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Phenol-Formaldehyde Resins: Properties, Fields of Application, and Methods of

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Article in Catalysis in Industry · April 2021

DOI: 10.1134/S2070050421020033

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ISSN 2070-0504, Catalysis in Industry, 2021, Vol. 13, No. 2, pp. 119–124. © Pleiades Publishing, Ltd., 2021.
Russian Text © The Author(s), 2021, published in Kataliz v Promyshlennosti.

CATALYSIS IN CHEMICAL AND PETROCHEMICAL INDUSTRY

Phenol-Formaldehyde Resins: Properties, Fields of Application,

and Methods of Synthesis
P. V. Berdnikovaa, *, E. G. Zhizhinaa, and Z. P. Paia
a Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
*e-mail: polina@catalysis.ru
Received June 1, 2020; revised June 30, 2020; accepted July 1, 2020

Abstract—This review considers the current situation in the market of phenol-formaldehyde resins, which
serve as a basis for a wide range of binders, whose properties can be varied to obtain different materials for
certain technological problems. The properties, types, and application fields of phenol-formaldehyde resins
are characterized, and their advantages, disadvantages, and more promising potential analogues are dis-
cussed. The relevance and prospects of studies on the development of new processes and the upgrading of
existing ones for the production of phenol-formaldehyde resins by both varying the process conditions and
selecting the best catalyst are shown.

Keywords: phenol-formaldehyde, novolac, resole resins, acid-base catalysis

DOI: 10.1134/S2070050421020033

INTRODUCTION A disadvantage of this type of resins is the toxicity

of their main components, and the requirements for
Synthetic resins (SR), obtained via reactions of product quality in today’s world are constantly grow-
polycondensation and polymerization, adhere ing [4–9]. Manufacturers have to give great attention
strongly to a great many materials. They possess high to the compositions of the resins that are used and the
mechanical strength and are resistant to water, chem- technologies for preparing them.
icals, and heat. They are used as binders for composite
materials, adhesives, and in the paint and varnish The problem of toxicity can be partially solved by
industry. A wide range of possible combinations of dif- replacing PFR with urea-formaldehyde (UFR) and
ferent types of resins (urea, alkyd, epoxy, polyamide, melamine-formaldehyde resins (MFR), which are
phenol-formaldehyde) and additives allow us to products of the polycondensation of urea and
obtain materials with different technological and per- melamine with formaldehyde. Even though MFR are
formance characteristics that can be transferred to more environmentally friendly and provide the mois-
products made from them [1–3]. The demand for res- ture and weather resistance required for products, the
ins grows from year to year, along with the industries demand for phenol-formaldehyde resins is still quite
that consume them [1, 4, 5]. high in Russian industry. This is explained by
melamine, whose main raw material is urea, being
Along with other members of the class of synthetic produced in insufficient quantities in Russia. It is
resins, phenol-formaldehyde resins (PFR), which more expensive than phenol, and adhesive layers
belong to the group of phenolic resins, are widely used cured with MFR are more rigid than ones produced
in a number of industries. The advantages of PFR with PFR, affecting the durability of materials [5, 8].
include low costs; the availability of raw materials; ease The search for ways of improving the processes for the
of synthesis; and high capacities for wetting, impregnat- synthesis of PFR therefore remains relevant today.
ing, and solubility, allowing them to combine with According to forecasts [5], the Russian market for
almost all materials in their initial state. Products all types of formaldehyde resins will continue to grow,
obtained with PFR are chemically inert and resistant to and should total 2 million tons by 2025. In 2016, the total
water, heat, and fire. They have good electrical insulat- production of PFR in the Russian Federation was
ing properties and high mechanical strength [5, 6]. 375 thousand tons. The main Russian producers of PFR
PFR are most widely used as binders and adhesives are companies of the Metadynea group: Metafrax,
in the production of wood-based panels; casting Gubakha, Perm oblast; Hexion-Schekonazot, Pervo-
molds and rods; heat-insulating materials; laminated maisky, Tula oblast; Uralchimplast, Nizhny Tagil,
plastics, paints and varnishes; and abrasive, refractory, Sverdlovsk oblast; and Pigment, Tambov [5, 6]. It
and other materials (Fig. 1) [5]. should be noted that many woodworking enterprises

119
120 BERDNIKOVA et al.

35%—Woodworking industry (production porous materials and improve the elasticity of cured
of plywood, fiberboard, chipboard, etc.) materials. Different modifying additives ensure the
required dry specific properties of an adhesive’s compo-
14%—Injection molding products sition (e.g., resistance to water, electrical conductivity).
13%—Thermal insulation materials (mineral wool) PFR are liquid or solid oligomeric products of the
polycondensation of phenol, its homologs (cresols,
12%—Laminated plastics (textolite, fiberglass, etc.)
xylenols), and polyatomic phenols (e.g., resorcinol)
with aldehydes (formaldehyde or furfural). Of the
26%—Other (production of paintwork materials, greatest practical importance are PF resins obtained
abrasives, friction products, refractory materials, from phenol itself and formaldehyde. Depending on
foamed plastics, etc.)
the nature of the catalyst and the ratios of the compo-
nents, PFR reactions are divided into two types. These
are thermoplastic (reversibly curing) novolac resins
when using acid-type catalysts (e.g., hydrochloric,
26% sulfuric, oxalic), and thermosetting (irreversibly
35%
cured) resole resins when using alkaline catalysts
(ammonia, ammonium, sodium or barium hydroxide)
[12]. The general scheme for the formation of novolac
12% and resole resins is shown in Fig. 2 [11].
It should be noted that resole polymers form even
13% 14% in an acidic medium when the phenol : formaldehyde
ratio is reduced. Each type of resin (novolac and
resole) can also transform into the other. If a novolac
resin obtained from a trifunctional phenol is treated
with an excess of formaldehyde in the presence of an
alkaline catalyst, a resole is obtained from it or directly
Fig. 1. Applications of phenol-formaldehyde resins.
from a resite. On the other hand, the resole converts to
novolac resin when treated with excess phenol.
have their own resin production (e.g., Syktyvkar Ply- Novolac PFR are produced mainly in the form of
wood Mill; Sveza Uralsky, Perm oblast; Norilsk Sup- press powders; resole PFR, in the form of press pow-
port Complex [6]). ders, molding masses, and other primary forms [6].
According to the study “Market for Phenol-Form-
aldehyde Resins in Russia: Research and Forecast up 1. NOVOLAC PHENOL-FORMALDEHYDE
to 2024” [10], there was an increase in foreign produc- RESINS
tion of PFR in 2019 and a general drop in the produc-
tion of PFR by domestic producers. This led to a 1.1. Properties of Novolac Phenol-Formaldehyde Resins
reduced supply in the domestic market. The share of At room temperature, novolac resins are solid, brit-
imported products in the Russian Federation thus tle substances with densities of ~1200–1220 kg/m3.
grew by 6% and totaled 32000 tons in 2019. The main They are readily soluble in ethanol and acetone, and
importers of PFR to the Russian market are Finland their color depends on the type of catalyst used in syn-
and China, whose share of all imports is 76%. thesizing them. Light resins are obtained when using
PFRs are most often produced using the technol- organic acids (e.g., oxalic); dark brown ones, when
ogy of batch production. In general, the process con- using hydrochloric and sulfuric acids. Depending on
sists of the preparation and loading of raw materials; the conditions of preparation, novolac resins differ by
the condensation of phenol with formaldehyde and melting temperature (dropping point, 95–115°C);
the formation of phenol alcohols; subsequent poly- content of unreacted phenol (2–9%); solubility (in
condensation with the formation of resin; and cooling, phenols, alkali solutions, alcohols, ketones); and solu-
draining and packaging the resin [1, 5, 11, 12]. tion viscosity. When heated, novolac resins transform
Adhesives made from resins can have one compo- into a liquid, mobile state. When cooled, they solidify;
nent (pure resins) or two (a hardener, filler, or sol- when reheated, they melt again [11].
vent). In addition to resin and hardener, multicompo- Novolac resins are predominantly linear oligomers
nent compositions contain a variety of modifying and in whose molecules oxybenzene (phenolic) cores are
other additives [8, 13]. Hardeners allow the resin to connected by methylene bridges. The end groups in
transition to the cured state with the speed and degree these resins are almost always phenolic groups
of curing required for a particular process. The use of (−C6H4OH). Methyl groups (−CH2OH) at the end of
solvents (e.g., water, alcohol, acetone) allows us to novolac oligomer chains are rare (unlike resole resins).
reduce the viscosity and concentration of a binder. Methylene bridges connecting the –C6H3(OH)
Fillers can solve the problem of adhesive absorption by groups can be in the ortho- and para-positions with

CATALYSIS IN INDUSTRY Vol. 13 No. 2 2021

 PHENOL-FORMALDEHYDE RESINS: PROPERTIES, FIELDS 121

PHENOL + ALDEHYDE

with bifunctional phenols

of the phenol component

saturated homologues of

of trifunctional phenols
also with trifunctional
(at a lack of aldehyde,

Only in the presence

At pH > 7; an excess
with formaldehyde
of formaldehyde

of formaldehyde
Predominantly

Predominantly

Predominantly

Predominantly

or unsaturated
(with CH2O)
At an excess

at an excess
with higher

and pH < 7
At pH < 7

aldehydes

aldehydes
phenols)

Novolac Resol
Addition of a formaldehyde excess (if novolac
is synthesized on the basis of trifunctional phenols)
Resitol
Addition of a phenol excess and transition of alkaline
reaction into acidic one
Resite

Fig. 2. General scheme for the formation of novolac and resole resins [11].

OH OH OH
CH2 CH2 CH2

OH HO OH
2.2' 2.4' 4.4'

Fig. 3. Variants of the arrangement of methylene bridges in novolac oligomers.

respect to the hydroxyls of these groups (Fig. 3). The mers and polymer homologs [11]. The condensation
ratio of positions 2.2 ', 2.4' and 4.4' in novolac PF res- of phenol with formaldehyde is an exothermic reac-
ins affects its properties [12]. tion in which ~590 kJ is released per 1 kg of phenol [11,
Novolac PF resins are a mixture of oligomers with 12, 14]. Water is a by-product of polycondensation.
a wide range of molecular weights (600 to 1300). This Free formaldehyde (HCHO) is a highly reactive gas
corresponds to contents of 2 to 12 phenolic residues. that is difficult to obtain. It is normally not used to
The molecular weight of novolac resins depends on the obtain PFR; instead, we use either an aqueous solu-
phenol: formaldehyde [11] and falls as this ratio rises. It tion of formaldehyde (formalin containing up to 45%
should be noted that novolac resins distinguished by a HCHO) or solid trimeric paraformaldehyde (para-
narrower molecular weight distribution of oligomers are form) that is 91 to 96% of the basic substance.
obtained in the presence of 1-hydroxyethane-1,1'- Novolac-type PFR can be obtained in either the
diphosphonic acid. periodic or continuous mode. The process for the syn-
Novolac resins transform into an infusible state very thesis of a solid novolac oligomer includes stages of the
slowly at 180–200°C, but quickly when treated with preparation and loading of raw materials, conducting
formaldehyde or urotropin. Oligomers are usually cured the polycondensation reaction, drying the obtained
by heating in the presence of 10–15% urotropine. oligomer, and transferring it to a container for cooling
and grinding. In a mixed liquid raw material (molar
ratio phenol: formaldehyde, 6 : 5 or 7 : 6) [11, 12, 14],
1.2. Synthesis of Novolac Phenol-Formaldehyde Resins an acid catalyst is added until pH = 1.6–2.3. The mix-
The traditional scheme for the synthesis of novolac ture is heated with steam to 55–65°C, after which its
PFR is shown in Fig. 4 [11]. supply is stopped. The initiated polycondensation
Here, n = 4–8. In subsequent condensation, iso- reaction continues for 6−8 hours at around 95°C.
mers of dioxydiphenylmethane react with formalde- Aqueous solutions of oxalic acid are traditional cat-
hyde and phenol, forming a complex mixture of iso- alysts for the production of novolac resins [15]. Inor-

CATALYSIS IN INDUSTRY Vol. 13 No. 2 2021

122 BERDNIKOVA et al.

OH
H2
C OH
OH
CH2OH
OH
OH OH
H2 OH OH
C
(n + 1) + nCH2O H CH2

OH n

H2
HO C OH

CH2OH

o- and p-oxybenzyl Dioxydiphenylmethanes

alcohols

Fig. 4. Traditional scheme for the synthesis of novolac PFR.

ganic acids (e.g., sulfuric [16] or orthophosphoric with acetaldehyde in an acidic medium, 1.1-(dioxy-
[17]) are used less commonly. In the future, however, diphenyl) ethane forms and subsequently condenses to
these acids must be neutralized with aqueous solutions form novolacs.
of alkalis. In some cases, the role of a catalyst is played
by volatile formic acid, which is present as an impurity
in solutions of formaldehyde [18]. 1.3. Application of Novolac Resins
Novolac polymers with regular structures can be Novolac PFR are used as binders for abrasive prod-
obtained when using zinc chloride, zinc acetate, and ucts and shell molds; in the production of adhesives,
certain metal oxides as catalysts of polycondensation. anticorrosive paints, and varnishes; in the production
In later works, reports began to appear on the use of of laminated and other plastics; and in the production
unconventional acidic polycondensation catalysts. of photoresists. Also novolac resins are used in the
Japanese developers began to use 1-hydroxyethane- production of epoxy-novolac resins widely used in the
1,1'-diphosphonic acid in 2001 (Feliox 115) [19]. The electrical and electronic industries [6].
reaction is conducted in nonaqueous or biphasic
media. The solvents in this case include ethylene gly-
col and its ethers, dioxane, and diisobutyl ketone. This 2. RESOLE PHENOL-FORMALDEHYDE
allows the removal of unreacted phenol (which is very RESINS
important) and water from the reaction products. It 2.1. Properties of Resole Phenol-Formaldehyde Resins
was found that the process ends with the complete
conversion of phenol. An alternative way for the syn- The properties of resole resins depend greatly on
thesis of novolacs in the presence of the peroxidase the stage of their production. Resols have molecular
enzyme was also described in [20]. weights of 400 to 1000. The resin is heated when
obtaining products from them. The resol in this case
It was of interest to use acidic heterogeneous catalysts transitions into resitol first, and then into resit. There
for preparing novolac PF resins [21]. These include cat- is an increase in molecular weight, and the polymer
ion exchangers in the H+ form [22], Al2O3/SiO2 [22], acquires a spatial structure due to the formation of
Al/montmorillonite [23], zeolite YNa [24], and acidic methylene bridges and hydrogen bonds.
cesium salts of heteropoly acids [25]. Acidic ion exchange
resins are in some cases used as catalysts [26]. Resol is a liquid or solid oligomer that contains
water and is soluble in ethanol, acetone, acetic acid,
It should be noted that noncatalytic ways for the and aqueous solutions of alkalis. It has an average
synthesis of novolac PFR are also known, but they molecular weight of ≤1000. Resitol obtained at the
require much higher temperatures and pressures next stage is hard and brittle when cold, but at 120–
(385°C and 25 MPa) [27]. 150°C it is still elastic, capable of stretching into long
Reactions between phenol and other aldehydes threads, and partially dissolves in ethanol and acetone.
proceed somewhat differently. When phenol interacts Resit is a polymer that is hard, brittle, infusible and

CATALYSIS IN INDUSTRY Vol. 13 No. 2 2021

 PHENOL-FORMALDEHYDE RESINS: PROPERTIES, FIELDS 123

OH OH
H2
C
OH

CH2OH CH2OH
OH
H2
HO C OH
n + (n + 1) CH2O OH
CH2OH

OH OH
H2
CH2OH C CH2OH

CH2OH CH2OH

...
OH OH H2 C
H2 H2 H2
... C C C ...
OH OH

H CH2 CH2OH
H2C OH

CH2 H2 H2
n ... C C ...

OH

Fig. 5. Scheme for the synthesis of resole oligomers and polymers.

insoluble, and it contains virtually no low molecular Like the novolac oligomers discussed above, resole
weight soluble fractions. oligomers are obtained in a batchwise manner, with
the exception of drying and heat treatment. Phenol is
Resoles range from light yellow to red in color, usually loaded into the reactor at t ≤ 35–40°C, fol-
depending on the catalyst that is used. Their color is lowed by formalin and the catalyst. The molar ratio
light yellow when using barium hydroxide; yellow phenol : formaldehyde is 6: 7 [11, 12, 14]. The reaction
when using aqueous ammonia or organic amines; and
mixture is heated to 60–65°C in 15–20 min. The tem-
red when using caustic alkalis. The density of solid
perature then rises gradually to 80–95°C due to the
resole oligomers is 1250–1270 kg/m3. In comparison, heat of reaction. The polycondensation reaction usu-
novolac resins at room temperature are solid, fragile ally lasts 25 to 60 min [14].
substances with densities of ~1200–1220 kg/m3.
Drying is the most critical operation in the synthe-
sis of resole oligomers. It is done under the highest
2.2. Synthesis of Resole Phenol-Formaldehyde Resins possible vacuum at temperatures no higher than 95–
100°C. After monitoring the finished product accord-
The same phenol and formaldehyde are used to ing to the period of gelatinization, it is poured onto
obtain resole resins, but the catalysts of the process are baking sheets [11, 14]. The yield of rezole oligomers is
alkalis (sodium and barium hydroxides, aqueous 110–130% of the mass of phenols.
ammonia, organic amines). The exothermicity of the
reaction for obtaining resole oligomers is somewhat The scheme for obtaining resole oligomers and
lower (about 335 kJ per 1 kg of phenol). polymers is shown in Fig. 5 [11].

CATALYSIS IN INDUSTRY Vol. 13 No. 2 2021

124 BERDNIKOVA et al.

Glycine can be introduced into the reaction mix- governmental order for Boreskov Institute of Catalysis
ture to reduce the content of free formaldehyde in the (project АААА-А21-121011390007-7).
resin [28].
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