WO2011149388A1

WO2011149388A1 - Ruthenium catalyst for the metathesis polymerization of dicyclopentadiene (embodiments) and method for producing polydicyclopentadiene (embodiments)

Info

Publication number: WO2011149388A1
Application number: PCT/RU2011/000364
Authority: WO
Inventors: Василий Дмитриевич КОЛЕСНИК; Роман Витальевич АШИРОВ; Надежда Михайловна ЩЕГЛОВА; Роман Викторович ЯКИМОВ; Наталья Васильевна КИСЕЛЕВА; Мария Николаевна БОГОМОЛОВА
Original assignee: Закрытое Акционерное Общество "Сибур Холдинг"
Priority date: 2010-05-27
Filing date: 2011-05-26
Publication date: 2011-12-01
Also published as: RU2436801C1

Abstract

The invention relates to metal-organic chemistry and, more specifically, to novel ruthenium complex compounds which are used as catalysts for the metathesis polymerization of dicylcopentadiene. The catalysts are in the form of ruthenium complex compounds having as ligands 1,3-bis-(2,6-dimethylphenyl)-2-imidazolidinylidene or 1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene, two chlorine atoms and ortho-substituted benzylidene. The substituent in the benzylidene ligand is an amino-substituted methyl group, in which the dialkylamino-, di(2-hydroxyethyl)amino- and alkylphenylamino- groups as well as cyclic amines, in particular piperidine and morpholine, or alkyl phenyl amine serve as amines. The amine-containing substituent additionally coordinates to a ruthenium atom and forms a six-membered chelate ring. A method for producing polydicyclopentadiene using the above-mentioned catalysts is described. The invention makes it possible to reduce the unit consumption of the catalyst, thus reducing the cost of polydicyclopentadiene, and to control the start time of the polymerization process.

Description

RUTHENIUM CATALYST METATESIS POLYMERIZATION OF DICYCLOPENTADIENE (OPTIONS) AND METHOD FOR PRODUCING

POLYDicyclopentadiene (OPTIONS)

The invention relates to organometallic chemistry, in particular to new complexes of transition metals of group 8, 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.

The catalytic metathesis of olefins is a method that has recently become the subject of close attention, as a universal method for the formation of carbon-carbon bonds, which has been widely used in organic synthesis (R. N. Grubbs, Handbook of Metathesis, Volume 2 - Applications in Organic Synthesis Wiley-VCH, Weinheim, 2003) and Polymer Chemistry (RH Grubbs, Handbook of Metathesis, Volume 3 - Applications in Polymer Synthesis; Wiley-VCH, Weinheim, 2003). The metathesis reaction was widespread with the advent of highly active molybdenum and ruthenium complexes with a specific structure (R. N. Grubbs, Handbook of Metathesis, Volume 1 - Catalyst Development; Wiley-VCH, Weinheim, 2003).

One of these complexes are Grubbs catalysts of the first (Grl) and second (Grll) generations having the following structural formulas.

Grl grll

Of great interest is the metathesis polymerization of dicyclopentadiene to obtain polydicyclopentadiene.

Polydicyclopentadiene (PDCPD) is a promising thermoset having a number of unique mechanical properties and high inertness, which makes it possible to produce impact-resistant products of large sizes and complex shapes from it. The main disadvantages of PDCPD products obtained by the currently widely used Metton and Te1epe technologies are

SUBSTITUTE SHEET (RULE 26) they have a stable odor of monomer and a dark color, which limits their use. The introduction of new catalysts based on ruthenium carbenium complexes makes it possible to obtain polymers devoid of these disadvantages.

There is a catalyst for the metathesis polymerization of ring-opening cyclic compounds (California Institute of Technology, Patent Application Publication US 2005261451 24.1 1.05), which is a ruthenium complex of the following structure:

This catalyst has a long induction period during the metathesis polymerization, which allows for the controlled polymerization of dicyclopentadiene. When using this catalyst, polymerization begins after 25 minutes at a temperature of 30 ° C and a molar ratio of monomer: catalyst of 30,000: 1.

The disadvantage of this catalyst is the need to use large amounts of catalyst relative to the monomer to achieve a high degree of polymerization.

The closest structural catalyst is the metathesis polymerization catalyst for ring-opening cyclic compounds (California Institute of Technology, Patent Application Publication US 2005261451 24.1 1.05), which is a ruthenium complex of the following structure:

In the case of using the above catalyst, the metathesis polymerization of dicyclopentadiene begins after 4 minutes at 30 ° C and

SUBSTITUTE SHEET (RULE 26) the molar ratio of monomer: catalyst is 30,000: 1.

The disadvantage of the prototype catalyst is a short induction period, which makes it difficult to control the onset and progress of the polymerization process. The disadvantages of the prototype also include the need to use large quantities of expensive catalyst in relation to the monomer, which leads to an increase in the cost of the final product.

The objective of the invention is the creation of new effective catalysts for the controlled metathesis polymerization of dicyclopentadiene, as well as a method for producing polydicyclopentadiene.

The problem is solved in that a catalyst is proposed, which is a complex ruthenium compound having 1, 3-bisaryl-2-imidazolidinylidene, two chlorine atoms and ortho-substituted benzylidene as ligands. In this case, the aryl substituent in the 1, 3-bisaryl-2-imidazolidinylidene ligand is 2,6-dimethylphenyl, and the substituent in the benzylidene ligand is the amino-substituted methyl group, where the dialkylamino, di (2-hydroxyethyl) amino, alkylphenylamino acts as an amine -groups, as well as cyclic amines, namely piperidine and morpholine. The amino-containing substituent additionally coordinates to the ruthenium atom and forms a six-membered chelate cycle.

The catalyst has the following formula:

where X = (Alk) ₂ N, N (CH ₂ —CH ₂ —OH) ₂ , piperidine, morpholine, NAlkPh;

Alk = CH ₃ , C ₂ H ₅ ; PH = phenyl

A catalyst is also proposed which is a complex compound of ruthenium having 1, 3-bisaryl-2-imidazolidinylidene, two chlorine atoms and ortho-substituted benzylidene as ligands. In this case, aryl substitute with gel in 1, 3-bisaryl-2-imidazolidinylidene ligand

SUBSTITUTE SHEET (RULE 26) is 2,4,6-trimethylphenyl, and the substituent in the benzylidene ligand is an alkyl phenylamino substituted methyl group.

The catalyst has the general formula:

Alk = CH ₃ , C ₂ H ₅ ; Pb = phenyl

Owing to the original ligand environment, the claimed catalysts are active during the metathesis polymerization of dicyclopentadiene, with a molar ratio of catalyst: monomer from 1: 70,000 to 1: 250,000, are readily soluble in the monomer, have high thermal stability, are insensitive to impurities contained in the monomer, and are stable during storage , and also are steady at contact with oxygen and air humidity.

Also an object of the invention is a method for producing polydicyclopentadiene, which consists in the fact that the polymerization of dicyclopentadiene is carried out in the presence of the proposed catalysts to control the induction period of the polymerization process, with a molar ratio of monomer-catalyst of from 70,000: 1 to 250,000: 1. In addition, the technical result when implementing this method can be achieved by using [1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (2- (Гч [, Ы-bis (2-hydroxyethyl) amine k) benzylidene) ruthenium at a molar ratio of monomer-catalyst of 70,000: 1 to 250,000: 1 or [1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene | dichloro (o- (piperidin-1-methylmethyl) ) benzylidene) ruthenium at a molar ratio of monomer-catalyst of from 70,000: 1 to 250,000: 1.

Achievable technical result is expressed in a decrease in the consumption rate of the catalyst, which leads to a decrease in the cost of polydicyclopene gadiene, as well as the ability to control the time of the start of the polymerization process.

SUBSTITUTE SHEET (RULE 26) Example 1

Preparation of [1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro (2-PM, Y-dimethylaminomethyl) benzylidene) genius

The synthesis is carried out in an argon atmosphere. 3.60 g (4.5 mmol) of the first generation Grabbs catalyst (bis (tricyclohexylphosphine) dichloro (3-methylbut-2-enylidene) ruthenium) are placed in a 250 ml round bottom flask equipped with a magnetic stirrer, 2, 86 g (7.2 mmol) of 1, 3-bis- (2,6-dimethylphenyl) -2-trichloromethylimidazolidine and 90 ml of dry toluene. The reaction mass is stirred at a temperature of 75 ° C for 2 hours, after which 2.35 g (8.9 mmol) of o- (M, M-dimethylaminomethyl) styrene are added to the reaction flask and the reaction mass is stirred in this mode for another 2 ,5 o'clock. The reaction mass is removed from the glove box, filtered. The solvent is removed on a vacuum rotary evaporator. The residue is suspended in 80 ml of heptane, filtered. The powder is washed with heptane (10 ml), methanol (3x20) ml and dried in a vacuum oven at a temperature of 45 ° C. 2.09 g of a green catalyst are obtained. The yield is 74.4%.

The resulting catalyst has the following structural formula:

1 H NMR (CDC1 ₃ , 400 MHz), ppm: 18.65 (1 H, s); 7.43 (1 N, t, J; 7.6 Hz); 7.28-7.35 (2H, m); 7.18-7.26 (4H, m); 7.10 (1 N, t, J; 7.6 Hz); 6.93 (1 N, d, J 7.6 Hz); 6.67 (1 N, d, J 7.6 Hz); 4, 12 (6H, s); 2.54 (12H, s); 1, 86 (6H, s).

Synthesis of polydicyclopentadiene: 3.47 mg, (0.0058 mmol) [1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro (2- (L1, L-dimethylaminomethyl) benzylidene) ruthenium is dissolved in 100 , 0 g (757.5 mmol) of DCPD 97.0% (molar ratio of monomer: catalyst is 130,000: 1) at 25 ° C. The mixture is heated in aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 1 15 ° C.

SUBSTITUTE SHEET (RULE 26) Example 2

Preparation of [1, 3-6is- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro (2-HY, Y-diethylaminomethyl) benzylidene) ruthenium

The synthesis is carried out in an argon atmosphere. 2.00 g (2.5 mmol) 1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene (tricyclohexylphosphine) isopentylidene ruthenium dichloride is placed in a 100 ml round bottom flask equipped with a magnetic stirrer, air cooler and oil bath. , 60 ml of dry toluene and 0.95 g (5.0 mmol) of 2- (T, Y-diethylaminomethyl) styrene. The reaction mass is stirred at a temperature of 75 ° C for 2 hours, after which it is removed from the glove box and passed through a 60 A silica gel layer (silica gel mass 10 g, layer thickness 1 cm), the silica gel is washed with a mixture of toluene and dichloromethane in the ratio of dichloromethane: toluene, equal to 2: 1. The solvent is removed on a vacuum rotary evaporator. The residue was suspended in 20 ml of heptane, filtered and washed with heptane (2x10 ml). The obtained green powder is dried in a vacuum oven at a temperature of 45 ° C. 0.94 g of catalyst is obtained. The yield is 59.4%.

The resulting catalyst has the following structural formula:

1 H NMR (CDCb, 400 MHz), ppm: 1 8.63 (1 H, s); 7.44 (111, t, J 7.4Hz); 7.30-7.37 (2H, br s); 7, 19 (4H, m); 7.09 (1 N, t, J 7.4 Hz); 6.95 (1 N, d, J 7.4 Hz); 6.55 (1 N, d, J 7.4 Hz); 4.20 (2H, br s); 4.08 (4H, br.m); 2.92 (2H, q, J, 6.7); 2.70 (6H, s); 2.40 (6H, s); 1, 99 (2H, q, J 6.7 Hz); 0.46 (6H, t, J 7.3 Hz).

Synthesis of polydicyclopentadiene: 3, 13 mg (0.0050 mmol) [1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro (2- (S, diethylaminomethyl) benzylidene) ruthenium is dissolved in 100.0 g (757.5 mmol) of DCPD 97.0% (molar ratio of monomer: catalyst is 150,000: 1) at 25 ° C. The mixture is heated in aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg

SUBSTITUTE SHEET (RULE 26) (glass transition temperature) 120 ° C.

Example 3

Preparation of [1, 3-bis- (2,6-dimegylphenyl) -2-imidazolidinylidene1 dichloro (2-morpholinomethylbenzylidene) ruthenium

The synthesis is carried out in an argon atmosphere. 2.00 g (2.5 mmol) of 1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene) are placed in a 100 ml round bottom flask equipped with a magnetic stirrer, air cooler and oil bath.

(tricyclohexylphosphine) isopentylidene ruthenium dichloride, 60 ml of dry toluene, 1.03 g (5.0 mmol) of 2- (morpholinomethyl) styrene and 60 mg (0.6 mmol) of copper (I) chloride. The reaction mass is stirred at a temperature of 75 ° C for 4 hours, after which it is removed from the glove box and passed through a 60 A silica gel layer (silica gel mass 10 g, layer thickness 1 cm), the silica gel is washed with a mixture of toluene and dichloromethane in the ratio of dichloromethane: toluene, equal to 2: 1. The solvent is removed on a vacuum rotary evaporator. The residue was suspended in 20 ml of heptane, filtered and washed with heptane (2x 10 ml). The obtained green powder is dried in a vacuum oven at a temperature of 45 ° C. 0.86 g of catalyst is obtained. The yield is 53.8%.

The resulting catalyst has the following structural formula:

1 H NMR (CDCh, 400 MHz), ppm: 18.84 (1 H, s); 7.44 (1 S, g, J 7.4Hz); 7.37 (2H, m); 7.29 (4H, m); 7.20 (1 N, t, J 7.4Hz); 7.01 (1 N, d, J 7.4Hz); 6.61 (1 N, d, J 7.4Hz); 4, 18 (6H, s); 3.59 (2H, m); 3.27 (2H, m); 3, 10 (2H, m); 2.61 (14H, broad s); 2.10 (2H, m).

Synthesis of polydicyclopentadiene: 6.08 mg, (0.0095 mmol) [1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro (2-morpholinomethyl benzylidene) ruthenium is dissolved in 100.0 g (757, 5 mmol) DCPD 97.0% (molar ratio of monomer: catalyst is 80,000: 1) at 25 ° C. The mixture is heated in

SUBSTITUTE SHEET (RULE 26) aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 133 ° C.

Example 4

Obtaining \ KZ-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene dichloro (2-

(piperidi-1-methylmethyl) benzylidene) ruthenium

The synthesis is carried out in an argon atmosphere. 0.50 g (0.63 mmol) of 1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene) are placed in a 25 ml round bottom flask equipped with a magnetic stirrer, air cooler and oil bath.

(tricyclohexylphosphine) isopentylidene ruthenium dichloride, 15 ml dry toluene and 0.25 g (1, 2 mmol) of 2- (piperidi-1-methylmethyl) styrene. The reaction mass is stirred at a temperature of 75 ° C for 3 hours, after which it is taken out of the glove box. The precipitated green precipitate is filtered, washed with 10 ml of heptane and dried in a vacuum oven at a temperature of 45 ° C. 0.21 g of catalyst is obtained. The yield is 52.7%.

The resulting catalytic formula:

1 H NMR (CDCh, 400 MHz), ppm: 18.49 (1 H, s); 7.41 (1 H, t, J 7.4Hz); 7.28 (2H, brpm); 7.20 (4H, m); 7.08 (1 H, t, J 7.4Hz); 6.98 (1 H, J 7.4 Hz); 6.63 (1 H, J 7.4 Hz); 4.48 (2H, s); 4, 10 (4H, s); 2.2-2.8 (16H, m) 1, 55 (2H, m); 1, 45 (1 N, m); 1, 1 -1, 3 (1 N, m); 1, 0 (2 N, m).

Polydicyclopentadiene Synthesis: 5 mg (0.0078 mmol) [1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro (2- (piperidi-1-ylmethyl) benzylidene) ruthenium is dissolved in 0.2 ml dichloromethane, the resulting solution is mixed with 100.0 g (757.5 mmol) of DCPD 97.0% (molar ratio of monomer: catalyst is 100000: 1) at 25 ° C. The mixture is heated in

SUBSTITUTE SHEET (RULE 26) aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 149 ° C.

Example 5

Preparation of [1, 3-bis- (2A6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o-O-methyl-U-phenylaminomethylbenzylidene) ruthenium

The synthesis is carried out in an argon atmosphere. 0.30 g (0.43 mmol) of the third-generation Grubbs catalyst ((1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene) (bis) is dissolved in a 25 ml round bottom flask equipped with a magnetic stirrer -pyridine) isopentylidene ruthenium dichloride) in 10 ml of dry toluene, after which 273 mg (1, 1 mmol) of o- (N-methyl-α-phenylaminomethyl) styrene are added to the reaction flask. The reaction mixture is stirred for 2 hours at a temperature of 40 ° C and taken out of the glove box. The solvent is removed on a vacuum rotary evaporator. The residue is suspended in 15 ml of hexane, filtered, washed with hexane (10 ml), methanol (3x10 ml), dried in a vacuum oven at a temperature of 45 ° C. Obtain 0.1 1 g of a green catalyst. The yield is 37.9%.

The resulting catalyst has the following structural formula:

1 H NMR (CDCb. 400 MHz), ppm: 1 8.82 (1 H, s); 7.49 (1 H, t, J 6.9 Hz); 7.0-7.2

(9H, m); 6.86 (1 H, s); 6.68 (1 H, s); 6.66 (1 H, doublet, J = 7.6 Hz); 6.1 1 (1 N, d, J 12.8 Hz); 4.05 (2H, m); 3.86 (2H, m); 3.45 (1 H, doublet, J = 12.8 Hz); 2.83 (ZN, s); 2.70 (ZN, s); 2.40 (ZN, s); 2.35 (ZN, s); 2.18 (ZN, s); 2.05 (ZN, s); 1, 95 (ZN, s).

Synthesis of polydicyclopentadiene: 7.43 mg (0.0108 mmol) [1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o-1-methyl-Y-phenylaminomethylbenzylidene) ruthenium is dissolved in 10 , 0 g (75.75 mmol) of DCPD 97.0% (molar ratio of monomer: catalyst is 70,000: 1) at

SUBSTITUTE SHEET (RULE 26) 25 ° C. The mixture is heated in aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 123 ° C.

Example 6

Preparation of [1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene 1 dichloro (2- (Thr - methyl-phenylaminomethyl) benzylidene) ruthenium

The synthesis is carried out in an argon atmosphere. 0.50 g (0.63 mmol) 1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene) (tricyclohexylphosphine) is dissolved in a 25 ml round bottom flask equipped with a magnetic stirrer.

isopentylidene ruthenium dichloride in 15 ml of dry toluene, after which 349 mg (1.6 mmol) of 2- (N-Memri-N-phenylaminomethyl) styrene was added to the reaction flask. The reaction mixture is stirred for 3 hours at a temperature of 75 ° C and taken out of the glove box. The solvent is removed on a vacuum rotary evaporator. The residue is suspended in 20 ml of hexane, filtered, washed with hexane (20 ml), methanol (3x15 ml), dried in a vacuum oven at a temperature of 45 ° C. 0.119 g of a green catalyst is obtained. The yield is 45.4%.

The resulting catalyst has the following structural formula:

1 H NMR (CDCb, 400 MHz), ppm: 18.81 (W, s); 7.47 (1 N, t, J 6.9 Hz); 7.25-7.32

(2H, brpm); 7.0-7.2 (9H, m); 6.87 (1 H, s); 6.69 (1 N, s); 6.65 (1 H, doublet, J = 7.6 Hz); 6, 12 (1 N, d, J 12.8 Hz); 4.06 (2H, m); 3.87 (2H, m); 3.44 (1 N, d, J 12.8 Hz); 2.82 (ZN, s); 2.71 (ZN, s); 2, 18 (ZN, s); 2.06 (ZN, s); 1, 94 (ZN, s).

Synthesis of polydicyclopentadiene: 6.27 mg (0.0095 mmol) [1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro (2- (-methyl- - phenylaminomethyl) benzylidene) ruthenium Mw = 659, 65 g / mol is dissolved in 100.0 g (757.5 mmol) of DCPD 97.0% (molar ratio of monomer: catalyst

SUBSTITUTE SHEET (RULE 26) is 80,000: 1) at 25 ° C. The mixture is heated in aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 152 ° C.

Example 7

Preparation of 1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene dichloro (2-, bis (hydroxyethyl) aminomethyl) benzylidene) ruthenium

isopentylidene ruthenium dichloride in 15 ml of dry toluene, after which 346 mg (1, 6 mmol) of 2- (N, N-bis (hydroxyethyl) aminomethyl) styrene are added to the reaction flask. The reaction mixture is stirred for 3 hours at a temperature of 75 ° C, taken out of the glove box and passed through a 60 A silica gel layer (silica gel mass 10 g, layer thickness 1 cm), the silica gel is washed with a mixture of methanol and dichloromethane with a dichloromethane: methanol ratio of 50 : 1. The solvent is removed on a vacuum rotary evaporator. The residue was suspended in 10 ml of hexane, filtered, washed with pentane (10 ml), dried in a vacuum oven at a temperature of 45 ° C. Obtain 46 mg g of a green catalyst. The yield is 1 1, 2%.

The resulting catalyst has the following structural formula:

NMR III (CDC1 ₃ , 400 MHz), ppm: 17.75 (1 H, s); 7.28-7.36 (2H, brpm); 7.24 (1 H, t, J 7.5Hz); 7.08 (1 H, t, J 7.5); 7.01 (4H, m); 6.84 (1 H, d, J 7.5); 6.51 (1 H, d, J 7.5); 4.33 (1 H, doublet, J = 13.8 Hz); 4.01 (4H, s); 3.06 (1 N, m); 2.96 (2H, m); 2.85 (1 N, d, J 19.8 Hz); 2.47 (6H, s); 2.42 (6I, s); 2.25 (1 s, m); 1, 95 (2H, d, J, 10.2 Hz); 1, 69 (2H, d, J, 10.2 Hz).

Synthesis of polydicyclooyen gadiene: 4, 14 mg (0.0063 mmol) [1, 3-bis- (2.6-

SUBSTITUTE SHEET (RULE 26) dimethylphenyl) -2-imidazolidinylidene] dichloro (2- (, 1 - bis (hydroxyethyl) aminomethyl) benzylidene) ruthenium Mw = 657.64 g / mol is dissolved in 100.0 g (757.5 mmol) of DCPD 97.0% (molar ratio monomer: catalyst is 120,000: 1) at 25 ° C. The mixture is heated in aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 127 ° C.

Example 8

Synthesis of Polydicyclopentadiene

5.23 mg, (0.0076 mmol) [1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (2- (1, bis (2-hydroxyethyl) aminomethyl) benzylidene) ruthenium Mw = 687.64 g / mol is dissolved in 100.0 g (757.5 mmol) of DCPD 97.0% (molar ratio of monomer: catalyst is 100000: 1) at 25 ° C. The mixture is heated in aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 133 ° C.

Example 9

Synthesis of Polydicyclopentadiene

4.21 mg, (0.0063 mmol) [1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o- (piperidin-1-methylmethyl) benzylidene) ruthenium Mw = 667, 65 g / mol is dissolved in 100.0 g (757.5 mmol) of DCPD 97.0% (molar ratio of monomer: catalyst is 120,000: 1) at 25 ° C. The mixture is heated in aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 132 ° C.

SUBSTITUTE SHEET (RULE 26)

Claims

CLAIM

1. Ruthenium catalyst for the metathesis polymerization of dicyclopentadiene, which is a complex ruthenium compound having ligands 1, 3-bisaryl-2-imidazolidinylidene, two chlorine atoms and ortho-substituted benzylidene, characterized in that the aryl substituent is 1, 3-bisaryl- The 2-imidazolidinylidene ligand is 2,6-dimethylphenyl, and the substituent in the benzylidene ligand is an amino-substituted methyl group, where the dialkylamino, di (2-hydroxyethyl) amino or alkyl phenylamino group acts as an amine esky amine selected from piperidine and morpholine; moreover, the catalyst has the General form:

where X = (Alk) ₂ N, N (CH ₂ CH ₂ —OH) ₂ , piperidine, morpholine, NAlkPh;

Alk = CH ₃ , C ₂ H ₅ ; Pb = phenyl. ^''

2. Ruthenium catalyst for the metathesis polymerization of dicyclopentadiene, which is a complex ruthenium compound having 1, 3-bisaryl-2-imidazolidinylidene, two chlorine atoms and ortho-substituted benzylidene as ligands, characterized in that the aryl substituent is 1, 3-bisaryl- The 2-imidazolidinylidene ligand is 2,4,6-trimethylphenyl, and the substituent in the benzylidene ligand is an alkyl phenylamino substituted methyl group; the catalyst has the general formula:

SUBSTITUTE SHEET (RULE 26)

where Alk = CH ₃ , C ₂ S ₅ ; Pb = phenyl.

3. A method of producing polydicyclopentadiene, characterized in that the polymerization of dicyclopentadiene is carried out using a catalyst according to claim 1 or claim 2 with a molar ratio of monomer: catalyst from 70,000: 1 to 250,000: 1.

4. A method of producing polydicyclopentadiene, characterized in that the polymerization of dicyclopentadiene is carried out using the compound [1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidine ordene] dichloro (2- (M, bis) as a catalyst (2-hydroxyethyl) aminomethyl) benzylidene) ruthenium, of the formula:

at a molar ratio of monomer: catalyst from 70,000: 1 to 250,000: 1 5. A method for producing polydicyclopentadiene, characterized in that the polymerization of dicyclopentadiene is carried out using the compound [1, 3-bis- (2,4,6-trimethylphenyl) - as a catalyst 2-imidazolidine ylidene] dichloro (o- (piperidin-1-methylmethyl) benzylidene) ruthenium of the formula:

SUBSTITUTE SHEET (RULE 26)

at a molar ratio of monomer: catalyst from 70,000: 1 to 250,000: 1.

SUBSTITUTE SHEET (RULE 26)