ISSN:
0887-624X
Keywords:
2,5-dimethylene-2,5-dihydrofuran
;
kinetics
;
copolymerization
;
polymeriza-bility
;
highly conjugative
;
electron-donating
;
new monomer
;
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Spontaneous homopolymerization of 2,5-dimethylene-2,5-dihydrofuran (DDF) was studied. The polymerization rates in two different initial monomer concentrations of DDF were analyzed with the first-order and second-order kinetics, and the homopolymerization of DDF was found to obey the first-order kinetics. The Arrhenius plot of the apparent rate constants at 30, 40, 50, and 60° gave an overall activation energy of 68.0 kJ/mol for the polymerization of DDF. From the comparison of the apparent rate constants at -78° and the time (the so-called half-life time) to decrease in half the monomer concentration for DDF with the corresponding values for p-xylylene (QM), DDF was found to be a less reactive monomer than QM. The copolymerizations of DDF with vinyl monomers such as acrylonitrile (AN), α-chloroacrylonitrile (CIAN), diethyl fumarate (DEF), and fumaronitrile (FN) were carried out in chloroform at 50° in the presence of AIBN to obtain the monomer reactivity ratios r1(DDF) = 30.0 ± 3.0 and r2 (AN) = 0 for the DDF-AN system, r1 (DDF) = 1.55 ± 0.2 and r2(CIAN) = 0 for the DDF-CIAN system, r1(DDF) = 3.88 ± 0.2 and r2(DEF) = 0 for the DDF-DEF system, and r1(DDF) = 2.41 ± 0.1 and r2 (FN) = 0 for the DDF-FN system, respectively. As the monomer reactivity ratios of r2 for all systems were zero, Q and e values of DDF were calculated from the combination of two r1 (DDF) values of any two copolymerization systems to be the 7.64 to 6.63 ×1021 range for Q and the -0.70 to -6.31 range for e, indicating that DDF is a highly conjugative and electron-donating monomer. © 1995 John Wiley & Sons, Inc.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pola.1995.080330915
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