4-(5-氨基-6-羟基-2-苯并噁唑基)苯甲酸盐的合成、性能及应用  

Synthesis,characteristics and application of 4-(5-amino-6-hydroxybenzoxazole-2-yl)benzoic acid salt

作　　者：金宁人[1] 张建庭[1] 赵德明[1] 金宁东 王学杰[3] 

机构地区：[1]浙江工业大学化学工程与材料学院,浙江杭州310032 [2]盐城鼎龙化工有限公司,江苏滨海224555 [3]浙江教育学院化学系,浙江杭州310012

出　　处：《化工学报》2008年第10期2680-2686,共7页CIESC Journal

基　　金：江苏省科技攻关重大项目(BE2006077)~~

摘　　要：系统地研究了AB型新单体4-(5-氨基-6-羟基-2-苯并噁唑基)苯甲酸盐(ABAS)的合成新方法、性能及其在聚对亚苯基苯并二噁唑制备中的应用。结果表明:采用以4-(5-硝基-6-羟基-2-苯并噁唑基)苯甲酸甲酯(MNB)为原料,经碱性水解及水解液直接还原合成高纯度ABAS的新技术,具有工艺简练、污染少及经济性良好等特点,总收率达84%,它经历以水解物4-(5-硝基-6-羟基-2-苯并噁唑基)苯甲酸的二钾盐为中间物质的加氢还原、酸析反应历程;对于95%以下纯度的MNB采用水解分离后再还原的两步法合成工艺,也能获得近99%纯度的ABAS;经1HNMR、13CNMR和FT-IR等确认为ABAS后,TG测得起始热分解温度为290℃,具有优异的热稳定性和抗氧化性;99%纯度的ABAS在玻璃反应器中以聚合13h最后升温至230℃的方式可制得特性黏数大于15dl.g-1的PBO树脂,具有完全等当比缩聚、操作安全、易工业化等技术特征。Novel synthesis, characteristics and application of new AB-PBO monomer 4- （5-amino-6- hydroxyhenzoxazole-2-yl） benzoic acid salt （ABAS） were studied. The results showed that ABAS was one-pro synthesized from methyl 4- （5-nitro-6 hydroxybenzoxazole-2-yl） benzoate （MNB） with a yield of 84% and purity of 99% via alkali hydrolysis and reduction, which had the advantages of simple procedure, low pollution and cost saving. The mechanisms of alkali hydrogenation and acidification with 4- （5-nitro-6- hydroxy benzoxazole-2-yl） benzoic acid dipotassium salt as intermediate were proposed. With MNB below 95% purity, the ABAS approaching 99% purity could also be prepared by the two-step method of hydrolysis and reduction. The ABAS was identified with ^1H NMR, ^13C NMR, FT-IR. Its initial decomposition temperature was measured to be 290℃, and it had excellent thermostability, oxidation resistance and outstanding storage stability. Using ABAS of 99% purity, PBO resin was easily prepared by self-polycondensation for 13 h at 230℃ as end-polymerization temperature in glassware and its intrinsic viscosity was more than 15 dl·g^-1. The procedure had the characteristics of equi-molar polycondensing group, safe operation , easy industrialization and etc.

关 键 词：4-(5-氨基-6-羟基-2-苯并噁唑基)苯甲酸盐 AB型PBO新单体 聚对亚苯基苯并二噁唑 

分 类 号：TQ316.342[化学工程—高聚物工业]