Process for the formation of polyhedral oligomeric silsesquioxanes

Abstract

Three processes for the manufacture of polyhedral oligomeric silsesquioxanes (POSS) which utilize the action of bases that are capable of either attacking silicon or any compound that can react with a protic solvent (e.g. ROH, H₂O etc.) and generate hydroxide [OH]⁻, alkoxide [RO]⁻, etc. The first process utilizes such bases to effectively redistribute the silicon-oxygen frameworks in polymeric silsesquioxanes [RSiO_1.5]_∞ where ∞=1−1,000,000 or higher into POSS nanostructures of formulas [(RSiO_1.5)_n]_Σ#, homoleptic, [(RXSiO_1.5)_n]_Σ#, functionalized homoleptic, [(RSiO_1.5)_m(R′SiO_1.5)_n]_Σ#, heteroleptic, and {(RSiO_1.5)_m(RXSiO_1.0)_n}_Σ#, functionalized heteroleptic nanostructures. The second process utilizes base to aid in the formation of POSS nanostructures of formulas [(RSiO_1.5)_n]_Σ# homoleptic and [(RSiO_1.5)_m(R′SiO_1.5)_n]_Σ# heteroleptic and [(RSiO_1.5)_m(RXSiO_1.0)_n]_Σ# functionalized heteroleptic nanostructures from silanes RSiX₃ and linear or cyclic silsesquioxanes of the formula RX₂Si—(OSiRX)_m—OSiRX₂ where m=0-10, X═OH, Cl, Br, I, alkoxide OR, acetate OOCR, peroxide OOR, amine NR₂, isocyanate NCO, and R. The third process utilizes base to selectively ring-open the silicon-oxygen-silicon (Si—O—Si) bonds in POSS structures to form POSS species with incompletely condensed nanostructures. These processes also afford stereochemical control over X. The three processes result in new POSS species that can undergo additional chemical manipulations to ultimately be converted into POSS-species suitable for polymerization, grafting, or other desirable chemical reactions.

Description

RELATED APPLICATIONS [0001] This application is: a continuation of U.S. patent application Ser. No. 09 / 631,892 filed Aug. 14, 2000 (which claims priority from U.S. Provisional Patent Application Ser. No. 60 / 147,435, filed Aug. 4, 1999); a continuation of U.S. patent application Ser. No. 10 / 351,292, filed Jan. 23, 2003 (which claims priority from U.S. Provisional Patent Application Ser. No. 60 / 351,523, filed Jan. 23, 2002), which is a continuation-in-part of U.S. patent application Ser. No. 09 / 818,265, filed Mar. 26, 2001, now U.S. Pat. No. 6,716,919 (which claims priority from U.S. Provisional Patent Application Ser. No. 60 / 192,083, filed Mar. 24, 2000); a continuation of U.S. patent application Ser. No. 09 / 747,762, filed Dec. 21, 2000 (which claims priority from U.S. Provisional Patent Application Ser. No. 60 / 171,888, filed Dec. 23, 1999); and a continuation of U.S. patent application Ser. No. 10 / 186,318, filed Jun. 27, 2002 (which claims priority from U.S. Provisional Patent Appli...

AI Technical Summary

Benefits of technology

[0006] In contrast to the prior art (see, e.g., Brown, J. F., Vogt, L. H., and P. I. Prescott J., Am. Chem. Soc. 1964, 86, 1120-1125; Marsmann, H. C. and Rilowski, E., Polyhedron, 1997, 16, 33

Problems solved by technology

In most cases, however, hydrolytic condensation reactions of trifunctional organosilicon monomers afford complex polymeric resins and POSS molecules that are unsuitable for use in polymerization or grafting reactions because they do not possess the desired type or degree of reactive functionality.

While these methods are highly useful for varying the organic functionality (substituents) contained on POSS molecules they are not always amenable to low-cost manufacturing nor do they offer the ability to selectively cleave and or manipulate the silicon-oxygen frameworks of such compounds.

Thus, these methods are of no utility for transforming the multitude of readily available and low cost silane, silicate, polysilsesquioxane (aka T-resins o

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