系统地研究了AB型新单体4-5-氨基-6-羟基-2-苯并口恶唑基)苯甲酸盐(ABAS)的合成新方法、性能及其在聚对亚苯基苯并二口恶唑制备中的应用。结果表明:采用以4-(5-硝基-6-羟基-2-苯并-口恶唑基)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-苯并口恶唑基)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1 H NMR、13C NMR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13 h最后升温至230℃的方式可制得特性黏数大于15 dl·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。
Abstract
Novel synthesis
characteristics and application of new AB-PBO monomer 4-(5-amino-6-hydroxybenzoxazole-2-yl) benzoic acid salt(ABAS)were studied The results showed that ABAS was onepot 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 savingThe mechanisms of alkali hydrogenation and acidification with 4-(5-nitro-6-ydroxy benzoxazole-2-yl)benzoic acid dipotassium salt as intermediate were proposedWith MNB below 95% purity
the ABAS approaching 99% purity could also be prepared by the twostep method of hydrolysis and reductionThe ABAS was identified with 1 H NMR
13C NMR
FT-IRIts initial decomposition temperature was measured to be 290℃
and it had excellent thermostability
oxidation resistance and outstanding storage stabilityUsing ABAS of 99% purity
PBO resin was easily prepared by self-polycondensation for 13 h at 230℃ as endpolymerization temperature in glassware and its intrinsic viscosity was more than 15 dl·g-1. The procedure had the characteristics of equimolar polycondensing group
Novel synthesis route and preparation of poly(p-phenylenebenzobisoxazole)
Experimental study of heat transfer enhancement by pressure waves in cross flow tube bundles
Thermodynamic performance of tower-type solar-assisted supercritical compression CO2 energy storage system
Controlled synthesis of Bi2MoO6/MoO3 composite fibers via in-situ hydrothermal method and their high-efficiency photocatalytic hydrogen production performance
New universal corresponding state equation for correlation and extrapolation of saturated vapor-liquid density