Synthesis characterization and application of Bola silicone quaternary ammonium salt

doi:10.11949/0438-1157.20201235

Abstract

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

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

CLC Number:

TQ 317.4

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.

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.

Figures/Tables 14

Fig.1 Synthesis route of Bola silicone quaternary ammonium salts

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

Fig.2 Conversion rate of PTSO with different reaction conditions

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

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%

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

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

Fig.5 Stability of BPTSO emulsion

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

Fig.7 SEM images of fabrics treated with BPTSO

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

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

Fig.10 Amplification production of BPTSO emulsion

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

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