支链型硅烷、聚醚烷基共改性硅油乳化剂的制备及性能研究

doi:10.3969/j.issn.1001-1803.2019.09.003

摘要/Abstract

摘要：

以乙烯基三乙氧基硅烷和三甲基乙氧基硅烷为原料水解缩合得到了乙烯基三（三甲基硅氧烷基）硅烷（即支链型硅烷）。以含氢硅油、支链型硅烷、烯丙基聚醚及1-十二烯为原料,氯铂酸为催化剂,异丙醇为溶剂,合成了共改性硅油乳化剂,并对产物结构进行了红外和核磁表征。研究了温度、时间、催化剂用量、物料比等因素对共改性硅油乳化剂转化率的影响及其结构对油包水乳液稳定性的影响。结果表明,95 ℃下反应5 h,催化剂用量0.20%,物料比n（Si-H）∶n（混合物组成的C=C）=1∶1.1时合成的有机硅乳化剂,转化率高达94.97%;当乳化剂HLB=5,疏水基接枝比为n（支链型硅烷）∶n（烷基）=25∶75时,可以制备硅油、酯油和烃油为混合油相的稳定油包水乳液。

关键词: 硅油乳化剂, 硅氢加成, 油包水乳液

Abstract:

The vinyltris（trimethylsiloxy）silane（branched-silicone）was synthesized by the hydrolytic condensation of triethoxyvinylsilane and ethoxytrimethylsilane. The modified silicone emulsifier was synthesized through hydrosilylation reactions, using hexachloroplatinic acid as catalyst, isopropanol as solvent, and polymethylhydrosiloxane, vinyltris（trimethylsiloxy）silane, allyl polyther and 1-dodecene as raw materials. The structure of the modified silicone was characterized by ¹H NMR and FT-IR. The effects of reaction temperature（T）, time（t）, catalyst dosage and material ratio on the conversion were investigated. The effects of the structure of modified silicone emulsifier on the stability of water-in-oil emulsion was also studied. The results show that the conversion is 94.97% when T=95 ℃, t=5 h, the catalyst dosage of 0.20% and n（Si-H）∶n（C=C content of the mixture）=1∶1.1. When the HLB value of the emulsifier is equal to 5 and n（branched-silicone）∶n（alkyl）=25∶75, stable water-in-oil emulsion can be prepared by using the mixed oil phase composed of silicone oil, ester oil and hydrocarbon oil.

Key words: silicone emulsifier, hydrosilylation, water-in-oil emulsion

中图分类号:

TQ423

何彤,杨成. 支链型硅烷、聚醚烷基共改性硅油乳化剂的制备及性能研究[J]. 日用化学工业, 2019, 49(9): 572-578.

HE Tong,YANG Cheng. Synthesis and properties of the modified silicone emulsifier with branched-silicone-polyether and alkyl group[J]. China Surfactant Detergent & Cosmetics, 2019, 49(9): 572-578.

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参考文献 14

[1]	Wang Anqi, Guo Rui, Yang Xu , et al. Synjournal of long-chain alkyl and polyether modified polysiloxane and its application in defoamer[J]. Textile Auxiliaries, 2014,31(10) : 20-23.
[2]	He Ting, Ji Yongxin . Synjournal and properties of polyether modified silicone surfactant[J]. Chemistry and Adhesion, 2013,35(4) : 10-13.
[3]	Wang Min, Guo Rui . Synthesis and application of long chain alkyl ester and polyther modified silicone oil[D]. Xi’an: Shaanxi University of Science & Technology, 2015.
[4]	Huang Wenrun . Branched silicone[J]. Silicone Material, 2005,19(1) : 36-39.
[5]	Huang Wenrun . MT siloxane oilgomers and polysiloxane containing MT structure (I)[J]. Silicone Material, 2015,29(5) : 403-410.
[6]	Kong Fanzhen, Yang Tiantian, Li Hanghang. Synpatent of vinyl tris(dimethylsiloxy) silane:108069995[P] .2018-05-25.
[7]	Tetsuo Nakanishi, Ichiro Ono . Silicone compound and cosmetic materials containing the same: 6576623 B1[P]. 2003-06-10.
[8]	Lv Ximing, Yang Cheng . Preparation of silicone elastomer microspheres coated by nano-SiO₂[J]. Silicone Material, 2018,32(1) : 16-22.
[9]	Wang Chunyan, An Qiufeng, Gao Tongluo . Synjournal and characterization of silicone oil modified by long alkyl ester and (poly) ether containing epoxy groups[J]. Fine Chemicals, 2014,31(1) : 132-136.
[10]	Chen Jian, Wu Guojie, Zhao Mouming. Principle of food chemistry[M]. Guang Zhou: South China University of Technology Press, 2015: 46-47.
[11]	Yang Lichao, Jia Xiaolong, Chen Xiangming . Stability test on the products using new high internal phase W/O emulsifier A-7[J]. Materials Research and Application, 2008,2(2) : 155-157.
[12]	Chang Jinhua, Xue Hefei . Preparation of diosgenin nanosuspensions[J]. Chinese Traditional Patent Medicine, 2017,39(9) : 1819-1823.
[13]	Li Chunjing, Lu Yihe, Gong Suzhi . Synjournal of polyther modified polysiloxan deforming agent[J]. China Surfactant Detergent & Cosmetics, 2006,36(5) : 284-293.
[14]	Meng Shengnan, Hu Rongfeng. Pharmaceutical chemistry experimental guidance[M]. Bei Jing: China Medical Science Press, 2016: 15-16.

	原料	w/%
油相	硅油	7.67
	GTCC	7.67
	异十二烷	7.67
	改性硅油乳化剂	2.00
水相	去离子水	至100
	NaCl	0.50
	1,3-丁二醇	6.00

序号	反应温度/ ℃	时间/h	催化剂用量/%	n（Si-H）∶ n（C=C）	转化率/%
1	85	4	0.10	1∶1.05	77.84
2	85	5	0.15	1∶1.1	86.76
3	85	6	0.20	1∶2	83.73
4	90	4	0.15	1∶2	86.98
5	90	5	0.20	1∶1.05	88.98
6	90	6	0.10	1∶1.1	89.77
7	95	4	0.20	1∶1.1	92.29
8	95	5	0.10	1∶2	93.65
9	95	6	0.15	1∶1.05	89.29
均值K₁	85.75	85.70	87.08	85.37	-
均值K₂	88.58	89.80	87.68	89.61	-
均值K₃	91.74	87.60	88.34	88.12	-
极差R	5.99	4.10	1.25	4.24	-
主次顺序	A>D>B>C
最优方案	A₃B₂C₃D₂

物质	σ/cm^-1	红外峰归属
含氢硅油	2 950~2 873	-CH₃、-CH₂伸缩振动
	2 150	Si-H伸缩振动
	1 120~1 031	Si-O-Si伸缩振动
乙烯基三（三甲基硅氧烷基）硅烷	1 605	C=C伸缩振动
	1 250	Si-（CH₃） ₃非对称伸缩振动
	1 054~1 013	Si-O-Si伸缩振动
	794	Si-C伸缩振动
共改性硅油	3 492	-OH伸缩振动
	2 960~2 865	-CH₃、-CH₂伸缩振动
	1 090~1 013	C-O-C、Si-O-Si伸缩振动
	757	-CH₂面内摇摆

HLB值	粒径/μm	PDI
4	5.3±0.9	1.17±0.08
5	4.8±0.7	1.06±0.01
6	5.5±1.1	1.09±0.04
7	7.7±1.5	1.33±0.13

n（支链硅）∶n（烷基）	油相
	硅油			异十二烷
	外观	粒径/μm	PDI	外观	粒径/μm	PDI
100/0	稳定	5.4±0.4	1.04±0.01	分水	-	-
75/25	稳定	6.2±0.9	1.09±0.03	分油	8.6±2.1	1.31±0.11
50/50	稳定	6.7±0.9	1.13±0.07	稳定	7.1±1.1	1.18±0.06
25/75	稳定	6.8±1.0	1.15±0.07	稳定	5.5±0.9	1.07±0.03
0/100	分油	8.9±1.8	1.32±0.12	稳定	5.1±0.7	1.06±0.02