Dicyclopentadiene metathesis polymerisation catalyst, preparation method thereof and polymerisation method

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

 

The invention relates to the field of catalysis for the production of catalyst metathetical polymerization of Dicyclopentadiene (DCPD).

The number of known catalysts metathetical polymerization with controlled catalytic activity, published by Grabban and patented the California Institute of Technology [UNG THAY; YANN SCHRODI, US 2005261451 2005-11-24; A. Hejl, M.W. Day, R.H.Grubbs Organometallics 2006, 25, 6149-6154, T. Ung, A. Hejl, R.H.Grubbs, Y.Schrodi Organometallics 2004, 23, 5399-5401].

The catalysts used to produce polymers of cycloolefins and bicycloalkanes reaction metathetical polymerization disclosure of the cycle when the molar ratio of monomer:catalyst in the range of 30,000:1 to 40,000:1.

The high activity of these catalysts complicates their use in polymerization DCPD, since the catalyst particles are coated 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 polymer - polydicyclopentadiene (PGCPD).

A known method of producing catalyst metathetical polymerization of Dicyclopentadiene (US 2005261451 2005-11-24), namely, that kata is isator the verification of the second generation or its derivatives are processed by the corresponding styrene in methylene chloride at 40°C.

The drawback of the method according to patent US 2005261451 is the low yield of the target product, which ranges from 50 to 65% based on the catalyst of the first generation. This is due to the multi-stage synthesis and imperfection of methods.

From the above patent also known way metathetical polymerization of Dicyclopentadiene, which consists in the fact that the polymerization of Dicyclopentadiene is carried out at a ratio of monomer:catalyst not exceeding 40000:1.

The problem solved by the claimed invention is to create a new efficient catalyst metathetical polymerization of Dicyclopentadiene, allowing to reduce its consumption, by increasing the solubility of the monomer, method of its production, which increases the output of the catalyst, and a method of polymerization of Dicyclopentadiene.

In accordance with the task created the catalyst metathetical polymerization of Dicyclopentadiene having the formula:

,

where L is the Deputy selected from the group:

,,

The structure and purity of the obtained compounds is confirmed by the method of1H NMR:

(300 MHz, CDCl3) δ [n]: 0,48 (3H, t, J 7,1 Hz)of 1.64 (3H, s)of 1.97 (4H, m), 2,35-2,93 (N, m), 3,24 (1H, m), a 4.03 (4H, m), of 5.26 (1H, is, J 14.4 Hz), 6,55 (1H, d, J 7.2 Hz), 6.90 to-7,1 (6N, m), 7,41 (1H, t, J 7.2 Hz), 18,70 (1H, s).

Supporting data for [1,3-bis-(2,4,6-trimetilfenil)-2-imidazolidinone]sodium dichloro(o-N,N-methylethylketone-aminomethylpyrimidine)ruthenium formula:

(300 MHz, CDCl3) δH: is 1.81 (3H, s), 2,19-2,58 (N, m), 2,96-3,14 (6N, m)to 3.38 (1H, m), of 3.95 (1H, m), Android 4.04 (4H, m), of 5.34 (1H, d, J of 13.7 Hz), to 6.58 (1H, d, J 7,3 Hz), 6,95-7,13 (6N, m), 7,46 (1H, t, J 7,3 Hz), 18,75 (1H, s).

(300 MHz, CDCl3) δn: 1,56 (2H, s)to 2.06 (2H, m), 2,32-2,75 (N, m)is 3.08 (2H, m)of 3.25 (2H, m), of 3.57 (2H, m), 4,11 (4H m), is 4.15 (2H m), 6,60 (1H, d, J 7.2 Hz), 7,00 (1H, d, J 8.2 Hz), 7.07 (4H, s), 7,17 (1H, t, J 7.2 Hz), 7,42 (1H, t, J 7.2 Hz), 18,92 (1H, s).

The claimed catalysts are superior to the catalysts disclosed in the patent [US 2005261451] and allow you to get polydicyclopentadiene with high consumer properties at a molar ratio of monomer:catalyst from 70000:1 to 200000:1, while for known catalysts the ratio of 30000:1 and 40000:1 (US 2005261451 2005-11-24).

In accordance with the task developed methods for producing the claimed catalyst.

To obtain a catalyst having the formula

where

,,,

the catalyst for the verification of the second generation (GII) is subjected to interaction with N,N-dialkyl-(2-what vinylbenzyl) - amine or 4-(2-vinylbenzyl)morpholine in an inert atmosphere at temperatures of 60-85°C in the presence of a solvent, however dialkyl - is methylethyl or methyl(2-methoxyethyl).

To obtain a catalyst having the formula

,

where L is the Deputy selected from the group:

,,,,

triphenylphosphine ruthenium complex was subjected to interaction with 1,1-diphenyl-2-propyne-1-I in tetrahydrofuran at the boiling temperature of the solvent in an inert atmosphere, and then tricyclohexylphosphine at room temperature in an inert atmosphere, was allocated formed inteeligence ruthenium complex, which sequentially in the same reactor was subjected to interaction with 1,3-bis-(2,4,6-trimetilfenil)-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°With in an inert atmosphere, with dialkyl represents diethyl-, or methylethyl-, or methyl(2-methoxyethyl)-.

This method consists of 2 parts. Instead of expensive catalyst verification is used inteligency complex In(1.2)are obtained by an improved method.

The first part (the synthesis of the precursor consists of two stages, carried out without isolation between the exact product synthesis inteeligence triphenylphosphino karbonovogo complex of ruthenium processing RuCl2(PPh3)3diphenylpropyl and receiving from him tricyclohexylphosphine complex. The second part includes the processing of this complex of ruthenium N-heterocyclic carbene ligand: [1,3-bis-(2,4,6-trimetilfenil)-2-trichloromethylpyridine, H2IMesHCCl3] and the corresponding aminosterols with the formation of the target product. In this method, instead of a catalyst for the verification of the first generation used inteligency complex (In1.2)obtained by an improved method. The yield of the target product on the published work is 75-90%.

In our proposed method achieved output inteeligence complex 90-93% by reducing the number of stages - the process is conducted without separating inteligencia triphenylphosphine complex. Upgraded the allocation method of the product, which consists in leaching inteeligence complex In(1.2) with acetone instead of hexane.

where L is the Deputy selected from the group:

,,,,

The way metathetical polymerization of Dicyclopentadiene is that the polymerization is performed with IP is the use of the claimed catalyst at a molar ratio of substrate:catalyst from 70000:1 to 200,000:1. Holding metathetical polymerization using this catalyst allows to reduce the consumption of the catalyst by increasing its solubility in the monomer as the catalyst is soluble in the monomer at 35°C.

The receipt of the catalyst is carried out by interaction of the catalyst for the verification of the second generation (G II) and the appropriate amine derivative is 2-vinylbenzene in an inert atmosphere at a temperature of 60-85°C in the presence of a solvent

The outline of this process:

The yield of the target product is 70-98%.

Obtaining catalysts of triphenylphosphine complex of ruthenium chloride carried out according to the scheme:

where L is the Deputy selected from the group:

Triphenylphosphine complex of ruthenium chloride interacts with diphenyl-propanolol, forming identidentify ruthenium complex with triphenylphosphine ligands In(1.1). Forth In(1.1) is introduced into the reaction tricyclohexylphosphine with subsequent treatment of a chloroform adduct of imidazole and aminosterols.

Stage 1 is 99% yield, boiling RuCl2(PPh3) with the corresponding carbinol in tetrahydrofuran.

Stage 1.1 is carried out at room temperature after stage I, excluding the allocation of the product is with the release of 90-93%.

Stage 2.1 is carried out in toluene at 60-70°C with the release of 86-90%.

Stage 2 is carried out in toluene at 60-70°C with a yield of 40-50%.

Metathesis polymerization of Dicyclopentadiene is performed with the use of the catalyst at a molar ratio of substrate: catalyst from 70000:1 to 200,000:1. The catalyst is dissolved at 35°C in DCPD. Then the resulting mixture is heated at 50°C for 20 min, then to 200°C for 30 min

The invention is illustrated by the following examples.

The synthesis of the catalyst is carried out under conditions preventing ingress of moisture and air in the reaction system. Used equipment and reactors of Slanka connected to the vacuum system and line dry argon. Solvents: methylene chloride, toluene, hexane, methanol was absoluteradio by standard methods and stored in an inert atmosphere [Armarego, Wilfred, L.F.; Chai, Christina, L.L. (2003). Purification of Laboratory Chemicals (5th Edition). Elsevier]. 2-vinyl-N,N-alkyl-benzylamine received by well-known methods [Kolesnikov G.S. Synthesis of the vinyl derivatives of aromatic and heterocyclic compounds 1960].

Example 1.

In the flask Slanka 25 ml was placed 220 mg (0.26 mmol) of the catalyst for the verification of the second generation (GII). The flask was filled with argon and added a solution of 186 mg (of 0.91 mmol) (2-methoxyethyl)methyl(2-vinylbenzyl)amine in 4 ml of absolute toluene. The reaction mixture was heated for 10 minutes PR is 85°C, then cooled and drove the solvent in vacuo. The residue was washed with hexane and dried in vacuum. Got the catalyst N2 170 mg (98%) in the form of green crystals.1H NMR (300 MHz, CDCl3) δH: is 1.81 (3H, s), 2,19-2,58 (N, m), 2.96-3.14 (6N, m), 3.38 (1H, m), 3.95 (1H, m), Android 4.04 (4H, m), of 5.34 (1H, d, J of 13.7 Hz), to 6.58 (1H, d, J 7,3 Hz), 6,95-7.13 (6N, m), 7,46 (1H, t, J 7,3 Hz), 18.75 (1H, s).

Example 2.

Analogously to example 1 was heated at 60°C for 1 hour got N2 163 mg (94%).

Example 3.

In the flask Slanka 25 ml was placed 200 mg (0.23 mmol) of the catalyst for the verification of the second generation (GII). The flask was filled with argon was added a solution of 140 mg (0.78 mmol) of N-methyl-N-(2-vinylbenzyl)ethylamine in 4 ml of absolute toluene. The reaction mixture was heated for 20 min at 85°C, then cooled and kept off the solvent in vacuo. The residue was washed with methanol and dried in vacuum. Got the catalyst N1 - 125 mg (83%) in the form of green crystals.1H NMR (300 MHz, CDCl3) δH: 0,48 (3H, t, J 7,1 Hz)of 1.64 (3H, s)of 1.97 (4H, m), 2,35-2,93 (N, m), 3,24 (1H, m), a 4.03 (4H, m), of 5.26 (1H, d, J 14.4 Hz), 6,55 (1H, d, J 7.2 Hz), 6.90 to-7.1 (6N, m), 7,41 (1H, t, J 7.2 Hz), 18.70 (1H, s).

Example 4.

Analogously to example 3 was heated at 60°C for 1 hour. Received N1, exit 127 mg (84%)

Example 5.

220 mg (0.26 mmol) of the catalyst for the verification of the second generation (GII) was heated in 4 ml of absolute toluene with 186 mg (0.91 mmol) of 4-(2-vinylbenzyl)research 10 minutes at 85°C. the Toluene was evaporated and added 5 ml of hexane. OSA is OK filtered and washed with hexane and ice-cold methanol, 4 ml. Received 148 mg, 86% complex N3.1H NMR (300 MHz, CDCl3) δn: 1,56 (2H, s), 2.06 (2H, m), 2,32-2,75 (N, m), 3.08 (2H, m), 3.25 (2H, m), 3.57 (2H, m), 4.11 (4H, m), 4.15 (2H, m), 6,60 (1H, d, J 7.2 Hz), 7,00 (1H, d, J 8.2 Hz), 7.07 (4H, s), 7,17 (1H, t, J 7.2 Hz), 7,42 (1H, t, J 7.2 Hz), 18.92 (1H, s).

Example 6.

Analogously to example 5 was heated at 60°C for 1 hour, the output N3 145 mg (83%).

Example 7.

In the flask Slanka volume of 1000 ml, were placed 15 g (15.64 mmol) of RuCl2(PPh3)2, 5.3 g (at 25.45 mmol) of 1,1-diphenyl-2-propyne-1-ol unit filled with argon. Added 800 ml of absolute tetrahydrofuran and heated in an argon atmosphere for 3 hours under stirring. The mixture was evaporated in vacuum at room temperature for 50% and added in a stream of argon 14 g (50.04 mmol) tricyclohexylphosphine, stirred 3 hours. The solvent is kept in vacuum and to the residue was added 400 ml of acetone, after which the suspension was kept at -20°C for 10 hours. The precipitate was filtered and washed successively with methanol, acetone, hexane, and dried in vacuum. Received 15.3 g inteeligence complex of ruthenium In (1.2) with output (14.83 mmol) (94.8%).

In the flask 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-trimetilfenil)-2-trichloromethylpyridine 210 ml of absolute toluene. Was heated in an inert atmosphere at 70°C. for 15 hours. The mixture was cooled in a stream of argon was added 0.662 g (3.5 mmol) of diethyl(2-vinylbenzyl)amine. Was heated in an inert atmosphere 6hours. The mixture was cooled and filtered from the precipitate, toluene drove in vacuum and the residue suspended in 5.5 ml of hexane. The mixture was left at -20°C for 10 hours. The precipitate was filtered and washed with hexane and methanol. After drying in vacuum has been the catalyst N4 - 0.477 g (73%).

Example 8.

Analogously to example 7 was heated at 60°C for 15 and 6 hours got N4 0.424 g (64%)

Example 9.

In the flask 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-trimetilfenil)-2-trichloromethylpyridine 210 ml of absolute toluene. Was heated in an inert atmosphere at 70°C. for 15 hours. The mixture was cooled in a stream of argon was added 0.655 g (3.5 mmol) of 1-(2-vinylbenzyl)pyrrolidine. Was heated in an inert atmosphere for 6 hours. The mixture was cooled and filtered from the precipitate, toluene drove in vacuum and the residue suspended in 5.5 ml of hexane. The mixture was left at -20°C for 10 hours. The precipitate was filtered and washed with hexane and methanol. After drying in vacuum has been the catalyst N5 - 0.488 g (75%).

Example 10.

Analogously to example 9 was heated at 60°C for 15 hours, got the N5 after 0.437 g (67%)

Example 11.

In the flask 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-trimetilfenil)-2-trichloromethylpyridine 210 ml of absolute toluene. Was heated in an inert atmosphere at 70°C. for 15 hours. The mixture was cooled in a stream of argon was added 0.628 g (3.5 mmol) of N-methyl-N-(2-VI is ylbenzyl)ethylamine. Was heated in an inert atmosphere for 3.5 hours. The mixture was cooled and filtered from the precipitate, toluene drove in vacuum and the residue suspended in 5.5 ml of hexane. The mixture was left at -20°C for 10 hours. The precipitate was filtered and washed with hexane and methanol. After drying in vacuum has been the catalyst N1 - 0.510 g (78%).

Example 12.

Analogously to example 11 was heated at 60°C for 15 hours, got N1 0.503 g (77%)

Example 13.

In the flask 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-trimetilfenil)-2-trichloromethylpyridine 210 ml of absolute toluene. Was heated in an inert atmosphere at 70°C. for 15 hours. The mixture was cooled in a stream of argon was added 0.715 g (3.5 mmol) (2-methoxyethyl)methyl(2-vinylbenzyl)amine. Was heated in an inert atmosphere for 3.5 hours. The mixture was cooled and filtered from the precipitate, toluene drove in vacuum and the residue suspended in 5.5 ml of hexane. The mixture was left at -20°C for 10 hours. The precipitate was filtered and washed with hexane and methanol. After drying in vacuum has been the catalyst N2 - 0.540 g (81%).

Example 14.

Analogously to example 13 was heated at 60°C for 15 hours, got N2 0.542 g (81%)

Example 15.

In the flask 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-trimetilfenil)-2-trichloromethylpyridine 210 ml of absolute toluene. Was heated in an inert atmosphere at 70°C. for 15 hours. The mixture was cooled is in a stream of argon was added 0.710 g (3.5 mmol) of 4-(2-vinylbenzyl)of the research. Was heated in an inert atmosphere for 3.5 hours at 70°C. the Mixture was cooled and filtered from the precipitate, toluene drove in vacuum and the residue suspended in 5.5 ml of hexane. The mixture was left at -20°C for 10 hours. The precipitate was filtered and washed with hexane and methanol. After drying in vacuum has been the catalyst N3, the output - 0.522 g (79%).

Example 16.

Analogously to example 15 was heated at 60°C for 15 hours, got N3 0.516 g (78%).

Example 17.

In the flask Slanka 25 ml was placed 253 mg (0.26 mmol) of the complex In (2.2) Flask filled with argon and added a solution of 170 mg (0,94 mmol) N-methyl-N-(2-vinylbenzyl)ethylamine in 4 ml of absolute toluene. The reaction mixture was heated for 7 hours at 70°C, then cooled and kept off the solvent in vacuo. The residue was washed with methanol and dried in vacuum. Got the catalyst N1 - 135 mg (80%) in the form of green crystals.

Example 18.

Analogously to example 17 was heated at 60°C. for 7 hours, got N3, yield 127 mg (75%).

Example 19.

The catalyst N2, 1.6 mg (0.0024 mmol) was dissolved at 35°C in at 26.87 g (173 mmol) DCPD 99% (the molar ratio of catalyst: DCPD = 1:70000). The mixture was heated in a beaker at 50°C until the beginning of the exothermic reaction, and then at 200°C for 30 minutes Got solid transparent sample PGCPD odorless. The glass transition temperature of 168°C., the modulus of elasticity of 1.80 GPA, coefficient of linear thermal expansion 56,0, limit flowed the honor tensile 58,5 MPa, ultimate tensile stress, 43.5 MPa, elongation at yield point, 9.1%, elongation at break, 31.8%.

Example 20.

Analogously to example 19 with a ratio of a molar ratio DCPD:N2 100000:1.

Examples 21.

Analogously to example 19 with a ratio of a molar ratio DCPD:N2 150000:1.

Examples 22.

Analogously to example 19 at a molar ratio DCPD:N2 200000:1.

Technical characteristics of the obtained polymers are shown in the table.

DCPD/N2Tg, °CThe modulus of elasticity in bending, HPaCoeff-t linear thermal expansion µm/(m°C)Yield strength, MPaUltimate tensile stress, MPaRel. elongation at yield, %Rel. elongation at break, %
70000:11681,805658,543,59,1of 31.8
100000:11641,9185,4 57,043,58,999
150000:11561,8463,456,141,49,447,1
200000:11381,81

Industrial applicability

The catalyst metathetical polymerization of Dicyclopentadiene may be used in the production of politikoptionen. The resulting polymers have no smell, mechanical and thermal indices correspond to, and in some cases surpass those for industrial materials from polydicyclopentadiene.

1. The catalyst metathetical polymerization of Dicyclopentadiene formula:
,
where L is the Deputy selected from the group including:
,,

2. The method of obtaining a catalyst having the formula:
,
where L is the Deputy selected from the group including:
,,
characterized the clinical topics the catalyst for the verification of the second generation is subjected to interaction with (N,N-dialkyl-(2-vinylbenzyl) - amine or 4-(2-vinylbenzyl)morpholine in an inert atmosphere at temperatures of 60-85°C in the presence of a solvent, with a dialkyl - is methylethyl or methyl(2-methoxyethyl).

3. The method of obtaining a catalyst having the formula
,
where L is the Deputy selected from the group including:
,,,,
characterized in that triphenylphosphine ruthenium complex is subjected to interaction with 1,1-diphenyl-2-propyne-1-I in tetrahydrofuran at the boiling temperature 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-trimetilfenil)-2-trichloromethylpyridine and 2-(N,N-dialkylaminomethyl)styrene or 1-(2-vinylbenzyl)pyrrolidino or 4-(2-vinylbenzyl)morpholine in toluene when heated To 60-70°C in an inert atmosphere, with dialkyl represents diethyl-, or methylethyl-, or methyl(2-methoxyethyl)-.

4. The way metathetical polymerization is of ecyclopedia, characterized in that the polymerization is performed with the use of the catalyst according to claim 1 at a molar ratio of substrate:catalyst from 70000:1 to 200,000:1.



 

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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.

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3 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 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: method is described for producing electrocatalytic composition based on polypyrrole, involving polymerisation of pyrrole in the presence of platinised soot and surface-active additive, wherein the process is carried out under the effect of a radical initiator in an organic solvent at temperature of approximately 0°C, where the radical initiator is dicyclohexylperoxy dicarbonate, the surface-active additive is a product from reacting tertiary amine (CH3)2NR (R - aliphatic residue C12-14) and propylene oxide in ethyl cellosolve, containing an ionic component - quaternary ammonium base (CH3)2RN+R1(OH)-, where R1- propylene oxide oligomers and a nonionic component - propylene oligomers, and the organic solvent is ethyl cellosolve. After mixing, the components the mixture undergo vacuum treatment at 10-2 mm Hg, and during the initiation process, the system is exposed to an acoustic field with frequency 20 to 22 kHz. Polymerisation process of pyrrole is carried out until obtaining an electrocatalytic composition system which is soluble in organic solvents. In this process electrocatalytic composition is obtained, with the following ratio of said components, wt %: pyrrole 15 to 17; platinised soot 6 to 8; surface-active additive 8-10; dicyclohexylperoxy dicarbonate 5-7; ethyl cellosolve - the rest.

EFFECT: design of an efficient method of producing electrocatalytic composition based on polypyrrole.

2 cl, 2 ex

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