有机硅聚合物—聚甲基丙烯酸甲酯梯度材料制备研究
|
摘要
本论文为了能得到有机硅聚合物-聚甲基丙烯酸甲酯梯度材料,以解决传统多次涂膜法存在的界面粘结问题。首先要让有机硅单体更好的乳化,所以用硫酸酯化反应,以聚醚改性聚硅氧烷为原料,合成了聚醚改性聚硅氧烷硫酸酯钠乳化剂,该乳化剂属于非离子、阴离子复合型乳化剂。经实验发现,与未进行硫酸酯化的乳化剂相比,其浊点明显提高,能让常规乳液聚合更稳定的进行。
利用甲基丙烯酸甲酯(MMA)和自制的γ-甲基丙烯酰氧丙基三(三甲硅氧基)硅烷(TRIS)为原料,以聚醚改性聚硅氧烷硫酸酯钠、十二烷基硫酸钠和1-丙烯基-2-羟基烷机磺酸钠为复配乳化剂,采用单体乳液半连续滴加法,分别制备了有机硅均聚物(PTRIS)乳液、有机硅-甲基丙烯酸甲酯共聚物(P(MMA-co-TRIS))乳液和聚甲基丙烯酸甲酯(PMMA)乳液。用粒径分析仪,TEM测试了乳液的胶粒,并用IR,TEM,水滴接触角测试等方法对所制备的均聚物和共聚物膜进行了表征。结果表明:当乳化剂用量在6%～8%(相对单体量)、改性乳化剂、十二烷基硫酸钠和1-丙烯基-2-羟基烷机磺酸钠复配比为2:1:1、引发剂用量在0.8～1%(相对单体量)、聚合温度为80℃、搅拌速度在200～250rpm时,得到的均聚物和共聚物乳液稳定,而且粒径分布均匀;对于共聚物乳液来说,随着单体中TRIS含量的增加,所得聚合物膜的水滴接触角增加,即其表面能增加。
通过乳液共混成膜时发生自结构,本文以乳液共混法制备了有机硅聚合物-聚丙烯酸酯梯度复合材料。结果发现PTRIS和PMMA的相容性较差,加入不同聚合比例的共聚物P(MMA-co-TRIS)后相容性得到改善,并可以得到一面富集丙烯酸酯聚合物:然后结构渐变成另一面富集有机硅聚合物的梯度膜。
In this theses,in order to get polysilane-polyacrylate gradient material and solve interfacial coherence problems which existents etraditional times coating process. First to get preferable emulsification for organosilicon monomer. The emulsifier, sodium polyether sulfovinate modified polysiloxane, was synthesized by sulfuric acid esterification between chlorosulfonic acid and polyether modified polysiloxane. It was a kind of nonionic and anionic mixed emulsifier. In experiments, it was found that the mixed emulsifier has higher cloud point, and was able to let emulsion polymerization more stable, compared with emulsifier unesterified.With sodium polyether sulfovinate modified polysiloxane, sodium lauryl sulfate and sodium 3-allyoxy-2-hydroxypropanesulfonate(COPS-l) as composite emulsifier system, using methyl methacrylate(MMA) and self-made monomer Y -[tris(trimethylsiloxy)silyl]propyl methacrylate(TRIS) as raw materials, we prepared the homopolymer of TRIS, MMA, and the copolymers (P(MMA-co- TRIS)) by means of semi-continuous method of monomer preemulsion.Used Zeta.PALS, TEM test .galactic colloidal particle was clearly observed. Then, IR, TEM, DMA and water contact angle measurements were utilized to study these polymers and their films. The result indicated that the stable homopolymer and copolymer emulsion with uniform size distribution was got, when the ratio of sodium polyether sulfovinate modified polysiloxane, sodium lauryl sulfate and sodium 3-allyoxy-2-hydroxypropanesulfonate was 2:1:1, the quantity of the emulsifiers ranged from 6% to 8%(relative to monomer), the quantity of initiator ranged from 0.8% to l%(relative to monomer), the stirring speed ranged from 200rpm to 250rpm, the polymerization temperature was 80 centigrade degree. As for the copolymer emulsion, the more the TRIS content in the monomers, the larger the water contact angle of their films became, namely, the surface energy of the copolymer films increased with the TRIS content in the monomers.The testing results indicated that adding different P(MMA-co-PTRIS) can improve the poor miscibility of PMMA and PTRIS. The obtained polysilane -polyacrylate gradient films showed no macro-interface with the silicone content reducing gradually from the top surface to the bottom one.
利用甲基丙烯酸甲酯(MMA)和自制的γ-甲基丙烯酰氧丙基三(三甲硅氧基)硅烷(TRIS)为原料,以聚醚改性聚硅氧烷硫酸酯钠、十二烷基硫酸钠和1-丙烯基-2-羟基烷机磺酸钠为复配乳化剂,采用单体乳液半连续滴加法,分别制备了有机硅均聚物(PTRIS)乳液、有机硅-甲基丙烯酸甲酯共聚物(P(MMA-co-TRIS))乳液和聚甲基丙烯酸甲酯(PMMA)乳液。用粒径分析仪,TEM测试了乳液的胶粒,并用IR,TEM,水滴接触角测试等方法对所制备的均聚物和共聚物膜进行了表征。结果表明:当乳化剂用量在6%～8%(相对单体量)、改性乳化剂、十二烷基硫酸钠和1-丙烯基-2-羟基烷机磺酸钠复配比为2:1:1、引发剂用量在0.8～1%(相对单体量)、聚合温度为80℃、搅拌速度在200～250rpm时,得到的均聚物和共聚物乳液稳定,而且粒径分布均匀;对于共聚物乳液来说,随着单体中TRIS含量的增加,所得聚合物膜的水滴接触角增加,即其表面能增加。
通过乳液共混成膜时发生自结构,本文以乳液共混法制备了有机硅聚合物-聚丙烯酸酯梯度复合材料。结果发现PTRIS和PMMA的相容性较差,加入不同聚合比例的共聚物P(MMA-co-TRIS)后相容性得到改善,并可以得到一面富集丙烯酸酯聚合物:然后结构渐变成另一面富集有机硅聚合物的梯度膜。
In this theses,in order to get polysilane-polyacrylate gradient material and solve interfacial coherence problems which existents etraditional times coating process. First to get preferable emulsification for organosilicon monomer. The emulsifier, sodium polyether sulfovinate modified polysiloxane, was synthesized by sulfuric acid esterification between chlorosulfonic acid and polyether modified polysiloxane. It was a kind of nonionic and anionic mixed emulsifier. In experiments, it was found that the mixed emulsifier has higher cloud point, and was able to let emulsion polymerization more stable, compared with emulsifier unesterified.With sodium polyether sulfovinate modified polysiloxane, sodium lauryl sulfate and sodium 3-allyoxy-2-hydroxypropanesulfonate(COPS-l) as composite emulsifier system, using methyl methacrylate(MMA) and self-made monomer Y -[tris(trimethylsiloxy)silyl]propyl methacrylate(TRIS) as raw materials, we prepared the homopolymer of TRIS, MMA, and the copolymers (P(MMA-co- TRIS)) by means of semi-continuous method of monomer preemulsion.Used Zeta.PALS, TEM test .galactic colloidal particle was clearly observed. Then, IR, TEM, DMA and water contact angle measurements were utilized to study these polymers and their films. The result indicated that the stable homopolymer and copolymer emulsion with uniform size distribution was got, when the ratio of sodium polyether sulfovinate modified polysiloxane, sodium lauryl sulfate and sodium 3-allyoxy-2-hydroxypropanesulfonate was 2:1:1, the quantity of the emulsifiers ranged from 6% to 8%(relative to monomer), the quantity of initiator ranged from 0.8% to l%(relative to monomer), the stirring speed ranged from 200rpm to 250rpm, the polymerization temperature was 80 centigrade degree. As for the copolymer emulsion, the more the TRIS content in the monomers, the larger the water contact angle of their films became, namely, the surface energy of the copolymer films increased with the TRIS content in the monomers.The testing results indicated that adding different P(MMA-co-PTRIS) can improve the poor miscibility of PMMA and PTRIS. The obtained polysilane -polyacrylate gradient films showed no macro-interface with the silicone content reducing gradually from the top surface to the bottom one.
引文
[1] 朱震刚,水嘉鹏.金属与合金的单晶相梯度材料.94秋季中国材料研讨会会议论摘要集,北京:83～88
[2] 张联盟,涂溶,袁润章.梯度材料的研究进展与发展新动向.高技术陶瓷,1995.2(1):23～26
[3] Bever M B, et al. Morphology of Polymeric Alloys. Mater Sci Eng, 1972. 10: 1
[4] 新野正之,平井敏雄,渡边龙三.倾斜机能材料-宇宙机用超耐热材料应用.日本复合材料学会志,1987.13(6):257～264
[5] M. Niino, T. Hirai and R. Watanabe. Functionally gradient materials. Journal of Japanese Society of Composite Material, 1987. 13(6): 275～279
[6] 新野正之.倾斜机能材料发想开发动向.工业材料,1990.38(12):18～22
[7] Kawasaki and R. Watanabe. Microstructural designing and fabrication of disk shaped functionally gradient materials. Journal of Japanese Society of Powder and Powder metallurgy. 1990. 37(2): 253～259
[8] 张小玲,陈一民,张馨等.有机梯度功能材料的研究.功能材料,1994.25(6):511～514
[9] B. Hschner, N. Cherradi (Editors). Abstracts of the Third International Symposium on Structural and Functional Gradient Materials. Lausanne, Switzweland, Oct. 10-12, 1994
[10] Kano, Yoshinisa. Trend of polymer base gradient structure. Setchachu, 1998. 42 (7): 315～324
[11] J. Rodel, A. Neubrand. Research Program on Gradient Materials in Germany Functionally Materials (Edited by LCHIRO SHIOTA). Japan, Oct. 21～24, 1996: 9～14
[12] J. B. Holt, M. Doizumi, T. Hirai and Z. A. Munir. Proceedings of the Second International Symposiu on Functionally Gradient Materias. U. S. A. Nov. 1-4, 1992: 1～4
[13] S. Suresh. Currret research on grade materials in the USA. FGM'(Edited by LCHIRO SHOTA). Oct. Japan, 21-24, 1996: 15～18
[14] B. Llschner. Lessons Learned in 7 Years of FGM Research at Lausanne (Edited by LCHIRO SHIOTA). Japan, Oct. 21-24. 1996: 15～20
[15] 黄旭涛,严密.功能梯度材料:回顾与展望.材料科学与工程,1997.115(4):35～38
[16] 武汉理工大学材料复合新技术实验室论文集(Ⅲ).材料复合研究工作新进展.1990
[17] M. Omori, A. Okubo, K. Gilhwan, T. Hirai. Fourth Int. Symp. FGM'96 Abst., 1996. 98～102
[18] J. Z. Yu, C. Lei, F. K. Ko, Annu. Tech. Conf. SPE, 52th, 1994. 2352
[19] 加东次雄,善積章.硬化性樹脂,16(3),1995.126
[20] P. Milczarek, M. Kryszewski. Coll. & Polym. Sci., 1987. 265～481
[21] 张帆,张其锦.梯度折射率聚合物细棒的制备和数学模拟.高分子学报,2000.(5):538～544
[22] Y. Koike, N. Tanio, E. Nihei, Y. Ohtsuka. Polym. Eng. Sci., 1989. 29(17): 1200～1211
[23] C. Lee, J. Jang, J. S, Shim. Preprints 5th Pacific Polymer Conference. 1997, Oct. 26～30, Kyongju, Kongju, Korea, 1997. 174～189
[24] 浅井新一郎.倾斜机能分子构造有共重合体.科学工业,1997.71(2):51～56.
[25] 张彬,张兆斌等.水分散体系中苯乙烯和甲基丙烯酸甲酯梯度共聚物的合成与表征.高等学校化学学报,2004.25(6):1170～1173
[26] KanoY, Akiyama S, Sano H. etal. The Gragient Domain Morphology of Binary Poly-acrylate adhesive/fluorocopolymer Blend Film. J. Electron. Microsc, 1995. 44(5): 344～350.
[27] 佐野博成,仓尺羲博,西田耕治.系射出成形品中相反特殊转倾斜构造形成.KobunshiRonbunshu,1997.54:244～254
[28] T. Okazaki, M. Furukawa, T. Yokoyama. Polym. J., 1997, 29: 617
[29] 钱浩,林志勇.聚乙二醇/聚乙烯共混物薄膜表面的浓度梯度.高分子材料科学与工程,2005.21(2):236～240
[30] 上利泰幸,進田雅之,上田明等.高分子学会要旨集,1994,43(3):1210
[31] XieXum, Matsuoka. M, Takemura. K. Formation of Gradient Phase Structure During Annealing of a Polymer Blend. Polymer, 1992. 33(9): 1996～1998
[32] 高分子学会编.基础应用-.东京化学同人,1993
[33] D. J. Walbridge. Self-stratifying coatings-an overview of a European Community Research Project. Progress in Organic Coating, 1996. 28 (3): 155～159
[34] 朱信华,孟中岩.梯度功能材料的研究现状与展望.功能材料,1998.29(2):121～127
[35] W. Funke and M. Schmitthenner, Dtsch. Farben-Z, 30(1976) 506
[36] V. V. Verkholantsev. Heterophase and Self-stratifying Polymer Coatings. Progress in Organic Coating, 1995. 26(1): 31～52
[37] 张先亮,蔡乾德等.有机硅表面活性剂的结构与应用.有机硅材料及应用,1999.(3):13～17
[38] 梁治齐,李金华.功能性乳化剂与乳状液.北京:中国轻工业出版社,2000
[39] 赵国玺.表面活性剂物理化学.北京:北京大学出版社,1991
[40] 朱埗瑶,赵国玺.液体表(界)面张力的测定-滴体积法介绍.化学通报,1981,(6):21～26
[41] 龚兴宇,范晓东.γ-甲基丙烯酰氧丙基三甲氧基硅烷改性丙烯酸酯乳液的研究.高分子材料科学与工程,2003.19(1):61～64
[42] Quaal, George, J. Tris(alkylsiloxy)silylalkyl acylates. U. S. 3377377
[43] 张超灿,韦丽莉,廖海军,黄芳.γ-甲基丙烯酰氧丙基三(三甲硅氧基)硅烷的制备.武汉理工大学学报,2003.25(9):5～6
[44] 曹同玉,刘庆普,胡金生.聚合物乳液合成原理性能及应用.北京:化学工业出版社,1997
[45] 复旦大学化学系高分子教研室编.高分子实验技术.上海:复旦大学出版社,1983
[46] 董雪,戎宗明.自分层涂料的理论与应用.涂料工业,2001.(1):1～6
[47] 赵德仁,张慰盛等.高聚物合成工艺学.北京:化学工业出版社,1997
[48] 马德柱,何平笙等编.高聚物的结构与性能.北京:北京科学出版社,2000
[49] 吴人洁等编.现代分析技术—在高聚物中的应用.上海:上海科学技术出版社,1987
[50] Toussiaint. A, Self-stratifying Coatings for Plastic Substrates. Progress in Organic Coating, 1996. 28(3): 183～195
[51] Satoh, Kuniaki, Stratification of Polysiloxanes at the Film-air and Film-substrate Interfaces in Silicone-modified Acrylic Coatings;an ATR FT-IR Spectroscopic Study, 1996. 29(1-4): 195～199
[52] Benjamin. S, Cart. C, Walbridge. D. J. Self-stratifying Coatings for Metallic Substrates, 1996. 28(3): 197～207
[53] V. V. Verkholantsev. Polymer Structure and Properties of Heterophase and Self-stratifying Coatings. Progress in Organic Coating, 1996. 29 (1-4): 239～246
[54] Carr. C, Benjamin. S, Walbridge. D. J. Fluorinated Resinsin Self-stratifying Coatings. European Coatings Journal, 1995, 28(4): 262～266
[55] Kryszewski. M. Gradient polymers and copolymers. Polym. Adv. Technol. 1998, 9(4): 244～259
[56] A. Toussaint. CoRI Final Rep. on Self-stratifying Coatings. July 1992
[57] Bfite Project No. RI 1B 0246, Tech. Rev. Res., Paint Research Association, Jan. -June 1989
[58] P. A. Small. J. Appl. Chem.. 3(1953): 71
[59] K. L. Hoy. J. Paint Technol.. 42(1970): 76
[60] C. M. Hansen. J. Paint. Teehnol., 39(1967): 511
[61] A. M. Jolly. Statistical Treatment of data from the European Community Research on Self-stratification. Progress in Organic Coating, 1996, 28(3): 209～222
[62] 曹同玉,刘庆普,胡金生.聚合物乳液合成原理性能及应用.北京:化学工业出版社,1997.170
[63] 大森英三(日).丙烯酸酯及其聚合物.北京:化学工业出版社,1985.184
[2] 张联盟,涂溶,袁润章.梯度材料的研究进展与发展新动向.高技术陶瓷,1995.2(1):23～26
[3] Bever M B, et al. Morphology of Polymeric Alloys. Mater Sci Eng, 1972. 10: 1
[4] 新野正之,平井敏雄,渡边龙三.倾斜机能材料-宇宙机用超耐热材料应用.日本复合材料学会志,1987.13(6):257～264
[5] M. Niino, T. Hirai and R. Watanabe. Functionally gradient materials. Journal of Japanese Society of Composite Material, 1987. 13(6): 275～279
[6] 新野正之.倾斜机能材料发想开发动向.工业材料,1990.38(12):18～22
[7] Kawasaki and R. Watanabe. Microstructural designing and fabrication of disk shaped functionally gradient materials. Journal of Japanese Society of Powder and Powder metallurgy. 1990. 37(2): 253～259
[8] 张小玲,陈一民,张馨等.有机梯度功能材料的研究.功能材料,1994.25(6):511～514
[9] B. Hschner, N. Cherradi (Editors). Abstracts of the Third International Symposium on Structural and Functional Gradient Materials. Lausanne, Switzweland, Oct. 10-12, 1994
[10] Kano, Yoshinisa. Trend of polymer base gradient structure. Setchachu, 1998. 42 (7): 315～324
[11] J. Rodel, A. Neubrand. Research Program on Gradient Materials in Germany Functionally Materials (Edited by LCHIRO SHIOTA). Japan, Oct. 21～24, 1996: 9～14
[12] J. B. Holt, M. Doizumi, T. Hirai and Z. A. Munir. Proceedings of the Second International Symposiu on Functionally Gradient Materias. U. S. A. Nov. 1-4, 1992: 1～4
[13] S. Suresh. Currret research on grade materials in the USA. FGM'(Edited by LCHIRO SHOTA). Oct. Japan, 21-24, 1996: 15～18
[14] B. Llschner. Lessons Learned in 7 Years of FGM Research at Lausanne (Edited by LCHIRO SHIOTA). Japan, Oct. 21-24. 1996: 15～20
[15] 黄旭涛,严密.功能梯度材料:回顾与展望.材料科学与工程,1997.115(4):35～38
[16] 武汉理工大学材料复合新技术实验室论文集(Ⅲ).材料复合研究工作新进展.1990
[17] M. Omori, A. Okubo, K. Gilhwan, T. Hirai. Fourth Int. Symp. FGM'96 Abst., 1996. 98～102
[18] J. Z. Yu, C. Lei, F. K. Ko, Annu. Tech. Conf. SPE, 52th, 1994. 2352
[19] 加东次雄,善積章.硬化性樹脂,16(3),1995.126
[20] P. Milczarek, M. Kryszewski. Coll. & Polym. Sci., 1987. 265～481
[21] 张帆,张其锦.梯度折射率聚合物细棒的制备和数学模拟.高分子学报,2000.(5):538～544
[22] Y. Koike, N. Tanio, E. Nihei, Y. Ohtsuka. Polym. Eng. Sci., 1989. 29(17): 1200～1211
[23] C. Lee, J. Jang, J. S, Shim. Preprints 5th Pacific Polymer Conference. 1997, Oct. 26～30, Kyongju, Kongju, Korea, 1997. 174～189
[24] 浅井新一郎.倾斜机能分子构造有共重合体.科学工业,1997.71(2):51～56.
[25] 张彬,张兆斌等.水分散体系中苯乙烯和甲基丙烯酸甲酯梯度共聚物的合成与表征.高等学校化学学报,2004.25(6):1170～1173
[26] KanoY, Akiyama S, Sano H. etal. The Gragient Domain Morphology of Binary Poly-acrylate adhesive/fluorocopolymer Blend Film. J. Electron. Microsc, 1995. 44(5): 344～350.
[27] 佐野博成,仓尺羲博,西田耕治.系射出成形品中相反特殊转倾斜构造形成.KobunshiRonbunshu,1997.54:244～254
[28] T. Okazaki, M. Furukawa, T. Yokoyama. Polym. J., 1997, 29: 617
[29] 钱浩,林志勇.聚乙二醇/聚乙烯共混物薄膜表面的浓度梯度.高分子材料科学与工程,2005.21(2):236～240
[30] 上利泰幸,進田雅之,上田明等.高分子学会要旨集,1994,43(3):1210
[31] XieXum, Matsuoka. M, Takemura. K. Formation of Gradient Phase Structure During Annealing of a Polymer Blend. Polymer, 1992. 33(9): 1996～1998
[32] 高分子学会编.基础应用-.东京化学同人,1993
[33] D. J. Walbridge. Self-stratifying coatings-an overview of a European Community Research Project. Progress in Organic Coating, 1996. 28 (3): 155～159
[34] 朱信华,孟中岩.梯度功能材料的研究现状与展望.功能材料,1998.29(2):121～127
[35] W. Funke and M. Schmitthenner, Dtsch. Farben-Z, 30(1976) 506
[36] V. V. Verkholantsev. Heterophase and Self-stratifying Polymer Coatings. Progress in Organic Coating, 1995. 26(1): 31～52
[37] 张先亮,蔡乾德等.有机硅表面活性剂的结构与应用.有机硅材料及应用,1999.(3):13～17
[38] 梁治齐,李金华.功能性乳化剂与乳状液.北京:中国轻工业出版社,2000
[39] 赵国玺.表面活性剂物理化学.北京:北京大学出版社,1991
[40] 朱埗瑶,赵国玺.液体表(界)面张力的测定-滴体积法介绍.化学通报,1981,(6):21～26
[41] 龚兴宇,范晓东.γ-甲基丙烯酰氧丙基三甲氧基硅烷改性丙烯酸酯乳液的研究.高分子材料科学与工程,2003.19(1):61～64
[42] Quaal, George, J. Tris(alkylsiloxy)silylalkyl acylates. U. S. 3377377
[43] 张超灿,韦丽莉,廖海军,黄芳.γ-甲基丙烯酰氧丙基三(三甲硅氧基)硅烷的制备.武汉理工大学学报,2003.25(9):5～6
[44] 曹同玉,刘庆普,胡金生.聚合物乳液合成原理性能及应用.北京:化学工业出版社,1997
[45] 复旦大学化学系高分子教研室编.高分子实验技术.上海:复旦大学出版社,1983
[46] 董雪,戎宗明.自分层涂料的理论与应用.涂料工业,2001.(1):1～6
[47] 赵德仁,张慰盛等.高聚物合成工艺学.北京:化学工业出版社,1997
[48] 马德柱,何平笙等编.高聚物的结构与性能.北京:北京科学出版社,2000
[49] 吴人洁等编.现代分析技术—在高聚物中的应用.上海:上海科学技术出版社,1987
[50] Toussiaint. A, Self-stratifying Coatings for Plastic Substrates. Progress in Organic Coating, 1996. 28(3): 183～195
[51] Satoh, Kuniaki, Stratification of Polysiloxanes at the Film-air and Film-substrate Interfaces in Silicone-modified Acrylic Coatings;an ATR FT-IR Spectroscopic Study, 1996. 29(1-4): 195～199
[52] Benjamin. S, Cart. C, Walbridge. D. J. Self-stratifying Coatings for Metallic Substrates, 1996. 28(3): 197～207
[53] V. V. Verkholantsev. Polymer Structure and Properties of Heterophase and Self-stratifying Coatings. Progress in Organic Coating, 1996. 29 (1-4): 239～246
[54] Carr. C, Benjamin. S, Walbridge. D. J. Fluorinated Resinsin Self-stratifying Coatings. European Coatings Journal, 1995, 28(4): 262～266
[55] Kryszewski. M. Gradient polymers and copolymers. Polym. Adv. Technol. 1998, 9(4): 244～259
[56] A. Toussaint. CoRI Final Rep. on Self-stratifying Coatings. July 1992
[57] Bfite Project No. RI 1B 0246, Tech. Rev. Res., Paint Research Association, Jan. -June 1989
[58] P. A. Small. J. Appl. Chem.. 3(1953): 71
[59] K. L. Hoy. J. Paint Technol.. 42(1970): 76
[60] C. M. Hansen. J. Paint. Teehnol., 39(1967): 511
[61] A. M. Jolly. Statistical Treatment of data from the European Community Research on Self-stratification. Progress in Organic Coating, 1996, 28(3): 209～222
[62] 曹同玉,刘庆普,胡金生.聚合物乳液合成原理性能及应用.北京:化学工业出版社,1997.170
[63] 大森英三(日).丙烯酸酯及其聚合物.北京:化学工业出版社,1985.184