RU2393171C1 - Dicyclopentadiene metathesis polymerisation catalyst, preparation method thereof and polymerisation method - Google Patents

Abstract

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

Description

The invention relates to the field of catalysis and relates to the production of a metathesis polymerization catalyst for dicyclopentadiene (DCPD).

A number of metathesis polymerization catalysts with controlled catalytic activity are known, published by Grubbs and patented by the California Institute of Technology [UNG THAY; SCHRODI YANN, 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].

Catalysts are used to prepare polymers from cycloolefins and bicycloolefins by a metathesis polymerization reaction with a ring opening at a molar ratio of monomer: catalyst in the range from 30,000: 1 to 40,000: 1.

The high activity of these catalysts makes it difficult to use them in the polymerization of DCPD, since the catalyst particles are covered with a layer of the formed 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 indicators of the polymer - polydicyclopentadiene (PDCPD).

A known method of producing a catalyst for the metathesis polymerization of dicyclopentadiene (US 2005261451 2005-11-24), which consists in the fact that the second-generation Grubbs catalyst or its derivatives are treated with appropriate styrene in methylene chloride at 40 ° C.

The disadvantage of the method according to patent US 2005261451 is the low yield of the target product, which is from 50 to 65% in terms of the first generation catalyst. This is due to the multi-stage synthesis and the imperfection of the technique.

From the above patent, a method for metathesis polymerization of dicyclopentadiene is also known, which consists in the fact that the polymerization of dicyclopentadiene is carried out at a ratio of monomer: catalyst of not higher than 40,000: 1.

The problem solved by the claimed invention is to create a new effective catalyst for the metathesis polymerization of dicyclopentadiene, which allows to reduce its consumption by increasing the solubility in the monomer, its production method, which provides an increase in the yield of the catalyst, as well as the method of polymerization of dicyclopentadiene.

In accordance with the task created a catalyst for the metathesis polymerization of dicyclopentadiene, having the formula:

,

,

where L is a Deputy selected from the group:

,

,

,

,

The structure and purity of the obtained compounds is confirmed by ¹ H NMR:

(300 MHz, CDCl ₃ ) δH: 0.48 (3H, t, J 7.1 Hz), 1.64 (3H, s), 1.97 (4H, m), 2.35-2.93 ( 16H, m), 3.24 (1H, m), 4.03 (4H, m), 5.26 (1H, d, J 14.4 Hz), 6.55 (1H, d, J 7.2 Hz), 6.90-7.1 (6H, m), 7.41 (1H, t, J 7.2 Hz), 18.70 (1H, s).

Supporting data for [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o-N, N-methylethylmethoxyaminomethylphenylmethylene) ruthenium of the formula:

(300 MHz, CDCl ₃ ) δH: 1.81 (3H, s), 2.19-2.58 (18H, m), 2.96-3.14 (6H, m), 3.38 (1H, m), 3.95 (1H, m), 4.04 (4H, m), 5.34 (1H, d, J 13.7 Hz), 6.58 (1H, d, J 7.3 Hz) 6.95-7.13 (6H, m), 7.46 (1H, t, J = 7.3 Hz), 18.75 (1H, s).

(300 MHz, CDCl ₃ ) δH: 1.56 (2H, s), 2.06 (2H, m), 2.32-2.75 (16H, 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, 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 in efficiency to the catalysts disclosed in the patent [US 2005261451] and allow to obtain polydicyclopentadiene with high consumer properties with a molar ratio of monomer: catalyst from 70,000: 1 to 200,000: 1, while for known catalysts this ratio is 30,000: 1 and 40,000: 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

, где

where

,

,

,

,

,

,

the second generation (GII) Grubbs catalyst is reacted 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, while dialkyl-represents methylethyl or methyl (2-methoxyethyl).

To obtain a catalyst having the formula

,

,

where L is a Deputy selected from the group:

,

,

,

,

,

,

,

,

The ruthenium triphenylphosphine complex was reacted with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran at the boiling point of the solvent in an inert atmosphere, and then with a tricyclohexylphosphine at room temperature in an inert atmosphere, the formed ruthenium indenylidene complex was isolated, which was sequentially in one the reactor was 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 to toluene e when heated to 60-70 ° C in an inert atmosphere, while dialkyl- is diethyl- or methylethyl- or methyl (2-methoxyethyl) -.

This method consists of 2 parts. Instead of the expensive Grubbs catalyst, the indelide complex In (1.2), obtained by an improved technique, is used.

The first part (precursor synthesis) consists of two stages, which are carried out without isolating the intermediate product - the synthesis of the ruthenium indenylidene triphenylphosphine carbene complex by treating RuCl ₂ (PPh ₃ ) _{3 with} diphenylpropinol and obtaining the tricyclohexylphosphine complex from it. The second part involves treating this ruthenium complex with an N-heterocyclic carbene ligand: [1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine, H ₂ IMesHCCl ₃ ] and the corresponding aminostyrene to form the desired product. In this method, instead of the first-generation Grubbs catalyst, an indelide complex (In1.2) is used, obtained by an improved method. The yield of the target product for published works is 75-90%.

In our proposed method, the yield of an indenylidene complex of 90-93% is achieved by reducing the number of stages — the process was carried out without isolation of the indelidene triphenylphosphine complex. The product isolation method was modernized, which consists in washing the Indenylidene complex In (1.2) with acetone instead of hexane.

where L is a Deputy selected from the group:

,

,

,

,

,

,

,

,

The method of metathesis polymerization of dicyclopentadiene is that the polymerization is carried out using the claimed catalyst with a molar ratio of substrate: catalyst from 70,000: 1 to 200,000: 1. Carrying out metathesis polymerization using this catalyst allows to reduce the consumption of the catalyst by increasing its solubility in the monomer, since the catalyst is well soluble in the monomer at 35 ° C.

The preparation of the catalyst is carried out by the interaction of the second generation Grubbs catalyst (G II) and the corresponding amine derivative - 2-vinylbenzylamine in an inert atmosphere at a temperature of 60-85 ° C in the presence of a solvent

Scheme of this process:

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

The preparation of catalysts from the triphenylphosphine complex of ruthenium chloride is carried out according to the scheme:

where L is a Deputy selected from the group:

The triphenylphosphine complex of ruthenium chloride interacts with diphenylpropinol to form the rheniumdenylidene complex with triphenylphosphine ligands In (1.1). Further, In (1.1) is reacted with tricyclohexylphosphine followed by treatment with a chloroform adduct of imidazole and aminostirol.

Stage 1 is carried out in 99% yield by boiling RuCl ₂ (PPh ₃ ) with the corresponding carbinol in tetrahydrofuran.

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

Stage 2.1 is carried out in toluene at 60-70 ° C with a yield 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 carried out using the claimed catalyst with a molar ratio of substrate: catalyst from 70,000: 1 to 200,000: 1. The catalyst was dissolved at 35 ° C. in DCPD. Then the resulting mixture is heated at a temperature of 50 ° C for 20 min, then 200 ° C for 30 min

The invention is illustrated by the following examples.

The synthesis of the catalyst was carried out under conditions excluding the ingress of moisture and air into the reaction system. We used Schlenk equipment and reactors connected to a vacuum system and a dry argon line. Solvents: methylene chloride, toluene, hexane, methanol were absolutized 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-benzylamines were obtained by a known method [G. Kolesnikov Synthesis of vinyl derivatives of aromatic and heterocyclic compounds 1960].

Example 1

In a 25 ml Schlenk flask, 220 mg (0.26 mmol) of the second generation Grabbs catalyst (GII) was placed. The flask was filled with argon and a solution of 186 mg (0.91 mmol) (2-methoxyethyl) methyl (2-vinylbenzyl) amine in 4 ml of absolute toluene was added. The reaction mixture was heated for 10 minutes at 85 ° C, after which it was cooled and the solvent was distilled off in vacuo. The residue was washed with hexane and dried in vacuo. Catalyst N2 170 mg (98%) was obtained as green crystals. ¹ H NMR (300 MHz, CDCl ₃ ) δH: 1.81 (3H, s), 2.19-2.58 (18H, m), 2.96-3.14 (6H, m), 3.38 (1H, m), 3.95 (1H, m), 4.04 (4H, m), 5.34 (1H, d, J 13.7 Hz), 6.58 (1H, d, J 7.3 Hz), 6.95- 7.13 (6H, m), 7.46 (1H, t, J 7.3 Hz), 18.75 (1H, s).

Example 2

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

Example 3

In a 25 ml Schlenk flask was placed 200 mg (0.23 mmol) of the second generation Grabbs catalyst (GII). The flask was filled with argon and a solution of 140 mg (0.78 mmol) of N-methyl-N- (2-vinylbenzyl) ethylamine in 4 ml of absolute toluene was added. The reaction mixture was heated for 20 min at 85 ° C, after which it was cooled and the solvent was distilled off in vacuo. The residue was washed with methanol and dried in vacuo. Catalyst N1 was obtained - 125 mg (83%) as green crystals. ¹ H NMR (300 MHz, CDCl ₃ ) δH: 0.48 (3H, t, J 7.1 Hz), 1.64 (3H, s), 1.97 (4H, m), 2.35-2 93 (16H, m), 3.24 (1H, m), 4.03 (4H, m), 5.26 (1H, d, J 14.4 Hz), 6.55 (1H, d, J 7.2 Hz), 6.90-7.1 (6H, 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, yield 127 mg (84%)

Example 5

220 mg (0.26 mmol) of the second generation (GII) Grubbs catalyst was heated in 4 ml of absolute toluene with 186 mg (0.91 mmol) of 4- (2-vinylbenzyl) morpholine for 10 minutes at 85 ° C. The toluene was evaporated and 5 ml of hexane was added. The precipitate was filtered and washed with 4 ml of hexane and ice-cold methanol. Received 148 mg of 86% complex N3. ¹ H NMR (300 MHz, CDCl ₃ ) δH: 1.56 (2H, s), 2.06 (2H, m), 2.32-2.75 (16H, 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, yield N3 145 mg (83%).

Example 7

15 g (15.64 mmol) of RuCl ₂ (PPh ₃ ) ₂ , 5.3 g (25.45 mmol) of 1,1-diphenyl-2-propin-1-ol were placed in a 1000 ml Schlenk flask; the device was filled with argon. 800 ml of absolute tetrahydrofuran was added and boiled under argon for 3 hours with stirring. The mixture was evaporated in vacuo at room temperature by 50% and 14 g (50.04 mmol) of tricyclohexylphosphine were added in an argon stream, stirred for 3 hours. The solvent was distilled off in vacuo and 400 ml of acetone was added to the residue, after which the suspension was kept at -20 ° C for 10 hours. The precipitate was filtered off and washed successively with methanol, acetone, hexane, and dried in vacuo. 15.3 g of Indenylidene ruthenium complex In (1.2) were obtained in a yield (14.83 mmol) (94.8%).

In a Schlenk flask with a volume of 25 ml, 0.923 g (1 mmol) In (1.2) 0.723 g (1.7 mmol) of 1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine was added 210 ml of absolute toluene. Heated in an inert atmosphere at 70 ° C for 15 hours. The mixture was cooled, 0.662 g (3.5 mmol) of diethyl (2-vininylbenzyl) amine was added in a stream of argon. Heated in an inert atmosphere for 6 hours. The mixture was cooled and filtered off from the precipitate, toluene was distilled off in vacuo and the residue was 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 vacuo, catalyst N4 — 0.477 g (73%) was obtained.

Example 8

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

Example 9

In a Schlenk flask with a volume of 25 ml, 0.923 g (1 mmol) of In (1.2) 0.723 g (1.7 mmol) of 1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine was added 210 ml of absolute toluene. Heated in an inert atmosphere at 70 ° C for 15 hours. The mixture was cooled and 0.655 g (3.5 mmol) of 1- (2-vinylbenzyl) pyrrolidine was added in a stream of argon. Heated in an inert atmosphere for 6 hours. The mixture was cooled and filtered off from the precipitate, toluene was distilled off in vacuo and the residue was 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 vacuo, catalyst N5 — 0.488 g (75%) was obtained.

Example 10

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

Example 11

In a Schlenk flask with a volume of 25 ml, 0.923 g (1 mmol) In (1.2) 0.723 g (1.7 mmol) of 1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine was added 210 ml of absolute toluene. Heated in an inert atmosphere at 70 ° C for 15 hours. The mixture was cooled and 0.628 g (3.5 mmol) of N-methyl-N- (2-vinylbenzyl) ethylamine was added under argon flow. Heated in an inert atmosphere for 3.5 hours. The mixture was cooled and filtered off from the precipitate, toluene was distilled off in vacuo and the residue was 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 vacuo, catalyst N1 - 0.510 g (78%) was obtained.

Example 12

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

Example 13

In a Schlenk flask with a volume of 25 ml, 0.923 g (1 mmol) In (1.2) 0.723 g (1.7 mmol) of 1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine was added 210 ml of absolute toluene. Heated in an inert atmosphere at 70 ° C for 15 hours. The mixture was cooled and 0.715 g (3.5 mmol) of (2-methoxyethyl) methyl (2-vinylbenzyl) amine was added under argon flow. Heated in an inert atmosphere for 3.5 hours. The mixture was cooled and filtered off from the precipitate, toluene was distilled off in vacuo and the residue was 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 vacuo, catalyst N2 — 0.540 g (81%) was obtained.

Example 14

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

Example 15

In a Schlenk flask with a volume of 25 ml, 0.923 g (1 mmol) In (1.2) 0.723 g (1.7 mmol) of 1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine was added 210 ml of absolute toluene. Heated in an inert atmosphere at 70 ° C for 15 hours. The mixture was cooled and 0.710 g (3.5 mmol) of 4- (2-vinylbenzyl) morpholine was added in an argon stream. Heated in an inert atmosphere for 3.5 hours at 70 ° C. The mixture was cooled and filtered off from the precipitate, toluene was distilled off in vacuo and the residue was 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 vacuo, catalyst N3 was obtained; the yield was 0.522 g (79%).

Example 16

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

Example 17

253 mg (0.26 mmol) of In complex was placed in a 25 ml Schlenk flask (2.2). The flask was filled with argon and a solution of 170 mg (0.94 mmol) of N-methyl-N- (2-vinylbenzyl) ethylamine in 4 ml of absolute was added. toluene. The reaction mixture was heated for 7 hours at 70 ° C, after which it was cooled and the solvent was distilled off in vacuo. The residue was washed with methanol and dried in vacuo. Catalyst N1 — 135 mg (80%) was obtained in the form of green crystals.

Example 18

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

Example 19

Catalyst N2, 1.6 mg (0.0024 mmol) was dissolved at 35 ° C in 26.87 g (173 mmol) of 99% DCPD (molar ratio of catalyst: DCPD = 1: 70,000). The mixture was heated in a beaker at 50 ° C until the start of the exothermic reaction, then at 200 ° C for 30 minutes. A solid, transparent, odorless PDCPD sample was obtained. Glass transition temperature 168 ° C, elastic modulus 1.80 GPa, linear thermal expansion coefficient 56.0, tensile strength 58.5 MPa, tensile stress, 43.5 MPa, elongation at yield strength, 9.1%, elongation at break, 31.8%.

Example 20

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

Examples 21

Analogously to example 19 with a ratio of the molar ratio of DCPD: N2 150,000: 1.

Examples 22.

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

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

DCPD / N2 Tg, ° C Bending modulus, GPa The coefficient of linear thermal expansion, µm / (m ° C) Yield Strength, MPa Destructive stress, MPa Rel elongation in yield strength,% Rel elongation at break,% 70,000: 1 168 1.80 56 58.5 43.5 9.1 31.8 100000: 1 164 1.91 85,4 57.0 43.5 8.9 99 150,000: 1 156 1.84 63,4 56.1 41,4 9,4 47.1 200000: 1 138 1.81

Industrial applicability

The metathesis polymerization catalyst of dicyclopentadiene can be used in the production of polycyclopentadienene. The resulting polymers do not have an odor, mechanical and thermal indicators correspond, and in some cases surpass those for industrial materials from polydicyclopentadiene.

Claims (4)

1. The catalyst for the metathesis polymerization of dicyclopentadiene of the formula:

,
where L is a Deputy selected from the group including:

,

,

2. A method of producing a catalyst having the formula:

,
where L is a Deputy selected from the group including:

,

,

characterized in that the second-generation Grubbs catalyst is reacted 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, while dialkyl - represents methylethyl or methyl (2-methoxyethyl). 3. A method of producing a catalyst having the formula

,
where L is a Deputy selected from the group including:

,

,

,

,

characterized in that the triphenylphosphine ruthenium complex is reacted with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran at the 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 isolated, which is sequentially reacted in a single reactor with 1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine and 2- (N, N-dialkylaminomethyl) styrene or 1- (2-vinylbenzyl) pyrrolidine or 4- (2-vinyl benzyl) morpholine in toluene with heating at 60-70 ° C under an inert atmosphere, with dialkyl- represents diethyl-, or methylethyl- or methyl (2-methoxyethyl) -. 4. The method of metathesis polymerization of dicyclopentadiene, characterized in that the polymerization is carried out using the catalyst according to claim 1 with a molar ratio of substrate: catalyst from 70,000: 1 to 200,000: 1.