A method of obtaining a catalyst on the carrier

 

(57) Abstract:

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 of olefins, α-olefins and polar monomers, rubbers, in particular in the production of polypropylene. The invention allows to obtain a highly active catalyst on the carrier, producing polypropylene with a relatively high bulk density, high stereoregularity and size distribution in a narrow range. For this method of preparation of the catalyst on a carrier includes the following operations: processing of silicon dioxide with liquid chlorine compound selected from the group: trichloride boron, trichloride aluminum, silicon tetrachloride, adding the treated silicon dioxide to liquid hydrocarbon, adding to the resulting suspension of 2-methylpentylamine of minikleid, then a complex ester of titanium selected from the group tetramethylsilane, tetrabutoxide titanium, tetragonal titanium, Tetra-2-ethylhexylamine, washing the solid product and its branch, the addition of titanium tetrachloride. Before processing deoxidization. Product contacting a suspension of silicon dioxide with 2-methylphenylacetonitrile can be further processed with liquid chlorine compound selected from the group: trichloride boron, trichloride aluminum, silicon tetrachloride, and ethylbenzoic. By separating the washed solid product from the stage of contact with the complex air titanium product can be treated with ethylbenzoic. 4 C. p. F.-ly, 8 PL.

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 of olefins, olefins and polar monomers, rubbers, in particular in the production of polypropylene with a relatively high bulk density, high bulk density, high stereoregularity and size distribution in a narrow range.

A known method of producing catalyst for polymerization of olefins, which consists in the interaction of chemically treated by silica media connection dihydroquinine and connection halogenated tetravalent titanium. Chemical treatment silicate media includes the use of chlorin [1] This catalyst also includes components, which have an adverse effect on the receipt of stereoregular polymers, especially polypropylene. Therefore, this catalyst is proposed to use for the polymerization of polyethylene.

A method of obtaining a solid component of catalyst for polymerization by interacting media (resulting from the interaction of silica with not containing halogen monofunctional silylium connection with magnetogenesis compound and compound of tetravalent titanium [2] In this patent provides only data for the polymerization of ethylene.

The closest technical solution to the invention is a method of obtaining a catalyst on the carrier by reacting compounds of titanium, magnesium and inorganic media, which may be silicon dioxide [3]

Use in the process of preparation of the catalyst of electron-donor compounds aliphatic alcohol, aromatic alcohol, simple ester, etc. leads to the production of polypropylene with low stereoregularity and catalytic activity.

The technical result of the invention is to provide a highly active catalyst is areregularly and size distribution in a narrow range.

The result is achieved that the inorganic carrier is silica pre-treated with liquid chlorine compound selected from the group: trichloride boron, trichloride aluminum, silicon tetrachloride-treated silicon dioxide added to the liquid hydrocarbon, the resulting suspension is added 2-methylphenylacetonitrile, and then an ester of titanium selected from the group tetramethylsilane, tetrabutoxide titanium, tetragonal titanium, Tetra-2-ethylhexylamine, after washing the solid product and each of its subsidiaries is added titanium tetrachloride.

As options, before processing of silicon dioxide with liquid chlorine compound either calcined or treated with hexamethyldisilazane, by separating the washed solid product from the stage of contact with the complex air titanium product is treated with ethylbenzoic, the product of contacting a suspension of silicon dioxide with 2-methylphenylacetonitrile further treated with liquid chlorine compound selected from the group: trichloride boron, trichloride aluminum, silicon tetrachloride, and ethylbenzoic.

The catalyst according to the invention is produced by modified hydroxyl groups. The surface modification of the purpose of obtaining a controlled aggregate surface hydroxyl groups is carried out by annealing the silicon dioxide in an inert atmosphere, preferably at a temperature of 200aboutC. is Preferable, if the annealing of silicon dioxide is performed at a temperature in the range of from 550 to 650aboutWith in an inert atmosphere, preferably under nitrogen atmosphere. However, this modification of the media affected resorbtive moisture and restore its original shape, so it should be treated with caution.

In another embodiment of this invention the removal of the surface hydroxyl groups are produced by processing the silicon dioxide monofunctional organosilicon compound, such as hexamethyldisilazane. To facilitate flow throughout the reaction using an excess of hexamethyldisilazane. After the interaction of silicon dioxide or aluminum oxide with hexamethyldisilazane should not produce heat treatment, it is only necessary to remove the excess hexamethyldisilazane and the reaction by-products by vacuum suction, washing with a solvent in which the preferred solvent is LM is s 200aboutC. silicon Dioxide, the surface of which is modified as described above, preferably is determined by the surface area in the range from 80 to 400 m2/g, an average particle size of from 20 to 200 μm and a porosity in the range of from 0.6 to 3.0 cm3.

In the preferred embodiment of this invention, the modification of the surface of the carrier is performed by interacting with the halides of boron, aluminum or silicon at a temperature in the range from 0 to 100aboutWith over a period of time from 30 minutes to 2 hours, more preferably from 45 to 90 minutes at a temperature in the range of 50-75aboutC. Modified silicate carrier is then treated soluble in the hydrocarbon compound magnesium-2-methylpentanediol - house. The interaction between the silicate carrier and 2-methylphenylacetonitrile takes place at a temperature in the range from 0 to 160aboutC. is Preferable, if this interaction is carried out at a temperature in the range from 50 to 150aboutC. Most preferably, if this interaction occurs at a temperature in the range from 60 to 150aboutC. This interaction occurs over a period of time from 5 minutes to 6 hours is Preferred, it maintains the Oia interaction occurs in the presence of a minimum quantity of solvent in which 2-methylphenylacetonitrile dries on the surface of silicon dioxide, maximizing interaction with reactive surface groups, after which the system was washed with a large amount of solvent and variant subjected to interaction with the modifying agent, such as a silicon halide, boron halide or a halide of aluminum. As for leaching discussed in the description of the invention and in the examples, it is common to add a portion of the inert solvent, such as heptane, mixed with a carrier and merge. Reacted this way silicate carrier containing magnesium, is catalytically active in the process of further interaction with titanium compounds. Then silicate carrier is in contact with esters of titanium selected from the group tetramethylsilane, tetrabutoxide titanium, tetragonal titanium, Tetra-2-ethylhexylamine. The molecular size of the organic part of these compounds is important for the performance of the resulting catalyst when arranging the location and geometric configuration of the catalytic sites on the carrier in such a way as to direct the production of the target polymer limernyh properties in the resulting product. Usually I prefer organic parts with larger molecular size, which without any limitations due to the spatial difficulty, deformation or other influences contribute to the formation of the catalyst surface, they are effective to obtain a product with desired properties. Thus, due to the combination of variable reactivity of the surface resistant to abrasion media and geometrically complicated reactions between groups of magnesium and titanium to create a unique effective catalyst without the need to switch the internal electron donor. The best results are achieved when using cresylate titanium. The interaction between the modified carrier and a compound of titanium occurs at a temperature in the range from 0 to 120aboutWith over a period of time from 5 min to 2 h or more. It is preferable, if this interaction occurs at a temperature in the range from 10 to 100aboutC. And more preferable if this interaction occurs at a temperature in the range from 10 to 80aboutC.

The last stage of the manufacture of the catalyst according to this invention includes contacted the composition and the titanium halide is at a temperature in the range from 0 to 150aboutC. Preferably from 50 to 120aboutC. Most preferably, if the temperature probe is from 80 to 100aboutC. Compound of titanium and titanium silicate composition interact during the period of time from 1 to 4 hours is Preferable, if the interaction occurs during the time period from 1.5 to 3.5 hours Most preferred interaction time is from 1 to 3 o'clock

The morphology of the polymer obtained by using this catalyst, corresponds to the morphology of the medium in which there are considered the interaction, the absence of any halogen in the media contributes to the preservation of the content of halogen in the obtained polymer at a very low level, relatively low concentrations of titanium and magnesium silicate carrier allow you to keep the concentration of magnesium and titanium residues in the obtained polymer at similarly low levels; the synthesis of the catalyst occurs at moderate temperatures, preferably in the range from 0 to 100aboutAnd, since this catalyst does not require electron donor for achieving good stereoregularity, they can only be used if desired. In the case of the use of the electron donor preference is given to clucene polymer with the use of this catalyst in the presence of socializaton aluminium-containing compounds, which use alkylamine, halide alkylamine or mixtures thereof. Preferably, if socialization is aluminiuim. Among aluminiumraw particular preference is given to triethylaluminium and triisobutylaluminum.

In the polymerization of propylene according to the invention is also applicable to the second socializaton. The second socialization according to the invention is at least one silane compound. The silane compound is hydrocarbonylation. Preferred hydrocarbonylation include hydrocarbonrich - keilany, dihydrocarbamazepine and trihydrosicariolane. Among hydrocarbonengineering particular preference is given to those compounds in which hydrocarbon matter phenyl and C1-C6the alkyl and C1-C10dialkoxy. Especially preferred compounds include hexyltrimethoxysilane, amyltrichlorosilane and isobutyltrimethoxysilane.

Conventional propylene polymerization conditions include a polymerization temperature in the range from 35 to 100aboutC. More preferably, if the temperature of this reaction is in the range from 50 to 80aboutC. the Pressure of the reaction primeriaet from 400 pounds per square inch up to 500 pounds per square inch. Of course, you can apply methods of polymerization known in this area, although this is not required for effective use of this catalyst.

To illustrate the scope of the invention are the following examples. Because these examples are given only for purposes of illustration, they in no case should not limit this invention.

In accordance with the most preferred options for implementation of this invention can be obtained vysokostoimostnyh polypropylene (>98% heptane insoluble) with a high bulk density (>25 lb/ft3and size distribution in a narrow range (200-1500 μm) in the performance of the catalyst 5000 g polymer/g catalyst/h

P R I m e R 1. Obtaining a catalyst.

The catalyst was prepared by introduction of 12.5 mmol of silicon tetrachloride and 5.0 g of silica, previously calcined in nitrogen at a temperature of 600aboutWith, in suspension in 500 ml of heptane, in a three-neck flask with a round base with a capacity of 250 ml, equipped with a device for flushing with nitrogen, a paddle mixer, a mixing baffle, condenser and barbatum example, has a surface area equal to 300 m2/g, average particle size equal to 80-90 μm, and a porosity equal to 1.3 cm3/, After that add 12.5 mmol chloride 2-methylpentylamine and subjected to interaction with a suspension of silicon dioxide for 1 h at a temperature of 70aboutC. Following this, add 3,175 mmol of tetramethylsilane (derived from the mixed isomers of cresol). This titanate leave for interaction with the suspension for one hour at a temperature of 70aboutC. the Solid product obtained in accordance with these stages of the reaction, leave to defend, then poured the pop-up layer. To solid substance add fifty ml of fresh heptane and stirred without further heating. The solid is then left to defend and pop-up layer is drained. This washing was repeated three times until, until you remove a total of 200 ml of a pop-up layer. To the washed solid matter add liquid titanium tetrachloride and leave for interaction with solids for 2 hours at a temperature of from 80 to 100aboutWith producing and mixing. The solid product of this reaction three times washed with heptane, as described in the previous studyarea with the formation of free current, having the spherical shape of the solid catalyst orange-pink color.

P R I m m e R 2. Obtaining a catalyst.

The catalyst was prepared according to the method described in example 1. However, due to minor changes in the methods of washing specified in example 1 is changed, the concentration of magnesium and titanium in the final product. In particular, if the concentration of Mg and Ti in the catalyst of example 1 is from 1 to 3.49 wt. and 2.56 wt. accordingly, the concentration of Mg and Ti in the catalyst according to the present example is of 3.60 respectively and are 3.90 wt.

P R I m e R s 3-5. Obtaining catalysts.

Three additional catalyst was prepared in accordance with the method described in example 1, except that 5.0 g of silica pre-treated with hexamethyldisilazane and not subjected to annealing, as is done in examples 1 and 2. The modified silica is dried in the reactor for 1 h at a temperature of 100aboutC, under stirring and purging with nitrogen in an amount of 2.7 l/min in Addition, the concentration of magnesium being the result of processing the chloride 2-methylpentylamine, and the concentration of titanium, defined tetrakis is the reamers 3, 4 and 5 respectively of 3.60, 1.92 and 3,10 wt. based on the total weight of the final catalyst. Similarly, the titanium content in the catalysts according to examples 3, 4, and 5 respectively of 3.60, 1,37, and 2.50 wt. These differences are associated with minor changes in the methods of washing.

P R I m e R 6. Polymerization of propylene using catalysts according to examples 1-5.

Liquid propylene separately subjected to interaction with each of the catalysts according to examples 1-5, except 40 mg of catalyst in each of examples 1-5 using two socializaton. These socialization are triethylaluminium and isobutyltrimethoxysilane (IBTS). Triethylaluminium and isobutyltrimethoxysilane used in such quantities that the molar ratio of aluminum, titanium and isobutyltrimethoxysilane is 40:1:8. Each reaction polymerization of propylene is carried out at a pressure of 460 psig and a temperature of 70aboutC. In each of these trials used a 4.5 mmol of hydrogen to control the molecular weight of homopolymer propylene. The results are summarized in table. 1. It should be noted that the reaction time of polymerization is equal to 1 h in all cases, except the polymerization catalyst is ocessi polymerization using catalysts according to examples 2 and 5 repeat 2 and 3 times.

These tests and their results are summarized in table. 1.

P R I m e R 7.

A. obtaining a catalyst.

The catalyst obtained by pre-treatment of silica (surface area 300 m2/g, average particle size equal to 80-90 μm, and a porosity equal to 1.3 cm3/g) (1.25 mmol hexamethyldisilazane per gram of silica), which is then dried in the reactor for more than 4 hours at a temperature of 100aboutWith stirring and purging with nitrogen in an amount of 2.7 l/min Modified carrier is placed in a three-neck flask with a round base with a capacity of 250 ml, equipped with a device for flushing with nitrogen, a paddle mixer, a mixing baffle, condenser and bubbler. Then add 2.5 mmol chloride 2-methylpentylamine on g SiO2, is subjected to the interaction with a suspension of silicon dioxide at a temperature of 20aboutWith and dried at a temperature of 40-115aboutWith the reactor under stirring for 2 h and purging with nitrogen in an amount of 2.7 l/min Obtained dried solid is then contacted with 10 ml of heptane per 1 g of silicon dioxide and 2.5 mmol silicon tetrachloride per 1 g of silicon dioxide for 1 h at a temperature of 40aboutWith, and then subjected to interaction with 18 mmol of titanium tetrachloride per 1 g of silicon dioxide at a temperature of 100aboutC for 2 h, then washed four times as described above. Changes in methods of preparation of the catalyst, contribute to the regulation of catalytic activity and properties of the polymer. For example, incomplete drying reduces productivity and bulk density of the polymer, while longer periods of drying or too high initial drying temperature leads to the decrease of catalytic activity. Usually drying after interaction with the magnesium compound is carried out at a temperature of 70-80aboutWith over a period of time from 1.5 to 2.5 hours

Century. Polimerizaciya.

The catalyst used for polymerization of propylene using 40 mg of catalyst and socialization representing triethylaluminium and isobutyltrimethoxysilane (IBTS). Three of the Tana and isobutyltrimethoxysilane respectively is 40:1:8. Each reaction polymerization of propylene is carried out at a pressure of 460 psig and a temperature of 70aboutWith in the period of reaction equal to 1 hour In each of these trials used a 4.5 mmol of hydrogen to control the molecular weight of homopolymer propylene.

The results of the tests in the specified conditions of preparation of the catalyst and polymerization are presented in table. 2.

Analytical data on the content in the catalyst are given in table. 3.

P R I m e R s 8 and 9. The influence of the second socializaton.

In these examples describe the effect of the second socializaton (SC). In examples 8 and 9 polymerization of propylene is carried out in accordance with the method described in example 6. Using the catalyst according to example 2. In addition, in these examples, use the first socialization in example 2, triethylaluminium. However, the second acetalization used in example 2 and representing isobutyltrimethoxysilane replaced in examples 8 and 9, the second socialization, phenyltriethoxysilane (PES). In addition, the molar ratio of aluminum, titanium and the second socializaton (Al/Ti/CK) according to example 2, representing 40: 1: 8, is replaced in example 7 20:1:10 and in example 8 at 20:1,2,5. The same is olymerization.

The results of examples 8 and 9 are given in table. 4. For comparison purposes in the table. 4 experiment included on the polymerization of example 2.

P R I m e R s 10-11 and comparative examples 1-5. The influence of compounds modifying the surface of silicon dioxide.

In these examples, the effect of compounds modifying the surface of silica. In all these examples, the silica is pre-treated with 1.25 mmol hexamethyldisilazane (HMDS) per 1 g of silicon dioxide, which corresponds to 1.25 mmol of reactive surface hydroxyl on the media. Changes in the examples relate to the nature and quantity of the modifying compounds. The nature and quantity of the modifying compounds are described in the table. 5. The use of modifying compounds, not included in the scope of the catalyst according to the invention or produced in accordance with reception of a catalyst according to example 4, in particular 2-methyl-2 - chloropropanol, phosphorus trichloride, benzoyl chloride, ethylchloride and trichloroethane in comparative examples 1, 2, 3, 4 and 5, respectively, allows to obtain polypropylene, which is not only characterized by low productivity, but also leads to the creation of polymers, Aenea 95% it Should be noted, all these connections are not included in the scope of the modifying compounds of the catalyst according to this invention, are like modifying compounds of the present invention, halides, in particular chloride. Also it should be emphasized that the two compounds included in the scope of the present invention, boron trichloride and aluminum trichloride (examples 10 and 11, respectively), allow to obtain excellent results in terms of performance and properties of the obtained polymer. In fact these results exceed the results obtained in example 4, which differs from examples 10 and 11 only in that the modifying compound according to example 4, which silicon tetrachloride is replaced l3and AlCl3.

All these results are given in table. 5. For comparison purposes included in this table example 4, because without taking into account differences in the surface processing of silicon dioxide all the catalysts of these examples were obtained in accordance with example 4.

P R I m e R 12 and comparative example 6. The influence of the solubility of compounds of magnesium.

In these examples, it is noted critical source of soluble magnesium. In example 12 is used mixed source dia the tats, are given in table. 5.

In comparative example 6 equal molar amounts dioxirane mixed with magnesium chloride by co-grinding of solid magnesium chloride and liquid dioxirane. The catalyst obtained in accordance with comparative example 6, which is a solid substance, characterized by unacceptably low productivity and very low stereoregularity, as indicated by the content of 78.4% of the insoluble substances heptane, and too high a flow velocity of the melt, which indicates a very low degree of polymerization. These results are summarized in table. 6, which includes the results obtained for the catalyst of example 1. The results obtained by polymerization of propylene using the catalyst of example 1 are similar, because the catalysts according to example 12 and comparative example 6 was manufactured according to the method of example 1 except for changes relating to the use of compounds of magnesium.

P R I m e R s 13-15 and comparative example 7. The influence of esters of titanium.

These examples illustrate the value of esters of titanium to create catalyst is receiving stage, related to communication silicate carrier with a complex ester of titanium. In examples 13 and 14, an ester of titanium, used in example 1 is replaced by tetrabutoxide titanium and tetragonality titanium. The concentration of esters in examples 13 and 14 is identical to that in example 1. In example 15 the replacement of ester titanium Tetra-2-ethylhexylamine used in the same concentration. In all three examples, the characteristics of the polypropylene obtained is acceptable, although lower compared to the products obtained by using the catalyst of example 1. The performance of the catalysts in examples 13-15 lower than the catalyst of example 1, though, and reaches acceptable levels. In comparative example 7 is omitted stage processing of silicon dioxide complex ether titanium. The catalyst of this example is characterized by performance, which is unacceptable for industrial production. The results obtained in these examples are added to the table. 7, which also includes the results of example 1 as a comparison.

Comparative example 8. The influence of the media on the basis of aluminum oxide.

The catalyst was prepared in accordance with the method of examples 1 and 2 for issue aluminum, calcined at a temperature of 200aboutC in nitrogen atmosphere. When this catalyst is used for polymerization of propylene in accordance with the method according to example 6, the catalytic activity equals 52600 grams polypropylene per gram of titanium, an unacceptably low value. In addition, the degree of stereoregularity defined percentage of insoluble substances heptane is just 90,7, which is much below the required 95% of stereoregularity reached when using the catalysts included in the scope.

P R I m e R s 16 and 17. The effect of using an internal electron donor.

Examples 16 and 17 illustrate the inuence of electron donors on the formation of the catalysts included in the scope of the present invention. In these two examples, the catalyst was prepared in accordance with the method used in obtaining the catalyst of example 1. However, in examples 16 and 17 when creating a catalyst as an internal electron donor used ethylbenzoic. In example 16 5,90 mmol of ethylbenzoic introduced into the catalyst in the pre-mixed with tetramethylsilane. In example 17 2,98 mmol of ethylbenzoic introduced into the catalyst in the pre is H. In both of these examples using the internal electron donor received a satisfactory catalyst for propylene polymerization, although not as effective as in the preferred embodiment of this invention in example 1. The inclusion of example 1, the catalyst which is obtained in the same manner but without the introduction of an electron donor, the table shows the quantitative superiority of the catalyst of example 1 over the catalysts according to examples 16 and 17.

Propylene, which is the product of polymerization using the catalyst according to the invention is characterized by a homogeneous size distribution, good spherical morphology and high bulk density. These characteristics of polypropylene increase the efficiency and workability of the polymer. In addition, the catalyst itself is highly active, resulting in a high performance polymer, as evidenced by the mass of polymer per unit weight of catalyst.

The catalyst according to the invention is also characterized by a safe and simple way to obtain. Since the catalyst does not contain halogen in the media, the resulting polymer characteristics which arise during the processing of such polymers. In addition, since the catalyst has a low content of residual metal is not required obessolivanie polymer product. Finally, the reaction of polymerization using this catalyst is enhanced by a relatively constant activity over long periods of time. Next, by using this catalyst allows simple control over the molecular weight of the polymer by adding a certain amount of hydrogen.

1. A method of OBTAINING a CATALYST ON the CARRIER, including the processing of silicon dioxide magnesium and titanium containing compounds, characterized in that the silica is pre-treated with liquid chlorine compound selected from the group: trichloride boron, trichloride aluminum, silicon tetrachloride-treated silicon dioxide added to the liquid hydrocarbon, the resulting suspension is added 2-methylphenylacetonitrile, and then an ester of titanium selected from the group tetramethylsilane, tetrabutoxide titanium, tetragonal titanium, Tetra-2-ethylhexylamine, after washing the solid product and each of its subsidiaries is added titanium tetrachloride.

2. The method according to p. 1, characterized in that the about on p. 1, characterized in that prior to the processing of silicon dioxide with liquid chlorine connection it is treated by hexamethyldisilazane.

4. The method according to p. 1, characterized in that the product of contacting a suspension of silicon dioxide with 2-methylphenylacetonitrile treated with liquid chlorine compound selected from the group trichloride boron, trichloride aluminum, silicon tetrachloride, and ethylbenzoic.

5. The method according to p. 1, characterized in that when the separation of the washed solid product from the stage of contact with the complex air titanium product is treated with ethylbenzoic.

 

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EFFECT: high catalyst activity, ensuring novel complexes based on definite transition metals.

34 cl, 30 tbl, 15 dwg, 121 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to the method of obtaining ultra-high molecular polyethylene using Ziegler type catalyst, containing a transition metal compound on a magnesium-containing carrier. The described catalyst for obtaining ultra-high molecular polyethylene contains a vanadium compound (VCI4, VOCI3, V(OR)xCl3-x) on a magnesium-containing carrier, which is obtained from reaction of a solution of an organo-magnesium compound containing: Mg(C6H5)2n MgCl2 mR2O, where n=0.37-0.7, m=2, R2O is simple ether where R=i-Am, n-Bu, with a product of the reaction of alkylchloro silane containing: R'kSiCl4-k, where R is an alkyl or phenyl, k=0, 1, 2 and silicon tetraalkoxide Si(OEt)4. The organo-magnesium compound contains dialkylaromatic ester D. The ultra-high molecular polyethylene is obtained as a suspension in a medium of a hydrocarbon diluent using the catalyst described above, together with an organo-aluminium cocatalyst at high polymerisation temperatures (>70°C) in a hydrocarbon diluent medium.

EFFECT: increased output of the reactor.

4 cl, 7 ex, 1 tbl

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely XkSiCl4-k, wherein X is OR' or R', in which R can be C1-C4-alkyl or phenyl, and k=1-2. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 13 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to catalytic systems used in polymerization of alpha-olefins, methods for preparing catalytic systems for polymerization of alpha-olefins and methods for polymerization (and copolymerization) of alpha-olefins. Invention describes the catalytic system for polymerization of olefins comprising solid titanium component of catalyst, organoaluminum compound comprising at least one bond aluminum-carbon and organosilicon compound comprising at least one (cycloalkyl)-methyl group used as an external donor of electrons. Also, invention describes the catalytic system for polymerization of olefins comprising solid titanium component of the catalyst prepared by contacting titanium compound with magnesium compound and comprising from about 0.01 to about 500 moles of titanium compound per one mole of magnesium compound, organoaluminum compound comprising at least one bond aluminum-carbon wherein the mole ratio of aluminum to titanium in the catalytic system is in the range from about 5 to about 1000, and organosilicon compound comprising at least one (cycloalkyl)-methyl group and used a external donor of electrons wherein the mole ratio of organoaluminum compound and organosilicon compound in the catalytic system is in the range from about 2 to about 90. Also, invention describes methods for preparing catalyst used in polymerization of olefins and comprising interaction of Grignard reactive comprising (cycloalkyl)-methyl group with ortho-silicate to form organosilicon compound comprising a (cycloalkyl)-methyl link, mixing organosilicon compound with organoaluminum compound comprising at least one bond aluminum-carbon and solid titanium component of the catalyst to form the catalyst, and a method for polymerization of olefins. Invention provides preparing propylene block-copolymer showing good fluidity in the melt, capacity for molding, hardness, impact viscosity and impact strength in combination with high effectiveness of the catalyst and good technological effectiveness of the preparing process.

EFFECT: improved and valuable properties of catalysts.

17 cl, 10 ex

FIELD: polymer production.

SUBSTANCE: superhigh-molecular weight polyethylene is obtained in suspension conditions at temperature between 40 and less than 70°C in hydrocarbon solvent medium using supported catalyst. The latter is prepared through interaction of compound Mg(C6H5)2n*MgCl2*mR2O (R2O is ether, R = i-Am, n-Bu) with silicon compound, which is a product prepared by reaction of compound R1kSiCl4-k with silicon tetraethoxide Si(OR)4 (R1 represents methyl or phenyl and k=0.1) at molar ratio R1kSiCl4-k/Si(OR)4 = 2-4 at 15-45°C and Si/Mg = 1-2.5. Loose weight of obtained polymer is higher than 0.35 g/cc.

EFFECT: increased yield of superhigh-molecular weight polyethylene with improved morphology.

1 tbl, 13 ex

FIELD: polymerization processes and catalysts.

SUBSTANCE: invention relates to preparing supported titanium-magnesium catalyst for production of polyethylene and superhigh-molecular weight polyethylene via suspension polymerization of ethylene in hydrocarbon solvent. Invention provides a method for preparing supported ethylene polymerization catalyst containing titanium compound on magnesium-containing support, which is prepared by interaction of dissolved organomagnesium compound having following composition: MgPh2·nMgCl2·mR2O, wherein R represents butyl or isoamyl, n=0.37-0.7, and m=1-2, with compounds inducing conversion of organomagnesium compound into solid magnesium-containing support. As such compounds, there is used a composition including product of reaction of alkylsilane R'kSi4-k, wherein R is alkyl or phenyl and k=1, 2, with silicon tetraalkoxide Si(OEt)4 at molar ratio 2-4, respectively, and a dialkylaromatic ether. Catalyst is characterized by high activity at temperatures ≤60°C and particle size within a range 5.5 to 3.0 μm. Catalyst allows a polymer powder with average particle size ≤150 μm, narrow particle size distribution, and high loose density (≥250 g/L) to be obtained.

EFFECT: enhanced low-temperature catalyst activity and selectivity.

3 cl, 1 tbl, 15 ex

FIELD: polymerization catalyst and polymer production.

SUBSTANCE: invention relates to preparation of high-activity catalyst deposited on solid support and designed for suspension polymerization of ethylene and copolymerization of ethylene with α-olefins, in particular, for production of ultrahigh-molecular weight polyethylene. Catalyst according to invention comprises organoaluminum compound (40-200 wt parts) and solid component (1 wt part) containing 12-15% catalytically active titanium compounds and 85-88% magnesium dichloride support prepared by interaction of magnesium metal, ethanol, aluminum, silicon, and titanium compounds, said solid component being represented by particles containing titanium, magnesium, chlorine, aluminum, and silicon at atomic ratio between 1.0:6:16:0.07:0,02 and 1:7:18:0.06:0.01, respectively. Described are also preparation of solid catalyst component, and (co)polymerization of ethylene at temperature between 0 and 100°C and pressure between 0.1 and 5.0 MPa. Catalyst according to invention allows obtaining polyethylene with elevated molecular weight under high polymer yield conditions, which minimizes time required for preparation of homogenous spinning solutions in the gel formation process and minimizes degree of degradation of dissolved polymer properties.

EFFECT: increased molecular weight and yield of polyethylene .

8 cl, 1 dwg, 3 tbl, 26 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to butene-1 (co)polymers and a method of their synthesis. Except for, invention relates to articles made of butene-1 (co)polymers. Homopolymers of butene-1 are characterized by the following properties: (i) value of molecular-mass partition expressed as the ratio Mw/Mn based on measurement with using analysis carried out by gel-permeation chromatography method is less 6, and (ii) strength value of melt is above 2.8 g. These homopolymers are used for making tubes. Method for synthesis of butene-1 homopolymers is carried out in the presence of a stereospecific catalyst comprising (A) a solid component containing Ti compound and internal electron-donor compounds chosen from phthalates and applied on a carrier MgCl2; (B) alkylaluminum compound, and (C) tert.-hexyltrimethoxysilane as an external electron-donor compound. Butene-1 homopolymers possess a set of mechanical properties providing the presence both barostability after prolonged period time and their easy processing for making tubes.

EFFECT: valuable properties of (co)polymers, improved method of synthesis.

12 cl, 1 tbl, 3 ex

FIELD: polymer production.

SUBSTANCE: invention relates to 1-butene copolymers containing up to 40 mol % ethylene or propylene derivatives. Copolymer of 1-butene with ethylene or propylene is described, which copolymer contains up to 40 mol % of ethylene and/or propylene units derivatives and manifests following properties: (a) product of copolymerization constants r1·r2 ≤ 2; (b) content of 1-butene units in the form of stereoregular pentads (mmmm) > 98%; and (c) lack of 4,1-inclusions of 1-butene units. Described are also: polymer compositions for manufacturing films, which contains above-indicated polymer; industrial product obtained from this copolymer; and a method for preparing such copolymer comprising 1-butene/ethylene (and/or propylene) copolymerization in presence of stereoregular catalyst containing (A) solid catalytic component including Ti compound and electron-donor compound selected from MgCl2-supported phthalates; (B) alkylaluminum compound; and (C) outer electron-donor compound of formula Ra5Rb6Si(OR7)c, wherein a and b are integers from 0 to 2, c is integer from 1 to 3, and sum (a+b+c)= 4, R5, R6, and R7 represent alkyl, cycloalkyl, or aryl radicals with 1-18 carbon atoms, optionally containing heteroatoms.

EFFECT: achieved specific balance between stereoregularity and distribution of comonomer, lack of 4,1-inclusions, and increased stretching strength.

26 cl, 8 tbl, 14 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to a method for preparing supported titanium -manganese catalyst for synthesis of super-high molecular weight polyethylene via suspension ethylene polymerization process in hydrocarbon solvent. Titanium-containing catalyst supported by magnesium-containing carrier is prepared by reaction of organomagnesium compound Mg(C6H5)2•nMgCl2•mR2O, where n=0.37-0.7, m=2, R20 represents ether wherein R is i-amyl or n-butyl, with a silicon compound, namely product obtained by reaction of compound R'kSiCl4-k (R' is methyl or phenyl and k=0-1) with silicon tetraethoxide Si(OEt)4 at molar ratio R'kSiCl4-k/Si(OEt)4 = 6 to 40. Ethylene polymerization process in presence of above-defined catalyst in combination with co-catalyst is also described, wherein obtained super-high molecular weight polyethylene has loose density ≥ 0.39 g/cc.

EFFECT: increased molecular weight and loose density of polyethylene.

4 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to the method of obtaining ultra-high molecular polyethylene using Ziegler type catalyst, containing a transition metal compound on a magnesium-containing carrier. The described catalyst for obtaining ultra-high molecular polyethylene contains a vanadium compound (VCI4, VOCI3, V(OR)xCl3-x) on a magnesium-containing carrier, which is obtained from reaction of a solution of an organo-magnesium compound containing: Mg(C6H5)2n MgCl2 mR2O, where n=0.37-0.7, m=2, R2O is simple ether where R=i-Am, n-Bu, with a product of the reaction of alkylchloro silane containing: R'kSiCl4-k, where R is an alkyl or phenyl, k=0, 1, 2 and silicon tetraalkoxide Si(OEt)4. The organo-magnesium compound contains dialkylaromatic ester D. The ultra-high molecular polyethylene is obtained as a suspension in a medium of a hydrocarbon diluent using the catalyst described above, together with an organo-aluminium cocatalyst at high polymerisation temperatures (>70°C) in a hydrocarbon diluent medium.

EFFECT: increased output of the reactor.

4 cl, 7 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to the method of obtaining polyethylene and copolymers of ethylene with alpha-olefins with a wide range of molecular mass distribution, using Ziegler type supported catalyst, containing a compound of a transition metal on a magnesium containing carrier. The process is carried out in the presence of a catalyst which contains a vanadium compound (VCl4, VOCI3, V(OR)xCl3-x) on a magnesium containing carrier, which is obtained from reacting a solution of organomagnesium compound with the formula: Mg(C6H5)2n MgCl2 mR2O, where: n=0.37-0.7, m=2, R2O is ether with R=i-Am, n-Bu, with a product of reacting alkylchlorosilane with the formula: R'kSiCl4-k, where R is alkyl or phenyl, k=0, 1, 2, and silicon tetraalkoxide Si(OEt)4. Dialkylaromatic ether D is used in the organomagnesium compound MOC. Polyethylene and copolymers of ethylene and alpha-olefins with wide molecular-mass distribution are obtained using the above described catalyst in conjunction with organoaluminum co-catalyst at 50-100°C in a medium of hydrocarbon diluent. Hydrogen, taken in amount of 5-50 vol.%, is used as the regulator of molecular mass of the polymer.

EFFECT: during polymerisation of ethylene on this catalyst, polyethylene is produced with high packed density and narrow particle size distribution, as well as wide molecular mass distribution.

3 cl, 5 ex, 1 tbl

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