Synthesis of styryl-capped polypropylene via metallocene-mediated coordination polymerization: Apply to polypropylene macromolecular engineering |
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Authors: | Hua-hua Huang Chuan-hui Zhang Ya-wei Qin Hui Niu Jin-yong Dong |
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Affiliation: | 1. CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China ;University of Chinese Academy of Sciences, Beijing 100049, China 2. CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China |
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Abstract: | In this paper, we review our recent progress in the synthesis and application of styryl-capped polypropylene (PP-t-St), an excellent reactive polyolefin that is both convenient and efficient in synthesis and facile and versatile in application for preparing advanced polypropylene materials via macromolecular engineering. The synthesis of PP-t-St is made possible by a unique chain transfer reaction coordinated by a bis-styrenic molecule, such as 1,4-divinylbenzene (DVB) and 1,2-bis(4-vinylphenyl)ethane (BVPE), and hydrogen in typical C 2-symmetric metallocene (e.g. rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2, in association with methylaluminocene, MAO) catalyzed propylene polymerization. The regio-selective 2,1-insertion of the styrenic double bond in DVB or BVPE into the overwhelmingly 1,2-fashioned Zr-PP propagating chain enables substantial dormancy of the catalyst active site, which triggers selective hydrogen chain transfer that, with the formed Zr-H species ultimately saturated by the insertion of propylene monomer, results in an exclusive capping of the afforded PP chains by styryl group at the termination end. With a highly reactive styryl group at chain end, PP-t-St has been used as a facile building block in PP macromolecular engineering together with the employment of state-of-the-art synthetic polymer chemistry to fabricate broad types of new polypropylene architectures. |
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Keywords: | Polypropylene Coordination polymerization Styryl terminal group Macromolecular engineering |
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