The method of preparation of the catalyst and method for producing high molecular weight poly-alpha-olefins using the catalyst

 

The invention relates to methods for macromolecular higher poly-alpha-olefins and catalysts for carrying out the method. High molecular weight higher poly-alpha-olefins are used in various fields, in particular, as agents of reducing the hydrodynamic resistance during movement of hydrocarbon liquids, for example, pumping of oil by pipeline. The described method of preparation of the catalyst, which includes a step for magnesium-containing media followed by the interaction of the carrier with titanium tetrachloride and alkylaromatic ether, magnesium-containing carrier get in two stages, where in the first stage interact metal magnesium with an aromatic halide in the presence of a simple ester with formation of a suspension containing solution magyarkanizsa connection and a solid phase, and the second stage carry out the sequential interaction of the resulting suspension with alkoxysilanes silicon and then alcohol. Also described polymerization process of alphaolefins at a temperature of from 0 to 50oIn the presence of a catalyst obtained by the method described above. Effect: simplified method recip C. and 5 C.p. f-crystals, 2 tab.

The invention relates to methods for macromolecular higher poly-alpha-olefins and catalysts for carrying out the method. High molecular weight higher poly-alpha-olefins are used in various fields, in particular, as agents of reducing the hydrodynamic resistance during movement of hydrocarbon liquids, for example, during transfer of oil through the pipeline.

A method of obtaining higher poly-alpha-olefins by polymerization of higher alphaolefins with the number of carbon atoms from 6 to 10 in the environment of the hydrocarbon solvent in the presence of a catalyst obtained by reduction of titanium tetrachloride alyuminiiorganicheskikh connection, and alyuminiiorganicheskikh of socializaton (RF Patent 2075485, C 08 F 10/14, 20.03.1997). This catalyst allows at a temperature of from -30 to 20oWith (mostly at 0oC) for 5 hours to achieve product conversion 58-98%. In this way we obtain a high molecular weight polymers with a characteristic viscosity []=1.2-1.9 m3/kg. the Disadvantages of this method are the low activity of the used catalyst, the necessity of using low TimesTen way of getting higher poly-alpha-olefins using the catalyst system, consisting of applied titanomagnievoe catalyst containing titanium tetrachloride on the media - magnesium chloride and stereoregular additive (e.g., dibutyl phthalate), and socializaton, representing a mixture of trialkylamine with alkoxysilanes silicon. This catalytic system has a significantly higher activity than catalysts based on TiCl3and is widely used to obtain polypropylene and copolymers of propylene with alphaolefins. A number of cooking methods applied titanomagnievyj catalysts are described, for example, in the book by E. P. Moore (Jr.), Polypropylene Handbook, Hansen Publishers, 1996.

The closest in technical essence and the achieved result is a method of polymerization using the catalyst obtained in three stages (RF Patent 2152404, C 08 F 4/64, 10.07.2000).

Stage (a). The contacting metallic magnesium with an aromatic halide RX, in which R is an aromatic group containing from 6 to 20 carbon atoms, X is a halogen atom. The result is a suspension that contains the solution magyarkanizsa compounds and solid by-product consisting mainly of magnesium chloride. The solution manyorganizations silicon compound, contains alkoxygroup or alloctype, the solution magyarkanizsa compounds at a temperature of from -20 to 20oWith the formation of a solid product, which is used in the subsequent stage (s) in contact with the titanium tetrachloride with the formation of the catalyst.

This catalyst has a narrow distribution of particle size and produces a polypropylene powder with a small amount of fine fraction, which is an important advantage in obtaining polypropylene in modern industrial processes in the liquid monomer in the gas phase. The catalyst provides a much higher output at higher polymerization of olefins as compared with a catalyst based on il3(RF patent 2075485, C 08 F 10/14, 20.03.1997).

The disadvantage of this method of preparation of the catalyst is the presence of significant amounts of solid waste in the first stage of preparation of the catalyst. The need to separate these wastes complicates the technology of preparation of the catalyst.

The invention solves the problem of simplifying the method of preparation of the catalyst, further increasing the activity of the catalyst, but also solves the problem of increasing the molecular weight of the obtained polymer and is erinacei catalyst, which is prepared in three stages as follows.

Stage (a). In the interaction of magnesium metal with an aromatic halide by known methods (Patent RF 2152404, C 08 F 4/64, 10.07.2000) receive a suspension (product (I) containing solution magyarkanizsa connection and a solid phase, and then use this suspension without separation of the solution and the solid phase to the next stage (b).

Stage (b). At this stage, carry out the sequential interaction of the suspension obtained in stage (a), with alkoxysilanes silicon and then alcohol with the formation of magnesium-containing media (product II).

The interaction of magnesium-containing carrier with titanium tetrachloride and alkylaromatic ether to obtain the final catalyst [stage (C)] performed similarly well-known solution.

In addition to simplifying the technology of preparation of the catalyst and reduce the amount of waste at the stage (a), a further advantage of the catalyst compared to the prototype is a higher activity, which is achieved through the use of alcohol at the stage (b) (synthesis magniysoderzhaschego media).

Stage (a) in the process of preparation of the catalyst according to the invention spend butanols chlorobenzene, bramasol and iadanza. You can also use a combination of two or more organic halides.

Preferably the magnesium and the organic halide is brought into contact with each other in the presence of an inert hydrocarbon solvent and a simple ether. Examples of solvents are aliphatic, alicyclic or aromatic solvents containing 4-10 carbon atoms. Examples of ethers are diethyl ether, diisopropyl ether, disutility ether, dietarily ether, dellroy ether, tetrahydrofuran (THF) and anisole, preferably disutility or dietarily ether.

The reaction temperature in stage (a) is from 20 to 150oWith, mainly to 110o; Time of interaction is up to 20 hours, mostly 4-8 PM

After the completion of stage (a) receive a suspension (product I), consisting of a solution magyarkanizsa connection structure of Mg3PhnClm(n=3.5-4.5; m= 1.5-2.5) and sediment. This product is used for the subsequent stage (b).

At the stage (b) the suspension obtained in stage (a) is brought into contact with alkoxysilanes silicon and alcohol. This is carried out by adding a first silicon compound containing alkoxygroup, Derici reaction medium at a temperature of from 20 to 70oWith and purification of the obtained product II by washing the hydrocarbon solvent.

As alkoxysilane silicon is used as a compound of General formula R1nSi(OR2)4-nwhere R1and R2is a hydrocarbon group containing from 1 to 6 carbon atoms, n=02, preferably tetraethoxysilane.

As alcohol at the stage (b) use alcohols ROH, where R is a hydrocarbon group containing from 2 to 8 carbon atoms, preferably ethanol.

The molar ratio between silicon and magnesium in stage (b) can vary from 0.2 to 20, preferably from 0.2 to 1. The molar ratio between alcohol and magnesium at the stage (b) can vary from 0.5 to 5, preferably from 1 to 3.

Formed in stage (b) the product II is then used for the preparation of the catalyst in stage (C).

The preparation of the catalyst is conducted by contacting stage (s) of product II obtained in stage (b), with titanium tetrachloride and alkylaromatic ether.

The problem is solved also by way of high molecular weight poly-alpha-olefins, which is carried out by polymerization of the corresponding alphaolefin in the presence Catt trialkyl aluminum, for example, triethylamine. The polymerization process is carried out at a temperature from 0 to 50oC.

In the polymerization of olefins in the reaction medium usually impose additional electron-donating compound, which increases stereoregular the ability of the catalyst. As such compounds can be used alkoxysilane silicon composition R1nSi(OR2)4-nwhere R1and R2is a hydrocarbon group containing from 1 to 6 carbon atoms, n=12.

Prepared according to the proposed method, the catalyst suitable for the polymerization of olefins containing from 2 to 10 carbon atoms, such as ethylene, propylene, butylene, hexene, octene, the mission dodecen. This catalyst is particularly suitable for the polymerization of hexene and other senior alphaolefins (from C6to C14).

The polymerization is carried out mainly in the liquid phase in the presence of a hydrocarbon solvent, such as hexane, heptane, octane, cyclohexane, benzene, toluene or xylene.

The polymerization temperature is 0 to 50oC. Important technological advantage of the obtained catalyst is the possibility of carrying out the polymerization process when s is the buy will be further explained with examples, which do not limit the invention.

Example 1 Preparation of the catalyst of stage (a). In a three-neck flask, equipped with reflux condenser and addition funnel, load 26 g of magnesium powder (1.07 mol). The flask is rinsed with nitrogen. Magnesium is heated 1 h at 80oAnd then add a mixture of 173 ml dibutylamino ether and 80 ml of chlorobenzene. Then the reaction mixture was added 0.03 g of iodine and 3 ml of chloride n-butane. After the disappearance of the iodine staining raise the temperature of the mixture up to 97oWith and slowly add 250 ml of chlorobenzene for 2.5 hours the reaction mixture is intensively stirred for 8 h at 97oC. the result is a suspension (product (I) containing solution magyarkanizsa connection structure of Mg3Ph4Cl2and a solid phase containing MgCl2in the ratio of Mg3Ph4Cl2/MgCl2= 2:1.

Stage (b). A suspension of the product I received at stage (a) (100 ml, 0.25 mol Mg), loaded into the reactor. The reactor is cooled to 0oC and for 2 h add a mixture of 22 ml of tetraethoxysilane (TES) and 38 ml of heptane under stirring.

Then the reaction mixture was kept at 0oWith another 0.5 h under vigorous stirring dosed during uderjivayut at this temperature for 2 hours After stirring and heating stopped and the solid product is allowed to settle. The liquid above the precipitate is removed by decantation. The solid is washed with heptane (4 x 250 ml). Obtain 25.2 g of solid magnesium-containing product II, suspended in 100 ml of heptane.

Stage (C). The reactor is rinsed with nitrogen and load it consistently mixture of 150 ml of titanium tetrachloride and 150 ml of chlorobenzene and 12 g of product II in 48 ml of heptane. The reaction mixture is heated with stirring to 115oWith, give it 7.2 ml of dibutyl phthalate and maintained at 115oC for 1 h After mixing is stopped and the solid product is allowed to settle.

The liquid above the precipitate is removed by decantation, and then add the mixture. consisting of 150 ml of titanium tetrachloride and 150 ml of chlorobenzene. The reaction mixture is again heated to 115oC and stirred for 30 min, then the solid product is allowed to settle for 30 minutes This last cycle was repeated once more. The obtained solid is washed 5 times using 300 ml of heptane at 60oC. Get the catalyst, suspended in heptane. The content of titanium in the catalyst - 1.9 wt.%.

Polymerization reactor of 1 l load p is mol/ml (1.45 mmol CHIBA), 1.2 mmol of propyltrimethoxysilane (PTMS) and 62 ml (0.5 mol) of hexene-1, which corresponds to the concentration of 1-hexene in the reactor 2.5 mol/l and 0.0144 g of catalyst. The polymerization is carried out at a temperature of 20oC for 1 h, the Polymer is discharged, add 20 ml of isopropanol and 20 ml of stabilizer ANOX in acetone with a concentration of 1 g/l Polymer is dried to constant weight. The output polyacene is 1.0 kg/g cat.; conversion of 1-hexene is 46%. The characteristic viscosity of the polymer [] dened in gasoline at 20oS, 1.3 m3/kg.

Example 2 a Catalyst was prepared as described in example 1 except that in stage (b) use 21.9 ml of ethanol (0.375 mol, the molar ratio of ethanol : Mg=1.5) and 38.1 ml of heptane.

Polymerization of 1-hexene carried out analogously to example 1, but using 0.0121 g of catalyst. The output polyacene is 1.2 kg/g catalyst, the conversion of hexene-1 - 46%. Get polyhexes the characteristic viscosity of 1.6 m3/kg.

Example 3 a Catalyst was prepared as described in example 1 except that in stage (b) use 43.8 ml of ethanol (0.75 mol, the molar ratio of ethanol : Mg=3) and 16.2 ml of heptane.

Polymerization of 1-hexene spend analogizer>3/kg.

Example A (comparative) Preparation of the catalyst of stage (a). In a three-neck flask, equipped with reflux condenser and addition funnel, load 26 g of magnesium powder (1.07 mol). The flask is rinsed with nitrogen. Magnesium is heated 1 h at 80oAnd then add a mixture of 173 ml dibutylamino ether and 80 ml of chlorobenzene. Then the reaction mixture was added 0.03 g of iodine and 3 ml of chloride n-butane. After the disappearance of the iodine staining raise the temperature of the mixture up to 97oWith and slowly add 250 ml of chlorobenzene for 2.5 hours the reaction mixture is intensively stirred for 8 h at 97oC. Then, the stirring and heating is stopped and the solid product is allowed to settle for 48 hours After it is separated from the sludge solution magyarkanizsa compounds with a concentration of 1 mol/L. This solution is used for carrying out stage (b).

Stage (b). To a solution of magyarkanizsa connection (100 ml, 1 mol/l) add a mixture of 11.2 ml of tetraethoxysilane (TES) and 38 ml dibutylamino ether under stirring at 0oC for 2 h then the reaction mixture was kept at 0oWith another 0.5 h and then increase the temperature to 60oC. Then the reaction soucat 13.5 g of light yellow solid, suspended in 40 ml of heptane.

Stage (C) preparation of the catalyst carried out analogously to example 1.

Polymerization of 1-hexene carried out analogously to example 1, but using 0.015 g of catalyst. The output polyacene is 0.50 kg/g cat., the characteristic viscosity of the polymer - 1.2 m3/kg.

The example In (comparative) Stage (a) is carried out analogously to example 1.

Stage (b) is conducted as described in example 1, except that in this case, the product obtained after adding tetraethoxysilane, not treated with ethanol.

Stage (C) and polymerization of 1-hexene carried out analogously to example 1. The output polyacene is 0.55 kg/g cat., characteristic viscosity of polyacene - 1.2 m3/kg.

Example 4 Stage (a) preparation of the catalyst were carried out as described in example 1, except that use of 24.3 g of magnesium (1 mol), 169.5 ml dibutylamino ether (1 mol) and 370 ml of chlorobenzene. The result is a suspension of the product I.

Stage (b). Suspension of product I (100 ml, 0.2 mol Mg) is loaded into the reactor and added under stirring to 40 ml of heptane. The reactor is cooled to -15oC and for 1 h add a mixture of 17.9 ml of tetraethoxysilane (TES, 0.08 mol) and 42.4 ml of heptane under stirring. PolioC. Then the reaction mixture was kept at 60oC for 1 h, cooled to a temperature of 20oC and at this temperature with vigorous stirring metered in over 3 hours a mixture of 7.8 ml of 2-ethylhexanol (2-EH, 0.05 mol), 8.8 ml of ethanol and 73.4 ml of heptane. Then increase the temperature within 1 h to 70oC and maintained at 70oC for 2 hours After mixing and heating stopped and the solid product is allowed to settle. The liquid above the precipitate is removed by decantation. The solid is washed 4 times using 250 ml of heptane. Get the magnesium-containing product II, suspended in 100 ml of heptane.

Stage (C) and polymerization of 1-hexene carried out analogously to example 1. The output polyacene is 0.65 kg/g cat., the characteristic viscosity of the polymer - 1.3 kg/m3.

Example 5
Stage (a) and (b) the preparation of the catalyst were carried out as described in example 4, except that in stage (b) a mixture of 15.6 ml of 2-ethylhexanol (0.1 mol), 17.5 ml of ethanol (0.3 mol) and 56.9 ml of heptane.

Stage (C) and polymerization of 1-hexene carried out analogously to example 1. The output polyacene is 0.72 kg/g cat., the characteristic viscosity of the polymer - 1.3 kg/m3.

Example 6
Preparation katalizatoram in the presence of vitaminology ether at a molar ratio of ester/Mg=1. Polymerization of 1-hexene is carried out in the conditions of example 1. The output polyacene is 1.0 kg/g cat., the characteristic viscosity of the polymer - 1.2 kg/m3.

Example 7
The preparation of the catalyst were carried out as in example 1, except that the synthesis magyarkanizsa connections on the stage (a) is carried out in the presence of vitaminology ether at a ratio of ester/Mg=1 and a suspension of the product (I) is treated With6H5Si(OS2H5)3when the ratio Si/Mg=1. Polymerization of 1-hexene is carried out in the conditions of example 1. The output polyacene is 1.1 kg/g cat., the characteristic viscosity of the polymer - 1.3 kg/m3.

Example 8
Using the catalyst prepared according to example 2. Polymerization of 1-hexene is carried out in the conditions of example 1 except that the polymerization time is 2 hours Output polyctena in these conditions is 1.5 kg/g cat. ; conversion of hexene-1 - 53%. The characteristic viscosity of the polymer is 1.4 m3/kg.

Example 9
Using the catalyst prepared according to example 1. Polymerization of 1-hexene is carried out in the conditions of example 8, but as socializaton use triethylaluminium (tea). The output polyctena in these conditions is 1.2 kg/g cat. ; CONV is jut catalyst, prepared according to example 1. Carry out the polymerization of octene-1 in the conditions of example 8. Output polyctena is 2.0 kg/g cat. The resulting polymer has a characteristic viscosity of 0.25 m3/kg.

Example 11
Using the catalyst prepared according to example 1. Conduct polymerization fraction of olefins, C12-C14in the conditions of example 8. The polymer yield was 3 kg/g cat. The resulting polymer has a characteristic viscosity of 0.32 m3/kg.

Example 12
Using the catalyst prepared according to example 1. Polymerization of 1-hexene is carried out in the conditions of example 8, but at the temperature of polymerization of the 30oWith and hanging catalyst 0.0086, the polymer Yield is 3.1 kg/g cat., conversion of 67%. Received polyhexes has a characteristic viscosity - 0.69 m3/kg.

Example 13
Using the catalyst prepared according to example 2. Polymerization of 1-hexene is carried out in the conditions of example 1, but instead PTMS using tetraethoxysilane (TES). The output polyacene is 1.0 kg/g cat.; the conversion rate is 44%. Get polyhexes the characteristic viscosity of 1.4 m3/kg.

As seen from the above examples and tables, the present invention can simplify the cooking method katalizatoru. The use of the catalyst according to the proposed method in the polymerization process of alphaolefins increases the molecular weight of the resulting poly-alpha-olefins and / or temperatures of polymerization.


Claims

1. The method of preparation of a catalyst to obtain high molecular weight poly-alpha-olefins, comprising a step for magnesium-containing media and the subsequent interaction of the carrier with titanium tetrachloride and alkylaromatic ether, characterized in that the magnesium-containing carrier get in two stages, where in the first stage interact metal magnesium with an aromatic halide in the presence of a simple ester with formation of a suspension containing solution magyarkanizsa connection and a solid phase, and the second stage carry out the sequential interaction of the resulting suspension with alkoxysilanes silicon and then alcohol.

2. The method according to p. 1, characterized in that the ether in the first stage is disutility or dietarily ether.

3. The method according to any of paragraphs.1 and 2, characterized in that alkoxysilanes silicon in the second stage is the connection R1nSi(OR2)

5. The method according to any of paragraphs.1-4, characterized in that the molar ratio between alcohol and magnesium is 1-3.

6. A method of obtaining a poly-alpha-olefins by polymerization of alphaolefinsnH2nwhere n6, in the presence of a catalytic system comprising a solid component containing titanium tetrachloride, magnesium-containing carrier and electron-donating compound and socialization consisting of trialkylamine and electron-donating compounds, characterized in that the use of the catalyst obtained according to any one of paragraphs.1-5.

7. The method according to p. 6, characterized in that the polymerization is carried out at a temperature of 0-50C.

 

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