阳离子型可聚合乳化剂的合成及应用研究
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摘要
可聚合乳化剂本身既可在乳液聚合中起乳化剂的作用,又能参与聚合反应过程,其与聚合反应单体以共价键结合,使其成为聚合物分子的一部分,因而可聚合乳化剂可以大大提高聚合物乳液的稳定性,改善膜的力学性能、光泽性、粘接性、耐水性等。阳离子表面活性剂在抗静电剂和杀菌剂等领域广泛应用,其乳化、分散性能虽不如阴离子表面活性剂,在乳液聚合中单独使用效果不理想,但通过引入非离子表面活性剂有望提高其使用性能。
本文首先合成了一系列的既含有季铵盐阳离子基团,又含有聚氧乙烯非离子基团的可聚合乳化剂。由脂肪醇聚氧乙烯醚与马来酸酐进行单酯化反应,然后引入阳离子中间体,反应生成系列的马来酸脂肪醇聚氧乙烯醚双酯型乳化剂(E系列),通过质谱对产品进行表征,用两相滴定法确定了阳离子活性物含量。将所合成的阳离子型可聚合乳化剂,应用于醋酸乙烯酯—丙烯酸丁酯—叔碳酸乙烯酯—甲基丙烯酸六氟丁酯的半连续式乳液共聚合当中,聚合物乳液的多分散性系数(PDI)均小于0.1。相对于传统阳离子乳化剂十六烷基三甲基溴化铵(CTAB),可聚合乳化剂得到的聚合物乳液耐电解质稳定性得到了提高,乳液成膜后的耐水性也得到了很大的提高,且冻融稳定性能表现优越。
本文又以马来酸酐为母体,采用PCl_3酰化,生成反式的富马酸类结构,通过引入叔胺和进行季铵化,得到了一类新型的富马酸类阳离子可聚合乳化剂(F系列)。通过核磁和质谱进行表征,合成化合物结构正确。将所合成的F系列阳离子型可聚合乳化剂,应用于醋酸乙烯酯—丙烯酸丁酯—叔碳酸乙烯酯—甲基丙烯酸六氟丁酯的半连续式乳液共聚合中,聚合物乳液的多分散性系数(PDI)均小于0.1,键合率100%。所制得的乳液,在冻融稳定性和贮存稳定性方面有所提高,在成膜耐水性方面,可聚合乳化剂F2、F3、F4、F5、F6制得的乳胶膜分别浸入水中28天后,吸水率为47.06%、44.24%、16.48%、26.50%、33.12%,CTAB的吸水率是104.50%,是可聚合乳化剂的F2的2.22倍、F3的2.38倍、F4的6.34倍、F5的3.94倍、F6的3.16倍,可聚合乳化剂很好地提高了乳液成膜后的耐水性。F系列的可聚合乳化剂对大肠杆菌的最低抑菌浓度以及乳液成膜后的抗菌性测试,体现该系列乳化剂的良好杀菌性,有望开发出新型的抗菌涂料。
Polymerizable surfactants not only play as an emulsifier in emulsion polymerization,but also take part in polymerization.They adsorb in chemical action to the surface of latex particles and to be one part of the polymer.Therefore polymerizable surfactants can improve the stability of the lattices versus electrolyte and freeze/thaw,as well as the water sensitivity of the film formed.Cationic surfactants have been a widely applications in antistatic agents, bactericide and other special areas,but their performance of emulsification and dispersion are worse than anionic surfactants,while non-ionic groups being introduced in emulsion polymerization may improve their performance.
A series of polymerization surfactants(surfmers)were synthesized,whose structures combined the characteristics of polyoxyethylene as nonionic group and quaternary ammonium as cationic group.The structures of the product were confirmed by MS,and the content of cationic-activity matter was determined by two-phase titration.The surfmers were then used with constant addition profiles in semicontinuous polymerization of vinyl acetate-butyl acrylate-Veova 10-hexafluorobutyl methacrylate.And the polydispersity indexes (PDI)were lower than 0.1.The particle size,amount of coagulum,and stability against electrolyte and freeze/thaw were evaluated.As a reference,an unreactive surfactant cetyl trimethyl ammonium bromide(CTAB)was also used for the polymerization.Compared to CTAB,the surfmers behaved much better.Not only stabilities to electrolyte and water resistance were improved,but also freeze/thaw stability got a superior performance.
A series of surfrners(F)were also synthesized.[2-(N,N-diethylamino)ethyl]long-chain ethyl fumarate quaternary ammonium salt,cationic fumaric surfmers,were prepared with maleic anhydride,then reacting with PCl_3.The chemical structures of the surfmers were confirmed by MS and ~1H NMR.The surfmers were then used with constant addition profiles in semicontinuous polymerization of vinyl acetate-butyl acrylate-Veovea 10-hexafluorobutyl methacrylate.Polydispersity indexes(PDI)of latexes were all lower than the limit(0.1)of monodispersity.The results of bonding rate for series polymerizable surfactants were all 100%.Compared to CTAB,the surfmers behaved better in either the stability to electrolytes or storage stability of the lattices.When the films,which were prepared from the CTAB and surfmers,were immersed into water after 28 days,water absorption of the film made with CTAB(104.50%)was 2.22 times higher than that with F2(47.06%),2.38 times than F3(44.24%),6.34 times than F4(16.48%),3.94 times than F5(26.50%)and 3.16 times higher than that with F6(33.12%).So,polymerizable surfactant can greatly improve the water resistance of films.The Minimal Inhibitory Concentration(MIC)of escherichia coli and the antibacterial activities of the films were tested.The results manifested F series emulsifiers were good bactericide.So,it will be helpful to develop new antibacterial coating.
本文首先合成了一系列的既含有季铵盐阳离子基团,又含有聚氧乙烯非离子基团的可聚合乳化剂。由脂肪醇聚氧乙烯醚与马来酸酐进行单酯化反应,然后引入阳离子中间体,反应生成系列的马来酸脂肪醇聚氧乙烯醚双酯型乳化剂(E系列),通过质谱对产品进行表征,用两相滴定法确定了阳离子活性物含量。将所合成的阳离子型可聚合乳化剂,应用于醋酸乙烯酯—丙烯酸丁酯—叔碳酸乙烯酯—甲基丙烯酸六氟丁酯的半连续式乳液共聚合当中,聚合物乳液的多分散性系数(PDI)均小于0.1。相对于传统阳离子乳化剂十六烷基三甲基溴化铵(CTAB),可聚合乳化剂得到的聚合物乳液耐电解质稳定性得到了提高,乳液成膜后的耐水性也得到了很大的提高,且冻融稳定性能表现优越。
本文又以马来酸酐为母体,采用PCl_3酰化,生成反式的富马酸类结构,通过引入叔胺和进行季铵化,得到了一类新型的富马酸类阳离子可聚合乳化剂(F系列)。通过核磁和质谱进行表征,合成化合物结构正确。将所合成的F系列阳离子型可聚合乳化剂,应用于醋酸乙烯酯—丙烯酸丁酯—叔碳酸乙烯酯—甲基丙烯酸六氟丁酯的半连续式乳液共聚合中,聚合物乳液的多分散性系数(PDI)均小于0.1,键合率100%。所制得的乳液,在冻融稳定性和贮存稳定性方面有所提高,在成膜耐水性方面,可聚合乳化剂F2、F3、F4、F5、F6制得的乳胶膜分别浸入水中28天后,吸水率为47.06%、44.24%、16.48%、26.50%、33.12%,CTAB的吸水率是104.50%,是可聚合乳化剂的F2的2.22倍、F3的2.38倍、F4的6.34倍、F5的3.94倍、F6的3.16倍,可聚合乳化剂很好地提高了乳液成膜后的耐水性。F系列的可聚合乳化剂对大肠杆菌的最低抑菌浓度以及乳液成膜后的抗菌性测试,体现该系列乳化剂的良好杀菌性,有望开发出新型的抗菌涂料。
Polymerizable surfactants not only play as an emulsifier in emulsion polymerization,but also take part in polymerization.They adsorb in chemical action to the surface of latex particles and to be one part of the polymer.Therefore polymerizable surfactants can improve the stability of the lattices versus electrolyte and freeze/thaw,as well as the water sensitivity of the film formed.Cationic surfactants have been a widely applications in antistatic agents, bactericide and other special areas,but their performance of emulsification and dispersion are worse than anionic surfactants,while non-ionic groups being introduced in emulsion polymerization may improve their performance.
A series of polymerization surfactants(surfmers)were synthesized,whose structures combined the characteristics of polyoxyethylene as nonionic group and quaternary ammonium as cationic group.The structures of the product were confirmed by MS,and the content of cationic-activity matter was determined by two-phase titration.The surfmers were then used with constant addition profiles in semicontinuous polymerization of vinyl acetate-butyl acrylate-Veova 10-hexafluorobutyl methacrylate.And the polydispersity indexes (PDI)were lower than 0.1.The particle size,amount of coagulum,and stability against electrolyte and freeze/thaw were evaluated.As a reference,an unreactive surfactant cetyl trimethyl ammonium bromide(CTAB)was also used for the polymerization.Compared to CTAB,the surfmers behaved much better.Not only stabilities to electrolyte and water resistance were improved,but also freeze/thaw stability got a superior performance.
A series of surfrners(F)were also synthesized.[2-(N,N-diethylamino)ethyl]long-chain ethyl fumarate quaternary ammonium salt,cationic fumaric surfmers,were prepared with maleic anhydride,then reacting with PCl_3.The chemical structures of the surfmers were confirmed by MS and ~1H NMR.The surfmers were then used with constant addition profiles in semicontinuous polymerization of vinyl acetate-butyl acrylate-Veovea 10-hexafluorobutyl methacrylate.Polydispersity indexes(PDI)of latexes were all lower than the limit(0.1)of monodispersity.The results of bonding rate for series polymerizable surfactants were all 100%.Compared to CTAB,the surfmers behaved better in either the stability to electrolytes or storage stability of the lattices.When the films,which were prepared from the CTAB and surfmers,were immersed into water after 28 days,water absorption of the film made with CTAB(104.50%)was 2.22 times higher than that with F2(47.06%),2.38 times than F3(44.24%),6.34 times than F4(16.48%),3.94 times than F5(26.50%)and 3.16 times higher than that with F6(33.12%).So,polymerizable surfactant can greatly improve the water resistance of films.The Minimal Inhibitory Concentration(MIC)of escherichia coli and the antibacterial activities of the films were tested.The results manifested F series emulsifiers were good bactericide.So,it will be helpful to develop new antibacterial coating.
引文
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