聚甲基丙基二烯丙基氯化铵的合成及表征

Synthesis and Characterization of Poly(N,N-diallyl-N-methylpropylammonium Chloride)

摘要:

以甲基丙基二烯丙基氯化铵(MPDAAC)为单体、2,2'-偶氮二异丁基脒二盐酸盐(V50)为引发剂，通过水溶液聚合法制备了聚甲基丙基二烯丙基氯化铵(PMPDAAC)。在单因素实验基础上，以产物特征黏度值为考察指标，采用响应分析法中的Box-Behnken模型对PMPDAAC的制备工艺进行了优化。得到最优条件为： T1=56.13℃、T2=61.24℃、T3=80.22℃、w(MPDAAC)=71.03%、w(V50) =2.50%和w(Na4EDTA) =0.0074%，得到PMPDAAC的特征黏度值平均为1.17dL/g，单体转化率为92.05%。采用FTIR、NMR和GPC-MALLS对其产物进行了结构表征及相对分子量测定，测得Mw最高为2.658×105，多分散指数d(Mw/Mn)为1.358。研究表明，取代基丙基引入所带来的空间位阻和可能的溶剂效应是影响二烯丙基季铵盐聚合反应活性的主要因素。

Abstract:

Poly(N,N-diallyl-N-methylpropylammonium chloride)(PMPDAAC) was prepared by N,N-diallyl-N-methylpropylammonium chloride (MPDAAC) as monomer and 2’2-azobis(2-methylpropionamidine) dihydrochloride (V50) as initiator in aqueous solution. On the basis of single factor experiments, the Box-Behnken mathematical relational model between the intrinsic viscosity values of PMPDAAC and their affecting factors was established, and the preparation conditions of PMPDAAC were optimized. The optimum preparation conditions were: T1=56.13℃, T2=61.24℃, T3=80.22℃, w(MPDAAC)= 71.03%, w(V50)= 2.50% and w(Na4EDTA)= 0.0074%, the average value of intrinsic viscosity of PMPDAAC and conversion rate of monomer under optimal conditions reached 1.17dL/g and 92.05%, respectively. The structure of the product was characterized by FTIR and NMR, and its Mw and polydespersity d(Mw/Mn) was measured by GPC-MALLS. The results showed that the maximum Mw of the product PMPDAAC was 2.658×105, polydespersity d(Mw/Mn) was 1.358. The research showed that the space effect and possible solvent effect brought about by the substituent propyl group were the main factors affecting the polymerization activity of diallyl quaternary ammonium salt.