二醚型 Ziegler-Natta 催化剂催化丙烯与极性单体共聚

 以三乙基铝 (TEA) 为保护剂, 研究了 TiCl4/MgCl2/芴二醚/Al(C2H5)3 体系催化丙烯与十一烯醇或十一烯酸的共聚反应. 结果表明, 在极性单体存在下, 聚合反应活性随极性单体加入量的增加而降低, 但可保持丙烯均聚活性的一半以上, 反应活性衰减较小. 同时, 随着极性单体加入量的增加, 极性单体在共聚物中的含量增加. 与十一烯酸相比, 十一烯醇共聚具有更高的共聚活性和共单体含量. 随着共聚物中极性单体含量的增加, 聚合物的熔点和结晶温度都有所降低. 反应温度对丙烯和十一烯醇共聚的反应活性和共单体含量影响较小.

Copolymerization of Propylene and Polar Monomers by a New Ziegler-Natta Catalyst System with Diether as Internal Donor

The functionalization of polyolefins has been an area of scientific challenge and industrial importance for many years because the lack of polar groups in polyolefins significantly limits their applications. In all of the ways, copolymerization with polar monomers is the most efficient one to functionalize polyolefins. In this article, copolymerization of propylene with 10-undecen-1-ol and 10-undecenoic acid using triethylaluminum as the protection reagent has been performed in the TiCl4/MgCl2/diether/Al(C2H5)3 catalysis system. In the presence of both comonomers, activity of copolymerization decreases with the increase of comonomer in the feed, but the decadence of polymerization activity is less. With increasing polar monomer in the feed, the content of comonomer in copolymer increases. 10-Undecen-1-ol shows better performance, in terms of not only activity but also the comonomer content in copolymer. With increasing the content of comonomer in copolymer, both melting point and crystallize temperature of copolymers decrease. The polymerization temperature has less effect on po-lymerization activity and comonomer content in the copolymerization of propylene and 10-undecen-1-ol.