负载缓蚀剂的有机—无机杂化材料的制备
摘要
有机-无机杂化材料的制备通常是通过溶胶-凝胶法将金属(如Si、Ti、Zr等)烷氧基引入到高分子聚合物链中，起到综合有机和无机化合物优势的作用，这种有机无机杂化材料具有优异的力学性能，且耐老化性能好，适用于铁质文物的封护涂层。但是常规的出水、出土铁质文物基体内部都或多或少含有无机离子，且目前无法在不破坏铁质文物的前提下完全去除这些无机离子，有机无-机杂化涂层虽然能够防护外部环境中氧、水等对铁质文物造成的破坏却不能阻止其自身内部发生的腐蚀，因此需要在涂层材料中添加缓蚀剂进一步阻止文物内部发生的破坏。基于这种情况，本文将有机硅引入丙烯酸酯树脂中形成一个有机-无机杂化材料，并将缓蚀剂包封在二氧化硅微胶囊中，二者复配使用，以期达到较好保护文物的效果。
本文制备了一种负载缓蚀剂的有机-无机杂化材料。首先通过预乳化半连续种子乳液聚合法合成了有机硅/丙烯酸酯共聚乳液，研究了温度、引发剂投料方式及含量、乳化剂含量及复合乳化剂比、PH值等条件对聚合物乳液稳定性的影响，以及有机硅氧烷含量对聚合物乳液稳定性的影响。通过核磁氢谱~1H-NMR）和红外光谱（FT-IR）等方法表征了共聚物的结构。对比了有机硅改性丙烯酸酯乳液和纯丙烯酸酯乳液形成的聚合物膜的力学及热性能。
采用反相乳液聚合法制备了负载缓蚀剂的微胶囊，将水溶性缓蚀剂溶解在反相乳液的水相液滴中，利用四乙氧基硅烷（TEOS）在有水存在的条件下发生缩合反应的特点，在反相体系中形成一个由交联的二氧化硅包覆缓蚀剂水液滴的微胶囊。并通过扫描电镜-能谱（SEM-EDS）、扫描透射电镜-能谱（STEM-EDS）、等离子体发射光谱（ICP）等表征方法对缓蚀剂的包覆及释放进行了研究。
将负载缓蚀剂的微胶囊添加到有机硅改性丙烯酸酯聚合物乳液中，初步研究了所形成的复合乳液的力学性能及耐老化、耐腐蚀性能。
Organic-inorganic materials show excellent mechanical properties andgood aging resistance, in that, it could be used in the conservation of ironrelics. During the conservation of iron relics, coating materials are usuallyused as the barrier of moisture and oxygen. But for the excavated iron objects,great deal of salt deposited in the holes and cracks after many years burial.During the conservation, salt could not be eliminated thoroughly. The inneranion, especially Cl-1could immigrate to the surface of the object, and causecorrosion of the substrate by autocatalysis, which will result in the failure ofthe coating. As a result, introducing the corrosion inhibitor during theconservation of iron relics is indispensable. In this dissertation,organic-inorganic hybrid coating materials encapsulated with inhibitor wasprepared. Firstly, organosilicon was introduced into the polymerization ofacrylate to form copolymer. Secondly, corrosion inhibitor sodium tungstatewas encapsulated in the silica particles. Then the organic-inorganic materialsencapsulated with inhibitor was obtained by mixing the coating materials andthe silica particles.
Organosilicon/acrylate copolymer was prepared through semi-continuousseed emulsion polymerization. The polymerization conditions includingtemperature, the content of initiator, the content of emulsifier, pH value ofthe polymerization system and the content of organic siloxane were discussed.The chemical structure of the copolymer was characterized with~(1)H NMR andFT-IR. The mechanical properties and thermal properties were studied.Silica particles encapsulated with corrosion inhibitor sodium tungstate wassynthesized through reverse emulsion polymerization. In the emulsionpolymerization system, cyclohexane was used as dispersion medium, Span80and OP-10was used as emulsifier, TEOS was used as monomer, ammonia wasused as catalyst. The morpHology of the particles was characterized with SEM.The distribution of the corrosion inhibitor sodium tungstate was investigatedthrough Scanning Transmission Electron Microscope-X Ray EnergyDispersive Spectrometer (STEM-EDS). And the release of the corrosioninhibitor was studied by ICP.
Micro capsules loaded with inhibitor sodium tungstate was added into theorganosolicon and acrylate copolyer to form the hybrid coating materials. Andthe mechanical properties and corrosion resistance was studied preliminarily.
本文制备了一种负载缓蚀剂的有机-无机杂化材料。首先通过预乳化半连续种子乳液聚合法合成了有机硅/丙烯酸酯共聚乳液，研究了温度、引发剂投料方式及含量、乳化剂含量及复合乳化剂比、PH值等条件对聚合物乳液稳定性的影响，以及有机硅氧烷含量对聚合物乳液稳定性的影响。通过核磁氢谱~1H-NMR）和红外光谱（FT-IR）等方法表征了共聚物的结构。对比了有机硅改性丙烯酸酯乳液和纯丙烯酸酯乳液形成的聚合物膜的力学及热性能。
采用反相乳液聚合法制备了负载缓蚀剂的微胶囊，将水溶性缓蚀剂溶解在反相乳液的水相液滴中，利用四乙氧基硅烷（TEOS）在有水存在的条件下发生缩合反应的特点，在反相体系中形成一个由交联的二氧化硅包覆缓蚀剂水液滴的微胶囊。并通过扫描电镜-能谱（SEM-EDS）、扫描透射电镜-能谱（STEM-EDS）、等离子体发射光谱（ICP）等表征方法对缓蚀剂的包覆及释放进行了研究。
将负载缓蚀剂的微胶囊添加到有机硅改性丙烯酸酯聚合物乳液中，初步研究了所形成的复合乳液的力学性能及耐老化、耐腐蚀性能。
Organic-inorganic materials show excellent mechanical properties andgood aging resistance, in that, it could be used in the conservation of ironrelics. During the conservation of iron relics, coating materials are usuallyused as the barrier of moisture and oxygen. But for the excavated iron objects,great deal of salt deposited in the holes and cracks after many years burial.During the conservation, salt could not be eliminated thoroughly. The inneranion, especially Cl-1could immigrate to the surface of the object, and causecorrosion of the substrate by autocatalysis, which will result in the failure ofthe coating. As a result, introducing the corrosion inhibitor during theconservation of iron relics is indispensable. In this dissertation,organic-inorganic hybrid coating materials encapsulated with inhibitor wasprepared. Firstly, organosilicon was introduced into the polymerization ofacrylate to form copolymer. Secondly, corrosion inhibitor sodium tungstatewas encapsulated in the silica particles. Then the organic-inorganic materialsencapsulated with inhibitor was obtained by mixing the coating materials andthe silica particles.
Organosilicon/acrylate copolymer was prepared through semi-continuousseed emulsion polymerization. The polymerization conditions includingtemperature, the content of initiator, the content of emulsifier, pH value ofthe polymerization system and the content of organic siloxane were discussed.The chemical structure of the copolymer was characterized with~(1)H NMR andFT-IR. The mechanical properties and thermal properties were studied.Silica particles encapsulated with corrosion inhibitor sodium tungstate wassynthesized through reverse emulsion polymerization. In the emulsionpolymerization system, cyclohexane was used as dispersion medium, Span80and OP-10was used as emulsifier, TEOS was used as monomer, ammonia wasused as catalyst. The morpHology of the particles was characterized with SEM.The distribution of the corrosion inhibitor sodium tungstate was investigatedthrough Scanning Transmission Electron Microscope-X Ray EnergyDispersive Spectrometer (STEM-EDS). And the release of the corrosioninhibitor was studied by ICP.
Micro capsules loaded with inhibitor sodium tungstate was added into theorganosolicon and acrylate copolyer to form the hybrid coating materials. Andthe mechanical properties and corrosion resistance was studied preliminarily.
引文
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