水性环氧中子屏蔽涂料的研制
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摘要
本文采用化学改性法,成功开发了一种水性环氧树脂分散液。该分散液是以环氧树脂为母体,甲基丙烯酸、丙烯酸丁酯及苯乙烯为接枝单体,通过自由基接枝聚合,合成了一种在分子结构上既具有环氧基团,又具有亲水基团的苯丙接枝环氧树脂。通过考察引发剂种类和用量、接枝单体用量、亲水单体含量、接枝温度、中和剂的种类和用量等因素对单体接枝率、水分散液粒径、贮存稳定性和耐水性的影响,确定了接枝水性环氧树脂的最佳合成条件。结果表明:亲水单体(MAA)含量为10%,混合单体总量为环氧树脂总量的25%,接枝温度为110～120℃,反应时间为6h时,接枝率可达82.3%。
研究以所制备的水性环氧树脂分散液为成膜物,与碳化硼填料进行复配,制备了一种新型水性环氧中子屏蔽涂料。通过考察固化剂、助剂、颜料体积浓度、涂层厚度等因素对涂层性能的影响,确定了水性中子屏蔽涂料的最佳配方,并探讨了水性涂料的固化成膜机理。结果表明:该涂料性能优异,与溶剂型涂料相比具有VOC含量低,毒性小、无火灾危险性、涂装简便且安全卫生,同时降低了成本,表明所研制的水性中子屏蔽涂料是一种性能优异的新型环保实用核辐射防护涂料。
This paper aims at developing a kind of epoxy aqueous dispersion with excellent stability and good chemical resistance. In this paper, a kind of modified resin which had both epoxy groups and hydrophilic groups was synthesized. In the radical graft copolymerization, the epoxy resin was used as matrix, and methacrylic acid, butyl acrylate, styrene were used as graft monomers. In order to find out the optimum reaction conditions, the effects of reaction conditions such as initiators, initiators concentration, the amount of monomers for grafting, the mass ratio of hydrophilic monomer, the temperature of grafting, and neutralization reagent were studied. The results showed that when the10% of MAA, 25% of the mixed monomers, 110～120℃of grafting temperature, 6h of reaction time, the grafting ratio can reach to 82.3%.
The waterborne epoxy neutron shielding is a kind of radiation-proof coating which consists of boron carbide powder and the modified waterborne epoxy emulsion. The influences of curing agent、pigment volume concentration (PVC) and coating thickness on the features of the coating are discussed. The curing mechanism of the waterborne epoxy radiation-proof coating is described. The specimens coated with the modified coating were examined by routine property testing. Problems occurred in coating process and corresponding solutions are discussed. The optimum formulation of the waterborne epoxy experiment was studied. Research results show that coating is determined by the waterborne epoxy radiation-proof coating of double-package has excellent performance, low temperature curing and environment protection.
研究以所制备的水性环氧树脂分散液为成膜物,与碳化硼填料进行复配,制备了一种新型水性环氧中子屏蔽涂料。通过考察固化剂、助剂、颜料体积浓度、涂层厚度等因素对涂层性能的影响,确定了水性中子屏蔽涂料的最佳配方,并探讨了水性涂料的固化成膜机理。结果表明:该涂料性能优异,与溶剂型涂料相比具有VOC含量低,毒性小、无火灾危险性、涂装简便且安全卫生,同时降低了成本,表明所研制的水性中子屏蔽涂料是一种性能优异的新型环保实用核辐射防护涂料。
This paper aims at developing a kind of epoxy aqueous dispersion with excellent stability and good chemical resistance. In this paper, a kind of modified resin which had both epoxy groups and hydrophilic groups was synthesized. In the radical graft copolymerization, the epoxy resin was used as matrix, and methacrylic acid, butyl acrylate, styrene were used as graft monomers. In order to find out the optimum reaction conditions, the effects of reaction conditions such as initiators, initiators concentration, the amount of monomers for grafting, the mass ratio of hydrophilic monomer, the temperature of grafting, and neutralization reagent were studied. The results showed that when the10% of MAA, 25% of the mixed monomers, 110～120℃of grafting temperature, 6h of reaction time, the grafting ratio can reach to 82.3%.
The waterborne epoxy neutron shielding is a kind of radiation-proof coating which consists of boron carbide powder and the modified waterborne epoxy emulsion. The influences of curing agent、pigment volume concentration (PVC) and coating thickness on the features of the coating are discussed. The curing mechanism of the waterborne epoxy radiation-proof coating is described. The specimens coated with the modified coating were examined by routine property testing. Problems occurred in coating process and corresponding solutions are discussed. The optimum formulation of the waterborne epoxy experiment was studied. Research results show that coating is determined by the waterborne epoxy radiation-proof coating of double-package has excellent performance, low temperature curing and environment protection.
引文
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[49]Massingill J L, SheikP S, Fundamental studies of epoxy resins for can and coil coatings flexibility and adhesion of epoxy resins, JCoat Tech,l990,62(781):31~39
[50]Woo J K, Ting V, Evans J, Synthesis and characterization of water-reducible graft epoxy copolymers, J Coat Tech,1982,54 (689):41~55
[51]朱国民,王善琦,席海萍等,环氧磷酸酷一丙烯酸接枝共聚反应的研究,涂料工业,1995(2): 5~8
[52]Philip A Reitano, Tom Szurgyjlo, Using emulsifiers to improve water-reducibleresin systems, Modem Paint Coatings,1990,7: 44 ~47
[53]B.Del Amo, R. Romagnoli and J.A.Gonzalez, High performance water-based paints with non-toxic anticorrosive pigments, Progress in Organic Coatings, 2002,45(4):389~397
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[67]张凯,硅氧烷改性接枝型水性环氧树脂的合成与研究:[硕士学位论文],广州;华南师范大学,2005
[2]刘小平,郑天亮,环氧树脂的水性化技术,涂料工业,2000, 30(10):33～35
[3]张子勇,水溶性涂料的发展(一),涂料工业,1991(4):9～32
[4]李桂林,环氧树脂与环氧涂料,北京,化学工业出版社,2003.402～414
[5]涂伟萍,水性涂料,北京,化学工业出版社,2005.266～285
[6]莫雄,接枝型水性环氧树脂的合成与性能研究:[硕士学位论文],湖南;湖南大学,2003
[7]刘国杰,水分散涂料,北京:中国轻工业出版社,2004,361～362
[8]葛爱兰,冉全印,张志平,自乳化聚氨酯水乳液的合成及性能研究,高分子材料与工程,1993(6): 24～28
[9]陈尔凡,程远杰,赵常礼,接枝环氧水溶性涂料,涂料工业,1997(5):16～18
[10]徐丽真,环氧改性丙烯酸涂料的研制,涂料工业,1998(6): 17～18
[11]方允之,都绍萍,冯宝俊,环氧-丙烯酸接枝共聚物水性化的研究,涂料技术,1991(1):30～32
[12]张凯,硅氧烷改性接枝型水性环氧树脂的合成与研究:[硕士学位论文],广州;华南师范大学,2005
[13]本山卓彦,环氧树脂乳液,Technology of adhesion and sealing,1998,42(6): 1～6
[14]上井幸夫,环氧树脂乳液,Journal of the adhesion society of Japan,1999,35(5): 13～17
[15]James, TK Woo, Water-based epoxy-acrylic graft copolyme, Progressin organic Coatings,1993,21(2):371～385
[16]TK Woo, Preprint Organic Coating and Plastics Division, American Chemical Society,1981,45:516
[17]陈尔凡,程远杰,赵常礼,接枝环氧水溶性涂料,涂料工业,1997(5):16～18
[18]徐丽真,史立平,环氧改性丙烯酸涂料的研制,涂料工业,1998(6): 17～18
[19]方允之,都绍萍,冯宝俊,环氧-丙烯酸接枝共聚物水性化的研究,涂料技术,1991(1):30～32
[20]刘国杰,水分散涂料,北京:中国轻工业出版社,2004,361～362
[21]杨勋兰,孙绍晖,孙培勤,丙烯酸/环氧树脂接枝共聚物及其水性涂料,热固性树脂2005,20(1):9～11
[22]刘晓东,陈志明,董劲,单组分水性环氧乳液的合成研究,应用化工,2007,36(1):68～71
[23]Gebhardt O, Gavillet D, SIMS imaging analyses of inreactorirradiated boron carbide control rodsamples,Journal of Nuclear Materials,2000,279:368~371
[24]Gwaily S E, Badawy M M, Hassan H H, Natural rubber composites as thermal neutron radiation shields, PolymerTesting,2002,21:129~133
[25]Mohamed A, Abdou, Nuclear design of the blanket/shieldsystem for a tokamak experimental power reactor, Nuclear Technology,1976,29:7~36
[26]Robinson P V, Design of water reducible polymers for use in food contact applications, Journal of coating Technology, 1981,674(53):23~30
[27]黄先威,肖鑫,易翔,水性环氧防腐涂料的研制,电镀与涂饰,2005,24(1):50～53
[28]王春艳,陈涛,朱传方,环氧接枝改性水性丙烯酸树脂的合成研究,应用化工,2006,35(1):27～29
[29]于晓辉,郭忠诚,水性环氧涂料体系进展,电镀与涂饰,2005,24(9):53～57
[30]莫雄,徐伟箭,水性环氧树脂的研究及其固化,化工新型材料,2002,30(12):31～33
[31]郝达菲,徐佳,自乳化环氧树脂的研究进展及其固化,广东化工,2005,(11):8～10
[32]黄立,室温固化水性环氧涂料的研究进展,现代涂料与涂装,2006(8):17～19
[33]Kojima S, Moriga T, Watanabe Y, Development of high performance, water-based emulsion coatings for can coatings application, Coat Tech, 1993, 65: 25～38
[34]De Wet-R D, Knoetze J H, Cooray R, Emulsion polymerization of an epoxy-acrylate emulsion stabilized with polyacrylate, J Appl Poly Sci,2000,76:368~381
[35]朱国民,王善琦,席海萍,环氧磷酸酯-丙烯酸接枝共聚反应的研究,涂料工业,1995(2):5～8
[36]顾宇听,黄玉惠,廖兵,离聚体水基微乳液化的研究,高分子学报,1999(4): 477～482
[37]刘小平,郑天亮,环氧树脂的水性化技术,涂料工业,2000,30(10):33～35
[38]杨振忠,许元泽,赵得禄,环氧树脂微粒化水基化体系,高分子通报,1997(3): 190～194
[39]孙凌,陈声锐,水性环氧树脂涂料,上海化工,1991,16(5):19～21
[40]杨振忠,许元泽,赵得禄等,相反转技术制备环氧树脂水基体系-相反转过程的流变行为研究,高分子学报,1998(1): 78～82
[41]Kojima S, Watanabe Y, Development of high performance waterborne coatings emulsification of epoxy resin, Polym Eng Sci,1993,33:25 3～259
[42]王进,杜宗良,李瑞霞,环氧树脂水基分散体系的相反转乳化,功能高分子学报,2000 (2): 141～144
[43]Yang Z Z, Xu Y Z, Preparation of waterborne dispersions of epoxy resin by the phase inversion technique, Colloid Polym Sci,2000,278(12):1164～1171
[44]杨振忠,许元泽,赵得禄等,环氧树脂相反转乳化过程相态发展的研究,高等学校化学学报,1999(5):809～813
[45]张肇英,黄玉惠,廖兵,环氧树脂水性化改性及其固化,高分子通报,2000(3): 77～81
[46]Robinson P V, Design of water reducible polymers for use in food contact applications, J Coat Tech,1981,53 (674):23~30
[47]Krishnamurti N, Shirsalkar M M, Sivasamban M A, Water soluble epoxy resin acid esters, Paint&Resin,1989,59 (6):30~34
[48]胡惠萍,刘素琴,黄可龙等,水基改性环氧树脂涂料的合成研究,湖南化工,1999(6):41～43
[49]Massingill J L, SheikP S, Fundamental studies of epoxy resins for can and coil coatings flexibility and adhesion of epoxy resins, JCoat Tech,l990,62(781):31~39
[50]Woo J K, Ting V, Evans J, Synthesis and characterization of water-reducible graft epoxy copolymers, J Coat Tech,1982,54 (689):41~55
[51]朱国民,王善琦,席海萍等,环氧磷酸酷一丙烯酸接枝共聚反应的研究,涂料工业,1995(2): 5~8
[52]Philip A Reitano, Tom Szurgyjlo, Using emulsifiers to improve water-reducibleresin systems, Modem Paint Coatings,1990,7: 44 ~47
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