聚丙烯酸酯无皂乳液的合成及应用研究
|
摘要
传统聚丙烯酸酯乳液中含有大量的小分子乳化剂,其造成了乳液胶膜的耐水性、耐污性差,粘结力及强力下降等缺点,并且将该乳液用于涂料印花、涂料染色时,织物的湿摩擦牢度效果不甚理想。尽管以上缺陷可通过无皂乳液加以改善,但是采用传统的无皂乳液聚合技术制备的乳液稳定性差,并且固含量低。为了有效解决上述问题,本文采用极少量实验室自制的可聚合乳化剂,通过预乳化半连续滴加工艺进行无皂乳液聚合反应研究。然而,该聚丙烯酸酯无皂乳液同样存在“热脆冷粘”的缺点,使得涂料染色后织物的牢度与手感之间存在矛盾,为了化解这一矛盾,本文还利用有机硅优良的柔软性、低粘度及低表面张力对聚丙烯酸酯无皂乳液进行改性,所制备的乳液具有优良的应用性能。
本文以甲基丙烯酸甲酯、丙烯酸异辛酯、丙烯酸丁酯、丙烯酸羟乙酯及丙烯酸等单体合成了聚丙烯酸酯无皂乳液,通过单因素实验,确定了聚合反应的最佳条件:反应温度为80℃,可聚合乳化剂B/A的质量比为10︰0,阴-非复合型可聚合乳化剂B用量为0.4%(对丙烯酸酯类总单体质量的重,下同),预乳化液滴加时间为1h,保温时间为1h,引发剂KPS用量为0.4%。
在无皂乳液的应用实验中,通过对焙烘温度、焙烘时间及粘合剂用量等影响涂料印花、染色织物性能(如织物手感、柔软度、干湿摩擦牢度和K/S值等)的因素进行分析,确定了涂料印花、染色的最佳工艺条件;通过改变硅丙无皂乳液中乙烯基硅油的用量、硅丙无皂乳液的用量及不同纯丙无皂乳液的Tg,评价自制纯丙、硅丙无皂乳液在织物柔软整理及抗起毛起球整理中的效果,研究了整理后织物的柔软度、白度和抗起毛起球性能。
通过测试乳液的外观及各项稳定性等指标,评价了自制无皂乳液的理化性能;通过红外波谱分析(FT-IR)、差示扫描量热仪(DSC)、热重分析(TG)、透射电子显微镜(TEM)及激光粒度仪等现代仪器分析手段,确定了自制无皂乳液的结构、Tg、热性能、粒径形貌及大小分布等。
结果表明,自制的纯丙、硅丙无皂乳液固含量高且稳定性好。通过应用实验发现,自制的无皂乳液已基本达到工业品的应用效果,特别是硅丙无皂乳液用于涂料染色后,织物的柔软度及手感较纯丙的有了较为明显的改善。因此,自制的纯丙、硅丙无皂乳液有望成为一种集涂料印花、染色、柔软(针对涂料染色织物)、抗起毛起球等多功能性于一体的印染助剂。
When the traditional polyacrylate emulsion containing a large number of small molecule emulsifiers which cause water resistance, cohesion and strength of the films decline, are used as pigment printing and dyeing adhesives, the wet rubbing fastness of finished fabric are not good enough. Although the above shortcomings can be improved by emulsifier-free emulsion, the stability and solid content of the emulsion prepared by traditional soap-free emulsion polymerization technology are low. In order to solve the problems effectively, emulsifier-free polymerization was studyed by pre-emulsified and semi-continuous adding method with small quantities of the self-made polymerizable emulsifier in this paper. However, the polyacrlate soap-free emulsion also have some disadvantages, for example, it is brittle under freezing and viscous under warming, which causes a conflict between fastness and hand feeling of the fabric. Polyacrylate soap-free emulsion was modified by organic silicon with excellent softness, low viscosity and surface tension so as to resolve this contradiction, and the final emulsifier-free emulsion shows excellent application performance.
In the paper, the soap-free emulsion was synthesized by methyl methacrylate, iso-octyl acrylic, butyl acrylate, 2-hydroxyethyl acrylate and acrylic acid. According to the single factor experiment, the best conditons for the polymerization reaction were determined: reaction tempreture was 80℃, mass ratio of the polymerizable emulsifier B/A was 10︰ 0, dosage of the anionic and nonionic composite polymerizable emulsifier B was 0.4% (on weight of total monomers, the same as below) , dropping time of pre-emulsion was 1h, holding time was 1h and dosage of initiator KPS was 0.4%.
In the application experiment of soap-free emulsion, the optimum conditions for printing and dyeing were confirmed by analyzing the factors with baking temperature, baking time and dosage of the adhesive, which affecting performance of pigment printing and dyeing (such as fabric feel, softness, wet and dry rubbing fastness and the K/S values). The softness, whiteness and pilling resistance were studied by changing dosage of vinyl silicone oil, dosage of the silicone-acrylate soap-free emulsion and different Tg of polyacrylate soap-free emulsion.
The physical and chemical properties of self-made soap-free emulsion were evaluated by testing appearance and all kinds of stabilities of the emulsion, and the structure, Tg, thermal properties, particle morphology and size distribution of the self-made soap-free emulision were determined according to FT-IR, DSC, TG, TEM and laser particle size analyzer.
The results shows that the self-made soap-free emulsion has high solid content and good stability, and the sele-made soap-free emulsion has basically reached the industrial application effect, especially the fabric softness and feel were improved obviously with silicone-acrylate soap-free emulsion compared with polyacrylate soap-free emulsion. Therefore, the self-made soap-free emulsion is expected to become a set of multifunctional dyeing and printing auxiliary with pigment printing, dyeing, softness (for pigment dyeing fabric) and pilling resistance.
本文以甲基丙烯酸甲酯、丙烯酸异辛酯、丙烯酸丁酯、丙烯酸羟乙酯及丙烯酸等单体合成了聚丙烯酸酯无皂乳液,通过单因素实验,确定了聚合反应的最佳条件:反应温度为80℃,可聚合乳化剂B/A的质量比为10︰0,阴-非复合型可聚合乳化剂B用量为0.4%(对丙烯酸酯类总单体质量的重,下同),预乳化液滴加时间为1h,保温时间为1h,引发剂KPS用量为0.4%。
在无皂乳液的应用实验中,通过对焙烘温度、焙烘时间及粘合剂用量等影响涂料印花、染色织物性能(如织物手感、柔软度、干湿摩擦牢度和K/S值等)的因素进行分析,确定了涂料印花、染色的最佳工艺条件;通过改变硅丙无皂乳液中乙烯基硅油的用量、硅丙无皂乳液的用量及不同纯丙无皂乳液的Tg,评价自制纯丙、硅丙无皂乳液在织物柔软整理及抗起毛起球整理中的效果,研究了整理后织物的柔软度、白度和抗起毛起球性能。
通过测试乳液的外观及各项稳定性等指标,评价了自制无皂乳液的理化性能;通过红外波谱分析(FT-IR)、差示扫描量热仪(DSC)、热重分析(TG)、透射电子显微镜(TEM)及激光粒度仪等现代仪器分析手段,确定了自制无皂乳液的结构、Tg、热性能、粒径形貌及大小分布等。
结果表明,自制的纯丙、硅丙无皂乳液固含量高且稳定性好。通过应用实验发现,自制的无皂乳液已基本达到工业品的应用效果,特别是硅丙无皂乳液用于涂料染色后,织物的柔软度及手感较纯丙的有了较为明显的改善。因此,自制的纯丙、硅丙无皂乳液有望成为一种集涂料印花、染色、柔软(针对涂料染色织物)、抗起毛起球等多功能性于一体的印染助剂。
When the traditional polyacrylate emulsion containing a large number of small molecule emulsifiers which cause water resistance, cohesion and strength of the films decline, are used as pigment printing and dyeing adhesives, the wet rubbing fastness of finished fabric are not good enough. Although the above shortcomings can be improved by emulsifier-free emulsion, the stability and solid content of the emulsion prepared by traditional soap-free emulsion polymerization technology are low. In order to solve the problems effectively, emulsifier-free polymerization was studyed by pre-emulsified and semi-continuous adding method with small quantities of the self-made polymerizable emulsifier in this paper. However, the polyacrlate soap-free emulsion also have some disadvantages, for example, it is brittle under freezing and viscous under warming, which causes a conflict between fastness and hand feeling of the fabric. Polyacrylate soap-free emulsion was modified by organic silicon with excellent softness, low viscosity and surface tension so as to resolve this contradiction, and the final emulsifier-free emulsion shows excellent application performance.
In the paper, the soap-free emulsion was synthesized by methyl methacrylate, iso-octyl acrylic, butyl acrylate, 2-hydroxyethyl acrylate and acrylic acid. According to the single factor experiment, the best conditons for the polymerization reaction were determined: reaction tempreture was 80℃, mass ratio of the polymerizable emulsifier B/A was 10︰ 0, dosage of the anionic and nonionic composite polymerizable emulsifier B was 0.4% (on weight of total monomers, the same as below) , dropping time of pre-emulsion was 1h, holding time was 1h and dosage of initiator KPS was 0.4%.
In the application experiment of soap-free emulsion, the optimum conditions for printing and dyeing were confirmed by analyzing the factors with baking temperature, baking time and dosage of the adhesive, which affecting performance of pigment printing and dyeing (such as fabric feel, softness, wet and dry rubbing fastness and the K/S values). The softness, whiteness and pilling resistance were studied by changing dosage of vinyl silicone oil, dosage of the silicone-acrylate soap-free emulsion and different Tg of polyacrylate soap-free emulsion.
The physical and chemical properties of self-made soap-free emulsion were evaluated by testing appearance and all kinds of stabilities of the emulsion, and the structure, Tg, thermal properties, particle morphology and size distribution of the self-made soap-free emulision were determined according to FT-IR, DSC, TG, TEM and laser particle size analyzer.
The results shows that the self-made soap-free emulsion has high solid content and good stability, and the sele-made soap-free emulsion has basically reached the industrial application effect, especially the fabric softness and feel were improved obviously with silicone-acrylate soap-free emulsion compared with polyacrylate soap-free emulsion. Therefore, the self-made soap-free emulsion is expected to become a set of multifunctional dyeing and printing auxiliary with pigment printing, dyeing, softness (for pigment dyeing fabric) and pilling resistance.
引文
[1]徐继红,陶俊,陆娅君. PMMA/BA无皂乳液聚合[J].上海塑料,2008(01): 16-18.
[2]蔡晓音,王直刚.无皂乳液聚合体系稳定性的研究与发展[J].炼油与化工,2005,16(03): 10.
[3]陈平,黄懋加.涂料印花的生态环保问题探讨[J].染整技术,2008,30(09): 21.
[4]潘瑞花,陈建华,张剑锋.针对欧盟禁用APEO想到的几个问题[J].化学分析计量,2008,17(01): 62-64.
[5]潘祖仁.高分子化学(增强版)[M].北京:化学工业出版社,2007: 167.
[6]王玉霞,张芳,王艳君,等.无皂乳液聚合的进展[J].化学工业与工程,2003,20(01): 16.
[7]曹同玉,刘庆普,胡金生.聚合物乳液合成原理性能及应用[M].北京:化学工业出版社,2007: 480.
[8]王波,王合情,周新平,等.无皂乳液聚合研究及应用进展[J].粘接,2008,29(05): 44-46.
[9] Robert M. Fitch, Michael B. Prenosil, Karen J. Sprick. J Polym Sci PartC, 1969, 27: 95.
[10] Kotera A, Furasawa K, Takeda Y. Kolloid-ZUZ Polymere, 1970, 239: 677.
[11] Kotera A, Furasawa K, Takeda Y. Kolloid-ZuZ polymere, 1970, 240: 837.
[12] J. W. Goodwin, Hearn J, C. C. Ho, et al. Br Polym J, 1973, 5.
[13] K Hansen F.,J Ugelstad. J Polym Sci Polym Chem Ed,1978,16: 1953.
[14] Feeney P. J, Donald H. Napper, Robert G. Gilber. Macromolecules, 1987, 20: 2922.
[15] Goodwall A. R.,Wilkinson M. C.,Hearn J. J Polym Sci Polym Chem Ed,1977,15: 2139.
[16] Z. Song, W. P. Gary. Particle mucleation in emulifier-free aqueous-phase polymerization, stage I[J]. Journal of Colliod and Interface Science, 1989, 128(2): 486, 501.
[17]杨冬花,林芸,俞开钰,等. St-BA-MAA无皂乳液聚合机理的研究[J].太原理工大学学报,1998,29(04): 390-392.
[18]张茂根,翁学志,黄志明,等.离子型表面活性单体存在下的MMABA乳液聚合(I)——表面活性单体的合成及其(共)聚合活性[J].高等学校化学学报,1999,20(12): 1969-1973.
[19]张茂根,翁志学,黄志明,等. MMA/BA无皂乳液聚合机理研究──三阶段成粒机理[J].高等学校化学学报,1999,20(11): 1975-1979.
[20]许涌深,袁才登,王艳君,等.无皂乳液共聚合的动力学和机理[J].高分子材料科学与工程,2000,10(01): 46-52.
[21] R. H. Ottewill, J. W. Syaw. Preparation and characterization of core-shell monodispersed microspheres[J]. Discuss Faraday Science, 1966, 42(01): 154-160.
[22]孙亦周,王颖,姚雄健.无皂乳液聚合原理及其制备[J].航天工艺,2001(02): 24-27.
[23]焦书科,余鼎声,李效玉,等.丙烯酸乙酯无皂聚合的研究[J].合成橡胶工业,1986(02): 115.
[24] Guillaume J. L. Antiamebic and Trichomonacidic Activities of Secnidazole in the Laboratory Colloid[J]. Polym. Sci., 1979, 257: 61.
[25]许涌深,曹同玉,龙复,等. St-MMA无皂乳液共聚合的研究[J].合成橡胶工业,1992(02): 23-25.
[26] B. R. Vijaendran. Synthesis and properties of soap-free poly(methyl methacrylate-ethyl acrylate-methacrylic acid)latex particles prepared by seeded emulsion polymerization[J]. Journal of Applied Polymer Science, 1979, 23(03): 893-901.
[27] Yan C, Zhang X, Sun Z. Poly (Styrene-CO-Acrolein) Latex Particle: Copolyerization and Characterization[J]. J Appl Polym Sci, 1990(3): 295.
[28] Zushun Xu, Changfeng Yi, Guohong Lu, et al. Styrene-Butyl Acrylate-N,N-Dimethyl N-Butyl N-Methacrylate-Lamidino Propyl Ammonium Bromide Emulsifier-Free Emulsion Copolymerization[J]. Polymer International, 1993, 44: 149.
[29] Guo T. Y, Song M. D, Zhou Q. Y, et al. Semibatch Emulsifier-free Emulsion Copolymerization of MMA and n-f HEMA[J]. Chinese Chem Letter, 1998(7): 683-686.
[30]程时远,纪庆绪. MMA/BA无皂乳液聚合[J].高分子学报,1993(3): 295.
[31]闫翠娥,程时远,李小琴.苯乙烯-甲基丙烯酸甲酯-丙烯醛三元无皂共聚胶乳性质的研究[J].胶体与聚合物,1999,17(01): 9-12.
[32]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[J].离子交换与吸附,1999(6): 453-459.
[33]易昌凤,王焱,徐祖顺.甲基丙烯酸甲酯/羟甲基丙烯酰胺无皂乳液共聚合的研究[J].胶体与聚合物,2003,21(04): 5-7.
[34]邱治国,方治齐,张晓东.高固含量无皂丙烯酸酯乳液的制备[J].涂料工业,2004,34(01): 1-3.
[35]李福,方治齐,方华高.几种功能性单体在无皂乳液聚合中的作用[J].高分子材料科学与工程,2005,21(06): 63-65.
[36]刘敏,侯丽华,耿兵,等.醋酸乙烯酯/丙烯酸钠阴离子型无皂乳液的制备与性能[J].化学建材,2007,23(03): 20-23.
[37]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(03): 266-270.
[38]王强,曹爱丽,黄积涛.以两亲聚合物为乳化剂研制高固含量乳液[J].高分子材料科学与工程,1999,15(2): 35-37.
[39]唐宏科,张瑜,张根峰.高固含量无皂丙醋乳液的制备[J].涂料工业,2007,37(06): 26-29.
[40]唐黎明,董汉鹏,刘德山,等.新型无皂聚丙烯酸酯乳液的合成及性能研究[J].高分子材料科学与工程,1998,14(01): 17-19.
[41]孔祥文,王静,王传胜,等.无皂聚丙烯酸酯乳液的合成及稳定性研究[J].化学世界,2004(02): 81-84.
[42]张瑜,韦亚兵,陈风雨,等. PBA/PMMA核壳无皂聚合反应速率的研究[J].试验与研究,2004(05): 251-255.
[43]艾照全,周奇龙,孙桂林.高固含量低粘度P(MMA/BA/AA)乳液的制备及性能研究[J].高分子学报,2005(5): 754-759.
[44]赵晨阳,李效玉.高固含量的苯乙烯/丙烯酸丁酯/丙烯酸共聚物乳液的制备[J].现代化工,2004,24(7): 44-46.
[45] Unzue M, Schoonbrood Has. Reactive Surfactants in Heterophase Polymerization Vl Synthesis and Screening of Polymerizable Surfactants (surtemers) with Varying Reactivity in High Solids Styrene-Butyl Acrylate-Acrylic Acid Emulsion Polymerization[J]. Journal of Applied Polymer Science, 1997, 66: 1803-1820.
[46] Schoonbrood Has, Unzue M, J. Beck O. J. Reactive Surfactants in Heterophase Polymerization. 7. Emulsion Copolymerization Mechanism Invoving Three Anionic Polymerizable Surfactants (Surtimers) with Styrene-Butyl Acrylate-Acrylic Acid[J]. Nacromoloecules, 1997, 30: 6024-6033.
[47]王国建.有机硅氧烷/丙烯酸酯乳液的无皂共聚合研究[J].建筑材料学报,2002,5(03): 269-273.
[48]朱志博,张力,刘敬芹,等.甲基丙烯酸甲酯/丙烯酸丁酯无皂水性涂料的研究[J].华南师范大学学报(自然科学版),2003(01): 71-75.
[49]朱再盛,吕广镛.丙烯酸酯无皂乳液的研究[J].涂料工业,2004,34(06): 4-6.
[50]彭慧,杨婷婷,廖启金,等.离子型共聚单体参与下的全氟丙烯酸酯无皂乳液共聚[J].应用化学,2005,22(02): 187-194.
[51]王波,周新平,王合情,等.含AMPS的丙烯酸酯无皂乳液的合成与性能研究[J].粘接,2008,29(12): 27-29.
[52]张宝莲,魏冬青,王岩,等. AMPS稳定的有机硅丙烯酸酯无皂乳液共聚合研究[J].化工新型材料,2008,36(08): 82-85.
[53]朱再盛. MMA/BA二元无皂乳液性质的研究[J].化工时刊,2006,20(10): 39-41.
[54]王金刚,朱晓丽,张志国,等.功能单体α-烯烃磺酸钠用于无皂乳液共聚合[J].高分子学报,2006(07): 903-907.
[55]付永祥,温家伶,李磊,等.丙烯酸酯无皂乳液半连续聚合研究[J].中国水运(学术版),2007,7(05): 44-45.
[56]杨世芳,祝媛媛,丁秀芬,等.用可聚合乳化剂制备氟化丙烯酸酯无皂乳液[J].粘接,2007,28(05): 19-21.
[57]郑海涛,徐小波,安卫兵.高固含量无皂丙烯酸酯共聚乳液的合成研究[J].辽宁化工,2009,38(04): 233-235.
[58]肖新颜,王叶,徐蕊,等.可聚合乳化剂合成含氟丙烯酸酯无皂乳液及其性能[J].化工进展,2009,28(04): 650-655.
[59]侯艳青,李中华,高献英,等.反应性乳化剂在无皂硅溶胶苯丙乳液聚合中的应用[J].应用化学,2009,26(05): 616-618.
[60]王金,曾幸荣,欧阳喜仁,等.核壳型无皂含氟丙烯酸酯共聚乳液的合成[J].高分子材料科学与工程,2009,25(04): 24-27.
[61]陈斌.丙烯酸酯无皂乳液的合成及成膜特征[D].南京理工大学,硕士,2007,4.
[62]庄严,张复盛.无皂乳液聚合技术及其应用[J].涂料工业,1998,28(04): 35-37.
[63]胡军.无皂乳液聚合制备聚合物纳米棒及第四统计理论在无皂乳液聚合和常规乳液聚合中应用的研究[D].北京化工大学,硕士,2006,4.
[64]吴庆云,杨建军,张建安,等.无皂型乳液聚合的研究进展[J].精细石油化工进展,2006,7(02): 40-44.
[65] Arai M, Arai K, Saito S. Soapless emulsion polymerization of Methyl Methacrylate in water in the presence of barjum sulfate[J]. J Polym. Sci. Polym. Chem. Ed, 1982, 20(1021-1029).
[66] Chen S. A, Lee S. T. Kinetics and mechanism of emulsifier-free emulsion polymerization:Styrenn/hydrophilic comonomer (acrylamide) system[J]. amacrom olecules, 1991, 24(11): 3340-3351.
[67] Pan T. C. The effect of sodium methacrylate on the soapless emulsion co-polymerization of methyl methacrylate and n-butyl acrylate[J]. Joumal of Polymer Science Part A: Polymer Chemistry, 1991, 29(5): 709-718.
[68]刘娟.聚丙烯酸酯无皂核壳乳液的合成及性能研究[D].重庆大学,硕士,2005,2.
[69]吕京宁.无皂法亲和高分子乳液微球的分子构筑及表征[D].浙江大学,硕士,2008,10.
[70]唐广粮,郝广杰,宋谋道,等.离子型共聚单体用于高固含量无皂乳液聚合的研究——甲基丙烯酸异丁酯/甲基丙烯酸甲酯/丙烯酸丁酯无皂乳液聚合体系[J].高分子学报,2000(03): 267-270.
[71]张莉,陈桐,陈梦瑜,等.无皂乳液聚合反应机理和制备方法的研究进展[J].中国胶粘剂,2008,17(04): 50.
[72]殷年伟,陈克强.超声辐照下BA/AM体系的无皂乳液聚合[J].四川大学学报(工程科学版),2003,35(03): 62-65.
[73]殷年伟,陈克强,卢新安.超声波无皂乳液制备BA/AM/纳米SiO_2复合材料的粒径及其分布[J].高分子材料科学与工程,2004,20(03): 199-201.
[74]殷年伟,陈克强,康维.超声无皂乳液聚合制备BA/St/AM三元共聚物乳胶粒及其聚合机理研究[J].高分子学报,2006(02): 253-257.
[75]熊金钰,纪旭.超声辐射丙烯腈的无皂乳液聚合[J].胶体与聚合物,2005,23(04): 4-6.
[76]王艳丽,谭德新,徐国财,等.超声无皂乳液原位合成Pd-P(MMA-AMPS)复合微球及其表征[J].复合材料学报,2009,26(03): 67-72.
[77]唐业仓.微波辐照合成无皂阳离子高分子微球及机理研究[D].安徽师范大学,硕士,2002,4.
[78]何卫东,潘才元,卢涛.甲基丙烯酸丁酯微波无皂乳液聚合[J].功能高分子学报,1999,12(01): 11-14.
[79]胡晓熙,李磊,陈浩,等.微波辐射无皂乳液聚合制备单分散热敏性微球[J].胶体与聚合物,2005,23(02): 27-29.
[80]汪地强,刘白玲,胡杰.乙醇及NaCl存在下甲基丙烯酸甲酯的无皂乳液聚合[J].高分子材料科学与工程,2004,20(06): 109-112.
[81]王艺峰,陈艳军.表面活性单体和丙酮共作用下甲基丙烯酸三氟乙酯无皂乳液聚合研究[J].化学建材,2007,23(05): 10-13.
[82]程纪瑜,罗朝瑛,马光复.在18-冠-6存在下苯乙烯无乳化剂乳液聚合[J].高分子通讯,1986(1): 36-42.
[83]纪庆绪,程时远.聚乙二醇在无皂乳液共聚体系中的应用[J].涂料工业,1998(05): 18-19.
[84]杨勇,罗川南.无皂乳液聚合制备碳酸钙-聚苯乙烯复合物胶粒[J].化工科技,2001,9(03): 9-11.
[85]戴李宗,邹友思,陈世群. KPS-CuSO4-NaSO3参与的无皂乳液聚合[J].高等学校化学学报,1993,14(03): 428-431.
[86]李翾,沈一丁,费贵强,等.自交联苯丙乳液的无皂聚合及其结构与表面施胶性能[J].中国造纸学报,2009,24(01): 100-103.
[87]李培枝,李小瑞,徐旋.聚乙烯醇接枝阳离子聚丙烯酸酯的无皂乳液聚合及表征[J].高分子材料科学与工程,2009,25(01): 19-22.
[88] Dicke H. R, Heitz W. Colloid Polym. Sci., 1982, 260: 3.
[89]储鸿,王志英,倪忠斌,等. VPE引发的苯乙烯无皂乳液聚合研究[J].化工新型材料,2007,35(01): 31-34.
[90]励杭泉.表面活性单体存在下的浓乳液聚合[D].北京化工大学,硕士,2001,12.
[91]孙立国,陈海华,张帅,等.沸腾无皂乳液聚合制备单分散高分子纳米微球[C].中国化学会第二十五届学术年论文摘要集(上册),2006.
[92]张洪涛,黄锦霞.乳液聚合新技术及应用[M].北京:化学工业出版社,2007: 95-97.
[93] Akihiko Kondo, Hiroko Kamura, Ko Higashitani. Development and application of thermosensitive magnetic immunomicrospheres ofr antibody purification[J]. Applied Microbiology And Biotechnology, 1994, 41(01): 99-105.
[94] Mahasen A. R, Iman Y. Z, Zinat H. A. In vivo performance of parenteral theophylline-loaded polyisobultylcyanoacrylate nanopartieles in rats[J]. Eur. J. Pharmaceutical Sci., 1999, 8(01): 95-98.
[95]梁其辉,张延武,刘金盾,等.用作砂浆改性剂的三元无皂乳液制备及表征[J].新型建筑材料,2009(04): 58-61.
[96]李玮,谢志明,李卓美.丙烯酸酯接枝炭黑无皂水性涂料的性能研究[J].功能高分子学报,2002,15(02): 181-184.
[97]常玉,梁剑锋.防水涂料用无皂乳液的制备[J].涂料工业,2004,34(08): 21-24.
[98]李小瑞,张勇,费贵强,等.无皂苯丙聚合物/AKD乳液表面施胶剂的制备与应用[J].中华纸业,2008(22): 48-50.
[99]曾庆辉.无皂法亲和高分子载体微球的制备与表征[D].浙江大学,硕士,2006,19.
[100]郭林晖,马承银,陈红梅.无皂乳液聚合的理论研究、制备方法及应用[J].化学世界,2003(01): 49-52.
[101]程艳玲,易昌凤,徐祖顺.氧化还原引发无皂乳液聚合制备单分散热敏性微球[J].高分子材料科学与工程,2008,24(12): 38-41.
[102]杜虹,赵淑贤,徐国财.超声辐照无皂乳液聚合制备P(AMPS-MMA)/Pd纳米复合乳液[J].湖南师范大学自然科学学报,2009(01): 79-82.
[103]王竹青,葛圣松,王青尧.无皂纳米苯丙复合乳液的制备[J].化工中间体,2009(01): 26-30.
[104]龙斌,黄春保,王海南,等.硅/丙复合乳液的制备方法及应用进展[J].纺织学报,2006,27(3): 9-11.
[105]张宝莲,张日新,魏冬青,等.有机硅丙烯酸酯无皂乳液共聚合研究[J].天津大学学报,2006,39(增刊): 193.
[106]甘孟瑜,谭尊燕,杨治国.丙烯酸酯乳液的改性研究[J].涂料工业,2006,36(3): 11.
[107]闫翠娥,程时远,封麟先.三元无皂乳液共聚合动力学及其模型的研究[J].高分子学报,1999(05): 67-72.
[108]青晨,蔡佩英,徐建军,等.醋酸乙烯-丙烯酸无皂乳液共聚的研究[J].涂料工业,2006(02): 42-45.
[109]秦总根,涂伟萍.四元纯丙无皂共聚物乳液的研制[J].涂料工业,2004(02): 24-27.
[110]萧继华,俞宏,宋心远.环保型低温自交联印花粘合剂的合成与性能[J].印染助剂,2004,34(6): 4.
[111]唐雅娟,李成海,张海明.丙烯酸酯无皂乳液的制备及性能研究[J].化学建材,2007(01): 22-25.
[112]叶慈南,曹伟丽.应用数理统计[M].北京:机械工业出版社,2007: 289-290.
[113]汪长春,包启宇.丙烯酸酯涂料[M].北京:化学工业出版社,2005: 61.
[114]徐祖顺,易昌凤,肖卫东.织物用胶黏剂及粘接技术[M].北京:化学工业出版社,2004: 214.
[115]王宏丽.提高涂料大红FFG织物印花摩擦牢度[J].染整技术,2004,26(3): 47-48.
[116]曾幸荣,吴振耀.高分子近代测试分析技术[M].广州:华南理工大学出版社,2000: 36.
[2]蔡晓音,王直刚.无皂乳液聚合体系稳定性的研究与发展[J].炼油与化工,2005,16(03): 10.
[3]陈平,黄懋加.涂料印花的生态环保问题探讨[J].染整技术,2008,30(09): 21.
[4]潘瑞花,陈建华,张剑锋.针对欧盟禁用APEO想到的几个问题[J].化学分析计量,2008,17(01): 62-64.
[5]潘祖仁.高分子化学(增强版)[M].北京:化学工业出版社,2007: 167.
[6]王玉霞,张芳,王艳君,等.无皂乳液聚合的进展[J].化学工业与工程,2003,20(01): 16.
[7]曹同玉,刘庆普,胡金生.聚合物乳液合成原理性能及应用[M].北京:化学工业出版社,2007: 480.
[8]王波,王合情,周新平,等.无皂乳液聚合研究及应用进展[J].粘接,2008,29(05): 44-46.
[9] Robert M. Fitch, Michael B. Prenosil, Karen J. Sprick. J Polym Sci PartC, 1969, 27: 95.
[10] Kotera A, Furasawa K, Takeda Y. Kolloid-ZUZ Polymere, 1970, 239: 677.
[11] Kotera A, Furasawa K, Takeda Y. Kolloid-ZuZ polymere, 1970, 240: 837.
[12] J. W. Goodwin, Hearn J, C. C. Ho, et al. Br Polym J, 1973, 5.
[13] K Hansen F.,J Ugelstad. J Polym Sci Polym Chem Ed,1978,16: 1953.
[14] Feeney P. J, Donald H. Napper, Robert G. Gilber. Macromolecules, 1987, 20: 2922.
[15] Goodwall A. R.,Wilkinson M. C.,Hearn J. J Polym Sci Polym Chem Ed,1977,15: 2139.
[16] Z. Song, W. P. Gary. Particle mucleation in emulifier-free aqueous-phase polymerization, stage I[J]. Journal of Colliod and Interface Science, 1989, 128(2): 486, 501.
[17]杨冬花,林芸,俞开钰,等. St-BA-MAA无皂乳液聚合机理的研究[J].太原理工大学学报,1998,29(04): 390-392.
[18]张茂根,翁学志,黄志明,等.离子型表面活性单体存在下的MMABA乳液聚合(I)——表面活性单体的合成及其(共)聚合活性[J].高等学校化学学报,1999,20(12): 1969-1973.
[19]张茂根,翁志学,黄志明,等. MMA/BA无皂乳液聚合机理研究──三阶段成粒机理[J].高等学校化学学报,1999,20(11): 1975-1979.
[20]许涌深,袁才登,王艳君,等.无皂乳液共聚合的动力学和机理[J].高分子材料科学与工程,2000,10(01): 46-52.
[21] R. H. Ottewill, J. W. Syaw. Preparation and characterization of core-shell monodispersed microspheres[J]. Discuss Faraday Science, 1966, 42(01): 154-160.
[22]孙亦周,王颖,姚雄健.无皂乳液聚合原理及其制备[J].航天工艺,2001(02): 24-27.
[23]焦书科,余鼎声,李效玉,等.丙烯酸乙酯无皂聚合的研究[J].合成橡胶工业,1986(02): 115.
[24] Guillaume J. L. Antiamebic and Trichomonacidic Activities of Secnidazole in the Laboratory Colloid[J]. Polym. Sci., 1979, 257: 61.
[25]许涌深,曹同玉,龙复,等. St-MMA无皂乳液共聚合的研究[J].合成橡胶工业,1992(02): 23-25.
[26] B. R. Vijaendran. Synthesis and properties of soap-free poly(methyl methacrylate-ethyl acrylate-methacrylic acid)latex particles prepared by seeded emulsion polymerization[J]. Journal of Applied Polymer Science, 1979, 23(03): 893-901.
[27] Yan C, Zhang X, Sun Z. Poly (Styrene-CO-Acrolein) Latex Particle: Copolyerization and Characterization[J]. J Appl Polym Sci, 1990(3): 295.
[28] Zushun Xu, Changfeng Yi, Guohong Lu, et al. Styrene-Butyl Acrylate-N,N-Dimethyl N-Butyl N-Methacrylate-Lamidino Propyl Ammonium Bromide Emulsifier-Free Emulsion Copolymerization[J]. Polymer International, 1993, 44: 149.
[29] Guo T. Y, Song M. D, Zhou Q. Y, et al. Semibatch Emulsifier-free Emulsion Copolymerization of MMA and n-f HEMA[J]. Chinese Chem Letter, 1998(7): 683-686.
[30]程时远,纪庆绪. MMA/BA无皂乳液聚合[J].高分子学报,1993(3): 295.
[31]闫翠娥,程时远,李小琴.苯乙烯-甲基丙烯酸甲酯-丙烯醛三元无皂共聚胶乳性质的研究[J].胶体与聚合物,1999,17(01): 9-12.
[32]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[J].离子交换与吸附,1999(6): 453-459.
[33]易昌凤,王焱,徐祖顺.甲基丙烯酸甲酯/羟甲基丙烯酰胺无皂乳液共聚合的研究[J].胶体与聚合物,2003,21(04): 5-7.
[34]邱治国,方治齐,张晓东.高固含量无皂丙烯酸酯乳液的制备[J].涂料工业,2004,34(01): 1-3.
[35]李福,方治齐,方华高.几种功能性单体在无皂乳液聚合中的作用[J].高分子材料科学与工程,2005,21(06): 63-65.
[36]刘敏,侯丽华,耿兵,等.醋酸乙烯酯/丙烯酸钠阴离子型无皂乳液的制备与性能[J].化学建材,2007,23(03): 20-23.
[37]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(03): 266-270.
[38]王强,曹爱丽,黄积涛.以两亲聚合物为乳化剂研制高固含量乳液[J].高分子材料科学与工程,1999,15(2): 35-37.
[39]唐宏科,张瑜,张根峰.高固含量无皂丙醋乳液的制备[J].涂料工业,2007,37(06): 26-29.
[40]唐黎明,董汉鹏,刘德山,等.新型无皂聚丙烯酸酯乳液的合成及性能研究[J].高分子材料科学与工程,1998,14(01): 17-19.
[41]孔祥文,王静,王传胜,等.无皂聚丙烯酸酯乳液的合成及稳定性研究[J].化学世界,2004(02): 81-84.
[42]张瑜,韦亚兵,陈风雨,等. PBA/PMMA核壳无皂聚合反应速率的研究[J].试验与研究,2004(05): 251-255.
[43]艾照全,周奇龙,孙桂林.高固含量低粘度P(MMA/BA/AA)乳液的制备及性能研究[J].高分子学报,2005(5): 754-759.
[44]赵晨阳,李效玉.高固含量的苯乙烯/丙烯酸丁酯/丙烯酸共聚物乳液的制备[J].现代化工,2004,24(7): 44-46.
[45] Unzue M, Schoonbrood Has. Reactive Surfactants in Heterophase Polymerization Vl Synthesis and Screening of Polymerizable Surfactants (surtemers) with Varying Reactivity in High Solids Styrene-Butyl Acrylate-Acrylic Acid Emulsion Polymerization[J]. Journal of Applied Polymer Science, 1997, 66: 1803-1820.
[46] Schoonbrood Has, Unzue M, J. Beck O. J. Reactive Surfactants in Heterophase Polymerization. 7. Emulsion Copolymerization Mechanism Invoving Three Anionic Polymerizable Surfactants (Surtimers) with Styrene-Butyl Acrylate-Acrylic Acid[J]. Nacromoloecules, 1997, 30: 6024-6033.
[47]王国建.有机硅氧烷/丙烯酸酯乳液的无皂共聚合研究[J].建筑材料学报,2002,5(03): 269-273.
[48]朱志博,张力,刘敬芹,等.甲基丙烯酸甲酯/丙烯酸丁酯无皂水性涂料的研究[J].华南师范大学学报(自然科学版),2003(01): 71-75.
[49]朱再盛,吕广镛.丙烯酸酯无皂乳液的研究[J].涂料工业,2004,34(06): 4-6.
[50]彭慧,杨婷婷,廖启金,等.离子型共聚单体参与下的全氟丙烯酸酯无皂乳液共聚[J].应用化学,2005,22(02): 187-194.
[51]王波,周新平,王合情,等.含AMPS的丙烯酸酯无皂乳液的合成与性能研究[J].粘接,2008,29(12): 27-29.
[52]张宝莲,魏冬青,王岩,等. AMPS稳定的有机硅丙烯酸酯无皂乳液共聚合研究[J].化工新型材料,2008,36(08): 82-85.
[53]朱再盛. MMA/BA二元无皂乳液性质的研究[J].化工时刊,2006,20(10): 39-41.
[54]王金刚,朱晓丽,张志国,等.功能单体α-烯烃磺酸钠用于无皂乳液共聚合[J].高分子学报,2006(07): 903-907.
[55]付永祥,温家伶,李磊,等.丙烯酸酯无皂乳液半连续聚合研究[J].中国水运(学术版),2007,7(05): 44-45.
[56]杨世芳,祝媛媛,丁秀芬,等.用可聚合乳化剂制备氟化丙烯酸酯无皂乳液[J].粘接,2007,28(05): 19-21.
[57]郑海涛,徐小波,安卫兵.高固含量无皂丙烯酸酯共聚乳液的合成研究[J].辽宁化工,2009,38(04): 233-235.
[58]肖新颜,王叶,徐蕊,等.可聚合乳化剂合成含氟丙烯酸酯无皂乳液及其性能[J].化工进展,2009,28(04): 650-655.
[59]侯艳青,李中华,高献英,等.反应性乳化剂在无皂硅溶胶苯丙乳液聚合中的应用[J].应用化学,2009,26(05): 616-618.
[60]王金,曾幸荣,欧阳喜仁,等.核壳型无皂含氟丙烯酸酯共聚乳液的合成[J].高分子材料科学与工程,2009,25(04): 24-27.
[61]陈斌.丙烯酸酯无皂乳液的合成及成膜特征[D].南京理工大学,硕士,2007,4.
[62]庄严,张复盛.无皂乳液聚合技术及其应用[J].涂料工业,1998,28(04): 35-37.
[63]胡军.无皂乳液聚合制备聚合物纳米棒及第四统计理论在无皂乳液聚合和常规乳液聚合中应用的研究[D].北京化工大学,硕士,2006,4.
[64]吴庆云,杨建军,张建安,等.无皂型乳液聚合的研究进展[J].精细石油化工进展,2006,7(02): 40-44.
[65] Arai M, Arai K, Saito S. Soapless emulsion polymerization of Methyl Methacrylate in water in the presence of barjum sulfate[J]. J Polym. Sci. Polym. Chem. Ed, 1982, 20(1021-1029).
[66] Chen S. A, Lee S. T. Kinetics and mechanism of emulsifier-free emulsion polymerization:Styrenn/hydrophilic comonomer (acrylamide) system[J]. amacrom olecules, 1991, 24(11): 3340-3351.
[67] Pan T. C. The effect of sodium methacrylate on the soapless emulsion co-polymerization of methyl methacrylate and n-butyl acrylate[J]. Joumal of Polymer Science Part A: Polymer Chemistry, 1991, 29(5): 709-718.
[68]刘娟.聚丙烯酸酯无皂核壳乳液的合成及性能研究[D].重庆大学,硕士,2005,2.
[69]吕京宁.无皂法亲和高分子乳液微球的分子构筑及表征[D].浙江大学,硕士,2008,10.
[70]唐广粮,郝广杰,宋谋道,等.离子型共聚单体用于高固含量无皂乳液聚合的研究——甲基丙烯酸异丁酯/甲基丙烯酸甲酯/丙烯酸丁酯无皂乳液聚合体系[J].高分子学报,2000(03): 267-270.
[71]张莉,陈桐,陈梦瑜,等.无皂乳液聚合反应机理和制备方法的研究进展[J].中国胶粘剂,2008,17(04): 50.
[72]殷年伟,陈克强.超声辐照下BA/AM体系的无皂乳液聚合[J].四川大学学报(工程科学版),2003,35(03): 62-65.
[73]殷年伟,陈克强,卢新安.超声波无皂乳液制备BA/AM/纳米SiO_2复合材料的粒径及其分布[J].高分子材料科学与工程,2004,20(03): 199-201.
[74]殷年伟,陈克强,康维.超声无皂乳液聚合制备BA/St/AM三元共聚物乳胶粒及其聚合机理研究[J].高分子学报,2006(02): 253-257.
[75]熊金钰,纪旭.超声辐射丙烯腈的无皂乳液聚合[J].胶体与聚合物,2005,23(04): 4-6.
[76]王艳丽,谭德新,徐国财,等.超声无皂乳液原位合成Pd-P(MMA-AMPS)复合微球及其表征[J].复合材料学报,2009,26(03): 67-72.
[77]唐业仓.微波辐照合成无皂阳离子高分子微球及机理研究[D].安徽师范大学,硕士,2002,4.
[78]何卫东,潘才元,卢涛.甲基丙烯酸丁酯微波无皂乳液聚合[J].功能高分子学报,1999,12(01): 11-14.
[79]胡晓熙,李磊,陈浩,等.微波辐射无皂乳液聚合制备单分散热敏性微球[J].胶体与聚合物,2005,23(02): 27-29.
[80]汪地强,刘白玲,胡杰.乙醇及NaCl存在下甲基丙烯酸甲酯的无皂乳液聚合[J].高分子材料科学与工程,2004,20(06): 109-112.
[81]王艺峰,陈艳军.表面活性单体和丙酮共作用下甲基丙烯酸三氟乙酯无皂乳液聚合研究[J].化学建材,2007,23(05): 10-13.
[82]程纪瑜,罗朝瑛,马光复.在18-冠-6存在下苯乙烯无乳化剂乳液聚合[J].高分子通讯,1986(1): 36-42.
[83]纪庆绪,程时远.聚乙二醇在无皂乳液共聚体系中的应用[J].涂料工业,1998(05): 18-19.
[84]杨勇,罗川南.无皂乳液聚合制备碳酸钙-聚苯乙烯复合物胶粒[J].化工科技,2001,9(03): 9-11.
[85]戴李宗,邹友思,陈世群. KPS-CuSO4-NaSO3参与的无皂乳液聚合[J].高等学校化学学报,1993,14(03): 428-431.
[86]李翾,沈一丁,费贵强,等.自交联苯丙乳液的无皂聚合及其结构与表面施胶性能[J].中国造纸学报,2009,24(01): 100-103.
[87]李培枝,李小瑞,徐旋.聚乙烯醇接枝阳离子聚丙烯酸酯的无皂乳液聚合及表征[J].高分子材料科学与工程,2009,25(01): 19-22.
[88] Dicke H. R, Heitz W. Colloid Polym. Sci., 1982, 260: 3.
[89]储鸿,王志英,倪忠斌,等. VPE引发的苯乙烯无皂乳液聚合研究[J].化工新型材料,2007,35(01): 31-34.
[90]励杭泉.表面活性单体存在下的浓乳液聚合[D].北京化工大学,硕士,2001,12.
[91]孙立国,陈海华,张帅,等.沸腾无皂乳液聚合制备单分散高分子纳米微球[C].中国化学会第二十五届学术年论文摘要集(上册),2006.
[92]张洪涛,黄锦霞.乳液聚合新技术及应用[M].北京:化学工业出版社,2007: 95-97.
[93] Akihiko Kondo, Hiroko Kamura, Ko Higashitani. Development and application of thermosensitive magnetic immunomicrospheres ofr antibody purification[J]. Applied Microbiology And Biotechnology, 1994, 41(01): 99-105.
[94] Mahasen A. R, Iman Y. Z, Zinat H. A. In vivo performance of parenteral theophylline-loaded polyisobultylcyanoacrylate nanopartieles in rats[J]. Eur. J. Pharmaceutical Sci., 1999, 8(01): 95-98.
[95]梁其辉,张延武,刘金盾,等.用作砂浆改性剂的三元无皂乳液制备及表征[J].新型建筑材料,2009(04): 58-61.
[96]李玮,谢志明,李卓美.丙烯酸酯接枝炭黑无皂水性涂料的性能研究[J].功能高分子学报,2002,15(02): 181-184.
[97]常玉,梁剑锋.防水涂料用无皂乳液的制备[J].涂料工业,2004,34(08): 21-24.
[98]李小瑞,张勇,费贵强,等.无皂苯丙聚合物/AKD乳液表面施胶剂的制备与应用[J].中华纸业,2008(22): 48-50.
[99]曾庆辉.无皂法亲和高分子载体微球的制备与表征[D].浙江大学,硕士,2006,19.
[100]郭林晖,马承银,陈红梅.无皂乳液聚合的理论研究、制备方法及应用[J].化学世界,2003(01): 49-52.
[101]程艳玲,易昌凤,徐祖顺.氧化还原引发无皂乳液聚合制备单分散热敏性微球[J].高分子材料科学与工程,2008,24(12): 38-41.
[102]杜虹,赵淑贤,徐国财.超声辐照无皂乳液聚合制备P(AMPS-MMA)/Pd纳米复合乳液[J].湖南师范大学自然科学学报,2009(01): 79-82.
[103]王竹青,葛圣松,王青尧.无皂纳米苯丙复合乳液的制备[J].化工中间体,2009(01): 26-30.
[104]龙斌,黄春保,王海南,等.硅/丙复合乳液的制备方法及应用进展[J].纺织学报,2006,27(3): 9-11.
[105]张宝莲,张日新,魏冬青,等.有机硅丙烯酸酯无皂乳液共聚合研究[J].天津大学学报,2006,39(增刊): 193.
[106]甘孟瑜,谭尊燕,杨治国.丙烯酸酯乳液的改性研究[J].涂料工业,2006,36(3): 11.
[107]闫翠娥,程时远,封麟先.三元无皂乳液共聚合动力学及其模型的研究[J].高分子学报,1999(05): 67-72.
[108]青晨,蔡佩英,徐建军,等.醋酸乙烯-丙烯酸无皂乳液共聚的研究[J].涂料工业,2006(02): 42-45.
[109]秦总根,涂伟萍.四元纯丙无皂共聚物乳液的研制[J].涂料工业,2004(02): 24-27.
[110]萧继华,俞宏,宋心远.环保型低温自交联印花粘合剂的合成与性能[J].印染助剂,2004,34(6): 4.
[111]唐雅娟,李成海,张海明.丙烯酸酯无皂乳液的制备及性能研究[J].化学建材,2007(01): 22-25.
[112]叶慈南,曹伟丽.应用数理统计[M].北京:机械工业出版社,2007: 289-290.
[113]汪长春,包启宇.丙烯酸酯涂料[M].北京:化学工业出版社,2005: 61.
[114]徐祖顺,易昌凤,肖卫东.织物用胶黏剂及粘接技术[M].北京:化学工业出版社,2004: 214.
[115]王宏丽.提高涂料大红FFG织物印花摩擦牢度[J].染整技术,2004,26(3): 47-48.
[116]曾幸荣,吴振耀.高分子近代测试分析技术[M].广州:华南理工大学出版社,2000: 36.