纺织学报 ›› 2022, Vol. 43 ›› Issue (03): 103-109.doi: 10.13475/j.fzxb.20200903107

• 染整与化学品 • 上一篇    下一篇

烯丙基聚烷氧基环氧醚的制备及其性能

杨振声1,2(), 王炳帅2   

  1. 1.沈阳工业大学 石油化工学院, 辽宁 辽阳 111003
    2.辽宁科隆精细化工股份有限公司, 辽宁 辽阳 111013
  • 收稿日期:2020-09-15 修回日期:2021-12-30 出版日期:2022-03-15 发布日期:2022-03-29
  • 作者简介:杨振声(1985—),男,讲师,博士生。主要研究方向为环氧乙烷下游精细化工产品。E-mail: ssssjqrr@sina.com。

Preparation and performance of allyl polyalkoxy epoxy ether

YANG Zhensheng1,2(), WANG Bingshuai2   

  1. 1. School of Petrochemical Engineering, Shenyang University of Technology, Liaoyang, Liaoning 111003, China
    2. Liaoning Kelong Fine Chemical Co., Ltd., Liaoyang, Liaoning 111013, China
  • Received:2020-09-15 Revised:2021-12-30 Published:2022-03-15 Online:2022-03-29

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摘要：

针对烯丙基聚烷氧基环氧醚中存在催化剂和钾钠离子含量高,导致制备的三元共聚嵌段硅油反应活性差的问题,研究了在无相转移催化剂的条件下制备烯丙基聚烷氧基环氧醚的方法,表征了产物的结构,分析了制备条件对产物pH值与环氧指数的影响;以其为原料制备了三元共聚嵌段硅油,并对棉织物进行柔软整理,分析了整理后织物的亲水性、手感及物理力学性能。结果表明:当原料烯丙基聚氧乙烯醚、环氧氯丙烷和氢氧化钠的量比为1∶2.5∶1.5,冰醋酸的添加量是过量氢氧化钠的1.1倍时,产物烯丙基聚烷氧基环氧醚的环氧指数为1.77 mol/kg,pH值小于7,精制后钾钠离子含量可降低到5 μg/g以下;织物经过硅油整理后具有较好的亲水性,当整理液质量浓度为30 g/L时,毛效达到7.3 cm,手感评级达到4.7级以上,织物整体性能有所提高。

关键词: 柔软整理剂, 三元共聚嵌段硅油, 烯丙基聚烷氧基环氧醚, 无相转移, 毛效, 亲水性

Abstract:

Targeting at the poor reactive activity in preparing terpolymer block silicone oil caused by high contents of catalyst,potassium and sodium ions in allyl polyalkoxy epoxy ether, the preparation of allyl polyalkoxy epoxy ether without transfer catalyst was studied. The structure of the product was characterized, and the effect of preparation conditions on pH value and epoxy index of the product were analyzed. Terpolymer block silicone oil was prepared from it and was used to soften the fabric. And hydrophilicity, hand feeling, physical and mechanical properties of finished fabric were studied. The results show that when the molar ratio of raw material allyl polyoxyethylene oxide/ECH/sodium hydroxide is 1∶2.5∶1.5 and the amount of glacial acetic acid added is 1.1 times that of excessive base, the epoxy index is 1.77 mol/kg, the pH value is less than 7, and the content of potassium and sodium ions is reduced to less than 5 μg/g after refining. And the fabric has good hydrophilicity after finishing with silicone oil. The capillary effect reaches 7.3 cm and the fabric handle reaches grade 4.7 when the finishing liquid mass concentration is 30 g/L, and the overall performance of the fabric is improved.

Key words: softening agent, terpolymer block silicone oil, allyl polyalkoxy epoxy ether, non-phase-transfer, capillary effect, hydrophilicity

中图分类号: 

  • TS101

图1

相转移催化剂对产物环氧指数的影响"

图2

反应物的相转移过程"

表1

反应原料的量比对产物环氧指数的影响"

序号 反应原料的量/mol 环氧指数/
(mol·kg-1)
烯丙基聚氧乙烯醚 环氧氯丙烷 氢氧化钠
1 0.10 0.10 0.10 0.73
2 0.10 0.15 0.10 1.13
3 0.10 0.20 0.10 1.35
4 0.10 0.25 0.10 1.51
5 0.10 0.25 0.12 1.63
6 0.10 0.25 0.15 1.77
7 0.10 0.30 0.15 1.78
8 0.10 0.30 0.20 1.78

表2

冰醋酸加入量对产物pH值和不饱和度的影响"

序号 冰醋酸的量/mol 产物pH值 产物不饱和度/(mol·kg-1)
1 0.000 8.6 1.75
2 0.040 7.5 1.75
3 0.045 7.3 1.74
4 0.050 7.1 1.74
5 0.055 6.7 1.74
6 0.060 6.5 1.73
7 0.064 6.4 1.73

表3

磷酸加入量对产物pH值和不饱和度的影响"

序号 磷酸的量/mol 产物pH值 产物不饱和度/(mol·kg-1)
1 0.000 8.6 1.75
2 0.013 7.8 1.75
3 0.015 7.7 1.73
4 0.017 7.4 1.65
5 0.018 7.3 1.62
6 0.020 7.1 1.60
7 0.022 7.1 1.59

图3

磷酸与烯丙基聚烷氧基环氧醚的副反应过程"

表4

蒸馏水和吸附剂对K+和Na+的影响"

序号 蒸馏水质
量分数/%		 吸附剂质
量分数/%		 K+含量/
(μg·g-1)		 Na+含量/
(μg·g-1)
1 0 0 103 130.0
2 3 0.10 23 31.0
3 4 0.15 9 7.0
4 5 0.15 4 3.0
5 5 0.20 1 0.6

图4

烯丙基聚烷氧基环氧醚的红外光谱"

图5

烯丙基聚烷氧基环氧醚的核磁共振氢谱"

图6

整理液质量浓度对织物亲水性的影响"

表5

不同含氢硅油制备三元共聚嵌段硅油乳液的整理评级效果对比"

整理液质量浓度/
(g·L-1)		 手感评级/级
整理液a 整理液b
0 2.8 2.8
10 3.9 4.3
20 4.3 4.7
30 4.7 4.9
40 4.7 4.9

表6

由KES测试的织物基本物理力学性能指标"

样品 LT WT RT G 2HG 2HG5 B 2HB LC WC RC T0 W MIU MMD SMD
1 0.751 3 11.254 42.856 1.854 3.140 6.954 0.073 6 0.072 1 0.706 3 0.186 4 48.64 0.453 6 6.92 0.135 4 0.013 2 3.864 2
2 0.695 3 10.981 54.169 1.346 0.914 2.169 0.026 4 0.025 1 0.272 1 0.164 9 46.84 0.450 1 6.95 0.086 2 0.013 2 1.468 1
[1] 刘彦杰, 吴明华, 侯彦敏, 等. 超支化氨基改性聚硅氧烷的合成及其应用[J]. 纺织学报, 2014,35(12):73-79.
LIU Yanjie, WU Minghua, HOU Yanmin, et al. Synjournal and application of hyperbranched amino modified polysiloxane[J]. Journal of Textile Research, 2014,35(12):73-79.
doi: 10.1177/004051756503500108
[2] 王小娟. 有机硅柔软剂的发展及应用[J]. 印染, 2020,42(6):10-13.
WANG Xiaojuan. Development and application of silicone softener[J]. China Dyeing & Finishing, 2020,42(6):10-13.
[3] 鲁涛, 游奎一, 易兵, 等. 新型三元共聚嵌段硅油的合成及应用[J]. 印染, 2016,42(16):39-42.
LU Tao, YOU Kuiyi, YI Bing, et al. Synjournal and application of a new type terpolymer block silicone oil[J]. China Dyeing & Finishing, 2016,42(16) :39-42.
[4] YUAN W, CHENG Z, PENG C, et al. Synjournal of multiblock linear polyether functional amino silicone softener and its modification of surface properties on cotton fabrics[J]. Polymer Bulletin, 2019,76(1):447-467.
doi: 10.1007/s00289-018-2375-1
[5] JASON P M, WAKE F, JACOB W, et al. Method for enzymatic treatment of wool: US, 6051033[P]. 2000-04-18.
[6] MOHAMMAD M A, AMIN J, REZA T, et al. Processing and performance properties of amino silicone-based softener on various textile substrates[J]. Polymer Bulletin, 2020,77(5):2557-2572.
doi: 10.1007/s00289-019-02877-x
[7] 王娟, 宋秘钊, 刘玉龙. 有机硅柔软剂的研究进展[J]. 应用化工, 2020,49(2):458-461.
WANG Juan, SONG Mizhao, LIU Yulong. Research progress of silicone softeners[J]. Applied Chemical Industry, 2020,49(2):458-461.
[8] 王小娟. 聚醚改性有机硅柔软剂的合成[J]. 轻纺工业与技术, 2020,49(9):6-8.
WANG Xiaojuan. Synjournal of polyether modified organosilicone softener[J]. Light and Textile Industry and Technology, 2020,49(9):6-8.
[9] 王彦珍, 宋秘钊, 王娟, 等. 氨基聚醚改性硅油柔软剂在亚麻织物上的应用[J]. 棉纺织技术, 2021,49(10):38-41.
WANG Yanzhen, SONG Mizhao, WANG Juan, et al. Application of amino polyether modified silicone oil softener on flax fabric[J]. Cotton Textile Technology, 2021,49(10):38-41.
[10] 于岩, 章若红, 钟毅, 等. 用气相色谱-质谱法测定纺织柔软剂中的环硅氧烷[J]. 纺织学报, 2020,41(8):69-73.
YU Yan, ZHANG Ruohong, ZHONG Yi, et al. Determination of cyclicsilicates in textile softeners by gas chromatography-mass spectrometry[J]. Journal of Textile Research, 2020,41(8):69-73.
[11] 陈焜, 周向东. 有机硅柔软剂的结构、性能、表征及其吸附模型[J]. 印染助剂, 2019,36(9):7-12.
CHEN Kun, ZHOU Xiangdong. Structure, performance, characterization and adsorption model of silicone softener[J]. Textile Auxiliaries, 2019,36(9):7-12.
[12] CZECH A M, PAVLENYI J, SABIA A J. Modified silicone softeners for fluorocarbon soil release treatments[J]. Textile Chemist and Colorist, 1997,29(9):26-29.
[13] 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):1-7.
MA Xianqi, YIN Hong, YUAN Shenfeng, et al. Study on progress of working model of amino silicone softener[J]. Textile Auxiliaries, 2011,28(8):1-7.
[14] 鲁涛, 游奎一, 易兵, 等. 新型三元共聚嵌段硅油的合成及应用研究[J]. 纺织科技进展, 2016(8):15-18.
LU Tao, YOU Kuiyi, YI Bing, et al. Synjournal and application of a new type terpolymer block silicone[J]. Progress in Textile Science and Technology, 2016(8):15-18.
[15] 周勇. 三元嵌段有机硅柔软剂的制备及其在纺织品上的应用[D]. 广州:华南理工大学, 2017:4-6.
ZHOU Yong. Preparation of ternary block silicone softener and its application in textiles[D]. Guangzhou: South China University of Technology, 2017:4-6.
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