新型含氟环氧单体的合成及其光固化行为的初步研究  

Synthesis of New Fluorinated Epoxides and Preliminary Investigations on Their UV-curing Properties

作　　者：郦聪[1] 胡芳瑜[1] 江黎明[1] 程新钗 陈耀祖 

机构地区：[1]高分子合成与功能构造教育部重点实验室,浙江大学高分子科学与工程学系,杭州310027 [2]浙江池禾化工有限公司

出　　处：《应用化学》2011年第2期177-181,共5页Chinese Journal of Applied Chemistry

基　　金：浙江省重点科技专项(2009C11129)资助项目

摘　　要：由六氟环氧丙烷二聚体、三聚体分别与4-环己烯-1,2-二甲醇反应合成了2种新型的双全氟烷氧基取代的环氧环己烷衍生物（EFPO1和EFPO2）,其结构经FT-IR和1HNMR确证。与常见全氟烷基型功能单体不同,此类含氟环氧化合物与环氧树脂预聚物具有良好的相容性并且可改善其疏水性能。初步考察了上述单体对环氧树脂紫外光固化涂料的改性作用,结果表明,随涂料中含氟单体用量的增加,固化膜的初始水接触角线性增大;其中,EFPO2因其含较长的全氟烷氧基团而具有比EFPO1更好的疏水效果。如加入1%EFPO2时,固化膜接触角为99°,比未添加含氟单体的固化膜大14°,而相同含量EFPO1固化膜接触角为87°。当EFPO2含量为5%时,固化膜的疏水性能进一步提高,接触角为113°。此外,固化膜经加热处理（110℃,6 h）后疏水性能明显增强,如EFPO2含量为1%~5%时,固化膜经热处理后,接触角由99°~113°提高至113°~118°,EFPO1固化膜经热处理后接触角也由87°~100°提高至99°~110°。固化膜疏水性能的提高可能是由于经过加热处理,含氟链段向表面迁移。由此可见,这类含氟单体可作为表面改性剂应用于涂料、油墨和离型材料。Perfluoroalkyoxy-substituted cyclohexene oxides（EFPO1 and EFPO2） were obtained by two-step reactions using the dimer and trimer of hexafluoropropylene oxide and 4-cyclohexene-1,2-dimethanol as main raw materials.The structures of as-synthesized products were confirmed by spectroscopy analyses including FT-IR and 1H NMR.These fluoro-epoxides are compatible with the prepolymers such as bisphenol-A diglycidyl ether and ethylene glycol diglycidyl ether,thereby endowing the coatings composed of them with improved hydrophobicity as evidenced by the photoinitiated curing experiments.The preliminary investigation of their UV-curing performance shows that the hydrophobicity increases linearly with increasing fluoro-epoxide content in the composition.As expected,the hydrophobic effect is more pronounced for EFPO2 than EFPO1 at the same conditions,because the former has a longer ferfluoroalkyoxy group.For example,upon addiing 1% mass fraction of EFPO2,the water contact angle of the UV-cured films was 99° and was higher 14° than that found for the films without the fluoro-component,whereas the value for EFPO1-modified films was 87°.When containing 5% EFPO2,high hydrophobic surface was achieved with a water contact angle of 113 for the UV-cured films.In addition,it should be pointed out that the hydrophobic surface can be further improved by heating the UV-cured films at 110 ℃ for 6 h.For the coatings containing 1%~5% EFPO2,the post-heating treatment resulted in a change of the water contact angles from the range 99°~113° to 113°~118°,while the changes were from 87°~100° to 99°~110° for EFPO1 analogs.The thermal migration of fluoro-chains and aggregation on the film surface seems to be responsible for the enhancement in hydrophobicity.Consequently,this new type of fluorine-containing epoxy monomers is expected as the surface modifier used in coatings,inks and release materials.

关 键 词：含氟环氧单体 紫外光固化 疏水性 涂料 

分 类 号：O632.7[理学—高分子化学]