三甲基硅基普鲁兰多糖的制备与性能

doi:10.3969/j.issn.1001-1803.2020.11.005

摘要/Abstract

摘要：

以N,O-双（三甲基甲硅烷基）乙酰胺（BSA）作为甲硅烷基化试剂,合成了三甲基硅基普鲁兰多糖,并用红外、核磁及XPS表征。当n（P-OH）:n（BSA）=9:15时,取代度高达2.89。三甲基硅基普鲁兰多糖具有优异的成膜性,膜的拉伸强度及断裂伸长率随取代度增加而降低,但当取代度超过1.55时,不再随取代度增加而下降。随取代度的增加,膜与水及皮脂的接触角随之增大,疏水的同时有一定的抗皮脂性。三甲基硅基普鲁兰多糖能乳化水相形成油包水乳液,研究了取代度和油相种类对乳化性能的影响,表明取代度为1.91,乳化性能最佳。对比乳化剂EM90形成的乳液,虽然三甲基硅基普鲁兰多糖形成乳液的粒径较大,但乳液黏度高,稳定性更好。

关键词: 甲硅烷基化, 改性普鲁兰多糖, 成膜, 油包水乳液, 化妆品添加剂

Abstract:

Trimethylsilyl pullulan was synthesized using N, O-bis（trimethylsilyl）acetamide （BSA） as the silylation agent. The structure of the modified pullulan was characterized by ¹H NMR, FT-IR and XPS. When n（P-OH）:n（BSA） was 9:15, the degree of substitution（DS） was as high as 2.89. Trimethylsilyl pullulan has excellent film-forming properties. The tensile strength and elongation at break of the film decrease with the increase of DS, but this phenomenon disappears when the DS is above 1.55. As the DS increases, the contact angle of the membrane with water and sebum increases, and the hydrophobic film has a certain degree of sebum resistance. Trimethylsilyl pullulan can emulsify the water phase to form a water-in-oil emulsion. The effects of DS and the type of oil phase on emulsification properties were studied. It shows that when the DS is 1.91, the emulsification performance is the best. Compared with the emulsion stabilized by EM90, although the size of emulsion stabilized by trimethylsilyl pullulan is larger, it has higher viscosity and better stability.

Key words: silylation, modified pullulan, film-forming, water-in-oil emulsion, cosmetic additives

中图分类号:

TQ658

姬迎迎,杨成. 三甲基硅基普鲁兰多糖的制备与性能[J]. 日用化学工业, 2020, 50(11): 762-770.

JI Ying-ying,YANG Cheng. Preparation and properties of trimethylsilyl pullulan[J]. China Surfactant Detergent & Cosmetics, 2020, 50(11): 762-770.

图/表 14

表 1

图 1

图 2

图 3

图 4

表 2

图 5

图 6

图 7

图 8

图 9

图 10

图 11

图 12

参考文献 20

[1]	Sroková I, Tomanová V, Ebringerová A, et al. Water-soluble amphiphilic o-(carboxymethyl) cellulose derivatives-synjournal and properties[J]. Macromolecular Materials and Engineering, 2004,289(1): 63-69. doi: 10.1002/(ISSN)1439-2054
[2]	Prochaska K, Kędziora P, Le Thanh J, et al. Surface activity of commercial food grade modified starches[J]. Colloids and Surfaces B: Biointerfaces, 2007,60(2): 187-194. doi: 10.1016/j.colsurfb.2007.06.005 pmid: 17644351
[3]	Sun Fangyan, Wang Meng, Wang Jianzi, et al. Hygroscopicity, moisture retention and viscosity stability of pullulan polysaccharides[J]. Journal of Tianjin University of Science & Technology, 2016,31(4): 20-24.
[4]	Kanmani P, Lim S T. Development and characterization of novel probiotic-residing pullulan/starch edible films[J]. Food Chemistry, 2013,141(2): 1041-1049. doi: 10.1016/j.foodchem.2013.03.103
[5]	Niu B, Shao P, Chen H, et al. Structural and physiochemical characterization of novel hydrophobic packaging films based on pullulan derivatives for fruits preservation[J]. Carbohydrate Polymers, 2019,208:276-284. doi: 10.1016/j.carbpol.2018.12.070 pmid: 30658801
[6]	Shah N N, Vishwasrao C, Singhal R S, et al. n-Octenyl succinylation of pullulan: Effect on its physico-mechanical and thermal properties and application as an edible coating on fruits[J]. Food Hydrocolloids, 2016,55:179-188. doi: 10.1016/j.foodhyd.2015.11.026
[7]	Zhao Z, Xiong X, Zhou H, et al. Effect of lactoferrin on physicochemical properties and microstructure of pullulan‐based edible films[J]. Journal of the Science of Food and Agriculture, 2019,99(8): 4150-4157. doi: 10.1002/jsfa.9645 pmid: 30767229
[8]	Uchida S, Yamamoto A, Fukui I, et al. Siloxane-containing pullulan and method for the preparation thereof: US5583244 [P]. 1996-12-10.
[9]	Kikuchi H. Oil-based thickening agent, oil-based thickening composition, and cosmetic preparation: US14/889733 [P]. 2016-04-28.
[10]	Masato Izume. Process for producing silylated pullulan and cosmetic preparation: US9125837B2 [P]. 2015-09-08.
[11]	Fujiyama N, Yoda Y, Miyazawa K, et al. Oily cosmetic: US15/329081 [P]. 2017-08-10.
[12]	Cécile Nouvel, Philippe Dubois, Edith Dellacherie, et al. Silylation reaction of dextran: Effect of experimental conditions on silylation yield, regioselectivity, and chemical stability of silylated dextrans[J]. Biomacromolecules, 2003,4(5): 1443-1450. doi: 10.1021/bm034119m pmid: 12959617
[13]	He Tong, Yang Cheng. Preparation and properties of branched silane, polyether alkyl co-modified silicone oil emulsifier[J]. China Surfactant Detergent & Cosmetics, 2019,49(9): 572-578.
[14]	Yan Meiling. Preparation of nano cellulose by anhydrous phosphoric acid and modification by acetylation[D]. Haerbin: Northeast Forestry University, 2015.
[15]	Jiang Chao. Study on fully degraded amphiphilic graft copolymer based on hydroxyethyl cellulose[D]. Wuxi: Jiangnan University, 2008.
[16]	Jia Xue. Preparation and properties of maize starch-based film materials[D]. Wuxi: Jiangnan University, 2018.
[17]	Xing Songmin, Wang Yilu. Synthesis technology and product application of organic silicon [M]. Beijing: Chemical Industry Press, 2000: 818-821.
[18]	Bruneel D, Schacht E, Bruyn A D. Structural analysis of succinoylated and chloroformate activated pullulan: NMR study in DMSO solution[J]. Journal of Carbohydrate Chemistry, 1993,12(6): 769-778. doi: 10.1080/07328309308019006
[19]	He Tong. Synthesis and properties of modified branched silicone emulsifier[D]. Wuxi: Jiangnan University, 2019.
[20]	Jin Qiangwei. Comparative study of natural polymer emulsifiers[D]. Shanghai: Shanghai Jiaotong University, 2017.

原料		质量分数/%
油相	5黏硅油	7.67
	15号白油	7.67
	异十二烷	7.67
	乳化剂	2.00
水相	去离子水	至100.00
	NaCl	1.00
	甘油	6.00

样品（取代度）	PBSA3（0.06）	PBSA6（1.55）	PBSA9（1.91）	PBSA15（2.89）
水	+	–	–	–
DMSO	+	–	–	–
DMF	+	○	○	○
甲苯	○	+	+	+
丙酮	–	+	+	○
四氯化碳	–	+	+	+
乙酸乙酯	–	+	+	+
四氢呋喃	○	+	+	+
吡啶	+	+	+	○
甲醇	○	○	–	–
异丙醇	○	+	+	+
正己烷	–	+	+	+
液体石蜡	–	+	+	+
异十二烷	–	+	+	+
角鲨烷	–	○	+	+
D5	–	○	+	+
5黏硅油	–	○	+	+
GTCC	–	+	+	○
霍霍巴油	–	○	○	–