Ruthenium catalyst for metathesis polymerisation of dicyclopentadiene and method of preparing said catalyst

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

 

The invention relates to ORGANOMETALLIC chemistry, in particular to new complexes of transition metals of the eighth group, which are used as catalysts for the polymerization of cyclic olefins, in particular Dicyclopentadiene (DCPD). The invention can be applied in the field of catalysis, organic synthesis and ORGANOMETALLIC chemistry.

Catalytic metathesis of olefins is a method that has recently become the subject of great attention, as a universal method of forming carbon-carbon bonds, which is widely used in organic synthesis (R.H.Grubbs, Handbook of Metathesis, Volume 2 - Applications in Organic Synthesis Wiley-VCH, Weinheim, 2003) and polymer chemistry (R.H.Grubbs, Handbook of Metathesis, Volume 3 - Applications in Polymer Synthesis; Wiley-VCH, Weinheim, 2003). Widespread reactions metathesis received with the advent of highly active molybdenium and ruthenium complexes with a specific structure (R.H.Grubbs, Handbook of Metathesis, Volume 1 - Catalyst Development; Wiley-VCH, Weinheim, 2003).

Some of these complexes are catalysts for the verification of the first (GrI) and the second (GrII) generations, having the following structural formula:

Of great interest is the metathesis reaction of Dicyclopentadiene with opening cycle and polymerization getting polydicyclopentadiene. Polydicyclopentadiene (PGCPD) is a promising thermosetting, the possession is the overall number of unique mechanical properties and high inertia, that enables us to produce from it a high-impact products of large size and complex shape. The main disadvantages of products from PGCPD received on common nowadays technologies "Metton and Telene are persistent smell of monomer and dark color, which limits their application. The introduction of new catalysts based on carbenium complexes of ruthenium allows to obtain polymers devoid of these shortcomings.

There is a catalyst metathetical polymerization of cyclic compounds with opening cycle (California Institute of Technology, Patent Application Publication US 2005261451, 24.11.05), which is a ruthenium complex of the following structure:

This catalyst has a long induction period during metathetical polymerization, which allows for the controlled polymerization of Dicyclopentadiene. When using this catalyst, the polymerization starts in 25 minutes at a temperature of 30°C and the ratio of catalyst:monomer 1:30000.

The disadvantage of this catalyst is the necessity of using large quantities of catalyst relative to the monomer to achieve a high degree of polymerization.

The closest catalyst structure and purpose is the catalyst metathetical polymerization of cyclic compounds is s disclosure cycle (California Institute of Technology, Patent Application Publication US 2005261451, 24.11.05), which is a ruthenium complex of the following structure:

In the case of the use of the above catalyst process metathetical polymerization of Dicyclopentadiene starts after 4 minutes at 30°C and the ratio of catalyst:monomer 1:30000.

The disadvantage of the catalyst of the prototype is a short induction period, making it difficult to control the beginning and the course of the polymerization process. The disadvantages of the prototype also includes the necessity of using large amounts of expensive catalyst relative to the monomer, which increases the cost of the final product.

Synthesis of karbinovykh complexes of ruthenium containing N-heterocyclic Kurbanova ligands usually go through a stage of intermediate education intermediate, which is the catalyst for the verification of the second generation (GrII).

There is a way to get karbonovogo complex of ruthenium, which consists in the fact that this intermediate (GrII) get in the interaction of the catalyst for the verification of the first generation (GrI) with the compound capable of generating in the reaction conditions N-heterocyclic Karben (Trnka, M.; Morgan, J.P.; Sanford, M. S.; Wilhelm, IE; Scholl, M.; Choi, T.-L.; Ding, S.; Day, M.W.; Grubbs, R.H. J. Am. Chem. Soc. 2003, 125, 2546-2558).

The disadvantage of this method I have is the need for an intermediate unstable compounds, generating N-heterocyclic Karben.

There is a way to get karbonovogo complex of ruthenium, which is that the intermediate catalyst for the verification of the second generation is formed by the interaction of the catalyst for the verification of the first generation with N-heterocyclic vinylcarbene, obtained by the action of a strong base on dihydroimidazolium salt (Frank Glorius "N-Heterocyclic Carbenes in Transition Metal Catalysis Series: Topics in Organometallic Chemistry, Vol.21 Berlin; New York: Springer, 2007).

The implementation of this method is limited to use as substrates and products of the compounds are stable in the presence of a strong base.

The task of the invention to provide an effective catalyst for the controlled metathetical polymerization of Dicyclopentadiene.

The problem is solved in that the proposed catalyst comprising a complex compound of ruthenium, having as ligands 1,3-dimethylimidazolidine, two chlorine atoms and substituted benzylidene. When this Deputy in benzilidene the ligand is aminosilane methyl group, where the amine are di(hydroxyalkyl)amino group, and cyclic amines, in particular piperidine. Aminecontaining Deputy additionally coordinated to the ruthenium atom and forms a six-membered chelate cycle.

The catalyst has a General formula

where X=N(Alk-OH)2, (CH2)5N

It is also an object of the invention is a method of producing a catalyst, which consists in the fact that 1,3-dimetil-4,5-dihydro-imidazole chloride successively in the same reactor is subjected to interaction with tert-piperonyl potassium catalyst for the verification of the first generation (GrI), and then listeriosis styrene.

Technical result achieved in the implementation of this method is to obtain a new catalyst product yield 20-60%. The output depends on the structure of aminosterol. The catalyst obtained by this method is stable in air and inert to most functional groups.

This method of preparation of the catalyst avoids intermediate synthesis and excretion unstable compounds, which is the source of N-heterocyclic vinylcarbene.

The claimed catalyst is active in the process metathetical polymerization of Dicyclopentadiene at a molar ratio catalyst:monomer 1:70000 to 1:250,000, it is soluble in the monomer, stable during storage, stable when exposed to oxygen and moisture of the air.

Obtaining the claimed catalyst from catalyst verification I (GrI) reactions

The present invention, and the catalyst is illustrated by examples of specific performance.

Example 1. Getting [1,3-bis-(2,4,6-trimetilfenil)-2-imidazolidinone]sodium dichloro(o-N,N-diethylaminobenzylidene)ruthenium

Synthesis is carried out in a glove box in argon atmosphere.

In glass of 100 ml dissolve 0,98 g (a total of 8.74 mmol) of tert-butoxide potassium in 50 ml of dry tetrahydrofuran, and then add 3,43 g (9,99 mmol) of 1,3-bis-(2,4,6-trimetilfenil)dihydroimidazolium chloride, stirred for 15 minutes. The solution is filtered and added to a round bottom flask of 250 ml, equipped with a magnetic stirrer, oil bath and air refrigerator, containing a solution of 5.0 g (6,24 mmol) of the catalyst for the verification of the first generation (bis-(tricyclohexylphosphine), sodium dichloro-(3-methylbut-2-enylidene)ruthenium) in 150 ml dry toluene. The reaction mass is stirred at a temperature of 80°C for 1.5 hours. Then add of 2.51 g (15.6 mmol) of N,N-diethylaminomethyl and stirred for 2.5 hours. The solvent is removed on a vacuum rotary evaporator. The residue is suspended in 100 ml of hexane, filtered, washed with hexane (2×30 ml), then with methanol (4×30 ml), dried. Get 2,44 g light green powder. The yield is 60%. 1H NMR (CDCl3, 400 MHz), ppm: 18,68 (1H, s); 7,42 (1H, t, J7,5 Hz); 7,07 (1H, t, J7,5 Hz); 6,99 (4H, s); 6,9 (1H, d, J7.5); 6,53 (1H, d, J7,5); is 4.21 (2H, s); 4,04 (4 H, m); only 2.91 (2H, m); 2.63 in (6N, s); 2.40 a (3H, s); 2,32 (6N, C); is 2.30 (3H, s); a 1.96 (2H, m); 0,43 (6N, t, J7.2).

By the above method were also obtained:

- [1,3-bis-(2,4,6-trimetilfenil)-2-imidazolidinone]sodium dichloro(2-morpholinosydnonimine)ruthenium

1H NMR (CDCl3, 400 MHz), ppm: 18,87 (1H, s); 7,38 (1H, t, J7,4 Hz); for 7.12 (1H, t, J7,4 Hz); 7,02 (4H, s); to 6.95 (1H, d, J7,4 Hz); 6,55 (1H, d, J7, 4 Hz); 4,11 (2H, s); 4,07 (4H, s); 3,50 (2H, m); 3,20 (2H, m); 3,05 (2H, m); 2,30-2,65 (N, m); is 2.05 (2H, m);

- [1,3-bis-(2,4,6-trimetilfenil)-2-imidazolidinone]sodium dichloro(2-(piperidin-1-ylmethyl)benzylidene)ruthenium

1H NMR (CDCl3, 400 MHz), ppm: 18,67 (1H, s); 7,40 (1H, t, J7,5 Hz); was 7.08 (1H, t, J7,5 Hz); 7,00 (4H, s); 6,97 (1H, d, J7,5 Hz); 6,62 (1H, d, J7,5 Hz); 4,48 (2H, s); 4,06 (4H, s); 2,2-2,7 (22N, m); 1,4-1,65 (6N, m);

- [1,3-bis-(2,4,6-trimetilfenil)-2-imidazolidinone]sodium dichloro(2-(N,N-bis(hydroxyethyl)aminomethyl)benzylidene)ruthenium

1H NMR (CDCl3, 400 MHz), ppm: 17,75 (1H, s); from 7.24 (1H, t, J7,5 Hz); 7,07 (1H, t, J7,5); 7,02 (4H, s); 6,83 (1H, d, J7,5); of 6.50 (1H, d, J7,5); to 4.33 (1H, d, J13,8 Hz); 4,01 (4H, s); 3,05 (1H, m); 2,95 (2H, m); 2,85 (1H, d, J9,8 Hz); 2,47 (6N, C); 2,43 (6N, C); 2,36 (6N, C); of 2.25 (1H, m); 1,95 (2H, d, J10,2 Hz); 1,68 (2H, d, J10,2 Hz).

Example 2. Catalytic properties [1,3-bis-(2,4,6-trimetilfenil)-2-imidazolidinone]sodium dichloro(o-N,N-diethylamino methylbenzylidene)ruthenium

Ruthenium complex (0.5 mg, 0,00076 mmol) is dissolved in 10.0 g (75,75 mmol) DCPD 97,0% (1:100000) at 25°C. the Mixture is heated in a beaker at 60°C for 15 min and 15 min at 180°is. Get a solid transparent sample odorless. Tg (glass transition) is 133°C, the module panel. Th 1.72 GPa; tensile strength tensile - 44.7 MPa.

1. Ruthenium catalyst metathetical polymerization of Dicyclopentadiene, representing the complex compound of ruthenium, having as ligands 1,3-dimethylimidazolidine, two chlorine atoms and substituted benzylidene, characterized in that the substituent in benzilidene the ligand is aminosilane methyl group, where the amine is di(hydroxyalkyl)amino group, and piperidine; the catalyst has the General formula:

where X=N(Alk-OH)2, (CH2)5N, where Alk is unbranched saturated hydrocarbon chain containing 2 carbon atom.

2. The method of preparation of the catalyst according to claim 1, in which the catalyst for the verification of the first generation interacts with 1,3-dimetil-4,5-dihydro-imidazole chloride in the presence of a base, wherein sequentially in the same reactor 1,3-dimetil-4,5-dihydro-imidazole chloride is subjected to interaction with tert-piperonyl potassium catalyst for the verification of the first generation (GrI), and then listeriosis styrene.



 

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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

Epoxide composition // 2383568

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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.

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EFFECT: method increases output of product.

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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:

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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: polyethylene in form of ethylene homopolymers and copolymers of ethylene with α-olefins and having molecular weight distribution range Mw/Mn from 6 to 100, density from 0.89 to 0.97 g/cm3, weight-average molecular weight Mw from 5000 g/mol to 700000 g/mol and from 0.01 to 20 branches/1000 carbon atoms and at least 0.5 vinyl groups/1000 carbon atoms, where the fraction of polyethylene with molecular weight less than 10000 g/mol has degree of branching from 0 to 1.5 branches on the side chains, longer than CH3/1000 carbon atoms. The catalyst composition for synthesis of polyethylene in paragraph 1 consists of at least two different polymerisation catalysts, from which A) is at least one polymerisation catalyst based on monocyclopentadienyl complex of a group IV-VI metal, in which the cyclopentadienyl system is substituted by an uncharged donor (A1) of formula Cp-Zk-A-MA (II), where variables assume the following values: Cp-Zk-A is , MA is a metal which is selected from a group consisting of titanium (III), vanadium, chromium, molybdenum and tungsten, and k equals 0 or 1, or with hafnocene (A2), and B) is at least one polymerisation catalyst based on a ferrous component with a tridentate ligand containing at least two ortho-, ortho-disubstituted aryl radicals (B).

EFFECT: obtaining polyethylene with good mechanical properties, possibility for processing and high content of vinyl groups.

27 cl, 12 ex, 2 tbl, 5 dwg

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