ISSN:
0360-6376
Schlagwort(e):
Physics
;
Polymer and Materials Science
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
When heated in solution at about 160°C, pyridine quaternary salts of bromomalonamides lose 1 mole of cyanic or isocyanic acid almost quantitatively in a manner quite analogous to the decarboxylation of an acid. By DTA and DSC, the crystalline salts are stable up to their melting points (〉220°C) at which temperatures concurrent fusion and decyanation processes occur (endotherm); these are immediately followed by an exotherm related to the trimerization of cyanic acid. TGA measurements on the solid salts do not clearly define the loss of 1 mole of cyanic acid because in the solid state, thermal decyanation is accompanied to some extent by other pyrolytic reactions. Preparative methods for quaternizing poly(4-vinylpyridine) with bromomalonamide are described and two polymeric quaternary salts (33 and 100% substituted) were prepared and analyzed. These polyelectrolytes are water soluble and upon the addition of base the yellow polymeric nitrogen ylids are generated. Infrared spectra on the polymeric quaternary salts and visible spectra on the polymeric ylids are included. The ylid chromophore has an ε = 1800 at λmax = 415 nm. The dilute solution viscosity behavior of these polymers in H2O and in 0.05N KBr is typical of polyelectrolytes. Both polymers in dilute solution show a maximum in ηsp versus pH plots. In water, the viscosity of these polymers decreases with time, and it is proven that this results from a conformational change which accompanies amide hydrolysis rather than polymer backbone degradation. Glass transitions are not detectable by DTA but both polymers show well-defined trimerization exotherms for cyanic acid starting at 170-175°C. Thus, decyanation of the solid polymeric quaternary salts is more analogous to decyanation of the crystalline quaternarys in solution than as solids. TGA measurements on the polymers show weight losses which are of the correct order of magnitude and in the correct temperature range for monodecyanation. Some data are presented which suggest that perhaps a second mole of cyanic acid is lost at about 250°C. Quaternization of poly(4-vinylpyridine) with bromomalonamide reduces its gross decomposition temperature from 385°C to about 285-317°C. It is demonstrated how thermal decyanation can be used for the in situ generation of cyanic acid for the modification of organic compounds. The preparation of a partial urethane of poly(vinyl alcohol) using this method is described. We have also shown that aliphatic quaternary salts can be prepared and that they too undergo the decyanation reaction.
Zusätzliches Material:
7 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/pol.1977.170150519
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