Catalyst preparation process and ethylene polymerization and ethylene-alpha-olefin copolymerization processes utilizing this catalyst

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 phenyltrichloromethane PhCCl3. 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, 4 ex

 

The invention relates to a method for preparing catalysts for the polymerization of ethylene and copolymerization of ethylene with α -olefins, more specifically applied to the catalysts ziperovich type, containing in its composition the compound of the transition metal to magnesium-containing media.

There are various ways of preparation of supported catalysts ziperovich type. However, only some of these methods allow you to adjust the morphology of the particles of the medium and, accordingly, the catalyst (size, shape and density of particles, the distribution of particle sizes). In the case of slurry and gas-phase polymerization, the morphology of the catalyst particles determines the morphology formed by the particles of the polymer. Obtaining polymer powder with a specific particle size, narrow distribution of particle size and high bulk density is an important condition for the technology of the polymerization process. For this purpose it is necessary to obtain catalysts having a narrow distribution of particle size, the required average particle size and improved morphology. For different technologies of polymerization and different applications of polymers require catalysts with different particle size.

Catalysts with a particle size of 5-25 μm is used in the case suspe the precise polymerization of ethylene. Catalysts with a particle size of 20-50 μm are used for gas-phase polymerization.

The catalyst with a narrow distribution of particle size, containing as a carrier of magnesium chloride, can be obtained by the interaction of a solution of the compound MgCl2·3i-C8H17OH in carbohydrate diluent with TiCl4in the presence of electron-donor compounds (ethylbenzoic, ationist and others) [Japan's Bid No. 59-53511, B 01 J 1/32, 1986]. The catalyst obtained in this way is characterized by a particle size of 5-15 microns, has a sufficiently high activity (up to 35 kg/g PE g Ti h ATM3H4) and allows to obtain a powder of polyethylene with a narrow grain size distribution and high bulk density. The disadvantage of this method of preparation of the catalyst is the use of low temperatures (down to -20° C), using as the reaction medium large quantities of liquid TiCl4the selection in the synthesis of catalyst a significant amount of hydrogen chloride. In addition, this method cannot obtain catalysts with a particle size greater than 15 microns.

There is a method of preparation of the catalyst by the interaction of magnesium-aluminum-alkyl compound composition RMgR‘· nlR3“· mD with chloropetalum and the subsequent interaction of the obtained solid product (carrier) with a halide of titanium is or vanadium [Application Germany No. 3626060, B 01 J 31/32, 1987]. At the same time as magyarkanizsa connection RMgR‘ use (n-Bu)Mg(i-Bu) or (n-Bu)Mg(Oct), soluble in hydrocarbons, and as chloropetalum preferable to use tret-BuCl. The main disadvantage of the catalysts prepared in this way is sufficiently high activity.

A method of obtaining the deposited catalyst for polymerization of ethylene and copolymerization of ethylene with alpha-olefins, containing the compound of the transition metal (TiCl4, Vl3, VCL4) on the media composition MgCl2·mR2O, by applying a compound of a transition metal on a carrier [U.S. Pat. Of the Russian Federation No. 2064836, B 01 J 31/38, 10.08.96]. When this carrier is produced by interaction magyarkanizsa connection (MOS) structure of Mg(C6H5)2·nMgCl2·mR2O, where n=0.37-0.7, m=2, R2O simple ether with R=i-Am, n-Bu, with carbon tetrachloride. The catalyst prepared in this way, allows to obtain polymers with narrow adjustable distribution of the particle size and high bulk density while maintaining high activity in the processes of the suspension and gas-phase polymerization of ethylene and copolymerization of ethylene with α -olefins.

The main disadvantage of this method is the use as glorieuses agent chetyrehhloristy is on carbon: the reaction of carbon tetrachloride with magnetogenesis connection is very intensive, with great heat, and difficult to be controlled, especially the preparation of the catalyst in large quantities.

The invention solves the problem of developing a method of producing a catalyst for polymerization of ethylene and copolymerization of ethylene with α -olefins, which allows to obtain polymers with narrow adjustable distribution of the particle size and high bulk density while maintaining high activity in the processes of the suspension and gas-phase polymerization of ethylene and copolymerization of ethylene with α -olefins, but without the use of a synthesis step of the carrier of carbon tetrachloride.

The task is solved in that to obtain a magnesium-containing carrier for catalyst as glorieuses agent for manyorganizations connection (MOS) composition(Mg6H5)2·nMgCl2·mR2O, where C6H5- phenyl, n=0.37-0.7, m=2, R2O - simple ether with R=i-Am, n-VI, use phenyltrichlorosilane6H5CCl3. Interaction magyarkanizsa connection with phenyltrichlorosilane6H5CCl3can be carried out at a molar ratio of C6H5CCl3/Mg≥ 1.0 and a temperature of 5-80° C.

Thus, the main characteristic of the proposed method is used in place of carbon tetrachloride is for chlorination magyarkanizsa connection MOS composition Mg(C 6H5)2·nMgCl2·mR2About phenyltrichlorosilane6H5CCl3.

The carrier obtained by this method has a narrow distribution of particle size in the range from 5 to 50 μm. The desired particle size of the carrier and accordingly the catalyst in this area are determined by the conditions of the process of interaction with MOS6H5CCl3. The resulting magnesium-containing carrier includes, mainly, wt.%: dichloride, magnesium 70-80, simple ether 7-15, and hydrocarbon products of complex composition in the amount of 10-15. The catalyst was prepared, followed by treatment of the carrier with a solution of titanium tetrachloride (TiCl4) or vanadium chloride (VCl4, Vl3) in a hydrocarbon solvent.

The proposed method provides receiving highly active catalysts with different particle size and a narrow distribution of particle size for various applications. For example, according to the invention it is possible to obtain catalysts with a particle size in the range from 5 to 40 μm for the suspension polymerization of ethylene.

The task is also solved by a process for the polymerization of ethylene and copolymerization of ethylene with alpha-olefins in the presence of a catalyst containing a transition metal compound on a magnesium-containing n is setele, characterized by the fact that using the catalyst prepared as described above.

In the polymerization of ethylene on this catalyst produces polyethylene with high bulk density (>0.3 g/cm3) and a narrow distribution of particle size. When used as an active ingredient for these catalysts of titanium chloride is formed polyethylene with a narrow molecular weight distribution, and the use of chlorides of vanadium forms polyethylene with a broad molecular weight distribution. The activity of the obtained catalyst reaches 290 kg of polyethylene/g Ti h or 250 kg (PE)/g V h

The catalysts used for the polymerization of ethylene or copolymerization of ethylene with α -olefins in combination with socialization - trialkyl aluminum, mainly triisobutylaluminum or triethylaluminum. The polymerization is carried out in the mode of suspension at temperatures of 50-100° in the environment of the hydrocarbon solvent such as hexane, heptane or in gas-phase mode without hydrocarbon diluent at a temperature of 60-100° and the pressure 2-40 ATM. As the regulator of the molecular weight of the polymer used hydrogen in the amount of 5-50 vol.%. When copolymerization of ethylene with a-olefins using propylene, butene-1, hexene-1, 4-methyl-penten-1 and other higher α -olefins.

The entity from whom retene is illustrated by the following examples.

Example 1.

(A). Preparation of the solution magyarkanizsa connection.

In a glass reactor of 1 liter equipped with a stirrer and a thermostatic device, download 29.2 g of powdered magnesium (1.2 mol) in 450 ml of chlorobenzene (4.4 mol), 203 ml dibutylamino ether (1.2 mol) and an activating agent representing a solution of 0.05 g of iodine in 3 ml of butyl chloride. The reaction is carried out in an atmosphere of inert gas (nitrogen, argon) at a temperature of from 80 to 100° C for 10 hours By the end of the reaction the reaction mixture defend and separate the liquid phase from the precipitate. The liquid phase is a solution in chlorobenzene magyarkanizsa compounds of the structure:

MgPh2·0.49MgCl2·2(C4H9)2O with a concentration of 1.0 mol Mg/l

(B). Synthesis media.

200 ml of the obtained solution (0.2 mol Mg) is loaded into the reactor with a stirrer and the temperature is 8° C for 35 minutes metered into the reactor a solution of 26 ml phenyltrichlorosilane (C6H5CCl3) (0.32 mol) in 30 ml of heptane (PhCCl3/Mg=1.0 (mol.)).

Then the reaction mixture is heated to 60° C for 30 min and kept at this temperature for 1 h to Remove the mother liquor and the precipitate is washed with heptane 4 times 250 ml at a temperature of 20° C. Obtain 33 g of powdered magnesium-containing carrier in the form with which spencie in heptane.

(In). The preparation of the catalyst.

To the resulting suspension of magnesium-containing medium in 150 ml of heptane poured 22 ml of TiCl4(TiCl4/Mg=1), the reaction mixture is heated to 60° C and maintained under stirring for 2 h, then the solid precipitate defend and washed with heptane at a temperature of 60-70° With 3 times 200 ml Get deposited catalyst with titanium content of 1.4 wt.%. The average particle size of the catalyst is 7.4 microns.

The polymerization of ethylene is carried out in a steel reactor with a volume of 0.7 l equipped with a stirrer and a thermostatic jacket. As a solvent for polymerization using heptane (250 ml) and socializaton Al(i-VI)3with a concentration of 5 mmol/liter Polymerization is carried out at a temperature of 70° C, pressure of 4 ATM ethylene within 2 hours the Results of polymerization are shown in table.

For experience use 0.0083 g of catalyst, obtain 68 g of the polymer, the catalyst activity 4.1 kg/g catalyst· an hour or 293 kg/g Ti h bulk density of the powder is PE is 0.35 g/cm3and the average particle size of PE according to the sieve analysis is 150 μm. The PE powder has a narrow distribution of particle sizes, which is characterized by a value SPAN=(d90-d10)/d50where d90d10and d50the particle sizes of PE corresponding to the integral content of h is CI 90, 50 and 10 wt.% respectively. The SPAN value for this example is 0.9.

Example 2. The catalyst obtained in the conditions of example 1, used in the polymerization of ethylene under the conditions of example 1, but in the presence of hydrogen. The polymerization is carried out at a temperature of 80° C, pressure of 4 ATM ethylene, as a carrier polymer chain is hydrogen at a pressure of 2 ATM, the polymerization of the 1 o'clock Catalytic properties shown in the table.

Example 3. The synthesis of the catalyst is carried out analogously to example 1, except that the dosage glorieuses agent is carried out at 60° C. After dosing solution With6H5CCl3the media is maintained at a temperature of 60° 1 h and washed 3 times in 200 ml of heptane. After that, the reactor for suspension media type 204 ml diethylaluminium chloride with a concentration of 1.6 mol/l at a molar ratio of AlEt2Cl/Mg=1.2 for 20 min at room temperature and then incubated the reaction mixture for 1 h at 45° C. After that, the carrier is washed 5 times with 200 ml of heptane.

The catalyst was prepared by treatment of a suspension of the carrier in heptane instead of titanium tetrachloride solution of vanadium tetrachloride in cetarehhloristam carbon (52 ml with the concentration of vanadium 0.035 g/ml) at a temperature of 50° C for 1 h and then washed 1 time with 200 ml of heptane. The catalyst contains the 3.2 wt.% vanadium and has an average particle size of 38 μm. The polymerization of ethylene is carried out in the conditions of example 1, except that the polymerization temperature of 90° C, the pressure of ethylene 9.5 atmospheres, a hydrogen pressure of 0.5 MPa, the polymerization of the 1 o'clock Catalytic properties shown in the table.

Example 4. The catalyst obtained in example 1 is used in the copolymerization of ethylene with hexene-1. The polymerization is carried out at a pressure of 3 ATM ethylene, hexene concentration 1-0 .19 mol/l, at 70° C for 30 minutes

Get copolymer containing 1.2 mol.% hexene-1, with a yield of 16 kg/g cat (catalyst 580 kg/g Ti h).

From the presented examples show that the use for the synthesis media phenyltrichlorosilane for chlorination magyarkanizsa compounds Mg(C6H5)2·nMgCl2·mR2O allows to obtain highly active catalysts for polymerization of ethylene with a narrow distribution of particle size, which is characterized by the value of SPAN<0.9 and controlled average particle size of from 7 to 40 μm.

An important difference synthesis media using6H5CCl3from chlorination magyarkanizsa connection (ISO) carbon tetrachloride is less intensive nature of the interaction MOS with gloriously agents with lower heat dissipation and slower formation of particles of the medium that is allows to easily monitor and regulate the synthesis of the catalyst.

1. The method of preparation of deposited catalyst for polymerization of ethylene and copolymerization of ethylene with alpha-olefins containing compound of titanium or vanadium on the magnesium-containing carrier, which is produced by the interaction of the solution magyarkanizsa compounds consisting of: Mg(C6H5)2·MgCl2·mR2O, where n=from 0.37 to 0.7, m=2, R2About - simple ether with R=i-Am, n-Bu, with gloriouse agent, characterized in that as glorieuses agent use phenyltrichlorosilane6H5CCl3.

2. The method according to claim 1, characterized in that the interaction magyarkanizsa connection with phenyltrichlorosilane6H5CCl3, is carried out at a molar ratio of C6H5CCl3/Mg≥ 1.0 and a temperature of 5-80° C.

3. The polymerization of ethylene and copolymerization of ethylene with alpha-olefins in the presence of a catalyst containing a transition metal compound on a magnesium-containing carrier, characterized in that the use of the catalyst obtained according to any one of claims 1 and 2.



 

Same patents:

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

The invention relates to methods for macromolecular higher poly-alpha-olefins, in particular polyacene, and catalysts for carrying out the method

The invention relates to the components of the catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and at least one 1,3-W, which forms complexes with anhydrous magnesium dichloride in an amount of less than 60 mmol per 100 g of MgCl2and without substitution reactions with TiCl4or reacting in the amount less than 50 mol%, and at least one ester of mono - or polycarboxylic acid, and 1,3-diesters selected from compounds of the formula (II)

where the group RIIIidentical or different, represent hydrogen or C1-C18hydrocarbon group; groups of RIVidentical or different, have the same meaning as RIIIexcept that they cannot be hydrogen; each of the groups RIII- RIVmay contain heteroatoms selected from Halogens, N, O, S and Si, and the radicals RVidentical or different, are selected from the group consisting of hydrogen; Halogens, preferably C1 or F; C1-C20alkyl radicals with a straight or branched chain; C3-C20cycloalkyl,6e radicals Rvcan be connected to each other to form a condensed cyclic structures, saturated or unsaturated, optionally substituted, RVIradicals selected from the group consisting of halogen, preferably C1 or F; C1-C20alkyl radicals, linear or branched; C3-C20cycloalkyl, C6-C20aryl, C7-C20alkalinic and C7-C20Uralkalij radicals; the radicals RVand RVIoptionally contain one or more heteroatoms as substitutes for carbon or hydrogen atoms, or both

The invention relates to a component of a solid catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and an electron donor selected from substituted succinates formula

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 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

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: polymers, chemical technology, catalysts.

SUBSTANCE: invention relates to the modified chrome oxide catalytic systems on a carrier used for polymerization of olefins and to a method for preparing polymers and ethylene copolymers. Invention describes a method for preparing copolymer of ethylene and 1-hexene wherein indicated copolymer shows swelling value by mass less about 380% and wherein swelling extruded flow is less about 42%, cracking resistance under external stress (ESCR) (condition A) is above about 400 h, onset of destruction of extrusion flow is at least about 2000 c-1 and result in testing for outlet for 1 min is at least about 1200 g/min in the content of xylene-soluble substances is less 0.7% and less 2 wt.-% of substance with molecular mass less 1000 Da. Method involves contact of the following components under condition of suspension polymerization in isobutene as a solvent at temperature from about 93.3°C to 110°C: (a) monomer of ethylene; (b) 1-hexene; (c) catalytic system comprising chrome applied on silicon dioxide-titanium oxide carrier that comprises from about 0.5 to about 3 wt.-% of titanium relatively to carrier mass wherein indicated catalytic system shows the surface square in the range from about 100 m2/g to about 500 m2/g, pore volume in the range from about 0.6 to about 1.4 ml/g and indicated catalytic system is activated at temperature in the range from about 538°C to about 650°C; (d) from about 0.1 to about 2.0 mg/kg relatively to a diluting agent in reactor, trialkylboron; and (e) extraction of copolymer. Also, invention describes copolymer of ethylene and 1-hexene prepared by above described method, catalytic composition and composition comprising copolymer of ethylene and 1-hexene. Invention provides enhanced yield of polymer, preparing copolymer of ethylene of high density with high resistance against cracking under stress, creating a polymer that is processed good in forming by bulge.

EFFECT: improved method for polymerization.

13 cl, 3 tbl, 1 ex

FIELD: chemical industry; production of catalytic compounds for polymerization of monomers.

SUBSTANCE: the invention is dealt with the field of polymerization of the monomers and with the methods of production of catalytic compounds and compounds, which are applied at polymerization of at least one monomer. The offered methods contain: 1) a treated solid oxide compound produced due to a contact at least of one solid oxide with at least of one compound having an electron-seeking anion; 2)a metallocenes compound of a metal from IVA group; 3) an organoaluminum compound. The technical result: production of a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

EFFECT: the invention allows to produce a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

71 cl, 99 ex, 13 tbl

FIELD: olefin polymerization.

SUBSTANCE: invention relates to method for introducing of several catalysts in gas-phase or suspension reactor. Claimed method includes integration before introducing into single reactor of (a) solution, suspension or emulsion containing the first catalytic substance; and (b) solution, suspension or emulsion containing the second catalytic substance and optionally activator; followed by (c) introducing of (a) and (b) composition into single reactor in presence of hydrogen and one or more olefins wherein one polyolefin composition is formed.

EFFECT: polymers with wide bimodal molecular mass distribution.

14 cl, 3 ex

FIELD: olefin polymerization.

SUBSTANCE: invention relates to method for introducing of several catalysts in gas-phase or suspension reactor. Claimed method includes integration before introducing into single reactor of (a) solution, suspension or emulsion containing the first catalytic substance; and (b) solution, suspension or emulsion containing the second catalytic substance and optionally activator; followed by (c) introducing of (a) and (b) composition into single reactor in presence of hydrogen and one or more olefins wherein one polyolefin composition is formed.

EFFECT: polymers with wide bimodal molecular mass distribution.

14 cl, 3 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to novel organometallic compounds and to olefin polymerization catalytic systems including such organometallic compounds, and also to a method for polymerization of olefins conduct in presence of said catalytic system. Novel organometallic compound is prepared by bringing into contact (i) compound of general formula I: (I), where Ra, Rb, Rc, and Rd, identical or different, represent hydrocarbon groups; and (ii) Lewis acid of general formula MtR

13
, where Mt represents boron atom and R1, identical or different, are selected from halogen and halogenated C6-C30-aryl groups.

EFFECT: enabled preparation of novel olefin polymerization cocatalysts, which reduce use of excess cocatalyst relative to alkylalumoxanes, do not lead to undesired by-products after activation of metallocene, and form stable catalytic compositions.

14 cl, 1 tbl, 32 ex

FIELD: vinylcyclohexane-based polymer or copolymer with isotactic structure.

SUBSTANCE: claimed polymer or copolymer may be obtained using comonomers selected from at least one monomer of group including olefine, (meth)acrylic alkyl esters, cyclopentadiene, cyclohexene, cyclohexadiene, optionally substituted norbornene, dicyclopentadiene, optionally substituted tetracyclododecenes, alkylated in nuclear styrene, alpha-methylstyrene, divinylbenzene, vinyl ester, vinyl ether, vinyl acetate, vinyl acid, (meth)acrylonitrile, maleic anhydride. Polymer contains more than 50.1 % and less than 74 % of isotactic diads.

EFFECT: polymer of high transparency useful as material for substrate in optical memory devices.

3 cl, 4 ex, 2 tbl

FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

FIELD: metalloorganic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to class of metallocene compounds of the general formula (I) wherein Y means fragment of the formula (II) wherein A means sulfur or selenium atom; B means carbon atom; D means carbon atom; R1, R2, R3, R4 and R5 mean hydrogen atom or hydrocarbon groups; Z is taken among fragment of the formula (II) and fragment of the formula (III) wherein R6, R7, R8 and R9 mean hydrogen atom or hydrocarbon groups; L means bivalent bridge group; M means zirconium atom; X means halogen atom; p = 2. Above described metallocenes are useful especially for polymerization of propylene.

EFFECT: improved preparing method, valuable properties of metallocenes.

15 cl, 5 tbl, 18 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention describes metallocene catalytic component of catalytic system for production of polyolefin with isotactic or syndiotactic/isotactic block structure with length of monomer unit up to C10, said component having general formula R"(CpR1R2R3)(Cp'R1R2')MQ2, where Cp represents cyclopentadienyl ring substituted by at least one substituent; Cp' is substituted fluorenyl ring; R" structural bridge imparting steric rigidity; R1 optional substituent in cyclopentadienyl ring located at a distance to bridge and including a bulky group XR*3 wherein X is selected from group IVA elements and R*, the same or different, are hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms; R2 optional substituent in cyclopentadienyl ring, nearest to bridge and not vicinal to remote substituent, which substituent has formula YR# wherein Y is selected from group IVA elements and R#, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R3 optional substituent in cyclopentadienyl ring, nearest to bridge and being hydrogen or having formula ZR$ wherein Z is selected from group IVA elements and Rs, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R1' and R2' are independent substituents in fluorenyl ring, one of them having formula AR3’’’ wherein A is selected from group IVA elements and each of R’’’ represents independently hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms and the other being hydrogen or second group AR3’’’; M is transition metal from group IVB or vanadium and each Q is either hydrocarbon radical with 1-20 carbon atoms or halogen.

EFFECT: enabled preparation isotactic or syndiotactic/isotactic block polymer with length of monomer unit up to C10.

30 cl, 13 dwg, 2 tbl, 10 ex

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

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