多羟基Bola有机硅季铵盐的合成、表征及其应用性能

doi:10.11949/0438-1157.20201235

摘要/Abstract

摘要：

以1，3-二（3-缩水甘油醚丙基）-1，1，3，3-四甲基二硅氧烷（EDH）和八甲基环四硅氧烷（D4）为原料合成了端环氧硅油（ETSO），以ETSO为原料与葡甲胺胺化得到中间体有机硅嵌段硅油（PTSO），然后用γ-氯丙基三甲氧基硅烷（CPTSO）季铵化改性制备了Bola有机硅季铵盐（BPTSO）。BPTSO的季铵化过程最优合成工艺条件为：反应温度为80℃，物料摩尔比为n（PTSO）∶n（CPTSO）=1∶1.2，反应时间为3 h，PTSO转化率达98.60%。通过FT-IR、¹H NMR、TGA、TEM对BPTSO的结构及BPTSO乳液整理后织物的微观形貌进行了表征。测试结果表明：BPTSO乳液的表面张力γ 为29.4 mN/m，临界胶束浓度CMC为0.036 mmol/L，具有囊泡结构和优越的稳定性，经BPTSO乳液整理后的棉织物具有优异的柔软度、白度及亲水性，当BPTSO乳液的用量为60 g/L时，对棉织物的增深率可达到46.5%。

关键词: Bola 有机硅, 表面活性剂, 乳液, 粒度分布, 稳定性, 柔软性

Abstract:

Epoxysilicone oil (ETSO) was synthesized with (3-glycidoxypropyl)-1,1,3,3- tetramethyldisiloxane (EDH) and octamethylcyclotetrasiloxane (D4) as raw material first. Then intermediate organosilicone block silicone oil (PTSO) was obtained by amination with meglumine. Finally, Bola silicone quaternary ammonium salt (BPTSO) was synthesized by quaternization of PTSO and γ-chloropropyltrimethoxysilane (CPTSO). The process conditions of BPTSO were optimized as follows: the reaction temperature was 80℃, the molar ratio of material was n(PTSO)∶n(CPTSO)=1∶1.2, the reaction time was 3 h, and the conversion rate of PTSO was 98.60%. The structure and morphology of BPTSO were characterized by FT-IR, ¹H NMR, TGA, SEM and TEM. The results of performance test show that BPTSO have core-shell structure and superior stability, the fabrics treated with BPTSO emulsion had excellent softness, whiteness and hydrophilicity. The depth enhancement rate of cotton fabric reached 46.5%.

Key words: Bola silicone, surfactants, emulsion, particle size distribution, stability, softness

中图分类号:

TQ 317.4

程文静, 余林, 程高, 钟远红, 郑成, 毛桃嫣. 多羟基Bola有机硅季铵盐的合成、表征及其应用性能[J]. 化工学报, 2021, 72(5): 2837-2848.

CHENG Wenjing, YU Lin, CHENG Gao, ZHONG Yuanhong, ZHENG Cheng, MAO Taoyan. Synthesis characterization and application of Bola silicone quaternary ammonium salt[J]. CIESC Journal, 2021, 72(5): 2837-2848.

图/表 14

图1 BPTSO的合成路线

Fig.1 Synthesis route of Bola silicone quaternary ammonium salts

表1 不同季铵化试剂对PTSO的转化率

Table 1 Conversion rates of PTSO with different quaternary ammonium reagents

季铵化试剂	转化率/%
γ-氯丙基三甲氧基硅烷	97.6
硫酸二甲酯	95.5
硫酸二乙酯	76.3
氯化苄	92.1
三甲基氯化铵盐酸盐	95.2

图2 不同反应条件时PTSO的转化率

Fig.2 Conversion rate of PTSO with different reaction conditions

表2 正交实验因素水平表

Table 2 Factors and levels of orthogonal experiments

水平	A(反应温度)/℃	B(反应物摩尔比)	C(反应时间)/h
1	60	1∶1	2
2	70	1∶1.1	3
3	80	1∶1.2	4

表3 正交实验方案与结果

Table 3 Result of orthogonal experiments

实验号	A	B	C	转化率/%
1	60	1∶1.0	2	96.11
2	60	1∶1.1	3	97.83
3	60	1∶1.2	4	96.72
4	70	1∶1.0	3	98.03
5	70	1∶1.1	4	96.74
6	70	1∶1.2	2	98.04
7	80	1∶1.0	4	98.27
8	80	1∶1.1	2	98.00
9	80	1∶1.2	3	98.22
K₁	290.66	292.15	292.41	—
K₂	292.81	292.57	294.08	—
K₃	294.49	292.98	291.73	—
k₁	96.89	97.47	97.38	—
k₂	97.60	97.52	97.03	—
k₃	97.16	97.66	97.24	—
极差R	3.83	0.57	2.35	—
因素主次		A＞C＞B
最优方案		A 80℃、B (1∶1.2)，C 3 h
重复实验		平均转化率98.60%

图3 BPTSO的红外吸收光谱图(a)和核磁共振氢谱图(b)

Fig.3 FT-IR spectrum(a) and 1H NMR spectra(b) of BPTSO

图4 BPSTO和ATSO乳液的TEM、粒径分布和BPTSO的γ-lgc曲线

Fig.4 TEM of BPTSO emulsion;TEM of ATSO emulsion;particle size and γ-lgc curve of BPTSO emulsion

图5 BPSTO乳液的稳定性

Fig.5 Stability of BPTSO emulsion

图6 BPTSO乳液整理后织物的柔软性能(a)和抗黄变性能(b)

Fig.6 Softness(a) and whiteness (b) of fabric treated with BPTSO emulsion

图7 BPTSO乳液整理后织物的SEM图

Fig.7 SEM images of fabrics treated with BPTSO

图8 BPTSO乳液整理后棉(a)和涤纶(b)的亲水性

Fig.8 Water contact angles and hydrophilicity of cotton(a) and dacron(b) treated with BPTSO emulsion

图9 BPTSO乳液对棉织物的固色效果

Fig.9 Color fixation effect of BPTSO emulsion on cotton fabric

图10 BPTSO乳液的放大生产

Fig.10 Amplification production of BPTSO emulsion

表4 BPTSO乳液放大产品指标

Table 4 Index of BPTSO emulsion after amplification

项目	指标
含量/%	15
成本(元/千克)	6.35
用量(g/L)	20
固色牢度	4.5级
摩擦牢度	4.5级
耐水洗效果	5级
手感	蓬松、软滑风格，5分

参考文献 36

1	Jin Y, Pu Q, Fan H. Synthesis of linear piperazine/polyether functional polysiloxane and its modification of surface properties on cotton fabrics[J]. ACS Applied Materials & Interfaces, 2015, 7(14): 7552-7558.
2	黄良仙, 肖波, 杨军胜, 等. 有机硅季铵盐的合成及其在织物整理中的应用研究进展[J]. 印染助剂, 2013, 30(10): 1-6.
	Huang L X, Xiao B, Yang J S, et al. Synthesis of polysiloxane quaternary ammonium salt and its application in the fabric finishing[J]. Textile Auxiliaries, 2013, 30(10): 1-6.
3	马现奇, 尹红, 袁慎峰, 等. 氨基硅油柔软剂作用模型的研究进展[J]. 印染助剂, 2011, 28(8): 1-4, 7.
	Ma X Q, Yin H, Yuan S F, et al. Study on progress of working model of amino silicone softener[J]. Textile Auxiliaries, 2011, 28(8): 1-4, 7.
4	Zhang Y, Zhang G Y, Han F. The spreading and superspeading behavior of new glucosamide-based trisiloxane surfactants on hydrophobic foliage[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2006, 276(1/2/3): 100-106.
5	Vidal L, Robin O, Parshintsev J, et al. Quaternary ammonium-functionalized silica sorbents for the solid-phase extraction of aromatic amines under normal phase conditions[J]. Journal of Chromatography A, 2013, 1285: 7-14.
6	习娟. 新型聚醚/氨基嵌段有机硅季铵盐的合成与应用[D]. 西安: 陕西科技大学, 2012.
	Xi J. Synthesis and application of novel quaternary ammonium functional polyether block aminopolysiloxane[D]. Xi'an: Shaanxi University of Science & Technology, 2012.
7	Cui X, Qiao C D, Wang S J, et al. Synthesis, surface properties, and antibacterial activity of polysiloxane quaternary ammonium salts containing epoxy group[J]. Colloid and Polymer Science, 2015, 293(7): 1971-1981.
8	Liu Y, Ma K K, Li R, et al. Antibacterial cotton treated with N-halamine and quaternary ammonium salt[J]. Cellulose, 2013, 20(6): 3123-3130.
9	Mao T Y, Wei Y, Zheng C, et al. Antibacterial cotton fabrics coated by biodegradable cationic silicone softeners[J]. Journal of Surfactants and Detergents, 2019, 22(6): 1429-1443.
10	魏渊. 有机硅表面活性剂的微波合成及构效规律研究[D]. 广州: 广州大学, 2019.
	Wei Y. Study on microwave synthesis and structural-activity rule of silicon surfactant[D]. Guangzhou: Guangzhou University, 2019.
11	Lin L H, Wang C C, Chen K M, et al. Synthesis and physicochemical properties of silicon-based gemini surfactants[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013, 436: 881-889.
12	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 G H, Qin S, Huang F P, et al. Synthesis and performance of a series of reactive cationic gemini surfactants[J]. Chemical Industry and Engineering Progress, 2015, 34(11): 4030-4034.
13	张帅, 武玉民. 衣康酸单酯羧酸盐Bola型表面活性剂性能[J]. 精细化工, 2017, 34(10): 1126-1131.
	Zhang S, Wu Y M. Properties of itaconic acid based monoester carboxylate bolaform surfactant[J]. Fine Chemicals, 2017, 34(10): 1126-1131.
14	陈鹏, 郑成, 毛桃嫣, 等. Bola型表面活性剂研究新进展[J]. 日用化学工业, 2014, 44(5): 285-291.
	Chen P, Zheng C, Mao T Y, et al. Recent progress in research work with respect to bolaform surfactants[J]. China Surfactant Detergent & Cosmetics, 2014, 44(5): 285-291.
15	鲍艳, 郭佳佳, 王宪. 季铵盐有机硅双子表面活性剂的合成及性能[J]. 精细化工, 2016, 33(6): 643-647.
	Bao Y, Guojia J, Wang X. Synthesis and properties of quaternary ammonium organic silicon gemini surfactant[J]. Fine Chemicals, 2016, 33(6): 643-647.
16	Ivanova N, Starov V, Rubio R, et al. Critical wetting concentrations of trisiloxane surfactants[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2010, 354(1/2/3): 143-148.
17	Zou M, Dong J F, Yang G F, et al. A comprehensive study on micellization of dissymmetric pyrrolidinium headgroup-based gemini surfactants[J]. Physical Chemistry Chemical Physics, 2015, 17(15): 10265-10273.
18	Zhai Z L, Xu J, Yan X Y, et al. pH-responsive foams based on a transition between a bola surfactant and a traditional surfactant[J]. Journal of Molecular Liquids, 2020, 298: 111968.
19	刘萍萍, 缪培培, 王祥荣. 阳离子Bola型表面活性剂的合成及在腈纶染色中的应用[J]. 印染助剂, 2011, 28(12): 22-24.
	Liu P P, Miao P P, Wang X R. Synthesis of cationic Bola surfactants and its application in dyeing acrylic fibers[J]. Textile Auxiliaries, 2011, 28(12): 22-24.
20	陈祎航, 刘娟, 徐紫薇, 等. 新型Bola型两亲性分子的合成及自组装行为[J]. 杭州师范大学学报(自然科学版), 2020, 19(4): 349-353.
	Chen Y H, Liu J, Xu Z W, et al. Synthesis and self-assemble of a new Bola amphiphile[J]. Journal of Hangzhou Normal University (Natural Science Edition), 2020, 19(4): 349-353
21	Tu S, Kim S H, Joseph J, et al. Self-assembly of a donor-acceptor nanotube. A strategy to create bicontinuous arrays[J]. Journal of the American Chemical Society, 2011, 133(47): 19125-19130.
22	陶月阳. 氨基酸改性Bola型聚硅氧烷表面活性剂的合成与性能研究[D]. 镇江: 江苏大学, 2017.
	Tao Y Y. Study on synthesis and solution properties of amino acid modified bola type polysiloxane surfactants[D]. Zhenjiang: Jiangsu University, 2017.
23	Deng Y, Han D, Deng Y Y, et al. Facile one-step preparation of robust hydrophobic cotton fabrics by covalent bonding polyhedral oligomeric silsesquioxane for ultrafast oil/water separation[J]. Chemical Engineering Journal, 2020, 379: 122391.
24	Wei Y, Zheng C, Zhang Z Q, et al. Synthesis, surface properties, and antibacterial activity of novel ester-containing cationic silicone surfactants and their utilization as fabric-finishing agents[J]. Journal of Surfactants and Detergents, 2019, 22(2): 285-299.
25	Fang L Y, Tan J L, Zheng Y, et al. Synthesis, aggregation behavior of novel cationic silicone surfactants in aqueous solution and their application in metal extraction[J]. Journal of Molecular Liquids, 2017, 231: 134-141.
26	Peng Z L, Wu Q, Cai T, et al. Syntheses and properties of hydrolysis resistant twin-tail trisiloxane surfactants[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2009, 342(1/2/3): 127-131.
27	Han F, Zhang G Y. New family of Gemini surfactants with glucosamide-based trisiloxane[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2004, 237(1/2/3): 79-85.
28	Wang B C, Liu J, Han X N, et al. Preparation, surface activities, and biodegradability of a Bola-type collagen hydrolysate-based siloxane surfactant[J]. Journal of Surfactants and Detergents, 2018, 21(3): 313-322.
29	蒋波. γ-氯丙基三甲氧基硅烷季铵化反应规律研究[D]. 杭州: 浙江大学, 2005.
	Jiang B. Study on quaternization of γ-chloropropyl trimethoxy siloxane[D]. Hangzhou: Zhejiang University, 2005.
30	段治华, 王瑞林, 曾宪诚, 等. 季铵化反应的热动力学研究[J]. 化学研究与应用, 1992, 4(2): 72-76.
	Duan Z H, Wang R L, Zeng X C, et al. Study of thermokinetics on quaterisation[J]. Chemical Research and Application, 1992, 4(2): 72-76.
31	程文静, 郑成, 毛桃嫣, 等. 十八烷基甲基二羟乙基溴化铵的微波合成及性能[J]. 化工学报, 2011, 62(2): 566-573.
	Cheng W J, Zheng C, Mao T Y, et al. Microwave synthesis technique and properties of octadecylmethyldihydroxyethyl ammonium bromide[J]. CIESC Journal, 2011, 62(2): 566-573.
32	熊燕. 碳原子上S_N2反应机理的理论研究[D]. 成都: 四川大学, 2004.
	Xiong Y. Theoretical study on the bimolecular nucleophilic substitution reaction at carbon[D]. Chengdu: Sichuan University, 2004.
33	涂文通, 干作飞, 赵丹. 卤代烷的SN₂反应的研究[J]. 广西师范学院学报(自然科学版), 2015, 32(3): 50-59.
	Tu W T, Gan Z F, Zhao D. Study on SN₂ reaction of alkyl halide[J]. Journal of Guangxi Teachers Education University (Natural Science Edition), 2015, 32(3): 50-59.
34	He S, Xu B, Zhang Y M. Krafft temperature, critical micelle concentration, and rheology of “pseudo-gemini” surfactant comprising fatty acid soap and Bola-type quaternary ammonium salt[J]. Journal of Surfactants and Detergents, 2019, 22(6): 1269-1277.
35	杨卓, 葛凤燕, 蔡再生. 有机硅对棉织物增深作用的研究[J]. 印染助剂, 2009, 26(6): 17-19, 22.
	Yang Z, Ge F Y, Cai Z S. Investigation of the deepening action of organic silicon on cotton[J]. Textile Auxiliaries, 2009, 26(6): 17-19, 22.
36	Ma T T, Cao Y X, Chen H L. Synthesis and characterization of cationic carbon black pigment with quaternary ammonium groups and its dyeing properties for wool fabrics[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 549: 43-49.

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