催化体系对稀土顺丁橡胶聚合反应和胶料性能的影响

Effect of Catalytic System on the Polymerization Reaction and Properties of Rare Earth Butadiene Rubber

研究催化体系对稀土(钕系)顺丁橡胶(Nd BR)聚合反应和胶料性能的影响。催化体系的优化组成为:新癸酸钕(NdV_3)作主催化剂,二异丁基氢化铝(简称铝剂)作还原剂,氯化二异丁基铝(简称氯剂)作路易斯酸;优化配制工艺为:在NdV_3中先加铝剂再加氯剂,聚合反应时丁二烯和催化体系3个组分陈化液一起加入;优化配合为:在100g丁二烯中n(NdV_3)为(1.36~1.58)×10^(-4)mol,n(NdV_3)/n(铝剂)/n(氯剂)为1/22/(1.71~2);适合的陈化时间为4~64 h。采用优化催化体系聚合的产品收率大于98%,制备的Nd BR顺式-1,4-结构质量分数大于0.98,生胶门尼粘度[ML(1+4)100℃]为45±5,胶料加工性能和物理性能与朗盛NdBR胶料相当,优于BR9000胶料。

The influence of catalytic system on the polymerization reaction and properties of rare earth（neodymium） butadiene rubber（Nd BR） was studied.The optimized catalyst system consisted of neodymium neodecanoate（NdV3） as the primary catalyst,diisobutyl aluminum hydride（aluminum agent） as a reducing agent and diisobutylaluminum chloride（chlorine agent） as a Lewis acid.In the preferred process to produce the mixed catalyst,aluminum agent was added into NdV3,and then the chlorine agent was added.During the polymerization,butadiene was added together with the mixed catalyst which was allowed to age for 4-64 hours.In the optimized recipe of polymerization,（1.36-1.58）×10^-4 mol of NdV_3 was applied for 100 grams of monomer butadiene,and the molar ratio of NdV3,aluminum agent and chlorine agent was 1/22/（1.71-2）.With the optimized polymerization catalyst system,the product yield was greater than 98%,cis-1,4-structure content of the produced NdBR was more than 0.98,Mooney viscosity [ML（1＋4）100 ℃]was 45±5,the processing and physical properties of the Nd BR was similar to LANXESS NdBR and better than BR9000.