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Polymerization of N-substituted methacrylamides–IV
Abstracts
157
*STUDIES IN CYCLIC P O L Y M E R I Z A T I O N A N D C O P O L Y M E R I Z A T I O N - - I I I . S Y N T H E S I S A N D CYCLIC P O L Y M E R I Z A T I O N OF A L I P H A T I C D I V I N Y L A C E T A L S . N E W M E T H O D OF P R E P A R A T I O N OF P O L Y V I N Y L A C E T A L S
S. G. M a t s o y a n , M. G. A v e t y a n N o . 4, 5 6 2 - 5 6 9 , 1961.
a n d M. G. V o s k a n y a n ,
V y s o k o m o l . s o e d i n . 3:
SEV~.RAL aliphatic divinylacetals have been synthesized b y interaction of aldehydes with ethylene chlorohydrin and dehydrochlorination of the resultant ]~,fl'-dichlorodiethylacetals. I t has been shown t h a t in the presence of radical initiators divinylacetals polymerize only according to the cyclic mechanism with the formation of acetal derivatives of polyvinyl alcohol, i.e., polyvinylacetates. Optical conditions for the cyclic polymerization process and the properties of the polydivinylacetals have been investigated. S P E C T R A L I N V E S T I G A T I O N OF T H E PRODUCTS F O R M E D D U R I N G P O L Y M E R I Z A T I O N OF S T Y R E N E W I T H 9 - V I N Y L A N T H R A C E N E A D D I T I O N S
A. S. C h e r k a s o v a n d K . G. V o l d a i k i n a , V y s o k o m o l . s o e d i n . 3: N o . 4, .570-576,1961. FROM a study of the absorption and fluorescence spectra of the products formed during the catalytic and thermal polymerization of styrene with 9-vinylanthraceno additions it was found t h a t interaction of these compounds leads mainly to low molecular monomesosubstituted anthracene and to products with disrupted anthracene structure. Only insignificant amounts of high molecular styrene-vinylanthracene polymers are formed. The possible structures of the reaction products of' styrene with 9-vinylanthracene in the polymerization process have been discussed. F O R M A T I O N OF P O L Y O R G A N O T I T A N O S I L O X A N E S
K . A. A n d r i a n o v a n d Sh. V. P i c h k h a d z e , V y s o k o m o l . s o e d i n . 3: N o . 4, 574-5811, 1961. THE co-hydrolysis of dimethyldichlorosilane, diethyldichlorosilane and methylphenyldichlorosilane with bis-(cyclopentadienyl) dichlorotitanium has been investigated. The reaction was found to be accompanied b y removal of cyclopentadiene groups. The double decomposition of disodium salts of dihydroxypolymethylsiloxanes and bis-(cyclopentadienyl) diehlorotitanium is accompanied b y formation of titanium-containing silicon polymers. POLYMERIZATION
OF N - S U B S T I T U T E D
M E T H A C R Y L A M I D E S -- IV
T. A. S o k o l o v a , G. M. C h e t y r k i n a a n d L. A. O v s y a n n i k o v a , V y s o k o m o l . s o e d i n . 3: N o . 4, 5 8 2 - 5 8 4 , 1961. INSOLUBLE polymers have been shown to form in radical polymerization of ~-octylmethacrylamide, o-, m- and p-polymeehacrylamides (TMA), m-xylyhnethacrylamide (XMA), m-methoxyphenyl, m-ethoxyphenylmethacrylamides, and p-carboethoxyphenyl methac .rylate (CEPM). The insolubility is evidently due to crosslinkage taking place in the polymerization process. Proof of this is the fact that soluble polymers are obtained when isomeric TMA and CEPM are polymerized to the extent of 20O/o and insoluble polymers, when the reaction is carried further. Moreover some of the monomers yield soluble polymers with methyl m e t h a c r y l a t e and styrene when the contents of the methacrylamides are The Publisher will be pleased to quote t'or the supply of a full English translation of any papers abstracted in these pages.
] 58
Abstracts
below 10%; with higher contents insoluble polymers are formed. Crosslinkage is assumed to be due to labile hydrogen atoms of the methyl and ethyl end groups. This is supported b y the fact t h a t analogs of TMA, namely m-trifluoromethylphneylmethacrylamidc (TFMPMA), all m e t h y l hydrogens of which are substituted b y fluorine, yield a soluble polymer. m-XMA and m-TFMPMA heretofore not reported in the literature have been synthesized and described. *POLYMERIZATION KINETICS AND POLYMERIZATION MECHANISM OF OLEFINS ON COMPLEX CATALYSTS--I. THE KINETIC EQUATIONS AND RATE CONSTANTS OF POLYMERIZATION OF a-OLEFINS ON THE SYSTEM TiCLa--AI(C2H5) 3 FOR DIFFERENT WAYS OF ACCOMPLISHING THE PROCESS
V. I . T s v e t k o v a , O. N. P i r o g o v , D. M. L i s i t s y n a n d N . M. C h i r k o v , V y s o k o m o ] . s o e d i n . 3: N o . 4, 5 8 5 - 5 9 3 , 1961. THE kinetic equations have been derived for various methods of investigating a-olefin polymerization on TiCla--AI(C2Hs)a catalysts. On the basis of the equations a comparison can be made of the rate constants and of the activities of various TiC1 a specimens for different experimental procedures. Illustrations have been presented. METHOD OF RECORDING THERMOMECHANICAL CURVES OF POLYMERS
B. Y a . T e i t e l b a u m a n d M. P . D i a n o v , V y s o k o m o 1 . s o e d i n . 3: N o . 4, 5 9 4 - 6 0 1 , 1961. THE design and operation of an arrangement for the automatic recording of thermomeehanical curves directly in strain-temperature coordinates has been described. W i t h the aid of the arrangement the effect of the load and the physical state of the specimen on the character of the thermomechanical curves has been investigated. INVESTIGATION OF THE DEGRADATION OF CONDENSATION RESINS--III. THERMOOXIDATIVE DEGRADATION OF H A R D E N E D EPOXY RESINS
M. B. N e i m a n , B. M. K o v a r s k a y a , s o e d i n . 3: N o . 4, 6 0 2 - 6 0 6 , 1961.
M. P . Y a z i k o v a a n d A. I. S i d n e v , V y s o k o m o l .
THERMOOXIDATIVE degradation of epoxide resins hardened b y polyethylenepolyamine and maleic anhydride is a self-accelerated chain reaction during which hydroperoxide accumulates in the resin. The induction period ~ of the reaction diminished with increase in oxygen pressure P and with temperature T according to the equation r : ( a l - k b / p ) e ~/RT where y / R T ~ 22,000 cal/mole. GAMMA-RAY INDUCED CHLORINATION OF MONOMERIC AND POLYMERIC ORGANOSILICON COMPOUNDS--I. CHLORINATION OF POLYPHENYLMETHYLSILOXANE LIQUID AND POLYDIMETHYL-SILOXANE RUBBER, INFRARED SPECTRA OF THE CHLORINATION PRODUCTS
R . V. D z h a g a t s p a n y a n , V. I. Z e t k i n , G. V. M o t s a r e v a n d M. T. F i l i p p o v , V y s o k o r e e l . s o e d i n . 3: N o . 4, 6 0 7 - 6 1 2 , 1961. SPECD1ENS of polydimethylsiloxane rubber [SKT] and polyphenylmethylsiloxane liquid (PPMS) were subjected to chlorination under the influence of y-rays from a ~°Co source. Chlorine to the extent of 63~/o was added to SKT. The reaction took place very rapidly,
157
*STUDIES IN CYCLIC P O L Y M E R I Z A T I O N A N D C O P O L Y M E R I Z A T I O N - - I I I . S Y N T H E S I S A N D CYCLIC P O L Y M E R I Z A T I O N OF A L I P H A T I C D I V I N Y L A C E T A L S . N E W M E T H O D OF P R E P A R A T I O N OF P O L Y V I N Y L A C E T A L S
S. G. M a t s o y a n , M. G. A v e t y a n N o . 4, 5 6 2 - 5 6 9 , 1961.
a n d M. G. V o s k a n y a n ,
V y s o k o m o l . s o e d i n . 3:
SEV~.RAL aliphatic divinylacetals have been synthesized b y interaction of aldehydes with ethylene chlorohydrin and dehydrochlorination of the resultant ]~,fl'-dichlorodiethylacetals. I t has been shown t h a t in the presence of radical initiators divinylacetals polymerize only according to the cyclic mechanism with the formation of acetal derivatives of polyvinyl alcohol, i.e., polyvinylacetates. Optical conditions for the cyclic polymerization process and the properties of the polydivinylacetals have been investigated. S P E C T R A L I N V E S T I G A T I O N OF T H E PRODUCTS F O R M E D D U R I N G P O L Y M E R I Z A T I O N OF S T Y R E N E W I T H 9 - V I N Y L A N T H R A C E N E A D D I T I O N S
A. S. C h e r k a s o v a n d K . G. V o l d a i k i n a , V y s o k o m o l . s o e d i n . 3: N o . 4, .570-576,1961. FROM a study of the absorption and fluorescence spectra of the products formed during the catalytic and thermal polymerization of styrene with 9-vinylanthraceno additions it was found t h a t interaction of these compounds leads mainly to low molecular monomesosubstituted anthracene and to products with disrupted anthracene structure. Only insignificant amounts of high molecular styrene-vinylanthracene polymers are formed. The possible structures of the reaction products of' styrene with 9-vinylanthracene in the polymerization process have been discussed. F O R M A T I O N OF P O L Y O R G A N O T I T A N O S I L O X A N E S
K . A. A n d r i a n o v a n d Sh. V. P i c h k h a d z e , V y s o k o m o l . s o e d i n . 3: N o . 4, 574-5811, 1961. THE co-hydrolysis of dimethyldichlorosilane, diethyldichlorosilane and methylphenyldichlorosilane with bis-(cyclopentadienyl) dichlorotitanium has been investigated. The reaction was found to be accompanied b y removal of cyclopentadiene groups. The double decomposition of disodium salts of dihydroxypolymethylsiloxanes and bis-(cyclopentadienyl) diehlorotitanium is accompanied b y formation of titanium-containing silicon polymers. POLYMERIZATION
OF N - S U B S T I T U T E D
M E T H A C R Y L A M I D E S -- IV
T. A. S o k o l o v a , G. M. C h e t y r k i n a a n d L. A. O v s y a n n i k o v a , V y s o k o m o l . s o e d i n . 3: N o . 4, 5 8 2 - 5 8 4 , 1961. INSOLUBLE polymers have been shown to form in radical polymerization of ~-octylmethacrylamide, o-, m- and p-polymeehacrylamides (TMA), m-xylyhnethacrylamide (XMA), m-methoxyphenyl, m-ethoxyphenylmethacrylamides, and p-carboethoxyphenyl methac .rylate (CEPM). The insolubility is evidently due to crosslinkage taking place in the polymerization process. Proof of this is the fact that soluble polymers are obtained when isomeric TMA and CEPM are polymerized to the extent of 20O/o and insoluble polymers, when the reaction is carried further. Moreover some of the monomers yield soluble polymers with methyl m e t h a c r y l a t e and styrene when the contents of the methacrylamides are The Publisher will be pleased to quote t'or the supply of a full English translation of any papers abstracted in these pages.
] 58
Abstracts
below 10%; with higher contents insoluble polymers are formed. Crosslinkage is assumed to be due to labile hydrogen atoms of the methyl and ethyl end groups. This is supported b y the fact t h a t analogs of TMA, namely m-trifluoromethylphneylmethacrylamidc (TFMPMA), all m e t h y l hydrogens of which are substituted b y fluorine, yield a soluble polymer. m-XMA and m-TFMPMA heretofore not reported in the literature have been synthesized and described. *POLYMERIZATION KINETICS AND POLYMERIZATION MECHANISM OF OLEFINS ON COMPLEX CATALYSTS--I. THE KINETIC EQUATIONS AND RATE CONSTANTS OF POLYMERIZATION OF a-OLEFINS ON THE SYSTEM TiCLa--AI(C2H5) 3 FOR DIFFERENT WAYS OF ACCOMPLISHING THE PROCESS
V. I . T s v e t k o v a , O. N. P i r o g o v , D. M. L i s i t s y n a n d N . M. C h i r k o v , V y s o k o m o ] . s o e d i n . 3: N o . 4, 5 8 5 - 5 9 3 , 1961. THE kinetic equations have been derived for various methods of investigating a-olefin polymerization on TiCla--AI(C2Hs)a catalysts. On the basis of the equations a comparison can be made of the rate constants and of the activities of various TiC1 a specimens for different experimental procedures. Illustrations have been presented. METHOD OF RECORDING THERMOMECHANICAL CURVES OF POLYMERS
B. Y a . T e i t e l b a u m a n d M. P . D i a n o v , V y s o k o m o 1 . s o e d i n . 3: N o . 4, 5 9 4 - 6 0 1 , 1961. THE design and operation of an arrangement for the automatic recording of thermomeehanical curves directly in strain-temperature coordinates has been described. W i t h the aid of the arrangement the effect of the load and the physical state of the specimen on the character of the thermomechanical curves has been investigated. INVESTIGATION OF THE DEGRADATION OF CONDENSATION RESINS--III. THERMOOXIDATIVE DEGRADATION OF H A R D E N E D EPOXY RESINS
M. B. N e i m a n , B. M. K o v a r s k a y a , s o e d i n . 3: N o . 4, 6 0 2 - 6 0 6 , 1961.
M. P . Y a z i k o v a a n d A. I. S i d n e v , V y s o k o m o l .
THERMOOXIDATIVE degradation of epoxide resins hardened b y polyethylenepolyamine and maleic anhydride is a self-accelerated chain reaction during which hydroperoxide accumulates in the resin. The induction period ~ of the reaction diminished with increase in oxygen pressure P and with temperature T according to the equation r : ( a l - k b / p ) e ~/RT where y / R T ~ 22,000 cal/mole. GAMMA-RAY INDUCED CHLORINATION OF MONOMERIC AND POLYMERIC ORGANOSILICON COMPOUNDS--I. CHLORINATION OF POLYPHENYLMETHYLSILOXANE LIQUID AND POLYDIMETHYL-SILOXANE RUBBER, INFRARED SPECTRA OF THE CHLORINATION PRODUCTS
R . V. D z h a g a t s p a n y a n , V. I. Z e t k i n , G. V. M o t s a r e v a n d M. T. F i l i p p o v , V y s o k o r e e l . s o e d i n . 3: N o . 4, 6 0 7 - 6 1 2 , 1961. SPECD1ENS of polydimethylsiloxane rubber [SKT] and polyphenylmethylsiloxane liquid (PPMS) were subjected to chlorination under the influence of y-rays from a ~°Co source. Chlorine to the extent of 63~/o was added to SKT. The reaction took place very rapidly,