Microwave synthesis process and properties of behenic acid diester-based silicone quaternary ammonium salt

doi:10.16085/j.issn.1000-6613.2017-2059

Abstract

Abstract: Diester-based silicon quaternary ammonium salts with long carbon chains were synthesized via esterification and quaternization reaction in two steps using behenic acid, N-methyldiethanolamine, and γ-chloropropyltrimethoxysilane. Single-factor and orthogonal array design experiments to synthesis desired products by microwave method were carried out to investigate the optimal reaction conditions, which were the microwave power 800W, material mole ratio n(silane):n(ester amine)=1.2:1, reaction temperature 170℃, the amount of solvent m(solvent):m(raw material)=0.8:1, and reaction time 12h, and a yield of 96.60%. The method overcame the long time-consuming difficulties in the quaterization process of long chain tertiary amine, improved the reaction rate, and obtained a good reaction repeatability. The chemical structures of the intermediates and target compounds were characterized by FTIR and ¹H NMR spectra, which were consistent with the expected results. A simple, rapid and accurate method for the purity determination of quaternary ammonium salts by HPLC-ELSD was established with some reference valuea. The purity of the product was confirmed to reach 98.77% with a stable baseline and sharp peak.The results of performance tests showed that, compared with DC-5700, the target products had good thermal stability, excellent emulsifying and solubilizing properties; the CMC of the aqueous solution was 1.81mmol/L, and the corresponding surface tension was 49.4mN/m.

Key words: surfactants, esterification, double-chain ester amine, silicone quaternary ammonium salt, microwave high-pressure, liquid chromatography, performance testing

摘要： 以山嵛酸、N-甲基二乙醇胺以及γ-氯丙基三甲氧基硅烷为主要原料，分别经过酯化和季铵化反应两步合成了一种超长碳链的双酯基有机硅季铵盐，并通过单因素、正交试验得到了微波法合成目标产物的最优工艺条件为：设置微波功率为800W，物料摩尔比为n（硅烷）∶n（酯胺）=1.2∶1，反应温度为170℃，溶剂用量为m（溶剂）∶m（原料）=0.8∶1，反应时间为12h，产品产率达96.60%。此方法克服了长链叔胺季铵化过程中普遍耗时过长的困难，提高了反应速率，而且实验重复性良好。实验中采用红外光谱、核磁共振氢谱对中间体及目标产物的结构进行了表征，与预期结果一致；建立了高效液相色谱-蒸发光散射检测器（HPLC-ELSD）测定季铵盐纯度的方法，基线稳定，峰型良好，产品纯度达98.77%，具有一定的参考价值。性能测试结果表明：对比DC-5700，目标产物具有良好的热稳定性，优异的乳化及增溶性能；其水溶液的临界胶束浓度为1.81mmol/L，表面张力（γ_CMC）为49.4mN/m。

关键词: 表面活性剂, 酯化, 双长链酯胺, 有机硅季铵盐, 微波高压, 液相色谱, 性能测试

CLC Number:

TQ423.12

WEI Yuan, ZHENG Cheng, MAO Taoyan, ZENG Zhaowen, ZHU Yiting, WANG Runhao, LIU Suizhen. Microwave synthesis process and properties of behenic acid diester-based silicone quaternary ammonium salt[J]. Chemical Industry and Engineering Progress, 2018, 37(08): 3169-3178.

魏渊, 郑成, 毛桃嫣, 曾昭文, 朱艺婷, 王润豪, 刘穗甄. 山嵛酸双酯基有机硅季铵盐的微波合成工艺及性能[J]. 化工进展, 2018, 37(08): 3169-3178.

References

[1] 赵洁, 安秋凤, 李献起, 等. 有机硅在抗菌整理剂中的应用[J]. 化学进展, 2014, 26(2):310-319. ZHAO Jie, AN Qiufeng, LI Xianqi, et al.Organosilicon in antimicrobial agent[J].Progress in Chemistry, 2014, 26(2):310-319.
[2] WU J, JIANG Y, HE J, et al. Thermo-responsive poly(N-isopropylacrylamide) grafted polyester textiles with switchable surface wettability[J]. Textile Research Journal, 2016, 86(7):677-684.
[3] FAN M, LUO C, WEI X, et al.Synthesis of biodegradable ester-containing quaternary ammonium salt by a novel route[J].Journal of the Taiwan Institute of Chemical Engineers, 2013, 44(2):202-204.
[4] LI J, ZHANG Q, WANG Y, et al.Synthesis and properties of organosilicon quaternary salts surfactants[J].Journal of Surfactants & Detergents, 2012, 15(3):339-344.
[5] 丁寒卫, 薛永强, 崔子祥, 等. 一种多头基有机硅季铵盐的合成及其性能[J]. 化工进展, 2014, 33(2):479-482. DING Hanwei, XUE Yongqiang, CUI Zixiang, et al.Synthesis and properties of a kind of organosilicon quaternary ammonium salt with multi-heads in its molecular structure[J].Chemical Industry and Engineering Progress, 2014, 33(2):479-482.
[6] GONG S Q, NIU L N, KEMP L K, et al. Quaternary ammonium silane-functionalized, methacrylate resin composition with antimicrobial activities and self-repair potential[J]. Acta Biomaterialia, 2012, 8(9):3270-3282.
[7] SATASIA S P, KALARIA P N, RAVAL D K.Acidic ionic liquid immobilized on cellulose:an efficient and recyclable heterogeneous catalyst for the solventfree synthesis of hydroxylated trisubstituted pyridines[J]. RSC Advances, 2013, 3(10):3184-3188.
[8] 李盼, 徐红, 解鸿宇, 等.衣康酸双酯磺酸钠型双子表面活性剂的合成与性能[J].化工进展, 2017, 36(8):3047-3052. LI Pan, XU Hong, XIE Hongyu, et al.Synthesis and properties of itaconic acid diester disulfonate gemini surfactant[J]. Chemical Industry and Engineering Progress, 2017, 36(8):3047-3052.
[9] HAN B, GENG T, JIANG Y, et al.Synthesis and properties of di-chain esterquat surfactants[J].Journal of Surfactants & Detergents, 2014, 18(1):1-5.
[10] TEHRANI-BAGHA A R, OSKARSSON H, GINKEL C G V, et al. Cationic ester-containing gemini surfactants:chemical hydrolysis and biodegradation[J].Journal of Colloid & Interface Science, 2007, 312(2):444-452.
[11] MIAO Z, YANG J, WANG L, et al.Synthesis of biodegradable lauric acid ester quaternary ammonium salt cationic surfactant and its utilization as calico softener[J]. Materials Letters, 2008, 62(19):3450-3452.
[12] 姜贞贞, 李秋小, 耿涛, 等.双酯柔软剂2,3-二(硬脂酰氧基)-丙基三甲基胺季铵盐的合成[J]. 精细化工, 2010, 27(1):80-83. JIANG Zhenzhen, LI Qiuxiao, GENG Tao, et al. Synthesis of diesterquats-2,3-bis(stearoloxy)-propyltrimethylamine quaternary[J]. Fine Chemicals, 2010, 27(1):80-83.
[13] 刘红芹, 刘静伟, 赵秋瑾, 等.油脂基表面活性剂研究进展[J]. 精细化工, 2013, 30(4):378-384. LIU Hongqin, LIU Jingwei, ZHAO Qiujin, et al.Progress in research into oleo-based surfactants[J].Fine Chemicals, 2013, 30(4):378-384.
[14] 丁寒卫, 郭文涛, 薛永强, 等.新型含双长链和苄基的有机硅季铵盐的合成[J].合成化学, 2014, 22(6):797-799. DING Hanwei, GUO Wentao, XUE Yongqiang, et al.Synthesis of a novel organosilicon quaternary ammonium salt containing double long-chain alkyls and benzyl[J]. Chinese Journal of Synthetic Chemistry, 2014, 22(6):797-799.
[15] LIU Y, MA K, LI R, et al. Antibacterial cotton treated with N-halamine and quaternary ammonium salt[J]. Cellulose, 2013, 20(6):3123-3130.
[16] HEGAZY M A, EL-TABEI A S. Synthesis, surface properties, synergism parameter and inhibitive performance of novel cationic gemini surfactant on carbon steel corrosion in 1 M HCl solution[J]. Journal of Surfactants & Detergents, 2013, 16(2):221-232.
[17] 朱新海, 杨纯, 陈功, 等.微波辅助法合成有机硅季铵盐[J]. 中山大学学报(自然科学版), 2009, 48(3):56-59. ZHU Xinhai, YANG Chun, CHEN Gong, et al.Microwave-assisted synthesis of siloxane quaternary ammonium salt[J].Acta Scientiarum Naturalium Universitatis Sunyatseni, 2009, 48(3):56-59.
[18] KUPERKAR K, MODI J, PATEL K.Surface-active properties and antimicrobial study of conventional cationic and synthesized symmetrical gemini surfactants[J]. Journal of Surfactants & Detergents, 2012, 15(1):107-115.
[19] 杨建洲, 匡登云, 王伟平, 等.含酯基Gemini双季铵盐表面活性剂的合成及应用[J]. 精细化工, 2008, 25(8):739-741. YANG Jianzhou, KUANG Dengyun, WANG Weiping, et al. Synthesis and application of bisquaternary ammonium salt gemini surfactant with ester bond[J].Fine Chemicals, 2008, 25(8):739-741.
[20] 牛华, 娄平均, 朱红军, 等.含酯基Gemini季铵盐柔软剂的合成工艺研究[J].精细化工, 2010, 27(8):823-827. NIU Hua, LOU Pingjun, ZHU Hongjun, et al.Synthesisof gemini quaternary ammonium salt fabric softener with ester group[J].Fine Chemicals, 2010, 27(8):823-827.
[21] 安秋凤, 肖丽萍, 黄玲, 等.季铵化硅烷的合成与应用[J].有机硅材料, 2003, 17(4):16-19. AN Qiufeng, XIAO Liping, HUANG Ling, et al.Synthesis and applications of quaternary ammonium silane[J].Silicone Material, 2003, 17(4):16-19.
[22] 彭忠利, 吴小娟.甲基二乙氧基硅烷季铵盐的合成[J].精细化工, 2006, 23(9):873-877. PENG Zhongli, WU Xiaojuan.Synthesis of quaternary ammonium functional Methyldiethoxysilane[J]. Fine Chemicals, 2006, 23(9):873-877.
[23] 黄武欢, 郑成, 毛桃嫣, 等.酯基有机硅季铵盐柔软整理剂的合成与表征[J].精细化工, 2012, 29(12):1167-1171. HUANG Wuhuan, ZHENG Cheng, MAO Taoyan, et al.Synthesis and characterization of silicone based esterquat for fabric softening application[J].Fine Chemicals, 2012, 29(12):1167-1171.
[24] 张光华, 秦松, 黄凤萍, 等.系列反应型阳离子Gemini表面活性剂的合成及性能[J]. 化工进展, 2015, 34(11):4030-4034. ZHANG Guanghua, QIN Song, HUANG Fengping, et al.Synthesis and performance of a series of reactive cationic gemini surfactants[J]. Chemical Industry and Engineering Progress, 2015, 34(11):4030-4034.
[25] 徐清, 蒋波, 詹晓力, 等.γ-氯丙基三甲氧基硅烷季铵化反应中的溶剂效应研究[J]. 高校化学工程学报, 2007, 21(4):640-644. XU Qing, JIANG Bo, ZHAN Xiaoli, et al.Study on solvent effect on quaternization of γ-chloropropyl trimethoxy siloxane[J]. Journal of Chemical Engineering of Chinese Universities, 2007, 21(4):640-644.
[26] 蒋波, 詹晓力, 陈丰秋.季铵化反应中的溶剂效应[J]. 化学通报:网络版, 2006, 69(1):1-6. JIANG Bo, ZHAN Xiaoli, CHEN Fengqiu.Advances in solvent effect of quaternarization[J]. Chemistry Online, 2006, 69(1):1-6.
[27] 蒋波, 詹晓力, 陈丰秋. γ-氯丙基三甲氧基硅烷季铵化反应规律探讨[J].化学反应工程与工艺, 2006, 22(1):33-36. JIANG Bo, ZHAN Xiaoli, CHEN Fengqiu. Quaternization of 3-chloropropyl trimethoxy siloxane[J]. Chemical Reaction Engineering and Technology, 2006, 22(1):33-36.
[28] 吴乐, 陶乃旺, 江水旺.季铵盐检测技术研究进展[J]. 涂料工业, 2015, 45(9):83-87. WU Le, TAO Naiwang, JIANG Shuiwang.Progress in quaternary ammonium analysis technology[J].Paint & Coatings Industry, 2015, 45(9):83-87.
[29] 卢姝, 纪然. 高效液相色谱法测定微量季铵盐的改进方法[J]. 工业水处理, 2011, 31(9):76-78. LU Shu, JI Ran.Improved method for the determination of trace quaternary ammonium salt by high performance liquid chromatography[J]. Industrial Water Treatment, 2011, 31(9):76-78.