Synthesis, Structure, Composition, and Properties of Rolivsans

Article abstract of DOI:10.1023/A:1025759808918

Novel thermosetting resins Rolivsans were prepared, and their structure, composition, and properties were studied. The structural parameters of Rolivsans as influenced by the synthesis conditions were determined.

Full text of DOI:10.1023/A:1025759808918

Russian Journal of Applied Chemistry, Vol. 76, No. 4, 2003, pp. 634 638. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 4, 2003,
pp. 658 662.
Original Russian Text Copyright
2003 by Zaitsev, Khramova, Tsygankova.
MACROMOLECULAR CHEMISTRY
AND POLYMERIC MATERIALS
Synthesis, Structure, Composition, and Properties of Rolivsans
B. A. Zaitsev, G. I. Khramova, and T. S. Tsygankova
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Received February 17, 2002; in final form, January 2003
Abstract Novel thermosetting resins Rolivsans were prepared, and their structure, composition, and
properties were studied. The structural parameters of Rolivsans as influenced by the synthesis conditions
were determined.
Novel thermosetting liquid (solvent-free) resins
named Rolivsans are used for preparing polymeric and
composite materials with enhanced resistance to heat
and to the most aggressive agents [1 12]. They are
used in various branches of engineering. Rolivsans
have been prepared by acid-catalyzed reactions of
bis[4-(1-hydroxyethyl)phenyl] ether with methacrylic
acid [13 15].
structure of Rolivsans, and reveal correlations between
their structural characteristics and properties. The
starting compound in the synthesis is diphenyl ether I,
which is quantitatively converted to di(4-acetylphenyl)
ether II by the Friedel Crafts acylation. Compound II
is subsequently hydrogenated in the presence of Raney
nickel to obtain bis[4-(1-hydroxyethyl)phenyl] ether
III, which is then refluxed with methacrylic acid IV
in an aromatic solvent in the presence of an acid cat-
alyst (e.g., p-toluenesulfonic acid) and a polymeriza-
tion inhibitor (e.g., hydroquinone):
The goals of this study were to analyze in detail the
synthesis conditions, elucidate the composition and
O
O
O
AcCl, CH2Cl2, T < 20 C
H2, Raney Ni, C2H5OH
H3C
H3C
O
OH
CH3
AlCl3
T > 20 C, p = 20 100 atm
O
CH3
OH
I
II, 98%
III, 85%
+, T = 70 145 C
CH2=C(CH3)CO2H (IV), H
Rolivsans.
(M1 + M2 + M3 + OL + AO), 95%
where M1 M3 are monomers, OL is an oligomer, and
AO denotes antioxidants (products of alkylation of
phenolic compounds with monomers M1 and M2 and
with oligomer OL).
compound and methacrylic acid [13 15, 19, 20]; step-
wise (co)polymerization of (di)vinyl-substituted aro-
matic compounds by the polyaddition mechanism with
proton transfer (oligomerization) [13 15, 18, 21 23];
and alkylation of dihydric phenols (e.g., hydroqui-
none) with unsaturated aromatic compounds [24].
Comprehensive studies have shown that a one-pot
process resembling the synthesis of oligoether acry-
lates and performed in the course of one or several
hours at 70 110 C involves the following successive-
parallel reactions: polycondensation of diol III [15,
16]; esterification with methacrylic acid of this diol
and oligoethers containing terminal hydroxy groups
and formed by polycondensation (formation of mono-
meric and oligomeric methacrylates [13 15]); dehydra-
tion of diol III and oligoethers [15, 17, 18]; cleavage
of (di)methacrylates to (di)vinyl-substituted aromatic
Each of these reactions was studied separately with
model compounds and Rolivsan components; also,
separate stages of the synthesis of Rolivsan as a
system of monomers and oligomers were examined.
The composition and structure of Rolivsans were
studied by exclusion liquid chromatography (ELC)
1
(Figs. 1, 2), IR and H NMR spectroscopy, elemental
analysis, and analysis for functional groups (ester and
1
bromine numbers, ozonolysis). The IR and H NMR
1070-4272/03/7604-0634 $25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS, STRUCTURE, COMPOSITION, AND PROPERTIES OF ROLIVSANS
635
Fig. 1. Gel chromatograms of sample K (Table 2), obtained
at 20 C with (1) one column and (2) six series-connect-
ed columns. Eluent tetrahydrofuran. (M ) Number-average
n
molecular weight; the same for Fig. 3.
Fig. 3. Gel chromatograms of Rolivsans prepared in ben-
zene at the ratio diol III : acid IV = 1 : 2.5. Initial con-
centration of sulfo acid V 13.5 mM. Samples were taken
(a) 45, (b) 90, and (c) 120 min after the beginning of
the synthesis.
Fig. 2. Composition of Rolivsan vs. synthesis time
(benzene, 13.5 mM sulfo acid V, 80 C). (c) Content of
components.
spectra of model compounds and separate Rolivsan
components M1, M2, M3, and OL have been dis-
cussed previously [15, 22 25]. Naturally, the spectra
of Rolivsan as a system of monomers and oligomers
contain a much greater number of absorption bands
associated with various functional groups than the
spectra of the components taken separately.
ene group give an AA BB pattern centered at
=
7.25 ppm. Protons of the unsaturated groups appear
as a set of signals (ppm) at = 6.7 5.2, namely, at
6.66 (CH= in CH2=CH), 6.21 and 5.75 [CH2= in
CH2=C(CH3)], doublets at 5.63 (5.60 and 5.66;
CH2= in CH2=CH) abd 5.23 (5.20 and 5.26; CH2=
in CH2=CH), and a doublet of doublets at 6.45. The
signal at 6.21 ppm also belongs to the trans-CH=CH
protons, since similar signals of the internal double
bond ( 6.19, 6.24 ppm) are observed in the 1H NMR
spectrum of the related compound, unsaturated styrene
dimer [PhCH=CHCH(CH3)Ph]. The tert-H proton in
the >CHPh group appears as a broad ill-resolved
multiplet at 3.67 ppm and a multiplet at 4.32 ppm
(PhCHPh). The methyl and methylene groups give
signals at 2.01 and 1.45 (MeC=CH2), 1.61 and 1.64
A typical IR spectrum of Rolivsan contains absorp-
tion bands of unsaturated and aromatic groups at
3080, 3060, 3030, 2975, 1630, 1600, 1500, 985, 965,
1
940, and 905 cm , and also bands of methyl and
1
methylene groups at 2960, 2925, 2870, and 2850 cm
1
and methine groups at 2900 cm . The IR spectrum
also contains strong absorption bands related to car-
1
bonyl groups in methacrylates (1715 cm ) and to
1
aromatic ether groups (1240 cm ), and to other ab-
1
1
sorption bands (1170, 1100, 1060 cm , etc.) assign-
(MeCHAr), and 2.59 ppm (CH2Ar). The H NMR
able to stretching vibrations of ester and ether groups.
spectrum contains no signals at 2.3 ppm, which are
characteristic of toluene methyl protons. This fact
suggests that, under the conditions of Rolivsan syn-
thesis, acid-catalyzed aralkylation of the solvent (tol-
uene) with M1, M2, and OL does not occur.
1
The H NMR spectrum of Rolivsan contains sig-
nals typical of such related compounds as styrene, its
unsaturated dimer trans-1,3-diphenyl-1-butene [24],
and methacrylates. Protons of the substituted phenyl-
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 4 2003

636
ZAITSEV et al.
Table 1. Influence of the synthesis time
on the composition and properties of Rolivsans
Resin composition, wt %
,
Unsaturation,
mol >C=C</100 g product
Ester number,
mg KOH/g product
nD
(T, C)
min
M1
M2
M3
OL
AO
45
90
120
14
20
16
37
24
20
30
21
15
18
34
48
1
1
1
0.559
0.592
0.610
190
160
135
1.577 (20)
1.597 (40)
1.609 (40)
Table 2. Characteristics of Rolivsan M1
Component content, wt %
25
Unsaturation,
mol >C=C</100 g product
,
d20
,
g cm
Grade
Mn
nD20
3
cP
M1
M2
M3
OL
Ar(OH)n
K
S
14
12
27
22
25
18
32
46
2
2
0.58
0.55
420
480
1.590
1.600
1620
3500
1.09
1.10
Figures 2 and 3 show how the composition and
molecular-weight distribution (MWD, found by ELC)
depend on the synthesis conditions. Initially, reflux-
ing in benzene or toluene results in fast polyconden-
sation of diol III, which results in the formation of an
oligoether with terminal hydroxy groups [15, 16]. The
competing reactions are esterification of the oligoether
of diol III with methacrylic acid [15, 16] and dehydra-
tion; these reactions yield oligomeric methacrylates
(OL), monomer M1 [15, 18], and water removed by
azeotropic distillation. Acidolysis of the oligoether
and oligomeric methacrylates yields monomeric meth-
acrylates M2 and M3 [13 15].
acid IV and, respectively, monomers M1 and M2
(Table 1):
CH2
O
H2C
M1
H2C
H3C
O
O
O
H2C
CH3
M2
H2C
H3C
O
It is known that the components of Rolivsans are
M1, M2, M3, OL, and AO. The composition and
properties of Rolivsans can be varied widely by en-
suring a greater extent of oligomerization of M1 and
M2 in the presence of p-toluenesulfonic acid V
by the step (dimerization) addition mechanism with
proton transfer to the monomer and formation of,
first, dimers, then trimers [13 15, 21 23], etc. Meth-
acrylates M2 and M3 are gradually cleaved to form
H3C
O
O
O
CH3
CH3
CH2
O
M3
CH3
CH3
CH3 O CH3
H2C HCC6H4OC6H4CH(CH CHC6H4OC6H4CH)n CH CHC6H4OC6H4 CHOCC CH2
OL
80 110 C, [H+]V
80 110 C, [H+]V
80 110 C, [H+]V
M3
M2 + IV
M1 + 2IV
m2
[m1]n
m2
80 110 C, [H+]V
H [m1]n 1CH CH X CH CH2
OL
IV
m1 = CH=CH X CH(CH3), m2 = H2C=CMeCO2MeHC X CHMe, X = C6H4OC6H4.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 4 2003

SYNTHESIS, STRUCTURE, COMPOSITION, AND PROPERTIES OF ROLIVSANS
637
Tables 1 and 2 show that, at relatively low conver-
sions, when the concentrations of methacrylates M2
and M3 are relatively high and the content of oligo-
2. Zaitsev, B.A., Khramova, G.I., Tsygankova, T.S.,
et al., Mekh. Kompozit. Mater., 1982, no. 5,
pp. 775 778.
mers (mainly dimers) is low, the refractive index nD20
3. Zaitsev, B.A., Sintez, struktura i svoistva polimerov
(Synthesis, Structure, and Properties of Polymers),
Leningrad: Nauka, 1989, pp. 66 77.
25
and viscosity
of the resin are comparatively low
(1.56 and 450 cP, respectively).
4. Zaitsev, B.A., Abstracts of Papers, 1st China Japan
USSR Joint Symp. on Advanced Polymers, Moscow,
September 15 21, 1991, p. A-21.
Oligomerization leads to lower content of M2 and
M3 and higher content of linear unsaturated oligomers
with increased molecular weights (mainly dimers to
pentamers); as a result, the refractive index and vis-
cosity grow substantially (to nD20 = 1.60 1.62 and
5. Zaitsev, B.A., Polym. Mater. Sci. Eng., 1992, vol. 66,
pp. 70 71.
25
= 2500 4000 cP).
6. Zaitsev, B.A., Abstracts of Papers, XVI Mendeleevskii
s ezd po obshchei i prikladnoi khimii (25 29 maya
1998 g., Sankt-Peterburg), (XVI Mendeleev Congr. on
General and Applied Chemistry (May 25 29, 1998,
St. Petersburg)), Moscow, 1998, no. 2, pp. 304 305.
Thus, the composition and properties of Rolivsans,
molecular-weight distribution of oligomeric compo-
nents, and distribution of functional groups can be
varied within prescribed limits by changing the syn-
thesis conditions.
7. Zaitsev, B.A., Tsygankova, T.S., and Khramova, G.I.,
Abstracts of Papers, VII Mezhdunarodnaya konferen-
tsiya po khimii i fizikokhimii oligomerov Oligomery-
2000 (4 8 sentyabrya 2000 g., Perm’), (VII Int.
Conf. on Chemistry and Physical Chemistry of Olig-
omers Oligomers-2000 (September 4 8, Perm)),
Moscow, 2000, p. 330.
EXPERIMENTAL
The IR spectra were measured on a Specord 75-IR
spectrophotometer (thin films), and the 1H NMR
spectra, on a JEOL C-60 HL spectrometer (60 MHz,
CDCl3, internal reference TMS). The ELC analysis of
Rolivsans and their components was performed using
a Waters gel-permeation chromatograph with col-
umns packed with Ultrastyrogel (500 ) at 20 C; elu-
ent THF, CHCl3, or toluene. The number-average
molecular weight Mn was determined with a Hitachi
Perkin Elmer 115 vapor osmometer. The content of
unsaturated bonds was found by ozonation (ADS-3
ozonizer, 0 C, solvent CCl4) and by the bromide
bromate method (determination of the bromine num-
ber, followed by recalculation to the iodine number).
The ester number was found by dissolving the resin
sample in dioxane purified by distillation from KOH
and Na, adding 0.1 N solution of KOH in ethanol
dioxane, refluxing for 7 h (the reflux condenser was
equipped with a tube packed with soda lime), and
titrating with 0.1 N HCl.
8. Zaitsev, B.A., Abstracts of Papers, VII Mezhdunarod-
naya konferentsiya po khimii i fizikokhimii oligomerov
Oligomery-2000 (4 8 sentyabrya 2000 g., Perm’),
(VII Int. Conf. on Chemistry and Physical Chemistry
of Oligomers Oligomers-2000 (September 4 8,
Perm)), Moscow, 2000, p. 122.
9. Zaitsev, B.A., Maik, V.Z., Pomerantsev, V.I., and
Shvabskaya, I.D., Abstracts of Papers, VII Mezhdu-
narodnaya konferentsiya po khimii i fizikokhimii oli-
gomerov Oligomery-2000 (4 8 sentyabrya 2000 g.,
Perm’), (VII Int. Conf. on Chemistry and Physical
Chemistry of Oligomers Oligomers-2000 (Septem-
ber 4 8, Perm)), Moscow, 2000, p. 278.
10. Zaitsev, B.A., Elokhovskaya, N.A., Kotelyanets, N.P.,
et al., Abstracts of Papers, VII Mezhdunarodnaya kon-
ferentsiya po khimii i fizikokhimii oligomerov Oli-
gomery-2000 (4 8 sentyabrya 2000 g., Perm’), (VII
Int. Conf. on Chemistry and Physical Chemistry of
Oligomers Oligomers-2000 (September 4 8, Perm)),
Moscow, 2000, p. 329.
CONCLUSIONS
(1) The mechanism of formation of Rolivsans,
novel thermosetting resins whose curing yields heat-
resistant network polymers, was elucidated.
11. Zaitsev, B.A., Khramova, G.I., Tsygankova, T.S.,
et al., Abstracts of Papers, VIII Mezhdunarodnaya
konferentsiya po khimii i fizikokhimii oligomerov
Oligomery-2002 (9 14 sentyabrya 2002 g., Cher-
nogolovka), (VIII Int. Conf. on Chemistry and Phys-
ical Chemistry of Oligomers Oligomers-2002 (Sep-
tember 4 8, Chernogolovka)), Moscow, 2002, p. 252.
(2) The composition and structure of Rolivsans
1
were determined by IR and H NMR spectroscopy,
vapor osmometry, elemental and functional analysis,
and exclusion liquid chromatography.
12. Zaitsev, B.A., Khramova, G.I., and Tsygankova, T.S.,
Abstracts of Papers, VIII Mezhdunarodnaya konferen-
tsiya po khimii i fizikokhimii oligomerov Oligomery-
2002 (9 14 sentyabrya 2002 g., Chernogolovka),
(VIII Int. Conf. on Chemistry and Physical Chemistry
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