Patent EA-000644-B1 (EA)
Title: Composition for methathesis polymerization
Inventor: MUHLEBACH ANDREAS
IPC: C08F4/06
Filed: 1996-01-29
Abstract: A composition containing catalytic quantities of a single-component metathesis polymerisation catalyst and at least one polymer with repeating structural elements, which comprise a radical of a hindered cycloalkenyl bound by a bivalence bridging group, if necessary in combination with hindered cycloolefins as copolymers, characterized in that a single-component catalyst contains: (a) a composition of ruthenium or osmium which comprises at least one photolabile ligand, bound with ruthenium or osmium atom, and in which remaining coordination sites are saturated by nonphotolabile ligands; 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 a ring of hindered cycloolefins is a monocyclic or polycyclic condensed and/or having a bridging bond ring systems. 3. A compound of Claim 1, characterized in that polycyclic condensed and/or having a bridging bond ring systems comprise from 2 to 6 rings. 4. A compound of Claim 2, characterized in that some cyclic rings comprise from 3 to 16 elements. 5. A compound of Claim 2, characterized in that some cyclic rings comprise from 4 to 12 elements. 6. A compound of Claim 2, characterized in that some cyclic rings comprise from 5 to 8 elements. 7. A compound of Claim 2, characterized in that cycloalkenyl radicals correspond to formula A,   wherein Q1 is a radical with at least one carbon atom, which forms together with -CH=CQ2-group at least 3-membered alicyclic ring, comprising if necessary one or more heteroatoms selected from the group of silicon, phosphorus, oxygen, nitrogen and sulfur and which is unsubstituted or substituted halogen, =O, -CN, -NO2, R1R2R3Si-(O)u-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -S03(M1)1/2, -P03(M1)1/2, C1-C20-alkyl, C1-C20-hydroxyalkyl, C1-C20-halogenalkyl, C1-C6-cyanoalkyl, C3-C6-cycloalkyl, C6-C16-aryl, C7-C17-aralkyl, C3 C6-heterocycloalkyl, C3-C16-heteroaryl, C4-C16-heteroaralkyl or R4X-substituent; or two adjacent carbon atoms of which are substituted by -CO-O-CO-or -CO-NR5-CO-; or in which if necessary near adjacent carbon atoms of alicyclic ring, alicyclic, aromatic or heteroaromatic ring is condensed, unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-(O)u-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -S03(M1)1/2, -P03(M1)1/2, C1-C20-alkyl, C1-C20-hydroxyalkyl, C1-C20-halogenalkyl, C1-C6-cyanoalkyl, C3-C6-cycloalkyl, C6-C16-aryl, C7-C17-aralkyl, C3 C6-heterocycloalkyl, C3-C16-heteroaryl, C4-C16-heteroaralkyl or R13X1-substituent; X and X1 stand independently of one another for -O-, -S-, -CO-, -SO-, -SO2-, -O-C(O)-, -C(O)-O-, -C(O)-NR5-, -NR10-C(O)-, -SO2-O- or -O-SO2-; R1, R2 and R3 are independently of one another C1-C12-alkyl, C1-C12-perfluoralkyl, phenyl or Benzyl; R4 and R13 are independently of one another C1-C20-alkyl, C1-C20-halogenalkyl, C1-C20-hydroxyalkyl, C3-C8-cycloalkyl, C6-C16-aryl, C7-C16-aralkyl; R5 and R10 are independently of one another hydrogen, C1-C12-alkyl, phenyl or benzyl wherein alkyl groups are unsubstituted or substituted by C1-C12-alkoxy or C3-C8-cycloalkyl; R6, R7 and R8 are independently of one another C1-C12-alkyl, C1-C12-perfluoralkyl, phenyl or benzyl; M stands for alkali metal; M1 stands for alkali earth metal; u is 0 or 1; wherein formed by Q1 alicyclic ring comprises if necessary additional nonaromatic double bonds; Q2 is hydrogen, C1-C20-alkyl, C1-C20-halogenalkyl, C1-C12-alkoxy, halogen, -CN, R11- X2; R11 is C1-C20-alkyl, C1-C20-halogenalkyl, C1-C20-hydroxyafkyl, C3-C8-cycloalkyl, C6-C16-aryl or C7-C16-aralkyl; X2 is -C(O)-O- or -C(O)-NR12; R12 is hydrogen, C1-C12-alkyl, phenyl or benzyl; wherein the above cycloalkyl-, heterocycloatkyl-, aryl-, heteroaryl-, aralkyl-and heteroaralkyl groups are unsubstituted or substituted by C1-C12-alkyl, C1-C12-alkoxy, -NO2, -CN or halogen, and heteroatoms of the above heterocycloalkyl-, heteroaryl- and heteroaralkyl groups are selected from -O-, -S-, -NR9- and -N=; and R9 is hydrogen, C1-C12-alkyl, phenyl or benzyl. 8. A compound of Claim 7, characterized in that radical of formula A is an alicyclic ring formed from Q1 and a group -CH==CQ2- comprising from 3 to 8 ring atoms and is a monocyclic or bicyclic, tricyclic or tetracyclic condensed ring system. 9. A compound of Claim 7, characterized in that in a radical of formula A Q1 is a radical having at least one carbon atom, which together with -CH=CQ2-group forms 3- 20-membered alicyclic ring comprising if necessary one or more heteroatoms selected from a group of silicon, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, =O, -CN, -NO2, R1R2R3Si-(O)u-, -COOM, -SO3M. -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -P03(M1)1/2, C1-C12-alkyl, C1-C12-hatogenalkyl, C1-C12-hydroxyalkyl, C1-C4-cyanoalkyl, C3-C6-cycloalkyl, C6-C12-aryl, C7-C12-aralkyl, C3-C6-heterocycloalkyl, C3-C12-heteroaryl, C4-C12-heteroaralkyl or R4-X-; or in which two adjacent carbon atoms in Q1 radical are substituted by -CO-O-CO- or -CO-NR5-CO- or in which if necessary near adjacent carbon atoms an alicyclic, aromatic or heteroaromatic ring is condensed, unsubstituted or substituter by halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -P03(M1)1/2, C1-C12-alkyl, C1-C12-hatogenalkyl, C1-C12-hydroxyalkyl, C1-C4-cyanoalkyl, C3-C6-cycloalkyl, C6-C12-aryl, C7-C12-aralkyl, C3-C6-heterocycloalkyl, C3-C12-heteroaryl, C4-C12-heteroaralkyl or R13-X1-; X and X1 stand independently for -O-, -S-, -CO-, -SO-, -SO2-, -O-C(O)-, -C(O)-O-, -C(O)-NR5-, -NR10-C(O)-, -SO2-O- or -O-SO2-; R1 R2 and R3 are independently of one another -C1 C6-alkyl, C1 C16 perfluoralkyl, phenyl or benzyl; R4 and R13 are independently of one another C1-C12-alkyl, C1-C12-halogenalkyl, C1-C12- hydroxyalkyl, C3-C8-cydoalkyI, C6-C12-aryl, C7-C12-aralkyl; R5 and R10 are independently of one another hydrogen, C1-C6-alkyl, phenyl or, wherein alkyl groups are unsubstituted or substituted by C1-C6-alkoxy or C3-C6-cycloalkyl; R6, R7 and R8 are independently of one another C1-C6-alkyl, C1-C6-perfluoralkyl, phenyl or benzyl; M stands for alkali metal M1 stands for alkali earth metal; u is 0 or 1; wherein formed by Q1 an alicyclic ring comprises if necessary additional nono aromatic double bonds; Q2 is hydrogen, C1-C12-alkyl, C1-C12-halogenalkyl, C1-C6-alkoxy, halogen, -CN, R11-X2-; R11 is C1-C12-alkyl, C1-C12-halogenalkyl, C1-C12-hydroxyalkyl, C3-C6-cycloalkyl, C6-C12-aryl or C7-C12-aralkyl; X2 stands for -C(O)-O- or -C(O)-NR12-; R12 is hydrogen, C1-C6-alkyl, phenyl or benzyl; Wherein cycloalkyl-, heterocycloalkyl-, aryl-, heteroaryl-, aralkyl- and heteroaralkyl groups are unsubstituted or substituted by C1-C6-alkyl, C1-C6-alkoxy, -N02. -CN or halogen, and wherein heteroatoms of heterocycloalkyl-, heteroaryl- and heteroaralkyl groups are selected from a group of O-, -S-, -NR9- and -N=; and R9 is hydrogen, C1-C6-alky l, phenyl or benzyl. 10. A compound of Claim 7, characterized in that in a radical of formula A Q1 is a radical having at least one carbon atom, which together with -CH=CQ2-group forms 3- 10-membered alicyclic ring comprising if necessary one heteroatom selected from a group of silicon, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, -CN, -NO2, R1, R2, R3 Si-, -COOM, -SO3M. -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -P03(M1)1/2, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-hydroxyalkyl, C1-C4-cyanoalkyl, C3-C6-cycloalkyl, phenyl, benzyl or R4-X; or in which two adjacent carbon atoms in Q1 radical are substituted by -CO-O-CO- or -CO-NR5-CO- or in which if necessary near adjacent carbon atoms an alicyclic, aromatic or heteroaromatic ring is condensed unsubstituted or substituter by halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M. -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -P03(M1)1/2, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-hydroxyalkyl, C1-C4-cyanoalkyl, C3-C6-cycloalkyl, phenyl, benzyl or R13-X1-; X and X1 stand independently for -O-, -S-, -CO-, -SO- or -SO2; R1, R2 and R3 are independently C1-C4-alkyl, C1-C4-perfluoralkyl, phenyl or benzyl; R4 and R13 are independently C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-hydroxyalkyl or C3-C6-cycloalkyl; R6, R7 and R8 are independently C1-C4-alkyl, C1-C4-perfluoralkyl, phenyl or benzyl; M stands for alkali metal M1 stands for alkali earth metal; Q2 is hydrogen.