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Molecular Growth Pathways in Silica Sol-Gel Polymerization

Published online by Cambridge University Press:  25 February 2011

W. G. Klemperer and
S. D. Ramamurthi
W. G. Klemperer
Affiliation:
Department of Chemistry and Materials Research Laboratory, University of Illinois, Urbana, IL 61801
S. D. Ramamurthi
Affiliation:
Department of Chemistry and Materials Research Laboratory, University of Illinois, Urbana, IL 61801
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Abstract

Capillary gas chromatography has been used to monitor the stoichi-ometries, structures, and abundances of low molecular weight polysilicate esters formed by partial hydrolysis of methanolic tetramethylorthosili-cate and redistribution of methanolie hexamethyoxydisiloxane under acidic (HC1) and basic (KOH) conditions. The polysilicate molecular size distributions, expressed in terms of mole percent of total silicon present as a function of degree of polymerization, show maxima near the number average degree of polymerization under acidic conditions. Under basic conditions, the distribution has its maximum at the monomer percent and extends to very high molecular weights, yielding a distribution far broader than the one observed under acidic conditions. These features are in agreement with covalent network theories of silica gelation, as opposed to particle aggregation theories. Weight fraction distributions of the type observed under acidic conditions are characteristic of linear polymers with a low degree of crosslinking and weight fraction distributions of the type observed under basic conditions are characteristic of branched polymers with high degree of crosslinking. The low degree of crosslinking obtained under acidic conditions is observed to arise from steric crowding that discourages branching in polysilicate structures.

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Type
Research Article
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MRS Online Proceedings Library (OPL) , Volume 121: Symposium H – Better Ceramics Through Chemistry III , 1988, 1
Copyright
Copyright © Materials Research Society 1988

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