Synthesis of Rolivsans containing unsaturated biphenyl units by acid-catalyzed transformations of 4,4′-di(1-hydroxyethyl)biphenyl

Article abstract of DOI:10.1134/S1070427207050187

The mechanism and kinetics of formation, and also the structure, composition, and properties of thermosetting resins of a new class, Rolivsans with biphenyl units, were studied.

Full text of DOI:10.1134/S1070427207050187

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 5, pp. 783 789. Pleiades Publishing, Ltd., 2007.
Original Russian Text B.A. Zaitsev, G.I. Khramova, I.D. Shvabskaya, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 5, pp. 804 811.
MACROMOLECULAR CHEMISTRY
AND POLYMERIC MATERIALS
Synthesis of Rolivsans Containing Unsaturated Biphenyl Units
by Acid-Catalyzed Transformations
of 4,4 -Di(1-hydroxyethyl)biphenyl
B. A. Zaitsev, G. I. Khramova, and I. D. Shvabskaya
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Received February 9, 2007
Abstract The mechanism and kinetics of formation, and also the structure, composition, and properties of
thermosetting resins of a new class, Rolivsans with biphenyl units, were studied.
DOI: 10.1134/S1070427207050187
Rolivsans are thermosetting polyfunctional resins
exhibiting high thermal and chemical resistance and
containing diphenyl ether units with terminal vinyl
and methacrylate groups. They are used as insulating
materials operating under extreme conditions [1 4].
Rolivsans are prepared from various aromatic com-
pounds and unsaturated carboxylic acids [5 8]. Roliv-
san MV-1 resin has been developed and has found
practical application. Its synthesis is based on trans-
formations of methacrylic acid and bis[4-(1-hydroxy-
ethyl)phenyl] ether, catalyzed by strong acids. The
starting ether, in turn, is prepared from diphenyl ether
[9, 10].
aromatic solvent in the presence of p-toluenesulfonic
acid monohydrate V and polymerization inhibitors:
AcCl, CH Cl ,
H3 C
O
O
2
2
AlCl , T
0 C
3
CH3
HCl
II, 97.5%
I
H3 C
H
O
H , Raney Ni, C H OH
2
5
2
60 C,
T
P=15 70 atm
CH3
O
H
III, 87%
CH C(CH )CO H (IV)
2
3
2
Rolivsans (monomer oligomer
p-CH C H SO H H O, systems) with biphenyl groups.
3
6
4
3
2
T = 80 110 C
(M1 + M2 + M3 + OL), 95%
The goal of this study is detailed examination of
the conditions of synthesis, structure, and properties
of unsaturated biphenyl compounds and of composi-
tions and resins of Rolivsan type based on them.
Previously we studied in detail acid-catalyzed de-
hydration of di[4-(1-hydroxyethyl)phenyl] ether VI
both in the presence of carboxylic acids (mainly meth-
acrylic acid) and without them. The reaction was per-
formed with refluxing in an aromatic solvent, with
azeotropic distillation of the released water [6 10].
Comprehensive studies showed that the process in-
volves consecutive-parallel reactions: polycondensa-
tion of the bisecondary diol, its esterification with
methacrylic acid, dehydration of this diol and its poly-
condensation products, cleavage of (di)methacrylates
with the formation of a (di)vinylaromatic compound
and methacrylic acid, and dimerization of (di)vinyl-
aromatic compounds by the polyaddition mechanism
with the proton transfer (oligomerization) [12 16].
It is known that biphenyl is a readily available
starting compound and that biphenyl units incorpo-
rated in some heat-resistant polymers are characterized
by high resistance to thermal oxidation and hydrol-
ysis; they also tend to form mesomorphic structures.
The synthesis and molecular design of Rolivsans [6
8] determine in this case the choice of 4,4 -di(1-hy-
droxyethyl)biphenyl as the starting compound. This
compound is prepared in two steps. The first step is
Friedel Crafts acetylation of biphenyl I, giving 4,4 -
diacetylbiphenyl II in quantitative yield [8, 11]. In the
second step, compound II is subjected to catalytic
hydrogenation on Raney nickel to obtain 4,4 -di(1-hy-
droxyethyl)biphenyl, also in quantitative yield. Roliv-
sans with bifunctional units were prepared by heating
of bisecondary diol III with methacrylic acid IV in an
However, first we studied a simpler process, poly-
condensation of 4,4 -di(1-hydroxyethyl)biphenyl (III)
itself without a carboxylic acid. Based on the previ-
783

784
ZAITSEV et al.
Table 1. Synthesis conditions and composition of divinylbiphenyl systems obtained
Concentration, M
Product composition,** wt %
Found, %
Treact,*
,
h
Run no.
Tm, C
C
cdiolIII
ccatV 103
M1
(m1)2 (m1)3 (m1)n > 3
C
H
1
2***
0.2173
0.1588
0.1585
0.2392
0.2392
0.2582
0.2173
5.0
10.1
10.1
19.7
19.7
4.9
111
111
111
111
111
144
144
2.0
1.0
1.5
0.2
0.3
0.8
1.0
75
70
35
15
42
77
89
19
15
25
17
25
17
8
5
5
10
17
10
4
1
10
30
51****
23****
2
1
135 151
135 151
132 134
91.7
91.7
91.6
7.0
7.0
7.5
3
4
5
6
7
135 145
150 153
3.0
2
* Refluxing in toluene (111 C) or o-xylene (144 C).
** (m ) , (m ) , and (m ) refer to dimers, trimers, and higher oligomers, respectively.
1 2
1 3
1 n > 3
*** The degree of unsaturation of the product (run no. 3), determined by ozonolysis, is 0.00773 mol of double bonds per gram.
**** Mixture of unsaturated oligoethers (OL) and produtcs of imcomplete dehydration (cleavage) of oligoerthers described previously
[6, 7, 13].
ously suggested mechanism [6, 7, 8, 11 16], after the
polycondensation of bisecondary aromatic diols [13]
catalyzed by strong acids and the subsequent dehydra-
tion of oligoethers VII [12], formation of divinylbi-
phenyl monomer oligomer systems of various com-
positions could be expected:
temperature (run no. 7) and low c results in the
cat
formation of 4,4 -divinylbiphenyl (M1) in almost
quantitative yield. This monomer, like low-melting
divinylarene compositions listed in Table 1, is readily
miscible with the known thermosetting resins and is
of interest as a heat-resistant and chemically stable
cross-linking agent. Pure divinylbiphenyl monomer
M1 (melting point 152 154 C) can be readily sepa-
rated from such compositions by sublimation.
Me
Me Me
Me
Catalyst V
n
HO HC Ar CH OH
n OH
H(O HC Ar CH)
(n 1)H O
2
VII
III
In accordance with the established mechanism, in
the case of similar polycondensation of biphenyl
diol III with carboxylic acid IV we could expect for-
mation of divinylarene monomer oligomer systems of
the following compositions:
Catalyst V
n H2 C=HC Ar CH=CH2
nH O
2
M1
Me
Catalyst V
Catalyst V
H2 C=HC Ar CH+... A + (n 1)M1
CH2=CH
CH=CH2
Me Me
H2 C=HC Ar CH CH=CH Ar CH+A
M1
+ (n 2 )M1
Dimer
Me
Me
Catalyst V
H2 C=HC Ar CH (CH=CH Ar CH)n 2 CH
Trimer
HA CH =
CH Ar CH,
(OL)
2
where Ar = 4,4 -Ph Ph; n = 0, 1, 2, 3, etc.; HA is
catalyst V.
Indeed, as seen from Table 1 and Fig. 1, acid-cata-
lytic transformations of diol III lead to compositions
consisting of 4,4 -divinylbiphenyl (M1), its unsatu-
rated dimer, trimer, tetramer, and oligomers of higher
molecular weights. The product composition strongly
depends on the synthesis conditions. For example,
refluxing of diol III in o-xylene at a relatively high
Tetramer
v, arb. units
Fig. 1. Gel chromatogram of the monomer oligomer sys-
tem prepared in toluene (Table 1, run no. 3). Eluent
toluene; sample concentration 2 g per 100 ml of solvent.
(v) Retention volume; the same for Figs. 3 and 4.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 5 2007

SYNTHESIS OF ROLIVSANS CONTAINING UNSATURATED BIPHENYL UNITS
785
CH2=CH
CH(CH3)OCOC(CH3)=CH2
M2
CH2=C(CH 3)COO(CH 3)CH
CH(CH3)OCOC(CH3)=CH2
M3
CH2=C(CH3)COO(CH3)CH C6H4 C6H4 CH(CH3) [CH=CH C6H4 C6H4CH(CH3)]n OCOC(CH3)=CH2
OL
The results of these transformations are given in
Tables 2 and 3. The composition and structure of
Rolivsans containing biphenyl units were examined
by exclusion liquid chromatography, IR spectroscopy,
elemental analysis, and analysis for functional groups
(ester numbers, ozonolysis). As seen from Fig. 2, the
initial rates of the dehydration of aromatic diols with
biphenyl (III) and diphenyl ether (VI) groups on heat-
ing with methacrylic acid are essentially different.
Despite the fact that the concentration of acid catalyst
V in the system with biphenyl diol III is approximate-
ly 2.5 times higher, the initial dehydration rate in this
system is considerably lower. To compare the rates of
both processes, the kinetic data can be reduced to the
same synthesis conditions, taking into account the fact
that the initial dehydration rate is proportional to the
concentration of the acid catalyst [6 8, 17]. Calcula-
tion shows that in this case the rate of water release
from the start of the process to 70 80% conversion is
approximately five times higher for the system with
diphenyl ether diol VI. This effect, apparently, cannot
be assigned to the influence of the chemical structure
of diols III and VI on the reactivity of terminal hy-
droxy groups in the dehydration. The difference in the
electronic effects seems to be insignificant in this
case. The difference in the catalyst acidity in these
media is considerably more pronounced. The acidity
of catalyst V in the medium of diphenyl ether diol VI
is considerably higher, because it forms a protonated
species with the lone electron pair of the ether oxygen
atom [17].
It should be noted that monomer M1 can also be
prepared by sublimation from methacrylate composi-
tions; however, in this case it contains an impurity of
jointly subliming methacrylate M2 (Fig. 3).
As seen from Tables 2 and 3, and from Figs. 4 and
5, the composition and properties of products formed
by reaction of diol III with carboxylic acid IV regu-
larly vary in accordance with the established mechan-
Table 2. Synthesis conditions and characteristics of unsaturated monomer oligomer systems containing biphenyl com-
pounds with terminal vinyl and methacrylate groups*
Run
no.**
(sample) cdiolIII
Concentration, M
Found, %
Treact,***
,
h
>C=C<
EN
Tm,
C
nDt
C
cIV
ccatV 103
C
H
8
9
10
11(1)
11(2)
11(4)
12
13
14
0.3687
0.4160
0.2393
0.2390
0.2390
0.2390
0.2393
0.2373
0.2373
0.2373
0.3815
0.9207
1.0241
0.5763
0.5756
0.5756
0.5756
0.5763
0.5714
0.5714
0.5714
1.9121
11.7
13.2
19.7
19.7
19.7
19.7
19.7
19.5
19.5
19.5
12.1
81
81
3.5
1.7
0.5
0.5
1.5
3.5
2.2
0.7
1.5
2.5
1.5
82.5
81.5
81.6
81.7
84.1
90.5
91.5
7.2
7.5
7.5
7.0
6.9
7.1
7.0
156
30 35
1.59040
1.59540
111
111
111
111
111
111
111
111
111
0.540
0.708
0.755
30 32
112 118
132 134
123 128
95 110
110 115
80 108
35 45
15
16
0.552
250
79.9
7.2
1.58840
* (>C=C<) Degree of unsaturation, mol of double bonds per 100 g of product; (EN) ester number, mg KOH per gram of product.
** c /c = 1 : 2.5 (run nos. 8, 9), 1 : 2.4 (run nos. 10 15), or 1 : 5 (run no. 16).
III IV
*** In refluxing benzene (81 C) or toluene (111 C).
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 5 2007

786
ZAITSEV et al.
Table 3. Composition of Rolivsans containing biphenyl
units and prepared at various catalyst concentrations and
synthesis times*
Composition, wt %
OL
Run ccatV 103,
,
h
no.
M
M1
M2
M3 OL
11(1)
11(2)
11(3)
11(4)
17(2)
17(5)
17(13)
18(6)
18(8)
18(10)
18(12)
19.7
19.7
19.7
19.7
19.7
19.7
19.7
7.0
0.5
1.5
2.5
3.5
0.3
1.0
4.5
6.0
8.0
6
24
37
45
10
29
10
30
38
48
54
35
42
38
30
45
30
8
45
42
34
29
38
30
23
20
34
31
22
22
17
14
12
21
6
2
5
11
10
60
3
3
4
v, arb. units
7.0
7.0
7.0
Fig. 4. Gel chromatograms of samples taken (1) 20, (2) 60,
and (3) 270 min after the start of the synthesis of the mono-
mer oligomer system (Table 3, run no. 17, samples 2, 5,
and 13). The molecular weights of the components are
given in parentheses.
10.0
12.0
5
* The products were prepared by refluxing the reaction mixtures
containing 0.239 M diol III and 0.576 M methacrylic acid IV
in toluene (111 C).
W, wt %
, %
OL
, h
Fig. 5. Kinetics of formation of components W of the
monomer oligomer system (Table 3, run no. 17). ( ) Syn-
thesis time.
, min
Fig. 2. Kinetics of dehydration of the system bisecondary
aromatic diol methacrylic acid in toluene at 111 C. ( ) De-
ism and kinetics of the process. In the initial and mid-
dle steps of the process, primary oligoethers undergo
dehydration, and the maximal amounts of vinyl- and
divinylaromatic monomers (M1, M2) and of methac-
rylates (M2, M3) are formed. Further steps involve
consecutive-parallel cleavage of methacrylates (M2,
M3) to form again monomers M1 and M2, which, in
turn, enter into stepwise dimerization reactions (cati-
onic polyaddition with the proton transfer), etc. The
final products of these transformations are oligomers
(OL) of type m (m ) m , where m and m are
degree of dehydration and ( ) time. (1) Molar ratio diol VI :
3
acid IV = 1 : 2.47, c
diol VI : acid IV = 1 : 2.41, c
= 7.86 10 M; (2) molar ratio
catV
3
= 19.7 10 M.
catV
2
1 n
2
1
2
units of monomers M1 and M2, respectively.
The IR spectra of unsaturated biphenyl compounds
containing terminal vinyl and methacrylate groups and
internal double bonds (Fig. 6) exhibit bands of unsatu-
rated and aromatic groups at 1630, 1600, 1495, 990,
v, arb. units
Fig. 3. Gel chromatogram of components M1 and M2 (mp
122 123 C) sublimed from the monomer oligomer compo-
sition (Table 2, run no. 12).
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 5 2007

SYNTHESIS OF ROLIVSANS CONTAINING UNSATURATED BIPHENYL UNITS
787
T, %
2
1
10 , cm
Fig. 6. IR spectrum of the monomer oligomer composition [Table 3, run no. 11 (2)]. (T) Transmission and ( ) wavenumber.
1
965, 945, and 905 cm , bands of methyl and meth-
20]. The unsaturated compositions obtained are pasty
or low-melting compounds curing on heating and
forming monolithic network polymers and plastics
with a high softening point (Table 4).
1
ylene groups at 2960, 2925, 2870, and 2850 cm ,
bands of methine groups at 2900 cm , and also
strong bands of stretching vibrations of the carbonyl
group, characteristic of methacrylates, at 1710 cm
1
1
[18, 19]. With the progress of the reaction, the carbon-
yl band at 1710 cm and of the out-of-plane vibration
EXPERIMENTAL
1
bands of the H C= group in p-CH =CH Ph Ph and
4,4 -Di(1-hydroxyethyl)biphenyl III was prepared
by Friedel Crafts acetylation of biphenyl I [8, 11]
followed by catalytic hydrogenation or reduction of
the resulting aromatic diketone II. Diketone II was
prepared as follows. To a mixture of 80 ml of CH Cl
2
1
CH =C(CH )COO fragments at 902 and 940 cm ,
2
3
respectively, decrease in the intensity, whereas the
1
band at 965 cm , belonging to the out-of-plane vibra-
tions of the H C= group in trans- CH=CH frag-
ments, increases; the concentration of these fragments
grows in the course of stepwise dimerization (cationic
polyaddition) of vinylaromatic compounds [14 16,
2
2
and 133.2 g (1.0 mol) of anhydrous AlCl , cooled to
3
approximately 0 C, 85.2 ml (94.2 g, 1.20 mol) of
acetyl chloride was added with stirring over a period
Table 4. Thermal and physicomechanical properties of glass fiber laminates based on Rolivsans with biphenyl units*
DTGA
Ultimate bending stress, MPa
Run
no.
Tm,
C
, C
405
407
20 C
b
320 C
T5%, C T10%, C
20 C**
320 C**
b
b
b
9***
11(1)
11(2)
11(4)
12
30 35
30 32
112 118
132 134
123 128
400
430
260
460
300
290
320
160
300
240
200
160
240****
220
220
220
180
420
450
220
* ( ) Softening point of the cured compound (binder); (T , T
** After thermal oxidative aging in air at 320 C for 10 h.
*** Gelation time 2 h at 140 C.
) temperatures of 5 and 10% weight loss, respectively.
5%
10%
**** Weight loss 1.7 or 5.8% for binder (counting on its 30% content in the glass fiber laminate).
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 5 2007

788
ZAITSEV et al.
of 15 20 min. To the resulting acetylating complex,
the residue was recrystallized from toluene. Yield
18.6 g (70%), mp 160 161 C.
a solution of 61.6 g of biphenyl I in 80 ml of CH Cl
2
2
was added over a period of 1 h at 0 5 C with vigor-
ous stirring; the released HCl was absorbed by an
alkaline solution. The resulting complex of the acetyl-
4,4 -Divinylbiphenyl (M1). A mixture of 5.0020 g
(0.02064 mol) of diol III, 0.0500 g of tert-butylcate-
chol, 0.0742 g of catalyst V, and 75 ml of o-xylene
was refluxed ( 144 C) for 50 min with azeotropic dis-
tillation of the released water. Then the mixture was
worked up as described above. Yield of unsaturated
monomer oligomer composition containing about
75% monomer M1 (data of exclusion liquid chroma-
tography) 3.8 g, mp 135 145 C. Sublimation of
0.500 g of the composition at a bath temperature of
160 C and residual pressure of 1 2 mm Hg for 7
10 min gave 0.33 g of pure monomer M1, mp 152
154 C (published data [21, 22]: 152.5 153 C).
ated product with AlCl in methylene chloride was
3
stirred for 0.5 h at 0 C and for an additional 3 h at
40 C. Diketone II was isolated by decomposing the
complex with a mixture of 900 g of finely crushed ice,
2 l of distilled water, and 1.2 l of 20% HCl, which
was followed by washing with water and drying at
60 70 C. The yield of dry diketone II was 95.8 g
(97.5%), mp 165 170 C; after recrystallization from
ethanol and repeated recrystallization from toluene,
the melting point of II increased to 185 190 and 193
195 C, respectively (published data [21]: 190 192 C).
The content of acetyl groups in II was determined by
oximation.
Biphenyl compounds with terminal vinyl and
methacrylate groups, and also their oligomerization
products containing unsaturated dimers, trimers, tetra-
mers, and higher oligomers were prepared as follows.
A solution of biphenyl diol III in an aromatic solvent
(benzene, toluene, o-xylene), containing inhibitors of
radical polymerization (hydroquinone, CuCl) and a
catalyst (p-toluenesulfonic acid monohydrate, V) was
refluxed in the presence of methacrylic acid VI or
without it in a flask equipped with a Dean Stark trap.
Water formed by polycondensation, esterification, and
dehydration was removed by azeotropic distillation.
Then the mixture was cooled and, after filtering CuCl
Found, %: >C=O 24.1.
C16H14O2.
Calculated, %: 23.5.
4,4 -Di(1-hydroxyethyl)biphenyl III was prepared
by two procedures: (A) hydrogenation of II on Raney
nickel and (B) reduction of II with sodium borohy-
dride. In procedure A, a mixture of 250 ml of ethanol,
5.0 g of Raney nickel (Merck Schuchardt) containing
about 88% Ni and 12% Al, and 30.0 g (0.126 mol) of
II was stirred in a pressure vessel at 60 70 C at ini-
tial hydrogen pressure of 50 70 C for approximately
1 h. Then the catalyst was separated by decanting and
centrifugation of the solution of the hydrogenated
product in ethanol; the alcohol was distilled off at
reduced pressure, and the residue was recrystallized
from toluene. Yield of aromatic diol III 26.5 g (87%),
mp 158 159.5 C (published data [21]: 159 161 C).
off, washed successively with water, 5% NaHCO
3
solution, and again water, after which it was dried
over CaCl and passed through a 2 3-cm Al O bed;
2
2 3
the solvent was distilled off at reduced pressure. The
conditions of synthesis, composition, and properties of
the unsaturated biphenyl compounds [4,4 -divinylbi-
phenyl (M1), dimethacrylate of diol III (M3), 4-vinyl-
4 -(1-hydroxyethyl)biphenyl methacrylate (M2)] and
of unsaturated aromatic monomer oligomer systems
containing Rolivsans with biphenyl-containing units
are listed in Tables 1 3. The IR spectra were recorded
on a Specord 75-IR device from thin films or solu-
Found, %: C 79.2; H 7.4.
C16H18O2.
Calculated, %: C 79.3; H 7.5.
The content of hydroxy groups was determined by
acetylation.
tions in CHCl . Exclusion liquid chromatography was
3
performed on a KhZh-1307 chromatograph at 20 C;
the column was packed with Ultrastyrogel sorbent
(500 ); the eluent was toluene; the product concen-
tration was 0.20 0.50 g in 100 ml of a solvent. The
degree of unsaturation was determined on an ADS-4
Found, %: OH 13.7.
C16H18O2.
Calculated, %: OH 14.
ozonizer at 0 C (solvent CCl ). The ester number was
In procedure B, a mixture of 200 ml of absolute
ethanol, 5.0 g (0.13 mol) of sodium borohydride, and
25.8 g (0.11 mol) of diketone II was heated at 60 C
for 2 h. The reaction mixture was treated with 50 ml
of water, the precipitated hydroxides were filtered off,
the solvent was distilled off at reduced pressure, and
4
determined by dissolving a resin sample in dioxane
purified by distillation from KOH and Na, which was
followed by adding a 0.1 N solution of KOH in eth-
anol dioxane, refluxing the mixture for 7 h (in so
doing, the reflux condenser was equipped with a soda
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 5 2007

SYNTHESIS OF ROLIVSANS CONTAINING UNSATURATED BIPHENYL UNITS
789
lime tube), and titrating with 0.1 N HCl. Samples of
glass fiber laminates in the form of 1.6 2.0-mm-thick
plates were prepared by hot pressing of prepregs (eight
sheets of T-10-80 glass fiber fabric impregnated with
a melt of the unsaturated composition) in a mold at a
AN SSSR (Synthesis, Structure, and Properties of
Polymer: Coll. of Papers of Inst. of Macromolecular
Compounds, USSR Acad. Sci.), Koton, M.M., Ed.,
Leningrad: Nauka, 1989, pp. 66 77.
4. Zaitsev, B.A., Khramova, G.I., Tsygankova, T.S.,
2
pressure of 1 kgf cm , followed by thermal curing of
et al., Plast. Massy, 2003, no. 10, pp. 23 25.
1
the stack at 120 250 C (heating rate 10 deg h ). The
5. USSR Inventor’s Certificate no. 794026.
ultimate bending stress at three-point bending was
determined with 3 4-mm-wide samples at a support
spacing of 15 min and a loading rate of 15 mm min .
6. Zaitsev, B.A., Khramova, G.I., and Dantsig, L.L.,
Vysokomol. Soedin., Ser. A, 1982, vol. 24, no. 12,
pp. 2467 2474.
1
Dynamic thermogravimetric analysis (DTGA) was
performed in air on a C derivatograph (MOM, Hun-
7. Zaitsev, B.A., Dantsig, L.L., and Khramova, G.I.,
Zh. Org. Khim., 1983, vol. 19, no. 11, pp. 2340 2349.
1
gary) at a heating rate of 4.5 deg min . The softening
8. Zaitsev, B.A., Regular Trends in Formation, Structure,
and Properties of Heat-Resistant Network Polyaryl-
enes, Doctoral Dissertation, Leningrad, 1983.
point was determined on a Vicat-type device designed
at the Institute of Macromolecular Compounds, Rus-
sian Academy of Sciences at an indenter load of 1 kg
9. Zaitsev, B.A., Khramova, G.I., and Tsygankova, T.S.,
2
and an indenter cross section of 1 mm .
Zh. Prikl. Khim., 2003, vol. 76, no. 4, pp. 658 662.
10. Zaitsev, B.A., Khramova, G.I., and Shvabskaya, I.D.,
CONCLUSIONS
Zh. Prikl. Khim., 2007, vol. 80, no. 4, pp. 637 642.
11. Zaitsev, B.A., Dantsig, L.L., Khramova, G.I., et al.,
(1) The previously suggested method for preparing
polyfunctional aromatic compounds, divinylaromatic
monomer oligomer compositions, and heat-resistant
thermosetting resins of a new type (Rolivsans), based
on acid-catalyzed transformations of bisecondary aro-
matic diols, was applied to biphenyl derivatives.
Zh. Prikl. Khim., 1977, vol. 50, no. 2, pp. 411 415.
12. Zaitsev, B.A. and Kiseleva, R.F., Vysokomol. Soedin.,
Ser. A, 1981, vol. 23, no. 8, pp. 1783 1790.
13. Zaitsev, B.A., Fedorova, A.V., Kiseleva, R.F., et al.,
Vysokomol. Soedin., Ser. A, 1983, vol. 25, no. 5,
pp. 1076 1081.
(2) Previously unknown unsaturated monomeric
and oligomeric compounds with biphenyl groups, e.g.,
4,4 -di(1-hydroxyethyl)biphenyl dimethacrylate, 4-vin-
yl-4 -(1-hydroxyethyl)biphenyl methacrylate, and dif-
ficultly accessible 4,4 -divinylbiphenyl, and their com-
positions can be prepared in high yield by a one-pot
process: dehydration of 4,4 -(1-hydroxyethyl)biphenyl
and of the system 4,4 -di(1-hydroxyethyl)biphenyl
methacrylic acid.
14. Zaitsev, B.A. and Kiseleva, R.F., Acta Polym., 1983,
vol. 36, no. 10, pp. 527 530.
15. Zaitsev, B.A., Kiseleva, R.F., Denisov, V.M., et al.,
Vysokomol. Soedin., Ser. A, 1984, vol. 26, no. 8,
pp. 1602 1609.
16. Zaitsev, B.A., Kiseleva, R.F., and Gusarova, I.O.,
J. Polym. Sci., Polym. Chem. Ed., 1996, vol. 34,
pp. 1165 1181.
17. Denisov, E.T., Kinetika gomogennykh khimicheskikh
reaktsii (Kinetics of Homogeneous Chemical Reac-
tions), Moscow: Vysshaya Shkola, 1978.
(3) Rolivsans containing biphenyl units and based
on the above (di)vinylbiphenyl compounds and meth-
acrylates of secondary alcohols form heat-resistant
network polymers and plastics on curing.
18. Zaitsev, B.A., Khramova, G.I., and Tsygankova, T.S.,
Zh. Prikl. Khim., 2003, vol. 76, no. 10, pp. 1708
1714.
19. Bellamy, L.J., The Infra-Red Spectra of Complex Mol-
ecules, New York: Wiley, 1957.
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RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 5 2007