylic COO copolymer.
<90°C, 5h O PDI=1.17-1.36
Acrylic rosin COOH COO ( COO)n( )m
O
Acrylic rosin ethyl methacryl
Rosin-tung oil Diels-Alder adduct is a yellowish solid. It can be prepared from levopimaric acid
O O
diester yield: 92% Poly(styrene-co- O
and tung oil according HO to Scheme 82, prior toO precipitation and -acrylic
drying rosin ester)
[265,266].
O Its application is a
ZnO, HQ promoter in polyurethane [265] AIBN
filler, tackifier and adhesion
Scheme 81. Preparation of styrene
O and acrylic and UV-curable
gelatin rosin O adhesives
ester copolymer. ( )n([266].
)m
200-230°CPreparation of styrene and
COOH Scheme 81.
3.5h COO in H2O rosinCOO
acrylic ester copolymer.
O
<90°C, 5h O
Acrylic rosin
O
Rosin-tung oil Diels-Alder adduct is a yellowish solid. It can be prepared ( from
)n(levopimaric
)m HOOCacid
Poly(styrene-co-acrylic
and tung O oil (CH
according Acrylic rosin ethyl
canmethacryl
to Scheme 82, prior to precipitation and drying [265,266]. Its application isofa acrylic
rosin ester) be prepared via suspension polymerization
2)7
diester yield: 92% Poly(styrene-co-
rosin methacryl ester
filler, tackifier and and styrene
adhesion according
promoter to Scheme[265]
in polyurethane 81, and
prior to washing,
UV-curable
-acrylic filtration
adhesives
O rosin ester)
[266]. and vacuum
O O (CH )
2 7
drying [124]. O
Its application is 81.
Scheme microspheres [124]. and acrylic rosin ester copolymer.
Preparation of styrene
O O (CH2)7 HOOC
O
Rosin-tung
(CH2)7 oil Diels-Alder adduct is a yellowish solid. It can be prepared from levopimaric acid
O (CH2)7
and tung oilRosin-tung
according oilto
Diels-Alder
Scheme 82, adduct is ato
prior yellowish solid.
O
precipitation It can
andObe prepared
drying from levopimaric
(CH2)7 [265,266]. acid
Its application is a
and O
O tung oil
O according
(CH2)7 to Scheme 82, prior to precipitation and O drying [265,266]. Its application is a
filler, tackifier
Tung oil and adhesion promoter in polyurethane (CH )
[265] and UV-curable
O adhesives [266].
filler, tackifier
O and adhesion promoter in polyurethane2[265]
7 andO UV-curable
HOOC
(CH2)7
adhesives [266].
O
(CH2)7
O O O (CH2)7 HOOC
Levopimaric acid HOOC
HOOC O
O (CH2)7
Tung oil HQ; 170-260°C; 4-7h (CH2)7
O
HOOC Rosin-tung oil adduct
O
O O (CH2)7 conversion: 72%
O Scheme 82. Preparation Levopimaric
of idealized
O HOOC acid rosin-tung oil
O Diels-Alder
(CH2)7 adduct. HOOC
(CH2)7
HQ; 170-260°C; 4-7h O O (CH2)7
Rosin-tung oil adduct
O conversion: 72%
Tung oil Scheme 82. Preparation of idealized (CH
rosin-tung
2)7
O
oil Diels-Alder
HOOC adduct.
Levopimaric acid HOOC

HOOC
HQ; 170-260°C; 4-7h Rosin-tung oil adduct
conversion: 72%
Scheme 82. Preparation of idealized rosin-tung oil Diels-Alder adduct.
Scheme 82. Preparation of idealized rosin-tung oil Diels-Alder adduct.
Molecules 2019, 24, 1651 36 of 52
Molecules
Molecules 2019,
2019, 24,24, x FOR
x FOR PEER
PEER REVIEW
REVIEW 36 36
of of
51 51
Acrylic-vinyl
Acrylic-vinyl
Acrylic-vinyl copolymer
copolymer
copolymer with
with rosin
with moieties
rosin
rosin is aisslightly
moieties
moieties is yellow
a slightly
a slightly solid.
yellow
yellow It can
solid.
solid. be
It It
can prepared
can
bebe from from
prepared
prepared rosin
from
ethyl
rosinmethacrylate,
ethyl styrene
methacrylate, and divinylbenzene
styrene and according
divinylbenzene to Scheme
according to83, prior
Scheme
rosin ethyl methacrylate, styrene and divinylbenzene according to Scheme 83, prior to washing, to washing,
83, prior tofiltration
washing,
and drying
filtration
filtration [267].
and
and Its application
drying
drying [267].
[267]. ItsIts isapplication
polymerismicrospheres
application is polymer
polymer for adsorption
microspheres
microspheres and
forfor separation
adsorption
adsorption [267].
and
and separation
separation
[267].
[267].
PDI=1.30-3.25
PDI=1.30-3.25 O O
O O C C
O O O O
( ( )m()m( )n )n
C C O O
O gelatin, toluene, AIBN
O O O gelatin, toluene, AIBN
O O in2O
in H H 2O
Rosin
Rosin ethyl
ethyl methacryalte
methacryalte 80-90°C,
80-90°C, 5h 5h
( ( )m()m( )n )n
Acrylic-vinylO O
Acrylic-vinyl O O
microspheres O O
microspheres C C
with
with rosin
rosin moieties
moieties O O
Scheme
Scheme 83.83. Preparation
Preparation
Preparation ofof
of acrylic-vinyl
acrylic-vinyl
acrylic-vinyl copolymer
copolymer
copolymer with
with rosin
rosin moieties.
moieties.
Rosin/lignin
Rosin/lignin
Rosin/lignin grafted
graftedcopolymers
grafted copolymers can can
copolymers becan
prepared from lignin
bebeprepared
prepared from
from and dehydroabietic
lignin
lignin acid derivatives
anddehydroabietic
and dehydroabietic acid
acid
in two ways:
derivatives
derivatives in insimple
twotwo grafting
ways:
ways: simple
simple or ATRP
grafting
grafting polymerization,
oror ATRP
ATRP according
polymerization,
polymerization, to Scheme
according
according to to 84 and
Scheme
Scheme using
8484 and
and such
using
using
separation
such methods
separation as precipitation,
methods as filtration,
precipitation, washing and
filtration, vacuum
washing drying
and [169].
vacuum
such separation methods as precipitation, filtration, washing and vacuum drying [169]. These These
drying materials
[169]. are
These
characterized
materials
materials areareby strongly
characterized increased
characterized byby hydrophobicity
strongly
strongly increased
increased compared to
hydrophobicity
hydrophobicity raw lignin
compared
compared [169].
to to raw
raw lignin
lignin [169].
[169].
O O X =X2=or2 4or 4
O O Y =YH-
= H- or CH
or CH 3- 3
-
O O O O O O O O
COCl
COCl LIGLIG
(CH(CH 2)XO
2)XO
(C2(C
H52)H3N
5)3N O O O O
O O
in
in THF THF
50°C, Br Br
( ( )L )L
50°C, 12h12h
Y Y O O
O O
OHOH O O O O Y Y
O OLIGLIG O O
LIGLIGOHOHBr Br O O
O O O ( ( )L )Br Br
L
OHOH O OLIGLIG O O
Br Br Br Br O
O (CH
(CH O )
2)X 2 X
Lignin
Lignin (C2(C
H52)H3N
5)3N O O O O O O O O O
Br Br O O O O ( O O O
in THF
in THF (CH(CH )
2)x 2 x
( O (CH )
0°C, 24h Br Br O O O (CH 2)X 2 X
0°C, 24h ) O
Lignin
Lignin ATRP
ATRP O O )L L Br O
LIG( OH) = HOHO CuBr Br
LIG( OH) 3 =3 CuBr Y Y
macroinitiator
macroinitiator in THF
in THF O O Y Y
OHOHOHOH 65°C,
65°C, 24h24h
O O
O O Rosin
Rosin
O O polymer
polymer grafted
grafted from
from lignin
lignin
HOHO O O
O O MnMn=5470-56
=5470-56 400400 g/mol
g/mol
O O
OHOHOHOH
Scheme
Scheme 84.84. Preparation
Preparation
Preparation ofof
of lignin
lignin
lignin materials
materials
materials hydrophobized
hydrophobized byby rosin.
rosin.
Rosin-caprolactone
Rosin-caprolactone diblock
diblock
diblock copolymers
copolymers
copolymers can be canbebeprepared
prepared
can prepared
from fromdehydroabietic
dehydroabietic
from dehydroabietic
ethyl methacrylate, ethyl
ethyl
methacrylate,
ε-caprolactone
methacrylate, ε-caprolactone
and 2-hydroxyethyl
ε-caprolactone andand 2-hydroxyethyl
2-bromoisobutyrate
2-hydroxyethyl 2-bromoisobutyrate
according to Scheme
2-bromoisobutyrate according
according to to
85 prior toScheme 8585 prior
precipitation
Scheme prior
and
to to precipitation
washing [170].
precipitation and washing
They can
and washing [170].
be They
[170]. They
applied can be applied
caninbeareas
applied in
designed areas
in areasfor designed for
simultaneously
designed simultaneously
bio-based bio-
for simultaneously bio-
and
based
based and
biodegradable
and biodegradable materials
materials [170].
biodegradable materials [170].
[170].
Acrylpimaric
Acrylpimaric
Acrylpimaric acid
acid
acid hydroxyethyl
hydroxyethyl
hydroxyethyl polyesters
polyesters
polyesters areare light
light yellow
yellow solids.
solids. They
They
They can
can
can bebe
be prepared
prepared viavia
polycondensation
polycondensation of
polycondensation of corresponding
of corresponding acrylpimaric
corresponding acrylpimaric
acrylpimaric diols diols according
diols according
according to to Scheme
to Scheme
Scheme 86 86 prior
86 prior
prior to to grinding,
to grinding,
grinding,
washing
washing and
and drying
drying [138].
[138]. Such
Such polymers
polymers can
can bebe potentially
potentially applied
applied in in
thethe modern
modern electrical
electrical andand
electronic industries, especially for the environmentally friendly green products
electronic industries, especially for the environmentally friendly green products [138]. [138].
Molecules 2019, 24, 1651 37 of 52

Molecules 2019,
washing and 24, x FOR [138].
drying PEER REVIEW
Such polymers can be potentially applied in the modern electrical 37 ofand
51
electronic industries, especially for the environmentally friendly green products [138].
Furthermore, rosin can be pyrolized in order to prepare a matrix for silver nanoparticles to apply
Furthermore,rosin
Furthermore, rosincan
canbebepyrolized
pyrolizedinin order
order toto prepare aa matrix for silver
silvernanoparticles totoapply
as antibacterial filler for wooden furniture or air prepare
filter for matrix
indoors for[268], ananoparticles
catalyst carrier apply
with
as antibacterial filler for wooden furniture or air filter for indoors [268], a catalyst carrier with
as antibacterial filler for wooden furniture or air filter for indoors [268], a catalyst carrier
potential application as counter electrode for dye-sensitized solar cells [269], a coating for bentonite with potential
potential application as counter electrode for dye-sensitized solar cells [269], a coating for bentonite
application
particles as counter electrode for dye-sensitizedfor solar cells [269], a coating for bentonite particles and
particlesand andsupport
support forfor Fe
Fe22O
O33 nanoparticles chromium
nanoparticles for chromium ions
ions adsorption
adsorption [270],and
[270], and activated
activated
support
carbons for Fe2 O3 nanoparticles for chromium ions adsorption [270], and activated carbons [271,272].
carbons[271,272].
[271,272].
Dehydroabietic
Dehydroabietic
O
O
Br
Br O O
O
O
ethyl
ethylmethacrylate
methacrylate O OO
)n
O Br ( )m OO
)n
(DAEMA) OO O
O
O
O Br ( )m OO
(DAEMA) HO
HO OO
CuBr
CuBr // tris(2-(dimethyl-
tris(2-(dimethyl- Sn(II)2-ethyl-
Sn(II) 2-ethyl- OO
OO amino)ethyl)amine
amino)ethyl)amine hexanoate
hexanoate
O in
in toluene
toluene
O
120°C, 16h16h OO
OO OO
Rosin-caprolactone
Rosin-caprolactone
M
Mnn=4700-22
=4700-22 800 g/mol
(
(
diblock copolymer
diblock copolymer HH
Scheme 85.
85.Preparation
Scheme85.
Scheme of rosin-caprolactone
Preparation of
Preparation rosin-caprolactone diblockcopolymer.
rosin-caprolactone diblock
diblock copolymer.
copolymer.
Acrylpimaric acid
Acrylpimaric acid
hydroxyethyl ester
hydroxyethyl ester COO COO
COO Acrylpimaric
Acrylpimaricacid
acid
cat.
cat. hydroxyethyl
yield:86%
yield: 86% vacuum
hydroxyethyl
vacuum polyester
OO <245°C
<245°C polyester
OO yield:
OO
OH
OH 8h
8h OO HH yield:91%
91%
(C2H5)3N COOH
COOH MM (experimental) = 418
COOH (C2H5)3N HO
HO CC nn (experimental) = 418
COOH 165°C,1.5h
1.5h (C2HH)N nn
165°C, OO O
(C 2 55)33N
OO
O 165°C, 1.5h
OO 165°C, 1.5h
COO
COO COO
COO
cat.
cat.
Acrylpimaric
Acrylpimaricacid
acid
vacuum HO dihydroxyethyl
COOH vacuum HO dihydroxyethyl
COOH <245°C
OH
OH OH <245°C
10h O H polyester
polyester
Acrylpimaric OH O H
Acrylpimaric Acrylpimaric COO 10h yield: 70%
Acrylpimaric COO O C yield: 70%
acid acid dihydroxyethyl ester yield: 82% O C n MM
n (experimental) = 462
acid acid dihydroxyethyl ester yield: 82% O
O n n (experimental) = 462
Scheme86.
Preparation of acrylpimaric acid
acid hydroxyethyl
hydroxyethylpolyester.
polyester.
Scheme 86. Preparation of acrylpimaric acid hydroxyethyl polyester.
4.4.Conclusions
Conclusions
4. Conclusions
Rosin
Rosinisisaahighly
highlymodifiable
modifiableraw raw material
material forfor both
both low
lowmolecular
molecularweight weightproducts
productsand andpolymers.
polymers.
Rosin origin
ItsItsnatural is a highlyis modifiable raw
accompanied with material
low forand
price bothalow molecular
diterpene weightnature,
chemical products andispolymers.
which readytoto
natural origin is accompanied with low price and a diterpene chemical nature, which is ready
Its natural
introduce origin is accompanied with low price and a diterpene chemical nature, which
many ready
is to
introduceuseful
useful reactive
reactivechemical
chemical groups,
groups,and and
it exhibits a stiffaconstitution
it exhibits improving
stiff constitution improving thermal,
many
introduce
physical, useful
thermal,mechanical reactive
physical, mechanical chemical
and functional groups,
properties
and functional and it exhibits
of the final
properties of the a stiff
materials. constitution
In recent
final materials. improving
yearsyears
In recent many
rosin-based
rosin-
thermal,
chemicals physical,
have mechanical
attracted growing and functional
interest. Theyproperties
offer greatof the final
opportunities
based chemicals have attracted growing interest. They offer great opportunities to produce materials.
to In
produce recent
usefulyears rosin-
products:
useful
based
resins, chemicals
curing
products: have
agents,
resins, attracted
surfactants,
curing growing interest.
medicines, medicines,
agents, surfactants, They
biocides, materialsoffer great
biocides,for opportunities
biomedical
materials to
application,
for biomedical produce useful
elastomers,
application,
products:
coatings, resins,
adhesives,
elastomers, curing
coatings, agents,
sorbents
adhesives,andsurfactants,
catalysts.and
sorbents medicines,
catalysts.biocides, materials for biomedical application,
elastomers,
Takingcoatings,
Taking into adhesives, the
intoconsideration
consideration sorbents
the declared and properties
declared catalysts.
propertiesofofthethe prepared
prepared chemicals
chemicals theythey
seemseem to beto
Taking
becompetitive
competitive into consideration
alternatives
alternatives to to the declared
existing
existing properties
products
products on onthe the of the
market.
market. prepared
This This
review chemicals
review they
presents
presents seem
well to
well over over
100 be
competitive
100reproducible
reproduciblealternatives
recipes.
recipes. to existing
Sadly, some
Sadly, some products
of ofthethe on thedo
publications
publications market.
donot
not This complete
contain
contain review
complete presents
data, wellmakes
data,which
which over
makes 100
itit
reproducible
difficult to recipes.
repeat Sadly,
the some
syntheses. of the
According publications
to our do not
subjective contain
opinion,
difficult to repeat the syntheses. According to our subjective opinion, the following information shouldcomplete
the data,
following which makes
information it
difficult
beshould
providedto repeat
be provided
(or obvious) the syntheses.
(or for
obvious)
a recipeforAccording
toaberecipe to
considered our subjective
be considered
as complete: opinion,
asproduct
complete: the following
product
name, productname,information
product
morphology,
should be provided
morphology,
substrate(s) names, (or obvious)
substrate(s)
reaction names,
scheme, forcatalyst,
a recipe
reaction to becatalyst,
scheme,
media, consideredmedia,
temperature, aspressure,
complete:
temperature, product
time, pressure,name,
yield and time, product
yield
separation
morphology,
and separation substrate(s)
techniques. names,
Figure reaction
2 shows scheme,
the catalyst,
number of media,
complete
techniques. Figure 3 shows the number of complete and incomplete recipes in the individual parts temperature,
and incompletepressure,
recipestime,in yield
theof
and
this separation
individual techniques.
parts of this review.
review. Interestingly, Figure 2 shows
Interestingly,
the highest number thethe number of
highest number
of complete complete
recipes of and
complete
(both incomplete
absolute recipes
and (bothrecipes
relative) canthe
in
absolute be
individual
and relative)
found among parts of be
can thisfound
hardeners, review.
resins Interestingly,
among hardeners,
and monomers, theresins
highest
and andnumber
also monomers,
biologicallyof complete
and also
active recipes (bothThe
biologically
compounds. absolute
active
most
andcompounds.
common relative)
missingThe
can mostbe common
found
parameter among missing
is yield. Aparameter
hardeners,
large resinsis yield.
number andofA large number
monomers,
incomplete and ofalso
recipes incomplete recipes
inbiologically
macromolecular in
active
macromolecular compounds section may result from the fact that
compounds. The most common missing parameter is yield. A large number of incomplete recipes in polymerizations are often carried
out in order to achieve
macromolecular compounds appropriate
sectionmaterial
may result properties,
from thenot specific
fact yields. The summary
that polymerizations presented
are often carried
out in order to achieve appropriate material properties, not specific yields. The summary presented
Molecules 2019, 24, 1651 38 of 52

compounds section may result from the fact that polymerizations are often carried out in order to
achieve appropriate
out in order material
to achieve properties,
appropriate notproperties,
material specific yields. The summary
not specific yields. Thepresented
summaryinpresented
Figure 3
shows that
in Figure resins, that
2 shows monomers, hardeners and
resins, monomers, biologically
hardeners active compounds
and biologically are the mostare
active compounds completely
the most
described rosin-based chemicals in the recent decade, which makes them the
completely described rosin-based chemicals in the recent decade, which makes them themost promising subjects
most
for scaling-up and commercialization. However, this does not change the fact that rosin chemistry
promising subjects for scaling-up and commercialization. However, this does not change the fact that is
able
rosintochemistry
deliver a serious
is able amount of new
to deliver environmentally-friendly
a serious solutions in many fields
amount of new environmentally-friendly of science,
solutions in
medicine and engineering. The current review confirms this, and encourages further intensive
many fields of science, medicine and engineering. The current review confirms this, and encourages research
on rosinintensive
further in the near future.on rosin in the near future.
research
Figure 2.
3. Number
Number of
of complete
complete and
and incomplete
incomplete recipes
recipes presented in this review.
review.
Funding: This work was financially supported by National Centre for Research and Development (project no.
Abbreviations:
LIDER/7/0045/L-8/16/NCBR/2017).
AA, adipic acid;
Conflicts of Interest: The authors declare no dihydrochloride;
AIBA, 2,2′-azobis(2-methylpropionamidine) conflict of interest.
AIBN, 2,2′-azobisisobutyronitrile;
Abbreviations
ATRP, atom transfer radical polymerization;
BA, butyl acrylate;
AA Bu, butyl
adipic acid; group; cat., catalyst;
DA,
AIBA dehydroabietic 0 acid; DBU, 1,8-diazabicyclo[5.4.0]undec-7-ene;
2,2 -azobis(2-methylpropionamidine) dihydrochloride;
DCC,
AIBN 0
N,N′-dicyclohexylcarbodiimide;
2,2 -azobisisobutyronitrile;
DDPD, dehydroabietyl
ATRP phosphate
atom transfer diester;
radical DMAP, 4-dimethylaminopyridine;
polymerization;
DMF, dimethylformamide;
BA butyl acrylate;
DMSO, dimethylbutyl
Bu sulfoxide;
group;
Cat. catalyst;
EC, ethyl cellulose;
DA dehydroabietic
EEW, epoxy equivalent weight; acid;
DBU
Et, ethyl group; 1,8-diazabicyclo[5.4.0]undec-7-ene;
DCC N,N0 -dicyclohexylcarbodiimide;
HDMA Cl, hexadecyltrimethylammonium chloride;
DDPD
HDTMAB, hexadecyldehydroabietyl phosphate diester;
trimethyl ammonium bromide;
DMAP 4-dimethylaminopyridine;
HPI, hydrophilic polyester intermediate;
DMF dimethylformamide;
HPLC, high-performance liquid chromatography;
DMSO dimethyl sulfoxide;
HQ, hydroquinone;
EC ethyl cellulose;
IPA, isophtalic acid;
EEW epoxy equivalent weight;
JCR, Journal Citation Reports;
Et ethyl group;
m.p., melting point; Me, methyl group;
HDMA Cl hexadecyltrimethylammonium chloride;
MEK, methyl ethyl ketone; MPA, maleopimaric acid;
HDTMAB hexadecyl trimethyl ammonium bromide;
NMP, N-methyl pyrrolidone;
HPI hydrophilic polyester intermediate;
NMR, nuclear magnetic
HPLC resonance;liquid chromatography;
high-performance
NPG,
HQ neopentyl glycol;
hydroquinone;
PAA, poly(acrylic acid);
PEG, poly(ethylene glycol);
Ph, phenyl group;
PMDETA, pentamethyldiethylenetriamine;
Molecules 2019, 24, 1651 39 of 52
IPA isophtalic acid;

JCR Journal Citation Reports;
m.p. melting point;
Me methyl group;
MEK methyl ethyl ketone;
MPA maleopimaric acid;
NMP N-methyl pyrrolidone;
NMR nuclear magnetic resonance;
NPG neopentyl glycol;
PAA poly(acrylic acid);
PEG poly(ethylene glycol);
Ph phenyl group;
PMDETA pentamethyldiethylenetriamine;
PPh3 triphenylphosphine;
PSA pressure sensitive adhesives;
pTSA p-toluene sulfonic acid;
RAFT reversible addition-fragmentation chain-transfer polymerization;
ROMP ring-opening metathesis polymerization;
UV ultraviolet;
TBA Br tetrabutylammonium bromide;
TEBAC benzyltriethylammonium chloride;
THF tetrahydrofuran;
TMP trimethylolpropane;
TPT tetraisopropyl titanate;
TRL technology readiness level;
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© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

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molecules

Keywords: rosin; curing agent; resin; surfactant; biocide; medicine; polymer

Molecules 2019, 24, 1651; doi:10.3390/molecules24091651 www.mdpi.com/journal/molecules

Molecules 2019, 24, x FOR PEER REVIEW 2 of 51

COOH COOH COOH COOH

A) Abietic acid B) Levopimaric acid C) Palustric acid D) Neoabietic acid

Molecules 2019, 24, x FOR PEER REVIEW 4 of 51

Abietane-type Acids Content (wt.%) Other Acids

3.1. General Comments on the Whole Review

3.2. Small and Medium Molecule Compounds

3.2.2. Resins and Monomers

Scheme 2. Synthesis of triglycidyl ester of maleopimaric acid.

COOH COOH COOH Rosin OO

Acrylate resin based on epoxidized maleopimaric-trimethylolpropane adduct can be prepared

Dehydroabietic ethyl methacrylate is a white powder. It can be prepared from dehydroabietyl

Rosin acid in ethanol

Scheme 16. Preparation of ethylene glycol maleic rosinate acrylate.

Molecules 2019, 24, x FOR PEER REVIEW 11 of 51

significant thermal 2. (CH2O)n

systems. Moreover, rosin-based anhydrides are non-toxic, as opposed to conventional anhydride

Methyl abietate Abietic Levopimaric

Scheme 31. Preparation of rosin bisquaternary ammonium salt.

S NH2 Scheme 40. Synthesis of rosinRacid amides

Maleated rosin-based dithioureacompounds

Molecules 2019, 24, 1651 22 of 52

[218]. They can be used

HOOC Scheme 47. 70°C of Nacrylpimaryl

Molecules 2019, 24, x FOR PEER REVIEW 25 of 51

The rosin derivative quaternized poly-(N,N-dimethylaminoethyl methacrylate) can be prepared via

O O butyl acrylate (BA) instead of BA

C4H9 O also works

Rosin alcohols are colorless prepared O(CH

Molecules 2019, 24, x FOR PEER REVIEW 28 of 51

is polymerization, or block copolymerization with norbornene, via “living” ring-opening metathesis

3.3.3. Coatings and Adhesives

Poly(acrylic acid) Mn=?=? activation) ( )n (nucleophilic addition

Rosin glycidyl esterScheme is 71.

Levopimaric acid HOOC

Molecules 2019, 24, x FOR PEER REVIEW 37 of 51

Molecules 2019, 24, x FOR PEER REVIEW 38 of 51

IPA isophtalic acid;

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