铁系催化剂聚合1，3-双烯烃的研究

1，2-聚丁二烯和3，4-聚异戊二烯是制造高性能轮胎的原料。本论文研究了以含磷化合物为第三组份的铁催化剂合成1，2-聚丁二烯和3，4-聚异戊二烯的反应规律：1．以二乙基亚磷酸酷为第三组份的铁催化剂可在己烷中，较高温度（50℃）下聚合1，3-丁二烯。通过控制催化剂组份的配比，可制备间同和无规1，2-聚丁二烯。所得间同1，2-聚丁二烯的1，2-结构含量为91％，间规度为90％；所得无规1，2-聚丁二烯的硫化胶具有优异的抗干、湿滑性能。2．以三苯基磷酸酷为第三组份的铁催化剂是合成高间同1，2一聚丁二烯的高效催化剂。所得聚合物具有高的1，2-结构含量（ca.95％），高的间规度（ca.95％）。聚合物的微观结构与催化剂组成等反应因素无关。3．以二烷基亚磷酸醋为第三组份的铁催化剂可在己烷中，较高温度（50℃）下聚合异戊二烯。二烷基亚磷酸醋中烷基影响聚合活性的顺序为乙基一甲基＞正丁基＞异辛基。所得聚异戊二烯的3，4（含1，2）结构含量保持在60％左右，不受反应条件的影响。4．改性甲基铝氧烷（MMAO）活化的铁催化剂聚合异戊二烯，在相当低的MMAO用量下（Al／Fe=20，摩尔比）即有高的催化活性。溶剂影响聚合活性的顺序为甲苯＞环己烷＞己烷＞二氯甲烷。所得聚异戊二烯的3，4（含1，2）结构含量稳定在60％。

Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

Synthesis and properties of ferrocene-functionalised polythiophene derivatives

The ferrocene-functionalised thiophene derivatives (TFn) with different length of oxyethylene chains were synthesized and polymerized chemically with iron (III) chloride as an oxidant. The resulting ferrocene-functionalised polythiophenes (PTFn) show good solubility in most solvents, such as chloroform (CHCl3) tetrahydrofuran (THF), acetone, etc. The structure and properties of the PTFn polymers were confirmed by IR, H-1 NMR, AFM and photoluminescence (PL). The polymers PTFn show good redox activity with no attenuation of the electroactivity after multiple potential cycling. (C) 2009 Elsevier B.V. All rights reserved.