MXPA97003613A

MXPA97003613A - Procedure of thermal polymerization by metatesis and polymerize composition

Info

Publication number: MXPA97003613A
Application number: MXPA/A/1997/003613A
Authority: MX
Inventors: Adriaan Van Der Schaaf Paul; Hafner Andreas
Original assignee: Cibageigy Ag; Hafner Andreas; Muehlebach Andreas; Adriaan Van Der Schaaf Paul
Priority date: 1994-11-17
Filing date: 1997-05-16
Publication date: 1997-08-01

Abstract

Composition of (a) at least one cycloolefin tained, and (b) a catalytic amount of at least one ruthenium or bivalent, cationic osmium compound, containing the ruthenium compound or metal unatomic osmium, wherein 1 to 3 ligands of tertiary phosphines with, in the case of the ruthenium compounds, sterically demanding substituents, optionally neutral non-photolabile ligands and anions for charge compensation, with the proviso that in dihalides or ruthenium hydride halides (trisphenylphosphine), the Phenyl groups are substituted with alkyl of 1 to 18 carbon atoms, halogenoalkyl of 1 to 18 carbon atoms of 1 to 10 carbon atoms. The composition is suitable for the manufacture of molded parts of all types and coatings

Description

PROCEDURE OF THERMAL POLYMERIZATION BY METATTHESIS AND POLYMERIZABLE COMPOSITION The present invention relates to a process for the thermal polymerization of taut cycloolefins; to a thermally polymerizable composition from said cycloolefins and to a one-component catalyst for thermally induced metathesis polymerization; and carrier materials coated with the thermally polymerizable composition or the crosslinked polymers. Demonceau et al. [Demonceau, A., Noels, A.F .., Saive,. Hubert, A.J., J. Mol. Catal. 76: 123-132 (1992)] describe [(C6H5) 3P] 3RuCl2, (p-cumen) RuCl2P (C6H1; L) 3 and [(C6JH5) 3P] 3RuHCl as thermal catalysts for ring-opening metathesis polymerization of norborene, a condensed polycycloolefin. These catalysts could not be imposed on industrial productions due to too little activity. Therefore it is proposed to increase the activity by the addition of diazo esters. It is also mentioned that only (p-cumen) RuC02P (C6Hn) 3 of norborene can be polymerized in a relatively short time at 60 seconds. Cyclooctene is also mentioned as another monomer. In WO 93/13171 there are disclosed one and two component, air and water stable catalysts, based on molybdenum and tungsten compounds containing carbonyl groups, as well as ruthenium and osmium compounds with at least one polyene ligand for thermal polymerization by metathesis and polymerization by photoactivated metathesis of taut cycloolefins, in particular norborene and norborene derivatives. Other polycyclic cycloolefins, especially non-condensed polycyclics, are not mentioned. The one-component catalysts used for the ruthenium compounds, namely [Ru (cumen) Cl2] 2 and [(CgH6) Ru (CH3CN) 2Cl] PFe "can be activated by ultraviolet irradiation, however the storage stability of the compounds with norborene is completely insufficient.These catalysts can only supply insufficiently to the known two-component catalysts. , it has surprisingly been found that the bivalent cationic ruthenium and osmium complexes are highly effective one-component catalysts for thermally induced metathesis polymerization, if they contain at least one phosphine group with substituents that fill the space in the metal atom. found that the compositions are stable to air and moisture and that they can be processed without protective precautions.The polymerizable compositions containing ruthenium and osmium complexes are also sufficiently stable, so that they do not polish antiesters of the processing type. desired.An object of the invention is a composition of (a) the menu a cycloolefin tained, and (b) a catalytic amount of at least one ruthenium compound or bivalent, cationic osmium, the ruthenium compound or osmium containing a metal atom, wherein 1 to 3 tertiary phosphine ligands are linked with, in the case of ruthenium compounds, sterically demanding substituents, optionally neutral non-photolabile ligands and anions for charge compensation, with the proviso that in dihalogenides or ruthenium hydride halides (trisphenylphosphine), the phenyl groups are substituted with alkyl of 1 to 18 carbon atoms, halogenalkyl of 1 to 18 carbon atoms or alkoxy of 1 to 18 carbon atoms. The cyclic olefins can be monocyclic or polycyclic ring systems, condensed, or bridged, for example with two to four rings, which are unsubstituted or substituted and contain heteroatoms such as, for example, O, S, N or Si in one or various aromatic or heteroaromatic rings and / or rings, such as for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. Each cyclic ring may contain 3 to 16, preferably 3 to 12 and particularly preferred 3 to 8 ring members. Cyclic olefins may contain other non-aromatic double bonds, according to the size of the ring of preference 2 to 4 of said double bonds. The ring substituents are those which are inert, that is, do not affect the chemical stability of the ruthenium and osmium compounds. Cycloolefins are rings, or tight ring systems. When the cyclic olefins contain more than one double bond, for example 2 to 4 double bonds, depending on the reaction conditions, the chosen monomer and the amount of catalyst, cross-linked polymerisates can also be formed. In a preferred embodiment of the process according to the invention, the cycloolefins correspond to the formula I where Q? is a radical with at least one carbon atom, which forms together with the group -CH = CQ2 an alicyclic ring of at least three members, which, if appropriate, contains one or more heteroatoms chosen from the group consisting of silicon, phosphorus, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, = 0, -CN, -N02, R? R2R3SÍ- (0) u-, -C00M, -S03M, -P03M, -C00 (M1)? 2, -S03 (M?) 1/2, -P? 3 (M?)? / 2 ^ alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms , cyanoalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms, heterocycloalkyl of 3 to 16 carbon atoms, heteroaryl of 3 to 16 carbon atoms, heteroaralkyl of 4 to 16 carbon atoms or R 4 -X-; or are substituted on the two neighboring carbon atoms with -C0-0-C0- or -CO-NR5-CO-; or wherein, in the case of the neighboring carbon atoms of the alicyclic ring, an alicyclic, aromatic or heteroaromatic ring is condensed, which is unsubstituted or substituted by halogen -CN, -N02, R6R7R8SÍ- (0) u-, -C00M, -S03M, -P03M, -C00 (M?)? / 2, -S? 3 (M?)? / 2, -P03 (M?)? / 2, alkyl of 1 to 20 carbon atoms, halogenalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cyanoalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms, heterocycloalkyl of 3 to 16 carbon atoms, heteroaryl of 3 to 16 carbon atoms, heteroaralkyl of 4 to 16 carbon atoms or Ri3-X? -; X and Xi, independently of each other, represent -O-, -S-, - CO-, -SO-, -S02-, -OC (O) -, -C (O) -, -C (0) -NR5 -, -NR10- c (0) -, -so2-o- u -o-so2-; Ri, R2 and R3, independently of each other, mean alkyl of 1 to 12 carbon atoms, perfluoroalkyl of 1 to 12 carbon atoms, phenyl or benzene; R4 and R13 independently represent alkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms; R5 and Rl? > independently of one another, they mean hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene, the alkyl groups being in turn unsubstituted or substituted by alkoxy of 1 to 12 carbon atoms or cycloalkyl of 3 to 8 carbon atoms; R6 / R7 and R8 independently of one another, mean alkyl of 1 to 12 carbon atoms, perfluoroalkyl of 1 to 12 carbon atoms, phenyl or benzene; M represents an alkali metal and Mi an alkaline earth metal; and u represents 0 or 1; wherein the alicyclic ring formed with Qi contains, if necessary, other non-aromatic double enlices; Q2 means hydrogen, alkyl of 1 to 20 carbon atoms, halogenalkyl of 1 to 20 carbon atoms, alkoxy of 1 to 12 carbon atoms, halogen, -CN, Rn ~ x2-; Rii means alkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms or aralkyl of 7 to 16 carbon atoms; X2 means -C (0) -0- or -C (0) -NR12; R 12 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene; wherein the aforementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted with alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, -N0, -CN or halogen, and where the heteroatoms of the aforementioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are selected from the group -O-, -S-, -NRg- and -N =; and Rg means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene. The fused alicyclic rings preferably contain 3 to 8, especially preferred 4 to 7 and particularly preferred 5 or 6 ring carbon atoms. If there is an asymmetric center in the compounds of formula IThis has the consequence that the compounds can be present in optically isomeric forms. Some compounds of the formula I can be present in tautomeric forms (for example, keto-enol tautomerism). If there is a double aliphatic bond C = C, geometric isomerism (form E or form Z) can also occur. In addition, exo-endo configurations are also possible. Formula I thus includes all possible stereoisomers which occur in the form of enantiomers, tautomers, diastereoisomers, E / Z isomers or their mixtures. In the definitions of the substituents, the alkyl, alkenyl and alkynyl groups may be straight or branched chain. The same goes for the or the corresponding alkyl part of alkoxy, thioalkyl, alkoxycarbonyl groups and other alkyl-containing groups. These alkyl groups preferably contain 1 to 12, more preferably 1 to 8 and in particular preferred 1 to 4 carbon atoms. These alkenyl or alkynyl groups preferably contain 2 to 12, more preferably 2 to 8 and particularly preferably 2 to 4 carbon atoms. Alkyl includes, for example, methyl, ethyl, isopropyl, normal propyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, as well as the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxy-iso-butyl, 1-hydroxy-sec. -butyl, 1-hydroxy-ter. -butyl, as well as the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals. Halogenoalkyl includes, for example, fluomethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloethyl, as well as halogenated alkanes, in particular fluorinated or chlorinated, such as, for example, isopropyl, normal propyl, normal butyl, isobutyl, secondary butyl, tertiary butyl and the various isomeric radicals pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. Alkenyl includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n- dodec-2-enyl, iso-dodecenyl, n-octadec-2-enyl, n-octadec-4-enyl. The cycloalkyl is preferably cycloalkyl of 5 to 8 carbon atoms, particularly preferred cycloalkyl of 5 carbon atoms or 6 carbon atoms. Some examples are cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cyanoalkyl includes, for example, cyanomethyl (methyl nitrile), cyanoethyl (ethyl nitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyano-iso-butyl, 1-cyano- sec. -butyl, 1-cyano-ter. -butyl, as well as the various cyanopentyl and cyanohexyl radicals. Aralkyl preferably contains 7 to 12 carbon atoms and particularly preferably 7 to 10 carbon atoms.

It can be, for example, benzene, phenethyl, 3-phenylpropyl, a-methylbenzene, phenylbutyl or a, a-dimethylbenzene. Aryl preferably contains 6 to 10 carbon atoms. It can be, for example, phenyl, pentalin, indene, naphthalene, bluish or anthracene. Heteroaryl preferably contains 4 or 5 carbon atoms and one or two heteroatoms of the group of O, S and N. It can be, for example, pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, purine or quinoline.

Heterocycloalkyl preferably contains 4 or 5 carbon atoms and one or two heteroatoms of the group of O, S and N. It can be, for example, oxirane, azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, tetrahydrofuran or tetrahydrothiophene. Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, i-butyloxy, secondary butyloxy and t-butyloxy. In the context of the present invention, alkali metal is to be understood as meaning lithium, sodium, potassium, rubidium and cesium, in particular lithium, sodium and potassium. In the context of the present invention, alkaline earth metal should be understood as beryllium, magnesium, calcium, strontium and barium, in particular magnesium and calcium. In the above definitions, halogen, fluorine, chlorine, bromine and iodine should preferably be understood as meaning fluorine, chlorine and bromine. The compounds of formula I which are especially suitable for the process according to the invention are those in which Q2 is hydrogen. Furthermore, for the polymerization, preferred are compounds of the formula I in which the alicyclic ring, formed jointly by Qi and the group -CH = CQ2-, has 3 to 16, preferably 3 to 12 and particularly preferably 3 to 8. ring atoms, and wherein it can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system. The process according to the invention can be carried out in a particularly advantageous manner with those compounds of the formula I, wherein: Q 1 is a radical with at least one carbon atom, which forms together with the group -CH = C 2 a alicyclic ring 3 to 20 members, which, if appropriate, contains one or more heteroatoms selected from the group consisting of silicon, oxygen, nitrogen and sulfur; and that is unsubstituted or substituted with halogen, = 0, -CN, -N02, R! R2R3SÍ- (0) u-, -C00M, -S03M, -P03M, -COO (M1) 1/2, -SS? 3 (M?)? 2, -P? 3 (M1) 1/2, alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl from 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 12 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 12 carbon atoms, heteroaralkyl of 4 to 12 atoms carbon or R4-X-; or wherein two neighboring carbon atoms in this Qi radical are substituted with -CO-O-CO- or -CO-NR5-CO-; or in which, if appropriate, in neighboring carbon atoms, an alicyclic, aromatic or heteroaromatic ring is condensed, which is unsubstituted or substituted with halogen -CN, -N02, R6 7R8Si- (0) u-, -COOM , -SO3M, -PO3M, -COO (M!) 1/2, -S03 (M?)? / 2, -P03 (M?)? / 2, alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 12 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 12 carbon atoms, heteroaralkyl of 4 to 12 carbon atoms or R 13 -X 1 -; X and Xl, independently of each other, represent -O-, -S-, - CO-, -SO-, -S02-, -OC (O) -, -C (O) -, -C (0) -NR5 -, -NR10- C (O) -, -S02-0- or -O-SO2-; R1, R2 and R3, independently of each other, mean alkyl of 1 to 6 carbon atoms, perfluoroalkyl of 1 to 6 carbon atoms, phenyl or benzene; M represents an alkali metal and Mi an alkaline earth metal; and R4 and R13 independently represent alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 12 carbon atoms , aralkyl of 7 to 12 carbon atoms; R5 and Rio, independently of one another, mean hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzene, the alkyl groups for their part being unsubstituted or substituted with alkoxy of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 atoms of carbon; R6, R7 and Re, independently of each other, mean alkyl of 1 to 6 carbon atoms, perfluoroalkyl of 1 to 6 carbon atoms, phenyl or benzene; u represents 0 or 1; wherein the alicyclic ring formed with Qi contains, if appropriate, other non-aromatic double bonds; 0.2 means hydrogen, alkyl of 1 to 12 carbon atoms, halogenalkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, halogen, -CN, Rn ~ X2-; R n means alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms or aralkyl of 7 to 12 carbon atoms; X2 means -C (0) -0- or -C (0) -NR? 2; and R 12 signifies hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzene; wherein the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted by alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, -NO2, -CN or halogen, and wherein the heteroatoms of the heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group -0-, -S-, -NR9- and -N =; and Rg means hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzene. Of this group, those compounds of the formula I are preferred, in which Q 1 is a radical with at least one carbon atom, which together with the group -CH = C 2, forms an alicyclic ring of 3 to 10 members, which , if appropriate, contains one or more heteroatoms selected from the group consisting of silicon, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, = 0, -CN, -NO2, R? R2R3SÍ-, -COOM, -SO3M, -P03M, -COO (Mi)? / 2, -S03 (M?)? / 2 , -P? 3 (M?)? /, Alkyl of 1 to 6 carbon atoms, halogenoalkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl, benzene or RX-; or in which, if appropriate, in neighboring carbon atoms, an alicyclic, aromatic or heteroaromatic ring is condensed, which is unsubstituted or substituted by halogen -CN, -N02, R6R7R8SÍ- (0) u-, -COOM, -SO3M, -PO3M, -COO (M?)? / 2, -SS? 3 (M?)? / 2, -P? 3 (M].)? / 2, alkyl of 1 to 6 carbon atoms, halogenalkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl, benzene or Ri3-X? _; Ri, R2 and R3, independently of each other, mean alkyl of 1 to 4 carbon atoms, perfluoroalkyl of 1 to 4 carbon atoms, phenyl or benzene; M represents an alkali metal and Mi an alkaline earth metal; and R and Ri3 independently represent alkyl of 1 to 6 carbon atoms, halogenalkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; X and Xi, independently of each other, mean -O-, -S-, -CO-, -SO- or -S02-; R6 »R7 and R8 independently of one another, mean alkyl of 1 to 4 carbon atoms, perfluoroalkyl of 1 to 4 carbon atoms, phenyl or benzene; u represents 0 or 1; and Q means hydrogen. In particular, the process according to the invention is suitable for the polymerization of norborene and norborene derivatives. Of these norborene derivatives, those corresponding to either the formula II in which X 3 means -CHR 6 -, oxygen or sulfur are particularly preferred; R14 and R15 'independently of one another, mean hydrogen, -CN, trifluoromethyl, (CH3) 3Si-0-, (CH3) 3-Si or -COOR; and R16 and R17 / independently from each other, mean hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene; or to formula III wherein X 4 means -CHR g, oxygen or sulfur; Ri9 means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene; and Ris means hydrogen, alkyl of 1 to 6 carbon atoms or halogen; or to formula IV (IV), wherein X5 means -CHR22-, oxygen or sulfur; R 22 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene; R20 and R2 ?, independently of each other, mean hydrogen, CN, trifluoromethyl, (CH3) 3Si-0-, (CH3) 3Si- or -COOR23; and R23 means hydrogen, alkyl of 1 to 22 carbon atoms, phenyl or benzene; or to formula V wherein X6 means -CHR24 ~, oxygen or sulfur; R 24 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene; means oxygen or > N-R25, "and R 25 is hydrogen, methyl, ethyl or phenyl. The following compounds of formula I are especially suitable for the polymerization process according to the invention, with bi-and polycyclic systems being accessible through Diels-Alder reactions: In a preferred embodiment, cycloolefins contain only carbon and hydrogen atoms, and it is preferably 5 or 6 membered rings or ring systems with one to three 5 or 6 membered ring, for example, norborne, alkylated norborne and dicylopentadiene. The ruthenium and osmium compounds preferably contain 2 to 3 tertiary phosphine groups. In the context of the invention, phosphine groups are understood to be tertiary phosphines. The number of additional neutral ligands, not photolabile, is governed on the one hand according to the number of phosphine ligands, and on the other side by the valence of the neutral ligands. Neutral ligands of a bond are preferred. In a preferred embodiment, the bivalent cationic ruthenium and osmium compounds to be used according to the invention contain 3 phosphine groups and two univalent anions for the compensation of the charge; or 3 phosphine groups, two neutral non-photolabile ligands of one bond or one of two bonds, and two univalent anions for charge compensation; or 2 phosphine groups, a neutral non-monolabial monoanionic ligand, additionally of a bond, and a univalent anion for the compensation of the charge. Within the framework of the present invention, a non-photolabile ligand (also referred to as a strongly coordinating ligand), means that the ligand, when irradiating the catalyst in the visible or near ultraviolet spectral range, does not dissociate or dissociate only to an extent irrelevant of the catalyst. Neutral non-monolabial, monoanionic ligands, additionally of a bond, are preferably cyclopentadienyl or indenyl, which are unsubstituted or substituted with one to five alkyls of 1 to 4 carbon atoms, in particular methyl, or -Si (alkyl of 1 to 4 carbon atoms), in particular - Si (CH3) 3. The non-photolabile ligands can be, for example, organic and inorganic solvating compounds containing O, S or N heteroatoms, which are often also used as solvents. Examples of said compounds are H20, H2S, NH3; aliphatic or cycloaliphatic alcohols or mercaptans with 1 to 18, preferably 1 to 12 and particularly preferably 1 to 6 carbon atoms, optionally halogenated, in particular fluorinated or chlorinated; alcohols or aromatic thiols with 6 to 18, preferably 6 to 12 carbon atoms; alcohols or araliphatic thiols with 7 to 18, preferably 7 to 12 carbon atoms; ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid ester, lactone, optionally NC? -C4-mono- or dialkyl carboxylic acid amides with 2 to 20, preferably 2 to 12 and in particular 2 to 6 carbon atoms, and lactams given the case NC? -C4-alkylated open chain or cyclic and aliphatic, araliphatic or aromatic; primary, secondary and tertiary amines, open chain or cyclic and aliphatic, araliphatic or aromatic, with 1 to 20, preferably 1 to 12 and particularly preferably 1 to 6 carbon atoms. Examples of said non-photolabile ligands are methanol, ethanol, n- and i-propanol, n-, i- and t-butanol, 1,1,1-trifluoroethanol, bistrifluoromethylmethanol, tristrifluoromethylmethanol, pentanol, hexanol, methyl- or ethylmercaptan, cyclopentanol. , cyclohexanol, cyclohexyl mercaptan, phenol, methylphenol, fluorophenol, phenylmercaptan, benzyl mercaptan, benzylalcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n- or di-t-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether, tetrahydrothiophene, di-ethyl sulfoxide, diethylsulfoxide, tetra -and pentamethylene sulphoxide, dimethylsulphone, diethylsulphone, tetra- and pentamethylene sulfone, acetone, methyl ethyl ketone, diethyl ketone, phenyl methyl ketone, ethyl isobutyl ketone, benzyl methyl ketone, acetaldehyde, propionaldehyde, trifluoroacetaldehyde, benzaldehyde, acetic acid ethyl ester, butyrolactone, dimethylformamide, dimethylacetamide, pyrrolidone and N-methylpyrrolidone, indenyl, cyclopentadienyl, methyl- or dimethyl- or pentamethylcyclopentadienyl and trimethylsilylcyclopentadienyl. The primary amines may correspond to the formula R26NH2 the amines secondary to the formula R6R27NH and the tertiary amines to the formula R26R27R28N "wherein R26 means alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, unsubstituted or substituted with alkyl of 1 to 4 carbon atoms or with alkoxy of 1 to 4 carbon atoms, or aryl of 6 to 18 carbon atoms or aralkyl of 7 to 12 carbon atoms, unsubstituted or substituted with alkyl of 1 to 4 atoms of carbon or with alkoxy of 1 to 4 carbon atoms; R27 independent of the meaning of R26, or R26 and 27 together mean tetramethylene, pentamethylene, 3-oxa-l, 5-pentylene or -CH2-CH2-NH-CH2-CH2- or -CH2-CH2-N (alkyl of 1 to 4 carbon atoms) -CH2-CH2-, and 28 independent of the meaning of R26"The alkyl preferably contains 1 to 12 and particularly preferably 1 to 6 carbon atoms. The aryl preferably contains 6 to 12 carbon atoms and the aralkyl preferably contains 7 to 9 carbon atoms. Examples of the amines are methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-, methyl-ethyl-, dimethyl-ethyl-, n-propyl-, di-n-propyl-, tri-n-butyl -, cyclohexyl-, phenyl- and benzylamine, as well as pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine. In a preferred subgroup, the non-photolabile ligands are H20, NH3, alkanoles of 1 to 4 carbon atoms unsubstituted or partially or fully fluorinated, or cyclopentadienyl. Very particular preference is given to H20, NH3, cyclopentadienyl, methanol and ethanol. In the context of the invention, sterically demanding substituents are those which sterically cover the ruthenium and osmium atoms. Thus, it was surprisingly found that linear alkyl groups as substituents on the phosphine ligands, result in ruthenium compounds without any thermal activity for the polymerization by metathesis of taut cycloolefins. It was also observed that in osmium compounds, surprisingly, the linear alkyl groups as substituents in the phosphine ligands, possess an excellent thermocatalytic activity for the polymerization by metathesis of taut cycloolefins; they are preferably also used for the osmium compounds, phosphine ligands with sterically demanding substituents. It was further found that the steric coating of triphenylphosphine ligands in ruthenium dihalides and ruthenium hydride halides is insufficient and said catalysts possess only moderate catalytic activity for the polymerization by metathesis of taut cycloolefins. The catalytic activity can surprisingly be raised significantly when the tertiary phosphine groups contain phenyl substituted with alkyl or alkoxy groups. Preferably, the phosphine ligands correspond to the formulas VI or Via PR2gR3? R31 (VI), R2 R3? P-Zl-P 29R3? (Via), where R29 / R3? and R31 / independently from each other, mean alkyl of 3 to 20 a-branched carbon atoms; cycloalkyl of 4 to 12 carbon atoms unsubstituted or substituted with alkyl of 1 to 18 carbon atoms, halogenoalkyl of 1 to 18 carbon atoms or alkoxy of 1 to 18 carbon atoms; or aryl of 6 to 16 carbon atoms, unsubstituted or substituted with alkyl of 1 to 18 carbon atoms, halogenoalkyl of 1 to 18 carbon atoms or alkoxy of 1 to 18 carbon atoms; the radicals R 2 and R 30 together stand for unsubstituted tetra- or pentamethylene or substituted with alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms; or tetra- or mentamethylene unsubstituted or substituted with alkyl of 1 to 6 carbon atoms, halogenoalkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms or condensed with 1 or 2 1,2-phenylene, and R31 has the meaning indicated above; and Zi means linear or branched alkylene of 2 to 12 carbon atoms, unsubstituted or substituted by alkoxy of 1 to 4 carbon atoms; 1,2- or 1,3-cycloalkylene with 4 to 8 carbon atoms, unsubstituted or substituted with alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; or 1,2- 0 1, 3-heterocycloalkylene with 5 or 6 ring members and a heteroatom of the group O or N, unsubstituted or substituted with alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms. The radicals R29, 3o and R31 are < * e preference the same radicals. The substituents are preferably in one or two ortho and / or meta positions with respect to the carbon atom of the P-C bond in the phosphine. R29f R3? and R3i as alkyl, may contain 3 to 12, preferably 3 to 8 and particularly preferably 3 to 6 carbon atoms. Particularly preferred is α-branched alkyl, for example of the formula -CRbRcRd > wherein Rb means H or alkyl of 1 to 12 carbon atoms, Rc means alkyl of 1 to 12 carbon atoms, and R < j means alkyl of 1 to 12 carbon atoms or phenyl unsubstituted or substituted with alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; and the sum of the carbon atoms in the radical -CR ^ cRa is from 3 to 18. Examples of alkyl are i-propyl, i- and t-butyl, 1-methyl- or 1,1-dimethylprop-1-yl , 1-methyl- or 1, 1-dimethylbut-1-yl, 1-methyl- or 1,1-dimethylpent-1-yl, 1-methyl- or 1,1-dimethylhex-1-yl, 1-methyl- or 1,1-dimethylhept-1-yl, 1-methyl- or 1,1-dimethyloct-1-yl, 1-methyl- or 1,1-dimethylnon-1-yl, 1-methyl- or 1, 1- dimethyl-dec-l-yl, 1-methyl- or 1,1-dimethylundec-l-yl, 1-methyl- or 1,1-dimethyldodec-1-yl, 1-methyl- or 1,1-dimethyltridec-l -yl, 1-methyl- or 1,1-dimethyltetradec-1-yl, 1-methyl- or 1,1-dimethylpentadec-1-yl, 1-methyl- or 1,1-dimethylhexadec-1-yl, 1- methylheptadec-1-yl, phenyl-dimethyl-methyl. Preferred examples are i-propyl, i- and t-butyl. In the osmium compounds used, R29, R30 and R31 can also represent alkyl with 1 to 18, preferably 1 to 12, more preferably 1 to 8, and particularly preferred 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, n-butyl, n-pentyl , n-hexyl, n-heptyl and n-octyl. If R2, R30 and 3i mean cycloalkyl, then it is preferably cycloalkyl of 5 to 8 carbon atoms, and particularly preferred of cycloalkyl of 5 or 6 carbon atoms. Some examples are cyclobutyl, cycloheptyl, cyclooctyl and in particular cyclopentyl and cyclohexyl, which are preferably unsubstituted or substituted with 1 to 3 alkyl, haloalkyl or alkoxy groups. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl- and tristrifluoromethyl-cyclopentyl and -cyclohexyl. If R29, R30 and R3i mean aryl, then it is preferably aryl of 6 to 12 carbon atoms and particularly preferred of phenyl or naphthyl. Examples of substituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl- and tristrifluoromethylphenyl. Examples of tetra- and pentamethylene linked to the P atom, optionally substituted or condensed, are: Other suitable tertiary phosphines are cycloaliphatic bridged with a group = PRa, with 6 to 8 carbon atoms in the ring, for example: wherein Ra means alkyl of 1 to 6 carbon atoms, cyclohexyl, phenyl unsubstituted or substituted with 1 or 2 alkyl of 1 to 4 carbon atoms. In a preferred embodiment, the phosphine ligands correspond to the formula VI, wherein R29, R30 and R3i, independently of one another, mean alkyl of 3 to 8 carbon atoms branched, cyclopentyl or cyclohexyl unsubstituted or substituted with alkyl of 1 to 4 carbon atoms, or phenyl unsubstituted or substituted with alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or trifluoromethyl. Particularly preferred examples of the phosphine ligands of the formula VI are (CQHS) ^ P, (C5H9) 3P, (i-C3H7) 3P, (t-C4H9) 3P, [C2H5-CH (CH3)] 3P, [C2H5-C (CH3) 2] 3P, (2-methylphenyl) 3P, (2, 3-dimethylphenyl) 3P, (2,4-dimethylphenyl) 3P, (2,6-dimethylphenyl) 3P, (2-methyl-4-y-propylphenyl) 3P, (2-methyl-3-y-propylphenyl) 3P, (2-Methyl-5-i-propylphenyl) 3P, (2-methyl-6-i-propylphenyl) 3P, (2-methyl-3-t-butylphenyl) 3P, (2-methyl-4-t-butylphenyl) 3P, (2-methyl-5-i-butylphenyl) 3P, (2,3-di-t-butylphenyl) 3P, (2,4-di-t-butylphenyl) 3P, (2, 5-di-t- butylphenyl) 3P, (2,6-di-t-butylphenyl) 3P. Suitable anions of inorganic or organic acids are, for example, hydride (H ~), halide (for example, F ~, Cl ~, Br ~ and I ~), the anion of an oxacid, and BF4 ~, PFs ~, SbFe "or AsFg". It should be mentioned that the cyclopentadienyl indicated above is in ligand and an anion. Other suitable anions are alcoholates of 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and particularly preferred of 1 to 4 carbon atoms, which are especially branched, for example corresponding to the formula RxRyRzC-0 ~, wherein Rx represents H or alkyl of 1 to 10 carbon atoms, Ry represents alkyl of 1 to 10 carbon atoms and Rz represents alkyl of 1 to 10 carbon atoms or phenyl, and the sum of the carbon atoms of Rx, Ry and Rz is 11. Examples are i-propyloxy and t-butyloxy. Other suitable anions are acetylides of 3 to 18 carbon atoms, preferably of 5 to 14 carbon atoms and particularly preferred of 5 to 12 carbon atoms, which may correspond to the formula RW-C = C ~, where Rw represents alkyl of 1 to 16 carbon atoms, preferably alkyl of 3 to 12 carbon atoms to branched, or phenyl or benzene unsubstituted or substituted with 1 to 3 alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 atoms of carbon. Examples are i-propyl-, i- and t-butyl-, phenyl-, benzyl-, 2-methyl-, 2,6-dimethyl-, 2-i-propyl-, 2-i-propyl-6-methyl -, 2-t-butyl-, 2,6-di-t-butyl- and 2-meyyl-6-t-butyl-phenylacetyl. The oxacid anions can be, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a carboxylic acid of 1 to 8 carbon atoms, such as formate, acetate, propionate. , butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, sulfonates such as, for example, methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethyl sulfonate (triflate), phenylsulfonate or benzylsulphonate optionally substituted with alkyl of 1 to 4 atoms carbon, alkoxy of 1 to 4 carbon atoms or halogen, in particular fluorine, chlorine or bromine, such as, for example, tosylate, mesylate, brosylate, p-methoxy- or p-ethoxy-phenylsulfonate, pentafluorophenylsulfonate or 2,4,6- triisopropylsulfonate, and phosphonates such as methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphonate and benzylphosphonate. Particularly preferred are H ~, Cl ~, BF ~, PF6 ~, SbF6 ~, AsF6 ~, CF3S? 3 ~, C6H5-S03 ~, 4-methyl-C6H5-S03 ~, 3,5-dimethyl-C6H5-S03 ~, 2, 4, 6-trimethyl-C6H5-S0 ~ and 4-CF3-C6H5-S03 ~. In a preferred embodiment, the ruthenium and osmium compounds are particularly preferred to formulas VII, Vlla, Vllb, VIIc or Vlld: Me2T (L?) 2 (L2) (Y) 2 (VII), Me2 (L?) 2L3 (Y) (Vllb), Me2? (L?) 3L4 (Y) 2 (VIIc), Me2? L? (L2) 3 (Y) 2 (Vlld), where Ru or Os represents Me; Yi represents the anion of a unibasic acid; Li represents a phosphine of formula VI or Via; L2 represents a neutral ligand; L3 represents cyclopentadienyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; and L4 represents CO. For the individual meanings of Ll L2, L3 e Yi the previous preferences are valid. In a particularly preferred embodiment, in formulas VII and Vlld, L2 represents an alkanol of 1 to 4 carbon atoms, in formulas VII, Vlla and Vlld, Yi represents an anion of a unibasic acid, in formula Vllb, Yi represents Cl or Br, in the formula VIle, Yi represents H, and in the formulas VII to Vlld, Li represents tri-i-propylphosphine, tricyclohexylphosphine, triphenylphosphine or triphenylphosphine substituted in the phenyl groups with 1 to 3 alkyl of 1 to 4 carbon atoms. carbon. The ruthenium and osmium compounds to be used according to the invention are known or can be obtained according to known and analogous processes, starting from metal halides [for example, MeX3, (MeArenX2) 2 or [Me (diolefin) X2] 2] and the reaction with phosphines and ligand formers. The composition according to the invention can additionally contain other non-volatile open chain comonomers, which form copolymers with the taut cycloolefins. In the case of using, for example, dienes, crosslinked polymerisates can be formed. Some examples of such comonomers are mono- or di-unsaturated olefinic compounds, such as olefins and dienes from the group of pentene, hexene, heptene, octene, decene, dodecylene, acrylic and methacrylic acid, their esters and amides, vinyl ether, styrene, butadiene, isoprene and chlorbutadiene. The other olefins suitable for metathesis polymerization are contained in the composition according to the invention, for example, in an amount of up to 80% by weight, preferably from 0.1 to 80% by weight, more preferably from 0.5 to 60% by weight and particularly preferred from 5 to 40% by weight, based on the total amount of the compound of the formula I and other olefins suitable for the metathesis polymerization. The composition according to the invention may contain auxiliaries of the formulation. The known auxiliaries are antistatic agents, antioxidants, light-protecting agents, softeners, dyes, pigments, fillers, fortifying fillers, lubricants, binders, viscosity-increasing agents and deformation aids. The fillers can be added in surprisingly high proportions without negatively influencing the polymerization, for example in amounts of up to 70% by weight, preferably from 1 to 70% by weight, more preferably from 5 to 60% by weight, particularly preferred from 10 to 50% by weight, and especially preferred from 10 to 40% by weight, based on the composition. Fillers and fillers fortifiers to improve the optical, physical, mechanical and electrical characteristics are known in a large number. Some examples are glass and quartz in the form of powder, spheres and fibers, metal oxides and imetals, carbonates such as MgC03, CaC03, dolomite, metal sulfates such as gypsum and heavy spar, natural and synthetic silicates such as talc, zeolite, volastonite, plagioclase, clays such as white clay, rock flours, whisker, carbon fibers, fibers or plastic powders and carbon black. The agents for increasing the viscosity are in particular polymerized by metathesis which have olefinic unsaturated groups and can be incorporated with the polymerization in the polymer. Said polymerizations by metathesis are known and can be purchased, for example, under the trade name of Vestenamere. Other agents for increasing the viscosity are polybutadiene, polyisoprene or polychlorbutadiene, as well as copolymers of butadiene, isoprene and chloroprene with olefins. The agents for increasing the viscosity can be contained in an amount of 0.1 to 50, preferably 1 to 30, and particularly preferred 1 to 20% by weight, based on the composition.

In the context of the present invention, catalytic amount preferably means an amount of 0.0001 a % by mol, particularly preferred 0.001 to 15% by mol and very especially preferred 0.001 to 10% by mol, based on the amount of the monomer. Another object of the invention is a process for thermal polymerization by metathesis, characterized in that a composition of (a) at least one taut cycloolefin is polymerized, and (b) a catalytic amount of at least one cationic bivalent ruthenium or osmium compound , the ruthenium compound or osmium containing a metal atom, wherein 1 to 3 tertiary phosphine ligands are bound with, in the case of the ruthenium compounds, sterically demanding substituents, optionally neutral non-photolabile ligands and anions for the charge compensation, with the proviso that in dihalogenides or ruthenium hydride halides (trisphenylphosphine), the phenyl groups are substituted with alkyl of 1 to 18 carbon atoms, halogenoalkyl of 1 to 18 carbon atoms or alkoxy of 1 to 18 carbon atoms. The process according to the invention can be carried out in the presence of an inert solvent. A particular advantage of the process according to the invention is that, in the case of liquid monomers, the process can be carried out without using a solvent. Inert means that the choice of solvent is governed by the reactivity of the ruthenium and osmium compounds, for example, that polar protic solvents are not used, when substitution reactions are expected such as the exchange of halogen by alkoxy. Suitable inert solvents are, for example, protic-polar and aprotic solvents, which can be used individually or in mixtures of at least two solvents. Examples are: ether (dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether or ethylene glycol dimethyl ether, ethylene glycol methyl ether or ethylene glycol ethylether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether), halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane, 1,1-trichloroethane, 1: 1) , 2, 2-tetraclorethane), esters of carboxylic acid and lactones (ethyl ester of acetic acid, methyl ester of propionic acid, ethyl ester of benzoic acid, 2-methoxyethyl acetate, β-butyrolactone, d-valerolactone, pivalolactone), amides of carboxylic acid and lactams (N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, tetramethylurea, hexamethyl triamide of phosphoric acid, β-butyrolactam, e-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaprolactam), sulphoxides (dimethyl sulfoxide), sulfones (dimethyl sulfone, diethyl sulfone, trimethylene sulfone, tetramethylene sulfone), tertiary amines (N-methylpiperidine, N-methylmorpholine), aliphatic and aromatic hydrocarbons, such as petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene or substituted benzoles (chlorbenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene, xylene) and nitriles (acetonitrile, propionitrile, benzonitrile, phenylacetonitrile). Preferred solvents are polar and non-polar aprotic solvents. Preferred solvents are alkanols and aromatic hydrocarbons, as well as mixtures of said solvents. A particular advantage of the catalysts to be used according to the invention is their stability against water and protic polar solvents, which can therefore also be used as solvents. It should be noted in particular that the compositions used according to the invention in the process, starting from a substituted cycloolefin and a catalyst, are often insensitive to oxygen, which makes it possible to keep them stored, as well as carrying out the reactions without gas protective. Many of these compositions also exhibit good storage resistance, which simplifies their processing. The monomers of the formula I and the catalysts used for the process according to the invention, they can be stored both separately, and also together as a mixture, since the catalyst used has a particularly high stability. The mixture can be stored before the thermal polymerization as a ready-to-use formulation, which is an advantage for the large-scale technical application of the process according to the invention. Warehouse maintenance and processing do not have to be carried out excluding light, since the catalysts used do not initiate polymerization by photometathisis. The temperature of the reaction depends basically on the activity, quantity and thermal stability of the catalysts used. Some catalysts are so active that they can initiate polymerization even at room temperature. The process according to the invention can be carried out at room temperature or at a slightly elevated temperature, preferably at least 40 ° C and more preferably at least 60 ° C. Particularly, the process according to the invention is carried out at temperatures of 40 to 300 ° C, preferably 40 to 250 ° C, particularly preferred 40 to 2002 C and especially preferred 60 to 140 ° C. After the polymerization it may be advantageous to subsequently anneal the polymers at elevated temperatures, for example 80 to 2002C. Cycloolefins are, in a known manner, tight rings. In general, cyclohexene can not be polymerized with olefin metathesis. This exception is known to the person skilled in the art and is described, for example, in Ivin [Ivin, K.J. in: Ivin, KJ, Saegusa, T. (ed.), Ring-Opening Polymerisation 1: 139-144 Elsevier Applied Science Publishers, London and New York (1984) .The polymers obtained according to the invention can be homopolymers or copolymers with distribution statistics of the structural units, graft polymers or block polymers, as well as cross-linked polymers of this type They may have an average molecular weight (Mw) of, for example, 500 to 2 million Daltons, preferably 1000 to 1 mlL of Dalton (determined according to GPC by comparison with narrowly distributed polystyrene standards) If the cycloolefins contain at least 2 double bonds, crosslinked polymers can also be formed With the process according to the invention, thermoplastically deformable materials can be obtained for manufacturing of molded bodies of all types and coatings Advantageously, molding and polymerization are combined in the system s solvent-free reagents, processing procedures can be applied, such as, for example, injection molding, extrusion, polymerizations in predated molds (optionally under pressure). Depending on the monomer used, the polymers according to the invention can have very different characteristics. Some are characterized by a very high oxygen permeability, low dielectric constant, good thermal stability and low water absorption. Others have excellent optical characteristics, such as high transparency or low refractive index. In addition, the low eincogimiento should be especially highlighted. For these reasons, they can be used in the most diverse technical fields. The polymers obtained according to the invention are characterized as layers on the surfaces of carrier materials, by a high adhesive force. In addition, the coated materials are characterized by a very high surface smoothness and gloss. Under the good mechanical characteristics should be emphasized especially the low shrinkage and high resistance to shock, but also the thermal resistance. It should also mention the easy moldability and high resistance to solvents. These polymers are suitable for the manufacture of medical devices, implants or contact lenses; for the manufacture of electronic components; as binders for lacquers; as photo-hardening compositions for the construction of models or as glues for the bonding of substrates with low surface energies (for example, Teflon, polyethylene and polypropylene). The polymers obtained according to the invention can also be used for the production of lacquers by photopolymerization, it being possible to use clear (transparent) and even pigmented compositions on the one hand. Both white pigment and colored pigment can be used. Mention should also be made of the manufacture of molded bodies according to thermoplastic molding processes for objects of all kinds. The polymerizable compositions to be used according to the invention are also suitable for the production of protective layers. Another object of the invention is a variant of the process according to the invention for the production of coated materials, in which a cyclic olefin composition, catalyst and, optionally, solvent is applied as a layer on the carrier, for example by means of for immersion, brush application, casting, rolling, spinning or centrifugal casting, if necessary the solvent is removed and the layer is heated for polymerization. With this procedure, the substrate surfaces can be modified. Another object of the present invention is a carrier material, which is coated with an oligomer or polymer according to the invention and which contains a crosslinking agent. Another object of the present invention is a carrier material, which is coated with an oligomer or polymer according to the invention. These materials are suitable for the production of protective layers or the reproduction of reliefs by irradiation (optionally under a photomask) and subsequent development with a solvent. Suitable crosslinking agents, which may be contained, for example, in an amount of 0..01 to 20% by weight, are especially organic bisazides, in particular 2,6-bis (4-azidobenzilidene) -4- methyl-cyclohexanone that can be purchased. Another object of the present invention is in addition a coated carrier material, which is characterized in that, in a carrier, a layer of (a) is applied to at least one taut cycloolefin and (b) a catalytic amount of at least one ruthenium compound or of cationic bivalent osmium, the ruthenium or osmium compound containing a metal atom, to which 1 to 3 tertiary phosphine ligands are bound with, in the case of ruthenium compounds, sterically demanding substituents, optionally neutral non-photolabile ligands and anions for charge compensation, with the proviso that in dihalogenides or ruthenium hydride halides (trisphenylphosphine), the phenyl groups are substituted with alkyl of 1 to 18 carbon atoms, halogenoalkyl of 1 to 18 carbon atoms or alkoxy with 1 to 18 carbon atoms. Another object of the present invention is the use of a ruthenium or cationic bivalent osmium compound, the ruthenium or osmium compound containing a metal atom, to which 1 to 3 tertiary phosphine ligands are linked with, in the case of the compounds of ruthenium, sterically demanding substituents, optionally non-photolabile neutral ligands and anions for charge compensation, with the proviso that in dihalogenides or ruthenium hydride halides (trisphenylphosphine), the phenyl groups are substituted with alkyl of 1 to 18 atoms of carbon, halogenalkyl of 1 to 18 carbon atoms or alkoxy with 1 to 18 carbon atoms, as catalysts for the thermal polymerization by metathesis of taut cycloolefins. Suitable carrier materials are, for example, those of glass, minerals, ceramics, plastics, woods, semimetals, metals, metal oxides and metal nitrides. The thicknesses of layer are basically governed by the desired application and can be, for example, from 0.1 to 1000 μm, preferably from 0.5 to 500 μm, particularly preferred from 1 to 100 μm. The coated materials are characterized by a high bond strength and good thermal and mechanical characteristics. The preparation of the coated materials according to the invention can be carried out according to known methods, such as brush application, raking, casting processes such as screen casting or centrifugal casting. In coatings, good results are often achieved when cycloolefins are used for the polymerization, which additionally contain 1 to 3 and, preferably, a further double bond and which, in the context of the invention, represent fused polycyclic ring systems. or linked directly or through bridging groups. The following examples illustrate the invention in more detail.

Examples 1 and 2: Polymerization of dicyclopentadiene in substance 2 g of biscyclopentadiene are mixed with 12 mg of catalyst and poured into a mold. The times and temperatures indicated in Table 1 are then polymerized and subsequently cured for 2 hours at 150 seconds. The following catalysts are used (abbreviations: MeOH: methanol, Cough: tosylate, Cp: cyclopentadienyl, Ph: phenyl, Cy: cyclohexyl): A = Ru (PCy3) 2 (MeOH) 2 (Cough) 2 B = RuCl2 (PCy3) 2 C = Ru (H) 2 (CO) (PPh3) 3 D = RuCpCl (PPh3) 3 E = RuCl2 [P (2-methyl-C6H4) 3] 3 Table 1 E "Example Catalyst Conversion Time Polymer-% Temperature 1 A 100 12 h; 802C Tg = 122 ° C 2 B 100 12 h; 1002C Tg = 118sc * crosslinked Examples 3 to 7: Polymerization of norborene 500 mg of norborene are dissolved in 3 ml of chloroform and mixed with 3 mg of catalyst. Then, the times and the temperatures indicated in table 2 are polymerized. TA in table 2 means room temperature. The conversion is determined with ethanol after precipitation. Table 2 Example Catalyst Conversion Time, Mw Mw / Mn in% Temperature 3 A 97.5 10 min; TA 540 k 1.9 4 B 93 15 min; TA 300 k 2.0 5 C 25 2 h; 50SC crosslinked 6 D 30 10 h; 502C 80 k 2.4 7 E 65 10 h; Reticulated 502C

Claims

NOVELTY OF THE INVENTION CLAIMS

1. A composition of (a) at least one cycloolefin tained, and (b) a catalytic amount of at least one ruthenium or bivalent, cationic osmium compound, the ruthenium compound or osmium containing a metal atom, to which they are linked 1 to 3 tertiary phosphine ligands with, in the case of ruthenium compounds, sterically demanding substituents, optionally neutral non-photolabile ligands and anions for charge compensation, with the proviso that in dihalides or ruthenium hydride halides (trisphenylphosphine) , the phenyl groups are substituted with alkyl of 1 to 18 carbon atoms, halogenoalkyl of 1 to 18 carbon atoms or alkoxy of 1 to 18 carbon atoms.

2. A composition according to claim 1, characterized in that the cyclic olefins are monocyclic rings or polycyclic ring systems, bridged or condensed with 2 to 4 rings, which are unsubstituted or substituted and, if necessary, contain one or more heteroatoms of group C, S, N and Si in one or more rings, and aromatic or heteroaromatic rings, if appropriate, condensed.

3. A composition according to claim 2, characterized in that the cyclic rings contain 3 to 16 ring members.

4. A composition according to claim 3, characterized in that the cyclic rings contain 3 to 12 ring members.

5. A composition according to claim 2, characterized in that the cyclic olefins contain other non-aromatic double bonds.

6. A composition according to claim 1, characterized in that the cycloolefins correspond to the formula I wherein: Qi is a radical with at least one carbon atom, which together with the group -CH = CQ2 forms an alicyclic ring with at least three members, which, if appropriate, contains one or more heteroatoms selected from the group composed of silicon, phosphorus, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted with halogen, = 0, -CN, -N02, R? R2R3SÍ- (0) u-, -COOM, -S03M, -P03M, -COO (M?)? 2, -S03 (M?)? / 2, -P03 (M?)? / 2, alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms, cyanoalkyl from 1 to 6 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms, heterocycloalkyl of 3 to 16 carbon atoms, heteroaryl of 3 to 16 atoms of carbon, heteroaralkyl of 4 to 16 carbon atoms or R -X-; or are substituted on the two neighboring carbon atoms with -CO-O-CO- or -CO-NR5-CO-; or wherein, in the case of the neighboring carbon atoms of the alicyclic ring, an alicyclic, aromatic or heteroaromatic ring is condensed, which is unsubstituted or substituted by halogen -CN, -N02, R6R7R8SÍ- (0) u-, -COOM, -S03M, -P03M, -COO (M?)? / 2, -S03 (M?)? / 2, -P03 (M?)? / 2, alkyl of 1 to 20 carbon atoms, halogenoalkyl 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cyanoalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms carbon, heterocycloalkyl of 3 to 16 carbon atoms, heteroaryl of 3 to 16 carbon atoms, heteroaralkyl of 4 to 16 carbon atoms or Ri3"Xi-; X and Xi, independently of each other, represent -O-, -S-, - CO-, -SO-, -S02-, -OC (O) -, -C (O) -, -C (0) -NR5 -, -NR? 0- C (O) -, -S02-0- or -0-S02-; Ri / R2 and R3Í independently from each other, mean alkyl of 1 to 12 carbon atoms, perfluoroalkyl of 1 to 12 carbon atoms, phenyl or benzene; R4 and R13 independently represent alkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms; R5 and Ri? / Independently from each other, mean hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene, the alkyl groups being in turn unsubstituted or substituted by alkoxy of 1 to 12 carbon atoms or cycloalkyl of 3 to 8 carbon atoms; R6 / R7 and R8 / independently of each other, mean alkyl of 1 to 12 carbon atoms, perfluoroalkyl of 1 to 12 carbon atoms, phenyl or benzene; M represents an alkali metal and Mi an alkaline earth metal; and u represents 0 or 1; wherein the alicyclic ring formed with Qi contains, if appropriate, other non-aromatic double bonds; Q2 means hydrogen, alkyl of 1 to 20 carbon atoms, halogenoalkyl of 1 to 20 carbon atoms, alkoxy of 1 to 12 carbon atoms, halogen, -CN, R-X2-; R n means alkyl of 1 to 20 carbon atoms, halogenalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 16 carbon atoms or aralkyl of 7 to 16 carbon atoms; X2 means -C (0) -0- or -C (0) -NR? 2; R 12 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene; wherein the aforementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted with alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, -N02, -CN or halogen, and where the heteroatoms of the aforementioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are selected from the group -0-, -S-, -NRg- and -N =; and Rg means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene.

7. A composition according to claim 6, characterized in that the alicyclic ring, which is formed by Qi together with the group -CH = CQ2-, has 3 to 16 ring atoms, and in the case of a monocyclic, bicyclic ring system , tricyclic or tetracyclic.

8. A composition according to claim 6, characterized in that Q2 in formula I means hydrogen.

9. A composition according to claim 6, characterized in that in the compounds of the formula I Q1 is a radical with at least one carbon atom, which forms together with the group -CH = CQ2 an alicyclic ring of 3 to 20 members, which, if appropriate, contains one or more heteroatoms selected from the group consisting of silicon, oxygen, nitrogen and sulfur; and that is unsubstituted or substituted with halogen, = 0, -CN, -NO2, RlR2R3SÍ- (0) u-, -COOM, -S03M, -P03M, -C00 (M?) 1/2, -S03 (M?)? /, -P03 (M?)? 2, alkyl of 1 to 12 carbon atoms, halogenalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 12 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 12 carbon atoms, heteroaralkyl of 4 to 12 carbon atoms or R4-X-; or wherein two neighboring carbon atoms in this Qi radical are substituted with -CO-O-CO- or -CO-NR5-CO-; or in which, if appropriate, in neighboring carbon atoms, an alicyclic, aromatic or heteroaromatic ring is condensed, which is unsubstituted or substituted with halogen -CN, -N0, R6R7R8Si- (0) u-, -COOM, -S03M, -P03M, -COO (Mi)? / 2, -S03 (M?)? 2, -P03 (M?)? 2 alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 12 carbon atoms, heterocycloalkyl of 3 to 6 carbon atoms, heteroaryl of 3 to 12 carbon atoms, heteroaralkyl of 4 to 12 carbon atoms or? 3-X? ~; X and Xl, independently of each other, represent -O-, -S-, - CO-, -SO-, -S02-, -OC (O) -, -C (0) -, -C (0) -NR5 -, -NR10- C (O) -, -S02-0- or -0-S02-; Ri, R and R3, independently of each other, mean alkyl of 1 to 6 carbon atoms, perfluoroalkyl of 1 to 6 carbon atoms, phenyl or benzene; M represents an alkali metal and Mi an alkaline earth metal; and R4 and R13 independently represent alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, aryl of 6 to 12 carbon atoms , aralkyl of 7 to 12 carbon atoms; R5 and Ri? F independently of each other, mean hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzene, the alkyl groups being in turn unsubstituted or substituted by alkoxy of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; R6 / R7 and R8f independently of one another, mean alkyl of 1 to 6 carbon atoms, perfluoroalkyl of 1 to 6 carbon atoms, phenyl or benzene; u represents 0 or 1; wherein the alicyclic ring formed with Qi contains, if appropriate, other non-aromatic double bonds; Q2 means hydrogen, alkyl of 1 to 12 carbon atoms, halogenalkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, halogen, -CN, Rn ~ X2-; Rll means alkyl of 1 to 12 carbon atoms, halogenoalkyl of 1 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 12 carbon atoms or aralkyl of 7 to 12 carbon atoms; X2 means -C (0) -0- or -C (0) -NR2; and R 1 means hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzene; wherein the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted with alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, -N02, -CN or halogen, and wherein the heteroatoms of the heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group -O-, -S-, -NRg- and -N =; and Rg means hydrogen, alkyl of 1 to 6 carbon atoms, phenyl or benzene.

10. A composition according to claim 6, characterized in that in the compounds of the formula I Qi is a radical with at least one carbon atom, which forms together with the group -CH = CQ2 an alicyclic ring of 3 to 10 members , Which, if appropriate, contains one or more heteroatoms chosen from the group consisting of silicon, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, = 0, -CN, -N0, RlR2R3SÍ-, -COOM, -S03M, -P03M, -C00 (M?) 1 2, -S03 (M?) 1/2, - P03 (M?)? / 2, alkyl of 1 to 6 carbon atoms, halogenoalkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl, benzene or R4-X-; or in which, if necessary, in atoms; of neighboring carbon, an alicyclic, aromatic or heteroaromatic ring is condensed, which is unsubstituted or substituted by halogen -CN, -N02, R6R7R8SÍ- (0) u-, -COOM, -S03M, -PO3M, -C00 (M? )? / 2, - S? 3 (M?)? / 2, -P? 3 (M?)? /, Alkyl of 1 to 6 carbon atoms, halogenoalkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms, cyanoalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl, benzene or R 13 -X 1 -; R1 (R and R3, independently of each other, mean alkyl of 1 to 4 carbon atoms, perfluoroalkyl of 1 to 4 carbon atoms, phenyl or benzene, M represents an alkali metal and Mi an alkaline earth metal, and R4 and R13 independently represent alkyl of 1 to 6 carbon atoms, halogenalkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; X and Xi, independently of each other, mean -O-, - S-, - CO-, -SO- or -S02-; R6 »R7 and R8, independently of one another, mean alkyl of 1 to 4 carbon atoms, perfluoroalkyl of 1 to 4 carbon atoms, phenyl or benzene; 0 or 1, and Q2 means hydrogen

11. A composition according to claim 1, characterized in that the cyclic olefins are norborene or norborene derivatives

12. A composition according to claim 11, characterized in that the norborene derivatives are those of the formula II wherein X3 means -CHRiß-, oxygen or sulfur; R14 and R15, independently of each other, mean hydrogen, -CN, trifluoromethyl, (CH3) 3Si-0-, (CH3) 3-Si or -COOR? 7; and R16 and R17 'independently from each other, mean hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene; or of formula III where X4 means -CHRig, oxygen or sulfur; Rig means hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene; and Ri8 means hydrogen, alkyl of 1 to 6 carbon atoms or halogen; or of formula IV wherein X5 means -CHR2-, oxygen or sulfur; R 22 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene; 2? and R2ir independently of each other, mean hydrogen, CN, trifluoromethyl, (CH3) 3Si-0-, (CH3) 3Si- or -COOR23; and R23 means hydrogen, alkyl of 1 to 22 carbon atoms, phenyl or benzene; or of the formula V O where? 6 means -CHR24-, oxygen or sulfur; R 24 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or benzene; And it means oxygen or > N-R s; and R25 means hydrogen, methyl, ethyl or phenyl.

13. A composition according to claim 1, characterized in that the tensed cycloolefins contain only carbon and hydrogen atoms.

14. A composition according to claim 1, characterized in that the tense cycloolefins are rings of 5 or 6 members or ring systems with one to three rings of 5 or 6 members.

15. A composition according to claim 1, characterized in that the taut cycloolefins are norborene, alkylated norborenes and dicyclopentadiene.

16. A composition according to claim 1, characterized in that the cycloolefins are

17. A composition according to claim 1, characterized in that the ruthenium and osmium compounds contain 2 or 3 tertiary phosphine groups.

18. A composition according to claim 1, characterized in that the ruthenium and osmium compounds contain 3 phosphine groups and two univalent anions to compensate the charge; or 3 phosphine groups, two non-photolabile neutral ligands of two bonds or one of a bond and two univalent anions to compensate for the charge; or 2 phosphine groups, a neutral non-monolabial monoanionic ligand, additionally of a bond, and a univalent anion to compensate for the charge.

19. A composition according to claim 18, characterized in that the neutral, non-photolabile, monoanionic ligands, additionally of a bond, are cyclopentadienyl or indenyl, which are unsubstituted or substituted by one to five alkyl of 1 to 4 carbon atoms or - Yes (alkyl of 1 to 4 carbon atoms).

20. A composition according to claim 18, characterized in that the non-photolabile ligands, of a bond, are H20, HS, NH3; aliphatic or cycloaliphatic alcohols or mercaptans with 1 to 18 carbon atoms, optionally halogenated, in particular fluorinated or chlorinated; alcohols or aromatic thiols with 6 to 18 carbon atoms, alcohols or araliphatic thiols with 7 to 18 carbon atoms; ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid ester, lactone, optionally NC? -C4-mono- or dialkyl carboxylic acid amides with 2 to 20 carbon atoms, and lactams, in the case of NC ? C4-alkylated open-chain or cyclic and aliphatic, araliphatic or aromatic; primary, secondary and tertiary amines, open chain or cyclic and aliphatic, araliphatic or aromatic, with 1 to 20 carbon atoms.

21. A composition according to claim 1, characterized in that the phosphine ligands correspond to the formulas VI or Via PR29R3oR3l (VI), R29R30R-Zl-PR29R30 (VIa) / where R29, R3? and R31 > independently of one another, they mean alkyl of 3 to 20 carbon atoms branched; cycloalkyl of 4 to 12 carbon atoms unsubstituted or substituted with alkyl of 1 to 18 carbon atoms, halogenoalkyl of 1 to 18 carbon atoms or alkoxy of 1 to 18 carbon atoms; or aryl of 6 to 16 carbon atoms, unsubstituted or substituted with alkyl of 1 to 18 carbon atoms, halogenoalkyl of 1 to 18 carbon atoms or alkoxy of 1 to 18 carbon atoms; the radicals R2g and R3Q together mean unsubstituted tetra- or pentamethylene or substituted with alkyl of 1 to 6 carbon atoms, halogenoalkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms; or tetra- or mentamethylene unsubstituted or substituted with alkyl of 1 to 6 carbon atoms, halogenoalkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms or condensed with 1 or 2 1,2-phenylene, and R31 has the meaning indicated above; and Zi means linear or branched alkylene of 2 to 12 carbon atoms, unsubstituted or substituted by alkoxy of 1 to 4 carbon atoms; 1,2- or 1,3-cycloalkylene with 4 to 8 carbon atoms, unsubstituted or substituted with alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; or 1,2- or 1,3-heterocycloalkylene with 5 or 6 ring members and a heteroatom of the group O or N, unsubstituted or substituted with alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.

22. A composition according to the claim 21, characterized in that the α-branched alkyls are those of the formula -CRbRcRd, wherein Rb means H or alkyl of 1 to 12 carbon atoms, Rc means alkyl of 1 to 12 carbon atoms, and R¿ means alkyl of 1 to 12 carbon atoms or phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; and the sum of the carbon atoms in the radical -CRDRcRd is from 3 to 18.

23. A composition according to the claim 21, characterized in that the phosphine ligands correspond to the formula VI, wherein Rg, R3Q and R31, independently of one another, mean alkyl of 3 to 8 carbon atoms to-branched, cyclopentyl or cyclohexyl unsubstituted or substituted with alkyl of 1 to 4 carbon atoms, or phenyl unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or trifluor ethyl.

24. A composition according to claim 1, characterized in that the phosphine ligands are (C6H5) 3P, (C5H9) 3P, (I-C3H7) 3P, (t-C4H9) 3P, [C2H5-CH (CH3)] 3P , [C2H5-C (CH3) 2_3p / (2-methylphenyl) 3P, (2, 3-dimethylphenyl) 3P, (2,4-dimethylphenyl) 3P, (2,6-dimethylphenyl) 3P, (2-methyl-4 -i-propylphenyl) 3P, (2-methyl-3-i-propylphenyl) 3P, (2-methyl-5-i-propylphenyl) 3P, (2-methyl-6-i-propylphenyl) 3P, (2-methyl) -3-t-butylphenyl) 3P, (2-methyl-4-t-butylphenyl) 3P, (2-methyl-5-i-butylphenyl) 3P, (2,3-di-t-butylphenyl) 3P, (2 , 4-di-t-butylphenyl) 3P, (2,5-di-t-butylphenyl) 3P, (2,6-di-t-butylphenyl) 3P.

25. A composition according to claim 1, characterized in that the anions of the inorganic or organic acids are a hydride (H ~), a halide, the anion of an oxacid, BF4 ~, PFß ", SbF'ß" or AsFe ".

26. A composition according to claim 25, characterized in that the anions of oxacids are sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a carboxylic acid of 1 to 8 carbon atoms, sulfonates, phenylsulfonate or benzylsulphonate optionally substituted with alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen

27. A composition according to claim 25, characterized in that the anions are H ~, Cl ~ , BF4 ~, PFß ", SbFg", AsF6 ~, CF3S03 ~, C6H5-SO3", 4-methyl-C6H5-S03 ~, 3,5-dimethyl-C6H5-S03 ~, 2,4,6-trimethyl-C6H5 -S03 ~ and 4-CF3-C6H5-S03 ~.

28. A composition according to claim 1, characterized in that the ruthenium and osmium compounds correspond to the formulas VII, Vlla, Vllb, VIIc or Vlld, Me2? (L?) 2 (2) (Y) 2 (VII), Me2f (L?) 3 (Y) 2 (Vlla), Me2f (L?) 2L3 (YD (Vllb), Me2T (L?) 3L4 (Y) 2 (Vllc), Me2? L? (L2) 3 (Y ) 2 (Vlld), where Me represents Ru or Os, Yi represents the anion of a unibasic acid, Li represents a phosphine of formula VI or Via, L represents a neutral ligand, L3 represents cyclopentadienyl unsubstituted or substituted with alkyl of 1 to 4 carbon atoms, and L4 represents CO.

29. A composition according to claim 28, characterized in that in the formulas VII and Vlld, L2 represents an alkanol of 1 to 4 carbon atoms, in the formulas VII, Vlla and Vlld , Y represents an anion of a unibasic acid, in the formula Vllb, Yi represents Cl or Br, in the formula VIIc, Y represents H, and in the formulas Vil to Vlld, Li represents tri-i-propylphosphine, tricyclohexylphosphine, trifen ilphosphine or triphenylphosphine substituted in the phenyl groups with 1 to 3 alkyl of 1 to 4 carbon atoms.

30. A composition according to claim 1, characterized in that the ruthenium and osmium compounds are present in an amount of 0.0001 to 20 mol%.

31. A process for thermal polymerization by metathesis, characterized in that a composition of (a) at least one taut cycloolefin is polymerized, and (b) a catalytic amount of at least one cationic bivalent ruthenium or osmium compound, containing the compound of ruthenium or osmium a metal atom, where 1 to 3 tertiary phosphine ligands are bound with, in the case of the ruthenium compounds, sterically demanding substituents, optionally non-photolabile neutral ligands and anions for charge compensation, with the proviso that in dihalides or ruthenium hydride halides (trisphenylphosphine), the phenyl groups are substituted with alkyl of 1 to 18 carbon atoms. carbon, halogenalkyl of 1 to 18 carbon atoms or alkoxy of 1 to 18 carbon atoms.

32. A process for the production of coated materials, in which a composition according to claim 1 is applied to a carrier, where appropriate, the solvent is removed and the layer is heated for polymerization.

33. A carrier material, which is coated with an oligomer or polymer of the composition according to claim 1, and which contains a crosslinking agent.

34. A carrier material, which is characterized in that a layer of a composition according to claim 1 is applied to a substrate.

35. A carrier material characterized in that a layer of (a) at least one taut cycloolefin is applied to a carrier. (b) a catalytic amount of at least one ruthenium or cationic bivalent osmium compound, the ruthenium or osmium compound containing a metal atom, to which 1 to 3 tertiary phosphine ligands are linked with, in the case of the compounds of ruthenium, sterically demanding substituents, optionally non-photolabile neutral ligands and anions for charge compensation, with the proviso that in dihalogenides or ruthenium hydride halides (trisphenylphosphine), the phenyl groups are substituted with alkyl of 1 to 18 atoms of carbon, halogenalkyl of 1 to 18 carbon atoms or alkoxy with 1 to 18 carbon atoms.

36. Use of a ruthenium compound or cationic bivalent osmium, the ruthenium or osmium compound containing a metal atom, to which 1 to 3 tertiary phosphine ligands are bound with, in the case of the ruthenium compounds, sterically demanding substituents, optionally non-photolabile neutral ligands and anions for charge compensation, with the proviso that in dihalogenides or ruthenium hydride halides (trisphenylphosphine), the phenyl groups are substituted with alkyl of 1 to 18 carbon atoms, halogenoalkyl of 1 to 18 carbon atoms or alkoxy with 1 to 18 carbon atoms, as catalysts for thermal polymerization by metathesis of taut cycloolefins.