Cationic polymerization of phenylbutadienes. II. Initiation reaction in cationic polymerization of phenylbutadienes catalyzed by triphenylmethylstannic pentachloride.
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- Asami Ryuzo
- Department of Synthetic Chemistry, Nagoya Institute of Technology
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- Hasegawa Kan-ichi
- Department of Synthetic Chemistry, Nagoya Institute of Technology
Abstract
Initiation in cationic polymerization of phenyl-substituted 1,3-butadienes with triphenylmethylstannic pentachloride as catalyst was studied. The rates of consumption of Ph3CSnCl5 with 1-phenyl-substituted butadienes are represented by the following equation<BR>−d[Ph3CSnCl5]⁄dt=ki′[Ph3CSnCl5][M], where M means monomer.<BR>On the other hand, in the case of 2-phenyl-substituted butadienes the rate is represented as follows<BR>−d[Ph3CSnCl5]⁄dt=ki′[Ph3CSnCl5][M]+k[Ph3CSnCl5]([M]0−[M])<BR>and the formation of a π-complex between the monomer and a carbonium ion is suggested. The initiation rate constants decreased according to the following order:<BR>1-phenyl-1,3-butadiene>2-phenyl-1,3-butadiene>1,1-diphenyl-1,3-butadiene>1,2-diphenyl-1,3-butadiene>2,3-diphenyl-1,3-butadiene.<BR>1,4-Diphenyl-1,3-butadiene did not react with Ph3CSnCl5 at all. The high reactivity of phenylbutadienes toward Ph3CSnCl5 in comparison with that of vinyl monomers could be ascribed to the stabilization of allyl-type cations which were formed by an attack of a trityl cation onto the 4-position and the 1-position carbon for 1-phenylbutadienes and 2-phenylbutadiene, respectively.
Journal
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- Polymer Journal
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Polymer Journal 8 (1), 53-59, 1976
The Society of Polymer Science, Japan
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Keywords
Details 詳細情報について
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- CRID
- 1390001206293556736
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- NII Article ID
- 130004769463
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- COI
- 1:CAS:528:DyaE28Xht1ansrc%3D
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- ISSN
- 13490540
- 00323896
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- Text Lang
- en
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- Data Source
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- JaLC
- Crossref
- CiNii Articles
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- Abstract License Flag
- Disallowed