Synthesis of polyethylene containing a terminal p-methylstyrene group: Metallocene-mediated ethylene polymerization with a consecutive chain transfer reaction to p-methylstyrene and hydrogen

J. Y. Dong, Tze-chiang Chung

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Abstract

This paper discusses a novel polymerization process for preparing polyethylene having a terminal p-methylstyrene (p-MS) group. The chemistry involves metallocene-mediated ethylene polymerization in the presence of p-MS and hydrogen. Apparently, the reaction mechanism, including the copolymerization and chain transfer reactions, can be controlled with a favorable combination of metallocene catalyst and hydrogen concentration. Under some specific reaction conditions, the Cp2ZrCl2/MAO catalyst selectively forms PE with a terminal p-MS terminal group (PE-t-p-MS) via a consecutive chain transfer reaction to p-MS and then hydrogen. The catalyst activity increases with the hydrogen concentration, and the polymer molecular weight is inversely proportional to the p-MS concentration. In contrast, [C5Me4(SiMe2NtBu)]TiCl2/M AO initiates a copolymerization reaction between ethylene and p-MS, and hydrogen has little effect on the catalyst activity. The terminal p-MS unit at the PE chain end is a valuable reactive group that can be metalated to form a stable polymeric anion, which can be used to prepare functionalized PE polymers containing a polar terminal group or diblock copolymers.

Original languageEnglish (US)
Pages (from-to)1622-1631
Number of pages10
JournalMacromolecules
Volume35
Issue number5
DOIs
StatePublished - Feb 26 2002

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Polyethylene
Polyethylenes
Hydrogen
Ethylene
Polymerization
Copolymerization
Catalyst activity
Catalysts
Polymers
Block copolymers
Negative ions
Molecular weight
ethylene
metallocene
vinyltoluene
Monoamine Oxidase
Anions

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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title = "Synthesis of polyethylene containing a terminal p-methylstyrene group: Metallocene-mediated ethylene polymerization with a consecutive chain transfer reaction to p-methylstyrene and hydrogen",
abstract = "This paper discusses a novel polymerization process for preparing polyethylene having a terminal p-methylstyrene (p-MS) group. The chemistry involves metallocene-mediated ethylene polymerization in the presence of p-MS and hydrogen. Apparently, the reaction mechanism, including the copolymerization and chain transfer reactions, can be controlled with a favorable combination of metallocene catalyst and hydrogen concentration. Under some specific reaction conditions, the Cp2ZrCl2/MAO catalyst selectively forms PE with a terminal p-MS terminal group (PE-t-p-MS) via a consecutive chain transfer reaction to p-MS and then hydrogen. The catalyst activity increases with the hydrogen concentration, and the polymer molecular weight is inversely proportional to the p-MS concentration. In contrast, [C5Me4(SiMe2NtBu)]TiCl2/M AO initiates a copolymerization reaction between ethylene and p-MS, and hydrogen has little effect on the catalyst activity. The terminal p-MS unit at the PE chain end is a valuable reactive group that can be metalated to form a stable polymeric anion, which can be used to prepare functionalized PE polymers containing a polar terminal group or diblock copolymers.",
author = "Dong, {J. Y.} and Tze-chiang Chung",
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AU - Dong, J. Y.

AU - Chung, Tze-chiang

PY - 2002/2/26

Y1 - 2002/2/26

N2 - This paper discusses a novel polymerization process for preparing polyethylene having a terminal p-methylstyrene (p-MS) group. The chemistry involves metallocene-mediated ethylene polymerization in the presence of p-MS and hydrogen. Apparently, the reaction mechanism, including the copolymerization and chain transfer reactions, can be controlled with a favorable combination of metallocene catalyst and hydrogen concentration. Under some specific reaction conditions, the Cp2ZrCl2/MAO catalyst selectively forms PE with a terminal p-MS terminal group (PE-t-p-MS) via a consecutive chain transfer reaction to p-MS and then hydrogen. The catalyst activity increases with the hydrogen concentration, and the polymer molecular weight is inversely proportional to the p-MS concentration. In contrast, [C5Me4(SiMe2NtBu)]TiCl2/M AO initiates a copolymerization reaction between ethylene and p-MS, and hydrogen has little effect on the catalyst activity. The terminal p-MS unit at the PE chain end is a valuable reactive group that can be metalated to form a stable polymeric anion, which can be used to prepare functionalized PE polymers containing a polar terminal group or diblock copolymers.

AB - This paper discusses a novel polymerization process for preparing polyethylene having a terminal p-methylstyrene (p-MS) group. The chemistry involves metallocene-mediated ethylene polymerization in the presence of p-MS and hydrogen. Apparently, the reaction mechanism, including the copolymerization and chain transfer reactions, can be controlled with a favorable combination of metallocene catalyst and hydrogen concentration. Under some specific reaction conditions, the Cp2ZrCl2/MAO catalyst selectively forms PE with a terminal p-MS terminal group (PE-t-p-MS) via a consecutive chain transfer reaction to p-MS and then hydrogen. The catalyst activity increases with the hydrogen concentration, and the polymer molecular weight is inversely proportional to the p-MS concentration. In contrast, [C5Me4(SiMe2NtBu)]TiCl2/M AO initiates a copolymerization reaction between ethylene and p-MS, and hydrogen has little effect on the catalyst activity. The terminal p-MS unit at the PE chain end is a valuable reactive group that can be metalated to form a stable polymeric anion, which can be used to prepare functionalized PE polymers containing a polar terminal group or diblock copolymers.

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