Synthesis of chain end functional isotactic polypropylene by the combination of metallocene/MAO catalyst and organoborane chain transfer agent

Wentian Lin, Jinyong Dong, Tze-chiang Chung

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

This paper discusses a simple and effective route to prepare chain end functionalized PP and PP diblock copolymers, with high molecular weight and high purity. The reaction scheme involves a versatile "intermediate" of borane-terminated isotactic polypropylene (PP-t-B), which was prepared under a specific reaction condition, involving an iso-specific metallocene catalyst, purified MAO activator (without TMA), 9-borabicyclononane (9-BBN) dimmer chain transfer agent, and ambient reaction temperature. During the propylene polymerization mediated by the rac-Me2Si[2-Me-4-Ph(Ind)] 2ZrCl2/MAO catalyst system, the PP propagating chain end (C-Zr active site) engages in a selective ligand exchange reaction with a B-H group in the 9-BBN dimmer. Evidently, the side reaction between the 9-BBN dimmer and the purified MAO is very slow at <35 °C, so that the normal polymerization-chain transfer reaction mechanism can effectively take place to form the PP-t-B polymer. The polymer molecular weight is inversely proportional to the molar ratio of [9-BBN]/[propylene] with a chain transfer constant (k tr/kp) of 1/65. Despite the high molecular weight and heterogeneous reaction conditions, the terminal borane group in PP-t-B is quantitatively interconverted to the OH group under a mild ionic oxidation reaction condition. It is also selectively auto-oxidized by oxygen to form a control radical macroinitiator that affords the chain extension with methymethacrylate monomers to form PP-b-PMMA diblock copolymers.

Original languageEnglish (US)
Pages (from-to)8452-8457
Number of pages6
JournalMacromolecules
Volume41
Issue number22
DOIs
StatePublished - Nov 25 2008

Fingerprint

Polypropylenes
Monoamine Oxidase
Molecular weight
Boranes
Catalysts
Block copolymers
Propylene
Polymerization
Polymers
Polymethyl Methacrylate
Monomers
Ligands
Oxidation
Oxygen
metallocene
9-borabicyclononane
Temperature
propylene

All Science Journal Classification (ASJC) codes

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

Cite this

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abstract = "This paper discusses a simple and effective route to prepare chain end functionalized PP and PP diblock copolymers, with high molecular weight and high purity. The reaction scheme involves a versatile {"}intermediate{"} of borane-terminated isotactic polypropylene (PP-t-B), which was prepared under a specific reaction condition, involving an iso-specific metallocene catalyst, purified MAO activator (without TMA), 9-borabicyclononane (9-BBN) dimmer chain transfer agent, and ambient reaction temperature. During the propylene polymerization mediated by the rac-Me2Si[2-Me-4-Ph(Ind)] 2ZrCl2/MAO catalyst system, the PP propagating chain end (C-Zr active site) engages in a selective ligand exchange reaction with a B-H group in the 9-BBN dimmer. Evidently, the side reaction between the 9-BBN dimmer and the purified MAO is very slow at <35 °C, so that the normal polymerization-chain transfer reaction mechanism can effectively take place to form the PP-t-B polymer. The polymer molecular weight is inversely proportional to the molar ratio of [9-BBN]/[propylene] with a chain transfer constant (k tr/kp) of 1/65. Despite the high molecular weight and heterogeneous reaction conditions, the terminal borane group in PP-t-B is quantitatively interconverted to the OH group under a mild ionic oxidation reaction condition. It is also selectively auto-oxidized by oxygen to form a control radical macroinitiator that affords the chain extension with methymethacrylate monomers to form PP-b-PMMA diblock copolymers.",
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Synthesis of chain end functional isotactic polypropylene by the combination of metallocene/MAO catalyst and organoborane chain transfer agent. / Lin, Wentian; Dong, Jinyong; Chung, Tze-chiang.

In: Macromolecules, Vol. 41, No. 22, 25.11.2008, p. 8452-8457.

Research output: Contribution to journalArticle

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