ISSN:
0887-624X
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Using a model reaction we have studied the crosslinking chemistry of hydroxy-functional polymers and hexamethoxymethylmelamine. The transetherification of optically active monofunctional alcohols and hexamethoxymethylmelamine was monitored with polarimetry and 1H-NMR. The reaction rate constants for both the forward (k1) and the backward (k-1) reaction of the sulphonic-acid-catalyzed alcoholysis were determined. Primary and secondary alcohols showed the same reaction rate and activation energy (Ea = 96 kJ/mol) for the forward reaction. However, the backward reaction in the equilibrium is considerably slower for primary alcohols than for secondary alcohols, with activation energies of Ea = 96 and 79 kJ/mol, respectively. When amine salts of sulphonic acids are used as catalysts, the Ea is increased from 97 to 116 kJ/mol in the case of primary alcohols. In concentrated aprotic solutions the reaction order in acid is 2.5. The same order in acid is found for the alcoholysis of acetaldehyde diethyl acetal. All the results strongly support the statement that the crosslinking reaction proceeds by an Sn-1 mechanism. The results of this model study are compared with results obtained in network-forming reactions. The important role of the evaporation of the condensation product methanol is discussed.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pola.1986.080240914
