| Summary: | 碩士 === 大同大學 === 化學工程學系(所) === 94 === This thesis consists of three parts. The first part deals with the syntheses and characterization of novel aromatic poly(amine amide)s and poly(amine imide)s bearing a 4-fluorotriphenylamine unit on the main chian. A new triphenylamine-based diamine monomer, 4,4’-diamino-4”-fluorotriphenylamine (2) was synthesized via the cesium fluoride-mediated N,N-diarylation of 4-fluoroaniline with 1-fluoro-4-nitrobenzene, followed by palladium-on-charcoal-catalyzed hydrazine reduction of the dinitro intermediate. Amorphous and organosoluble poly(amine amide)s were prepared by the phosphorylation polyamidation of the newly synthesized diamine monomer (2) with various aromatic dicarboxylic acids. Poly(amine imide)s were prepared in conventional two-step method by the reaction of diamine 2 with various aromatic dianhydrides to form poly(amic acid)s, followed by thermal or chemical cyclodehydration. Basic properties of these poly(amine amide)s and poly(amine imide)s, such as inherent viscosity, molecular weights, film-forming ability, mechanical properties, crystallinity, solubility, thermal properties, optical and electrochemical properties were investigated and compared with those of parent poly(amine amide)s and poly(amine imide)s derived from 4,4’-diaminotriphenylamine with the same aromatic diacids and dianhydrides.
The second part of this thesis describes the synthesis and properties of novel poly(amine amide)s on the basis of 4,4’-dicarboxy-4”-fluorotriphenylamine (8). The new triphenylamine-containing dicarboxylic acid monomer 8, was synthesized via the double N-arylation of 4-fluoroaniline with 4-fluorobenzonitrile, followed by alkaline hydrolysis of the dinitrile intermediate. A new family of poly(amine amide)s with inherent viscosities of 0.44-0.97 dL/g were prepared by the direct phosphorylation polycondensation from the diacid monomer 8 with various aromatic diamines. All of the poly(amine amide)s were readily soluble in a variety of organic solvents and formed strong and tough films via solution casting. The wholly aromatic poly(amine amide)s have useful levels of thermal stability associated with moderately high glass transtion temperatures (243-314 ℃) and 10 % weight loss temperatures in excess of 466 ℃ in nitrogen. The photoluminescence (PL) spectra of these polymers in N-methyl-2-pyrrolidone (NMP) solution (10-5M) exhibited a strong emission in the blue region at 421~433 nm.
The final part of this thesis reports the synthesis and properties of novel fluorinated poly(amine-hydrazide)s and poly(amine-1,3,4-oxadiazole)s based on 4,4’-dicarboxy-4”-fluorotriphenylamine. Novel wholly aromatic poly(amine hydrazide)s were synthesized via the Yamazaki phosphorylation reaction from the diacid and various commercially available aromatic dihydrazides, followed by thermal cyclodehydration to poly(amine-1,3,4-oxadiazole)s. All aromatic polymers exhibited strong UV-Vis absorption bands at 347~385 nm in NMP solution. The photoluminescence spectra showed maximum bands around 458~528 nm in the blue and green region. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. For a comparative study, analogous poly(amine-hydrazide)s and poly(amine-1,3,4-oxadiazole)s based on 4,4’-dicarboxytriphenylamine were also prepared and characterized.
|
|---|
