聚甲基丙基二烯丙基氯化铵的合成及表征
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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:三步升温温度分别为56.1、61.2、80.2℃,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1.17 dL/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2.658×10~5,多分散指数d(M_w/M_n)=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。
Poly(N,N-diallyl-N-methylpropylammonium chloride)(PMPDAAC) was prepared using N,Ndiallyl-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 as follows: the three-steps heating process temperature was 56.1 ℃,61.2 ℃, 80.2 ℃, respectivity,w(MPDAAC)=71.03%, w(V50)=2.50% and w(Na4 EDTA)=0.0074%. The average value of intrinsic viscosity of PMPDAAC and the conversion of monomer under optimal conditions reached 1.17 dL/g and 92.05%, respectively. The structure of the product was characterized by FTIR and NMR, and its Mw and polydispersity index, d(M_w/M_n), was measured by GPC-MALLS. The results showed that the maximum Mw of PMPDAAC was 2.658×10~5, and the polydispersity index was 1.358. The research indicated that steric hindrance and possible solvent effect caused by substituent propyl group were the main factors affecting the polymerization activity of diallyl quaternary ammonium salt.
Poly(N,N-diallyl-N-methylpropylammonium chloride)(PMPDAAC) was prepared using N,Ndiallyl-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 as follows: the three-steps heating process temperature was 56.1 ℃,61.2 ℃, 80.2 ℃, respectivity,w(MPDAAC)=71.03%, w(V50)=2.50% and w(Na4 EDTA)=0.0074%. The average value of intrinsic viscosity of PMPDAAC and the conversion of monomer under optimal conditions reached 1.17 dL/g and 92.05%, respectively. The structure of the product was characterized by FTIR and NMR, and its Mw and polydispersity index, d(M_w/M_n), was measured by GPC-MALLS. The results showed that the maximum Mw of PMPDAAC was 2.658×10~5, and the polydispersity index was 1.358. The research indicated that steric hindrance and possible solvent effect caused by substituent propyl group were the main factors affecting the polymerization activity of diallyl quaternary ammonium salt.
引文
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[24]Tao Xianping(陶贤平),Zhang Yuejun(张跃军).Synthesis and characterization of diallylmethylalkyl quaternary ammonium salts[J].Fine Chemicals(精细化工),2014,31(7):931-936.
[25]Wang Xiyun(王喜云),Wang Yuanliang(王远亮),Wu Yanglan(吴扬兰),et al.Use of gel permeation chromatography/eighteen-angle laser scattering(GPC/MALLS)[J].The Journal of Light Scattering(光散射学报),2007,19(1):49-54.
[26]Tuezuen N S,Aviyente V,Avei D,et al.A computational approach to the polymerizabilities of diallylamines[J].Journal of Molecular Modeling,2001,7(7):257-264.
[2]Du L,Kong F P,Chen G Y,et al.A review of applications of poly(diallyldimethyl ammonium chloride)in polymer membrane fuel cells:From nanoparticles to support materials[J].Chinese Journal of Catalysis,2016,37(7):1025-1036.
[3]Zhang Z J,Zhang Q L,Chen Y Z,et al.Poly(dimethyldiallylammonium chloride)(polyDADMAC)assisted cellulase pretreatment for microfibrillated cellulose(MFC)preparation and MFC analysis[J].Holzforschung,2018,72(7):531-538.
[4]Zhou J H,Wu C H,Cheng G F,et al.Impact of poly dimethyldiallylammonium chloride on membrane fouling mitigation in a membrane bioreactor[J].Environmental Technology,2018,1:1-7.
[5]Liao Y,Zheng X Y,Zhang Z Q,et al.Ultrasound-assisted polymerization of P(AM-DMDAAC):Synthesis,characterization and sludge dewatering performance[J].Journal of Environmental Chemical Engineering,2017,5(6):5439-5447.
[6]Zhu Tao(朱涛).Research progresses of synthetic processes for cationic monomers with quaternary ammonium groups[J].Chemical Research and Application(化学研究与应用),2014,26(10):1527-1533.
[7]Tao Xianping(陶贤平),Zhang Yuejun(张跃军),Zhu Beibei(朱蓓蓓).Synthsis and properties for cationic monomers of allyldimethylalkyl quaternary ammonium salt[J].Speciality Petrochemicals(精细石油化工),2016,33(2):27-31.
[8]Timofeeva L M,Kleshcheva N A,Shleeva M O,et al.Nonquaternary poly(diallylammonium)polymers with different amine structure and their biocidal effect on Mycobacterium tuberculosis and Mycobacterium smegmatis[J].Applied Microbiology and Biotechnology,2015,99(6):2557-2571.
[9]Liu Cheng(刘程),Zhang Yuejun(张跃军).Research progress in the synthesis of cationic polymers containing dimethyldiallylammonium chloride[J].Fine Chemicals(精细化工),2011,28(5):417-423.
[10]Timofeeva L M,Balakaeva I V,Lileev A S,et al.General trends in concentration and temperature behavior of equivalent conductance of N,N-diallylammonium polymers aqueous solutions:Effect of counterion nature and amine structure[J].Polymer Science Series C,2017,59(1):141-148.
[11]Gao D G,Ma J Z,Guo H Q.Swelling properties of pH-responsive hydrophobically modified hydrogels of poly(methacrylic acid-codiallylammonium salt)in aqueous solution[J].Polymers for Advanced Technologies,2012,23(11):1494-1499.
[12]Mahdavi H,Mahdi M.Synthesis and applications of cross-linked poly(diallyldimethyl ammonium chloride)and its derivative copolymers as efficient phase transfer catalyst for nucleophilic substitution reactions[J].Chinese Journal of Polymer Science,2011,29(2):165-172.
[13]Liu Lihua(刘立华),Xiao Tile(肖体乐),Chen Jinwen(陈金文),et al.Synthesis and sterilizing property of poly(N,N-diallyl-N-carbobutoxymethylammonium chloride)[J].Chinese Journal of Apply Chemistry(应用化学),2010,27(8):887-892.
[14]Liu Lihua(刘立华),Li Xin(李鑫),Cao Jing(曹菁),et al.Synthesis and viscosity behavior of poly(diallylmethylbenzylammonium chloride)[J].Chinese Journal of Apply Chemistry(应用化学),2011,28(7):777-784.
[15]Olsson J S,Pham T H,Jannasch P.Poly(N,N-diallylazacycloalkane)s for anion-exchange membranes func-tionalized with n-spirocyclic quaternary ammonium cations[J].Macromolecules,2017,50(7):2784-2793.
[16]Losada R,Wandrey C.Copolymerization of a cationic doublecharged monomer and electrochemical properties of the copolymers[J].Macromolecules,2009,42(9):3285-3293.
[17]Azab M M.Study of the copolymerization parameters of 2-thiozyl methacrylamide with different alkyl acrylates[J].Journal of Polymer Research,2005,12(1):9-15.
[18]Pan Zuren(潘祖仁).Polymer Chemistry[M].Beijing:Chemical Industry Press(北京:化学工业出版社),2011:85-92
[19]Jia X,Zhang Y J.Preparation and characterization of poly(dimethyldiallylammonium chloride)with high molar mass using high purity industrial monomer[J].Journal of Applied Polymer Science,2010,118(2):1152-1159.
[20]Jiang Shaojie(蒋绍阶),Feng Xinrui(冯欣蕊),Li Xiaoen(李晓恩),et al.Preparation of PAC-PDMDAAC hybrid flocculant by response surface method and its characterization[J].Journal of Chemical Industry and Engineering(化工学报),2014,65(2):731-736.
[21]Hao Haiyan(郝海艳),Wang Gang(王刚),Xu Min(徐敏),et al.Optimization of preparation conditions of chelating flocculant with mercaptoacetyl polyacrylamide by response surface methodology[J].Environmental Chemistry(环境化学),2016,35(6):1269-1279.
[22]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).Water treatment chemicals-poly(diallydimethylammonium chloride):GB/T 33085-2016[S].Beijing:Standards Press of China(北京:中国标准出版社),2016:4-7.
[23]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).Plastics-polyacrylamide-determination for residual acrylamide:GB/T 22312-2008[S].Beijing:Standards Press of China(北京:中国标准出版社),2008:3-4.
[24]Tao Xianping(陶贤平),Zhang Yuejun(张跃军).Synthesis and characterization of diallylmethylalkyl quaternary ammonium salts[J].Fine Chemicals(精细化工),2014,31(7):931-936.
[25]Wang Xiyun(王喜云),Wang Yuanliang(王远亮),Wu Yanglan(吴扬兰),et al.Use of gel permeation chromatography/eighteen-angle laser scattering(GPC/MALLS)[J].The Journal of Light Scattering(光散射学报),2007,19(1):49-54.
[26]Tuezuen N S,Aviyente V,Avei D,et al.A computational approach to the polymerizabilities of diallylamines[J].Journal of Molecular Modeling,2001,7(7):257-264.
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