RU2596197C1 - Catalyst for ethylene oligomerisation to higher olefins c10-c30 and its preparation method - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: catalyst for ethylene oligomerisation to higher olefins C₁₀-C₃₀ is characterised by general formula (I), where substitute R is selected from the group: R=H, (4,5-bis(difenilfosfanil)-2H-1,2,3-triazole)-P,P)-trihlorohrom(III)-K1, R=(CH₂)₅CH₃, (4,5-bis(difenilfosfanil) -1-hexyl-1H-1,2,3-triazole)-P, P)-trihlorohrom(III)-K2, R=(CH₂)₂S(CH₂)₇CH₃, (4,5-bis(difenilfosfanil)-1-(2-octylthio) ethyl)-1H-1,2,3-triazole)-P,P)-trihlorohrom(III)-K3, R = CH₃, (4,5-bis(difenilfosfanil)-2-(methyl)-2H-1,2,3-triazole)-P,P)-trihlorohrom(III)-K4, R=n-Bu, (4,5-bis(difenilfosfanil)-2-(butyl)-2H-1,2,3-triazole)- P,P)-trihlorohrom(III)-K5, R = (CH₂)₅CH₃, (4,5-bis(difenilfosfanil)-2-(hexyl)-2H-1,2,3-triazole)- P,P)-trihlorohrom(III)-K6, R=(CH₂)₇CH₃, (4,5-bis (difenilfosfanil) -2-(octyl)-2H-1,2,3-triazole)- P,P)-trihlorohrom(III)-K7, R=allyl , (4,5-bis(difenilfosfanil)-2-(allyl)-2H-1,2,3-triazole)- P,P)-trihlorohrom (III)-K8, R = (CN₂)₄CH = CH₂, (4.5-bis (difenilfosfanil)-2-(hex-5-ene-1-yl)-2H-1,2,3-triazole)- P,P)-trihlorohrom(III)-K9, R=CH₂CN, (4,5-bis(difenilfosfanil)-2-(cianometil)-2H-1,2,3-triazole)- P,P)-trihlorohrom(III)-K10, R = CH₂C₆H₄CH = CH₂-o , (4,5-bis (difenilfosfanil)-2-(vinilbenzil)-2H-1,2,3-triazole)- P,P)-trihlorohrom(III)-K11, R=CH₂COOEt, (ethyl (2-(4,5-bis(difenilfosfanil)-2H-1,2,3-triazol-2-yl) acetate)- P,P)-trihlorohrom(III)-K12. Catalyst is obtained by treatment of commercially available source of chromium Cr(THF)₃Cl₃ corresponding to bis (difenilfosfanil)-1,2,3-triazole L1-L12, selected from the specified group of bis(difenilfosfanil)-1,2,3-triazoles. Process is carried out in a solution of tetrahydrofuran in an argon atmosphere; the obtained suspension is degassed and stirred during 17-18 hours at the room temperature. Obtained product is separated and dried.

EFFECT: this provides a high output of the catalyst and its purity, minimization of the side impurities during synthesis, higher yield of target fraction of higher olefins C₁₀-C₃₀ in oligomerisation of ethylene, as well as reduced amount of ethylene polymerisation products.

2 cl, 14 ex

Description

The invention relates to the field of homogeneous metal complex catalysis and relates, in particular, to a method for producing ethylene oligomerization catalysts to higher olefins, and also to its use, the possibility of producing higher C ₁₀ -C ₃₀ olefins from ethylene in maximum yield.

Higher olefins, mainly linear alpha olefins, are valuable multi-purpose raw materials having various fields of application. Alpha olefins are found as comonomers in the production of high-pressure and low-density polyethylene and linear low-pressure and high-density polyethylene, in the production of oxo-alcohols for the production of plasticizers, in the production of fatty acids, mercaptans, surfactants, as well as for the synthesis of polyalphaolefins which, after hydrogenation and refining processes, are used as basic components of synthetic lubricants and motor oils.

The literature discloses the use of complexes of various metals as a base for the catalyst systems in the oligomerization of ethylene to higher olefins are C ₁₀ -C _30.

A known ethylene oligomerization catalyst based on a complex of ferrous iron with a tridentate ligand with benzimidazole and pyridyl moieties. At the maximum content of C ₁₀₊ olefin fraction (34 wt.%) In products of ethylene pressure of 10 atm and a temperature of 20 ° C, process productivity is 60 kg / g _Fe · hr. Activated MMAO complexes of cobalt (II) with similar NNN ligands under the same conditions selectively catalyze the dimerization of ethylene with the formation of up to 90 wt.% Butene. Raising the process temperature to 60 ° C leads to a significant increase in the fraction of C ₄ olefins in the products to 70 wt.% And a significant decrease in the productivity of the process. L. Xiao, R. Gao, M. Zhang, Y. Li, X. Cao, W.-H. Sun. Organometallics, 2009, v. 28, p. 2225-2233.

The disadvantages of this catalyst include the low yield of the C ₁₀₊ fraction, as well as the sensitivity of the process to an increase in temperature.

Catalytic systems based on Fe (III) complexes with tridentate NNN ligands make it possible to achieve selectivity for the C ₈₊ fraction equal to 66 wt.%, However, the content of C ₁₆ -C ₂₆ olefins in the fraction is about 25 wt.%. The performance of the process is 31 kg / g _Fe · h. P. Nao, Y. Chen, T. Xiao, W.-H. Sun. J. Organomet. Chem., 2010, v. 695, p. 90-95.

The disadvantage of this method is the relatively low productivity of the process.

The known two-step process for the preparation of higher olefins using a catalytic system based on iron complexes with tridentate NNN ligands, activated by an aluminum compound and alkyl aluminum, patented by E.I. Dupont de Nemours and Company. The process of ethylene oligomerization with its participation leads to the formation of a mixture of alpha-olefins, from which a fraction containing predominantly 1-dodecene is isolated. The obtained olefin fraction undergoes further oligomerization catalyzed by Lewis acids to form polyolefins having a number average molecular weight in the range of 300-5000. US 2013/0012675 A1, 01/10/2013.

The disadvantages of the method include the two-stage process, as well as the need to use toxic Lewis acids.

It is known that additives of organozinc compounds to the catalytic system of ethylene oligomerization Cr (PNP) Cl ₃ / MAO (PNP = Ph ₂ PN (i-Pr) PPh ₂ ) are used to increase the productivity and selectivity of the process according to the fraction of C ₁₀ -C ₂₂ oligomers (35- 60 wt.%), As well as reducing the amount of by-produced polyethylene and its molecular weight. The process is carried out at a temperature of 25-45 ° C and an ethylene pressure of 14 bar. Kyung-sun Son, R.M. Waymouth Organometallics, 2010, v. 29, p. 3515-3520.

The disadvantage of this method is its two-stage nature, the need to use toxic organozinc reagents, and also not always high process performance.

Brookhart and M.J. employees Rachita, R.L. Huff, J.L. Bennett, M. Brookhart. Journal of Polymer Science: Part A: Polymer Chemistry, 2000, v. 38, p. 467-4640 synthesized a series of neutral nickel (II) phosphinosulfonamide complexes that catalyze the ethylene oligomerization reaction to form branched oligomers. The catalysts are active in various solvents, including toluene, methylene chloride, tetrahydrofuran, ethyl acetate and methanol, however, they show a decrease in activity at a process temperature above 40 ° C. The reaction is carried out at an ethylene pressure of 14-41 bar. The complexes do not require activation by organoaluminum compounds, while this ensures a low productivity of the catalyzed process of ethylene oligomerization.

The disadvantage of this method is its low productivity, as well as the sensitivity of the process to temperature increase.

A known method of producing linear alpha olefins by oligomerization of ethylene. In this process, a number of linear alpha olefins from C ₄ to C _{24+ are formed} . The process proceeds using tetra (aryloxy) titanium (Ti (OAr) ₄ ) and triphenylphosphine or trialkylphosphine in a 1: 2 ratio as a catalyst and dialkylaluminium chloride as an activator in a 36-fold molar excess in an inert aliphatic solvent. GL Tembe, M. Ravindranathan. Ind. Eng. Chem. Res., 1991, v. 30, p. 2247-2252.

The disadvantages of the method include the relatively low yield of the target fraction With ₁₀ -C ₃₀ .

Closest to the claimed one is a catalyst based on complexes of chromium (III) with tridentate NNN ligands activated by MMAO (Al / Cr = 1500), the catalytic oligomerization system based on it makes it possible to obtain ethylene oligomerization products with a content of C ₁₀₊ olefins fraction up to 74 wt. .%. The process is characterized by high productivity and is carried out at a temperature of 20 ° C and an ethylene pressure of 10 atm. L. Xiao, M. Zhang, Cao, W.-H. Sun. Polyhedron, 2010, v. 29, p. 142-147.

The disadvantage of the catalytic system based on this complex is the presence of a large number of polymerization reaction products.

The technical problem solved by the claimed group of inventions is to create a new effective chromium catalyst for the oligomerization of ethylene into higher olefins, providing a high yield of the target fraction C ₁₀ -C ₃₀ and the absence of a large number of ethylene polymerization products, as well as a method for its production, providing high yield and purity catalyst with high catalytic activity.

The technical result from the implementation of the claimed group of inventions is to ensure a high yield of the catalyst and its purity, minimize side impurities in the synthesis process, increase the yield of the target fraction of higher C ₁₀ -C ₃₀ olefins in the ethylene oligomerization reaction, and also reduce the amount of ethylene polymerization products.

The technical result is achieved by the fact that the Deputy R in the General formula:

is selected from the group: R = H, (4,5-bis (difenilfosfanil) -2H-1,2,3-triazole) -P, P) -trihlorohrom (III) - R1, R = (CH _{2) 5} CH ₃ , (4,5-bis (diphenylphosphanyl) -1-hexyl-1H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K2, R = (CH ₂ ) ₂ S (CH ₂ ) ₇ CH ₃ , (4,5-bis (diphenylphosphanyl) -1- (2-octylthio) ethyl) -1H-1,2,3-triazole) -P, P) -trichlorochrom (III) -K3, R = CH ₃ , (4,5-bis (diphenylphosphanyl) -2- (methyl) -2H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K4, R = n-Bu, (4, 5-bis (diphenylphosphanyl) -2- (butyl) -2H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K5, R = (CH ₂ ) ₅ CH ₃ , (4,5 bis (diphenylphosphanyl) -2- (hexyl) -2H-1,2,3-triazole) -P, P) trichlorochrom (III) - K6, R = (CH ₂ ) ₇ CH ₃ , (4,5- bis (diphenylphosphanyl) -2- (octyl) -2H-1,2,3-t iazole) -P, P) -trichlorochrom (III) - K7, R = allyl, (4,5-bis (diphenylphosphanyl) -2- (allyl) -2H-1,2,3-triazole) -P, P) trichlorochrom (III) - K8, R = (CH ₂ ) ₄ CH = CH ₂ , (4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2, 3-triazole) -P, P) -trichlorochrom (III) - K9, R = CH ₂ CN, (4,5-bis (diphenylphosphanyl) -2- (cyanomethyl) -2H-1,2,3-triazole) - P, P) trichlorochrom (III) - K10, R = CH ₂ C ₆ H ₄ CH = CH ₂ -o, (4,5-bis (diphenylphosphanyl) -2- (vinylbenzyl) -2H-1,2,3 triazol) -P, P) -trihlorohrom (III) - K11, R ² = CH ₂ COOEt, (ethyl (2- (4,5-bis (difenilfosfanil) -2H-1,2,3-triazol-2- il) acetate) -P, P) -trichlorochrom (III) -K12.

The claimed catalyst allows the oligomerization of ethylene in toluene, at a concentration of [Cr] in the reaction mixture from 10 to 60 μmol / L, with a molar ratio of [Cr]: [MAO] from 1: 1000 to 1: 300, at a temperature of from 50 ° C up to 120 ° С, ethylene pressure from 1 MPa to 5 MPa. The cycle time is from 30 minutes to 2 hours. The catalyst has a high catalytic activity and expands the technological capabilities in the production of higher olefins. Changing the concentration of the catalyst, temperature and pressure during the oligomerization process allows to obtain a fraction of C ₁₀ -C ₃₀ olefins with maximum yield and low content of ethylene polymerization products.

Examples of ethylene oligomerization using a catalyst based on the claimed complexes.

Example 1

In a Schlenk vessel under argon atmosphere, 3.6 ml of absolute toluene is added to 0.9 μmol of catalyst K1, and stirred for 15 min at room temperature. Then add 0.7 ml of a 1.2 M solution of methylaluminoxane (MAO) in toluene (1: 1000), mix for another 5 min and transfer to an autoclave in a stream of argon. The temperature and pressure of ethylene in the autoclave during the synthesis are kept constant (50 ° C, 1 MPa) for 30 minutes. Then depressurize and cool the autoclave to room temperature, add methanol and internal standard (n-decane), mix for 10 minutes. Then add 10 ml of a 20% aqueous solution of HCl and 5 ml of toluene, stirred for 1 h, the organic layer is separated and washed with water (5 × 50 ml). The polymer is separated, the organic fraction is dried with Na ₂ SO ₄ , analyzed.

The yield of the fraction of higher olefins With ₁₀ -C ₃₀ is 59.3 wt.% With a content of ethylene polymerization products of 3.3 wt.%.

Example 2. Oligomerization of ethylene using a catalyst based on a complex of chromium (III) K12

The example is similar to example 1, but instead of 0.9 μmol of catalyst K1, 5.4 μmol of catalyst K2 is added, 1.3 ml of a 1.2 M solution of MAO (1: 300) in toluene is added. The synthesis is carried out at a temperature of 120 ° C and an ethylene pressure of 6 MPa for 120 minutes

The yield of the fraction of higher olefins With ₁₀ -C ₃₀ is 60.4 wt.% With a content of ethylene polymerization products of 1.8 wt.%.

In accordance with the task developed a method for producing the claimed catalyst.

A method of preparing a catalyst of the above formula involves treating a commercially available chromium source Cr (THF) ₃ Cl ₃ with the corresponding bis (diphenylphosphanyl) -1,2,3-triazole L1-L12 selected from the desired bis (diphenylphosphanyl) -1,2,3- group triazoles:

where L1 is 4,5-bis (diphenylphosphanyl) -2H-1,2,3-triazole, L2 is 4,5-bis (diphenylphosphanyl) -1-hexyl-1H-1,2,3-triazole, L3 - 4 , 5-bis (diphenylphosphanyl) -1- (2-octylthio) ethyl) -1H-1,2,3-triazole, L4 - 4,5-bis (diphenylphosphanyl) -2- (methyl) -2H-1,2 , 3-triazole, L5 - 4,5-bis (diphenylphosphanyl) -2- (butyl) -2H-1,2,3-triazole, L6 - 4,5-bis (diphenylphosphanyl) -2- (hexyl) -2H -1,2,3-triazole, L7 - 4,5-bis (diphenylphosphanyl) -2- (octyl) -2H-1,2,3-triazole, L8 - 4,5-bis (diphenylphosphanyl) -2- ( allyl) -2H-1,2,3-triazole, L9 - 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole, L10 - 4,5-bis (diphenylphosphanyl) -2- (cyanomethyl) -2H-1,2,3-triazole, L11 4,5-bis (diphenylphosphanyl) -2- (vinylbenzyl) -2H-1,2,3-triazole, L12-ethyl 2- (4,5-bis (diphenylphosphanyl) -2H-1,2,3-triazol-2-yl) acetate) in a solution of tetrahydrofuran (THF) in the atmosphere argon, the resulting suspension is degassed and stirred for 17-18 hours at room temperature, the resulting product is isolated and dried.

The output of the complex is up to 85 wt.%.

The invention is illustrated by the following examples.

Example 3. Obtaining catalyst K1

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. The solvent is absolutized by standard techniques and stored in an inert atmosphere. The purity of the catalysts is estimated on the basis of proton magnetic resonance spectra (1H NMR) and thin-layer chromatography TLC (hexane / ethyl acetate 4/1).

3.39 g (9.1 mmol) Cr (THF) ₃ Cl ₃ and 4.4 g (10.1 mmol) 4,5-bis (diphenylphosphanyl) -2- are placed in a 100 ml Schlenk flask equipped with a magnetic anchor (hex-5-en-1-yl) -2H-1,2,3-triazole L1. The flask is evacuated and filled with argon. In a stream of argon, 50 ml of absolute THF are added, the resulting suspension is degassed and stirred at room temperature for 18 hours. The solvent is evaporated, the residue is washed with hexane, and dried under vacuum. 3.9 g (71 wt.%) Of a blue-violet powder are obtained. T _mp> 250 ° C. C ₂₆ H ₂₁ Cl ₃ CrN ₃ P ₂ . Calculated: C 52.42 H 3.55; N, 7.05. Found: C, 52.66; H 3.99; N, 7.44.

Example 4. Obtaining catalyst K2

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1 take 5.29 g (10.1 mmol ) 4,5-bis (diphenylphosphanyl) -1-hexyl-1H-1,2,3-triazole L2. Obtain 5.1 g (82 wt.%) Blue-violet powder. _Mp > 250 ° C. C ₃₂ H ₃₃ Cl ₃ CrN ₃ P ₂ . Calculated: C 56.53; H 4.89; N, 6.18. Found: C 56.37; H 5.29; N, 5.94.

Example 5. Obtaining catalyst K3

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1 take 6.2 g (10.1 mmol ) 4,5-bis (diphenylphosphanyl) -1- (2-octylthio) ethyl) -1H-1,2,3-triazole L3. 4.4 g (80 wt.%) Of a blue-violet powder are obtained. _Mp > 250 ° C. C ₃₆ H ₃₉ Cl ₃ CrN ₃ OP ₂ S. Calculated: C 56.29; H 5.38; N, 5.47. Found: C 55.88; H 5.91; N, 5.38.

Example 6. Obtaining catalyst K4

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1, 4.98 g (10.1 mmol) are taken ) 4,5-bis (diphenylphosphanyl) -2- (methyl) -2H-1,2,3-triazole L4. 3.9 g (71% by weight) of a dark blue powder are obtained. _Mp > 250 ° C. C ₂₇ H ₂₃ Cl ₃ CrN ₃ P ₂ . Calculated: C 53.18; H 3.80; N, 6.89. Found: C, 52.79; H 4.24; N, 6.72.

Example 7. Obtaining catalyst K5

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1, 4.98 g (10.1 mmol) are taken ) 4,5-bis (diphenylphosphanyl) -2- (butyl) -2H-1,2,3-triazole L5. Obtain 4.1 g (69 wt.%) Of blue powder. _Mp > 250 ° C. C ₃₂ H ₃₃ Cl ₃ CrN ₃ P ₂ . Calculated: C 55.28; H 4.48; N, 6.45. Found: C 54.89; H 4.84; N, 5.98.

Example 8. Obtaining catalyst K6

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1 take 5.29 g (10.1 mmol ) 4,5-bis (diphenylphosphanyl) -2- (hexyl) -2H-1,2,3-triazole L6. 5.82 g (85% by weight) of blue powder are obtained. T _pl > 250 ° C. C ₃₂ H ₃₃ Cl ₃ CrN ₃ P ₂ . Calculated: C 56.53; H 4.89; N, 6.18. Found: C 56.37; H 5.29; N, 5.94.

Example 9. Obtaining catalyst K7

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1 take 5.55 g (10.1 mmol ) 4,5-bis (diphenylphosphanyl) -2- (octyl) -2H-1,2,3-triazole L7. Obtain 5.3 g (77 wt.%) Of a blue-violet powder. T _pl > 250 ° C. C ₃₄ H ₃₇ Cl ₃ CrN ₃ P ₂ . Calculated: C 57.68; H 5.27; N, 5.94. Found: C 57.31; H 5.56; N, 5.54.

Example 10. Obtaining catalyst K8

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1 take 4.8 g (10.1 mmol ) 4,5-bis (diphenylphosphanyl) -2- (allyl) -2H-1,2,3-triazole L8. 5.8 g (78 wt.%) Of blue powder are obtained. _Mp > 250 ° C. C ₂₉ H ₂₅ Cl ₃ CrN ₃ P ₂ . Calculated: C 54.78; H 3.96; N, 6.61. Found: C 55.20; H 4.01; N, 6.43.

Example 11. Obtaining catalyst K9

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1, take 5.24 g (10.1 mmol4 , 5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L9. 4.93 g (72 wt.%) Of a blue-violet powder are obtained. T _mp > 250 ° C. C ₃₂ H ₃₁ Cl ₃ CrN ₃ P _2. Calculated: C 56.70; H 4.61; N 6.20. Found: C 56.29; H 5.96; N6.14.

Example 12. Obtaining catalyst K10

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1 take 4.8 g (10.1 mmol ) 4,5-bis (diphenylphosphanyl) -2- (cyanomethyl) -2H-1,2,3-triazole L10. 4.2 g (72 wt.%) Of a blue-violet powder are obtained. _Mp > 250 ° C. C ₂₈ H ₂₂ Cl ₃ CrN ₄ P ₂ . Calculated: C 52.98; H, 3.49; N, 8.83. Found: C, 52.07; H, 3.61; N, 8.65.

Example 13. Obtaining catalyst K11

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1 take 5.6 g (10.1 mmol ) 4,5-bis (diphenylphosphanyl) -2- (vinylbenzyl) -2H-1,2,3-triazole L11. Obtain 5.0 g (77 wt.%) Of blue powder. _Mp > 250 ° C. C ₃₅ H ₂₉ Cl ₃ CrN ₃ P ₂ . Calculated: C 59.05; H, 4.11; N, 5.90. Found: C, 58.79; H, 4.02; N, 5.75.

Example 14. Obtaining catalyst K12

The example is similar to example 3, but instead of 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole L1 take 5.3 g (10.1 mmol ) 2- (4,5-bis (diphenylphosphanyl) -2H-1,2,3-triazol-2-yl) acetate L12. 4.9 g (79 wt.%) Of blue powder are obtained. T _pl > 250 ° C. C ₃₀ H ₂₇ Cl ₃ CrN ₃ O ₂ P _2. Calculated: C 52.85; H, 3.99; N, 6.16. Found: C, 52.91; H, 4.04; N, 6.00.

Ethylene oligomerization catalysts can be used to produce C ₁₀ -C ₃₀ higher olefin fractions, which are a valuable multi-purpose raw material with various applications.

Claims (2)

1. The catalyst for the oligomerization of ethylene into higher olefins With ₁₀ -C ₃₀ General formula:

characterized in that the substituent R is selected from the group: R = H, (4,5-bis (diphenylphosphanyl) -2H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K1, R = (CH ₂ ) ₅ CH ₃ , (4,5-bis (diphenylphosphanyl) -1-hexyl-1H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K2, R = (CH ₂ ) ₂ S (CH ₂ ) ₇ CH ₃ , (4,5-bis (diphenylphosphanyl) -1- (2-octylthio) ethyl) -2,3-triazole) -P, P) -trichlorochrom (III) - K3, R = CH ₃ , (4,5-bis (diphenylphosphanyl) -2- (methyl) -2H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K4, R = n-Bu, (4,5-bis (diphenylphosphanyl) -2- (butyl) -2H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K5, R = (CH ₂ ) ₅ CH ₃ , ( 4,5-bis (diphenylphosphanyl) -2- (hexyl) -2H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K6, R = (CH ₂ ) ₇ CH ₃ , (4,5-bis (diphenylphosphanyl) -2- (octyl) -2H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K7, R = allyl, (4,5- bis (diphenylphosphanyl) -2- (allyl) -2H-1,2,3-triazole) -P, P) trichlorochrom (III) - K8, R = (CH ₂ ) ₄ CH = CH ₂ , (4,5 bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K9, R = CH ₂ CN, ( 4,5-bis (diphenylphosphanyl) -2- (cyanomethyl) -2H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K10, R = CH ₂ C ₆ H ₄ CH = CH ₂ -o, (4,5-bis (diphenylphosphanyl) -2- (vinylbenzyl) -2H-1,2,3-triazole) -P, P) -trichlorochrom (III) - K11, R = CH ₂ COOEt, (ethyl (2- (4,5-bis (diphenylphosphanyl) -2H-1,2,3-triazol-2-yl) acetate) -P, P) -trichlorochrom (III) - K12. 2. A method of producing a catalyst according to claim 1, characterized in that a commercially available source of chromium Cr (THF) ₃ Cl _{3 is} treated with the corresponding bis (diphenylphosphanyl) -1,2,3-triazole L1-L12 selected from a given group of bis (diphenylphosphanyl ) -1,2,3-triazoles:

where L1 is 4,5-bis (diphenylphosphanyl) -2H-1,2,3-triazole, L2 is 4,5-bis (diphenylphosphanyl) -1-hexyl-1H-1,2,3-triazole, L3 - 4 , 5-bis (diphenylphosphanyl) -1- (2-octylthio) ethyl) -1H-1,2,3-triazole, L4 - 4,5-bis (diphenylphosphanyl) -2- (methyl) -2H-1,2 , 3-triazole, L5 - 4,5-bis (diphenylphosphanyl) -2- (butyl) -2H-1,2,3-triazole, L6 - 4,5-bis (diphenylphosphanyl) -2- (hexyl) -2H -1,2,3-triazole, L7 - 4,5-bis (diphenylphosphanyl) -2- (octyl) -2H-1,2,3-triazole, L8 - 4,5-bis (diphenylphosphanyl) -2- ( allyl) -2H-1,2,3-triazole, L9 - 4,5-bis (diphenylphosphanyl) -2- (hex-5-en-1-yl) -2H-1,2,3-triazole, L10 - 4,5-bis (diphenylphosphanyl) -2- (cyanomethyl) -2H-1,2,3-triazole, L11 4,5-bis (diphenylphosphanyl) -2- (vinylbenzyl) -2H-1,2,3-triazole, L12-ethyl 2- (4,5-bis (diphenylphosphanyl) -2H-1,2,3-triazol-2-yl) in a solution of tetrahydrofuran in argon atmosphere, the resulting suspension is degassed and stirred for 17-18 hours at room temperature, the resulting product is isolated and dried.