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Polyurethanes: characterization, structural evaluation and effect induced by gamma radiation

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Author(s):
Laércio Gomes Lage
Total Authors: 1
Document type: Doctoral Thesis
Press: São Paulo.
Institution: Universidade de São Paulo (USP). Conjunto das Químicas (IQ e FCF) (CQ/DBDCQ)
Defense date:
Examining board members:
Yoshio Kawano; Teresa Dib Zambon Atvars; Maria Isabel Felisberti; Jivaldo do Rosario Matos; Denise Freitas Siqueira Petri
Advisor: Yoshio Kawano
Abstract

Polyurethane (PUR) is a class of polymers that possesses urethane groups [O-C(=O)-NH-] in its structure and that find many applications, including biomedical ones. This variety is due to the use of different monomers in its synthesis. The use of aliphatic isocyanates, one of PUR monomers, is more valuable in applications that demand stability to UV radiation, resistance to hydrolysis, and a greater thermal stability. The aromatic isocyanate-based PUR produces, when processed incorrectly, carcinogenic compounds, a fact that is not observed in the cycloaliphatic isocyanate-based PUR. The PUR modification to use it in biomedical artifacts has been made, among some procedures, through the incorporation of ionic groups into the polymer chain, forming ionomers. The biomedical materials sterilization is made employing ethylene oxide or gamma radiation. The objectives of this work are the synthesis and characterization of PUR and its sulfonated ionomer, both based on a cycloaliphatic isocyanate, as well as the study of the effect of gamma radiation in the polymers. It has been observed the formation of allophanate linkages through the analysis of vibrational spectra and elemental analysis data. Comparing the synthesized PUR and a commercial, amorphous, linear PUR used in biomedical artifacts, it has been noted that the former has crystallinity. The kinetic study of thermal decomposition of PUR allowed to establish the decomposition mechanism of PUR. The thermal stability and crystallinity of sulfonated PUR are greater than of PUR, probably due to the contribution of sulfonic groups. The lifetime of sulfonated PUR is greater than that of PUR, in the temperature range studied. The samples irradiation has permitted the observation of poliol and/or chain extender oxidation, by means of the decreasing of the intensity of the vibrational bands related to these groups and the decreasing of crystallinity in DSC. (AU)