Synthesis and thermal transformations of bis[4-(1-hydroxyethyl)phenyl] ether dimethacrylate

Article abstract of DOI:10.1023/B:RJAC.0000015734.96608.da

Thermal curing of bis[4-(1-hydroxyethyl)phenyl] ether dimethacrylate was studied.

Full text of DOI:10.1023/B:RJAC.0000015734.96608.da

Russian Journal of Applied Chemistry, Vol. 76, No. 10, 2003, pp. 1662 1668. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 10, 2003,
pp. 1708 1714.
Original Russian Text Copyright
2003 by Zaitsev, Khramova, Tsygankova.
MACROMOLECULAR CHEMISTRY
AND POLYMERIC MATERIALS
Synthesis and Thermal Transformations
of Bis[4-(1-hydroxyethyl)phenyl] Ether Dimethacrylate
B. A. Zaitsev, G. I. Khramova, and T. S. Tsygankova
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Received January 30, 2003
Abstract Thermal curing of bis[4-(1-hydroxyethyl)phenyl] ether dimethacrylate was studied.
Processing of thermoreactive resins into heat-
resistant polymeric materials involves a serious prob-
lem: For curing to be efficient, the curing temperature
Tc should be maintained higher than the glass transi-
tion point Tg of the system being cured. In the high-
ly viscous medium of a thickly cross-linked poly-
meric matrix at a temperature below Tg, curing dras-
tically decelerates, because transport of reactants to
the reaction zone becomes severely hindered. Partic-
ipation of adjacent functional groups in polymer-
analogous transformations might eliminate this pro-
blem [1 3].
diol methacrylates [7 9]. However, a specific feature
of DM is the presence of latent ( sleeping ) fragments
C6H4 CH(CH3) O CO , allowing high-temperature
rearrangement of the initial polymeric network of DM
in the course of further curing at elevated tempera-
tures. In this study, we analyzed the mechanism of
thermal transformations of DM and the structure and
properties of the cured products.
Bis[4-(1-hydroxyethyl)phenyl] ether dimethacrylate
is formed in synthesis of Rolivsan MV-1, which is a
monomer oligomer compound prepared chemically,
i.e., by transformations of a secondary aromatic diol,
bis[4-(1-hydroxyethyl)phenyl] ether (BOPE), in the
presence of methacrylic acid (MAA), catalyzed with
strong mineral acids [10 14]. Pure DM was prepared
for the first time by acylation of BOPE with methac-
ryloyl chloride (MAC) [12, 13]. According to ozonol-
ysis data, the content of double bonds in DM is
0.504 mol per 100 g; ester number, 272 mg KOH per
gram; n2D0, 1.5410; gelation time at 150 C, 2 min.
Being a polyfunctional monomer, bis[4-(1-hydroxy-
ethyl)phenyl] ether dimethacrylate (DM) may be of
considerable interest in this respect. It is a component
of Rolivsans, novel heat-resistant thermoreactive resins
used in modern engineering [4 6]. Owing to the pres-
ence of unsaturated methacrylate groups, it is involved
in common three-dimensional (3D) polymerization,
forming network polymers similar to the well-known
H
H
H
CH3
O
3C
CH3
H3C O
3C
3C
O
CH3
4-H2C C C O HC C6H4 O C6H4 CH O C C CH2-4
DM
4-HOCHC6H4 O C6H4CHOH-4 + CH2 C C Cl
HCl
MAC
BOPE
Thermal transformations of DM were studied by
IR spectroscopy, differential scanning calorimetry
(DSC), and elemental, thermogravimetric, and ther-
momechanical analyses. The IR study of DM was per-
foirmed in the temperature range 140 370 C (iso-
thermal heating at 140 C and dynamic heating of a
thin film between KBr and NaCl plates at an average
The IR spectrum of DM (Fig. 1a, curve 1) contains
absorption bands of unsaturated and aromatic groups
at 3070 3060, 3030, 2975, 1630, 1600, 1500, 940,
1
870, and 830 cm , of methyl and methylene groups
1
at 2975, 2930, and 2870 cm , and of methine groups
1
at 2900 cm ; it also contains strong absorption bands
of methacrylate ester and diphenyl ether groups at
1
1
rate of 1.4 deg h .
1715 and 1240 cm ; bands at 1170, 1060, and
1070-4272/03/7610-1662 $25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS OF BIS[4-(1-HYDROXYETHYL)PHENYL] ETHER DIMETHACRYLATE
1663
1
1010 cm originate from stretching vibrations of the
previously [12, 13, 15]. DM can be expected to
behave similarly (with corrections for differences in
the structure and reactivity), and the following scheme
of cleavage (or activation) of latent ester groups with
formation of MAA, MV, and bis(4-vinylphenyl) ether
(DV) can be suggested:
C O bond in ester and ether groups.
The mechanism of thermal transformations of an-
other monomer, 4-vinylphenyl-4-(1-methacryloyloxy-
ethyl)phenyl ether (MV), which is also a component
of Rolivsan MV-1 [12, 13, 15], has been studied
H
O
O CH3
CH3
3C
T > 130
DM
H2C C C O H + 4-H2C HC C6H4 O C6H4 CH O C C CH2-4
MV
H
O
3C
T > 130
H2C C C O H + 4-H2C HC C6H4 O C6H4 CH CH2-4
DV
It should be noted that, in contrast to MV, even
short (1 2 h) heating of DM at 140 C causes substan-
tial changes in the IR spectrum (Fig. 1a, curve 2),
which are due not only to the onset of the expected
3D radical polymerization (the gelation time of
DM at 140 C is as short as several minutes) but
also to the cleavage of the ester groups, according to
the above scheme. Dimethacrylate and bridging units
of the initial network polymer, formed by it, are un-
stable at this temperature and start to noticeably de-
compose to give MAA and MV, which, in turn, de-
composes to DV, MAA, and/or their units. This pro-
cess gives rise in the IR spectrum of DM to a new
band of out-of-plane bending vibrations of the H C=C
fragment of the 4-CH2=CH C6H4 O C6H4 group
Therefore, it is not surprising that, in the initial pe-
riod (1 2 h) of DM heating, the bands at 902 and
1630 cm noticeably grow in intensity (Fig. 1a,
1
curve 2), compared to the starting monomer. How-
ever, further heating causes the intiensities of these
bands to decrease owing to participation of the meth-
acrylate and styrene groups in (co)polymerization
(Fig. 1a, curves 3 5). Therefore, upon prolonged heat-
ing of the sample at 140 C and higher temperatures,
these bands gradually decrease in intensity, as also
1
does the band at 940 cm belonging to out-of-plane
bending vibrations of the H C= fragment of the meth-
acrylate group (Fig. 1a, curves 1, 2). Thus, at high
temperatures, unsaturated products formed from DM
by cleavage of methacrylate groups (see above) are
involved in thermal copolymerization of the system,
which becomes multicomponent.
1
at 902 cm [15 18]. The C=C stretching vibration
1
band at 1630 cm simultaneously grows in intensity.
1
Fig. 1. IR spectra of DM and products of its thermal transformations. Heating rate 1.4 deg h . (a) (1) Initial DM; heating range
140 190 C; final temperature, C: (2) 142, (3) 160, (4) 180, and (5) 190. (b) Heating range 200 350 C; final temperature, C:
(1) 200, (2) 260, (3) 290, and (4) 350. ( ) Wave number and (T) transmission.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 10 2003

1664
ZAITSEV et al.
1
Table 1. Conversion of unsaturated and ester groups in the course of dynamic ( 1.4 deg h ) heating of DM, according
to IR data*
D
c / c0
D
D
D
c / c0
D
c / c0
1
T,
C
at indicated , cm
1060
1630
1240
940
902
130
0.24
0.20
0.15
0.09
0.06
0.04
0
0.84
0.77
0.83
0.82
0.85
0.80
0.60
0.05
0.01
0.28
0.18
0.15
0.11
0.06
0.02
0
0.00
0.11
0.09
0.05
0.02
0.01
0
140
150
160
170
180
0.83
0.62
0.38
0.25
0.17
0.64
0.54
0.39
0.21
0.07
0.61
0.50
0.28
0.11
0.06
*
1
(D) Optical density; ( ) wave number, cm ; (c, c ) running and initial concentrations of functional groups in DM, M. It is assumed
0
that the ratio of the optical densities D/D (D , before heating; D, after heating) of DM is proportional to the conversion c/c of
0
0
0
the corresponding unsaturated group.
Table 2. Variation of the intensity of some absorption bands in the IR spectra of DM in the course of dynamic
1
( 1.4 deg h ) heating*
1
1
1
1
1
D (1803 cm ),
canhydr
,
D (1600 cm ),
D (1500 cm ), D (1240 cm ), D (830 cm ),
T,
C
C=O
%
Ar
Ar
O C in Ar
H C= in Ar
140/ 3 h**
140/ 6 h**
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
370
0.02
0.03
0.04
0.05
0.07
0.13
0.14
0.15
0.16
0.18
0.17
0.18
0.16
0.14
0.14
0.10
0.08
0.05
0.04
0.04
0.03
0.03
0.01
0.00
2.0
3.3
4.4
5.6
7.8
14.4
15.6
16.7
17.8
20.0
18.9
20.0
17.8
15.6
15.6
11.1
8.9
5.6
4.4
4.4
3.3
3.3
1.1
0.0
0.20
0.20
0.20
0.19
0.19
0.19
0.20
0.20
0.21
0.22
0.21
0.24
0.24
0.28
0.30
0.31
0.31
0.31
0.33
0.35
0.30
0.34
0.28
0.25
0.42
0.44
0.62
0.63
0.50
0.55
0.43
0.42
0.40
0.42
0.37
0.43
0.42
0.41
0.40
0.36
0.30
0.28
0.27
0.26
0.29
0.21
0.17
0.19
0.77
0.77
0.87
0.86
0.82
0.80
0.73
0.74
0.78
0.76
0.68
0.76
0.71
0.73
0.77
0.70
0.67
0.61
0.59
0.61
0.64
0.56
0.46
0.38
0.21
0.21
0.20
0.20
0.19
0.16
0.16
0.15
0.15
0.16
0.15
0.15
0.14
0.14
0.14
0.14
0.13
0.13
0.12
0.13
0.12
0.10
0.09
0.11
*
1
(D) Optical density; 1803 cm is the C=O vibration frequency of methacrylic anhydride; Ar = 4-C H O C H -4; (c ) con-
anhydr
6
4
6
4
tent of anhydride groups.
**
Isothermal heating at 140 C.
Comparison of the IR spectra of DM, MV, and DV
varies in the course of slow dynamic heating in the
range 130 180 C. For this purpose, we first deter-
mined the experimental intensities of the absorption
monomers (Tables 1, 2) with those of DM thermal
transformation products, measured under similar con-
ditions, shows how the degree of DM unsaturation
1
bands (at 900, 940, and 1630 cm ) of DM, MV, and
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 10 2003

SYNTHESIS OF BIS[4-(1-HYDROXYETHYL)PHENYL] ETHER DIMETHACRYLATE
DV monomers used as reference; the IR spectra were
1665
recorded under similar conditions.
Let us denote as A and B the contributions from
methacrylate and styrene (4-CH2=CH C5H4 ) groups
to the total intensity of an absorption band of the
monomer and assume these contributions to be addi-
tive. Then the spectrum of DM corresponds to 2A;
that of MV, to A + B; and that of DV, to 2B. From
the spectra of these three monomers, we can estimate
that contribution A to the bands at 1630, 940, and
1
900 cm is 0.12 0.13, 0.14 0.18, and 0.00, and
contribution B to the same bands, 0.10 0.11, 0.00,
and 0.14 0.18, respectively.
From these data, we can determine how the con-
version c/c0 of the CH2=CH and CH2=C(CH3) groups
varies in the course of DM heating. Table 1 shows
that, in the range 160 180 C, the concentration of
unsaturated groups of the styrene and methacrylate
types in the system abruptly decreases owing to their
involvement in the radical copolymerization of the
system components. It should be noted that the kinetic
data obtained in the isothermal (Fig. 2) and dynamic
modes of DM heating are well consistent.
Fig. 2. Kinetics of transformations of unsaturated groups in
the course of isothermal heating of DM (140 C) between
As for other major IR manifestations of the cleav-
age of ester groups in DM, Fig. 1 shows that, on
heating, the methacrylate C=O absorption band at
(a) KBr and (b) NaCl plates. (c, c ) Initial and running
concentrations of functional groups, M. , cm : (1) 1630
0
1
[CH =CH and CH =C(CH )], (2) 940 [CH =C(CH )], and
2
2
3
2
3
1
(3) 902 (CH =CH). The c/c ratios were calculated from
1715 cm gets broadened and shifted toward lower
2
0
1
changes in the intensities of the indicated absorption bands
in the IR spectra of transformation products of DM and
model monomers (MV, DV).
frequencies (1700 1685 cm ) corresponding to ab-
sorption of the carboxy group in MAA [15, 18]. Final-
ly, the intensity of the methacrylate C O stretching
1
band at 1060 cm abruptly decreases already at the
pared by thermal polymerization of MV are also
cleaved to give DV units.
very beginning of DM heating at 140 C. Simulta-
neously, the methacrylate H C= bending band at
1
940 cm gets considerably broadened and shifted
As the temperature is raised further to 180
200 C and more, one more parallel reaction starts
to make a major contribution to the thermal trans-
formations: formation of methacrylic anhydride (MA)
units from MAA units in the network polymer, which
yields substituted glutaric anhydride units. In the IR
spectra of DM recorded in the course of curing, the
owing to superposition of the carboxyl O H bending
1
band of MAA and/or its unit at 935 15 cm ; also,
broad OH stretching bands of carboxy group appear
1
at 3570 3500 and 2700 2500 cm , and a band of
1
the C O bond in carboxy group appears at 1420 cm
[19].
1
carbonyl absorption bands at 1803 and 1755 cm ,
It could be expected that cleavage of DM according
to the above scheme would be accompanied by a
decrease in the content of CH3 and CHtert groups.
Indeed, the intensities of the stretching vibration
characteristic of the anhydride group, steadily grow in
intensity (Fig. 1a, curves 4, 5; Fig. 1b, curves 1, 2;
Fig. 3; Table 2). To compare, glutaric anhydride
shows carbonyl absorption at 1802 and 1761 cm
[19]. Naturally, as anhydride units are formed, the ab-
sorption band of carboxyl C=O group at 1690 cm
decreases in intensity.
1
1
bands of the methyl (2980, 2930, 2870 cm ) and
1
methylene (2890 cm ) C H bonds and of the C H
1
1
bending vibrations (1370 cm ) appreciably decrease
in the course of DM heating. A similar pattern has
been observed previously in thermal transformations
of other methacrylates of secondary aromatic alcohols
[12, 13, 15, 18], e.g., MV [15]. In particular, it was
shown that MV units in the network (co)polymer pre-
Heating to 250 300 C causes give rise to broad
1
bands at 1660 1680 cm in the IR spectra of DM
curing products (Fig. 1b); these bands originate from
stretching vibrations of ketone carbonyl group [19].
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 10 2003

1666
ZAITSEV et al.
gradually decrease in the course of prolonged heating,
but remain relatively high even after heating to 370 C
(Table 2). An exception is an appreciable growth of
1
the band at 1600 cm , belonging to the C=C bond in
Ar and sensitive to conjugation [19]; apparently, high-
temperature degradation results in the formation of
polyconjugated (polycyclic) structures.
High-temperature curing of DM and related com-
pounds [15, 18], causing cardinal structural changes
as indicated by IR spectroscopy, was also studied by
DSC. The observed pattern of thermal effects is con-
sistent with the above-considered mechanism of ther-
mal transformations of DM following from IR data,
taking into account a significant difference in the
heating rates (IR, 1.4 deg h ; DSC, 4 deg min ).
At high heating rates, structural changes are usually
manifested much more sharply than under conditions
of isothermal heat treatment or slow heating.
Fig. 3. Kinetics of formation of methacrylic anhydride units
in the course of DM heating in the temperature range
1
140 370 C at average rate of 1.4 deg min between KBr
plates: (c) concentration of anhydride groups and (T) tem-
perature.
1
1
Figure 4 shows that the exothermic peak observed
at 231 C (first step of thermal transformations of DM)
is apparently due to prevailing 3D (co)polymeriza-
tion of methacrylate and styrene monomers. Such
processes are accompanied by substantial heat release
[20]. In the range 234 238 C, the heat release ab-
ruptly weakens, which may be due to prevalent con-
tribution of concomitant endothermic cleavage of
ester groups. Finally, the exothermic peaks observed
at 240 and 246 C may be due to the major contribu-
tion from copolymerization of unsaturated compounds
formed by DM cleavage (as shown above) and from
polycyclization (formation of anhydride units from
MAA units) in the final stage of DM curing (post-
curing). The total thermal effect of DM transforma-
Fig. 4. Thermogram of DM curing (DSC, scanning rate
4 deg min ). (T) Temperature and ( H) thermal effect.
1
As shown previously in comprehensive studies of
related compounds and systems by various methods
[12, 13, 15, 18], these changes in the IR spectra are
due to fast solid-phase Friedel Crafts acylation of
diphenyl ether groups with adjacent MA units, yield-
ing thermally stable methylenetetralone units in the
network copolymer. Figure 3 shows that the consump-
tion of anhydride groups in polymer-analogous acyla-
tion reactions results in a fairly sharp decrease in their
content in the network copolymer in the final stage of
DM curing (in the temperature range 250 300 C).
1
tions is about 69 kJ mol , whereas the heat of
polymerization of DV (which contains no cleavable
ester groups), determined under the same conditions
1
(kJ mol ), is considerably higher: 97 [21] or 114
[16]. Thus, the difference in the total heats of curing
of DM and DV is mainly due to the fact that curing
of DV involves only exothermic reactions of 3D po-
lymerization, whereas curing of DM is accompanied,
along with polymerization, by endothermic cleavage
of ester groups.
The IR spectra of products of DM curing in the
range 300 370 C allow evaluation of the resistance
of units and some groups of the resulting network co-
polymer to thermal oxidative degradation in air. Fig-
ures 1b (curve 4) and 3 show that the least thermally
stable fragments of the copolymer are MA units; they
degrade in the course of slow heating of the sample
from 300 to 370 C. The intensities of the absorption
bands of aromatic and diphenyl ether groups also
The structural transformations of DM can be gen-
erally regarded as high-temperature dehydration, with
water removal from the glassy polymeric matrix by
molecular diffusion. Presumably, total cleavage of
1 mol of DM or its polymer (polyDM) by the above-
given scheme is accompanied by release of 2 mol of
MAA (or polyMAA); its transformation into the anhy-
dride, in turn, results in release of 1 mol of H2O:
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 10 2003

SYNTHESIS OF BIS[4-(1-HYDROXYETHYL)PHENYL] ETHER DIMETHACRYLATE
1667
Fast solid-phase reactions in thickly cross-linked
polymeric matrices have been studied previously as
applied to curing of Rolivsans [5, 6, 21], model sys-
tems [12, 13, 18], and related compounds [15, 21]. As
noted above, the fact that the reactions occur in thick-
ly cross-linked polymeric matrices at temperatures
much lower than the softening point ( 403 C), when
the transport of reactants to the reaction zone is usual-
ly hindered, is an advantage of such systems. How-
ever, in the systems under consideration, the vibra-
tional and rotational motion of adjacent groups is suf-
ficiently free for the reactions to be fast [12].
160 230 C
H2O
(C24H26O)n
PolyDM
(C16H14O)n
(C8H10O3)m ,
m
DV MA copolymer
where n = 1, m = 0.5.
In this case, the molar ratio of DV and MA units
in the copolymer will be 1 : 1. Then, if we assume
that the high-temperature Friedel Crafts acylation of
diphenyl ether groups with adjacent anhydride groups
in polymer chains to give methylenetetralone and
MAA units goes to completion, then the composition
of the acylated copolymer can be determined from the
following scheme:
The above-discussed mechanism of DM curing
explains why it is possible to prepare heat-resistant
polymers and plastics from this thermally unstable
(C16H14O)0.5 (C8H10O3)0.5
DV MA copolymer
Acylation with MA
1
monomer. According to dynamic (4.5 deg min )
(C20H18O2)0.5 (C8H10O3)0.25
0.25H2O
thermogravimetric analysis in air, the temperatures
of 5 and 10% weight loss by thermally rearranged
polyDM are 340 and 390 C, respectively, and the
breaking bending stress of fiber glasses based on
polyDM is 330 (20 C), 220 (300 C), and 50 MPa
(320 C).
Acylated DV MA copolymer
Elemental analysis shows that, upon heating of DM
samples to 300 C, the carbon content grows from 73.2
to 77.7%. The latter value is intermediate between the
values calculated for the copolymer compositions be-
fore (76.6% C) and after (78.5% C) acylation. Calcu-
lation shows that, in the course of formation of these
copolymers, transformation of carboxy groups into
anhydride groups (followed in the latter case by acy-
lation) should result in the release of 9.6 and 12.1%
H2O, respectively. However, the total amount of vola-
EXPERIMENTAL
DM was prepared according to [12, 13]; a colorless
glycerol-like liquid, yield 45 50%, nD20 1.541. Found,
%: C 73.20, H 6.6. Ester number (mg KOH per gram
product): found 272.0; calculated 274.8.
1
tiles released in the course of dynamic (1.4 deg h )
heating of DM from 20 to 300 C does not exceed
7.7%. The fact that the amount of released water is
lower than expected may be due to partial degradation
(decarboxylation) of MAA and anhydride units upon
prolonged heating of the samples (for more than 70 h)
in the range 200 300 C. Previous mass-spectrometric
studies have shown [12, 18] that, at temperatures ex-
ceeding 200 C, thermal degradation (mainyl decar-
boxylation) of methacrylic acid units makes a small
but appreciable contribution.
Bis(4-vinylphenyl) ether (DV) and 4-vinylphenyl
4-(1-methacryloyloxyethyl)phenyl ether (MV) were
prepared as described in [12 14].
The IR spectra were measured on a Specord 75-IR
spectrometer in a thin film. Calorimetric measure-
ments were performed with a Perkin Elmer DSC-1B
differential scanning microcalorimeter, as described
in [20]. Exclusion liquid chromatography (ELC) was
carried out on a GPC-Waters chromatograph at 20 C
Based on the above data, the polymeric structure
finally formed in the course of DM curing at 250
300 C can be represented as follows:
using columns packed with Ultrastyragel 500
and
CHCl3 or toluene as eluent. Dynamic thermogravimet-
ric analysis of samples was performed on a Paulik
Paulik Erdey MOM C derivatograph (Hungary) at a
.
.
.
.
.
.
1
heating rate of 4.5 deg min . The softening point
was determined with a Vicat device (Institute of
Macromolecular Compounds, Russian Academy of
Sciences; indenter load 1 kg, indenter cross section
1 mm2).
O
O
O
O
O
O
O
O
O
O
Fiber glasses were prepared by hot pressing of
prepregs on T-10-80 fiber glass fabric at a pressure of
O
2
1 kg cm , with heating from 20 to 300 C at a rate
.
.
.
.
1
.
.
of 1.4 deg min .
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 10 2003

1668
ZAITSEV et al.
efirakrilaty (Polyether Acrylates), Moscow: Nauka,
CONCLUSIONS
1967.
(1) Thermal transformations of DM yield heat-
resistant thermoreactive polymers; common 3D radical
polymerization of DM, giving the initial thermally
unstable network polymer, is accompanied by ther-
mally initiated solid-phase consecutive-parallel reac-
tions between adjacent groups in chains of the poly-
mer network.
8. Berlin, A.A., Korolev, G.V., Kefeli, T.Ya., and Si-
vergin, Yu.M., Akrilovye oligomery i materialy na ikh
osnove (Acrylic Oligomers and Materials Based on
Them), Moscow: Khimiya, 1983.
9. Korolev, G.V., Mogilevich, M.M., and Golikov, I.V.,
Setchatye poliakrilaty (Network Polyacrylates), Mos-
cow: Khimiya, 1995.
10. Zaitsev, B.A., Khramova, G.I., and Dantsig, L.L.,
Vysokomol. Soedin., Ser. A, 1982, vol. 24, no. 12,
pp. 2467 2474.
(2) Thermal transformations of DM involve a set
of consecutive-parallel reactions of 3D polymeriza-
tion, cleavage of ester groups of the monomeric unit
in the network polymer, formation of anhydride from
adjacent MAA units, acylation of diphenyl ether
groups with adjacent anhydride groups, decarboxyla-
tion of MAA, and degradation of methacrylic anhy-
dride units.
11. Zaitsev, B.A., Dantsig, L.L., and Khramova, G.I.,
Zh. Org. Khim., 1983, vol. 19, no. 11, pp. 2340 2349.
12. Zaitsev, B.A., Regular Trends in Formation, Structure,
and Properties of Heat-Resistant Network Polyaryl-
enes, Doctoral Dissertation, Leningrad, 1983.
13. Khramova, G.I., Regular Trends in Formation and
Cross-Linking of Secondary Aromatic Diol Methac-
rylates and Monomer Oligomer Systems Based on
Them, Cand. Sci. Dissertation, Leningrad, 1985.
14. Zaitsev, B.A., Khramova, G.I., Tsygankova, T.S.,
et al., Abstracts of Papers, VIII Mezhdunarodnaya
konferentsiya po khimii i fizikokhimii oligomerov
Oligomery-2002 (VIII Int. Conf. on Chemistry and
Physical Chemistry of Oligomers Oligomers-2002 ),
Chernogolovka, September 9 14, 2002, p. 252.
REFERENCES
1. Chemical Reactions of Polymers, Fettes, E.M., Ed.,
New York: Interscience, 1964. Translated under the
title Khimicheskie reaktsii polimerov, Moscow: Mir,
1967, vol. 1, pp. 41 44.
2. Zaitsev, B.A., Abstracts of Papers, XVI Mendeleevskii
s ezd po obshchei i prikladnoi khimii (XVI Men-
deleev Congr. on General and Applied Chemistry),
Moscow, 1998, no. 2, pp. 304 305.
3. Zaitsev, B.A., Abstracts of Papers, VIII Mezhduna-
rodnaya konferentsiya po khimii i fizikokhimii oligo-
merov Oligomery-2002 (VIII Int. Conf. on Chem-
istry and Physical Chemistry of Oligomers Olig-
omers-2002 ), Chernogolovka, September 9 14, 2002,
p. 193.
15. Zaitsev, B.A., Khramova, G.I., Tsygankova, T.S.,
et al., Acta Polym., 1985, vol. 36, no. 10, pp. 521 526.
16. Zaitsev, B.A., Lukasov, S.V., Kiseleva, R.F., et al.,
Acta Polym., 1985, vol. 36, no. 10, pp. 527 530.
17. Zaitsev, B.A., Kiseleva, R.F., and Gusarova, I.O.,
J. Polym. Sci. A, 1996, vol. 34, no. 7, pp. 1165 1181.
18. Zaitsev, B.A., Tsygankova, T.S., and Khramova, G.I.,
Vysokomol. Soedin., Ser. B, 1982, vol. 24, no. 7,
pp. 507 511.
4. Zaitsev, B.A., Khramova, G.I., Dantsig, L.L., et al.,
Plast. Massy, 1981, no. 9, pp. 12 13.
19. Bellamy, L.J., The Infra-Red Spectra of Complex Mol-
ecules, New York: Wiley, 1957.
5. Zaitsev, B.A., Khramova, G.I., Tsygankova, T.S.,
et al., Mekh. Kompozitn. Mater., 1982, no. 5,
pp. 775 778.
6. Zaitsev, B.A., Sintez, struktura i svoistva polimerov
(Synthesis, Structure, and Properties of Polymers),
Leningrad: Nauka, 1989, pp. 66 77.
20. Bresler, S.E. and Erusalimskii, B.A., Fizika i khimiya
makromolekul (Physics and Chemistry of Macromol-
ecules), Moscow: Nauka, 1965, pp. 214 215.
21. Lukasov, S.V., Zaitsev, B.A., Tsygankova, T.S., et al.,
Plast. Massy, 1985, no. 2, pp. 56 58.
7. Berlin, A.A., Kefeli, T.Ya., and Korolev, G.V., Poli-
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 10 2003