采用膨胀计法研究了以过硫酸铵-亚硫酸氢钠为引发剂的二甲基二烯丙基氯化铵(DMDAAC)和丙烯酰胺(AM)的水溶液共聚合动力学,测定了相应的聚合速率方程、聚合表观活化能和单体竞聚率。结果表明,聚合反应温度为45℃,当DMDAAC与AM物质的量比分别为1∶9,2∶8和3∶7时,共聚速率方程分别为Rp1=k[M]^2.61[IO]^0.51[IR]^0.52,Rp2=k[M]^2.70[IO]^0.50[IR]^0.53和Rp3=k[M]^2.73[IO]^0.50[IR]^0.56,表观活化能分别为Ea1=79.10 kJ/mol,Ea2=81.39 kJ/mol和Ea3=85.15 kJ/mol,两单体的竞聚率分别为rDMDAAC=0.14,rAM=6.11。上述实验结果可从动力学角度为不同阳离子度PDA聚合速率差别及产物特征黏度值差异进行解释。
The polymerization kinetics of dimethyldiallylammonium chloride (DMDAAC) and acrylamide (AM) initiated by ammonium persulfate-sodium bisulfate redox complex in aqueous mlution were studied, the polymerization rate equation was obtained, the apparent activation energy and reactivity ratio were measured. The results show that when the polymerization temperature is 45 ℃, n (DMDAAC) : n (AM) is 1:9, 2:8 and 3 : 7, the copolymerization rate equation is Rp1=k[M]^2.61[IO]^0.51[IR]^0.52,Rp2=k[M]^2.70[IO]^0.50[IR]^0.56, the apparent activation energy is Eal = 79.10 kJ/mol, Ea2 = 81.39 kJ/mol and Ea3 =85.15 kJ/mol, respectively. The reactivity ratio of DMDAAC and AM is rDMDAAC = 0.14, raM = 6.11. The kinetics results can explain the difference of copolymerization rate and product results of PDA with different cationicities.
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