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
< / BR>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
< / BR>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
< / BR>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, C3
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
< / BR>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
< / BR>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
< / BR>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
< / BR>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>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>< / BR>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
< / 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
(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-C
< / 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-Z2-1
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 50o
(R26R27R28P)L1Me2+(Z11Z2-1< / BR>(R26R27R28P)2L1Me2+(Z11-Z2-1
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
(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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Vinylcyclohexane-based polymers // 2248375
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.
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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 70°C 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 70°C 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 70°C 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 70°C 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 15-70°C.
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 60-85°C 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 60-70°C 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
