Mixed substituent poly[(vinyloxy)cyclotriphosphazenes] |
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| Authors: | Kenneth R Carter Christopher W Allen |
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| Institution: | Department of Chemistry, University of Vermont, Burlington, Vermont 05405‐0125 |
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| Abstract: | The mixed substituent cyclophosphazene monomers N3P3Cl4(OCH?CH2)(OCH2CF3) ( 2 ) and N3P3Cl3(OCH?CH2) (OCH2CF3)2 ( 3 ) undergo polymerization under radical initiation conditions to yield the mixed substituent poly(vinyloxy)cyclotriphosphazenes] CH2CH(ON3P3Cl4(OCH2CF3))]n( 5 ) and CH2CH(ON3P3Cl3(OCH2CF3)2)]n ( 6 ), respectively. A significant, progressive reduction in molecular weight compared to the parent polymer of the series CH2CH(ON3P3Cl5)]n ( 4 ) was observed and attributed to increased chain transfer. The thermal decomposition of 5 and 6 is similar to that observed for 4 with an exothermic elimination of HCl at modest temperatures. An alternative synthetic pathway involving nucleophilic substitution reactions of 4 provided CH2CH(ON3P3(OCH2CF3)5)]n ( 7 ), CH2CH(N3P3Cl2(OC6H5)3)]n ( 8A) , CH2CH(ON3P3Cl1.7(OC6H5)3.3)]n ( 8B ), CH2CH(ON3P3Cl1.5(NHCH3)3.5)]n ( 9 ), CH2CH(ON3P3Cl3.8 (N(CH2CH3)2)1.2]n ( 10A ), CH2CH(ON3P3Cl3.4(N(CH2CH3)2)1.6)]n ( 10B ), and N3P3Cl2(OCHCH2)(N(CH3)2)]n, ( 11 ). The thermal behaviors of all of the new polymers were examined by TGA, DTA, DSC, and pyrolysis mass spectrometry. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 |
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| Keywords: | cyclophosphazenes inorganic polymers radical polymerization thermal properties |
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