配体种类对二氯二氧钼催化丁二烯聚合的影响

摘要

分别以乙酸乙酯(EA)、磷酸三丁酯(TBP)及正辛醇改性的MoO2Cl2为主催化剂,AI(OPhCH3) (i-Bu)2(简称Al)为助催化剂催化丁二烯(Bd)聚合.探讨配体种类和用量对主催化剂溶解性以及聚合条件对丁二烯聚合反应的影响,采用FT-IR、GPC表征聚合产物微观结构.结果表明:TBP与MoO2Cl2最佳物质的量比为2,EA与MoO2Cl2最佳物质的量比为4；正辛醇作配体时,聚合活性很低.EA和TBP作为配体时的最佳聚合条件:n(Al) (Mo)为10～30,n(Mo) (Bd)为(2.0～3.0)×10-4,聚合温度为60℃,聚合时间为6h.TBP做配体时,聚合产物特性粘数较低.%Butadiene was polymerized with main catalyst MoO2Cl2 (simplified as Mo), cocatalyst Al(OPhCH3)(i-Bu)2(simplified as Al),and MoO2Cl2 was modified with EA,TBP and n-Octyl alcohol respectively. The effect of the amount of the three solubilizers on polymerization of butadiene was investigated in this work,and the optimum polymerization conditions were studied. The microstructure of polymers was characterized by FT-IR and GPC. The result showed that the catalyst exhibited high activity when TBP/Mo was 2 and EA/Mo was 4, respectively, but when n-octyl alcohol was used as ligand,the activity was quite low. The optimum conditions for EA and TBP used as ligand were that the mole ratio of Al/Mo was 10~30,the mole ratio of Mo/Bd was(2. 0~3. 0) ×10-4 at 60 ℃ for 6 h. Compared with EA,the activity and the intrinsic viscosity of polymer were low when TBP was used as ligand.