Method of preparing catalyst for metathesis polymerisation of dicyclopentadiene

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

 

The technical field to which the invention relates.

The present invention relates to ORGANOMETALLIC chemistry, in particular to a method for [1,3-bis-(2,4,6-trimetilfenil)-2-imidazolidinone]sodium dichloro (o-N,N-dimethylaminomethylphenol)ruthenium, which is a catalyst for the polymerization of cyclic olefins, in particular Dicyclopentadiene (DCPD).

The level of technology

Among the many known to date catalysts for metathesis of olefins, karbinovykh complexes of ruthenium - only a small number applicable to the polymerization of cyclic olefins, including Dicyclopentadiene (DCPD) [Coordination Chemistry Reviews 251 (2007) 765-794]. The simplest and most are commercially available catalysts of the verification of the first and second generation:

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. 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), zakluchalsya, the catalyst for the verification of the second generation or its derivatives are processed by the corresponding styrene in methylene chloride at 40C.

The disadvantage of existing catalysts is their high consumption and, as a consequence, the high cost of obtaining polydicyclopentadiene. Also a method of obtaining a catalyst according to the patent [US 2005261451] does not provide a high output, 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 of use of copper chloride to remove tricyclohexylphosphine and solvent is methylene chloride, which does not allow under normal conditions to raise the temperature of the reaction mixture above 40C. in Addition, methylene chloride contains impurities that reduce the yield of the final product.

Disclosure of inventions

The problem solved by the claimed invention is the development of a new efficient way to obtain (1,3-bis-(2.4,6-trimetilfenil)-2-imidazolidinone)sodium dichloro(o-N,N-dimethylaminomethylphenol)ruthenium (H) based on readily available source components.

The technical result is to increase the output at the final stage of preparation of the catalyst (H).

The technical result is achieved by the fact that triphenylphosphine ruthenium complex subject in which aerodactyl with 1,1-diphenyl-2-propyne-1-I in boiling tetrahydrofuran 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-dimethylaminomethyl)with styrene in toluene under heating in an inert atmosphere.

The claimed method of preparation of the catalyst (N) consists of 2 parts. In a new way instead of the hard-to-catalyst verification is used inteligency complex (In)obtained by an improved method.

The first part (the synthesis of the precursor consists of two stages, carried out without isolation of intermediate compounds - 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, H2IMesCCl3,] and the corresponding aminosterols with the formation of the target product. In a new way instead of the hard-to-catalyst for the verification of the first generation used inteligency complex (In)obtained by an improved method. The yield of the target about the ukta on the published works is 75-80%.

In our proposed method achieved output inteeligence complex 90-93% by reducing the number of stages is a process carried out without isolating inteligencia triphenylphosphino. Upgraded the allocation method of the product, which consists in leaching idealizing of the complex (In-II) acetone instead of hexane.

The implementation of the invention

Obtaining the claimed catalysts is carried out from triphenylphosphine complex of ruthenium chloride:

Triphenylphosphine complex of ruthenium chloride interacts with diphenylpropyl, forming identidentify ruthenium complex with triphenylphosphine ligands (In-1). Next (In-1) is introduced into the reaction tricyclohexylphosphine with subsequent treatment of a chloroform adduct of imidazole and aminosterols.

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

Stage IA is carried out at room temperature after stage I, except the selection of the product with the release of 90-93%.

Stage IIA is carried out in toluene at 70C with the release of 86-90%

Stage IIB is carried out in toluene at 65C With a yield of 40-50%

The invention is illustrated by the following examples.

Example 1.

The synthesis of the catalyst is carried out under conditions precluding helped it become one of the of the 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 obtained by the known method [Kolesnikov G.S. Synthesis of the vinyl derivatives of aromatic and heterocyclic compounds, 1960].

In the vessel Slanka volume of 1000 ml was placed 15 g (15.64 mmol) of RuCl2(PPh3), 5.3 g (at 25.45 mmol) of 1,1-diphenyl-2-propyne-1-ol unit filled with argon. Add 800 ml of absolute tetrahydrofuran and heated in an argon atmosphere for 3 hours under stirring. The mixture is evaporated in vacuum at room temperature for 50% and added in a stream of argon 14 g (50.04 mmol) tricyclohexylphosphine and stirred for 3 hours. The solvent is distilled off in vacuo and to the residue add 400 ml of acetone, after which the suspension is incubated at -20C for 10 hours. The precipitate is filtered and washed with methanol, 2 times with 70 ml, acetone 2 times in 80 ml cold 80 ml of hexane and dried in vacuum. Obtain 15.3 g inteeligence complex of ruthenium (In II) with output (14.83 mmol) (94.8%).

Example 2.

The reaction is carried out analogously to example 1, but without adding tricyclohexylphosphine. After complete evaporation of the tetrahydrofuran of pili is with 500 ml of hexane and stirred until complete suspension of sediment incubated at -20C for 10 hours. The precipitate is filtered and washed with hexane and dried in vacuum. Get inteeligence complex (In I) with the release of more than 98%.

Example 3.

In the vessel Slanka volume of 250 ml was placed 9.23 g (10 mmol) (In II) 7.232 g (17 mmol) chloroform adduct of imidazole 210 ml of absolute toluene. Was heated in an inert atmosphere at 70C. for 15 hours. The mixture was cooled in a stream of argon was added 4.036 g (25 mmol) of aminosterol. Was heated in an inert atmosphere for 3.5 hours. The mixture was cooled and was filtered, the toluene was distilled in vacuum and the residue suspended in 55 ml of hexane. The mixture was left at -20C for 10 hours. The precipitate was filtered and washed 215 ml hexane and 315 ml methanol. After drying in vacuum received 5.366 g (85.8%) of the complex (H) NMR1H (300 MHz, CD2Cl2) 1.75 (6N, s); 2.33 (S, usher. d); 4.01 (6N, user. s); 6.63 (1H, d, J 7.6 Hz); 6.94 m (5H); 7.11 (1H, t, J 7.6 Hz); 7.43 (1H, t, J 7.6 Hz); 18.58 S.(1H).

Industrial primenimosti

New carbene ruthenium complex [1,3-bis-(2.4,6-trimetilfenil)-2-imidazolidinone]sodium dichloro(o-N,N-dimethylaminomethylphenol)ruthenium can be used as catalyst for the production of polydicyclopentadiene polymerization disclosure cycle Dicyclopentadiene.

The method of producing catalyst metathetical polymerization of Dicyclopentadiene-[1,3-bis-(2,4,6-trimetilfenil)-2-imidazolidinone]sodium dichloro(o-N,N-dimethylaminomethylphenol is)ruthenium, characterized in that triphenylphosphine ruthenium complex is subjected to interaction with 1,1-diphenyl-2-propyne-1-I in boiling tetrahydrofuran in an inert atmosphere, and then tricyclohexylphosphine at room temperature and 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-dimethylaminomethyl)with styrene in toluene under heating in an inert atmosphere.



 

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