A method of producing a catalyst for polymerization of olefins and a method of polymerization of olefin monomers with its use

 

(57) Abstract:

The invention relates to a method for producing a catalyst for polymerization of olefins and method of polymerization of olefin monomers with its use. The described method of preparation of the catalyst by contacting metallic magnesium with an organic halide RX, in which R is an organic group containing from 1 to 20 carbon atoms, X is a halogen atom, to form a soluble product (I), by adding a silicon compound containing alkoxygroup or alloctype, to the product of (I), with the formation of the solid product (II), and processing of the product (II) titanium tetrachloride and electrothermal connection, and the connection of the silicon and the product (I) is injected simultaneously into the reactor to obtain a product (II). There is also described a method of polymerization of olefin monomers using a catalyst obtained in the above way. The technical result is an improvement of the morphology of the catalyst particles, especially for the catalyst particles are larger in size. Powder polyolefin obtained by using the catalyst, has the same morphology as the catalyst. When using the catalyst prepared with the (d) less than 1.5 and good fluidity. 2 S. and 6 C.p. f-crystals, 4 PL.

The invention relates to a method for producing a catalyst for polymerization of olefins.

The catalysts on supports for the polymerization of olefins have a high activity and high stereospecificity. These catalysts known for a long time. Significant items for the preparation of such catalysts are magnesium-containing carrier and a compound of titanium, associated with it. As socializaton use aluminum compounds.

Currently, high-level applied catalysts are most commonly used for the polymerization of olefins, such as propylene. The high activity of the catalyst provides a high yield of polyolefin in terms of the connection of titanium in the catalyst.

There are several known methods for the preparation and activation of the magnesium-containing carrier for catalyst. For example, you can grind magnesium chloride, to obtain magnesium chloride by the method of spray drying or to obtain a magnesium-containing media by precipitation. Several other methods of preparation of magnesium-containing media described in the book by E. P. Moore (Jr.), Polypropylene Handbook, Hansen Publishers, 1996, p. 22.

The closest is the ora carried out by contact of the compounds of magnesium with a titanium compound. Compound magnesium receive the following way:

a) contacting metallic magnesium with an aromatic halide RX, where R is an aromatic group containing from 6 to 20 carbon atoms, X is halogen, then a water soluble product (I) of the reaction is separated from the solid residual products;

b) adding to the resulting product of (I) a silicon compound containing an alkoxy - or alloctype at a temperature of from -20 to 20oWith the formation of a solid product (II);

b) adding to the resulting product of (I) a silicon compound containing an alkoxy - or alloctype at a temperature of from -20 to 20oWith the formation of a solid product (II);

(C) product (II) is in contact with TiCl4and alkylaromatic ether such as dibutyl phthalate, with the formation of a catalyst containing magnesium chloride as a carrier, titanium tetrachloride and alkylaromatics ether.

The invention solves the problem of the development of a catalyst having activity and selectivity in excess of these figures in a known catalyst.

The problem is solved by the following method of preparation of the catalyst.

At the stage (b) the silicon compound and the reaction is "co-administration" means the administration of the reaction product (I) and compounds of silicon in this way, that the molar ratio of Mg/Si essentially not changed in the process of introducing these components in the device.

This method has the advantage that improves the morphology of the catalyst particles, especially for the catalyst particles are larger in size. Hereinafter, the term "morphology" refers not only to the form of catalyst particles, but also to the distribution of particle size and bulk weight of the catalyst particles.

Powder polyolefin obtained by using the catalyst, has the same morphology as the catalyst. This is a known effect called "effect of replication" (S. van der Ven, Polypropylene and other Polyolefins, Elsevier 1990, p. 8-10). When using the catalyst prepared according to the present invention, receive particles of the polymer is almost round shape with the ratio of length/diameter (l/d) less than 1.5 and a good fluidity, whereas according to (RF patent 2152404, IPC 7 C 08 F 4/64, 10.07.2000) are formed elongated particles of polymer with l/d greater than 2.5.

At the stage (b) a water soluble product (I) obtained after carrying out stage (a), enter into contact with the silicon compound containing an alkoxy - or alloctype, the way that the product (I) and a compound of silicon introduced simultaneously into the reactor.

which of the silicon compound with the product (I), with the subsequent flow of the reaction medium in the reactor (II), which completes the formation of the product (II).

The reactor (I) for preliminary mixing of the silicon compound with the product (I) may be a device, in which premixing perform dynamic or static way. Premixing dynamic by implementing, for example, by mixing, stirring, shaking and ultrasonic waves. Preliminary mixing by static exercise, for example, static mixers or in the tube, where the contact connection of the silicon and the product (I). For the preparation of the catalyst in large quantities can be used both static and dynamic mixing. Premixing by dynamic preferably used for the preparation of the catalyst in small quantities. For the preparation of the catalyst in large quantities, preferably using a static mixer. Preferably, the silicon compound and the product (I) are pre-mixed before the mixture is introduced into the reactor (II), which is formed of the reaction product (II). In this way there is formed a catalyst, providing particles of polymer with the best the of from 1 to 50 C. The temperature during the preliminary mixing is from 0 to 80oC, preferably from 10 to 50oC.

The silicon compound and the product (I) can be continuously or in portions to enter into the reactor. Preferably continuously.

The formation of the product (II) typically occurs at a temperature of from -20 to 100oC, preferably at temperatures from 0 to 80oC.

Preferably the product of (I) and the silicon compound containing an alkoxy - or alloctype, are in contact in the presence of an inert solvent, such as solvents, further note as the dispersant in the discussion stage (a). The solvent may be a solvent for the silicon compound, a dispersant for the product (I) or be present in the reactor where the product (II). There are three possible combinations. Preferably, the reactor (II), which completes the formation of the product (II) was with a mixing device.

The molar ratio Si/Mg at the stage (b) range from 0.2 to 20. Preferably from 0.4 to 1.

Formed in stage (b) the product II is washed with an inert hydrocarbon solvent and then used for preparation of the catalyst in stage (C).

We can note the following pemutakhiran, tetraazamacrocycle, tetrafunctional, Tetra(p-methylphenoxy)silane, tetramethylsilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyldimethylsilyl, butyltrichlorosilane, butyldimethylsilyl, butyldiphenoquinone, isobutyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzylideneaniline, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, diethyldichlorosilane, dietedisintossicanti, deacidification, dibutylethanolamine, deputydirector, dibutylethanolamine, diisobutyldimethoxysilane, diisobutyldimethoxysilane, diphenylmethylsilane, diphenyldichlorosilane, diphenyldichlorosilane, dibenzodioxocin, divinerdiagnostician, diallyldimethyl, diphenyldichlorosilane and methylphenyldichlorosilane. Preferably using tetraethoxysilane.

Stage (a) in the process of preparation of the catalyst is carried out by contactyour metal magnesium, however, preferably used finely ground magnesium metal, such as magnesium powder. For quick reaction it is preferable to use warm up the magnesium in the atmosphere of nitrogen. In organic halide RX group R is an organic group containing from 1 to 20 carbon atoms, and X is a chlorine atom or bromine.

Examples of organic groups R are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, octyl, phenyl, tolyl, xylyl, mesityl and benzyl. Can also be used in combination of two or more organic halides RX.

Magnesium and an organic halide RX can react with each other without using a special dispersing agent, in this case, the organic halide is used in excess. Magnesium and an organic halide RX can react with each other in the presence of an inert dispersing agent. Examples of dispersing agents are: aliphatic, alicyclic or aromatic solvents containing 4-10 carbon atoms. At stage (a) in the reaction mixture was added ether. Examples of ethers are diethyl ether, diisopropyl ether, disutility ether, dietarily ether, differ. It is preferable to use an excess of chlorobenzene as an organic halide RX. Thus, the chlorobenzene is used as a dispersing agent, and as an organic halide.

The ratio of the organic halide/ether affects the catalyst activity. The volumetric ratio of chlorobenzene/disutility ether may vary, for example, between 75:25 and 35:65. When the ratio of chlorobenzene/disutility ether decreases the bulk density of the powder of polyolefin produced using this catalyst becomes smaller, and when the ratio of chlorobenzene/disutility ether increases, the amount of dissolved product (I) is reduced. Therefore, the best results are obtained when the volume ratio of chlorobenzene/disutility ether is between 70:30 and 50:50.

You can add a small amount of iodine and/or alkylhalogenide to cause interaction between the metal magnesium and an organic halide RX, and that it proceeded with high speed. Examples of alkylhalogenide are butyl chloride, butyl bromide and 1,2-bromatan. If the organic halide is an alkyl halide, preferably using iodine and 1,2-bromatan.

Temperature p>/P>After completion of the reaction product dissolved (I) is separated from the solid residual products.

The preparation of the catalyst is conducted by contacting stage (C) purified reaction product (II) with titanium tetrachloride.

At the stage (C) is also electrothermo connection (D1). Examples (D1are carboxylic acids, anhydrides of carboxylic acids, esters of carboxylic acids, galodamadruga carboxylic acids, alcohols, ethers, ketones, amines, amides, NITRILES, aldehydes, alcoholate, sulfonamide, thio-ethers, thioethers and organic compounds containing heteroatom, such as nitrogen, oxygen and phosphorus.

Preferably as a (D1) using dibutyl phthalate.

The molar ratio of TiCl4/Mg at the stage (C) is 10-100, preferably 10-50. The molar ratio of electron donor, if used, to the magnesium at the stage (C) is 0.05 to 0.75. Preferably 01-04.

At the stage (C) using solvent - aliphatic or aromatic hydrocarbon, toluene or chlorobenzene.

The reaction temperature in stage (C) 50-150oWith, preferably 60-120oWith reduced or increased temperature is Rigden to obtain polyolefins by polymerization of olefins in the presence of a catalyst and socializaton. Socialization typically an ORGANOMETALLIC compound containing a metal of the 1.2, 12, or 13 groups of the Periodic system of the elements (Handbook of chemistry and physics, 70th edition of the firm si-al-cu Press, 1989-1990). The preferred acetalization is alyuminiiorganicheskikh connection. As alyuminiiorganicheskikh connections use compounds having the formula Rnl3-nin which R is an alkyl or aryl group, X is a halogen atom or hydrogen, and n 1 and 3. Examples alyuminiiorganicheskikh compounds are trimethylaluminum, triethylaluminum, dimethylaluminum chloride, diethylaluminium.

In the polymerization of olefins you can enter additional electrothermo connection (D2). As (D2) use the organosilicon compounds.

Examples of organosilicon compounds suitable as (D2), are: tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, deacidification, diisobutyldimethoxysilane, diisobutyldimethoxysilane, propyltrimethoxysilane, cyclohexanedimethanol, dicyclopentadienyliron, excelan, bis(perhydrosqualene)dimethoxysilane, dicyclohexylammonium, deerbenevskaya, di(n-propyl)dimethoxysilane and di(n-butyl)dimethoxysilane. Preferably use the alkoxysilane.

The molar ratio of metal in socializaton relative to titanium in the course of polymerization is 0.1-2000. Preferably 5 are 300. The molar ratio of aluminum/electron donor in the polymerization mixture is 0.1-200; preferably 3-100.

This catalyst suitable for the polymerization of mono - and diolefins containing from 2 to 10 carbon atoms, such as ethylene, propylene, butylene, hexene, octene, butadiene and mixtures thereof. This catalyst is particularly suitable for the polymerization of propylene and mixtures of propylene with ethylene.

The polymerization is carried out in gas phase or in the liquid phase. In the case of polymerization in the liquid phase is present dispersing agent, such as n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene or xylene. In addition, as a dispersing agent using a liquid olefin.

The temperature of polymerization 0-1202oC, preferably 40-100oC. A Pressure Of 0.1 To 6 MPa. The molecular weight of the polyolefin produced in the course of floor is suitable for this purpose.

The polymerization can be performed continuously or periodic manner. The polymerization can be carried out in several successive stages. In addition, the polymerization can be conducted initially in the liquid phase, and then in the gas phase.

The present invention is illustrated by the following examples.

Example 1.

The product I.

Into a flask equipped with reflux condenser, dropping funnel and stirrer, load the powder magnesium (24.3 g, 1 g/atom). The flask is rinsed with nitrogen. Magnesium is heated 1 h at 80oAnd then add a mixture of 170 ml dibutylamino ether and 60 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 97oAnd slowly for 25 h metered 220 ml of chlorobenzene. The resulting process is the dark reaction mixture is stirred for 8 h at 97oC. Then, the stirring and heating is stopped, and the solid material give be deposited within 48 hours After desantirovaniya solution above the sediment get the solution formanilide (PhxMgCl2-xthe product (I)) with a concentration of 1.36 mol Mg/L. This solution Edyta (I) (200 ml, 0,272 mol Mg) and 100 ml of tetraethoxysilane (TES) in debutalbum the ether (the RHEED), (33,4 ml TPP and 66.6 ml of the RHEED), cooled to 15oAnd then simultaneously metered into the reactor pre-mixing (I) a volume of 0.45 ml, equipped with a stirrer and jacket (minimixer). Minimixer cooled to 10oBy cold water circulating in the jacket of minimixer. The contact time of the reactants in minimixer and the tube connecting minimixer reactor is 13 C. the stirring Speed in minimixer is 1000 rpm, the Temperature of the mixture at the outlet of minimixer 40oC. Formed in minimixer mixture is introduced into the reactor (II) the volume of 0.7 l with masalai. In the reactor, (II) pre-loaded with 100 ml of the RHEED and cooled to 5oC. the dosing Time is 1 h mixing Time in the reactor (II) is 200 rpm

After dispensing the reaction mixture in the reactor was kept for 0.5 h at 5oC, then heated to 60oC and kept at this temperature for 1 h then stirring is stopped and the solid substance allow to settle. The liquid above the precipitate is removed by decantation. The solid is washed 3 times using 300 ml of heptane. In polucau.

The reactor is rinsed with nitrogen and loaded into a 300 ml titanium tetrachloride, and the suspension containing 12 g of product (II) in 36 ml of heptane and 7.2 ml of dibutyl phthalate. Then the reaction mixture was incubated for 2 h at 115oC. thereafter, the stirring is stopped and the solid substance allow to settle. The liquid above the precipitate is removed by decantation, and then add the mixture of titanium tetrachloride (150 ml) and chlorobenzene (150 ml). The reaction mixture is kept for 0.5 h at 115oWith, after which a solid substance, allow to settle, and the last treatment with a mixture of titanium tetrachloride and chlorobenzene again. The obtained solid is washed 5 times at 60oWith using 300 ml of heptane, and then get the catalyst, suspended in heptane.

Polymerization of propylene.

The polymerization of propylene is carried out in a steel reactor volume 07 l in the environment heptane (300 ml) at a temperature of 70oWith a total pressure of 0.5 MPa and in the presence of hydrogen (55 ml) for 2 hours, the Concentration of catalyst is 0,033 g/l; the concentration of triethylaluminum - 0.4 mmol/l; the concentration of propyltrimethoxysilane - 0.4 mmol/L. the Performance of the catalyst in the polymerization of propylene are presented in table the example 1, except that the preliminary mixing solutions of the product (I) and tetraethoxysilane are not in minimixer in a thin tube. Pre-mixing is 4 C.

Preparation of catalyst and polymerization of propylene is conducted according to example 1. The results are presented in table.1. The powder particles of the polymer are partially elongated shape.

Comparative example A.

Product (I) prepared as in example 1.

Preparation of product (II).

A solution of the product (I) (200 ml, 0,272 mole of Mg) is loaded into the reactor and cooled to 5oC. a Solution of TPP (33,4 ml) in the RHEED (66,6 ml) is metered into the reactor with stirring for 1 h After dosing preparation of the product (II) is conducted according to example 1.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 1. All powder particles of polymer have an elongated shape.

Example 3.

The product (I).

Into a flask equipped with reflux condenser, dropping funnel and stirrer, load the powder magnesium (24.3 g, 1 g/atom). The flask is rinsed with nitrogen. Magnesium is heated 1 h at 80oAnd then sequentially loaded into REGO staining raise the temperature of the mixture up to 80oC and slowly for 2.5 h metered mixture of chloride n-butane (110 ml) and dibutylamino ether (750 ml). The reaction mixture is stirred for another 3 h at 80oC. Then, the stirring and heating is stopped, and a small amount of solid material can settle within 24 hours After decanting get a colorless solution of butylmagnesium (product (I)) with a concentration of 1 mol Mg/l

Preparation of product (II) is conducted according to example 1, except that a solution of the product (I) from Example 3 (200 ml of 0.2 mol of Mg) and 100 ml of TES in the RHEED (17 ml TPP and 83 ml of the RHEED) is cooled to 10oAnd then simultaneously metered into minimixer volume of 0.45 ml for 100 min Minimixer cooled to 10oBy cold water circulating in the jacket of minimixer. The contact time of the reactants in minimixer and the tube connecting minimixer reactor is 13 C. After pre-mixing the mixture is introduced into a 0.7 liter reactor under stirring. In the pre-reactor download 100 ml of the RHEED and cooled to -12oC. After completion of the dosing preparation of the product (II) is conducted according to example 1.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results of p is ptx2">

Product (I) prepared as in example 3.

Preparation of product (II).

A solution of the product (I) (200 ml of 0.2 mol of Mg) is loaded into the reactor and cooled to -12oC. a Solution of TPP (17 ml) in the RHEED (83 ml) was metered into the reactor with stirring for 100 minutes After dosing preparation of the product (II) is conducted according to example 1.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table.1. The powder particles of the polymer are rounded.

Example 4.

The product (I).

Into a flask equipped with reflux condenser, dropping funnel and stirrer, load the powder (19.5 g, 0.8 g/atom). The flask is rinsed with nitrogen. Magnesium is heated 1 h at 80oC and then loaded into the reactor under stirring 100 ml of heptane, 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 70oAnd slowly for 2.5 h metered mixture of chloride n-butane (38,5 ml), methyl ethyl (30 ml) and heptane (800 ml). The reaction mixture is stirred for another 3 h at 70oC. Then, the stirring and heating is stopped, and the solid material can precipitate within SS="ptx2">

Preparation of product (II).

A solution of the product (I) (200 ml of 0.07 mole of Mg) and 100 ml of TPP solution in heptane (12.5 ml TPP and 87.5 ml of heptane) heated to 30oAnd then simultaneously metered into minimixer volume of 0.45 ml for 100 min Minimixer heated to 30oC. the contact Time of the reactants in minimixer and the tube connecting minimixer reactor, is 22 C. After pre-mixing the mixture is introduced into a 0.7 liter reactor under stirring. In the reactor is pre-loaded with 100 ml of heptane and heated to 30oC. After completion of dosing, the reaction mixture was incubated at 30oC for 0.5 h, then raise the temperature to 60oC and kept at this temperature for 1 h Then the preparation of the product (II) is conducted according to example 1.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 1. The powder particles of the polymer has an irregular shape.

Comparative example C.

Product (I) prepared as in example 4.

Preparation of product (II).

A solution of the product (I) (200 ml of 0.07 mole of Mg) is loaded into the reactor and cooled to 30oC. a Solution of TPP (12.5 ml) in the RHEED (87,5 ml) is metered into the reactor at premesis>The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table.1. The powder particles of the polymer has an irregular shape.

Example 5.

Product (I) prepared as in example 1.

Preparation of product (II).

100 ml dibutylamino ether is loaded into the reactor and cooled to 5oC. 200 ml of product (I) and 100 ml of TPP solution (33.4 ml of TES and 66.6 ml of the RHEED) uniformly metered into the reactor through a separate tube for 1 h After dosing preparation of the product (II) is conducted according to example 1.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 2.

Example 6.

Product (I) prepared as in example 1, but using 196 g of magnesium powder, 140 ml dibutylamino ether and 310 ml of chlorobenzene. The result is a solution of the product (I) with a concentration of 1.1 mol Mg/l

Preparation of product (II).

100 ml dibutylamino ether is loaded into the reactor and cooled to 10oC. 200 ml of product (I) and 100 ml of TPP solution (27 ml TPP and 73 ml of the RHEED) uniformly metered into the reactor through a separate tube for 1 h After dosing preparation of the product (II) is conducted according to predstavleny in table. 2.

Example 7.

Product (I) prepared as in example 1.

The product (II) prepared as in example 6, but the temperature at the stage of dosing in the reactor is 20oC.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 2.

Example 8.

Product (I) prepared as in example 1.

The product (II) prepared as in example 6, but the temperature at the stage of dosing in the reactor is 30oC.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 2.

Example 9.

Product (I) prepared as in example 1.

The product (II) prepared as in example 1, but prior to mixing the solutions of the product (I) and tetraethoxysilane cooled to -15oWith, and as a result the temperature of the mixture at the outlet of minimixer is 16oC.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 3.

Example 10.

Product (I) prepared as in example 1.

The product (II) prepared as in example 1, but prior to mixing the solutions of the product (I) and retreat the oC.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 3.

Example 11.

Product (I) prepared as in example 1.

The product (II) prepared as in example 1, but the number of solutions of the product (1) and tetraethoxysilane was two times higher than in example 1, and the resulting pre-mixture was twice as less: 6,5 C.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 3.

Example 12.

Product (I) prepared as in example 1.

The product (II) prepared as in example 1, but the total amount of minimixer and tubes between minimixer and the reactor was two times higher than in example 1, and the resulting pre-mixture was twice: 26 C.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 3.

Example 13.

Product (I) prepared as in example 1.

The product (II) prepared as in example 12, a solution of the product of (I) and tetraethoxysilane cooled to -15oWith, as in the example 9, and the resulting temperature of the mixture at the outlet of minimixer sostavliaete presented in table. 3.

Example 14.

Product (I) prepared as in example 1, but get a solution with a concentration of 1.3 mol Mg/l

The product (II) prepared as in example 1, but the reactor is cooled to 0oC.

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 4.

Example 15.

Product (I) prepared as in example 14.

The product (II) prepared as in example 14, but the pre-mixing was 6.5 and the dosing time 30 minutes

The preparation of the catalyst and the polymerization of propylene is conducted according to example 1. The results are presented in table. 4.

Example 16.

Product 1 was prepared as in example 1, but the number of reagents were: magnesium - 360 g, disutility ether - 2,6 l; chlorobenzene - 4,6 l, chloride n-butane - 50 ml, iodine and 0.5, the solution Preparation is carried out in a reactor of stainless steel with a volume of 9 liters of the result 4 l of a solution of the product 1 with a concentration of 1 to 3 mol Mg/l

Product II was prepared as in example 1, but the number of reagents used were 10 times more premixing of the reactants spend in mymixer volume of 4 ml and the volume of the reactor was 5 L. the dosing Time was 120 minutes Near the tion of the catalyst is carried out as in example 1, but the number of reagents was 20 times larger, and the preparation is carried out in a steel reactor with a volume of 9 liters of the results of the propylene polymerization are presented in table. 4.

Example 17.

Product 1 was prepared as in example 1, but the number of reagents were: magnesium - 292 g, disutility ether - 2 l chlorobenzene - 4,6 l, chloride n-butane - 50 ml, iodine and 0.5, the result is 4 l of a solution of the product 1 with a concentration of 1 mol Mg/l

Product II was prepared as in example 1, but the amount of minimixer was 0.15 ml, pre-mixing was 19, the dosing time was 120 min and the volume of the RHEED in the reactor was 250 ml.

The preparation of the catalyst is conducted according to example 1. The results of the propylene polymerization are presented in table. 4.

Example 18.

The product I was prepared as in example 17.

Product II get in a steel reactor with a volume of 5 liters, the volume of minimixer 1.4 ml, the number of reagents was 8 times higher than in example 17, the pre-mixing was 19 and with the dosing time was 240 minutes

The preparation of the catalyst is conducted according to example 1, but the number of reagents was 20 times more and the preparation is carried out in a steel reactor with a volume of 9 liters Resultarea 16, but the number of reagents were: magnesium - 380 g, disutility ether - 2,6 l chlorobenzene - 4,6 l, chloride n-butane - 50 ml, iodine and 0.5, the solution Preparation is carried out in a reactor of stainless steel with a volume of 9 liters In the gain of 3.6 l of a solution of the product 1 with a concentration of 14 mol Mg/l

Product II was prepared as in example 1, but the number of reagents used were 10 times more premixing of the reactants spend in mymixer volume of 4 ml and the volume of the reactor was 5 L. the pre-mixing was 7.5 C, the dosing time is 70 min, the temperature in the reactor 10oC, stirring speed of 125 rpm

The preparation of the catalyst is conducted according to example 1, but the number of reagents was 20 times larger, and the preparation is carried out in a steel reactor with a volume of 9 liters of the results of the propylene polymerization are presented in table. 4.

Example 20.

Preparation of product I is conducted according to example 16.

Preparation of product II.

130 ml dibutylamino ether is loaded into the reactor. The reactor thermostatic at 20oC. Then a solution of the product 1 (400 ml of 0.52 mol Mg) and 200 ml of tetraethoxysilane (64 ml TPP and 136 ml of the RHEED) dosed simultaneously 400 min minimixer volun who is 18 C. After dispensing the product formulation II is conducted according to example 1.

The preparation of the catalyst is conducted according to example 1. The results of the propylene polymerization are presented in table. 4.

Example 21.

Preparation of product I is conducted according to example 16.

Preparation of product II is conducted according to example 20, but temperature is a temperature of the reactor was 30oC.

The preparation of the catalyst is conducted according to example 1. The results of the propylene polymerization are presented in table. 4.

Example 22.

Preparation of product I is conducted according to example 16.

Preparation of product II is conducted according to example 21, but the number of reagents were 2.5 times more than in example 21, and accordingly, the dosing time - 18 hours

The preparation of the catalyst is conducted according to example 1. The results of the propylene polymerization are presented in table. 4.

When comparing examples 1 and 2 with example And improved morphology is illustrated by obtaining particles of rounded shape and increase the bulk weight of the polymer.

When comparing example 3 with example In improving the morphology is illustrated a more narrow distribution of particle size and increase napolitanian bulk density of the polymer.

Methods of measuring and marking.

- The weight percent atactic polypropylene (APP) is determined as follows: 100 ml of filtrate (ml) obtained in the allocation of polypropylene powder (x, g), dried over a steam bath and then in vacuum at 60oC. This gives the value of z (g) APT. The total number of DSA (g, g) is: (y/100) z. The weight proportion of atactic polypropylene is defined as: (g/(g+x)100%).

- Index isotacticity (AI) powder of polypropylene is determined as follows: 5 g of polypropylene powder is extracted with n-heptane in a Soxhlet extraction apparatus for 4 h Index isotacticity represents the weight proportion (weight. %) of the polypropylene powder, which is insoluble in boiling n-heptane.

- Bulk density (VD) of the polypropylene powder is determined by the standard USA Hey-ES-Tee-Em Di.

- d50powder of polypropylene and the range of d90-d10/d50define standard USA Hey-ES-Tee-Em Di.

the value of d50for catalyst calculated as follows: d50PP(1/3Y1/3)-1where Y is the output of polypropylene in grams per gram of catalyst.

1. A method of producing a catalyst for polymerization of olefins by contaduria from 1 to 20 carbon atoms, X is a halogen atom, to form a soluble product (I), by adding a silicon compound containing alkoxygroup or alloctype, to the product of (I), with the formation of the solid product (II), and processing of the product (II) titanium tetrachloride and electrothermal connection, characterized in that the silicon compound and the product (I) is injected simultaneously into the reactor to obtain a product (II).

2. The method according to p. 1, characterized in that the interaction of the product (I) and a compound of silicon is carried out by pre-mixing the product of (I) and compounds of silicon in a separate reactor (I), followed by the introduction of the reaction mixture in the reactor (II), where the formed product (II).

3. The method according to PP.1 and 2, characterized in that the preliminary mixing is carried out in a reactor with a stirrer.

4. The method according to PP. 1-3, characterized in that the premixing is carried out within 1-300 C.

5. The method according to PP.1-4, characterized in that the temperature during the preliminary mixing is 0-80oC.

6. The method according to p. 1, characterized in that the formation of product (II) directly into the reactor with a stirrer.

7. The method of polymerization of olefin McHenry on PP.1-6.

8. The method according to p. 7, characterized in that will polimerizuet propylene or a mixture of propylene and ethylene.

 

Same patents:

The invention relates to the manufacture of catalysts, namely the production of catalysts of the Ziegler-Natta, which can be used for the synthesis of high molecular weight Homo - and copolymers-olefins, α-olefins and polar monomers, rubbers, in particular in the production of polypropylene

The invention relates to a method (generowania type in a suspension of liquid monomer) obtain ethylene-propylene elastomers (EP) and ternary ethylene-propylene-diene elastomers (EPDM)

The invention relates to methods of producing ultra-high molecular weight polyethylene (UHMWPE), synthesized in powder form in the conditions of suspension polymerization of ethylene in the environment of a hydrocarbon diluent at temperatures of 40-70oWith the use of supported catalysts ziperovich type

The invention relates to methods of producing polymers-olefins, effectively reducing the hydrodynamic resistance of hydrocarbon liquids and can be used for transporting petroleum products in pipelines

The invention relates to a multistage process for the polymerization of olefins of the formula CH2= CHR where R is hydrogen or alkyl, cycloalkyl or aryl group with 1-10 carbon atoms), carried out in two or more reactors

- olefins and method of reception" target="_blank">

The invention relates to precatalytic compositions suitable for Homo - and copolymerization of olefins and to a method for producing such composition precatalytic

The invention relates to precatalytic component of the catalytic composition of the Ziegler-Natta, suitable for the production of polymers of ethylene

The invention relates to a system and method controlled exothermic polymerization of durable solution

The invention relates to metal complexes of the formula (I), where M is titanium, zirconium or hafnium in the formal oxidation state of +2,+3 or +4; R' is phenyl, biphenyl or naphthyl; R* is hydrogen or hydrocarbon; X is halogen or methyl, to catalysts for the polymerization of olefins containing these ligands, and the method of polymerization WITH2-C100000--olefins, especially ethylene and styrene using these catalysts

The invention relates to catalytic compositions and can be used in addition reactions of olefineverbund monomers, for example, in the polymerization of

The invention relates to new compounds having an element of group III, associated with mono - or dianions tridentate ligand, the method of their production and their use in particular as a catalyst for (co)polymerization

The invention relates to catalysts for (co)polymerization of ethylene containing chromium trioxide deposited on a solid inorganic oxide carrier of nature, i.e

The invention relates to a polyethylene having a narrow molecular weight distribution and narrow composition distribution

The invention relates to storage-based catalysts on the media that are used in the polymerization of olefins
Up!