脂环含氟环氧化合物的光固化及其性能研究

UV-curing and Properties of Fluorine-containing Cycloaliphatic Diepoxides

脂环环氧树脂是高活性的光固化材料,但折射率、介电常数以及耐水性方面需要改进。本文对比研究了两种脂环型含氟环氧化合物1,4-双(2,3-环氧环己基氧基)四氟丁烷(TCE)和1,6-双(2,3-环氧环己基氧基)八氟己烷(OCE),并与结构相近的商品脂环环氧树脂ERL-4221比较了光固化动力学,动态力学、热、光学以及表面能性能。TCE和OCE具有类似ERL-4221的高光固化反应活性,提高固化反应温度对含氟环氧化合物的速率和转化率的促进作用更明显;DMA以及TGA测试的结果显示,光固化的含氟环氧化合物C-TCE和C-OCE的玻璃化转变温度都高于150℃,分子链更柔软,耐热性略优于C-ERL-4221;接触角测试结果表明,氟原子取代提高了材料表面的疏水和疏油性,氟含量越高,表面能越低;光固化的C-TCE和C-OCE在可见-近红外波段光学透明。表明TCE和OCE作为先进可光固化材料有极大的应用前景。

Although cycloaliphatic epoxides are highly active in photocuring reaction,they need to be improved in refractive index,dielectric constant and resistance to water to satisfy the requirement for optoelectronic applications.In this work we comparatively study two cycloaliphatic fluorine-containing diepoxides,2,2′-((2,2,3,3-tetrafluorobutane-1,4-diyl)bis(oxy))bis(7-oxabicyclo[4.1.0]heptane)(TCE)and 2,2′-((2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl)bis(oxy))bis(7-oxabicyclo[4.1.0]heptane)(OCE),with a commercial available cycloaliphatic epoxy resin ERL-4221 with the similar structure in their photocuring kinetics,dynamic mechanical,thermal,optical and surface energy properties.TCE and OCE are reactive in photocuring similar to ERL-4221,but are more sensitive in the effects of photocuring temperature on curing rate and conversion.The DMA and TGA data show that both the UV-cured fluorine-containing epoxy compounds,C-TCE and C-OCE,exhibited glass transition temperature higher than 150℃,and are more thermally resistant than the cured C-ERL-4221.The contact angle tests indicate that the hydrophobicity and oleophobicity of the material surfaces of C-TCE and C-OCE are greatly improved by the fluorine atoms.C-TCE and C-OCE are optically transparent in the range from visible to near infrared.This work shows that TCE and OCE have great application prospects as advanced photocurable materials.