Copolymerization of styrene and conjugated dienes with half-sandwich titanium(IV) catalysts: The effect of the ligand structure on the monomer reactivity, monomer sequence distribution, and insertion mode of dienes

Naofumi Naga, Yukio Imanishi

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

The copolymerization of styrene and 1,3-butadiene (Bd) or isoprene (Ip) was carried out with half-sandwich titanium(IV) Cp′TiCl3 catalysts (where Cp′ is cyclopentadienyl 1, indenyl 2, or pentamethylcyclopentadienyl 3) with methylaluminoxane as a cocatalyst. For the copolymerization with Bd, catalyst 3 gave the copolymers containing the highest amount of Bd among the catalysts used. The resulting copolymers were composed of a styrene-Bd multiblock sequence. High melting points were observed in the copolymers prepared with catalyst 1. The structures of hydrogenated poly(styrene-co-Bd) were studied by 13C NMR spectroscopy, and the long styrene sequence length was detected in the copolymers prepared with catalyst 1. For styrene/Ip copolymerization, random copolymers were obtained. Among the used catalysts, catalyst 1 gave the copolymers containing the highest amount of Ip. The copolymers prepared with catalyst 1 showed a steep melting point depression with increasing Ip content because of the high ratio of 1,4-inserted Ip units and/or the low molecular weights of the copolymers.

Original languageEnglish
Pages (from-to)939-946
Number of pages8
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume41
Issue number7
DOIs
Publication statusPublished - 2003 Apr 1
Externally publishedYes

Fingerprint

Styrene
Titanium
Copolymerization
Copolymers
Monomers
Isoprene
Ligands
Butadiene
Catalysts
Melting point
Nuclear magnetic resonance spectroscopy
Molecular weight
isoprene
1,3-butadiene

Keywords

  • 1,3-butadiene
  • Copolymerization
  • Half-sandwich titanium (IV) catalyst
  • Isoprene
  • Structure
  • Styrene
  • Thermal properties

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics

Cite this

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abstract = "The copolymerization of styrene and 1,3-butadiene (Bd) or isoprene (Ip) was carried out with half-sandwich titanium(IV) Cp′TiCl3 catalysts (where Cp′ is cyclopentadienyl 1, indenyl 2, or pentamethylcyclopentadienyl 3) with methylaluminoxane as a cocatalyst. For the copolymerization with Bd, catalyst 3 gave the copolymers containing the highest amount of Bd among the catalysts used. The resulting copolymers were composed of a styrene-Bd multiblock sequence. High melting points were observed in the copolymers prepared with catalyst 1. The structures of hydrogenated poly(styrene-co-Bd) were studied by 13C NMR spectroscopy, and the long styrene sequence length was detected in the copolymers prepared with catalyst 1. For styrene/Ip copolymerization, random copolymers were obtained. Among the used catalysts, catalyst 1 gave the copolymers containing the highest amount of Ip. The copolymers prepared with catalyst 1 showed a steep melting point depression with increasing Ip content because of the high ratio of 1,4-inserted Ip units and/or the low molecular weights of the copolymers.",
keywords = "1,3-butadiene, Copolymerization, Half-sandwich titanium (IV) catalyst, Isoprene, Structure, Styrene, Thermal properties",
author = "Naofumi Naga and Yukio Imanishi",
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T1 - Copolymerization of styrene and conjugated dienes with half-sandwich titanium(IV) catalysts

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AU - Naga, Naofumi

AU - Imanishi, Yukio

PY - 2003/4/1

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N2 - The copolymerization of styrene and 1,3-butadiene (Bd) or isoprene (Ip) was carried out with half-sandwich titanium(IV) Cp′TiCl3 catalysts (where Cp′ is cyclopentadienyl 1, indenyl 2, or pentamethylcyclopentadienyl 3) with methylaluminoxane as a cocatalyst. For the copolymerization with Bd, catalyst 3 gave the copolymers containing the highest amount of Bd among the catalysts used. The resulting copolymers were composed of a styrene-Bd multiblock sequence. High melting points were observed in the copolymers prepared with catalyst 1. The structures of hydrogenated poly(styrene-co-Bd) were studied by 13C NMR spectroscopy, and the long styrene sequence length was detected in the copolymers prepared with catalyst 1. For styrene/Ip copolymerization, random copolymers were obtained. Among the used catalysts, catalyst 1 gave the copolymers containing the highest amount of Ip. The copolymers prepared with catalyst 1 showed a steep melting point depression with increasing Ip content because of the high ratio of 1,4-inserted Ip units and/or the low molecular weights of the copolymers.

AB - The copolymerization of styrene and 1,3-butadiene (Bd) or isoprene (Ip) was carried out with half-sandwich titanium(IV) Cp′TiCl3 catalysts (where Cp′ is cyclopentadienyl 1, indenyl 2, or pentamethylcyclopentadienyl 3) with methylaluminoxane as a cocatalyst. For the copolymerization with Bd, catalyst 3 gave the copolymers containing the highest amount of Bd among the catalysts used. The resulting copolymers were composed of a styrene-Bd multiblock sequence. High melting points were observed in the copolymers prepared with catalyst 1. The structures of hydrogenated poly(styrene-co-Bd) were studied by 13C NMR spectroscopy, and the long styrene sequence length was detected in the copolymers prepared with catalyst 1. For styrene/Ip copolymerization, random copolymers were obtained. Among the used catalysts, catalyst 1 gave the copolymers containing the highest amount of Ip. The copolymers prepared with catalyst 1 showed a steep melting point depression with increasing Ip content because of the high ratio of 1,4-inserted Ip units and/or the low molecular weights of the copolymers.

KW - 1,3-butadiene

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KW - Structure

KW - Styrene

KW - Thermal properties

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