无皂高分子纳米微球制备、机理与稳定性研究
|
摘要
用无皂乳液聚合的方法制备的高分子纳米胶乳粒子表面洁净，分散均匀，有很好的粘接性和抗水性，在生物体系中亦有广泛的应用。由于微波辐照制备稳定的无皂高分子纳米粒子与常规无皂乳液聚合相比，具有速率快，制备的粒子粒径小，粒径分布窄的优点，本论文工作主要利用常压微波辐照下无皂乳液聚合的方法合成高分子微球。并且通过对无皂乳液聚合中聚合单体、助溶剂、引发剂、反应温度等因素对聚合反应动力学及所得高分子微球的粒径、粒径分布影响的系统研究，探讨了制备稳定的均分散无皂纳米胶乳粒子的条件，并对所制备的无皂胶乳进行了常温贮存稳定性、低温贮存稳定性以及电解质稳定性的测试。
通过分析各种因素对无皂聚合反应的影响，并对反应过程中的转化率、透光率、体系中的粒子平均水化半径及粒径分布的测定，深入探讨了丙酮-微波法合成无皂高分子共聚胶乳粒子机理，认为在微波辐照和助溶剂丙酮的存在下，无皂共聚胶乳粒子的成核机理为“均相成核”与“胶束成核”并存，而且随着反应的进行存在“多次成核”。同时也探讨了微波辐照下丙酮-水体系无皂聚苯乙烯胶乳粒子、甲醇-水体系无皂聚苯乙烯和苯乙烯与甲基丙烯酸甲酯共聚胶乳粒子的形成机理。
The latexes obtained by emulsifier-free emulsion polymerization show good adhesion and water-resistant properties and are characterized by having a narrow size distribution and 'clear' surface. They had been widely applied in biological systems.
Emulsifier-free macromolecule nanoparticle latex can be obtained by conventional heating method but the reaction takes more time and the particle size distribution is wide in comprision with those obtained by microwave heating method. So in this paper, the monodisperse emulsifier-free macromolcule nanoparticle latex is obtained by the use of microwave radiation under ambient pressure. The suitable condition for the preparation of such latex is discussed through analyzing the factors such as the kind and content of monomer, cosolvent, initiator and the temperature of the reaction. The stability testing of the synthesized latex such as the storage stability at normal or low temperature and the stability to electrolyte is done.
The particle formation mechanism of emulsifier-free macromolecule nanoparticles under microwave radiation is discussed through analyzing several kinds of factors affecting the emulsifier-free polymerization and the data or phenomena obtained during the polymerization such as the curve of the conversion vs. time, the curve of the transparency of the system vs. time, the hydrodynamic radius and its distribution during the polymerization. It is considered that both the homogeneous nucleation and the micelle nucleation exist in acetone-water medium or in methanol-water system. Furthermore, the nucleation will happen several times during the polymerization.
通过分析各种因素对无皂聚合反应的影响，并对反应过程中的转化率、透光率、体系中的粒子平均水化半径及粒径分布的测定，深入探讨了丙酮-微波法合成无皂高分子共聚胶乳粒子机理，认为在微波辐照和助溶剂丙酮的存在下，无皂共聚胶乳粒子的成核机理为“均相成核”与“胶束成核”并存，而且随着反应的进行存在“多次成核”。同时也探讨了微波辐照下丙酮-水体系无皂聚苯乙烯胶乳粒子、甲醇-水体系无皂聚苯乙烯和苯乙烯与甲基丙烯酸甲酯共聚胶乳粒子的形成机理。
The latexes obtained by emulsifier-free emulsion polymerization show good adhesion and water-resistant properties and are characterized by having a narrow size distribution and 'clear' surface. They had been widely applied in biological systems.
Emulsifier-free macromolecule nanoparticle latex can be obtained by conventional heating method but the reaction takes more time and the particle size distribution is wide in comprision with those obtained by microwave heating method. So in this paper, the monodisperse emulsifier-free macromolcule nanoparticle latex is obtained by the use of microwave radiation under ambient pressure. The suitable condition for the preparation of such latex is discussed through analyzing the factors such as the kind and content of monomer, cosolvent, initiator and the temperature of the reaction. The stability testing of the synthesized latex such as the storage stability at normal or low temperature and the stability to electrolyte is done.
The particle formation mechanism of emulsifier-free macromolecule nanoparticles under microwave radiation is discussed through analyzing several kinds of factors affecting the emulsifier-free polymerization and the data or phenomena obtained during the polymerization such as the curve of the conversion vs. time, the curve of the transparency of the system vs. time, the hydrodynamic radius and its distribution during the polymerization. It is considered that both the homogeneous nucleation and the micelle nucleation exist in acetone-water medium or in methanol-water system. Furthermore, the nucleation will happen several times during the polymerization.
引文
[1]夏和生，王琪，纳米技术进展，高分子材料科学与工程，2001，17(4)，1-6
[2]张中太，林元华，唐子龙等，纳米材料及其技术的应用前景，材料工程，2000，3，42-48
[3]Chi, W.; Jun, G.; Mci, L.; Wenmin, Z.,etc. Formation, stabilization, and application of polymeric nanoparticles. Macromol. Symp., 2000,150, 219-227
[4]Atik, S.S.; Thomas, K. J., Polymerized microemulsion, J. Am. Chem. Soc. 1981,103,4279
[5]Guo, J. S.; EIAasser, M.S.; Vanderhoff, J. W. J. Polym. Sci. Polym. Chem. 1989,27,691
[6]Bigg, S.; Grieser, F., Preparation of polystyrene latex with ultrasonic initiation, Macromolecules 1995,28,4877
[7]Wu, C., A simple modle for the structure of spherical microemulsions, Macromolecules 1994,27,298;1994,27,709
[8]Schmidt, M.; Baumann, F.; Deubzer, B., On the preparation oforgano-silicon m-spheres: A polycondensation in m-emulsion, Macromolecules 1994,27,6102
[9]Markus Antonietri; Wolfgang Bremser; Dorothea Mii.,etc. Synthesis and size control of polystyrene latices via polymerization in microemulsion, Macromolecules 1991,24,6636-6643
[10]徐相凌，殷亚东，葛学武等，微乳液聚合研究进展，高等学校化学学报，1993，20(3)，478-485
[11]王群，府寿宽，于同隐，乳液聚合的最新进展(上)，高分子通报，1996，3，141
[12]T. R. Aslamazova, Emulsifier-free latexes and polymers on their base, Progress in Organic Coatings, 1995,25,109-167
[13]Tamai, H.; Fujii, A.; Suzawa, S. J Colloid Interface Sci 1987,116,37
[14]Feeney, J. P.; Napper, D. H.; Gilbert, R. G. Surfactant-free emulsion polymerizations: predictions of the coagulative nucleation theory, Macromolecules 1987120,2922
[15]Kawaguchi, H.; Sugi, Y.; Ohtsuka, Y. Copolymerization of styrene with acrylamide derivatives in an emulsifier-free aqueous medium. J. Appl. Polym. Sci.,1981, 26(5),1649-57
[16]程时远，李建宗，纪庆绪，无皂乳液聚合，高分子通报，1991，3，129-137
[17]阎翠娥，徐章煌，程时远，生物活性高分子微球，高分子材料科学与工程，1999，1
[18]Zurkova, E.; Bouchal, K.; Zdenkova, D.,etc., Preparation of monodisperse reactive styrene-glycidyl methacrylate latexes by the emulsifier-free dispersion copolymerization technique. J. Polym. Sci., Polym. Chem. Ed., 1983,21 (10), 2949-60
[19]Kunio A.; Masahiko A.; Shigeo l.,etc. Agitation effect on the rate of soapless emulsion polymerization of methyl methacrylate in water, J. Polym. Sci., Polym Ed,. 1981, 19, 1203-1215
[20]Liu, Li Jen; Krieger, lrvin M., Emulsifier-free emulsion polymerization with cationic comonomer. J. Polym. Sci., Polym. Chem. Ed., 1981, 19(11), 3013-3026
[21]Furusawa, Kunio. Preparation of surfactant-free polystyrene latexes with high surface charge and electrical double layer on their surfaces. Bull. Chem. Soc. 1982, 55(1), 48-51
[22]Li, Pei; Xu, Jianjun; Wu, Chi, Functionalization of poly(methylstyrene) latex particles in an emulsifier-free system. Colloids Surf., A, 1999, 153(1-3), 363-366
[23]Javier I.; Maria J.; Harold A. Reactive surfactants in heterophase polymerization Ⅱ Particle nucleation, Macromolecules 1998,31,5631-5638
[24]程纪渝，罗朝瑛，马光复，在18-冠-6存在下苯乙烯无乳化剂乳液聚合，高分子通讯，1986,1，36-42
[25]纪庆绪，程时远，李建宗，MMA-BA 无皂乳液共聚合Ⅰ，高等学校化学学报，1992,13(6)，853-856
[26]唐广粮，郝广杰，宋谋道等，可乳化共聚单体 AGES 用于无皂乳液聚合的研究，高等学校化学学报，1999,20(11)，1804-1807
[27]Verrier-Charleux, B.; Graillat, C.; Chevalier, Y. Synthesis and characterization of emulsifier-free quaternarized vinyibenzyl chloride latexes. Colloid Polym. Sci., 1991,269(4), 398-405
[28]Guillaume, J. L.; Pichot, C.; Guillot, J.Emulsifier-free emulsion copolymerization of styrene and butyl acrylate. Ⅰ. Kinetic studies in the absence of surfactant. J. Polym. Sci., Part A: Polym. Chem., 1991, 28(1), 119-36
[29]Guillaume, J. L.; Pichot, C.; Guillot, J.Emulsifier-free emulsion copolymerization of styrene and butyl acrylate. Ⅲ. Kinetic studies in the presence of a surface active comonomer, the sodium acrylamido undecanoate,J. Polym. Sci., Part A: Polym. Chem., 1990,28(1), 137-52
[30]Xu, Jianjun; Li, Pei; Wu, Chi, Formation of highly monodispersed emulsifier-free cationic poly(methylstyrene) latex panicles. J. Polym. Sci., Part A: Polym. Chem.,1999, 37(13),2069-2074
[31]Guo, Tian Ying; Song, Mou Dao; Zhou, Qing Ye,etc. Semibatch emulsifier-free emulsion copolymerization of methyl methacrylate and n-butyl acrylate in the presence of 2-hydroxyethyl methacrylate. Chin. Chem. Lett., 1998,9(7), 683-686
[32]Tang, Guangliang; Hao, Guangjie; Song, Moudao,etc. Studies on high solid content and stable emulsifier-free emulsion polymerization. Chin. J. React. Polym., 1998, 7(2), 61-67
[33]Lee, D. Y.; Kim, J. H.,Emulsion polymerization of styrene using an alkali-soluble random copolymer as polymeric emulsifier. J. Polym. Sci., Part A: Polym. Chem., 1998,36(16), 2865-2872
[34]Aslamazova, T. R. ,The role of polymer surface in the hydrodynamic stability of particles of emulsifier-free poly(methacrylate) latexes. Colloid J., 1999, 61 (2), 139-143
[35]Guo, Tianying; Song, Moudao; Hao, Guangjie,etc. Effect of 2-hydroxyethyl methacrylate on semibatch emulsifier-free emulsion copolymerization of methyl methacrylate and butyl acrylate. Chin. J. React. Polym., 1999,8(1-2), 38-45
[36]Li, Pei; Xu, Jianjun; Wang, Qun; Wu, Chi, Surface functionalization of polymer latex particles: 4. tailor-making of aldehyde-functional poly(methylstyrene) latexes in an emulsifier-free system. Langmuir, 2000,16(9), 4141-4147
[37]M.Okubo,;Y. Yamamoto,M.;S.Kamei,etc. Immunoactivity of polymer microspheres with their hydrophilic/hydrophobic heterogeneous surface sensitized with an antibody, Colloid and Polymer Sci 1987,265,1061-1066
[38]Brown, W.; Zhao, J., The surface tension of polymer bends, Macromolecules 1993,26,2771
[39]Song Z.Q. and poehlein G.W., Particle nucleation in emulsifier-free aqueous-phase polymerization: stage 1, J.Colloid. and Int. Sci., 1989,128:486
[41]Fitch R.M., Preparation and characterization of charge stabilized polymer colloids, Charged React. Polym. 1975,2:51
[42]Arai, M.; Ami, K.; Saito, S. ,Polymer Particle Formation in Soapless Emulsion Polymerization, J Polym Sci, Polym Chem Ed 1979,17,3655
[43]Goodall.A.R,Wilkison. M.C.,Mechanism of emulsion polymerization of ST in soap-free systems. J.Polym. Sci.Polym.Chem. Sd, 1977.15:2193
[44]Goodwin J.W., Hearn J., Ho C.C., Ottewill R.H.,Preparation and characterization of polymer latices formed in the absence of surface active agents, Br. Polym.J., 1973,5:347
[45]Hansen F.K. and Ugelstad J., Particle nucleation in emulsion polymerization.I.A theory for homogeneous nucleation. J.Polym.Sci. Part A: Polym.Chem.,1978,16:1953
[46] Goodall A.R., Wilkinson.M.C.,Characterization of particles during growth in emulsifier-free emulsion polymerization of ST., Polym.eolloids, 1978.2:629
[47] Xiaosn L.;R.Salovey. Oligomer formation in the emulsifier-free emulsion polymerization of styrene J. Polym. Sci. A: Polym Chem 2000,38:1323-1336
[48] 张茂根，翁志学，黄志明等，无皂乳液的稳定性及增加稳定性的原理，高分子材料科学与工程，1999，15(5)30-33
[49] Ali, S. A.; Sengupta, M.Preparation and characterization of monodisperse polystyrene latexes of varying particle sizes without the use of surfactants. J Polym Mater, 1991, 8(3), 243-9
[50] Li, Xiaosan: Salovey. R.. Oligomer formation in the emulsifier-free emulsion polymerization of styrene. J. Polym. Sci.. Pall A: Polym. Chem., 2000, 38(8). 1323-1336
[51] Jun G.; Tengjiao H.: Yubao Z..etc. The adsorption of linear poly(N-isopropylacrylamide) chains on surfactant-free polystyrene nanoparticles, Chin. J. Polym. Sci. 1999, 17(6), 595-601
[52] 邵明望，张文敏，微波化学与工程，安徽大学出版社，1999
[53] 金钦汉，微波化学，科学出版社，1999
[54] 樊兴君，尤进茂，谭干祖等，微波促进有机化学反应研究进展，化学进展，1998，10(3)，285-295
[55] 何德林，王锡臣，微波技术在聚合反应中的应用研究进展，高分子材料科学与工程，2001．17(1)20-24
[56] Gourdenne. A. Polymerization under microwaves: fifteen years of experience,Ceram. Trans.. 1997.80. 425-436
[57] Ma, J.; Huang. X.; Cheng, H.; Zhao, Z.; Qi, L., Preparation. of nanosized ZnS panicles in water/oil emulsions by microwave heating. J. Mater. Sci. Lett., 1996, 15(14), 1247-1248
[58] Palacios, J.: Valverde, C,. Microwave initiated emulsion polymerization of styrene: reaction conditions. New Polym. Mater., 1996,5(1), 93-101
[59] Murry M.; David, C.; Linda S.,etc. Microwave Synthesis of the Colloidal Poly(Nisopropylacrylamide) Microgel System, J. Chem. Soc. Faraday Trans, 1994, 90(13), 1999-2000
[60] Wenmin Z.; Jun, G.; Chi, W. Microwave Preparation of Narrowly Distributed Surfactant-Free Stable Polystyrene Nanospheres, Macromolecules 1997,30,6388-6390
[61] Zhang Y B. Xiang M L, Jiang M, Wu C. Laser-Light-Scattering Studies on the Complexation between Poly(styrene-co-4-vinylphenol)and Isorefractive Poly(ethyl methacrylate)in Toluene. Macromolecules, 1997,30:2035
[62] 何卫东，潘才元，卢涛，甲基丙烯酸丁酯微波无皂乳液聚合，功能高分子学报．1999，12(1)，11-14
[63] 张文敏，唐业仓，张洪涛等，微波合成均分散胶体高分子微球，物理化学学报，1996，12(10)，943-945
[64] 张文敏，吴奇，魏涛等，高浓度窄分布高分子纳米粒子胶乳的制备，物理化学学报，2000．16(2)，116-120
[65] 纪庆绪，助溶剂存在下制备丙烯酯无皂胶乳，高分子材料科学与工程．1993，2，113-117
[66] 常津，毛津淑，常青等，聚苯乙烯-孕酮免疫微球的新法制备与检测，中国生物医学工程学报．1999，18(2)
[67] Masayoshi O.: Akira Y.; Susumu S.; Katsuhiko N. Studies on suspension and emulsion XL Ⅵ. Emulsifier-free emulsion polymerization of styrene in acetone-water, J Appl Polym Sci, 1981, 26, 1675-1679
[68] A.M.Homola, M.Inooe, A. Robertson, Experiments with soap-free polymerization of styrene in the presence of alcohols, J Appl Polym Sci, 1975, 19, 3077-3086
[69] Y. Chonde, I.M.Krieger, Emulsion polymerization of styrene with ionic comonomer in the presence of methanol, J Appl Polym Sci, 1981, 1819-1827
[70] F.L.Baines, S.Dionisio, N.C.Billingham, Use of block copolymer stabilizers for the dispersion polymerization of styrene in alcoholic media, Macromolecules, 1996, 29, 3096-3102
[71] 胡金生，曹同玉，刘庆普，乳液聚合，化学工业出版社，1987，196
[72] Zhang, Mao-Gen; Weng, Zhi-Xue; Huang, Zhi-Ming,etc. Stability of emulsifier-free emulsion copolymerization of methyl methacrylate/butyl acrylate/sodium mono(ethyl polyoxyethylene) maleate. Chin. J. Polym. Sci., 1999,17(6),571-577
[73] Kluss, B. U.; Zimehl, R., Some aspects of colloidal polymers. Solvent structure-originated interactions. Prog. Colloid Polym. Sci., 1998, 111,144-150
[74] Biota, Henk P.; Gauthier, Marlo; Li, Kai,etc. Soap-free emulsion polymerization of n-butyl acrylate: copolymerization with l,1-(dimethyl)-1-(3-methacryloxyethyl)-1-(sulfopropyl)ammonium betaine. J. Appl. Polym. Sci., 1998, 70(2), 227-238
[75] Ganachaud, F.; Bouali, B.; Veron, L.,etc,Surface characterization of amine-containing latexes by charge titration and contact angle measurements. Colloids Surf., A, 1998, 137(1-3), 141-154
[76] Zhang, Mao-Gen; Went, Zhi-Xue; Huang, Zhi-Ming,etc, Effects of monomer polarity on MMA/BA/NaMA emulsifier-free emulsion copolymerization. Eur. Polym. J.,1998, 34(9), 1243-1247
[77] Tauer, K.; Deckwer, R., Polymer and groups in persulfate-initiated styrene emulsion polymerization. Acta Polym., 1998, 49(8), 411-416
[78] Kampes, A.; Tieke, B., Emulsifier-free emulsion polymerization of the comonomer system styrene/tetrahydrofuffuryl methacrylate. Colloid Polym. Sci. 1997, 275(12), 1136-1143
[79] 朱永群，高分子基础，杭州，浙江教育出版社，1985，69
[80] 许涌深，袁才登，王艳君等，无皂乳液共聚合动力学和机理，高分子材料科学与工程，2000，16(1)，46-48，52
[81] Cheng, Shiyuan; Yan, Cui'e; Feng, Linxian, Effect of AA on properties of St-MMA-AA emulsifier-free latex particles. Macromol. Syrup., 2000,150,135-141
[82] Aslamazova, T. R., Stability of emulsifier-free acrylate latexes with respect to freezing and thawing Colloid J., 1999, 61(3), 268-273
[83] Twigt, F.; Piet, P.; German, A.Preparation and cocatalytic properties of fanctionalized latexes, Eur Polym J, 1991,27(9), 93945
[84] 阎翠娥，黄世强，封麟先，St-MMA-AA 三元无皂共聚胶粒作蛋白质载体的研究，应用化学，1999，16(2)31-34
[85] 阎翠娥，黄世强，封麟先，St-MMA-AA 二元无皂共聚胶乳性质的研究，高分子材料科学与工程，2000，16(6)，75-78，82
[86] 阎翠娥，程时远，封麟先，二元无皂乳液共聚合动力学及其模型的研究，高分子学报，1999，5，534-539
[87] Shoaf, G.L.; Poehlein, G.W., Kinetics of emulsion copolymerization with acrylic acids, J Appl Polym Sci, 1991,42,1213
[88] Sakota K.: Okaya T.: J Appl Polym Sci, 1977, 21, 1035
[89] 郝海涓，郝广杰，郭天瑛等，MMA/BA/AA/HEMA 无皂乳液体系的合成与性能表征，离子交换与吸附，1999，15(6)，453-459
[90]张茂根，翁志学，黄志明等，MMA/BA/双官能团单体无皂共聚乳液的稳定性，高等学校化学学报，1998,19(11)，1848-1852
[91]LeDissez, C.; Wong, C.; Mitchell, K.Analysis of surface aldehyde functions on surfactant-free polystyrene/polyacrolein latex. Macromolecules, 1996,29(9),3338
[92]Shin-Chang H.; Yuan-Ling L.;Chia-Fen L.Polymer latex containing carboxylic acid functional groups Ⅰ Systhesis of polymer latex from MMA and AA, J Appl Polym Sci, 1999,74,3111-3120
[93]Gardon J.L. Emulsion polymerization Ⅱ Review of experimental data in the context of the revised Smith-Ewart theory, J Polym Sci.,A1,1968,6,643-664
[94]Yanmei W.;Youxiang W.;Linxian F.;Preparation and magnetic properties of [P(St-co-AA)]Ni Microspheres, J Appl Polym Sci, 1997,64,1843-1848
[95]Chomg-shyan Chern, Chi-huei Lin, Semibatch surfactant-free polymerization of butyl acrylate, Polymer Journal, 1995,11:1094-1103
[96]Tamai, H.; Fujii, A.; Suzawa, T. Some colloidal considerations on the surface characteristics of various emulsifier-free polymer latices. J. Colloid Interface Sci., 1987,116(1),37-41
[97]Chern C S, Chen Y C. Stability of the polymerizable surfactant stabilized latex particle during semibatch emulsion polymerization, Colloid and Polym Sci, 1997,2:124-130
[98]Oho H, Saeki H. Preparation and properties of polymethyl methacrylate latex dispersions having no surfactant, Colloid and Polymer Sci,1975,9:744-749
[99]黄志虹，谢志明，李卓美，丙烯酸酯无皂乳液稳定性研究，功能高分子学报，2000，13(1)，29-32
[100]程时远，纪庆绪，甲基丙烯酸甲酯-丙烯酸正丁酯-ω-十一烯酸钠无皂乳液共聚合研究，高分子学报，1993，3,295-303
[101]张洪涛，李建宗，谭必恩等 BA-St-MMA 复合乳液共聚合动力学和成核机理研究，高分子材料科学与工程，1998，14(2)，47-50
[102]戴李宗，邹友思，潘荣华，苯乙烯-丙烯酸丁酯无皂乳液聚合动力学及 TEM 分析，高等学校化学学报，1992,13(11)，1424-1427
[103]Show-An C.; Song-Tai L. Kinetics and mechanism of emulsifier-free emulsion polymerization: styrene/hydrophilic comonomer(acrylamide) system, Macromolecules, 1991, 24, 3340-3351
[104]M. Slawinski; M. Schellekens; J. Meuldlik. Seeded emulsion polymerization of styrene: influence of acrylic acid on the particle growth process, J Appl Polym Sci, 2000,76:1186-1196
[105]D.Munro;A.R. Goodall;M.C.Wilkinson. Study of particle nucleation, flocculation, and growth in the emulsifier-free polymerization of styrene in water by total intensity light scattering and photon correlation spectroscopy, J Colloid and Interface Sci, 1979,68(1)
[106]Yanmei W.; Linxian F.; Caiyuan P.; Preparation and characterization of p(St-co-4VP) paticles produced by using emulsifier-free emulsion polymerization, J Appl Polym Sci, 1999,74, 1502-1507
[107]Henmei N.; Yongzhong D.; Guanghui M.; Mechanism of soap-free emulsion polymerization of styrene and 4-vinylpyridine: characteristics of reaction in the monomer phase, aqueous phase, and their interface, Macromolecules, 2001,34,6577-6585
[2]张中太，林元华，唐子龙等，纳米材料及其技术的应用前景，材料工程，2000，3，42-48
[3]Chi, W.; Jun, G.; Mci, L.; Wenmin, Z.,etc. Formation, stabilization, and application of polymeric nanoparticles. Macromol. Symp., 2000,150, 219-227
[4]Atik, S.S.; Thomas, K. J., Polymerized microemulsion, J. Am. Chem. Soc. 1981,103,4279
[5]Guo, J. S.; EIAasser, M.S.; Vanderhoff, J. W. J. Polym. Sci. Polym. Chem. 1989,27,691
[6]Bigg, S.; Grieser, F., Preparation of polystyrene latex with ultrasonic initiation, Macromolecules 1995,28,4877
[7]Wu, C., A simple modle for the structure of spherical microemulsions, Macromolecules 1994,27,298;1994,27,709
[8]Schmidt, M.; Baumann, F.; Deubzer, B., On the preparation oforgano-silicon m-spheres: A polycondensation in m-emulsion, Macromolecules 1994,27,6102
[9]Markus Antonietri; Wolfgang Bremser; Dorothea Mii.,etc. Synthesis and size control of polystyrene latices via polymerization in microemulsion, Macromolecules 1991,24,6636-6643
[10]徐相凌，殷亚东，葛学武等，微乳液聚合研究进展，高等学校化学学报，1993，20(3)，478-485
[11]王群，府寿宽，于同隐，乳液聚合的最新进展(上)，高分子通报，1996，3，141
[12]T. R. Aslamazova, Emulsifier-free latexes and polymers on their base, Progress in Organic Coatings, 1995,25,109-167
[13]Tamai, H.; Fujii, A.; Suzawa, S. J Colloid Interface Sci 1987,116,37
[14]Feeney, J. P.; Napper, D. H.; Gilbert, R. G. Surfactant-free emulsion polymerizations: predictions of the coagulative nucleation theory, Macromolecules 1987120,2922
[15]Kawaguchi, H.; Sugi, Y.; Ohtsuka, Y. Copolymerization of styrene with acrylamide derivatives in an emulsifier-free aqueous medium. J. Appl. Polym. Sci.,1981, 26(5),1649-57
[16]程时远，李建宗，纪庆绪，无皂乳液聚合，高分子通报，1991，3，129-137
[17]阎翠娥，徐章煌，程时远，生物活性高分子微球，高分子材料科学与工程，1999，1
[18]Zurkova, E.; Bouchal, K.; Zdenkova, D.,etc., Preparation of monodisperse reactive styrene-glycidyl methacrylate latexes by the emulsifier-free dispersion copolymerization technique. J. Polym. Sci., Polym. Chem. Ed., 1983,21 (10), 2949-60
[19]Kunio A.; Masahiko A.; Shigeo l.,etc. Agitation effect on the rate of soapless emulsion polymerization of methyl methacrylate in water, J. Polym. Sci., Polym Ed,. 1981, 19, 1203-1215
[20]Liu, Li Jen; Krieger, lrvin M., Emulsifier-free emulsion polymerization with cationic comonomer. J. Polym. Sci., Polym. Chem. Ed., 1981, 19(11), 3013-3026
[21]Furusawa, Kunio. Preparation of surfactant-free polystyrene latexes with high surface charge and electrical double layer on their surfaces. Bull. Chem. Soc. 1982, 55(1), 48-51
[22]Li, Pei; Xu, Jianjun; Wu, Chi, Functionalization of poly(methylstyrene) latex particles in an emulsifier-free system. Colloids Surf., A, 1999, 153(1-3), 363-366
[23]Javier I.; Maria J.; Harold A. Reactive surfactants in heterophase polymerization Ⅱ Particle nucleation, Macromolecules 1998,31,5631-5638
[24]程纪渝，罗朝瑛，马光复，在18-冠-6存在下苯乙烯无乳化剂乳液聚合，高分子通讯，1986,1，36-42
[25]纪庆绪，程时远，李建宗，MMA-BA 无皂乳液共聚合Ⅰ，高等学校化学学报，1992,13(6)，853-856
[26]唐广粮，郝广杰，宋谋道等，可乳化共聚单体 AGES 用于无皂乳液聚合的研究，高等学校化学学报，1999,20(11)，1804-1807
[27]Verrier-Charleux, B.; Graillat, C.; Chevalier, Y. Synthesis and characterization of emulsifier-free quaternarized vinyibenzyl chloride latexes. Colloid Polym. Sci., 1991,269(4), 398-405
[28]Guillaume, J. L.; Pichot, C.; Guillot, J.Emulsifier-free emulsion copolymerization of styrene and butyl acrylate. Ⅰ. Kinetic studies in the absence of surfactant. J. Polym. Sci., Part A: Polym. Chem., 1991, 28(1), 119-36
[29]Guillaume, J. L.; Pichot, C.; Guillot, J.Emulsifier-free emulsion copolymerization of styrene and butyl acrylate. Ⅲ. Kinetic studies in the presence of a surface active comonomer, the sodium acrylamido undecanoate,J. Polym. Sci., Part A: Polym. Chem., 1990,28(1), 137-52
[30]Xu, Jianjun; Li, Pei; Wu, Chi, Formation of highly monodispersed emulsifier-free cationic poly(methylstyrene) latex panicles. J. Polym. Sci., Part A: Polym. Chem.,1999, 37(13),2069-2074
[31]Guo, Tian Ying; Song, Mou Dao; Zhou, Qing Ye,etc. Semibatch emulsifier-free emulsion copolymerization of methyl methacrylate and n-butyl acrylate in the presence of 2-hydroxyethyl methacrylate. Chin. Chem. Lett., 1998,9(7), 683-686
[32]Tang, Guangliang; Hao, Guangjie; Song, Moudao,etc. Studies on high solid content and stable emulsifier-free emulsion polymerization. Chin. J. React. Polym., 1998, 7(2), 61-67
[33]Lee, D. Y.; Kim, J. H.,Emulsion polymerization of styrene using an alkali-soluble random copolymer as polymeric emulsifier. J. Polym. Sci., Part A: Polym. Chem., 1998,36(16), 2865-2872
[34]Aslamazova, T. R. ,The role of polymer surface in the hydrodynamic stability of particles of emulsifier-free poly(methacrylate) latexes. Colloid J., 1999, 61 (2), 139-143
[35]Guo, Tianying; Song, Moudao; Hao, Guangjie,etc. Effect of 2-hydroxyethyl methacrylate on semibatch emulsifier-free emulsion copolymerization of methyl methacrylate and butyl acrylate. Chin. J. React. Polym., 1999,8(1-2), 38-45
[36]Li, Pei; Xu, Jianjun; Wang, Qun; Wu, Chi, Surface functionalization of polymer latex particles: 4. tailor-making of aldehyde-functional poly(methylstyrene) latexes in an emulsifier-free system. Langmuir, 2000,16(9), 4141-4147
[37]M.Okubo,;Y. Yamamoto,M.;S.Kamei,etc. Immunoactivity of polymer microspheres with their hydrophilic/hydrophobic heterogeneous surface sensitized with an antibody, Colloid and Polymer Sci 1987,265,1061-1066
[38]Brown, W.; Zhao, J., The surface tension of polymer bends, Macromolecules 1993,26,2771
[39]Song Z.Q. and poehlein G.W., Particle nucleation in emulsifier-free aqueous-phase polymerization: stage 1, J.Colloid. and Int. Sci., 1989,128:486
[41]Fitch R.M., Preparation and characterization of charge stabilized polymer colloids, Charged React. Polym. 1975,2:51
[42]Arai, M.; Ami, K.; Saito, S. ,Polymer Particle Formation in Soapless Emulsion Polymerization, J Polym Sci, Polym Chem Ed 1979,17,3655
[43]Goodall.A.R,Wilkison. M.C.,Mechanism of emulsion polymerization of ST in soap-free systems. J.Polym. Sci.Polym.Chem. Sd, 1977.15:2193
[44]Goodwin J.W., Hearn J., Ho C.C., Ottewill R.H.,Preparation and characterization of polymer latices formed in the absence of surface active agents, Br. Polym.J., 1973,5:347
[45]Hansen F.K. and Ugelstad J., Particle nucleation in emulsion polymerization.I.A theory for homogeneous nucleation. J.Polym.Sci. Part A: Polym.Chem.,1978,16:1953
[46] Goodall A.R., Wilkinson.M.C.,Characterization of particles during growth in emulsifier-free emulsion polymerization of ST., Polym.eolloids, 1978.2:629
[47] Xiaosn L.;R.Salovey. Oligomer formation in the emulsifier-free emulsion polymerization of styrene J. Polym. Sci. A: Polym Chem 2000,38:1323-1336
[48] 张茂根，翁志学，黄志明等，无皂乳液的稳定性及增加稳定性的原理，高分子材料科学与工程，1999，15(5)30-33
[49] Ali, S. A.; Sengupta, M.Preparation and characterization of monodisperse polystyrene latexes of varying particle sizes without the use of surfactants. J Polym Mater, 1991, 8(3), 243-9
[50] Li, Xiaosan: Salovey. R.. Oligomer formation in the emulsifier-free emulsion polymerization of styrene. J. Polym. Sci.. Pall A: Polym. Chem., 2000, 38(8). 1323-1336
[51] Jun G.; Tengjiao H.: Yubao Z..etc. The adsorption of linear poly(N-isopropylacrylamide) chains on surfactant-free polystyrene nanoparticles, Chin. J. Polym. Sci. 1999, 17(6), 595-601
[52] 邵明望，张文敏，微波化学与工程，安徽大学出版社，1999
[53] 金钦汉，微波化学，科学出版社，1999
[54] 樊兴君，尤进茂，谭干祖等，微波促进有机化学反应研究进展，化学进展，1998，10(3)，285-295
[55] 何德林，王锡臣，微波技术在聚合反应中的应用研究进展，高分子材料科学与工程，2001．17(1)20-24
[56] Gourdenne. A. Polymerization under microwaves: fifteen years of experience,Ceram. Trans.. 1997.80. 425-436
[57] Ma, J.; Huang. X.; Cheng, H.; Zhao, Z.; Qi, L., Preparation. of nanosized ZnS panicles in water/oil emulsions by microwave heating. J. Mater. Sci. Lett., 1996, 15(14), 1247-1248
[58] Palacios, J.: Valverde, C,. Microwave initiated emulsion polymerization of styrene: reaction conditions. New Polym. Mater., 1996,5(1), 93-101
[59] Murry M.; David, C.; Linda S.,etc. Microwave Synthesis of the Colloidal Poly(Nisopropylacrylamide) Microgel System, J. Chem. Soc. Faraday Trans, 1994, 90(13), 1999-2000
[60] Wenmin Z.; Jun, G.; Chi, W. Microwave Preparation of Narrowly Distributed Surfactant-Free Stable Polystyrene Nanospheres, Macromolecules 1997,30,6388-6390
[61] Zhang Y B. Xiang M L, Jiang M, Wu C. Laser-Light-Scattering Studies on the Complexation between Poly(styrene-co-4-vinylphenol)and Isorefractive Poly(ethyl methacrylate)in Toluene. Macromolecules, 1997,30:2035
[62] 何卫东，潘才元，卢涛，甲基丙烯酸丁酯微波无皂乳液聚合，功能高分子学报．1999，12(1)，11-14
[63] 张文敏，唐业仓，张洪涛等，微波合成均分散胶体高分子微球，物理化学学报，1996，12(10)，943-945
[64] 张文敏，吴奇，魏涛等，高浓度窄分布高分子纳米粒子胶乳的制备，物理化学学报，2000．16(2)，116-120
[65] 纪庆绪，助溶剂存在下制备丙烯酯无皂胶乳，高分子材料科学与工程．1993，2，113-117
[66] 常津，毛津淑，常青等，聚苯乙烯-孕酮免疫微球的新法制备与检测，中国生物医学工程学报．1999，18(2)
[67] Masayoshi O.: Akira Y.; Susumu S.; Katsuhiko N. Studies on suspension and emulsion XL Ⅵ. Emulsifier-free emulsion polymerization of styrene in acetone-water, J Appl Polym Sci, 1981, 26, 1675-1679
[68] A.M.Homola, M.Inooe, A. Robertson, Experiments with soap-free polymerization of styrene in the presence of alcohols, J Appl Polym Sci, 1975, 19, 3077-3086
[69] Y. Chonde, I.M.Krieger, Emulsion polymerization of styrene with ionic comonomer in the presence of methanol, J Appl Polym Sci, 1981, 1819-1827
[70] F.L.Baines, S.Dionisio, N.C.Billingham, Use of block copolymer stabilizers for the dispersion polymerization of styrene in alcoholic media, Macromolecules, 1996, 29, 3096-3102
[71] 胡金生，曹同玉，刘庆普，乳液聚合，化学工业出版社，1987，196
[72] Zhang, Mao-Gen; Weng, Zhi-Xue; Huang, Zhi-Ming,etc. Stability of emulsifier-free emulsion copolymerization of methyl methacrylate/butyl acrylate/sodium mono(ethyl polyoxyethylene) maleate. Chin. J. Polym. Sci., 1999,17(6),571-577
[73] Kluss, B. U.; Zimehl, R., Some aspects of colloidal polymers. Solvent structure-originated interactions. Prog. Colloid Polym. Sci., 1998, 111,144-150
[74] Biota, Henk P.; Gauthier, Marlo; Li, Kai,etc. Soap-free emulsion polymerization of n-butyl acrylate: copolymerization with l,1-(dimethyl)-1-(3-methacryloxyethyl)-1-(sulfopropyl)ammonium betaine. J. Appl. Polym. Sci., 1998, 70(2), 227-238
[75] Ganachaud, F.; Bouali, B.; Veron, L.,etc,Surface characterization of amine-containing latexes by charge titration and contact angle measurements. Colloids Surf., A, 1998, 137(1-3), 141-154
[76] Zhang, Mao-Gen; Went, Zhi-Xue; Huang, Zhi-Ming,etc, Effects of monomer polarity on MMA/BA/NaMA emulsifier-free emulsion copolymerization. Eur. Polym. J.,1998, 34(9), 1243-1247
[77] Tauer, K.; Deckwer, R., Polymer and groups in persulfate-initiated styrene emulsion polymerization. Acta Polym., 1998, 49(8), 411-416
[78] Kampes, A.; Tieke, B., Emulsifier-free emulsion polymerization of the comonomer system styrene/tetrahydrofuffuryl methacrylate. Colloid Polym. Sci. 1997, 275(12), 1136-1143
[79] 朱永群，高分子基础，杭州，浙江教育出版社，1985，69
[80] 许涌深，袁才登，王艳君等，无皂乳液共聚合动力学和机理，高分子材料科学与工程，2000，16(1)，46-48，52
[81] Cheng, Shiyuan; Yan, Cui'e; Feng, Linxian, Effect of AA on properties of St-MMA-AA emulsifier-free latex particles. Macromol. Syrup., 2000,150,135-141
[82] Aslamazova, T. R., Stability of emulsifier-free acrylate latexes with respect to freezing and thawing Colloid J., 1999, 61(3), 268-273
[83] Twigt, F.; Piet, P.; German, A.Preparation and cocatalytic properties of fanctionalized latexes, Eur Polym J, 1991,27(9), 93945
[84] 阎翠娥，黄世强，封麟先，St-MMA-AA 三元无皂共聚胶粒作蛋白质载体的研究，应用化学，1999，16(2)31-34
[85] 阎翠娥，黄世强，封麟先，St-MMA-AA 二元无皂共聚胶乳性质的研究，高分子材料科学与工程，2000，16(6)，75-78，82
[86] 阎翠娥，程时远，封麟先，二元无皂乳液共聚合动力学及其模型的研究，高分子学报，1999，5，534-539
[87] Shoaf, G.L.; Poehlein, G.W., Kinetics of emulsion copolymerization with acrylic acids, J Appl Polym Sci, 1991,42,1213
[88] Sakota K.: Okaya T.: J Appl Polym Sci, 1977, 21, 1035
[89] 郝海涓，郝广杰，郭天瑛等，MMA/BA/AA/HEMA 无皂乳液体系的合成与性能表征，离子交换与吸附，1999，15(6)，453-459
[90]张茂根，翁志学，黄志明等，MMA/BA/双官能团单体无皂共聚乳液的稳定性，高等学校化学学报，1998,19(11)，1848-1852
[91]LeDissez, C.; Wong, C.; Mitchell, K.Analysis of surface aldehyde functions on surfactant-free polystyrene/polyacrolein latex. Macromolecules, 1996,29(9),3338
[92]Shin-Chang H.; Yuan-Ling L.;Chia-Fen L.Polymer latex containing carboxylic acid functional groups Ⅰ Systhesis of polymer latex from MMA and AA, J Appl Polym Sci, 1999,74,3111-3120
[93]Gardon J.L. Emulsion polymerization Ⅱ Review of experimental data in the context of the revised Smith-Ewart theory, J Polym Sci.,A1,1968,6,643-664
[94]Yanmei W.;Youxiang W.;Linxian F.;Preparation and magnetic properties of [P(St-co-AA)]Ni Microspheres, J Appl Polym Sci, 1997,64,1843-1848
[95]Chomg-shyan Chern, Chi-huei Lin, Semibatch surfactant-free polymerization of butyl acrylate, Polymer Journal, 1995,11:1094-1103
[96]Tamai, H.; Fujii, A.; Suzawa, T. Some colloidal considerations on the surface characteristics of various emulsifier-free polymer latices. J. Colloid Interface Sci., 1987,116(1),37-41
[97]Chern C S, Chen Y C. Stability of the polymerizable surfactant stabilized latex particle during semibatch emulsion polymerization, Colloid and Polym Sci, 1997,2:124-130
[98]Oho H, Saeki H. Preparation and properties of polymethyl methacrylate latex dispersions having no surfactant, Colloid and Polymer Sci,1975,9:744-749
[99]黄志虹，谢志明，李卓美，丙烯酸酯无皂乳液稳定性研究，功能高分子学报，2000，13(1)，29-32
[100]程时远，纪庆绪，甲基丙烯酸甲酯-丙烯酸正丁酯-ω-十一烯酸钠无皂乳液共聚合研究，高分子学报，1993，3,295-303
[101]张洪涛，李建宗，谭必恩等 BA-St-MMA 复合乳液共聚合动力学和成核机理研究，高分子材料科学与工程，1998，14(2)，47-50
[102]戴李宗，邹友思，潘荣华，苯乙烯-丙烯酸丁酯无皂乳液聚合动力学及 TEM 分析，高等学校化学学报，1992,13(11)，1424-1427
[103]Show-An C.; Song-Tai L. Kinetics and mechanism of emulsifier-free emulsion polymerization: styrene/hydrophilic comonomer(acrylamide) system, Macromolecules, 1991, 24, 3340-3351
[104]M. Slawinski; M. Schellekens; J. Meuldlik. Seeded emulsion polymerization of styrene: influence of acrylic acid on the particle growth process, J Appl Polym Sci, 2000,76:1186-1196
[105]D.Munro;A.R. Goodall;M.C.Wilkinson. Study of particle nucleation, flocculation, and growth in the emulsifier-free polymerization of styrene in water by total intensity light scattering and photon correlation spectroscopy, J Colloid and Interface Sci, 1979,68(1)
[106]Yanmei W.; Linxian F.; Caiyuan P.; Preparation and characterization of p(St-co-4VP) paticles produced by using emulsifier-free emulsion polymerization, J Appl Polym Sci, 1999,74, 1502-1507
[107]Henmei N.; Yongzhong D.; Guanghui M.; Mechanism of soap-free emulsion polymerization of styrene and 4-vinylpyridine: characteristics of reaction in the monomer phase, aqueous phase, and their interface, Macromolecules, 2001,34,6577-6585