A novel consecutive chain transfer reaction to p-methylstyrene and hydrogen during metallocene-mediated olefin polymerization

Tze-chiang Chung, J. Y. Dong

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106 Citations (Scopus)

Abstract

This paper describes the first example of consecutive chain transfer reaction, first to p-methylstyrene (or styrene) and then to hydrogen, during metallocene-catalyzed propylene polymerization by rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2/MAO complex. The PP molecular weight is inversely proportional to the molar ratio of [p-methylstyrene]/[propylene] and [styrene]/[propylene] with the chain transfer constants of ktr/kp = 1/6.36 and 1/7.5, respectively. Although hydrogen does not influence the polymer molecular weight, it greatly affects the catalyst activity. Each PP chain formed contains a terminal p-methylstyrene (or styrene) unit. The terminal p-MS unit can be metalated to form a stable polymeric anion for living anionic polymerization to prepare new PP diblock copolymers, such as PP-b-PS, which are very difficult to prepare by other methods. The overall process resembles a transformation reaction from metallocene to living anionic polymerization.

Original languageEnglish (US)
Pages (from-to)4871-4876
Number of pages6
JournalJournal of the American Chemical Society
Volume123
Issue number21
DOIs
StatePublished - Oct 9 2001

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Styrene
Alkenes
Polymerization
Olefins
Propylene
Hydrogen
Living polymerization
Anionic polymerization
Molecular Weight
Molecular weight
Monoamine Oxidase
Block copolymers
Anions
Catalyst activity
Polymers
Negative ions
metallocene
vinyltoluene
propylene

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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abstract = "This paper describes the first example of consecutive chain transfer reaction, first to p-methylstyrene (or styrene) and then to hydrogen, during metallocene-catalyzed propylene polymerization by rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2/MAO complex. The PP molecular weight is inversely proportional to the molar ratio of [p-methylstyrene]/[propylene] and [styrene]/[propylene] with the chain transfer constants of ktr/kp = 1/6.36 and 1/7.5, respectively. Although hydrogen does not influence the polymer molecular weight, it greatly affects the catalyst activity. Each PP chain formed contains a terminal p-methylstyrene (or styrene) unit. The terminal p-MS unit can be metalated to form a stable polymeric anion for living anionic polymerization to prepare new PP diblock copolymers, such as PP-b-PS, which are very difficult to prepare by other methods. The overall process resembles a transformation reaction from metallocene to living anionic polymerization.",
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N2 - This paper describes the first example of consecutive chain transfer reaction, first to p-methylstyrene (or styrene) and then to hydrogen, during metallocene-catalyzed propylene polymerization by rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2/MAO complex. The PP molecular weight is inversely proportional to the molar ratio of [p-methylstyrene]/[propylene] and [styrene]/[propylene] with the chain transfer constants of ktr/kp = 1/6.36 and 1/7.5, respectively. Although hydrogen does not influence the polymer molecular weight, it greatly affects the catalyst activity. Each PP chain formed contains a terminal p-methylstyrene (or styrene) unit. The terminal p-MS unit can be metalated to form a stable polymeric anion for living anionic polymerization to prepare new PP diblock copolymers, such as PP-b-PS, which are very difficult to prepare by other methods. The overall process resembles a transformation reaction from metallocene to living anionic polymerization.

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