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Radical polymerization of ortho-(1,3-dioxolan-2-yl)phenyl ethyl fumarate involving intramolecular hydrogen abstraction and ring opening of cyclic acetal

✍ Scribed by Tsuneyuki Sato; Sumio Shimooka; Makiko Seno


Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
232 KB
Volume
36
Category
Article
ISSN
0887-624X

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✦ Synopsis


The polymerization of o- (1,3-dioxolan-2-yl)phenyl ethyl fumarate (DOPEF) initiated with dimethyl 2,2-azobisiso-butyrate (MAIB) was studied kinetically in benzene. The polymerization rate (R p ) at 60ЊC was given by R p Å k [MAIB] 0.76 [DOPEF] 0.71 . The overall activation energy of polymerization was calculated to be 98.3 kJ/mol. The numberaverage molecular weight of resulting poly(DOPEF) was in the range of 1000-3100. 1 Hand 13 C-NMR spectra of resulting polymers revealed that the radical polymerization of DOPEF proceeds in a complicated manner involving vinyl addition, intramolecular hydrogen abstraction, and further ring opening of the cyclic acetal at higher temperatures. From the copolymerization of DOPEF (M 1 ) and styrene (St) (M 2 ) at 60ЊC, the monomer reactivity ratios were obtained to be r 1 Å 0.02 and r 2 Å 0.20, the values of which are similar to those of the copolymerization of ethyl o-formylphenyl fumarate and St.