二乙基二烯丙基氯化铵均聚及其与丙烯酰胺或丙烯酸共聚动力学研究

采用膨胀计法研究了以过硫酸铵为引发剂,二乙基二烯丙基氯化铵(DEDAAC)在水溶液中的均聚及其与丙烯酰胺(AM)和丙烯酸(AA)共聚动力学,测定了相应的聚合表观活化能;采用元素分析法测定了DEDAAC分别与AM和AA在低转化率下共聚物的组成,并采用氯离子选择性电极法测定了DEDAAC-AM共聚物中的氯离子含量,按Kelen-Tudos方法求得了相应的竞聚率.结果表明,DEDAAC均聚速率方程为RP=kM]0.99I]0.76,表观活化能Ea=77.00kJ/mol,说明链终止为单基终止和双基终止并存,引发过程与单体浓度无关;DEDAAC与AM在摩尔比为4∶1时,共聚动力学方程为RP=M]2.53I]0.90,表观活化能Ea=67.06kJ/mol,单体竞聚率为rDE=0.31±0.02、rAM=5.27±0.53;DEDAAC与AA在摩尔比为4∶1时,共聚动力学方程为RP=kM]2.94I]0.83,表观活化能Ea=70.07kJ/mol,竞聚率为rDE=0.28±0.03、rAA=5.15±0.28;DEDAAC与AM和AA等共聚为非理想共聚,得到的产物均为无规共聚物.

KINETICS STUDIES ON POLYMERIZATION OF DIETHYLDIALLYLAMMONIUM CHLORIDE AND ITS COPOLYMERIZATION WITH ACRYLAMIDE AND ACRYLIC ACID

The kinetics of diethyldiallylammonium chloride(DEDAAC)polymerization and its copolymerization with acrylamide(AM)and acrylic acid(AA)initiated by ammonium persulfate(APS)in aqueous solution was studied by dilatometer method,and the apparent activation energy was measured.In the meantime,the compositions of copolymers of DEDAAC with AM or AA at low conversion were determined by elemental analysis,and the content of chloride ions of the DEDAAC-AM copolymer was determined by chloride ion-selective electrode method,and the reactivity ratios of monomers in copolymerization were obtained by Kelen-Tudos method.The results show that the polymerization rate equation for DEDAAC is R_P=kM] 0.99I] 0.76 and the apparent activation energy is 77.00 kJ/mol,which displays that the chain termination reaction is according to the modes of mono-and bi-molecule termination,and the initiating process is independent of monomer concentration.When the monomer feed ratio n(DEDAAC)∶n(AM)is 4∶1,the copolymerization rate equation for DEDAAC with AM is R_P=kM] 2.53I] 0.90,the apparent activation energy is 67.06 kJ/mol,and the values of reactivity ratios r_ DE and r_ AM are 0.31±0.02 and 5.27±0.53,respectively.While the copolymerization rate equation for DEDAAC with AA is R_P=kM] 2.94I] 0.83 at the monomer feed ratio n(DEDAAC)∶n(AA)= 4∶1,the apparent activation energy is 70.07 kJ/mol,and the values of reactivity ratios r_ DE and r_ AA are 0.28±0.03 and 5.15±0.28,respectively.The copolymerization for DEDAAC with AM or AA is a non-ideal copolymerization,and the products are random copolymers.