ISSN:
0887-624X
Keywords:
polyurethanes
;
solution polymerization
;
naphtalene diisocyanate
;
kinetics
;
NMR spectroscopy
;
size exclusion chromatography
;
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction between polycaprolactone and 1,5-naphtalene diisocyanate has been investigated in solvents with different dielectric constants and hydrogen bonding powers (toluene, ethyl acetate, ethyl methyl ketone), and in the same solvents with the addition of a catalytic amount of dimethyl sulfoxide (DMSO). The reaction was considered to proceed over two steps, the reaction of the first NCO group being faster. The course of the reaction was measured by titration of the unreacted NCO groups, 1H- and 13C-NMR spectroscopy, and size exclusion chromatography. By titration only the overall reaction order and reaction rate constants could be determined. DMSO accelerated the reaction in all three solvents, which was explained by the stabilization of the activation complex by DMSO. Both steps of the reaction could be specified by NMR spectroscopy. The ratio between the reaction rate constants for the first and the second step decreased with the increased hydrogen bonding strength of the solvent and with DMSO. By SEC only the reaction of the first NCO group could be determined due to the low resolution for higher molar mass reaction products with a broad distribution. The values obtained for the first step reaction rate constants were in good agreement with NMR values. © 1995 John Wiley & Sons, Inc.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pola.1995.080331003
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