聚酰亚胺—无机物杂化节能玻璃贴膜的制备及性能研究
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摘要
用节能玻璃贴膜对既有建筑进行改造,是目前我国建筑领域节能降耗所采用的主要措施之一。发达国家玻璃贴膜的市场普及率通常在75%以上,而我国仅在北京、上海、广州等城市的部分建筑中推广使用,普及率极低,市场还被国外品牌如美国3M、CPF(龙膜)等垄断。本论文旨在开发一种具有自主知识产权的有机-无机杂化薄膜材料,将其应用玻璃贴膜领域,发挥节能作用。
本文选用具有良好光学性能、热稳定性能的聚酰亚胺(PI)为薄膜的有机相主体,掺杂SiO2、ZnO、Al2O3等无机组分,经热亚胺化制备出PI／SiO2、PI／ZnO、PI／Al2O3杂化薄膜材料。以紫外-可见光透过率为标准,筛选出SiO2为性能最佳的无机相掺杂物。实验结果表明：影响聚酰胺酸(PAA)溶胶粘度的因素包括反应温度、单体摩尔比、陈化时间等,镀膜质量最佳的粘度范围为85～122mPa·s,溶胶体系陈化24h后粘度趋于稳定。影响PI／SiO2杂化薄膜透光率的主要因素为Si02添加量、单体摩尔比、偶联剂加入量。优化的PI／SiO2杂化薄膜制备工艺参数为Si02添加量5%,单体摩尔比(ODA：PMDA)0.95：1,偶联剂添加量为1：25。
PI／SiO2杂化薄膜的透光性、隔热性、热稳定性、微观形貌及其结构分析结果表明：PI／SiO2杂化玻璃贴膜在可见光区、紫外光区的平均透光率分别为85.6%、12.9%；镀有PI／SiO2杂化薄膜的玻璃片所在的暗室,比未镀膜玻璃片所在暗室温度低3.5℃,采用GB／T2680-94中的方法,对窗墙比为0.22的建筑进行预测,使用镀膜玻璃后遮阳系数降低,总传热系数减小,传入室内的热量由34.67w／m2降至23.60 w／m2；掺杂Si02后杂化薄膜的热稳定性比纯PI提高,失重5%的温度由520℃提高到544℃；无机相在有机相中分散均匀,两相间结合紧密,过渡自然；热亚胺化处理后,形成了酰亚胺环状结构,初步分析认为偶联剂γ-氨丙基三乙氧基硅烷以氢键结构连接在无机相和有机相之间。
The energy saving reconstruction of existing buildings is an important measure in our country. In which energy-saving films were pated on the window glasses. In developed countries, the popularization rate of energy-saving films is more than 75%. However, the films are only used in Beijing, Shanghai, Guangzhou and other major cities in our nation, as well as the market is monopolized by the foreign brands, such as the United states 3M, CPF (Long membrane) and other monopolistic brands. In this dissertation, the author aims to develop an organic-inorganic hybrid materials with independent intellectual property. With a view to the application of this hybrid materials in the film posting field, playing an important role in energy conservation.
In this dissertation, the polyimide materials was selected for the organic main phase of the films, owing to its excellent optical properties and thermal stability properties. The hybrid sol was prepared by doping inorganic components such as SiO2, ZnO, Al2O3 to the organic phases. After the thermal imidization, the polyimide/SiO2, polyimide/ZnO, polyimide/Al2O3 were obtained. As a standard of uv-visible light transmittance, SiO2 was chosen as the optimal inorganic phase dopants. The effect of PAA sol viscosity factors include reaction temperature, monomer molar ratio and aging time.The viscosity of best coating quality was at the range of 85～122mPa·s, and the sol systems was stabilized after aging 24h.The effect of the light transmission rate factors were:the addition amount of SiO2, monomer molar ratio and the addition amount of coupling agent. The optimization process of PI/SiO2 hybrid films preparation was:the addition amount of SiO2 5%, the monomer molar ratio (ODA:PMDA) 0.95:1, coupling agent addition amount 1:25.
The analysis for the transmittance of PI/SiO2 hybrid films, insulation, thermal stability, microstructure and structural showed that:the average light transmission rate of PI/SiO2 hybrid films in the visible district and ultraviolet district, was 85.6% and 12.9%.Compared with the darkroom without coating glass, the temperature of darkroom whose glass coated PI/SiO2 hybrid films was lower 3.5℃. According to technique of GB/T2680-94,as an example of a building whose window-wall ratio was 0.22, pasted films, its shading coefficient and total heat transfer coefficient decreased. The incoming heat was reduced from 34.67w/m2 to 23.60 w/m2.The thermal stability of PI was improved after doped SiO2, compared with PI, the PI/SiO2 temperature of loss 5% weight raised from 520℃to 544℃.The inorganic phase uniformly dispersed in the organic phase, two phases are linked closely. Preliminary analysis showed that:Imide ring structure was formed by thermal imidization treatment, the coupling agentγ-aminopropyl triethoxysilane connection between the inorganic phase and organic phase by hydrogen bond structure.
本文选用具有良好光学性能、热稳定性能的聚酰亚胺(PI)为薄膜的有机相主体,掺杂SiO2、ZnO、Al2O3等无机组分,经热亚胺化制备出PI／SiO2、PI／ZnO、PI／Al2O3杂化薄膜材料。以紫外-可见光透过率为标准,筛选出SiO2为性能最佳的无机相掺杂物。实验结果表明：影响聚酰胺酸(PAA)溶胶粘度的因素包括反应温度、单体摩尔比、陈化时间等,镀膜质量最佳的粘度范围为85～122mPa·s,溶胶体系陈化24h后粘度趋于稳定。影响PI／SiO2杂化薄膜透光率的主要因素为Si02添加量、单体摩尔比、偶联剂加入量。优化的PI／SiO2杂化薄膜制备工艺参数为Si02添加量5%,单体摩尔比(ODA：PMDA)0.95：1,偶联剂添加量为1：25。
PI／SiO2杂化薄膜的透光性、隔热性、热稳定性、微观形貌及其结构分析结果表明：PI／SiO2杂化玻璃贴膜在可见光区、紫外光区的平均透光率分别为85.6%、12.9%；镀有PI／SiO2杂化薄膜的玻璃片所在的暗室,比未镀膜玻璃片所在暗室温度低3.5℃,采用GB／T2680-94中的方法,对窗墙比为0.22的建筑进行预测,使用镀膜玻璃后遮阳系数降低,总传热系数减小,传入室内的热量由34.67w／m2降至23.60 w／m2；掺杂Si02后杂化薄膜的热稳定性比纯PI提高,失重5%的温度由520℃提高到544℃；无机相在有机相中分散均匀,两相间结合紧密,过渡自然；热亚胺化处理后,形成了酰亚胺环状结构,初步分析认为偶联剂γ-氨丙基三乙氧基硅烷以氢键结构连接在无机相和有机相之间。
The energy saving reconstruction of existing buildings is an important measure in our country. In which energy-saving films were pated on the window glasses. In developed countries, the popularization rate of energy-saving films is more than 75%. However, the films are only used in Beijing, Shanghai, Guangzhou and other major cities in our nation, as well as the market is monopolized by the foreign brands, such as the United states 3M, CPF (Long membrane) and other monopolistic brands. In this dissertation, the author aims to develop an organic-inorganic hybrid materials with independent intellectual property. With a view to the application of this hybrid materials in the film posting field, playing an important role in energy conservation.
In this dissertation, the polyimide materials was selected for the organic main phase of the films, owing to its excellent optical properties and thermal stability properties. The hybrid sol was prepared by doping inorganic components such as SiO2, ZnO, Al2O3 to the organic phases. After the thermal imidization, the polyimide/SiO2, polyimide/ZnO, polyimide/Al2O3 were obtained. As a standard of uv-visible light transmittance, SiO2 was chosen as the optimal inorganic phase dopants. The effect of PAA sol viscosity factors include reaction temperature, monomer molar ratio and aging time.The viscosity of best coating quality was at the range of 85～122mPa·s, and the sol systems was stabilized after aging 24h.The effect of the light transmission rate factors were:the addition amount of SiO2, monomer molar ratio and the addition amount of coupling agent. The optimization process of PI/SiO2 hybrid films preparation was:the addition amount of SiO2 5%, the monomer molar ratio (ODA:PMDA) 0.95:1, coupling agent addition amount 1:25.
The analysis for the transmittance of PI/SiO2 hybrid films, insulation, thermal stability, microstructure and structural showed that:the average light transmission rate of PI/SiO2 hybrid films in the visible district and ultraviolet district, was 85.6% and 12.9%.Compared with the darkroom without coating glass, the temperature of darkroom whose glass coated PI/SiO2 hybrid films was lower 3.5℃. According to technique of GB/T2680-94,as an example of a building whose window-wall ratio was 0.22, pasted films, its shading coefficient and total heat transfer coefficient decreased. The incoming heat was reduced from 34.67w/m2 to 23.60 w/m2.The thermal stability of PI was improved after doped SiO2, compared with PI, the PI/SiO2 temperature of loss 5% weight raised from 520℃to 544℃.The inorganic phase uniformly dispersed in the organic phase, two phases are linked closely. Preliminary analysis showed that:Imide ring structure was formed by thermal imidization treatment, the coupling agentγ-aminopropyl triethoxysilane connection between the inorganic phase and organic phase by hydrogen bond structure.
引文
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