水性含磷环氧化合物的合成与性能

Preparation and Properties of Phosphorus-Containing Waterborne Epoxy Compound

对9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）改性合成水性含磷环氧化合物。首先，以酚醛环氧树脂F-51和DOPO（初始F-51环氧基与IX）PO摩尔比为3：2）合成出F-51-DOPO加成物。然后，在摩尔比（n（F-51-DOPO的环氧基）／n（MEA））为1：1下，F-51-DOPO加成物与乙醇胺（MEA）反应合成出F-51-DOPO-MEA加成物；最后，在摩尔比（PEGGE环氧基／F-51-DOPO-MEA）为2：1下，F-51-DOPO-MEA加成物与聚醚醇二缩水甘油醚（PEGGE）反应，合成了F-51-DOPO-MEA-PEGGE加成物。性能研究结果表明，其在室温下能均匀分散于水性体系中，与涂膜中的环氧树脂基材相容性良好；并可使涂膜在保持良好硬度前提下，耐冲击性明显得到提高。热重分析结果表明。其可使固化涂膜在450-800℃高温下的残炭率和耐热性显著提高。氧指数测定结果表明，其能有效提高水性环氧树脂材料的极限氧指数（LOI）及阻燃性能。

Epoxy resins were inherently brittle and flammable. 9, 10-Dihydro-9-oxa-10-phosphaphenanthren-10- oxide（DOPO） is efficient flame retardant. While the prospect of using it in the waterborne epoxy coatings is limited because it is insoluble in water and incompatible with epoxy resins. Accordingly, a novel phosphorus-containing waterborne epoxy compound was prepared as follows. Firstly, with the initial mole ratio between the epoxy group of phenolic epoxy resin （F-51） and DOPO of 3：2, F-51 reacted with DOPO in butyl glycol ether using triphenylphosphine as catalyst to synthesis F-51-DOPO addut. Secondly, with the mole ratio between the epoxy group of F-51-DOPO addut and monoethanolamine（MEA） of 1 ： 1, F-51-DOPO addut reacted dropwise with MEA in propylene glycol methyl ether （PM） under the conditions of reaction temperature（70℃ ）, reaction time（8 h） to synthesize F-51-DOPO-MEA adduct. Finally, in order to incorporate the hydrophilic and soft polyglycol segment, F- 51-DOPO-MEA adduet reacted dropwise with diglycidyl ether of polyglycol （PEGGE） in PM under the condition of mole ratio between F-51-DOPO-MEA and the epoxy group of PEGGE （1：2）, reaction temperature（65℃ ）, reaction time（5 h） to synthesize F-51-DOPO-MEA-PEGGE adduct. The synthesized DOPO-based epoxy compound is soluble in water and compatible with epoxy resins when used in the waterborne epoxy resin coatings. The effects of the content of the synthesized adduct on the film property were discussed. The results indicate that it can improve mechanical performance of the films, heat resistance and char yield within 450-800℃ remarkably. And the incorporation of it into waterborne epoxy resin materials could improve the limiting oxygen index （LOI） and flame retardancy of cured materials obviously.