水性环氧改性丙烯酸红外热屏蔽涂层材料的研究
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摘要
本项课题基于国内外装备、石油化工、城市基础建设用防腐、降温、节能涂层材料的研究及应用状况,吸取国内外先进研究经验,开发利用国内外新型功能性材料,综合利用材料科学、有机化学、无机化学、物理化学、光学、热学等多门科学知识,由基础理论研究与应用研究相结合,研究出迷彩色水性环氧-改性丙烯酸红外热屏蔽涂层材料。
首先采用半连续种子乳液聚合技术合成出红外热屏蔽结构涂层材料的成膜物—水性环氧—丙烯酸酯杂化乳液。试验结果表明:环氧树脂的滴加顺序直接影响乳液的性能,在第一阶段逐渐加入丙烯酸、苯乙烯单体,第二阶段加入环氧树脂,杂化乳液性能最佳。复合乳化剂用量增加,乳液粒径减小;引发剂和环氧树脂用量的增加,均导致粒径呈增大的趋势。最佳种子乳液用量为20-30%,最佳搅拌强度为180rpm,最佳聚合温度为80℃。所得乳液VOC低、干燥速度快,硬度大、耐腐蚀性好。
通过FT-IR、GPC、UV-Vis测试,证明环氧树脂与丙烯酸-苯乙烯发生了接枝反应。用PH1.5 PTA对MMA/EP、EP/MMA结构乳胶粒和不同环氧树脂含量的环氧-丙烯酸乳胶粒染色,TEM测试结果表明pH1.5 PTA能对环氧树脂染色,环氧-丙烯酸乳胶粒为以丙烯酸为核、环氧树脂为壳的结构,且丙烯酸核层以中心球或偏心球的形式位于环氧树脂壳层内。
制备了DAAM参与聚合的含有酮羰基的环氧—丙烯酸乳液,向其中加入己二酸二酰肼(ADH),制得可以室温交联的水乳液。对涂膜固化过程的FTIR和TEM分析表明,乳液成膜时酮羰基与肼发生了交联反应。对DAAM与ADH反应条件的探索及乳液固化过程模拟的FTIR表明,酮羰基与肼发生反应的最佳条件为体系呈弱酸性或碱性。
通过对乳液性能影响因素的研究,工艺条件的优化,制备出几种玻璃化温度不同的乳液,利用玻璃化温度为10.6℃的杂化乳液做红外热屏蔽涂层材料的成膜物。其物理化学性能均满足红外热屏蔽涂层材料的指标要求。
第二、本课题以高效降温为目标,以环保长效为宗旨,以性价比优良、具有实际应用价值为出发点,研究了涂层的热反射、热发射和热阻隔和光催化降温机理。设计了热屏蔽涂层的涂层结构。通过对不同阻热材料的阻热性能及其协效性的研究、制备工艺研究、涂层的微观结构表征,制备出了导热系数为0.114w/m.k、具有良好防腐性能的防腐隔热底涂。
通过研究颜填料的种类、形状、大小、粒径分布、与基料数量的相对多少和多种功能性材料的配合使用等对涂层的反射率和发射率的影响。揭示了涂层材料的降温性能与涂层材料的关系。针对目前国内对降温涂层材料研究存在的问题,本课题对深色(迷彩)涂层的降温效果进行了研究,对多种彩色颜料的反射率进行测试,建立相应的小型数据库,从而在此平台上合理的选择反射材料,制备出了反射率为:驼灰色80%,军绿色72%,墨绿色68%,辐射率皆为93%的热反射与热辐射面涂,同时也为相关领域的研究者提供了参考依据。
通过热反射、热辐射、热阻隔、光催化剂降温机理及协效性,制备工艺的研究,模拟试验与实际应用效果研究,制备出了迷彩色水性环氧-改性丙烯酸红外热屏蔽涂层材料。此涂层材料可使被涂封闭物内部的温度降低5-10℃,表面的温度可降低12-15℃。
Based on the researches and applications of antiseptic,cooling,energy saving coatings used in arming,petrochemical industry and urban construction,some novel functional materials ware used to obtain a kind of camouflage color infrared heat shielding coating of water-based epoxy-modified acrylic acid by utilizing multidisciplinary knowledge such as material science,organic chemistry,inorganic chemistry,physic chemistry,optics and calorifics etc.and absorbing advanced research experience at home and abroad.
The film forming matter of water-based epoxy-acrylic ester hybrid emulsion was fist prepared by semicontinuous seed emulsion polymerization for the infrared heat shielding coating.The test results showed that the addition order of epoxy resin directly influenced the properties of emulsion,optimum of which was obtained by the following process:the monomers of acrylic acid and styrene were gradually added in the first step and epoxy resin was added in the second step.The particle size was reduced with the increase of hybrid emulsifier content while it increased as the increase of initiator and epoxy resin content.The optimum seed emulsion content,stirring speed and polymerization temperature respectively was 20-30%, 180rpm and 80℃,by which an emulsion with low VOC,fast dry speed,high hardness and good corrosion resistance was obtained.
The graft reaction between epoxy resin and acrylic acid-styrene was proved by FT-IR、GPC、UV-Vis tests.TEM results showed that pH1.5 PTA could dye epoxy resin after the latex particles of MMA/EP、EP/MMA and epoxy-acrylic acid with different epoxy resin content were dyed by pH1.5 PTA.The latex particles of epoxy-acrylic acid presented a structure of acrylic acid as the core and epoxy resin as the shell,where the acrylic acid core located in the epoxy resin shell as central ball or eccentric ball.
The emulsion of epoxy-acrylic acid with ketene group polymerized with DAAM was prepared first,ADH was then added and a water-based emulsion cross linked at room temperature was obtained.FTIR and TEM showed that crosslink reaction occurred between ketone group and hydrazine during emulsion forming film.The optimum reaction condition for ketone and hydrazine was slightly acidic or alkaline,which was proved by FTIR based on the simulation of emulsion solidifying.
Several kinds of emulsion with various glass transition temperatures were prepared based on the investigation for the effect factors of emulsion properties and technique conditions.The hybrid emulsion with Tg of 10.6℃was used to be the film forming matter for infrared heat shielding coating.Its physical and chemical properties all met the requirements of infrared heat shielding coating.
The heat reflective,thermal emission,heat insulation and photocatalytic cooling mechanism were investigated with purpose of effective cooling,friendly environment and excellent property/cost ratio.The coating structure of heat shielding coating was designed.A kind of bottom coating with thermal conductivity of 0.114w/m.k and good heat insulation and corrosion resistance was obtained by investigating and characterizing the heat insulation property and coating microstructure.
The relationship between cooling properties and coating was explored by investigating the effect of sort,shape,size,particle distribution and ratio in matrix of pigment fillers on the reflectivity and emissivity of coatings.The cooling effect of dark or camouflage color coatings and the reflectivity of various color pigments were tested to establish a data bank,from which a good reflective material was chosen and a serial of face coatings with radiance of 93%and camel gray reflectivity of 80%,army green reflectivity of 72%and dark green reflectivity of 68%were obtained.This could be a good reference for further research.
A kind of heat shielding coating of camouflage color water-based epoxy-modified acrylic acid was prepared based on the investigation of heat reflectivity,heat radiance,heat insulation and photocatalytic cooling mechanism and their cooperative action and the simulation of the real application.This coating could cool down 5-10℃for the inner temperature and 12-15℃for the exterior temperature of the coated substance.
首先采用半连续种子乳液聚合技术合成出红外热屏蔽结构涂层材料的成膜物—水性环氧—丙烯酸酯杂化乳液。试验结果表明:环氧树脂的滴加顺序直接影响乳液的性能,在第一阶段逐渐加入丙烯酸、苯乙烯单体,第二阶段加入环氧树脂,杂化乳液性能最佳。复合乳化剂用量增加,乳液粒径减小;引发剂和环氧树脂用量的增加,均导致粒径呈增大的趋势。最佳种子乳液用量为20-30%,最佳搅拌强度为180rpm,最佳聚合温度为80℃。所得乳液VOC低、干燥速度快,硬度大、耐腐蚀性好。
通过FT-IR、GPC、UV-Vis测试,证明环氧树脂与丙烯酸-苯乙烯发生了接枝反应。用PH1.5 PTA对MMA/EP、EP/MMA结构乳胶粒和不同环氧树脂含量的环氧-丙烯酸乳胶粒染色,TEM测试结果表明pH1.5 PTA能对环氧树脂染色,环氧-丙烯酸乳胶粒为以丙烯酸为核、环氧树脂为壳的结构,且丙烯酸核层以中心球或偏心球的形式位于环氧树脂壳层内。
制备了DAAM参与聚合的含有酮羰基的环氧—丙烯酸乳液,向其中加入己二酸二酰肼(ADH),制得可以室温交联的水乳液。对涂膜固化过程的FTIR和TEM分析表明,乳液成膜时酮羰基与肼发生了交联反应。对DAAM与ADH反应条件的探索及乳液固化过程模拟的FTIR表明,酮羰基与肼发生反应的最佳条件为体系呈弱酸性或碱性。
通过对乳液性能影响因素的研究,工艺条件的优化,制备出几种玻璃化温度不同的乳液,利用玻璃化温度为10.6℃的杂化乳液做红外热屏蔽涂层材料的成膜物。其物理化学性能均满足红外热屏蔽涂层材料的指标要求。
第二、本课题以高效降温为目标,以环保长效为宗旨,以性价比优良、具有实际应用价值为出发点,研究了涂层的热反射、热发射和热阻隔和光催化降温机理。设计了热屏蔽涂层的涂层结构。通过对不同阻热材料的阻热性能及其协效性的研究、制备工艺研究、涂层的微观结构表征,制备出了导热系数为0.114w/m.k、具有良好防腐性能的防腐隔热底涂。
通过研究颜填料的种类、形状、大小、粒径分布、与基料数量的相对多少和多种功能性材料的配合使用等对涂层的反射率和发射率的影响。揭示了涂层材料的降温性能与涂层材料的关系。针对目前国内对降温涂层材料研究存在的问题,本课题对深色(迷彩)涂层的降温效果进行了研究,对多种彩色颜料的反射率进行测试,建立相应的小型数据库,从而在此平台上合理的选择反射材料,制备出了反射率为:驼灰色80%,军绿色72%,墨绿色68%,辐射率皆为93%的热反射与热辐射面涂,同时也为相关领域的研究者提供了参考依据。
通过热反射、热辐射、热阻隔、光催化剂降温机理及协效性,制备工艺的研究,模拟试验与实际应用效果研究,制备出了迷彩色水性环氧-改性丙烯酸红外热屏蔽涂层材料。此涂层材料可使被涂封闭物内部的温度降低5-10℃,表面的温度可降低12-15℃。
Based on the researches and applications of antiseptic,cooling,energy saving coatings used in arming,petrochemical industry and urban construction,some novel functional materials ware used to obtain a kind of camouflage color infrared heat shielding coating of water-based epoxy-modified acrylic acid by utilizing multidisciplinary knowledge such as material science,organic chemistry,inorganic chemistry,physic chemistry,optics and calorifics etc.and absorbing advanced research experience at home and abroad.
The film forming matter of water-based epoxy-acrylic ester hybrid emulsion was fist prepared by semicontinuous seed emulsion polymerization for the infrared heat shielding coating.The test results showed that the addition order of epoxy resin directly influenced the properties of emulsion,optimum of which was obtained by the following process:the monomers of acrylic acid and styrene were gradually added in the first step and epoxy resin was added in the second step.The particle size was reduced with the increase of hybrid emulsifier content while it increased as the increase of initiator and epoxy resin content.The optimum seed emulsion content,stirring speed and polymerization temperature respectively was 20-30%, 180rpm and 80℃,by which an emulsion with low VOC,fast dry speed,high hardness and good corrosion resistance was obtained.
The graft reaction between epoxy resin and acrylic acid-styrene was proved by FT-IR、GPC、UV-Vis tests.TEM results showed that pH1.5 PTA could dye epoxy resin after the latex particles of MMA/EP、EP/MMA and epoxy-acrylic acid with different epoxy resin content were dyed by pH1.5 PTA.The latex particles of epoxy-acrylic acid presented a structure of acrylic acid as the core and epoxy resin as the shell,where the acrylic acid core located in the epoxy resin shell as central ball or eccentric ball.
The emulsion of epoxy-acrylic acid with ketene group polymerized with DAAM was prepared first,ADH was then added and a water-based emulsion cross linked at room temperature was obtained.FTIR and TEM showed that crosslink reaction occurred between ketone group and hydrazine during emulsion forming film.The optimum reaction condition for ketone and hydrazine was slightly acidic or alkaline,which was proved by FTIR based on the simulation of emulsion solidifying.
Several kinds of emulsion with various glass transition temperatures were prepared based on the investigation for the effect factors of emulsion properties and technique conditions.The hybrid emulsion with Tg of 10.6℃was used to be the film forming matter for infrared heat shielding coating.Its physical and chemical properties all met the requirements of infrared heat shielding coating.
The heat reflective,thermal emission,heat insulation and photocatalytic cooling mechanism were investigated with purpose of effective cooling,friendly environment and excellent property/cost ratio.The coating structure of heat shielding coating was designed.A kind of bottom coating with thermal conductivity of 0.114w/m.k and good heat insulation and corrosion resistance was obtained by investigating and characterizing the heat insulation property and coating microstructure.
The relationship between cooling properties and coating was explored by investigating the effect of sort,shape,size,particle distribution and ratio in matrix of pigment fillers on the reflectivity and emissivity of coatings.The cooling effect of dark or camouflage color coatings and the reflectivity of various color pigments were tested to establish a data bank,from which a good reflective material was chosen and a serial of face coatings with radiance of 93%and camel gray reflectivity of 80%,army green reflectivity of 72%and dark green reflectivity of 68%were obtained.This could be a good reference for further research.
A kind of heat shielding coating of camouflage color water-based epoxy-modified acrylic acid was prepared based on the investigation of heat reflectivity,heat radiance,heat insulation and photocatalytic cooling mechanism and their cooperative action and the simulation of the real application.This coating could cool down 5-10℃for the inner temperature and 12-15℃for the exterior temperature of the coated substance.
引文
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