纳米粉体/氟硅改性聚氨酯乳液的制备工艺及性能研究
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摘要
随着环保意识的增强,低表面能环保型涂料已成为涂料发展的主要方向。水性聚氨酯-聚丙烯酸酯乳液既具有聚氨酯(PU)优异的抗划伤性、拉伸性和粘附性,同时又具备了聚丙烯酸醋(PA)的耐候性、耐腐蚀性,但是,两者的性能都决定了聚氨酯-聚丙烯酸酯乳液(PUA)耐水性差。通过引入键能高,表面能极低的氟元素,则可以同时获得具有低表面能,耐水性优异的氟化水性聚氨酯-聚丙烯酸酯乳液。碳纳米管作为21世纪的新型材料,具有奇异的结构和独特的物理性能,可提高聚合物复合材料的多种性能,被认为是制备高性能聚合物复合材料最理想的候选填料之一
本实验首先以有机硅改性聚氨酯(SiWPU)为种子乳液,向种子乳液中滴加全氟丙烯酸酯、丙烯酸丁酯(BA)、甲基丙烯酸丁酯(BMA)三种单体,制备具有核壳结构的FSiPUA复合乳液。通过测试乳液的稳定性、乳液粒径、涂膜水接触角和吸水率,研究了反应温度、全氟丙烯酸酯用量、丙烯酸酯单体用量、引发剂用量、乳化剂用量及配比上述各因素对乳液性能及其涂膜性能的影响。同时对复合乳液涂膜进行了化学结构与表面形貌的表征。研究表明,制备出的氟硅改性聚氨酯-聚丙烯酸酯乳液(FSiWPUA)具有优异的性能,全氟单体的加入能够有效改善乳液胶膜的耐水性及表面疏水性。
在氟硅改性水性聚氨酯-聚丙烯酸酯乳液研究的基础上,分别用溶液共混法和原位聚合法制备了纳米粉体／氟硅改性水性聚氨酯-聚丙烯酸酯杂化乳液。研究了纳米粉体分散性、种类、加入量等因素对杂化乳液性能及涂膜性能的影响。选用端羟基的碳纳米管及通过超声分散和分散剂的加入使纳米粉体获得更优异的分散性及与基体的相容性,从而在使制备出的乳液性能更佳的同时,保证了杂化乳液胶膜的耐水性和疏水性不会变差。同时对杂化乳液胶膜进行了化学结构与表面形貌特征的表征。结果表明,纳米粉体的加入能够极大的改善乳液胶膜的粗糙度和表面能。
With the improvement of environment protection awareness, the green paint with low surface energy has been an important trend of coating development. Polyurethane-polyacrylate(PUA) emulsion has both the advantages in herited from polyrethane(PU) materials such as regards toughness, mar-resistance, elongation and excellent adesion. But the properties inherited from polyacrylate(PA) materials such as hardness and corrosion-resistance, the properties of both materials all determine the poor water resistance of PUA. A kind of fluorinated PUA emulsion with low surface energy and good water resistance can be prepared by adhibiting fluorine with high bond energy and low surface energy. Carbon nanotube(CNT), as a novel material in twenty-first century, was considered to be the most promising candidate as ideal filler owing to its unique structure and particular physical properties.
In this experiment, using siloxane-modified WPU as the seeds emulsions, adding three acrylate monomer (fluoride butyl acrrylate, butyl acrrylate, butyl methacrylate) to the seeds emulsions, the composite emulsions were synthesized with core-shell structure. Stability, particle size, water contact angle and water absorption of film coatings of the emulsion are tested. It was studied systemly that the effect of factors such as the reaction temperature, the content of acrylate monomer, the content of initiator, the ratio and content of emulsifier on the properties of emulsion. At the same time, the chemical structure and surface morphology of the film coatings was characted. The research indicates that the properties of emulsion is excellent and the water resistance can be improved with fluoride monomer.
On the base of FSiWPUA emulsion, the emulsion of FSiWPUA complexed with nanoparticles was prepared in-situ/polycondensation and blended in solution respectively. It was studied systemly that the effect of factors such as ability of disperse, species and content of the nano-particles on the properties of the emulsions and its film coatings. In order to obtain the compatibility of nanoparticles in the polyrethane and force of interaction, the carbon nanotube functionalezed with poly(lactic acid) and dispersant were used in experiment. The prepared emulsion's properties and water resistance of film coatings are better. At the same time, the chemical structure and surface morphology of the film coatings was characted. The results indicates that the roughness and surface energy of film coating can be improved with catbon nanotubes.
本实验首先以有机硅改性聚氨酯(SiWPU)为种子乳液,向种子乳液中滴加全氟丙烯酸酯、丙烯酸丁酯(BA)、甲基丙烯酸丁酯(BMA)三种单体,制备具有核壳结构的FSiPUA复合乳液。通过测试乳液的稳定性、乳液粒径、涂膜水接触角和吸水率,研究了反应温度、全氟丙烯酸酯用量、丙烯酸酯单体用量、引发剂用量、乳化剂用量及配比上述各因素对乳液性能及其涂膜性能的影响。同时对复合乳液涂膜进行了化学结构与表面形貌的表征。研究表明,制备出的氟硅改性聚氨酯-聚丙烯酸酯乳液(FSiWPUA)具有优异的性能,全氟单体的加入能够有效改善乳液胶膜的耐水性及表面疏水性。
在氟硅改性水性聚氨酯-聚丙烯酸酯乳液研究的基础上,分别用溶液共混法和原位聚合法制备了纳米粉体／氟硅改性水性聚氨酯-聚丙烯酸酯杂化乳液。研究了纳米粉体分散性、种类、加入量等因素对杂化乳液性能及涂膜性能的影响。选用端羟基的碳纳米管及通过超声分散和分散剂的加入使纳米粉体获得更优异的分散性及与基体的相容性,从而在使制备出的乳液性能更佳的同时,保证了杂化乳液胶膜的耐水性和疏水性不会变差。同时对杂化乳液胶膜进行了化学结构与表面形貌特征的表征。结果表明,纳米粉体的加入能够极大的改善乳液胶膜的粗糙度和表面能。
With the improvement of environment protection awareness, the green paint with low surface energy has been an important trend of coating development. Polyurethane-polyacrylate(PUA) emulsion has both the advantages in herited from polyrethane(PU) materials such as regards toughness, mar-resistance, elongation and excellent adesion. But the properties inherited from polyacrylate(PA) materials such as hardness and corrosion-resistance, the properties of both materials all determine the poor water resistance of PUA. A kind of fluorinated PUA emulsion with low surface energy and good water resistance can be prepared by adhibiting fluorine with high bond energy and low surface energy. Carbon nanotube(CNT), as a novel material in twenty-first century, was considered to be the most promising candidate as ideal filler owing to its unique structure and particular physical properties.
In this experiment, using siloxane-modified WPU as the seeds emulsions, adding three acrylate monomer (fluoride butyl acrrylate, butyl acrrylate, butyl methacrylate) to the seeds emulsions, the composite emulsions were synthesized with core-shell structure. Stability, particle size, water contact angle and water absorption of film coatings of the emulsion are tested. It was studied systemly that the effect of factors such as the reaction temperature, the content of acrylate monomer, the content of initiator, the ratio and content of emulsifier on the properties of emulsion. At the same time, the chemical structure and surface morphology of the film coatings was characted. The research indicates that the properties of emulsion is excellent and the water resistance can be improved with fluoride monomer.
On the base of FSiWPUA emulsion, the emulsion of FSiWPUA complexed with nanoparticles was prepared in-situ/polycondensation and blended in solution respectively. It was studied systemly that the effect of factors such as ability of disperse, species and content of the nano-particles on the properties of the emulsions and its film coatings. In order to obtain the compatibility of nanoparticles in the polyrethane and force of interaction, the carbon nanotube functionalezed with poly(lactic acid) and dispersant were used in experiment. The prepared emulsion's properties and water resistance of film coatings are better. At the same time, the chemical structure and surface morphology of the film coatings was characted. The results indicates that the roughness and surface energy of film coating can be improved with catbon nanotubes.
引文
[1]叶萍,阮传清.海洋生物对船舶的污损及其无公害防治.福建农业科技,2006,3：79-80.
[2]孙博,邱星林.船舶防污涂料的研究现状及进展.广州化工,2008,36(3)：13-16.
[3]李昕.无毒防污涂料的研究发展.涂料工业,2005,35(4)：38-41.
[4]韩磊,张秋禹.低表面能防污涂料的最新研究进展.材料保护,2006,39(2)：37-41.
[5]边蕴静.低表面能防污涂料的防污特性的理论分析.中国涂料,2000,15(5)：36-39.
[6]田军,薛群基.含氟聚合物低表面能防污(蜡)降噪功能涂层的研制以应用.塑料,1997,26(3)：27-29.
[7]Shimokawa W., Fukazawa Y.. Fluorine-Containing a Crylic Polymer Aqueous Emulsions. 0517538.1993-01-26.
[8]Slater D..美国专利 5331074.1994.
[9]刘剑涛,聚氨酯合成反应动力学.深圳大学学报,1994,(12)：40-41.
[10]陈丽珠,黄洪,陈焕钦.水性聚氨酯的发展与应用研究进展.涂料综述.
[11]Hepburn C.. Polyurethane Elastomers. New York:Applied Science Publishers,1982: 290.
[12]Dieterieh D.. Aqueous emulsions, dispersions and solutions of polyurethanes; Synthesis and Properties. Prog org Coat,1981,9(3):281.
[13]Chen G., Chen K.. Selfcuring Behaviors of Single Pack Aqueous-based Polyurethane System. Journal of Applied Polymer Science,1997,63(12):1-6.
[14]Dieterieh D., Rieck, J. N.. Aqueous Polyurethane systems and their possible uses. Adhes. Age,1978,21(2):24.
[15]许戈文等.水性聚氨酯材料.北京：化学工业出版社,2006：49.
[16]贾战旭.水性聚氨酯的制备与应用.黎明化工,1994,2：1.
[17]Xu H. S., Yang C. Z.. The ionic conduetive property of Sulfonated polyethylene oxide polyurethane ionomers. J. Polym. Sci., Part B:Polym. Phys.,1995,33(5):745.
[18]Kim B. K., Lee Y. M.. Structure-property relationship of polyurethane ionome. Colloid & Polymer Science,1992,270(10):956-961.
[19]马伟.高性能水性聚氨酯基乳胶的研究.天津：天津科技大学,2007.
[20]佘文骊.硅烷偶联剂封端改性水性聚氨酯的研究.中国胶粘剂.2008,17(6)：10-14.
[21]李刚辉,李小瑞,沈一丁.聚氨酯-含氟丙烯酸酯复合乳液的制备及其表面性能.化工学报.2006,57(1)：192-195.
[22]傅和青,黄洪,张心亚.聚氨酯-环氧树脂-丙烯酸酯杂合分散体的合成.化工学报.2007, 58(2)：495-500.
[23]易翔,何德良.水性聚氨酯化学改性研究进展.上海涂料,2009,47(2)：28-31.
[24]王小君,杨建军,吴庆云等.氟化聚氨酯-丙烯酸酯乳液研究进展.涂料工业,2007,37(4)：55-58.
[25]靳东杰,刘治猛,哈成勇.聚丙烯酸酯改性水性聚氨酯的制备.涂化进展,2002,21(11)：831-850.
[26]侯青顺,张剑秋,张翔飞.聚氨酯／聚丙烯酸酯复合乳液的研制进展.涂料工业,2007,(1)：71-77.
[27]王平华,伍胜利,刘春华.核壳型水性聚氨酯-丙烯酸酯复合乳液研究.高分子材料科学与工程,2005,21(5)：28-32.
[28]Hirose M., Kadowakl F.. The structure and properties of core-shell type Acrylic-polyurethane hybrid aqueous emulsions. Progress in Organic Coatings,1997(31) 157-169.
[29]瞿金清,陈焕钦.聚氨酯-聚丙烯酸酯复合乳液的研究.中国皮革,2004,33(5)：6-10.
[30]Rink H. P., Weinert P.. Polyurethanharz, verfahren Zu seiner herstellung and seine verwendung in waessrigen zweikomponenten-klarlacken. DE19 728 411,1999.
[31]傅荣兴,沈介发.聚氨酯工业,1994,(1)：22-25,45.
[32]傅荣,李坚.一种制备聚氨酯-丙烯酸酯共聚乳液的新方法.CN 19940727,1996.
[33]Takayanayi H.. Water-base resin composition and its production. JP 5 186 543,1993.
[34]Nishimura S.. Aqueous covering composition. JP 95-24285,1995.
[35]Okamoto Y., Numa N.. Two-pack aqueous coating composition. EP 665 252,1995.
[36]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,1997：415-420.
[37]Takemoto, Noborn. Aqueous Acrylate-polyurethane Dispersions for Weather resis-tant Coatings with good toughness, elasticity and curability and their manafacture. JP 97-12051.1997,727, CA 1999.130:14965.
[38]易长海,李艳青,刘功芬.水性含氟聚合物涂料的研究进展.长江大学报,2004,1(1)：92.
[39]王婷婷,王世敏,徐祖顺等.聚合物氟化改性.化学通报,2004,64：1-6.
[40]Ameduri B., Boutevin B., Kostov G.. Prog. Polym. Sci.,2001; 26(1):105.
[41]Hougham G., Johns K., Cassidy P. E., et al. Fluoropolymers:synthesis and polymeri-zation, Vol 1 and 2. NewYork:Plenum Press,1999.
[42]Delucchi M., Turri S.,Barbucci A.. Fluoropolymer coating:relationship of electro-chemical impendance spectroscopy measurement barric properties and polymer surface. J. of polymer science,Part B:polymer physics,2002,40(1):52.
[43]潘学梅,武元鹏,邓甄妮等.水性含氟聚氨酯的研究进展.高分子通报,2：33-41.
[44]郭年华,陈先,张强等.聚氨酯改性高氯化聚乙烯热反射涂料.涂料工业,1999,29(7)：11-13.
[45]姜敏,丁晓斌,郑朝辉等.含氟聚氨酯的研究进展.高分子通报,2006,(10)：10-15.
[46]阐成友,杜奕,刘德山.种子乳液聚合中复合乳胶粒结构形态的热力学分析.化学学报,2002,60,(6)：1129-1133.
[47]唐传兵,储富祥.核壳型复合高分子乳液乳胶粒子形态学.中国胶粘剂,2000,10(6)：30-35.
[48]张心亚,涂伟萍,陈焕钦.核／壳乳液聚合中影响乳胶粒形态的因素.化学工程师,2002,19(4)：19-22.
[49]Noble K. L.. Waterborne polyurethanes. Progress in Organic Coatings.1997,32 131-136.
[50]Tanakau H., Suzuki Y., Yoshino F.. Colloids and Surfaces A. Physiochemical and Eng Asp,1999,153:597-601.
[51]Kraetschmer W., Lamb L. D., Fostiropoulos K., et al. Solid C60:A new form of carbon. Nature.1990,347(6291):354-358.
[52]Hrris P. J. F.. Carbon nanotubes and related strures.London:Cambridge University Press,1999.
[53]苏勋文.碳纳米管技术发展概况.南京工业职业技术学院学报,2005,5(2)：88-91.
[54]孙静.碳纳米管及其研究进展.世界科学,2006,5(2)：28-29.
[55]方少明,陈朋,周立明等.丙烯酸酯类聚氨酯／碳纳米管复合材料的制备和性能研究.工程塑料应用,2007,35(9)：13-16.
[56]力虎林,王成伟,李梦珂等.用多孔氧化铝模板制备高度取向碳纳米管阵列膜的研究.科学通报.2000,45(5)：493-497.
[57]Ajayan P. M., Schadler L. S., Giannaris C.,et al. Single-walled carbon nanotube-polymer composites:strength and weakness. AdV. Mater,2000,12:750-753.
[58]Butt F. H., Rahman F., Baduruthamal U.. Desalination,1997,109:323-332.
[59]A. Dufresne, M. Paillet, J. L. Putaux, et al. Processing and characterization of carbon nanotube/poly(styrene-cobutyl acrylate)nanocomposites. J. Mater Sci,2002,37: 3915-3923.
[60]A. A. Mamedov, N. A. Kotov, M. Prato, et al. Molecular design of strong single-wall carbon nanotubes/polyelectrolyte multiplayer composites. Nature Materials,2002(1): 190-194.
[61]N. G. Sahoo, Y. C. Jung, H. J. Yoo, et al. Influence of carbon nanotubes and polypyrrole on the thermal, mechanical and electroactive shape-memory properties of polyurethane nano-composites. Composites Science and Technology,2007,67:1920-1929.
[62]Yao X., Wu H. X., Wang J., et al. Carbon nanotube/poly(methyl methacrylate) (CNT/PMMA) composite electrode fabricated by in situ polymerization for microchip capillary electrophoresis. Chemistry A European Journal 2007; 13 (3):846-53.
[63]周铭.聚氨酯水分散体的制备、表征及性能研究.郑州：郑州大学,2004.
[64]Xia H. S., Song M.,Jin J.,et al. Poly(propylene glycol)-grafted multi-walled carbon nanotube polyurethane. Macromolecular Chemistry and Physics.2006,207:1945-1952.
[65]郑晶静,童昕.纳米碳管在聚合物复合材料领域的研究进展.塑料,2006,35(6)：65-70.
[66]Mickelson E. T., Huffman C. B.,Rinzler A.G.,et al. Chemical Physics Letters 1998,296:94-188.
[67]王建国.多壁碳纳米管／环氧树脂复合材料结构与性能的研究.浙江：浙江大学,2006.
[68]王静荣,谢华涛.聚氨酯／碳纳米管复合材料的研究进展.玻璃钢／复合材料,2008,4：53-56.
[69]Xiong J. W., Zheng Z., Qin X., et al. The thermal and mechanical properties of a polyurethane/multi-walled carbon nanotube composite. Carbon,2006,44:2701-2707.
[70]魏锦生.关于船舶防污涂料探讨.航海技术,1994,(4)：63-64.
[71]周陈亮.舰船防污涂料的历史、现状及未来.中国涂料,1998(6)：9-12.
[72]赵晓燕.海洋天然产物防污研究进展.材料开发与应用,2001,16(4)：34-37.
[73]Li G. H., Shen Y. D.. Effect of fluorinated acrylate on the surface properties of cationic fluorinated polyurethane-acrylate hybrid dispersions. Journal of Applied Polymer Science,2005,97, (6):2192-2196.
[74]陈建兵,王武生,王宇等.聚含氟丙烯酸酯-聚氨酯三嵌段共聚物水基分散体的合成及膜结构.应用化学,2006,23(2)：198-202.
[75]Masakazu H., Zhou J. H., Katsutoshi N.. Progres in Organic Coatings.2000,38:27-34.
[76]王成.丙烯酸酯-聚氨酯核壳乳液的合成.化学过程与装备.2008,3)：48-50.
[77]李靖靖.新型建筑密封材料用无乳聚合胶乳的研制.化学与粘合,2001,24(5)：211-215.
[78]傅和青,黄洪,陈焕钦.引发剂及其对乳液聚合的影响.合成材料老化与应用,2004,33(3)： 39-42.
[79]潘祖仁.高分子化学.北京：化学工业出版社.2005,113.
[80]于海深,高丽华.丙烯酸酯改性水性聚氨酯树脂合成工艺的研究.化学世界.2009.(3)： 149-152.
[81]Qu L. W., Veca L., Lin Y.,et al. Soluble nylon-functionalized carbon nanotubes from anionic ring-opening polymerization from nanotube surfaoe. Macromolecules,2005, 38(24):10328-10331.
[82]Zheng M. J., Zhang L. D., Li G. H., et al. Fabrication and optical properties of large-Scale unifom zinc oxide nanowire arrays by One-step electrochemical deposition technique. Chem Phys Lett,2002,363(1-2):123-128.
[2]孙博,邱星林.船舶防污涂料的研究现状及进展.广州化工,2008,36(3)：13-16.
[3]李昕.无毒防污涂料的研究发展.涂料工业,2005,35(4)：38-41.
[4]韩磊,张秋禹.低表面能防污涂料的最新研究进展.材料保护,2006,39(2)：37-41.
[5]边蕴静.低表面能防污涂料的防污特性的理论分析.中国涂料,2000,15(5)：36-39.
[6]田军,薛群基.含氟聚合物低表面能防污(蜡)降噪功能涂层的研制以应用.塑料,1997,26(3)：27-29.
[7]Shimokawa W., Fukazawa Y.. Fluorine-Containing a Crylic Polymer Aqueous Emulsions. 0517538.1993-01-26.
[8]Slater D..美国专利 5331074.1994.
[9]刘剑涛,聚氨酯合成反应动力学.深圳大学学报,1994,(12)：40-41.
[10]陈丽珠,黄洪,陈焕钦.水性聚氨酯的发展与应用研究进展.涂料综述.
[11]Hepburn C.. Polyurethane Elastomers. New York:Applied Science Publishers,1982: 290.
[12]Dieterieh D.. Aqueous emulsions, dispersions and solutions of polyurethanes; Synthesis and Properties. Prog org Coat,1981,9(3):281.
[13]Chen G., Chen K.. Selfcuring Behaviors of Single Pack Aqueous-based Polyurethane System. Journal of Applied Polymer Science,1997,63(12):1-6.
[14]Dieterieh D., Rieck, J. N.. Aqueous Polyurethane systems and their possible uses. Adhes. Age,1978,21(2):24.
[15]许戈文等.水性聚氨酯材料.北京：化学工业出版社,2006：49.
[16]贾战旭.水性聚氨酯的制备与应用.黎明化工,1994,2：1.
[17]Xu H. S., Yang C. Z.. The ionic conduetive property of Sulfonated polyethylene oxide polyurethane ionomers. J. Polym. Sci., Part B:Polym. Phys.,1995,33(5):745.
[18]Kim B. K., Lee Y. M.. Structure-property relationship of polyurethane ionome. Colloid & Polymer Science,1992,270(10):956-961.
[19]马伟.高性能水性聚氨酯基乳胶的研究.天津：天津科技大学,2007.
[20]佘文骊.硅烷偶联剂封端改性水性聚氨酯的研究.中国胶粘剂.2008,17(6)：10-14.
[21]李刚辉,李小瑞,沈一丁.聚氨酯-含氟丙烯酸酯复合乳液的制备及其表面性能.化工学报.2006,57(1)：192-195.
[22]傅和青,黄洪,张心亚.聚氨酯-环氧树脂-丙烯酸酯杂合分散体的合成.化工学报.2007, 58(2)：495-500.
[23]易翔,何德良.水性聚氨酯化学改性研究进展.上海涂料,2009,47(2)：28-31.
[24]王小君,杨建军,吴庆云等.氟化聚氨酯-丙烯酸酯乳液研究进展.涂料工业,2007,37(4)：55-58.
[25]靳东杰,刘治猛,哈成勇.聚丙烯酸酯改性水性聚氨酯的制备.涂化进展,2002,21(11)：831-850.
[26]侯青顺,张剑秋,张翔飞.聚氨酯／聚丙烯酸酯复合乳液的研制进展.涂料工业,2007,(1)：71-77.
[27]王平华,伍胜利,刘春华.核壳型水性聚氨酯-丙烯酸酯复合乳液研究.高分子材料科学与工程,2005,21(5)：28-32.
[28]Hirose M., Kadowakl F.. The structure and properties of core-shell type Acrylic-polyurethane hybrid aqueous emulsions. Progress in Organic Coatings,1997(31) 157-169.
[29]瞿金清,陈焕钦.聚氨酯-聚丙烯酸酯复合乳液的研究.中国皮革,2004,33(5)：6-10.
[30]Rink H. P., Weinert P.. Polyurethanharz, verfahren Zu seiner herstellung and seine verwendung in waessrigen zweikomponenten-klarlacken. DE19 728 411,1999.
[31]傅荣兴,沈介发.聚氨酯工业,1994,(1)：22-25,45.
[32]傅荣,李坚.一种制备聚氨酯-丙烯酸酯共聚乳液的新方法.CN 19940727,1996.
[33]Takayanayi H.. Water-base resin composition and its production. JP 5 186 543,1993.
[34]Nishimura S.. Aqueous covering composition. JP 95-24285,1995.
[35]Okamoto Y., Numa N.. Two-pack aqueous coating composition. EP 665 252,1995.
[36]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,1997：415-420.
[37]Takemoto, Noborn. Aqueous Acrylate-polyurethane Dispersions for Weather resis-tant Coatings with good toughness, elasticity and curability and their manafacture. JP 97-12051.1997,727, CA 1999.130:14965.
[38]易长海,李艳青,刘功芬.水性含氟聚合物涂料的研究进展.长江大学报,2004,1(1)：92.
[39]王婷婷,王世敏,徐祖顺等.聚合物氟化改性.化学通报,2004,64：1-6.
[40]Ameduri B., Boutevin B., Kostov G.. Prog. Polym. Sci.,2001; 26(1):105.
[41]Hougham G., Johns K., Cassidy P. E., et al. Fluoropolymers:synthesis and polymeri-zation, Vol 1 and 2. NewYork:Plenum Press,1999.
[42]Delucchi M., Turri S.,Barbucci A.. Fluoropolymer coating:relationship of electro-chemical impendance spectroscopy measurement barric properties and polymer surface. J. of polymer science,Part B:polymer physics,2002,40(1):52.
[43]潘学梅,武元鹏,邓甄妮等.水性含氟聚氨酯的研究进展.高分子通报,2：33-41.
[44]郭年华,陈先,张强等.聚氨酯改性高氯化聚乙烯热反射涂料.涂料工业,1999,29(7)：11-13.
[45]姜敏,丁晓斌,郑朝辉等.含氟聚氨酯的研究进展.高分子通报,2006,(10)：10-15.
[46]阐成友,杜奕,刘德山.种子乳液聚合中复合乳胶粒结构形态的热力学分析.化学学报,2002,60,(6)：1129-1133.
[47]唐传兵,储富祥.核壳型复合高分子乳液乳胶粒子形态学.中国胶粘剂,2000,10(6)：30-35.
[48]张心亚,涂伟萍,陈焕钦.核／壳乳液聚合中影响乳胶粒形态的因素.化学工程师,2002,19(4)：19-22.
[49]Noble K. L.. Waterborne polyurethanes. Progress in Organic Coatings.1997,32 131-136.
[50]Tanakau H., Suzuki Y., Yoshino F.. Colloids and Surfaces A. Physiochemical and Eng Asp,1999,153:597-601.
[51]Kraetschmer W., Lamb L. D., Fostiropoulos K., et al. Solid C60:A new form of carbon. Nature.1990,347(6291):354-358.
[52]Hrris P. J. F.. Carbon nanotubes and related strures.London:Cambridge University Press,1999.
[53]苏勋文.碳纳米管技术发展概况.南京工业职业技术学院学报,2005,5(2)：88-91.
[54]孙静.碳纳米管及其研究进展.世界科学,2006,5(2)：28-29.
[55]方少明,陈朋,周立明等.丙烯酸酯类聚氨酯／碳纳米管复合材料的制备和性能研究.工程塑料应用,2007,35(9)：13-16.
[56]力虎林,王成伟,李梦珂等.用多孔氧化铝模板制备高度取向碳纳米管阵列膜的研究.科学通报.2000,45(5)：493-497.
[57]Ajayan P. M., Schadler L. S., Giannaris C.,et al. Single-walled carbon nanotube-polymer composites:strength and weakness. AdV. Mater,2000,12:750-753.
[58]Butt F. H., Rahman F., Baduruthamal U.. Desalination,1997,109:323-332.
[59]A. Dufresne, M. Paillet, J. L. Putaux, et al. Processing and characterization of carbon nanotube/poly(styrene-cobutyl acrylate)nanocomposites. J. Mater Sci,2002,37: 3915-3923.
[60]A. A. Mamedov, N. A. Kotov, M. Prato, et al. Molecular design of strong single-wall carbon nanotubes/polyelectrolyte multiplayer composites. Nature Materials,2002(1): 190-194.
[61]N. G. Sahoo, Y. C. Jung, H. J. Yoo, et al. Influence of carbon nanotubes and polypyrrole on the thermal, mechanical and electroactive shape-memory properties of polyurethane nano-composites. Composites Science and Technology,2007,67:1920-1929.
[62]Yao X., Wu H. X., Wang J., et al. Carbon nanotube/poly(methyl methacrylate) (CNT/PMMA) composite electrode fabricated by in situ polymerization for microchip capillary electrophoresis. Chemistry A European Journal 2007; 13 (3):846-53.
[63]周铭.聚氨酯水分散体的制备、表征及性能研究.郑州：郑州大学,2004.
[64]Xia H. S., Song M.,Jin J.,et al. Poly(propylene glycol)-grafted multi-walled carbon nanotube polyurethane. Macromolecular Chemistry and Physics.2006,207:1945-1952.
[65]郑晶静,童昕.纳米碳管在聚合物复合材料领域的研究进展.塑料,2006,35(6)：65-70.
[66]Mickelson E. T., Huffman C. B.,Rinzler A.G.,et al. Chemical Physics Letters 1998,296:94-188.
[67]王建国.多壁碳纳米管／环氧树脂复合材料结构与性能的研究.浙江：浙江大学,2006.
[68]王静荣,谢华涛.聚氨酯／碳纳米管复合材料的研究进展.玻璃钢／复合材料,2008,4：53-56.
[69]Xiong J. W., Zheng Z., Qin X., et al. The thermal and mechanical properties of a polyurethane/multi-walled carbon nanotube composite. Carbon,2006,44:2701-2707.
[70]魏锦生.关于船舶防污涂料探讨.航海技术,1994,(4)：63-64.
[71]周陈亮.舰船防污涂料的历史、现状及未来.中国涂料,1998(6)：9-12.
[72]赵晓燕.海洋天然产物防污研究进展.材料开发与应用,2001,16(4)：34-37.
[73]Li G. H., Shen Y. D.. Effect of fluorinated acrylate on the surface properties of cationic fluorinated polyurethane-acrylate hybrid dispersions. Journal of Applied Polymer Science,2005,97, (6):2192-2196.
[74]陈建兵,王武生,王宇等.聚含氟丙烯酸酯-聚氨酯三嵌段共聚物水基分散体的合成及膜结构.应用化学,2006,23(2)：198-202.
[75]Masakazu H., Zhou J. H., Katsutoshi N.. Progres in Organic Coatings.2000,38:27-34.
[76]王成.丙烯酸酯-聚氨酯核壳乳液的合成.化学过程与装备.2008,3)：48-50.
[77]李靖靖.新型建筑密封材料用无乳聚合胶乳的研制.化学与粘合,2001,24(5)：211-215.
[78]傅和青,黄洪,陈焕钦.引发剂及其对乳液聚合的影响.合成材料老化与应用,2004,33(3)： 39-42.
[79]潘祖仁.高分子化学.北京：化学工业出版社.2005,113.
[80]于海深,高丽华.丙烯酸酯改性水性聚氨酯树脂合成工艺的研究.化学世界.2009.(3)： 149-152.
[81]Qu L. W., Veca L., Lin Y.,et al. Soluble nylon-functionalized carbon nanotubes from anionic ring-opening polymerization from nanotube surfaoe. Macromolecules,2005, 38(24):10328-10331.
[82]Zheng M. J., Zhang L. D., Li G. H., et al. Fabrication and optical properties of large-Scale unifom zinc oxide nanowire arrays by One-step electrochemical deposition technique. Chem Phys Lett,2002,363(1-2):123-128.