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Self-Initiated UV-Curable Allyl Ether and Vinyl Ether Urethane Monomers

and Oligomers

Conference Paper · March 2019

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Igor V. Khudyakov
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 Self-Initiated UV-Curable Allyl Ether and Vinyl Ether Urethane
Monomers and Oligomers

Igor V. Khudyakov*, Joseph A. Leon, R. David Zopf,

Bomar Specialties

Abstract

We prepared adducts of hydroxylated unsaturated ethers with di- and triisocyantes and tri-, tetra-,
hexafunctional thiols. The presence of a double bond and thiol group in the same molecule
makes it self-initiated. UV-irradiation of such monomers in the presence of air leads to their
polymerization with a formation of films with valuable properties. Adducts of hydroxylated
unsaturated ethers and hydroxylated acrylates with isocyanates were synthesized. These new
oligomers provide tough coatings under cure but require photoinitiators.

Introduction

Free radical photopolymerization of coatings (UV- and visible light cure) usually requires an
®
addition of photoinitiator (PI), which produces free radicals. Our research group develops LS
1-5
oligomers, which are urethane acrylate oligomers with grafted hydroxyl-substituted PI. Grafting
PI to oligomer has advantages over dissolution of the same PI in the same concnetration in a
formulation. Cured coating with grafted PI has low migration and much lower extractability, lower
odor, often-higher rates of photopolymerization. The formulator does not need to dissolve PI in a
viscous formulation, which may be a problem. In some cases PI can be used not as a capping
® ®
agent but as a chain extender incorporated into the backbone (Irgacure 2959, Irgacure 127,
6
substituted benzophenones, others.)
7,8
Vinyl monomers in combination with thiols RSH can undergo UV-cure in the absence of PIs. In
addition, such “thiol-ene” systems have many attractive properties for coatings application, such
as very little dioxygen inhibition, low shrinkage, formation of structurally homogeneous network,
7
high conversion. To the best of our knowledge, thiol-ene systems have found very limited
industrial application.

The present work has two goals. First, we explored multifunctional RSH as grafted PIs in allyl
ether and vinyl ether monomers and prepared (thio)urethanes. Second, we prepared and began
studying the “mixed” multifunctional monomers of allyl/vinyl ethers and acrylates. We searched
for coatings, in which abrasion resistance will be not only due to the presence of multifunctional
acrylates but also due to resilience, which may be provided by unsaturated ethers.
Reagents

Chemical structures of reagents used in this work are presented in the Schemes 1-3:
O O O
SH HS SH
O O O O

HS O O O O
SH HS SH
O O O

TriSH TetraSH

O O
HS SH

HS O O SH
O CH2 O CH2 O
O O O O
HS HexaSH SH
O O

Scheme 1. Chemical structures and name designations of multifunctional thiols RSH

We used two RSH of Evans Chemetics trimethyolpropane tris(3-mercaptopropionate) (TriSH)

and pentaerythritol tetrakis(3-mercaptopropionate) (TetraSH), dipentaerythritol hexa(3-
mercaptopropionate) (HexaSH) of Sakai; two allyl ether compounds of Perstorp: 2,2-
bis(allyloxymethyl)-butan-1-ol (DAE) and pentaerthrytol triallyl ether (TAE). We present in
®
Schemes 1-3 in brackets designations of compounds. Diisocyanate Vestanat IPDI (IPDI),
® ®
triisocyanates Vestanat HT2500/100 (HDT) and Vestanat HB2640/100 (DESN100) were of
Evonik-Degussa, cf. Scheme 2. Pentaethrytol triacrylate PETA (Kowa) is not an individual
compound: it is a mixture of di-, tri- and tetra acrylates; triacrylate PETA (Scheme 2) is the main
component. We used common polyols, and in particular Teraphane 650 (PolyTHF 650) of Invista.
#
Manufacturers provide OH of hydroxy compounds and -NCO content in HDT and DESN100.
There values were confirmed by in-house measurements, and the equivalent weights of reagents
became known. Common reactive diluents were used in a number of cases to decrease viscosity
of oligomer. Scheme 3 lists the diluents: tripropylene glycol diacrylate (TRPGDA), 1-6 hexanediol
diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), all three from Cytec, and triethylene
glycol divinyl ether (DVE-3) of ISP. All compounds were used as received.
 HO O
HO O
O O O

DAE TAE

NCO

HO O CH CH2
CH2 NCO

IPDI HBVE

O
NH (CH2)6 NCO
(CH2)6 (CH2)6 NCO
ONC C O
N N
N (CH2)6 NCO
O N O
C O
(CH2)6 NCO
NH (CH2)6 NCO

HDT DESN100

O
CH 2 O C CH
CH2
O
HOCH2 CH2 O C CH CH PETA
2
CH2 O C CH CH2
O
Scheme 2. Chemical structures and designations of polyisocyanates and hydroxy vinyl
compounds
 O O
H3C CH3
CH2 CH C O C3H6O C CH CH2
3

O CH TRPGDA

H3 C C CH2
CH2 CH O C2H4O O CH CH2
O 3
IBOA
DVE-3
O
CH 2 O C CH
CH2
O O
O
C2H5 CH2 O C CH CH CH2 CH C O CH2 O C CH CH2
2 6
CH2 O C CH CH2
O HDDA
TMPTA

Scheme 3. Chemical structures and designations of reactive diluents

Synthesis, cure of oligomers and evaluation of properties of cured films

We synthesized a number urethane and thiourethane oligomers/monomers in the usual way

9,10
described elsewhere. Briefly, in reactions of polyisocyanates with hydroxyl compounds di-n-
butyltin dilaurate (DBTDL of Arkema under a commercial name Fascat 4202) was used as a
catalyst. All hydroxyl compounds and polyisocyanates (no RSH) were added in one pot in the
presence of DBTDL. Hydroxy allyl and vinyl compounds are highly reactive towards isocyanates.
In the case of using Poly THF 650 and other polyols, polyols were added simultaneously with
hydroxy ene compounds. We will name all our products oligomers below in the sake of brevity of
the presentation.

Mixed oligomers were prepared in two-step synthesis: first, hydroxyl compound reacted with
polyisocyanate in the presence of DBTDL. After that the residual -NCO groups reacted with
multifunctional RSH in the presence tertiary amine catalyst DABCO LV-33 of Air Products. Thus,
such oligomers were mixed urethanes and thiourethanes. RSH was taken in a three-fold excess
in order to (i) avoid gelation of a product and (ii) have free -SH groups for photoinitiation.
Structure of oligomers were confirmed by IR, 1H NMR spectroscopy and by GPC.6,9 We did not
synthesize mixed RSH – acrylate products because such products will be unstable due to
Michael addition of RSH to electron deficient acrylate groups. (Vinyl ethers and allyl ethers are
electron rich compounds.) Polymerizable products of the syntheses were stabilized with the
known inhibitors of spontaneous polymerization (MEHQ, Irganox 1010, stable nitroxyl radical 4-
hydroxy TEMPO, others) added in the concentration of ~100 ppm. Measurement of GPC traces
6,9
and IR spectra of liquid/cured oligomers is described elsewhere.

Cure was performed with Fusion 300 W/in UV-processor with a D- bulb in the air. D-bulb was
found to be the most efficient in our experimental conditions to initiate cure by photolysis of RSH
compared to H-bulb or some other light sources. A cure with PI Omnirad 481 (IGM Resins) was
also performed with D-bulb. We used in this work 2.0% of Irgacure 184 in formulations. We used
triarylsulfonium hexafluorophosphate of Sartomer (cationic PI) in the concentration 3-5% for
cationic cure. Usually we ran three passes at 20 ft/min, and a total radiant exposure of samples to
2
UV-light was ~ 1 J/cm as measured by PowerPuck radiometer.
 6,9
Measurement of mechanical properties of cured oligomers is described elsewhere. We used
the known in the industry “pick test” in order to estimate adhesion of cured oligomers to common
substrates, estimated a number of “MEK double rubs,” measured “Durometer hardness.” All
measurements in this work were performed at room temperature.

Results and Discussion

Scouting experiments were performed with goal to find promising oligomers. By promising or by
high performance oligomers we mean oligomers which impart at least some of the following
properties: good adhesion, toughness, abrasion (scuff, scratch, mar) resistance, weatherability,
tear resistance, chemical resistance, self-initiated cure or easy to cure, not very high viscosity.
Compositions of oligomers and corresponding formulations were optimized in order to get useful
for industrial applications properties by design of experiments (DOE). We describe three
synthesized oligomers below in more detail.

Oligomers A and B

Oligomer A was prepared by a reaction of IPDI with TAE and with an excess of TriSH. In order to
reduce viscosity of A, it was dissolved with 30 wt.% of MEK, applied to a substrate, and MEK was
evaporated. The cure of A is self-initiated, and it is rather efficient. A short irradiation of A
11
demonstrates a relatively long postcure, which was noticed for many urethane acrylates.
B is similar to A with an exception that TetraSH was used in oligomer B instead of TriSH.

Table 1
Properties of oligomers A and B

A B
, cPa (diluted by 30 50 100
wt.% of MEK)
a
Tensile modulus, MPa 9.5 1160
Tensile strength at
a
break, MPa 1.4 26
a
Elongation-to-break, % 28 10
a
Durometer hardness 52A 78A
MEK, double rubs >200 ~30
PI No No
a
Determination error is 10-15%

Figure 1 demonstrates an IR spectrum of A. It can be seen that upon cure allyl group
 0.30

0.25 Oligomer A
allyl
Absorption, arb. units

0.20

0.15

0.10

0.05

0.00

1800 1600 1400 1200 -1

1000 800
Wavenumber, cm

Figure 1. IR spectra of uncured A (solid line) and of cured A (dotted line)

-1
( = 919 cm ) is consumed. A relatively small consumption of allyl groups (Figure 1) leads to a
-1
film. Characteristic bands of –S-H at 2570 cm has low extinction coefficient, and is not observed
in mid IR spectrum of A. Our estimation of Mw of A based on GPC measurement (Figure 2) is

150
Responce, arb. units

100 OIigomer A

50

8 9 10 11
Retention time, min
Figure 2. GPC trace of A.

Mw = 1.6 kg/mol; molecular weight distribution MWD = 1.6.

Oligomer C

C was prepared by a reaction of HDT with PETA and TAE; the two capping agents were taken in
1:1 ratio on equivalent basis. Properties

O
O
H O O
N C O
O

CH2 N C O CH 2 O C CH
CH2
O
H O CH2 C CH2 O C CH CH2
CH2 O C CH CH2
TAE-IPDI-PETA O

Scheme 4. A generic structure of oligomer C. Besides TEA-IPDI-PETA, C includes

TEA-IPDI-PETA and PETA-IPDI-PETA.

Table 2

Properties of diluted oligomer C

Diluent, its wt.% in IBOA, TRPGDA, IBOA, TMPTA, HDDA,

a formulation 30 50 50 50 50
a
, cP 14,500 1,050 1,190 6,500 460
a
Tensile modulus, MPa 9.5 1160
Tensile strength at 35 41 51 36 44
a
break, MPa
a
Elongation-to-break, % 3.4 3.8 3.5 3.0 3.2
a
Durometer hardness 89D 86D 87D 92D 88D
MEK, double rubs ~200 ~200 ~200 ~200 ~200
2.0% of PI Yes Yes Yes Yes Yes
a
Determination error is 10-15%

In our work, adhesion properties of oligomers and formulations are important. Table 3 presents
data on adhesion
 Table 3
Adhesion properties of oligomers A, B and C by pick testa
b b b b b
C, C, C, C, C,
Substrate A B IBOA, TRPGDA, IBOA, TMPTA, HDDA,
30 50 50 50 50
steel 5 2 0 1 1 0 0
aluminum 5 2 0 0 0 0 0
stainless
steel 5 5 0 1 1 0 0
ABS 2 2 0 2 1 4 4
acrylic 2 2 1 1 1 1 0
poly-
carbonate 2 2 1 0 1 0 0
glass 5 5
HDPE 2 1 0 0 0 1 1
a
Results are known to be semiqunatitative
b
Cf. Table 2 for composition of a formulation

Other oligomers

We prepared two trifunctional adducts HDT-HBVE and DESN100-HBVE. A structure of the latter
oligomer is presented below:

H O
NH (CH2)6 N C O O CH CH2
C O H O
N (CH2)6 N C O O CH CH2
C O H O
NH (CH2)6 N C O O CH CH2

DESN100 - HBVE

Scheme 5. A structure of an oligomer DESN100-HBVE, which is an adduct of HBVE with

DESN100.

Both oligomers HDT-HBVE and DESN100-HBVE can we cured with PI in the presence of
TRPGDA, 50 wt.%, with a formation of a tough film.

We compared properties of hexafunctional diadducts PETA-IPDI-PETA and TEA-IPDI-TEA. The

first oligomer gives very tough films. All formulations were diluted either by 30 wt.% IBOA or by
50 wt.% of TRPGDA, and we compared properties of oligomers diluted with the same diluent. We
have observed that, in accordance with the expectations, a 1:1 by mass mixture of PETA-IPDI-
PETA and TEA-IPDI-TEA and oligomer C (Scheme 4) manifests intermediate mechanical
properties between those of individual oligomers.

It was observed that polyisocyanates capped by DAE demonstrate much lower tensile modulus
and lower toughness compared to polyisocyanates capped by TAE. An obvious explanation is
that higher functionality of oligomer leads to higher crosslink density and in turn to a higher
modulus/toughness.

We were looking for possible advantages of binding thiols and vinyls into one urethane oligomer
vs. the same thiol-vinyl as a mixture under the same equivalent ratio of vinyl : -SH groups in both
cases. It was found that cured urethane oligomers possess essentially higher toughness, tensile
modulus and hardness. The probable reason is the properties impart by the “hard” urethane
9
segments.

It was mentioned above, that oligomers A and B have high viscosity . Fortunately, a relatively
small amount of MEK was required to decrease their  dramatically, cf. Table 1. A and B can be
applied as solventless coatings in the presence of reactive diluents. We have found that DVE-3
and IBOA dilute effectively dilute A and B. It turned out that thiol groups of A and B have
relatively long pot life in the presence of acrylate IBOA. Many formulations had the desired 1:1
7,8
equivalent ratio of ene: -SH groups.

We studied changes in IR spectra of formulation including reactive groups –SH, acrylates,

vinyl/allyl oxides under cure with PI. At present, we do not report consumption of thiols. We have
observed that acrylates are almost completely disappearing under the cure, whereas a decrease
of vinyl/allyl groups was much 20-50% in our experiments (cf. Figure 1 as an example.) We
mean by “cure” a formation of a film, which can be delaminated from a substrate. (It is well-
4,11
known, that formation of a film can occur under low degree of polymerization. )

It can be expected that oligomers (formulations) with electron rich vinyl/allyl oxides can be cured
cationically with a cationic PI. However, we observed only gelation of a formulation under cure
without a formation of a film so far. Electron rich R–S; –S–H and N–H groups of oligomers can
interfere with the cationic cure. However, we continue study of cationic cure of our products.
Preliminary results demonstrate that under certain conditions our oligomers can be cured
cationically. Moreover, a reaction slowly proceeds outside the irradiated area.

Synthesis of oligomers with PolyTHF 650 and other polyols led to a decrease of hardness and
toughness of films based on such oligomers, and the use of polyols seems not promising.
Oligomers with HexaSH were unstable, prone to gelation.
 Conclusions

Prepared oligomers were cured by UV- light initiated polymerization via free-radical way (high
efficiency) and as well as by cationic way (poor efficiency so far). Properties of cured films based
on thiol-vinyl oligomers strongly depend upon the nature of thiol (TriSH or TetraSH, cf. Table 1).
A synthesis of thiol- vinyl urethanes oligomers was performed the way that the monomer has
grafted thiol groups. Properties of oligomers (cured films) strongly depend also on the
composition of oligomer (ratios of grafted hydroxy vinyl to grafted thiol groups and to free RSH.)
These monomers are self-initiated (so called “thiol-ene” chemistry); they do not require
photoinitiator under UV-cure. Contrary to the well-studied thiol-ene chemistry, where thiol and an
unsaturated compound are individual reagents, our monomers have two reactive sites bound in
one molecule, which gives beneficial properties. We have not received evidence that the optimal
ratio of equivalents of vinyl: -SH is 1:1 Tri- and hexaene urethanes with vinyl(allyl) oxides/acrylate
groups undergo easy polymerization with PI producing films with valuable mechanical properties.
In our experiments consumptions of vinyl/allyl oxides was 20-50%. Taber experiments and Tg
measurements by DMA of our products are in progress.

Acknowledgement

The authors are grateful to Dr. S. Cantor for help in the work and fruitful discussions.

References

1. www.bomarspecilaties.com
2. Leon, J.A.; Khudyakov, I.V.; Zopf, R.D. in RadTech Asia 2005, p. 243.
3. Leon, J.A.; Khudyakov, I.V. in RadTech Europe 2005, p. 359.
4. Khudyakov, I.V.; Turro, N.J. in Photochemistry and UV Curing: New Trends; Fouassier,
J.P., Ed.; Research Singpost: India, 2006; Vol. 25, p. 241.
5. Khudyakov, I.V. Paints & Coatings Industry 2004, March, p.52.
6. DeSousa, J.D.; Khudyakov, I.V. Ind. Eng. Chem. Res. 2006, 45, 6413.
7. Hoyle, C.E.; Lee, T.Y.; Roper, T. J. Polym. Sci. A 2004, 42, 5301.
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