纳米无机/有机硅杂化UV涂料的研制
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摘要
传统杂化方法主要是通过偶联剂对无机纳米粒子进行包覆改性,利用偶联剂的两性化学结构,使改性后的无机粒子更容易分散到有机相中,并通过偶联剂中的有机结构与有机相缠绕在一起。通常偶联剂不与有机相主体发生化学反应,当涂层磨损到一定程度时候,包覆改性的无机粒子会加速从涂膜中抽离脱落。针对这一问题,本文合成一种可UV固化的新型杂化材料。首先通过杂化方法制备了可UV固化的无机有机杂化低聚物,再利用UV固化技术,将UV固化树脂和无机有机杂化低聚物交联固化,从而使有机相和无机相以化学键结合,形成“二次杂化”,并且由于杂化材料的加入,增强了涂料涂膜的耐磨、耐温和硬度等性能。
本文以四氯化硅、甲基丙烯酸β羟基乙酯、苯基三氯硅烷、基苯基二氯硅烷和纳米二氧化硅为主要原料合成了一种新型聚丙烯酰氧基β羟乙基硅氧烷/纳米SiO_2杂化材料。杂化材料与环氧丙烯酸树脂和脂肪族聚氨酯丙烯酸树脂进行复配制备了UV固化杂化涂料,并对新型杂化材料对涂层的热稳定性和力学性能进行测试。主要研究内容包括:
(1)对聚丙烯酰氧基硅烷的合成路线进行了探索研究,制定了氯硅烷共水解缩聚法制备聚丙烯酰氧基硅烷的合成路线,并对其产物进行了红外光谱表征,红外谱图上出现明显的Si-O-C键和Si-O-Si(线性聚硅氧烷)键特征振动峰,表明可能生成了有机硅链,间接证明合成产物中可能成功引入碳碳双键,使聚硅氧烷的具有了光固化的活性。进一步对合成物料配比,反应条件进行优化。以二甲苯乙醚混合液为溶剂,水解温度控制在60～70℃之间,n(苯基丙烯酰氧基二氯硅烷):n(PhCH_3SiCl_2):n(二丙烯酰氧基二氯硅烷)=1:7.5:5,GZJ用量为1.5%,n(H_2O):nCl=0.9:1,产物置阴暗处静止一周未发生凝胶或交联现象,粘度没有明显变化,粘度为198mpa·s。
(2)对聚丙烯酰氧基硅烷与纳米二氧化硅杂化制备的杂化机理进行了探讨;考察了聚丙烯酰氧基硅烷与纳米二氧化硅以不同比例杂化得到的杂化材料对涂膜耐磨性能、附着力和固化时间的影响,聚丙烯酰氧基硅烷与纳米二氧化硅的最佳杂化比例(质量比)为11:2;通过IR、SEM、TG等检测手段对杂化材料进行表征。从化学结构和微观结构推测了杂化材料在耐磨性、抗冲击性能方面的优势。
(3)考察了杂化材料对涂层的附着力、硬度、耐磨性、耐温性及抗冲击性的影响,确定杂化材料在复合涂料体系中的最佳加入量为17wt%,耐磨性能提高45.5%,硬度为3H,附着力为1级,抗冲击性为50kg·cm;从化学键及微观结构特性解释了杂化材料提高涂层的附着力、硬度、耐磨性、耐温性及抗冲击性的原因。
Traditional hybrid method is that inorganic nanoparticles are coated by silane coupling agent,because silane coupling agent possess characteristics both of Organic and inorganic, The modified inorganic nanoparticles which are coated by silane coupling agent easily are spreaded in organic phase and the organic structure of silane coupling agent and organic phase entwine.Usually silane coupling agents don't react with the organic resins.The inorganic modified nanoparticles and organic resins are not combined by chemical combination that led to the modified inorganic nanoparticles may be removed from the organic phase.In response to this problem,a new type of UV-curable hybrid materials was designed.First,UV-curable hybrid materials be prepared by hybrid method,then using UV curing technology,UV-curable resin and UV-curable hybrid materials curing cross-linked,so that organic and inorganic chemical combine with organic phase,"second hybrid" is achieved between UV resin organic and UV-curable hybrid materials,and because the hybrid materials can enhance the wear-resistant of coatings,temperature-resistant and hardness properties.
Based on silicon tetrachloride,methyl ethyl acrylate hydroxy-β,phenyl chloride, dichloro-phenyl silane as the main raw material,a new hybrid material that polypropylene para-siloxane / nano SiO_2 hybrid materials is synthesized.Hybrid materials compound with epoxyacrylic resins and aliphatic urethane acrylate resin produced hybrid UV-curable coatings.The thermal stability and mechanical properties hybrid UV curable coating were tested.Main contents include:
(1)The polypropylene para-silane synthetic routes were explored.The polypropylene para-silane was synthesized by hydrolysis between chlorosilanes.The functional group of product was characterized by Fourier Transform Infrared Ray(FT-IR).The results show that the IR vibration characteristics spectrum of Si-O-Si chemical bond and Si-O-Si(linear polysiloxane)chemical bond are evidence,this characteristics show that silicone chain is generated,indirectly show that carbon-carbon double bond may be combine with silicone chain,the polysiloxane will possess light-cured activity.The ratio of synthetic materials and the reaction conditions are optimized,The hydrolysis temperature is controlled in 60～70℃, the mixture of ether and xylene are as solvent,nAPS:nPhCH_3SiCl_2:nTAS = 1:7.5:5,GZJ amount is 1.5wt%,H_2O:PhCH_3SiCl_2/(mol)=3.2:1,product did not gel or cross-linked after a week,viscosity of product is 198mpa·s.
(2)The hybrid mechanism of polypropylene para-silane and nano-silica was discussed; The experiment which polypropylene para-silane and the nano-silica hybride on different ratios were done,the best ratio of polypropylene para-silane and the nano-silica hybride(wt)is PAS:SiO2.Hybrid materials were characterized by IR,SEM,TG.
(3)The relation of hybride matrials to compound coatings on adhesion,hardness,wear resistance,impact resistance and temperature resistance were studied;The experimental making sure best amount of hybrid materials in the composite coating system is 17%, wear-resistant is raised 45.5%,the hardness reach 4 H,adhesion reach 1 level,the impact resistance is 50 kg·cm;According as the chemical bond and the micro-structure of hybrid materials,the reasons that hybrid materials can raising the adhesion of coatings,hardness, wear-resistance,temperature-resistance and impact-resistance were speculated.
本文以四氯化硅、甲基丙烯酸β羟基乙酯、苯基三氯硅烷、基苯基二氯硅烷和纳米二氧化硅为主要原料合成了一种新型聚丙烯酰氧基β羟乙基硅氧烷/纳米SiO_2杂化材料。杂化材料与环氧丙烯酸树脂和脂肪族聚氨酯丙烯酸树脂进行复配制备了UV固化杂化涂料,并对新型杂化材料对涂层的热稳定性和力学性能进行测试。主要研究内容包括:
(1)对聚丙烯酰氧基硅烷的合成路线进行了探索研究,制定了氯硅烷共水解缩聚法制备聚丙烯酰氧基硅烷的合成路线,并对其产物进行了红外光谱表征,红外谱图上出现明显的Si-O-C键和Si-O-Si(线性聚硅氧烷)键特征振动峰,表明可能生成了有机硅链,间接证明合成产物中可能成功引入碳碳双键,使聚硅氧烷的具有了光固化的活性。进一步对合成物料配比,反应条件进行优化。以二甲苯乙醚混合液为溶剂,水解温度控制在60～70℃之间,n(苯基丙烯酰氧基二氯硅烷):n(PhCH_3SiCl_2):n(二丙烯酰氧基二氯硅烷)=1:7.5:5,GZJ用量为1.5%,n(H_2O):nCl=0.9:1,产物置阴暗处静止一周未发生凝胶或交联现象,粘度没有明显变化,粘度为198mpa·s。
(2)对聚丙烯酰氧基硅烷与纳米二氧化硅杂化制备的杂化机理进行了探讨;考察了聚丙烯酰氧基硅烷与纳米二氧化硅以不同比例杂化得到的杂化材料对涂膜耐磨性能、附着力和固化时间的影响,聚丙烯酰氧基硅烷与纳米二氧化硅的最佳杂化比例(质量比)为11:2;通过IR、SEM、TG等检测手段对杂化材料进行表征。从化学结构和微观结构推测了杂化材料在耐磨性、抗冲击性能方面的优势。
(3)考察了杂化材料对涂层的附着力、硬度、耐磨性、耐温性及抗冲击性的影响,确定杂化材料在复合涂料体系中的最佳加入量为17wt%,耐磨性能提高45.5%,硬度为3H,附着力为1级,抗冲击性为50kg·cm;从化学键及微观结构特性解释了杂化材料提高涂层的附着力、硬度、耐磨性、耐温性及抗冲击性的原因。
Traditional hybrid method is that inorganic nanoparticles are coated by silane coupling agent,because silane coupling agent possess characteristics both of Organic and inorganic, The modified inorganic nanoparticles which are coated by silane coupling agent easily are spreaded in organic phase and the organic structure of silane coupling agent and organic phase entwine.Usually silane coupling agents don't react with the organic resins.The inorganic modified nanoparticles and organic resins are not combined by chemical combination that led to the modified inorganic nanoparticles may be removed from the organic phase.In response to this problem,a new type of UV-curable hybrid materials was designed.First,UV-curable hybrid materials be prepared by hybrid method,then using UV curing technology,UV-curable resin and UV-curable hybrid materials curing cross-linked,so that organic and inorganic chemical combine with organic phase,"second hybrid" is achieved between UV resin organic and UV-curable hybrid materials,and because the hybrid materials can enhance the wear-resistant of coatings,temperature-resistant and hardness properties.
Based on silicon tetrachloride,methyl ethyl acrylate hydroxy-β,phenyl chloride, dichloro-phenyl silane as the main raw material,a new hybrid material that polypropylene para-siloxane / nano SiO_2 hybrid materials is synthesized.Hybrid materials compound with epoxyacrylic resins and aliphatic urethane acrylate resin produced hybrid UV-curable coatings.The thermal stability and mechanical properties hybrid UV curable coating were tested.Main contents include:
(1)The polypropylene para-silane synthetic routes were explored.The polypropylene para-silane was synthesized by hydrolysis between chlorosilanes.The functional group of product was characterized by Fourier Transform Infrared Ray(FT-IR).The results show that the IR vibration characteristics spectrum of Si-O-Si chemical bond and Si-O-Si(linear polysiloxane)chemical bond are evidence,this characteristics show that silicone chain is generated,indirectly show that carbon-carbon double bond may be combine with silicone chain,the polysiloxane will possess light-cured activity.The ratio of synthetic materials and the reaction conditions are optimized,The hydrolysis temperature is controlled in 60～70℃, the mixture of ether and xylene are as solvent,nAPS:nPhCH_3SiCl_2:nTAS = 1:7.5:5,GZJ amount is 1.5wt%,H_2O:PhCH_3SiCl_2/(mol)=3.2:1,product did not gel or cross-linked after a week,viscosity of product is 198mpa·s.
(2)The hybrid mechanism of polypropylene para-silane and nano-silica was discussed; The experiment which polypropylene para-silane and the nano-silica hybride on different ratios were done,the best ratio of polypropylene para-silane and the nano-silica hybride(wt)is PAS:SiO2.Hybrid materials were characterized by IR,SEM,TG.
(3)The relation of hybride matrials to compound coatings on adhesion,hardness,wear resistance,impact resistance and temperature resistance were studied;The experimental making sure best amount of hybrid materials in the composite coating system is 17%, wear-resistant is raised 45.5%,the hardness reach 4 H,adhesion reach 1 level,the impact resistance is 50 kg·cm;According as the chemical bond and the micro-structure of hybrid materials,the reasons that hybrid materials can raising the adhesion of coatings,hardness, wear-resistance,temperature-resistance and impact-resistance were speculated.
引文
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