有机硅聚合物-聚甲基丙烯酸甲酯梯度材料制备研究
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摘要
本论文以聚醚改性聚硅氧烷为原料,进行硫酸酯化反应,并进一步用碱中和,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。与未进行硫酸酯化的乳化剂相比,其浊点明显提高,适用于常规的乳液聚合。
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与十二烷基硫酸钠为复配乳化剂,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。并用IR,TEM,DMA,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)、改性乳化剂与十二烷基硫酸钠复配比为2:1、引发剂用量在0.4～0.8%(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:另外,随着共聚单体中TRIS含量的增加,共聚物的玻璃化转变温度从PMMA的Tg的高温区向PTRIS的Tg的低温区移动。
对聚合物乳液共混行为的研究表明:在PTRIS和PMMA均聚物乳液中,加入共聚物(P(MMA-co-TRIS))后,可改善PTRIS和PMMA的相容性;多组分乳液共混时,可以得到一面是聚甲基丙烯酸甲酯端,另一面是有机硅聚合物端的结构渐变的梯度膜。对该膜的DMA,DSC,UV测试结果表明:所得梯度膜的玻璃化转变范围比各组分材料的玻璃化转变范围宽;该梯度膜具有较好的热稳定性、良好的憎水性能和紫外吸收性能。
In this paper, the emulsifier sodium polyether sulfovinate modified polysiloxane was synthesized by sulfuric acid esterification between chlorosulfonic acid and polyether modified polysiloxane, then alkali neutralization. It was a kind of nonionic and anionic composite emulsifier. Compared with emulsifier unesterified, it has higher cloud point, which could apply to conventional emulsion polymerization.With sodium polyether sulfovinate modified polysiloxane and sodium lauryl sulfate as composite emulsifier system, using methyl methacrylate(MMA) and self-made monomer γ-[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 dropwise method of monomer emulsion. Then, IR, TEM, DMA and water contact angle measurements were utilized to study these polymers and their films. The result indicated that we can get stable homopolymer and copolymer emulsion with uniform size distribution, when the ratio of sodium polyether sulfovinate modified polysiloxane to sodium lauryl sulfate was two, the quantity of the emulsifiers ranged from 6% to 8%(relative to monomer), the quantity of initiator ranged from 0.4% to 0.8%(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. In addition, the glass-transition temperature of the copolymers ranged from high temperature region to low temperature region with the increasing of TRIS content in the monomers.The study of blend manner of homopolymer and copolymer emulsion indicated that we can improve the miscibility between PMMA and PTRIS by adding P(MMA-co-TRIS) copolymer, and we can obtain organosilicon polymer-poly(methyl methacrylate) gradient films with poly(methyl methacrylate) at the top surface and organosilicon polymer at the bottom one. The analysis result of DMA, DSC, UV measurements showed that the glass-transition range of the gradient films was wider than the component ones, and the gradient films had good thermo-stability, hydrophobic
performance and absorption capacity to ultraviolet ray.
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与十二烷基硫酸钠为复配乳化剂,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。并用IR,TEM,DMA,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)、改性乳化剂与十二烷基硫酸钠复配比为2:1、引发剂用量在0.4～0.8%(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:另外,随着共聚单体中TRIS含量的增加,共聚物的玻璃化转变温度从PMMA的Tg的高温区向PTRIS的Tg的低温区移动。
对聚合物乳液共混行为的研究表明:在PTRIS和PMMA均聚物乳液中,加入共聚物(P(MMA-co-TRIS))后,可改善PTRIS和PMMA的相容性;多组分乳液共混时,可以得到一面是聚甲基丙烯酸甲酯端,另一面是有机硅聚合物端的结构渐变的梯度膜。对该膜的DMA,DSC,UV测试结果表明:所得梯度膜的玻璃化转变范围比各组分材料的玻璃化转变范围宽;该梯度膜具有较好的热稳定性、良好的憎水性能和紫外吸收性能。
In this paper, the emulsifier sodium polyether sulfovinate modified polysiloxane was synthesized by sulfuric acid esterification between chlorosulfonic acid and polyether modified polysiloxane, then alkali neutralization. It was a kind of nonionic and anionic composite emulsifier. Compared with emulsifier unesterified, it has higher cloud point, which could apply to conventional emulsion polymerization.With sodium polyether sulfovinate modified polysiloxane and sodium lauryl sulfate as composite emulsifier system, using methyl methacrylate(MMA) and self-made monomer γ-[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 dropwise method of monomer emulsion. Then, IR, TEM, DMA and water contact angle measurements were utilized to study these polymers and their films. The result indicated that we can get stable homopolymer and copolymer emulsion with uniform size distribution, when the ratio of sodium polyether sulfovinate modified polysiloxane to sodium lauryl sulfate was two, the quantity of the emulsifiers ranged from 6% to 8%(relative to monomer), the quantity of initiator ranged from 0.4% to 0.8%(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. In addition, the glass-transition temperature of the copolymers ranged from high temperature region to low temperature region with the increasing of TRIS content in the monomers.The study of blend manner of homopolymer and copolymer emulsion indicated that we can improve the miscibility between PMMA and PTRIS by adding P(MMA-co-TRIS) copolymer, and we can obtain organosilicon polymer-poly(methyl methacrylate) gradient films with poly(methyl methacrylate) at the top surface and organosilicon polymer at the bottom one. The analysis result of DMA, DSC, UV measurements showed that the glass-transition range of the gradient films was wider than the component ones, and the gradient films had good thermo-stability, hydrophobic
performance and absorption capacity to ultraviolet ray.
引文
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[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. Ilschner, 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.l-4, 1992:1-4
[13] S. Suresh. Curmet 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.Microse, 1995.44(5):344～350.
[27] 佐野博成,仓尺羲博,西田耕治.(2,6-1,4)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,造田雅之,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.基礎应用.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
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