化工学报 ›› 2021, Vol. 72 ›› Issue (5): 2837-2848.doi: 10.11949/0438-1157.20201235

• 材料化学工程与纳米技术 • 上一篇    下一篇

多羟基Bola有机硅季铵盐的合成、表征及其应用性能

程文静1(),余林1(),程高1,钟远红1,郑成2,毛桃嫣2   

  1. 1.广东工业大学轻工化工学院,广东省教育厅清洁化学技术重点实验室,广东 广州 510006
    2.广州大学精细化工研究所,广东 广州 510006
  • 收稿日期:2020-08-28 修回日期:2020-12-28 出版日期:2021-05-05 发布日期:2021-05-05
  • 通讯作者: 余林 E-mail:chengwj609@126.com;gych@gdut.edu.cn
  • 作者简介:程文静(1984—),女,博士研究生,chengwj609@126.com
  • 基金资助:
    国家自然科学基金项目(21808044)

Synthesis characterization and application of Bola silicone quaternary ammonium salt

CHENG Wenjing1(),YU Lin1(),CHENG Gao1,ZHONG Yuanhong1,ZHENG Cheng2,MAO Taoyan2   

  1. 1.Key Laboratory of Clean Chemistry Technology of Guangdong Regular Higher Education Institutions, School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, 510006, Guangdong, China
    2.Institute of Fine Chemical Engineering, Guangzhou University, Guangzhou 510006, Guangdong, China
  • Received:2020-08-28 Revised:2020-12-28 Published:2021-05-05 Online:2021-05-05
  • Contact: YU Lin E-mail:chengwj609@126.com;gych@gdut.edu.cn

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

图1

BPTSO的合成路线"

表1

不同季铵化试剂对PTSO的转化率"

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"

表2

正交实验因素水平表"

水平A(反应温度)/℃B(反应物摩尔比)C(反应时间)/h
1601∶12
2701∶1.13
3801∶1.24

表3

正交实验方案与结果"

实验号ABC转化率/%
1601∶1.0296.11
2601∶1.1397.83
3601∶1.2496.72
4701∶1.0398.03
5701∶1.1496.74
6701∶1.2298.04
7801∶1.0498.27
8801∶1.1298.00
9801∶1.2398.22
K1290.66292.15292.41
K2292.81292.57294.08
K3294.49292.98291.73
k196.8997.4797.38
k297.6097.5297.03
k397.1697.6697.24
极差R3.830.572.35
因素主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)"

图4

BPSTO和ATSO乳液的TEM、粒径分布和BPTSO的γ-lgc曲线"

图5

BPSTO乳液的稳定性"

图6

BPTSO乳液整理后织物的柔软性能(a)和抗黄变性能(b)"

图7

BPTSO乳液整理后织物的SEM图"

图8

BPTSO乳液整理后棉(a)和涤纶(b)的亲水性"

图9

BPTSO乳液对棉织物的固色效果"

图10

BPTSO乳液的放大生产"

表4

BPTSO乳液放大产品指标"

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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