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The dehydrochlorination of polyvinylchloride by potassium amide in liquid ammonia
Dehydroehlorination of polyvinylchloride
485
(4) It is shown that some luminophores, for example hydroxyphenylbenzoxazole (HI~BO) can at the same time possess properties characteristic of thermophores. The addition of DNPDA and H P B O to polyamides increases the light resistance of the polyamide fibres as well as their heat stability. Translated by E. O. PHILLIPS REFERENCES 1. HALLE, Texture, 3, 18-20, 1956 2. N. V. MIKHAILOV, L. G. TOKAREVA and M. V. KOVALEVA, Vysokomol. soedin. 2: 581, 1960 3. G. ACHI-IAMMER, W. REIGART and M. I~LINE, J. Applied Chem. 1: 301, 1951; L. URBANCOVA, Chem. prumysl. 5: 75-78, 1955; I. GUNDAVDA, J. Textile Inst. 5: 289, 1956 4. N. N. SEMENOV, O nekotorykh problemakh khimicheskoi kinetiki i reaktsionnoi sposobnosti. (Some Problems of Chemical Kinetics and Reactivity). Izd. Akad. Nauk SSSR, 1954 5. A. S. KUZ'MINSKII and A. G. ANGERT, Dokl. Akad. Nauk SSSR 82: 747, 1952; 96: 1147, 1954; P. P. MARSCH a n d M. L. BUTLER, Ind. Eng. Chem. 38: 701, 1946; G. S. HAMMAUND and {3. E. BOOSER, J. Amer. Chem. Soc. 77: 3238, 1955 6. V. V. KORSHAK, K. K. MOZGOVA and V. P. LAVRISHCHEV, Vysokomol. soedin, l : 1164, 1959
Letter to the Editor THE DEHYDROCHLORINATION OF POLYVINYLCHLORIDE BY POTASSIUM AMIDE IN LIQUID AMMONIA* I. V. A S T A F ' E V a n d A. K . P I S K U N O V
(Received 5 July 1960)
DEHYDROCHLORINATION of polyvinylchloride (PVC) is one of the methods of producing polymers with systems of conjugated double bonds, possessing heat stability and semiconductor properties [1]. We used for this purpose a solution of potassium amide in liquid ammonia and carried out the reaction under pressure at room temperature, considering that b y the action of the amide on secondary and tertiary halides olefines are produced exclusively [2]. From PVC (mol. ~ t > 75,000) the product obtained was a black powder, insoluble in benzene. On investigation of the electron spin resonance (ESR) at a frequency of~9370 m herz at room temperature the powder gives a single absorption line with weak a s y m m e t r y toward the side of high field strength. The width of the line between * Vysokomol. soedin. 2: No. 11, 1745, 1960.
486
I.V. ASTAF'EVand A. K. PISKUNOV
the points of m a x i m u m slope is 11+1 gauss and the g-value, 2.000±0.005. The values obtained for the width of the line and the g-factor indicate the exist~ ence of volume effects and the absence of significant orbital overlapping-in the paramv gnetism of the product. On standing in air for several hours a change in colour from black to red occurs, together with a charge in weight in the first two hours, by an average of 30%, and disappearance of the E S R signal. No chlorine or nitrogen were detected b y microanalysis. Carbon content 80.27, 80.90%, hydrogen 7.38, 7.589/. The remainirg 12% is e v i d e n t l y oxygen absorbed during the time when the powder was washed with water to remove chlorine ions. On heating in vacuo (in the absence c,f oxygen) between 100 ° and 150 ° the eolour charges from black to red. On further heatirg to 400 ° the powder becomes dark brown and melts at 400-410 °. The solidified melt is black, it is easily ground to a powder, gives an E S R signal, is not oxidized in air and again melts at 400-410 °. While this work was in hand publications appeared, concerning the dehydro: chlorination of PVC by heating (to 250 °) with alkali [3] and with solutions of alcoholates in alcohol at the boilirg point [4]. In the latter case a product was obtained with properties close to those described above. The use of a solution of potassium amide enables dehydrochlorination to be achieved at a lower temperature. We wish to t h a n k A. J. Shatenshtein and D. N. Shigorin for their interest in this work. Tran, lated by E.O. PHILLIPS REFERENCES
1. A. A. BERLIN~ Khimiya i tekhnologiya polimerov, No. 7-8, 139, 1960 2. HOUBEN-WEYL, Methoden der organischen Chemie, XII/1 : II, p. 74. 4th ed., Stuttgalqs, 1957 3. M. A. GEIDERIKH, B. E. DAVIDOV, B. A. KRENTSEL', I. M. KUSTANOVICH, L. S.
POLAK, A. V. TOPCHIEV and R. M. VOITENKO, Mezhdunarodnyi simpozium po makromolekulyarnoi khimii. Doklady i avtoreferaty. Sektziya III. (International Symposium on Macromoleeulax Chemistry. Reports and Summaries. Section III.) p. 85, Moscow, 1960 .... ' 4. L. TOKARZEWSKI, Roezniki Chemii 83: 619, 849, 1959
485
(4) It is shown that some luminophores, for example hydroxyphenylbenzoxazole (HI~BO) can at the same time possess properties characteristic of thermophores. The addition of DNPDA and H P B O to polyamides increases the light resistance of the polyamide fibres as well as their heat stability. Translated by E. O. PHILLIPS REFERENCES 1. HALLE, Texture, 3, 18-20, 1956 2. N. V. MIKHAILOV, L. G. TOKAREVA and M. V. KOVALEVA, Vysokomol. soedin. 2: 581, 1960 3. G. ACHI-IAMMER, W. REIGART and M. I~LINE, J. Applied Chem. 1: 301, 1951; L. URBANCOVA, Chem. prumysl. 5: 75-78, 1955; I. GUNDAVDA, J. Textile Inst. 5: 289, 1956 4. N. N. SEMENOV, O nekotorykh problemakh khimicheskoi kinetiki i reaktsionnoi sposobnosti. (Some Problems of Chemical Kinetics and Reactivity). Izd. Akad. Nauk SSSR, 1954 5. A. S. KUZ'MINSKII and A. G. ANGERT, Dokl. Akad. Nauk SSSR 82: 747, 1952; 96: 1147, 1954; P. P. MARSCH a n d M. L. BUTLER, Ind. Eng. Chem. 38: 701, 1946; G. S. HAMMAUND and {3. E. BOOSER, J. Amer. Chem. Soc. 77: 3238, 1955 6. V. V. KORSHAK, K. K. MOZGOVA and V. P. LAVRISHCHEV, Vysokomol. soedin, l : 1164, 1959
Letter to the Editor THE DEHYDROCHLORINATION OF POLYVINYLCHLORIDE BY POTASSIUM AMIDE IN LIQUID AMMONIA* I. V. A S T A F ' E V a n d A. K . P I S K U N O V
(Received 5 July 1960)
DEHYDROCHLORINATION of polyvinylchloride (PVC) is one of the methods of producing polymers with systems of conjugated double bonds, possessing heat stability and semiconductor properties [1]. We used for this purpose a solution of potassium amide in liquid ammonia and carried out the reaction under pressure at room temperature, considering that b y the action of the amide on secondary and tertiary halides olefines are produced exclusively [2]. From PVC (mol. ~ t > 75,000) the product obtained was a black powder, insoluble in benzene. On investigation of the electron spin resonance (ESR) at a frequency of~9370 m herz at room temperature the powder gives a single absorption line with weak a s y m m e t r y toward the side of high field strength. The width of the line between * Vysokomol. soedin. 2: No. 11, 1745, 1960.
486
I.V. ASTAF'EVand A. K. PISKUNOV
the points of m a x i m u m slope is 11+1 gauss and the g-value, 2.000±0.005. The values obtained for the width of the line and the g-factor indicate the exist~ ence of volume effects and the absence of significant orbital overlapping-in the paramv gnetism of the product. On standing in air for several hours a change in colour from black to red occurs, together with a charge in weight in the first two hours, by an average of 30%, and disappearance of the E S R signal. No chlorine or nitrogen were detected b y microanalysis. Carbon content 80.27, 80.90%, hydrogen 7.38, 7.589/. The remainirg 12% is e v i d e n t l y oxygen absorbed during the time when the powder was washed with water to remove chlorine ions. On heating in vacuo (in the absence c,f oxygen) between 100 ° and 150 ° the eolour charges from black to red. On further heatirg to 400 ° the powder becomes dark brown and melts at 400-410 °. The solidified melt is black, it is easily ground to a powder, gives an E S R signal, is not oxidized in air and again melts at 400-410 °. While this work was in hand publications appeared, concerning the dehydro: chlorination of PVC by heating (to 250 °) with alkali [3] and with solutions of alcoholates in alcohol at the boilirg point [4]. In the latter case a product was obtained with properties close to those described above. The use of a solution of potassium amide enables dehydrochlorination to be achieved at a lower temperature. We wish to t h a n k A. J. Shatenshtein and D. N. Shigorin for their interest in this work. Tran, lated by E.O. PHILLIPS REFERENCES
1. A. A. BERLIN~ Khimiya i tekhnologiya polimerov, No. 7-8, 139, 1960 2. HOUBEN-WEYL, Methoden der organischen Chemie, XII/1 : II, p. 74. 4th ed., Stuttgalqs, 1957 3. M. A. GEIDERIKH, B. E. DAVIDOV, B. A. KRENTSEL', I. M. KUSTANOVICH, L. S.
POLAK, A. V. TOPCHIEV and R. M. VOITENKO, Mezhdunarodnyi simpozium po makromolekulyarnoi khimii. Doklady i avtoreferaty. Sektziya III. (International Symposium on Macromoleeulax Chemistry. Reports and Summaries. Section III.) p. 85, Moscow, 1960 .... ' 4. L. TOKARZEWSKI, Roezniki Chemii 83: 619, 849, 1959