聚二烯丙基乙基苄基氯化铵的合成及溶液性质

Synthesis and Solution Properties of Poly(diallylethylbenzylammonium chloride)

在少量水存在下,将二烯丙基乙基胺（DAEA）与氯化苄直接反应合成单体二烯丙基乙基苄基氯化铵（DAEABC）。以2,2′-偶氮（2-甲基丙基脒）二盐酸盐为引发剂,采用水溶液聚合,合成了聚二烯丙基乙基苄基氯化铵（PDAEABC）。采用FT-IR、1H-NMR和元素分析对PDAEABC的结构进行表征,并考察了其在氯化钠、氯化钾、溴化钾、碘化钾、硫酸镁和硫酸钠溶液中的黏度行为。结果表明,当V（H2O）∶V（DAEA）为0.01~0.02时,能获得高纯的DAEABC晶体,收率达94%以上。PDAEABC的比浓黏度随外加盐浓度的增加而降低。在0.1 mol/L的NaCl溶液中,当PDAEABC的质量浓度低于0.005 g/dL时,表现为聚电解质行为;当PDAEABC的质量浓度大于0.025 g/dL时,表现为中性聚合物的黏度行为。外加盐对比浓黏度的影响顺序为Na2SO4〈NaCl〈KCl〈MgSO4〈KBr〈KI。阴离子的屏蔽作用是引起比浓黏度降低的主要因素。

The monomer diallylethylbenzylammonium chloride（DAEABC） was synthesized from diallylethylamine（DAEA） and benzyl chloride in the presence of tiny amount of water,and then used in the synthesis of poly（diallylethylbenzylammonium chloride）（PDAEABC） initiated with 2,2′-azobis（2-methylpropionamide） dihydrochloride in aqueous solution.The structures of PDAEABC were characterized by FT-IR,1H-NMR and elementary analysis.Its viscosity behaviors in sodium chloride,potassium chloride,potassium bromide,potassium iodide,magnesium sulfate and sodium sulfate solution were investigated as well.Results show that when V（H2O）∶V（DAEA） is from 0.01 to 0.02,crystalline DAEABC with high purity is obtained in over 94% yield.The reduced viscosity of PDAEABC decreases with the increasing of the concentration of salt.In 0.1 mol/L NaCl solution,it behaves as a polyelectrolyte at below 0.005 g/dL and a neutral polymer at above 0.025 g/dL.The influence order of salts is： Na2SO4NaClKClMgSO4KBrKI.The shielding effect of anion to quaternary ammonium cation is the main reason of the decreasing of reduced viscosity.