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    • 75. 发明公开
    • PEROXIDE CROSSLINKING OF ROMP POLYMERS
    • PEROXIDVERNETZUNG VON ROMP POLYMEREN
    • EP0837885A4
    • 2003-05-21
    • EP96924356
    • 1996-07-03
    • CALIFORNIA INST OF TECHN
    • GRUBBS ROBERT HWOODSON CHARLES S JR
    • C08F4/80C08F2/00C08F32/00C08G61/08C08F8/00
    • C08G61/08
    • 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 general formula (I), wherein M is Os or Ru; R and R are independently selected from hydrogen or a hydrocarbon selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy and aryloxy; X and X are independently selected from any anionic ligand; and L and L are independently selected from any neutral electron donor. Preferably, L and L 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)3, P(cyclopentyl)3 and P(cyclohexyl)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.
    • 公开了形成交联密度高的聚环烯烃的方法。 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期间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电子给体。 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)己炔-3,二叔丁基过氧化物和2,5-二甲基-2, (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)或无环的。 降冰片烯或降冰片烯衍生物是特别优选的。
    • 76. 发明公开
    • TEMPLATE-DIRECTED RING-CLOSING METATHESIS AND RING-OPENING METATHESIS POLYMERIZATION OF FUNCTIONALIZED DIENES
    • MATRIZENGESTEURERTE RINGSCHLUSSMETHATHESE UND RINGEFEFNUNGSMETHATHESE-POLYMERISATION VON FUNKTIONALISIERTEN DIENEN
    • EP0970069A4
    • 2002-05-02
    • EP97952650
    • 1997-12-19
    • CALIFORNIA INST OF TECHN
    • GRUBBS ROBERT HMARSELLA MICHAEL JMAYNARD HEATHER D
    • C07D323/00C08F2/00C08G65/329C08F34/02
    • C07D323/00C08G65/329
    • Functionalized cyclic olefins and methods for making the same are disclosed. Methods include template-directed ring-closing metathesis ('RCM') of functionalized acyclic dienes and template-directed depolymerization of functionalized polymers possessing regularly spaced sties of unsaturation. Although the template species may be any anion, cation, or dipolar compound, cationic species, especially alkali metals, are preferred. Functionalized polymers with regularly spaced sites of unsaturation and methods for making the same are also disclosed. One method for synthesizing these polymers is by ring-opening metathesis polymerization ('ROMP') of functionalized cyclic olefins. The metathesis catalysts for both RCM and ROMP reaction are ruthenium or osmium carbene complex catalysts of formula (I) where M is Os or Ru; R and R1 each may be hydrogen, C¿2?-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl or C1-C20 alkylsulfinyl; X and X?1¿ may be any anionic ligand; and L and L1 may be any neutral electron donor.
    • 公开了官能化的环状烯烃及其制备方法。 方法包括功能化无环二烯的模板定向闭环复分解('RCM')和具有规则间隔不饱和度的官能化聚合物的模板定向解聚。 尽管模板物质可以是任何阴离子,阳离子或偶极化合物,但阳离子物质,特别是碱金属是优选的。 还公开了具有规则间隔的不饱和位点的官能化聚合物及其制备方法。 合成这些聚合物的一种方法是通过官能化环烯烃的开环易位聚合('ROMP')。 用于RCM和ROMP反应的复分解催化剂是式(I)的钌或锇卡宾络合物催化剂,其中M是Os或Ru; R和R1各自可以是氢,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烯氧基,C 2 -C 20炔氧基, 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; X和X→1可以是任何阴离子配体; L和L1可以是任何中性电子供体。