Synthesis of Tetraphenol Ethane Tetraglycidyl Ether Epoxy Resin
|Keywords||epoxy resin tetraphenol ethane tetraglycidyl ether epoxy resin tetraphenol ethane epichlorohydrin etherification epoxidation|
Electronic materials are the basic of the microelectronic industry, as the mostly structural materials of integrated circuits——epoxy resin molding compounds are developing fast along with the development of the technology of chips. It is a stringent problem to be researched that how to researching and exploiting epoxy resin molding compounds with high properties and using domestic packages to replace import products.1,1,2,2-tetrakis(hydroxyphenyl) ethane tetraglycidyl ether epoxy resin (tetraphenol ethane tetraglycidyl ether epoxy resin ) which is electronic encapsulation materials of the symmetric framework of high strength and toughness. It has not only the properties of common epoxy resin, but also has high glass transition temperature, high heat-resistant, UV-block and AOI(Automatic Optic Inspection) properties and so on. It is little reported on the study of the product in home. 1,1,2,2-tetrakis(hydroxyphenyl) ethane tetraglycidyl ether epoxy resin was prepared in a two-step process by using phenol, glyoxal, epichlorohydrin and sodium hydroxide as raw materials.Firstly, 1,1,2,2-tetrakis(hydroxyphenyl) ethane was synthesized by nueleophilie addition and condensation reaction of phenol with glyoxal in the presence of oxalic acid and methanol. The factors affecting the yield of the production was investigated, including the amount of oxalic acid, reaction temperature, reaction time and reagent proportion . The result showed that oxalic acid was the 2% , the molar ratio of phenol to glyoxal was 20:1; the temperature of the reaction was 82℃, the time of the reaction was 8 h, the yield could reach 42% .Then, the 1,1,2,2-tetrakis(hydroxyphenyl) ethane tetraglycidyl ether epoxy resin was obtained with 1,1,2,2-tetrakis(hydroxyphenyl) ethane and epichlorohydrin in the presence of both the tetraethylammonium bromide as a etherification catalyst and the isopropanol as a solvent. First the etherification reaction and then the epoxidation reaction (dehydrochlorination) occurred by adding an equivalent amount of sodium hydroxide. Subsequently water washing and refining were performed. The effects of reagent proportion, reaction time and reaction temperature on both the chlorine content and the epoxy value for synthesized resin product were investigated. The obtained results showed that under the conditions of the molar ratio of epichlorohydrin to tetraphenol ethane 21:1, the molar ratio of tetraphenol ethane to sodium hydroxide 1:4, the etherification reaction temperature 85℃, the etherification reaction time 4h, the ring-closing reaction temperature 70℃and the ring-closing reaction time 2.5h, the epoxy value, softening point, the hydrolyzable chlorine and the yield of resin product were 0.513, 83℃, 57% and 1.92×10-4 respectively.The structure of epoxy resin of 1,1,2,2-tetrakis(hydroxyphenyl) ethane tetraglycidyl ether was preliminary confirmed by analysis of both the Fourier Transform Infrared Spectrum (FTIR) and the Nuclear Magnetic Resonance (1HNMR and 13CNMR).