磷酸酯钕催化剂合成高顺式液体聚丁二烯的研究

Synthesis of high cis LPB by Nd phosphate catalyst

以二(2-乙基己基)膦酸酯钕(Nd)/二异丁基氢化铝(Al)/乙基倍半氯化铝(Cl)/丁二烯(Bdcat)为催化体系进行了液体丁二烯的聚合,制备了高顺式含量的聚丁二烯(LPB),考察了各种因素对聚合的影响,并采用红外光谱和核磁波谱表征了聚合物的微观结构及序列结构。结果表明,本催化体系下进行高顺式LPB的聚合条件范围为:Al/Nd(摩尔比,下同)为20～30、Cl/Nd为1.5～2.0、Bdcat/Nd为10～50、催化剂用量为3.3×10^(-4)。所制得的LPB样品顺式含量高于92%,以顺式-1,4-长序列结构为主。

The high cis liquid polybutadiene was synthesized by polymerization of 1,3-butadiene(Bd)with neodymium tris[bis(2-ethylhexyl)phosphate](Nd)/diisobutyl aluminium hydride(Al)/sesquiethylaluminum chloride(Cl)/Bdcatcatalyst system.The effect factors of polymerization of Bd were investigated,and the microstructure and sequence structure of polymer was characterized by infrared spectroscopy and13 C-nuclear magnetic resonance.The results showed that the optimum polymerization conditions of high cis LPB were Al/Nd(mole ratio)20~30,Cl/Nd(mole ratio)1.5~2.0,Bdcat/Nd 10~50,and the amount of catalyst was 3.3×10-4.The cis content of samples was higher than 92%,most of which were long cis-1,4-sequence structure.