Polysilsesquioxanes through base-catalyzed redistribution of oligohydridosiloxanes

Conference · Mon May 01 04:00:00 UTC 2000

OSTI ID:756093

RAHIMIAN, KAMYAR ^[1]; ASSINK, ROGER A; LANG, DAVID P; LOY, DOUGLAS A

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1. Sandia National Laboratories

Organopolysilsesquioxanes have recently gained much interest as materials for low-K dielectrics, ceramic precursors and photoresists. Typical sol-gel synthesis of polysilsesquioxanes involves the hydrolysis of organotricholorosilanes and/or organotrialkoxysilanes in the presence of acid or base catalysts and organic solvents. However, under sol-gel conditions most organotrialkoxysilanes do not afford silsesquioxane gels. This limits the range of organic functionalities that can be introduced into these hybrid organic-inorganic materials. An alternative route to polysilsesquioxanes is through oligohydridosiloxanes. Catalytic disproportionation, by titanium complexes, of linear or cyclic oligomers of methylhydridosiloxanes can lead to polymethylsilsesquioxanes. The authors have shown that disproportionation of oligomethylhydridosiloxanes can also be catalyzed by tetrabutylammonium hydroxide to yield polymethylsilsesquioxanes (scheme 1). This replaces the step-growth sol-gel polymerization process of organotrialkoxysilanes, which requires solvent, stoichiometric water and produces alcohol and water condensation by-products. Tetraalkylammonium hydroxides, as catalysts, are also attractive because they readily decompose by heating above 150 C; thus, they can be easily removed from the final materials. In this paper the authors report on both the catalytic and stoichiometric redistribution of organohydridosiloxanes to produce polysilsesquioxane foams and gels of the formula (RSiO{sub 1.5}){sub n} which otherwise cannot be obtained through traditional sol-gel means.

• Research Organization: Sandia National Labs., Albuquerque, NM (US); Sandia National Labs., Livermore, CA (US)
• Sponsoring Organization: US Department of Energy (US)
• DOE Contract Number: AC04-94AL85000
• OSTI ID: 756093
• Report Number(s): SAND2000-1088C
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
CATALYSTS
FOAMS
GELS
ORGANIC POLYMERS
ORGANIC SILICON COMPOUNDS
SILOXANES
SOL-GEL PROCESS
SYNTHESIS