ISSN:
0025-116X
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
This work deals with the modification reaction of dextran with ethyl and butyl chloroformate using tertiary amines as catalyst/acceptor systems and the DMF/LiCl system as solvent. The structure of the resulting polymers was determined by means of IR, 1H and 13C NMR spectroscopy as well as by chemical analyses. The reaction rate was found to increase in the following order: N,N′-dimethylaniline 〈 pyridine 〈 triethylamine. The presence of cyclic carbonates was observed when triethylamine was used as catalyst. A linear dependence of the reaction rate on polymer and pyridine concentrations and a more complex dependence on the n-alkyl chloroformate concentration were found. Reaction rate and yield decrease with increasing amount of LiCl in the solvent medium and increase with increasing chain length of the n-alkyl chloroformate. The activation energy was found to be 64 kJ/mol (15,3 kcal/mol). The equilibrium water content (EWC) values decreases progressively when either the content of carbonate groups or the side chain length increases. The hydrolysis in the heterogeneous phase showed that the time required for the polymer solubilization is dependent upon the nature of the carbonate groups, the temperature as well as the pH value of the medium. Dextranase was found to be inactive in the hydrolysis of water-insoluble modified dextrans. However, the hydrolysis takes place when water-soluble modified dextrans were used.
Additional Material:
10 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/macp.1985.021860103
