摘要
利用小釜实验考察了在多种新溶剂中钯（Ⅱ）催化ＣＯ／乙烯共聚制备聚酮高分子的反应，并利用高分辨核磁共振１ＨＮＭＲ、１３ＣＮＭＲ技术对在不同溶剂中制得产品的主链和端基进行了分析，实验结果表明除甲醇外，在丙酮、丙醛、Ｎ，Ｎ二甲基甲酰胺、Ｎ，Ｎ二甲基乙酰胺、冰乙酸、二甲基亚砜等溶剂中，钯（Ⅱ）双膦催化剂仍具有较好的催化活性，尤其以冰乙酸为溶剂，在没有强酸阴离子存在的条件下，催化反应亦可顺利进行．实验结果同时表明适宜的溶剂除作为稀释剂外，还对中心金属钯（Ⅱ）具有适宜的稳定作用．产品端基分析结果表明在非醇类溶剂中共聚反应由乙烯插入ＰｄＨ键引发，在醇类溶剂中共聚反应主要由ＣＯ插入ＰｄＯＲ键引发．
Many new solvents were investigated for the copolymerization of CO with ethylene to prepare polyketones with small reactor experiments.The backbone and the end groups of the polyketones prepared in different solvents were analyzed with high resolution 1H NMR and 13C NMR techniques.The experimental results showed that,besides in methanol,in acetone,propionaldehyde,N,N dimethylformamide,N,N dimethylacetamide,glacial acetic acid,dimethylsulfoxide,palladium(Ⅱ) bisphosphine catalyst also had high reactivity,especially in glacial acetic acid,the copolymerization could be performed without anions of strong acid.The experimental results also showed that suitable solvent should have suitable stability on central metal palladium(Ⅱ) besides acting as diluent.End groups analysis showed that the copolymerization was initiated by insertion of ethylene into Pd H bond in non alcohol solvents,was mainly initiated by insertion of CO into Pd OR bond in alcohol solvents.
出处
《高分子学报》
SCIE
CAS
CSCD
北大核心
1998年第3期299-303,共5页
Acta Polymerica Sinica
关键词
一氧化碳
乙烯
聚酮
催化剂
溶剂效应
钯催化剂
Carbon monoxide,Ethylene,Polyketone,Palladium(Ⅱ) catalyst,Solvent effect
