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公开(公告)号：US06433101B1
公开(公告)日：2002-08-13
申请号：US09453020
申请日：1999-12-02
IPC分类号： C08F818
摘要： The present invention relates to the post-polymerization fluorination methods of polymers produced via ring-opening metathesis polymerization. Unlike prior art methods that result in low product yields and generally involve chemically aggressive reagents, the inventive methods produce fluorinated polymers in quantitative yields and under mild conditions. In preferred embodiments, a source of difluorocarbene is reacted with the desired polydiene to form a fluorinated polymer product. In preferred embodiments, the source of difluorocarbene is hexafluoropropylene oxide and the polydiene is poly-dicyclopentadiene (“poly-DCPD”). Fluorination and the concomitant removal of unsaturated bonds result in polymers having improved physical properties such as improved strength characteristics, enhanced oxidative and chemical stability, and low surface energies.
摘要翻译： 本发明涉及通过开环易位聚合制备的聚合物的后聚合氟化方法。 不同于导致低产物产率并且通常涉及化学腐蚀性试剂的现有技术方法，本发明方法以定量产率和温和条件下产生氟化聚合物。 在优选的实施方案中，将二氟卡宾源与所需的聚二烯反应以形成氟化聚合物产物。 在优选的实施方案中，二氟卡宾的来源是六氟环氧丙烷，聚二烯是聚二环戊二烯（“poly-DCPD”）。 氟化和伴随去除不饱和键导致具有改进的物理性质的聚合物，例如改进的强度特性，增强的氧化和化学稳定性和低表面能。
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2.发明授权Romp of functionalized cyclic olefins using ruthenium and osmium carbene complexes 失效使用钌和咔咔啉络合物对官能化环烯烃进行反应
公开(公告)号：US5849851A
公开(公告)日：1998-12-15
申请号：US969969
申请日：1997-11-13
IPC分类号： B01J23/46 , B01J31/22 , C07C51/353 , C07C67/475 , C07F15/00 , C08F4/80 , C08F8/50 , C08F10/00 , C08F32/00 , C08F210/02 , C08G61/08 , C08G61/12
CPC分类号： B01J31/2265 , B01J31/24 , B01J31/2404 , C07C51/353 , C07C67/333 , C07C67/475 , C07F15/002 , C07F15/0046 , C08C19/08 , C08F10/00 , C08F32/00 , C08F8/50 , C08G61/08 , C08G61/128 , B01J2231/14 , B01J2231/543 , B01J23/462 , B01J23/466 , B01J2531/821 , B01J2531/825 , C07C2101/10 , C08C2019/09 , C08F210/02 , Y10S525/938
摘要： Disclosed are ruthenium and osmium carbene compounds which are stable in the presence of a variety of functional groups and which can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins. Specifically, the present invention relates to carbene compounds of the formula ##STR1## wherein: M is Os or Ru; R and R.sup.1 are independently selected from hydrogen and functional groups C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.2 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl or C.sub.1 -C.sub.20 alkylsulfinyl; each optionally substituted with C.sub.1 -C.sub.5 alkyl, a halogen, C.sub.1 -C.sub.5 alkoxy or with a phenyl group optionally substituted with a halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy; X and X.sup.1 are independently selected from any anionic ligand; and L and L.sup.1 are each trialkyl phosphine ligands where at least one of the alkyl groups on the phosphine is a secondary alkyl or a cycloalkyl. A broad array of metathesis reactions are enabled including ring-opening metathesis polymerization of cyclic olefins, ring closing metathesis of acyclic dienes, cross metathesis involving at least one acyclic or unstrained cyclic olefin, and depolymerization of unsaturated polymers.
摘要翻译： 公开了在各种官能团存在下稳定的钌和咔咔啉化合物，其可用于在未应变的环状和无环烯烃上催化烯烃复分解反应。 具体地说，本发明涉及下式的卡宾化合物：其中：M是Os或Ru; R和R 1独立地选自氢和官能团C 2 -C 20烯基，C 2 -C 20炔基，C 1 -C 20烷基，芳基，C 1 -C 20羧酸酯，C 2 -C 20烷氧基，C 2 -C 20链烯氧基，C 2 -C 20炔氧基，芳氧基， C 2 -C 20烷氧基羰基，C 1 -C 20烷硫基，C 1 -C 20烷基磺酰基或C 1 -C 20烷基亚磺酰基; 每个任选被C 1 -C 5烷基，卤素，C 1 -C 5烷氧基或任选被卤素，C 1 -C 5烷基或C 1 -C 5烷氧基取代的苯基取代; X和X 1独立地选自任何阴离子配体; L和L1各自为三烷基膦配体，其中膦上的至少一个烷基是仲烷基或环烷基。 复分解反应的范围广泛，包括环烯烃的开环易位聚合，无环二烯的闭环复分解，涉及至少一个无环或非应变的环烯烃的交叉复分解，以及不饱和聚合物的解聚。
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3.发明授权
公开(公告)号：US5880231A
公开(公告)日：1999-03-09
申请号：US548445
申请日：1995-10-26
IPC分类号： B01J23/46 , B01J31/22 , C07C51/353 , C07C67/475 , C07F15/00 , C08F4/80 , C08F8/50 , C08F10/00 , C08F32/00 , C08F210/02 , C08G61/08 , C08G61/12 , C08F32/04
CPC分类号： B01J31/2265 , B01J31/24 , B01J31/2404 , C07C51/353 , C07C67/333 , C07C67/475 , C07F15/002 , C07F15/0046 , C08C19/08 , C08F10/00 , C08F32/00 , C08F8/50 , C08G61/08 , C08G61/128 , B01J2231/14 , B01J2231/543 , B01J23/462 , B01J23/466 , B01J2531/821 , B01J2531/825 , C07C2101/10 , C08C2019/09 , C08F210/02 , Y10S525/938
摘要： Disclosed are ruthenium and osmium carbene compounds which are stable in the presence of a variety of functional groups and which can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins. Specifically, the present invention relates to carbene compounds of the formula ##STR1## wherein: M is Os or Ru; R and R.sup.1 are independently selected from hydrogen and functional groups C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.2 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl or C.sub.1 -C.sub.20 alkylsulfinyl; each optionally substituted with C.sub.1 -C.sub.5 alkyl, a halogen, C.sub.1 -C.sub.5 alkoxy or with a phenyl group optionally substituted with a halogen, C.sub.1 -C.sub.5 alkyl or C.sub.1 -C.sub.5 alkoxy; X and X.sup.1 are independently selected from any anionic ligand; and L and L.sup.1 are each trialkyl phosphine ligands where at least one of the alkyl groups on the phosphine is a secondary alkyl or a cycloalkyl. A broad array of metathesis reactions are enabled including ring-opening metathesis polymerization of cyclic olefins, ring closing metathesis of acyclic dienes, cross metathesis involving at least one acyclic or unstrained cyclic olefin, and depolymerization of unsaturated polymers.
摘要翻译： 公开了在各种官能团存在下稳定的钌和咔咔啉化合物，其可用于在未应变的环状和无环烯烃上催化烯烃复分解反应。 具体地说，本发明涉及下式的卡宾化合物：其中：M是Os或Ru; R和R 1独立地选自氢和官能团C 2 -C 20烯基，C 2 -C 20炔基，C 1 -C 20烷基，芳基，C 1 -C 20羧酸酯，C 2 -C 20烷氧基，C 2 -C 20链烯氧基，C 2 -C 20炔氧基，芳氧基， C 2 -C 20烷氧基羰基，C 1 -C 20烷硫基，C 1 -C 20烷基磺酰基或C 1 -C 20烷基亚磺酰基; 每个任选被C 1 -C 5烷基，卤素，C 1 -C 5烷氧基或任选被卤素，C 1 -C 5烷基或C 1 -C 5烷氧基取代的苯基取代; X和X 1独立地选自任何阴离子配体; L和L1各自为三烷基膦配体，其中膦上的至少一个烷基是仲烷基或环烷基。 复分解反应的范围广泛，包括环烯烃的开环易位聚合，无环二烯的闭环复分解，涉及至少一个无环或非应变的环烯烃的交叉复分解，以及不饱和聚合物的解聚。
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4.发明授权Romp polymerization in the presence of peroxide crosslinking agents to form high-density crosslinked polymers 失效在过氧化物交联剂存在下进行聚合以形成高密度交联聚合物
公开(公告)号：US5728785A
公开(公告)日：1998-03-17
申请号：US678397
申请日：1996-07-02
CPC分类号： C08G61/08
摘要： Methods of forming polycycloolefins having high crosslink density are disclosed. Olefins are polymerized via a metathesis mechanism in the presence of a crosslinking agent and a catalyst. The crosslinking agent generally comprises a peroxide that decomposes into reactive species forming crosslinks during post-cure. The catalyst is a ruthenium or osmium carbene complex of the formula: ##STR1## wherein M is Os or Ru; R and R.sup.1 are independently selected from hydrogen or a hydrocarbon selected from the group consisting of C.sub.1 -C.sub.20 alkyl, C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.2 -C.sub.20 alkoxycarbonyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.1 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy and aryloxy; X and X.sup.1 are independently selected from any anionic ligand; and L and L.sup.1 are independently selected from any neutral electron donor. Preferably, L and L.sup.1 are trialkylphosphine ligands and at least one of the alkyl groups on the phosphine ligand may be a secondary alkyl or cycloalkyl group, especially P(isopropyl).sub.3, P(cyclopentyl).sub.3 and P(cyclohexyl).sub.3. Preferred crosslinking agents are peroxides, such as t-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexyne-3, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexane or mixtures thereof. Olefins may be cyclic (e.g., monocyclic, bicyclic or tricyclic) or acyclic. Norbornene or norbornene derivatives are especially preferred.
摘要翻译： 公开了形成具有高交联密度的聚环烯烃的方法。 在交联剂和催化剂存在下，烯烃通过复分解机理聚合。 交联剂通常包含在后固化中分解成反应性物质形成交联的过氧化物。 催化剂是下式的钌或锇卡宾络合物：其中M是Os或Ru; R和R 1独立地选自氢或选自C 1 -C 20烷基，C 2 -C 20烯基，C 2 -C 20炔基，C 2 -C 20烷氧基羰基，芳基，C 1 -C 20羧酸酯，C 1 -C 20烷氧基，C 2 -C 20烯氧基，C 2 -C 20炔氧基和芳氧基; X和X 1独立地选自任何阴离子配体; L和L 1独立地选自任何中性给电子体。 优选地，L和L1是三烷基膦配体，并且膦配体上的至少一个烷基可以是仲烷基或环烷基，特别是P（异丙基）3，P（环戊基）3和P（环己基）3。 优选的交联剂是过氧化物，例如叔丁基过氧化物，2,5-二甲基-2,5-二（叔丁基过氧基）己炔-3，二叔丁基过氧化物和2,5-二甲基-2， 5-二 - （叔丁基过氧）己烷或其混合物。 烯烃可以是环状的（例如单环，双环或三环）或非环状的。 降冰片烯或降冰片烯衍生物是特别优选的。
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公开(公告)号：US06383319B1
公开(公告)日：2002-05-07
申请号：US09369051
申请日：1999-08-04
IPC分类号： C06B2700
摘要： Preferred embodiments of the present invention relate to rocket fuels comprising metal hydrides and poly-dicyclopentadiene (“poly-DCPD”). Although poly-DCPD also has physical and chemical properties that are compatible with being used as a rocket fuel in its own right, its primary function is as a binder for the metal hydride. Illustrative examples of metal hydrides include but are not limited to as aluminum hydrides, lithium hydrides, and lithium aluminum hydrides.
摘要翻译： 本发明的优选实施方案涉及包含金属氢化物和聚二环戊二烯（“poly-DCPD”）的火箭燃料。 虽然poly-DCPD也具有与其本身用作火箭燃料相容的物理和化学性质，但其主要功能是作为金属氢化物的粘合剂。 金属氢化物的说明性实例包括但不限于氢化铝，氢化锂和氢化锂铝。
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6.发明授权Method for extending the pot life of an olefin metathesis polymerization reaction 失效延长烯烃易位聚合反应的适用期的方法
公开(公告)号：US5939504A
公开(公告)日：1999-08-17
申请号：US759018
申请日：1996-12-02
CPC分类号： C08G61/08
摘要： Compositions and methods for catalyzing and controlling the rate of olefin metathesis reactions including Ring Opening Metathesis Polymerization (ROMP) reactions. The molding of polymer articles using ROMP polymers. The composition includes a Ruthenium or Osmium carbene complex catalyst and a gel modification additive. The Ruthenium or Osmium carbene complex catalyst having the formula ##STR1## where M may be Os or Ru; R and R.sup.1 may be the same or different and may be hydrogen or a substituent group including C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.1 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl and C.sub.1 -C.sub.20 alkylsulfinyl; X and X.sup.1 may be the same or different and may be any anionic ligand; and L and L.sup.1 may be the same or different and may be neutral electron donor. The gel modification additive may be a neutral electron donor or a neutral Lewis base including phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine, or thioether. The gel modification additive may be a trialkylphosphine or triarylphosphine. Examples of gel modification additives include P(cyclohexyl).sub.3, P(cyclopentyl).sub.3, P(isopropyl).sub.3, P(phenyl).sub.3, and pyridine.
摘要翻译： 用于催化和控制烯烃复分解反应速率的组合物和方法，包括开环复分解聚合（ROMP）反应。 使用ROMP聚合物成型聚合物制品。 该组合物包括钌或锇卡宾络合物催化剂和凝胶改性添加剂。 具有下式的钌或锇卡宾络合物催化剂其中M可以是Os或Ru; R和R 1可以相同或不同，并且可以是氢或包括C 2 -C 20烯基，C 2 -C 20炔基，C 1 -C 20烷基，芳基，C 1 -C 20羧酸酯，C 1 -C 20烷氧基，C 2 -C 20链烯氧基， C 2 -C 20炔氧基，芳氧基，C 2 -C 20烷氧基羰基，C 1 -C 20烷硫基，C 1 -C 20烷基磺酰基和C 1 -C 20烷基亚磺酰基; X和X 1可以相同或不同，并且可以是任何阴离子配体; L和L 1可以相同或不同，并且可以是中性的电子给体。 凝胶改性添加剂可以是中性给电子体或中性路易斯碱，包括膦，磺化膦，亚磷酸酯，次膦酸，亚膦酸，胂，锑，醚，胺，酰胺，亚砜，羧基，亚硝酰基，吡啶或硫醚。 凝胶改性添加剂可以是三烷基膦或三芳基膦。 凝胶改性添加剂的实例包括P（环己基）3，P（环戊基）3，P（异丙基）3，P（苯基）3和吡啶。
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7.发明授权公开(公告)号：US06310121B1
公开(公告)日：2001-10-30
申请号：US09130586
申请日：1998-08-07
IPC分类号： C08J504
CPC分类号： C08G61/08
摘要： Compositions including fibers, fillers, reinforcing agents or other property-enhancing agents added to a polymeric matrix formed from DCPD monomer or related compounds such as norbornene and norbornadiene are disclosed. The composition has a mechanically forgiving matrix due to the polymer with the inherent strength and other physical properties of the enhancement agent according to the invention. Enhancement agents according to the invention generally include inorganic, organic and metallic substances in a variety of forms.
摘要翻译： 公开了添加到由DCPD单体或相关化合物如降冰片烯和降冰片二烯形成的聚合物基质中的纤维，填料，增强剂或其它性能增强剂的组合物。 由于具有本发明增强剂的固有强度和其它物理性能的聚合物，所述组合物具有机械原始基质。 根据本发明的增强剂通常包括各种形式的无机，有机和金属物质。
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8.发明授权Polymerization of low grade DCPD monomers using an olefin metathesis catalyst 失效使用烯烃复分解催化剂聚合低级DCPD单体
公开(公告)号：US6020443A
公开(公告)日：2000-02-01
申请号：US796865
申请日：1997-02-06
CPC分类号： C08G61/08
摘要： Methods for synthesizing polyDCPD via ROMP of low grade DCPD starting materials using Ruthenium or Osmium carbene complex catalyst. Transparent or translucent polyDCPD materials. The Ruthenium or Osmium carbene complex catalysts having the formula ##STR1## where M may be Os or Ru; R and R.sup.1 may be the same or different and may be hydrogen or a substituent group including C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.1 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl and C.sub.1 -C.sub.20 alkylsulfinyl; X and X.sup.1 may be the same or different and may be any anionic ligand; and L and L.sup.1 may be the same or different and may be neutral electron donor. The low grade DCPD starting materials containing less than about 97% by weight of DCPD monomers.
摘要翻译： 使用钌或锇卡宾复合催化剂，通过低品位DCPD原料的ROMP合成聚DDP的方法。 透明或半透明的聚DDP材料。 具有下式的钌或锇卡宾络合物催化剂其中M可以是Os或Ru; R和R 1可以相同或不同，并且可以是氢或包括C 2 -C 20烯基，C 2 -C 20炔基，C 1 -C 20烷基，芳基，C 1 -C 20羧酸酯，C 1 -C 20烷氧基，C 2 -C 20链烯氧基， C 2 -C 20炔氧基，芳氧基，C 2 -C 20烷氧基羰基，C 1 -C 20烷硫基，C 1 -C 20烷基磺酰基和C 1 -C 20烷基亚磺酰基; X和X 1可以相同或不同，并且可以是任何阴离子配体; L和L 1可以相同或不同，并且可以是中性的电子给体。 含有低于约97重量％的DCPD单体的低品位DCPD原料。
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9.发明授权Cyclic alkyl amino carbene (CAAC) ruthenium complexes as improved catalysts for ethenolysis reactions 有权环烷基氨基卡宾（CAAC）钌络合物作为乙烯解离反应的改进催化剂公开(公告)号：US09249170B2
公开(公告)日：2016-02-02
申请号：US14249704
申请日：2014-04-10
申请人： Vanessa M. Marx , Mohand-Ameziane Melaimi , Scott C. Virgil , Benjamin K. Keitz , Robert H. Grubbs , Guy Bertrand
发明人： Vanessa M. Marx , Mohand-Ameziane Melaimi , Scott C. Virgil , Benjamin K. Keitz , Robert H. Grubbs , Guy Bertrand
IPC分类号： C07D405/04 , C07F15/00 , C07C1/207 , C07C6/04
CPC分类号： C07F15/0046 , C07C1/2078 , C07C6/04 , C07C2531/22 , C07D405/04 , C07C11/02
摘要： Described herein are compounds and methods of catalyzing ethenolysis reactions, optionally on an industrial scale. In certain embodiments, the catalysts bear cyclic alkyl amino carbene (CAAC) ligands with an ortho substituent, such as a methyl substituent, on an N-aryl ring. When used to catalyze ethenolysis reactions, certain such compounds produce a turnover number greater than 50,000.
摘要翻译： 本文描述了任选地在工业规模上催化乙烯解反应的化合物和方法。 在某些实施方案中，催化剂在N-芳基环上具有带有邻位取代基的环状烷基氨基卡宾（CAAC）配体，例如甲基取代基。 当用于催化乙烯分解反应时，某些此类化合物产生大于50,000的周转数。
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公开(公告)号：US08703965B2
公开(公告)日：2014-04-22
申请号：US12741568
申请日：2008-11-10
申请人： Kevin Kuhn , Robert H. Grubbs
发明人： Kevin Kuhn , Robert H. Grubbs
IPC分类号： C07D233/06
CPC分类号： C07D233/06 , C07D239/06
摘要： Methods for the preparation of saturated imidazolinium salts and related compounds that comprises reaction of formamidines with compounds such as dihaloethane and an optional base are disclosed. Alternatively, the imidazolinium salts and related compounds can be prepared in a one-step process without purification of the formamidine reactant. These methods make it possible to obtain numerous imidazolinium salts and related compounds under solvent-free reaction conditions and in excellent yields.
摘要翻译： 公开了制备饱和咪唑啉盐和相关化合物的方法，其包括甲酰胺与诸如二卤代乙烷和任选碱的化合物的反应。 或者，咪唑啉鎓盐和相关化合物可以以一步法制备而不净化甲脒反应物。 这些方法使得可以在无溶剂反应条件下以优异的产率获得许多咪唑啉鎓盐和相关化合物。
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