Please cite this article as: Bortolato SA, Thomas KE, McDonough K, Gurney RW, Martino DM, Evaluation of photo-induced crosslinking of thymine polymers using FT-IR spectroscopy and chemometric analysis, Polymer (2012), doi: 10.1016/j.polymer.2012.09.007. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT 2 ABSTRACTThe photo-induced immobilization of 4-vinylbenzyl thymine (VBT) and 4-vinylbenzyl triethyl ammonium chloride (VBA) copolymers has been investigated with the aid of grazing-angle specular-reflectance FT-IR spectroscopy. As irradiation time increases, changes in the structure of pendant thymine groups in the copolymer due to the crosslinking process result in shifts of the copolymer network's vibrational frequencies, as well as changes in numerous IR band intensities.In this work, chemometric methods have been applied to the FTIR data obtained while
A study on the thermo-oxidative stabilization (cyclization) of polyacrylonitrile (PAN) terpolymers using dynamic mechanical thermal analysis (DMTA) is reported in this article. When the changes in viscoelastic properties were monitored in a rectangular tension mode, besides the tan d peak characteristic of the glass transition observed below 200-C, the copolymer and the terpolymer displayed a second peak above 200-C due to the cyclization leading to the formation of ladder structures. The initiation temperature of the cyclization process as well as the peak temperature is found to depend on the acid value and the composition of the precursor polymer. The results presented show that monitoring the changes in viscoelastic properties during cyclization provides insight into the material properties as a result of the chemical changes that are taking place. These observations were confirmed by structural characterization using IR spectroscopy, and the observed chemical changes agree with the literature studies, as due to the thermal cyclization process.
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