United States of America As Represented by the Secretary of the Air Force

University of Dayton

Hybrid Plastics, Inc.

Other

University of California

Frank J Feher

Joseph D Lichtenhan

Joseph J Schwab

Daravong Soulivong

Jeffrey W Gilman

William A Reinerth

Ngo Quang Vu

Yi-Zong An

Timothy S Haddad

Shawn H Phillips

Qibo Liu

Rene I Gonzalez

William A Reinerth, Sr

Michael J Carr

Joseph J Schwabb

Raquel Terroba

Sixun Zheng

Steven A Svejda

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, HO 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]where &#x221e;=1-1,000,000 or higher into POSS nanostructures of formulas [(RSiO)&#x3a3;#, homoleptic, [(RXSiO)]&#x3a3;#, functionalized homoleptic, [(RSiO)(R&#x2032;SiO)], heteroleptic, and {(RSiO)(RXSiO)}, functionalized heteroleptic nanostructures. The second process utilizes base to aid in the formation of POSS nanostructures of formulas [(RSiO)]&#x3a3;# homoleptic and [(RSiO)(R&#x2032;SiO)]heteroleptic and [(RSiO)(RXSiO)]functionalized heteroleptic nanostructures from silanes RSiXand linear or cyclic silsesquioxanes of the formula RXSi&#x2014;(OSiRX)&#x2014;OSiRXwhere m=0-10, X=OH, Cl, Br, I, alkoxide OR, acetate OOCR, peroxide OOR, amine NR, isocyanate NCO, and R. The third process utilizes base to selectively ring-open the silicon-oxygen-silicon (Si&#x2014;O&#x2014;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.

Process for the formation of polyhedral oligomeric silsesquioxanes

The nanoscopic dimensions of polyhedral oligomeric silsesquioxanes (POSS) and polyhedral oligomeric silicates (POS) materials ranges from 0.7 nm to 5.0 nm and enables the thermomechanical and physical properties of polymeric materials to be improved by providing nanoscopic reinforcement of polymer chains at a length scale that is not possible by physically smaller aromatic chemical systems or larger fillers and fibers. A simple and cost effective method for incorporating POSS/POS nanoreinforcements onto polymers via the reactive grafting of suitably functionalized POSS/POS entities with polymeric systems amenable to such processes is described. The method teaches that the resulting POSS-grafted-polymers are particularly well suited for alloying agents by nongrafted POSS entitles such as molecular silicas. The successful alloying of POSS-polymers is aided because their interfacial tensions are reduced relative to non-POSS containing systems.

Reactive grafting and compatibilization of polyhedral oligomeric silsesquioxanes

Processes have been developed for the manufacture of polyhedral oligomeric silsesquioxanes (POSS), polysilsesquioxanes, polyhedral oligomeric silicates (POS), and siloxane molecules bearing reactive ring-strained cyclic olefins (e.g. norbornenyl, cyclopentenyl, etc. functionalities). The preferred manufacturing processes employ the silation of siloxides (Si&#x2014;OA, where A=H, alkaline or alkaline earth metals) with silane reagents that contain at least one reactive ring-strained cyclic olefin functionality [e.g., XSi(CH)(CH)where y=1-2 and X=OH, Cl, Br, I, alkoxide OR, acetate OOCR, peroxide OOR, amine NR, isocyanate NCO, and R]. Alternatively, similar products can be prepared through hydrosilation reactions between silanes containing at least one silicon-hydrogen bond (Si&#x2014;H) with ring-strained cyclic olefin reagents [e.g., 5-vinyl, 2 norbornene CH&#x2550;CH, cyclopentadiene]. The two processes can be effectively practiced using polymeric silsesquioxanes [RSiO]where &#x221e;=1-1,000,000 or higher and which contain unreacted silanol or silane groups at chain terminus or branch points, on POSS nanostructures of formulas [(RSiO)], homoleptic, [(RSiO)(R'SiO)], heteroleptic, and {(RSiO)(RXSiO)}, functionalized heteroleptic nanostructures, on silanes RSiX, linear, cyclic, oligomeric and polymeric siloxanes (polymeric formula RXSi&#x2014;(OSiRX)&#x2014;OSiRXwhere m=0-1000, X=OH, Cl, Br, I, alkoxide OR, acetate OOCR, peroxide OOR, amine NR, isocyanate NCO, and R). Each of the processes result in new chemical species bearing one or more ring strained olefins that can undergo polymerization, grafting, or other desirable chemical reactions to form polymeric products. These polymeric systems are most desirably utilized in polymerizations for the modification of properties of thermoplastic or thermoset resin systems or for the preparation of polymers with utility in electronics, medical devices, sporting goods, and aerospace as coatings and structural components.

Polyhedral oligomeric -silsesquioxanes, -silicates and -siloxanes bearing ring-strained olefinic functionalities

Method is provided for selectively opening rings of polyhedral oligomeric silsesquioxane (POSS) compounds to from functionalized derivatives thereof or new POSS species. Per the inventive method, the POSS compound is reacted with an acid to selectively cleave bonds in the POSS rings to add functionalities thereto for grafting, polymerization or catalysis, to thus form new familes of POSS derived compounds. Also provided are the new compounds so formed. Method is also provided for expanding rings of POSS compounds. Per the inventive method, a POSS compound is reacted with silane reagents to obtain an expanded POSS framework with added Si ring substituends to form new families of POSS compounds. Also provided are the new compounds so formed.

Altering of poss rings

Performance additives in high performance polymers using polyhedral oligomeric silsesquioxanes (POSS) and polyhedral oligomeric silicates (POS) as nanoscopic reinforcements, porosity control agents, thermal and oxidative stability aids to improve the properties of the polymers.

Polyhedral oligomeric silsesquioxane polyimide composites

Method is provided for reacting silsesquioxane resins or polyhedral oligomeric silsesquioxanes (POSS) bearing one or more olefinic groups with strong acids to cleave one or more olefin bonds of the olefinic groups to form POSS species of monomers or polymers having one or more functionalities suitable for reaction with a wide range of polymeric systems, to thus form new POSS derived compounds. Also provided are the new compounds so formed.

Functionalizing olefin bearing silsesquioxanes

A synthetic process for the selective preparation of reactive polyhedral oligomeric silsesquioxanes (POSS) as well as polyhedral oligomeric silicate (POS) (spherosilicate) is provided. The method claimed herein employs metal catalyzed metathesis reactions for the selective reaction of .alpha.-olefin containing polyhedral oligomeric silsesquioxanes or silicates with olefinic reagents bearing functionalities useful for grafting reactions, polymerization chemistry and sol-gel processes. The use of metal catalyzed metathesis chemistry to form both linear or network polyhedral silsesquioxane polymers directly from .alpha.-olefin-containing polyhedral oligomeric silsesquioxanes is also described.

Method of functionalizing polycyclic silicones and the resulting

A synthetic process for the selective preparation of reactive polyhedral oligomeric silsesquioxanes (POSS) as well as polyhedral oligomeric silicate (POS) (spherosilicate) is provided. The inventive process employs the use of metal catalyzed hydrosilylation reactions for the selective reaction of silane containing polyhedral oligomeric silsesquioxanes or silicates with olefinic reagents bearing functionalities useful for grafting reactions, polymerization chemistry and sol-gel processes. The invention also discloses metal-catalyzed hydrosulfidation reactions and metal-catalyzed hydrophosphidation reacttions for functionalization of polycyclic silicones.

Method of functionalizing polycyclic silicones and the compounds so

A synthesis process for polysilsesquioxanes which produces a high yield, tractable copolymer of perfectly alternating silsesquioxane and bridging group segments is provided. A difunctional silsesquioxane monomer of the formula Si.sub.8 R.sub.8 O.sub.11 (OA).sub.2 or Si.sub.7 R.sub.7 O.sub.9 (OSiR.sup.4 R.sup.5 R.sup.6) (OA).sub.2 is reacted with a difunctional compound of the formula X-M-X which forms a bridging group for a time sufficient to condense the difunctional silsesquioxane monomers and bridging groups into a linear polymer containing alternating silsesquioxane and bridging group segments. The resulting linear copolymer is essentially free of impurities and has controllable properties through the proper selection of the monomeric starting materials.

Polymers containing alternating silsesquioxane and bridging group

A process for preparation of reactive polyhedral oligomeric silsesquioxanes and the subsequent synthesis of polysilsesquioxanes which produce high yield, tractable polymers containing silsesquioxane segments is provided. A trifunctional polyhedral oligomeric silsesquioxane of the formula Si.sub.7 R.sub.7 O.sub.9 (OA).sub.3 is corner capped by reacting it with a compound of the formula M-Z to form a polyhedral oligomeric silsesquioxane which can be reacted in various ways with oligomers, polymers, catalysts, or co-monomers to form polyhedral silsesquioxane polymers containing silsesquioxanes as pendant, block, or end group segments. The resulting polymers are essentially free of impurities and have controllable properties through the proper selection of the synthesis process and starting materials.

Process for preparation of polyhedral oligomeric silsesquioxanes and

A synthesis process for polysilsesquioxanes which produces a high yield, tractable copolymer of perfectly alternating silsesquioxane and bridging group segments is provided. A difunctional silsesquioxane monomer of the formula Si.sub.8 R.sub.8 O.sub.11 (OA).sub.2 or Si.sub.7 R.sub.7 O.sub.9 (OSiR.sup.4 R.sup.5 R.sup.6)(OA).sub.2 is reacted with a difunctional compound of the formula X--M--X which forms a bridging group for a time sufficient to condense the difunctional silsesquioxane monomers and bridging groups into a linear polymer containing alternating silsesquioxane and bridging group segments. The resulting linear copolymer is essentially free of impurities and has controllable properties through the proper selection of the monomeric starting materials.

Growing community of inventors

Costa Mesa, CA, United States of America

Frank J Feher