高化学开环聚合.ppt

,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,高化学开环聚合,开环聚合的单体：,环醚、环酯、环酰胺、环硅氧烷、环硫化物等。,Kinetically,Themodynamically,Free Energy for Ring-Opening Polymerization,For cycloalkanes,but trends is the same for heteroatomic ring,3,，,45,，,7,1112,以上，,6,Ring Stability,C16H33O(EO)nH,CH3O-Na+EO CH3OEO-Na+,Kinetically stable!,Representative monomers,Polymerization mechanism,阴离子聚合 主要用于模内浇铸（MC）技术，即以碱金属引发己内酰胺成预聚体，浇铸入模内，继续聚合成整体铸件，制备大型机械零部件，成为工程塑料。,Themodynamically,Ring Stability,Cationic polymerization,Polymerization mechanism,以乙二醇为起始剂，环氧乙烷开环聚合物为聚乙二醇或聚醚二醇H(OCH2CH2)nOH，分子量不等（2005000），主要用作聚氨酯的预聚体,Ring Stability,H=29 kJ/mol,交换反应(引入长链R),Ring Stability,(stability,C=OC=C),CH3O-Na+EO CH3OEO-Na+,Representative monomers,It is difficult to find some reaction pathway to open cycloalkane!,(Kinetically unfavorable,nonpolar),Polymerization mechanism,Anionic polymerization,Cationic polymerization,8.1,聚醚与非离子表面活性剂的制备,CH3O-Na+EO CH3OEO-Na+,以乙二醇为起始剂，环氧乙烷开环聚合物为聚乙二醇或聚醚二醇,H(OCH2CH2)nOH,，分子量不等（,2005000,），主要用作聚氨酯的预聚体,阴离子开环聚合,非离子型表面活性剂的制备,交换反应,(,引入长链,R),Kinetically,环醚、环酯、环酰胺、环硅氧烷、环硫化物等。,RO(PO)m(EO)nH,非离子型表面活性剂的制备,HO(EO)a(PO)b(EO)aH,C9H19-C6H4O(EO)nH,Representative monomers,以乙二醇为起始剂，环氧乙烷开环聚合物为聚乙二醇或聚醚二醇H(OCH2CH2)nOH，分子量不等（2005000），主要用作聚氨酯的预聚体,H=29 kJ/mol,Ring Stability,Polymerization mechanism,表8-4 聚醚型非离子表面活性剂,以乙二醇为起始剂，环氧乙烷开环聚合物为聚乙二醇或聚醚二醇H(OCH2CH2)nOH，分子量不等（2005000），主要用作聚氨酯的预聚体,Kinetically stable!,Kinetically stable!,表,8-4,聚醚型非离子表面活性剂,起始剂,环氧乙烷加成物,N,wt%EO,HLB,烷基酚,R-C,6,H,4,OH(C=89),C,9,H,19,-C,6,H,4,O(EO),n,H,1.540,2090,4.617.8,脂肪醇,ROH(C=1218),C,16,H,33,O(EO),n,H,250,1590,脂肪醇,ROH(C=818),RO(PO),m,(,EO),n,H,m8,2595,脂肪酸,RCOOH(C=1117),RCOO(EO),n,H,丙二醇,HOC,3,H,6,OH,HO(EO),a,(PO),b,(EO),a,H,b=1556,1080,环氧丙烷阴离子开环聚合,8.2,环醚的阳离子开环,胺纶,羰基化合物,(carbonyl compound),的聚合,Reactivity Considerations,Anionic polymerization,Cationic polymerization,Thermodynamic considerations,(stability,C=OC=C),H=29 kJ/mol,聚甲醛的制备,Stablization,Kinetically stable!,己内酰胺开环聚合,阴离子聚合 主要用于模内浇铸（,MC,）技术，即以碱金属引发己内酰胺成预聚体，浇铸入模内，继续聚合成整体铸件，制备大型机械零部件，成为工程塑料。,聚硅氧烷的制备,聚酯,Polyesters,合成多肽,Polypeptide,Polyphosphazenes,聚磷氮烯,