杯芳烃钕配合物的合成及其催化丁二烯聚合

Synthesis and catalytic property of 1,3-butadiene of calixarene neodynium complex

首次应用新型配体——杯芳烃·钕配合物与三异丁基铝构成催化体系催化丁二烯聚合 .研究发现杯 [6,8]芳烃钕 / Al( i- Bu) 3/汽油体系中 ,当 Al/ Nd=4 0～ 10 0 ,50℃时具有中等催化聚合活性 ,所制得聚丁二烯的粘均分子量为 10～ 2 0万 ,顺 - 1,4结构含量为 89%左右 .添加适量 Al2 Et3Cl3,或 Al( i- Bu) 2 Cl能提高催化活性 .但不能提高顺 - 1,4结构含量 .降低聚合反应温度 ,5℃聚合所得产物的顺 - 1,4结构含量可达 96% .

Three kinds of calixarene neodynium complexes (C\NdCl,C\NdCl,C\Nd\-2Cl\-2) were synthesized. Polymerization of 1,3\|butadiene with binary catalytic systems composed of calixarene neodynium/triisobutyl\|aluminum and ternary catalytic system composed of calixarene neodynium, triisobutyl\|aluminum, and a Lewis acid (Al\-2Et\-3Cl\-3 or Al(i\|Bu)\-2Cl or PhCH\-2Cl) as the third component was studied. The binary catalysts were found to be active even in the absence of halogen source, the sequence of catalytic activity of calixarene neodynium complexes is C\Nd\-2Cl\-2>C\NdCl>C\NdCl. While the ternary system has higher activity especially using Al\-2Et\-3Cl\-3.as the third component, and the polymer obtained has higher cis\|1,4 content. The effect of chloride sort and catalyst preparation mode, Cl/Nd ratio, and the reaction temperature on polymerization and polymer microstructure of ternary system use C\Nd\-2Cl\-2 was investigated. It was found that when Al\-2Et\-3Cl\-3 as the third component and Cl/Nd=1, the catalytic system has highest activity to polymerization of 1,3\|butadiene. The cis\|1,4 content of polybutadiene is decreased with the increase of reaction temperature. High cis\|polybutadiene(96%) formed when polymerization was carried out at 5 ℃.