固载杂多酸催化合成双酚芴  

Synthesis of Bisphenol Fluorene Catalyzed by Supported Heteropolyacid

作　　者：刘文彬[1] 邱琪浩[1] 王军[1] 嵇雷[1] 张密林[1] 

机构地区：[1]哈尔滨工程大学材料科学与化学工程学院,黑龙江哈尔滨150001

出　　处：《精细化工》2007年第12期1153-1157,1162,共6页Fine Chemicals

基　　金：哈尔滨市科技攻关计划项目(2004AA5CG080);哈尔滨工程大学基础研究基金项目(HEUF04070)~~

摘　　要：以固载磷钨酸为催化剂,芴酮和苯酚为原料催化合成了双酚芴,考察了影响反应的因素,采用FTIR、NMR和MS对产品结构进行了表征,并对自制双酚芴环氧树脂的湿热性能进行了评价。实验结果表明,活性炭固载磷钨酸用于催化合成双酚芴,催化活性高,催化剂易于回收。当固载磷钨酸用量为反应物总质量的15%,n(苯酚)∶n(芴酮)=10∶1,助催化剂β-巯基丙酸用量为0.2mL,反应温度95℃,反应时间12h时,经甲苯重结晶,双酚芴产品的质量分数及收率分别可达99.1%、81.5%。当共混树脂中芴基环氧树脂的质量分数为50%时,二氨基二苯砜(DDS)固化E-44、AG-80和F-44共混树脂的吸水率分别比纯树脂下降了15%、25%、28%,其中F-44共混树脂的玻璃化转变温度提高了近50℃,表明双酚芴作为环氧树脂单体可明显改善树脂的湿热性能。Bisphenol fluorene（BHPF） was synthesized from fluorenone and phenol in the presence of supported heteropolyacid,and the major factors affecting the reaction were investigated. The chemical structure of bisphenol fluorene was confirmed with FTIR, NMR and MS. Furthermore, the hot-wet property of cured epoxy resin derived from BHPF was evaluated and compared with that of other kinds of epoxy resins. The results show that tungstophosphoric acid supported on activated carbon has high catalytic activity and is easy to recover. The mass percentage and yield of BHPF reached 99. 1% and 81.5% respectively after recrystallization with toluene under optimal process conditions that the molar ratio of phenol to fluorenone was 10 to 1, the mass percentage of catalyst was 15% of the total reactants, quantity of the co-catalyst β-mercaptopropionic acid was 0. 2 mL, reaction temperature was 95 ℃ and reaction time was 12 h. For comparison,cured blending matrices composed of fifty mass percent of neat epoxides （ E - 44, AG - 80 and F - 44） and fifty mass percent of fluorene-containing epoxy resins were prepared using DDS as the curing agent. Compared with neat matrix resins,the water pickup ratio of resulting blending resins decreased by 15% ,25% and 28% respectively, and the glass transition temperature of F -44 blending resin increased by 50 ℃ approximately, indicating that bisphenol fluorene is a potential candidate for improving the hot-wet property of epoxy resin systems.

关 键 词：杂多酸 负载型催化剂 双酚芴 芴基环氧树脂 功能材料 

分 类 号：TQ426.91[化学工程]