RU2583790C1 - Catalyst for metathesis polymerisation of dicyclopentadiene, containing thiobenzylidene fragment and preparation method thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis and production of catalysts for metathesis polymerisation of dicyclopentadiene. Catalyst of general formula (1)

where substitute R is selected from: R = i-Pr, R = n-C-₈H₁₇, R = Ph or R = C₆H₄COOH-o. Method of producing catalyst includes following steps. Triphenylphosphine complex of ruthenium is reacted with 1,1-diphenyl-2-propyn-1-ol in tetrahydrofuran or dioxane at reflux temperature under an inert atmosphere, and then with tricyclohexylphosphine at room temperature in an inert atmosphere. Formed indenylidene complex of ruthenium is recovered and subsequently reacted with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and thiomethyl styrene selected from thiomethyl styrenes: S1 - isopropyl(2-vinylbenzyl)sulphide, S2 - octyl(2-vinylbenzyl)sulphide, S3 - phenyl(2-vinylbenzyl)sulphide, S4 - 2-((2-vinylbenzyl)thio)benzoic acid. Obtained product is separated and dried.

EFFECT: invention provides an increase in catalytic activity, high yield and purity of catalyst, minimisation of incidental impurities in synthesis process, broader process capabilities of polymerisation product of dicyclopentadiene and reception of polydicyclopentadiene with high application properties.

2 cl, 5 ex

Description

The invention relates to the field of homogeneous catalysis, in particular to a method for producing metathesis polymerization catalysts of dicyclopentadiene (DCPD) with high catalytic activity, and also to its use, the ability to control metathesis polymerization of DCPD.

The catalytic reaction of olefin metathesis in recent years has established itself as a universal method for the formation of C – C bonds and has found great application in organic synthesis and polymer chemistry (R. N. Grubbs, Handbook of Metathesis, Vol 2 and 3; Wiley VCH, Weiheim, 2003 )

The family of olefin metathesis reactions includes chain-closed metathesis (cyclization) (RCM), ring-opening metathesis polymerization (ROMP), cross-metathesis (CM), acyclic α, ω-diene metathesis (ADMET) (R. N. Grubbs , Handbook of Metathesis, Vol 1; Wiley VCH, Weiheim, 2003).

It has been shown that ruthenium alkylidene complexes (first and second generation Grubbs and Hoveid catalysts) catalyze various metathesis reactions (S. Nguyen, L. Johnson, R. Grubbs, J. Ziller. Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media., J. Am. Chem. Soc. 1992, 114 (10), 3974-3975; M. Scholl, S. Ding, Lee, W. Choon, R. Grubbs. Synthesis and activity of a new generation of ruthenium-based olefin metathesis catalysts coordinated with l, 3-dimesityl-4,5-dihydroimidazol-2-ylidene ligands., Org. Lett., 1999, 1 (6), 953-956; J. Kingsbury, J. Harrity, P. Bonitatebus, A. Hoveyda. A recyclable Ru-based metathesis catalyst. J. Am. Chem. Soc. 1999, 121 (4), 791-799; S. Garber, J. Kingsbury, B. Gray , and A. Hoveyda. Efficient and recyclable monomeric and dendritic Ru-based metathesis catalysts. , J. Am. Chem. Soc. 2000, 122, 8168-8179).

The first generation Grubbs catalysts based on ruthenium alkylidene complexes are used for ring opening polymerization of cyclo- and bicycloolefins by metathesis. Known methods for producing polydicyclopentadiene under the action of ruthenium catalysts - carbene complexes with phosphine ligands, which are characterized by good stability and efficiency, are 5 times higher than tungsten complexes, which allows the use of a molar ratio of monomer: catalyst up to 15000: 1 (WO 9960030 A1, 11/25/1999 and WO 9720865 A1, June 12, 1997).

The main disadvantage of ruthenium catalysts of the first generation is the low catalytic activity, which necessitates the use of a large amount of catalyst from 1: 8000 to 1: 15000.

The activity of ruthenium catalysts of the second generation is several times superior to catalysts of the first generation. Their disadvantages include their poor solubility, which, along with the high polymerization rate of dicyclopentadiene, makes their use difficult. The catalyst, not having time to dissolve in the monomer, is covered with a polymer layer - encapsulated and loses activity. This necessitates a substantial increase in catalyst consumption. In addition, in the manufacture of polydicyclopentadiene (PDCPD) products by injection molding, technological problems arise, since it is not possible to control the start time of the polymerization and the polymer formed too early can clog the feed units of the monomer and catalyst mixture.

A number of controlled catalytic activity metathesis polymerization catalysts are known, published by Grubbs and patented by the California Institute of Technology (complexes A and B) (A. Hejl, M. Day, R. Grubbs. Latent olefin metathesis catalysts featuring chelating alkylidenes II. Organomet. 2006, 25, 25 , p. 6149-6154; T. Ung, A. Hejl, R. Grubbs, Y. Schrodi. Latent Ruthenium olefin metathesis catalysts that contain an N-Heterocyclic carbene ligand. Organomet. 2004, 23, p. 5399-5401).

Catalysts are used to produce 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 disadvantages of these catalysts are similar to the disadvantages of complexes of the second generation.

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, which consists in the fact that the second-generation Grubbs catalyst or its derivatives are treated with appropriate styrene in methylene chloride at a temperature of 40 ° C. The metathesis polymerization of dicyclopentadiene begins after 4 minutes at 30 ° C and the monomer: catalyst molar ratio is from 30,000: 1 to 40,000: 1 (US 2005261451 A, 11.24.2005).

The disadvantage of this method is the low yield of the target product, which is due to the multi-stage synthesis and the imperfection of the method.

Known catalyst for the polymerization of dicyclopentadiene of the General formula

where NAlk _{2 is} selected from the group of amines (complex C).

The catalyst is prepared by reacting the ruthenium triphenylphosphine complex with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran or dioxane at the boiling point of the solvent in an inert atmosphere, and then the ruthenium indenylidene complex formed is isolated with tricyclohexylphosphine at room temperature in an inert atmosphere. Serial interaction with 1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine and the corresponding 2-vinylbenzylamine leads to the formation of the target product (RU 2393171 C1, 08.27.2010).

The metathesis polymerization of dicyclopentadiene begins after 4 minutes at 30 ° C and the monomer: catalyst molar ratio is from 30,000: 1 to 40,000: 1.

Known catalyst for the polymerization of dicyclopentadiene (DCPD), having the formula

where L is a substituent selected from the group of corresponding aminostirols.

The catalyst is prepared by reacting the ruthenium triphenylphosphine complex with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran or dioxane at the boiling point of the solvent in an inert atmosphere, and then the ruthenium indenylidene complex formed is isolated with tricyclohexylphosphine at room temperature in an inert atmosphere. Sequential interaction with 1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine and the corresponding 2-vinylbenzylamine leads to the formation of the target product (RU 2462308 C1, 09.27.2012).

Closest to the technical nature of the proposed is a metathesis polymerization catalyst (US 20100113722 A1, 05/06/2010) having the formula

where R-S is selected from the group of aliphatic or aromatic thiols.

The catalyst is prepared by reacting the corresponding thiostyrene with (1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidine) dichloro (phenylmethylene) - (tricyclohexylphosphine) ruthenium in the presence of copper chloride, boiling in a dichloromethane solution, followed by chromatographic isolation .

Its disadvantages include the high cost and complexity of the hardware design of the synthesis, as well as the insufficient activity of the catalyst.

The main disadvantages of the known catalysts for the production of polydicyclopentadiene and materials based on it are insufficient catalytic activity, difficulty in controlling the start time of the polymerization and the inability to involve modifying additives in the reaction, which leads to disruptions in the technological cycle and heterogeneity of the resulting product.

The technical problem solved by the invention is to create a new effective ruthenium catalyst for the metathesis polymerization of dicyclopentadiene with a thiobenzylidene group in the composition, which allows controlling the start time of the polymerization and the method for its preparation, providing a high yield and purity of the catalyst with high catalytic activity.

The technical result from the implementation of the group of inventions is to increase the catalytic activity of the catalyst with respect to DCPD and a wide range of additives used. Changing the concentration of the catalyst and the polymerization temperature allows you to set the start time and polymerization rate. This achieves a high yield of catalyst and its purity, minimizes side impurities in the synthesis process. All this allows you to expand technological capabilities in the polymerization of dicyclopentadiene and to obtain products from polydicyclopentadiene with high consumer properties.

The technical problem is solved by the fact that the Deputy R in the General formula

selected from the group: R = i-Pr, [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o-S-isopropylthiomethylphenylmethylene) ruthenium - K1, R = nC ₈ H ₁₇ , [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o-S-octylthiomethyl-phenylmethylene) ruthenium - K2, R = Ph, [1,3-bis- (2 , 4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o-S-phenylthiomethyl-phenylmethylene) ruthenium - K3 or R = C ₆ H ₄ COOH-o [1,3-bis- (2,4,6-trimethylphenyl ) -2-imidazolidinylidene] dichloro (o-8- (2-carboxyphenyl) thiomethyl-phenylmethylene) ruthenium-K4.

The claimed catalyst allows the polymerization of dicyclopentadiene with a molar ratio of substrate: catalyst from 20,000: 1 to 250,000: 1 in the temperature range from 0 ° C to 200 ° C. The cycle time is from 10 minutes to 4 hours. The polymerization cycle time and speed are controlled by the set temperatures in the indicated interval. The catalyst has a high catalytic activity, is chemically active in relation to a wide range of additives and expands the technological capabilities in the manufacture of products from polydicyclopentadiene.

An example of the polymerization of DCPD.

Example 1. A solution of 1.25 mg of catalyst K1 and 0.33 g (1.2 wt.%) Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxycinnamate) in 26.44 g of DCPD (molar ratio of DCPD : catalyst = 100000: 1) placed in an injection mold heated to a temperature of 40 ° C, raise the temperature to 200 ° C and maintain this temperature for 30 minutes A solid, transparent, odorless PDCPD sample was obtained. Glass transition temperature Tg 154 ° С, bending modulus 1.61 GPa, tensile strength: yield strength 59.3 MPa, breaking stress 49.7 MPa, elongation at break 92%. Izod impact strength with a notch of 4.6 kJ / m ² , shore hardness D83.

In accordance with the task developed a method for producing the claimed catalyst. The method for producing the catalyst of the above formula is carried out in two stages:

The first stage is the synthesis of the Indenylidene complex In (1.2) according to the following scheme:

The second stage involves the treatment of the ruthenium indenylidene complex with an N-heterocyclic carbene ligand: [1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine, H ₂ IMesHCCl ₃ ,] and the corresponding thiomethyl styrene selected from the given group of thiomethyl styrenes:

where S1 is isopropyl (2-vinylbenzyl) sulfide, S2 is octyl (2-vinylbenzyl) sulfide, S3 is phenyl (2-vinylbenzyl) sulfide, S4 - 2 - ((2-vinylbenzyl) thio) benzoic acid.

.

.

The resulting product is isolated and dried. The yield of catalyst is up to 74%. The invention is illustrated by the following examples.

Example 2

The synthesis of the catalyst is carried out under conditions excluding the ingress of moisture and air into the reaction system. They use Schlenk equipment and reactors connected to a vacuum system and a dry argon line. Solvents: methylene chloride, toluene, hexane, methanol are absolute according to standard methods and stored in an inert atmosphere. The purity of the catalysts is estimated based on proton magnetic resonance spectra (1H NMR) and thin-layer chromatography TLC (hexane / ethyl acetate 4/1).

15 g (15.64 mmol) of RuCl ₂ (PPh ₃ ) ₃ , 5.3 g (25.45 mmol) of 1,1-diphenyl-2-propin-1-ol are placed in a 1000 ml Schlenk vessel; the device is filled with argon. Add 800 ml of absolute tetrahydrofuran and boil 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 under argon flow and 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 a temperature of - 20 ° C for 10 hours. The precipitate is filtered off and washed with methanol 2 times 70 ml, acetone 2 times 80 ml and cold hexane 80 ml and dried in vacuum. 15.3 g of Indenylidene ruthenium complex In (1.2) are obtained in a yield of 14.83 mmol (94.8%).

Similarly, 14.8 g of In (1.2) were obtained with a yield of 92% by reaction in dioxane by boiling instead of tetrahydrofuran.

3.521 g (3.8 mmol) In (1.2) 1.942 g (4.56 mmol) 1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine 50 ml of absolute toluene are placed in a 100 ml Schlenk vessel . Heated in an inert atmosphere at a temperature of 70 ° C for 15 hours. The mixture is cooled and 1.1 g (5.71 mmol) of isopropyl (2-vinylbenzyl) sulfide-S1 are added under argon flow. Heated in an inert atmosphere for 6 hours. The mixture is cooled and filtered. The toluene is distilled off in vacuo and the residue is suspended in 25 ml of hexane. The mixture was kept at −20 ° C. for 10 hours. The precipitate was filtered off and washed with 3 × 8 ml of hexane and 2 × 8 ml of methanol. After drying under vacuum, 1.8 g of catalyst K1 is obtained in the form of a green powder. Catalyst yield 71%, pure according to TLC and NMR. 1 H NMR spectrum (600 MHz, CDCl ₃ ) δH, ppm: 1.04 (9H, s, SC (CH ₃ ) ₃ ), 1.92-2.84 (18H, m, 6CH ₃ Ar), 3.41 (1H, br s, SCH ₂ Ar), 4.11 (4H, br s, NCH ₂ CH ₂ N), 5.32 (1H, s, SCH ₂ Ar), 6.45 (1H d, J = 7.5 Hz, H _Ar ), 6.82-7.16 (6H, m, H _Ar ), 7.42 (1H, t, J = 7.5 Hz, H _Ar ), 18 93 (1H, s, Ru = CH).

Example 3

Carried out analogously to Example 2, but instead of isopropyl (2-vinylbenzyl) sulfide - S1 taken 1.5 g of octyl (2-vinylbenzyl) sulfide - S2. Catalyst K2 was obtained in an amount of 1.9 g in the form of a light green powder. Yield 68%, pure according to TLC and NMR. 1 H NMR spectrum (600 MHz, CDCl ₃ ) δH, ppm: 0.72-1.54 (17H, m, SC ₈ H ₁₇ ), 2.29-2.66 (18H, m, 6CH ₃ Ar) 3.73-4.01 (1H, s, SCH ₂ Ar), 4.10 (4H, s, NCH ₂ CH ₂ N), 4.55-4.75 (1H, s, SCH ₂ Ar), 6.59 (1H, d, J = 7.6 Hz, H _Ar ), 7.01-7.29 (6H, m, H _Ar ), 7.51 (1H, t, J = 7.5 Hz, H _Ar ), 18.98 (1H, s, Ru = CH).

Example 4

Carried out analogously to Example 2, but instead of isopropyl (2-vinylbenzyl) sulfide - S1 taken 1.3 g of phenyl (2-vinylbenzyl) sulfide - S3. The obtained catalyst K3 in the amount of 1.9 g in the form of a dark green powder. Yield 74%, pure according to TLC and NMR. 1H NMR spectrum (600 MHz, CDCl ₃ ) δH, ppm: 1.69 (3H, s, CH ₃ ), 1.88 (3H, s, CH ₃ ), 2.09 (3H, s, CH ₃ ), 2.33 (3H, s, CH ₃ ), 2.85 (3H, s, CH ₃ ), 2.95 (3H, s, CH ₃ ), 3.81 (2H, s, NCH ₂ CH ₂ N), 4.17 (2H, s, NCH ₂ CH ₂ N), 5.61 (1H, d, J = 11.44 Hz, SCH ₂ Ar), 5.81 (1H, s, SCH ₂ Ar ), 6.34 (1H, s, H _Ar ), 6.45 (s, 1H) 7.00-7.51 (8H, m, H _Ar ), 7.83 (2H, br.s, H _Ar ), 18.43 (1H, s, Ru = CH).

Example 5

Carried out analogously to Example 2, but instead of isopropyl (2-vinylbenzyl) sulfide - S1 taken 1.5 g of 2 - ((2-vinylbenzyl) thio) benzoic acid - S4. Catalyst K4 was obtained in an amount of 1.8 g as a dark green powder. Yield 65%, pure according to TLC and NMR. 1H NMR spectrum (600 MHz, CDCl ₃ ) δH, ppm: 2.16-2.79 (18H, m, 6CH ₃ Ar), 4.15 (4H, s, NCH ₂ CH ₂ N), 4 39 (1H, d, J = 11.44 Hz, SCH ₂ Ar), 5.02 (1H, d, J = 11.44 Hz, SCH ₂ Ar), 6.43 (1H, d, J = 7 6 Hz, H _Ar ), 6.89-7.36 (9H, m, H _Ar ), 7.44 (1H, t, J = 7.3 Hz, H _Ar ), 7.78 (1H, t , J = 7.5 Hz, H _Ar ), 18.94 (1H, s, Ru = CH).

Catalysts for metathesis polymerization of dicyclopentadiene can be used for the industrial production of products of various sizes from polydicyclopentadiene. 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 (2)

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

characterized in that the substituent R is selected from the group: R = i-Pr, [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o-S-isopropylthiomethylphenylmethylene) ruthenium - K1 , R = nC ₈ H ₁₇ , [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o-S-octylthiomethyl-phenylmethylene) ruthenium - K2, R = Ph, [1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o-S-phenylthiomethyl-phenylmethylene) ruthenium - K3 or R = C ₆ H ₄ COOH-o [1,3-bis- (2 , 4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (o-S- (2-carboxyphenyl) thiomethylphenylmethylene) ruthenium-K4. 2. The method of producing a catalyst according to claim 1, characterized in that the ruthenium triphenylphosphine complex is reacted with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran or dioxane at the boiling point of the solvent in an inert atmosphere, and then with tricyclohexylphosphine at at room temperature in an inert atmosphere, the formed ruthenium indenylidene complex is isolated, which is subsequently reacted with 1,3-bis- (2,4,6-trimethylphenyl) -2-trichloromethylimidazolidine and thiomethylstyrene selected from the group ti methyl styrenes:

where S1 is isopropyl (2-vinylbenzyl) sulfide, S2 is octyl (2-vinylbenzyl) sulfide, S3 is phenyl (2-vinylbenzyl) sulfide, S4 - 2 - ((2-vinylbenzyl) thio) benzoic acid, the resulting product is isolated and are dried.