New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers) LVII. Chlorine telechelic poly(p-chlorostyrene)

M. Zsuga, J. P. Kennedy

Research output: Article

3 Citations (Scopus)

Abstract

The polymerization of p-chlorostyrene (pClSt) under carbocationic conditions has been investigated. The use of binifers 1,4-di(2-chloro-2-propyl)benzene (pDCC) and 1,3-di(2-chloro-2-propyl)-5-tert-butylbenzene (m-tBuDCC) in conjunction with BCl3 coinitiator in CH3Cl diluent at -60 and -35°C give α,ω-di-benzylic chlorine-capped polymer sCl-PpClSt-Cls. According to kinetic investigations the inifer mechanism is operative and both binifers are efficient in controlling the end structures, molecular weights, and to a certain extent molecular weight distributions (MWD). Strong circumstantial evidences have been generated to demonstrate the satisfactory synthesis of sCl-PpClSt-Cls and the absence of indanyl end-groups, i.e., structural considerations, linearity of inifer plots, quantitative Cl end-group microanalysis, FTIR spectroscopy, and blocking experiments. The latter involved the blocking of THF from the sec-benzylic chlorine end-groups by AgPF6 and thus led to the synthesis of a new triblock copolymer PTHF-b-PpClSt-b-PTHF. Interestingly, the isotactic content (mm triads and mmmm pentads) of PpClSt is significantly higher than that of polymer prepared by free-radical induced polymerization. The Tg of a PpClSt of M̄n = 5700 g/mol was 123°C.

Original languageEnglish
Pages (from-to)875-880
Number of pages6
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume29
Issue number6
Publication statusPublished - máj. 1991

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Chlorine
Polymers
Copolymers
Polymerization
Microanalysis
Molecular weight distribution
Benzene
Free radicals
Block copolymers
Free Radicals
Molecular weight
Spectroscopy
Kinetics
Experiments
4-chlorostyrene
tert-butylbenzene

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics

Cite this

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title = "New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers) LVII. Chlorine telechelic poly(p-chlorostyrene)",
abstract = "The polymerization of p-chlorostyrene (pClSt) under carbocationic conditions has been investigated. The use of binifers 1,4-di(2-chloro-2-propyl)benzene (pDCC) and 1,3-di(2-chloro-2-propyl)-5-tert-butylbenzene (m-tBuDCC) in conjunction with BCl3 coinitiator in CH3Cl diluent at -60 and -35°C give α,ω-di-benzylic chlorine-capped polymer sCl-PpClSt-Cls. According to kinetic investigations the inifer mechanism is operative and both binifers are efficient in controlling the end structures, molecular weights, and to a certain extent molecular weight distributions (MWD). Strong circumstantial evidences have been generated to demonstrate the satisfactory synthesis of sCl-PpClSt-Cls and the absence of indanyl end-groups, i.e., structural considerations, linearity of inifer plots, quantitative Cl end-group microanalysis, FTIR spectroscopy, and blocking experiments. The latter involved the blocking of THF from the sec-benzylic chlorine end-groups by AgPF6 and thus led to the synthesis of a new triblock copolymer PTHF-b-PpClSt-b-PTHF. Interestingly, the isotactic content (mm triads and mmmm pentads) of PpClSt is significantly higher than that of polymer prepared by free-radical induced polymerization. The Tg of a PpClSt of M̄n = 5700 g/mol was 123°C.",
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T1 - New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers) LVII. Chlorine telechelic poly(p-chlorostyrene)

AU - Zsuga, M.

AU - Kennedy, J. P.

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N2 - The polymerization of p-chlorostyrene (pClSt) under carbocationic conditions has been investigated. The use of binifers 1,4-di(2-chloro-2-propyl)benzene (pDCC) and 1,3-di(2-chloro-2-propyl)-5-tert-butylbenzene (m-tBuDCC) in conjunction with BCl3 coinitiator in CH3Cl diluent at -60 and -35°C give α,ω-di-benzylic chlorine-capped polymer sCl-PpClSt-Cls. According to kinetic investigations the inifer mechanism is operative and both binifers are efficient in controlling the end structures, molecular weights, and to a certain extent molecular weight distributions (MWD). Strong circumstantial evidences have been generated to demonstrate the satisfactory synthesis of sCl-PpClSt-Cls and the absence of indanyl end-groups, i.e., structural considerations, linearity of inifer plots, quantitative Cl end-group microanalysis, FTIR spectroscopy, and blocking experiments. The latter involved the blocking of THF from the sec-benzylic chlorine end-groups by AgPF6 and thus led to the synthesis of a new triblock copolymer PTHF-b-PpClSt-b-PTHF. Interestingly, the isotactic content (mm triads and mmmm pentads) of PpClSt is significantly higher than that of polymer prepared by free-radical induced polymerization. The Tg of a PpClSt of M̄n = 5700 g/mol was 123°C.

AB - The polymerization of p-chlorostyrene (pClSt) under carbocationic conditions has been investigated. The use of binifers 1,4-di(2-chloro-2-propyl)benzene (pDCC) and 1,3-di(2-chloro-2-propyl)-5-tert-butylbenzene (m-tBuDCC) in conjunction with BCl3 coinitiator in CH3Cl diluent at -60 and -35°C give α,ω-di-benzylic chlorine-capped polymer sCl-PpClSt-Cls. According to kinetic investigations the inifer mechanism is operative and both binifers are efficient in controlling the end structures, molecular weights, and to a certain extent molecular weight distributions (MWD). Strong circumstantial evidences have been generated to demonstrate the satisfactory synthesis of sCl-PpClSt-Cls and the absence of indanyl end-groups, i.e., structural considerations, linearity of inifer plots, quantitative Cl end-group microanalysis, FTIR spectroscopy, and blocking experiments. The latter involved the blocking of THF from the sec-benzylic chlorine end-groups by AgPF6 and thus led to the synthesis of a new triblock copolymer PTHF-b-PpClSt-b-PTHF. Interestingly, the isotactic content (mm triads and mmmm pentads) of PpClSt is significantly higher than that of polymer prepared by free-radical induced polymerization. The Tg of a PpClSt of M̄n = 5700 g/mol was 123°C.

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