系列烯丙基二甲基烷基氯化铵的合成和性能
|
摘要
以不同碳链的N-二甲基烷基胺(N-二甲基癸基胺、N-二甲基十二烷基胺、N-二甲基十四烷基胺)和氯丙烯为主要原料,合成了3种烯丙基二甲基烷基氯化铵季铵盐(产物分别记为C_(10),C_(12),C_(14)),合成条件为乙醇用量50 mL、n(N-二甲基烷基胺)∶n(氯丙烯)=1.0∶3.0、反应温度50℃、反应时间22～25 h,所得C_(10),C_(12),C_(14)的收率分别为86.6%,88.1%,87.0%。通过IR和~1H NMR方法对产物进行了结构表征,测定了季铵盐的热稳定性、表面活性、泡沫性能和絮凝性能。实验结果表明,C_(10),C_(12),C_(14)的主要分解温度为170～300℃,对应失重率分别为88.5%,89.1%,90.6%;临界胶束浓度和临界胶束浓度下的表面张力分别为13.5,6.6,2.0 mmol/L和36.1,34.7,33.7 mN/m;季铵盐的低温水溶性好,随着烷基链长度的增加,发泡力及对高岭土的絮凝能力依次增强。
Three allyldimethylalkyl ammonium chlorides(allyldimethyldecyl ammonium chloride,allyldimethyldodecyl ammonium chloride,allyldimethyltetradecyl ammonium chloride,labeled C_(10),C_(12),C_(14))were synthesized by using N-dimethylalkylamine of straight chain and allylchloride as the main raw materials.The synthesis conditions were ethanol 50 mL,n(N-dimethylalkylamine)∶n(allylchloride)1.0∶3.0,reaction temperature 50℃,and reaction time 22-25 h.The product yields achieved 86.6%,88.1%,87.0%,respectively.The chemical structure of the products was confirmed by IR and ~1H NMR.The thermal stability,surface activity,foaming properties and flocculating properties of the quaternary ammonium salts C_(10),C_(12) and C_(14) were determined.The results showed that C_(10),C_(12)and C_(14) decomposed at a temperature in a range of 170-300℃,and their mass loss rates were 88.5%,89.1%and 90.6%,respectively.Their critical micelle concentration(cmc)and the surface tension at the cmc of C_(10),C_(12) and C_(14) were 13.5,6.6 and 2.0 mmol/L,and 36.1,34.7 and 33.7 mN/m,respectively.The water solubility of C_(10),C_(12) and C_(14) was good at a low temperature.With the increase of the alkyl chain length,their foaming abilities and flocculating abilities to kaolin increased sequentially.
Three allyldimethylalkyl ammonium chlorides(allyldimethyldecyl ammonium chloride,allyldimethyldodecyl ammonium chloride,allyldimethyltetradecyl ammonium chloride,labeled C_(10),C_(12),C_(14))were synthesized by using N-dimethylalkylamine of straight chain and allylchloride as the main raw materials.The synthesis conditions were ethanol 50 mL,n(N-dimethylalkylamine)∶n(allylchloride)1.0∶3.0,reaction temperature 50℃,and reaction time 22-25 h.The product yields achieved 86.6%,88.1%,87.0%,respectively.The chemical structure of the products was confirmed by IR and ~1H NMR.The thermal stability,surface activity,foaming properties and flocculating properties of the quaternary ammonium salts C_(10),C_(12) and C_(14) were determined.The results showed that C_(10),C_(12)and C_(14) decomposed at a temperature in a range of 170-300℃,and their mass loss rates were 88.5%,89.1%and 90.6%,respectively.Their critical micelle concentration(cmc)and the surface tension at the cmc of C_(10),C_(12) and C_(14) were 13.5,6.6 and 2.0 mmol/L,and 36.1,34.7 and 33.7 mN/m,respectively.The water solubility of C_(10),C_(12) and C_(14) was good at a low temperature.With the increase of the alkyl chain length,their foaming abilities and flocculating abilities to kaolin increased sequentially.
引文
[1]王湘英,朱建林,刘敏,等.N,N-二甲基丙烯基十六烷基溴化铵在水溶液中胶束化行为的研究[J].材料研究与应用,2008,2(2):133-136.
[2]Wang G J,Engberts J B F N.Non-cross-linked and crosslinked poly(alkylmethyldiallyl ammonium halides):Synthesis and aggregation behavior[J].J Phys Org Chem,1998(11):305-320.
[3]Exxon Research and Engineering Company.Polymerizable cationic viscoelastic monomer fluids:US5066753[P].1991-11-19.
[4]曹翠,乔卫红.阳离子可聚合表面活性剂的研究进展[J].高分子通报,2008(12):67-74.
[5]Hossein M,Mahdi M.Synthesis and applications of crosslinked poly(diallyldimethyl ammonium chloride)and its derivative copolymers as efficient phase transfer catalyst for nucleophilic substitution reactions[J].Chin J Polym Sci,2011,29(2):165-172.
[6]西南石油大学.堵漏剂及其制备方法:103396774 A[P].2013-11-20.
[7]谢瑜,张昌辉,徐旋.聚合季铵盐阳离子表面活性剂的合成和性能研究[J].日用化学品科学,2008,31(2):21-24.
[8]陶贤平,张跃军,朱蓓蓓.烯丙基二甲基烷基季铵盐阳离子单体的合成与性能研究[J].精细石油化工,2016,33(2):27-31.
[9]陶贤平,张跃军,马志军.烯丙基型可聚合表面活性剂的合成及性能[J].石油化工,2015,44(11):1357-1362.
[10]Wu Minghua,Wu Renan,Wang Fangjun,et al.“One-pot”process for fabrication of organic-silica hybrid monolithic capillary columns using organic monomer and alkoxysilane[J].Anal Chem,2009,81(9):3529-3536.
[11]Zhao Wenshan,Yu Li,Yan Junhui,et al.Synthesis and characterization of dimethylallyl p-methylbenzyl ammonium chloride[J].Chem Res,2006,17(4):54-55,59.
[12]陶贤平,张跃军,李侠,等.二烯丙基甲基烷基溴化铵的结构与性质的关系[J].应用化学,2015,32(3):342-349.
[13]国家技术监督局.GB/T 7462-1994表面活性剂发泡力的测定改进Ross-Miles法[S].北京:中国标准出版社,1994.
[14]陶贤平,张跃军.系列二烯丙基甲基烷基溴化铵的结构与性能[J].石油化工,2015,44(1):70-76.
[15]贾旭.PDMDAAC合成工艺、聚合反应机理及结构与性质的关系[D].南京:南京理工大学,2011.
[16]崔正刚.表面活性剂、胶体与界面化学基础[M].北京:化学工业出版社,2013:327.
[17]崔正刚,蒋建中.表面活性剂和胶界面现象[M].北京:化学工业出版社,2015:105-107,166,214.
[18]卢庆祥,傅式洲,尹宝霖,等.季铵盐型双子表面活性剂的合成和性能[J].日用化学工业,2009,39(2):81-84,96.
[19]陈荣圻.表面活性剂化学与应用[M].北京:纺织工业出版社,1990:224-233.
[20]胡三清,张友浩,胡志朋,等.DMDAAC的合成条件优选及防膨性能评价[J].长江大学学报:自然科学版,2010,7(1):30-32,54.
[2]Wang G J,Engberts J B F N.Non-cross-linked and crosslinked poly(alkylmethyldiallyl ammonium halides):Synthesis and aggregation behavior[J].J Phys Org Chem,1998(11):305-320.
[3]Exxon Research and Engineering Company.Polymerizable cationic viscoelastic monomer fluids:US5066753[P].1991-11-19.
[4]曹翠,乔卫红.阳离子可聚合表面活性剂的研究进展[J].高分子通报,2008(12):67-74.
[5]Hossein M,Mahdi M.Synthesis and applications of crosslinked poly(diallyldimethyl ammonium chloride)and its derivative copolymers as efficient phase transfer catalyst for nucleophilic substitution reactions[J].Chin J Polym Sci,2011,29(2):165-172.
[6]西南石油大学.堵漏剂及其制备方法:103396774 A[P].2013-11-20.
[7]谢瑜,张昌辉,徐旋.聚合季铵盐阳离子表面活性剂的合成和性能研究[J].日用化学品科学,2008,31(2):21-24.
[8]陶贤平,张跃军,朱蓓蓓.烯丙基二甲基烷基季铵盐阳离子单体的合成与性能研究[J].精细石油化工,2016,33(2):27-31.
[9]陶贤平,张跃军,马志军.烯丙基型可聚合表面活性剂的合成及性能[J].石油化工,2015,44(11):1357-1362.
[10]Wu Minghua,Wu Renan,Wang Fangjun,et al.“One-pot”process for fabrication of organic-silica hybrid monolithic capillary columns using organic monomer and alkoxysilane[J].Anal Chem,2009,81(9):3529-3536.
[11]Zhao Wenshan,Yu Li,Yan Junhui,et al.Synthesis and characterization of dimethylallyl p-methylbenzyl ammonium chloride[J].Chem Res,2006,17(4):54-55,59.
[12]陶贤平,张跃军,李侠,等.二烯丙基甲基烷基溴化铵的结构与性质的关系[J].应用化学,2015,32(3):342-349.
[13]国家技术监督局.GB/T 7462-1994表面活性剂发泡力的测定改进Ross-Miles法[S].北京:中国标准出版社,1994.
[14]陶贤平,张跃军.系列二烯丙基甲基烷基溴化铵的结构与性能[J].石油化工,2015,44(1):70-76.
[15]贾旭.PDMDAAC合成工艺、聚合反应机理及结构与性质的关系[D].南京:南京理工大学,2011.
[16]崔正刚.表面活性剂、胶体与界面化学基础[M].北京:化学工业出版社,2013:327.
[17]崔正刚,蒋建中.表面活性剂和胶界面现象[M].北京:化学工业出版社,2015:105-107,166,214.
[18]卢庆祥,傅式洲,尹宝霖,等.季铵盐型双子表面活性剂的合成和性能[J].日用化学工业,2009,39(2):81-84,96.
[19]陈荣圻.表面活性剂化学与应用[M].北京:纺织工业出版社,1990:224-233.
[20]胡三清,张友浩,胡志朋,等.DMDAAC的合成条件优选及防膨性能评价[J].长江大学学报:自然科学版,2010,7(1):30-32,54.