稀土催化极性单体配位均聚及与非极性单体共聚合的研究

将极性基团引入大分子链中可改善非极性聚烯烃材料的表面性能,扩展其应用范围甚至带来不可预见的新功能,是市场需求并由企业驱动.与聚合后功能化改性和物理共混方法相比,极性与非极性单体配位共聚合是最直接和简便的方法,适用范围广,并可保持聚烯烃的立构规整度,一直以来,相关研究备受企业和科研工作者瞩目.然而,极性基团通常具有Lewis碱性,容易与Lewis酸性的聚合催化剂强烈螯合而致其毒化,因此,这又是极具挑战性的课题.目前,该领域的研究取得了很大的进展,已经实现了乙烯与很多极性单体的共聚合.今后,将集中解决如何实现极性单体均聚合,提高共聚合活性,特别是极性单体插入率和分布可调节性,保持立体选择性,以及获得高分子量、具有实际应用意义的共聚产物等问题.本文旨在将课题组近年来在极性功能化苯乙烯和共轭双烯烃单体的均聚合及与苯乙烯、乙烯和共轭双烯烃等非极性单体共聚合方面的最新研究成果以及国内外该领域的相关报道进行综合阐述,为读者提供解决上述关键问题采用的研究路线、实施方法和创新性思维.

Studies on Homo-and Co-polymerizations of Polar and Non-polar Monomers Using Rare-earth Metal Catalysts

The homo-and co-polymerizations of polar and non-polar monomers,since they can remain the stereo-regularity of the non-polyolefin precursors and meanwhile introduce polar groups into the non-polar polyolefins to improve their surface properties or bring unpredicted new functionalities,have attracted great attention of both academia and industries.However,polar groups are Lewis-basic while the catalysts employed in the polymerizations are usually Lewis acidic,which are prone to interact with the catalytic metal center to poison the catalysts,thus the study on homo-and co-polymerizations has been a challenging project.To date,many achievements have been obtained,and the following research should focus on realizing the homopolymerizations of polar monomers,increasing the activity and insertion ratio of the polar monomer in the copolymers,regulating the polar monomer composition and distribution along the copolymer macromolecular chains and isolating high molecular weight and practically available products.In this review,we summarized the recent developments of our group on the homo-and co-polymerizations of polar monomers,in particular polar styrenes and conjugated dienes with styrene,ethylene,butadien,isoprene and other popular nonpolar olefins,aiming to provide the readers novel strategies for designing new catalysts and polar monomers,as well as the unprecedented mechanisms.