Catalyst of metathesis polymerisation of dicyclopentadiene in form of ruthenium complex and method of obtaining thereof

FIELD: chemistry.

SUBSTANCE: catalyst of dicyclopentadiene polymerisation in the form of a ruthenium complex represents [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(2-((2-dimethylaminoethylmethylamino)methyl))benzylidene)ruthenium of formula (I) The catalyst is obtained by the interaction of a ruthenium triphenylphosphine complex with 1,1-diphenyl-2-propin-1-ol in tetrahydrofurane or dioxane at a temperature of the solvent boiling in an inert atmosphere, then with tricyclohexylphosphine at room temperature in an inert atmosphere the formed indenylidene complex of ruthenium is extracted. The latter is successively subjected to interaction with 1,3-bis-(2,4,6-trimethylphenyl)-2-tricloromethylimidazolidine and 2-vinylbenzylamine, the formed product is extracted and dried.

EFFECT: extension of technological abilities in the process of polymerisation, and improvement of rheological, mechanical and thermal indices of the obtained polycyclopentadiene.

2 cl, 3 ex

 

The invention relates to the field of homogeneous catalysis, in particular to a method for producing catalysts metathetical polymerization of Dicyclopentadiene (DCPD), as well as to its use - management capabilities metathetical polymerization DCPD.

Catalytic metathesis reaction of olefins in recent years has established itself as a versatile method for the formation of C-C-bonds and has found wide application in organic synthesis and polymer chemistry. R. N. Grubbs, Handbook of Metathesis, v.2 and 3; Wiley VCH, Weiheim, 2003.

Family mattesini reactions of olefins comprises a metathesis with the circuit closing (cyclization) (RCM), metatezisnaya polymerization with the disclosure of the cycle (ROMP), cross-metathesis (CM), the metathesis of acyclic α,ω-dienes (ADMET). R. N. Grubbs, Handbook of Metathesis, v.1; Wiley VCH, Weiheim, 2003.

The number of known catalysts metathetical polymerization with controlled catalytic activity published by Grubbs and patented the California Institute of Technology. HEJL, A., M. W. DAY, R. H. GRUBBS Latent Olefin Metathesis Catalysts Featuring Chelating Alkylidenes II. Organomet. 2006, 25, p.6149-6154, T. UNG, A. HEJL, R. H. GRUBBS, SCHRODI Y. Latent Ruthenium Olefin Metathesis Catalysts That Contain an N-Heterocyclic Carbene Ligand. Organomet., 2004, 23, p.5399-5401.

The catalysts used to produce polymers from cycloolefins and bicycloalkanes by the reaction metathetical polymerization with the disclosure of the cycle with a molar ratio of monomer:catalyst in the interval�Les from 30000:1 to 40,000:1.

The high activity of these catalysts makes them difficult to use in the polymerization DCPD, since the catalyst particles are covered with a layer formed of the polymer with the formation of microcapsules, which prevents the dissolution of the catalyst in the monomer. This leads to a large consumption of catalysts and, as a consequence, the high cost of obtaining polydicyclopentadiene.

Preliminary dissolution of the catalyst in an inert solvent reduces the quality of the polymer - polydicyclopentadiene (PGCPD).

A method of producing a catalyst metathetical polymerization of Dicyclopentadiene, namely that the Grubbs catalyst second generation or its derivatives are processed by the corresponding styrene chloride, the methylene chloride at 40°C. the Process metathetical polymerization of Dicyclopentadiene begins after 4 min at 30°C and a molar ratio of monomer:catalyst of 30,000:1 to 40,000:1. US 2005261451 AND, 24.11.2005.

The disadvantage of this method is the low yield of target product, which ranges from 50 to 65%. This is due to the multistage synthesis and imperfection of the method.

Currently, widespread catalysts based on carbene complexes of ruthenium for the polymerization of cyclo - and bicycloalkanes with ring opening via metathesis. Known methods Paul�offering polydicyclopentadiene under the action of ruthenium catalysts - carbene complexes with phosphine ligands (catalysts of the Grubbs first generation), which are highly resistant and efficiency, a 5 times greater than the complexes of tungsten, which allows the use of the molar ratio of monomer:catalyst to 15000:1. WO 9960030 And, on 25.11.1999 and WO 9720865 And, 12.06.1997.

The main disadvantage of the ruthenium catalysts of the first generation is the low catalytic activity that necessitates the use of large amounts of catalyst of from 1:8000 to 1:15000.

The activity of the ruthenium catalysts of the second generation 5 or more times superior to that for the catalysts of the first generation, however, the poor solubility and high rate of polymerization of Dicyclopentadiene complicates their use. The catalyst, not having time to dissolve in the monomer, is covered with a layer of polymer - capsulesa and loses activity. This leads to the need of a substantial increase in the consumption of catalyst. In addition, in the manufacture of products from polydicyclopentadiene (PGCPD) injection molded technological problems arise because there is no possibility to control the start time of polymerization, and the resulting too early polymer can score the nodes supplying the mixture of monomer and catalyst.

A known catalyst for the polymerization titilope�of Tatiana General formula

where L is a substituent selected from the group including

Its production method involves the interaction triphenylphosphine complex of ruthenium with 1,1-diphenyl-2-propen-1-olomu in tetrahydrofuran at the boiling point of the solvent in an inert atmosphere, and then tricyclohexylphosphine at room temperature in an inert atmosphere, allocate formed inteeligence ruthenium complex, which sequentially in the same reactor is subjected to interaction with 1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylpyridine and 2-(N,N-dialkylaminomethyl)styrene or 1-(2-vinylbenzyl)pyrrolidino or 4-(2-vinylbenzyl)morpholine in toluene by heating to 60-70°C in an inert atmosphere. And dialkyl represents diethyl-, or methylethyl-, or methyl(2-methoxyethyl)-. EN 2393171 C1, 27. 08.2010.

The closest in technical essence to the proposed is a catalyst for the polymerization of Dicyclopentadiene (DCPD), having the formula

where L is a substituent selected from the group of aminosterols. Get the catalyst interaction triphenylphosphine complex of ruthenium with 1,1-diphenyl-2-propen-1-olomu in tetrahydrofuran or dioxane at the boiling point of the solvent in an inert atmosphere, and then tricyclohexylphosphine at room�temperature in an inert atmosphere distinguish formed inteeligence the ruthenium complex. Consistent interaction with 1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylpyridine and the corresponding 2-vinylbenzene leads to the formation of the target product. EN 2462308 Cl, 27.09.

The main disadvantages of the known catalysts for production of polydicyclopentadiene and materials based on it is difficult to control the start time of polymerization and the inability to engage in reaction modifiers, which leads to violations of the technological cycle and the heterogeneity of the resulting product.

The technical problem solved by the claimed group of inventions is to create a new efficient catalyst metathetical polymerization of Dicyclopentadiene in the form of a ruthenium complex, allowing to control the start time of polymerization, and a method thereof, which provides clean and high catalytic activity of the catalyst.

The technical result of the implementation of the claimed group of inventions is to enhance technological capabilities during polymerization by reducing the consumption of the substrate from 30000 to when the expansion of the boundaries of the molar ratio of substrate:catalyst to from 30000:1 to 200000:1, in which it is possible to control the speed of the polymerization reaction, and improve the rheological, mechanical and thermal data of the police, the�of clofentezine.

The technical problem is solved in that the polymerization catalyst of Dicyclopentadiene in the form of a ruthenium complex is a [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinone]dichloro(2-((2-(dimethylaminomethylene)methyl) benzylidene)ruthenium General formula

In the structure of the catalyst, a fundamentally new Deputy with the formula

providing new properties of the catalyst, allowing a controlled polymerization of Dicyclopentadiene with a molar ratio of substrate:catalyst of 30,000:1 to 200000:1 in an optimal during polymerization the temperature range from 50°C to 200°C.

The structural difference between the claimed catalyst from the nearest analogue is that the Deputy belonging to the class of aminosterols, stated in the ruthenium complex is a tridentate unlike bidentate in analog. In addition, the coordination number of ruthenium stated in the ruthenium catalyst is equal to 6, in the analogue - 5. All the above allows us to speak about the claimed catalyst metathetical polymerization of Dicyclopentadiene in the form of a ruthenium complex as undoubtedly the new catalyst metathetical polymerization of Dicyclopentadiene.

The purity of the catalyst confirmed the above range I�P, the absence of signals that are not related to the structure of the catalyst, said at least 95% purity of the catalyst. The molecular structure of the catalysts was definitely experimentally confirmed by x-ray diffraction analysis.

The catalyst has high catalytic activity, chemically active against a wide range of additives and expanding technological capabilities in the manufacture of products from polydicyclopentadiene.

In accordance with the task developed a method of producing the claimed catalyst.

A method of producing the catalyst is carried out in two stages.

The first stage is the synthesis inteeligence complex (In) according to the following scheme:

The second stage includes the processing inteeligence complex of ruthenium N-heterocyclic carbene ligand: [1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylpyridine, H2IMesHCCl3and 2-vinylbenzene formula

with the formation of the desired product according to the following scheme:

isolation and drying. The outlet of the catalyst is up to 70%.

The polymerization of Dicyclopentadiene is carried out with the use of the inventive catalyst at a molar ratio of substrate:catalyst of 30,000:1 to 200000:1 in the temperature range from 50°C �about 200°C. The cycle time is from 10 min to 4 h. the cycle Time of polymerization and regulate the speed set by the temperature in the specified range.

Examples of polymerization DCPD.

Example 1.

A solution of 1.25 mg of catalyst Nla and 0.33 grams (1.2 wt.%) pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxycinnamic) in 26,44 g DCPD (the molar ratio DCPD:catalyst = 100000:1) placed in a casting mold, heated to 40°C, and the temperature was raised to 200°C and maintained at that temperature for 30 min. Get solid transparent sample PGCPD odorless. The glass transition temperature Tg Of 153°C, the modulus of elasticity in bending was 1.62 GPA, tensile strength: yield strength of 59.3 MPa, a breaking stress of 49.5 MPa, elongation at break of 93%. Impact strength Izod notched to 4.5 kJ/m3the shore hardness D83.

Example 2.

A solution of 4.2 mg of the catalyst Nla and 0.33 grams (1.2 wt.%) pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxycinnamic) in 26,44 g DCPD (the molar ratio DCPD:catalyst = 30000:1) placed in a casting mold, heated to 50°C and the temperature was raised to 200°C, maintained at that temperature for 30 min. Get solid transparent sample PGCPD odorless. The glass transition temperature Tg Of 170°C, the modulus of elasticity in bending of 2.05 GPA, tensile strength: yield strength of 60.1 MPa, a breaking stress of 49.9 MPa, relative lengthened�e at break of 97%. Impact strength Izod notched to 6.0 kJ/m2the shore hardness D83.

The invention is illustrated by the following example.

Example 3.

The synthesis of the catalyst Nla is carried out under conditions preventing ingress of moisture and air in the reaction system. Use the technique and the reactors Slanka connected to a vacuum system and line dry argon. Solvents: methylene chloride, toluene, hexane, methanol absolutetruth according to standard procedures and stored under an inert atmosphere. The purity of the catalysts evaluated on the basis of the spectra of proton magnetic resonance (NMR1N) and(or) TLC (hexane/ethyl acetate 4/1).

In the vessel Slanka volume of 1000 ml, were placed 15 g (15,64 mmol) of RuCl2(PPh3), 5.3 g (25,45 mmol) of 1,1-diphenyl-2-propyn-1-ol, the device is filled with argon. Add 800 ml of absolute tetrahydrofuran and heated in an argon atmosphere for 3 h with stirring. The mixture is evaporated in vacuo at room temperature for 50% and add in flowing argon 14 g (50,04 mmol) tricyclohexylphosphine and stirred for 3 h. the Solvent was distilled off in vacuo and the residue was added 400 ml of acetone, after which the suspension was kept at -20°C for 10 h. the Precipitate was filtered off and washed with methanol 2 times in 70 ml acetone 2 times in 80 ml cold 80 ml of hexane and dried in vacuo. Gain of 15.3 g of indenyl�novogo complex of ruthenium In(1.2) with access 14,83 mmol (94,8%).

Similarly obtained 14,8 g In(1.2) with a yield of 92% when carrying out the reaction in dioxane by boiling instead of tetrahydrofuran.

In the vessel Slanka volume of 25 ml was placed 0,923 g (1 mmol) In(1.2), 0,723 g (1.7 mmol) of 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylpyridine, 10 ml of absolute toluene. Heated in an inert atmosphere at 70°C for 15 h. the Mixture was cooled in flowing argon is added 0,545 g (2.5 mmol) of 2-vinylanthracene S. Heated in an inert atmosphere for 6 h. the Mixture is cooled and filtered. The toluene was distilled off in vacuo and the residue suspended in 5.5 ml of hexane. The mixture was incubated at -20°C for 10 h. the Precipitate was filtered and washed with 3×2 ml hexane and 2×2 ml of methanol. After drying under vacuum, the catalyst Nla 0,464 g in the form of a green powder. The outlet of the catalyst 68% pure according to TLC and NMR.

The catalyst metathetical polymerization of Dicyclopentadiene may be used for the industrial manufacture of products of different sizes from polydicyclopentadiene. The resultant polymers odorless, mechanical and thermal indices correspond to, and in some cases superior to those for industrial materials from polydicyclopentadiene.

1. The catalyst metathetical polymerization of Dicyclopentadiene in the form of a ruthenium complex, predstavlâûŝi� a [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinone]dichloro(2-((2-(dimethylaminomethylene)methyl) benzylidene)ruthenium formula

2. The method for producing the catalyst according to claim 1, characterized by the fact that triphenylphosphino the ruthenium complex is subjected to interaction with 1,1-diphenyl-2-propen-1-olomu in tetrahydrofuran or dioxane at the boiling point of the solvent in an inert atmosphere, and then tricyclohexylphosphine at room temperature in an inert atmosphere distinguish formed inteeligence ruthenium complex, which is sequentially subjected to the interaction with 1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylpyridine and 2-vinylbenzene with the formula

spend the isolation and drying of the target catalyst.



 

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SUBSTANCE: catalyst of polymerisation has the general formula (I)

where a novel substituent is selected from the group of aminostyrenes. It ensures fundamentally novel properties of the catalyst. The catalyst is obtained by the interaction of a triphenylphosphine complex of ruthenium with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran or dioxane at a temperature of the solvent boiling in an inert atmosphere, and then with tricyclohexylphospine at room temperature in an inert atmosphere, the formed ruthenium indenylidenic complex is extracted. The latter is successively subjected to interaction with 1,3-bis-(2,4,6-trimethylphenyl)-2- tricloromethylimidazolidine and respective aminostyrene with the formation of a target product.

EFFECT: reduction of the catalyst consumption, reduction of the time before beginning of the polymerisation process and improvement of rheological, mechanical and thermal indices of the obtained polydicyclopentadiene, which ensures obtaining the product from polydicyclopentadiene with high consumer properties.

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SUBSTANCE: invention relates to novel complexes of group 8 transition metals, which are used as polymerisation catalysts for cyclic olefins, particularly dicyclopentadiene (DCPD). Described is a catalyst for metathesis polymerisation of dicyclopentadiene which is a ruthenium complex compound, having ligands in form of 1,3-bis-(2,6-dimethylphenyl)-2-imidazolidinylidene, two chromium atoms and ortho-substituted benzylidene. The substitute in the benzylidene ligand is an amino-substituted methyl group, where the amine is a dialkylamino-, di(2-hydroxyethyl)amino-, alkylphenylamino-group, as well as cyclic amines, particularly piperidine and morpholine; the catalyst has general formula: , where X=(Alk)2N, N(CH2-CH2-OH)2, piperidine, morpholine, NAlkPh; Alk=CH3, C2H5; Ph is phenyl. Described also is a catalyst for metathesis polymerisation of dicyclopentadiene, which is a ruthenium complex compound having ligands in form of 1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene, two chromium atoms and ortho-substituted benzylidene. The substitute in the benzylidene ligand is an alkylphenylamino-substituted methyl group. The catalyst has general formula: Alk=CH3, C2H5; Ph=phenyl. The invention describes methods of producing polydicyclopentadiene, involving polymerisation of dicyclopentadiene in the presence of the described catalysts, as well as catalysts which are compounds of [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(2-(N,N-bis(2-hydroxyethyl)aminomethyl)benzylidene)ruthenium or a compound of [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-9piperidin-1-ylmethyl)benzylidene)ruthenium with molar ratio of monomer: catalyst ranging from 70000:1 to 250000:1.

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SUBSTANCE: invention relates to organometallic chemistry, in particular to novel complexes of group 8 transition metals, which are used as polymerisation catalysts of cyclic olefins, particularly dicyclopentadiene (DCPD). The catalyst is a ruthenium complex compound of general formula (1), having ligands in form of 1,3-dimesitylimidazolidinylidene, two chlorine atoms and substituted benzylidene. The substitute in the benzylidene ligand is an amino-substituted methyl group, where the amine is a di(hydroxyalkyl)amino group, as well as piperidine. The amine-containing substitute also coordinates to the ruthenium atom and forms a six-member chelate ring where X=N (Alk-OH)2, (CH2)5N , where Alk is a straight saturated hydrocarbon chain containing 2 carbon atoms. The method of preparing the catalyst involves successive reaction in a single reactor of 1,3-dimesityl-4,5-dihydro-imidazolium chloride with potassium tert-butoxide, first generation Grubb's catalyst (GrI) and then amino-containing styrene.

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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.

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where a novel substituent is selected from the group of aminostyrenes. It ensures fundamentally novel properties of the catalyst. The catalyst is obtained by the interaction of a triphenylphosphine complex of ruthenium with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran or dioxane at a temperature of the solvent boiling in an inert atmosphere, and then with tricyclohexylphospine at room temperature in an inert atmosphere, the formed ruthenium indenylidenic complex is extracted. The latter is successively subjected to interaction with 1,3-bis-(2,4,6-trimethylphenyl)-2- tricloromethylimidazolidine and respective aminostyrene with the formation of a target product.

EFFECT: reduction of the catalyst consumption, reduction of the time before beginning of the polymerisation process and improvement of rheological, mechanical and thermal indices of the obtained polydicyclopentadiene, which ensures obtaining the product from polydicyclopentadiene with high consumer properties.

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EFFECT: high heat resistance of the proppant material.

4 cl, 36 ex

FIELD: chemistry.

SUBSTANCE: described is material (version) which contains 1-99.8 wt % polydicyclopentadiene, 0.05-0.99 wt % antioxidant selected from: sterically hindered phenols, phenol derivatives, sterically hindered amine bases, 0.05-0.99 wt % saturated or unsaturated elastomer, 0.000018-0.00010 wt % catalyst; the rest of the amount of the material is modifying additives, which can be contained both separately and together in form of their different combinations, wherein the modifying additives are selected from a group A) cyclopentene, cyclooctene, cyclooctadiene, norbornene, norbornadiene; B) cyclopentadiene trimers and/or tetramers; C) dyes; D) compounds which alter activity of the catalyst system, selected from: amines, phosphines, phosphites, phosphoramides, organoaluminium compounds; E) filler materials, selected from: chopped glass or carbon fibres with diameter of 6-17 mcm and length 4-24 m, as well as structural glass, carbon and basalt fabric with thickness of 0.20-0.87 mm and density of 250-900 g/m2; F) multi-wall carbon nanotubes with 2-20 walls and diameter of 7-30 nm. Described is a method of producing said material, which contains polydicyclopentadiene, involving mixing, in any sequence, dicyclopentadiene, catalyst, antioxidant, elastomer and modifying additives with subsequent polymeriseation of the obtained reaction mass while heating from 30 to 210°C. Described also is material (version) which contains 1-98.9 wt % polycyclopentadiene and 1-98.9 wt % "полиэндикатов", and containing an antioxidant, an elastomer, a catalyst and modifying additives, the quality and amount of which correspond to said version of the material. Described is a method of obtaining said material, which involves further addition of "полиэндикатов" to the reaction mass before polymerisation.

EFFECT: high impact viscosity and glass-transition temperature of the obtained material owing to addition of small amounts of elastomer into the reaction mass, reduced amount of antioxidant used, high rate of polymerisation and possibility of using starting material with different purity.

30 cl, 26 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis and preparation of dicyclopentadiene polymerisation catalysts. Described is a polymerisation catalyst having the formula: The structure of the catalyst employs a fundamentally new L substitute which gives the catalyst new properties. Described is a method of producing the catalyst by reacting a ruthenium triphenylphosphine complex with 1,1-diphenyl-2-propyn-1-ol in tetrahydrofuran or dioxane at boiling point of the solvent in an inert atmosphere, and then with tricyclohexylphosphine at room temperature in an inert atmosphere; the formed ruthenium indenylidene complex is separated and then successively reacted with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and the corresponding 2-vinylbenzylamine to form the end product.

EFFECT: high output of the catalyst and obtaining polydicyclopentadiene with improved application properties.

3 cl, 26 ex

FIELD: chemistry.

SUBSTANCE: elastomers contain at least two or more cyclic olefin monomers. Said elastomers are obtained as a result of metathesis ring-opening polymerisation in the presence of Grubbs catalyst or a metathesis ring-opening polymerisation catalyst based on ruthenium or osmium. The elastomer interpolymers are characterised by lack of crystallinity, glass transition temperature (Tg) less than 80°C, and number-average molecular weight (Mn) equal to at least 40 kg/mol. To obtain the elastomer interpolymers, characterised by lack of crystallinity, at least two cyclic olefin monomers are used, said monomers being selected from a group consisting of cyclopropene, cyclobutene, benzocyclobutene, cyclopentene, norbornene, norbornadiene, cycloheptene, cyclooctene, 7-oxanorbornene, 7-oxanorbornadiene, cyclodecene, 1,3-cyclooctadiene, 1,5-cyclooctadiene, 1,3-cycloheptadiene, [2.2.1]bicycloheptenes, [2.2.2]bicyclooctenes, cyclohexenyl norbornenes, norbornene dicarboxylic anhydrides, cyclododecene, 1,5,9-cyclododecatriene and mixtures thereof. The elastomer interpolymers are used in rubber mixtures for making covers and cores of golf balls etc.

EFFECT: invention enables to obtain elastomer interpolymers having a suitable balance between dynamic rigidity and hysteresis and satisfactory balance between collision coefficient and compression response.

22 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel complexes of group 8 transition metals, which are used as polymerisation catalysts for cyclic olefins, particularly dicyclopentadiene (DCPD). Described is a catalyst for metathesis polymerisation of dicyclopentadiene which is a ruthenium complex compound, having ligands in form of 1,3-bis-(2,6-dimethylphenyl)-2-imidazolidinylidene, two chromium atoms and ortho-substituted benzylidene. The substitute in the benzylidene ligand is an amino-substituted methyl group, where the amine is a dialkylamino-, di(2-hydroxyethyl)amino-, alkylphenylamino-group, as well as cyclic amines, particularly piperidine and morpholine; the catalyst has general formula: , where X=(Alk)2N, N(CH2-CH2-OH)2, piperidine, morpholine, NAlkPh; Alk=CH3, C2H5; Ph is phenyl. Described also is a catalyst for metathesis polymerisation of dicyclopentadiene, which is a ruthenium complex compound having ligands in form of 1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene, two chromium atoms and ortho-substituted benzylidene. The substitute in the benzylidene ligand is an alkylphenylamino-substituted methyl group. The catalyst has general formula: Alk=CH3, C2H5; Ph=phenyl. The invention describes methods of producing polydicyclopentadiene, involving polymerisation of dicyclopentadiene in the presence of the described catalysts, as well as catalysts which are compounds of [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(2-(N,N-bis(2-hydroxyethyl)aminomethyl)benzylidene)ruthenium or a compound of [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-9piperidin-1-ylmethyl)benzylidene)ruthenium with molar ratio of monomer: catalyst ranging from 70000:1 to 250000:1.

EFFECT: reduced unit consumption of catalyst, which leads to low cost of polydicyclopentadiene, possibility of controlling the starting time of the polymerisation process.

5 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry, in particular to novel complexes of group 8 transition metals, which are used as polymerisation catalysts of cyclic olefins, particularly dicyclopentadiene (DCPD). The catalyst is a ruthenium complex compound of general formula (1), having ligands in form of 1,3-dimesitylimidazolidinylidene, two chlorine atoms and substituted benzylidene. The substitute in the benzylidene ligand is an amino-substituted methyl group, where the amine is a di(hydroxyalkyl)amino group, as well as piperidine. The amine-containing substitute also coordinates to the ruthenium atom and forms a six-member chelate ring where X=N (Alk-OH)2, (CH2)5N , where Alk is a straight saturated hydrocarbon chain containing 2 carbon atoms. The method of preparing the catalyst involves successive reaction in a single reactor of 1,3-dimesityl-4,5-dihydro-imidazolium chloride with potassium tert-butoxide, first generation Grubb's catalyst (GrI) and then amino-containing styrene.

EFFECT: simple technology of obtaining an efficient catalyst for metathesis polymerisation of dicyclopentadiene.

2 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention describes a method of producing polydicyclopentadiene (PDCPD) by mixing diclopentadiene (DCPD) with a catalyst in molar ratio of catalyst to DCPD ranging from 1:70000 to 1:1000000 and polymerisation by heating the reaction mixture from 30°C to 200°C. Described also is a method of producing polymer materials based on PDCPD, involving further addition of modifying additives selected from cycloolefin comonomers, cyclopentadiene oligomers in form of a mixture of trimmers and tetramers, dicarboxylic acid esters, alkylphenols or combinations thereof. The catalyst used for production of PDCPD and polymer materials based on PDCPD is a compound of formula: where L is a substitute selected from the group:

, , , , , .

EFFECT: low catalyst consumption, possibility of controlling time for onset of polymerisation, improved physical and mechanical properties of the obtained product.

6 cl, 51 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

FIELD: chemistry.

SUBSTANCE: catalyst of polymerisation has the general formula (I)

where a novel substituent is selected from the group of aminostyrenes. It ensures fundamentally novel properties of the catalyst. The catalyst is obtained by the interaction of a triphenylphosphine complex of ruthenium with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran or dioxane at a temperature of the solvent boiling in an inert atmosphere, and then with tricyclohexylphospine at room temperature in an inert atmosphere, the formed ruthenium indenylidenic complex is extracted. The latter is successively subjected to interaction with 1,3-bis-(2,4,6-trimethylphenyl)-2- tricloromethylimidazolidine and respective aminostyrene with the formation of a target product.

EFFECT: reduction of the catalyst consumption, reduction of the time before beginning of the polymerisation process and improvement of rheological, mechanical and thermal indices of the obtained polydicyclopentadiene, which ensures obtaining the product from polydicyclopentadiene with high consumer properties.

2 cl, 7 ex

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