CA2205117A1 - Thermal metathesis polymerization process and a polymerizable composition - Google Patents

Abstract

Disclosed is a composition comprising (a) at least one tight cycloolefin and (b) a catalytic quantity of at least one divalent-cationic compound of ruthenium or osmium with a metal atom, to which are bound 1-3 tertiary phosphine ligands with (in the case of ruthenium compounds) sterically exacting substituents, optionally non-photolabile neutral ligands and anions for charge balancing. The following condition must be observed: in ruthenium (tris-phenyl phosphine) dihalides or hydride-halides, the phenyl groups are substituted by C1-C18-alkyl, C1-C18- alkyl halide or C1-C18 alkoxy. The composition is suitable for the production of moulded parts of all kinds and of coatings.

Description

CA 0220~117 1996-0~-12 1~ T~ L~
-Thermal metathesis PolYmerization Process and a Polvmerizable co",posilion The present invention relates to a prucess for the thermal polymerization of strained cycloolefins; a thermally polymerizable composition of such a cycloolefin and a one-component catalyst for thermally induced metathesis polymerization; and carrier materials coated with the thermally polymerizable or the cl ossli"ked polymers.

Demonceau et al. [Demonceau, A., Noels, A.F., Saive, E., Hubert, A.J., J. Mol. Catal.
76:123-132 (1992)l describes [(C6H5)3P]3RuCI2, (p-cumene)RuCI2P(C6H")3 and [(C6H5)3P]3RuHCI as thermal catalysts for ring-opening metathesis polymerization of norbomene, a fused polycycloolefin. Because the activity is too low, these catalysts have not found acceptance in industrial preparaLion. It has therefore been suggested that the activity be increased by the addition of diazo esters. It is also mentioned that only (p-cumene)RuCI2P(C6H")3 is cap,, ~le of polymerizing norbornene in a relatively short time at 60C. Cyclooctene is also mentioned as a further monomer.

WO 93/13171 des.;,il.es air- and water-stable one-component and two-component catalysts based on molybdenum compounds and tungsten compounds containing carbonyl groups and ruthenium compounds and osmium compounds with at least one polyene ligand for the thermal metathesis polymerization and a photoactivated metathesis polymerization of strained cycloolefins, in particular norbomene and norbornene derivatives. No other polycyclical - above all non-fused polycyclical - cycloolefins are mentioned. The one-component catalysts of the ruthenium compounds used, that is to say [Ru(cumene)CI2]2 and [(C6H6)Ru(CH3CN)2Cl]'PF6-, can indeed be activated by UV i"~didlion; however, the storage stability of the cor"posilions with norbomene is completely inadequate. These catalysts are c~p7~'e of replacing the known two-component catalysts only inadequately.

It has now been found, s~ .ri~i"yly, that divalent-cationic ruthenium and osmium complexes are highly active one-component catalysts for thermally induced metathesis polymerization if they contain at least one phosphine group with bulky substituents bound to the metal atom. It has furthermore been found that the compositions are stable to air and moisture and can be processed without safety prec~utions. The polymerizable compositions comprising ruthenium and osmium complexes are moreover sufficiently stable, so that they do not polymerize before the desired type of ~rocessing.

CA 0220~117 1996-0~-12 The invention relates to a composition of (a) at least one strained cycloolefin and (b) a catalytic quantity of at least one divalent-cationic compound of ruthenium or osmium, wherein the ruthenium or osmium compound contains a metal atom to which are bound 1 to 3 tertiary phosphine ligands with, in the case of the ruthenium compounds, sterically exacting substituents, optionally non-photolabile neutral ligands and anions for charge balancing, with the proviso that in ruthenium (trisphenylphosphine)dil ,-' des or hydride-halides the phenyl groups are sllhstitlltpd by C,-C,8alkyl, C,-C,8haloalkyl or C,-C,8alkoxy.

The cyclical olefins can be monocyclical or polycyclical condensed or bridged ring systems, having for example from two to four rings, which are unsl Ihstihlted or suhstitut~d and can contain heterc,dlo"1s, for example 0, S, N or Si in one or more rings and/or can contain condensed aromatic or heteroar~",alic rings, for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. The individual cyclical rings can contain 3 to 16, p,~fer~bly 3 to 12 and, particularly prererably, 3 to 8 ring members. The cyclical olefins can include further nonaromatic double bonds, depending on the ring size preferably 2 to 4 such additional double bonds. The ring s~ ~hstituents are those which are inert, in other words which do not adversely affect the chemical stability of the ruthenium compounds and osmium compounds. The cycloolefins are strained rings or ring systems.

If the cyclical olefins contain more than one double bond, for example 2 to 4 double bonds, crosslinked polymers can also form, depending on the reaction condilions, the monomer chosen and the amount of catalyst.

In a p,t:~r,ed embodiment of the process according to the invention, the cycloolefins cor, espond to the formula I

CH CQ
\ / (1), in which Q, is a radical having at least one carbon atom which, together with the -CH=CQ2 group, forms an at least 3-membered alicyclical ring which optionally cor,lai"s one or more heteroatoms chosen from the group consiili-,g of silicon, phosphorus, oxygen nitrogen and sulfur; and which is unsl ~hstitnted or sl Ihstitllted by halogen, =0, -CN, CA 0220~117 1996-0~-12 -NO2, R1R2R3Si-(O)U-,-COoM~-so3M~-po3M~-coo(M1)w-so3(M~ 2~-po3(Ml)1/2 C1-C20-alkyl, C,-C20hydroxyalkyl, C,-C20haloalkyl, C,-C6cyanoalkyl, C3-C8cycloalkyl, C6-C,6aryl, CrC,6aralkyl, C3-C6heterocycloalkyl, C3-C,6heteroaryl, C4-C,6heteroaralkyl or R4-X-; or in which two adjacent C atoms are substituted by -CO-O-CO- or-CO-NRs-CO-; or in which an alicyclical, aromatic or heteroaromatic ring which is unsl ~hstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-(O)U-, -COOM, -SO3M, -PO3M, -COO(M,)"2, -SO3(M,)"2, -PO3(M,)"2, C,-C20alkyl, C,-C20haloalkyl, C,-C20hydroxyalkyl, C1-C6cyanoalkyl, C3-C8cycloalkyl, C6-C16aryl, C7 C16aralkyl,C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C16h~:teroa,all;yl or R13-X,- is optionally fused onto adjacent carbon atoms of the alicyclical ring;
X and X, independently of one another are -O-, -S-, -CO-, -SO-, -SO2-, -O-C(O)-, -C(O)-Q-, -C(O)-NRs-, -NR,0-C(O)-, -SO2-O- or-O-S02-;
R" R2 and R3 independently of one another are C,-Cl2alkyl, C,-C,2perfluoroalkyl, phenyl or benzyl;
R4 and R,3 independently are C,-C20alkyl, C,-C20haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C,6aryl or CrC,6aralkyl;
R5 and R~o independently of one another are hydrogen, C1-C12alkyl, phenyl or benzyl, where the alkyl groups in turn are unsubstituted or silhstitllted by C1-C12alkoxy or C3-C8cycloalkyl;
R6, R~ and R8 independently of one another are C,-C,2alkyl, C,-C,2per~uoroalkyl, phenyl or benzyl;
M is an alkali metal and M, is an alkaline earth metal; and uisOor1;
where the alicyclical ring formed with Q1 optionally contains further nonaromatic double bonds;
Q2 is hydrogen, C,-C20alkyl, C,-C20haloalkyl, C,-C12alkoxy, halogen, -CN or R11-X2-;
R11 is C,-C20alkyl, C,-C20haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl or CrC16aralkyl;
X2 is -C(O)-O- or -C(O)-NR12-;
R12 is hydrogen, C1-C12alkyl, phenyl or benzyl;
where the abovementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or sl Ihsfftl Ited by C1-C12alkyl, C1-C12alkoxy, -NO2, -CN
or halogen, and where the heteroatoms of the abovementioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group consi~li"g of -O-, -S-, -NRg- and -N=;
and R8 is hydrogen, C1-C,2alkyl, phenyl or benzyl.

CA 0220~117 1996-0~-12 Fused-on alicyclical rings preferably contain 3 to 8, particularly preferably 4 to 7, and especially preferably 5 or 6 ring C atoms.

If an asymmetric center is present in the compounds of the formula 1, the compounds can occur in optically isomeric forms as a result. Some compounds of the formula I can occur in tautomeric forms (for example keto-enol tautomerism). If an aliphatic C=C double bond is present, geometric isomerism (E form or Z form) can also occur. Exo-endo configurations are furthermore also possible. Formula I thus includes all the possiL)le stereoisomers which are present in the form of enantiomers, tautomers, diastereomers, E/Z isomers or mixtures thereof.

In the definitions of the s~hstitllents, the alkyl, alkenyl and alkynyl groups can be straight-chain or branched. The same also applies to the alkyl or each alkyl moiety of alkoxy, alkylthio, alkoxycarbonyl and further alkyl-conLd;"i"g groups. These alkyl groups preferably contain 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 4 C atoms. These alkenyl and alkynyl groups pr~::r~rdbly contain 2 to 12, more preferably 2 to 8, and particularly preferably 2 to 4 C atoms.

Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.

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-tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.

Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl and halogenated, in particular fluorinated or chlorinated, alkanes, such as, for example, the isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.

~ CA 0220~117 1996-0~-12 ~

., 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 and n-octadec-4-enyl.

Cycloalkyl is preferably Cs-C8cycloalkyl, in particular Cs-or C6cycloalkyl. Some examples are cyclopropyl, dimethylcycloprupyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Cyanoalkyl includes, for example, cyanomethyl (methylnitrile [sic]), cyanoethyl (ethylnitrile [sic]), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyano-iso-butyl, 1-cyano-sec-butyl, 1-cyano-tert-butyl and the various isomeric cyanopentyl and -hexyl radicals.

Aralkyl preferably contains 7 to 12 C atoms, and particularly preferably 7 to 19 C atoms. It can be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, phenbutyl or a,a-dimethylbenzyl.

Aryl preferably contains 6 to 10 C atoms. It can be, for example, phenyl, penlali", indene, naphthalene, azulene or anthracene.

Heteroaryl preferably cor,Ldi"s 4 or 5 C atoms and one or two heteroatoms from the group consisting of 0, S and N. It can be, for example, pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, purine or quinoline.

Heterocycloalkyl pr~r~rdbly contains 4 or 5 C atoms and one or two heteroatoms from the group consisli"g of 0, 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, sec-butyloxy and t-butyloxy.

Alkali metal in the context of the present invention is to be understood as meaning lithium, sodium, potassium, rubidium and cesium, in particular lithium, sodium and poLassium.

CA 0220~117 1996-0~-12 Alkaline earth metal in the context of the present invention is to be understood as meaning beryllium, magnesium, calcium, strontium and barium, in particular magnesium and calcium.

In the above deri"ilions, halogen is to be understood as meaning fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

Compounds of the formula I which are particularly s~ ~it~'e for the process according to the invention are those in which Q2 is hydrogen.

Compounds of the formula I which are furthermore preferred for the polymerization are those in which the alicyclical ring which Q, forrns together with the -CH=CQ2- group has 3 to 16, more preferably 3 to 12, and particularly preferably 3 to 8 ring atoms, where the ring system can be monocyclical, bicyclical, tricyclical or tetracyclical.

The process according to the invention can be carried out particularly advantageously with those compounds of the formula I in which Q, is a radical with at least one carbon atom which, together with the -CH=CQ2- group, forms a 3- to 20-membered alicyclical ring which optionally contains one or moreheteroatoms chosen from the group cons;sling of silicon, oxygen, nitrogen and sulfur;
and which is unsl ~hstituted or svhstituted by halogen, =O, -CN, -NO2, R1R2R3si-(o) -COOM, -SO3M, -PO3M, -COO(M,)"2, -SO3(M,)"2, -PO3(M,)"2, C,-C,2alkyl, C,-C,2haloalkyl, C,-C,2hydroxyalkyl, C,-C4cyanoalkyl, C3-C6cycloalkyl, C6-C,2aryl, CrC,2aralkyl, C3-C6heterocycloalkyl, C3-C,2heteroaryl, C4-C,2heteroaralkyl or R4-X-; or in which two adjacent C atoms in this radical Q,are 5llhstitllted by -CO-O-CO- or -CO-NRs-CO-; or in which an alicyclical, aromatic or heteroaromatic ring which is unsl ~hstihlted or sl ~bstihlted by halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M,-PO3M, -COO(M,)1,2, -SO3(M,)"2, -PO3(M,)"2, C,-C,2alkyl, C,-C,2haloalkyl, C,-C,2hydroxyalkyl, C,-C4cyanoalkyl, C3-C6cycloalkyl, C6-C,2aryl, C7-C,2aralkyl,C3-C6heterocycloalkyl, C3-C,2heteroaryl, C4-C,2heteroaralkyl or R,3-X,- is optionally fused onto adjacent carbon atoms;
X and X, independently of one another are -O-, -S-, -CO-, -SO-, -SO2-, -O-C(O)-, -C(O)-O-, -C(O)-NRs-, -NR,0-C(O)-, -SO2-O- or-O-SO2-;
R" R2 and R3 independently of one another are C,-C6alkyl, C,-C6perfluoroalkyl, phenyl or benzyl;
M is an alkali metal and M, is an alkaline earth metal;

CA 0220~117 1996-0~-12 R4 and R,3 independently of one another are C,-C,2alkyl, C,-C12haloalkyl, C,-C,2hydroxyalkyl, C3-C8cycloalkyl, C6-C,2aryl or C7-C,2aralkyl;
R5 and R,o independently of one another are hydrogen, C1-C6alkyl, phenyl or benzyl, where the alkyl groups in turn are unsubstituted or substituted by C~-C6alkoxy or C3-C6cycloalkyl;
R6, R7 and R8 independently of one another are C,-C6alkyl, C,-C6perfluoroalkyl, phenyl or benzyl;
uisOor1;
where the alicyclical ring formed with Q, optionally contains further nonaromatic double bonds;
Q2 is hydrogen, C,-C,2alkyl, C,-C,2haloalkyl, C,-C6alkoxy, halogen, -CN or R"-X2-;
R" is C,-C,2alkyl, C,-C,2haloalkyl, C,-C,2hyclroxyalkyl, C3-C6cycloalkyl, C6-C,2aryl or C7-C,2aralkyl;
X2 is -C(O)-O- or-C(O)-NR,2; and R-2 is hydrogen, C,-C6alkyl, phenyl or benzyl;
where the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted by C,-C6alkyl, C,-C6alkoxy, -NO2, -CN or halogen, and where the helerudLoms of the heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group cons,~ ,g of -O-, -S-, -NRg- and -N=; and R~ is hydrogen, C,-C6alkyl, phenyl or benzyl.

Preferred compounds of the formula I from this group are those in whichQ, is a radical with at least one carbon atom which, together with the -CH=CQ2- group, forms a 3- to 1 O-membered alicyclical ring which opLiondlly contains a heteroatom chosen from the group consi~li"g of silicon, oxygen, nitrogen and sulfur and is unsllhstituted orsllhstituted by halogen, -CN, -NO2, R,R2R3Si-, -COOM, -SO3M, -PO3M, -COO(M,)"2, -SO3(M,)"2, -PO3(M,)"2, C,-C6alkyl, C,-C6haloalkyl, C,-C6hydroxyalkyl, C,-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or R4-X-; or in which an alicyclical, aromatic or heteroaromatic ring which is unsubstituted or sllhstituted by halogen, -CN, -NO2, R6R~R8Si-, -COOM, -S03M, -PO3M, -COO(M,)"2, -SO3(M,)"2, -PO3(M,)"2, C,-C6alkyl, C,-C6haloalkyl, C,-C6hydroxyalkyl, C,-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or R,3-X,- is optionally fused onto adjacent carbon atoms;
R" R2 and R3 independently of one another are C,-C4alkyl, C,-C4perfluoroalkyl, phenyl or benzyl;
M is an alkali metal and M, is an alkaline earth metal;

CA 0220~117 1996-0~-12 R4 and R,3 independently of one another are C1-C6alkyl, C,-C6haloalkyl, C1-C6hydroxyalkyl or C3-C6cycloalkyl;
X and X, independently of one another are -O-, -S-, -CO-, -SO- or -SO2-;
R6, R7 and R8 independently of one another are C,-C4alkyl, C1-C4perfluoroalkyl, phenyl or benzyl;
and Q2 is hydrogen.

The process according to the invention is particularly suitable for polymerization of norbornene and norbornene derivatives. Particularly preferred compounds from these norbornene derivatives are those which correspond either to the formula ll (Il).
~3 ~R14 in which X3 is -CHR,6-, oxygen or sulfur;
R14 and R,5 independently of one another are hydrogen, -CN, trifluoromethyl, (CH3)3Si-O-, (CH3)3Si- or-COOR17; and R.6 and R,7 independently of one another are hydrogen, C,-C,2-alkyl, phenyl or benzyl;
or to the formula lll ~ (111) R.8 in which X4 is -CHR19-, oxygen or sulfur;
R,9 is hydrogen, C,-C,2alkyl, phenyl or benzyl; and R.8 is hydrogen, C,-C6alkyl or halogen;
or to the formula IV

~ CA 0220~117 1996-0~-12 ~

_ g _ (IV), ~ R20 in which Xs is -CHR22-, oxygen or sulfur;
R22 is hydrogen, C1-C,2alkyl, phenyl or benzyl;
R20 and R2, independently of one another are hydrogen, CN, trifluoromethyl, (CH3)3Si-O-, (CH3)3Si- or-COOR23; and R23 is hydrogen, C,-C,2alkyl, phenyl or benzyl;
or to the formula V

X6~Y ~, (~0 in which )(6 is -CHR24-, oxygen or sulfur;
R24 is hydrogen, C,-C12alkyl, phenyl or benzyl;

Y' Is oxygen or N--R2s . and R2s is hydrogen, methyl, ethyl or phenyl.

The following compounds of the formula I are particularly s~ le for the polymerization process according to the invention, bi- and polycyclical systems being ~ccessihle by Diels-Alder reactions:

~\ COOH ~\ _COOCH, (1), ~ (2), ~y (3), COOCH2-Phenyl ~ COOCH2CH3 COOCH2-Phcnyl COOCH2CH3 O O
(CH2)3CH~ (6) ~ COO(CH2),CH3 (7 COO(CH2)3CH, COO(CH2)sCHJ

o o (CH2)'CH3 (8) ~ COO(CH2)"CH3 COO(CH2)~CH3 COO(CH2)"CH3 ~CN (10), ~CH2O(CH2)socH3 (11), (c~Hs)2 (12) ~ Si(CH3)3 (1 3), P(C3Hs)2 CA 1l22osll7 1996-115-12 ~CH2NHCH3 (14)/7~ // (15), CH2NHCH3 ~C

~ (16), ~ (17), o ~/c ~

~3 (20),~-- (21)~

(22), ~ (23), CA 1l22osll7 1 96-llS-12 (24), ~(25), CH, o ~oc~, (26), 9 (27), ~) (28), H,CO
@J (29), ~¦ (30), 13 (31), ~> (32), ~ (33)~ ~ (34), ~3X~3 (35) ~CH3 (36), l-l,CO~ ~ F,C~ ;~ (38), CA 0220~ll7 l996-0~-l2 ~3 (39), ~ ~ (40).

~3(41)' ~1 (42), ~ (43) and G ~ (44) In a preferred embodiment, the cycloolefins contain only carbon and hydrogen atoms, and are preferably 5- or 6-membered rings or ring systems with one to three 5- or 6-membered rings, for example norbornene, alkylated norbornenes and dicyclopentadiene.

The ruthenium and osmium compounds preferably contain 2 or 3 tertiary phosphine groups.
Phosphine groups in the context of the invention are understood as meaning tertiary phosphines. The number of additional non-photolabile neutral ligands depends on the one hand on the number of phosphine ligands and on the other hand on the valency of the neutral ligands. Monovalent neutral ligands are preferred.

In a preferred embodiment, the divalent-cationic ruthenium and osmium compounds to be used accordi"g to the invention contain 3 phosphine groups and 2 monovalent anions for charge balancing; or 3 phosphine groups, two monovalent or one divalent non-photolabile neutral ligands, and two monovalent anions for charge balancing; or 2 phosphi"e groups, one monoanionic, additionally monovalent non-photolabile neutral ligands, and one monovalent anion for charge balancing.

~ CA 0220~117 1996-0~-12 ~
-Non-photolabile ligand (also called highly coordinating ligand) in the context of the present invention means that the ligand does not dissociate, or dissociates to only an insignificant extent, from the catalyst on i" ~dialion of the catalyst in the visible or near ultraviolet range of the spectrum.

The monoanionic, additionally monovalent non-photolabile neutral ligands are preft:r~bly cyclopenla.lianyl or indenyl, which are uns~hstituted or s~ ~hstituted by 1 to 5 C,-C4alkyl, in particular methyl, or -Si(C,-C4alkyl), in particular -Si(CH3)3.

The non-photolabile ligands can be, for example, solvating inorganic and organiccompounds which contain the heteroator"s O, S or N and are often also used as solvents.
Examples of such compounds are H2O, H2S, NH3; optionally halogenated, in particular fluorinated or chlorinated, aliphatic or cyclo31iphatic alcohols or me,~aptans having 1 to 18, preferably 1 to 12, and particularly preferably 1 to 6 C atoms, aror"~lic alcohols or thiols having 6 to 18, preferably 6 to 12 C atoms, araliphatic alcohols or thiols having 7 to 18, preferably 7 to 12 C atoms; open-chain or cyclical and ali~,halic, araliphatic or aromatic ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid esters, lactones, optionally N-C,-C4mono- or-dialkylated carboxylic acid amides having 2 to 20, preferably 2 to 12, and in particular 2 to 6 C atoms, and optionally N-C,-C4alkylated lactams; open-chain or cyclical and aliphatic, ara'i,.h~lic or aromatic primary, secondary and tertiary amines having 1 to 20, preferably 1 to 12, and particularly preferably 1 to 6 C atoms.

Examples of such non-photolabile ligands are methanol, ethanol, n- and i-propanol, n-, i- and t-butanol, 1,1,1-trifluoruell,anol, bistrifluorornell,ylmethanol, tristrifluoromethylmethanol, pentanol, hexanol, methyl- or ethylmer-;apl~n, cyclopentanol, cyclohexanol, cyclohexylmercaptan, phenol, methylphenol, fluorophenol, phenylmercaptan, benzylmercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n- or di-t-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether, tetrahydlc,ll,iophene, dimethyl sulfoxide, diethyl sulfoxide, tetra- and pentamethylene sulfoxide, dimethyl sulfone, diethyl sulfone, tetra- and pentamethylene sulfone, acetone, methyl ethyl ketone, diethyl ketone, phenyl methyl ketone, methyl isobutyl ketone, benzyl methyl ketone, acetaldehyde, propion-'dehyde, trifluoro~Get.-'dehyde, benzaldehyde, ethyl acetate, butyrolactone, dimethylformamide, dimethylacelar"ide, pyrrolidone and N-methylpy"o' done, indenyl, cyclopenladienyl, methyl- or dimethyl- or pentamethylcyclopentadienyl and trimethylsilylcyclopentadienyl .

~ CA 0220~117 1996-0~-12 ~
-The primary amines can correspond to the formula R26NH2, the secondary amines can correspond to the formula R26R27NH and the tertiary amines can correspond to the formula R26R27R28N, in which R26 is C1-C,8alkyl, C5- or C6cycloalkyl which is unsubstituted or substituted by C,-C4alkyl or C,-C4alkoxy, or C6-C,8aryl or C7-C,2aralkyl which are unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, R2, independently has the meaning of R26, or R26 and R27 LogeLl,er are tetramethylene, pentamethylene, 3-oxa-1,5-pentylene or -CH2-CH2-NH-CH2-CH2- or-CH2-CH2-N(C,-C4alkyl)-CH2-CH2-, and R28 independently has the meaning of R26. The alkyl preferably contains 1 to 12, and particularly p,t ferably 1 to 6 C
atoms. The aryl prer~rably contains 6 to 12 C atoms and the aralkyl preferably contains 7 to 9 C atoms. Exa,nples of amines are methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-, methyl-ethyl-, dimethyl-ethyl-, n-propyl-, di-n-propyl-, tri-n-butyl-, cyclohexyl-, phenyl- and benzylamine, and py"olidi"e, N-methylpyrrolidine, p;"elidi"e, pi,uerd~i"e, morpholine and N-methylmorpholine.

In a preferred subgroup, the non-photolabile ligands are H20, NH3 and C,-C4alkanols which are unsubstitl ~ted or partly or completely fluorinated, or cyclopentadienyl. H20, NH3, cyclopentadienyl, methanol and ethanol are especially preferred.

Sterically exacting substituents in the context of the invention are understood as meaning those which shield the ruthenium and osmium atoms sterically. It has thus been found, surprisingly, that linear alkyl groups as substituents in the phosphine ligands give ruthenium compounds without any thermal activity for melall ,esis polymerization of strained cycloolefins. It has also been found that in the case of osmium compounds, linear alkyl groups as s~hstituents in the phosphine ligands su"~ lyly have an excellent thermocatalytic activity for the metathesis polymeri~dlion of strained cycloolefins; ho/~evcr, phosphine ligands with sterically exacting sl Ihstit~ ~ents are also preferably used for the osmium compounds. It has furthermore been found that the steric shielding of triphenylphosphi"e ligands is inadequ~te in ruthenium dihalides and ruthenium hydride-halides, and such catalyts have only a moderate catalytic activity for the metathesis polymerization of strained cyGloclerins. Sul,~ri~inyly, the catalytic activity can be increased considerably if the tertiary phosphine groups contain phenyl which is suhstituted by alkyl or alkoxy groups.

The phosphine ligands preferably correspond to the formulae Vl or Vla CA 0220~ll7 l996-0~-l2 PR29R3oR31 (Vl) R2gR30P-Z1-PR29R3o (Vla) in which R29, R30 and R3, independently of one another are cx-branched C3-C20alkyl; C4-C,2cycloalkyl which is unsl Ihstituted or sl Ihstituted by C,-C,8alkyl, C,-C,8haloalkyl or C,-C,8alkoxy; or C6-C,6aryl which is unsuhstitl Ited or sl ~hstituted by C,-C,8alkyl, C~-C~8haloalkyl or C,-C,8alkoxy;
the radicals R28 and R30 togelher are tetra- or penlar"ell,ylene which is unsubstituted or sl ~hstituted by C,-C6alkyl, C,-C6haloalkyl or C,-C6alkoxy, or tetra- or pentamethylene which is unsl Ihstituted or substituted by C,-C6alkyl, C,-C6haloalkyl or C,-C6alkoxy and fused with 1 or 2 1,2-phenylene, and R3, has the abovementioned meaning; and Z, is linear or branched C2-C,2alkylene which is unsubstituted or sl ~hstituted by C,-C4alkoxy, 1,2- or 1,3-cycloalkylene which has 4 to 8 C atoms and is unsubstituted or substituted by C,-C4alkyl or C1-C4alkoxy, or 1,2 or 1,3-heterocycloalkylene which has 5 or 6 ring members and one heteroatom from the group consisting of O and N and is unsuhstituted or suhstituted by C,-C4alkyl or C,-C4alkoxy.

The radicals R29, R30 and R3, are preferably identical rad;cals. Substituents are preferably in one or both ortho- and/or meta-positions relative to the C atom of the P-C bond in the phosphine.

Alkyl R29, R30 and R3, can contain 3 to 12, preferably 3 to 8, and particularly preferably 3 to 6 C atoms. It is preferably ol-branched alkyl, for example of the formula -CRbRCRd~ in which Rb is H or C,-C,2alkyl, Rc is C,-C,2alkyl, and R~, is C,-C,2alkyl or phenyl which is unsl Ihstituted or sl IhstihlPd by C,-C4alkyl or C,-C4alkoxy, and the sum of the C atoms in the radical -CRbRCRd is 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-dimethylpenty-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-dimethyldec-1-yl, 1-methyl- or 1,1-dimethylundec-1-yl, 1-methyl- or 1,1-dimethyldodec-1-yl, 1-methyl- or 1,1-dimethyltridec-1-yl, 1-methyl- or 1,1-dimethyltetradec-1-yl, 1-methyl- or 1,1-dimethylpentadec-1-yl, 1-methyl- or CA 0220~ll7 l996-0~-l2 1,1-dimethylhexadec-1-yl, 1-methylheptadec-1-yl and phenyl-dimethyl-methyl. Preferred examples are i-propyl and i- and t-butyl.

In the osmium compounds used, R29, R30 and R3, can also be linear alkyl having 1 to 18, preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 6 C atoms, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.

Cycloalkyl R29, R30 and R3, is preferably C5-C8cycloalkyl, and particularly preferably Cs~ or C6cycloalkyl. Some examples are cyclobutyl, cycloheptyl, cyclooctyl and, in particular, cyclopentyl and cyclohexyl, which are prert:r~bly uns~ ~hstituted or substituted by 1 to 3 alkyl, haloalkyl or alkoxy groups. Exa",ples of sllt-stituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl and tristrifluoromethylcyclopentyl and -cyclohexyl.

Aryl R29, R30 and R3, is preferably C6-C12aryl, and particularly prere:r~bly phenyl or naphthyl.
Examples of sl ~bstituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluorometl1yl and tristrifluoromethylphenyl.

Examples of optionally suhstituted or fused tetra- and pentamethylene bonded to the P atom are CH3 (~ ~

Other suitable tertiary phosphines are cycloali~hdlics which have 6 to 8 ring carbon atoms and are bridged with a =PRa group, for example [~3 ' ~ ' ~) and ~3, CA 0220~ll7 l996-0~-l2 ~ . .

in which Ra is C,-C6alkyl, cyclohexyl, or phenyl which is unsubstituted or sl~hstit~lted by 1 or 2 C,-C4alkyl.

In a preferred embodiment, the phosphine ligands cor,espond to the formula Vl, in which R29, R30 and R31 independently of one another are ~-branched C3-C8alkyl, cyclopentyl or cyclohexyl which are unsl Ihstitl Ited or s' Ihstit~ ~ted by C,-C4alkyl, or phenyl which is unsubstituted or substituted by C,-C4alkyl, C1-C4alkyl lsic], C1-C4alkoxy or trifluoromethyl.
Particularly prerer, ~d examples of phosphine ligands of the formula Vl are (C6H5)3P, (C5H~)3P, (C6H")3P, (i-C3H,)3P, (i-C4Hg)3P, (t-C4Hg)3P, ~C2H5CH(CH3)]3P, [C2H5CH(CH3)2]3P, (2-methylphenyl)3P, (2,3-dimethylphenyl)3P, (2,4-dimethylphenyl)3P, (2,6-dimethylphenyl)3P, (2-methyl~-i-propylphenyl)3P, (2-methyl-3-i-propylphenyl)3P, (2-methyl-~-i-propylphenyl)3P
(2-methyl-6-i-propylphenyl)3P, (2-methyl-3-t-butylphenyl)3P, (2-methyl4-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 and (2,6-di-t-butylphenyl)3P.

Suitable anions of inorganic or organic acids are, for example, hydride (He), halide (for example F~, Cle Bre and le), the anion of an oxygen acid and BF4e, PF6e, SbF6e or AsF6e. It should be mentioned that the abovementioned cyclopentadienyl is a ligand and an anion.

Further sl l -'- 'e anions are C,-C,2-, preferably C,-C6-, and particularly preferably C,-C4alcoholates, which, in particular, are branched, for example correspond to the formula RXRyRzC~Oe~ in which Rx is H or C,-C,Oalkyl, Ry is C,-C,Oalkyl and Rz is C,-C,Oalkyl or phenyl, and the sum of the C atoms of Rx~ Ry and Rz is 11. Examples are, in particular, i-propyloxy and t-butyloxy.

Other sllit-~'e anions are C3-C,8-, p~t:fer~bly C5-C,4-, and particularly preferably C5-C,2acetylides, which can correspond to the formula RW-C=Ce, in which Rw is C,-C,6alkyl, preferably a-branched C3-C,2alkyl, or is phenyl or benzyl which are unsubstituted or suhstituted by 1 to 3 C,-C4alkyl or C,-C4alkoxy. Some exar, F'es 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-methyl-6-t-butylphenylacetylide.

The anions of oxygen acids can be, for example, sulfate, phosphate, perchlorate,perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a CA 0220~ll7 l996-0~-l2 C,-C8carboxylic acid, such as, for exar"F'e, formate, acetate, propionate, butyrate, benzoate, phenylacetate or mono-, di- or trichloro-or -Fluoroacetate, sulfonates, such as, for example, methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate) or phenylsulfonate or benzylsulfonate which are optionally substituted by C,-C4alkyl, C,-C4alkoxyl or halogen, in particular fluorine or bromine, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate, and phosphates, for example methylphosphonate, ethylphosphonate, propylphosphonate, butyl,uhosphonate, phenylphosphonate, p-methylphosphonate or benzylphosphonate.

He, Fe, Cle, Bre, BF4e, PF6e, SbF6e, AsF6e, CF3SO3e, C6H5-SO3e, 4-methyl-C6H5-SO3e, 3,5-dimethyl-C6H5-SO3e, 2,4,6-trimethyl-C6H5-SO3e and 4-CF3-C6H5-SO3e are particularly preferred.

In a preferred embodiment, the ruthenium and osmium compounds particularly preferably correspond to the formulae Vll, Vlla, Vllb, Vllc or Vlld Me2 (L,)2(L2)(Y,e)2 (Vll) Me2 (L,)3(y, )2 (Vlla) Me2 (L,)2L3((Y,3) (Vllb) Me2 (L,)3L4(Y,e)2 (Vllc) Me2~3L,(L2)3(Y,e)2 (Vlld) in which Me is Ru or Os;
Y, is the anion of a monobasic acid;
L, is a phosphine of the formula Vl or Vla, L2 iS a neutral ligand;
L3 iS a cyclopentadienyl which is unsllhstihlted or suhstituted by C,-C4alkyl; and CA 0220~117 1996-0~-12 - 20 ~
r L4 is CO.

The above preferences apply to the individual meanings of L" L2, L3 and Y,.

In a particularly preferred embodiment, L2 in formula Vll and Vlld is a C,-C4alkanol, Yl in the formulae Vll, Vlla and Vlld is an anion of a monobasic acid, Y, in formula Vllb is Cl or Br, Y, in formula Vllc is H, and L, in the formulae Vll to Vlld is tri-i-propylphosphine, tricyclohexylphosphine, triphenylphosphi"e or triphenylphosphine which is suhstitllted by 1 to 3 C1-C4alkyl in the phenyl groups.

The ruthenium and osmium compounds to be used according to the invention are known or can be prepar~d by known and analogous processes starting from the metal halides lfor example MeX3, (Me-areneX2)2 or [Me(diolefin)X2]2] and reaction with phosphines and agents which form ligands.

The composition according to the invention can addilionally comprise other non-volatile open-chain comonomers which form copolymers with the strained cycloolefins. If dienes, for example, are co-used, c,osslil.ked polymers can form. Some examples of such comonomers are ol~.,"ically mono- or di-unsaturated compounds, such as olefins and dienes from the group consisli"g of pentene, hexene, heptene, octene, decene and dodecylene, acrylic and methacrylic acid, esters and amides thereof, vinyl ether, styrene, butadiene, isoprene and chlorobutadiene .

The other olehns which are cap-'le of meldll,esis polymerization are contained in the composition according to the invention, for example, in an amount of up to 80 % by weight, preferably 0.1 to 80 % by weight, more preferably 0.5 to 60 % by weight, and particularly preferably 5 to 40 % by weight, based on the total amount of compounds of the formula I
and other olefins c~p-'-le of meLdll,esis polymerization.

The composition accordi"g to the invention can comprise formulation auxiliaries. Known auxiliaries are a"li~ldlics, antioxidants, light sl~hi';~er~, plasticizers, dyes, pigments, fillers, reinforcing fillers, lubricants, adhesion promoters, viscosity-increasing agents and mold release auxiliaries. The fillers can be present in surprisingly high proportions without adversely influencing the polymeri,dlion, for example in amounts of up to 70 % by weight, preferably 1 to 70 % by weight, more preferably 5 to 60 % by weight, particularly preferably 10 to 50 % by weight, and espe-,ia"y preferably 10 to 40 % by weight, based on the CA 0220~ll7 l996-0~-l2 composition. A very large number of fillers and reinforcing fillers for improving the optical, physical, mechanical and electrical properties have been disclosed. Some examples are glass and quartz in the form of powders, beads and fibers, metal and semimetal oxides, carbonates, such as MgCO3, CaCO3 and dolomite, metal sulfates, such as gypsum and baryte, naturally occurring and synthetic silicates, such as talc, zeolites, wollastonite and felspars, aluminas, such as china clay, rock powders, whiskers, carbon fibers, synthetic fibers, powdered plastics and carbon black. Viscosity-increasing agents are, in particular metathesis polymers which contain ol~ri, lically unsaturated groups and can be incorporated into the polymer during the polymerization. Such metathesis polymers are known and are commercially obtainable, for example under the tradename Vestenamere~. Other viscosity-increasing agents are polybut~iene, polyisoprene or polychlorobutadiene, as well as copolymers of butadiene, isoprene and chloroprene with olefins. The viscosity increasing agents can be contained in an amount of 0.1 to 50, preferably 1 to 30, and particularly preferably 1 to 20 % by weight, based on lthe composilion.

Catalytic quanliLies in the context of the present invention preferably means an amount of 0.0001 to 20 mol%, particularly preferably 0.001 to 15 mol%, and especially pr~rerdbly 0.001 to 10 mol%, based on the amount of the monomer.

The invention also relates to a process for thermal metdll ,esis polymerization, which is chara~;leri~ed in that a composition of (a) at least one strained cycloolefin and (b) a catalytic quantity of at least one divalent-cationic compound of ruthenium or osmium in which the ruthenium or osmium compound contdi"s a metal atom to which are bound 1 to 3 tertiary phosphine ligands with, in the case of ruthenium compounds, sterically exacting substituents, optionally non-photolabile neutral ligands and anions for charge balancing, with the proviso that in ruthenium (trisphen~,lpl-osphi"e).lil, ' ~'es or hydride-halides the phenyl groups are substihlted by C,-C,8alkyl, C,-C,8haloalkyl or C,-C,8alkoxy, is polymerized.

The process accorcli"g 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 one that, in the case of liquid monomers, the process can be carried out without the use of a solvent. Inert means that the choice of solvent depends on the reactivity of the ruthenium and osmiumcompounds, for example that protic polar solvents are not used if suhstitution reactions, such as the replacement of halogen by alkoxy, are to be expected.

CA 0220~117 1996-0~-12 Suitable inert solvents are, for example, protic-polar and aprotic solvents, which can be used by themselves or in mixtures of at least two solvents. Examples are: ethers (dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethyl or diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether), halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane), carboxylic acid esters and lactones (ethyl acetate, methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, ~-butyrolactone, ~-valerolactone, piv '~lactone), carboxylic acid amides and lactams (N,N-dimethylformamide, N,N-diethylfor-"ar"ide, N,N-dimethylacetamide, tetramethylurea, hexamethylphosphoric acid triamine, ~-butyrolactam, ~-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaprolactam), sulfoxides (dimethyl sulfoxide), sulfones (dimethyl sulfone, diethyl sulfone, trimethylene sulfone, tel,~n,~ll,ylene sulfone), tertiary amines (N-methylpiperidine, N-methylmorpholine), aliphatic and aromatic hydrocarbons, for example petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene or substituted benzenes (chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene, xylene) and nitriles (acetonitrile, prop.onil,i!e, ben~onillile, phenylacetonillile).
Preferred solvents are protic polar and non polar solvents.

Preferred solvents are alkanols and aromatic hydrocarbons, and mixtures of such solvents.

A particular advantage of the catalysts to be used according to the invention is their stability to water and polar protic solvents, which can therefore likewise be used as solvents.

It is to be particularly e"~phasi~ed that the composilions of an optionally suhstituted cycloolefin and catalyst which are employed according to the invention in the process are often insensitive to oxygen, which allows storage and a reaction procedure without an inert gas. Many of these compositions also have a good storage stability, which likewise simplifies their processing.

The monomers of the formula I and the catalysts employed for the process according to the invention can be stored both separately and together as a mixture, since the catalyst used has a particularly high stability. Before the photochemical polymerization, the mixture can be stored as a ready-to-use formulation, which is of advantage for use of the process according to the invention on a large industrial scale. Storage and processing do not have to be carried out with exclusion of light, since the catalysts used are not capa~'e of initiating photometathesis polymerization.

CA 0220~ll7 l996-0~-l2 The reaction temperature essentially depends on the activity, the amount and the heat stability of the catalysts used. Some catalysts are so active that they are capable of already initiating the polymerization at room temperature.

The process according to the invention can be carried out at room temperature or slightly elevated temperature, preferably at least 40C, and more preferably at least 60C. In particular, the process according to the invention is carried out at temperatures from 40 to 300C, preferably 40 to 250C, particularly prer~rdbly 40 to to [sic] 200C, and especially preferably 60 to 140C. After the polymerization, it may be advantageous to after-heat the polymers at elevated temperatures, for example 80 to 200C.

As is known, the cycloolefins are strained rings. Cyclohexene generally cannot be polymerized by olefin metathesis. This exception is known to the expert as described, for example, in Ivin ~Ivin, K.J. in: Ivin, K.J., Saegusa, T. (editors), Ring-Opening Polymerisation 1:139-144 Elsevier Applied Science Publishers, London and New York (1984)].

The polymers prepared according to the invention can be homopolymers or copolymers with random distribution of the structural units, graft polymers or block polymers, and crosslinked polymers of this type. They can have an average molecular weight (Mw) of, for example, 500 up to 2 million daltons, preferably 1000 to 1 million daltons (determined by GPC by comparison with polystyrene standards of narrow distribution). If the cycloolefins contain at least 2 double bonds, crosslinked polymers can also be formed.

Thermoplastically deformable materials for the production of all types of shaped articles and coatings can be prepared by the process according to the invention. Shaping and polymerization are pr~ferdbly combined in solvent-free reactive systems, it being possible for processing procedures such as injection molding, extrusion and polymerization inpredetermined forms (if appropriate under pressure) to be used.

The polymers according to the invention can have very different properties, depending on the monomer used. Some of them are distinguished by a very high permeability to oxygen, low dielectric constants, good heat stability and low absor~lion of water. Others have outstanding optical properties, for example high transparency and low refractive indices. The low shrinkage is furthermore to be emphasized in particular. They can therefore be used in very different industrial fields.

~ CA 0220~117 1996-0~-12 ~

-As layers on the surfaces of carrier materials, the compositions according to the invention are distinguished by a high adhesive strength. The coated materials are furthermore distinguished by a very high surface smoolllness and gloss. Of the good mechanical properties, the low shrinkage and the high impact strength, as well as the heat stability is [sic] to be emphasized in particular. The easy release from the mold and the high resistance to solvents is [sic] furthermore to be mentioned.

These polymers are suit~hle for the production of medical equipment, i, l Iplanl~ or contact lenses; for the production of electronic componenl:,; as binders for coatings; as photocurable compositions for model construction or as adhesives for gluing suL,~LIdtes with low surface energies (for example Teflon, polyethylene and polypropylene). The polymers prepared according to the invention can also be used for the production of coali,)gs by photopolymerization, it being possible on the one hand for clear (Llansparent) and even pigmented compositions to be used. Both white and colored pigments can be used. The production of shaped articles by thermoplastic shap.ng processes for all types of commodity articles may furthermore be mentioned.

The polyll,er '-le compositions to be used according to the invention are also suitable for the production of protective coatings. The invention also relates to a variant of the process according to the invention for the production of coated materials in which a composition of a cyclical olefin, catalyst and optionally solvent is applied as a layer to a carrier, for example by dipping, brushing, pouring, rolling, knife-coating or whirler pouring processes, the solvent is removed, if appropri~le, and the layer is heated for polymerization. Surfaces of SUL)SLI ~les can be modified by this process.

The present invention also relates to a carrier material which is coated with an oligomer or polymer according to the invention and comprises a closslinl~illg agent. The present invention also relates to a carrier material which is coated with an oligomer or polymer according to the invention. These materials are sllit~l-'e for the production of protective coatings or images in relief by irradiation (if appropriate under a photo,l~ask) and suhsequent development with a solvent. Suitable crosslinking agents, which can be conL~ined, for example, in an amount of 0.01 to 20 % by weight, are, above all, organic bis~ides, in particular the commercially available 2,6-bis(4-azidobenzylidene)-4-methyl-cyclohexanone.

The present invention furthermore also relates to a coated carrier material, which is characterized in that a layer of (a) at least one strained cycloolefin and (b) a catalytic CA 0220~117 1996-0~-12 .. --quantity of at least one divalent-cationic compound of ruthenium or osmium, in which the compound of ruthenium or osmium conlai. ,s a metal atom to which are bound 1 to 3 tertiary phosphine ligands with, in the case of the ruthenium compounds, sterically exacting substituents, optionally non-photolabile neutral ligands and anions for charge balancing, with the proviso that in ruthenium (trisphenylphosphine) dihalides or hydride-halides the phenyl groups are substituted by C,-C,8alkyl, C,-C,8haloalkyl or C,-C18alkoxy, is applied to a carrier.

The present invention also relates to the use of a divalent-cationic compound of ruthenium or osmium, in which the compound of ruthenium or osmium conldi"s a metal atom to which are bound 1 to 3 tertiary phosphine ligands with, in the case of the ruthenium compounds, sterically exacting s~ ~bstituents, optionally non-pholo';~ neutral ligands and anions for charge balancing, with the proviso that in ruthenium (trisphenyl,~,hosph;"e)dihalides or hydride-halides, the phenyl groups are s~ ~hstituted by C,-C18alkyl, C,-C,8haloalkyl or C,-C,8alkoxy, as catalysts for thermal metathesis polymerization of strained cycloolefins.

Suitable carrier rndLel '?~5 are, for example, those of glass, minerals, ceramics, plastics, wood, semimetals, metals, metal oxides and metal nitrides. The layer thicknesses essentially depend on the desired use and can be, for example, 0.1 to 1000 I~m, preferably 0.5 to 500 ,um, particularly preferably 1 to 100 I~m. The coated materials are distinguished by a high adhesive strength and good thermal and mechanical properties.

The production of the coated materials accordi"9 to the invention can be carried out by known methods, for example brushing, knife-coating, pouring processes, such as curtain coating or whirler pouring.

In the case of coatings, particularly good results are often achieved if cycloolefins which addiLionally contain 1 to three, and preferably one further double bond and which, in the context of the invention, are polycyclical fused ring systems or ring systems linked directly or via bridge groups are used for the polymerization.

The following exdri,F'es illustrate the invention further.

Examples 1 and 2: Polymerization of dicyclopentadiene in bulk 2 9 of biscyclopentadiene are mixed with 12 9 of catalyst and the mixture is poured into a mold. Polymerization is then carried out for the times and at the temperatures stated in Table 1 and after-curing is carried out for 2 hours at 1 50C.

CA 1)2205117 1996-05-12 The following catalysts are used (abbreviations: MeOH: methanol, Tos: tosylate, Cp:
cyclopentadienyl, Ph: phenyl, Cy: cyclohexyl):
A = Ru(PCy3)2(MeOH)2(Tos)2 B = RuC12(PCy3)2 C = Ru(H)2(CO)(PPh3)3 D = RuCpCl(PPh3)3 E = RuCI2[P(2-methyl-C6H4)3]3 Table 1 Example CatalYst Conversion in %Time, te",perdLure Polymer*

A 100 12 hours; 80C Tg = 122C
2 B 100 12 hours; 100C Tg = 118C
* crosslinked ExamPles 3 to 7: Polymerization of norbomene 500 mg of norbornene are dissolved in 3 ml of ch'oroform and the solution is mixed with 3 mg of catalyst. Polymerization is then carried out for the times and at the temperatures stated in Table 2. RT in Table 2 means room temperature. The conversion is determined after prec;~,iLdlion with ethanol.

Table 2 ExamPle CatalYst Conversion in %Time, ter"Peralure MwMw/Mn3 A 97.5 10 minutes; RT 540 k 1.9 4 B 93 15 minutes; RT 300 k 2.0 C 25 2 hours; 50C crosslinked 6 D 30 10 hours; 50C 80 k 2.4 7 E 65 10 hours; 50C crosslinl;ed

Claims (36)

CLAIMS:

1. Composition of (a) at least one strained cycloolefin and (b) a catalytic quantity of at least one divalent-cationic compound of ruthenium or osmium, in which the compound of ruthenium or osmium contains a metal atom to which are bound 1 to 3 tertiary phosphine ligands with, in the case of the ruthenium compounds, sterically exacting substituents, optionally non-photolabile neutral ligands and anions for charge balancing, with the proviso that in the case of the ruthenium compounds, no p-cumene is bonded to the metal atom, and in ruthenium (trisphenylphosphine)dihalides or hydride-halides the phenyl groups are substituted by C1-C18alkyl, C1-C18haloalkyl or C1-C18alkoxy.

2. Composition according to claim 1, characterized in that the cyclical olefins are monocyclical rings or polycyclical, bridged or fused ring systems with 2 to 4 rings, which are unsubstituted or substituted and optionally contain one or more heteroatoms from the group consisting of O, S, N and Si in one or more rings and optionally contain fused, aromatic orheteroaromatic rings.

3. Composition according to claim 2, characterized in that the cyclical rings contain 3 to 16 ring members.

4. Composition according to claim 3, characterized in that the cyclical rings contain 3 to 12 ring members.

5. Composition according to claim 2, characterized in that the cyclical olefins contain further nonaromatic double bonds.

6. Composition according to claim 1, characterized in that the cycloolefins correspond to the formula I

(I) 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, -PO3(M1)1/2,C1-C20alkyl, C1-C20hydroxyalkyl, C1-C20haloalkyl, C1-C6cyanoalkyl, C3-C8cycloalkyl, C6-C16aryl, C7-C16aralkyl, C3-C6heterocycloalkyl, C3-C6heteroaryl, C4-C16heteroaralkyl or R4-X-; or in which two adjacent C atoms are substituted by -CO-O-CO- or -CO-NR5-CO-; or in which an alicyclical, aromatic or heteroaromatic ring which is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-(O)u-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2, C1-C20alkyl, C1-C20haloalkyl, C1-C20hydroxyalkyl, C1-C6cyanoalkyl, C3-C8cycloalkyl, C6-C16aryl, Cr-C16aralkyl,C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C16heteroaralkyl or R13-X1- is optionally fused onto adjacent carbon atoms of the alicyclical ring;
X and X1 independently of one another are -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 independently of one another are C1-C12alkyl, C1-C12perfluoroalkyl, phenyl or benzyl;
R4 and R13 independently are C1-C20alkyl, C1-C20haloalkyl, C1-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl or C7-C16aralkyl;
R5 and R10 independently of one another are hydrogen, C1-C12alkyl, phenyl or benzyl, where the alkyl groups in turn are unsubstituted or substituted by C1-C12alkoxy or C3-C8cycloalkyl;
R6, R7 and R8 independently of one another are C1-C12alkyl, C1-C12perfluoroalkyl, phenyl or benzyl;
M is an alkali metal and M1 is an alkaline earth metal; and u is O or 1;
where the alicyclical ring formed with Q1 optionally contains further nonaromatic double bonds;
Q2 is hydrogen, C1-C20alkyl, C1-C20haloalkyl, C1-C12alkoxy, halogen, -CN or R11-X2-;
R11 is C1-C20alkyl, C1-C20haloalkyl, C1-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl or C7-C16aralkyl;
X2 is -C(O)-O- or-C(O)-NR12-;
R12 is hydrogen, C1-C12alkyl, phenyl or benzyl;
where the abovementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted by C1-C12alkyl, C1-C12alkoxy, -NO2, -CN
or halogen, and where the heteroatoms of the abovementioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group consisting of -O-, -S-, -NR9- and -N=;
and R9 is hydrogen, C1-C12alkyl, phenyl or benzyl.

7. Composition according to claim 6, characterized in that the alicyclical ring which Q1 forms together with the -CH=CQ2-groups has 3 to 16 ring atoms, the ring system being amonocyclical, bicyclical, tricyclical or tetracyclical ring system.

8. Composition according to claim 6, characterized in that Q2 in formula I is hydrogen.

9. 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, together with the -CH=CQ2- group, forms a 3- to 20-membered alicyclical ring which optionally contains one or moreheteroatoms chosen from the group consisting 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, -PO3(M1)1/2, C1-C12alkyl, C1-C12haloalkyl, C1-C12hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, C6-C12aryl, C7-C12aralkyl, C3-C6heterocycloalkyl, C3-C12heteroaryl, C4-C12heteroaralkyl or R4-X-; or in which two adjacent C atoms in this radical Q1 re substituted by -CO-O-CO- or -CO-NR5-CO-; or in which an alicyclical, aromatic or heteroaromatic ring which is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2, C1-C12alkyl, C1-C12haloalkyl, C1-C12hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, C6-C12aryl, C7-C12aralkyl,C3-C6heterocycloalkyl, C3-C12heteroaryl, C4-C12heteroaralkyl or R13-X1- is optionally fused onto adjacent carbon atoms;
X and X1 independently of one another are -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 independently of one another are C1-C6alkyl, C1-C6perfluoroalkyl, phenyl or benzyl;
M is an alkali metal and M1 is an alkaline earth metal;
R4 and R13 independently of one another are C1-C12alkyl, C1-C12haloalkyl, C1-C12hydroxyalkyl, C3-C8cycloalkyl, C6-C12aryl or C7-C12aralkyl;
R5 and R10 independently of one another are hydrogen, C1-C6alkyl, phenyl or benzyl, where the alkyl groups in turn are unsubstituted or substituted by C1-C6alkoxy or C3-C6cycloalkyl;
R6, R7 and R8 independently of one another are C1-C6alkyl, C1-C6perfluoroalkyl, phenyl or benzyl;
u is 0 or 1;

where the alicyclical ring formed with Q, optionally contains further nonaromatic double bonds;
Q2 is hydrogen, C1-C12alkyl, C1-C12haloalkyl, C1-C6alkoxy, halogen, -CN or R11-X2-;
R11 is C1-C12alkyl, C1-C12haloalkyl, C1-C12hydroxyalkyl, C3-C6cycloalkyl, C6-C12aryl or C7-C,2aralkyl;
X2 is -C(O)-O- or -C(O)-NR,2; and R.2 is hydrogen, C1-C6alkyl, phenyl or benzyl;
where the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted by C1-C6alkyl, C1-C6alkoxy, -NO2, -CN or halogen, and where the heteroatoms of the heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group consisting of -O-, -S-, -NR9- and -N=; and R9is hydrogen, C1-C6alkyl, phenyl or benzyl.

10. 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, together with the -CH=CQ2- group, forms a 3- to 10-membered alicyclical ring which optionally contains a heteroatom chosen from the group consisting of silicon, oxygen, nitrogen and sulfur and is unsubstituted or substituted by halogen, -CN, -NO2, R1R2R3Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or R4-X-; or in which an alicyclical, aromatic or heteroaromatic ring which is unsubstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2, C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl,C1-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or R13-X,- is optionally fused onto adjacent carbon atoms;
R1, R2 and R3 independently of one another are C1-C4alkyl, C1-C4perfluoroalkyl, phenyl or benzyl;
M is an alkali metal and M, is an alkaline earth metal;
R4 and R13 independently of one another are C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl or C3-C6cycloalkyl;
X and X1 independently of one another are -O-, -S-, -CO-, -SO- or -SO2-;
R6, R7 and R8 independently of one another are C1-C4alkyl, C1-C4perfluoroalkyl, phenyl or benzyl;
and Q2 is hydrogen.

11. Composition according to claim 1, characterized in that the cyclical olefins are norbornene or norbornene derivatives.

12. Composition according to claim 11, characterized in that the norbornene derivatives are those of the formula II

(II) in which X3 is -CHR16-, oxygen or sulfur;
R14 and R15 independently of one another are hydrogen, -CN, trifluoromethyl, (CH3)3Si-O-, (CH3)3Si- or -COOR17; and R16 and R17 independently of one another are hydrogen, C1-C12-alkyl, phenyl or benzyl;
or those of the formula III

(III), in which X4 is -CHR19-, oxygen or sulfur;
R19 is hydrogen, C1-C12alkyl, phenyl or benzyl; and R18 is hydrogen, C1-C6alkyl or halogen;
or those of the formula IV

(IV), in which X5 is -CHR22-, oxygen or sulfur;
R22 is hydrogen, C1-C12alkyl, phenyl or benzyl;
R20 and R21 independently of one another are hydrogen, CN, trifluoromethyl, (CH3)3Si-O-, (CH3)3Si- or-COOR23; and R23 is hydrogen, C1-C12alkyl, phenyl or benzyl;
or those of the formula V

(V), in which X6 is -CHR24-, oxygen or sulfur;
R24 is hydrogen, C1-C12alkyl, phenyl or benzyl;

Y is oxygen or ; and R25 is hydrogen, methyl, ethyl or phenyl.

13. Composition according to claim 1, characterized in that the strained cycloolefins contain only carbon and hydrogen atoms.

14. Composition according to claim 1, characterized in that the strained cyclolefins are 5- or 6-membered rings or ring systems with one to three 5- or 6-membered rings.

15. Composition according to claim 1, characterized in that the strained cyclolefins are norbomenes, alkylated norbomenes and dicyclopentadiene.

16. Composition according to claim 1, characterized in that the strained cycloolefins are (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17), (18) (19), (20), (21), (22), (23), (24), (25), (26), (27), (28), (29), (30) , (31), (32), (33), (34), (35), (36), (37), (38), (39), (40), (41), (42), (43) or (44).

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

18. Composition according to claim 1, characterized in that the ruthenium and osmium compounds contain 3 phosphine groups and two monovalent anions for charge balancing; or 3 phosphine groups, two monovalent or one divalent non-photolabile neutral ligands, and two monovalent anions for charge balancing or 2 phosphine groups, one monoanionic, additionally monovalent non-photolabile neutral ligands, and one monovalent anion for charge balancing.

19. Composition according to claim 18, characterized in that the monoanionic, additionally monovalent non-phololabile neutral ligands are cyclopentadienyl or indenyl, which are unsubstituted or substituted by 1 to 5 C1-C4alkyl or -Si(C1-C4alkyl).

20. Composition according to claim 18, characterized in that the monovalent, non-photolabile ligands are H2O, H2S, NH3; optionally halogenated, in particular fluorinated or chlorinated, aliphatic or cycloaliphatic alcohols or mercaptans having 1 to 18 C atoms, aromatic alcohols or thiols having 6 to 18 C atoms, araliphatic alcohols or thiols having 7 to 18 C atoms;
open-chain or cyclical and aliphatic, araliphatic or aromatic ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid esters, lactones, optionally N-C1-C4mono- or -dialkylated carboxylic acid amides having 2 to 20 C atoms, and optionally N-C1-C4alkylated lactams;
open-chain or cyclical and aliphatic, araliphatic or aromatic primary, secondary and tertiary amines having 1 to 20 C atoms.

21. Composition according to claim 1, characterized in that the phosphine ligands correspond to the formulae VI or Via PR29R30R31 (Vl).

R29R30P-Z1-PR29R30 (Via) in which R29, R30 and R31 independently of one another are .alpha.-branched C3-C20alkyl; C4-C12cycloalkyl which is unsubstituted or substituted by C1-C18alkyl, C1-C18haloalkyl or C1-C18alkoxy; or C6-C16aryl which is unsubstituted or substituted by C1-C18alkyl, C1-C18haloalkyl or C1-C18alkoxy;
the radicals R29 and R30 together are tetra- or pentamethylene which is unsubstituted or substituted by C1-C6alkyl, C1-C6haloalkyl or C1-C6alkoxy, or tetra- or pentamethylene which is unsubstituted or substituted by C1-C6alkyl, C1-C6haloalkyl or C1-C6alkoxy and fused with 1 or 2 1,2- phenylene, and R31 has the abovementioned meaning; and Z1 is linear or branched C2-C12alkylene which is unsubstituted or substituted by C1-C4alkoxy, 1,2- or 1,3-cycloalkylene which has 4 to 8 C atoms and is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, or 1,2 or 1,3-heterocycloalkylene which has 5 or 6 ring members and one heteroatom from the group consisting of O and N and is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy.

22. Composition according to claim 21, characterized in that the .alpha.-branched alkyl is a radical of the the formula -CRbRcRd, in which Rb is H or C1-C12alkyl, Rc is C1-C12alkyl, and Rd is C1-C12alkyl or phenyl which is unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, and the sum of the C atoms in the radical -CRbRcRd is 3 to 18.

23. Composition according to claim 21, characterized in that the phosphine ligands correspond to the formula VI in which R29, R30 and R31 independently of one another are .alpha.-branched C3-C8alkyl, cyclopenlyl or cyclohexyl which are unsubstituted or substituted by C1-C4alkyl, or phenyl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkyl [sic], C1-C4alkoxy or trifluoromethyl.

24. Composition according to claim 1, characterized in that the phosphine ligands are (C6H5)3P, (C5H9)3P, (C6H11)3P, (i-C3H7)3P, (i-C4H9)3P, (t-C4H9)3P, [C2H5CH(CH3)]3P, [C2H5CH(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 or (2,6-di-t-butylphenyl)3P.

25. Composition according to claim 1, characterized in that the anions of inorganic or organic acids are a hydride (H-), a halide, the anion of an oxygen acid, BF4-, PF6-, SbF6- or AsF6-.

26. Composition according to claim 25, characterized in that the anions of oxygen acids are sulfate, phosphate, perchloroate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C1-C8carboxylic acid, sulfonate, or phenylsulfonate orbenzylsulfonate which are optionally substituted by C1-C4alkyl, C1-C4alkoxy or halogen.

27. Composition according to claim 25, characterized in that the anions are H-, Cl-, Br-, BF4-, PF6-, SbF6-, AsF6-, CF3SO3-, C6H5-SO3-, 4-methyl-C6H5-SO3-, 3,5-dimethyl-C6H5-SO3- 2,4,6-trimethyl-C6H5-SO3- or 4-CF3-C6H5-SO3-.

28. Composition according to claim 1, characterized in that the ruthenium and osmium compounds correspond to the formulae VII, VIIa, VIIb, VIIc or VIId Me2-(L1)2(L2)(Y1-)2 (VII) Me2-(L1)3(Y,-)2 (VIIa) Me+(L1)2L3((Y1-) (VIIb) Me+(L1)3L4(Y1-)2 (VIIc) Me+L1(L2)3(Y1-)2 (VIId) in which Me is Ru or Os;
Y1 is the anion of a monobasic acid;
L1 is a phosphine of the formula VI or VIa according to claim 21, L2 is a monovalent neutral ligand;
L3 is cyclopentadienyl which is unsubstituted or substituted by C1-C4alkyl; and L4 is CO.

29. Composition according to claim 28, characterized in that L2 in formula VII and VIId is a C1-C4alkanol, Y1 in the formulae VII, VIIa and VIId is an anion of a monobasic acid, Y1 in formula VIIb is CI or Br, Y1 in formula VIIc is H, and L1 in the formulae VII to VIId is tri-i-propylphosphine, tricyclohexylphosphine, triphenylphosphine or triphenylphosphine which is substituted by 1 to 3 C1-C4alkyl in the phenyl groups.

30. 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. Process for thermal metathesis polymerization, which is characterized in that a composition of (a) at least one strained cycloolefin and (b) a catalytic quantity of at least one divalent-cationic compound of ruthenium or osmium in which the ruthenium or osmium compound contains a metal atom to which are bound 1 to 3 tertiary phosphine ligands with, in the case of ruthenium compounds, sterically exacting substituents, optionallynon-photolabile neutral ligands and anions for charge balancing, with the proviso that in ruthenium (trisphenylphosphine)dihalides or hydride-halides the phenyl groups are substituted by C1-C18alkyl, C1-C18haloalkyl or C1-C18alkoxy, is polymerized.

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

33. Carrier material which is coated with an oligomer or polymer from the composition according to claim 1 and which comprises a crosslinking agent.

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

35. Coated carrier material, which is characterized in that a composition of (a) at least one strained cycloolefin and (b) a catalytic quantity of at least one divalent-cationic compound of ruthenium or osmium in which the ruthenium or osmium compound contains a metal atom to which are bound 1 to 3 tertiary phosphine ligands with, in the case of ruthenium compounds, sterically exacting substituents, optionally non-photolabile neutral ligands and anions for charge balancing, with the proviso that in ruthenium (trisphenylphosphine)dihalides or hydride-halides the phenyl groups are substituted by C1-C18alkyl, C1-C18haloalkyl or C1-C18alkoxy, is polymerized.

36. Use of a divalent-cationic ruthenium or osmium compound which contains a metal atom to which are bound 1 to 3 tertiary phosphine ligands with, in the case of the ruthenium compounds, sterically exacting substituents, optionally non-photolabile neutral ligands and anions for charge balancing, with the proviso that in ruthenium (trisphenylphosphine)dihalides or hydride-halides the phenyl groups are substituted by C1-C18alkyl, C1-C18haloalkyl or C1-C18alkoxy, as catalysts for thermal metathesis polymerization of strained cyclooleflns.