摘要
高性能低成本丙烯酸乳液是近年来建筑涂料研究方面的热点之一。有机硅改性的丙烯酸乳液具有较高的耐刷洗和抗粉化性能,在外墙建筑涂料中有良好的应用前景。目前,研究较多的是硅溶胶与丙烯酸乳液的冷混,冷混硅溶胶的丙烯酸乳液能够较好地改善乳液的耐水性和耐光性。普通硅丙乳液因分子链结构和活性基团不相容而带来的储存稳定性差、乳胶膜相分离严重等缺陷,影响了市场推广。
近年来,利用有机硅改性丙烯酸酯乳液的研究日趋活跃,由于其综合性能良好,具有良好的开发前景。
论文以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)通过乳液聚合形成种子,然后向种子乳液中滴加苯乙烯(St)和乙烯基三乙氧基硅烷(VTEOS),合成了以丙烯酸酯为核,有机硅为壳层的核壳型复合乳液。研究了单体和功能单体配比、反应温度、乳化剂用量等有机硅改性丙烯酸酯乳液合成与性能的影响。确定了乳液合成的最佳工艺条件。
以苯乙烯(St)和乙烯基三乙氧基硅烷(VTEOS)为共聚单体,合成乳液种子,以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)混合单体为壳层单体,半连续法合成了以有机硅为核,丙烯酸酯为壳层的核壳型复合乳液。研究了单体和功能单体配比、反应温度、乳化剂用量等有机硅改性丙烯酸酯乳液合成与性能的影响。确定了乳液合成的最佳工艺条件。
用预乳化工艺和半连续种子乳液聚合技术,合成出了具有核/壳结构的苯乙烯-丙烯酸丁酯-甲基丙烯酸甲酯-丙烯酸四元共聚苯丙乳液,粒径分布均匀,讨论了乳化剂和引发剂体系以及引发剂、交联剂用量等因素对乳液性能的影响,用TEM及FTIR表征了所得聚合物乳液的结构。
In recent years, development of styrene-acrylic emulsion with high performance and low cost stays on one of the hottest subjects in the research field of architecture coatings. Silicone-modified styrene-acrylic emulsion has excellent properties like scratch/weather resistance and long time to go chalks etc. Thus there brings a good market prospect for it to be deployed in the architecture coatings as for external wall decoration applications. Styrene-acrylic emulsion mixing with silicate gel also has better properties on water resistance and weather resistance than those without adding it. This subject had been widely studied into to maximum extent by scientists in the world. However due to the limits that silicon molecular chain structure and styrene-acrylic component’s active groups is not well compatible with each other, there occurs with its poor applicaions from silicone modified acrylic emulsion such as settling of storage and serious separation of different latex films and so on., thus its commercial application is much effected.
The research of using silicone-modified acrylic emulsion has become increasingly active in recent years, and there will be good prospects of development because it have better total performance than others.
Herewithin being stated in this article, the seeds are synthesized through emulsion polymerization with MMA and BA, then into which styrene and VTEOS were added to produce organic composite latex with acrylic-core/silicon-shell. The effects resulting from a varity of reaction conditions on reaction control and emulsion’s performance was studied, for example, mass ratio of the monomer to functional monomer, reaction temperature and the amount of emulsifier. a series of optimal conditions to achieve sound performance were concluded.
The organic silicon modified acrylic copolymer emulsion with core-shell structure was synthesized by semi-continuous emulsion polymerization, in which MMA, BA was used as core-monomers and St, VTEOS was used as shell-monomers. The influence of reaction conditions on the preparation and their performance was studied, eg mass ratio of the monomer to functional monomer, reaction temperature and the amount of emulsifier, optimal conditions were obtained.
Styrene-acrylate emulsion with core-shell structure has been prepared based on styrene- butylacrylate-methyl methacrylate-acrylic acid terabasic polymer and by the use of pre- emulsification and semi-continuous seed polymerization technology, its particles distribution is in good equality and the demonstrated performance is extremely superior, where it is suitable in interior coating, adhesion, printing ink usage and so on.The influence of different emulsifier system, initiator system and the amount of initiator, modifying agents on the emulsion performance were studied.
The prepared samples were characterized by FTIR, TEM. The result shows that the emulsion obviously possessed core-shell structure.
引文
[1]曹同玉,刘庆普,胡金生编.聚合物乳液合成原理、性能及应用[M].北京:化学工业出版社, 1997
[2]袁才登编.乳液胶粘剂[M].北京:化学工业出版社,2004
[3] JW Ha,IJ park,DK Kim etc. Surface Properties of core-shell Particles containing perfluoroalkyl acrylate in shell [J]. Surface Sci. 2003,532
[4] GJ Wang, CS Kang, RG Jin. Synthesis of acrylic core-shell composite polymers and properties of plastisol-gels [J]. Progress in Organic Coatings,2004,50: 55
[5] AJ Dong,Y An, SY Feng, etc. Preparation and morphology studies of core-shell type waterbornepolyacrylate polyurethane microspheres [J]. Colloid Interface Sci, 1999, (214): 118
[6]蔡斯让,郑田菱,张瑞珠.丙烯酸醋无皂乳液聚合的研究[J].中国胶粘剂, 1997,6(5): 4
[7]王群,府寿宽,于同隐.乳液聚合的最新进展(上)[J].高分子通报, 1996, (3): 141
[8]王正辉,王红娟.乳液聚合新进展[J].胶体与聚合物, 2001, 19(1): 36
[9]王群,府寿宽,于同隐.乳液聚合的最新进展(下)[J].高分子通报, 1996, (4): 210
[10]管蓉,艾照全,李建宗,等.影响聚丙烯酸酯乳液胶粘剂性能的因素[J].中国胶粘剂, 1998, 7(1): 36
[11]王孟钟、黄应昌.胶粘剂使用手册[M].北京:化学工业出版社,1987
[12] (日)大森应三著,张育川、朱传肇译.功能性丙烯酸酯[M].北京:化学工业出版社, 1986
[13]费广泰,龚辈凡.我国合成胶粘剂工业的进展[J].中国胶粘剂, 2000, 9(4): 47
[14]潘祖仁著.高分子化学[M].北京:化学工业出版社, 1997
[15]张开.高分子界面科学[M].北京:中国石化出版社, 1991
[16]耿耀宗,曹同玉.合成聚合物乳液制造与应用技术[M].北京:中国轻工业出版社,1996
[17]陈冠荣.化工百科全书(第一卷)[M].北京:化学工业出版社, 1990
[18] JL Gardon. Emulsion polymerization M: Theoretical prediction of the effects of slow termination rate with later particles [J]. J Polym.Sci. 1986, 6: 665
[19] C Graillat,C Pichot,A Guyot, etc. Inverse emulsion polymerization of acrylamide: Contribution to the study of some mechanistic aspects [J]. J Polym.Sci, 1986, 24(3): 427
[20] M Antonieti, K Landfester. Polyreactions in miniemulsions [J]. Prog Polym Sci, 2002, 27: 689
[21] MF Cunningham. Living/controlled radical polymerization in dispersed phase systems [J]. Prog Polym Sci, 2002, 27: 1039
[22] K Landfester. Miniemulsions for Nanoparticle Synthesis [J]. Top Curr Chem, 2003, 227: 75
[23] M Okubo, Y Iwasaki,Y Yamamoto. Preparation of micro-size monodisperse polymer microspheres having cationic groups [J]. Colloid Polym Sci, 1992, 270(8): 733
[24]耿耀宗主编.现代水性涂料[M].北京:中国石化出版社, 2003
[25] Z Song, GW Poehlein. Particle nucleation in emulsifier-free aqueous phase polymerization: stage I [J]. Colloid Surface, 1989, 128(2): 486
[26] S Dietrich, VB Betina. Microgels in organic coatings [J]. Prog Org Coat, 1996, 28(l): 33
[27] S Chen, L Chen. Structure and properties of polyurethane/ polyacrylate latex interpenetrating networks hybrid emulsions[J]. Colloid Poym Sci, 2003, 282(1): 14
[28] K Yoshida, K Ishigure, H Garreau,etal. Radiation and chemical grafting of styrene to polybutadiene latex [J].Polym Sci Chem,1980, 14(5) : 739
[29]龙复,许涌.乳液聚合技术进展(三):第二讲反相乳液聚合[J].涂料技术, 1991, (3): 58
[30]段洪东,孟霞.乳液聚合方法新进展-幂级加料法[J].化学与粘合, 2000, (3): 138
[31]齐亦民.丙烯酸乳胶漆在建筑中应用[J].化学建材,1990, (6): 9
[32]潘宝骅.丙烯酸树酯涂料文集.化工部情报所编
[33]陈玲芳.丙烯酸乳胶地面涂料[J].化学建材, 1990 (6): 6
[39]沈林元,周志伟.丙烯酸乳胶防水涂料[J].化学建材, 1991, (1): 13
[40]阎桂萍,查亿春.涂布纸用丙烯酸型胶乳PC-02的研制[J].丙烯酸化工, 1993, 6(2): 13
[41]吴庆云,杨建军,张建安,等.核壳型丙烯酸乳液的制备[J].湖北化工,2003, (3): 37
[42]王清滨.丙烯酸核/壳乳液的应用[J].山东建材, 2004, (4): 40
[43]裴世红,赵宗诚,王丽达,等.降低丙烯酸乳液最低成膜温度的途径[J].沈阳化工, 1998, 27(2): 18
[44]卢素敏,王洪卫.丙烯酸乳液聚合粒度影响因素的研究[J].化工时刊, 2004, 18(12): 47
[45]甘孟瑜,刘娟,等.核壳结构丙烯酸酯乳液的合成及性能研究[J].涂料工业,2005,(6): 5
[46]邓爱民,穆锐.核壳丙烯酸聚合物微粒子乳液的合成与解析[J].化学与粘合,2004,(6): 370
[47]王莹,于雄,张鹏.半连续法制备核壳型丙烯酸聚合物乳液的研究[J].四川理工学院学报(自然科学版), 2006, 19(5): 26
[48]刘方方,孙立明,牛魁哲.聚合工艺和组成对丙烯酸乳液最低成膜温度的影响[J].中国胶粘剂, 2000, 9(2): 27
[49]冯丽欣,刘方方.降低丙烯酸聚合物乳液最低成膜温度的途径[J].河北化工,2002,(6): 13
[50]杜奕,袁志,刘德山,等.有机硅-丙烯酸乳液最低成膜温度的研究[J].涂料工业, 2004, 34(5): 35
[51]马祥梅,王斌,王武生.我国丙烯酸乳液的研究进展[J].化学与粘合, 2003(1): 31
[52]罗正汤,候有军,等.涂料用丙烯酸酯-苯乙烯超微乳液的研究[J].华南理工大学学报(自然科学版), 2001, (3):71
[53] RM Fitch. Research of SoaPless Polymer [J]. Polymer, 1973, 14(5): 215
[54] Z Song, GW Poehiein. Thesis of Soapless Emulsion [J]. Polym Sci, 1990,28 (9): 2355
[55]张瑜,韦亚兵,熊家文.聚丙烯酸酯无皂核壳乳液聚合反应的研究[J].化学与粘合,2002,(3): 113t
[56]王香梅,王久芬,杜拴丽.丙烯酸酯类无皂复合乳液聚合研究[J].华北工学院学报,1997,18(3): 266
[57]黄志虹,谢志明,李卓美.丙烯酸酯无皂乳液稳定性研究[J].功能高分子学报,2000,13(1): 29
[58]穆锐,王桂萍.无皂乳液聚合方法合成丙烯酸酯聚合物微粒子的研究[J].沈阳工业学院学报, 2002, 21(2): 90
[59]纪庆绪,程时远,李建中.无皂乳液聚合法合成功能高分子微球[J].高分子材料科学与工程, 1994, (2): 35
[60]唐黎明,等.新型无皂乳液聚丙烯酸酯乳液的合成及性能研究[J].高分子材科科学与工程, 1995, (4): 217
[61] JY Wang,RY Lin,WH Li,et al. Studies on the damping performance of polystyrene/polyacrylate latex IPN [J]. Polym Int, 1996, 39(2): 101
[62]斯柏林.互穿聚合物网络和有关材料[M].北京:科学出版社, 1987
[63]杜桂焕.互穿网络聚酯/丙烯酸酯涂料的制备[J].华中科技大学学报(自然科学版), 2002,(3): 114
[64]黄茂福. PU/PA互穿网络涂料印花粘合剂的研究[J].印染,2004, 30 (4): 1
[65]武利民,李丹,游波.现代涂料工业[M].北京:化学工业出版社, 2001
[66]马祥梅,王斌,王武生,戒国.苯丙乳液的研究进展[J].化学与粘合.2003(1): 7
[67]罗正汤,候有军,等.涂料用丙烯酸酯-苯乙烯超微乳液的研究[J].华南理工大学学报(自然科学版), 2001, (3): 71
[68]万波,王得宁.反应型乳化剂的合成及其在乳液聚合中的应用[J].合成橡胶工业, 2003, 26(2): 94
[69]邓爱民,穆锐.核壳丙烯酸聚合物微粒子乳液的合成与解析[J].化学与粘合, 2004, (6): 370
[70]王莹,于雄,张鹏.半连续法制备核壳型苯丙聚合物乳液的研究[J],四川理工学院学报(自然科学版),2006, l9(5): 26