SYNTHESIS AND PROPERTIES OF AROMATIC HETEROCYCLIC POLYMERS BASED ON THE BIS(ETHER ANHYDRIDE)S AND BIS(ETHER CARBOXYLIC ACID)S FROM HYDROQUINONE AND ITS DERIVATIVES

• Main Authors: Dai Liang-Ru, 戴良如
• Other Authors: Sheng-Huei Hsiao
• Format: Others
• Language: zh-TW
• Published: 1998
• Online Access: http://ndltd.ncl.edu.tw/handle/61487000994521690028

碩士 === 大同工學院 === 化學工程研究所 === 86 === Four bis(ether anhydride)s, that included 4,4'-(1,4-phenylenedioxy)diphthalic anhydride, 4,4'-(2,5-tolylenedioxy)diphthalic anhydride, 4,4'-(2-chloro-1,4-phenylenedioxy)diphthalic anhydride, and 4,4'-(2,5-biphenylenedioxy)diphthalic anhydride, were prepared in three steps starting from the nucleophilic nitro-displacement of 4-nitrophthalonitrile with the corresponding hydroquinones, followed by alkaline hydrolysis and dehydration. Four series of poly(ether imide)s were prepared from these dianhydrides with various aromatic diamines by a classical two-step procedure. In addition, four bis(ether benzoic acid)s including 4,4'-(1,4-phenylenedioxy)dibenzoic acid, 4,4'-(2,5-tolylenedioxy)dibenzoic acid, 4,4'-(2-tert-butyl-1,4-phenylenedioxy)dibenzoic acid, and 4,4'-(2,5-biphenylenedioxy)dibenzoic acid were synthesized in two main steps from the nucleophilic of p-fluorobenzonitrile by the bisphenoxide ions of their hydroquinone precursors and subsequent alkaline hydrolysis and acidification. Furthermore, the bis(ether benzoic acid)s were converted to the corresponding bis(ether benzoyl chloride)s. Hydrazide polymers were prepared from these bis(ether benzoic acid)s or their diacyl chlorides with terephthalic dihydrazide, isophthalic dihydrazide or p-aminobenzoyl hydrazide by means of the phosphorylation polyhydrazidation reaction or low-temperature solution polycondensation. All the hydrazide polymers could be thermally cyclodehydrated into the corresponding oxadiazole polymers. Besides, poly(o-hydroxy amide)s were also prepared by the low-temperature solution polycondensation of bis(ether benzoyl chloride)s with three bis(o-aminophenol)s. Subsequent thermal cyclodehydration of the poly(o-hydroxy amide)s afforded polybenzoxazoles. Basic characterization of the polymers is described in this thesis. Effect of the introduction of pendent groups on the properties of polymers are also investigated.