Ethylene/styrene copolymerization by various (cyclopentadienyl)(aryloxy)titanium(IV) complexes-MAO catalyst systems

Kotohiro Nomura, Hiroshi Okumura, Takashi Komatsu, Naofumi Naga

Research output: Contribution to journalArticle

126 Citations (Scopus)

Abstract

Copolymerizations of ethylene with styrene by various (cyclopentadienyl)(aryloxy)titanium(IV) complexes of the type Cp'TiCl2(O-2,6-iPr2C6H3) [Cp' = tBuC5H4 (2), 1,3-Me2C5H3 (3), 1,2,3-Me3C5H3 (4), 1,2,4-Me3C5H3 (5)] have been explored in the presence of methylaluminoxane (MAO) as the cocatalyst. Effect of cyclopentadienyl fragment was explored and the catalytic activity increased in the order 3, 4 > 2 > 5, suggesting that effects of both electronic and steric bulk play an essential role for the copolymerization. Resultant polymers by these catalyst systems were poly(ethylene-co-styrene)s exclusively in all cases, and the use of 4 was quite effective for preparing relatively high molecular weight polymer with unimodal molecular weight distribution as well as with efficient styrene incorporation. The styrene incorporation efficiency did not strongly depend upon the cyclopentadienyl fragment used, and this is somewhat different from those obtained by the linked cyclopentadienyl-amide titanium catalyst [Me2Si(C5Me4)(NR)]TiCl2 [R = tert-Bu (6), cyclohexyl (7)]. The resultant copolymers possessed unimodal comonomer distributions (single composition) confirmed by both cross-fractionation chromatography (CFC) and GPC/FT-IR. The microstructure for the resultant copolymer by 2-5 was different from those prepared by a linked type catalyst (6) and was fairly dependent upon the cyclopentadienyl fragment used.

Original languageEnglish
Pages (from-to)5388-5395
Number of pages8
JournalMacromolecules
Volume35
Issue number14
DOIs
Publication statusPublished - 2002 Jul 2
Externally publishedYes

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Styrene
Titanium
Copolymerization
Ethylene
Catalysts
Polymers
Copolymers
Molecular weight distribution
Fractionation
Chromatography
Amides
Catalyst activity
Molecular weight
Microstructure
ethylene
Chemical analysis

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

Ethylene/styrene copolymerization by various (cyclopentadienyl)(aryloxy)titanium(IV) complexes-MAO catalyst systems. / Nomura, Kotohiro; Okumura, Hiroshi; Komatsu, Takashi; Naga, Naofumi.

In: Macromolecules, Vol. 35, No. 14, 02.07.2002, p. 5388-5395.

Research output: Contribution to journalArticle

Nomura, Kotohiro ; Okumura, Hiroshi ; Komatsu, Takashi ; Naga, Naofumi. / Ethylene/styrene copolymerization by various (cyclopentadienyl)(aryloxy)titanium(IV) complexes-MAO catalyst systems. In: Macromolecules. 2002 ; Vol. 35, No. 14. pp. 5388-5395.
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