Borane chain transfer reaction in olefin polymerization using trialkylboranes as chain transfer agents

Wentian Lin, Hui Niu, Tze-chiang Chung, Jin Yong Dong

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

This article discusses a new borane chain transfer reaction in olefin polymerization that uses trialkylboranes as a chain transfer agent and thus can be realized in conventional single site polymerization processes under mild conditions. Commercially available triethylborane (TEB) and synthesized methyl-B-9-borabicyclononane (Me-B-9-BBN) were engaged in metallocene/MAO [depleted of trimethylaluminum (TMA)]-catalyzed ethylene (Cp 2ZrCI 2 and rac-Me 2Si(2-Me-4-Ph) 2ZrCI 2 as a catalyst) and styrene (Cp*Ti(OMe) 3 as catalyst) polymerizations. The two trialkylboranes were found-in most cases-able to initiate an effective chain transfer reaction, which resulted in hydroxyl (OH)-terminated PE and s-PS polymers after an oxidative workup process, suggesting the formation of the B-polymer bond at the polymer chain end. However, chain transfer efficiencies were influenced substantially by the steric hindrances of both the substituent on the trialkylborane and that on the catalyst ligand. TEB was more effective than TMA in ethylene polymerization with Cp 2ZrCl 2/MAO, whereas it became less effective when the catalyst changed to racMe 2Si(2-Me-4-Ph) 2ZrCl 2. Both TEB and Me-B-9-BBN caused an efficient chain transfer in the Cp 2ZrCl 2/MAO-catalyzed ethylene polymerization; nevertheless, Me-B-9-BBN failed in vain with rac-Me 2Si(2-Me-4-Ph) 2ZrCl 2/MAO. In the case of styrene polymerization with Cp*Ti(OMe) 3/MAO, thanks to the large steric openness of the catalyst, TEB exhibited a high efficiency of chain transfer. Overall, trialkylboranes as chain transfer agents perform as well as B-H-bearing borane derivatives, and are additionally advantaged by a much milder reaction condition, which further boosts their applicability in the preparation of borane-terminated polyolefins.

Original languageEnglish (US)
Pages (from-to)3534-3541
Number of pages8
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume48
Issue number16
DOIs
StatePublished - Aug 15 2010

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Boranes
Alkenes
Monoamine Oxidase
Olefins
Polymerization
Catalysts
Polymers
Ethylene
Styrene
Bearings (structural)
Polyolefins
Hydroxyl Radical
Ligands
Derivatives
triethylborane
ethylene

All Science Journal Classification (ASJC) codes

  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry

Cite this

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title = "Borane chain transfer reaction in olefin polymerization using trialkylboranes as chain transfer agents",
abstract = "This article discusses a new borane chain transfer reaction in olefin polymerization that uses trialkylboranes as a chain transfer agent and thus can be realized in conventional single site polymerization processes under mild conditions. Commercially available triethylborane (TEB) and synthesized methyl-B-9-borabicyclononane (Me-B-9-BBN) were engaged in metallocene/MAO [depleted of trimethylaluminum (TMA)]-catalyzed ethylene (Cp 2ZrCI 2 and rac-Me 2Si(2-Me-4-Ph) 2ZrCI 2 as a catalyst) and styrene (Cp*Ti(OMe) 3 as catalyst) polymerizations. The two trialkylboranes were found-in most cases-able to initiate an effective chain transfer reaction, which resulted in hydroxyl (OH)-terminated PE and s-PS polymers after an oxidative workup process, suggesting the formation of the B-polymer bond at the polymer chain end. However, chain transfer efficiencies were influenced substantially by the steric hindrances of both the substituent on the trialkylborane and that on the catalyst ligand. TEB was more effective than TMA in ethylene polymerization with Cp 2ZrCl 2/MAO, whereas it became less effective when the catalyst changed to racMe 2Si(2-Me-4-Ph) 2ZrCl 2. Both TEB and Me-B-9-BBN caused an efficient chain transfer in the Cp 2ZrCl 2/MAO-catalyzed ethylene polymerization; nevertheless, Me-B-9-BBN failed in vain with rac-Me 2Si(2-Me-4-Ph) 2ZrCl 2/MAO. In the case of styrene polymerization with Cp*Ti(OMe) 3/MAO, thanks to the large steric openness of the catalyst, TEB exhibited a high efficiency of chain transfer. Overall, trialkylboranes as chain transfer agents perform as well as B-H-bearing borane derivatives, and are additionally advantaged by a much milder reaction condition, which further boosts their applicability in the preparation of borane-terminated polyolefins.",
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Borane chain transfer reaction in olefin polymerization using trialkylboranes as chain transfer agents. / Lin, Wentian; Niu, Hui; Chung, Tze-chiang; Dong, Jin Yong.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 48, No. 16, 15.08.2010, p. 3534-3541.

Research output: Contribution to journalArticle

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N2 - This article discusses a new borane chain transfer reaction in olefin polymerization that uses trialkylboranes as a chain transfer agent and thus can be realized in conventional single site polymerization processes under mild conditions. Commercially available triethylborane (TEB) and synthesized methyl-B-9-borabicyclononane (Me-B-9-BBN) were engaged in metallocene/MAO [depleted of trimethylaluminum (TMA)]-catalyzed ethylene (Cp 2ZrCI 2 and rac-Me 2Si(2-Me-4-Ph) 2ZrCI 2 as a catalyst) and styrene (Cp*Ti(OMe) 3 as catalyst) polymerizations. The two trialkylboranes were found-in most cases-able to initiate an effective chain transfer reaction, which resulted in hydroxyl (OH)-terminated PE and s-PS polymers after an oxidative workup process, suggesting the formation of the B-polymer bond at the polymer chain end. However, chain transfer efficiencies were influenced substantially by the steric hindrances of both the substituent on the trialkylborane and that on the catalyst ligand. TEB was more effective than TMA in ethylene polymerization with Cp 2ZrCl 2/MAO, whereas it became less effective when the catalyst changed to racMe 2Si(2-Me-4-Ph) 2ZrCl 2. Both TEB and Me-B-9-BBN caused an efficient chain transfer in the Cp 2ZrCl 2/MAO-catalyzed ethylene polymerization; nevertheless, Me-B-9-BBN failed in vain with rac-Me 2Si(2-Me-4-Ph) 2ZrCl 2/MAO. In the case of styrene polymerization with Cp*Ti(OMe) 3/MAO, thanks to the large steric openness of the catalyst, TEB exhibited a high efficiency of chain transfer. Overall, trialkylboranes as chain transfer agents perform as well as B-H-bearing borane derivatives, and are additionally advantaged by a much milder reaction condition, which further boosts their applicability in the preparation of borane-terminated polyolefins.

AB - This article discusses a new borane chain transfer reaction in olefin polymerization that uses trialkylboranes as a chain transfer agent and thus can be realized in conventional single site polymerization processes under mild conditions. Commercially available triethylborane (TEB) and synthesized methyl-B-9-borabicyclononane (Me-B-9-BBN) were engaged in metallocene/MAO [depleted of trimethylaluminum (TMA)]-catalyzed ethylene (Cp 2ZrCI 2 and rac-Me 2Si(2-Me-4-Ph) 2ZrCI 2 as a catalyst) and styrene (Cp*Ti(OMe) 3 as catalyst) polymerizations. The two trialkylboranes were found-in most cases-able to initiate an effective chain transfer reaction, which resulted in hydroxyl (OH)-terminated PE and s-PS polymers after an oxidative workup process, suggesting the formation of the B-polymer bond at the polymer chain end. However, chain transfer efficiencies were influenced substantially by the steric hindrances of both the substituent on the trialkylborane and that on the catalyst ligand. TEB was more effective than TMA in ethylene polymerization with Cp 2ZrCl 2/MAO, whereas it became less effective when the catalyst changed to racMe 2Si(2-Me-4-Ph) 2ZrCl 2. Both TEB and Me-B-9-BBN caused an efficient chain transfer in the Cp 2ZrCl 2/MAO-catalyzed ethylene polymerization; nevertheless, Me-B-9-BBN failed in vain with rac-Me 2Si(2-Me-4-Ph) 2ZrCl 2/MAO. In the case of styrene polymerization with Cp*Ti(OMe) 3/MAO, thanks to the large steric openness of the catalyst, TEB exhibited a high efficiency of chain transfer. Overall, trialkylboranes as chain transfer agents perform as well as B-H-bearing borane derivatives, and are additionally advantaged by a much milder reaction condition, which further boosts their applicability in the preparation of borane-terminated polyolefins.

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