Patent EA-000643-B1 (EA)
Title: Composition for methathesis polymerization
Inventor: MUHLEBACH ANDREAS
IPC: B32B27/00
Filed: 1996-01-18
Abstract: 1. A composition containing catalytic quantities of a single-component metathesis polymerisation catalyst and at least one polymer with tensioned cycloalkenylene radicals bonded in the polymer skeleton with tensioned cyclo-olefines characterized in that comprises as a single-component catalyst: (a) a composition with ruthenium or osmium from the group of compounds; Ru(CH3CN)6(tos)2, Ru(CH3CH2CN)6(tos)2, Ru(CH3CN)6(CF3SO3)2, (CH3CH2CN)6(CF3SO3)2, Ru(C6H6)2(tos)2, [Ru(C6H6)(C6H5OCH3)](BF4)2, [Ru(C6H6)(C6H5i-propyl)](BF4)2, [Ru(C6H6)(1,3.5-trimethylphenol)](BF4)2, [Ru(C6H6)(hexamethylbenzol)](BF4)2, [Ru(C6H6)(biphenyl)](BF4)2, [Ru(C6H6) (chrysen)](BF4)2, [Ru(C6H6)(naphtalin)](BF4)2, [Ru(cyclopentadienyl)(4-methylcumyl)]PF6, [Ru(cyanophenyl)6](tos)2, [Ru(cyanophenyl)6(CF3SO3)2, [Ru(C6H6)(tetramethylthiophen)3](tos)2, [Ru(C6H6) [Ru(C6H6)(CH3CN)3](tos)2, [Ru(C6H6)(tetramethylthiophen)3](CF3SO3)2, [Ru(C6H6) (CH3CN)3](CF3SO3)2, [Ru(C6H6)(CH3OH)3](tos)2. [Ru(C6H6)(CH3OH)3](tis)2, [Os(NH3)5N2] (PF6)2], [Ru(NH3)5N2](PF6)2, [Ru(NH3)5(CH3CN)]BF4, [Ru(C6H6)(NH3)3](tis)2, [Ru(C6H6)(tetrahydrothiophen)3], (CF3SO3)2, [Ru((CH3)2S)3C6H6](tos)2, [Ru(dimethylsulfoxide)3C6H6](PF6)2, [Ru(dimethylformamide)3C6H6](PF6)2, [Ru(C6H6)Cl2]2 and [Os(C6H6)Cl2]2 or (b) a composition with molybdenum(VI) or tungsten (VI) which comprises at least two methyl groups or two monosubstituted methyl groups bonded with metal, wherein the substituent do not contain a hydrogen atom in α position; or (c) a composition with titanium (IV), niobium (V), tantalum l(V), molybdenum (VI) or tungsten (VI) in which silylmethyl group and at least one halogen are bound with metal; or (d) a composition with niobium (V) or tantalum (V) which comprises at least two methyl groups or two monosubstituted methyl groups in α position; or (e) a composition with titanium (IV) which comprises at least two methyl groups or two monosubstituted methyl groups bound with metal, wherein the substituent do not contain a hydrogen atom in α position; or (f) a composition with ruthenium or osmium which comprises at least one phosphin group, at least one photolabile ligand, bound with a metal atom, wherein there are from 2 to 5 legands and acid anions for equalizing charges; or (g) bivalence cation-active compound of ruthenium or osmium with a metal atom, with which bound 1-3 ligands of tertiary phosphines with volume substituents (if it is a compound with ruthenium), if necessary non-photolabile neutral ligands and anions for equalizing charges with the proviso that in ruthenium(trisphenylphosphine)-dihalogenides or -hydride-halogenides, phenyl groups are substituted by C1-C18-alkyl, C1-C18-halogenalkyl or C1-C18-alkoxy. 2. A compound of Claim 1, characterized in that those related to polymers, which have repeating structural units of formula (a) in the polymer chain   wherein R01 and R02 represent independently hydrogen or C1-C6-alkyl or R01 and R02 represent together a bond, and A forms together with C-C group unsubstituted or substituted ring of hindered cycloolefins. 3. A compound of Claim 2, characterized in that the structural units of formula (a) are bound directly or via bridging groups. 4. A compound of Claim 2, characterized in that R01 and R02 represent hydrogen. 5. A compound of Claim 2, characterized in that the substituents of the cycloilefin ring are C1-C8-alkyl or -alkoxy; C1-C4-halogenalkyl or -alkoxy; halogen; -CN; -NH2; secondary amines having from 2-to 18 atoms; tertiary amines having from 3 to 18 atoms; -C(O)-OR03 or -C(O)-NR03R04 where R03 and R04 independently represent H, C1-C18-alkyl, phenyl or benzyl. 6. A compound of Claim 2, characterized in that in formula (a) R01 and R02 represent together a bond, and A represent unsubstitu or substituted C1-C12-alkylen; unsubstituted or substituted C2-C12-heteroalkylen with at least one heteroatom from the group O, S and N; unsubstituted or substituted C5-C12-cycloalkylen; unsubstituted or substituted C4-C12-heterocycloalkylen with at least one heteroatom from the group O, S and N; unsubstituted or substituted C2-C12-alkenylen; unsubstituted or substituted C3-C12-heteroalkenylen with at least one eteroatom from the group O, S and N; unsubstituted or substituted C5-C12-cycloalkenylen; or unsubstituted or substituted C4-C12-heterocycloalkenylen with at least one eteroatom from the group O, S and N; or R01 and R02 represent independently H or C1-C6-alkyl and A represents unsubstituted or substituted C5-C12-cycloalkenylen; unsubstituted or substituted C4-C12-heterocycloalkenylen with at least one heteroatom from the group O, S and N; or unsubstituted or substituted C5-C12-cyctoalkdienylen; or R01 together with standing at the end carbon atom of radical A represents double bond; R02 represents H or C1-C6-alkyl; and A represents unsubstituted or substituted C1-C12-alkylen, unsubstituted or substituted C3-C12-heteroalkylen with at least one heteroatom from the group O, S and N; unsubstitututed or substituted C5-C12-cycloalkylen; unsubstituted or substituted C4-C12-heterocycloalkylen with at least one heteroatom from the group O, S and N; unsubstituted or substituted C2-C12-alkenylen; unsubstituted or substituted C3-C12-heteroalkenylen with at least one heteroatom from the group O, S and N; unsubstituted or substituted C5-C12-Cycloalkenylen; or unsubstituted or substituted C4-C12-heterocycloalkenylen with at least one heteroatom from the group O, S and N; or R01 and R02 together with one, standing at the end carbon atom of radical A, represent by one double bond, and A represents unsubstituted or substituted C3-C12-alkylen; unsubstituted or substituted C3-C12-heteroalkylen with at least one heteroatom from the group O, S and N; unsubstituted or substituted C5-C12-cycloalkylen; or unsubstituted or substituted C4-C12-heterocycloalkylen with at least one heteroatom from the group O, S and N; wherein alkylen, heteroalkylen, cycloalkylen, heterocycloalkylen, alkenylen, heteroalkenylen, cycloalkenylen, heterocycloalkenylen, alkdienylen, heteroalkdienylen, cycloalkdienylen and heterocycloalkdienylen are condensed, if necessary, with phenylen, C4-C8-cycloalkylen or C4-C8-heterocycloalkylen. 7. A compound of Claim 6, characterized in that R01 and R02 together represent a bond, and A represents unsubstituted or substituted C2-C6-alkylen, unsubstituted or substituted C3-C7-cycloalkylen, unsubstituted or substituted C2-C6-alkenylen, unsubstituted or substituted C5-C7-cycloalkenylen; or R01 and R02 independently of each other represent H or C1-C4-alkyl and A represents unsubstituted or substituted C5-C7-cycloalkenylen; or R01 together with standing at the end carbon atom of radical A represents a double bond; R02 represents H or C-C4-alkyl; and A represents unsubstituted or substituted C2-C6-alkenylen, unsubstituted or substituted C5-C7-cycloalkylen, unsubstituted or substituted C2-C6-alkenylen or unsubstituted or substituted C5-C7-cycloalkenylen; or R01 and R02 together with one, standing at the end carbon atom of radical A, represent by one double bond, and A represents unsubstituted or substituted C3-C6-alkylen, unsubstituted or substituted C5-C7-cycloalkylen. 8. A compound of Claim 1, characterized in that polymers are gomo- or copolymers. 9. A compound of Claim 2, characterized in that the structural elements of formula (a) are present in quantity of at least 5 mol % on conversion to the polymer quantity. 10. A compound of Claim 2, characterized in that the structural elements of formula (a) are present in quantity from 5 to 100 mol %.