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通过（MeSiCH）TiCl（O-2,6-Pr-4-RCH）（R = H，SiEt）-MAO催化剂进行乙烯/苯乙烯共聚：SiMe基团对用于高效引入苯乙烯的Cp的影响

Ethylene/Styrene Copolymerization by (MeSiCH)TiCl(O-2,6-Pr-4-RCH) (R = H, SiEt)-MAO Catalysts: Effect of SiMe Group on Cp for Efficient Styrene Incorporation.

作者信息

Huang Tiantian, Fujioka Taiga, Shimoyama Daisuke, Nomura Kotohiro

机构信息

Department of Chemistry, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji 192-0397, Tokyo, Japan.

出版信息

Molecules. 2024 Sep 20;29(18):4473. doi: 10.3390/molecules29184473.

DOI:10.3390/molecules29184473
PMID:39339468
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11434206/
Abstract

The synthesis and structural analysis of (MeSiCH)TiCl(OAr) [OAr = O-2,6-Pr-4-RCH; R = H, SiEt] revealed that it exhibits higher catalytic activities than (BuCH)TiCl(OAr), Cp*TiCl(OAr), with efficient comonomer incorporation in ethylene/styrene copolymerization in the presence of a methylaluminoxane (MAO) cocatalyst. The catalytic activity in the copolymerization increased upon increasing the charged styrene concentration along with the increase in the styrene content in the copolymers, whereas the activities of other catalysts showed the opposite trend. (MeSiCH)TiCl(O-2,6-PrCH) displayed the most suitable catalyst performance in terms of its activity and styrene incorporation, affording amorphous copolymers with styrene contents higher than 50 mol% (up to 63.6 mol%) and with random styrene incorporation confirmed by C-NMR spectra.

摘要

(MeSiCH)TiCl(OAr) [OAr = O-2,6-Pr-4-RCH；R = H，SiEt] 的合成与结构分析表明，在甲基铝氧烷（MAO）助催化剂存在下，它在乙烯/苯乙烯共聚反应中表现出比 (BuCH)TiCl(OAr)、Cp*TiCl(OAr) 更高的催化活性，且能有效引入共聚单体。随着进料苯乙烯浓度的增加以及共聚物中苯乙烯含量的增加，共聚反应中的催化活性提高，而其他催化剂的活性则呈现相反趋势。就活性和苯乙烯引入而言，(MeSiCH)TiCl(O-2,6-PrCH) 表现出最合适的催化剂性能，可得到苯乙烯含量高于50 mol%（高达63.6 mol%）的无定形共聚物，且通过碳 - 核磁共振光谱证实苯乙烯为无规引入。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/95e9ef0f7d13/molecules-29-04473-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/090465e30116/molecules-29-04473-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/0896198ab995/molecules-29-04473-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/9835a92f9d10/molecules-29-04473-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/efe10be9c350/molecules-29-04473-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/717344617c31/molecules-29-04473-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/95e9ef0f7d13/molecules-29-04473-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/090465e30116/molecules-29-04473-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/0896198ab995/molecules-29-04473-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/9835a92f9d10/molecules-29-04473-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/efe10be9c350/molecules-29-04473-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/717344617c31/molecules-29-04473-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4803/11434206/95e9ef0f7d13/molecules-29-04473-g004.jpg

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