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dc.contributor.authorLiu, Yanchunen_US
dc.date.accessioned2017-06-09T18:30:47Z
dc.date.available2017-06-09T18:30:47Z
dc.date.issued2012-03-22en_US
dc.identifier.otheretd-04032012-133528en_US
dc.identifier.urihttp://hdl.handle.net/10919/77999
dc.description.abstractA series of random and amorphous copolyesters containing different cycloaliphatic rings within the polymer chains were prepared by melt polycondensaton of difunctional monomers (diesters and diols) in the presence of a catalyst. These polyesters were characterized by nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), tensile tests and/or dynamic mechanical analysis (DMA). The copolyester based on dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate (DMCD-2) was observed to have a higher Tg, about 115ºC, than the other copolyesters with the same compositions in this study. For copolyesters containing different compositions of dimethyl-1,4-cyclohexane dicarboxylate (DMCD) and DMCD-2, the Tg increased linearly with the increase of DMCD-2 mole content. DMA showed that all of the cycloaliphatic copolyesters had secondary relaxations, resulting from conformational transitions of the cyclohexylene rings. The polyester based on DMCD-3 in the hydrolytic tests underwent the fastest hydrolytic degradation among these samples. A new triptycene diol (TD) was synthesized and incorporated into a series of cycloaliphatic copolyester backbones by melt condensation polymerization. Straight chain aliphatic spacers, including ethylene glycol (EG), 1,4-butanediol (BD) and 1,6-hexanediol (HD), were used as co-diols to explore their effects on polyester properties. An analogous series of non-triptycene copolyesters based on various hydroxyethylated bisphenols were also prepared for comparison. The results revealed that the TD-containing polymers had higher thermal stability and higher Tg's than the corresponding non-TD analogs. For TD-containing copolyesters, the mechanical properties were found to be dependent on the types and compositions of the co-diols. A 1,4-butanediol-based triptycene copolyester was observed to have a significantly increased Tg and modulus while maintaining high elongation at ambient temperature. Furthermore, it was demonstrated that the triptycene polyester exhibited higher Tg and modulus than those containing bisphenol derivatives. However, all of the 1,4-butanediol based copolyesters were brittle and had comparable moduli at low temperatures (-25°C or -40 °C). Melt polycondensation was also used to prepare a series of all-aliphatic block and random copolyesters including the following aliphatic monomers: trans-DMCD, DMCD-2, neopentyl glycol (NPG), diethylene glycol (DEG) and dimethyl succinate (DMS). The polymer compositions were determined by 1H NMR, and the molecular weights were determined using SEC. The polyesters were also characterized by TGA, DSC, DMA and tensile tests. Phase separation was not observed in these block copolyesters. However, the block copolyester containing DMCD-2 and NPG was observed to have a higher Tg than the block copolyester based on trans-DMCD and NPG. In addition, these block copolyesters were found to have better mechanical properties than the corresponding random copolyesters.en_US
dc.language.isoen_USen_US
dc.publisherVirginia Techen_US
dc.rightsI hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to Virginia Tech or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.en_US
dc.subjectcycloaliphatic monomersen_US
dc.subjectstructure-property relationshipen_US
dc.subjectglass transition temperatureen_US
dc.subjectmelt-phase polymerizationen_US
dc.subjectamorphous copolyestersen_US
dc.titleSynthesis and Characterization of Amorphous Cycloaliphatic Copolyesters with Novel Structures and Architecturesen_US
dc.typeDissertationen_US
dc.contributor.departmentChemistryen_US
dc.description.degreePhDen_US
thesis.degree.namePhDen_US
thesis.degree.leveldoctoralen_US
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen_US
dc.contributor.committeechairTurner, S. Richarden_US
dc.contributor.committeememberRiffle, Judy S.en_US
dc.contributor.committeememberDeck, Paul A.en_US
dc.contributor.committeememberMarand, Hervé L.en_US
dc.contributor.committeememberLong, Timothy E.en_US
dc.type.dcmitypeTexten_US
dc.identifier.sourceurlhttp://theses.lib.vt.edu/theses/available/etd-04032012-133528/en_US
dc.date.sdate2012-04-03en_US
dc.date.rdate2014-11-06
dc.date.adate2012-04-26en_US


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