Efficient synthesis of diallyl esters of the furan series from fructose and preparation of copolymers on their basis

Article abstract of DOI:10.1007/s11172-019-2456-9

New unsaturated derivatives of the furan series, diallyl esters of furan-2,5-dicarboxylic acid and 5,5′-[oxybis(methylene)]di(2-furoic acid), which can be used as monomers and cross linking agents, were synthesized by the aerobic oxidation of 5-hydroxymethylfurfural and 5,5′-oxybis(5-methylene-2-furaldehyde) obtained by catalytic dehydration of fructose. Optimum conditions for the synthesis of the above-mentioned compounds and their copolymerization with butyl methacrylate were determined. Varying the amount of the cross-linking agent, the thermal stability, adhesion, strength and optical properties of copolymers can be controlled. New cross-linking agents obtained from renewable resources can be considered as an alternative to the important cross-linking agent, diallyl phthalate, produced from petroleum.

Full text of DOI:10.1007/s11172-019-2456-9

Russian Chemical Bulletin, International Edition, Vol. 68, No. 3, pp. 570—577, March, 2019
570
Efficient synthesis of diallyl esters of the furan series from fructose
and preparation of copolymers on their basis
V. A. Klushin, V. P. Kashparova, I. S. Kashparov, Yu. A. Chus, A. A. Chizhikova, T. A. Molodtsova, and N. V. Smirnova
Department of Technology, Platov South-Russian State Polytechnic University,
132 ul. Prosvescheniya, 346428 Novocherkassk, Russian Federation.
E-mail: victorxtf@yandex.ru
New unsaturated derivatives of the furan series, diallyl esters of furan-2,5-dicarboxylic acid
and 5,5´-[oxybis(methylene)]di(2-furoic acid), which can be used as monomers and cross
linking agents, were synthesized by the aerobic oxidation of 5-hydroxymethylfurfural and
5,5´-oxybis(5-methylene-2-furaldehyde) obtained by catalytic dehydration of fructose. Optimum
conditions for the synthesis of the above-mentioned compounds and their copolymerization
with butyl methacrylate were determined. Varying the amount of the cross-linking agent, the
thermal stability, adhesion, strength and optical properties of copolymers can be controlled.
New cross-linking agents obtained from renewable resources can be considered as an alternative
to the important cross-linking agent, diallyl phthalate, produced from petroleum.
Key words: 5-hydromethylfurfural, copolymerization, raw biomaterials, diallyl esters.
Studies on production of polymers from renewable
plant resources are of considerable interest as a part of solu-
tion to the problem of environmental pollution with polymer
wastes.1—6 The number of reagents and polymers synthe-
sized on the basis of biomass-produced platform com-
pounds is ever increasing. Among them, 5-hydroxymethyl-
furfural (HMF) holds a specific place due to the avail-
ability of raw materials, carbohydrates (fructose, glucose,
sucrose, inulin, cellulose, etc.).7,8 Its derivatives, such as
2,5-diformylfuran (DFF),9—12 furan-2,5-dicarboxylic acid
(FDCA),13—18 and 5,5´-[oxybis(methylene)]di(2-furoic
acid)] (OBFA)19, are considered as the most attractive
monomers for the synthesis of new-generation polymers.
All above-mentioned monomers of the furan series
(DFF, FDCA, and OBFA) are used in polycondensa-
tion processes for the preparation of polyesters,19 poly-
amides,1,3,4,20 urea-aldehyde21 and polyurethane resins,
and polyimines.22 There are few examples of furan-series
monomers containing unsaturated substituents which can
be used in homo- and copolymerization with other vinyl
compounds.23—26
Polymers on the basis of renewable raw materials can
substitute general-purpose materials, such as polyethylene,
polyvinyl chloride, and polystyrene, which are currently
produced and used in large scales worldwide. Since com-
pounds of the furan series are heat resistant, polymers
based on HMF derivatives should be expected to preserve this
quality after polymerization and to be close in properties
to copolymers of styrene and diallyl phthalate (DAP).24,25
We obtained new unsaturated derivatives of the furan
series (diallyl esters of corresponding furandicarboxylic
acids, FDCA and OBFA) from fructose, as well as co-
polymers on their basis. The above-mentioned materials
can substitute in some cases poly(diallyl phthalate) and
their copolymers with styrene, acrylates, and metha-
crylates. It should be noted that poly(diallyl phthalate) is
currently widely applied as a thermosetting resin for the
manufacture of composite materials27,28 used in cases
requiring size stability, low water sorption, as well as per-
fect optical and electrical properties.1 Similar properties
could be expected from polymers based on diallyl esters
of FDCA and OBFA.
The aim of the present work was to study homopoly-
merization and copolymerization of diallyl furandicarb-
oxylates (DA-FDCA and DA-OBFA) with butyl metha-
crylate (BMA) and to obtain data on branching and cross
linking reactions upon the formation of corresponding
copolymers, as well as on their properties.
Results and Discussion
Scheme 1 shows main steps in the preparation of new
allyl monomers of the furan series, DA-FDCA and
DA-OBFA, and their copolymers with BMA.
One of the main problems in the preparation of HMF
from hexose raw materials of plant origin is a large number
of side products and wastes which on going to industrial
production scales will create limitations for the develop-
ment of such processes.29 However, it should be noted that
these wastes often contain valuable substances30 and can
be used with benefit.31,32
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0570—0577, March, 2019.
1066-5285/19/6803-0570 © 2019 Springer Science+Business Media, Inc.

Synthesis of diallyl esters of the furan series
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 3, March, 2019
571
Scheme 1
Reagents and conditions: i. aqueous NaHSO4—MIBK, H2SO4, 2 h, 85 °C; ii. Pt/C, PO2 = 0.25 MPa, 6 h, 110 °C; iii. allyl alcohol,
H2SO4, 2 h, 110 °C; iv. butyl methacrylate, AIBN, 24 h, 80 °C.
Earlier,29,33 we have developed and optimized a method
for the preparation of HMF from the hecose raw material
in an aqueous NaHSO4—methyl isobutyl ketone (MIBK)
system (see Scheme 1). When the substrate was fructose,
the yield of HMF was 78 %. Solid wastes (humins) (~7%)
and liquid wastes (resin) (15%) are produced simultane-
ously. In turn, the resin contains up to 60% of 5,5´-oxybis-
(5-methylene-2-furaldehyde) (OBMF).
The aerobic oxidation of HMF and OBMF according to
the earlier published procedure34 afforded FDCA and OBFA
(see Scheme 1). The yield of OBFA, synthesized for the first
time according to this procedure from OBMF, was 65%.
DA-FDCA and DA-OBFA were synthesized by es-
terification of carboxylic acids with alcohols in the presence
of H2SO4 (as a catalyst) and a dehydrating agent. Since
the synthesis of these esters was carried out for the first
time, it was important to establish optimum synthesis
conditions. Our studies, the data from which are shown
in Fig. 1, revealed that the optimum content of H2SO4 in
the reaction medium was 75 mol.% and the optimum
synthesis time was 2 h. Upon an increase in these para-
meters, the yield of ester decreased dramatically due to
furan ring opening and resinification.35,36
It should be noted that, in contrast to diallyl phthalate
which forms a thermosetting polymer upon homopoly-
merization,27,37 DA-FDCA and DA-OBFA do not form
homopolymers. Upon bulk or solvent (toluene) polymer-
ization in the presence of initiating agents (AIBN or

572
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 3, March, 2019
Klushin et al.
YDA-FDCA (%)
YDA-FDCA (%)
80
b
a
80
60
40
20
60
40
20
25
50
75
100 [H2SO4] (mol.%)
1
2
3
t/h
Fig. 1. Yield of (Y) DA-FDCA as a function of the H2SO4 content (a) (2 h, 110 °C) and of the synthesis time (b) (75 mol.% H2SO4).
benzoyl peroxide), starting unsaturated esters of corre-
sponding dicarboxylic acids (FDCA and OBFA) were
isolated. One can assume that this is due to a stability of
radicals produced from DA-FDCA and DA-OBFA.
In contrast to homopolymerization, copolymerization
of DA-FDCA or DA-OBFA with BMA proceeded with
success. Copolymers I and II obtained from DA-FDCA
and DA-OBFA (see Scheme 1), respectively, appear as
a colorless glassy mass. The yield of the copolymers de-
creases from 100 to 98% with an increase in the content
of comonomers above 7.5%. In this case, DA-FDCA and
DA-OBFA undergo copolymerization not completely and,
being in a mixture with polymer, have a plasticizing effect.
Diallyl phthalate is known to be used as a plasticizer for
different polymers.38
Limitation on the amount of unsaturated diester added to
the copolymer can be explained also by the stability of rad-
icals produced from DA-FDCA and DA-OBFA which can-
1143.6
1722.15
964.25
1000.89
1240.03
1267.03
1062.61
1020.18
1450.23
944.97
844.68
879.4
748.25
1465.66
1364.67
1
1800
1700
1600
1600
1500
1400
1300
1200
1100
1000
900
800
800
ν/cm–1
1143.6
1722.15
1170.6
944.97
1000.89
1240.03
1268.96
1299.81
844.68
1062.61
1450.23
964.25
748.25
1020.18
1465.66
1364.67
875.54
2
1800
1700
1500
1400
1300
1200
1100
1000
900
ν/cm–1
1722.15
1143.6
964.25
998.96
1020.18
1240.03
1268.96
842.76
879.4
944.97
1062.61
1450.23
1465.66
748.26
765.62
1364.67
1299.81
3
1800
1700
1600
1600
1500
1400
1300
1200
1100
1000
900
800
ν/cm–1
1722.15
1143.6
998.96
842.76
1268.96
944.97
1450.23
1465.66
1240.03
1064.53
748.26
966.18
1018.25
1382.74
765.62
1299.81
879.4
4
701.98
1800
1700
1500
1400
1300
1200
1100
1000
900
800
ν/cm–1
Fig. 2. IR spectra of copolymer I with different content of the DA-FDCA cross-linking agent: 1.0 (1), 2.5 (2), 5.0 (3), and 7.5% (4).

Synthesis of diallyl esters of the furan series
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 3, March, 2019
573
Table 1. Degree of swelling α* (%) and swelling rate constant k (min–1) of the copolymers in different solvent
Comonomer
content (%)
Copolymer I
Copolymer II
Toluene
Chloroform
Toluene
Chloroform
α
k
α
k
α
k
α
k
0
Soluble
9.1
—
Soluble
17.1
—
Soluble
—
—
Soluble
—
24.5
22.5
22.0
—
1
0.0086
0.0068
0.0098
0.0116
0.0151
.—
—
2.5
5
7.5
8.5
0.0091
0.0098
0.01
15.8
16
0.0089
0.011
0.014
0.0088
0.0102
0.0114
8.1
6.4
14.2
12.0
14.5
12
* Degree of swelling was measured for 240 min.
not react with own monomer (this is confirmed by the inabil-
ity to be homopolymerized) and slowly reacts with BMA. The
formation of copolymers is likely explained by the fact that re-
active radicals react with both own and foreign monomers.
Figure 2 shows the IR spectra of the obtained copoly-
mers I and II. The peaks corresponding to the carbonyl
group of aromatic acids (1299.81 and 1268.96 cm–1) and
to the furan ring (765.62 cm–1) are weak, but their inten-
sities increase with an increase in the content of the cross-
linking agent (DA-FDCA or DA-OBFA).
than that of noncross-linked ones.41 The application of
DA-FDCA and DA-OBFA as cross-linking agents in-
creases the heat resistance of copolymers: the higher is the
number of cross links the higher is stability (Fig. 3). The
half decomposition temperature increases from 270 °C for
PBMA to 340 °C for copolymers containing 7.5% of the
cross-linking agent (Fig. 4, a).
The resulting copolymers I and II differ in mechanical
properties from PBMA. With an increase in the content
To prove the cross-linked structure of the polymer, the
degree and rate of swelling of copolymers I and II in differ-
ent solvents, as well as their heat resistances were studied.
The obtained copolymers like poly(butyl methacrylate)
(PBMA) do not swell in water. In chloroform and toluene,
they swell partially, while PBMA completely dissolves in
these solvents (Table 1). With an increase in the number
of DA-FDCA and DA-OBFA units, the cross-link density
increases and the ultimate degree of swelling decreases.39
However, the degree of copolymer swelling (α) is suffi-
ciently high to be 6.4 and 12% in toluene and 12 and 22%
for copolymers I and II, respectively, even at the highest
content of the cross-linking agent (7.5%). High α values
suggest a low cross-link density in these copolymers. For more
significantly cross-linked copolymers of methyl metha-
crylate and divinyl benzene, the swelling ratios are consider-
ably lower.40 For copolymers II cross-linked with DA-
OBFA units, the α value in both solvents is higher than that
for copolymer I due to a larger size of its molecule com-
pared to that of DA-FDCA. For this reason, the distance
between the cross-linked PBMA molecules in the case of
copolymer II is longer and the solvent easier penetrates
into the polymer structure. The rate and degree of swelling
in chloroform for both copolymers is higher than those in
toluene due to a higher polarity of the former.
ΔQ/mW mg–1
a
1.0
0.8
0.4
4
0
–0.4
–0.8
–1.2
3
2
1
5
40 80 120 160 200 240 280 320 360 T/°C
ΔQ/mW mg–1
1.2
b
0.8
0.4
3
0
–0.4
–0.8
–1.2
–1.6
2
4
5
Since the packing characteristic of the polymer de-
creases upon insertion of cross linkages between the PBMA
molecules, the rate of swelling increases with an increase
in the content of the comonomer (see Table 1).
1
40 80 120 160 200 240 280 320 360 T/°C
The heat resistances of the obtained copolymers were
studied by DSC. It is known that the heat resistance
of cross-linked polymers in some cases can be higher
Fig. 3. Heat of polymer decomposition as a function of the con-
tent of DA-FDCA (a) and DA-OBFA (b) cross-linking units:
1 (1), 2.5 (2), 5 (3), and 7.5% (4), and PBMA (5).

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Russ. Chem. Bull., Int. Ed., Vol. 68, No. 3, March, 2019
Klushin et al.
T/°C
Shore hardness/MPa
2.5
a
b
360
340
320
300
280
2.0
1.5
1.0
1
2
1
2
0
2
4
6
8
C (%)
0
2
4
6
8
C (%)
Shear strength/MPa
14
Contact angle/deg
80
с
d
12
10
8
75
70
65
1
2
2
1
6
1
2
3
4
5
6
7
8
C (%)
0
2
4
6
8 C (%)
Fig. 4. Effect of the content of DA-FDCA (1) and DA-OBFA (2) units on the half decomposition temperature (a), the Shore hardness (b),
and the shear strength of adhesive binding (c), and the contact angle (d).
of DA-FDCA and DA-OBFA, the Shore hardness of the
copolymers decreases compared to PBMA (see Fig. 4, b).
Probably, their effect is similar to that of diallyl phthalate
being a reactive plasticizer.42,43
interface is higher than that of intraphase intermolecular
interaction. This allows one to consider the obtained
polymers as adhesives.
An increase in the polarity of the copolymers is re-
flected also on wetting effects. The contact angle of PBMA
wetting with water is 78° and this value for the copolymers
is slightly lower (65—70°), i.e., the surface polarity in-
creases due to the presence of polar groups (carbonyl,
carboxyl, ester) (see Fig. 4, d).
It should be noted that the obtained polymer are totally
transparent (Fig. 5). They absorb only UV radiation with
λ < 300 nm and do not absorb in the visible region.
An increased heat resistance and a high transparence
make them promising adhesive materials, as well as prom-
ising materials for production of lamps and reinforced
automotive glasses (such as triplex).
Thus, new unsaturated furan derivatives, diallyl esters
of furan-2,5-dicarboxylic acid and 5,5´-[oxybis(methyl-
ene)]di(2-furoic acid), were synthesized for the first time
from fructose via 5-hydromethylfurfural and 5,5´-oxybis-
(5-methylene-2-furaldehyde). Butyl methacrylate copo-
lymers possessing high adhesive properties, increased heat
resistance, good strength properties, and high transparence
Copolymers I and II exhibited extremely high adhe-
sive properties. For example, the strength of adhesive
binding at the interface between metal (steel) and these
copolymers significantly increases compared to PBMA
(see Fig. 4, c). The strength of steel/steel adhesion bind-
ing increases when 1% of the cross-linking agent was
added; this is due to the presence of polar carboxyl and
ester groups in the molecules of both esters. The use
of the copolymer containing 1% of DA-OBFA units
increases the adhesion of the adhesive layer to steel
more than two-fold compared to PBMA. However,
upon an increase in the amount of the additive above 2.5%
the copolymer cohesion decreases as a result of plastic-
ization.
It was found that, with an increase in the content of
cross-linking agents, the type of their cleavage changes.
For example, while pure PBMA shows an adhesion cleav-
age, a cohesion cleavage is observed upon introduction of
comonomers, i.e., the energy of interaction at the steel

Synthesis of diallyl esters of the furan series
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 3, March, 2019
575
A
heated for 2 h at 100 °C with simultaneous distilling off a water–
allyl alcohol azeotrope. The reaction mixture was cooled and
sodium bicarbonate (1.8 g, 0.022 mol) was added to neutralize
sulfuric acid. The mixture was stirred for 20 min and filtered on
a Buchner funnel. The filtrate was cooled in a freezer (–18 °C)
to give diallyl ester crystals after 2 h (1.5 g of DA-FDCA and 2.7 g
of DA-OBFA) which were separated by filtration. The purity of
final diallyl esters was at least 98% (according to the GC-MS
data). For further purification, the products were recrystallized
from heptane (m.p. 33—35 °C for DA-FDCA and 35—37 °C for
DA-OBFA). The total yield was 76% for DA-FDCA and 65% for
DA-OBFA.
4
3
2
1
0
DA-FDCA. 1H NMR (CDCl3), δ: 7.22 (s, 2 H, =CH); 5.99
(m, 2 H, CH); 5.39 (d, 2 H, CH2, J = 17.2 Hz); 5.28 (d, 2 H,
CH2, J = 10.4 Hz); 4.81 (d, 4 H, =CH2, J = 5.7 Hz). 13C NMR
(CDCl3), δ: 157.56 (COO), 146.7 (=C), 131.41 (=CH), 119.11
(CH), 118.49 (CH2), 65.95 (=CH2).
300
400
500
600
700
800 λ/nm
Fig. 5. UV spectrum of copolymer I and the photograph of a text
made through its plate showing its transparence.
DA-OBFA. 1H NMR (CDCl3), δ: 7.18 (d, 2 H, =CH,
J = 3.4 Hz); 6.49 (d, 2 H, =CH, J = 3.4 Hz); 6.02 (m, 2 H, CH);
5.42 (dd, 2 H, CH2, J = 17.2 Hz, J = 1.3 Hz); 5.31 (dd, 2 H,
CH2, J = 17.2 Hz, J = 1.3 Hz); 5.28 (d, 2 H, CH2, J = 10.4 Hz);
4.82 (d, 4 H, =CH2, J = 5.7 Hz); 4.59 (s, 4 H, CH2). 13C NMR
(CDCl3), δ: 158.23 (COO), 155.46 (=C), 144.42 (=C), 131.78
(=CH), 118.81 (CH), 111.34 (CH2), 65.49 (=CH2), 64.22 (CH2).
Bulk and solvent homopolymerization of DA-FDCA or
DA-OBFA. DA-FDCA (0.01 mol, 2.35 g) or DA-OBFA (3.46 g)
was placed in a glass-stoppered test tube. Azobisisobutironitrile
(AIBN) or benzoyl peroxide in an amount of 0.05% was added
as a polymerization initiator. The reaction mixture was purged
with argon for 5 min; the test tube was stoppered and heated on
an oil bath for 24 h at 80 °C. During heating, low-melting mono-
mers underwent melting (m.p. 32—34 °C for DA-FDCA and
34–36 °C for DA-OBFA). The reaction mixture became slightly
darkened, but not viscous. On completion of the synthesis time,
the melt was withdrawn from the test tube and recrystallized from
heptane. The resulting monomer was obtained in the same
amount as taken for homopolymerization (2.23 g, 95% for
DA-FDCA and 3.2 g, 94% for DA-OBFA).
were obtained. These copolymers may be recommended
as a replacement of copolymers obtained from petroleum-
produced diallyl phthalate.
Experimental
Fructose, dichloromethane, heptane, sulfuric acid, allyl
alcohol, butyl methacrylate, AIBN (>99%), benzoyl peroxide,
and sodium sulfate decahydrate were purchased from Aldrich
Chemical Co.
Synthesis of 5-hydroxymethylfurfural (HMF) and 5,5´-oxybis-
(5-methylene-2-furaldehyde) (OBMF). HMF and OBMF were
synthesized in an aqueous NaHSO4—MIBK two-phase system
in the presence of sulphuric acid with vigorous stirring for 2 h at
85 °C.29,33 The starting carbon raw material was fructose. OBMF was
isolated from resinous wastes produced upon the synthesis of HMF.
The obtained OBMF had m.p. 113—114 °C. IR (ATR), ν/cm–1
:
730, 828, 947, 1029, 1193, 1268, 1351, 1402, 1447, 1518, 1663, 2845.
Pure OBMF was isolated dissolving the resin in hot water
followed by cooling; the resulting precipitate of pure product was
separated by filtration.
An attempt was made to homopolymerize DA-FDCA or
DA-OBFA in solution. The solvent was toluene. The starting
monomer (2.2 g, 94% for DA-FDCA and 3.32 g, 97% for
DA-OBFA) was isolated analogously.
Synthesis of furan-containing dicarboxylic acids, FDCA and
OBFA. The synthesis was carried out according to a known
procedure34 by the aerobic catalytic oxidation of HMF or OBMF
on Pt/C for 6 h under an oxygen pressure of 0.25 MPA at 110 °C.
The Pt/C catalysts (Pt = 30 wt.%) were synthesized by the elec-
trochemical method using pulse alternate current. A high content
of Pt in the catalyst (30 wt.%) made it possible to use concen-
trated aqueous solutions of HMF (0.1 M) and OBMF (0.01 M)
to give FDCA and OBFA in yields of 55—65%. M.p. 208—210 °C
(cf. Ref. 19: m.p. 207—210 °C). IR (ATR), ν/cm–1: 761, 891, 951,
1029, 1059, 1159, 1208, 1283, 1342, 1424, 1525, 1674, 3128.
1H NMR (DMSO-d6), δ: 4.53 (s, 4 H, 2X-CH2O); 6.64 (d, 2 H,
C(4,4´), J = 3.4 Hz); 7.18 (d, 2 H, C(3,3´), J = 3.4 Hz); 13.13
(s, 2 H, 2X-COOH). 13C NMR (DMSO-d6), δ: 63.8, 112.2, 118.9,
145.2, 155.5, 159.7
Synthesis of polymers. A comonomer mixture of DA-FDCA
(or DA-OBFA) and BMA was prepared in a wide glass-stoppered
test tube. The copolymerization initiator was AIBN (0.05%). The
total weight of the monomer mixture was 10 g. The reaction
mixture was purged with argon, the test tube was stoppered, and
the mixture was heated on an oil bath for 24 h at 80 °C. The
mixture was cooled and the polymer was withdrawn as a colorless
glassy mass.
Research methods. 1H and 13C NMR spectra were recorded
on a Bruker DRX 500 instrument (500 and 125 MHz, respec-
tively) as solutions in CDCl3 or DMSO-d6 using tetramethylsilane
(TMS) as the internal standard.
ATR-IR spectra were recorded on a Varian 640 FT-IR
spectrometer (Varian, United States) in a region from 650 to
4000 cm–1
.
Synthesis of diallyl furandicarboxylates (DA-FDCA and
DA-OBFA). Allyl alcohol (22 mL) and concentrated sulfuric acid
(0.4 mL) were placed in a 50-mL round-bottom flask. The mix-
ture was stirred for 10—15 min and FDCA (1.56 g, 0.01 mol) or
OBFA (2.56 g, 0.01 mol) was added. The reaction mixture was
UV spectra were obtained on a Shimadzu UV-1800 spectro-
photometer in a wavelength range from 220 to 700 nm.
Thermal analysis (DSC) was performed in air using
a METTLER TOLEDO DSC 3 instrument. DSC curves were

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Russ. Chem. Bull., Int. Ed., Vol. 68, No. 3, March, 2019
Klushin et al.
recorded in a temperature range of 25—600 °C at a scan rate of
10 deg min–1
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The degree of swelling and the swelling rate constants of
comonomers were determined by gravimetry on an LSU instru-
ment in distilled water, toluene, and chloroform. Each sample
was weighed prior to experimentation and submerged in solvent.
The volume change was measured every 30 min. The run time
for each sample was 240 min at 20 °C. The degree of swelling α
was calculated by the formula
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α = ΔV•ρ/m0,
where ΔV is the solvent volume absorbed by a polymer, ρ is the
density of a solvent, and m0 is the initial weight of a sample.
The swelling rate constant k = tgθ was determined from the
plot of ln (αmax/(αmax – ατ)) as a function of time τ.
The adhesion of a random cross-linked butyl acrylate–
methyl acrylate copolymer was studied on bonded stainless
steel surfaces.
The strength properties of the samples were determined ac-
cording to ASTM D882-10. The samples with a width of 25.4 mm
were tested on an Instron multipurpose machine (model 5500R)
operating with a 50 N strain gage sensor at a rate of 500 mm min–1
.
The initial distance between clamps was 50 mm. The tensile
strength was calculated as a ratio of the maximum tensile
force to the initial cross-section area of the sample film and
the tensile elongation was calculated in percentage of the ini-
tial length.
The hardness was determined according to GOST 24621-2015
(ISO 868:2003) “Plastics and Ebonite”. The indentation hardness
(Shore hardness) was determined using a durometer.
The contact angle θ of copolymer wetting with water was
measured placing the sample under study on a microscope stage.
A droplet of distilled water was placed on its surface using
a needle syringe (the inner diameter of the needle was 0.1 mm).
The droplet was illuminated with a light source and the diameter
of droplet–surface contact was measured using a graduated eye
lens. The measurements were performed five times. The cosine
of contact angle was calculated by the formula:
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Matrix Composites, Elsevier, 2001, 1129.
.
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Krivodaeva, O. A. Kravchenko, N. V. Smirnova, V. M.
Chernyshev, V. P. Ananikov, Russ. J. Org. Chem., 2016,
52, 767.
The contact angle was determined using the cosine value
averaged for seven measurements.
30. K. I. Galkin, E. A. Krivodaeva, L. V. Romashov, S. S.
Zalesskiy, V. V. Kachala, J. V. Burykina, V. P. Ananikov,
Angew. Chem., 2016, 55, 8338.
This work was financially supported by the Russian
Science Foundation (Project No. 16-13-10444).
31. I. I. Kashparov, V. A. Klushin, I. P. Vinokurov, A. F. Zubenko,
V. P. Kashparova, N. V. Smirnova, Mezhdunarodnyi Nauchnyi
Zhournal "Alternativnaya Energetika i Ekologiya" [Int. Sci. J.
Altern. Energ. Ecol.], 2017, 19—21, 116 (in Russian).
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vina, L. S. Pudova, N. V. Smirnova, O. A. Kravchenko,
V. M. Chernyshev, V. P. Ananikov, ChemSusChem, 2018, 20,
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Received October 9, 2018;
in revised form November 28, 2018;
accepted December 12, 2018