The way photocatalytic polymerization of cyclic olefins in the presence of ruthenium or osmanaga catalyst containing photolabile ligands, composition and media coverage

 

(57) Abstract:

Describes how photocatalytic polymerization of a cyclic olefin or at least two different cyclic olefins with disclosure cycle in the presence of a catalyst containing a compound of ruthenium or osmium, characterized in that exercise photochemical metathesis polymerization in the range of from the ultraviolet region through the visible region to near infrared region in the presence of catalytic amounts of at least one thermostable compounds of ruthenium or osmium containing at least one photolabile ligand connected to the metal atom, while the other focal points are occupied photolabile ligands. The technical result is to simplify the process and increase efficiency of the process. 3 C. and 50 C.p. f-crystals, 6 PL.

The invention relates to a method of polymerization of cyclic olefins by photochemical metathetical polymerization erection cycle with the use of catalytic amounts of a catalyst based on a transition metal and to compositions containing these olefins with a catalytic amount of a catalyst.

Thermal metatezisnaya polymerization p is sustained fashion for a long time and are described in several publications (see, for example, K. J. Ivin, Olefin Metathesis, Academic Press, London, 1983). Such polymers synthesized by heating, get on an industrial scale, and they are commercially available.

On the other hand, there are only a small number of publications on photochemical metathetical polymerization disclosure of cycle and still not applied in industrial production. Further, the above publication, it is known that the reaction of metathesis of olefins can be initiated photochemically in the presence of catalysts WCl6. However, this type of catalyst is extremely sensitive to oxygen and moisture, which greatly complicates its storage and use. In addition, these catalysts can be used in a relatively narrow range of temperatures and tend to decompose at elevated temperatures.

From U.S. patent 4060468 known implementation metathetical polymerization of olefin by adding a two-component mixture of a metal salt selected from the group consisting of salts of tungsten, molybdenum, rhenium and tantalum, and a substituted phenol or benzyl alcohol as socialization in the reaction vessel with Monomeric olefin and by subsequent exposure of the entire reaction mixture UV what cities without functional groups or substituents. Separate storage of the catalyst components and the presence of phase mixing them immediately before the reaction leads to the known method requires large expenditures for implementation in industry is difficult.

C. Tanielan and others described in Tetrahedron Letters No. 52, page 4589-4592 (1977) catalytic system W(CO)6/CCl4which after exposure to UV-light can be used for metathetical polymerization of cyclopentene and norbornene. The CARBONYLS of metals are volatile and toxic, so using them requires expensive precautions for physiological reasons.

In addition, it is noted that alternative reaction is a free radical reaction of accession with the formation of Monomeric 1-chloro-2-trichlorotrifluoroethane.

From the publication of H. H. Thoi and others in the Journal of Molekular Catalysis, 15 (1982), pp. 245-270, it is known that the complex PENTACARBONYL tungsten-Karben formula

< / BR>
is thermal catalyst metathetical polymerization of dimethylcarbonate disclosure cycle and together with phenylacetylene as socializaton also forms a photocatalytic system for the polymerization. This catalytic system has serenio, carbonyl compound is physiologically acceptable and compatible with the functional groups in cycloolefinic too small.

Thus, known photochemically activated catalysts always require socializaton, which means that the quality of the obtained polymers can vary considerably depending on the nature and sequence of addition of reagents.

Known methods for producing polymers of cyclic olefins by photochemical metathetical polymerization disclosure cycle are very expensive and impractical from an economic point of view. Found that especially the big disadvantages are the lack of stability during storage, which allows the components are mixed just before cooking, in the absence of compatibility with functionalized cyclic olefins and requiring the use of a catalytic system consisting of two components. Therefore, there is a need to create a method, enhanced with industrial, economic and environmental points of view, which can be used to obtain polymers of cyclic olefins positions of cycloolefins and one-component catalyst can dry out photochemically, if the composition comprises a thermally stable compound of ruthenium or osmium containing at least one photolabile ligand attached to the metal atom. Unexpectedly, these thermally stable compounds proved to be active catalysts polonizirovannaya metathetical polymerization disclosure cycle while maintaining stability during storage of mixtures of cycloolefins and compounds of ruthenium or osmium despite photochemical reactivity.

In addition, it was found that these catalysts after a short irradiation unexpectedly actively catalyze the photopolymerization if necessary in the environment of the solvent or act as thermal catalysts after exposure if necessary in the environment of the solvent and/or in the presence of cycloolefins, therefore, photochemical and thermal polymerization can be used in combination.

The present invention relates to a method photocatalytic polymerization of a cyclic olefin or at least two different cyclic olefins in the presence of compounds of metal as a catalyst, which includes the implementation of photochemical metathetical polymerization with the disclosure of the amount of at least one thermostable compounds of ruthenium or osmium, which contains at least one photolabile ligand attached to the metal atom, while the other focal points are occupied photolabile ligands.

The cyclic olefins can be mono - or polycyclic systems, for example, containing 2-4 cycle, which is unsubstituted or substituted and can contain heteroatoms, such as O, S, N or Si, in one or more cycles and/or condensed aromatic or heteroaromatic nucleus, for example o-phenylene, o-naftilan, peridinin or o-pyrimidinyl. Loops can contain 3 to 16, preferably 3 to 12 and particularly preferably 3-8 members. The cyclic olefins may also contain non-aromatic double bond depending on the size of the cycle, preferably 2-4 such additional double bond. Deputies in the cycle are inert, i.e., those which do not impair the chemical stability and thermal stability of the compounds of ruthenium or osmium. The stability in the context of the present description means that the photocatalytic active compound of ruthenium or osmium when heated do not form active products for metathetical polymerization disclosure cycle. For example, it was found that after heating and videological. The catalyst may not initiate metathesis polymerization disclosure cycle, for example, at a temperature of from room temperature to slightly elevated, for example at +40oC, during the period of time from several weeks to several months in the absence of light, and during this period reacts less than 0.2 wt.% the monomer. The stability can be determined, for example, by storing an ethanol solution containing 20 wt.% monomer and 0.33 wt.% ruthenium or osmanaga catalyst, in the dark at 50oC for 96 hours, with any number of the formed polymer (detected by turbidity) should not exceed 0.2, preferably 0.1 wt.%.

According to a preferred variant of the process according to the invention cycloolefin are compounds of the formula I

< / BR>
where Q1means a radical containing at least one carbon atom which, together with the-CH=CQ2group forms an at least 3-membered alicyclic ring which may contain one or more heteroatoms selected from the group consisting of silicon, phosphorus, oxygen, nitrogen or sulfur; and which is unsubstituted or substituted with halogen, =O, -CN, -NO2, R1R2R31/2C1-C20the alkyl, C1-C20hydroxyalkyl, C1-C20haloalkyl, C1-C6lanakila, C3-C8cycloalkyl, C6-C16the aryl, C7-C16aralkyl, C3-C6heterocyclization, C3-C16heteroaryl, C4-C16heteroalkyl or R4-X-; or in which two adjacent carbon atoms replaced by-CO-O-CO - or-CO-NR5-CO-; or in which an aromatic or heteroaromatic ring which is unsubstituted or substituted with halogen, -CN, -NO2, R6R7R8Si-(O)u-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2C1-C20the alkyl, C1-C20haloalkyl, C1-C20hydroxyalkyl, C1-C6lanakila, C3-C8cycloalkyl, C6-C16the aryl, C7-C16aralkyl, C3-C6heterocyclization, C3-C16heteroaryl, C4-C16heteroalkyl or R13-X1- is condensed with the adjacent carbon atoms, alicyclic ring;

X and X1independently of one another denote-O-, -S-, -CO-, -SO-, -SO2-, -O-C(O)-, -C(O)-O-, -C(O)-NR5-, -NR10-C(O)-, 2alkyl, C1-C12perfluoroalkyl, phenyl or benzyl;

R4and R13independently of one another denote C1-C20-alkyl, C1-C20haloalkyl, C1-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl or C7-C16aralkyl;

R5and R10independently of one another denote hydrogen, C1-C12alkyl, phenyl or benzyl, the alkyl groups in turn unsubstituted or substituted C1-C12alkoxygroup or C3-C8cycloalkyl;

R6, R7and R8independently of one another denote C1-C12alkyl, C1-C12perfluoroalkyl, phenyl or benzyl;

M means an alkali metal;

M1mean alkaline earth metal, and

u is 0 or 1;

and in which the alicyclic ring formed with Q1may also contain non-aromatic double bond;

Q2means hydrogen, C1-C20alkyl, C1-C20haloalkyl, C1-C12alkoxy, halogen, -CN, or R11-X2-;

R11means C1-C20alkyl, C1-C20haloalkyl, C1-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl Il the SUB>1-C12alkyl, phenyl or benzyl;

and in which the above-mentioned cycloalkyl, heteroseksualci, aryl, heteroaryl, aralkyl and heteroaryl unsubstituted or substituted C1-C12the alkyl, C1-C12alkoxy, -NO2, -CN or halogen, and where the heteroatoms of the above geterotsiklicheskie, heteroaryl and heteroalkyl selected from the group consisting of-O-, -S-, -NR9- or - N=; and

R9means hydrogen, C1-C12alkyl, phenyl or benzyl.

Other olefins which are capable of metathesis can be used together with the above-mentioned olefins in the method according to the invention, for example, in quantities of up to 40 mol.%, preferably 0.01 to 30 mol.% and particularly preferably 0.1 to 20 mol.% in the calculation of the total number of cycloolefins and olefins.

The olefins which are capable of metathesis and which may optionally contain a mixture of formula I, polymerized according to the invention can be used, for example, the crosslinking or for regulating molecular weight. Examples of suitable olefins are cyclooctadiene or-triene or compounds having the following structure:

< / BR>
Suitable are compounds such as 2-butene-1,4 - diol, described the asymmetric centre, this means that the compounds can exist in optically isomeric forms. Some compounds of formula I may be in tautomeric forms (for example, cetainly tautomerism). If there aliphatic double bond C=C, then there may be a geometric isomerism (E-form and Z-form). Alternatively, the Exo-endo-configuration. Thus, the formula I encompasses all possible stereoisomers, which are in the form of enantiomers, tautomers, diastereomers, E/Z-isomers or mixtures thereof.

In the definitions of the values of the substituents alkyl, alkenyl and quinil can be linear or branched. The same applies to each alkyl in the alkoxy, alkylthio, alkoxycarbonyl and other alkalmazasa groups. These alkyl groups preferably contain 1 to 12, more preferably 1 to 8 and particularly preferably 1 to 4 atom C. These alkeneamine and alkyline groups preferably contain 2 to 12, more preferably 2 to 8 and especially preferably 2-4 atom C.

Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec. -butyl, tert.-butyl and the various isomeric Pintilie, hexylene, heptylene, aktalnye, monilinia, decile, undecylenate, dodecylthio and akosile radicals.

Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxy-isobutyl, 1-hydroxy-Deut. -butyl, 1-hydroxy-tert.-butyl and hydroxy forms of various isomeric pantiliner, hexylene, heptylene, aktiline, monilinia, decile, undecylenic, modelling, tridecyl, tetradecyl, pentadecyl, hexadecimally, heptadecyl, octadecyl, mondellini and ensiling radicals.

Haloalkyl includes, for example, vermeil, deformity, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-triptorelin, 2-foretel, 2-chloroethyl, 2,2,2-trichloroethyl and halogenated, in particular fluorinated or chlorinated alkanes, such as isopropyl, n-propyl, n-butyl, isobutyl, sec. -butyl, tert.-butyl and the various isomeric Pintilie, hexylene, heptylene, aktalnye, monilinia, decile, undecylenate, modelline, tridecylamine, tetradecyl, pentadecyl, hexadecyne, heptadecyl, octadecyl, nonadecane and akosile radicals.

Alkenyl includes, for example, propenyl, Isopropenyl, 2-butenyl, 3-butenyl, Isobutanol, n-Penta-2,4-dienyl, 3-methyl-but-2-enyl, n-Oct-2-enyl, n-dodec-2-enyl, isododecane 8cycloalkyl, in particular, C5or C6-cycloalkyl. Some examples include cyclopropyl, dimethylcyclopropene, cyclobutyl, cyclopentyl, methylcyclopentene, cyclohexyl, cycloheptyl and cyclooctyl.

Cianelli includes, for example, tianmei (maternity), Tianeti (eternity), 1-linisopril, 1-cyan-n-propyl, 2-cyan-n - butyl, 1-lanzorote, 1-cyan-Deut.-butyl, 1-cyan-tert.-butyl and the various isomeric lenitilia and-hexylene radicals.

Aralkyl preferably contains 7 to 12 C atoms and particularly preferably 7-10 atoms C. It can be, for example, benzyl, Venetian, 3-phenylpropyl - methylbenzyl, penbutolol and - dimethylbenzyl.

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

Heteroaryl preferably contains 4 or 5 C atoms and one or two heteroatoms from the group consisting of O, S and N. It can be, for example, pyrrole, furan, thiophene, oxazole, thiazolo, pyridine, pyrazino, pyrimidine, pyridazine, indole, purine and quinoline.

Heteroseksualci preferably contains 4 or 5 C atoms and one or two heteroatoms from the group consisting of O, S and N. It is m, morpholine, tetrahydrofuran, and tetrahydrothiophene.

Alkoxy is, for example, methoxy, ethoxy, propyloxy, isopropoxy, n-Butylochka, isobutoxy, Deut.- bucalossi and tert.-butylochki.

Alkali metal in the context of the present invention means a lithium, sodium, potassium, rubidium and cesium, especially lithium, sodium and potassium.

Alkaline earth metal in the context of this invention means beryllium, magnesium, calcium, strontium and barium, primarily magnesium and calcium.

In the above definitions, halogen means fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

Particularly suitable compounds of the formula I for the method according to the invention are compounds in which Q2means hydrogen.

The compounds of formula I which are also preferred to perform the polymerization, are those compounds, in which the alicyclic ring, which Q1forms together with the-CH=CO2group contains 3 to 16, more preferably 3 to 12 and particularly preferably 3 to 8 atoms in the ring, and a cyclic system may be monocyclic, bicyclic, tricyclic or tetracyclic,

THE Q1means a radical containing at least one carbon atom which, together with the-CH= CQ2the group forms a 3-20 membered alicyclic ring which may contain one or more heteroatoms selected from the group consisting of silicon, oxygen, nitrogen and sulfur and which is unsubstituted or substituted with halogen, =O, -CN, -NO2, R1R2R3Si-(O)u-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3M1)1/2, -PO3(M1)1/2C1-C12the alkyl, C1-C12haloalkyl, C1-C12hydroxyalkyl, C1-C4lanakila, C3-C6cycloalkyl, C6-C12the aryl, C7-C12aralkyl, C3-C6heterocyclization, C3-C12heteroaryl, C4-C12heteroalkyl or R4-X-; or in which two adjacent C atom in the radical Q1replaced by-CO-O-CO-or-CO-NR5-CO-; or in which an aromatic or heteroaromatic ring which is unsubstituted or substituted with halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2C1-C12the alkyl, C1-C12halodule the12the aryl, C7-C12aralkyl, C3-C6heterocyclization, C3-C12heteroaryl, C4-C12heteroalkyl or R13-X1- can be condensed with the adjacent carbon atoms; X and X1independently of one another denote-O-, -S-, -CO-, -SO-, -SO2-, -O-C(O)-, -C(O)-O-, -C(O)-NR5-, -NR10-C(O)-, -SO2-O - or-O-SO2-;

and R1, R2and R3independently of one another denote C1-C6alkyl, C1-C6perfluoroalkyl, phenyl or benzyl;

M stands for alkali metal;

M1mean alkaline earth metal;

R4and R13independently of one another denote C1-C12alkyl, C1-C12haloalkyl, C1-C12hydroxyalkyl, C3-C8cycloalkyl, C6-C12aryl or C7-C12aralkyl;

R5and R10independently of one another denote hydrogen, C1-C6alkyl, phenyl or benzyl, the alkyl groups in turn unsubstituted or substituted C1-C6alkoxy or C3-C6cycloalkyl;

R6, R7, R8independently of one another denote C1-C6alkyl, C1-C6perfluoroalkyl, phenyl or benzyl;

u is 0 or 1; the data communication;

Q2means hydrogen, C1-C12alkyl, C1-C12haloalkyl, C1-C6alkoxy, halogen, -CN, or R11-X2-;

R11means C1-C12alkyl, C1-C12haloalkyl, C1-C12hydroxyalkyl, C3-C6cycloalkyl, C6-C12aryl or C7-C12aralkyl;

X2means-C(O)-O - or-CO-NR12and

R12means hydrogen, C1-C6-alkyl, phenyl or benzyl;

and in which cycloalkyl, heteroseksualci, aryl, heteroaryl, aralkyl and heteroaryl unsubstituted or substituted C1-C6the alkyl, C1-C6alkoxy, -NO2, -CN or halogen, and in which the heteroatoms geterotsiklicheskikh, heteroaryl and heteroalkyl groups selected from the group consisting of-O-, -S-, -NR9- or-N=; and

R9means hydrogen, C1-C6alkyl, phenyl or benzyl.

Of this preferred group of compounds of formula I are those compounds in which Q1is a radical containing at least one carbon atom which, together with the - CH=CQ2the group forms a 3-10-membered alicyclic ring which may contain heteroatom, selected from the group consisting 2R3Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2C1-C6the alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C4lanakila, C3-C6cycloalkyl, phenyl, benzyl, or R4-X-; or in which an aromatic or heteroaromatic ring which is unsubstituted or substituted with halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2C1-C6the alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl, C1-C4lanakila, C3-C6cycloalkyl, phenyl, benzyl, or R13-X1- can be condensed with the adjacent carbon atoms;

R1, R2and R3independently of one another denote C1-C4alkyl, C1-C4perfluoroalkyl, phenyl or benzyl;

M means an alkali metal and M1mean alkaline earth metal;

R4and R13independently of one another denote C1-C6alkyl, C1-C6haloalkyl, C1-C6hydroxyalkyl or C3-C6cycloalkyl; X is awesime from each other mean C1-C4alkyl, C1-C4perfluoroalkyl, phenyl or benzyl and

Q2means hydrogen.

The method according to the invention is particularly suitable for the polymerization of norbornene derivative. Especially preferred derivatives of norbornene or formula V

< / BR>
in which X3means-CHR40)-, oxygen, or sulfur;

R29and R30independently of one another denote hydrogen, CN, trifluoromethyl, (CH3)3Si-O-, (CH3)3Si - or-COOR31;

R31and R40independently of one another denote hydrogen, C1-C12alkyl, phenyl or benzyl;

or of the formula VI

< / BR>
in which X4means-CHR41-, oxygen or sulfur;

R41means hydrogen, C1-C12alkyl, phenyl or benzyl and

R32means hydrogen, C1-C6alkyl or halogen;

or formula VII

< / BR>
in which X5means-CHR41-, oxygen or sulfur;

R42means hydrogen, C1-C12alkyl, phenyl or benzyl;

R33and R34independently of one another denote hydrogen, CN, trifluoromethyl, (CH3)3Si-O-, (CH3)3Si - or-COOR35and

R35means hydrogen, C1-C12alkyl, Fe is
R43means hydrogen, C1-C12alkyl, phenyl or benzyl;

Y represents oxygen or and

R36means hydrogen, methyl, ethyl or phenyl. Group R40-R43preferably attached to the double bond in the Exo-position.

For polymerization according to the invention, it is preferable to use the compound of formula V in the Exo-configuration.

For the implementation of the polymerization process according to the invention is particularly suitable compounds of the formula I given in the end of the description.

Ligands for compounds of ruthenium and osmium, which should be used according to the invention, are organic or inorganic compounds, atoms or ions are coordinated to the metal center.

Photolabile ligand in the context of the present invention is a ligand, which is separated from the catalyst by irradiation of the catalyst light in the visible or ultraviolet region of the spectrum and forms a catalytically active centers for metathetical polymerization. According to the invention preferred nonionic photolabile ligands.

Photolabile ligands can be, for example, nitrogen (N2), monocyclic, policy C, which is unsubstituted or substituted by OH, C1-C4the alkyl, C1-C4alkoxy, C6-C12the aryl or halogen, or monocyclic heteroarenes, condensed heteroarenes or condensed arenas-heteroarenes containing 3-22, preferably 4-16 primarily 4-10 C atoms and 1-3 heteroatoms selected from the group consisting of O, S and N, which are unsubstituted or substituted C1-C4the alkyl, C1-C4alkoxygroup or halogen; or aliphatic, cycloaliphatic, aromatic or analiticheskie NITRILES containing 1-22, preferably 1 to 18, particularly preferably 1 to 12 and most preferably 1 to 7 C atoms, which is unsubstituted or substituted C1-C4the alkyl, C1-C4alkoxy or halogen. Preferred substituents are methyl, ethyl, methoxy, ethoxy, fluorine, chlorine and bromine. Arena and heteroarenes preferably substituted by one or two radicals, and particularly preferable are unsubstituted. Preferred heteroarenes are heteroarenes enriched with electrons. Arena and heteroarenes can be attached in the form or-form; in the latter case, the radicals are the corresponding aryl and heteroaryl radicals. Aryl before the C.

Some examples of arenes and heteroarenes are benzene, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysin, fluoranthrene, furan, thiophene, pyrrole, pyridine, / -Piran, -thiopyran, pyrimidine, pyrazin, indole, kumaran, Tinatin, carbazole, dibenzofuran, dibenzothiophen, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazol, isothiazol, quinoline, isoquinoline, acridine, chrome, fenesin, phenoxazin, phenothiazines, triazine, tianren and purine. Preferred arenas and heteroarenes are benzene, naphthalene, thiophene and benzothiophene. Arenas benzene and heteroaryl thiophene especially preferred.

The NITRILES can be substituted, for example, methoxy, ethoxy, fluorine or chlorine; preferred unsubstituted NITRILES. Alternately are preferably linear. Some examples of NITRILES are acetonitrile, propionitrile, butyronitrile, intilnirile, hexanetriol, cyclopentyl and cyclohexylmethyl, benzonitrile, methylbenzonitrile, benzenetriol and naphthylmethyl. The NITRILES are preferably linear C1-C4alkyllithium or benzonitrile. Especially preferred alkylation is acetonitrile.

A preferred subgroup photolabeling LaCie called vysokomotiviruet ligand) in the context of the present invention is the ligand, which is not cleaved or cleaved only to a small extent from the catalyst when the catalyst is irradiated in the visible or near ultraviolet region of the spectrum.

Photolabile ligands can be, for example, Salvaterra inorganic and organic compounds that contain the heteroatoms O, S or N and are also often used as solvents, or cyclopentadienyl or indenyl, which are unsubstituted or substituted C1-C4alkyl, C1-C4alkoxy, (C1-C4alkyl)3Si - or (C1-C4alkyl)3SiO-. Examples of such compounds are H2O, H2S and NH3; legalaidboard.ie or halogenated, in particular fluorinated or chlorinated, aliphatic or cycloaliphatic alcohols or mercaptans containing 1-18, preferably 1-12, particularly preferably 1-6 C atoms, aromatic alcohols or thiols containing 6 to 18, preferably 6 to 12 C atoms, or analiticheskie alcohols or thiols containing 7 to 18, preferably 7 to 12 C atoms; acyclic or cyclic and aliphatic, analiticheskie or aromatic ethers, thioethers, sulfoxidov, sulfones, ketones, aldehydes, esters of carboxylic collagenase 2-20, preferably 2 to 12 and especially 2 to 6 C atoms, and dealkilirovanie or N-C1-C4alkylated lactams; acyclic or cyclic and aliphatic, analiticheskie or aromatic, primary, secondary and tertiary amines containing 1-20, preferably 1-12, and especially preferably 1 to 6 C atoms; and cyclopentadienyl, for example, cyclopentadienyl, indenyl and cyclopentadienyl or indenyl that contain one or more methyl groups or trimethylsilyl groups.

Examples of such photolabile ligands are methanol, ethanol, n-and ISO-propanol, n-, ISO - and tert.-butanol, 1,1,1 - triptoreline, bistrifluormethylbenzene, tretretretretretre, pentanol, hexanol, methyl - or ethyl mercaptan, Cyclopentanol, cyclohexanol, cyclohexylurea, phenol, METHYLPHENOL, terfenol, phenylmercaptan, benzylmercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n - or di-tert.- butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, ditertiary, tetrahydrothiophene, dimethyl sulfoxide, diethylsulfoxide, Tetra-and pentamethyldisiloxane, dimethyl sulfone, diethylsulfate, Tetra - and pentamethylene, acetone, methyl ethyl ketone, diethylketone, feniletilic, the ethyl acetate, butyrolactone, dimethylformamide, dimethylacetamide, pyrrolidone and N-organic, indenyl, cyclopentadienyl, methyl - or dimethyl - or pentamethylcyclopentadienyl and trimethylsilylcyanation.

Primary amines can be compounds of the formula R24NH2secondary amines - compounds of formula R24R25NH and tertiary amines - compounds of formula R26R27R28N, where R24means C1-C18alkyl, C5or C6-cycloalkyl, which is unsubstituted or substituted C1-C4alkyl or C1-C4alkoxy, or C6-C18aryl or C7-C12aralkyl, which is unsubstituted or substituted C1-C4alkyl or C1-C4alkoxy,

R25independently has a value specified for R24or

R24and R25together means tetramethylene, pentamethylene, 3-oxa-1,5-pentile or-CH2-CH2-NH-CH2-CH2- or-CH2-CH2-N(C1-C4-alkyl)-CH2-CH2-, R26, R27and R28independently of one another have the meanings indicated for R24or R26and R27together form the same radical, R24and R25together, and R28has meant is in C. Aryl preferably contains 6 to 12 C atoms and aralkyl preferably contains 7 to 9 atoms C. Examples of amines are methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-, methylethyl, dimethylethyl-n-propyl-, di-n-propyl-, tri-n-butyl-, cyclohexyl-, phenyl - and benzylamine and pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine.

A preferred subgroup photolabile ligands consists of H2O, NH3and unsubstituted or partially or fully fluorinated C1-C4alkanols. H2O, NH3, cyclopentadienyl, methanol and ethanol are particularly preferred.

Compounds of ruthenium and osmium, which are used according to the invention can be mono - or polynuclear, for example, those which have two or three metal center. The metal atoms in this case can be linked via a bridging group, or through the connection metal to metal.

Preferred compounds with many metal centers are characterized by the formula X:

< / BR>
in which Lig means photolabile ligand;

Me means Ru or Os;

A9, A10and A11mean divalent bridging group, and

Ymeans single-shaft is occhialino is a halide, first of all, chloride, bromide or iodide. Photolabile ligands are preferably the same or different arenas and Ymay be the anion from those shown below, and particularly preferably chloride, bromidum or iodide. An example of such complexes is [C6H6Ru(Cl)3RuC6H6]Cl.

Preferred catalysts according to the invention are the compounds of formula II:

[(Me+n)(Lz11)m(Lz22)o(Lz33)p(Lz44)q(Lz55)r(Lz66)s](Lz77)t(II)

in which Me means ruthenium or osmium;

n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

L1means photolabile ligand;

L2, L3, L4, L5and L6independently from each other mean photolabeling or photolabile ligand;

m is 1, 2, 3, 4, 5 or 6;

o, p, q, r and s independently of one another 0, 1, 2, 3, 4 or 5;

z1, z2, z3, z4, z5, z6and z7independently from each other equal -4, -3, -2, -1,0, +1 or +2 and

L7means gecoordineerde cation or any the 3 + qz4+ rz5+ sz6)/z7. In formula II, L7preferably means a halogen (such as Cl, Br and I), the anion oxygen-containing acid, BF4PF6, SiF6or AsF6.

The anions of oxygen acids can be, for example, sulfate, phosphate, perchlorate, perbromates, periodates, antimonate, arsenate, nitrate, carbonate, the anion of C1-C8carboxylic acids, such as formate, acetate, propionate, butyrate, benzoate, phenylacetate or mono-, di - or trichloro - or-fluoroacetate, sulfonates, such as methylsulfonate, ethylsulphate, propylsulfonyl, butylsulfonyl, triftormetilfullerenov (triplet), vinylsulfonate or benzylmalonate, which is unsubstituted or substituted C1-C4the alkyl, C1-C4alkoxy or halogen, in particular fluorine, chlorine or bromine, for example, tosylate, mesilate, brasilata, p-methoxy - or p-ethoxyphenylurea, pentafluoroethanesulfonyl or 2,4,6-triisopropylsilane, and phosphonates, such as methylphosphonates, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methylenephosphonate and benzylphosphonate.

Me in formula II preferably is rotoroa ligands L1, L2, L3, L4, L5and L6independently of one another represent aliphatic, cycloaliphatic, aromatic or analiticheskie NITRILES containing 1-22 of an atom, which is unsubstituted or substituted C1-C4the alkyl, C1-C4alkoxy or halogen, or C6-C18aryl; or L1, L2and L3together means a monocyclic, polycyclic or condensed arena containing 6 to 24, preferably 6 to 18 and particularly preferably 6 to 12 C atoms, which is unsubstituted or substituted by-OH, C1-C4the alkyl, C1-C4alkoxy, C6-C12the aryl or halogen, or monocyclic heteroarenes, condensed heteroarenes or condensed arenas-heteroarenes containing 4-22 atoms and 1-3 heteroatoms selected from the group consisting of O, S and N, which are unsubstituted or substituted by-OH, C1-C4the alkyl, C1-C4alkoxy or halogen, and L4, L5and L6together have the same value or each separately and independently from each other mean N2or the nitrile or the C6-C18aryl.

A preferred subgroup of the above compounds of formula II includes will cotnact N2C1-C20alkynylaryl, C6-C12urinary, C7-C12aralkylated or C6-C12aryl, or L1, L2and L3in each case, together mean a group AND1or a2and L4, L5and L6also have this value or in each case independently denote N2these NITRILES or the specified C6-C12aryl,

< / BR>
in which R14, R15, R16, R17, R18, R19, R20, R21, R22and R23independently of one another denote hydrogen, C1-C20alkyl, C1-C20alkoxy, aryl or SiR37R38R39and where in the case of groups AND1and a2aromatic or heteroaromatic ring heteroatoms selected from oxygen, sulfur and nitrogen can be condensed with the adjacent carbon atoms; and

R37, R38and R39independently of one another denote C1-C12alkyl, phenyl or benzyl, preferably C1-C8alkyl, phenyl or benzyl, particularly preferably C1-C4alkyl, phenyl or benzyl.

Preferred compounds of this preferred group of compounds of formula II represent the Ute C1-C12alkynylaryl, C6-C12urinary or

L1, L2and L3in each case, together mean a group AND1or a2and L4, L5and L6also have this value or in each case independently denote N2these NITRILES or specified aryl, where

R14, R15, R16, R17, R18, R19, R20, R21, R22and R23independently of one another denote hydrogen, C1-C6alkyl, C1-C6alkoxy, SiR37R38R39or phenyl, and in which in the case of groups A1and a2the benzene ring may be condensed with the adjacent carbon atoms, and R37, R38and R39mean methyl, ethyl or phenyl.

According to a preferred variant of the process according to the invention is used, the catalyst is a compound of formula II in which L1, L2, L3, L4, L5and L6independently from each other mean maternity, eternity or fininical or

L1, L2and L3in each case, together mean a group AND1or a2and

L4, L5and L6also have/SUB>, R17, R18, R19, R20, R21, R22and R23independently of one another denote hydrogen, methyl, methoxy or phenyl,

and in which in the case of groups AND1and a1the benzene ring may be condensed with the adjacent carbon atoms.

Another particularly preferred subgroup of compounds of formula II includes compounds in which

L1, L2and L3together means a monocyclic, polycyclic or condensed arena containing 6 to 24, preferably 6 to 18 and particularly preferably 6 to 12 C atoms, which is unsubstituted or substituted C1-C4the alkyl, C1-C4alkoxy, C6-C12the aryl or halogen, or monocyclic heteroarenes, condensed heteroarenes or condensed arenas-heteroarenes containing from 4 to 22, preferably 4-16 primarily 4-10 C atoms and 1-3 heteroatoms selected from the group consisting of O, S and N, which are unsubstituted or substituted C1-C4the alkyl, C1-C4alkoxy or halogen, and

L4, L5and L6mean photolabile ligand, and in this case also applicable to the above preferred values.

L1, L2and L32O, NH3, unsubstituted or fluoro-substituted C1-C4alkanol or alkanethiol, aliphatic ethers, thioethers, sulfoxidov and sulfones containing 2-8 C atoms, dimethylformamide or N-organic.

Another preferred subgroup of compounds of formula II includes compounds of ruthenium and osmium formula XI:

[L1Me(L8)5]2-butyrolactone, -valerolactone, pivalate), amides of carboxylic acids and lactams (N, N-dimethylformamide, N, N-diethylformamide, N,N-dimethylacetamide, tetramethylrhodamine, triamide hexamethylphosphoric acid-butyrolactam, -caprolactam, N-organic N-acetylpyrrolidine, N-methylcaprolactam), sulfoxidov(dimethyl sulfoxide), sulfones(dimethyl sulfone, diethylsulfate, trimetilindolom, tetramethylarsonium), 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, propionitrile, benzonitrile, phenylacetonitrile). Preferred solvents are aprotic polar and nonpolar Rasta, alcohols, for example methanol, ethanol, propanol and butanol, methylene chloride and chloroform, and mixtures thereof.

A particular advantage of the method according to the invention is that it is possible to apply environmentally compatible solvents. Solvents which are particularly suitable for implementing the method according to the invention, therefore, is chosen from the group consisting of alcohols, such as methanol, ethanol, propanol or isopropanol, or water.

It should be particularly emphasized that the compositions of substituted or unsubstituted of cycloolefin and catalyst, which are used according to the invention, are often not sensitive to oxygen, which allows the storage and reaction process without inert gas. However, it is reasonable to exclude moisture, i.e., to carry out the reaction and storage in the absence of moisture.

The monomers of formula I and the catalysts used in the method according to the invention, can be stored separately or together as a mixture, as used catalyst has a particularly high stability. The mixture can be stored in the form of a composition that is ready to use, up to photochemical polymerization, which is an advantage when using the method according to the invention in which the super store the mixture in the absence of light.

Further, the invention relates to photopolymerizable composition containing a cyclic olefin or at least two different cyclic olefins and a catalytically active amount of at least one thermostable compounds of ruthenium or osmium, which contains at least one photolabile ligand connected to the metal atom, and other focal points are occupied photolabile ligands.

The composition of the invention can contain adjuvants. Appropriate adjuvants are compounds defined above as solvents. Particularly preferred solvents for the compositions according to the invention are water and ethanol. Other known auxiliary additives are plasticizers, dyes, pigments, fillers, reinforcing fillers, lubricants, antioxidants, light stabilizers and anti-adhesive grease.

In the method according to the invention, the irradiation of the reaction mixture throughout the reaction is not necessary. Once polymerization begins after photochemical initiation, subsequent reaction proceeds automatically, even in the dark. The exposure time saveasaction the infrared region of the spectrum depending on the absorption bands of the catalysts. According to the invention, it is preferable to use UV lasers or UV lamp. Irradiation of the catalyst with the formation of catalytically active particles can be performed before, during or after adding the monomers. Turned out to be preferable to choose the sources of radiation so that the wavelength was in the range of energetically recovered absorption bands catalysts.

The corresponding exposure time is from one minute to 8 hours, especially from 5 min to 4 h, the Sequence of addition of the monomers and catalyst is not critical. The monomer can either first enter into the reaction vessel, or add after the introduction of the catalyst. Moreover, the catalyst can be irradiated in advance and then added to the monomer. In addition, it is also possible to irradiate the solution containing the catalyst and monomer.

The method according to the invention is preferably carried out at a temperature of from room temperature to slightly elevated. The temperature increase is solely to increase the rate of reaction because it is not due to the catalysts that initiate thermal polymerization, and due to the catalytically active particles.

In UP>oC.

Special and unexpected advantage of the method according to the invention is that the used compounds of ruthenium and osmium are after irradiation as thermal catalysts. This leads to the possibility of continuation and termination of polymerization by heat after a short time exposure, which provides economic and industrial advantages in various fields of production of molded articles or coatings. First of all, the combined method is useful for obtaining thermoplastic.

The invention further relates to a method photocatalytic polymerization of a cyclic olefin or at least two different cyclic olefins in the presence of compounds of metal as a catalyst, which includes:

(a) the initial activation of thermostable compounds of ruthenium or osmium, which contain at least one photolabile group connected with metal, and other focal points are occupied photolabile ligands by direct irradiation, if necessary, in the environment of the solvent, and subsequent mixing of the catalyst with at least one cycloolefin or put the Itala, and

b) subsequent termination of polymerization by heating and without radiation.

The preferred conditions outlined above, are to stage a) of the method. The exposure time depends substantially on the desired implementation procedures of the reaction. For example, if the polymerization should only be initiated by irradiation and fail when heated, choose a small time exposure. A short exposure can be up to 60, preferably 5-60 s and particularly preferably 10-40 C. If the polymerization should occur mainly during irradiation and the final polymerization must be terminated only after heating, then choose a longer exposure time.

Heating in stage b) of the method may be carried out at the reaction temperature from 50 to 200oC, preferably at 50-150oC and particularly preferably at 70 -120oC.

In ruthenium and osmaevyh catalysts intended for the irradiation, the transition metal is preferably two - or trivalent. If you use a trivalent transition metals, in General, disproportionation occurs in the divalent and tetravalent state, the catalyst Otsego of the invention preferably ranges from 0.001 to 20 mol.%, particularly preferably 0.01 to 15 mol. %, even more preferably 0.1 to 10 mol.% and most preferably 0.5 to 5 mol.% in relation to the number of monomer.

Further, the invention relates to a method for thermal catalysts for metathetical polymerization of cyclic olefins with opening cycle, which includes the irradiation of the compounds of ruthenium or osmium containing photolabile ligand connected to the metal atom, and the other focal points involved photolabile ligands, in bulk or in a solvent environment.

Usually cyclohexen cannot homopolymerization by metathesis of olefin. This exception is known to the expert and are described, for example, in K. Y. Ivin, T. Saegusa, Ring-Opening Polymerization, I. 1, page 139, Elsevier Applied Science Publishers, London and New York.

Further, the invention relates to utverzhdennym exposure to oligomers and polymers containing the same or different structural units of the formula

< / BR>
where Q1and Q2are indicated for the formula I values.

The preferred designations listed above, refer to these polymers. They can be homopolymers or copolymers with random distribution of the structural units or block polymers.

Needlenose by the method of gel permeation chromatography (GPC) versus polystyrene standards with a narrow distribution).

According to the method according to the invention can be obtained termoplasticheskie deformable materials for manufacturing molded products of all types, coatings and relief images.

The polymers according to the invention can have very different properties depending on the monomer used. Some have a very high oxygen permeability, and a low dielectric constant, good thermal stability and low water absorption. Others have excellent optical properties such as high transparency and low refractive indices. In particular, mention should be made of low shrinkage. Therefore, they can be used in a variety of industries.

Compositions according to the invention are characterized by high adhesion to the surface of the substrate. Materials coated are also characterized by very high surface gloss and Shine. Among the good mechanical properties should particularly highlight low shrinkage and high impact strength, and heat resistance. In addition, mention should be made of easy removal from the mold and high resistance to solvents.

These polymers suitable for the manufacture of mV as a binder for paints; as fototerapia compositions for making models or as adhesives for bonding substrates having low surface energy (for example, Teflon, polyethylene and polypropylene), and as photopolymerizable composition in stereolithography. Compositions according to the invention can also be used for the production of paints by photopolymerization, and you can apply non-pigmented (transparent) and even pigmented compositions. You can use either white or colored pigments. Further mention should be made of the manufacture of molded products of all types by thermoplastic forming.

Fototerapia compositions in accordance with the invention is particularly suitable for the manufacture of protective layers and relief images. In addition, the invention relates to the modification of the method according to the invention for the manufacture of materials coated or embossed images on substrates, according to which a composition of cyclic olefin, catalyst and optionally solvent is applied as a layer on a substrate, for example, by dipping, by means of a brush, by casting, by roller, knife device or centrifugal method, the solvent, if he Ave the m solvent to remove unexposed areas. Surface of the substrate can be modified or protected or it is possible in this manner to produce, for example, printed circuits, printed circuit boards or printed cushions. In the manufacture of printed circuits compositions according to the invention can also be used as pripevami of resists. Other possible areas of use constitute the production of masks for screen printing and use as a radiation-curable printing ink for offset, screen and aniline printing.

Further, the present invention relates to media coverage of the oligomer or polymer obtained according to the invention.

In addition, the invention relates to the media that contains the coating oligomer or polymer obtained according to the invention, and which includes a crosslinking agent. These materials are suitable for the manufacture of protective coatings and relief images by irradiation (if required using photomasks) and subsequent manifestations with solvent. Appropriate cross-linking agents, which may contain such materials, for example, in an amount of 0.01-20 wt.%, represent, in particular, organic bisazide primarily commercial is referring to the media coverage, where the substrate is coated with the layer of at least one cyclic olefin, containing a catalytic amount of stable ruthenium or osmanaga a catalyst having at least one photolabile ligand connected to the metal atom, and other focal points (if present) engaged photolabile ligands.

Suitable substrates (materials media) made for example from glass, minerals, ceramics, plastics, wood, metals, oxides of metals and metal nitrides. The thickness of the layers are substantially dependent on the desired application and can be, for example, 0.1 to 1000 μm, preferably 0.5 to 500 μm, particularly preferably 1-100 μm. Materials with a coating of a high adhesive strength and good thermal and mechanical properties.

The following examples illustrate the present invention.

Examples of the synthesis of

Getting monomers for metathetical polymerization disclosure of cycle

Getting 7-oxabicyclo [2.2.1]5,6 - di(phenylmethanesulfonyl)hept-2-ene (compound N 1.01)

< / BR>
of maleic anhydride of the formula AND

23,26 g of maleic anhydride of the formula AND

< / BR>
and 151,4 g benzyl alcohol is ablaut 5 ml of concentrated hydrochloric acid (37%) and stirred the reaction mixture for one hour. After cooling and distillation under vacuum under a pressure of 266 PA and at the boiling temperature of 60oC (to remove excess benzyl alcohol, water and HCl) gain of 44.5 g (87.2% of theory) 7-oxabicyclo- [2.2.1] 5,6-di(phenylmethanesulfonyl)hept-2-ene (compound N 1.01) with a melting point of 85oC.1H-NMR (CDCl3): 2,85 (2H); 4,94, to 5.08 (4H); from 5.29 (2H); 6,44 (2H); 7,31 m (10H).

The compounds of formula III, are shown in table 1, obtained in the same way.

The monomers used for the polymerization are shown in table. 2.

The catalysts used for the polymerization are shown in table. 3.

The solvents used for the polymerization are shown in table. 4.

The light sources used for the polymerization are shown in table. 5.

Examples of the method according to the invention are given in table. 6.

Comparative example AND

Exposure to 200 mg of monomer 3 in solvent 1 light source 1 for 10 min and aging for 7 days at a temperature of 50oC in the absence of a catalyst according to the invention does not lead to the formation of the polymer.

Comparative example B

A solution of 20 wt.% [bicyclo(2,2,1)hept-2-ene] and 0.33 wt.% [Ru(acetonitrile)6] (triflate)2in the ethanol stored in tendelti measurable amount of polymer.

1. The way photocatalytic polymerization of a cyclic olefin or at least two different cyclic olefins with disclosure cycle in the presence of a catalyst containing a compound of ruthenium or osmium, characterized in that exercise photochemical metathesis polymerization in the range of from the ultraviolet region through the visible region to near infrared region in the presence of catalytic amounts of at least one thermostable compounds of ruthenium or osmium containing 1-3 metal centre, and the metal atoms attached through a bridge connection or bond metal to metal, and at least one photolabile ligand connected to the metal atom, other focal points are occupied photolabile ligands.

2. The method according to p. 1, characterized in that the cyclic olefins represent a monocyclic or polycyclic system containing 2-4 rings that are not substituted or substituted, may contain one or more heteroatoms from the group consisting of O, S, N and Si, in one or more rings and may contain condensed aromatic or heteroaromatic nucleus.

3. The method according to p. 2, characterized in that the loops containing the p. 2, characterized in that the cyclic olefins also contain non-aromatic double bond.

6. The method according to p. 1, characterized in that cycloolefine are compounds of formula 1

< / BR>
where Q1means a radical containing at least one carbon atom which, together with the-CH = Q2group forms an at least 3-membered alicyclic ring which may contain one or more heteroatoms selected from the group consisting of silicon, phosphorus, oxygen, nitrogen or sulfur, and which is not substituted or substituted with halogen, =O, -CN, -NO2, R1R2R3Si-(O)u-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, PO3(M1)1/2C1-C20the alkyl, C1-C20hydroxyalkyl,1-C20haloalkyl,1-C6lanakila,3-C8cycloalkyl,6-C16-aryl, C7-C16aralkyl,3-C6heterocyclization,3-C16heteroaryl,4-C16heteroalkyl or R4-X-; or in which two adjacent carbon atoms replaced by-CO-O-CO - or-CO-NR5-CO-, or in which an aromatic or heteroaromatic ring, to the UB>3M, -COO(M1)1/2, -SO3(M1)1/2, PO3(M1)1/2WITH1-C20the alkyl, C1-C20haloalkyl,1-C20hydroxyalkyl,1-C6lanakila,3-C8cycloalkyl,6-C16the aryl, C7-C16aralkyl,3-C6heterocyclization,3-C16heteroaryl,4-C16heteroalkyl or R13-X1- is condensed with the adjacent carbon atoms, alicyclic ring;

X and X1independently of one another denote-O-, -S-, -CO-, -SO-, -SO2-, -O-C/O/ -,- /O/-O -/O/-NR5-, -NR10-C(O)-, -SO2-O - or-O-SO2-;

R1, R2and R3independently from each other mean WITH1-C12alkyl, C1-C12perfluoroalkyl, phenyl or benzyl;

R4and R13independently from each other mean WITH1-C20alkyl, C1-C20haloalkyl,1-C20hydroxyalkyl,3-C8cycloalkyl,6-C16aryl or7-C16aralkyl;

R5and R10independently of one another denote hydrogen, C1-C12alkyl, phenyl or benzyl, the alkyl groups in turn are not substituted or samewe what about from each other mean WITH1-C12alkyl, C1-C12perfluoroalkyl, phenyl or benzyl;

M stands for alkali metal;

M1mean alkaline earth metal;

and is equal to 0 or 1,

and in which the alicyclic ring formed with Q1may also contain non-aromatic double bond;

Q2means hydrogen, C1-C20alkyl, C1-C20haloalkyl,1-C12alkoxy, halogen, -CN, or R11-X2-;

R11means1-C20alkyl, C1-C20haloalkyl,1-C20hydroxyalkyl,3-C8cycloalkyl, C6-C16aryl or7-C16aralkyl;

X2means - With/About/ - About - or-With/About/-NR12- ,

R12means hydrogen, C1-C12alkyl, phenyl or benzyl,

and in which the above-mentioned cycloalkyl, heteroseksualci, aryl, heteroaryl, aralkyl and heteroaryl not substituted or substituted C1-C12the alkyl, C1-C12alkoxy, -NO2, -CN or halogen and in which the heteroatoms of the above geterotsiklicheskie, heteroaryl and heteroalkyl selected from the group consisting of-O-,-S-, -NR9- or-N=;

R9means hydrogen, C1-C12alkyl, phenyl or benzyl. forms together with the-CH =CQ2group contains 3-16 atoms in the ring and in which the ring is a monocyclic, bicyclic, tricyclic or tetracyclic system.

8. The method according to p. 6, characterized in that Q2in the formula 1 is hydrogen.

9. The method according to p. 6, characterized in that the compound of formula I, Q1means a radical containing at least one carbon atom which, together with the-CH = CQ2the group forms a 3-20 membered alicyclic ring which may contain one or more heteroatoms selected from the group consisting of silicon, oxygen, nitrogen and sulfur, and which is not substituted or substituted with halogen, = O, -CN, -NO2, R1R2R3Si-(O)u, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2WITH1-C12the alkyl, C1-C12haloalkyl,1-C12hydroxyalkyl,1-C4lanakila,3-C6cycloalkyl,6-C12the aryl, C7-C12aralkyl,3- C6heterocyclization,3-C12heteroaryl,4- C12heteroalkyl or R4-X-, or in which two adjacent atoms automatic ring which is not substituted or substituted with halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M, PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2WITH1-C12the alkyl, C1-C12haloalkyl,1-C12hydroxyalkyl,1-C4lanakila,3-C6cycloalkyl,6-C12the aryl, C7-C12aralkyl,3-C6heterocyclization,3-C12heteroaryl,4- C12heteroalkyl or R13-X1- can be condensed with the adjacent carbon atoms,

X and X1independently of one another denote-O-, -S-, -CO-, -SO-, -SO2-, -O-C/O/ -,- /O/-O- /O/-NR5-, -NR10-C(O)-, -SO2-O - or-O-SO2-; R1, R2and R3independently from each other mean WITH1-C6alkyl, C1-C6perfluoroalkyl, phenyl or benzyl;

M means an alkali metal,

M1means alkaline earth metal;

R4and R13independently from each other mean WITH1-C12alkyl, C1-C12haloalkyl,1-C12hydroxyalkyl,3-C8cycloalkyl,6-C12aryl or7-C12aralkyl; R1-C6alkoxy or3-C6cycloalkyl;

R6, R7, R8independently from each other mean WITH1-C6alkyl, C1-C6perfluoroalkyl, phenyl or benzyl;

and is equal to 0 or 1,

and in which the alicyclic ring formed with Q1may also contain non-aromatic double bond;

Q2means hydrogen, C1-C12alkyl, C1-C12haloalkyl,1-C6alkoxy, halogen, -CN, or R11-X2-;

R11means1-C12alkyl, C1-C12haloalkyl,1-C12hydroxyalkyl,3-C6cycloalkyl,6-C12aryl or7-C12aralkyl;

X2means- /O/-O - or-With/About/-NR12-;

R12means hydrogen, C1-C6alkyl, phenyl or benzyl,

and in which cycloalkyl, heteroseksualci, aryl, heteroaryl, aralkyl and heteroaryl not substituted or substituted C1-C6the alkyl, C1-C6alkoxy, -NO2, -CN or halogen, and in which the heteroatoms geterotsiklicheskikh, heteroaryl and heteroalkyl groups selected from the group consisting of-O-, -S-, -NR9- or-N=;

R9means hydrogen, C1-C62the group forms a 3-10-membered alicyclic ring which may contain heteroatom selected from the group consisting of silicon, oxygen, nitrogen and sulfur and which is unsubstituted or substituted with halogen, -CN, -NO2, R1R2R3Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, PO3(M1)1/2WITH1-C6the alkyl, C1-C6haloalkyl,1-C6hydroxyalkyl,1-C4lanakila,3-C6cycloalkyl, phenyl, benzyl, or R4-X-; or in which an aromatic or heteroaromatic ring which is unsubstituted or substituted with halogen, -CN, NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, PO3(M1)1/2WITH1-C6the alkyl, C1-C6haloalkyl,1-C6hydroxyalkyl,1-C4lanakila,3-C6cycloalkyl, phenyl, benzyl, or R13-X1- can be condensed with the adjacent carbon atoms;

R1, R2and R3independently from each other mean WITH1-Cmean alkaline earth metal;

R4and R13independently from each other mean WITH1-C6alkyl, C1-C6haloalkyl,1-C6hydroxyalkyl or3-C6cycloalkyl;

X and X1independently of one another denote-O-, -S-, -CO-, -SO - or-SO2-; R6, R7and R8independently from each other mean WITH1-C4alkyl, C1-C4perfluoroalkyl, phenyl or benzyl;

Q2means hydrogen,

11. The method according to p. 1, characterized in that the cyclic olefins are norbornene or norbornene derivatives.

12. The method according to p. 11, wherein the norbornene derivative is a compound of formula V

< / BR>
where X3means HR40-, oxygen or sulfur,

R29and R30independently of one another denote hydrogen, SP, trifluoromethyl, (CH3)3Si-O - or-COOR31,

R31and R40independently of one another denote hydrogen, C1-C12alkyl, phenyl or benzyl.

13. The method according to p. 11, characterized in that carry out the polymerization of the norbornene derivative of the formula VI

< / BR>
where X4means-CH R41-, oxygen or sulfur;

R41means hydrogen, C1-C12alkyl, phenyl, characterized in that carry out the polymerization of the norbornene derivative of the formula VII

< / BR>
where X5means - R42-, oxygen or sulfur;

R42means hydrogen, C1-C12alkyl, phenyl or benzyl;

R33and R34independently of one another denote hydrogen, SP, trifluoromethyl, /CH3/3Si-O - or-R35;

R35means hydrogen, C1-C12alkyl, phenyl or benzyl.

15. The method according to p. 11, characterized in that carry out the polymerization of the norbornene derivative of the formula VIII

< / BR>
where X6means-CH R43-, oxygen or sulfur;

R43means hydrogen, C1-C12alkyl, phenyl or benzyl;

Y represents oxygen or

< / BR>
R36means hydrogen, methyl, ethyl or phenyl.

16. The method according to p. 6, characterized in that the compounds of formula I is used as a compound selected from the group consisting of

< / BR>
< / BR>
17. The method according to p. 1, characterized in that photolabile ligand is a nitrogen (N2), monocyclic, polycyclic or condensed arenas containing 6-24 C atoms, which is unsubstituted or substituted IT WITH1-C4the alkyl, C1-C4alkoxy, C61
-C4the alkyl, C1-C4alkoxy or halogen; or aliphatic, cycloaliphatic, aromatic or analiticheskii nitrile containing 1-22 of an atom, which is unsubstituted or substituted WITH1-C4the alkyl, C1-C4alkoxy or halogen.

18. The method according to p. 17, characterized in that arena or heteroaryl attached in the form or-form.

19. The method according to p. 17, characterized in that arena or heteroarenes are unsubstituted or substituted benzene, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysin, fluoranthrene, furan, thiophene, pyrrole, pyridine, Piran, -thiopyran, pyrimidine, pyrazin, indole, kumaran, Tinatin, carbazole, dibenzofuran, dibenzothiophen, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazol, isothiazol, quinoline, isoquinoline, acridine, chrome, fenesin, phenoxazin, phenothiazines, triazine, tianren and purine.

20. The method according to p. 17, wherein the nitrile is unsubstituted or substituted acetonitrile, propionitrile, butyronitrile, intilnirile, hexanetriol, cyclopentyl and cyclohexylmethyl, Bentonit is determined as being the ligand is N2benzene , thiophene, benzonitrile or acetonitrile.

22. The method according to p. 1, characterized in that photolabile ligand is colatitude inorganic or organic compound that contains the heteroatoms O, S or N, or a cyclopentadienyl or indenyl, which is unsubstituted or substituted on a C1-C4alkyl, C1-C4alkoxy, (C1-C4alkyl)3Si - or (C1-C4alkyl)3SiO-.

23. The method according to p. 22, characterized in that photolabile ligand is H2O, H2S or NH3; fluorinated or chlorinated aliphatic or cycloaliphatic alcohol or mercaptan containing 1-18 C atoms; an aromatic alcohol or thiol containing 6-18 C atoms, or analiticheskii alcohol or thiol containing 7-18 atoms; acyclic or cyclic and aliphatic, analiticheskii or simple aromatic ether, thioether, sulfoxide, sulfon, ketone, aldehyde, ester carboxylic acids, lactone, dealkilirovanny or N-C1-C4-mono - or dialkylamines amide carboxylic acid containing from 2 to 20 atoms, or dealkilirovanny or N-C1-C4-alkilirovanny lactam; acyclic or cyclic and aliphatic, oralfacial, selected from the group consisting of cyclopentadienyl, indenyl or cyclopentadienyl or indenial that contain one or more methyl groups or trimethylsilyl groups.

24. The method according to p. 23, characterized in that photolabile ligand is methanol, ethanol, n - and ISO-propanol, n-, ISO-, and tert-butanol, 1,1,1-triptoreline, bestattorney.com, thestripturnedblue.com, pentanol, hexanol, methyl - or ethyl mercaptan, Cyclopentanol, cyclohexanol, cyclohexylmethanol, phenol, METHYLPHENOL, tortenelem, phenylmercaptan, benzylmercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n-or di-tert.-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethylthiourea, tetrahydrothiophene, dimethyl sulfoxide, diethylsulfoxide, Tetra - and pentamethyldisiloxane, dimethyl sulfone, diethylsulfide, Tetra - and pentamethylchroman, acetone, methyl ethyl ketone, diethylketone, phenylmethylene, isobutyl ketone, benzylmethylamine, acetaldehyde, Propionaldehyde, triftoratsetilatsetonom, benzaldehyde, ethyl acetate, butyrolactone, dimethylformamide, dimethylacetamide, what ntaganira and trimethylsilylcyanation.

25 . The method according to p. 23, characterized in that photolabile ligand is a primary amine of the formula R24NH2the secondary amine of the formula R24R25NH or tertiary amine of the formula R26R27R28N, where R24means1-C18alkyl, C5- or6-cycloalkyl, which is unsubstituted or substituted WITH1-C4the alkyl or C1-C4alkoxy, or C6-C18aryl or7-C12aralkyl, which is unsubstituted or substituted WITH1-C4the alkyl or C1-C4, alkoxy, R25independently has the meanings indicated for R24or R24and R25together form tetramethylene, pentamethylene, 3-oxa-1,5-pentile or-CH2-CH2-NH-CH2- CH2- or-CH2-CH2-N(C1-C4alkyl)-CH2-CH2-,

R26, R27and R28independently of one another have the meanings indicated for R24or R26and R27together have the meanings indicated for R24and R25and R28matter listed for R24.

26. The method according to p. 25, characterized in that the amine is methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-, methylethyl, dimethylethyl, n-propyl-, di-n-propyl-, trine or N-methylmorpholine.

27. The method according to p. 23, characterized in that photolabile ligand is H2O, NH3or unsubstituted or partially or fully fluorinated C1-C4alkanol.

28. The method according to p. 27, characterized in that photolabile ligand is H2O, NH3, cyclopentadienyl, methanol or ethanol.

29. The method according to p. 1, characterized in that a compound containing a number of metal centers, is a compound of the formula X

< / BR>
where Lig means photolabile ligand and IU means Ru or Os;

Hell, AND10and a11mean divalent bridging group;

Ymeans monovalent gecoordineerde anion.

30. The method according to p. 1, characterized in that the bridging group is a halide lamp.

31. The method according to p. 1, characterized in that photolabile ligand Lig contains identical or different arena.

32. The method according to p. 1, characterized in that Yis chloride, bromide or iodide.

33. The method according to p. 1, characterized in that the compound of ruthenium or osmium is a compound of formula II

[(Me+n)(L1Z1)m((L2Z2)o(L3Z3)p(L
n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

L1means photolabile ligand;

L2, L3, L4, L5and L6independently from each other mean photolabeling or photolabile ligand;

m is 1, 2, 3, 4, 5 or 6;

o, p, q, r and S independently of one another 0, 1, 2, 3, 4, or 5; Z1, Z2, Z3, Z4, Z5, Z6, Z7independently from each other equal -4, -3, -2, -1, 0, +1 or +2;

L7means gecoordineerde cation or anion,

and where the sum of m + o + p + q + r + s is an integer from 2 to 6;

t is private from the (n + m z1+ o z2+ pz3+ qz4+ r z5+ s z6)/z7.

34. The method according to p. 33, characterized in that in formula II, L7means halogen, oxygen-containing anion of the acid, BF4PF6, SiF6or AsF6.

35. The method according to p. 34, characterized in that the anion oxygen-containing acid is a sulfate, phosphate, perchlorate, perromat, peridot, antimonate, arsenate, nitrate, carbonate, formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di - or trichloro - or-fluoroacetate, methylsulfonate, ethylsulfonyl, propylsulfonyl, butylsulfonyl, triftormetilfullerenov (triplet), toilet, mesilate, brasilit is t, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphinic or benzylphosphonate.

36. The method according to p. 33, characterized in that in formula II Me means EN2+.

37. The method according to p. 33, characterized in that in formula II ligands L1, L2, L3, L4, L5and L6independently of one another are aliphatic, cycloaliphatic, aromatic or analiticheskii the NITRILES containing 1-22 of an atom which is not substituted or substituted C1-C4the alkyl, C1-C4alkoxy or halogen, or C6-C18by aryl; or L1, L2and L3together means a monocyclic, polycyclic or condensed arena containing 6-24 atom, which is unsubstituted or substituted-HE1-C4the alkyl, C1-C4alkoxy, C6-C12the aryl or halogen, or monocyclic heteroarenes, condensed heteroarenes or condensed arenas-heteroarenes containing 3-22 atoms and 1-3 heteroatoms selected from the group consisting of O, S and N, which is not substituted or substituted-HE1-C4-al-kilometres, WITH1-C4alkoxy or halogen, and L4, L5and L6together have the same value is UB>6-C18aryl.

38. The method according to p. 33, characterized in that in formula II ligands L1, L2, L3, L4, L5and L6independently from each other mean N2WITH1-C20alkynylaryl,6-C12urinary,7-C12aralkylated or6-C12aryl, or L1, L2and L3in each case, together mean a group AND1or a2and L4, L5and L6also have this value or each separately means N2these NITRILES or the specified C6-C12aryl,

< / BR>
< / BR>
where R14, R15, R16, R17, R18, R19, R20, R21, R22and R23independently of one another denote hydrogen, C1-C20alkyl, C1-C20alkoxy, aryl or SiR37R38R39and where in the case of groups AND1and a2aromatic or heteroaromatic ring heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen can be condensed with the adjacent carbon atoms;

R37, R38and R39independently from each other mean WITH1-C12alkyl, phenyl or benzyl.

39. The method according to p. 38, otlichanaja6-C12aryl, C1-C12alkynylaryl or6-C12urinary or L1, L2and L3in each case, together mean a group AND1or a2a L4, L5and L6also have this value or individually independent means N2these NITRILES or specified aryl, where R14, R15, R16, R17, R18, R19, R20, R21, R22and R23independently of one another denote hydrogen, C1-C6alkyl, C1-C6alkoxy, SiR37R38R39or phenyl, and where in the case of groups A1and a2the benzene ring may be condensed with the adjacent carbon atoms, and R37, R38and R39mean methyl, ethyl or phenyl.

40. The method according to p. 38, characterized in that in formula II, L1, L2, L3, L4, L5and L6independently from each other mean maternity, eternity or fininical or L1, L2and L3in each case, together mean a group AND1or a2and L4, L5and L6also have this value or each individually represents these NITRILES, where R14, R15, R161and a2the benzene ring may be condensed with the adjacent carbon atoms.

41. The method according to p. 33, characterized in that in formula II, L1, L2and L3together means a monocyclic, polycyclic or condensed arena containing 6-24 atom which is not substituted or substituted C1-C4the alkyl, C1-C4alkoxy, C6-C12the aryl or halogen, or monocyclic heteroarenes, condensed heteroarenes or condensed arenas-heteroarenes containing 4-22 atoms and 1-3 heteroatoms selected from the group consisting of O, S and N, which are unsubstituted or substituted C1-C4the alkyl, C1-C4alkoxy or halogen, and L4, L5and L6mean photolabile ligand.

42. The method according to p. 41, characterized in that the L1, L2and L3mean benzene or naphthalene, and photolabile ligand means H2OH, NH3, unsubstituted or fluoro-substituted C1-C4alkanol or alkanethiol, simple aliphatic ether, thioether, sulfoxide or sulfon containing 2-8 C atoms, dimethylformamide or N-organic.

43. The way the hearth L1means photolabile ligand;

L8means photolabile ligand;

IU mean Ru or Os;

Y1means gecoordineerde anion;

x means the number 1, 2 or 3.

44. Sposob on p. 43, characterized in that the L1means N2or1-C4alkynylaryl, benzonitrile, benzenetriol, NH3or amine containing 1 to 12 atoms; Y1means gecoordineerde anion and x means the number 1 or 2.

45. The method according to p. 1, characterized in that the compound of ruthenium or osmium are:

Ru(CH3SP)6(TOZ)2, Ru(CH3CH2SP)6(TOZ)2, Ru(CH3SP)6(CF3SO3)2; Ru(CH3CH2SP)6(CF3SO3)2, Ru(C6H6)2)(TOZ)2, [Ru(C6H6) (C6H5OCH3)] (F4)2;

[Ru(C6H6)(C6H5isopropyl)](BF4)2, [Ru(C6H6)(1,3,5-trimethylphenol)] (F4)2; [Ru(C6H6)(hexamethylbenzene)](F4)2, [Ru(C6H6- biphenyl)](F4)2;

[Ru(C6H6)(chrysin)](F4)2, [Ru(C6H6)(naphthalene)](F4)2, [Ru(cyclopentadienyl)(4-MB>6H6)(tetramethylthiuram)3](TOZ)2;

[Ru(C6H6)(CH3SP)3] (TOZ)2, [Ru(C6H6)(tetramethylthiuram)3] (CF3SO3)2; [Ru(C6H6)(CH3SP)3](CF3SO3)2, [RU(C6H6) (CH3OH)3](TOZ)2;

[Ru(C6H6)(CH3OH)3](Thies)2, [Os(NH3)5N2](F6)2, [Ru(NH3)5N2] (F6)2;

[Ru(NH3)5(CH3JV)]F4, [Ru(C6H6)(NH3)3](Thies)2, [Ru(C6H6)(tetrahydrothiophene)3](CF3SO3)2, [Ru((CH3)2S)3WITH6H6](TOZ)2,

[Ru(dimethylsulfoxide)3WITH6H6] (F6)2, [Ru(dimethylformamide)3WITH6H6] (F6)2,

[Ru(C6H6)Cl2)2or [Os(C6H6)CL2]2.

46. The method according to p. 1, characterized in that it is carried out without solvent or in the presence of a solvent.

47. The method according to p. 46, wherein the solvent is tetrahydrofuran, dioxane, acetone, water, alcohol, methylene chloride or chloroform.

50. The method according to p. 1, characterized in that the compound of ruthenium or osmium is used in amounts of 0.001 to 20 mol.% in relation to the number of monomer.

51. Composition comprising a cyclic olefin or at least two different cyclic olefins and at least one compound of ruthenium or osmium, characterized in that it comprises at least one thermostable compound of ruthenium or osmium containing 1-3 metal centre, and the metal atoms attached through a bridge connection or bond metal to metal, and at least one photolabile ligand connected to the metal atom, while the other focal points are occupied photolabile ligands, in the amount of 0.001 to 20 mol.% in relation to the number of monomer.

52. The media is coated in a layer of at least one cyclic olefin 0.001 to 20 mol.% in relation to the number of monomer thermostable compounds of ruthenium or osmium containing 1-3 metallic one photolabile ligand, coupled with the metal atom, while the other focal points are occupied photolabile ligands.

53. Media in p. 52, characterized in that it further contains a crosslinking agent.

Priority points

10.09.93 - PP. 1-53;

01.07.94 - PP. 1-5, 7-32, 35, 41-50, 51, 52-53.

 

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