ISSN:
0449-2951
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The alternating copolymerization of bicyclo[2.2.1]hept-2-ene and sulfur dioxide has been found to be quite unusual for a free-radical polymerization: (1) the initiation of copolymerization is spontaneous, even at -40°C.; (2) solution copolymerization is extremely fast, yielding very high molecular weight polymer within a few seconds; (3) conversions are high (up to 93% within a minute); (4) molecular weight during copolymerization increases at essentially constant conversion; (5) the reaction is incapable of being chemically inhibited indefinitely, short of exhausting one of the constituent monomers; (6) at elevated temperatures, the monomers and copolymer appear to be in equilibrium; (7) large concentrations of free radicals have been detected by electron paramagnetic resonance to be associated with the bulk copolymerization; and (8) the copolymerization appears to result in “living” free-radical polymers. A copolymerization mechanism is proposed to explain these observations. Bicycloheptene and sulfur dioxide initially form a 1 : 1 molecular charge transfer complex which rearranges to a biradical; subsequent coupling of biradicals with each other (and possibly also with the molecular complexes themselves) leads to rapid propagation to high molecular weight, alternating copolymer. Speculations that similar mechanisms may be important in other copolymerization reactions are also made.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1965.100030806
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