环氧树脂水性化的研究进展
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摘要
环氧树脂拥有诸多优异的性能,被广泛应用于各领域,然而溶剂型环氧树脂越来越难以满足市场对于绿色环保的要求,故寻求将环氧树脂水性化显得颇为关键。详细介绍了机械法、相反转法、化学改性法和固化剂乳化法等水性环氧树脂乳液的制备方法,系统阐述了各种方法的原理和流程,分析总结了影响水性环氧树脂乳液性能的重要因素,详尽地叙述了不同制备方法的优点和缺点,并对其优化和改进方向进行了展望。综述了国内外环氧树脂水性化的最新研究进展,指出了筛选生产配方、优化工艺流程以及有计划地功能性改性等是水性环氧树脂今后的发展趋势。
Epoxy resin has been widely used in various fields due to its many excellent properties. However,solvent-based epoxy resin is increasingly difficult to meet the requirements of environmental protection in the market. Therefore, it is very important to seek waterorne epoxy resin. The preparation methods of waterborne epoxy resin emulsions such as mechanical method, reverse conversion method, chemical modification method and curing agent emulsification method are reviewed in detail. The principle and process of various methods are systematically introduced, and the important factors affect the properties of waterborne epoxy resin areanalyzed and summarized. Inaddition, the advantages and disadvantages of different preparation methods are described. Finally, the optimization and improvement directions are prospected. The development trend of waterborne epoxy resins in the future is the selection of production formula, optimization of process flow and planned modification of functional monomers.
Epoxy resin has been widely used in various fields due to its many excellent properties. However,solvent-based epoxy resin is increasingly difficult to meet the requirements of environmental protection in the market. Therefore, it is very important to seek waterorne epoxy resin. The preparation methods of waterborne epoxy resin emulsions such as mechanical method, reverse conversion method, chemical modification method and curing agent emulsification method are reviewed in detail. The principle and process of various methods are systematically introduced, and the important factors affect the properties of waterborne epoxy resin areanalyzed and summarized. Inaddition, the advantages and disadvantages of different preparation methods are described. Finally, the optimization and improvement directions are prospected. The development trend of waterborne epoxy resins in the future is the selection of production formula, optimization of process flow and planned modification of functional monomers.
引文
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[14]Jin Yongxiang(金永香),Lian Hailan(连海兰).Research progress on reverse emulsification technology of epoxy resin[J].Cooling Industry(涂料工业),2018,48(9):70-76.
[15]Liu Xiaobei(刘晓蓓),Wang Xiaojie(王晓洁),Hui Xuemei(惠雪梅).Research progress in high temperature epoxy resin[J].Fiberglass/Composites(玻璃钢/复合材料),2013,(3):118-121.
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[18]Li Jinfeng(李金凤),Liu Lizhu(刘立柱),Zhang Xiaorui(张笑瑞).Preparation of water-based epoxy emulsions by phase inversion emulsification technique[J].Chemical Industry and Engineering Progress(化工进展),2015,34(9):3388-3391.
[19]Chen Kun(陈坤),Ma Jiangquan(马江权),Yin Zhengye(尹正烨),et al.Synthesis and application of a bifunctionalepoxy resin emulsifier[J].Fine Chemicals(精细化工),2016,33(5):524-529.
[20]Galindoalvarez J,Sadtler V,Choplin L,et al.Viscous oil emulsification by catastrophic phase inversion:influence of oil viscosity and process conditions[J].Industrial&Engineering Chemistry Research,2011,50(9):5575-5583.
[21]Li Peng(李鹏),Zhang Xuemei(张雪梅),Cheng Bin(程斌),et al.Study on maleic anhydride and sodium bisulfite modified epoxy resin[J].Glass Steel/Composites(玻璃钢/复合材料),2013,(2):17-21.
[22]Liu Youcai(刘有才),Li Lifeng(李丽峰),Zhong Hong(钟宏),et al.Preparation and characterization of polyethylene glycol bisglycidylether epoxy resin[J].Guangdong Chemical Industry(广东化工),2009,36(5):21-23.
[23]Zhang Xiucheng(张修成).Preparation of water-soluble epoxy resin:CN102952255A[P].2013-03-06.
[24]Liu M,Mao X,Zhu H,et al.Water and corrosion resistance of epoxy-acrylic-amine waterborne coatings:Effects of resin molecular weight,polar group and hydrophobic segment[J].Corrosion Science,2013,75(7):106-113.
[25]Hao R Z,Yun F Y,Xiao J L.Preparation of waterborne epoxy resin emulsion[J].Applied Mechanics&Materials,2013,364:627-630.
[26]Zheng Guo(郑帼),Liu Huibing(刘会兵),Zhou Cun(周存),et al.Hydroxyl-terminated polydimethylsiloxane modified shape memory epoxy resin[J].Polymer Materials Science&Engineering(高分子材料科学与工程),2018,34(1):154-159,165.
[27]Ke Zhigang(柯志刚),Yi Changfeng(易昌凤),Xu Zushun(徐祖顺),et al.Research progress in the waterborne epoxy resins[J].Modern Coatings&Coatings(现代涂料与涂装),2015,18(8):17-20.
[28]Wu Min(吴敏).Waterborne epoxy system and curing performancein coating[D].Shanghai:East China University of Science and Technology(华东理工大学),2014.
[29]Zhang Z,Huang Y,Liao B,et al.Studies of waterborne emulsion of chemically modified epoxy resin[J].Polymers for Advanced Technologies,2010,15(1/2):26-29.
[30]Li Ling(李令).Preparation of a waterborne epoxy emulsion:CN108084458A[P].2018-5-29.
[31]Yuan X,Zhu B,Cai X,et al.Improved interfacial adhesion in carbon fiber/epoxy composites through a waterborne epoxy resin sizing agent[J].Journal of Applied Polymer Science,2017,134(17):44757.
[32]Luo Xiping(罗锡平),Fu Shenyuan(傅深渊),Chen Jianjun(陈建军).Study on water-based modification of E-44 epoxy resin[J].Zhejiang Chemical Industry(浙江化工),2018,49(2):24-28.
[33]Deng Wei(邓威),Huang Hong(黄洪),Fu Heqing(傅和青).Progress of modification of waterborne polyurethane adhesive[J].Chemical Industry and Engineering Progress(化工进展),2011,30(6):1341-1346.
[34]Yan Caibin(颜财彬),Fu Heqing(傅和青).Research progress of modification technology for waterborne polyurethane[J].Chemical Industry and Engineering Progress(化工进展),2011,30(12):2658-2664.
[35]Wang G,Yang J.Influences of molecular weight of epoxy binder on fire protection of waterborne intumescent fire resistive coating[J].Surface&Coatings Technology,2012,206(8):2146-2151.
[36]Zhang Sheng(张胜),Wang Zhenxing(王振兴).Anionic waterborne epoxy resin emulsion and its preparation method and application:CN108178976A[P].2018-06-19.
[37]Wang H,Yang F,Zhu A,et al.Preparation and reticulation of styrene acrylic/epoxy complex latex[J].Polymer Bulletin,2014,71(6):1523-1537.
[38]Tang E,Bian F,Klein A,et al.Fabrication of an epoxy graft poly(St-acrylate)composite latex and its functional properties as a steel coating[J].Progress in Organic Coatings,2014,77(11):1854-1860.
[39]Lu Bin(吕斌),Li Rui(李蕊),Gao Dangge(高党鸽).Preparation and properties of carboxyl-containing waterborne epoxy resin[J].Fine Chemicals(精细化工),2015,32(2):186-189,210.
[40]Liu Zilong(刘子龙).Preparation and application properties of waterborne epoxy resin[D].Tianjin:Tianjin Polytechnic University(天津工业大学),2016.
[41]Li Junju,Huang Zhixiong.Research progress in epoxy resin aqueous method[C]//.Proceedings of the 16th Annual Conference on FRP/Composites(第十六届玻璃钢/复合材料学术年会论文集),2005:75-78.
[42]Huang Kai(黄凯),Liang Liang(梁亮),Li Dan(李丹),et al.Study on nonionic self-emulsifying waterborne epoxy emulsion[J].Paint&Coatings Industry(涂料工业),2010,40(9):53-57.
[43]Xiong Yuanqin(熊远钦),Deng Hongxia(邓红霞),Peng Hua(彭桦),et al.Synthesis of a waterborne epoxy curing agent and its properties[J].Journal of Hunan University(Natural Sciences),2009,36(11):53-56.
[44]Wang Feng(王丰),Liu Yali(刘娅莉),Xu Longgui(徐龙贵),et al.Research progress in waterborne epoxy coating curing agents[J].Paint&Coatings Industry(涂料工业),2004,(8):29-33,63.
[45]Kang Huihua(康惠花),Ma Shangquan(马尚权),Qian Rui(钱瑞).Research progress of waterborne epoxy resin curing agent[J].Shandong Chemical Industry(山东化工),2017,46(22):31-33.
[46]Wang Qing.Research progress in epoxy resin curing agents[J].Tianjin Chemical Industry(天津化工),2001,(6):12-14.
[47]Stark C J,Stark A B A E,Back G E,et al.Epoxy-functional amidoamine reacted with excess polyamine and monoepoxy as epoxy curative:US6277928[P].2001-08-21.
[48]Deng Hongxia(邓红霞).Synthesis and study on the property of a curing agent for room temperature curing of a aqueous epoxy resin emulsion[D].Changsha:Hunan University(湖南大学),2009.
[49]Liu Xiaofang(刘晓芳),Wang Rongwei(王荣威),Wei Ming(魏铭),et al.Study on preparation,properties and curing mechanism of nonionic self-emulsified waterborne epoxy curing agent[J].Coating industry(涂料工业),2017,47(5):44-50.
[50]Xiao Shuxin(肖淑欣),Jiang Xiaoqin(姜晓琴),Liu Xinhao(刘新浩),et al.Preparation of waterborne epoxy resin curing agentandits compatibility with emulsion[J].Coating industry(涂料工业),2018,48(3):1-5.
[2]Yu Kaishuo(于凯烁),Yang Jun(杨军),Wang Haihua(王海花).Performance of halloynanotubes/waterborne epoxy resin composites[J].Fine Chemicals(精细化工),2016,33(10):1176-1182.
[3]Tong Kuai(童快),Yan Fuan(闫福安),Dong Yuelin(董月林).Preparation and properties of nonionic waterborne epoxy resin emulsion[J].China Paint(中国涂料),2018,33(2):19-24.
[4]Wu Yangmin(吴杨敏),Zhou Shenguo(周升国),Lu Guangming(卢光明),et al.Research progress in preparation technology and anticorrosion properties of epoxy resin[J].Surface Technology(表面技术),2017,46(11):135-142.
[5]Li Liang(李亮),Wang Pinghua(王平华),Liu Chunhua(刘春华),et al.Synthesis and characterization of waterborne epoxy resin[J].Paint&Coatings Industry(涂料工业),2011,41(2):17-20.
[6]Guo Heyun(郭何云),Wang Xu(王煦).Research progress in preparation methods of waterborne epoxy resin[J].Chinese Journal of Synthetic Chemistry(合成化学),2017,25(5):457-460.
[7]Cui Jian(崔健),Xia Haibo(夏海渤),Kan Lulu(阚璐璐),et al.Comparative analysis of two kinds of emulsifying methods for waterborne epoxy resin[J].Modern Coatings&Coatings(现代涂料与涂装),2018,21(3):17-19.
[8]Elsesser M T,Hollingsworth A D.Revisiting the synthesis of a well-known comb-graft copolymer stabilizer and its application to the dispersion polymerization of poly(methyl methacrylate)in organic media[J].Langmuir,2010,26(23):17989~17996.
[9]Li Jianhui(李坚辉),Sun Mingming(孙明明),Zhang Xugang(张绪刚),et al.Research progress of waterborne epoxy resin[J].Heilongjiang Science(黑龙江科学),2013,(8):49-51,57.
[10]Hess M,Schneider H,Hiller M.Aqueous dispersion of epoxy resin and blend of epoxy resin-polyoxyalkylene amines:US 6077884[P].2000-6-20.
[11]Huang Juanping(黄娟萍),Li Sufang(李素芳),Li Jiao(李娇),et al.Synthesis and properties of waterborne epoxy composite emulsifier[J].Chinese Journal of Applied Chemistry(应用化学),2014,31(3):256-261.
[12]Liu B,Wang Y.A novel design for water-based modified epoxy coating with anti-corrosive application properties[J].Progress in Organic Coatings,2014,77(1):219-224.
[13]Guo Li(郭利),Liu Weiwei(刘薇薇),Liu Yun(柳昀),et al.Nonionic epoxy active emulsifier,preparation method and waterborne epoxy resin emulsion:CN107099026A[P].2017-8-29.
[14]Jin Yongxiang(金永香),Lian Hailan(连海兰).Research progress on reverse emulsification technology of epoxy resin[J].Cooling Industry(涂料工业),2018,48(9):70-76.
[15]Liu Xiaobei(刘晓蓓),Wang Xiaojie(王晓洁),Hui Xuemei(惠雪梅).Research progress in high temperature epoxy resin[J].Fiberglass/Composites(玻璃钢/复合材料),2013,(3):118-121.
[16]Xu J,Jamieson A M,Qutubuddin S,et al.Catastrophic emulsificationof epoxy resin using pluronicblock copolymers:?Preinversion behavior[J].Langmuir,2001,17(4):1310-1313.
[17]Lian Hailan(连海兰),Jin Yongxiang(金永香),Chen Ling(陈玲).Preparation of a waterborne epoxy resin emulsion:CN108070093A[P].2018-05-25.
[18]Li Jinfeng(李金凤),Liu Lizhu(刘立柱),Zhang Xiaorui(张笑瑞).Preparation of water-based epoxy emulsions by phase inversion emulsification technique[J].Chemical Industry and Engineering Progress(化工进展),2015,34(9):3388-3391.
[19]Chen Kun(陈坤),Ma Jiangquan(马江权),Yin Zhengye(尹正烨),et al.Synthesis and application of a bifunctionalepoxy resin emulsifier[J].Fine Chemicals(精细化工),2016,33(5):524-529.
[20]Galindoalvarez J,Sadtler V,Choplin L,et al.Viscous oil emulsification by catastrophic phase inversion:influence of oil viscosity and process conditions[J].Industrial&Engineering Chemistry Research,2011,50(9):5575-5583.
[21]Li Peng(李鹏),Zhang Xuemei(张雪梅),Cheng Bin(程斌),et al.Study on maleic anhydride and sodium bisulfite modified epoxy resin[J].Glass Steel/Composites(玻璃钢/复合材料),2013,(2):17-21.
[22]Liu Youcai(刘有才),Li Lifeng(李丽峰),Zhong Hong(钟宏),et al.Preparation and characterization of polyethylene glycol bisglycidylether epoxy resin[J].Guangdong Chemical Industry(广东化工),2009,36(5):21-23.
[23]Zhang Xiucheng(张修成).Preparation of water-soluble epoxy resin:CN102952255A[P].2013-03-06.
[24]Liu M,Mao X,Zhu H,et al.Water and corrosion resistance of epoxy-acrylic-amine waterborne coatings:Effects of resin molecular weight,polar group and hydrophobic segment[J].Corrosion Science,2013,75(7):106-113.
[25]Hao R Z,Yun F Y,Xiao J L.Preparation of waterborne epoxy resin emulsion[J].Applied Mechanics&Materials,2013,364:627-630.
[26]Zheng Guo(郑帼),Liu Huibing(刘会兵),Zhou Cun(周存),et al.Hydroxyl-terminated polydimethylsiloxane modified shape memory epoxy resin[J].Polymer Materials Science&Engineering(高分子材料科学与工程),2018,34(1):154-159,165.
[27]Ke Zhigang(柯志刚),Yi Changfeng(易昌凤),Xu Zushun(徐祖顺),et al.Research progress in the waterborne epoxy resins[J].Modern Coatings&Coatings(现代涂料与涂装),2015,18(8):17-20.
[28]Wu Min(吴敏).Waterborne epoxy system and curing performancein coating[D].Shanghai:East China University of Science and Technology(华东理工大学),2014.
[29]Zhang Z,Huang Y,Liao B,et al.Studies of waterborne emulsion of chemically modified epoxy resin[J].Polymers for Advanced Technologies,2010,15(1/2):26-29.
[30]Li Ling(李令).Preparation of a waterborne epoxy emulsion:CN108084458A[P].2018-5-29.
[31]Yuan X,Zhu B,Cai X,et al.Improved interfacial adhesion in carbon fiber/epoxy composites through a waterborne epoxy resin sizing agent[J].Journal of Applied Polymer Science,2017,134(17):44757.
[32]Luo Xiping(罗锡平),Fu Shenyuan(傅深渊),Chen Jianjun(陈建军).Study on water-based modification of E-44 epoxy resin[J].Zhejiang Chemical Industry(浙江化工),2018,49(2):24-28.
[33]Deng Wei(邓威),Huang Hong(黄洪),Fu Heqing(傅和青).Progress of modification of waterborne polyurethane adhesive[J].Chemical Industry and Engineering Progress(化工进展),2011,30(6):1341-1346.
[34]Yan Caibin(颜财彬),Fu Heqing(傅和青).Research progress of modification technology for waterborne polyurethane[J].Chemical Industry and Engineering Progress(化工进展),2011,30(12):2658-2664.
[35]Wang G,Yang J.Influences of molecular weight of epoxy binder on fire protection of waterborne intumescent fire resistive coating[J].Surface&Coatings Technology,2012,206(8):2146-2151.
[36]Zhang Sheng(张胜),Wang Zhenxing(王振兴).Anionic waterborne epoxy resin emulsion and its preparation method and application:CN108178976A[P].2018-06-19.
[37]Wang H,Yang F,Zhu A,et al.Preparation and reticulation of styrene acrylic/epoxy complex latex[J].Polymer Bulletin,2014,71(6):1523-1537.
[38]Tang E,Bian F,Klein A,et al.Fabrication of an epoxy graft poly(St-acrylate)composite latex and its functional properties as a steel coating[J].Progress in Organic Coatings,2014,77(11):1854-1860.
[39]Lu Bin(吕斌),Li Rui(李蕊),Gao Dangge(高党鸽).Preparation and properties of carboxyl-containing waterborne epoxy resin[J].Fine Chemicals(精细化工),2015,32(2):186-189,210.
[40]Liu Zilong(刘子龙).Preparation and application properties of waterborne epoxy resin[D].Tianjin:Tianjin Polytechnic University(天津工业大学),2016.
[41]Li Junju,Huang Zhixiong.Research progress in epoxy resin aqueous method[C]//.Proceedings of the 16th Annual Conference on FRP/Composites(第十六届玻璃钢/复合材料学术年会论文集),2005:75-78.
[42]Huang Kai(黄凯),Liang Liang(梁亮),Li Dan(李丹),et al.Study on nonionic self-emulsifying waterborne epoxy emulsion[J].Paint&Coatings Industry(涂料工业),2010,40(9):53-57.
[43]Xiong Yuanqin(熊远钦),Deng Hongxia(邓红霞),Peng Hua(彭桦),et al.Synthesis of a waterborne epoxy curing agent and its properties[J].Journal of Hunan University(Natural Sciences),2009,36(11):53-56.
[44]Wang Feng(王丰),Liu Yali(刘娅莉),Xu Longgui(徐龙贵),et al.Research progress in waterborne epoxy coating curing agents[J].Paint&Coatings Industry(涂料工业),2004,(8):29-33,63.
[45]Kang Huihua(康惠花),Ma Shangquan(马尚权),Qian Rui(钱瑞).Research progress of waterborne epoxy resin curing agent[J].Shandong Chemical Industry(山东化工),2017,46(22):31-33.
[46]Wang Qing.Research progress in epoxy resin curing agents[J].Tianjin Chemical Industry(天津化工),2001,(6):12-14.
[47]Stark C J,Stark A B A E,Back G E,et al.Epoxy-functional amidoamine reacted with excess polyamine and monoepoxy as epoxy curative:US6277928[P].2001-08-21.
[48]Deng Hongxia(邓红霞).Synthesis and study on the property of a curing agent for room temperature curing of a aqueous epoxy resin emulsion[D].Changsha:Hunan University(湖南大学),2009.
[49]Liu Xiaofang(刘晓芳),Wang Rongwei(王荣威),Wei Ming(魏铭),et al.Study on preparation,properties and curing mechanism of nonionic self-emulsified waterborne epoxy curing agent[J].Coating industry(涂料工业),2017,47(5):44-50.
[50]Xiao Shuxin(肖淑欣),Jiang Xiaoqin(姜晓琴),Liu Xinhao(刘新浩),et al.Preparation of waterborne epoxy resin curing agentandits compatibility with emulsion[J].Coating industry(涂料工业),2018,48(3):1-5.