DMC催化马来酸酐与环氧丙烷开环共聚行为类型及动力学的研究

Copolymerization type and kinetics of double metal cyanide catalyst for copolymerization of maleic anlydride and propylene oxide

研究了双金属氰化络合物(DMC)催化剂催化马来酸酐(MAn)与环氧丙烷(PO)开环共聚行为类型及动力学特征。用IR和1H-NMR表征了共聚物结构,结果表明MAn单体在DMC催化剂催化下不能开环均聚合,聚合为交替共聚。开环共聚合行为类型研究表明,以DMC催化剂催化MAn-PO开环共聚合中,PO单体竞聚率r1>0、MAn单体竞聚率r2=0,进一步证明此聚合为交替共聚。以共聚行为类型为依据,对聚合动力学进行了研究,结果表明:共聚合反应动力学方程式为Rp=K[C][M],聚合反应速率与单体浓度及催化剂浓度均成一次方关系。

Ring-opening alternating copolymerization of maleic anhydride with propylene oxide is conducted by double metal cyanide catalyst. All the reactions are carried out in small autoclaves. The copolymerization type of the copolymerization is studied. The copolymer is characterized by IR and ^1H - NMR. The results show that the double metal cyanide catalyst can not make maleic anhydride polymerazition with itself and the copolymer of maleic anhydride with propylene oxide is an alternate eopolymer. The results of the copolymerization type indicate that the reactivity ratio of propylene oxide is rPO〉0 and that of maleie anhydride is rMAn = 0, and the copolymerization is an alternate one. Based on this assumption a kinetic equation in which K is a rate constant is deduced： Rp = K[C] [M].