二氧化钛/聚氨酯紫外光屏蔽涂层的制备
摘要
目前,有机-无机纳米复合材料是材料领域的研究热点,而在涂料与胶粘剂领域中,由于一些无机纳米材料如二氧化钛,二氧化硅的特殊性质,因此对其与聚合物的复合以及复合材料的性能研究更是吸引了诸多研究人员的注意。
本论文主要研究了二氧化钛/聚氨酯紫外屏蔽涂层材料的制备,以及二氧化硅增强聚醚胶粘剂的制备,并详细探讨了制备方法、实验条件对材料结构和性能的影响。
(1)通过溶胶-凝胶法制备了二氧化钛乙醇溶胶以及二氧化钛-二氧化硅复合乙醇溶胶。在制备二氧化钛溶胶的过程中,首先通过乙酰丙酮对钛酸四正丁酯进行螯合处理,得到改性的有机钛前驱体,再在酸催化条件下制备透明二氧化钛溶胶。而在制备二氧化硅-二氧化钛复合溶胶的过程中,先在酸催化条件下于乙醇介质中制备了酸性二氧化硅溶胶,随后以乙酰丙酮螯合的钛酸四正丁酯作为二氧化钛前驱体,加入到酸性硅溶胶中,通过水解缩合反应以及硅烷偶联剂的作用,制备二氧化钛-二氧化硅复合溶胶。将所得的溶胶与聚氨酯水性分散体机械共混后,使用线棒制得透明的紫外屏蔽涂层。通过紫外可见光谱,紫外加速老化仪等考察了复合涂层的紫外吸收性能,同时考察了二氧化硅改性对涂层耐候性的提高作用。此外,为了进一步扩大复合溶胶的紫外屏蔽范围,进一步复合了二氧化铈的乙醇分散体,得到了性能更为优越的紫外屏蔽涂料。
(2)采用了细乳液结合溶胶-凝胶的方法得到以水相作为连续相的TiO_2-SiO_2紫外屏蔽剂。在制备过程中,首先通过超声细乳化过程制备了水包油的细乳液。该细乳液滴是由乙酰丙酮螯合后的钛酸正丁酯与二甲苯组成的。随后,再通过氨基硅烷和正硅酸乙酯的水解缩合直接在O/W乳液中包覆细乳液滴。与此同时,在水油界面上的TBT也开始水解,从而在油滴内部引发溶胶-凝胶反应,这样,便得到复合的胶体粒子。论文通过透射电子显微镜,表面元素分析,电子能谱等手段研究复合微球的元素组成,同时,考察了制备条件(如温度,油相组成,氨基硅烷用量等)对胶体粒子形貌的影响。并且,本论文通过紫外可见光谱以及染料底材光敏实验验证了紫外屏蔽涂层的有效性。
(3)通过不同二氧化硅源(正硅酸乙酯,二氧化硅溶胶以及气相法二氧化硅粉体)的复配得到了具有较高剪切强度的水性硅烷化聚醚胶粘剂。通过扫描电子显微镜和电子拉力机系统研究了二氧化硅含量以及种类对胶粘剂剪切强度的影响,并讨论了不同二氧化硅源对胶粘剂的增强机理。胶体二氧化硅粒子虽然不能显著地提高胶粘剂的剪切强度,但可以改善气相法二氧化硅粉体在胶粘剂中的分散性。三种不同表面性质的气相法二氧化硅粉体的应用研究表明,具有中等疏水程度的二氧化硅粉体对胶粘剂的增强效果最佳。研究表明,在复合水性胶粘剂中,正硅酸乙酯,二氧化硅溶胶以及气相法二氧化硅分别起着交联剂(与硅氧烷封端的聚合物链),助分散剂(气相法二氧化硅的分散)以及增强的效果。
Nowadays, inorganic-organic hybrid materials are becoming the hotspot in materials research, especially in coating and adhesive field. Because of the unique properties possessed by inorganic nano-materials, like silica and titania, the hybrid materials consisted of polymer and these inorganic nano-materials ulteriorly attracted the attention of researchers.
In this paper, the preparation of titania/polyurethane UV blocking coating and the preparation of nano-silica reinforced ether adhesive were discussed. Also, the effects of preparation methods and experiment conditions on the structure and performance of materials were investigated.
(1) Ethanol-based titania sol and titania-silica hybrid sol have been synthesized in this study. During the process to acquire titania sol, acetylacetone was used to chelate with tetrabutylorthotitanate, which led to modified organic titania precursor. Subsequently, transparent sol was obtained under acid-catalyzed condition. The preparation of silica-titania hybrid sol was based on this protocol. In order to get hybrid sol, acidic silica sol was prepared first with the catalysis effect of acid. Then, acetylacetone chelated tetrabutylorthotitanate was added into silica sol. Through hydrolysis and condensation process and the effect of silane, silica-titania hybrid was obtained. After mechanic mixing of sols with water-borne polyurethane dispersion, UV-blocking coating was acquired. Transparent UV-blocking films could be prepared by rods. UV-vis spectra and accelerated weathering tester were utilized to investigate the UV-blocking performance of the hybrid coatings. At the same time, the modification effect of silica on the weathering property of the films was also studied. Moreover, in order to extend the UV-shielding range, cerium oxide ethanol dispersion was doped into the silica-titania sol, through which coatings with better UV-blocking performance were obtained.
(2) A novel and facile miniemulsion-combined sol-gel process to fabricate water-borne UV-blocking additive was also presented. In this approach, the oil phase composed of acetylacetone(Acac) modified titanium (IV) butoxide (TBT)、dimethyl benzene(DB) and hexadecane(HD) were confined in the miniemulsion droplet microreactors with the aid of a cationic emulfier hexadecyltrimethylammonium bromide(CTAB). Then, a silica layer was coated onto the miniemulsion droplets by the co-condensation of amino-silane and tetraethyl silicate (TEOS). At the same time, TBT in the miniemulsion droplets diffused to the O/W interface and then initiated the sol-gel reaction, hence TiO_2-SiO_2 hybrid colloids were obtained. TEM、FTIR、EDX and XPS methods were utilized to investigate the structure of as-prepared hybrids Some influencing parameters, such as the concentrations of TBT in the oil droplet, the content of amino silane in the silica precursor, etc., on the morphology of the hybrid colloids were investigated. UV-visible spectra and dye degradation experiments showed that the polyurethane films doped with these hybrid colloids had a very good UV-blocking property.
(3) Nanosilica reinforced waterborne silylated polyether adhesives were prepared with silylated polyether emulsion, tetraethyl orthosilicate (TEOS), silica sol and fumed silica powder. Effects of TEOS content, silica sol content and the type and content of fumed silica on the shear strength of the adhesive and their strengthening mechanisms were investigated using a scanning electronic microscope and an electronic instron tester. Colloidal silica particles was less efficient than fumed silica particles for reinforcing the polyether adhesive but can increase the shear strength of fumed silica embedded adhesive. Comparing the adhesives with the hydrophilic fumed silica or the extremely hydrophobic fumed silica, the adhesive with moderate hydrophobic fumed silica had the highest shear strength. It seemed that TEOS, silica sol and fumed silica played crosslinking (with polyether chain), dispersing (for fumed silica) and reinforcing roles on waterborne adhesive, respectively.
本论文主要研究了二氧化钛/聚氨酯紫外屏蔽涂层材料的制备,以及二氧化硅增强聚醚胶粘剂的制备,并详细探讨了制备方法、实验条件对材料结构和性能的影响。
(1)通过溶胶-凝胶法制备了二氧化钛乙醇溶胶以及二氧化钛-二氧化硅复合乙醇溶胶。在制备二氧化钛溶胶的过程中,首先通过乙酰丙酮对钛酸四正丁酯进行螯合处理,得到改性的有机钛前驱体,再在酸催化条件下制备透明二氧化钛溶胶。而在制备二氧化硅-二氧化钛复合溶胶的过程中,先在酸催化条件下于乙醇介质中制备了酸性二氧化硅溶胶,随后以乙酰丙酮螯合的钛酸四正丁酯作为二氧化钛前驱体,加入到酸性硅溶胶中,通过水解缩合反应以及硅烷偶联剂的作用,制备二氧化钛-二氧化硅复合溶胶。将所得的溶胶与聚氨酯水性分散体机械共混后,使用线棒制得透明的紫外屏蔽涂层。通过紫外可见光谱,紫外加速老化仪等考察了复合涂层的紫外吸收性能,同时考察了二氧化硅改性对涂层耐候性的提高作用。此外,为了进一步扩大复合溶胶的紫外屏蔽范围,进一步复合了二氧化铈的乙醇分散体,得到了性能更为优越的紫外屏蔽涂料。
(2)采用了细乳液结合溶胶-凝胶的方法得到以水相作为连续相的TiO_2-SiO_2紫外屏蔽剂。在制备过程中,首先通过超声细乳化过程制备了水包油的细乳液。该细乳液滴是由乙酰丙酮螯合后的钛酸正丁酯与二甲苯组成的。随后,再通过氨基硅烷和正硅酸乙酯的水解缩合直接在O/W乳液中包覆细乳液滴。与此同时,在水油界面上的TBT也开始水解,从而在油滴内部引发溶胶-凝胶反应,这样,便得到复合的胶体粒子。论文通过透射电子显微镜,表面元素分析,电子能谱等手段研究复合微球的元素组成,同时,考察了制备条件(如温度,油相组成,氨基硅烷用量等)对胶体粒子形貌的影响。并且,本论文通过紫外可见光谱以及染料底材光敏实验验证了紫外屏蔽涂层的有效性。
(3)通过不同二氧化硅源(正硅酸乙酯,二氧化硅溶胶以及气相法二氧化硅粉体)的复配得到了具有较高剪切强度的水性硅烷化聚醚胶粘剂。通过扫描电子显微镜和电子拉力机系统研究了二氧化硅含量以及种类对胶粘剂剪切强度的影响,并讨论了不同二氧化硅源对胶粘剂的增强机理。胶体二氧化硅粒子虽然不能显著地提高胶粘剂的剪切强度,但可以改善气相法二氧化硅粉体在胶粘剂中的分散性。三种不同表面性质的气相法二氧化硅粉体的应用研究表明,具有中等疏水程度的二氧化硅粉体对胶粘剂的增强效果最佳。研究表明,在复合水性胶粘剂中,正硅酸乙酯,二氧化硅溶胶以及气相法二氧化硅分别起着交联剂(与硅氧烷封端的聚合物链),助分散剂(气相法二氧化硅的分散)以及增强的效果。
Nowadays, inorganic-organic hybrid materials are becoming the hotspot in materials research, especially in coating and adhesive field. Because of the unique properties possessed by inorganic nano-materials, like silica and titania, the hybrid materials consisted of polymer and these inorganic nano-materials ulteriorly attracted the attention of researchers.
In this paper, the preparation of titania/polyurethane UV blocking coating and the preparation of nano-silica reinforced ether adhesive were discussed. Also, the effects of preparation methods and experiment conditions on the structure and performance of materials were investigated.
(1) Ethanol-based titania sol and titania-silica hybrid sol have been synthesized in this study. During the process to acquire titania sol, acetylacetone was used to chelate with tetrabutylorthotitanate, which led to modified organic titania precursor. Subsequently, transparent sol was obtained under acid-catalyzed condition. The preparation of silica-titania hybrid sol was based on this protocol. In order to get hybrid sol, acidic silica sol was prepared first with the catalysis effect of acid. Then, acetylacetone chelated tetrabutylorthotitanate was added into silica sol. Through hydrolysis and condensation process and the effect of silane, silica-titania hybrid was obtained. After mechanic mixing of sols with water-borne polyurethane dispersion, UV-blocking coating was acquired. Transparent UV-blocking films could be prepared by rods. UV-vis spectra and accelerated weathering tester were utilized to investigate the UV-blocking performance of the hybrid coatings. At the same time, the modification effect of silica on the weathering property of the films was also studied. Moreover, in order to extend the UV-shielding range, cerium oxide ethanol dispersion was doped into the silica-titania sol, through which coatings with better UV-blocking performance were obtained.
(2) A novel and facile miniemulsion-combined sol-gel process to fabricate water-borne UV-blocking additive was also presented. In this approach, the oil phase composed of acetylacetone(Acac) modified titanium (IV) butoxide (TBT)、dimethyl benzene(DB) and hexadecane(HD) were confined in the miniemulsion droplet microreactors with the aid of a cationic emulfier hexadecyltrimethylammonium bromide(CTAB). Then, a silica layer was coated onto the miniemulsion droplets by the co-condensation of amino-silane and tetraethyl silicate (TEOS). At the same time, TBT in the miniemulsion droplets diffused to the O/W interface and then initiated the sol-gel reaction, hence TiO_2-SiO_2 hybrid colloids were obtained. TEM、FTIR、EDX and XPS methods were utilized to investigate the structure of as-prepared hybrids Some influencing parameters, such as the concentrations of TBT in the oil droplet, the content of amino silane in the silica precursor, etc., on the morphology of the hybrid colloids were investigated. UV-visible spectra and dye degradation experiments showed that the polyurethane films doped with these hybrid colloids had a very good UV-blocking property.
(3) Nanosilica reinforced waterborne silylated polyether adhesives were prepared with silylated polyether emulsion, tetraethyl orthosilicate (TEOS), silica sol and fumed silica powder. Effects of TEOS content, silica sol content and the type and content of fumed silica on the shear strength of the adhesive and their strengthening mechanisms were investigated using a scanning electronic microscope and an electronic instron tester. Colloidal silica particles was less efficient than fumed silica particles for reinforcing the polyether adhesive but can increase the shear strength of fumed silica embedded adhesive. Comparing the adhesives with the hydrophilic fumed silica or the extremely hydrophobic fumed silica, the adhesive with moderate hydrophobic fumed silica had the highest shear strength. It seemed that TEOS, silica sol and fumed silica played crosslinking (with polyether chain), dispersing (for fumed silica) and reinforcing roles on waterborne adhesive, respectively.
引文
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