二聚酸钠丙烯酸酯无皂乳液
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摘要
本文旨在开发一种性能优良的反应型阴离子乳化剂,并应用这种乳化剂合成丙烯酸酯无皂乳液。
采用源白天然原料的二聚酸合成了一种反应型乳化剂二聚酸钠(SDA),其结构具有双子乳化剂的特征一具有双亲水基双亲油基。单独使用该乳化剂以半连续种子乳液聚合法制备了丙烯酸酯无皂乳液。对自制的反应型乳化剂进行了乳化力测试和溶液表面张力的测试,研究了乳化剂用量及聚合工艺对乳液性能的影响,并用红外、核磁、粒度分析仪对聚合物进行了表征。
试验结果表明,二聚酸钠乳化力优于常用的阴离子乳化剂十二烷基硫酸钠(SDS),其临界胶束浓度为28.6mmol/L,水溶液的表面张力为28.8mN·m-1。乳化剂HLB计算值为29.5。用二聚酸钠制备的无皂乳液的表面张力测试结果比较高(50.4-64.8mN·m-1),接近于纯水的表面张力(72mmol／L),表明SDA键合在乳胶粒上,而残留在水溶液中甚少。
当乳化剂用量为单体质量的8%,反应温度78-80℃,采取两阶段保温法,引发剂用量为单体质量的0.7%,种子单体用量为全部单体质量15%时可以合成固含量为45%的丙烯酸酯无皂乳液,采用单体质量3%的甲基丙烯酸-β-羟乙酯作为功能单体对乳液性能有较大的改善。合成的无皂乳液平均粒径100nm,粒子呈单分散分布,PDI为0.0595,乳液的Zeta电位可达。70mv,可见乳液稳定性较好,各项性能指标均合格,乳胶膜耐水性能较好。对乳胶膜的核磁共振分析和红外分析均证实该反应型乳化剂参与了自由基共聚合。
The aim of this research is to develop a novel polymerizable anionic emulsifier with good emulsification and polymerization.An emulsifier-free acrylic emulsion was synthesized in the presence of this polymerizable emulsifier.
A polymerizable anionic emulsifier was successfully prepared by using dimer acid derived from nature,and it has the Gemini surfactants'structure-it has two hydrophilic groups and two lipophilic groups.The soap-free emulsion polymer was synthesized via semi-continuous seeded emulsion polymerization. Its emulsification and the surface tension were mensurated.The effects of level of emulsifier amount and polymerization process on the emulsion properties were investigated. In addition, the emulsion and the films were characterized by Fourier transformed infrared (FT-IR) spectrometry, nuclear magnetic resonance(1H-NMR) spectrometry, and size analysis, respectively.
Test results indicated:the novel polymerizable anionic emulsifier itself had better emulsifying capacity compared with the anionic emulsifier sodium dodecyl sulfate (SDS)used commonly. The maximum bubble method was used to test the surface tension and the results showed that the critical micelle concentration (CMC) of the polymerizable anionic emulsifier was 28.6mmol/L, the surface tension of its solution was 28.8mN·m-1.The calculated HLB value of this emulsifier was 29.5.The surface tension of emulsion obtained by the SDA was high(50.4-64.8 mN·m-1),which closed to the surface tension of pure water(72mmol/L), indicating that the SDA combined in latex particles by chemical bonds,only low concentrations of SDA existed in the water phase.
Monomer content of emulsifier-free acrylic emulsion up to 45wt% could be successfully synthesized when the emulsifier amount was 8%,reaction temperature was 78-80℃,the initiator amount was 0.7%,the seed monomer amount was 15%, adopting two stage heat preservation. It showed that emulsion properties could be greatly improved by using 3wt% of 2-hydroxyethyl methacrylate (HEMA) as a functional monomer. The emulsifier-free acrylic emulsion was synthesized at an average diameter of 100nm,with a monodisperse of particle, PDI of 0.0595,Zeta potential of -70mv. It showed that the stability of emulsion was very good, every performance index was qualified and the water resistance of latex film was outstanding.1H-NMR and IR analysis confirmed that the reactive emulsifier were involved in the radical copolymerization.
采用源白天然原料的二聚酸合成了一种反应型乳化剂二聚酸钠(SDA),其结构具有双子乳化剂的特征一具有双亲水基双亲油基。单独使用该乳化剂以半连续种子乳液聚合法制备了丙烯酸酯无皂乳液。对自制的反应型乳化剂进行了乳化力测试和溶液表面张力的测试,研究了乳化剂用量及聚合工艺对乳液性能的影响,并用红外、核磁、粒度分析仪对聚合物进行了表征。
试验结果表明,二聚酸钠乳化力优于常用的阴离子乳化剂十二烷基硫酸钠(SDS),其临界胶束浓度为28.6mmol/L,水溶液的表面张力为28.8mN·m-1。乳化剂HLB计算值为29.5。用二聚酸钠制备的无皂乳液的表面张力测试结果比较高(50.4-64.8mN·m-1),接近于纯水的表面张力(72mmol／L),表明SDA键合在乳胶粒上,而残留在水溶液中甚少。
当乳化剂用量为单体质量的8%,反应温度78-80℃,采取两阶段保温法,引发剂用量为单体质量的0.7%,种子单体用量为全部单体质量15%时可以合成固含量为45%的丙烯酸酯无皂乳液,采用单体质量3%的甲基丙烯酸-β-羟乙酯作为功能单体对乳液性能有较大的改善。合成的无皂乳液平均粒径100nm,粒子呈单分散分布,PDI为0.0595,乳液的Zeta电位可达。70mv,可见乳液稳定性较好,各项性能指标均合格,乳胶膜耐水性能较好。对乳胶膜的核磁共振分析和红外分析均证实该反应型乳化剂参与了自由基共聚合。
The aim of this research is to develop a novel polymerizable anionic emulsifier with good emulsification and polymerization.An emulsifier-free acrylic emulsion was synthesized in the presence of this polymerizable emulsifier.
A polymerizable anionic emulsifier was successfully prepared by using dimer acid derived from nature,and it has the Gemini surfactants'structure-it has two hydrophilic groups and two lipophilic groups.The soap-free emulsion polymer was synthesized via semi-continuous seeded emulsion polymerization. Its emulsification and the surface tension were mensurated.The effects of level of emulsifier amount and polymerization process on the emulsion properties were investigated. In addition, the emulsion and the films were characterized by Fourier transformed infrared (FT-IR) spectrometry, nuclear magnetic resonance(1H-NMR) spectrometry, and size analysis, respectively.
Test results indicated:the novel polymerizable anionic emulsifier itself had better emulsifying capacity compared with the anionic emulsifier sodium dodecyl sulfate (SDS)used commonly. The maximum bubble method was used to test the surface tension and the results showed that the critical micelle concentration (CMC) of the polymerizable anionic emulsifier was 28.6mmol/L, the surface tension of its solution was 28.8mN·m-1.The calculated HLB value of this emulsifier was 29.5.The surface tension of emulsion obtained by the SDA was high(50.4-64.8 mN·m-1),which closed to the surface tension of pure water(72mmol/L), indicating that the SDA combined in latex particles by chemical bonds,only low concentrations of SDA existed in the water phase.
Monomer content of emulsifier-free acrylic emulsion up to 45wt% could be successfully synthesized when the emulsifier amount was 8%,reaction temperature was 78-80℃,the initiator amount was 0.7%,the seed monomer amount was 15%, adopting two stage heat preservation. It showed that emulsion properties could be greatly improved by using 3wt% of 2-hydroxyethyl methacrylate (HEMA) as a functional monomer. The emulsifier-free acrylic emulsion was synthesized at an average diameter of 100nm,with a monodisperse of particle, PDI of 0.0595,Zeta potential of -70mv. It showed that the stability of emulsion was very good, every performance index was qualified and the water resistance of latex film was outstanding.1H-NMR and IR analysis confirmed that the reactive emulsifier were involved in the radical copolymerization.
引文
[1]Amalvy J I, Unzue M J,Schoonbrod H A S.Reactive surfactants in heterophase polymerization.11.Particle Nucleation. Macromolecules,1998,31(17):5631-5638
[2]唐雅娟.马来酸单胺可聚合乳化剂的合成及在丙烯酸酯乳液聚合中的应用：[广西大学硕士学位论文].南宁：广西大学,2006,1-2
[3]Guyot A, Tauer K. Reactive surfactants in emulsion polymerization. Advances in Polymer Science,1994,(111):43-65
[4]谢剑妹.新型表面活性剂的合成及其乳化性能的研究：[福建师范大学硕士学位论文].福州：福建师范大学,2009,11-12
[5]姚志刚,戴云信.氨基磺酸法合成反应型表面活型剂的进展.邵阳高等专科学校学报,2001,14(3)：195-198
[6]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.合成橡胶工业,2003,26(2)：94-97
[7]Menno G D, Guyot A.Nonionic reactive surfactants. L. Synthesis and characteri-zation. Colloid & Polymer Science,2003,(281):97-104
[8]张振华,刘长.十二烷基烯丙基琥珀酸酯磺酸钠的合成.南华大学学报,2004,18(4)：98-101
[9]唐雅娟,李成海,张海明.马来酸单十二胺丙基磺酸钠的合成与性能.日用化学工业,2006,36(6)：345-347
[10]胡艾希,陈学伟,姚志钢.琥珀酸双酯磺酸钠类反应型表面活性剂的合成.精细化工,2006,23(3)：234-237
[11]邓剑如,申红光,喻鸿钢,等.反应型乳化剂十二醇马来酸钠的合成及其性能研究.湖南大学学报,2008,35(10)：55-59
[12]Syed Q, Fu X A, Yousuf T. Synthesis of polystyrene-clay nanocomposites via emulsion polymerization using a reactive surfactant. Polymer Bulletin,2002, 48(2):143-149
[13]龚涛,鲁德平.马来酸酐双酯型阳离子可聚合表面活性剂的合成研究.湖北大学学报,2004,26(1)：52-56
[14]Yang S F, Xiong P T, Gong T, et al.St-BA copolymer emulsions prepared by using novel cationic maleic dialkyl polymerizable emulsifier. European Polymer Journal,2005,41(12):2973-2979
[15]靳丽强,徐清华.阳离子反应型表面活型剂DMHB的合成和性质.陕西科技大学学报,2004,22(3)：102-105
[16]张光华,解攀,刘静,等.松香型阳离子乳化剂的制备及性能.化工进展,2008,27(10)：1628-1631
[17]彭顺金,张贵军,方华.油溶性非离子型可聚合表面活性剂ASMO的制备.精细石油化工,2000,(1)：15-17
[18]陈大俊,李娜,李瑶君.反应型乳化剂的合成及结构表征.涂料工业,2002,(2)：38-40
[19]方少明,周立明,陈志军.新型两亲性聚氨酯丙烯酸酯大单体的合成及性能研究.精细石油化工,2005,(3)：26-29
[20]Laschewsky A.Oligoethyleneoxide spacer groups in polymerizable surfacet-ants.Colloid & Polymer Science,1991,(269):785-794
[21]Abele S,Graiuat C,Zicmanis A, et al.Hemiesters and hemiamides of maleic and succinie acid:synthesis and application of surfactants in emulsion polymerization with styrene and butyl acrylate. Polymers for Advanced Technologies,1999, 10(6):301-310
[22]谢亚杰,王伟,刘深.表面活性剂制备技术与技术分析测试.北京：化学工业出版社,2006：269-271
[23]蔡良珍,刘洪来,孙永峰,等.一种Gemini表面活性剂.中国专利.CN1966137A,2007-05-23
[24]王亚光,王利民,刘炼,等.阳离子型Gemini表面活性剂.中国专利.CN101007246A,2007-08-01
[25]姚志钢,李干佐,胡艾希.双子表面活性剂—二元醇双琥珀酸双酯磺酸钠(GMI-01)的合成与性能研究.精细化工,2003,20(11)：655-704
[26]张所信,王慧彦,徐晓阳,等.双子苯并咪唑表面活性剂的合成及性能研究.涂料工业,2005,35(11)：4-6
[27]郭天瑛,宋谋道,郝广杰,等.无皂乳液聚合稳定化研究进展.石油化工2001,30(1)：69-71
[28]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,2007：258,302,401,480,619,531-532
[29]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,1998,11(19)：1848-1852
[30]Chen S A,Lee S T. Kinetics and mechanism of emulsifier-free emulsion polymerization:styrene/hydrophilic comonomer(acrylamid)system.Macrom olecules,1991,24(11):3340-3351
[31]Pan T C,Kuo J F, Chen C Y. The effect of sodium methacrylate on the soapless emulsion copolymerization of methyl methacrylate and n-butyl acrylate. Journal of Polymer Science Part A:Polymer Chemistry,1991,29:709-718
[32]麻明友.偶氮二异丁基盐酸脒引发甲基丙烯酸甲酯微球的无皂乳液聚合.材料科学与工程学报,2006,24(6)：871-873
[33]白宝喜,董薇.苯丙系列阳离子无皂乳液的制备.化学工程师,2006,125(2)：56-57
[34]储鸿,王志英,倪忠斌,等.VPE引发的苯乙烯无皂乳液聚合研究.化工新型材料,2009,35(1)：31-34
[35]郝海娟,郝广杰,宋谋道,等.MMA/BA/AA/HEMA无皂乳液共聚物的结构与性能.高分子材料科学与工程,2001,17(2)：76-79
[36]廖晓兰,张宝莲,魏冬青.苯乙烯磺酸钠用于硅丙无皂乳液聚合研究.涂料工业,2009,39(9)：38-41
[37]易昌凤,高庆,肖桂林,等.苯乙烯／羟甲基丙烯酰胺无皂乳液共聚合的研究.胶体与聚合物,2005,23(2)：6-8
[38]李昊,杨玉昆.无皂丙烯酸酯乳液压敏胶的制备与性能研究.粘结,2005,26(5)：1-3
[39]关有俊,赵欣平,何唯平.一种聚氨酯型反应性乳化剂的制备方法.中国专利.CN1796431A,2006-07-05
[40]岳庆磊,周文华,潘湛昌,等.无皂乳液聚合研究进展.精细化工,2003,20(12)：766-768
[41]郭林晖,马承银.反应性乳化剂对MMA/BA乳液聚合的影响.涂料工业,2004,34(10)：30-32
[42]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
[43]肖新颜,王叶,万彩霞.可聚合乳化剂合成含氟聚丙烯酸酯无皂乳液.华南理工大学学报,2009,37(9)：133-138
[44]孔祥文,王静,王传胜,等.无皂聚丙烯酯乳液的合成及稳定性研究.化学世界,2004,45(2)：81-83
[45]侯慧玉,涂伟萍.超声波辐射无皂乳液聚合研究进展.化工新型材料,2005,33(6)：47-50
[46]殷万年,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.高分子学报,2006,(2)：253-257
[47]徐继红,徐国财,王贞平.超声辐射丙烯酸丁酯无皂乳液聚合.化工新型材料,2006,34(3)：27-30
[48]冯光炷,付黎敏,崔英德.二聚脂肪酸应用研究进展.中国油脂,2006,31(9)：37-42
[49]Tunca U,Koc S.Synthesis of aromatic poly(ether ketone)s cotaining C36 aliphatic unsaturated groups in the main chain. Journal of Applied Polymer Science,1997, 63(10):1275-1278
[50]Magdalena R G, Miroslawa E F. The effect of simulated body fluid on the mechanical properties of multiblock poly(aliphatic/aromatic-ester) copolymer. Biomaterials,2004,25(21):5191-5198
[51]Guo'W X, Huang K X. Preparation and properties of poly(dimer acid-edodecanedioic acid) copolymer and poly(dimer acid-etetradecanedioic acid) copolymer. Polymer Degradation and Stability,2004,84(3):375-381
[52]周志彬,黄开勋,许铭飞,等.聚二聚酸-癸二酸的合成和药物释放性能.华中科技大学学报,2001,29(1)：96-98
[53]张韬,张志强,刘宗霖,等.新型控释化疗系统的基础研究.生物医学工程学杂志,2003,20(4)：686-688
[54]冯光炷,崔英德,渠海,等.C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐的制备及性能表征.精细化工,2006,23(4)：341-345
[55]O'Lenick J, Amhony J.Capped dimmer acid polyesters in personal care applications. United States Patent,6800275,2004-10-05
[56]张秀鲁.二聚酸的现状与今后.日用化学工业,1993,(4)：21-24
[57]布鲁德尔F K,海泽W,维尔曼R,等.聚酯碳酸酯及用其制作的数据载体.中国专利.CN1418233,2003-05-14
[58]任彦强,任孝修.聚氨酯涂料用新型聚酯二醇的合成.涂料工业,2001,(9)：17-20
[59]孙翔月,郭文迅,袁华,等.二聚酸改性耐水乳液的合成.新型建筑材料,2009,(10)：6-10
[60]郭文迅,孙翔月,袁华,等.二聚酸改性丙烯酸酯耐水微乳液及其制备方法.中国专利.CN101544721,2009-09-30
[61]毛培坤.表面活性荆产品工业分析.北京：化学工业出版社,2003：7-14
[62]薛垠.甲基丙烯酸酯类改进微乳液聚合体系的进一步研究：[复旦大学硕士学位论文].上海：复旦大学,2006,16-17
[63]赵国玺.表面活性剂物理化学.北京：北京大学出版社,1991：130-135
[64]Abele S,Zicmanis A, Graillat C, et al.Cationic and zwitterionic polymeri zable surfactants:quaternary ammonium dialky maleates.L.Synthesis and haracterization.Langmuir,1999,15(4):1033-1044
[65]Abele S,Gauthier C,Graillat C,et al.Films from styrene-butyl acrylate lattices using maleic or succinic surfactants:mechanical properties, water rebound and grafting of the Surfactants.Polymer,2000,41(3):1147-1155
[66]吴跃焕,刘述梅,赵建青.加料方式对丙烯酸酯微乳液粒径的影响.华南理工大学学报,2008,36(3)：37-40
[67]Lu S L, Qu R J,Forcada J.Preparation of magnetic polymeric composite nanoparticles by seeded emulsion polymerization. Materials Letters,2009, 63(9-10):770-772
[68]Milosevic'I, Mauroy V, Dabboue H, et al.Synthesis and size control of poly-styrene nanoparticles via "liquid crystalline" nanoemulsion. Microporous and Mesoporous Materials,2009,120(1-2):7-11
[69]Wi Y, Lee K, Lee B H, et al.Soap-free emulsion polymerization of styrene using poly(methacrylic acid) macro-RAFT agent. Polymer,2008,49(26):5626-5635
[70]范圣强,曹瑞军,周心艳.可聚合乳化剂改性对弹性丙烯酸酯乳液粘度的影响.材料科学与工程学报,2004,22(6)：806-808
[71]Lapernt C, Bernard E, Richard J,et al.Polymerization in microemulsions with polymerizable Cosurfactants:A route to highly functionalized nano particles. Macromolecules,1997,30(2):354-362
[72]孙志娟,张心亚,黄洪,等.低VOC纯丙乳液及乳胶涂料的合成与配制.新型建筑材料,2006,(5)：36-39
[73]Guo F G, Zhang Q Y, Zhang B L, et al.Preparation and characterization of magnetic composite microspheres using a free radical polymerization system consisting of DPE.Polymer,2009,50(8):1887-1894
[74]陈尔凡,李素莲,马驰.微乳液聚合物纳米粒子的研究方法.功能材料,2006,37(6)：853-856
[2]唐雅娟.马来酸单胺可聚合乳化剂的合成及在丙烯酸酯乳液聚合中的应用：[广西大学硕士学位论文].南宁：广西大学,2006,1-2
[3]Guyot A, Tauer K. Reactive surfactants in emulsion polymerization. Advances in Polymer Science,1994,(111):43-65
[4]谢剑妹.新型表面活性剂的合成及其乳化性能的研究：[福建师范大学硕士学位论文].福州：福建师范大学,2009,11-12
[5]姚志刚,戴云信.氨基磺酸法合成反应型表面活型剂的进展.邵阳高等专科学校学报,2001,14(3)：195-198
[6]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.合成橡胶工业,2003,26(2)：94-97
[7]Menno G D, Guyot A.Nonionic reactive surfactants. L. Synthesis and characteri-zation. Colloid & Polymer Science,2003,(281):97-104
[8]张振华,刘长.十二烷基烯丙基琥珀酸酯磺酸钠的合成.南华大学学报,2004,18(4)：98-101
[9]唐雅娟,李成海,张海明.马来酸单十二胺丙基磺酸钠的合成与性能.日用化学工业,2006,36(6)：345-347
[10]胡艾希,陈学伟,姚志钢.琥珀酸双酯磺酸钠类反应型表面活性剂的合成.精细化工,2006,23(3)：234-237
[11]邓剑如,申红光,喻鸿钢,等.反应型乳化剂十二醇马来酸钠的合成及其性能研究.湖南大学学报,2008,35(10)：55-59
[12]Syed Q, Fu X A, Yousuf T. Synthesis of polystyrene-clay nanocomposites via emulsion polymerization using a reactive surfactant. Polymer Bulletin,2002, 48(2):143-149
[13]龚涛,鲁德平.马来酸酐双酯型阳离子可聚合表面活性剂的合成研究.湖北大学学报,2004,26(1)：52-56
[14]Yang S F, Xiong P T, Gong T, et al.St-BA copolymer emulsions prepared by using novel cationic maleic dialkyl polymerizable emulsifier. European Polymer Journal,2005,41(12):2973-2979
[15]靳丽强,徐清华.阳离子反应型表面活型剂DMHB的合成和性质.陕西科技大学学报,2004,22(3)：102-105
[16]张光华,解攀,刘静,等.松香型阳离子乳化剂的制备及性能.化工进展,2008,27(10)：1628-1631
[17]彭顺金,张贵军,方华.油溶性非离子型可聚合表面活性剂ASMO的制备.精细石油化工,2000,(1)：15-17
[18]陈大俊,李娜,李瑶君.反应型乳化剂的合成及结构表征.涂料工业,2002,(2)：38-40
[19]方少明,周立明,陈志军.新型两亲性聚氨酯丙烯酸酯大单体的合成及性能研究.精细石油化工,2005,(3)：26-29
[20]Laschewsky A.Oligoethyleneoxide spacer groups in polymerizable surfacet-ants.Colloid & Polymer Science,1991,(269):785-794
[21]Abele S,Graiuat C,Zicmanis A, et al.Hemiesters and hemiamides of maleic and succinie acid:synthesis and application of surfactants in emulsion polymerization with styrene and butyl acrylate. Polymers for Advanced Technologies,1999, 10(6):301-310
[22]谢亚杰,王伟,刘深.表面活性剂制备技术与技术分析测试.北京：化学工业出版社,2006：269-271
[23]蔡良珍,刘洪来,孙永峰,等.一种Gemini表面活性剂.中国专利.CN1966137A,2007-05-23
[24]王亚光,王利民,刘炼,等.阳离子型Gemini表面活性剂.中国专利.CN101007246A,2007-08-01
[25]姚志钢,李干佐,胡艾希.双子表面活性剂—二元醇双琥珀酸双酯磺酸钠(GMI-01)的合成与性能研究.精细化工,2003,20(11)：655-704
[26]张所信,王慧彦,徐晓阳,等.双子苯并咪唑表面活性剂的合成及性能研究.涂料工业,2005,35(11)：4-6
[27]郭天瑛,宋谋道,郝广杰,等.无皂乳液聚合稳定化研究进展.石油化工2001,30(1)：69-71
[28]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,2007：258,302,401,480,619,531-532
[29]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,1998,11(19)：1848-1852
[30]Chen S A,Lee S T. Kinetics and mechanism of emulsifier-free emulsion polymerization:styrene/hydrophilic comonomer(acrylamid)system.Macrom olecules,1991,24(11):3340-3351
[31]Pan T C,Kuo J F, Chen C Y. The effect of sodium methacrylate on the soapless emulsion copolymerization of methyl methacrylate and n-butyl acrylate. Journal of Polymer Science Part A:Polymer Chemistry,1991,29:709-718
[32]麻明友.偶氮二异丁基盐酸脒引发甲基丙烯酸甲酯微球的无皂乳液聚合.材料科学与工程学报,2006,24(6)：871-873
[33]白宝喜,董薇.苯丙系列阳离子无皂乳液的制备.化学工程师,2006,125(2)：56-57
[34]储鸿,王志英,倪忠斌,等.VPE引发的苯乙烯无皂乳液聚合研究.化工新型材料,2009,35(1)：31-34
[35]郝海娟,郝广杰,宋谋道,等.MMA/BA/AA/HEMA无皂乳液共聚物的结构与性能.高分子材料科学与工程,2001,17(2)：76-79
[36]廖晓兰,张宝莲,魏冬青.苯乙烯磺酸钠用于硅丙无皂乳液聚合研究.涂料工业,2009,39(9)：38-41
[37]易昌凤,高庆,肖桂林,等.苯乙烯／羟甲基丙烯酰胺无皂乳液共聚合的研究.胶体与聚合物,2005,23(2)：6-8
[38]李昊,杨玉昆.无皂丙烯酸酯乳液压敏胶的制备与性能研究.粘结,2005,26(5)：1-3
[39]关有俊,赵欣平,何唯平.一种聚氨酯型反应性乳化剂的制备方法.中国专利.CN1796431A,2006-07-05
[40]岳庆磊,周文华,潘湛昌,等.无皂乳液聚合研究进展.精细化工,2003,20(12)：766-768
[41]郭林晖,马承银.反应性乳化剂对MMA/BA乳液聚合的影响.涂料工业,2004,34(10)：30-32
[42]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
[43]肖新颜,王叶,万彩霞.可聚合乳化剂合成含氟聚丙烯酸酯无皂乳液.华南理工大学学报,2009,37(9)：133-138
[44]孔祥文,王静,王传胜,等.无皂聚丙烯酯乳液的合成及稳定性研究.化学世界,2004,45(2)：81-83
[45]侯慧玉,涂伟萍.超声波辐射无皂乳液聚合研究进展.化工新型材料,2005,33(6)：47-50
[46]殷万年,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.高分子学报,2006,(2)：253-257
[47]徐继红,徐国财,王贞平.超声辐射丙烯酸丁酯无皂乳液聚合.化工新型材料,2006,34(3)：27-30
[48]冯光炷,付黎敏,崔英德.二聚脂肪酸应用研究进展.中国油脂,2006,31(9)：37-42
[49]Tunca U,Koc S.Synthesis of aromatic poly(ether ketone)s cotaining C36 aliphatic unsaturated groups in the main chain. Journal of Applied Polymer Science,1997, 63(10):1275-1278
[50]Magdalena R G, Miroslawa E F. The effect of simulated body fluid on the mechanical properties of multiblock poly(aliphatic/aromatic-ester) copolymer. Biomaterials,2004,25(21):5191-5198
[51]Guo'W X, Huang K X. Preparation and properties of poly(dimer acid-edodecanedioic acid) copolymer and poly(dimer acid-etetradecanedioic acid) copolymer. Polymer Degradation and Stability,2004,84(3):375-381
[52]周志彬,黄开勋,许铭飞,等.聚二聚酸-癸二酸的合成和药物释放性能.华中科技大学学报,2001,29(1)：96-98
[53]张韬,张志强,刘宗霖,等.新型控释化疗系统的基础研究.生物医学工程学杂志,2003,20(4)：686-688
[54]冯光炷,崔英德,渠海,等.C36二聚脂肪酸聚乙二醇聚酯硫酸酯盐的制备及性能表征.精细化工,2006,23(4)：341-345
[55]O'Lenick J, Amhony J.Capped dimmer acid polyesters in personal care applications. United States Patent,6800275,2004-10-05
[56]张秀鲁.二聚酸的现状与今后.日用化学工业,1993,(4)：21-24
[57]布鲁德尔F K,海泽W,维尔曼R,等.聚酯碳酸酯及用其制作的数据载体.中国专利.CN1418233,2003-05-14
[58]任彦强,任孝修.聚氨酯涂料用新型聚酯二醇的合成.涂料工业,2001,(9)：17-20
[59]孙翔月,郭文迅,袁华,等.二聚酸改性耐水乳液的合成.新型建筑材料,2009,(10)：6-10
[60]郭文迅,孙翔月,袁华,等.二聚酸改性丙烯酸酯耐水微乳液及其制备方法.中国专利.CN101544721,2009-09-30
[61]毛培坤.表面活性荆产品工业分析.北京：化学工业出版社,2003：7-14
[62]薛垠.甲基丙烯酸酯类改进微乳液聚合体系的进一步研究：[复旦大学硕士学位论文].上海：复旦大学,2006,16-17
[63]赵国玺.表面活性剂物理化学.北京：北京大学出版社,1991：130-135
[64]Abele S,Zicmanis A, Graillat C, et al.Cationic and zwitterionic polymeri zable surfactants:quaternary ammonium dialky maleates.L.Synthesis and haracterization.Langmuir,1999,15(4):1033-1044
[65]Abele S,Gauthier C,Graillat C,et al.Films from styrene-butyl acrylate lattices using maleic or succinic surfactants:mechanical properties, water rebound and grafting of the Surfactants.Polymer,2000,41(3):1147-1155
[66]吴跃焕,刘述梅,赵建青.加料方式对丙烯酸酯微乳液粒径的影响.华南理工大学学报,2008,36(3)：37-40
[67]Lu S L, Qu R J,Forcada J.Preparation of magnetic polymeric composite nanoparticles by seeded emulsion polymerization. Materials Letters,2009, 63(9-10):770-772
[68]Milosevic'I, Mauroy V, Dabboue H, et al.Synthesis and size control of poly-styrene nanoparticles via "liquid crystalline" nanoemulsion. Microporous and Mesoporous Materials,2009,120(1-2):7-11
[69]Wi Y, Lee K, Lee B H, et al.Soap-free emulsion polymerization of styrene using poly(methacrylic acid) macro-RAFT agent. Polymer,2008,49(26):5626-5635
[70]范圣强,曹瑞军,周心艳.可聚合乳化剂改性对弹性丙烯酸酯乳液粘度的影响.材料科学与工程学报,2004,22(6)：806-808
[71]Lapernt C, Bernard E, Richard J,et al.Polymerization in microemulsions with polymerizable Cosurfactants:A route to highly functionalized nano particles. Macromolecules,1997,30(2):354-362
[72]孙志娟,张心亚,黄洪,等.低VOC纯丙乳液及乳胶涂料的合成与配制.新型建筑材料,2006,(5)：36-39
[73]Guo F G, Zhang Q Y, Zhang B L, et al.Preparation and characterization of magnetic composite microspheres using a free radical polymerization system consisting of DPE.Polymer,2009,50(8):1887-1894
[74]陈尔凡,李素莲,马驰.微乳液聚合物纳米粒子的研究方法.功能材料,2006,37(6)：853-856