摘要
为进一步提升聚对亚苯基苯并二口恶唑(PBO)材料的性价比并促进其工业化,研究了以4,6-二硝基间苯二酚为原料,先选择还原制得4-氨基-6-硝基间苯二酚盐酸盐,进而与对甲氧羰基苯甲酰氯进行缩环合获得苯并口恶唑化合物,再催化加氢合成AB型PBO新单体2-(对甲氧羰基苯基)-5-氨基-6-羟基苯并口恶唑(MAB),最后自缩聚反应制备PBO的新路线和新方法.结果表明该方法具有原料易得、反应条件缓和、中间体稳定等新技术优势.合成的PBO树脂总收率达64%、特性黏数η>10dl·g-1,新单体MAB的纯度>98%,具有稳定性优异和缩聚基团完全等当比等性质,以及均缩聚时间<20h和过程易操作等技术特点,均为4,6-二氨基间苯二酚(DAR)共缩聚路线所难以比拟的.其综合经济性优于三氯化苯经DAR共缩聚的工业化路线,有望发展成易于实施PBO产业化的一项新技术.
In order to upgrade the performance of poly（p-phenylenebenzobisoxazole） （PBO） materials and to promote its commercialization, a novel method for preparing PBO resin as developed by the homopolycondensation of a new AB-PBO monomer, 2- （ 4-methoxycarbonylphenyl ） -5-amino-6- hydroxybenzoxazole （MAB）, which was innovatively synthesized by the selective reduction of 4, 6- dinitroresorcinol （DNR）, then condensation-cyclization with 4-methoxycarbonylbenzoyl chloride and finaly catalytic-hydrogenation. The results showed that： （1） The intrinsic viscosity of PBO resin prepared from 98.2% purity MAB was more than 10 dl/g in glassware, the total yield （based on DNR） was more than 64 %, polymerization time was shortened to 15 h and the operation was convenient; （2） MAB was exactly identified by ^1H-NMR, ^13C-NMR, FT-IR and easily prepared at a total yield of 66%. The process has advantages of simple raw materials preparation, controllable selective reduction, one-pot condensationcyclization, mild hydrogenation condition, and good economics. The selective reduction product： 4- Amino-6-nitroresorcinol hydrochloride （ANR · HCl） could be used as a key intermediate in the improvement of PBO performance; （3） The novel synthesis route could be developed into a new technique for commercialization. The new AB-PBO monomer, has outstanding stability （purity decreases only 0.12 % after 270 days in the presence of air）. There is no need for antioxidant agent in storage and polycondensation. MAB has equi-molar polycondensing group. The novel synthesis route is better than the AA-type 4, 6-diamino resorcinol dihydrochloride plus BB-type terephthalic acid monomers copolycondensation route.
出处
《化工学报》
EI
CAS
CSCD
北大核心
2006年第6期1474-1481,共8页
CIESC Journal
基金
浙江省自然科学基金项目(502112).~~
