NMR analysis; calculation of [<i>M</i>]<sub><i>eq</i></sub>; calculation of reactivity ratios; non-isothermal DSC analysis. Mariacristina Gagliardi Angelo Bifone 10.1371/journal.pone.0199231.s001 https://plos.figshare.com/articles/journal_contribution/Ring-opening_copolymerization_thermodynamics_and_kinetics_of_-valerolactone_-caprolactone/6637421 <p>Fig A, <sup>1</sup>H-NMR spectra of materials; 1: 100/0, 2: 90/10, 3: 80/20, 4: 70/30. Fig B, <sup>13</sup>C-NMR spectra of materials; 1: 100/0, 2: 90/10, 3: 80/20, 4: 70/30. Fig C, Calibration curves used for the calculation of <i>β</i><sub><i>i</i>,<i>j</i></sub> coefficients; a) 100/0, b) 90/10, c) 80/20 and d) 70/30. Fig D, GPC traces of crude samples withdrawn at the end of equilibrium reactions performed at different temperatures; a) 100/0, b) 90/10, c) 80/20 and d) 70/30. Fig E, DSC analysis: a) thermograms of normalized heat flow (W g<sup>-1</sup>), b) <i>α</i> and c) d<i>α</i>/d<i>t</i> against T at different heating rates. Fig F, Friedman plots (monomer conversion range: 0.2–0.9); a) 100/0, b) 90/10, c) 80/20 and d) 70/30. Fig G, KAS plots (monomer conversion range: 0.2–0.9); a) 100/0, b) 90/10, c) 80/20 and d) 70/30. Fig H, OFW plots (monomer conversion range: 0.2–0.9); a) 100/0, b) 90/10, c) 80/20 and d) 70/30. Fig I, <i>E</i><sub><i>a</i></sub> <i>vs</i> <i>α</i> from Friedman, KAS and OFW methods; a) 100/0, b) 90/10, c) 80/20 and d) 70/30. Fig J, <i>E</i><sub><i>a</i></sub> evaluated by a) maximum reaction rate temperatures, b) isoconversional methods and c) numerical methods. Table A, <i>M</i><sub><i>n</i></sub> (Da) and <i>α</i> obtained from equilibrium polymerizations at different temperatures; values of <i>M</i><sub><i>n</i></sub> are referred to the polyester block. Table B, Calculated thermodynamic parameters for each monomer. Table C, <i>M</i><sub><i>n</i></sub> (Da) and [<i>M</i>]<sub><i>res</i></sub> (mol L<sup>−1</sup>) from low-conversion polymerization at different times; values of <i>M</i><sub><i>n</i></sub> are referred to the polyester block. Table D, <i>M</i><sub><i>n</i></sub> (Da) and <i>α</i> from non-isothermal ROP at different heating rates; values of <i>M</i><sub><i>n</i></sub> are referred to the polyester block.</p> <p>(PDF)</p> 2018-06-21 17:48:52 lactone-based copolymers reaction feed monomer ratio changes kinetic valerolactone-based copolymers reaction parameters five-membered cyclic esters valerolactone fraction Ring-opening copolymerization thermodynamics caprolactone degradable materials monomer mixture non-isothermal syntheses methoxy polyethyleneglycol monomer ratios reactive monomers activation energy