The composition capable of polymerization

 

(57) Abstract:

Describes a composition for metathetical polymerization, containing a) one Dicyclopentadiene or in a mixture with other difficult cycloolefins and b) a catalytic amount of cationic compounds of ruthenium or osmium as a catalyst. The composition differs in that the compound of ruthenium or osmium corresponds to the compound of formula VIII-VIIId

(R26R27R28P)L1Me2+(Z11Z2-1(VIII)

(R26R27R28P)2L1Me2+(Z11-Z2-1(VIIIa),

(R26R27R28P)L1L2Me2+(Z11-Z2-1(VIIIb),

(R26R27R28P)3L1Me2+(Z11-Z2-1(VIIIc),

(R26R27R28P)(L1)2Me2+(Z11-Z2-1(VIIId),

where Me is Ru or Os; Z1and Z2denotes independently from each other H-, cyclopentadienyl, CL-, Br-BF4-PF6-, SbF6-AsF6-, CF3SO3-,

C6H5-SO3-, 4-methyl-C6H5-SO3-, 3,5-Demeu>5-SO3-; R26, R27and R28denote independently from each other hydrogen, C1-C6-alkyl, unsubstituted or substituted WITH 1-31-C4-alkilani cyclopentyl, or cyclohexyl, or cyclopentyloxy, or cyclohexyloxy, or unsubstituted or is substituted by 1-3 C1-C4-alkilani phenyl, or benzyl, or phenyloxy, or benzyloxy; L1represents an unsubstituted or substituted by 1-3 C1-C4-alkilani, C1-C4-alkoxyl, -OH, -F, or C1-C6-C16-arenas or C5-C16-heteroaryl or1-C6-alkyl-CN, benzonitrile or benzenetriol, and L1in the formula VIIId is optionally different value; and2denotes H2On or1-C6-alkanol. The new composition capable of thermal polymerization (metastasises) and suitable for the manufacture of molded bodies and coatings. 23 C. p. F.-ly, 2 tab.

The invention relates to the composition of Dicyclopentadiene (DCPD) itself or in a mixture with at least one difficult cycloolefins and one catalyst from the group of phosphines of ruthenium and osmium; the method for conducting thermal metathetical polymerization of Dicyclopentadiene; covered with a layer of the of coolfin.

Caused by heating metatezisnaya polymerization with ring opening with the use of catalytic amounts of metal compounds has long been known and have been repeatedly described in literature(see, for example, Ivin, K. J., Olefin Metathesis 1-12, Academic Press, London (1983)]. Such polymers is an industrial way and you can find them on sale, for example Vestenamer.

Described molybdenum and wolframscience complexes [J. Feldman, R. R. Schrock, Lippard S. J. (Hrsg.), Progress in Inorganic Chemistry 39:1-74 (1991)], which themselves are weak, but in combination with lueinymi acids effective thermal catalysts for the polymerization of cycloolefins.

In WO 93/13171 describes resistant to atmospheric and water one-component and two-component catalysts based on compounds of molybdenum and tungsten, and ruthenium, and osmium containing a carbonyl group, at least one polyene ligand for conducting thermal metathetical polymerization and photo metathetical polymerization of difficult cycloolefins, especially norbornene, and norbornene derivative. Other polycyclic - and above all unfused polycyclic cycloolefin is not mentioned. Onecomponent 2Cl]+PF6-may, however, be activated by UV irradiation; however, the stability during storage of the compositions of the norbornene extremely unsatisfactory. These catalysts can replace the known two-component catalysts only slightly.

Description (C6H5)3]PRuCl2, (C6H5)3PRuHCl and (p-cumen)RuCl2P(C6H11)3[Demonceau, A., Noels, A. F., Saive E., Hubert A. J., J. Mol. Catal. 76:123-132 (1992)] , acting as thermal catalysts in the process metathetical polymerization with ring opening of norbornene, condensed politicalarena. Because of its low activity of these catalysts could be used in industrial production. It is therefore proposed to increase their activity by adding complex diazepino. Also mentions that only (p-cumen)RuCl2P(C6H6)3can polimerizuet norbornene in a relatively short time at a temperature of 60oC. as another monomer is mentioned, cycloocten. Other cycloolefin intended for metathetical polymerization't say that.

In WO 93/20111 as purely thermal catalysate is benavie compounds of osmium and ruthenium, containing phosphine ligands, such as [(H5C6)P] 2Cl2=CH-CH=C(C6H5)2and cyclodiene as Dicyclopentadiene, act as inhibitors and can't cure. These catalysts are difficult to obtain and they are not very resistant to moisture, so that the storage and processing of structures with such catalysts require special precautions.

Also described that the compound of ruthenium RuCl2[PC6H5)3]3loses activity due Dicyclopentadiene, and polymers by thermal metathetical polymerization are not formed [Tanielan C., Kieffer R., Harfouch A., Tetrahedron Letters 52:4589-4592 (1977)].

Unexpectedly it was discovered that it is possible to carry out thermal metathesis polymerization of Dicyclopentadiene with a single-component catalyst, if you apply phosphine catalysts of ruthenium (II) or osmium (II), not containing carbenes. It was also found that you can get even linear politicamente if we start the polymerization process suitable for this purpose solvents, and get "stitched" polymerizate if to the polymerization process in the matter.

It was also found that the polymerization occurs in the presence of the Oia, possessing excellent physical and mechanical properties. It was also observed that the compositions of DCPD and phosphine catalysts of ruthenium (II) or OS (P), not containing theoretically resistant to the atmosphere and moisture, and therefore, have a high stability during storage, if necessary, in the dark, and for polymerization does not require any special precautions that carries with it significant benefits in the process. It was found that DCPD you can copolymerizate when using these catalysts together with dull cycloolefine as comonomers.

The subject of the invention is the composition of (a) Dicyclopentadiene or in a mixture with difficulty cycloolefin and (b) a catalytic amount of at least one divalent cationic compounds of ruthenium or osmium as a one-component catalyst-free carbenes, containing at least one group of phosphines and only from 2 to 5 ligands associated with the metal atom, and the acid anions to balance the charge.

"Just" in the context of the invention refers to the sum of the group of phosphines and ligands. Compounds of ruthenium and osmium containing preferably consists of phosphites, in particular phosphines containing from 3 to 40, preferably from 3 to 30 and better from 3 to 24 carbon atoms.

The Dicyclopentadiene formula

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is a dimer of cyclopentadiene, which is known and commercially available. However, it is known that the Dicyclopentadiene to cyclopentadiene other forms addition products on Diels-Alder reaction and thus forms oligomers, which can also be used. Thus, according to the invention can be applied pure Dicyclopentadiene, Dicyclopentadiene oligomers or mixtures thereof in the composition. The oligomers may correspond to the formula

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where p denotes a number from 1 to 100, preferably from 1 to 50, most preferably from 1 to 20 and better from 1 to 10.

Employed cycloolefine that may be contained in the claimed composition as comonomers known in large numbers.

In respect of cyclic olefins can talk about monocyclic or polycyclic condensed and/or closed bridge connection ring systems having, for example, from 2 to 4 rings, which are unsubstituted or substituted and can contain heteroatoms, for example O, S, N or Si, in one or more rings and/or condensed aromatica is that the cyclic ring may contain from 3 to 16, preferably from 3 to 12 and most preferably from 3 to 8 ring elements. The cyclic olefins may have additional non-aromatic double bonds, depending on the size of the rings is preferably from 2 to 4 such additional double bonds. The Deputy of the rings we are talking about those that are inert, i.e. not violate the chemical stability of the compounds of ruthenium and osmium. In respect of cycloolefins it comes to difficult rings or systems of the rings.

If cyclic olefins containing more than one double bond, for example from 2 to 4 double bonds, depending on the reaction conditions, the selected monomer and the amount of catalyst may also be "stitched" polymerizate.

Condensed alicyclic rings contain preferably from 3 to 8, more preferably from 4 to 7 and the best 5 or 6 carbon atoms of the ring. In one preferred embodiment of the inventive method cycloolefin correspond to the formula I

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where Q1is a radical with at least one carbon atom which, together with the group-CH=CQ2forms an at least 3-membered alicyclic ring containing at neobhodimosti or substituted with halogen, =O, -CN, -NO2, R1R2R3Si(OH)u-, -COOM, -SO3M, -PO3M, -COO (M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2C1-C20-alkyl, C1-C20-hydroxyalkyl, C1-C20-halogenation, C1-C6-cyanoacrylat, C3-C8-cycloalkyl, C6-C16-aryl, C7-C16-aralkyl, C3-C6-heterocyclization, C3-C16-heteroaryl, C4-C16-heteroalkyl or R4-X-; or in which two adjacent carbon atom is substituted by-CO-O-CO - or-CO-NR5-CO-; or in which optionally at adjacent carbon atoms of the alicyclic ring condensed alicyclic, aromatic or heteroaromatic ring, 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-C20-alkyl, C1-C20-halogenation, C1-C20-hydroxyalkyl,

C1-C6-cyanoacrylat, C3-C8-cycloalkyl, C6-C16-aryl, C7-C16-aralkyl,

C3-C6-heterocyclization, C32-, -O-C(O)-, -C(O)-O-, -C(O)-NR5-, NR10-C(O)-, -SO2-O - or-O-SO2-;

R1, R2and R3independently of one another denote C1-C12-alkyl, C1-C12-perfluoroalkyl, phenyl or benzyl;

R4and R13independently represent C1-C20-alkyl, C1-C20-halogenated, C3-C8-hydroxyalkyl, C3-C8-cycloalkyl, C6-C16-aryl, C7-C16-aralkyl;

R5and R10independently of one another denote hydrogen, C1-C12-alkyl, phenyl or benzyl, and alkyl group in turn are unsubstituted or substituted C1-C12-alkoxyl or C3-C8-cycloalkyl; R6, R7and R8independently of one another denote C1-C12-alkyl, C1-C12-perfluoroalkyl, phenyl or benzyl; M is instead an alkali metal, a M1instead alkaline earth metal; and

u stands instead of 0 or 1;

and formed with Q1alicyclic ring optionally contains an additional non-aromatic double bond;

Q2represents hydrogen, C1-C20-alkyl, C1-C20-halogenated, C1-C120-halogenated, C1-C20-hydroxyalkyl, C3-C8-cycloalkyl, C6-C16-aryl or C7-C16-aralkyl;

X2denotes-C(O)-O - or-C(O)-NR12-;

R12represents hydrogen, C1-C12-alkyl, phenyl or benzyl;

moreover, the above-mentioned groups cycloalkyl, geterotsiklicheskie, aryl, heteroaryl, aralkyl and heteroaryl are unsubstituted or substituted C1-C12-alkyl, C1-C12-alkoxyl, -NO2-, -CN or halogen, and where the heteroatoms of the aforementioned groups geterotsiklicheskie, heteroaryl and heteroalkyl selected from the group of-O-, -S-, -NR9- or-N=; and

R9represents hydrogen, C1-C12-alkyl, phenyl or benzyl.

Condensed alicyclic rings contain preferably from 3 to 8, more preferably from 4 to 7, and preferably 5 or 6 carbon atoms of the ring.

If in the compounds of formula I have asymmetric center, it leads to the fact that the compounds can be in the form of optical isomers. Some compounds of formula I are of the form of the tautomers (e.g., keto-enol tautomerism). If there aliphatic double bond C=C, it can be also geometric isomerism (zoom, all possible stereoisomers, which are in the form of enantiomers, tautomers, diastereomers, E-Z-isomers or mixtures thereof.

In the definitions for the substituents of the alkyl group, alkenyl and quinil can have straight or branched chain of atoms. The same applies to parts of alkyl groups containing alkoxyl, alkylthio, alkoxycarbonyl, and other groups containing alkyl. These alkyl group contains preferably from 1 to 12, more preferably from 1 to 8, and preferably from 1 to 4 carbon atoms. These groups alkenyl and quinil contain preferably from 2 to 12, more preferably from 2 to 8, and preferably from 2 to 4 carbon atoms.

The alkyl include, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec. -butyl, tert. -butyl and the various isomeric radicals pentile, hexyl, heptyl, Attila, Manila, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Donatella and eicosyl.

To hydroxyalkyl include, 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 the various isomeric radicals pentilla, heptadecyl, octadecyl, Donatella and eicosyl.

Halogenated covers, for example, vermeil, deformity, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-triptorelin, 2-foretel, 2 - chloroethyl, 2,2,2-trichlorethyl, and also the halogenated, particularly fluorinated or chlorinated alkanes, such as, for example, isopropyl, n-propyl, n-butyl, isobutyl, Deut.-butyl, tert.-butyl and the various isomeric radicals pentile, hexyl, heptyl, Attila, Manila, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Donatella and eicosyl.

To alkenyl include, 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, ISO-dodecenyl, p-octadec-2-enyl, n-octadec-4-enyl.

Regarding cycloalkyl it is preferably about C5-C8-cycloalkyl, especially on C5or C6-cycloalkyl. Some examples are cyclopropyl, dimethylcyclopropene, cyclobutyl, cyclo-pentyl, methylcyclopentene, cyclohexyl, cycloheptyl and cyclooctyl.

Cianelli includes, for example, cyanomethyl (maternity), cyanoethyl (eternity), 1-linosopril, 1-tzia radicals cyanophenyl and cyanogenesis.

Aralkyl preferably contains from 7 to 12, and preferably from 7 to 10 carbon atoms. You can say, for example, benzyl, fenetre 3-phenylpropyl-methylbenzyl, terbutyl or-dimethylbenzyl.

Aryl preferably contains 6 to 10 carbon atoms. You can talk about, for example, phenyl, pentalene, indene, naphthalene, azulene or anthracene.

Heteroaryl preferably contains 4 or 5 carbon atoms and one or two heteroatoms from the group O, S or N. you Can talk about, for example, pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, purine or quinoline.

Heteroseksualci preferably contains 4 or 5 carbon atoms and one or two heteroatoms from the group O, S or N. you Can say, for example, about oxirane, azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, tetrahydrofuran or tetrahydrothiophene.

Alkoxyl represents, for example, methoxyl, ethoxyl, propyloxy, i-propyloxy, n-butyloctyl, i-butyloctyl, Deut.- butyloctyl and t-butyloctyl.

Under alkaline metals in the framework of the proposed invention it should be understood lithium, sodium, potassium, rubidium and cesium, particularly lithium, sodium and Li, magnesium, calcium, strontium and barium, especially magnesium and calcium.

In the definitions above, under the halogen should be understood fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

For the inventive method is especially good for those compounds of formula I in which Q2denotes hydrogen.

In addition, for polymerization are preferred those compounds of formula I, in which the alicyclic ring formed with Q1and the group-CH=CQ2contains from 3 to 16, preferably from 3 to 12, and preferably from 3 to 8 ring atoms, and it can be monocyclic, bicyclic, tricyclic or tetracyclic ring system.

With particular advantage it is possible to implement the claimed method with those compounds of formula I in which Q1is a radical with at least one carbon atom which, together with the group-CH=CQ2form a 3-20 membered alicyclic ring containing optionally one or more heteroatoms from the group 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, -SO3(M1-C12-hydroxyalkyl, C1-C4-cyanoacrylat, C3-C6-cycloalkyl, C6-C12-aryl, C7-C12-aralkyl, C3-C6-heterocyclization, C3-C12-heteroaryl, C4-C12-heteroalkyl or R4-X-; or in which two adjacent carbon atom in the radical Q1replaced by-CO-O-CO - or-CO-NR5-CO-; or in which optionally at adjacent carbon atoms of the condensed alicyclic, aromatic or heteroaromatic ring, unsubstituted or substituted by halogen, CN, -NO2, R6R7R8Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2- SO3(M1)1/2, -PO3(M1)1/2C1-C12-alkyl, C1-C12-halogenation, C1-C12-hydroxyalkyl, C1-C4-cyanoacrylat,3-C6-cycloalkyl, C6-C12-aryl, C7-C12-aralkyl,

C3-C6-heterocyclization, C3-C12-heteroaryl, C4-C12-heteroalkyl or R13-X1-; X and X1independently from each other stand instead of-O-, -S-, -CO-, -SO-, -SO2-, -O-C(O)-, -C(O)-O-, -C(O)-NR5-, -NR10-C(O)-, -SO2-O - or-O-SO2-; R1, R21instead alkaline earth metal; R4and R13independently of one another denote C1-C12-alkyl, C1-C12-halogenated, C1-C12-hydroxyalkyl, C3-C8-cycloalkyl, C6-C12-aryl, C7-C12-aralkyl; R5and R10independently of one another denote hydrogen, C1-C6-alkyl, phenyl or benzyl, and alkyl group in turn are unsubstituted or substituted C1-C6-alkoxyl or C3-C6-cycloalkyl, R6, R7and R8independently of one another represent C1-C6-alkyl, C1-C6-perfluoroalkyl, phenyl or benzyl; u stands instead of 0 or 1; and formed with Q1alicyclic ring optionally contains an additional non-aromatic double bond; Q2denotes hydrogen, C1-C12-alkyl, C1-C12-halogenated, C1-C6-alkoxyl, halogen, -CN, R11-X2-; R11represents C1-C12-alkyl, C1-C12-halogenated, C1-C12- hydroxyalkyl, C3-C6-cycloalkyl, C6-C12-aryl or C7-C12-aralkyl; X2denotes-C(kloeckera, geterotsiklicheskie, aryl, heteroaryl, aralkyl and heteroaryl are unsubstituted or substituted C1-C6-alkyl, C1-C6-alkoxyl, -NO2, -CN or halogen, and where the heteroatoms of groups geterotsiklicheskie, heteroaryl and heteroalkyl selected from the group of-O-, -S-, -NR9- or-N=; and R9denotes hydrogen, C1-C6-alkyl, phenyl or benzyl.

Of this group, preference is given to compounds of the formula I in which Q1is a radical with at least one carbon atom which, together with the group-CH=CQ2form a 3-10-membered alicyclic ring, which optionally contains one heteroatom from the group 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)1/2C1-C6-alkyl, C1-C6-halogenation, C1-C6- hydroxyalkyl, C1-C4-cyanoacrylat, C3-C6-cycloalkyl, phenyl, benzyl, or R4-X-; or in which adjacent carbon atoms of the condensed if necessary, alicyclic, aromati the8Si-, -COOM, -SO3M, -PO3M, -COO(M1)1/2, -SO3(M1)1/2, -PO3(M1)1/2C1-C6-alkyl, C1-C6-halogenation,

C1-C6-hydroxyalkyl, C1-C4-cyanoacrylat, C3-C6-cycloalkyl, phenyl, benzyl, or R13-X1-; R1, R2and R3independently of one another denote C1-C4-alkyl, C1-C4-perfluoroalkyl, phenyl or benzyl; M is instead an alkali metal, a M1instead alkaline earth metal; R4and R13independently of one another denote C1-C6-alkyl, C1-C6-halogenated, C1-C6-hydroxyalkyl or C3-C6-cycloalkyl; X and X1independently from each other stand instead of-O-, -S-, -CO-, -SO - or-SO2; R6, R7and R8independently of one another represent C1-C4-alkyl, C1-C4-perfluoroalkyl, phenyl or benzyl; and Q2denotes hydrogen.

The claimed method is suitable, in particular, for the polymerization of norbornene and norbornene derivative. Among the derivatives of norbornene particular preference is given to those that meet or formula II

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where X3designation is trifluoromethyl, (CH3)3Si-O-, (CH3)3Si - or-COOR17;

R16and R17independently of one another denote hydrogen, C1-C12-alkyl, phenyl or benzyl; or formula III

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where X4means-CHR19-, oxygen or sulfur;

R19represents hydrogen, C1-C12-alkyl, phenyl or benzyl; and

R18denotes hydrogen, C1-C6-alkyl or halogen; or formula IV

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where X5means-CHR22-, oxygen or sulfur;

R22represents hydrogen, C1-C12-alkyl, phenyl or benzyl;

R20and R21independently of one another represent hydrogen, CN, trifluoromethyl, (CH3)3Si-O-, (CH3)3Si - or-COOR23;

R23denotes hydrogen, C1-C12-alkyl, phenyl or benzyl;

or the formula V

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where X6means-CHR24-, oxygen or sulfur;

R24is hydrogen, C1-C12-alkyl, phenyl or benzyl;

Y denotes oxygen or , and

R25denotes hydrogen, methyl, ethyl or phenyl.

For the inventive method of polymerization are particularly well-suited the following compounds of formula I, and bicyclic and polycyclic < / BR>
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According to the invention, particular preference is given to using monomers and comonomers containing only carbon and hydrogen.

Demonomanie cycloolefin may be present in quantities from 0.01 to 99, preferably from 0.1 to 95, more preferably from 1 to 90 and better from 5 to 80 weight percent, calculated on the number of monomers present in the composition. The most preferred co monomer is a norbornene in number, for example, from 20 to 60 weight percent.

In the compounds of ruthenium and osmium used according to the invention, one monophosphine can be associated with the metal atom once, twice or three times, and one diphosphine once. In ruthenium and osmaevyh catalysts are connected preferably from 1 to 4, more preferably from 1 to 3, and best of all 2 ligand. Phosphine ligands are preferably correspond to the formulae VI and VIa.

PR26R27R28< / BR>
R26R27P-Z1-PR26R27< / BR>
where R-alkoxyl, unsubstituted or substituted C1-C6-alkyl, C1-C6-halogenation or C1-C6-alkoxyl C4-C12-cycloalkyl or cycloalkyl, or unsubstituted or substituted C1-C6-alkyl, C1-C6-halogenation or C1-C6-alkoxyl C6-C16-aryl or C6-C16-aryloxy, or unsubstituted or substituted C1-C6-alkyl, C1-C6-halogenation or C1-C6-alkoxyl C7-C16-aralkyl or C7-C16-aralkylated; the radicals R26and R27together represent unsubstituted or substituted C1-C6-alkyl, C1-C6-halogenation or C1-C6-arcoxia Tetra - or pentamethylene, or Tetra - or pentamethylene, or unsubstituted or substituted C1-C6-alkyl, C1-C6-halogenation or C1-C6-alkoxyl and condensed one or two 1,2-phenylene Tetra - or pentamethylene, or Tetra - or pentamethylene, or tetramethoxy, unsubstituted or substituted C1-C6-alkyl, C1-C6-halogenation or C1-C6-alkoxyl and condensed 1,2-phenylene put in the whelping C1-C4-alkoxyl C2-C12-alkylen with normal or branched chain of atoms, unsubstituted or substituted C1-C4-alkyl or C1-C4-arcoxia 1,2 - or 1,3-cycloalkyl containing from 4 to 8 carbon atoms, or unsubstituted or substituted C1-C4-alkyl or C1-C4-arcoxia 1,2 - or 1,3-heterocyclochain with five or six items rings and one heteroatom from the group O, or n

Relatively radicals R26, R27and R28it is preferably about the same radicals. In addition, preferred are those in need of space radicals, for example alkyl or alkoxyl branched-chain atoms, especially branched-chain, or cyclic radicals.

R26TO27and R28denoting alkyl, can be normal or branched chain atoms and contain from 1 to 12, preferably from 1 to 8, from 1 to 6 carbon atoms. Examples of alkyl are methyl, ethyl, n - and i-propyl, n-, i - and t-butyl, isomers pentile, hexyl, heptyl, Attila, Manila, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and eicosyl. Preferred examples of R28denoting alkoxyl may have a normal or branched chain atoms and contain from 1 to 12, preferably from 1 to 8, and preferably from 1 to 6 carbon atoms. Examples of alkoxyl are methoxy, ethoxyl, n - and i-propyloxy, n-, i - and t-butyloctyl, isomers of pentyloxide, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecylamine, tetradecanoyl, pentadecanolide, hexadecylamine, heptadecanoyl, octadecanoyl and eurosilesia. Preferred examples include methoxy, ethoxyl, n - and i-propyloxy, n-, i - and t-butyloctyl, 1-, 2 - or 3-pentyloxy and 1-, 2-, 3 - or 4-hexyloxy.

If R26, R27and R28substituted, as substituents it is preferably about C1-C4-alkyl, C1-C4-halogenoalkane or C1-C4-alkoxide. Halogen preferably denotes Cl, preferably F. Examples of preferred substituents are methyl, methoxyl, ethyl, ethoxyl and trifluoromethyl. R26, R27and R28substituted preferably from one to three times.

If R26, R27and R28denote cycloalkyl, it is preferably about C5-C8-cycloalkyl and more prepost cyclopentyl and cyclohexyl. Examples of the substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimetoksi-, trifluoromethyl-, bistritei and tretretretretretre and-cyclohexyl.

If R26, R27and R28denote cycloalkylation, it is preferably about5-C8-cycloalkylation, and most preferably about C5or C6-cycloalkylation. Here are some examples: cyclobutylamine, cycloheptylamine, cyclooctylamine and especially cyclopentyloxy and cyclohexyloxy. Examples of the substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimetoksi-, trifluoromethyl-, bistritei and distritoprovidencia.cl and-cyclohexyloxy.

If R26, R27and R28denote aryl, it is preferably about C6-C12the aryl and most preferably on the phenyl or naphthyl. Examples of the substituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimetoksi-, trifluoromethyl-, bistritei and trascriptional.

If R26, R27and R28denote aryloxy, it is preferably about C6-C12-aryloxy and most preferably about ndimethyl-, trimethyl-, methylisobutyl-, isopropyl-, aminobutiramida, triisopropyl-, tert.-butyl-, tert.-butyl, decret.-butyl, titre.-butyl-, methoxy-, dimethoxy-, trimetoksi-, trifluoromethyl-, bistritei and distritoprovidencia.cl.

If R26, R27and R28denote aralkyl, it is preferably about C7-C13-aralkyl, and a group of alkylene in aralkyl is preferably methylene. The best representative of aralkyl is benzyl. Examples of the substituted aralkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimetoksi-, trifluoromethyl-, bistritei and christiformitas.

If R26, R27and R28denote aralkylated, it is preferably about unsubstituted or substituted C7-C13-aralkylamines, and a group of alkylene in aralkylamines is preferably methylene. The best representative of aralkylated is unsubstituted or substituted benzyloxy. Examples of the substituted arancelaria are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimetoksi-, trifluoromethyl-, bistritei and distritoprovidencia.cl.

Examples of Tetra - and pentamethylene associated with atomo the relevant phosphines are cycloaliphatic, closed bridging the communications group =PRaand containing from 6 to 8 carbon atoms in the ring, for example

< / BR>
< / BR>
where Ra represents C1-C6-alkyl, cyclohexyl, benzyl, unsubstituted or substituted by one or two C1-C4-alkilani phenyl.

If Z1denotes alkylene with normal or branched chain of atoms, it is preferably about 1.2 to alkylene or 1,3 - alkylene, mainly containing from 2 to 6 carbon atoms, such as ethylene, 1,2-propylene or 1,2-butylene.

Examples of cycloalkyl, denoted as Z1are 1,2 - and 1,3-cyclopentane and 1,2 - or 1,3-cyclohexene. Examples of heterocyclization, denoted as Z1are 1,2 - and 1,3-pyrrolidin, 1,2 - and 1,3-piperidine, 1,2 - and 1,3-tetrahydrofuran.

In one preferred embodiment of the invention, the phosphine ligands correspond to the formula VI, where R26, R27and R28independently of one another denote hydrogen, C1-C6-alkyl, unsubstituted or substituted C1-C4the alkyl cyclopentyl or cyclohexyl, or unsubstituted or substituted C1-C4-alkyl, C1- C4-alkoxyl or trifluoromethyl phenyl
5
)H2P, (3-CH3-6-t-C4H9-C6H3)3P, (3-CH3-6-t-C4H9-C6H3)3P, PH3, (2,6-di-t-C4H9-C6H3)3P, (2,3-di-t-C4H9-C6H3)3P,

(2,4-di-t-C4H9-C6H3)3P, (2,4-di-CH3-C6H3)3P, (2,6-di-CH3-C6H3)3P,

(2-CH3-6-t-C4H9-C6H3)3P, (CH3)3P, (2-i-C3H7-C6H4)3P, (3-i-C3H7-C6H4)3P,

(4-i-C3H7-C6H4)3P (2-n-C4H9-C6H4)3P, (3-n-C4H9-C6H4)3P,

(4-n-C4H9-C6H4)3P, (2-i-C4H9-C6H4)3P, (3-i-C4H9-C6H4)3P,

(4-i-C4H9-C6H9)3P (2-t-C4H9-C6H4)3P, (3-t-C4H9-C6H4)3P,

(4-t-C4H9-C6H4)3P, (4-C2H5-C6H4)3P, (3-n-C3H7-C6H4)3P,

(2-n-C3H7-C6H4)3P, (4-n-C3H7-C6H<>)3P, (2-C2H5-C6H4)3P (3-C2H5-C6H4)3P, (i-C3H7)H2P (n-C4H9)H2P, (C6H5CH2)2HP, (C6H5CH2)H2P, (2-CH3-C6H4)3P, (C6H5)3P, (C5H11)H2P, (C6H5CH2)3P (n-C3H7)2HP, (i-C3H7)2HP

(n-C4H9)2HP, (n-C3H7)H2P, (C2H5)H2P, (C5H11)3P, (C6H5HP, (C5H11)2HP

(n-C7H7)3P, (i-C3H7)3P (n-C4H9)3P, (CH3)2HP, (C2H5)3P, (C6H11)3P,

(C6H11)2HP, (C5H9)3P, (C5H9)2HP and (CH3)H2P.

In another preferred embodiment, the phosphine ligands correspond to the formula VI, where R26, R27and R28independently of one another denote hydrogen, C1-C6-alkoxyl, unsubstituted or substituted C1-C4the alkyl cyclopentyloxy or cyclohexyloxy, or unsubstituted or zamestnaniu or substituted C1-C4-alkyl, C1-C4-alkoxyl or a trifluoromethyl benzyloxy.

Examples of phosphites are (CH3O)3P, (C2H5O)3P (n-C3H7O)3P, (i-C3H7O)3P (n-C4H9O)3P, (i-C4H9O)3P, (t-C4H9O)3P, (C6H5O)3P,

(2,4-di-CH3-C6H3O)3P, (2,6-di-CH3-C6H3O)3P, (2-C2H5-C6H4O)3P,

(3-C2H5-C6H4O)3P, (4-C2H5-C6H4O)3P (2-n-C3H7-C6H4O)3P,

(3-n-C3H7-C6H4O)3P, (4-n-C3H7-C6H4O)3P, (2-i-C3H7-C6H4O)3P,

(3-i-C3H7-C6H4O)3P (4-i-C3H7-C6H4O)3P (2-n-C4H9-C6H4O)3P,

(3-n-C4H9-C6H4O)3P, (4-n-C4H9-C6H4O)3P, (2-i-C4H9-C6H4O)3P,

(3-i-C4H9-C6H4O)3P, (4-i-C4H9-C6H4O)3P (2-t-C4H9-C6H4O)3UB>-C6H4O)3P,

(3-CH3-C6H4O)3P, (2-CH3-6-t-C4H9-C6H3O)3P, (3-CH3-6-t-C4H9-C6H3O)3P,

(3-CH3-6-t-C4H9-C6H3O)3P, (2,6-di-t-C4H9-C6H3O)3P, (2,3-di-t-C4H9-C6H3O)3P,

(2,4-di-t-C4H9-C6H3O)3P (4-CH3-C6H4)3P and the phosphites of the formula

< / BR>
where Ra represents C1-C6-alkyl, cyclohexyl, benzyl, unsubstituted or substituted by one or two C1-C4-alkilani phenyl.

Particular preference is given phosphines such as tri-i-propylphosphine, three t-butylphosphine, thrillometer and tricyclohexylphosphine.

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

In the framework of the proposed invention the most preferred ligands are, for example, selected from the group of ligands (A) consisting of nitrogen (N2); unsubstituted or substituted by OH, C1-C4-alkyl, C1-C1-C4-alkyl, C1-C4-alkoxyl or halogen monocyclic heteroarenes; condensed heteroarenes; condensed arenas-heteroarenes containing from 3 to 22, preferably from 4 to 16, and preferably from 4 to 10 carbon atoms and from 1 to 3 heteroatoms from the group O, S and N; unsubstituted or substituted C1-C4-alkyl, C1-C4-alkoxyl or halogen aliphatic, cycloaliphatic, aromatic or alifaticheskih NITRILES containing from 1 to 22, preferably from 1 to 18, most preferably from 1 to 12 and from 1 to 7 carbon atoms. As the substituents are preferred stands, ethyl, methoxyl, atoxyl, fluorine, chlorine and bromine. Arena and heteroarenes preferably substituted by one to three radicals. Among heteroarenes preferred heteroarenes with a large number of electrons.

Here are some examples of arenes and heteroarenes: benzene, cumin, biphenyl, naphthalene, anthracene, acenaphthene, Floren, phenanthrene, pyrene, Christ, Florentin, furan, thiophene, pyrrole, pyridine, Piran, -thiopyran, pyrimidine, pyrazin, indole, colazol, isothiazol, quinoline, isoquinoline, acridine, chrome, fenesin, phenoxazin, phenothiazines, triazine, tianren and purine. Preference is given to such arenas and heteroarenes as unsubstituted or substituted benzene, naphthalene, cumin, thiophene and benzothiophen. Particular preference is given to arena benzene or benzene substituted with one to three C1-C4-alkilani, such as toluene, xylene, trimethylbenzene, isopropylbenzene, tertiary butylbenzene or cumene. Preferred heteroatom is thiophene.

The NITRILES can be substituted, for example, metaxylem, ataxia, fluorine or chlorine; preference is given to the unsubstituted NITRILES. Alternately are preferably normal chain of atoms. Some examples of NITRILES are acetonitrile, propionitrile, butyronitrile, intilnirile, hexanetriol, cyclopentyl and cyclohexylmethyl, benzonitrile, methylbenzonitrile, benzenetriol and naphthylmethyl. In respect of NITRILES it is preferably about C1-C4-alkyllithium with normal chain of atoms or benzonitrile. Among alkylation particular preference is given to acetonitrile.

In one preferred sub-groups in respect of the ligands of group (A) we are talking about N2, S="ptx2">

If necessary, there are other ligands, for example selected from the group of ligands (b) consisting of inorganic and organic compounds containing heteroatoms O, S or N and Salvatierra often used as solvents; and unsubstituted or substituted C1-C4-alkyl, C1-C4-alkoxyl, (C1-C4-alkyl)3Si or (C1-C4-alkyl)3SiO-cyclopentadienyl or indenyl. Examples of such compounds are H2O, H2S, NH3; optionally halogenated, especially fluorinated or chlorinated aliphatic or cycloaliphatic alcohols or tosporte containing from 1 to 18, preferably from 1 to 12, most preferably from 1 to 6 carbon atoms, aromatic alcohols or thiols containing from 6 to 18, preferably from 6 to 12 carbon atoms, analiticheskie alcohols or thiols containing from 7 to 18, preferably from 7 to 12 carbon atoms; with an open chain or cyclic and aliphatic, analiticheskie or aromatic ethers, thioethers, sulfoacid, sulfones, ketones, aldehydes, esters of carboxylic acids, lactones, if necessary, N-C1-C4-mono - or dialkylamino-C4-alkylated lactams; having an open chain or cyclic and aliphatic, analiticheskie or aromatic, primary, secondary and tertiary amines containing from 1 to 20, preferably from 1 to 12, and preferably from 1 to 6 carbon atoms; and cyclopentadienyl, as, for example, cyclopentadienyl, indenyl, once or more methylated or trimethylsilylpropyne cyclopentadienyl or indenyl. Examples are allyl, methallyl and crotyl.

Additional examples of the group of ligands (In) are methanol, ethanol, n - and i-propanol, n-, i - and t-butanol, 1,1,1-triptoreline, bistrifluormethylbenzene, tretretretretretre, pentanol, hexanol, methyl or ethyl dispert, Cyclopentanol, cyclohexanol, cyclohexyloxy dispert, phenol, METHYLPHENOL, terfenol, the phenyl dispert, benzyl dispert, benzyl alcohol, simple diethyl, dimethyl, diisopropyl, di-n - or di-t-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethyl simple thioether, tetrahydrothiophene, dimethylsulphoxide, diethylsulfoxide, Tetra - and pentamethyldisiloxane, dimethyl sulfone, diethealth, Tetra - and pentamethylene, acetone, methyl ethyl ketone, diethylketone, phenylmercaptan, methy ethyl ester acetic acid, butyrolactone, dimethylformamide, dimethylacetamide, pyrrolidone and N-organic, indenyl, cyclopentadienyl, methyl - or dimethyl - or pentamethylcyclopentadienyl and trimethylsilylcyanation.

Primary amines can correspond to the formula R29NH2secondary amines of the formula R29R30NH, and tertiary - formula R29R30R31N, and R29represents C1-C18-alkyl, unsubstituted or substituted C1-C4-alkyl or C1-C4-alkoxyl C5or C6-cycloalkyl, or unsubstituted or substituted C1-C4-alkyl or C1-C4-alkoxyl C6-C18-aryl or C7-C12-aralkyl, R30is independently a value of R29or R29and R30together denote tetramethylene, pentamethylene, 3-oxa-1,5-pentile or-CH2-CH2-NH-CH2-CH2- or-CH2-CH2-N(C1-C4-alkyl)-CH2-C2-, and R31independently has a value of R29. Alkyl contains preferably from 1 to 12 and more preferably from 1 to 6 carbon atoms. Aryl preferably contains 6 to 12 carbon atoms, and aralkyl is preferably from 7 to 9 carbon atoms. Examples of peel, tri-n-butyl-, cyclohexyl-, phenyl - and benzylamine and pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine.

In one preferred sub-groups in respect of the ligands of group (C) we are talking about H2O, NH3, unsubstituted or partially or fully fluorinated C1-C4-alkanols or cyclopentadienyl, indenyl, allyl, Metallica or crotale. Particular preference is given to H2O, NH3, cyclopentadienyl, indenyl, methanol and ethanol.

In one preferred embodiment of the invention, ruthenium and omiewise the catalysts used according to the invention, contain arena and heteroarenes as related groups, phosphine groups and the anions to balance the charge. It is best if they contain a group of arenes as a ligand, a tertiary phosphine group and a monovalent or divalent anions to balance the charge.

Suitable anions of inorganic or organic acids are, for example, hydride (H), halogen (for example,,Cl,Brand I) the anion of an oxygen acid, and BF4PF6, SbF6or AsF6. Siocsifname compounds and, thus, also serve to equalize the charges.

Other suitable anions are C1-C12-, preferably C1-C6and most preferably C1-C4-alcoholate, in particular having a branched chain of atoms and corresponding, for example, the formula, RxRyRzC-Owhere Rxrepresents hydrogen or C1-C10- alkyl, Ryrepresents C1-C10-alkyl, a Rz- C1-C10-alkyl or phenyl, and the sum of carbon atoms of Rx, Ryand Rzequal to 11. As examples, it should be noted i-propyloxy and t-butyloctyl.

Other suitable anions are C3-C18-, preferably C5-C14and most preferably C5-C12-acetylide, which can correspond to the formula Rw-CCwhere Rwis C1-C16the alkyl, preferably C3-C12the alkyl branched-chain, for example of formula RxRyRzC-, or unsubstituted or substituted one to three C1-C4-alkilani or C1-C4-alkoxyl a phenyl or benzyl. Here are some examples: i-propyl-, i - and t-butyl-, phenyl-, benzyl-, 2-m>In respect of the anions of oxygen acids can talk about, for example, sulfate, phosphate, perchlorate, perbromates, periodates, antimonate, arsenate, nitrate, carbonate, the anion1-C8-carboxylic acids, such as formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di - or trichloro - or-fluoroacetate, sulfonates, for example methylsulfonate, ethylsulphate, propylsulfonyl, butylsulfonyl, triftormetilfullerenov (triflate), optionally substituted C1-C4-alkyl, C1-C4alkoxyl or halogen, especially fluorine, chlorine or bromine, vinylsulfonate or benzylmalonate, for example tosylate, mesylate, bracelate, p-methoxy - or p-ethoxyphenylurea, pentafluoroethanesulfonyl or 2,4,6-triisopropylsilane, and phosphonates, for example methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methylenephosphonate or benzylphosphonate.

Most preferred are

< / BR>
2,4,6-trimethyl-C6H5-SO3and 4-CF3-C6H5-SO3,

and cyclopentadienyl (Cp).

In one preferred embodiment of the invention, compounds of ruthenium and OSM is 2Me2+(Zn)2/n< / BR>
(R32)2L1Me2+(Zn)2/n< / BR>
(R32)3L1Me2+(Zn)2/n< / BR>
R32(L1)2Me2+(Zn-1)2/n< / BR>
where R32is a phosphine ligand of the formula VI or VIa;

Me is instead of Ru or Os;

n stands instead of the numbers 1, 2, or 3;

Z is the anion of an inorganic or organic acid;

(a) L1denotes the ligand group A, and differs if necessary, from the L1formula VIId,

and

(b) L2denotes the ligand group Century.

For R32, L1and L2saved preferences, when transcribed to single values.

In formulas VII-VIId n is preferably instead of 1 or 2, and it is better instead of 1. For R32saved preferences indicated above for the phosphine ligands of the formula VI and VIa, in particular we are talking about tertiary phosphines.

Particular preference is given to using the inventive method of the compounds of ruthenium or osmium one of formulas VIII-VIIId

(R26R27R28P)L1Me2+(Z11-Z2-1< / BR>
(R26R27R28P)2L1Me2+(Z11-Z2-127R28P)3L1Me2+(Z11-Z2-1< / BR>
(R26R27R28P)(L1)2Me2+(Z11-Z2-1< / BR>
where Me is instead of Ru or Os;

Z1and Z2independently of one another represent H, cyclopentadienyl,

R26, R27and R28independently of one another denote C1-C6-alkyl, unsubstituted or substituted with one to three C1-C4-alkilani cyclopentyl or cyclohexyl or cyclopentyloxy or cyclohexyloxy, or unsubstituted or substituted one to three C1-C4-alkilani phenyl or benzyl or phenyloxy go benzyloxy;

L1denotes unsubstituted or substituted with one to three C1-C4-alkilani, C1-C4-alkoxyl, -OH, -F, or Cl C6-C16-arenas or C5-C16-heteroaryl or C1-C6-alkyl-CN, benzonitrile or benzenetriol, and L1in the formula VIIId are optionally different value;

and L2is H2O or C1-C6-alkanols.

If getting ruthenium and osmaevyh catalysts occurs in solvents, which can be coordinated around the metal atom, as, for example, alkanol the situation within the application.

Here are some examples of compounds of ruthenium and osmium used according to the invention [Tos denotes toilet]: (C6H11)2HPRu(p-cumen)Cl2, (C6H11)3PRu(p-cumen)Cl2, (C6H11)3PRu(p-cumen)(Tos)2, (C6H11)3PRu(p-cumen)Br2, (C6H11)3PRu(p-cumen)ClF, (C6H11)3PRu(C6H6)(Tos)2, (C6H11)3PRu(CH3-C6H5)(Tos)2, (C6H11)3PRu(C10H8)(Tos)2(i-C3H7)3PRu(p-cumen)Cl2, (CH3)3PRu(p-cumen)Cl2, (C6H11)3PRu(CH3CN)(C2H5-HE)- (Tos)2, (C6H11)3PRu(p-cumen) (CH3-CN)2(PF6)2, (C6H11)3PRu(p-cumen)(CH3-CN)2(Tos)2, (n-C4H9)3PRu(p-cumen) (CH3-CN)2(Tos)2, (C6H11)3PRu(CH3-CN)Cl2,

(C6H11)3PRu(CH3-CN)2Cl2, (n-C4H9)3PRu(p-cumen)Cl2, (C6H11)3PRu(p-cumen)(C2H5OH)2(BF4)2, (C6H11)3PRu(p-cumen)(C2H5OH)2(PF6)2(i-C3H7B>,

[(C6H11)3P]3Ru(CH3CN), (C5H9)3PRu(p-cumen)Cl2, (C6H11)3PRu(p-cumen)HCl,

(C6H11)3PRu[1,2,4,5-(CH3)4C6H2]Cl2, (C6H11)3PRu[1,3,5-(i-C3H7)3C6H3]Cl2, (C6H11)3PRu[(C4H9)- C6H5]Cl2, (C6H11)3POs(p-cumen)Cl2,

(C6H5)3PRu(p-cumen)HCl, [(C6H11)3P] 2Ru(CH3CN) (Tos)2, RuCl2(p-cumen) [(C6H11)2PCH2CH2P(C6H11)2], [(C6H11)3PRu(p-cumen)(C2H5OH) (BF4)2, (C6H11)3PRu(C6H6) (C2H5OH)2(Tos)2, (C6H11)3PRu(i-C3H7-C6H5) (Tos)2, (C6H11)3PRu(C6H6)(p-cumen) Br2, (C6H11)3PRu(biphenyl)(Tos)2,

(C6H11)3PRu(anthracene)(Tos)2, (2-CH3-C6H4)3POs(p-cumen)Cl2and (C6H11)3PRu(Christ)(Tos)2.

Compounds of ruthenium and osmium used according to the invention, are known and for example, MeX3or [Mearth2]2using reaction with phosphines and shapers related groups.

The claimed composition may contain inert solvents. Particularly advantageous that, when the liquid monomers it is possible to carry out the process metathetical polymerization using no solvent. In addition, it is advantageous that the polymerization process can be conducted even in water, polar and proton solvents or mixtures of water and solvent. In these cases, under the proposed invention it is advantageous to use surface-active substance.

Suitable inert solvents are, for example, proton-polar and nephratonia solvents that can be used both independently and as mixtures of at least two solvents. As examples ethers (disutility, tetrahydrofuran, dioxane, etilenglikolevye or-dimethyl, etilenglikolevye or diethyl, dietilenglikoluretan, triethylenemelamine), halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachlorethane), esters of carboxylic acids and lactones (ethyl ester of acetic acid, Eulachon, pivalate), amides of carboxylic acids and lactams (N,N-dimethylformamide, N,N-diethylformamide, N, N-dimethylacetamide, tetramethyl-urea, triamide hexamethylphosphoric acid-butyrolactam, -caprolactam, N-organic N-acetylpyrrolidine, N-methylcaprolactam), solitarii (dimethyl sulphates), sulfones (dimethyl sulfone, diethylsulfate, trimetilindolom, tetramethylarsonium), tertiary amines (N-methylpiperidine, N-methylmorpholine), aliphatic and aromatic hydrocarbons, for example petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, the benzene or substituted benzenes (chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene, xylene) and NITRILES (acetonitrile, propionitrile, benzonitrile, phenylacetonitrile). Preference is given aprotonin polar and nonpolar solvents.

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

It should be noted that the claimed composition from DCPD, if necessary, cycloolefin and catalyst is often impervious to oxygen and moisture, which gives the opportunity to store and carry with it the reaction without the presence of a protective gas, preene preferably a number of from 0.001 to 20, more preferably from 0.01 to 15 and best from 0.01 to 10 molar percent, calculated on the amount of monomer. Because of the high thermal activity, particular preference is given to amounts of from 0.001 to 2 molar percent.

The claimed composition used in the polymerization process, can be obtained immediately before the polymerization process or used as a pre-prepared mixture, because of the used catalysts have a particularly high stability. Prior to the polymerization mixture can be stored even for a long time as ready-to-use composition that carries with it significant benefits for industrial applications.

The claimed composition may contain auxiliary substances. Known auxiliary substances are antistatics, antioxidants, antioxidants, protecting from the action of light or sunlight, softeners, dyes, pigments, fillers, active fillers, processing AIDS to improve the processing means improving adhesion, a means of increasing the viscosity and excipients that facilitate removing the product from (press) forms. Excipients the ECJ polymerization, for example in amounts of up to 70, preferably from 1 to 70, more preferably from 5 to 60, it is better from 10 to 50, especially from 10 to 40 weight percent, calculated on the amount of the compound. Excipients that improve optical, physical, mechanical and electrical properties, are known in large numbers. Here are some examples: glass and quartz in the form of powders, beads and fibers, oxide of metals and semimetals, carbonates as MgCO3, CaCO3, dolomite, sulfates of metals such as gypsum and heavy spar, natural and synthetic silicates as talc, zeolites, wollastonite, feldspar, alumina as kaolin, rock dust, "condition" (filamentary crystal), carbon fibers, synthetic fibers or powders and carbon black. Tools that increase viscosity, are, in particular, mattesini polymerizate containing unsaturated olefin groups capable of "embedded" in the polymer during polymerization. Such mattesini polymerizate known and are commercially available, for example under the brand name Vestenamer. Other means of increasing the viscosity are polybutadiene, polyisoprene or policarbonate, and copolymers of butadiene, isoprene and chloroprene with olefins.

The claimed method is implemented preferably at a temperature of at least 50oC, and preferably at least at 60oC. the Claimed method is implemented, in particular at temperatures of from 60 to 300oC, preferably from 60 to 250oC, better from 60 to 200oC, especially from 70 to 160oC. Upon completion of the polymerization process can be advantageous to hold the polymers at elevated temperatures, for example from 80 to 200oC.

To obtain linear polymers the reaction is carried out preferably in dilute solutions.

The polymerization process can be associated with the method of forming, for example by calandrinia, casting, pressing, injection molding or extrusion. Using the inventive method it is possible to obtain materials for the manufacture of avannah bodies of any type, as well as covering. Best way processes of molding and polymerization linked in reactive systems that do not contain solvents, and may apply such processing methods, such as injection molding, extrusion, polymerization in specified forms (optionally under pressure).

In respect of polymerization obtained according to the invention, it is possible to speak about the homopolymers or copolymers with a statistical distribution of the structural units, graft copolymers or block copolymers, and cross-linked polymers of this type. They can have an average molecular weight, for example from 500 to 2 million daltons, mostly from 1000 to 1 million daltons (determined by gel permeation chromatography by comparison with a more narrow polystyrene standard).

Unexpectedly it was found that the polymerization in a solvent with a high yield leads to a linear polydicyclopentadiene, a polymer having structural elements of the formula IX

< / BR>
The next subject of invention are linear copolymers having structural elements of the formula IX and the structural elements of the formula X

< / BR>
< / BR>
and cross-linked copolymers, in particular with streetmachine. "Unstitched" or linear polymers include oligomers and polymers and may contain, for example, from 5 to 5000, preferably from 10 to 2000, it is better from 20 to 1000, especially from 20 to 500, in particular from 20 to 300 units. If the polymers suitable for further processing, the desired lower molecular weight, and for processing to obtain molded bodies, it is advisable to use polymers with higher molecular weights.

The next subject of invention is polymerizate, which can be obtained using the claimed method.

Among the polymers, preference is given to those which contain only carbon and hydrogen.

Depending on the type and quantity of monomers used the claimed polymers can discover a completely different properties. Some have a very high degree of oxygen permeability, exceptional dielectric characteristics (low dielectric constant, low dielectric loss coefficients or slight tangent of dielectric loss angle), good depletability (critical temperature of the glass above the 100oC), good toughness (impact strength and toughness of the sample over which the glassing. Others have excellent optical performance, such as high transparency and low refractive index. In addition, there is also a small degree of shrinkage and excellent surface properties (smoothness, gloss, adhesion). So they can find application in various fields of technology.

The claimed compositions as coatings for the surfaces of materials carriers have a high strength adhesive. Covered with a layer materials have a very high degree of smoothness and surface gloss. Among the good mechanical properties, it should be noted, in particular, a small degree of shrinkage and high impact strength, and heat resistance. In addition, mention should be made of easily removed from the mold and good resistance to solvents. The surface can be further modified, for example to varnish or to fill the picture, and it is also necessary to mention the high degree of adhesion of the lacquer.

Received in accordance with the claimed method, the polymers suitable for the manufacture of medical devices, implants or contact lenses; for the manufacture of electric (casting reels) and electronic structural the manufacture of models, or as adhesives for bonding low surface energy (for example, Teflon, polyethylene and polypropylene), as well as capable of thermopolymerization composition in stereolithography. The claimed compositions can be used for the preparation of varnishes by thermopolymerization, and you can use transparent and even pigmented compositions. You can use both white and colored pigments. You can mention and manufacture of molded bodies by way of thermoplastic molding for commodities of all types.

The claimed compositions are particularly suitable for application of protective coatings. The next subject of invention is a variant of the claimed method of producing coated with a layer of material, wherein the composition of (a) Dicyclopentadiene or in a mixture with difficulty cycloolefins, (b) catalyst and optionally solvent is applied with a layer on a carrier, for example by makanya, spreading, casting, rolling, railroady or centrifugal casting, removing, if necessary, a solvent, and the layer is heated to conduct the polymerization process. In this way it is possible to modify the surface of materials or to protect them (e.g., corrosion).

As the subject of the proposed invention is a material which ialy suitable for application of protective coatings and relief images by heating and subsequent manifestations with a solvent. Suitable for these purposes, "cross-linking" substances that may be present, for example, in amounts of from 0.01 to 20 weight percent, are primarily organic bis-azides, especially the commercially available 2,6-bis(4-azidoanilide)-4-methyl-cyclohexanone.

Next, the subject of the proposed invention is covered with a layer of material of the carrier, characterized in that the substrate is coated with the layer of the claimed composition.

Also the subject of the invention is covered with a layer of the substrate with utverzhdennym layer of the claimed composition.

Suitable substrates (materials media) are glass, minerals, ceramics, plastic, wood, semimetals, metals, metallic oxides and metal nitrides. The thickness of the layer depends mainly on the purpose and may be, for example, from 0.1 to 1000 m, preferably from 0.5 to 500 m, most preferably from 1 to 100 m. Covered with a layer materials have a high degree of adhesion and good thermal and mechanical properties.

Declared covered with a layer of material can be obtained by known methods, for example by smearing, reclinomonas, casting, in particular centrifugal casting.

Especially good resultarray from one to three, and preferably one additional double bond and represented in the framework of the invention condensed polycyclic system of rings.

The invention is disclosed more in detail with the following examples.

Examples 1-13.

The Dicyclopentadiene (distilled or technical) and, if necessary, comonomer (additive) mixed and (p - cumen)RuCl2[P(C6H11)3] as the catalyst is dissolved in low heat. Add if necessary Vestenameror di-t-butyl-p-cresol (BHT), and the mixture is subjected to dry distillation in a vacuum at a temperature of 50-60oC. the Mixture was poured in a mold and subjected to heat curing. The critical temperature of the glass is determined by the DSA (Differential Scanning Analyse). Swelling in toluene is given in percent by weight absorption of toluene. Other information contained in the table. 1.

Examples 14-21.

Working as in example 1 and in addition use the filler shown in table. 2. Utverjdayut for 1 h at a temperature of 80oC, then for 1 h at 100oC and 2 h at 120oC. the Amount of catalyst is 0.5% in terms of DCPD. Other information given in the table. 2.

Example 22.

190 g those who ewout for 4 h at 90oC, then 1 h at 120oC and 4 h at 150oC. the resulting polymer has the following properties. Tg: 119oC; the decrease in weight at 300oC: 5,3%; Flexural strength: 102,6 N-2; longitudinal deformation of the fibers on the edge: 6,7%; E-module: 2100 N-2; K1c: 3,62 JM-2; toughness: 83,5 cjm-2; (45 Hz, R. T.): 2,4; (45 Hz, 200oC): 2,4; (1 kHz R. T.): 2,4; (1 kHz, 200oC): 2,4; tan (%, 45 Hz, R. T. ): 0,1; tan (%, 45 Hz, 200oC): 1,0; tan (%, 1 kHz, R. T.): 0,1; tan %, 1 kHz, 200oC): 0,7; water absorption (14 days, 70oC): <0,5%; electrical [breakdown] strength: 41,6 KVM-2.

Example 23.

170 g technical Dicyclopentadiene (Shell), 5,1 g of poly(norbornene) and 850 mg (C6H11)3PRu-(p-cumen)Cl2mixed and heated first 4 h at 90oC, then 1 h at 120oC and 4 h at 150oC. the resulting polymer has the following properties. Tg: 119oC; the decrease in weight at 300oC: 5,3%; Flexural strength: to 102.3 N-2; longitudinal deformation of the edge fibers: 6,2%; E-module: 2200 N-2; K1c: 3,11 JM-2; G1c: 3800 JM-2; toughness: 84,4 cjm-2.

Example 24.

150 g of technical Dicyclopentadiene (Shell), 4.5 g of poly(norbornene), 225 g of silica flour W12 at 120oC and 4 h at 150oC. the resulting polymer has the following properties. Tg: 118oC, Flexural strength: 41,5 N-2; longitudinal deformation of the edges of the fiber: 1.3 percent; E-module: 6800 N-2; K1c: of 2.51 JM-2; (45 Hz, R. T.): 3,2; (45 Hz, 200oC): 7,5; (1 kHz R. T. ): 3,2; (1 kHz, 200oC): 4,3; tan (%, 45 Hz, R. T.): 0,4; tan (%, 45 Hz, 200oC): >20; tan (%, 1 kHz R. T.): 0,1 tan ( %, 1 kHz, 200oC): >20; water absorption (14 days, 70oC): approximately 0.2%.

Example 25.

150 g of technical Dicyclopentadiene (Shell) 4.5 g of poly(norbornene), 279 g of silica flour W12 and 750 mg (C6H11)3PRu(p-cumen)Cl2mixed and heated 4 h at 90oC, then 1 h at 120oC and 4 h at 150oC. the resulting polymer has the following properties. Tg: 121oC; Flexural strength: 46,0 N-2; longitudinal deformation of the edges of the fiber is 1.1%; E-module: 7800 N-2; K1c: 3,45 JM-2; G1c: 1380 JM-2.

Example 26.

170 g technical Dicyclopentadiene (Shell), 5,1 g of poly(butadiene) and 850 mg (C6H11)3PRu(p-cumen)Cl2mixed and heated first 4 h at 90oC and then 1 h at 120oC and 4 h at 150oC. the resulting polymer has the following properties. Tg: 109o< is: 6,3%; E-module: 1900 N-2; K1C: 3,36 JM-2; G1c: 5050 JM-2; toughness: 75,2 cjm-2.

Example 27.

Mix 150 g of technical Dicyclopentadiene (Shell), 4.5 g of poly(butadiene), 225 g of silica flour W12 and 750 mg (C6H11)3PRu(p-cumen)Cl2and heated first 4 h at 90oC and then 1 h at 120oC and 4 h at 150oC. the resulting polymer has the following properties. Tg: 117oC; Flexural strength: 44,6 N-2; longitudinal deformation of the fibers on the edge: 1,7%; E-module: 6050 N-2; K1c: 3,52 JM-2, G1c: 1870 JM-2; toughness: 4,60 cjm-2.

Example 28.

In sulfator volume of 250 ml with a thermometer, inlet for N2and addition funnel serves 80 ml of water and N2. With vigorous stirring via an addition funnel over 30 add a solution of 0.5 weight percent (C6H11)3PRu(p-cumen)Cl2in 30 ml of Dicyclopentadiene, and sulfator put in an oil bath, preheated to a temperature of 120oC (internal temperature increased to 100oC). After 1.5 h, the resulting polymer is filtered off and dried in vacuum for 24 h at a pressure of 0.1 mbar and a temperature of 50o6
H11)3PRu(p-cumen)Cl2. After two hours stirring at a temperature of 150oC (bath temperature; the inside temperature was raised to 140oC) the mixture is cooled, and the formed polymer was precipitated in 300 ml of acetone. Yield: 1.50 g (18,8%); Tg=117oC.

Example 30.

Mix 12 ml of water, 8.0 g of Dicyclopentadiene and 40 mg (C6)H11)3PRu(p-cumen)Cl2. After four hours of stirring at a temperature of 150oC (bath temperature), the mixture is cooled and the formed polymer was precipitated in 300 ml of acetone. Output: 5,28 g (66%); Tg=59oC; elemental analysis: C 90,85 (calculated); 88,80 (found); H 9,14 (calculated); 9,15 (found).

Example 31.

Mix 12 ml of water, 160 mg of Triton X-100 (Fluka) (surfactant), 8.0 g of Dicyclopentadiene and 40 mg (C6H11)3PRu(p-cumen)Cl2. The mixture is stirred for 4 hours at a temperature of 150oC (bath temperature) and cooled, and the formed polymer was precipitated in 300 ml of acetone. Yield: 7.2 g (90%); Tg=143oC; elemental analysis: C 90,85 (calculated); 88,70 (found); H 9,14 (calculated); 9,26 (found).

Example 32.

Mix 12 ml of water, 160 mg of Disponible APE-256 (Henkel) (superficial is for 4 h at a temperature of 150oC (bath temperature) and the mixture is cooled, and the formed polymer was precipitated in 300 ml of acetone. Output: 7,3 g (91%); Tg= 92oC; elemental analysis: C 90,85 (calculation); 89,08 (found); H 9,14 (calculation); of 9.21 (found).

Example 33.

Mix 24 ml of water, 320 mg of Triton X-100 (Fluka) (surfactant), 16.0 g of Dicyclopentadiene and 80 mg (C6H11)3PRu(p-cumen)Cl2. Within 4 h intensively stirred at a temperature of 120oC (bath temperature; the inside temperature is increased up to a maximum of 90oC) and the mixture is cooled, and the formed polymer was precipitated in 300 ml of acetone. Output: 12,54 g (78,4%); Tg= 131oC; elemental analysis: C 90,85 (calculation); 87,95 (found); H 9,14 (calculation); 8,95 (found).

1. Composition for mattesini polymerization, containing a) one Dicyclopentadiene or in a mixture with other difficult cycloolefins and b) a catalytic amount of cationic compounds of ruthenium or osmium as a catalyst, characterized in that the compound of ruthenium or osmium corresponds to the compound of formula VIII - VIIId

(R26R27R28P)L1Me2+(Z11Z2-1< / BR>
(R26R27R28P)2L1Me2+(Z11-Z2-127R28P)3L1Me2+(Z11-Z2-1< / BR>
(R26R27R28P)(L1)2Me2+(Z11-Z2-1< / BR>
where Me is Ru or Os;

Z1and Z2denotes independently from each other H-, cyclopentadienyl, Cl-, Br1BF4-PF6-, SbF6-AsF6-, CF3SO3-C6H5-SO3-, 4-methyl-C6-H5-SO3-,

3,5-dimethyl-C6H5-SO3-; 2,4,6-trimethyl-C6H5-SO3or 4-CF3-C6H5-SO3; R26, R27and R28denotes independently from each other hydrogen, C1-C6-alkyl, unsubstituted or substituted by 1 to 3 C1-C4-alkilani cyclopentyl, or cyclohexyl, or cyclopentyloxy, or cyclohexyloxy, or unsubstituted or substituted by 1 to 3 C1-C4-alkilani phenyl, or benzyl, or phenyloxy, or benzyloxy;

L1represents an unsubstituted or substituted by 1 to 3 C1-C4-alkilani, C1-C4-alkoxyl, -OH, -F, or Cl-C6-C16-arenas or C5-C16-heteroaryl or C1-C6-alkyl-CN, benzonitrile or benzine the UB>O or C1-C6-alkanol.

2. Composition under item 1, characterized in that it employed cycloolefin are compounds with a monocyclic ring or polycyclic ring, closed bridge connection or condensed ring systems with 2 - 4 ring, unsubstituted or substituted, containing one or more heteroatoms from the group O, S, N or Si, in one or more rings or condensed aromatic or heteroaromatic rings.

3. Composition under item 1, characterized in that it employed cycloolefin contain rings with 3 to 16 elements of the ring.

4. Composition under item 1, characterized in that it employed cycloolefin contain other non-aromatic double bond.

5. Composition under item 1, characterized in that it employed cycloolefin correspond to the formula I

< / BR>
where Q1is a radical with at least one carbon atom which, together with the group-CH=CQ2- form an at least 3-membered alicyclic ring, which optionally contains one or more heteroatoms from the group of silicon, phosphorus, oxygen, nitrogen and sulfur; and which is not substituted or substituted with halogen, =O, -CN, -NO2, R13(M1)1/2C1-C20-alkyl, C1-C20-hydroxyalkyl, C1-C20-halogenation, C1-C6-cyanoacrylat, C3-C8-cycloalkyl, C6-C16-aryl, C7-C16-aralkyl, C3-C6-heterocyclization, C3-C16-heteroaryl, C4-C16-heteroalkyl or R4-X-; or two adjacent carbon atoms replaced by-CO-O-CO - or-CO-NR5-CO-; or in which optionally at adjacent carbon atoms of the alicyclic ring condensed alicyclic, aromatic or heteroaromatic ring, 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-C20-alkyl, C1-C20-halogenation, C1-C20-hydroxyalkyl, C1-C6-cyanoacrylat, C3-C8-cycloalkyl, C6-C16-aryl, C7-C16-aralkyl,

C3-C6-heterocyclization, C3-C16-heteroaryl, C4-C16-heteroalkyl or R13-X1-; X and X1denotes independently from each other-O-, -S-, -CO-, -SO-, -SO2< independently of each other C1-C12-alkyl, C1-C12-perfluoroalkyl, phenyl or benzyl; R4and R13denote independently of each other C1-C20-alkyl, C1-C20-halogenated, C1-C20-hydroxyalkyl, C3-C8-cycloalkyl, C6-C16-aryl, C7-C16-aralkyl; R5and R10denote independently from each other hydrogen, C1-C12-alkyl, phenyl or benzyl, and alkyl group, in turn, not substituted or substituted C1-C12-alkoxyl or C3-C8-cycloalkyl;

R6, R7, R8denote independently of each other C1-C12-alkyl, C1-C12-perfluoroalkyl, phenyl or benzyl;

M is alkali metal, and M1is an alkaline earth metal; and u is 0 or 1;

and formed with Q1alicyclic ring optionally contains other non-aromatic double bond;

Q2represents hydrogen, C1-C20-alkyl, C1-C20-halogenated,1-C12-alkoxyl, halogen, -CN, R11-X2-;

R11stands WITH1-C20-alkyl, C1-C20-halogenated,1-C20-hydroxyalkyl,3-Oh,- C(O)-O - or-C(O)-NR12-;

R12represents hydrogen, C1-C12-alkyl, phenyl or benzyl;

moreover, the above-mentioned groups cycloalkyl, geterotsiklicheskie, aryl, heteroaryl, aralkyl and heteroaryl not substituted or substituted C1-C12-alkyl, C1-C12-alkoxyl, -NO2, -CN or halogen and where the heteroatoms of these groups geterotsiklicheskie, heteroaryl and heteroalkyl selected from the group of-O-, -S-, -NR9-, and-N=; and

R9represents hydrogen, C1-C12-alkyl, phenyl or benzyl.

6. The composition according to p. 5, characterized in that the alicyclic ring formed with Q1together with the group-CH=CQ2has from 3 to 16 cyclic atoms, and we are talking about complicated, monocyclic, bicyclic, tricyclic or tetracyclic ring system.

7. The composition according to p. 5, characterized in that Q2in the formula I is instead of hydrogen.

8. Composition under item 1, characterized in that it employed cycloolefin are norbornene or norbornene derivatives.

9. The composition according to p. 8, characterized in that the employed norbornene derivatives are those derivatives of the formula II

< / BR>
where X33)3Si-O-, (CH3)3Si - or-COOR17;

R16and R17independently of one another denote hydrogen, C1-C12-alkyl, phenyl or benzyl;

or correspond to the formula III

< / BR>
where X4means-CHR19-, oxygen or sulfur, R19is hydrogen, C1-C12-alkyl, phenyl or benzyl; and

R18denotes hydrogen, C1-C6-alkyl or halogen;

or formula IV

< / BR>
where X5means-CHR22-, oxygen or sulfur, R22represents hydrogen, C1-C12-alkyl, phenyl or benzyl;

R20and R21independently of one another denotes hydrogen, CN, trifluoromethyl, (CH3)3Si-O-, (CH3)3Si - or-COOR23and R23denotes hydrogen, C1-C12-alkyl, phenyl or benzyl;

or correspond to the formula V

< / BR>
in which X6represents-CHR24-, oxygen or sulfur, R24; denotes hydrogen, C1-C12-alkyl, phenyl or benzyl;

Y represents oxygen or , and R25denotes hydrogen, methyl, ethyl or phenyl.

10. Composition under item 1, characterized in that hindered cycloolefin contains that is even is contained in an amount of from 0.01 to 99 wt.% in terms of the number of monomers, present in the composition.

12. Composition under item 1, characterized in that the ligands are phosphines are (C6H5)3P, (C6H5CH2)3P, (C5H11)3P, (CH3)3P, (C2H5)3P (n-C3H7)3P, (i-C3H7)3P (n-C4H9)3P, (C6H5)2HP, (C6H5CH2)2HP

(C5H11)2HP, (CH3)2HP, (C2H5)2HP, (n-C3H7)2HP, (i-C3H7)2HP, (n-C4H9)2HP

(C6H5)H2P, (C6H5CH2)H2P, (C5H11)H2P, (CH3)H2P, (C2H5)H2P (n-C3H7)H2P, (i-C3H7)H2P (n-C4H9)H2P, PH3, (2-methyl-C6H4)3P,

(3-CH3-C6H4)3P (4-CH3-C6H4)3P, (2,4-di-CH3-C6H3)3P, (2,6-di-CH3-C6H3)3P,

(2-C2H5-C6H4)3P (3-C2H5-C6H4)3P, (4-C2H5-C6H4)3P (2-n-C3H7-C6H4)3P,

(3-n-C3H
)3P,

(3-i-C3H7-C6H4)3P, (4-i-C3H7-C6H4)3P (2-n-C4H9-C6H4)3P,

(3-n-C4H9-C6H4)3P, (4-n-C4H9-C6H4)3P, (2-i-C4H9-C6H4)3P,

(3-i-C4H9-C6H4)3P, (4-i-C4H9-C6H4)3P (2-t-C4H9-C6H4)3P,

(3-t-C4H9-C6H4)3P, (4-t-C4H9-C6H4)3P, (2-CH3-6-t-C4H9-C6H3)3P,

(3-CH3-6-t-C4H9-C6H3)3P, (2,6-di-t-C4H9-C6H3)3P, (2,3-di-t-C4H9-C6H3)3P,

(C6H11)3P, (C6H11)2HP, (C5H9)3P, (C5H9)2HP or (2,4-di-t-C4H9-C6H3)3P. 13. Composition under item 1, characterized in that the ligands L1and L2are unsubstituted or substituted WITH 1-31-C4-alkilani benzene or thiophene, benzonitrile or acetonitrile.

14. Composition under item 1, characterized in that the ligands are illegal is it to arenas and heteroarenes include such compounds as benzene, cumin, biphenyl, naphthalene, anthracene, acenaphthene, Floren, phenanthrene, pyrene, chrysin, Florentin, furan, thiophene, pyrrole, pyridine, Piran, -thiopyran, pyrimidine, pyrazin, indole, kumaran, Tinatin, carbazole, dibenzofuran, dibenzothiophen, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isooctanol, isothiazol, quinoline, isoquinoline, acridine, chrome, fenesin, phenoxazin, phenothiazines, triazine, tianren or purine.

16. Composition under item 1, characterized in that compounds of ruthenium and osmium selected from the group consisting of [Tos denotes etisilat]: (C6H11)PRu(i-C3H7-C6H5)(Tos)2, (C6H11)PRu(C6H6) (C2H5OH)2(Tos)2, (CH3)3PRu(p-cumen)Cl2,

(C6H11)3PRu(anthracene)(Tos)2, (C6H5)3PRu(p-cumen)HCl, [(C6H11)3P]3Ru(CH3CN), (C5H9)3PRu(p-cumen)Cl2, (C6H11)3PRu[(C4H9)-C6H5)] Cl2, (C6H11)3POs(p-cumen)Cl2, (C6H5)3POs(p-cumen)Cl2, (2-CH3C6H4)3POs(p-cumen)Cl2, (C6H11)3PRu(C6H6)(p-cumen)Br2, (C6H11)PRu(CH3CN)Cl<2] Cl2, RuCl2(p-cumen)[(C6H11)2PCH2CH2P (C6H11)2], (C6H11)3PRu(p-cumen)(CH3-CN)2(PF6)2, (C6H11)3PRu(p-cumen) (CH3-CN)2(Tos)2, (C6H11)3PRu(p-cumen)(C2H5OH)2(BF4)2, (C6H11)3PRu(p-cumen)(C2H5OH)2(PF6)2,

(C6H11)3PRu[1,3,5-(i-C3H7)3C6H3]Cl2, (n-C4H9)3PRu(p-cumen)(CH3-CN)2(Tos)2,

(i-C3H7)3PRu (p-cumen)Cl2, (n-C4H9)3PRu(p-cumen)Cl2(i-C3H7)3POs(p-cumen)Cl2, (C6H11)3PRu(chrysin)(Tos)2, (C6H11)3PRu(p-cumen)Cl2, (C6H11)3PRu(p-cumen)Br2, (C6H11)3PRu(p-cumen)(Tos)2, (C6H11)3PRu(p-cumen)ClF, (C6H11)3PRu(C6H6)(Tos)2, (C6H11)3PRu(CH3-C6H5)(Tos)2,

(C6H11)3PRu(CH3-CN)2Cl2, (C6H11)3PRu(p-cumen)HCl, (C6H11)3HPRu(p-cumen)Cl2,

(C)(Tos)2,

(C6H11)3(p-cumen)(C2H5OH)(BF4)2, (C6H11)3PRu(biphenyl)(Tos)2and [(C6H11)3P]2RU(CH3-CN)Tos)2.

17. The composition according to p. 16, wherein the one-component catalyst is (C6H11)3PRu(p-cumen)Cl2, (C5H9)3PRu(p-cumen)Cl2or [CH(CH3)2]3PRu(p-cumen)Cl2.

18. Composition under item 1, characterized in that it also contains a solvent.

19. Composition under item 1, characterized in that the one-component catalyst is present in an amount of from 0.001 to 20 mol.% in terms of the number of monomer.

20. The composition according to p. 19, wherein the one-component catalyst is present in an amount of from 0.01 to 15 mol.%.

21. The composition according to p. 19, wherein the one-component catalyst is present in an amount of from 0.01 to 10 mol.%.

22. The composition according to p. 19, wherein the one-component catalyst is present in an amount of from 0.001 to 2 mol.%.

23. The composition according to p. 1 characterized in that it contains excipients.

24. The composition according to p. 23, characterized in that it contains auxiliary substances in amounts which

 

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FIELD: vinylcyclohexane-based polymer or copolymer with isotactic structure.

SUBSTANCE: claimed polymer or copolymer may be obtained using comonomers selected from at least one monomer of group including olefine, (meth)acrylic alkyl esters, cyclopentadiene, cyclohexene, cyclohexadiene, optionally substituted norbornene, dicyclopentadiene, optionally substituted tetracyclododecenes, alkylated in nuclear styrene, alpha-methylstyrene, divinylbenzene, vinyl ester, vinyl ether, vinyl acetate, vinyl acid, (meth)acrylonitrile, maleic anhydride. Polymer contains more than 50.1 % and less than 74 % of isotactic diads.

EFFECT: polymer of high transparency useful as material for substrate in optical memory devices.

3 cl, 4 ex, 2 tbl

FIELD: catalysts, chemical technology.

SUBSTANCE: invention relates to a method for preparing a catalyst used in additive polymerization of norbornene to polynorbornenes. Invention describes a method for preparing a catalyst for additive polymerization of norbornene involving interaction of palladium (II) compound with boron trifluoride etherate in toluene medium as a solvent. Components are mixed in the following order: palladium compound solution is added to norbornene solution in organic solvent followed by addition of boron trifluoride etherate. Optimal conditions for the process are the following: the molar ratio boron to palladium, B : Pd = (5-1):(60-1), temperature 15-60°C. Invention provides enhancing effectiveness of the polymerization process. Synthesized compounds are used in producing cover in electronics, television-communication materials, optical lens, substrates for plastic displays, photoresistors for producing chips and displays, dielectrics for semiconductors.

EFFECT: improved method of synthesis.

1 cl, 6 tbl, 27 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry, specifically to a method of producing ruthenium carbene complex and a method of metathesis polymerisation of dicyclopentadiene. The catalyst for metathesis polymerisation of dicyclopentadiene is(1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-N,N-dimethylamino-methylphenylmethylene)ruthenium of formula The method of producing the said catalyst involves reacting a second generation Grubbs catalyst with 2-(N,N-dimethylaminomethyl)styrene in toluene while heating in an inert atmosphere. In another version of the said method, a first generation Grubbs catalyst is successively reacted with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dimethylaminomethyl)styrene in a single reactor in toluene while heating in an inert atmosphere. The method of metathesis polymerisation of dicyclopentadiene is characterised by that, polymerisation is carried out using the proposed catalyst with ratio monomer: catalyst ranging from 75000:1 to 100000:1.

EFFECT: invention allows for obtaining a polymer with good mechanical properties at low expenses due to reduced catalyst consumption.

4 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: catalysts for metathesis polymerisation of dicyclopentadiene are described, which are represented by [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-N,N-diethylaminomethylphenylmethylene)ruthenium of formula (1) or [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-N-pyrrolidinylmethylphenylmethylene)ruthenium of formula (2) . A method is described for producing a catalyst of formula (1), involving successively reacting a first generation Grubb catalyst with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and N,N-diethyl-(2-vinylbenzyl)amine in an inert atmosphere at temperature between 40 and 70C in the presence of a solvent. In another version of the said method, a second generation Grubb catalyst is reacted with N,N-diethyl-(2-vinylbenzyl)amine in an inert atmosphere at temperature between 40 and 70C in the presence of a solvent. A method is described for producing a catalyst of formula (2), involving successively reacting a first generation Grubb catalyst with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 1-(2-vinylbenzyl)pyrrolidine in an inert atmosphere at temperature between 40 and 70C in the presence of a solvent. In another version of the method, a second generation Grubb catalyst is reacted with 1-(2-vinylbenzyl)pyrrolidine in an inert atmosphere at temperature between 40 and 70C in the presence of a solvent. A method is described for metathesis polymerisation of dicyclopentadiene, involving polymerisation using catalysts of formulae (1) or (2) in molar ratio monomer:catalyst ranging from 70000:1 to 100000:1.

EFFECT: increased output of catalyst and simpler synthesis due to less number of stages, obtaining polydicyclopentadiene with good application properties with low catalyst consumption.

7 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry, specifically to a method of preparing a catalyst for metathesis polymerisation of dicyclopentadiene -[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-N,N-dimethylaminomethylphenyl methylene)ruthenium. The method involves reacting a triphenylphosphine complex of ruthenium with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran while boiling in an inert atmosphere, and then with tricyclohexylphosphine at room temperature in an inert atmosphere. The indenylidene ruthenium complex formed is separated and successively reacted in a single reactor with 1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dimethylaminomethyl)styrene in toluene while heating in an inert atmosphere.

EFFECT: method increases output of product.

3 ex

FIELD: chemistry.

SUBSTANCE: described is a method of producing norbornene addition polymers (bicycle[2.2.1]heptene-2)through polymerisation of norbornene in the presence of a catalyst system obtained by reacting a palladium cationic complex in an organic solvent and etharate of boron trifluoride of formula BF3OEt2, distinguished by that the palladium complex used is tetrafluoroborate acetylacetonatobis(triarylphosphine) palladium with general formula [(Acac)Pd(PR3)2]BF4, where Acac is acetylacetonate, where R=o-tolyl, n - tolyl, phenyl. The process is carried out in molar ratio of boron to palladium B:Pd=5:1-40:1 and temperature 15-70C.

EFFECT: increased efficiency of norbornene polymerisation process through increased catalyst activity.

4 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis and preparation of dicyclopentadiene metathesis polymerisation catalysts. The metathesis polymerisation catalyst has the formula: , where L is a substitute selected from the group: , , . Several methods of preparing the catalyst are disclosed. The method of preparing the catalyst having formula , where , , is characterised by that, a second generation Grubbs catalyst is reacted with N,N-dialkyl-(2-vinylbenzyl)amine or 4-(2-vinylbenzyl)morpholine in an inert atmosphere at 60-85C in the presence of a solvent, where the dialkyl- is methylethyl- or methyl(2-methoxyethyl). The method of preparing the catalyst formula , where L is a substitute selected from the group: , , , , involves reacting a ruthenium triphenylphosphine complex with 1,1-diphenyl-2-propyn-1-ol in tetrahydrofuran at boiling point of the solvent in an inert atmosphere and then with tricyclohexylphosphine at room temperature in an inert atmosphere. The ruthenium indenylidene complex formed is extracted and then, successively in the same reactor, reacted with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dialkylaminomethyl)styrene or 1-(2-vinylbenzyl)pyrrolidine or 4-(2-vinylbenzyl)morpholine in toluene while heating to 60-70C in an inert atmosphere. The dialkyl- is diethyl-, methylethyl- or methyl(2-methoxyethyl)-. A dicyclopentadiene metathesis polymerisation method is disclosed, which involves polymerisation using the catalyst in paragraph 1 in molar ratio substrate: catalyst ranging from 70000:1 to 200000:1.

EFFECT: invention increases catalyst output and simplifies synthesis by reducing the number of steps, and also enables to obtain polydicyclopentadiene with good application properties.

4 cl, 1 tbl, 22 ex

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