紫外光固化TiO_2纳米复合胶粘剂研究
摘要
紫外光固化胶粘剂(UV固化胶)是一类绿色、高效的胶粘剂,具有固化速率快、固化过程无挥发性有机溶剂排放、能源利用率高、室温固化等多种优点,被广泛运用于汽车、医疗、微电子加工等国民经济生产的各个领域。然而目前市场上使用的自由基型UV固化胶也存在固化过程受空气氧阻聚、制品体积收缩率大、折射率低、透光性差、粘结强度不高、热稳定性差等缺陷,无法运用于具有较高要求的光学器件的粘结问题。本研究以阳离子型UV固化机理体系为胶粘剂基体,利用阳离子鎓盐类光引发剂“光生酸”反应,催化体系中无机前驱体钛酸异丙醇(TIP)发生水解缩合反应,溶胶凝胶原位合成的方法制备具有高折射率且同时具有高光学透过率的UV固化TiO_2纳米复合胶粘剂。
本文研究了引发剂种类及其含量、单体结构、光照强度、胶粘剂固化层厚度等对阳离子UV固化胶粘剂固化速率、拉伸强度、体积收缩率等方面的影响,结果表明以三芳基六氟磷酸硫鎓盐作为引发剂(3%),3,4-环氧环己基甲基-3,4-环氧环己基甲酸酯(S-06)单体组成的阳离子UV固化胶粘剂具有较短的固化时间(8s),较高的拉伸强度(15.8MPa)以及低体积收缩率(3.2%)。向此体系加入不同含量的钛酸异丙醇,红外动力学分析表明,当TIP含量较低时(<20%)对胶粘剂固化速率影响较小;体系中生成的无机TiO_2纳米区域在偶联剂(γ-缩水甘油醚氧基丙基三甲氧基硅烷,8wt.-%)的作用下均匀的分散在复合胶粘剂中,平均粒径大小在20nm左右;复合胶粘剂力学性能有所提高(17.9MPa);复合胶粘剂的折射率nD从1.5013升高至1.5439,且保持良好的透光性,在400nm光区以上复合胶粘剂的透光率均大于94%,复合胶粘剂的热稳定性等也得到明显提高,热分解温度从320℃升高到365℃。
UV-curable adhesives have been widely used in areas of national economic production such as automotive, medicine, microelectronics processing, et al, because it is a kind of green and efficient adhesives, and has the advantage of high curing rate, ambient curable condition, high energy efficiency and no emission of volatile organic slovent in curing process. However, there are some shortages in photo-initiated radical UV-curable adhesives, such as low bond strength, high volume shrinkage, low refractive index, poor thermal stability and easy inhibition by oxygen. In this paper, we used the cationic polymerization adhesive as the matrix and used the photoacids generated by the photoinitiators to catalyze sol-gel process of titanium isopropoxide (TIP). UV-curable nanocomposite adhesives with high refractive index and high transmittance were prepared by in-situ sol-gel process.
In this paper, the effect of type and content of photoinitiator, structure of monomer, light intensity and the thickness of adhesive on curing rate, tensile strength, volume shrinkage of the cationic UV-curable adhesive were studied. The results show that the adhesives with 3,4-Epoxycyclohexylmethyl-3'',4''-epoxycyclohexanecarboxylate (abbreviated as S-06) as monomer, triphenylsulfonium hexafluorophosphate salt as photoinitiators had short surface drying time (8s), high tensile strength (15.8MPa) and low volume shrinkage (3.2%). Then we added different content of titanium isopropoxide as the inorganic precursor into this system, and we researched the kinetic investigated of different TIP content by TTIR spectroscopy. The result showed that there was less influence on curing rate of nanocomposite adhesive when TIP content was low (<20%). The nano TiO_2 with an average diameter of 20nm generated by sol-gel processing dispersed in polymer matrix under the effect of coupling agent. The refractive index of the nanocomposite adhesive increased from 1.5013 to 1.5439, meanwhile had good transmittance in visible and near infrared region. The nanocomposite adhesive had good thermal stability, and the thermal decomposition temperature rose from 320℃to 365℃.
本文研究了引发剂种类及其含量、单体结构、光照强度、胶粘剂固化层厚度等对阳离子UV固化胶粘剂固化速率、拉伸强度、体积收缩率等方面的影响,结果表明以三芳基六氟磷酸硫鎓盐作为引发剂(3%),3,4-环氧环己基甲基-3,4-环氧环己基甲酸酯(S-06)单体组成的阳离子UV固化胶粘剂具有较短的固化时间(8s),较高的拉伸强度(15.8MPa)以及低体积收缩率(3.2%)。向此体系加入不同含量的钛酸异丙醇,红外动力学分析表明,当TIP含量较低时(<20%)对胶粘剂固化速率影响较小;体系中生成的无机TiO_2纳米区域在偶联剂(γ-缩水甘油醚氧基丙基三甲氧基硅烷,8wt.-%)的作用下均匀的分散在复合胶粘剂中,平均粒径大小在20nm左右;复合胶粘剂力学性能有所提高(17.9MPa);复合胶粘剂的折射率nD从1.5013升高至1.5439,且保持良好的透光性,在400nm光区以上复合胶粘剂的透光率均大于94%,复合胶粘剂的热稳定性等也得到明显提高,热分解温度从320℃升高到365℃。
UV-curable adhesives have been widely used in areas of national economic production such as automotive, medicine, microelectronics processing, et al, because it is a kind of green and efficient adhesives, and has the advantage of high curing rate, ambient curable condition, high energy efficiency and no emission of volatile organic slovent in curing process. However, there are some shortages in photo-initiated radical UV-curable adhesives, such as low bond strength, high volume shrinkage, low refractive index, poor thermal stability and easy inhibition by oxygen. In this paper, we used the cationic polymerization adhesive as the matrix and used the photoacids generated by the photoinitiators to catalyze sol-gel process of titanium isopropoxide (TIP). UV-curable nanocomposite adhesives with high refractive index and high transmittance were prepared by in-situ sol-gel process.
In this paper, the effect of type and content of photoinitiator, structure of monomer, light intensity and the thickness of adhesive on curing rate, tensile strength, volume shrinkage of the cationic UV-curable adhesive were studied. The results show that the adhesives with 3,4-Epoxycyclohexylmethyl-3'',4''-epoxycyclohexanecarboxylate (abbreviated as S-06) as monomer, triphenylsulfonium hexafluorophosphate salt as photoinitiators had short surface drying time (8s), high tensile strength (15.8MPa) and low volume shrinkage (3.2%). Then we added different content of titanium isopropoxide as the inorganic precursor into this system, and we researched the kinetic investigated of different TIP content by TTIR spectroscopy. The result showed that there was less influence on curing rate of nanocomposite adhesive when TIP content was low (<20%). The nano TiO_2 with an average diameter of 20nm generated by sol-gel processing dispersed in polymer matrix under the effect of coupling agent. The refractive index of the nanocomposite adhesive increased from 1.5013 to 1.5439, meanwhile had good transmittance in visible and near infrared region. The nanocomposite adhesive had good thermal stability, and the thermal decomposition temperature rose from 320℃to 365℃.
引文
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