环氧改性苯丙乳液及其涂料的制备与表征
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摘要
本文对环氧树脂改性苯丙乳液的国内外研究现状进行了综述,通过单体预乳化法结合核壳乳液聚合工艺,制备出了稳定的环氧改性苯丙乳液,并将所得环氧改性苯丙乳液进行了结构与性能的测试和表征。主要讨论了乳化剂、引发剂、温度、软硬单体配比、环氧树脂、功能性单体等因素对乳液聚合的影响,确定了各自的最佳条件。乳化剂的最佳用量为3.5 %,其中阴离子乳化剂和非离子乳化剂的配比为1/1.5;引发剂的最佳用量为0.6 %,最佳温度范围为75～78℃;软硬单体最佳配比为1/1;采用E-44型环氧树脂,用量取10%,功能单体甲基丙烯酸和N-羟甲基丙烯酰胺的最佳用量都为2%。为了促进固化,加入了潜固化剂,确定固化条件为150℃,40 min。通过红外光谱仪对环氧改性苯丙乳液进行了表征,1251 cm~(-1)处的苯醚的吸收峰,915 cm~(-1)处的环氧基吸收峰和1726 cm~(-1)处羰基吸收峰,验证了环氧参与了接枝共聚。通过热重分析得到改性后乳液的热分解温度大于未改性的乳液。接触角也从34.77°增大到为63.05°。乳液粒径分布较窄,接近正态分布。同时通过交流阻抗和极化曲线的测试,发现涂层电阻提高了1个数量级,腐蚀电位提高,腐蚀电流变小。说明所制得的新型环氧改性苯丙乳液比普通苯丙乳液具有更强的憎水性,更好的热稳定性,更优异的防腐性能。另外,环氧改性苯丙乳液在耐水性、冻融稳定性和硬度等方面与未改性苯丙乳液相比也有所提高。
采用该改性乳液配制的涂料,具有优异的耐水性、耐碱性、耐擦洗性和耐候性。实验确定了分散剂的最佳用量0.7 %,成膜助剂为2.0 %,流平剂为0.15 %,增稠剂为0.2 %,消泡剂为0.3 %,PVC在54 %时性能最佳。所制涂料绿色环保,综合性能优良。
The study of styrene-acrylic emulsion modified by epoxy resin both at home and abroad was reviewed. The emulsion was prepared by use of pre-emulsified addition and core-shell emulsion polymerization technology. The effect of surfactants, initiator, temperature, the ratio of soft monomer and hard monomer , epoxy resin, functional monomer on modified emulsion was investigated,and the best formulation was determined. The best formulation could be obtained when the contents of surfactants was 3.5 %, the ratio of surfactants was 1/1.5, the content of initiator was 0.6 %, the best temperature was 75℃~78℃, the ratio of soft monomer to hard monomer was 1/1, the content of E-44 was 2%,the content of functional monomer(MAA,N-MA) was 2 %. The latent curing agent was added for promoting curing. The best cure condition was under 150℃for baking 40 min. The structure of modified emulsion was characterized by FTIR, the peaks at 915 cm~(-1) and 1251 cm-1 and 1726 cm~(-1) correspond respectively to the motion of epoxy, phenylate and carbonyl group. The thermal graviting analysis found that thermal decomposition temperature of modified emulsion was higher than unmodified emulsion. The contact angle was also from 34.77°to 63.05°.The distribution of emulsion particle was narrow and close to normal distribution. The ESI and polarization curve testing found that coat resistance had one order of magnitude increased, the corrosion potential had raised and the corrosion current had decreased. It proved that modified emulsion possessed better hydrophobicity, thermal stability, anticorrosive property compared to styrene-acrylic emulsion. The modified emulsion also had better waterproof ability, frost and thaw stability compared to unmodified emulsion.
The coating was prepared with modified styrene-acrylic emulsion. This coating had outstanding waterproof ability, base proof ability, scrub ability and weather ability. The results showed: the best content of dispersant was 0.7 %, the content of film additive was 2.0 %, the content of leveling agent was 0.15 %, the content of bodying agent was 0.2 %, and the content of defoamer was 0.3 %. The best performance was obtained when PVC=54 %. The styrene-acrylic coating modified by epoxy resin was green and had good combination properties.
采用该改性乳液配制的涂料,具有优异的耐水性、耐碱性、耐擦洗性和耐候性。实验确定了分散剂的最佳用量0.7 %,成膜助剂为2.0 %,流平剂为0.15 %,增稠剂为0.2 %,消泡剂为0.3 %,PVC在54 %时性能最佳。所制涂料绿色环保,综合性能优良。
The study of styrene-acrylic emulsion modified by epoxy resin both at home and abroad was reviewed. The emulsion was prepared by use of pre-emulsified addition and core-shell emulsion polymerization technology. The effect of surfactants, initiator, temperature, the ratio of soft monomer and hard monomer , epoxy resin, functional monomer on modified emulsion was investigated,and the best formulation was determined. The best formulation could be obtained when the contents of surfactants was 3.5 %, the ratio of surfactants was 1/1.5, the content of initiator was 0.6 %, the best temperature was 75℃~78℃, the ratio of soft monomer to hard monomer was 1/1, the content of E-44 was 2%,the content of functional monomer(MAA,N-MA) was 2 %. The latent curing agent was added for promoting curing. The best cure condition was under 150℃for baking 40 min. The structure of modified emulsion was characterized by FTIR, the peaks at 915 cm~(-1) and 1251 cm-1 and 1726 cm~(-1) correspond respectively to the motion of epoxy, phenylate and carbonyl group. The thermal graviting analysis found that thermal decomposition temperature of modified emulsion was higher than unmodified emulsion. The contact angle was also from 34.77°to 63.05°.The distribution of emulsion particle was narrow and close to normal distribution. The ESI and polarization curve testing found that coat resistance had one order of magnitude increased, the corrosion potential had raised and the corrosion current had decreased. It proved that modified emulsion possessed better hydrophobicity, thermal stability, anticorrosive property compared to styrene-acrylic emulsion. The modified emulsion also had better waterproof ability, frost and thaw stability compared to unmodified emulsion.
The coating was prepared with modified styrene-acrylic emulsion. This coating had outstanding waterproof ability, base proof ability, scrub ability and weather ability. The results showed: the best content of dispersant was 0.7 %, the content of film additive was 2.0 %, the content of leveling agent was 0.15 %, the content of bodying agent was 0.2 %, and the content of defoamer was 0.3 %. The best performance was obtained when PVC=54 %. The styrene-acrylic coating modified by epoxy resin was green and had good combination properties.
引文
[1] T. J. M. Sinha, P. Dutta, A. S. Khanna. Formulation and performance study of low molecular weight, alkyd-based waterborne anticorrosive coating on mild steel[J]. Progress in Organic Coatings, 2007, 62(2):183-192.
[2] H. J. Yu, L. Wang, Q. Shi, et al. Study on nano-CaCO3 modified epoxy powder coatings [J]. Progress in Organic Coatings, 2006,55(3):296-300.
[3] C.Guobei, N. J. Frank. Low-temperatuer curing higher-solids polyester coating with melamine-formaldehyde resin crosslinkers[J].Jounral of coatings technology,1993,65(819):43-48.
[4] P. Roose, I. Fallais, C. Vandermiers, et al. Radiation curing technology: An attractive technology for metal coating [J]. Progress in Organic Coatings, 2009, 64(2):163-170.
[5]姜海燕,何立凡,李效玉.苯丙乳液的合成及水性防锈涂料的制备研究[J].涂料工业,2007,37(9):9-13.
[6]殷再球,张超灿,吴力立,等.建筑外墙涂料用核/壳苯乙烯-丙烯酸酯共聚乳液的研究[J].涂料工业,2004,34(7):14-16.
[7]刘平平,程江,文秀芳等.水性防腐涂料用苯丙乳液的研究进展[J].涂料工业.2005,35(7):53-56.
[8]王德中.环氧树脂生产与应用[M].北京:化学工业出版社,2001,1-2.
[9] V. C. Malshe, G. Waghoo. Weathering characteristics of epoxy-ester paints[J].Progress in Organic Coating,2006,56(2):131-134.
[10]危恒毅,岳庆磊.水性防腐涂料体系[J].精细石油化工进展.2002,3(4):44-46.
[11]王倩,张心亚,陈焕钦,等.有机硅改性丙烯酸酯乳液性能的研究[J].中国胶粘剂,2002,(2):5-8.
[12] L. K. Aggarwal, P. C. Thaliyal, S. R. Karade. Properties of polymer-modified mortars using epoxy and acrylic emulsion [J]. Construction and Building Materials, 2007,21(2):379-383.
[13] B. Lessard, S. C. Schmidt, M. Maric. Styrene/acrylic acid random copolymers synthesized by nitroxide-mediated polymerization: effect of free nitroxide on kinetics and copolymer composition[J].Macromolecules,2008,41(10):3446-3454.
[14]甘孟瑜,谈尊燕,杨治国.丙烯酸酯乳液的改性研究[J].涂料工业,2006,36(3):10-12.
[15]陈琨,辛秀兰.印刷用苯丙乳液研究进展[J].中国涂料,2009,1:27-29.
[16] F. Sahmill, A. Wenning, J. V. Weiss. Recent developments in aqueous twcomponent polyurethane coatings [J]. Progress in Organic Coatings, 2000, 15 (40):99-103.
[17]祝阳,吕满庚,孔中平,等.含氟丙烯酸酯改性水性聚氨酯纳米复合乳液制备及性能研究[J].功能材料,2007,38(9):3520-3522.
[18]瞿金清,陈焕钦.聚氨酯-丙烯酸酯复合乳液的合成与性能[J].现代化工,2004, 24(1):28-30.
[19]张炎,齐正旺,陈炜,等.丙烯酸酯改性水性聚氨酯的方法[J].聚氨酯工业,2008,23(5):9-11.
[20] M. M. El-molla. Synthesis of polyurethane acrylate oligomers as aqueous UV-curable binder for inks of ink jet in textile printing and pigment dyeing[J]. Dyes and Pigments, 2007, 74(2):371-379.
[21] M. Mazurek, D. J. Kinning, T. Kinoshita. Novel materials based on silicone-acrylate copolymer networks [J]. Journal of Applied Polymer Science, 2001, 80:159-180.
[22] J. N. Hamid, M. Shadpour, M. Nader. Synthesis and characterization of silicone-modified vinyl acetate-acrylic emulsion copolymers [J]. Progress in Organic Coatings, 2006, 55(1):375-381.
[23]张心亚,黄洪,黎永津,等.乙烯基硅氧烷改性丙烯酸酯乳液聚合的动力学及成核机理分析[J].化工学报,2006,57(1):197-202.
[24] H. S. Park, I. M. Yang, J. P. Wu. Synthesis of silicone-acrylic resins and their applications to super weatherable coatings [J]. Journal of Applied Polymer Science, 2001, 81: 1614-1623.
[25]梁军艳,和玲,郑元锁.核壳型含氟丙烯酸酯共聚物的合成及性能[J].高等学校化学学报,2008,29(7):1473-1478.
[26]倪勇,赵玉索,来国桥,等.有机氟硅改性聚丙烯酸树脂和乳液的研究[J].有机硅材料,2005,19(2):14-16.
[27]邱俊英,程艳玲,郭小丽,等.有机氟硅改性丙烯酸酯共聚物乳液的研究[J].涂料工业,2008,38(8):37-39.
[28] R. Y. Hong, J. H. Li, L. L. Chen, et al. Synthesis surface modification and photocatalytic property of ZnO nanoparticles. Powder Technology, 2009(189):426-432.
[29] H. Y. Yu, J. S. Gu, J. Du, et al. Study on the surface modification of nano-TiO2 grafting PMMA/PBMA and its thermal stability. Chinese Journal of Polymer Science, 2005(3):243-247.
[30] F. A. Zhang, D. K. Lee, J. P. Thomas. Pmma-mesocellular foam silica nanocomposites prepared through batch emulsion polymerization and compression molding. Polymer, 2009(50):4768-4774.
[31]李锡凯,李阳.纳米改性弹性涂料的研制[J]涂料工业,2003,33(3):12-13.
[32]洪啸吟,冯汉保.涂料化学[M].北京:科学出版社,2006.118-123
[33]涂料工艺编委会.涂料工艺(上册)[M].(第三版)北京:化学工业出版社,2001(3):626.
[34]王德中.环氧树脂生产与应用[M].北京:化学工业出版社,2001: 4-7.
[35]林璜,于海琴,吴雷.环氧改性苯丙乳液的研制[J].济南大学学报,2003,17(3):274-276.
[36]周小勇.水性丙烯酸-环氧接枝共聚型树脂的制备[J].中国涂料,2006(2):16-18.
[37]黄洪,傅和青,邓艳文,等.环氧树脂与丙烯酸酯复合改性水性聚氨酯的合成研究[J].高校化学工程学报,2006,20(4):583-587.
[38] J. T. Woo, T. Alan.Water-based epoxy-acrylic graft copolymer [J].Progress in organic coatings.1993 (2):371-385.
[39]孙绍辉.环氧-丙烯酸酯类复合水性涂料的研究进展[J].化工进展.2004(9):984-987.
[40]庞衍松,张力,石光.新型环氧丙烯酸树脂增韧剂的合成[J].应用化学,2009,26(12):1418-1421.
[41] M. U. Fawn, C. W. Dean, P. D. Siva, et al. UV curable epoxy acrylate–clay nanocomposites [J]. European Polymer Journal, 2006, 42(10):2596-2605.
[42] S.H.Mansour, N.Mostafa, L.Abd. Electrical and positron annihilation study on epoxy and epoxy acrylate composites [J]. European Polymer Journal, 2007, 43(11):4770-4782.
[43] D. E. Jim, S. K. Derek, C. K. Pratap. Waterborne epoxy protective coatings for metal [J].Journal of Coating Teehnology.2002, 74(931):63-72.
[44] H. Schonhorn, T. T. Wang, H. N. Vazirani, et al. Static and dynamic fatigue of high-strength glass fibers coated with a uv-curable epoxy-acrylate [J]. Journal of Applied Physics, 2009, 49(9):4783-4787.
[45]孙兴平,王德海.环氧丙烯酸酯合成及应用的研究进展[J].涂料工业,2007,37(11):53-56.
[46]王锋,胡剑青,涂伟萍.紫外光固化低黏度环氧丙烯酸酯的合成[J].涂料工业,2009,39(7):8-12.
[47]梁永升,梁亮.合成光敏性环氧丙烯酸酯的催化剂研究[J].精细化工,2006,23(3):278-281.
[48]刘宁,刘治猛,刘煜平,等.环氧丙烯酸酯粉末涂料的合成及固化研究[J].精细石油化工,2009,6:65-68.
[49]王锋,胡剑青,涂伟萍.异氰酸酯改性环氧丙烯酸酯的合成及其光固化动力学的研究[J].高校化学工程学报,2010,24(2):233-238.
[50]袁才登,段春华,许涌深,等.环氧单丙烯酸酯的合成[J].热固性树脂,2007,22(2):19-22.
[51]吴静.水溶性环氧-甲基丙烯酸树脂及在涂料中应用的研究[D].沈阳化工学院硕士学位论文.2002.
[52]李志强,温翠珠,王炼石,等.环氧树脂与丙烯酸酯单体的接枝共聚及其汽车阴极电泳涂料的性能[J].电镀与涂饰,2009,28(3):59-63.
[53] C. Robert, A. Stanley, A. Richard. Ageing of adhesive bonds with various surface treatments, part 2: acrylic modified amine–cured epoxy resin[J].Adhesion,2005,81:1183-1197.
[54] S. X. Li, W. F. Wang, L. M. Liu, et al. Morphology and characterization of epoxy-acrylate compositeparticles[J].Polymer Bulletin,2008,61:749-757.
[55] T. Wan, X. J. Li, W. B. Xiao. Preparation of epoxy-silica-acrylate hybrid coatings[J].Polymer Bulletin,2008,59;749-758.
[56] G. R. Pan, L. M. Wu, Z. Q. Zhang, et al. Synthesis and characterization of epoxy-acrylate composite latex [J]. Applied Polymer Science,2002,(83):1736-1743.
[57]万欢,张旭玲,曾繁涤,等.接枝型水性环氧树脂乳液的合成与粘接性能研究[J].粘结,2010,3:51-54.
[58] Noda, Sumio. Aqueous coating of carboxyl acrylic resin-epoxy resin product [P]. 5780532, 1998.
[59] D. Ratna, G. P. Simon. Mechnaical characterization and morphology of carboxyl randomized poly(2-ethylhexylacrylate)liquid rubber touhgned epoxy resins[J].Polymer,2001 (42):7739-7747.
[60]叶寒,陈松,李效玉,等.自乳化型环氧树脂接枝丙烯酸复合乳液的制备[J].涂料工业,2006,36(11):1-4.
[61] G. P. Craun, V. V. Kaminski. Low voc aqueous dispersed acrylic epoxy microgels [P], Us5554671, 1996.
[62]赵晓宁,方治齐.丙烯酸醋微凝胶乳液的研究[J].涂料工业,2000,(3):33-35.
[63]贺海量,张旭东,周杰,等.环氧树脂改性聚氨酯-丙烯酸酯乳液的合成[J].热固性树脂,2007,22(1):19-23.
[64]张洁,翟金清,张心亚,等.环氧改性苯丙乳液的合成及性能[J].涂料技术与文摘,2004,25(2):24-28.
[65]杨瑞芹,崔天放,陈尔凡.环氧-丙烯酸酯乳液的研制[J].化学世界,2002(l):23-24.
[66]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.
[67] G. L. Brown, M. A. Tobias. Epoxy modifide acyrlic lattiees and method of producing same[P]. Us4028294, 1977.
[68] D. D. Wet-roos, J. H. Knoteze, B. Cooray. Emulsion polymerization of an epoxy-acrylate emulsion stbailized with polyacrylateⅡ. using the results of statistically designed experiments to reduce a possible polymerization mechanism[J].Journal of Applied Polymer Scinece,2000,76:368-381.
[69] R. P.Minnis, E. P. Moschovis, et al. Aqueous emulsion laminating adhesive[P]. Us4555757, 1986.
[70] P. Saendee, P.Tangboriboonrat. Emulsion interpenetrating polymer networks of epoxidised natural rubber/poly(methyl methacrylate): an insight into the mechanism of epoxidation[J]. Colloid Polym Sci, 2006, 28(4): 634-643.
[71] D. L. Merlin, B. Sivasankar. Synthesis and characterization of semi-interpenetrating polymer networks using biocompatible polyurethane and acrylamide monomer[J]. European Polymer Journal, 2009, 45:165-170.
[72]曹同玉,刘庆普,胡金牛.乳液聚合原理性能及应用[M].化学工业出版社,2007,1-300.
[73]刘德峥,苗郁.种子乳液聚合法制备聚丙烯酸酷织物涂层剂[J].染料工业,2002,39(2):32-34.
[74]牛益江.新型固化促进剂的研究及应用[J].化学工程师,2007,3:53-54.
[75]刘宇艳,何利娜,万志敏,等.新型环氧树脂潜伏性促进剂的合成、表征及性能研究[J].航空材料学报,2008,28(1):71-75.
[76]朱诚身.聚合物结构分析[M].科学出版社,2004,100-120.
[77] M F Mei, B M Yu, L Luo, et al. A model for the contact angle of liquid droplets on rough surfaces[J].Chinese Physics Letter,2010,27(7):210-213.
[78]赵名师,吴明,董有智.ESI分析在防腐蚀涂层评价中的应用[J].金属表面处理,2007,26(10):39-42.
[79] Q Zhang, M Xiang. Using EIS to evaluate anti-corrosion properties of the SiC_p/5A06 aluminium MMC treated by cerium conversion coatings [J]. Rare earths, 2010, 28(1):109-117.
[80] A.G.Gilicinski, C.R.Hegedus. New applications in studies of waterborne coatings by atomic of microscopy[J], Progress in organic coatings,1997,32:81-88.
[81]曹楚南,张鉴清.电化学阻抗谱导论[M].北京:科学出版社,2004.
[82] J. T. Zhang, J. M. Hu, J. Q. Zhang. Studies of water transport behavior and importance models of epoxy-coated metals in NaCl solution by EIS[J].Progress in Organic Coatings,2004(51):145-151.
[83] R. Joseph. Reflective coating for sunlight, paint outside a spray booth, and case-by-case MACT for in mold painting[J]. Metal Finishing, 2001, 99(2):101-102.
[84]沈慧芳,傅和青,黄洪,等.成膜助剂在乳胶漆中作用分析[J].合成材料老化与应用,2004,33(2): 41-43.
[85] L. Kenneth. Coalescence and film formation from Latexes[J].Journal of Coating Technology,1996,68(853):33-39.
[86]殷耀兵,李国强,管文超.乳液涂料成膜过程中成膜助剂的挥发[J].涂料工业,2007,37(8):20-22.
[2] H. J. Yu, L. Wang, Q. Shi, et al. Study on nano-CaCO3 modified epoxy powder coatings [J]. Progress in Organic Coatings, 2006,55(3):296-300.
[3] C.Guobei, N. J. Frank. Low-temperatuer curing higher-solids polyester coating with melamine-formaldehyde resin crosslinkers[J].Jounral of coatings technology,1993,65(819):43-48.
[4] P. Roose, I. Fallais, C. Vandermiers, et al. Radiation curing technology: An attractive technology for metal coating [J]. Progress in Organic Coatings, 2009, 64(2):163-170.
[5]姜海燕,何立凡,李效玉.苯丙乳液的合成及水性防锈涂料的制备研究[J].涂料工业,2007,37(9):9-13.
[6]殷再球,张超灿,吴力立,等.建筑外墙涂料用核/壳苯乙烯-丙烯酸酯共聚乳液的研究[J].涂料工业,2004,34(7):14-16.
[7]刘平平,程江,文秀芳等.水性防腐涂料用苯丙乳液的研究进展[J].涂料工业.2005,35(7):53-56.
[8]王德中.环氧树脂生产与应用[M].北京:化学工业出版社,2001,1-2.
[9] V. C. Malshe, G. Waghoo. Weathering characteristics of epoxy-ester paints[J].Progress in Organic Coating,2006,56(2):131-134.
[10]危恒毅,岳庆磊.水性防腐涂料体系[J].精细石油化工进展.2002,3(4):44-46.
[11]王倩,张心亚,陈焕钦,等.有机硅改性丙烯酸酯乳液性能的研究[J].中国胶粘剂,2002,(2):5-8.
[12] L. K. Aggarwal, P. C. Thaliyal, S. R. Karade. Properties of polymer-modified mortars using epoxy and acrylic emulsion [J]. Construction and Building Materials, 2007,21(2):379-383.
[13] B. Lessard, S. C. Schmidt, M. Maric. Styrene/acrylic acid random copolymers synthesized by nitroxide-mediated polymerization: effect of free nitroxide on kinetics and copolymer composition[J].Macromolecules,2008,41(10):3446-3454.
[14]甘孟瑜,谈尊燕,杨治国.丙烯酸酯乳液的改性研究[J].涂料工业,2006,36(3):10-12.
[15]陈琨,辛秀兰.印刷用苯丙乳液研究进展[J].中国涂料,2009,1:27-29.
[16] F. Sahmill, A. Wenning, J. V. Weiss. Recent developments in aqueous twcomponent polyurethane coatings [J]. Progress in Organic Coatings, 2000, 15 (40):99-103.
[17]祝阳,吕满庚,孔中平,等.含氟丙烯酸酯改性水性聚氨酯纳米复合乳液制备及性能研究[J].功能材料,2007,38(9):3520-3522.
[18]瞿金清,陈焕钦.聚氨酯-丙烯酸酯复合乳液的合成与性能[J].现代化工,2004, 24(1):28-30.
[19]张炎,齐正旺,陈炜,等.丙烯酸酯改性水性聚氨酯的方法[J].聚氨酯工业,2008,23(5):9-11.
[20] M. M. El-molla. Synthesis of polyurethane acrylate oligomers as aqueous UV-curable binder for inks of ink jet in textile printing and pigment dyeing[J]. Dyes and Pigments, 2007, 74(2):371-379.
[21] M. Mazurek, D. J. Kinning, T. Kinoshita. Novel materials based on silicone-acrylate copolymer networks [J]. Journal of Applied Polymer Science, 2001, 80:159-180.
[22] J. N. Hamid, M. Shadpour, M. Nader. Synthesis and characterization of silicone-modified vinyl acetate-acrylic emulsion copolymers [J]. Progress in Organic Coatings, 2006, 55(1):375-381.
[23]张心亚,黄洪,黎永津,等.乙烯基硅氧烷改性丙烯酸酯乳液聚合的动力学及成核机理分析[J].化工学报,2006,57(1):197-202.
[24] H. S. Park, I. M. Yang, J. P. Wu. Synthesis of silicone-acrylic resins and their applications to super weatherable coatings [J]. Journal of Applied Polymer Science, 2001, 81: 1614-1623.
[25]梁军艳,和玲,郑元锁.核壳型含氟丙烯酸酯共聚物的合成及性能[J].高等学校化学学报,2008,29(7):1473-1478.
[26]倪勇,赵玉索,来国桥,等.有机氟硅改性聚丙烯酸树脂和乳液的研究[J].有机硅材料,2005,19(2):14-16.
[27]邱俊英,程艳玲,郭小丽,等.有机氟硅改性丙烯酸酯共聚物乳液的研究[J].涂料工业,2008,38(8):37-39.
[28] R. Y. Hong, J. H. Li, L. L. Chen, et al. Synthesis surface modification and photocatalytic property of ZnO nanoparticles. Powder Technology, 2009(189):426-432.
[29] H. Y. Yu, J. S. Gu, J. Du, et al. Study on the surface modification of nano-TiO2 grafting PMMA/PBMA and its thermal stability. Chinese Journal of Polymer Science, 2005(3):243-247.
[30] F. A. Zhang, D. K. Lee, J. P. Thomas. Pmma-mesocellular foam silica nanocomposites prepared through batch emulsion polymerization and compression molding. Polymer, 2009(50):4768-4774.
[31]李锡凯,李阳.纳米改性弹性涂料的研制[J]涂料工业,2003,33(3):12-13.
[32]洪啸吟,冯汉保.涂料化学[M].北京:科学出版社,2006.118-123
[33]涂料工艺编委会.涂料工艺(上册)[M].(第三版)北京:化学工业出版社,2001(3):626.
[34]王德中.环氧树脂生产与应用[M].北京:化学工业出版社,2001: 4-7.
[35]林璜,于海琴,吴雷.环氧改性苯丙乳液的研制[J].济南大学学报,2003,17(3):274-276.
[36]周小勇.水性丙烯酸-环氧接枝共聚型树脂的制备[J].中国涂料,2006(2):16-18.
[37]黄洪,傅和青,邓艳文,等.环氧树脂与丙烯酸酯复合改性水性聚氨酯的合成研究[J].高校化学工程学报,2006,20(4):583-587.
[38] J. T. Woo, T. Alan.Water-based epoxy-acrylic graft copolymer [J].Progress in organic coatings.1993 (2):371-385.
[39]孙绍辉.环氧-丙烯酸酯类复合水性涂料的研究进展[J].化工进展.2004(9):984-987.
[40]庞衍松,张力,石光.新型环氧丙烯酸树脂增韧剂的合成[J].应用化学,2009,26(12):1418-1421.
[41] M. U. Fawn, C. W. Dean, P. D. Siva, et al. UV curable epoxy acrylate–clay nanocomposites [J]. European Polymer Journal, 2006, 42(10):2596-2605.
[42] S.H.Mansour, N.Mostafa, L.Abd. Electrical and positron annihilation study on epoxy and epoxy acrylate composites [J]. European Polymer Journal, 2007, 43(11):4770-4782.
[43] D. E. Jim, S. K. Derek, C. K. Pratap. Waterborne epoxy protective coatings for metal [J].Journal of Coating Teehnology.2002, 74(931):63-72.
[44] H. Schonhorn, T. T. Wang, H. N. Vazirani, et al. Static and dynamic fatigue of high-strength glass fibers coated with a uv-curable epoxy-acrylate [J]. Journal of Applied Physics, 2009, 49(9):4783-4787.
[45]孙兴平,王德海.环氧丙烯酸酯合成及应用的研究进展[J].涂料工业,2007,37(11):53-56.
[46]王锋,胡剑青,涂伟萍.紫外光固化低黏度环氧丙烯酸酯的合成[J].涂料工业,2009,39(7):8-12.
[47]梁永升,梁亮.合成光敏性环氧丙烯酸酯的催化剂研究[J].精细化工,2006,23(3):278-281.
[48]刘宁,刘治猛,刘煜平,等.环氧丙烯酸酯粉末涂料的合成及固化研究[J].精细石油化工,2009,6:65-68.
[49]王锋,胡剑青,涂伟萍.异氰酸酯改性环氧丙烯酸酯的合成及其光固化动力学的研究[J].高校化学工程学报,2010,24(2):233-238.
[50]袁才登,段春华,许涌深,等.环氧单丙烯酸酯的合成[J].热固性树脂,2007,22(2):19-22.
[51]吴静.水溶性环氧-甲基丙烯酸树脂及在涂料中应用的研究[D].沈阳化工学院硕士学位论文.2002.
[52]李志强,温翠珠,王炼石,等.环氧树脂与丙烯酸酯单体的接枝共聚及其汽车阴极电泳涂料的性能[J].电镀与涂饰,2009,28(3):59-63.
[53] C. Robert, A. Stanley, A. Richard. Ageing of adhesive bonds with various surface treatments, part 2: acrylic modified amine–cured epoxy resin[J].Adhesion,2005,81:1183-1197.
[54] S. X. Li, W. F. Wang, L. M. Liu, et al. Morphology and characterization of epoxy-acrylate compositeparticles[J].Polymer Bulletin,2008,61:749-757.
[55] T. Wan, X. J. Li, W. B. Xiao. Preparation of epoxy-silica-acrylate hybrid coatings[J].Polymer Bulletin,2008,59;749-758.
[56] G. R. Pan, L. M. Wu, Z. Q. Zhang, et al. Synthesis and characterization of epoxy-acrylate composite latex [J]. Applied Polymer Science,2002,(83):1736-1743.
[57]万欢,张旭玲,曾繁涤,等.接枝型水性环氧树脂乳液的合成与粘接性能研究[J].粘结,2010,3:51-54.
[58] Noda, Sumio. Aqueous coating of carboxyl acrylic resin-epoxy resin product [P]. 5780532, 1998.
[59] D. Ratna, G. P. Simon. Mechnaical characterization and morphology of carboxyl randomized poly(2-ethylhexylacrylate)liquid rubber touhgned epoxy resins[J].Polymer,2001 (42):7739-7747.
[60]叶寒,陈松,李效玉,等.自乳化型环氧树脂接枝丙烯酸复合乳液的制备[J].涂料工业,2006,36(11):1-4.
[61] G. P. Craun, V. V. Kaminski. Low voc aqueous dispersed acrylic epoxy microgels [P], Us5554671, 1996.
[62]赵晓宁,方治齐.丙烯酸醋微凝胶乳液的研究[J].涂料工业,2000,(3):33-35.
[63]贺海量,张旭东,周杰,等.环氧树脂改性聚氨酯-丙烯酸酯乳液的合成[J].热固性树脂,2007,22(1):19-23.
[64]张洁,翟金清,张心亚,等.环氧改性苯丙乳液的合成及性能[J].涂料技术与文摘,2004,25(2):24-28.
[65]杨瑞芹,崔天放,陈尔凡.环氧-丙烯酸酯乳液的研制[J].化学世界,2002(l):23-24.
[66]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.
[67] G. L. Brown, M. A. Tobias. Epoxy modifide acyrlic lattiees and method of producing same[P]. Us4028294, 1977.
[68] D. D. Wet-roos, J. H. Knoteze, B. Cooray. Emulsion polymerization of an epoxy-acrylate emulsion stbailized with polyacrylateⅡ. using the results of statistically designed experiments to reduce a possible polymerization mechanism[J].Journal of Applied Polymer Scinece,2000,76:368-381.
[69] R. P.Minnis, E. P. Moschovis, et al. Aqueous emulsion laminating adhesive[P]. Us4555757, 1986.
[70] P. Saendee, P.Tangboriboonrat. Emulsion interpenetrating polymer networks of epoxidised natural rubber/poly(methyl methacrylate): an insight into the mechanism of epoxidation[J]. Colloid Polym Sci, 2006, 28(4): 634-643.
[71] D. L. Merlin, B. Sivasankar. Synthesis and characterization of semi-interpenetrating polymer networks using biocompatible polyurethane and acrylamide monomer[J]. European Polymer Journal, 2009, 45:165-170.
[72]曹同玉,刘庆普,胡金牛.乳液聚合原理性能及应用[M].化学工业出版社,2007,1-300.
[73]刘德峥,苗郁.种子乳液聚合法制备聚丙烯酸酷织物涂层剂[J].染料工业,2002,39(2):32-34.
[74]牛益江.新型固化促进剂的研究及应用[J].化学工程师,2007,3:53-54.
[75]刘宇艳,何利娜,万志敏,等.新型环氧树脂潜伏性促进剂的合成、表征及性能研究[J].航空材料学报,2008,28(1):71-75.
[76]朱诚身.聚合物结构分析[M].科学出版社,2004,100-120.
[77] M F Mei, B M Yu, L Luo, et al. A model for the contact angle of liquid droplets on rough surfaces[J].Chinese Physics Letter,2010,27(7):210-213.
[78]赵名师,吴明,董有智.ESI分析在防腐蚀涂层评价中的应用[J].金属表面处理,2007,26(10):39-42.
[79] Q Zhang, M Xiang. Using EIS to evaluate anti-corrosion properties of the SiC_p/5A06 aluminium MMC treated by cerium conversion coatings [J]. Rare earths, 2010, 28(1):109-117.
[80] A.G.Gilicinski, C.R.Hegedus. New applications in studies of waterborne coatings by atomic of microscopy[J], Progress in organic coatings,1997,32:81-88.
[81]曹楚南,张鉴清.电化学阻抗谱导论[M].北京:科学出版社,2004.
[82] J. T. Zhang, J. M. Hu, J. Q. Zhang. Studies of water transport behavior and importance models of epoxy-coated metals in NaCl solution by EIS[J].Progress in Organic Coatings,2004(51):145-151.
[83] R. Joseph. Reflective coating for sunlight, paint outside a spray booth, and case-by-case MACT for in mold painting[J]. Metal Finishing, 2001, 99(2):101-102.
[84]沈慧芳,傅和青,黄洪,等.成膜助剂在乳胶漆中作用分析[J].合成材料老化与应用,2004,33(2): 41-43.
[85] L. Kenneth. Coalescence and film formation from Latexes[J].Journal of Coating Technology,1996,68(853):33-39.
[86]殷耀兵,李国强,管文超.乳液涂料成膜过程中成膜助剂的挥发[J].涂料工业,2007,37(8):20-22.