纳米SiO_2粉体/聚丙烯酸酯复合乳液的制备及性能研究
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摘要
聚丙烯酸酯乳液是一种绿色环保型聚合乳液,它是由丙烯酸酯类和甲基丙烯酸酯类及其它单体共聚制成的树脂。聚丙烯酸酯具有优良的耐候性和成膜性,同织物的粘接性能好,且成本较低,但是聚丙烯酸酯乳液成膜后硬度低、热稳定性差,涂膜容易返粘。由于纳米粉体具有独特的性能,引入乳液体系中可显著提高乳液的刚性、硬度、强度、热稳定性、耐腐蚀性等,本文采用了纳米SiO_2粉体对乳液进行改性,制备了纳米粉体聚丙烯酸酯复合乳液。
考虑到纳米粉体表面极性大,表面能高,容易吸附而发生团聚,形成二次粒子,使其粒径变大而最终失去纳米粒子所具有的特殊功能。论文首先就纳米粉体的分散问题进行了讨论,详细叙述了粉体分散的机理和分散方法;其次对纳米粉体、单体、乳化剂、引发剂、分散介质等一些成分的类型和用量进行了合理选择,优化合成工艺,探讨了核壳比对乳液性能的影响,并且在乳液聚合过程中,通过添加纳米粉体对乳液进行改性处理,主要研究了不同纳米粉体配比对乳液性能及涂层玻璃纤维布耐碱性能的影响;最后利用复合乳液对玻纤布进行了涂层处理,研究了复合乳液的综合性能。
研究结果表明:纳米SiO_2粉体能够很好的和乳液进行复合,形成稳定的聚丙烯酸酯复合乳液。添加占纳米SiO_2粉体重量1%的分散剂OP-10和表面改性剂硅烷偶联剂(kh-550),并采用机械搅拌加超声分散相结合的方法可以有效改善纳米粉体的团聚现象。当反应温度为78℃、核/壳比为7/10、核层单体(MMA/VAC/BA)比为1/2/7、壳层单体比为7/2/1、纳米SiO_2粉体用量为4‰、乳化剂用量为4%、引发剂用量为1.1%、缓冲剂用量为0.3%,去离子水用量为140%时能形成性质稳定的复合乳液,当纳米SiO_2粉体用量为4‰时,丙烯酸酯乳液的固含量、粘度、稳定性,乳液粒径分布和乳液粘接力等都比较理想。
Polyacrylate emulsion in a green environment-friendly emulsion.It is a resin which is made by the acrylic esters,methacrylic acid esters and other monomers. Polyacrylate has many good performance such as excellent weather resistance, good film-forming, bonding with the fabric easily and low cosr. But polyacrylate emulsion film has low hardness and thermal stability, film easier to back stick. As the nano-powders with unique properties, the introduction of emulsion system can significantly increase the rigidity of latex, hardness, strength, thermal stability, corrosion resistance, etc. In this paper, nano-SiO2 powder on the emulsion was modified to prepare nano-powders-polyacrylate composite latex. This results show that nano-SiO2 powder show that: Nano-SiO2 powder and emulsion, can be a good compound to form a stable polyacrylate composite latex. Add the KH550 silane and OP-10, 1% of the powder, the mechanical stirring plus ultrasonic dispersion can avoid nano-powders’s agglomeration effectively.
Taking into account the high polarity and surface energy of nano-powder, it can easily be absorbed and reunite together, forming secondary particles. This will larger nano-particles’s size, which due to the loss of nano-powder’s special features. The nanometer powder dispersion is first discussed in this paper, including the diapersion mechanism and many methods in detail. During the process of emulsion polymerization, nano-particles is added to modify the emulsion. The main research of this paper is the influence of different ratio nano-powder on the emulsion’s properties and the coated glass cloth’s alkali-resistance performance.
Add the total weight of nano-SiO2 powder 1% of the dispersing agent OP-10 and surface modification agent silane coupling agent (kh-550), and using mechanical mixing method of combining the dispersed phase plus ultrasound can be effective in improving the phenomenon of agglomeration of nano-powders. When the reaction temperature is 78℃; core/shell ratio of 7/10; nuclear layer monomer (MMA/VAC/BA) ratio of 1/2/7; shell monomer ratio of 7/2/1; Nano-SiO2 Powder body dosage of 4‰, emulsifier dosage is 4%; initiator dosage is 1.1%; buffer dosage of 0.3%; de-ionized water consumption was 140% of the compound can form a stable emulsion in nature. When the nano-SiO_2 powder dosage is 4‰, the acrylic latex solid content, viscosity, stability, emulsion particle size distribution and emulsion adhesive force and so is ideal. the acrylic ester emulsion monomers are MMA、VAC and BA, the core ratio and shell ratio of MMA/VAC/BA is 1/2/7, 7/2/1 respectively, the core/shell ratio is 7/10, the amount of every components is: nanometer SiO_2 powder is 4‰, the water is 140%, the emulsifier is 4%, the initiator is 1.1%, buffer volume is 0.3%. When all this components are polymerized under 78℃, the composite latex is stable. Finally, composite emulsion is coated on the glass cloth to research it’s comprehensive properties.
考虑到纳米粉体表面极性大,表面能高,容易吸附而发生团聚,形成二次粒子,使其粒径变大而最终失去纳米粒子所具有的特殊功能。论文首先就纳米粉体的分散问题进行了讨论,详细叙述了粉体分散的机理和分散方法;其次对纳米粉体、单体、乳化剂、引发剂、分散介质等一些成分的类型和用量进行了合理选择,优化合成工艺,探讨了核壳比对乳液性能的影响,并且在乳液聚合过程中,通过添加纳米粉体对乳液进行改性处理,主要研究了不同纳米粉体配比对乳液性能及涂层玻璃纤维布耐碱性能的影响;最后利用复合乳液对玻纤布进行了涂层处理,研究了复合乳液的综合性能。
研究结果表明:纳米SiO_2粉体能够很好的和乳液进行复合,形成稳定的聚丙烯酸酯复合乳液。添加占纳米SiO_2粉体重量1%的分散剂OP-10和表面改性剂硅烷偶联剂(kh-550),并采用机械搅拌加超声分散相结合的方法可以有效改善纳米粉体的团聚现象。当反应温度为78℃、核/壳比为7/10、核层单体(MMA/VAC/BA)比为1/2/7、壳层单体比为7/2/1、纳米SiO_2粉体用量为4‰、乳化剂用量为4%、引发剂用量为1.1%、缓冲剂用量为0.3%,去离子水用量为140%时能形成性质稳定的复合乳液,当纳米SiO_2粉体用量为4‰时,丙烯酸酯乳液的固含量、粘度、稳定性,乳液粒径分布和乳液粘接力等都比较理想。
Polyacrylate emulsion in a green environment-friendly emulsion.It is a resin which is made by the acrylic esters,methacrylic acid esters and other monomers. Polyacrylate has many good performance such as excellent weather resistance, good film-forming, bonding with the fabric easily and low cosr. But polyacrylate emulsion film has low hardness and thermal stability, film easier to back stick. As the nano-powders with unique properties, the introduction of emulsion system can significantly increase the rigidity of latex, hardness, strength, thermal stability, corrosion resistance, etc. In this paper, nano-SiO2 powder on the emulsion was modified to prepare nano-powders-polyacrylate composite latex. This results show that nano-SiO2 powder show that: Nano-SiO2 powder and emulsion, can be a good compound to form a stable polyacrylate composite latex. Add the KH550 silane and OP-10, 1% of the powder, the mechanical stirring plus ultrasonic dispersion can avoid nano-powders’s agglomeration effectively.
Taking into account the high polarity and surface energy of nano-powder, it can easily be absorbed and reunite together, forming secondary particles. This will larger nano-particles’s size, which due to the loss of nano-powder’s special features. The nanometer powder dispersion is first discussed in this paper, including the diapersion mechanism and many methods in detail. During the process of emulsion polymerization, nano-particles is added to modify the emulsion. The main research of this paper is the influence of different ratio nano-powder on the emulsion’s properties and the coated glass cloth’s alkali-resistance performance.
Add the total weight of nano-SiO2 powder 1% of the dispersing agent OP-10 and surface modification agent silane coupling agent (kh-550), and using mechanical mixing method of combining the dispersed phase plus ultrasound can be effective in improving the phenomenon of agglomeration of nano-powders. When the reaction temperature is 78℃; core/shell ratio of 7/10; nuclear layer monomer (MMA/VAC/BA) ratio of 1/2/7; shell monomer ratio of 7/2/1; Nano-SiO2 Powder body dosage of 4‰, emulsifier dosage is 4%; initiator dosage is 1.1%; buffer dosage of 0.3%; de-ionized water consumption was 140% of the compound can form a stable emulsion in nature. When the nano-SiO_2 powder dosage is 4‰, the acrylic latex solid content, viscosity, stability, emulsion particle size distribution and emulsion adhesive force and so is ideal. the acrylic ester emulsion monomers are MMA、VAC and BA, the core ratio and shell ratio of MMA/VAC/BA is 1/2/7, 7/2/1 respectively, the core/shell ratio is 7/10, the amount of every components is: nanometer SiO_2 powder is 4‰, the water is 140%, the emulsifier is 4%, the initiator is 1.1%, buffer volume is 0.3%. When all this components are polymerized under 78℃, the composite latex is stable. Finally, composite emulsion is coated on the glass cloth to research it’s comprehensive properties.
引文
[1]熊玉钦.聚丙烯酸酯催溶胶复合乳液的制备及在水性涂料中的应用[D].北京:北京化工大学, 2006: 14-l8.
[2]陈湘南.建筑涂料用乳液的开发动向[J].中国涂料, 1997, 13(1): 23-27.
[3] http://www.kawise.com/Additive/Other/200707/20070720155450.shtml
[4] Chen X C, Wu L M,Zhou S X, et al. In situ polymeri-zation and characterization of polyester-based polyure-thane/nano-silica composites[J]. Polymer Int, 2003, 52(6): 993-998.
[5] Katsuji Matsuura, Kamagaya, Kunihito Arai.Process for treating the surface of glass fibre to impartresistance to alkalis[P]. US4188421, 1980.
[6] Rong M Z, et al. Friction and wear performance of grafted nano-SiO2/epoxy composites [J].J Mater Sci Lett, 2000. (19): 1159
[7]邹德荣,徐宇. EPDM橡胶基防水材料专用胶粘剂的研制[J].中国建筑防水,2002(4): 2l-24.
[8]孙多先,贾东海,郭长海等.水性聚氨酯包封原生纳米SiO2纳米复合材料的制备及表征[J].现代化工, 2003, 23(1): 41-43.
[9]马恒怡,魏根拴,张晓红等.丁腈弹性纳米粒子改性酚醛树脂的研究[J].高分子学报, 2005(3): 467-470.
[10]李晓俊,刘小兰,叶超等.纳米CaCO3改性环氧胶粘剂[J].青岛科技大学学报, 2005, 26(5): 42l-427.
[11]陈名华,姚武文,汪定江等.纳米TiO2对环氧树脂胶粘剂性能影响的研究[J].高分子学报, 2004, 25(6): l2-l5.
[12]张鹏,王兆华.丙烯酸树脂防腐蚀涂料及应用[M].北京:化学工业出版社, 2003.
[13]张超灿,汤先文等.纳米二氧化硅/聚丙烯酸酯乳胶涂料涂膜的制备及性能研究[J].涂料工业, 2003, 21(3): 1.
[14] Bourgeat-Lami E, Espiard Ph, Guyot A. Synthesis and Characterization of Silica/Poly Nanocomposite Latex Particles through Emulsion Polymerization Using a Cationic Azo Initiator[J]. Polymer, 1995, 36(23): 4386-4389.
[15] Espiard Ph, Guyot A. Progress on Synthesizing SiO2/Polymer Nanocomposite Emulsion[J]. Polymer International, 1995, 36(23): 4391-4395.
[16] Espiard Ph, Guyot A. Adhesion Parameters at the Interface in Nanoparticulate FilledPolymer Systems[J]. Polymer International, 1995, 36(23): 4397-4403.
[17] Tiarks F, Landfester K, Antonietti M. Recent Progress of Miniemulsion Polymerization Langmuir[J].Chemical Industry And Engineering Progress, 2001, 17: 5775-5780.
[18] Luna-Xavier J L, Guyot A, Bourgeat-Lami E. J Colloid Interface Sci, 2002, 250: 82-92.
[19]熊明娜,武利民,周树学等.纳米复合涂料的发展述评[J].涂料工业, 2002, 32(11): 1-3.
[20] Xiong M, Wu L, Zhou S, You B. Synthesis and Characterization of Poly(St-co-BA) Latex with an Organic-Inorganic Hybrid Compound as Emulsifier[J]. Polymer International, 2002, 51(8): 693-698.
[21] Li H, You B, Gu G, Wu L, Chen G. Formulation of shear rate sensitive multiple emulsions[J]. Polymer International, 2005, 54(5): 609-617.
[22]庞金兴,熊焰,张超灿等.有机硅-丙烯酸酯共聚乳液的合成研究[J].武汉理工大学学报, 2001, 23(12): 16-19.
[23]庞金兴,熊焰,吴力立等. Synthesis of Nanosized SiO2/Silicone/Acrylic Ester Complex Emulsion[J]. Nature Science Edition, 2002, 30(7): 108-110.
[24]夏宇正,李敬玮,石淑先等.聚丙烯酸酯/聚硅氧烷乳胶粒核壳结构相反转及控制[J].涂料工业, 2003, 33 (3): 19-21.
[25]徐伟平,黄锐,蔡碧华等.大分子偶联剂对HDPE/纳米CaC03复合材料性能的影响[J].中国塑料, 1999(9): 25-29.
[26]张玉龙,高树理.纳米改性剂[M].北京:国防工业出版社, 2004: 129.
[27]杨永康,何勇,铁旭初等.超细粉体在液体中的分散[J].建材技术与应用, 2006(5):17-20.
[28]李爱元.纳米粉体表面改性技术及应用[J].化工新型材料, 2002, 30(10): 25-28.
[29]汤国虎.无机纳米粉体表面改性研究现状[J].材料导报, 2003, 17(9): 33-36.
[30]庞金兴,熊焰,吴力立等.纳米SiO2/聚丙烯酸醋复合乳液涂料的研制[J].华中科技大学学报(自然科学版), 2002, 30(7): 108-110.
[31]耿耀宗,现代水性涂料[M].北京:中国石化出版社, 2003.
[32]林宣益.乳胶漆[M].北京:化学工业出版社, 2004.
[33]施冠成,华载文.织物涂层用聚丙烯酸酯乳液的新进展[J].中国纺织大学学报, 1997, 23(5): 122-125.
[34]吴秋兰,韩世洪,张尚勇.引发剂用量对聚丙烯酸类浆料性能的影响[J].纺织科技进展, 2007(4): 15-16.
[35]王文俊,李伯耿,于在璋等.半连续乳液聚合[J].高分子通报, 1995(1): 44.
[36] Chern CS, Hsu H. Semibatch emulsion copolymerization of methyl methacrylate and butylacrylate[J]. J Appl Polym Sci, 1995, 55(4): 571.
[37] Arzamend G,Asua JM. Monomer addition policies for copolymer composition control in semicontinuous emulsion copolymerization[J]. Appl PolymSci, 1989(38): 49.
[38]ChoshM, ForsythTH. Emulsion Polymerization[J]. AmChen SocSympser, 1976, 367.
[39] Bataile P, Mahalous M, Schreiber H P. Some effects of irradiation on properties of filled PVC compounds [J]. Polymer Engineer, 1994, 34(12): 981-985.
[40]邱光鸿.预乳化在乳液聚合中的应用[J].涂料工业, 1994(1): 20.
[41]司业光,韩光信,吴国贞.聚氯乙烯糊树脂及其加工方法[M].北京:化学工业出版社, 1993.
[42]熊明娜,武利民,周树学等.丙烯酸酯/纳米SiO2复合乳液的制备和表征[J].涂料工业, 2002, (11): 1-3.
[43]曾清华,王栋知,王淀佐.聚合物粘土矿物纳米复合材料[J].化工进展, 1998, 17(2): 13-16.
[44]章永华,龚克成.聚合物/层状无机物纳米复合材料的研究进展[J].材料导报, 1998, 12(2): 61-63.
[45]左美祥,黄志博.纳米SiO2在涂料中的分散作用[J].化工新型材料, 2001, (28): 21-22.
[46] Tsukruk VV, YangH. polymer nanocomposite coatings with nonlinear elastic response[J]. Polymer, 2002, (43): 1695-1699.
[47]熊明娜,武利民,周树学等.丙烯酸酯/纳米SiO2复合乳液的制备和表征[J].涂料工业, 2002, (11): 1-3.
[48] Musil J.Hard and superhard nanocomposite coatings[J]. Surface and Coatings Technology, 2000, (125): 322-330.
[49]李敬玮,夏宇正,焦书科等.原位水解法聚丙烯酸酯/纳米SiO2复合乳液的性能研究[J].胶体与聚合物, 2002, 20(4): 24-27.
[50]邬润德,王锐兰.聚丙烯酸酯原位乳液聚合包覆SiO2的研究[J].有机硅材料, 2002, 16(4): 1-4.
[51] Xiong Mingna, Wu Limin. Preparation and characterization of acrylic/nano-silica composite latex[J]. Polym. Int, 2002, (51): 1-7.
[52]谢海安,戴宏程.超微细二氧化硅的改性研究及其应用[J].湖北化工, 2001, 173:1.
[53] Xanthos M, Baltzis B C, Hsu P P. The nucleation, crystallization and dispersion behavior of PET-monodisperse SiO2 composites[J]. J Appl Polym Sci, 1997, 64(7): 1423.
[54]张心亚,涂伟萍,陈焕钦.丙烯酸酯类共聚物乳液的研究进展[J].化学工业与工程, 2003, 20(3): 84-89.
[55]黄洪,傅和青,张心亚等.丙烯酸酯改性的水性聚氨酯胶粘剂的合成[J].包装工程, 2006, 27(5): 93-95.
[56]吴庆云,杨建军,张建安等.核壳型苯丙乳液的制备[J].湖北化工, 2003 (3): 37-38.
[57]张心亚,涂伟萍,陈焕钦.核/壳型丙烯酸酯聚合物乳液胶粘剂的研制[J].化学建材, 2002(5): 33-36.
[58]林润雄,王基伟,潘榕伟等.核壳结构丙烯酸醋类聚合物的合成及性能研究[J].弹性体, 1999, 9(4): 1-3.
[59]钱亦萍,强西怀,乔永洛等.核壳型丙烯酸树脂乳液聚合稳定性的研究[J].化学建材, 2006, 22(6): 4-6.
[60] Smith W V, Ewart R H.J.Chem. Physical Chemistry of Polyelectrolytes - Tsetska Radeva[J]. Phys, 1984, 16: 592.
[61] Nomura M, Harada M, Eguchi S, Nagata S.Kinetics and Mechanism of the Emulsion polymerization of Vinyl Acetate[J]. ACS Symp. Ser. 1976.
[62] Friis N, Nyhagen L.J.Appl. Mathematical Modeling of Emulsion Polymerization Reactors A Population Balance Approach and Its Applications[J]. Polym Sci, 1973, 17: 2311.
[63]郭睿岚,赵彬,寇奕等.多层核壳丙烯酸酯乳液的合成及其性能的研究[J].高分子材料科学与工程, 2003, 19(2): 107-110.
[64]甘孟瑜,刘娟,杨治国.核壳结构丙烯酸酯乳液的合成及性能研究[J].涂料工业, 2005, 35(6): 5-10.
[65]徐小琳,邵谦.核壳型乳液聚合研究进展[J].胶体与聚合物, 2006, 24(1): 36-38.
[66]周梅村,杨波,易争明等.石蜡/丙烯酸核壳聚合乳液特性粘数的研究[J].石油化工, 2005, 34(4): 347-349.
[67]肖新颜,杜沛辉,万彩霞等.含氟丙烯酸酯聚合物乳液的合成及涂膜性能研究[J].新型建筑材料, 2007(11): 36-38.
[68]刘玉真,张丽华,陈党团.改性环氧-丙烯酸酯胶粘剂的特性研究[J].中国胶粘剂, 2006, 15(9): 15-18.
[69]张克杰,刘香兰,孙道兴.环氧改性丙烯酸乳液涂料的研制[J].中国涂料, 2005, 20(7): 20-22.
[70]苏克新,朱岩.核壳结构聚合物乳液性能的测试及综合评价[J].荆州师范学院学报(自然科学版), 2000, 23(5): 70-73.
[71]王平华,伍胜利,刘春华等.核壳型水性聚氨酯丙烯酸酯复合乳液研究[J].高分子材料科学与工程, 2005, 21(5): 28-31.
[72]曹同玉. Merry A J, Wilson M P.乳液聚合数学模型[J].化工学报, 1982,(1): 14.
[73] Li jing-wei,Xia yu-shi, Shi shu-xian, et al. Study of the properties of poly acrylate-silica nano-composites prepared by emulsion poly-merization in-siut hydrolysation method[J]. Chinese Journal of Colloid and Polymer, 2002, 4(12):24-27.
[74] PERCY M J, BARTHET C, LOBB J C, et al. Synthesis and characterization of vinyl polymer-silica colloidal nanocomposite langmuir[J]. 2000, 16(17): 6913-6920.
[2]陈湘南.建筑涂料用乳液的开发动向[J].中国涂料, 1997, 13(1): 23-27.
[3] http://www.kawise.com/Additive/Other/200707/20070720155450.shtml
[4] Chen X C, Wu L M,Zhou S X, et al. In situ polymeri-zation and characterization of polyester-based polyure-thane/nano-silica composites[J]. Polymer Int, 2003, 52(6): 993-998.
[5] Katsuji Matsuura, Kamagaya, Kunihito Arai.Process for treating the surface of glass fibre to impartresistance to alkalis[P]. US4188421, 1980.
[6] Rong M Z, et al. Friction and wear performance of grafted nano-SiO2/epoxy composites [J].J Mater Sci Lett, 2000. (19): 1159
[7]邹德荣,徐宇. EPDM橡胶基防水材料专用胶粘剂的研制[J].中国建筑防水,2002(4): 2l-24.
[8]孙多先,贾东海,郭长海等.水性聚氨酯包封原生纳米SiO2纳米复合材料的制备及表征[J].现代化工, 2003, 23(1): 41-43.
[9]马恒怡,魏根拴,张晓红等.丁腈弹性纳米粒子改性酚醛树脂的研究[J].高分子学报, 2005(3): 467-470.
[10]李晓俊,刘小兰,叶超等.纳米CaCO3改性环氧胶粘剂[J].青岛科技大学学报, 2005, 26(5): 42l-427.
[11]陈名华,姚武文,汪定江等.纳米TiO2对环氧树脂胶粘剂性能影响的研究[J].高分子学报, 2004, 25(6): l2-l5.
[12]张鹏,王兆华.丙烯酸树脂防腐蚀涂料及应用[M].北京:化学工业出版社, 2003.
[13]张超灿,汤先文等.纳米二氧化硅/聚丙烯酸酯乳胶涂料涂膜的制备及性能研究[J].涂料工业, 2003, 21(3): 1.
[14] Bourgeat-Lami E, Espiard Ph, Guyot A. Synthesis and Characterization of Silica/Poly Nanocomposite Latex Particles through Emulsion Polymerization Using a Cationic Azo Initiator[J]. Polymer, 1995, 36(23): 4386-4389.
[15] Espiard Ph, Guyot A. Progress on Synthesizing SiO2/Polymer Nanocomposite Emulsion[J]. Polymer International, 1995, 36(23): 4391-4395.
[16] Espiard Ph, Guyot A. Adhesion Parameters at the Interface in Nanoparticulate FilledPolymer Systems[J]. Polymer International, 1995, 36(23): 4397-4403.
[17] Tiarks F, Landfester K, Antonietti M. Recent Progress of Miniemulsion Polymerization Langmuir[J].Chemical Industry And Engineering Progress, 2001, 17: 5775-5780.
[18] Luna-Xavier J L, Guyot A, Bourgeat-Lami E. J Colloid Interface Sci, 2002, 250: 82-92.
[19]熊明娜,武利民,周树学等.纳米复合涂料的发展述评[J].涂料工业, 2002, 32(11): 1-3.
[20] Xiong M, Wu L, Zhou S, You B. Synthesis and Characterization of Poly(St-co-BA) Latex with an Organic-Inorganic Hybrid Compound as Emulsifier[J]. Polymer International, 2002, 51(8): 693-698.
[21] Li H, You B, Gu G, Wu L, Chen G. Formulation of shear rate sensitive multiple emulsions[J]. Polymer International, 2005, 54(5): 609-617.
[22]庞金兴,熊焰,张超灿等.有机硅-丙烯酸酯共聚乳液的合成研究[J].武汉理工大学学报, 2001, 23(12): 16-19.
[23]庞金兴,熊焰,吴力立等. Synthesis of Nanosized SiO2/Silicone/Acrylic Ester Complex Emulsion[J]. Nature Science Edition, 2002, 30(7): 108-110.
[24]夏宇正,李敬玮,石淑先等.聚丙烯酸酯/聚硅氧烷乳胶粒核壳结构相反转及控制[J].涂料工业, 2003, 33 (3): 19-21.
[25]徐伟平,黄锐,蔡碧华等.大分子偶联剂对HDPE/纳米CaC03复合材料性能的影响[J].中国塑料, 1999(9): 25-29.
[26]张玉龙,高树理.纳米改性剂[M].北京:国防工业出版社, 2004: 129.
[27]杨永康,何勇,铁旭初等.超细粉体在液体中的分散[J].建材技术与应用, 2006(5):17-20.
[28]李爱元.纳米粉体表面改性技术及应用[J].化工新型材料, 2002, 30(10): 25-28.
[29]汤国虎.无机纳米粉体表面改性研究现状[J].材料导报, 2003, 17(9): 33-36.
[30]庞金兴,熊焰,吴力立等.纳米SiO2/聚丙烯酸醋复合乳液涂料的研制[J].华中科技大学学报(自然科学版), 2002, 30(7): 108-110.
[31]耿耀宗,现代水性涂料[M].北京:中国石化出版社, 2003.
[32]林宣益.乳胶漆[M].北京:化学工业出版社, 2004.
[33]施冠成,华载文.织物涂层用聚丙烯酸酯乳液的新进展[J].中国纺织大学学报, 1997, 23(5): 122-125.
[34]吴秋兰,韩世洪,张尚勇.引发剂用量对聚丙烯酸类浆料性能的影响[J].纺织科技进展, 2007(4): 15-16.
[35]王文俊,李伯耿,于在璋等.半连续乳液聚合[J].高分子通报, 1995(1): 44.
[36] Chern CS, Hsu H. Semibatch emulsion copolymerization of methyl methacrylate and butylacrylate[J]. J Appl Polym Sci, 1995, 55(4): 571.
[37] Arzamend G,Asua JM. Monomer addition policies for copolymer composition control in semicontinuous emulsion copolymerization[J]. Appl PolymSci, 1989(38): 49.
[38]ChoshM, ForsythTH. Emulsion Polymerization[J]. AmChen SocSympser, 1976, 367.
[39] Bataile P, Mahalous M, Schreiber H P. Some effects of irradiation on properties of filled PVC compounds [J]. Polymer Engineer, 1994, 34(12): 981-985.
[40]邱光鸿.预乳化在乳液聚合中的应用[J].涂料工业, 1994(1): 20.
[41]司业光,韩光信,吴国贞.聚氯乙烯糊树脂及其加工方法[M].北京:化学工业出版社, 1993.
[42]熊明娜,武利民,周树学等.丙烯酸酯/纳米SiO2复合乳液的制备和表征[J].涂料工业, 2002, (11): 1-3.
[43]曾清华,王栋知,王淀佐.聚合物粘土矿物纳米复合材料[J].化工进展, 1998, 17(2): 13-16.
[44]章永华,龚克成.聚合物/层状无机物纳米复合材料的研究进展[J].材料导报, 1998, 12(2): 61-63.
[45]左美祥,黄志博.纳米SiO2在涂料中的分散作用[J].化工新型材料, 2001, (28): 21-22.
[46] Tsukruk VV, YangH. polymer nanocomposite coatings with nonlinear elastic response[J]. Polymer, 2002, (43): 1695-1699.
[47]熊明娜,武利民,周树学等.丙烯酸酯/纳米SiO2复合乳液的制备和表征[J].涂料工业, 2002, (11): 1-3.
[48] Musil J.Hard and superhard nanocomposite coatings[J]. Surface and Coatings Technology, 2000, (125): 322-330.
[49]李敬玮,夏宇正,焦书科等.原位水解法聚丙烯酸酯/纳米SiO2复合乳液的性能研究[J].胶体与聚合物, 2002, 20(4): 24-27.
[50]邬润德,王锐兰.聚丙烯酸酯原位乳液聚合包覆SiO2的研究[J].有机硅材料, 2002, 16(4): 1-4.
[51] Xiong Mingna, Wu Limin. Preparation and characterization of acrylic/nano-silica composite latex[J]. Polym. Int, 2002, (51): 1-7.
[52]谢海安,戴宏程.超微细二氧化硅的改性研究及其应用[J].湖北化工, 2001, 173:1.
[53] Xanthos M, Baltzis B C, Hsu P P. The nucleation, crystallization and dispersion behavior of PET-monodisperse SiO2 composites[J]. J Appl Polym Sci, 1997, 64(7): 1423.
[54]张心亚,涂伟萍,陈焕钦.丙烯酸酯类共聚物乳液的研究进展[J].化学工业与工程, 2003, 20(3): 84-89.
[55]黄洪,傅和青,张心亚等.丙烯酸酯改性的水性聚氨酯胶粘剂的合成[J].包装工程, 2006, 27(5): 93-95.
[56]吴庆云,杨建军,张建安等.核壳型苯丙乳液的制备[J].湖北化工, 2003 (3): 37-38.
[57]张心亚,涂伟萍,陈焕钦.核/壳型丙烯酸酯聚合物乳液胶粘剂的研制[J].化学建材, 2002(5): 33-36.
[58]林润雄,王基伟,潘榕伟等.核壳结构丙烯酸醋类聚合物的合成及性能研究[J].弹性体, 1999, 9(4): 1-3.
[59]钱亦萍,强西怀,乔永洛等.核壳型丙烯酸树脂乳液聚合稳定性的研究[J].化学建材, 2006, 22(6): 4-6.
[60] Smith W V, Ewart R H.J.Chem. Physical Chemistry of Polyelectrolytes - Tsetska Radeva[J]. Phys, 1984, 16: 592.
[61] Nomura M, Harada M, Eguchi S, Nagata S.Kinetics and Mechanism of the Emulsion polymerization of Vinyl Acetate[J]. ACS Symp. Ser. 1976.
[62] Friis N, Nyhagen L.J.Appl. Mathematical Modeling of Emulsion Polymerization Reactors A Population Balance Approach and Its Applications[J]. Polym Sci, 1973, 17: 2311.
[63]郭睿岚,赵彬,寇奕等.多层核壳丙烯酸酯乳液的合成及其性能的研究[J].高分子材料科学与工程, 2003, 19(2): 107-110.
[64]甘孟瑜,刘娟,杨治国.核壳结构丙烯酸酯乳液的合成及性能研究[J].涂料工业, 2005, 35(6): 5-10.
[65]徐小琳,邵谦.核壳型乳液聚合研究进展[J].胶体与聚合物, 2006, 24(1): 36-38.
[66]周梅村,杨波,易争明等.石蜡/丙烯酸核壳聚合乳液特性粘数的研究[J].石油化工, 2005, 34(4): 347-349.
[67]肖新颜,杜沛辉,万彩霞等.含氟丙烯酸酯聚合物乳液的合成及涂膜性能研究[J].新型建筑材料, 2007(11): 36-38.
[68]刘玉真,张丽华,陈党团.改性环氧-丙烯酸酯胶粘剂的特性研究[J].中国胶粘剂, 2006, 15(9): 15-18.
[69]张克杰,刘香兰,孙道兴.环氧改性丙烯酸乳液涂料的研制[J].中国涂料, 2005, 20(7): 20-22.
[70]苏克新,朱岩.核壳结构聚合物乳液性能的测试及综合评价[J].荆州师范学院学报(自然科学版), 2000, 23(5): 70-73.
[71]王平华,伍胜利,刘春华等.核壳型水性聚氨酯丙烯酸酯复合乳液研究[J].高分子材料科学与工程, 2005, 21(5): 28-31.
[72]曹同玉. Merry A J, Wilson M P.乳液聚合数学模型[J].化工学报, 1982,(1): 14.
[73] Li jing-wei,Xia yu-shi, Shi shu-xian, et al. Study of the properties of poly acrylate-silica nano-composites prepared by emulsion poly-merization in-siut hydrolysation method[J]. Chinese Journal of Colloid and Polymer, 2002, 4(12):24-27.
[74] PERCY M J, BARTHET C, LOBB J C, et al. Synthesis and characterization of vinyl polymer-silica colloidal nanocomposite langmuir[J]. 2000, 16(17): 6913-6920.