Bifunctional vinyl ether copolymers
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 10, October, 2008
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resin (97% yield). Found (%): C, 41.18; H, 6.29; S, 24.37.
Synthesis of polymeric bases (general procedure). A mixꢀ
ture of oxidized copolymer DDE—MVS (1.15 g), KOH (0.89 g,
Ethynylation of acetone in a sealed system (typical procedure).
A suspension of polymeric superbase containing ~5.09 mmol of
K in DMSO (10 mL) was saturated with acetylene for 1—1.5 h,
then, a mixture of acetone and toluene (~1 : 1 w/w, 2.7 mL) was
added. Toluene was used as the internal standard. The amount
of acetone was calculated with accounting of acetylene dissolved
in DMSO, keeping the ratio C H : acetone ≈ 1.5 : 1 (C H
2
amount was determined from the difference of masses, weighing
DMSO before and after saturation with acetylene). The converꢀ
sion of acetone and the yield of 2ꢀmethylbutꢀ3ꢀynꢀ2ꢀol (see
Table 3) were calculated from the GLC data using toluene as the
internal standard.
Isomerization of methyl propargyl ether. A mixture of methyl
propargyl ether (1.5 g, 21.43 mmol) and polymeric superbase
(0.24 g) was heated with stirring (55—60 °C, 5 h). Analysis of the
reaction products was performed by GLC: the content of allenyl
ether was 17—25%.
5
5.89 mmol), and toluene (12.5 mL) was refluxed for 6 h (Dean—
Stark trap), then toluene was evaporated. After drying in vacuo,
a dark powder (1.88 g) was obtained, which was insoluble in
organic solvents (diethyl ether, acetone, ethanol, toluene, benzene)
and contained 32.97% of K.
2
2
2
Polymerization of VGE. The reaction was carried out in sealed
tubes under argon atmosphere. Unpolymerized monomer was
evaporated in vacuo (2 Torr) at the bath temperature below 80 °C.
The polymer was purified by reprecipitation from benzene into
the mixture of diethyl ether and light petroleum (1 : 1) and dried
until the weight was constant. PolyꢀVGE was obtained as a viscous
resin (43% yield) well soluble in organic solvents (DMSO,
acetone, chloroform, toluene), the molecular mass was 1600.
Found (%): C, 58.85; H, 8.11. C H O . Calculated (%): C,
7
12
3
5
8.32; H, 8.39.
Vinylation of ethylene glycol. A mixture of ethylene glycol
(20 g, 322 mmol) and polymeric catalyst (4 g) was heated
(150 °C, 4 h) in a 0.25ꢀL steel rotary autoclave (the initial
pressure of acetylene was 12—15 atm). Analysis of products was
performed by GLC: the content of ethylene glycol monovinyl
ether was 7—20%.
Copolymers VGE with MVS were obtained by analogous
procedure (see Table 2).
Synthesis of polymeric bases polyꢀVGE (general procedure).
Powdered KOH (1.9 g, 33.9 mmol) was added to a solution of
polyꢀVGE (2.44 g) in toluene (100 mL) followed by reflux for
4
h with stirring. The crosslinked polymer obtained was filtered
off and continuosly washed with anhydrous ethanol for 6 h in
the Soxhlet apparatus until the extract was neutral. After drying
until the weight was constant, the crosslinked polyꢀVGE (2.62 g)
was obtained as fine granules, the yield was 64.9%. Found
References
1. B. A. Trofimov, Geteroatomnye proizvodnye atsetilena. Novye
polifunktsional´nye monomery, reagenty i poluprodukty [Acetyꢀ
lene Heteroatomic Derivatives. New Polyfunctional Monomers,
Reagents, and Intermediate Products], Nauka, Moscow, 1981,
319 pp. (in Russian).
(
%): C, 30.35; H, 5.1; K, 25.01. C H K O . Calculated (%):
7 12 2 4
C, 35.27; H, 5.07; K, 32.81. The conversion was 76% (calcuꢀ
lated on K).
Synthesis of copolymeric superbase (method A). Hydrogen
peroxide (35% aq. solution, 0.4 g) was added to a solution of
copolymer (0.90 g) containing VGE (49 mol.%) in a mixture
of benzene (0.90 mL) and acetone (8.0 mL) with stirring, the
reaction was carried out at 56 °C for 12 h. The polymer was
treated similarly to the procedure for the oxidized polyꢀMVS.
After drying, the oxidized copolymer (0.93 g) was obtained as a
clear yellowish block.
2. N. A. Nedolya, Dr. Sci. Thesis, A. E. Favorsky Irkutsk Instiꢀ
tute of Chemistry, Siberian Branch of the Russian Academy
of Sciences, Irkutsk, 1998, 52 pp. (in Russian).
3. B. A. Zhubanov, E. M. Shaikhutdinov, E. F. Osadchaya,
Prostye vinilovye efiry v radikal´noi polimerizatsii [Vinyl Ethers
in Radical Polymerization], Nauka, AlmaꢀAta, 1985, 155 pp.
(in Russian).
4. B. A. Trofimov, L. V. Morozova, A. I. Mikhaleva, M. V.
Markova, L. A. Oparina, T. Skotheim, Sulfur Lett., 2000,
23, 121.
The reaction of the oxidized copolymer obtained (preliminary
powdered) with KOH (0.2 g, 3.6 mmol) in ethanol (20 mL)
(
70 °C, 2 h) gave granulated copolymer, in which, after washing
5. L. N. Parshina, Dr. Sci. Thesis, A. E. Favorsky Irkutsk Instiꢀ
tute of Chemistry, Siberian Branch of the Russian Academy
of Sciences, Irkutsk, 2005, 341 pp. (in Russian).
6. Pat. RF 1821474 (1990); Byul. Isobret. [Bull. Invent.], 1993,
22 (in Russian).
with ethanol, 14.38% of K remains.
Synthesis of copolymeric superbase (method B). Powdered
KOH (1.87 g, 33.3 mmol) was added to a solution of copolymer
(
1.74 g) containing VGE (49 mol.%) in toluene (77 mL), the
reaction mixture was refluxed for 4 h with stirring using the
Dean—Stark trap. The crosslinked polymer formed was filtered
off, washed with ethanol to remove excess KOH until the
washings were neutral. After drying, the crosslinked polymeric
base (1.47 g, 84.5%) was obtained as fine granules. Found (%):
C, 51.13; H, 7.78; S, 12.68; K, 7.20.
7. A. A. Tager, M. V. Tsilipotkina, L. K. Kolmakova, E. V.
Morozov, V. M. Balakin, T. S. Vydrina, E. V. Medvedeva,
Vysokomolekulyar. Soedin., Ser. A, 1990, 32, 727 [Polym. Sci.
USSR, Ser. A, 1990, 32 (Engl. Transl.)].
8. L. Ya. Tsarik, O. N. Novikov, V. V. Magdinets, J. Polymer
Sci., Ser. A, 1996, 36, 371.
A mixture of copolymer obtained (0.89 g), benzene (0.9 mL),
acetone (8 mL), and H O (35% aq., 0.4 g) was stirred under
9. M. Sangermano, G. Malucell, F. Morel, C. Decker, A. Priola,
Eur. Polym. J., 1999, 35, 639.
2
2
heating (56 °C, 8 h). The oxidized copolymer was washed with
acetone and dried until the weight was constant to obtain a
powdered polymer (0.9 g, 95%). Found (%): C, 48.92; H, 8.65;
S, 12.80; K, 7.08.
10. Z. S. Nurkeeva, G. A. Mun, V. V. Khutoryanskii, Vysokoꢀ
molekulyar. Soedin., Ser. B, 2001, 43, 925 [Polym. Sci., Ser.
B, 2001, 43 (Engl. Transl.)].
11. L. V. Morozova, I. V. Tatarinova, N. P. Kuznetsova, M. V.
Markova, O. A. Tarasova, L. M. Sinegovskaya, T. I. Vakul´skaya,
A. I. Mikhaleva, B. A. Trofimov, Izv. Akad. Nauk, Ser. Khim.,
2006, 973 [Russ. Chem. Bull., Int. Ed., 2006, 55, 1010].
The subsequent reaction of this copolymer with KOH (0.2 g,
3
.6 mmol) in ethanol (20 mL) (70 °C, 2 h) led to granulated coꢀ
polymer, in which, after washing with ethanol, 14.38% of K remains.