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Catalysts 2013, 3(1), 104-124; doi:10.3390/catal3010104
Article

Preparation of Thiophene-Fused and Tetrahydroquinoline-Linked Cyclopentadienyl Titanium Complexes for Ethylene/α-Olefin Copolymerization

1
, 1
, 2
, 2
, 3
, 3
 and 1,*
1 Department of Molecular Science and Technology, Ajou University, Suwon 443-749, Korea 2 Honam Petrochemical Company and Catalyst Research Team 5th, 24-1 Jang-Dong, Yuseong-Gu, Daejeon 305-726, Korea 3 Department of Chemistry, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwangju 500-757, Korea
* Author to whom correspondence should be addressed.
Received: 17 December 2012 / Revised: 25 January 2013 / Accepted: 29 January 2013 / Published: 6 February 2013
(This article belongs to the Special Issue Molecular Catalysis for Precise Olefin Polymerization)
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Abstract

A synthetic scheme was developed for the large-scale preparation of a dimethylthiophene-fused and tetrahydroquinaldine-linked dimethylcyclopentadienyl titanium complex (2), which is a high-performance homogeneous Ziegler catalyst. 2,3,4,5-Tetramethyl-4,5-dihydrocyclopenta[b]thiophen-6-one was prepared without chromatography purification on the 40-g scale in a laboratory setting, from which the ligand precursor for 2 was obtained in 65% yield on a 50-g scale in a one-pot without the need for chromatography purification. Metallation was achieved in a high yield (78%) through reaction of the dilithiated compound with TiCl4. Many derivatives were prepared by employing the same synthetic scheme as applied for 2. Among them, the titanium complex prepared from 2-methyl-4,5-dimethyl-6-(2-n-butyl-2,3,4,5-tetrahydroquinolin-8-yl)-4H-cyclopenta[b]thiophene exhibited an exceptionally high activity. Under commercially relevant high-temperature polymerization conditions (160 °C), this compound showed a higher activity than 2 (126 × 106 g/molTi∙h versus 72 × 106 g/molTi∙h), albeit with the formation of a polymer of slightly lower molecular weight (Mw, 159,000 versus 218,000) and with a slightly lower 1-octene content (9.3 mol% versus 12 mol%).
Keywords: titanium complex; half-metallocene; thiophene-fused cyclopentadienyl; ethylene polymerization titanium complex; half-metallocene; thiophene-fused cyclopentadienyl; ethylene polymerization
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Kim, S.H.; Park, J.H.; Song, B.G.; Yoon, S.-W.; Go, M.J.; Lee, J.; Lee, B.Y. Preparation of Thiophene-Fused and Tetrahydroquinoline-Linked Cyclopentadienyl Titanium Complexes for Ethylene/α-Olefin Copolymerization. Catalysts 2013, 3, 104-124.

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