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URN etd-0223106-125712 Statistics This thesis had been viewed 2699 times. Download 1172 times. Author Wen-Tsuen Leu Author's Email Address email@example.com Department Chemical Engineering Year 2005 Semester 1 Degree Ph.D. Type of Document Doctoral Dissertation Language English Page Count 231 Title SYNTHESIS AND PROPERTIES OF AROMATIC POLY(ESTER-AMIDE)S AND POLY(ESTER-IMIDE)S WITH BIS(BENZOYLOXY)NAPHTHALENE UNITS Keyword Poly(ester-imide)s Poly(ester-amide)s Poly(ester-amide)s Poly(ester-imide)s Abstract This dissertation deals with the synthesis and characterization of six isomeric naphthalene ring-containing bis(ester-amine)s, 2,7-, 1,5-, and 2,3-bis(4-aminobenzoyloxy)naphthalenes (2,7-p-2, 1,5-p-2, and 2,3-p-2) and 2,7-, 1,5-, and 2,3-bis(3-aminobenzoyloxy)naphthalenes (2,7-m-2, 1,5-m-2, and 2,3-m-2), and their derived aromatic poly(ester-amide)s and poly(ester-imide)s.
First, the diamine monomers with the bis(benzoyloxy)naphthalene unit were successfully synthesized from the condensation of 2,7-, 1,5-, and 2,3-naphthalenediol with 4-nitrobenzoyl chloride and 3-nitrobenzoyl chloride, respectively, followed by subsequent catalytic hydrogen reduction of the intermediate diester-dinitro compounds. Six series of novel aromatic poly(ester-amide)s were successfully synthesized by the direct phosphorylation polyamidation from these bis(ester-amine)s with various aromatic dicarboxylic acids. For the improvement of the film-forming capability of the 2,3-series poly(ester-amide)s, copolymers based on an equimolar mixture of 2,3-p-2 or 2,3-m-2 and 4,4’-oxydianiline with various dicarboxylic acids were also prepared. These poly(ester-amide)s were obtained in quantitative yields with inherent viscosities of up to 1.20 dL g-1. Some of these poly(ester-amide)s could be cast into transparent, flexible, and tough films from DMAc solutions. Most of these poly(ester-amide)s had excellent solubility in polar aprotic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide, especially for the meta-series polymers, and showed well-defined glass transition temperatures between 179 and 237 oC in the DSC traces. The TGA curves displayed that all of these poly(ester-amide)s had excellent thermal stability with 10 wt% loss temperatures above 325 oC for 2,3-series polymers and 400 oC for 2,7- and 1,5-series polymers in nitrogen or air.
Second, six series of novel aromatic poly(ester-imide)s were also prepared from these bis(ester-amine)s with various commercially available aromatic tetracarboxylic dianhydrides via a conventional two-stage synthesis that included ring-opening polyaddition to give poly(amic acid)s followed by chemical imidization to polyimides. For improving film-forming capability and solubility, copolymers were also prepared from 2,7-substituted bis(ester-amine)s with an equimolar mixture of 6FDA and another dianhydride or an equimolar mixture of 2,3-substituted bis(ester-amine)s and 4,4’-oxydianiline with dianhydrides. The intermediate poly(amic acid)s obtained in the first stage had inherent viscosities of up to 1.37 dL g-1. Some of these poly(ester-imide)s, especially for the meta-series polymers derived from 6FDA, were soluble in all of the organic solvents tested including less polar m-cresol and THF at room temperature and could be solution-cast into transparent, flexible, and tough films with good mechanical properties. Most of these poly(ester-imide)s displayed a clear glass transition between 225 and 295 oC in the DSC traces. The TGA curves indicated that all of these poly(ester-imide)s showed excellent thermal stability with 10 wt% loss temperatures above 460 oC in nitrogen or air.
Finally, the investigation of the thermal decomposition of the aromatic poly(ester-amide) 2,7-p-4a and poly(ester-imide) 2,7-p-7a using pyrolysis-gas chromatography/mass spectrometry (pyrolysis-GC/MS) showed that the early degradation of the ester groups produced 2,7-naphthalenediol as the major product, which initiated the polymer chain scission. The ester linkage within the polymer main chain disconnected first at approximately 300 oC for the 2,7-p-4a and 350oC for the 2,7-p-7a, indicating that it is the weakest bond. The cleavages of the amide and imide groups initially occurred at 400 and 450 oC, respectively. Furthermore, the thermal degradation behaviour of a novel phosphorus-containing aromatic poly(ester-amide) ODOP-PEA was also investigated by pyrolysis-GC/MS. The P-C bond linked between the pendant DOPO group and the polymer chain disconnected first at approximately 275 oC, indicating that it is the weakest bond in the ODOP-PEA. The cleavage of the P-O bond in the pendant DOPO group initiated at 300 oC. The ester linkage within the polymer main chain was stable up to 400 oC, and the amide group scission occurred at greater than 400 oC. The structures of the decomposition products were used to propose the degradation processes and elucidate the sequence of bond cleavage.
Advisor Committee Sheng-Huei Hsiao - advisor
Guey-Sheng Liou - co-chair
Kuo-Chung Cheng - co-chair
Wen-Fu Lee - co-chair
Wenjeng Guo - co-chair
Yaw-Terng Chern - co-chair
Files Date of Defense 2006-01-20 Date of Submission 2006-02-23