RU2505551C2 - METHOD OF PRODUCING ANTI-TURBULENT ADDITIVE WITH MONOMER RECYCLING, METHOD OF PRODUCING ANTI-TURBULENT ADDITIVE, METHOD OF PRODUCING HIGHER POLY-α-OLEFINS FOR SAID METHODS AND ANTI-TURBULENT ADDITIVE BASED THEREON - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: described is a method of producing an anti-turbulent additive with monomer recycling, a method of producing an anti-turbulent additive, a method of producing higher poly-α-olefins for said methods and an anti-turbulent additive based thereon. The methods employ a substance with a boiling point higher than that of the starting monomer by not less than 73°C as a precipitation agent for the obtained polymer.

EFFECT: reduced monomer loss, low cost of the methods by preventing formation of azeotropic mixtures of the precipitation agent and the monomers while maintaining high degree of purity of the recycled monomers.

16 cl, 1 dwg, 2 tbl, 20 ex

Description

The present invention relates to the petrochemical and chemical industries, in particular to the production of anti-turbulent additives that reduce the hydrodynamic resistance in pipelines for transporting oil and oil products, as well as to methods for producing non-crystalline polyolefins for them.

When fluid flows through a conductive channel, such as a pipeline, friction energy is lost. Due to these energy losses, the fluid pressure in the conductive channel decreases over the entire length of the channel in the direction of flow. In a channel of constant diameter, the pressure decreases even more with increasing flow rate. A common method of reducing friction energy losses and changing the relationship between pressure reduction and flow rate for the case when the flow in the channel is turbulent (the Reynolds number is greater than about 2100) is the addition of some anti-turbulent additives - high-molecular substances - to the fluid flowing through the channel that reduce the hydraulic resistance of liquids during pumping in turbulent modes (Toms effect). The mechanism of action of anti-turbulent additives is based on the suppression of turbulent pulsations near the inner surface of the pipeline due to the interaction of long molecules of the additive with turbulent vortices originating near the walls of the pipeline. Reducing friction energy losses improves the throughput of pipelines, hoses, and other fluid-conducting channels. In addition, the use of anti-turbulent additives can reduce the cost of pumping liquids and the cost of pumping equipment, as well as the use of pipes of smaller diameter for a given throughput of the pipeline. Therefore, the creation of anti-turbulent additives that reduce resistance to flow is an urgent task.

There are two types of anti-turbulent additives based on polymers of higher α-olefins. The first type of additives is gel additives or solution type additives [RU 2277103 C2, 05.27.2006], obtained by polymerization of higher α-olefins in a hydrocarbon solution, which are a viscous solution. Anti-turbulent additives based on high molecular weight polymers of α-olefins soluble in hydrocarbon liquids, due to the possibility of obtaining relatively inexpensive ultra-high molecular weight, and therefore effective as anti-turbulent additives, polymers are widely used. In principle, all commercially available and commercially available agents for reducing flow resistance in oil pipelines are ultra-high molecular weight polyalphaolefin polymers (over 1,500,000), which are mainly amorphous, non-crystalline, highly and randomly branched polymers derived from various alpha-olefin monomers. Polyalphaolefins derived from alpha olefin monomers typically include C ₄ to C ₁₆ monomers. It was established that just such a composition of alpha-olefin monomers allows to obtain polymers characterized by the highest quality and greatest efficiency. Such polymers constitute the bulk of the currently available on the market and cost-effective products.

The disadvantages of mortar additives include the following. An ultra-high molecular weight polymer is obtained only at the initial stage of polymerization, and it must be interrupted at a 20% conversion of the monomer, since further polymerization leads to the formation of a ballast polymer that is not active in reducing the resistance [G.V. Nesyn, Yu.V. Suleymanova, N.M. Polyakova, G.P. Filatov. Suspension type anti-turbulent additive based on polymers of higher alpha-olefins. News of Tomsk Polytechnic University. 2006.V. 309. Number 3]. When the content of the nutrient in the additives of the solution type in the amount of 10-12%, the system loses fluidity, and it is difficult to pump it into the pipeline, so transportation costs are the main obstacle to their use, especially at large distances from the production site.

The second type of additives is suspension type additives [Bulletin of the Tomsk Polytechnic University. 2006.V. 309. Number 3. p.112-115; G.V. Nesyn, Yu.V. Suleymanova et al. Antiturbulent suspension type additive based on higher α-olefins]. Their preparation includes the polymerization of higher α-olefins in bulk, then the resulting polymer is ground at cryogenic temperatures and a suspension of ground polymer is prepared in an aqueous or non-aqueous medium [US 4837249, 06/06/1989; US 4826728, 05/02/1989]. During cryogenic grinding, the polymer is degraded, which reduces its molecular weight and its effectiveness as an anti-turbulent additive.

A known method of producing an agent for reducing the hydrodynamic resistance of hydrocarbon liquids (RU 2238282, published 10.10.2004., IPC C08F 10/14, C08F 4/64), which includes (co) polymerization of higher α-olefins on microspherical titanium trichloride, pre-treated a higher C ₆ -C _{16 a-} olefin in an amount of 0.13-0.52 M olefin per 1.0 M TiCl ₃ in the presence of an organoaluminum compound as a cocatalyst. The preliminary polymerization causes the grinding of TiCl ₃ particles to a colloidal degree of dispersion, as well as a slight increase in viscosity for a long time of a non-delaminating medium. The use of a catalyst pretreated in this way eliminates the need to mix the reaction mass, excluding the mechanical degradation factor of the resulting polymer, leading to an increase in the time of the polymerization process, which increases the molecular weight of the polymer. The method allows to obtain ultra-high molecular weight (co) polymers having high efficiency in reducing the hydrodynamic resistance of hydrocarbon liquids.

Nevertheless, block polymerization to deep degrees of monomer conversion is impractical, since the formation of a ballast low molecular weight polymer that is not active in reducing hydrodynamic resistance, which leads to a decrease in additive efficiency and the waste of expensive monomer and time.

The closest analogue to the selected method for producing polyalphaolefins described in [K. Konovalov, G.V. Nesyn et al. Comparison of methods for the production of anti-turbulent oil additives based on laboratory data. News of Tomsk Polytechnic University. 2011. V.318 No. 3], as well as an anti-turbulent additive based on polyalphaolefins obtained by this method. The method of producing polyalphaolefins includes:

- preliminary fluoride treatment of the catalyst, as in patent RU 2238282,

- polymerization or (co) polymerization in the mass of higher α-olefins C ₆ , C ₈ , C ₁₀ , C ₁₂ with a ratio of volume fractions of the starting monomers of 7: 1: 1: 1 using a catalyst system - microspherical catalyst (MSC) as a catalyst and diethylaluminium chloride (DEAC) as a cocatalyst with a ratio of the components of the reaction mass of monomers: catalyst: cocatalyst by weight, calculated as pure components, equal to 2200: 1: 5, respectively, to a low degree of conversion of 7-10%, with the formation of a copolymer solution in monomers

- squeezing nitrogen of the polymerizate into the tank for deposition with stopping the polymerization process,

- precipitation of the obtained copolymer precipitant isopropyl alcohol (IPA) in excess (two-stage washing with excess isopropyl alcohol in the extractor),

- separation of the polymer suspension from the monomers by purification of unreacted monomers from the impurities of the IPA by three-stage water washing in the extractor,

- drying of the monomer from residual water;

- azeotropic distillation of the mixture of IPA-water with the subsequent return of the precipitant for recycling.

Next, a suspension of an anti-turbulent additive was prepared by mixing a copolymer (25 wt.%) Obtained by the above method with a mixture of isopropyl alcohol and polyethylene glycol in a ratio of 10: 1. Polyethylene glycol was used here as an additive medium, adding it to an already precipitated (finely dispersed) polymer mixed with IPA.

Next, hydrodynamic testing of both the obtained polymer with heptane solvent and additives from it with the same solvent was carried out. Testing was carried out on a turbulent rheometer with the calculation of the reduction of hydrodynamic resistance (SGDS) according to the formula given in this source. Received good results:

- for the polymer with a 60% decrease in heptane resistance, the polymer concentration in the solution was 4.5 * 10 ^-4 wt.%;

- for additives at a polymer concentration in the additive of 25 wt.% with a 50% decrease in heptane resistance, the concentration of the additive was 13 * 10 ^-4 wt.%.

The disadvantage of the selected prototype is the use of isopropyl alcohol as a precipitant, which forms azeotropic mixtures with unreacted monomers, in particular with hexene, which complicates their purification by direct distillation to return to recycling and leads to the need to double wash the precipitated polymer from isopropyl alcohol monomers and stage washing the monomer with water in triplicate excess, which implies an increase in the volume of equipment used. At the same time, there is a loss of expensive monomers and a decrease in their return amount to recycling, the use of the complex process of azeotropic distillation of azeotropic compounds to return them to production, therefore, the production of suspension anti-turbulent additives is complicated and, as a consequence, the finished product becomes more expensive.

The objective of the invention is to reduce the loss of monomers, increase the return amount of unreacted monomers and thereby more fully use the monomers of higher alpha-olefins in the production of polymers from them and anti-turbulent additives based on them, reduce the cost of purification of unreacted monomers by eliminating the possibility of the formation of azeotropic mixtures of precipitant with the remaining monomers; reduction of waste production of anti-turbulent additives, simplification and reduction of the cost of this production by simplifying the process and units of equipment used while maintaining a high degree of purity of the return monomers.

The problem is solved, and the technical result is achieved by the claimed method of obtaining an anti-turbulent additive with a recycling of monomers, including:

- (co) polymerization in the mass of higher α-olefins using a catalyst system - microspherical catalyst (MSC) and diethylaluminium chloride (DEAC) as cocatalyst to a given low degree of conversion, with the formation of a solution of (co) polymer in the monomer (s),

- precipitation of the obtained (co) polymer upon reaching the specified degree of conversion by adding in excess precipitant to the reaction mixture (two-stage washing with excess precipitant in the sump); simultaneously with the addition of precipitant, the polymerization process is stopped,

- regeneration of monomers by distillation of unreacted (their) monomer (s),

- separation of the suspension of the dispersed (co) polymer from the liquid phase by decantation,

- purification of monomers from precipitant impurities by washing with water;

- drying of the monomers after washing with water,

- preparation of a suspension of an anti-turbulent additive by mixing (co) polymer (s) obtained by the above method with a precipitant — polymer medium (additive) and anti-agglomerate — a surfactant.

The difference of the proposed method from the prototype is the following:

- the ratio of the components of the reaction mass monomer (s), catalyst, cocatalyst by weight in terms of pure components is, wt.%:

Monomer (s) 99.7730-99.8927 Catalyst 0.0015-0.0055 Cocatalyst 0.1058-0, 2270

- polymerization is carried out to a degree of conversion of 5-15%,

- control the degree of conversion of the process (co) polymerization of higher α-olefins using the density measurement method,

- as a precipitant use a substance with a boiling point above the boiling point of the monomer (s) at least 73 ° C: monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof, which allows you to return to the cycle expensive monomers with a high degree of purity,

- while the precipitant is taken in excess in about. the ratio of the initial polymer solution: precipitant from 1: 1.25 to 1: 2.06,

- after sedimentation of the polymer, the fine polymer is separated from the liquid phase,

- the process of purification of monomers is carried out by simple distillation, or by distillation in vacuum, due to the large difference in boiling points of the monomer and precipitant

- before the distilled monomer is dried, it is additionally purified: the precipitant residues are extracted with water, the aqueous phase is separated from the monomer. This additional stage of monomer purification is much simpler and cheaper than purification using azeotropic distillation equipment, which requires the use of distillation columns; this achieves a polymerization degree of purity of the return monomer to its content of not less than 99.0%;

- for the preparation of a suspension of an anti-turbulent additive from a (co) polymer obtained by the above method, additives can be taken as substances with a boiling point above the boiling point of the starting monomer (s) at least 73 ° C: monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof, and substances with a low boiling point, such as lower alcohols, for example, isopropyl alcohol, butanol-1, or mixtures thereof,

- the components of the suspension of anti-turbulent additives are taken in the following quantitative ratio, wt.%:

(Co) polymer 25.0-55.0 Polymer medium 39.5-72.5 Surfactant 2.5-5.5.

The problem is solved, and the technical result is also achieved by the claimed method for producing anti-turbulent additives, including:

- (co) polymerization in the mass of higher α-olefins using a catalyst system - microspherical catalyst (MSC) and diethylaluminium chloride (DEAC) as cocatalyst to a given low degree of conversion, with the formation of a solution of (co) polymer in the monomer (s),

- precipitation of the obtained (co) polymer upon reaching the specified degree of conversion by adding in excess precipitant to the reaction mixture (two-stage washing with excess precipitant in the sump); simultaneously with the addition of precipitant, the polymerization process is stopped,

- separation of the suspension of the dispersed (co) polymer from the liquid phase by decantation,

- preparation of a suspension of an anti-turbulent additive by mixing (co) polymer (s) obtained by the above method with a precipitant — polymer medium (additive) and anti-agglomerate — a surfactant.

The difference of the proposed method from the prototype is the following:

- the ratio of the components of the reaction mass monomer (s), catalyst, cocatalyst by weight in terms of pure components is, wt.%:

Monomer (s) 99.7730-99.8927 Catalyst 0.0015-0.0055 Cocatalyst 0.1058-0.2270

- polymerization is carried out to a degree of conversion of 5-15%,

- control the degree of conversion of the process (co) polymerization of higher ά-olefins using the density measurement method,

- as a precipitant use a substance with a boiling point above the boiling point of the monomer (s) at least 73 ° C: monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof,

- while the precipitant is taken in excess in about. the ratio of the initial polymer solution: precipitant from 1: 1.25 to 1: 2.06,

- after sedimentation of the polymer, the fine polymer is separated from the liquid phase,

- to prepare a suspension of an anti-turbulent additive, a (co) polymer obtained by the above method is taken, as an additive medium can be taken as substances with a boiling point above the boiling point of the starting monomer (s) at least 73 ° C: monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof, and substances with a low boiling point, such as lower alcohols, for example, isopropyl alcohol, butanol-1, or mixtures thereof,

- the components of the suspension of anti-turbulent additives are taken in the following quantitative ratio, wt.%:

(Co) polymer 25.0-55.0 Polymer medium 39.5-72.5 Surfactant 2.5-5.5.

The problem is solved and the technical result is also achieved by the method of producing higher poly-α-olefins for anti-turbulent additives, including:

- (co) polymerization in the mass of higher α-olefins using a catalyst system - microspherical catalyst (MSC) and diethylaluminium chloride (DEAC) as cocatalyst to a given low degree of conversion, with the formation of a solution of (co) polymer in the monomer (s),

- precipitation of the obtained (co) polymer upon reaching the specified degree of conversion by adding in excess precipitant to the reaction mixture (two-stage washing with excess precipitant in the sump); simultaneously with the addition of precipitant, the polymerization process is stopped,

- separation of the suspension of the dispersed (co) polymer from the liquid phase by decantation.

The difference of the proposed method from the prototype is the following:

- the ratio of the components of the reaction mass monomer (s), catalyst, cocatalyst by weight in terms of pure components is, wt.%:

Monomer (s) 99.7730-99.8927 Catalyst 0.0015-0.0055 Cocatalyst 0.1058-0.2270

- polymerization is carried out to a degree of conversion of 5-15%,

- control the degree of conversion of the process (co) polymerization of higher ά-olefins using the density measurement method,

- as a precipitant use a substance with a boiling point above the boiling point of the monomer (s) at least 73 ° C: monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof,

- while the precipitant is taken in excess in about. the ratio of the initial polymer solution: precipitant from 1: 1.25 to 1: 2.06,

- after sedimentation of the polymer, a finely dispersed polymer is separated from the liquid phase.

The problem is solved, and the technical result is achieved by an anti-turbulent additive, which is a suspension of (co) polymer (s) with a polymer medium and anti-agglomerate - a surface-active substance (surfactant).

The difference of the proposed anti-turbulent additives from the prototype is the following:

- as (co) polymer take (co) polymer obtained by the above method using a precipitant in the form of a substance with a boiling point above the boiling point of the starting monomer by at least 73 ° C,

- as a medium, additives can be taken as substances with a boiling point above the boiling point of the starting monomer (s) for the indicated (co) polymer (s) at least 73 ° C: monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof, and lower boiling substances, such as lower alcohols, for example, isopropyl alcohol, butanol-1, or mixtures thereof,

- the components of the suspension of anti-turbulent additives are taken in the following quantitative ratio, wt.%:

(Co) polymer 25.0-55.0 Polymer medium 39.5-72.5 Surfactant 2.5-5.5.

As can be seen from the above operations, the purification of the monomer (s) from precipitant impurities by a three-stage water washing in an extractor by azeotropic distillation with the subsequent return of the monomer (s) for recycling in the proposed technology is absent, which became possible due to the low content of impurities in the monomer.

From the prototype it is known to use polyethylene glycol as a medium for preparing a commodity form of an anti-turbulent additive. However, its use for the deposition of the polymer is unknown (in the prototype it was used only after separation of the polymer from the monomer).

Known polymerization of higher alpha-olefins, carried out to a low degree of conversion of 4, 7, 10, 12%. It has its drawbacks - the low level of use of expensive monomers and the lengthening of the production cycle of the polymerization process due to the need to clean the monomer to return part of it to recycling, which complicates the method of returning using complex schemes and additional equipment for their purification and distillation. However, the distinguishing features of the proposed solution made it possible to simplify these schemes and equipment, partially eliminate these drawbacks, increasing the percentage of secondary use of monomers with the same degree of purity of the return monomer, making the polymerization process competitive to a low degree of conversion.

It is known to use a surfactant, for example, calcium stearate, in an amount of 5 wt.% As an anti-agglomerate [see K.B. Konovalov, G.V. Nesyn et al. Comparison of methods for the production of anti-turbulent oil additives based on laboratory data. News of Tomsk Polytechnic University. 2011. V.318 No. 3, cryogenic grinding method]. Surfactant is involved in the deposition of the polymer at its last stage, preventing the adhesion of the formed polymer particles.

Hexene-1 TU 2411-059-05766801-96 (with a boiling point of 63 ° C) was used as a monomer; and / or octen-1 TU 2411-057-05766801-96 (with a boiling point of 120 ° C); and / or decen-1 TU 2411-057-05766801-96 (with a boiling point of 190 ° C);

As the catalyst used microspherical titanium trichloride (MSC) - TU 2167-012-03533913-95.

Diethylaluminium chloride (DEAC) TU 2436-041-05796653-97 was used as a cocatalyst.

As a precipitant used

- ethyl cellosolve (2-ethoxyethanol) GOST 8313-88 (boiling point 136 ° C);

- glycols:

- monoethylene glycol GOST 19710-83 (boiling point 197 ° C);

- monopropylene glycol TU 2422-069-05766801-97 (boiling point 188 ° C);

- diethylene glycol GOST 10136-77 (boiling point 245 ° C);

- dipropylene glycol - ASTM D5164-05 (2011) (boiling point 232 ° C);

- polypropylene glycol TU U 24.1-32257423-107-2004 (the substance does not boil, the temperature is not standardized);

- polyethylene glycol 200 - TU 2483-007-71150986-2006 (the substance does not boil, the temperature is not standardized).

Other substances and components:

- gaseous nitrogen - GOST 9293-74;

- Surfactant-stearate (distearate) of calcium - TU 2432-061-5685807-04.

The method is as follows.

A mixture of comonomers (hexene-1, octene-1 and / or decen-1) 99.7730-99.8927 wt.% Purged with purified nitrogen, add 0.1058-0.2270 wt.% 10% solution of diethylaluminium chloride in heptane purged with nitrogen again and introduced 0.0015-0.0055 wt% MSC, after which the flask was sealed and shaken vigorously to evenly distribute the catalyst until slightly thickened, sufficient so that the dispersed catalyst did not settle to the bottom and was left under nitrogen at room temperature a pillow. In this case, the degree of conversion of the monomer is determined every 15 minutes from the start of polymerization. To determine the degree of monomer conversion, the method of determining the density of the medium is used using a high-precision density meter DM 45 DeltaRange from Mettler Toledo. This method is quite operational, which is important when monitoring an industrial process. To determine the density of the medium, 1.2 ml of the sample is placed in the measuring cell, the measurement is carried out by pressing the "Start" button. The measurement takes 30 seconds, the value of the density indicator is displayed on the scoreboard. After measuring the density, the measuring cell is freed from the sample, washed and dried. The figure shows the dependence of the density difference between the monomer and the polymer solution in the monomer on the polymer concentration. This dependence is strictly linear in the studied concentration range, which makes it possible to determine the polymer content in the reaction mixture at a given time with good accuracy.

To isolate a polymer suspension by precipitation from a solution, it is necessary to inhibit the polymerization by 5-15% conversion, otherwise the mass acquires a gelatinous consistency, which will prevent its mixing with precipitant. When establishing the polymerization to a predetermined degree of conversion within 5-15% of the conversion, a precipitant is added to the polymer, which is used as glycols, polyglycols, ethyl cellosolve with the formation of small polymer particles with an average size of 0.3-0.5 mm.

After the polymer precipitates in the form of a finely dispersed phase, in order to prevent the polymer from sticking together without an anti-agglomerator (SAS), an excess of precipitant is added in the ratio of the initial volume of the polymer solution in the monomer to the precipitant from 1: 1.25 to 1: 2.06.

To return unreacted monomers to the polymerization cycle, the following steps are taken.

From the liquid phase of the reaction mixture containing the monomer (s) that has not entered into the polymerization, they are removed by simple distillation at a temperature of a heat carrier of 90-95 ° C in the case of hexene; in the case of octene and decene, distillation is carried out in vacuum (12 mbar for decene, 65 mbar for octene) at the same coolant temperature.

Part of the precipitant enters the monomer fraction during the distillation of the monomers, which prevents their use in polymerization a second time. The purity of the monomer (s) was judged by the analysis of chromatography-mass spectrometry (GC-MS), which was carried out on a Thermo Fisher Scientific LCQ Fleet ™ instrument. Therefore, after a simple distillation of the monomers, the latter undergo an additional purification step. It consists in the aqueous extraction of precipitant residues, followed by separation of the aqueous fraction from the monomers and their drying with calcium chloride or aluminum oxide. After drying, the monomer purity was monitored a second time by GC-MS.

Next, sedimentation of the solid dispersed polymer is carried out with its subsequent separation from the liquid phase by decantation using the operation of squeezing the polymerizate with nitrogen into a sedimentation tank. The resulting polymer is used to prepare a commodity form of an anti-turbulent additive, for which it is mixed with a medium (precipitant) in the form of glycols, polyglycols, ethyl cellosolve and surfactants (calcium stearate).

Obtained by the claimed method, the agent that reduces the resistance to the turbulent flow is a suspension of polymers / copolymers of higher α-olefins in the environment of organic non-solvents (monoglycols, diglycols, polyglycols, ethyl cellosolve) for (co) polymers of higher α-olefins (polyhexene-1, polyoctene-1 , polydecene-1) with the addition of a surfactant - calcium stearate. As an additive medium, lower alcohols (butanol-1) or mixtures of lower alcohols with the above organic non-solvents can be taken. The composition of the additive is given below.

Component Content,% mass Statistical polymer 25.0-55.0 Wednesday 39.5-72.5 Surfactant 2.5-5.5

The chemical formula of the obtained polymer component:

- (CH ₂ -CHR) _x - (CH ₂ -CHR ') _y -

where R = R '= C ₄ H ₉ or C ₆ H ₁₃ or C ₈ H ₁₇ ;

where R = C ₄ H ₉ ; R ′ = and / or C ₆ H ₁₃ and / or C ₈ H ₁₇ ; x: y ~ 10: 1.

Next, hydrodynamic tests of the obtained anti-turbulent additive (agent) are carried out on a turbulent rheometer with the calculation of a decrease in hydrodynamic resistance (SGDS).

The invention is illustrated by examples of specific performance. The figure shows the change in the density of the solution depending on the concentration of polyhexene in hexene. The initial data and results of the examples are shown in Tables 1 and 2, while Table 1 relates entirely to polymerization and to polymers, Table 2 to the anti-turbulent additive and its characteristics.

Example 1. In a flask equipped with a three-arm W-shaped nozzle, two counter-pressure separating funnels and a capillary, 200 cm ^{3 of} hexene-1 were poured and purged with purified nitrogen for 30 minutes, 3.058 cm ³ (0.2220 wt.%) Was added A 10% solution of diethylaluminium chloride in heptane was purged for another 5-10 minutes. and introduced 0.0066 g (0.005 mass%) of TiCl ₃ MSC, after which the separatory funnels, capillary and nozzle were removed in a stream of nitrogen, hermetically closed the flask and shaken vigorously to distribute the catalyst evenly until slightly thickened, so that the dispersed catalyst did not settle on bottom, and started monitoring the conversion of monomer. Bringing the polymerization process to a level of 15% monomer conversion, 334.8 g of ethyl cellosolve precipitant was added to the reaction mixture, and the polymer was precipitated.

According to the last sample of the polymer solution in the monomer taken to determine the monomer conversion, the obtained polymer was tested by first washing the sample from the unreacted monomer and drying it in vacuum. Having prepared working solutions of the polymer in heptane, we determined the decrease in the hydrodynamic resistance of the latter with a Reynolds number of at least 4500. For the polyhexene in Example 1 for 30% SGDS, its concentration was 0.67 ppm.

To return unreacted hexene-1 to the polymerization cycle from the reaction mixture, unreacted hexene-1 was removed by simple distillation at a coolant temperature of 90-95 ° C.

Next, the precipitated polymer was separated from the liquid phase. The obtained finely dispersed polymer was used to prepare a commodity form of an anti-turbulent additive, for which polyhexene in a ratio of 25.0 wt.% (25 g) was mixed with a surfactant (calcium stearate) in an amount of 2.5 wt.% (2.5 g) and ethyl cellosolve in an amount of 72.5 wt.% (72.5 g). The resulting agent was a suspension of polyhexene-1 in ethyl cellosolve. Next, hydrodynamic tests of the obtained anti-turbulent additive in a heptane solution were carried out, the results of which showed an SGDS of 30% at an additive concentration of 2.35 ppm.

The distilled monomer was further purified by aqueous extraction from ethyl cellosolve impurities, followed by separation of the aqueous fraction and drying of hexene-1 with calcium chloride.

The percentage of hexene-1 in the return hexene was 99.7%).

The percentage of the return amount of hexene-1 was 99.2%.

Example 2. The polymerization was carried out analogously to example 1 with the following changes:

- monomers: mixture, wt.% hexene-1 94.3163 + decen-1 - 5.457;

- a solution of diethylaluminium chloride 0.2212 wt.% (0.3 g);

- MSC 0.0074 g (0.0055 wt.%);

- precipitant ethyl cellosolve 353.4 g;

- the degree of conversion of monomer 14.7%;

- for anti-turbulent additives (PTP), the copolymers were taken in an amount of 40.2 wt.% (40.2 g);

- surfactants were added to the copolymers in an amount of 4.0 wt.% (4.0 g)

- environment additives - ethyl cellosolve - in the amount of 55.8 wt.% (55.8 g),

At the same time, the results were:

- the concentration of copolymers for the same level of SGDS 30% was 0.6 ppm;

- the concentration of PTP for the same level of SGDS 30% was 1.50 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the total amount of regenerated monomer was 97.7%.

Example 3. The polymerization was carried out analogously to example 1 with the following changes:

- monomers mixture, vol.% hexene-1 - 90.0, decen-1 - 10.0;

- a solution of diethylaluminum chloride 0.2203 wt.% (0.3 g);

- MSC 0.0059 g (0.0043 wt.%);

- precipitant polypropylene glycol 280.0 g;

- the degree of conversion of monomer 13.9%;

- for PTP copolymers were taken in an amount of 35.8 wt.% (35.8 g);

- Surfactants were added to the copolymers in an amount of 3.5 wt.% (3.5 g)

- environment additives - a mixture of polypropylene glycol and butanol-1 in an amount of 60.7 wt.% (60.7 g), mass. 1: 9 ratio;

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 0.32 ppm;

- the concentration of anti-TB drugs for the same level of sgds 30% was 1.5 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the content of dencene-1 in the return decene was 99.0%;

- the total amount of regenerated monomer was 98.3%.

Example 4. The polymerization was carried out analogously to example 1 with the following changes:

- monomers mixture, vol.% hexene-1 - 85.0, decen-1 - 15.0;

- a solution of diethylaluminium chloride 0.2190 wt.% (0.3 g);

- MSC 0.0062 g (0.0045 wt.%);

- precipitant polypropylene glycol 280.6 g;

- the degree of conversion of monomer 13.7%;

- for PTP copolymers were taken in the amount of 29.6 wt.% (29.6 g);

- surfactants were added to the copolymers in an amount of 3.0 wt.% (3.0 g)

- environment additives - a mixture of ethyl cellosolve and isopropyl alcohol in an amount of 67.4 wt.% (67.4 g), mass, ratio 4: 6;

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 0.83 ppm;

- the concentration of anti-TB drugs for the same level of SGDS 30% was 3.4 pm;

- the content of hexene-1 in the return hexene was 99.7%;

- the content of decene-1 in the return decene was 99.0%;

- the total amount of regenerated monomer was 98.2%.

Example 5. The polymerization was carried out analogously to example 1 with the following changes:

- monomers mixture, vol.% hexene-1 - 90.0, decen-1 -10.0;

- a solution of diethylaluminum chloride 0.144 g (0.1058 wt.%);

- MSC 0.002 g (0.0015 wt.%);

- precipitant polyethylene glycol - 293.4 g;

- the degree of conversion of monomer 14.9%;

- for PTP, the copolymers were taken in an amount of 55.0 wt.% (55.0 g);

- Surfactants were added to the copolymers in an amount of 5.5 wt.% (5.5 g)

- environment additives - polyethylene glycol - in the amount of 39.5 wt.% (39.5 g),

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 0.30 ppm;

- the concentration of PTP for the same level of sgds 30% was 1.24 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the content of decene-1 in the return decene was 99.0%;

- the amount of regenerated monomer was 98.1%.

Example 6. The polymerization was carried out analogously to example 1 with the following changes:

- monomers mixture, vol.% hexene-1 - 80.0, decen-1 - 20.0;

- a solution of diethylaluminium chloride 0.2180 wt.% (0.3 g);

- MSC 0.0062 g (0.0045 wt.%);

- precipitant monopropylene glycol 274.5 g;

- the degree of conversion of the monomer 12.1%;

- for PTP, the copolymers were taken in an amount of 43.5 wt.% (43.5 g);

- surfactants were added to the copolymers in an amount of 4.4 wt.% (4.4 g)

- environment additives polypropylene glycol in an amount of 52.1 wt.% (52.1 g)

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 0.95 ppm;

- the concentration of ATP for the same level sgds 30% was 3.8 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the content of decene-1 in the return decene was 99.0%;

- the total amount of regenerated monomer was 98.3%.

Example 7. The polymerization was carried out analogously to example 1 with the following changes:

- monomer, vol.% octene-1 - 100.0;

- a solution of diethylaluminum chloride 0.2140 wt.% (0.3 g);

- MSC 0.0060 g (0.0043 wt.%);

- precipitant dipropylene glycol 281.435 g;

- the degree of conversion of monomer 11.7%;

- for PTP polymer was taken in an amount of 26.9 wt.% (26.9 g);

- surfactants were added to the polymer in an amount of 2.7 wt.% (2.7 g)

- environment additives - dipropylene glycol - in the amount of 70.4 wt.% (70.4 g),

At the same time, the results were:

- the polymer concentration for the same level of sgds 30% was 1.05 ppm;

- the concentration of PTP for the same level of sgds 30% was 5.5 ppm;

- the content of octene-1 in the return octene was 99.7%;

- the amount of regenerated monomer was 98.6%.

Example 8. The polymerization was carried out analogously to example 1 with the following changes:

- a mixture of monomers, vol.%: hexene-1 95.0 octene-1 - 5.0;

- a solution of diethylaluminum chloride 0.2220 wt.% (0.3 g);

- MSC 0.0063 g (0.0046 wt.%);

- precipitant monopropylene glycol 341.9 g;

- the degree of conversion of monomer 13.5%;

- for PTP copolymers were taken in an amount of 33.5 wt.% (33.5 g);

- surfactants were added to the copolymers in an amount of 3.4 wt.% (3.4 g)

- environment additives - a mixture of ethyl cellosolve with dipropylene glycol monomethyl ether in a ratio of 2: 8 in the amount of 63.1 wt.% (63.1 g).

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 0.40 ppm;

- the concentration of PTP for the same level of sgds 30% was 1.91 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the content of octene-1 in the return octene was 99.0%;

- the total amount of regenerated monomer was 97.3%.

Example 9. The polymerization was carried out analogously to example 1 with the following changes:

- a mixture of monomers, vol.%: hexene-1 90.0 octene-1 - 10.0;

- a solution of diethylaluminum chloride 0.2220 wt.% (0.3 g);

- MSC 0.0059 g (0.0044 wt.%);

- precipitant diethylene glycol 379.4 g;

- the degree of conversion of monomer 10.8%;

- for PTP copolymers were taken in an amount of 25.9 wt.% (25.9 g);

- Surfactants were added to the copolymers in an amount of 2.6 wt.% (2.6 g)

- environment additives - diethylene glycol in an amount of 71.5 wt.% (71.5 g);

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 0.52 ppm;

- the concentration of PTP for the same level of sgds 30% was 2.45 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the content of octene-1 in the return octene was 99.0%;

- the total amount of regenerated monomer was 99.1%.

Example 10. The polymerization was carried out analogously to example 1 with the following changes:

- a mixture of monomers, vol.%: hexene-1 85.0 octene-1-15.0;

- a solution of diethylaluminium chloride 0.2270 wt.% (0.3 g);

- MSC 0.0062 g (0.0047 wt.%);

- precipitant diethylene glycol 412.9 g;

- the degree of conversion of monomer 10.1%;

- for PTP copolymers were taken in an amount of 50.8 wt.% (50.8 g);

- surfactants were added to the copolymers in an amount of 5.0 wt.% (5.0 g)

- environment additives - a mixture of ethyl cellosolve with pentanol-1 mass. 3: 7 ratio in an amount of 44.2 wt.% (44.2 g),

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 0.60 ppm;

- the concentration of PTP for the same level of sgds 30% was 1.9 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the content of octene-1 in the return octene was 99.0%;

- the amount of regenerated monomer was 98.4%.

Example 11. The polymerization was carried out analogously to example 1 with the following changes:

- a mixture of monomers, vol.%: hexene-1 - 80.0 octene-1 - 20.0;

- a solution of diethylaluminum chloride 0.2210 wt.% (0.3 g);

- MSC 0.0062 g (0.0046 wt.%);

- precipitant monoethylene glycol 322.8 g;

- the degree of conversion of monomer 9.7%;

- for PTP, the copolymers were taken in the amount of 49.3 wt.% (49.3 g);

- surfactants were added to the copolymers in an amount of 5.0 wt.% (5.0 g)

- environment additives - butanol-1 in the amount of 45.7 wt.% (45.7 g),

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 0.65 ppm;

- the concentration of PTP for the same level of sgds 30% was 2.0 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the content of octene-1 in the return octene was 99.0%;

- the amount of regenerated monomer was 98.6%.

Example 12. The polymerization was carried out analogously to example 1 with the following changes:

- a mixture of monomers, vol.%: hexene-1 - 90.0 octene-1 - 10.0;

- a solution of diethylaluminum chloride 0.1072 wt.% (0.145 g);

- MSC 0.0020 g (0.0015 wt.%);

- precipitant diethylene glycol 323.6 g;

- the degree of conversion of monomer 14.2%;

- for PTP copolymers were taken in an amount of 30.8 wt.% (30.8 g);

- Surfactants were added to the copolymers in an amount of 3.1 wt.% (3.1 g)

- environment additives mixture of diethylene glycol with 2-ethylhexanol mass.

6: 4 ratio in an amount of 66.1 wt.% (66.1 g),

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 0.5 ppm;

- the concentration of anti-TB drugs for the same level of sgds 30% was 1.56 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the content of octene-1 in the return octene was 99.0%;

- the amount of regenerated monomer was 98.8%.

Example 13. The polymerization was carried out analogously to example 1 with the following changes:

- monomer, vol.%: decen-1 - 100.0;

- a solution of diethylaluminum chloride 0.2020 wt.% (0.3 g);

- MSC 0.0060 g (0.0040 wt.%);

- precipitant polypropylene glycol 250.5 g;

- the degree of conversion of monomer 5.0%;

- for PTP polymer was taken in an amount of 26.7 wt.% (26.7 g);

- surfactants were added to the polymer in an amount of 2.7 wt.% (2.7 g)

- environment additives - polypropylene glycol - in the amount of 70.6 wt.% (70.6 g),

At the same time, the results were:

- the polymer concentration for the same level of sgds 30% was 1.0 ppm;

- the concentration of anti-TB drugs for the same level of sgds 30% was 5.7 ppm;

- the content of decene-1 in the return decene was 99.0%;

- the amount of regenerated monomer was 98.3%.

Example 14. The polymerization was carried out analogously to example 1 with the following changes:

- monomers, vol.%: octene-1 - 90.0, decen-1 - 10.0;

- a solution of diethylaluminium chloride 0.2130 wt.% (0.3 g);

- MSC 0.0060 g (0.0043 wt.%);

- precipitant polyethylene glycol 336.0 g;

- the degree of conversion of monomer 5.1%;

- for PTP, the copolymers were taken in an amount of 27.7 wt.% (27.7 g);

Surfactants were added to the copolymers in an amount of 2.8 wt.% (2.8 g)

- environment additives: a mixture of polyethylene glycol and hexanol-1, mass. 1: 1 ratio in an amount of 69.5 wt.% (69.5 g),

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 1.05 ppm;

- the concentration of PTP for the same level of sgds 30% was 6.2 ppm;

- the content of octene-1 in the return hexene was 99.7%;

- the content of decene-1 in the return decene was 99.0%;

- the amount of regenerated hexene-1 was 98.7%.

Example 15. The polymerization was carried out analogously to example 1 with the following changes:

- monomers, vol.%: hexene-1 - 90.0, octene-1 - 5.0, decen-1 - 5.0;

- a solution of diethylaluminum chloride 0.2210 wt.% (0.3 g);

- MSC 0.0059 g (0.0043 wt.%);

- precipitant polyethylene glycol 330.4 g;

- the degree of conversion of monomer 12.7%;

- for PTP, the copolymers were taken in an amount of 31.9 wt.% (31.9 g);

- Surfactants were added to the copolymers in an amount of 3.2 wt.% (3.2 g)

- environment additives polyethylene glycol in the amount of 64.9 wt.% (64.9 g),

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 0 ppm;

the concentration of anti-TB drugs for the same level of sgds 30% was 1.85 ppm;

- the content of hexene-1 in the return hexene was 99.7%.

- the content of octene-1 in the return octene was 99.0%;

- the content of decene-1 in the return decene was 99.0%;

- the amount of regenerated monomer was 98.3%.

Example 16. The polymerization was carried out analogously to example 1 by the following changes: -monomer, vol.%: Hexene-1 - 100.0;

- a solution of diethylaluminium chloride 0.1070 wt.% (0.144 g);

- MSC 0.0020 g (0.0015 wt.%);

- precipitant ethyl cellosolve 334.8 g; conversion rate of 8.4%;

- for PTP polymer was taken in an amount of 25.0 wt.% (25.0 g);

- surfactants were added to the copolymers in an amount of 3.0 wt.% (3.0 g)

- medium for the polymer ethyl cellosolve in an amount of 72.0 wt.% (72.0 g),

At the same time, the results were:

- the polymer concentration for the same level of sgds 30% was 0.3 ppm;

- the concentration of PTP for the same level of sgds 30% was 1.6 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the amount of regenerated monomer was 98.1%.

Example 17 (prototype). The polymerization was carried out with the following conditions:

- monomers, vol.%: hexene-1 - 70.0, octene-1 - 10.0, decen-1 - 10.0, dodecene-1 - 10.0;

- a solution of diethylaluminum chloride 0.226 wt.% (0.314 g);

- MSC 0.0628 g (0.044 wt.%);

- precipitant isopropyl alcohol (IPA) 347.3 g;

- conversion rate of 7%;

- for PTP, the copolymers were taken in an amount of 25.0 wt.% (25 g);

- Surfactants were added to the copolymers in an amount of 5 wt.% (5 g)

- medium for the polymer, a mixture of isopropyl alcohol (IPA) with polyethylene glycol in a ratio of 10: 1,

At the same time, the results were:

- the concentration of copolymers for the same level of sgds 30% was 1.2 ppm;

- the concentration of PTP for the same level of sgds 30% was 6.5 ppm;

- the content of hexene-1 in the return hexene was 99.7%;

- the percentage of the return amount of hexene-1 was 92.47%.

Example 18. The polymerization was carried out analogously to example 1 with the following changes:

- monomer, vol.%: hexene-1 - 20.0; decen - 80.0;

- diethylaluminium chloride 0.3 wt.% (0.206 g);

- MSC 0.0060 g (0.0041 wt.%);

- precipitant polypropylene glycol 280.56 g;

- the conversion rate of 6.2%;

- for PTP polymer was taken in an amount of 30.0 wt.% (30.0 g);

- surfactants were added to the copolymers in an amount of 3.0 wt.% (3.0 g)

- environment additives - poliropylene glycol in an amount of 67.0 wt.% (67.0 g),

At the same time, the results were:

- the polymer concentration for the same level of sgds 30% was 0.6 ppm;

- the concentration of PTP for the same level of sgds 30% was 2.1 ppm;

- the content of decene-1 in the return decene was 99.0%.

- the content of octene-1 in the return octene was 99.0%.

- the total number of return monomer was 98.3%.

Example 19. The polymerization was carried out analogously to example 1 with the following changes:

- monomer, vol.%: octene-1 - 20.0; decen - 80.0;

- diethylaluminium chloride 0.3 wt.% (0.204 g);

- MSC 0.0062 g (0.0042 wt.%);

- precipitant polyethylene glycol 302.4 g;

- conversion rate of 9.8%;

- for PTP polymer was taken in an amount of 28.0 wt.% (28.0 g);

- Surfactants were added to the copolymers in an amount of 2.8 wt.% (2.8 g)

- environment additives - polyethylene glycol in an amount of 69.2 wt.% (69.2 g),

At the same time, the results were:

- the polymer concentration for the same level of sgds 30% was 0.75 ppm;

- the concentration of PTP for the same level of sgds 30% was 2.5ppm;

- the content of decene-1 in the return decene was 99.0%;

- the content of octene-1 in the return octene was 99.0%;

- the total amount of regenerated monomer was 98.5%.

Example 20. The polymerization was carried out analogously to example 1 with the following changes:

- monomer, vol.%: hexene-1 -20,0; octen-1 - 80.0;

- diethylaluminium chloride 0.3 wt.% (0.2155 g);

- MSC 0.0061 g (0.0044 wt.%);

- precipitant diethylene glycol 290.16 g;

- the conversion rate of 13.7%;

- for PTP polymer was taken in an amount of 33.0 wt.% (33.0 g);

- Surfactants were added to the copolymers in an amount of 3.3 wt.% (3.3 g)

- environment additives - monopropylene glycol in an amount of 63.7 wt.% (63.7 g),

At the same time, the results were:

- the polymer concentration for the same level of sgds 30% was 0.9 ppm;

- the concentration of PTP for the same level of sgds 30% was 4.6 ppm;

- the content of hexene-1 in the return hexene was 99.0%;

- the content of octene-1 in the return octene was 99.0%;

- the total number of return monomer was 98.3%.

Thus, as a result of using the proposed polymerization method and a method for preparing an anti-turbulent additive, the following results were obtained:

- the process of returning monomers to recycling has been simplified due to a simpler distillation of monomers, therefore, the cost of producing polymers for an anti-turbulent additive and the additive itself has decreased;

- with the achieved simplification of the method for the production of polymers and anti-turbulent additives based on them, the degree of purity of the return monomers with respect to the prototype did not deteriorate, 99.7% for hexene, and 99.0% for octene and decene, remaining within the requirements of TU;

- improved indicator of the amount of regenerated monomer relative to the prototype, increasing from 92.47% of the prototype to 97.3-99.2% for the invention;

- the quality of the additive has improved, its effectiveness has increased, based on its required amount for the prototype 6.5 ppm, for the additive according to the invention (6.2-1.24) ppm for all examples to achieve a 30% reduction in flow resistance. A similar result was obtained for the polymer: for the prototype 1.2 ppm, for the invention (1.05-0.3) ppm;

- a wider range of substances can be taken as the additive medium, which at the stage of preparation of the additive suspension do not affect the specified technical result.

Claims (16)

1. A method of producing an anti-turbulent additive with a monomer recycle, comprising polymerizing a mass of higher α-olefins using a catalytic system — a microspherical catalyst and diethyl aluminum chloride as a cocatalyst, to a predetermined degree of conversion, precipitating the obtained polymer upon reaching a predetermined degree of conversion by adding a precipitant to the reaction mixture taken in excess, regeneration of the unreacted monomer by distillation, separation of the polymer suspension from the liquid phase, purification from impurities, shku after washing with water, forming a slurry obtained by mixing protivoturbulentnyh additive polymer with the polymer and antiaglomeratorom medium, characterized in that the mass ratio of the reaction components: the monomer, catalyst, cocatalyst amounts, wt.%:
Monomer (s) 99.7730-99.8927 Catalyst 0.0015-0.0055 Cocatalyst 0.1058-0.2270,
the polymerization is carried out to a degree of conversion of 5-15%, the degree of conversion is monitored during the polymerization, a substance with a boiling point of not less than 73 ° C above the boiling point of the monomer is taken as the precipitant, while the precipitant is taken in the volume ratio of the initial polymer: precipitant solution from 1: 1.25 to 1: 2.06, after settling of the polymer, finely dispersed polymer is separated from the liquid phase, the monomer is purified by simple distillation or by distillation in vacuo, until the distilled monomer is dried, it is additional purification: the precipitant residues are extracted with water, the aqueous phase is separated from the monomer, to prepare the suspension of the anti-turbulent additive from the above polymer, the components of the suspension of the anti-turbulent additive are taken in the following quantitative ratio, wt.%:
Polymer 25.0-55.0 Polymer medium 39.5-72.5 Surfactant 2.5-5.5 2. The method according to claim 1, characterized in that the separation of the suspension of the dispersed polymer from the liquid phase is carried out by decantation. 3. The method according to claim 1, characterized in that the degree of conversion of the polymerization process of higher α-olefins is controlled using the density measurement method. 4. The method according to claim 1, characterized in that as the precipitant take monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof. 5. The method according to claim 1, characterized in that monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof are taken as the additive medium. 6. A method of obtaining an anti-turbulent additive, including polymerization in the mass of higher α-olefins using a catalytic system - a microspherical catalyst and diethylaluminium chloride as a cocatalyst, to a predetermined degree of conversion, precipitating the obtained polymer upon reaching a predetermined degree of conversion by adding a precipitant to the reaction mixture, taken in excess, the separation of the polymer suspension from the liquid phase, the preparation of a suspension of anti-turbulent additives by mixing the obtained polymer with the medium floor measure and antiaglomeratom, characterized in that the mass ratio of the reaction components: the monomer, catalyst, cocatalyst amounts, wt.%:
Monomer (s) 99.7730-99.8927 Catalyst 0.0015-0.0055 Cocatalyst 0.1058-0.2270,
the polymerization is carried out to a degree of conversion of 5-15%, the degree of conversion is monitored during the polymerization, a substance with a boiling point of not less than 73 ° C above the boiling point of the monomer is taken as the precipitant, while the precipitant is taken in the volume ratio of the initial polymer: precipitant solution from 1: 1.25 to 1: 2.06, after sedimentation of the polymer, finely dispersed polymer is separated from the liquid phase, to prepare the suspension of the antiturbulent additive from the above polymer, the components of the antiturbulent suspension isadki taken in the following quantitative ratio, wt.%:
Polymer 25.0-55.0 Polymer medium 39.5-72.5 Surfactant 2.5-5.5 7. The method according to claim 6, characterized in that the separation of the suspension of the dispersed polymer from the liquid phase is carried out by decantation. 8. The method according to claim 6, characterized in that the degree of conversion of the polymerization process of higher α-olefins is controlled using the density measurement method. 9. The method according to claim 6, characterized in that as the precipitant take monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof. 10. The method according to claim 6, characterized in that monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof are taken as the additive medium. 11. A method of producing higher poly-α-olefins, including polymerization in the mass of higher α-olefins using a catalytic system - a microspherical catalyst and diethylaluminium chloride as cocatalyst, to a predetermined degree of conversion, precipitation of the obtained polymer upon reaching a given degree of conversion by adding to the reaction mixture precipitant, taken in excess, the separation of the polymer suspension from the liquid phase, characterized in that the ratio of the components of the reaction mass: monomer, catalyst, cocatalyst Feenberg wt.%:
Monomer 99.7730-99.8927 Catalyst 0.0015-0.0055 Cocatalyst 0.1058-0.2270,
the polymerization is carried out to a degree of conversion of 5-15%, the degree of conversion is monitored during the polymerization, a substance with a boiling point of not less than 73 ° C above the boiling point of the monomer is taken as the precipitant, while the precipitant is taken in the volume ratio of the initial polymer: precipitant solution from 1: 1.25 to 1: 2.06, after sedimentation of the polymer, the polymer is separated from the liquid phase. 12. The method according to claim 11, characterized in that the separation of the suspension of the dispersed polymer from the liquid phase is carried out by decantation. 13. The method according to claim 11, characterized in that the degree of conversion of the polymerization process of higher α-olefins is controlled using the density measurement method. 14. The method according to claim 11, characterized in that monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof are taken as precipitant. 15. An anti-turbulent additive, comprising preparing a suspension by mixing a higher poly-α-olefin with an additive medium and an anti-agglomerate, characterized in that the polymer obtained using a precipitant in the form of a substance with a boiling point above the boiling point of the starting monomer is not less than 73 ° C, and the components of the suspension of anti-turbulent additives are taken in the following quantitative ratio, wt.%:
Polymer 25.0-55.0 Polymer medium 39.5-72.5 Surfactant 2.5-5.5 16. The anti-turbulent additive according to Claim 15, characterized in that monoglycols, diglycols, polyglycols, cellosolves or mixtures thereof are taken as the additive medium.

Images