含氧高分子金属络合物的合成及其催化性能研究-应用化学专业论文.docx

￥56530 ￥56530 7 含氧高分子金属络合物的合成及其催化性能研究 提要 本文研究了含氧的聚合物配体聚乙烯醇(PVA)以及聚丙烯酸一(4一醛基一3一羟 基)苯基醮d(P4A3HBA)与氯化铜所形成金属络合物的催化性能。考察了四种聚乙烯醇 一铜(II)络合物的催化性能差异，对比发现水解度高的聚乙烯醇一铜(II)络合物催化得 到的PMMA分子量较低、转化率较高，而聚合度不同的P、，A—cu(II)络合物的催 化性能无差别；同时还研究了PVA--Cu(II)催化甲基丙烯酸甲酯(MMA)和苯乙烯 fStl的共聚合反应，测得两种单体在35C的竟聚率分别为ru=5．23，rs=0．07，甲基丙 稀酸甲酯的活性远大于苯乙烯的活性，并考察了温度对竞聚率的影响。另外研究了 P4A3HBA--Cu(II)金属络合物催化MMA的聚合反应，发现其在与PVA—Cu(II) 络合物同等条件下的转化率高于PVA--Cu(II)络合物的转化率，30C下48hr的转 化率达到71％；所得PMMA的最高分子量为70万。 关键词：高分子金属络合物，聚乙烯醇，聚丙烯酸一(4一醛基一3一羟基)苯基酯，催 化，铜配位 作者：肖猛 指导教师：路建美 含氧高分子金属络合物的合成及其催化性能研究 含氧高分子金属络合物的合成及其催化性能研究 摘要 Summary In this dissertation，a P4A3HBA--Cu(10 and fbur types ofPV|A—Cu(Ir)complexes were obtained by the reaction of hydrated copper chloride with the corresponding polymer ligands in the presence of a few drops of ammonia．The all complexes were characterized by IR,TG XPS and‘H-NMR，and the copper contents in those complexes were determined by atomic absorption spectrophotometry．The all polychelates Call initiate the homopolymerization ofMMA and copolymerization ofmethyl methylacrylate(MMA)and styrene rst)in the water solution of sodium sulfite．We discover that tlle hydrolysis degree of PVA have specific impacts on their catalytic capabilities of their corresponding copper coordination．but the degree of polymerization have no affect on tlleir catalytic performances．The obtained monomer reactivity ratios values of MMA and St at 308K (rs=0．07，rM=5．23)are different from those determined by conventional free radical copolymefisations at the salne conditions，the influences of reaction temperature on the monomer reactivity ratios are also examined．In addition。me changes in molecular weight， conversion and tacticity based on PMMA catalyzed by the five systems of P—Cu(Ⅱ)／ Na2S03 Were inspected too． Keywords：Macromolecule—Metal Complexes，Poly(vinyl alcoh01)，Catalysis， Ppoly(4．aldehyde-3-hydroxy)phenyl acrylate，Cupric coordination Written by mengXiao S