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基于基团保护的用于乙烯与乙烯基极性单体共聚的含[OSSO]型双（酚盐）配体的钛配合物

Titanium complex with an [OSSO]-type bis(phenolate) ligand for ethylene copolymerization with vinyl polar monomer based on group protection.

作者信息

Zhu Yuqiong, Li Sihan, Liang Huaqing, Xie Xiuli, Zhu Fangming

机构信息

GDHPPC Lab, School of Chemistry and Chemical Engineering, Sun Yat-Sen University 510275 China

Key Lab for Polymer Composite and Functional Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Sun Yat-Sen University Guangzhou 510275 China.

出版信息

RSC Adv. 2019 Aug 27;9(46):26582-26587. doi: 10.1039/c9ra06271h. eCollection 2019 Aug 23.

DOI:10.1039/c9ra06271h
PMID:35528581
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9070498/
Abstract

The [OSSO]-type bis(phenolate) titanium complex 1 activated by methylaluminoxane (MAO) was tested as a homogeneous catalyst for ethylene coordination copolymerization with protected vinyl polar monomer of -butyl-dimethylsilyloxystyrene (-TBDMSOS). The results showed that the active species were almost not poisonous to the catalyst by the protected vinyl polar monomer. Moreover, the composition and sequence length as well as sequence distribution in the copolymers were investigated by theoretical calculation and C nuclear magnetic resonance (C NMR) characterization. Especially, the incorporation ratio of -TBDMSOS into the polyethylene chain could be controlled by changing -TBDMSOS concentration in the feed. Interestingly, an approximate alternating copolymer of poly(-(-TBDMSOS)) could be formed when the -TBDMSOS feed concentration increased to 1.0 mol L. Subsequently, the poly(ethylene--(-hydroxystyrene)) (poly(-(-HOS))) could be prepared by a facile deprotection in terms of desilylation of -butyldimethylsilyl ether. The hydrophilicity of poly(-(-HOS)) films were investigated by water contact angle measurements.

摘要

将由甲基铝氧烷（MAO）活化的[OSSO]型双（酚盐）钛配合物1作为乙烯与叔丁基二甲基硅氧基苯乙烯（-TBDMSOS）的受保护乙烯基极性单体进行配位共聚的均相催化剂进行了测试。结果表明，活性物种几乎不受受保护乙烯基极性单体对催化剂的毒害。此外，通过理论计算和碳核磁共振（C NMR）表征研究了共聚物中的组成、序列长度以及序列分布。特别是，通过改变进料中-TBDMSOS的浓度，可以控制-TBDMSOS在聚乙烯链中的掺入率。有趣的是，当-TBDMSOS进料浓度增加到1.0 mol/L时，可以形成聚（-（-TBDMSOS））的近似交替共聚物。随后，通过叔丁基二甲基硅基醚的脱硅基化的简便脱保护方法可以制备聚（乙烯-（-羟基苯乙烯））（聚（-（-HOS）））。通过水接触角测量研究了聚（-（-HOS））薄膜的亲水性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/772d3d70e395/c9ra06271h-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/9d5f199d5402/c9ra06271h-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/975c50287d1f/c9ra06271h-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/9718cc3498f0/c9ra06271h-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/84feed8a829d/c9ra06271h-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/0d0ab97fb2ee/c9ra06271h-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/c423c06d5132/c9ra06271h-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/772d3d70e395/c9ra06271h-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/9d5f199d5402/c9ra06271h-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/975c50287d1f/c9ra06271h-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/9718cc3498f0/c9ra06271h-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/84feed8a829d/c9ra06271h-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/0d0ab97fb2ee/c9ra06271h-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/c423c06d5132/c9ra06271h-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b9f6/9070498/772d3d70e395/c9ra06271h-f5.jpg

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