季铵盐有机硅双子表面活性剂的物化及抗菌性能
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摘要
以聚乙二醇二缩水甘油醚和不同黏度羟基封端聚二甲基硅氧烷为主要原料,在四丁基溴化铵(TBAB)和Na OH的催化下,合成出不同硅氧链长的环氧基聚醚改性硅氧烷EP-PSix-EP(x=40、80、315,下同),EP-PSix-EP再与N,N-二甲基十二烷基叔胺在盐酸催化下进行季铵化反应,制备得到连接基长度不同的季铵盐有机硅双子表面活性剂C12-PSix-C12(x=40、80、315,下同)。采用FTIR、1HNMR对产物结构进行了表征。考察了C12-PSix-C12中连接基长度对其表面张力、润湿性能、乳化稳定性等物化性能及抗菌性能的影响。结果表明,随着C12-PSix-C12中连接基长度的减小,C12-PSix-C12的表面活性、润湿性能及抗菌能力逐渐增强。它们的γCMC依次为29.74、31.17、44.95 m N/m;在玻璃表面的最大接触角依次为48.3?、59.9?、65.6?;对金黄色葡萄球菌的抑菌圈宽度分别为38.5、34.5、27.5 mm。并且C12-PSi40-C12对液体石蜡、煤油、油酸的乳化稳定性能最好,乳化稳定时间分别为260.5、732.3、1537.0 s。
A series of epoxy-modified polyether ploysiloxanes(EP-PSix-EP, x=40,80,315) were synthesized from ployethyleneglycol diglycidyl ether and polydimethylsiloxane by using tetrabutylammonium bromide(TBAB) and Na OH as catalyst. Then, corresponding quaternary ammonium organic silicon gemini surfactants, C12-PSix-C12(x=40,80,315,as the below), were synthesized by quaternarization of EP-PSix-EP with N,N-dimethyldodecylamine in the presence of a catalytic amount of hydrochloric acid. The samples were characterized by FTIR and 1 HNMR. The effect of spacer length on the characteristics of quaternary ammonium organic Gemini surfactant was investigated. The results showed that the surface activity, wetting property and antimicrobial ability of surfactant gradually enhanced with the decrease of the length of spacer group in C12-PSix-C12. The surface tension values of above three surfactants at CMC(γCMC) were 29.74, 31.17 and 44.95 m N/m, respectively. The maximal contact angle values on the glass were 48.3?, 59.9? and 65.6?. The diameter of inhibition zone of C12-PSix-C12(x =40,80,315) to Staphylococcus aureus was 38.5, 34.5 and 27.5 mm, respectively. Furthermore, C12-PSi40-C12 exhibited the best emulsion stability to liquid paraffin, kerosene and oleic acid, with corresponding emulsifying stability time of 260.5, 732.3 and 1537.0 s.
A series of epoxy-modified polyether ploysiloxanes(EP-PSix-EP, x=40,80,315) were synthesized from ployethyleneglycol diglycidyl ether and polydimethylsiloxane by using tetrabutylammonium bromide(TBAB) and Na OH as catalyst. Then, corresponding quaternary ammonium organic silicon gemini surfactants, C12-PSix-C12(x=40,80,315,as the below), were synthesized by quaternarization of EP-PSix-EP with N,N-dimethyldodecylamine in the presence of a catalytic amount of hydrochloric acid. The samples were characterized by FTIR and 1 HNMR. The effect of spacer length on the characteristics of quaternary ammonium organic Gemini surfactant was investigated. The results showed that the surface activity, wetting property and antimicrobial ability of surfactant gradually enhanced with the decrease of the length of spacer group in C12-PSix-C12. The surface tension values of above three surfactants at CMC(γCMC) were 29.74, 31.17 and 44.95 m N/m, respectively. The maximal contact angle values on the glass were 48.3?, 59.9? and 65.6?. The diameter of inhibition zone of C12-PSix-C12(x =40,80,315) to Staphylococcus aureus was 38.5, 34.5 and 27.5 mm, respectively. Furthermore, C12-PSi40-C12 exhibited the best emulsion stability to liquid paraffin, kerosene and oleic acid, with corresponding emulsifying stability time of 260.5, 732.3 and 1537.0 s.
引文
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[21]Fatma N,Panda M,Beg M.Ester-bonded cationic Gemini surfactants:Assessment of their cytotoxicity and antimicrobial activity[J].Journal of Molecular Liquids,2016,222:390-394.
[22]Negm N A,Tawfik S M.Characterization,surface properties and biological activity of some synthesized anionic surfactants[J].Journal of Industrial and Engineering Chemistry,2014,20(6):4463-4472.
[2]Shui Lingling(水玲玲),Zheng Liqiang(郑利强),Zhao Jianxi(赵剑曦),et al.Study on the interfacial activity of Gemini surfactant system[J].Fine Chemicals(精细化工),2001,18(2):67-69.
[3]Wang Jun(王军),Luan Lihui(栾立辉),Yang Xuzhao(杨许召),et al.Synthesis and surface activity of cationic Gemini surfactants[J].Fine Chemicals(精细化工),2009,26(1):14-17.
[4]Natalia Ivanova,Victor Starov,Ramon Rubio,et al.Critical wetting concentrations of trisiloxane surfactants[J].Colloids and Surfaces A:Physicochem and Engeering Aspects,2010,354:143-148.
[5]Huang Liangxian(黄良仙),An Qiufeng(安秋凤).Synthesis characterization and application performance study of new type aminopolysiloxane softener[J].Textile Auxiliaries(印染助剂),2006,23(9):22-24.
[6]Wang Guoyong,Zhang Dianlong,Du Zhiping,et al.Spontaneous vesicle formation from trisiloxane-tailed gemini surfactant[J].Journal of Molecular Liquids,2014,20:1247-1250.
[7]Han Fu(韩富),Zhang Gaoyong(张高勇).Synthesis and interfacial properties of glucosamide-based trisiloxane surfactants[J].Acta Chmica Sinica(化学学报),2004,62(7):733-737.
[8]Hao Chuanming,Cui Yuezhi,Yang Pengfei,et al.Effect of siloxane spacer length on organosilicon bi-quaternary ammonium amphiphiles[J].Colloids and Surfaces B:Biointerfaces,2015,128:528-536.
[9]Bao Yan(鲍艳),Guo Jiajia(郭佳佳),Wang Xian(王宪).Synthesis and properties of ammonium organic silicon Gemini surfactant[J].Fine Chemicals(精细化工),2016,33(6):644-647.
[10]Bao Yan,Guo Jiajia,Ma Jianzhong,et al.Cationic silicon-based Gemini surfactants:effect of hydrophobic chains on surface activity,physic-chemical properties and aggregation behaviors[J].Journal of Industrial&Engineering Chemistry,2017,53:51-61.
[11]Xu Yifei(徐怡斐).Experimental and theoretical study on the surface tensions of carbonated aqueous solution of aikanol amines[D].North China Electric Power University(Baoding)(华北电力大学保定校区),2012.
[12]Mao Peikun(毛培坤).Industrial analysis of surfactant products[M].Beijing:Chemical Industry Press(化学工业出版社),2002:430-433.
[13]Hu Xiaoxia(胡晓侠),He Jiangping(贺江平).Synthesis of anti-microbical agent with silicon quaternary ammonium salt[J].Dyeing and Finishing(印染),2014,40(8):13-17.
[14]Li Mingchun(李明春),Zhou Shengquan(周盛全),Xin Meihua(辛梅华),et al.Synthesis and antimicrobial activity of N-long chitosan quaternary ammonium salt[J].Functional Materials(功能材料).2012,17(43):2338-2342.
[15]Lin Qiuyun(林秋云),Du Guangwen(杜光文).Experimental study on antimicrobial effect of nano antibacterial disk[J].Chinese Journal of Health Laboratory Technology(中国卫生检验杂志),2005,15(2):211-212.
[16]Han Shiyan(韩世岩),Li Shujun(李淑君),Zhao Yanyan(赵颜颜),et al.Effect of spacer chain character on surface activities of rosinbased quaternary ammonium Gemini surfactants[J].Chemistry and Industry of Forest Products(林产化学与工业),2012,32(4):39-42.
[17]Zana R,Benrraou M,Rueff R.Effect of the spacer chain length on the critical micelle concentration and micelle ionization degree[J].Langmuir,1991,7(6):1072-1075.
[18]Ma Xiaodan(马小单),Li Huajing(李华静),Li Yuangang(李远刚),et al.Synthesis and properties of Gemini surfactants containing ester coupling groups[J].Journal of Xi'an University of Science and Technology(西安科技大学学报),2012,32(5):627-631.
[19]Zhang Yue,Zhang Gaoyong,Han Fu.The spreading and superspeading behavior of new glucosamide-basedtrisiloxane surfactants on hydrophobic foliage[J].Colloids and Surfaces A:Physicochem and Engeering Aspects,2006,276:100-106.
[20]Yang Jisheng(杨继生).Principle and application of surfactant[M].Nanjing:Southeast University Press(东南大学出版社),2012:52-54.
[21]Fatma N,Panda M,Beg M.Ester-bonded cationic Gemini surfactants:Assessment of their cytotoxicity and antimicrobial activity[J].Journal of Molecular Liquids,2016,222:390-394.
[22]Negm N A,Tawfik S M.Characterization,surface properties and biological activity of some synthesized anionic surfactants[J].Journal of Industrial and Engineering Chemistry,2014,20(6):4463-4472.