Kinetic studies of CuBr-PMDETA catalyzed 1,3-dipolar cycloaddition polymerization |
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| Authors: | Rongpeng Liu Bing Zhang Farong Huang Lei Du |
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| Affiliation: | Key Laboratory of Specially Functional Polymeric Materials and Related Technology (East China University of Science and Technology), Ministry of Education, Shanghai, China |
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| Abstract: | The kinetics for the reaction of diazide (4,4′-biphenyl dibenzyl azide) and diyne (dipropargyl bisphenol A) catalyzed by CuBr-PMDETA (N, N, N′, N″, N″-pentamethyldiethylenetriamine) was studied in this paper by means of nuclear magnetic resonance spectra (1H-NMR) and differential scanning calorimetry (DSC). 1H-NMR was carried out to analyze solution polymerizations under different CuBr-PMDETA ratios in DMSO-d6. The results showed that CuBr-PMDETA catalytic system was easy to be oxidation under ambient condition. However, different CuBr-PMDETA ratios influenced the catalytic efficiency and the optimal ratios were found in nitrogen gas. DSC was carried out to analyze bulk polymerizations. The results showed that the apparent activation energy (Eα) calculated by Kissinger's method was 69.2 kJ/mol, which was confirmed by Friedman's method. The two tests indicated that the catalyzed polymerization of diazide and diyne was a second order reaction. |
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| Keywords: | Click reaction kinetics apparent activation energy step-growth polymerization |
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