蛋白基表面活性剂的合成、性能与应用进展

doi:10.16085/j.issn.1000-6613.2016-2275

摘要/Abstract

摘要： 蛋白基表面活性剂是一类环境友好的生物质基表面活性剂，具有良好的表面活性，与传统表面活性剂相比，还具有低毒、易生物降解等特性。本文首先讨论了基于胶原蛋白、丝蛋白、角蛋白等动物蛋白水解物制备表面活性剂的方法，其中重点阐述了分子量和水解方法对作为表面活性剂亲水端的胶原蛋白水解物性质的影响，以及分别以脂肪碳链和硅氧烷链为疏水端的胶原基表面活性剂的合成方法。随后，总结并比较了蛋白基表面活性剂的表面张力、临界胶束浓度、起泡力和乳化力等表面性质。依据蛋白基表面活性剂的表面性质和环境友好等特性，介绍了它们在制革印染、日用化工、生物医药等领域的应用。最后，指出了蛋白基表面活性剂制备和应用中存在的一些问题，对新型表面活性剂（如Bola型、Gemini型）发展方向进行了展望。

关键词: 胶原, 角蛋白, 丝蛋白, 表面活性剂, 合成

Abstract: Protein based surfactants,a class of environmental-friendly biomass-based surfactants,possess excellent surface active properties and particular performances including low toxicity and easy biodegradability compared with traditional surfactants.This article firstly discussed the methods of synthesizing protein based surfactants,based on hydrolysates of animal proteins such as collagen,silk protein and keratin.This part was focused on the influence of molecular weight and hydrolysis methods on the properties of collagen hydrolysate as hydrophilic domains,and methods for preparing collagen based surfactants using hydrocarbon chain or siloxane chain as hydrophobic domains.Then,their surface properties were summarized and compared,such as surface tension,critical micell concentration,foaming and emulsifying properties.And the diverse applications in the fields of leather manufacturing,printing and dyeing,daily chemicals and biological medicine were also introduced on the basis of their surface properties and environmental-friendly features.Finally,some issues of preparation and application of protein based surfactants were pointed out,and in particular the developing trends in the new type surfactants,such as Bola and Gemini,were prospected.

Key words: collagen, keratin, silk protein, surfactants, synthesis

中图分类号:

TQ423

汪保川, 李宇鹏, 戴国琛, 李正军, 杨秦欢. 蛋白基表面活性剂的合成、性能与应用进展[J]. 化工进展, 2017, 36(07): 2607-2614.

WANG Baochuan, LI Yupeng, DAI Guochen, LI Zhengjun, YANG Qinhuan. Synthesis，properties and application of protein based surfactants:a review[J]. Chemical Industry and Engineering Progress, 2017, 36(07): 2607-2614.

参考文献

[1] 张腾,徐宝财,周雅文,等. 特种表面活性剂和功能性表面活性剂(Ⅶ)——生物表面活性剂的性能及应用研究进展[J]. 日用化学工业,2010,40(1):60-63. ZHANG T,XU B C,ZHOU Y W,et al. Special surfactants and functional surfactants (Ⅶ)——progress in properties and applications of biosurfactants[J]. China Surfactant Detergent & Cosmetics,2010,40(1):60-63.
[2] 宋湛谦,周永红. 利用生物质资源,发展表面活性剂[J]. 精细与专用化学品,2005,13(20):1-3. SONG Z L,ZHOU Y H. Development of surfactants utilizing biomass resources[J]. Fine and Specialty Chemicals,2005,13(20):1-3.
[3] VON RYBINSKI W, HILL K. Alkyl polyglycosides-properties and applications of a new class of surfactants[J]. Angewandte Chemie International Edition,1998,37(10):1328-1345.
[4] 李凯宇,王亚明,蒋丽红. 松香胺类衍生物在非表面活性剂方面的应用研究[J]. 化学通报,2015,6:513-517. LI K Y,WANG Y M,JIANG L H. Application of rosin amine derivatives in terms of non-surfactant[J]. Chemistry,2015,6:513-517.
[5] FOLEY P,BEACH E S,ZIMMERMAN J B. Derivation and synthesis of renewable surfactants[J]. Chemical Society Reviews,2012,41(4):1499-1518.
[6] 李红. N-月桂酰肌氨酸钠的合成与性能研究[D]. 厦门:厦门大学,2004. LI H. Preparation and properties of sodium N-lauroyl sarcosinate[D]. Xiamen:Xiamen University,2004.
[7] 关蕊,黄雅钦,黄明智. 明胶基表面活性剂[J]. 明胶科学与技术,2002,22(3):147-154. GUAN R,HUANG Y Q,HUANG M Z. Gelatin based surfactants[J]. The Science and Technology of Gelatin,2002,22(3):147-154.
[8] 汤克勇. 胶原物理与化学[M]. 北京:科学出版社,2012:406-460. TANG K Y. Physics and chemistry of collagen[M]. Beijing:Science Press,2012:406-460.
[9] 张忠楷. 胶原,明胶和胶原水解物的物理化学性能及护肤功能的研究[D]. 成都:四川大学,2006. ZHANG Z K. Study of physicochemical properties and skin-care functions of collagen,gelatin and collagen hydrolysate[D]. Chengdu:Sichuan University,2006.
[10] 张雪青,曾运航,廖学品,等. 相对分子质量对水解胶原性能的影响[J]. 皮革科学与工程,2015,25(3):11-16. ZHANG X Q,ZENG Y H,LIAO X P,et al. Effect of molecular weight of collagen hydrolysates on their properties[J]. Leather Science and Engineering,2015,25(3):11-16.
[11] 侯小东,章川波. 胶原的水解方法及其水解状况的检测[J]. 皮革科学与工程,2005,15(1):35-40. HOU X D,ZHANG C B. Methods of hydrolyzing collagen and measuring the state of hydrolysis[J]. Leather Science and Engineering,2005,15(1):35-40.
[12] 程海明,陈敏,李志强. 胶原及皮革等电点的表征方法综述[J]. 皮革科学与工程,2012,22(4):20-24. CHENG H M,CHEN M,LI Z Q. Review of the determination methods of the isoelectric point of collagen and leather[J]. Leather Science and Engineering,2012,22(4):20-24.
[13] 王堃,郑学晶,孟卓君,等. 影响胶原结构与性能的因素研究进展[J]. 化工进展,2010,29(1):88-93. WANG K,ZHENG X J,MENG Z J,et al. Factors that influence the structure and properties of collagen materials[J]. Chemical Industry and Engineering Progress,2010,29(1):88-93.
[14] 李贺,刘白玲,陈华林,等. 酶法提取猪皮胶原及其结构表征[J]. 中国皮革,2002,31(23):14-16. LI H,LIU B L,CHEN H L,et al. Preparation of pepsin-soluble collagen from pig skin and its characterization[J]. China Leather,2002,31(23):14-16.
[15] 李彦春,祝德义,侯立杰,等. 酶解胶原蛋白多肽的制备与分析[J]. 中国皮革,2004,33(5):22-26.LI Y C,ZHU D Y,HOU L J,et al. Preparation and analysis of the production of collagen hydrolysate from hides by enzymes[J]. China Leather,2004,33(5):22-26.
[16] 王碧,王坤余,叶勇,等. 水解胶原蛋白的溶解性和乳化性研究[J]. 皮革化工,2003,20(1):5-8. WANG B,WANG K Y,YE Y,et al. Study on functional properties of collagen from hide offal[J]. Leather Chemicals,2003,20(1):5-8.
[17] 迟原龙,崔敏,廖学品,等. 胶原多肽基表面活性剂合成工艺的优化[J]. 中国皮革,2011,40(23):8-11. CHI Y L,CUI M,LIAO X P,et al. Optimization of reaction parameters for synthesis of collagen-peptide based surfactant[J]. China Leather,2011,40(23):8-11.
[18] 秦树法,王芳,汤克勇,等. 利用水解胶原蛋白制备多肽酰胺表面活性剂[J]. 中国皮革,2013,42(9):13-15. QIN S F,WANG F,TANG K Y,et al. Preparation of polyamide surfactant with collagen hydrolysate from tannery solid wastes[J]. China Leather,2013,42(9):13-15.
[19] LI C,LIU W,DUAN L,et al. Surface activity of pepsin-solubilized collagen acylated by lauroyl chloride along with succinic anhydride[J]. Journal of Applied Polymer Science,2014,131(14):40174.1-40174.8.
[20] 梁育松,刘文涛,李国英. 一种保留胶原天然结构的新型生物表面活性剂的性能表征[J]. 皮革科学与工程,2014,24(6):5-9. LIANG Y S,LIU W T,LI G Y. Characterization of a novel biosurfactant based on collagen retaining its native structure[J]. Leather Science and Engineering,2014,24(6):5-9.
[21] 韩富,刘志妍,周雅文,等. 特种表面活性剂和功能性表面活性剂(Ⅲ)——有机硅表面活性剂的合成与性能[J]. 日用化学工业,2009,39(2):133-137. HAN F,LIU Z Y,ZHOU Y W,et al. Special surfactants and functional surfactants(Ⅲ)——preparation and properties of organic silicone surfactants[J].China Surfactant Detergent & Cosmetics,2009,39(2):133-137.
[22] 韩晓娜,杜卫宁,李宇鹏,等. 有机硅改性天然蛋白纤维的研究进展[J]. 皮革科学与工程,2015,25(2):23-26. HAN X N,DU W N,LI Y P,et al. Research progress of organic silicone modified natural protein fibers[J]. Leather Science and Engineering,2015,25(2):23-26.
[23] 韩晓娜,杜卫宁,李宇鹏,等. 胶原基有机硅表面活性剂的性能研究[J]. 日用化学工业,2015,45(9):481-484. HAN X N,DU W N,LI Y P,et al. Performance of collagen hydrolysate-based silicone surfactant[J]. China Surfactant Detergent & Cosmetics,2015,45(9):481-484
[24] HAN F,DENG Y,ZHOU Y,et al. Carbohydrate-modified silicone surfactants[J]. Journal of Surfactants and Detergents,2012,15(2):123-129.
[25] 韩富,陈艳红,周雅文,等. 糖苷改性三硅氧烷表面活性剂及保湿性能[J]. 精细化工,2012,29(4):318-321. HAN F,CHEN Y H,ZHOU Y W,et al. Glycoside-based trisiloxane surfactant and its moisturization[J]. Fine Chemicals,2012,29(4):318-321.
[26] SILVA N H C S,VILELA C,MARRUCHO I M,et al. Protein-based materials:from sources to innovative sustainable materials for biomedical applications[J]. Journal of Materials Chemistry B,2014,2(24):3715-3740.
[27] CAO T T,ZHANG Y Q. Processing and characterization of silk sericin from Bombyx mori and its application in biomaterials and biomedicines[J]. Materials Science and Engineering:C,2016,61:940-952.
[28] 经纬,李军生,黄国霞,等. 羧甲基丝素的制备工艺优化及其乳化性能[J]. 应用化学,2012,30(1):73-78. JING W,LI J S,HUANG G X,et al. Optimized preparation and emulsifying properties of carboxymethyl silk fibroin[J]. Chinese Journal of Applied Chemistry,2012,30(1):73-78.
[29] 程海涛,李军生,韦飞. 乙酰化丝素蛋白基表面活性剂的合成[J]. 食品科学,2009(20):241-245. CHENG H T,LI J S,WEI F. Synthesis of acetylated silk protein surfactant[J]. Food Science,2009(20):241-245.
[30] 汪钊,强西怀,夏庆友,等. 利用废弃蚕丝制备蛋白基表面活性剂的工艺技术[J]. 蚕业科学,2013,4:778-782. WANG Z,QIANG X H,XIA Q Y,et al. Preparation technology of protein-based surfactant using waste natural silk[J]. Science of Sericulture,2013,4:778-782.
[31] 冯艳妮. 丝肽基表面活性剂的合成和性能研究[D]. 苏州:苏州大学,2010. FENG Y N. Research on the synthesis and properties of silk peptide-based surfactant[D]. Suzhou:Soochow University,2010.
[32] WU M H,ZHANG Y Q. Nanofiltration recovery of sericin from silk processing waste and synthesis of a lauroyl sericin-based surfactant and its characteristics[J]. RSC Advances,2014,4(8):4140-4145.
[33] WANG F,CAO T T,ZHANG Y Q. Effect of silk protein surfactant on silk degumming and its properties[J]. Materials Science and Engineering:C,2015,55:131-136.
[34] 贾如琰,何玉凤,王荣民,等. 角蛋白的分子构成,提取及应用[J]. 化学通报,2008,71(4):265-271. JIA R Y,HE Y F,WANG R M,et al. Advanced in structure,extract and applications of keratins[J]. Chemistry,2008,71(4):265-271
[35] 强西怀,冯洪燕,张辉. 利用废弃羊毛制备蛋白型表面活性剂[J]. 皮革与化工,2010(6):6-8. QIANG X H,FENG H Y,ZHANG H. Preparation of protein-surfactant with waste wool[J]. Leather and Chemicals,2010(6):6-8.
[36] 季益梅. 羽毛角蛋白的提取及近临界水解制备表面活性剂[D]. 上海:上海大学,2015. JI Y M. Study on extraction of keratin from poultry feather and hydrolysis of the keratin to prepare peptide surfactant in sub-critical water[D]. Shanghai:Shanghai University,2015.
[37] 梁育松,刘文涛,李国英. 月桂醛和琥珀酸酐接枝改性天然胶原所得产物的表面活性[J]. 精细化工,2015,32(8):858-862. LIANG Y S,LIU W T,LI G Y. Surface activity of the product from native collagen graft modified by lauric aldehyde and succinic anhydride[J]. Fine Chemicals,2015,32(8):858-862.
[38] 杨威特,陈武勇,张小燕,等. 相对分子质量分布对水解蛋白质型表面活性剂性质的影响[J]. 皮革科学与工程,2009,19(1):9-14. YANG T W,CHEN W Y,ZHANG X Y,et al. The effect of the molecular weight distribution on the properties of collagen hydrolysate surfactant[J]. Leather Science and Engineering,2009,19(1):9-14.
[39] CHI Y L,ZHANG Q X,LIAO X P,et al. Physicochemical properties and surface activities of collagen hydrolysate-based surfactants with varied oleoyl group grafting degree[J]. Industrial & Engineering Chemistry Research,2014,53(20):8501-8508.
[40] 李从虎,田振华,刘文涛,等. 同步荧光光谱技术研究胶原基表面活性剂溶液中分子的聚集行为[J]. 光谱学与光谱分析,2016,36(1):151-156. LI C H,TIAN Z H,LIU W T,et al. Aggregation behavior of collagen-based surfactant molecules in aqueous solution based on synchronization fluorescence spectrum technology[J]. Spectroscopy and Spectral Analysis,2016,36(1):151-156.
[41] 李正军. 皮革制造用表面活性剂发展动态[J]. 西部皮革,2006,28(10):23-27. LI Z J. Process of surfactants applied in leather manufacturing[J]. West Leather,2006,28(10):23-27.
[42] 王杰兴,王全杰,曲家乐,等. 蛋白基表面活性剂的合成及性能研究[J]. 中国皮革,2015,44(3):6-11. WANG J X,WANG Q J,QU J L,et al. Synthesis and performance of protein-based surfactant[J]. China Leather,2015,44(3):6-11.
[43] 曲家乐. 利用废弃铬革屑制备制革用脱脂剂的研究[D]. 西安:陕西科技大学,2013. QU J L. Study on the preparation of degreasing agent for leather with waste leather shavings[D]. Xi'an:Shaanxi University of Science & Technology,2013.
[44] 李锐琴,张文华,廖学品,等. 阳离子型胶原蛋白絮凝剂的制备及性能研究[J]. 皮革科学与工程,2014,24(3):5-10. LI R Q,ZHANG W H,LIAO X P,et al. Flocculants preparation of cationization collagen protein andtheir flocculation performance investigation[J]. Leather Science and Engineering,2014,24(3):5-10.
[45] 周生鹏,唐奕,廖学品,等. 胶原多肽基表面活性剂对染料废水的泡沫分离性能[J]. 化工学报,2015,66(11):4493-4500. ZHOU S P,TANG Y,LIAO X P,et al. Foam separation behaviors of collagen-peptide based surfactant for treatment of dye wastewater[J]. CIESC Journal,2015,66(11):4493-4500.
[46] 王倩倩,王鸿儒. 阳离子角蛋白絮凝回收利用废水中的皮革助剂[J]. 精细化工,2016,33(2):195-199. WANG Q Q,WANG H R. The flocculant and recycle of the leather chemicals by using cationic keratin flocculation[J]. Fine Chemicals,2016,33(2):195-199.
[47] 张忠楷,李国英. 胶原,明胶和水解胶原蛋白的护肤功能比较[J]. 日用化学工业,2006,36(1):18-21. ZHANG Z K,LI G Y. Comparison of functions of collagen,gelatin and collagen hydrolysate as skin-care cosmetic materials[J]. China Surfactant Detergent & Cosmetics,2006,36(1):18-21.
[48] 梁飞,左红梅. 胶原和水解胶原蛋白的结构,性能和功效研究及应用前景[J]. 明胶科学与技术,2013,33(3):115-123. LIANG F,ZUO H M. A review of collagen and collagen hydrolysates:structure,properties,functions,applications and prospect[J]. The Science and Technology of Gelatin,2013,33(3):115-123.
[49] 迟原龙,崔敏,杨倩,等. 胶原多肽基表面活性剂的表面特性和生物降解性研究[J]. 中国皮革,2012,41(11):37-41. CHI Y L,CUI M,YANG Q,et al. Surface property and biodegradation of collagen-peptide based surfactant[J]. China Leather,2012,41(11):37-41.
[50] MONDAL M H,MALIK S,ROY A,et al. Modernization of surfactant chemistry in the age of Gemini and bio-surfactants:a review[J]. RSC Advances,2015,5(112):92707-92718.
[51] 金勇,苗青,张彪,等. Bola型表面活性剂合成及其应用[J]. 化学进展,2008,20(6):918-930. JIN Y,MIAO Q,ZHANG B,et al. Synthesis and application of bola form surfactants[J]. Progress in Chemistry,2008,20(6):918-930.
[52] 王娟,王丹,商士斌. 天然产物基Gemini表面活性剂研究进展[J]. 化工进展,2012,31(12):2761-2765. WANG J,WANG D,SHANG S B. Research progress in Gemini surfactants from natural products[J]. Chemical Industry and Engineering Progress,2012,31(12):2761-2765.