磷配体对镍系顺丁橡胶催化体系的影响

Effect of phosphorus ligands on nickel catalyst system in synthesis of high cis-polybutadiene rubber

研究在Ni(naph)2-Al(i-Bu)3-BF3.OEt2(简称Ni-Al-B)体系中添加含磷化合物作为配体对丁二烯聚合反应的影响,探索以磷酸三丁酯(TBP)为第4组分的催化体系中,Al/B、Al/Ni,TBP/Ni物质的量比对聚合活性和聚合产物特性粘数的影响,并用FT-IR等表征聚合物结构。结果表明,控制TBP的适量加入[n(TBP)/n(Ni)<3.0]对体系催化活性的影响很小,聚合产物的特性粘数较亚磷酸三壬基苯酯(TNPP)的低,TBP的加入对聚合产物的微观结构基本上没有影响,仍能合成高顺式-1,4聚丁二烯(顺式质量分数98.68%)。

The influence of organic phosphorus compound as additive on polymeric behaviour of butadiene initiated with nickel catalyst was investigated.The effect of polymerization conditions on polymerization activity and polymer＇s intrinsic viscosity of TBP-Al-Ni-B catalyst system for butadiene polymerization was also studied.The catalytic activity could keep high when the mole ratio of Al/B was 0.5～2.0 and TBP/Ni was less than 3.0.Furthermore,the TBP premixed with BF3·OEt2 have some solubilization effect on BF3·OEt2.With the increase of TBP/Ni,the intrinsic viscosity of polymer increased then decreased.TBP has basically no influence to the microstructure of the polymer characterized by FT-IR,also can synthesise high cis-1,4-polybutadiene.