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Polymerization of acrylonitrile by the action of organomagnesium compounds
Letters to the Editor
201
vl~r weight products obtained from vinyisilanes are soluble powders with softening points ranging from 100 to 400°C. IR-spectra of the polymers and elemental analysis indicate t h a t polymerization occurs at the multiple bond of the vinyl group and the silicon atom. Resuits of some experiments on polymerization of vinylsilanes are t~bul~ted. POLYMERIZATION OF VINYLTRIMETHYLSILANE AND VINYLDIMETHYL PHENYLSILANE
Monomer, ~o b y vol.
Compound
(CHs),SiCH
=
CH s
(CHz)sCsHsSiCH = CH s * 8oftent~ point SSO°, [~ t 8ofteui~ point 15o%I'~
Proportion Solvent of lithium, Temper (toluene), ~o b y wt. of a t u r e , °C °/o b y vol. the monomer
100 50
50
I00 50
5O
0.8 1
Time, hours
25
24
25
24
25
24
25
24
Yield,
%
63 93*
83t 100
-- 0"2 dl/g. -- 0 ~ 5 dl/g.
The data o b t a ~ e d leads us to hope t h a t this possible method of polymerizing vinylalkyl (phenyl) silanes can be used effectively to obtain polymers as well as by polymerization of these compounds initiated b y lithiumalkyls [1], as proposed earlier. Trwnslated by
E.
SEMERE
REFERENCES 1. A. Y. TOlqb'BIY]~, N. S. N ~ , ~ SYAO.1DEI, S. G. DU]~A3L~A.N and N. A. ][UZ~b~[NA, Auth. Cert. U.S.S.R., No. 162531, 1962; N. 8. N ~ , A. V. T O P / ~ I Y E V and S. G. DURGAR'YAN, J. Polymer SoL 4: 1053, 1964
POLYMERIZATION OF ACRYLONITRH.E BY ~ ACTION OF ORGANOMAGNF~ COMPOUNDS* B. L. YERUSALIMSKII and I. V. KULEVSKAYA (Received 5 Se/~mb~r 1964) DEAR EDITOR,
According to literature data, polymerization of acrylonitrile by Grignard re~gents produoes polymers at a high yield but with molecular weights of less than 8000 [1, 2]. There are indi~tlons in the patent literature of the formation in acrylonitrile-RMgX "-dm~thylform~mide (DMF) systems of a polymer with a molec,,1Ar weight of up to 150,000 [3] and of the synthesis of stereospecffio polyaerylonitrile b y the action of organic derivatives o f * Vysokomol. soyed. 7: No. 1, 184-185, 1965.
202
Letters to the E d i t o r
magnesium and other metals [4]; in the latter case no d a t a are given on the molecular weight of polymers. As we h a v e previously established, high-molecular weight polyacrylonitrile can be obtained b y the action of organomagnesium compounds a t a low temperature in a hydrocarbon m e d i u m [5]. As compared with polymerization in DMF, the process takes place a t a l o w e r rate. To stimulate polymerization, various etherates, butylmagnesium chloride ethoxides, dibutylmagnesium and a mixed catalyst, C4HgMgI--(C4H,)2Mg were used. The results of s t a n d a r d experiments are tabulated. POLYMERIZATION OF ACRYLONITRILE UNDER THE EFFECT OF DIBUTYLMAGNESIUM (Catalyst concentration 0.01 mole/L, reaction time 10 min) Solvent
Toluene DMF
Monomer concentration, mole/L
Polymerization temperature, °C
1.5 1"0
--75 --60
Conversion,
% 37 100
[~]
Mol. weight M × 10-3
2.85 1.97
280 170
Polymer viscosity was measured in D M F at 30 °, molecular weight was calculated according to Cleland a n d Stoekmayer [6]. The polymers formed under these conditions are colourless, completely soluble in D M F and exhibit I R - s p e c t r a which do not m a r k e d l y differ from those of conventional polyacrylonitriles. F o r a polymer with a molecular weight of 2.5 × 105, fibre tensile strength exceeds 40 k m [5]. Translated by E. S~,MERE REFERENCES 1. R. BEAMEN, J. Amer. Chem. Soc. 70: 3115, 1948 2. S. D. SAVRANSKAYA, M. A. ASKAROV a n d T. Kh. AZIZKHANOV, Fizika i k h i m i y a p r i r o d n y k h i sinteticheskikh polimerov. (Physics a n d Chemistry of N a t u r a l and Synthetic Polymers.) issue 1, p. 183, Tashkent, 1962 3. Jap. Pat., 13445, 1961; Chem. Abstrs 56: 472, 1962 4. Brit. Pat., 934469, 1963; Organometallic Compounds, 1~o. 9, 1963 5. B. L. YERUSAI.IMSKII, I. V. KULEVSKAYA, L. M. PYRKOV and S. Ya. FRENKEL',
Auth. cert. 838936/23, 1963 6. R. CLELAND and W. STOCKMAYER, J. Polymer Sci. 17: 473, 1955
CERTAIN NEW POSSIBILITIES OF STUDYING POLYMERIC COMPOUNDS BY GAS CHROMATOGRAPHY* V. G, B E R E Z K I N , V. P . P A K H O M O V , V. R . A L I S H O Y E V , L . L . S T A R O B I N E T S , Z. P . M A R K O V I C H a n d L . N . S E D O V
(Received 7 September 1964) GAS chromatography is widely used at present to s t u d y polymeric compounds in relation t o the spectrum of control pyrolytic products [1-3]. However, the interpretation of results * Vysokomol. soyed. 7: No. 1, 185-186, 1965.
201
vl~r weight products obtained from vinyisilanes are soluble powders with softening points ranging from 100 to 400°C. IR-spectra of the polymers and elemental analysis indicate t h a t polymerization occurs at the multiple bond of the vinyl group and the silicon atom. Resuits of some experiments on polymerization of vinylsilanes are t~bul~ted. POLYMERIZATION OF VINYLTRIMETHYLSILANE AND VINYLDIMETHYL PHENYLSILANE
Monomer, ~o b y vol.
Compound
(CHs),SiCH
=
CH s
(CHz)sCsHsSiCH = CH s * 8oftent~ point SSO°, [~ t 8ofteui~ point 15o%I'~
Proportion Solvent of lithium, Temper (toluene), ~o b y wt. of a t u r e , °C °/o b y vol. the monomer
100 50
50
I00 50
5O
0.8 1
Time, hours
25
24
25
24
25
24
25
24
Yield,
%
63 93*
83t 100
-- 0"2 dl/g. -- 0 ~ 5 dl/g.
The data o b t a ~ e d leads us to hope t h a t this possible method of polymerizing vinylalkyl (phenyl) silanes can be used effectively to obtain polymers as well as by polymerization of these compounds initiated b y lithiumalkyls [1], as proposed earlier. Trwnslated by
E.
SEMERE
REFERENCES 1. A. Y. TOlqb'BIY]~, N. S. N ~ , ~ SYAO.1DEI, S. G. DU]~A3L~A.N and N. A. ][UZ~b~[NA, Auth. Cert. U.S.S.R., No. 162531, 1962; N. 8. N ~ , A. V. T O P / ~ I Y E V and S. G. DURGAR'YAN, J. Polymer SoL 4: 1053, 1964
POLYMERIZATION OF ACRYLONITRH.E BY ~ ACTION OF ORGANOMAGNF~ COMPOUNDS* B. L. YERUSALIMSKII and I. V. KULEVSKAYA (Received 5 Se/~mb~r 1964) DEAR EDITOR,
According to literature data, polymerization of acrylonitrile by Grignard re~gents produoes polymers at a high yield but with molecular weights of less than 8000 [1, 2]. There are indi~tlons in the patent literature of the formation in acrylonitrile-RMgX "-dm~thylform~mide (DMF) systems of a polymer with a molec,,1Ar weight of up to 150,000 [3] and of the synthesis of stereospecffio polyaerylonitrile b y the action of organic derivatives o f * Vysokomol. soyed. 7: No. 1, 184-185, 1965.
202
Letters to the E d i t o r
magnesium and other metals [4]; in the latter case no d a t a are given on the molecular weight of polymers. As we h a v e previously established, high-molecular weight polyacrylonitrile can be obtained b y the action of organomagnesium compounds a t a low temperature in a hydrocarbon m e d i u m [5]. As compared with polymerization in DMF, the process takes place a t a l o w e r rate. To stimulate polymerization, various etherates, butylmagnesium chloride ethoxides, dibutylmagnesium and a mixed catalyst, C4HgMgI--(C4H,)2Mg were used. The results of s t a n d a r d experiments are tabulated. POLYMERIZATION OF ACRYLONITRILE UNDER THE EFFECT OF DIBUTYLMAGNESIUM (Catalyst concentration 0.01 mole/L, reaction time 10 min) Solvent
Toluene DMF
Monomer concentration, mole/L
Polymerization temperature, °C
1.5 1"0
--75 --60
Conversion,
% 37 100
[~]
Mol. weight M × 10-3
2.85 1.97
280 170
Polymer viscosity was measured in D M F at 30 °, molecular weight was calculated according to Cleland a n d Stoekmayer [6]. The polymers formed under these conditions are colourless, completely soluble in D M F and exhibit I R - s p e c t r a which do not m a r k e d l y differ from those of conventional polyacrylonitriles. F o r a polymer with a molecular weight of 2.5 × 105, fibre tensile strength exceeds 40 k m [5]. Translated by E. S~,MERE REFERENCES 1. R. BEAMEN, J. Amer. Chem. Soc. 70: 3115, 1948 2. S. D. SAVRANSKAYA, M. A. ASKAROV a n d T. Kh. AZIZKHANOV, Fizika i k h i m i y a p r i r o d n y k h i sinteticheskikh polimerov. (Physics a n d Chemistry of N a t u r a l and Synthetic Polymers.) issue 1, p. 183, Tashkent, 1962 3. Jap. Pat., 13445, 1961; Chem. Abstrs 56: 472, 1962 4. Brit. Pat., 934469, 1963; Organometallic Compounds, 1~o. 9, 1963 5. B. L. YERUSAI.IMSKII, I. V. KULEVSKAYA, L. M. PYRKOV and S. Ya. FRENKEL',
Auth. cert. 838936/23, 1963 6. R. CLELAND and W. STOCKMAYER, J. Polymer Sci. 17: 473, 1955
CERTAIN NEW POSSIBILITIES OF STUDYING POLYMERIC COMPOUNDS BY GAS CHROMATOGRAPHY* V. G, B E R E Z K I N , V. P . P A K H O M O V , V. R . A L I S H O Y E V , L . L . S T A R O B I N E T S , Z. P . M A R K O V I C H a n d L . N . S E D O V
(Received 7 September 1964) GAS chromatography is widely used at present to s t u d y polymeric compounds in relation t o the spectrum of control pyrolytic products [1-3]. However, the interpretation of results * Vysokomol. soyed. 7: No. 1, 185-186, 1965.