RU2660907C1 - Catalyst for producing synthetic high viscosity oils and method for preparation thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a technology for the preparation of catalysts for producing synthetic high viscosity base polyalphaolefin oils. To produce synthetic base polyalphaolefin oils, provided is a catalyst that is a mixture of modified methylaluminoxane MMAO-12 in toluene and bis(isopropylcyclopentadienyl)zirconium dichloride in toluene, having a molar ratio Al/Zr=(250–1,000), amount of Zr is (36-9) mcmol. Method for producing a catalyst is characterized in preparing isopropylcyclopentadiene ligand by mixing dimethylsulfoxide, potassium hydroxide and cyclopentadiene and stirring the reaction mass, cooling the mass to a temperature of 2–6 °C, adding isopropyl bromide and stirring for 1–3 hours, adding 5 % solution of hydrochloric acid, extraction with hexane, washing with water from dimethylsulfoxide residues, drying, distillation and selection of fractions in the temperature range of 50–63 °C, adding diethyl ether and a solution of butyllithium in hexane to the obtained isopropylcyclopentadiene, stirring for 30–60 minutes, adding zirconium (IV) chloride at 0–2 °C, stirring the mixture for 2–3 hours, further heating to room temperature and adding hexane to the resulting mass, filtering the mixture and separating from the filtrate bis(isopropylcyclopentadienyl)zirconium dichloride, which is dissolved in toluene, and the resulting solution is mixed with the modified methylaluminoxane MMAO-12 in toluene, based on calculation of molar ratio Al/Zr=(250–1,000), Zr – in an amount (36-9) mcmol, with constant stirring for 1–10 minutes. High conversion of octene-1 (more than 80 %) and production of synthetic polyalphaolefin base oils of different viscosity range from 15.09 to 115.9 mm²/s at 100 °C with high viscosity indexes (from 186 to 246) and low pour points (-47…-59 °C) are provided.

EFFECT: preparation of a catalyst exhibiting enhanced catalytic activity.

2 cl, 1 tbl, 5 ex

Description

The invention relates to the petrochemical industry, and in particular to a technology for the preparation of catalysts for synthetic high-viscosity polyalphaolefin base oils.

Currently, in connection with the development of technology, the development and implementation of new modern equipment, changes in the operating conditions of machines and mechanisms, the requirements for modern lubricants and, therefore, for base oils, which form the basis of commercial lubricants, are being tightened.

In order to improve the properties of synthetic lubricants, research has been focused on the development of fluids with the necessary viscosity characteristics in a wide temperature range, improved viscosity index, high thermal and oxidative stability, and low pour points.

Polyalphaolefin oils are the most demanded type of synthetic lubricating oils that fully meet the increased technical and environmental requirements for lubricating oil bases.

A special segment is occupied by highly viscous polyalphaolefin oils, which are oligomers predominantly obtained in the process of oligomerization of C ₆ -C ₂₀ alpha olefins in the presence of homogeneous and heterogeneous catalysts.

Highly viscous PAOMs are used as the basic bases for the production of synthetic and semi-synthetic motor, transmission, compressor and vacuum oils, oils for marine engines with a long service life and the basis of lubricants with a wide range of operating temperatures.

Of great importance is the type of catalyst used in the oligomerization process of alpha-olefins, which affects both the yield of the target product and the rheological properties of the obtained PAOM.

One of the significant directions at present is the development of metal complex catalysts that provide highly viscous products with a wide viscosity range with improved properties, which expands the potential field of application of lubricants.

A distinctive advantage of such catalysts is their high activity in the process of oligomerization of alpha olefins, namely, a high yield of polyalphaolefin base oils per gram of catalyst, as well as the production of highly viscous products with desired properties that are highly uniform.

The catalyst system based on a metallocene catalyst for the synthesis of highly viscous PAO typically includes a catalyst precursor (precursor) and a co-catalyst. Alkyl aluminum compounds or borates are often used as co-catalysts.

Among a wide range of metallocene catalytic systems, it is necessary to distinguish alkyl-substituted cyclopentadienyl nonbridge precursors, which, in comparison with indenyl and fluorenyl precursors, are characterized by high stability and ease of preparation:

In the catalysts of this type, the following type of compound can act as a precursor:

Where M is a metal of group IV (Ti, Zr, Hf);

X is an alkyl or halogen substituent (e.g. methyl, ethyl, chlorine);

L is a substituted cyclopentadienyl ligand:

The method for the synthesis of alkyl substituted cyclopentadienyl zirconium (titanium, hafnium) dichloride involves the following two steps.

1. Synthesis of alkylcyclopentadiene.

2. Synthesis of alkyl substituted cyclopentadienyl zirconium (titanium, hafnium) dichloride.

The following methods are known for producing an alkylcyclopentadienyl ligand.

1. Preparation of cyclopentadienyl magnesium chloride in tetrahydrofuran followed by the addition of alkyl bromide (for example, butyl bromide, propyl bromide, ethyl bromide).

2. Preparation of cyclopentadienyl sodium (potassium) followed by alkyl bromide (eg, butyl bromide, propyl bromide, ethyl bromide).

A known method of preparing a catalyst for producing synthetic base oils - bis (n-propylcyclopentadienyl) zirconium dichloride, according to which the ligand - n-propylcyclopentadiene was prepared in the following way.

6.5 kg of propyl bromide (53 mol) and 7 kg of THF were added to a 200 L stainless steel high pressure reactor with a jacket and stirrer. The mixture was heated to reflux to 64 ° C and CpMgCl feed was added, titrated to 1.06 molar content of CpMgCl / MeMgCl in THF with a CpMgCl content of 87% of Grignard reagent. To the resulting mixture, 50 kg of CpMgCl were added under pressure for 2.5 hours. 2.25 kg of glacial acetic acid and 9.1 kg of water were mixed in a 200 l glass receiving vessel. 40 minutes after completion of the CpMgCl feed, a mixture of acetic acid was added to a solution of propylcyclopentadiene in the first pressure vessel. When supplying raw materials, a strong exothermic effect was initially observed. At the end of the feed, the solution turned yellow transparent.

To this mixture was added 0.5 kg of sodium chloride and the solution was stirred for two hours. The solution was kept for 15 minutes, and the lower turbid aqueous solution was taken into a 400 L stainless steel vessel. 1.4 kg of sodium carbonate, 4.5 kg of sodium chloride, 150 g of solid sodium hydroxide and 4.5 kg of water were added to the organic layer. This mixture was stirred for 3 hours, precipitated for 15 minutes, and the clear aqueous solution was taken into a stainless steel vessel. The mixture of two-water mixtures was extracted with 8 kg of diethyl ether, stirred for 15 minutes, precipitated for 15 minutes, and clear water was dumped into a plastic drum. The top layer of organic ether was returned to the first pressure vessel.

To this mixture was added 2 kg of sodium sulfate and the solution was stirred for 10 hours. The solution was filtered through a filter with a pore diameter of 1 μm into a 100 L stainless steel vessel, where the solution was separated from ether and residual cyclopentadiene in a packed column. The maximum temperature of the cube was 27 ° C. After distillation, the cyclopentadiene concentration in the bottom residue sample was less than 0.5%. The yield of propylcyclopentadiene was 72 wt.%. US 6175027 B1, publ. 01/16/2001.

A known method of preparing a catalyst for the production of synthetic base oils - bis (ethylcyclopentadienyl) zirconium dichloride, according to which the ligand - ethylcyclopentadiene was prepared in the following way. In a 1 L round bottom flask equipped with a magnetic stirrer and an argon feed tube, 25 g (1029 mmol) of magnesium metal compounds and 500 ml of diethyl ether were charged. 84 ml (1126 mmol) of ethyl bromide in 100 ml of diethyl ether were added dropwise over a period of 3 hours. The reaction mixture was refluxed for 1 hour and the magnesium metal was completely dissolved. 75 ml (919 mmol) of freshly distilled cyclopentadiene were added dropwise with vigorous stirring and at room temperature (about 25 ° C) over a period of 1 h and the resulting greenish suspension was heated under reflux overnight. The reaction mixture was kept at 0 ° C and 147 ml (1126 mmol) of diethyl sulfate was added dropwise, resulting in a gray precipitate. After 4-5 hours of stirring at room temperature, the resulting suspension was carefully diluted with 1 L of a saturated solution of NH ₄ Cl in water. The organic layer was separated, dried over Na ₂ SO ₄ and concentrated. The residue was purified by vacuum distillation (80 mbar) at a temperature of 35-38 ° C to obtain 36.4 g of pure ethyl cyclopentadiene in 41% yield as a mixture of isomers. EP 2204375, publ. 07/07/2010.

The disadvantages of these methods of preparing the catalytic system is a complex preparation procedure using Grignard reagent and the insufficiently high yield of cyclopentadienyl ligand.

Closest to the proposed technical solution is a method for the synthesis of a catalyst for producing synthetic base oils, which describes methods for producing various cyclopentadienyl ligands using ethylcyclopentadiene as an example for the preparation of bis (ethylcyclopentadienyl) zirconium dichloride. The isopropylcyclopentadiene ligand was prepared as follows: NaH (49.3 g, 1.23 mol, 1.02 mol equiv., 60% in mineral oil) was dissolved in THF (600 cm ³ ) and cooled to 0 ° C in 1 dm ³ flask flask. Freshly monomerised cyclopentadiene (80 g, 1.21 mol, 100 cm ³ ) was added dropwise to the base-solvent mixture over one hour. The mixture was allowed to stir at a predetermined temperature for another hour, then warmed to room temperature and allowed to stand overnight. The reaction mixture was again cooled to 0 ° C, stirred for 30 minutes. Isopropyl bromide (111.2 g, 1.02 mol equiv, 76 cm ³ ) in THF (100 cm ³ ) was added dropwise over 1 h, the resulting solution was stirred at a given temperature for another 2 h after addition of electrophile. The reaction mixture was warmed to room temperature and held for 14 hours. The resulting solution was filtered through a column filled with zeolite to separate white solid (NaBr). The filtrate was washed with distilled water (3 × 50 cm ³ ), the organic layer was extracted with hexane (3 × 20 cm ³ ). The combined organic mixtures were dried over MgSO ₄ and filtered through a glass filter to give a pale yellow solution. The homogeneous solution was subjected to fractional distillation to remove the solvent (hexane and toluene). When the temperature was raised to 180 ° C, a monomerized mixture of isopropylcyclopentadiene (55.8 g) was obtained as a colorless liquid, which was stored at a temperature of -60 ° C for subsequent use. The yield of isopropylcyclopentadiene was 74 wt.%. The synthesis of the catalyst bis (isopropylcyclopentadienyl) zirconium dichloride was carried out as follows. Substituted cyclopentadiene dimers were monomerized and reacted with n-BuLi to produce nucleophiles, which were then reacted with zirconium (IV) chloride to produce substituted metallocenes.

The Diels-Alder reaction for the substituted cyclopentadiene dimer was carried out by heating the monomer at a temperature of 160 ° C under reflux to collect the resulting colorless monomer. In a separate flask, a solution of n-BuLi (2 mol equiv.) In hexane (200 cm ³ ) was prepared and cooled to a temperature of 0 ° C. Monomeric substituted cyclopentadiene was dissolved in an equal volume of hexane and cooled to a temperature of 0 ° C, then added dropwise over 20 minutes to the starting hexane mixture. A white solid precipitated during the reaction. The reaction was carried out at a predetermined temperature for an hour, then the reaction vessel was warmed to room temperature. The solvent was removed under reduced pressure to obtain a residue, a white solid, which was dissolved in cold toluene (400 cm ³ ) and kept at 0 ° C (a light yellow homogeneous solution was obtained). Zirconium (IV) chloride (1 mol equiv.) Was added to the resulting solution in small portions for 40 min in a stream of nitrogen at a temperature of 0 ° C. The reaction mixture was kept at this temperature for 2 hours, then warmed to room temperature and allowed to stand overnight. The solution was filtered through a column of degassed zeolite (diatomaceous earth, kieselguhr, infusoria, mountain flour) in order to capture the resulting salts. The solvent was removed in vacuo to give isopropylcyclopentadienyl zirconium dichloride as a solid (light yellow to colorless. ORGANOMETALLIC CHEMISTRY OF SOME MANGANESE AND ZIRCONIUM COMPLEXES: A GREEN CHEMISTRY APPROACH, Sunnyboy Stanley Manzini, the A Stanley Stanzel Manzini University, A Stanney Stanzel Manzini, A Thean Stanley Manzini University, A Stanley Manzini of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Doctor of Philosophy, Johannesburg, 2005, p. 234-248.

This method of producing isopropylcyclopentadiene has several disadvantages. The method of preparation of the ligand consists of two stages. The first step is the synthesis of cyclopentadienyl sodium, which involves the use of metallic sodium (or sodium hydride) and dry tetrahydrofuran. Metallic sodium and tetrahydrofuran are low-hazard and moderately hazardous substances. However, hydrogen is released during the synthesis of cyclopentadienyl sodium, which belongs to hazard class 2 (highly hazardous substances). With insufficient tightness of the reactor, an explosive mixture with air can form and therefore, at this stage, special control of the process is required. It should also be noted that this stage requires the use of dry tetrahydrofuran. The regeneration of tetrahydrofuran requires its purification from by-products of synthesis and an additional stage of drying, which requires additional costs. During the reaction, sodium chloride is formed, which precipitates out, and a filtration step is required to remove it. Filtered sodium chloride with impurities of organic substances also requires further disposal.

The technical problem solved by this invention is the development of a method for preparing a catalyst of high catalytic activity in relation to the production of synthetic polyalphaolefin base oils, a wide range of viscosity and excellent performance, expressed in the conversion of octene-1 and the yield of the target oil fraction (alpha olefin).

The technical result achieved by the invention is to increase the catalytic activity of the catalyst, which allows to increase the conversion of octene-1 more than 80% in high viscosity synthetic base polyalphaolefin oils with kinematic viscosity in the range of 15.09 ÷ 415.9 mm ² / s at 100 ° C, viscosity indices from 186 to 246, pour points of minus 47 ° C - minus 59 ° C, density 0.8380-0.8433 g / cm ³ .

The technical result is achieved by the fact that to obtain synthetic polyalphaolefin base oils, a catalyst is proposed that is a mixture of modified methylaluminoxane MMAO-12 in toluene and bis (isopropylcyclopentadienyl) zirconium dichloride in toluene having a molar ratio Al / Zr = (250-1000), amount of Zr - (36-9), which is prepared as follows.

A ligand is prepared - isopropylcyclopentadiene - by mixing dimethyl sulfoxide, potassium hydroxide and cyclopentadiene and stirring the reaction mixture, cool it to a temperature of 2-6 ° C, add isopropyl bromide and mix for 1-3 hours, add a 5 wt.% Hydrochloric acid solution, carry out extraction with hexane, washing with water from the residues of dimethyl sulfoxide, drying, distillation and selection of the fraction in the temperature range of 50-63 ° C, diethyl ether and a solution of butyl lithium in hexane are added to the obtained isopropylcyclopentadiene, stirred for 20 hours 30-60 min, add zirconium (IV) chloride at a temperature of 0-2 ° C, mix the mixture for 2-3 hours, then warm to room temperature and add hexane to the resulting mass, filter the mixture and isolate bis from the filtrate ( isopropylcyclopentadienyl) zirconium dichloride, which is dissolved in toluene, and modified methylaluminoxane MMAO-12 in toluene is introduced into the resulting solution (manufactured by Sigma Aldrich, 7% A1 wt. in toluene), based on the calculation of the molar ratio Al / Zr = (250-1000) , the amount of Zr - (36-9) μmol, with constant stirring for 1-10 min

These distinguishing features are significant.

The ligand obtained by the proposed method provides a 25-30% higher yield of cyclopentadienyl ligand in comparison with the closest analogue and is safer since no hydrogen is released at the stage of potassium cyclopentadienyl production, which significantly improves process safety. It should be noted that the regeneration of dimethyl sulfoxide does not require its complete drying. In addition, this method of producing a catalyst using DMSO due to its lower cost is more economical than using THF.

To obtain synthetic polyalphaolefin base oils in the presence of the specified catalyst, which is a mixture of modified methylaluminoxane MMAO-12 in toluene (manufactured by Sigma Aldrich, 7% A1 wt. In toluene) and bis (isopropylcyclopentadienyl) zirconium dichloride in toluene having an Al / Zr molar ratio = (250-1000), the amount of Zr - (36-9) μmol, the process of co-oligomerization of propylene and octene-1 in the presence of toluene is carried out.

The use of propylene as a raw material, which is 3-4 times cheaper than alpha-olefins, can reduce the cost of highly viscous oils in comparison with the known analogues obtained mainly in the process of oligomerization of higher alpha-olefins.

The use of the specified catalyst and the conditions for the process of co-oligomerization of octene-1 and propylene provide higher catalytic activity of the catalyst, the yield of the target oil fraction and the quality of the resulting polyalphaolefin base oil.

To obtain highly viscous synthetic polyalphaolefin base oils, the process of co-oligomerization of octene-1 and propylene is carried out in an autoclave reactor at a temperature of 20-40 ° C in the presence of toluene.

In the process of co-oligomerization of octene-1 and propylene, high process indicators are achieved: the conversion of octene-1 is more than 80%, the yield of the target oil fraction is more than 78.0 wt.%.

The specified catalyst, depending on the conditions of the process of co-oligomerization of propylene and octene-1, provides polyalphaolefin base oils of various viscosity ranges from 15.09 to 115.9 mm ² / s at 100 ° C, viscosity indices from 186 to 246 and low pour points (minus 47 - minus 59 ° C).

The obtained synthetic polyalphaolefin base oils can be used as the basis for the production of high-reliability automotive and transmission oils, high-temperature industrial protective lubricants and circulating oils, anti-seize gear oils (gear oils), long-life compression oils, oils for gas turbine engines and lubricants with a wide range of temperatures operating at low temperatures.

The invention is illustrated by the following examples.

Example 1

To prepare the ligand - isopropylcyclopentadiene - in a 500 ml three-necked flask equipped with a thermometer, a dropping funnel and a reflux condenser, 84 g of dimethyl sulfoxide (DMSO), 12 g (0.21 mol) of potassium hydroxide (KOH) and 14.54 are charged g (0.22 mol) of cyclopentadiene. The reaction mass is stirred for 1.5 hours at room temperature. After stirring, the mixture was cooled to 3 ° C and 50 ml of hexane and 44.1 g (0.35 mol) of isopropyl bromide were added to the resulting solution of potassium cyclopentadienyl in an argon stream through a dropping funnel over 30 minutes. After the addition of all isopropyl bromide, the reaction mass is stirred for 2 hours. After this, 50 ml of a 5% hydrochloric acid solution are added to the reaction mass, and the organic layer is separated. The aqueous layer was extracted with two 50 ml portions of hexane. The combined organic layer was washed with water from DMSO residues 3 times in 100 ml, then dried over anhydrous calcium chloride and distilled. The target fraction is taken in the temperature range of 50-63 ° C at a pressure of 13.5 kPa. Obtain 14.4 g of isopropylcyclopentadiene. The yield was 95.0 wt.%.

To prepare the catalyst, 150 ml of absolute diethyl ether and 7 g (0.067 mol) of isopropylcyclopentadiene are charged into a 500 ml four-necked flask equipped with a mechanical stirrer, reflux condenser, thermometer and dropping funnel. The mixture is cooled to a temperature of 0 ° C. 26.8 ml (0.065 mol) of a 2.5 M solution of butyl lithium in hexane are added to the reaction mass with vigorous stirring, after which the reaction mass is stirred for 30 minutes. To the resulting suspension of lithium isopropylcyclopentadienyl in ether, 7.8 g (0.0335 mol) of zirconium (IV) chloride are added in portions of 1-1.5 g in a funnel at a temperature of 0 ° C. After adding all zirconium chloride, the reaction mass is stirred for 2 hours, after which 100 ml of hexane is added to the reaction mass at room temperature. The mixture was filtered on a finely porous Schott filter and bis (isopropylcyclopentadienyl) zirconium dichloride was isolated from the filtrate. 13.6 mg of bis (isopropylcyclopentadienyl) zirconium dichloride (36 μmol Zr) is dissolved in 4 ml of toluene and 4 ml of a solution of modified methylaluminoxane MMAO-12 (Sigma Aldrich, 7% A1 wt. In toluene, 9 mmol A1) is introduced into the resulting solution, based on the molar ratio Al / Zr = 250, the resulting mixture is constantly stirred for 1 min.

The resulting catalyst is a mixture of modified methylaluminoxane MMAO-12 in toluene and bis (isopropylcyclopentadienyl) zirconium dichloride in toluene, has a molar ratio Al / Zr = 250, the amount of Zr is 36 μmol.

The copolymerization of octene-1 and propylene is carried out at a temperature of 20 ° C for 4 hours in the presence of toluene and the resulting catalyst.

The result is a polyalphaolefin oil with a viscosity of 20.86 mm ² / s at 100 ° C, viscosity index 210, pour point minus 51 ° C.

Example 2

To prepare a ligand - isopropylcyclopentadiene - in a 500 ml three-necked flask equipped with a thermometer, a dropping funnel and a reflux condenser, 84 g of DMSO, 12 g (0.21 mol) of KOH and 14.54 g (0.22 mol) are charged in an argon stream cyclopentadiene. The reaction mass is stirred for 1.5 hours at room temperature. After stirring, the mixture was cooled to 6 ° C and 50 ml of hexane and 44.1 g (0.35 mol) of isopropyl bromide were added to the resulting solution of potassium cyclopentadienyl in an argon stream through a dropping funnel over 30 minutes. After adding all isopropyl bromide, the reaction mass is stirred for 3 hours at a temperature of 6 ° C. After that, 50 ml of a 5% hydrochloric acid solution are added to the reaction mass, and the organic layer is separated. The aqueous layer was extracted with two 50 ml portions of hexane. The combined organic layer was washed with water from DMSO residues 3 times in 100 ml, then dried over anhydrous calcium chloride and distilled. The target fraction is taken in the temperature range of 50-63 ° C at a pressure of 13.5 kPa. 13.8 g of isopropylcyclopentadiene are obtained. The yield was 90.9 wt.%.

A 500 ml four-necked flask equipped with a mechanical stirrer, reflux condenser, thermometer and dropping funnel is charged with 150 ml of absolute diethyl ether and 7 g (0.067 mol) of isopropylcyclopentadiene. The mixture is cooled to a temperature of 0 ° C. 26.8 ml (0.065 mol) of a 2.5 M solution of butyllithium in hexane are added to the reaction mass with vigorous stirring, after which the reaction mass is stirred for 40 minutes. To the resulting suspension of lithium isopropylcyclopentadienyl in ether, 7.8 g (0.0335 mol) of zirconium (IV) chloride are added in portions of 1-1.5 g in a funnel at a temperature of 0 ° C. After the addition of all zirconium chloride, the reaction mixture was stirred for 2.5 hours, after which 100 ml of hexane was added to the reaction mixture at room temperature. The mixture was filtered on a finely porous Schott filter and bis (isopropylcyclopentadienyl) zirconium dichloride was isolated from the filtrate. 6.8 mg of bis (isopropylcyclopentadienyl) zirconium dichloride (18 μmol Zr) is dissolved in 4 ml of toluene and 4 ml of a solution of modified methylaluminoxane MMAO-12 (Sigma Aldrich, 7% Al wt. In toluene, 9 mmol Al) is introduced into the resulting solution, from the calculation of the molar ratio Al / Zr = 500, the resulting mixture is constantly stirred for 5 minutes

The resulting catalyst is a mixture of modified methylaluminoxane MMAO-12 in toluene and bis (isopropylcyclopentadienyl) zirconium dichloride in toluene, has a molar ratio Al / Zr = 500, the amount of Zr is 18 μmol.

The process of co-oligomerization of octene-1 and propylene is carried out at a temperature of 20 ° C for 4 hours in the presence of toluene and the resulting catalyst.

The result is a polyalphaolefin oil with a viscosity of 46.37 mm ² / s at 100 ° C, a viscosity index of 186, a pour point of minus 51 ° C.

Example 3

The ligand isopropylcyclopentadiene is prepared as in Example 1.

The preparation of the catalyst is carried out as in Example 1.

The resulting catalyst is a mixture of modified methylaluminoxane MMAO-12 in toluene and bis (isopropylcyclopentadienyl) zirconium dichloride in toluene, has a molar ratio Al / Zr = 250, the amount of Zr is 36 μmol.

The process of co-oligomerization of octene-1 and propylene is carried out at a temperature of 40 ° C for 4 hours in the presence of toluene and the resulting catalyst.

The result is a polyalphaolefin oil with a viscosity of 15.09 mm ² / s at 100 ° C, viscosity index 196, pour point minus 59 ° C.

Example 4

To prepare a ligand - isopropylcyclopentadiene - in a 500 ml three-necked flask equipped with a thermometer, a dropping funnel and a reflux condenser, 84 g of DMSO, 12 g (0.21 mol) of KOH and 14.54 g (0.22 mol) are charged in an argon stream cyclopentadiene. The reaction mass is stirred for 1.5 hours at room temperature. After stirring, the mixture was cooled to 5 ° C and 50 ml of hexane and 44.1 g (0.35 mol) of isopropyl bromide were added to the resulting solution of potassium cyclopentadienyl in an argon stream through a dropping funnel over 30 minutes. After adding all isopropyl bromide, the reaction mass is stirred for 2 hours at a temperature of 5 ° C. After that, 50 ml of a 5% hydrochloric acid solution are added to the reaction mass, and the organic layer is separated. The aqueous layer was extracted with two 50 ml portions of hexane. The combined organic layer was washed with water from DMSO residues 3 times in 100 ml, then dried over anhydrous calcium chloride and distilled. The target fraction is taken in the temperature range of 50-63 ° C at a pressure of 13.5 kPa. Obtain 14.6 g of isopropylcyclopentadiene. The yield was 96.2 wt.%.

A 500 ml four-necked flask equipped with a mechanical stirrer, reflux condenser, thermometer and dropping funnel is charged with 150 ml of absolute diethyl ether and 7 g (0.067 mol) of isopropylcyclopentadiene. The mixture is cooled to 0 ° C. 26.8 ml (0.065 mol) of a 2.5 M solution of butyllithium in hexane are added to the reaction mass with vigorous stirring, after which the reaction mass is stirred for 60 minutes. To the resulting suspension of lithium isopropylcyclopentadienyl in ether, 7.8 g (0.0335 mol) of zirconium (IV) chloride are added in portions of 1-1.5 g in a funnel at a temperature of 0 ° C. After adding all the zirconium chloride, the reaction mass is stirred for 3 hours, after which 100 ml of hexane is added to the reaction mass at room temperature. The mixture was filtered on a finely porous Schott filter and bis (isopropylcyclopentadienyl) zirconium dichloride was isolated from the filtrate. 3.4 mg of bis (isopropylcyclopentadienyl) zirconium dichloride (9 μmol Zr) is dissolved in 2 ml of toluene and 4 ml of a solution of modified methylaluminoxane MMAO-12 (Sigma Aldrich, 7% Al wt. In toluene, 9 mmol Al) is introduced into the resulting solution, based on the molar ratio Al / Zr = 1000, the resulting mixture was constantly stirred for 10 minutes

The resulting catalyst is a mixture of modified methylaluminoxane MMAO-12 in toluene and bis (isopropylcyclopentadienyl) zirconium dichloride in toluene, has a molar ratio Al / Zr = 1000, the amount of Zr is 9 μmol.

The process of co-oligomerization of octene-1 and propylene is carried out at a temperature of 20 ° C for 4 hours in the presence of toluene and the resulting catalyst.

The result is a polyalphaolefin oil with a viscosity of 115.9 mm ² / s at 100 ° C, viscosity index 246, pour point minus 48 ° C.

Example 5

To prepare a ligand - isopropylcyclopentadiene - in a 500 ml three-necked flask equipped with a thermometer, a dropping funnel and a reflux condenser, 84 g of DMSO, 12 g (0.21 mol) of KOH and 14.54 g (0.22 mol) are charged in an argon stream cyclopentadiene. The reaction mass is stirred for 1.5 hours at room temperature. After stirring, the mixture was cooled to 2 ° C and 50 ml of hexane and 44.1 g (0.35 mol) of isopropyl bromide were added to the resulting solution of potassium cyclopentadienyl in an argon stream through a dropping funnel over 30 minutes. After adding all isopropyl bromide, the reaction mass is stirred for 1 h at a temperature of 2 ° C. After that, 50 ml of a 5% hydrochloric acid solution are added to the reaction mass, and the organic layer is separated. The aqueous layer was extracted with two 50 ml portions of hexane. The combined organic layer was washed with water from DMSO residues 3 times in 100 ml, then dried over anhydrous calcium chloride and distilled. The target fraction is taken in the temperature range of 50-63 ° C at a pressure of 13.5 kPa. 12.9 g of isopropylcyclopentadiene are obtained. The yield was 85.2 wt.%.

The preparation of the catalyst is carried out as in Example 4.

The resulting catalyst is a mixture of modified methylaluminoxane MMAO-12 in toluene and bis (isopropylcyclopentadienyl) zirconium dichloride in toluene, has a molar ratio Al / Zr = 1000, the amount of Zr is 9 μmol.

The process of co-oligomerization of octene-1 and propylene is carried out at a temperature of 40 ° C for 4 hours in the presence of toluene and the resulting catalyst.

The result is a polyalphaolefin oil with a viscosity of 35.69 mm ² / s at 100 ° C, a viscosity index of 187, pour point minus 47 ° C.

The test results of the catalyst samples obtained and tested in accordance with examples 1-5 are shown in the table.

As can be seen from the table, the use of the catalyst obtained by the proposed method provides highly viscous synthetic polyalphaolefin base oils with high viscosity indices (from 186 to 246) and with a low pour point (minus 47 - minus 59 ° C).

Claims (2)

1. The catalyst for producing synthetic high-viscosity oils, which is a mixture of modified methylaluminoxane MMAO-12 in toluene and bis (isopropylcyclopentadienyl) zirconium dichloride in toluene, has a molar ratio Al / Zr = (250-1000), the amount of Zr is (36-9) μmol. 2. The method of preparation of the catalyst for producing synthetic high viscosity oils according to claim 1, characterized in that the isopropylcyclopentadiene ligand is prepared by mixing dimethyl sulfoxide, potassium hydroxide and cyclopentadiene and stirring the reaction mixture, cool it to a temperature of 2-6 ° C, add isopropyl bromide and mix for 1-3 hours, add a 5% solution of hydrochloric acid, carry out extraction with hexane, rinse with water from the residues of dimethyl sulfoxide, dry, distill and select a fraction in the temperature range of 50-63 ° C, to obtain diethyl ether and a solution of butyl lithium in hexane are added to this isopropylcyclopentadiene, stirred for 30-60 minutes, zirconium (IV) chloride is added at a temperature of 0-2 ° C, the mixture is stirred for 2-3 hours, after which it is warmed to room temperature and Hexane was added to the resulting mass, the mixture was filtered, and bis (isopropylcyclopentadienyl) zirconium dichloride was isolated from the filtrate, which was dissolved in toluene, and the resulting solution was mixed with modified methylaluminoxane MMAO-12 in toluene, in order to obtain a molar ratio A l / Zr = (250-1000), Zr - in the amount of (36-9) mmol, with constant stirring for 1-10 minutes.