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1. 发明授权

US5942638A Method of functionalizing polycyclic silicones and the resulting compounds 失效
标题翻译：官能化多环硅氧烷和所得化合物的方法
公开(公告)号：US5942638A
公开(公告)日：1999-08-24
申请号：US003083
申请日：1998-01-05
申请人： Joseph D. Lichtenhan , Joseph J. Schwabb , Frank J. Feher , Daravong Soulivong
发明人： Joseph D. Lichtenhan , Joseph J. Schwabb , Frank J. Feher , Daravong Soulivong
IPC分类号： C07F7/08 , C07F7/21
CPC分类号： C07F7/21 , C07F7/0878
摘要： 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.
摘要翻译：提供了选择性制备反应性多面体低聚倍半硅氧烷（POSS）以及多面体低聚硅酸盐（POS）（硅藻土）的合成方法。本文所要求的方法使用金属催化的复分解反应，用于选择性反应含α-烯烃的多面体低聚倍半硅氧烷或硅酸盐与含有可用于接枝反应，聚合化学和溶胶 - 凝胶方法的官能团的烯属试剂。还描述了使用金属催化的复分解化学直接从含α-烯烃的多面体低聚倍半硅氧烷形成直链或网络多面体倍半硅氧烷聚合物。

2. 发明授权

US6100417A Functionalizing olefin bearing silsesquioxanes 失效
标题翻译：官能化烯烃轴承倍半硅氧烷
公开(公告)号：US6100417A
公开(公告)日：2000-08-08
申请号：US387682
申请日：1999-08-31
申请人： Joseph D. Lichtenhan , Frank J. Feher , Daravong Soulivong
发明人： Joseph D. Lichtenhan , Frank J. Feher , Daravong Soulivong
IPC分类号： C07F7/21 , C07F2/08
CPC分类号： C07F7/21
摘要： 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.
摘要翻译：提供了将含有一个或多个烯属基团的倍半硅氧烷树脂或多面体低聚倍半硅氧烷（POSS）与强酸反应以切割烯烃基团的一个或多个烯烃键以形成具有一个或多个适合于反应的官能团的单体或聚合物的POSS种类的方法具有广泛的聚合体系，从而形成新的POSS衍生化合物。还提供了如此形成的新化合物。

3. 发明授权

US06770724B1 Altering of poss rings 失效
标题翻译：改变可能的环
公开(公告)号：US06770724B1
公开(公告)日：2004-08-03
申请号：US09783719
申请日：2001-02-16
申请人： Joseph D. Lichtenhan , Timothy S. Haddad , Frank J. Feher , Daravong Soulivong
发明人： Joseph D. Lichtenhan , Timothy S. Haddad , Frank J. Feher , Daravong Soulivong
IPC分类号： C08G7706
CPC分类号： C07F7/21 , C07F7/0876 , C08G77/04 , C08G77/045 , C08G77/38
摘要： 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.
摘要翻译：提供了从其官能化衍生物或新的POSS物质选择性地打开多面体低聚倍半硅氧烷（POSS）化合物的环的方法。按照本发明的方法，POSS化合物与酸反应以选择性地切割POSS环中的键，以便为其接枝，聚合或催化添加官能团，从而形成新的POSS衍生化合物。还提供了如此形成的新化合物。还提供了扩展POSS化合物环的方法。根据本发明的方法，POSS化合物与硅烷试剂反应以获得具有添加的Si环取代基的扩展的POSS框架，以形成新的POSS化合物族。还提供了如此形成的新化合物。

4. 发明授权

US5939576A Method of functionalizing polycyclic silicones and the compounds so formed 失效
标题翻译：使多环硅氧烷官能化的方法和如此形成的化合物
公开(公告)号：US5939576A
公开(公告)日：1999-08-17
申请号：US3084
申请日：1998-01-05
申请人： Joseph D. Lichtenhan , Joseph J. Schwab , Frank J. Feher , Daravong Soulivong
发明人： Joseph D. Lichtenhan , Joseph J. Schwab , Frank J. Feher , Daravong Soulivong
IPC分类号： C07F7/21 , C07F7/08 , C07F7/10
CPC分类号： C07F7/21
摘要： 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.
摘要翻译：提供了选择性制备反应性多面体低聚倍半硅氧烷（POSS）以及多面体低聚硅酸盐（POS）（硅藻土）的合成方法。本发明方法采用金属催化的氢化硅烷化反应来选择性反应含硅烷的多面体低聚倍半硅氧烷或硅酸盐与含有可用于接枝反应，聚合化学和溶胶 - 凝胶法的官能团的烯属试剂。本发明还公开了金属催化的加氢硫化反应和用于多环硅氧烷官能化的金属催化的氢磷化反应。

5. 发明授权

US06972312B1 Process for the formation of polyhedral oligomeric silsesquioxanes 有权
公开(公告)号：US06972312B1
公开(公告)日：2005-12-06
申请号：US09631892
申请日：2000-08-04
申请人： Joseph D. Lichtenhan , Joseph J. Schwab , Yi-Zong An , William Reinerth , Michael J. Carr , Frank J. Feher , Raquel Terroba , Qibo Liu
发明人： Joseph D. Lichtenhan , Joseph J. Schwab , Yi-Zong An , William Reinerth , Michael J. Carr , Frank J. Feher , Raquel Terroba , Qibo Liu
IPC分类号： C08G77/04 , C08G77/06 , C08G77/08
CPC分类号： C08G77/04 , C08G77/045 , C08G77/06 , C08G77/08
摘要： 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 [RSiO1.5]28 where ∞=1-1,000,000 or higher into POSS nanostructures of formulas [(RSiO1.5)nΣ#, homoleptic, [(RXSiO1.5)n]Σ#, functionalized homoleptic, [(RSiO1.5)m(R′SiO1.5)n]Σ#, heteroleptic, and {(RSiO1.5)m(RXSiO1.0)n}Σ#, functionalized heteroleptic nanostructures. The second process utilizes base to aid in the formation of POSS nanostructures of formulas [(RSiO1.5)n]Σ# homoleptic and [(RSiO1.5)m(R′SiO1.5)n]Σ# heteroleptic and [(RSiO1.5)m(RXSiO1.0)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.

6. 发明授权

US06933345B1 Reactive grafting and compatibilization of polyhedral oligomeric silsesquioxanes 失效
标题翻译：多面体低聚倍半硅氧烷的反应性接枝和增容
公开(公告)号：US06933345B1
公开(公告)日：2005-08-23
申请号：US10351292
申请日：2003-01-23
申请人： Joseph D. Lichtenhan , Frank J. Feher , Joseph J. Schwab , Sixun Zheng
发明人： Joseph D. Lichtenhan , Frank J. Feher , Joseph J. Schwab , Sixun Zheng
IPC分类号： C08F8/00 , C08K5/5419 , C08K7/00 , C08L83/00
CPC分类号： B82Y30/00 , C08K5/5419 , C08K7/00 , C08K2201/011 , C08L2205/14 , C08L23/10
摘要： 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.
摘要翻译：多面体低聚倍半硅氧烷（POSS）和多面体低聚硅酸盐（POS）材料的纳米尺寸范围为0.7nm至5.0nm，并且通过以长度尺度提供聚合物链的纳米级增强，可以改善聚合物材料的热机械和物理性能，通过物理上较小的芳族化学体系或较大的填料和纤维是不可能的。描述了通过适当功能化的POSS / POS实体与适合于这种方法的聚合物体系的反应性接枝将POSS / POS纳米增强剂结合到聚合物上的简单且成本有效的方法。该方法教导得到的POSS接枝聚合物特别适用于通过非接枝POSS权利如分子二氧化硅的合金化剂。有助于POSS聚合物的成功合金化，因为它们的界面张力相对于不含POSS的体系而降低。

7. 发明授权

US06911518B2 Polyhedral oligomeric -silsesquioxanes, -silicates and -siloxanes bearing ring-strained olefinic functionalities 有权
公开(公告)号：US06911518B2
公开(公告)日：2005-06-28
申请号：US09747762
申请日：2000-12-21
申请人： Joseph D. Lichtenhan , Joseph J. Schwab , Yi-Zong An , William Reinerth , Frank J. Feher
发明人： Joseph D. Lichtenhan , Joseph J. Schwab , Yi-Zong An , William Reinerth , Frank J. Feher
IPC分类号： C07F7/08 , C07F7/18 , C07F7/21 , C07F11/00 , C08G77/20 , C08G77/08
CPC分类号： C08G77/20 , C07F7/0829 , C07F7/0874 , C07F7/0879 , C07F7/1876 , C07F7/188 , C07F7/21 , C07F11/005
摘要： 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—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., X3-ySi(CH3)y(CH2)2 where y=1-2 and X=OH, Cl, Br, I, alkoxide OR, acetate OOCR, peroxide OOR, amine NR2, isocyanate NCO, and R]. Alternatively, similar products can be prepared through hydrosilation reactions between silanes containing at least one silicon-hydrogen bond (Si—H) with ring-strained cyclic olefin reagents [e.g., 5-vinyl, 2 norbornene CH2═CH, cyclopentadiene]. The two processes can be effectively practiced using polymeric silsesquioxanes [RSiO1.5]∞ where ∞=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 [(RSiO1.5)n]Σ#, homoleptic, [(RSiO1.5)m(R′SiO1.5)n]Σ#, heteroleptic, and {(RSiO1.5)m(RXSiO1.0)n}Σ#, functionalized heteroleptic nanostructures, on silanes RSiX3, linear, cyclic, oligomeric and polymeric siloxanes (polymeric formula RX2Si—(OSiRX)m—OSiRX2 where m=0-1000, X=OH, Cl, Br, I, alkoxide OR, acetate OOCR, peroxide OOR, amine NR2, 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.

8. 发明授权

US5484867A Process for preparation of polyhedral oligomeric silsesquioxanes and systhesis of polymers containing polyhedral oligomeric silsesqioxane group segments 失效
标题翻译：制备多面体低聚倍半硅氧烷的方法及含有多面体低聚硅氧烷基团的聚合物的合成
公开(公告)号：US5484867A
公开(公告)日：1996-01-16
申请号：US252226
申请日：1994-06-01
申请人： Joseph D. Lichtenhan , Jeffrey W. Gilman , Frank J. Feher
发明人： Joseph D. Lichtenhan , Jeffrey W. Gilman , Frank J. Feher
IPC分类号： C08G77/04 , C08G77/48 , C08G77/58 , C08G77/06
CPC分类号： C08G77/04 , C08G77/48 , C08G77/58
摘要： 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.
摘要翻译：提供了制备反应性多面体低聚倍半硅氧烷的方法以及随后的合成聚倍半硅氧烷，其产生含有倍半硅氧烷片段的高产率，可处理的聚合物。式Si7R7O9（OA）3的三官能多面体低聚倍半硅氧烷通过使其与式MZ的化合物反应形成多面体低聚倍半硅氧烷，其可以以各种方式与低聚物，聚合物，催化剂或共聚单体含有倍半硅氧烷作为侧基，嵌段或末端基团的多面体倍半硅氧烷聚合物。所得聚合物基本上不含杂质，并且通过适当选择合成方法和起始原料具有可控性质。

9. 发明授权

US5412053A Polymers containing alternating silsesquioxane and bridging group segments and process for their preparation 失效
标题翻译：含有交替倍半硅氧烷和桥连基团片段的聚合物及其制备方法
公开(公告)号：US5412053A
公开(公告)日：1995-05-02
申请号：US105148
申请日：1993-08-12
申请人： Joseph D. Lichtenhan , Ngo Q. Vu , Jeffrey W. Gilman , Frank J. Feher
发明人： Joseph D. Lichtenhan , Ngo Q. Vu , Jeffrey W. Gilman , Frank J. Feher
IPC分类号： C08G77/04 , C08G77/48 , C08G77/58
CPC分类号： C08G77/04 , C08G77/48 , C08G77/58
摘要： 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.
摘要翻译：提供了一种聚倍半硅氧烷的合成方法，该方法产生了完全交替的倍半硅氧烷和桥连基团段的高产率，可处理的共聚物。将式Si 8 R 8 O 11（OA）2或Si 7 R 7 O 9（OSiR 4 R 5 R 6）（OA）2）的双官能倍半硅氧烷单体与式XMX的双官能化合物反应，其形成桥连基团足以将双官能倍半硅氧烷单体和桥连基团缩合的时间含有交替的倍半硅氧烷和桥连基团的线性聚合物。所得到的线性共聚物基本上不含杂质，并且通过适当选择单体起始原料具有可控性质。

10. 发明授权

US06767930B1 Polyhedral oligomeric silsesquioxane polyimide composites 有权
标题翻译：多面体低聚倍半硅氧烷聚酰亚胺复合材料
公开(公告)号：US06767930B1
公开(公告)日：2004-07-27
申请号：US10238923
申请日：2002-09-09
申请人： Steven A. Svejda , Shawn H. Phillips , Rene I. Gonzalez , Frank J. Feher , Joseph D. Lichtenhan , Joseph J. Schwab , William A. Reinerth
发明人： Steven A. Svejda , Shawn H. Phillips , Rene I. Gonzalez , Frank J. Feher , Joseph D. Lichtenhan , Joseph J. Schwab , William A. Reinerth
IPC分类号： C08J900
CPC分类号： C08J9/26 , C08G73/106 , C08G77/455 , C08J2379/08 , C08K5/49
摘要： 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.
摘要翻译：使用多面体低聚倍半硅氧烷（POSS）和多面体低聚硅酸盐（POS）作为纳米增强剂的高性能聚合物的性能添加剂，孔隙度控制剂，热和氧化稳定性有助于改善聚合物的性能。

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