Fe-Zn双金属氰化物催化环氧丙烷开环聚合的研究  

RING-OPENING POLYMERIZATION OF PROPYLENE OXIDE INITIATED BY Fe-Zn DOUBLE METAL CYANIDE CATALYST

作　　者：黄亦军[1] 戚国荣[1] 钱锦文[1] 封麟先[1] 

机构地区：[1]浙江大学高分子科学和工程系,杭州310027

出　　处：《高分子学报》2001年第2期210-214,共5页Acta Polymerica Sinica

摘　　要：用Fe Zn双金属氰化物 (DMC)催化剂合成了数均分子量 30 0 0～ 12 0 0 0的聚氧化丙烯二元醇 .着重考察了聚合反应的温度、加料方式等对聚合物分子量及分布的影响 ,并初步探讨了Fe Zn双金属氰化物催化环氧丙烷开环聚合的反应特征 .实验发现 ,采用Fe ZnDMC催化剂 ,聚合物分子量可控 ;在较高温度下聚合所得的聚合物分子量分布呈双峰形 ,显示反应体系中至少存在两类活性中心 ,这可能与催化剂中存在两种价态的络合物有关 ,当降低聚合温度时 ,聚合物分子量分布呈单峰形 ,可能是一类活性中心没有引发 ;实验中还发现单体分批加料时聚合物分子量分布较窄 。Fe-Zn double metal cyanide (DMC) complexes are relatively cheap and effective catalysts for the ring-opening polymerization of propylene oxide. Polyoxypropylene diol oligomer is used as the initiator. Polyoxypropylene diols having M-n within the range of about 3000 to 12000 are prepared with Fe-Zn DMC catalyst under mild condition. The polymer is characterized by GPC and VPO. Effect of polymerization condition on molecular weight(MW) and molecular weight distribution (MWD) is investigated. The MW of polymer may be controlled by monomer/initiator molar ratio( M/I). It is assumed that each activated catalyst site is related with many different molecules during polymerization. Polymerization proceeded at 80 degreesC and 60 degreesC gives polymers with a bimodal MWD(at least two kinds of active centers) and a unimodal MWD, respectively. When polymerization proceeds at temperatures lower than 65 degreesC, the active center associated with Fe(CN)(6)(4-) may not act because of its low activity. Two types of anion Fe(CN)(6)(3-) and Fe(CN)(6)(4-) coexisting in Fe-Zn DMC catalysts, which possibly result in the bimodal MWD, have been proved by IR spectra and X-ray diffraction.

关 键 词：双金属氰化物 聚氧化丙烯二元醇 分子量分布 环氧丙烷 开环聚合 铁 锌 

分 类 号：TQ316[化学工程—高聚物工业]