Gagieva Svetlana Ch, Magomedov Kasim F, Tuskaev Vladislav A, Bogdanov Vyacheslav S, Kurmaev Dmitrii A, Golubev Evgenii K, Denisov Gleb L, Nikiforova Galina G, Evseeva Maria D, Saracheno Daniele, Buzin Mikhail I, Dzhevakov Pavel B, Privalov Viktor I, Bulychev Boris M
Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992 Moscow, Russia.
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Str., 28, 119991 Moscow, Russia.
Polymers (Basel). 2022 Oct 18;14(20):4397. doi: 10.3390/polym14204397.
A series of bis(phenoxy-imine) (FI) titanium(IV) and zirconium(IV) complexes have been synthesized. The effect of the nature of the activator (MAO, combinations EtAlCl + BuMg and iBuAl + [PhC][B(CF)]) on the catalytic activity and properties of the resulting polymers was studied. It was found that Ti-Fi complexes, despite the nature of the outgoing ligands (Cl or iPrO) in the presence of Al/Mg activators, effectively catalyze the polymerization of ethylene (with the formation of UHMWPE); copolymerization of ethylene with 1-octene (with the formation of ultra-high molecular weight copolymers); and the ternary copolymerization of ethylene, propylene and 5-vinyl-2-norbornene (with the formation of polyolefin elastomers). It has been shown that Zr-FI complexes are not activated by these Al/Mg compositions. The resulting UHMWPE can be processed by a solventless method into high-strength and high-modulus oriented films; however, their mechanical characteristics do not exceed those obtained using MAO.
已经合成了一系列双（苯氧基-亚胺）（FI）钛（IV）和锆（IV）配合物。研究了活化剂（甲基铝氧烷（MAO）、乙基氯化铝+丁基镁组合以及异丁基铝+[苯基-C][B（CF）]）的性质对所得聚合物的催化活性和性能的影响。发现Ti-Fi配合物，尽管在Al/Mg活化剂存在下离去配体（Cl或异丙氧基）的性质不同，但能有效催化乙烯聚合（形成超高分子量聚乙烯（UHMWPE））；乙烯与1-辛烯共聚（形成超高分子量共聚物）；以及乙烯、丙烯和5-乙烯基-2-降冰片烯的三元共聚（形成聚烯烃弹性体）。结果表明，Zr-FI配合物不能被这些Al/Mg组合物活化。所得的UHMWPE可以通过无溶剂方法加工成高强度和高模量的取向薄膜；然而，它们的机械性能不超过使用MAO获得的性能。
