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System of olefin polymerisation catalyst. RU patent 2511448.

IPC classes for russian patent System of olefin polymerisation catalyst. RU patent 2511448. (RU 2511448):

C08F4/649 -

C08F2/34 - MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS (production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation, C10G0050000000; fermentation or enzyme-using processes to synthesise a desired chemical compound or composition or to separate optical isomers from a racemic mixture C12P; graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics or fibrous goods made from such materials D06M0014000000)

C08F10/02 - Ethene

Another patents in same IPC classes:

Catalyst components for polymerisation of olefins / 2493175
Invention relates to polymerisation of CH2=CHR olefins, where R is hydrogen or a C1-C12hydrocarbon group, and to catalysts therefor. A pre-polymerised catalyst component contains a solid component containing Mg, Ti, a halogen and an electron donor (ID), selected from alkyl esters of aromatic dicarboxylic acids. The molar ratio ID/Mg ranges from 0.025 to 0.065 and the molar ratio Mg/Ti is greater than 13. Said pre-polymerised catalyst component contains up to 50 g of an ethylene prepolymer per g of said solid catalyst component.

Polymer films / 2489454
Film is made by extrusion from an ethylene and alpha-olefin compolymer. Said ethylene and alpha-olefin copolymer is obtained during a gas-phase polymerisation process with formation of particles in the presence of a monocyclopentadienyl metallocene complex, a co-catalyst of general formula (L*-H)+ d(Ad-), where L* is a neutral Lewis base, (L*-H)+ d is a Brоnsted acid, Ad- is a non-coordinating associative anion, having a charge d- and the anion includes an aryl-substituted borate, and d is an integer ranging from 1 to 3, of carrier material and alpha-olefin. Polymer film contains less than 300-600 gels/m2 with size from 100 to 2000 mcm according to the invention of an optical inspection system.

High melt flow rate, impact-resistant propylene copolymer and method for production thereof / 2487897
Polymerisation method involves contacting propylene and optionally at least one other olefin with a catalyst composition in a first polymerisation reactor under gas-phase polymerisation conditions, the catalyst composition containing a procatalyst, a cocatalyst and a mixed external electron donor (M-EED) containing a first selectivity control agent (SCA1), a second selectivity control agent (SCA2), and an activity limiting agent (ALA); forming, in a first polymerisation reactor, an active propylene-based polymer having a melt flow rate greater than about 100 g/10 min as measured in accordance with ASTM D1238-01 (230°C, 2.16 kg); contacting the active propylene-based polymer with at least one olefin in a second reactor under polymerisation conditions; and obtaining an impact-resistant propylene copolymer having a melt flow rate greater than about 60 g/10 min. A version of the method and the polymer is disclosed.

Self-limiting catalyst system with controlled aluminium to sca ratio and method / 2470947
Catalyst composition contains: one or more Ziegler-Natta procatalyst compositions having one or more transition metal compounds and one or more internal electron donors in form of esters of aromatic dicarboxylic acid, one or more aluminium-containing cocatalysts and a selectivity control agent (SCA) which contains a mixture of (i) a first alkoxy silane and a second alkoxy silane and (ii) an ester of C4-C30-aliphatic acid, and the molar ratio of aluminium to total SCA ranges from 0.5:1 to 4:1.

Self-limiting catalyst composition with no silane / 2461578
Described is a catalyst composition including one or more Ziegler-Natta procatalyst compositions containing one or more transition metal compounds and an internal electron donor, one or more aluminium containing cocatalysts, and a selectivity control agent (SCA), which contains a mixture of a carboxylic acid ester and a compound which does not contain silane, selected from the group consisting of a diether compound, a succinate compound, a piperidine compound and combinations thereof.

Preparation of catalyst paste for olefin polymerisation / 2448985
Present invention relates to a method of producing a catalyst composition in form of catalyst particles dispersed in a semi-liquid matrix. Described is a method of producing a catalyst composition for polymerisation of olefins in form of a dispersion of catalyst particles in a semi-liquid matrix, characterised by that said method comprises steps for: forming a suspension of catalyst particles in oil by loading, while stirring continuously, dry catalyst powder into a tank containing said oil, wherein the rate of loading the catalyst powder per metre of the oil boundary surface is less than 800 kg/h*m2; adding, while stirring, molten thickener having melting point ranging from 30 to 70°C, while holding the catalyst suspension in oil at such a temperature that said thickener solidifies upon contact with said suspension, wherein said oil has dynamic viscosity at 100°C ranging from 1 to 12 cP, and said catalyst particles fed into the tank at step a) are Ziegler-Natta catalyst components based on a titanium halide deposited on a magnesium halide. Described also is an olefin polymerisation method, which is realised in the presence of a solid polymerisation catalyst, wherein said solid polymerisation catalyst is treated and transferred into a polymerisation reactor through the following steps for: a) forming a suspension of catalyst particles in oil by loading, while stirring continuously, dry catalyst powder into a tank containing said oil, wherein the rate of loading the catalyst powder per m2 of the oil boundary surface is less than 800 kg/h*m2; b) adding, while stirring, molten thickener having melting point ranging from 30°C to 70°C, while holding the catalyst suspension in oil at such a temperature that said thickener solidifies upon contact with said suspension; c) the catalyst paste from step b) is brought into contact with an organoaluminium compound in the presence of an inert hydrocarbon, possibly an electron-donor compound, at temperature from 5°C to 30°C; d) polymerisation of one or more α-olefins of formula CH2=CHR, where R denotes hydrogen or a hydrocarbon radical having 1-12 carbon atoms, in one or more polymerisation reactors in the presence of the catalyst from step c), wherein said oil has dynamic viscosity at 100°C ranging from 1 to 12 cP, and said catalyst particles which are fed into the tank at step a) are Ziegler-Natta catalyst components based on a titanium halide deposited on a magnesium halide.

Solid catalytic component for polymerization of olefins, catalyst containing it, and use thereof / 2298014
Catalytic component according to invention contains magnesium, titanium, halogen, and electron donor, wherein the latter contains at least one compound, notably polyol ester I having general formula R1CO-O-CR3R4-A-CR5R6-O-CO-R2 (I), wherein groups R1 and R2, the same or different, represent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; groups R3-R5, the same or different, are selected from group consisting of hydrogen, halogen, and above-defined hydrocarbon residue, said groups R3-R6 optionally containing one or several heteroatoms substituting carbon and/or hydrogen atom, wherein said heteroatoms are selected from group consisting of oxygen and halogen atoms, or two or more groups R3-R6 being connected with each other to form saturated or unsaturated monocyclic ring; and A represents bivalent linking group between two hydrocarbon radicals having from 1 to 10 atoms, said linking group being selected from group consisting of aliphatic, alicyclic, and aromatic bivalent radicals and can bear linear or branched C1-C20-substituents, provided that two or more substituents of said linking group and above-defined R3-R6 groups can be interconnected to form saturated or unsaturated monocyclic ring. Invention further discloses catalyst containing above-defined solid catalytic component and its employment in polymerization of CH2=CHR hydrocarbons, wherein R represents hydrogen or C1-C6-alkyl group.

Catalytic composition and methods for preparation thereof as well as use thereof in polymerization process / 2255941
Invention provides catalytic composition prepared from polymerization catalytic system and at least one gelation agent, said gelation agent being selected from group including diester phosphates, steroid and anthryl derivatives, amino acid-type gelation agents, and tetraoctadecylammonium bromide and said polymerization catalytic system being selected from common-type catalytic compounds with transition metal and metallocene catalytic compounds. Invention discloses method of preparing indicated catalytic system and a method of continuous polymerization of an olefinic monomer.

Method of purifying fluorinated compound / 2510713
Invention relates to efficient method of purifying fluorinated compound, which includes distillation of liquid, which contains, at least, one member, selected from group, consisting of fluorinated compound, represented by the following formula (1), and fluorinated compound, represented by the following formula (2), keeping it at temperature of heating not higher than 150°C, where temperature of heating is internal temperature of distillation column boiler: RFOR1COOH, (1), RFOR1COOR2, (2) in which RF represents fluorinated alkyl group, which can have simple ether atom of oxygen in its main chain, R1 represents perfluoroalkylene group, and R2 represents C1-C3alkyl group, and in which liquid represents liquid obtained from any liquid waste product after coagulation of fluoropolymer water emulsion and separation of fluoropolymer, water liquid, obtained by washing of discharge gas at the stage of drying and/or stage of thermal processing of a separate fluoropolymer, or liquid, obtained by washing with alkali water solution of anion-exchange resin, which was brought in contact with liquid waste product or water dispersion, obtained from fluoropolymer water emulsion.

Method of transition between non-compatible systems of olefin polymerisation catalysts / 2510703
Invention relates to method of transition between non-compatible systems of olefin polymerisation catalysts in one reactor. Described is method of transition from system of Ziegler-Natta catalyst to system of Phillips catalyst for polymerisation of olefins in one reactor, where method includes the following stages: a) interruption of the reaction of the first polymerisation of olefins, carried out in presence of Ziegler-Natta catalyst as a result of suspension of supply of Ziegler-Natta catalyst into reactor and deactivation of Ziegler-Natta catalyst system, or suspension of supply of Ziegler-Natta catalyst system into reactor and increase of reactor temperature, or suspension of supply of Ziegler-Natta catalyst system into reactor and combined application of deactivating agent and increase or reduction of temperature; b) Supply of additional catalyst system, which contains (A) and (B) components resulting in obtaining, respectively, the first and the second polyolefin fractions, where Mw value of the first polyolefin fraction is less than Mw value of the second polyolefin fraction, carrying out reaction of the second polymerisation of olefins in presence of additional catalyst system, where initial activity of catalytic component (A) is higher than initial activity of catalytic component (B), suspension of supply of additional catalyst system into reactor; supply of Phillips catalyst system and carrying out reaction of the third polymerisation of olefins in presence of Phillips catalyst.

Heterophase polypropylene copolymer composition / 2510407
Described is a heterophase polypropylene polymer composition, the weight composition of which includes: (A) 45-70% propylene homo- or copolymer matrix with melt flow rate according to standard ISO 1133 (230°C, with nominal load of 2.16 kg) of ≥80 g/10 min, and (B) 25-40% elastomeric copolymer of propylene and ethylene with characteristic viscosity IV (standard ISO 1628, with decalin as solvent) of ≥3.3 dl/g, and weight content of ethylene of 20-50%, (C) 0-15% elastomeric random copolymer based on ethylene and alpha-olefin (D) 3-25% inorganic filler. The heterophase polypropylene composition has total melt flow rate (230°C/2.16 kg) according to standard ISO 1133, greater than or equal to 5 g/10 min, Charpy notch impact strength in accordance with standard ISO 179/leA at temperature of +23°C, greater than or equal to 15.0 kJ/m2, in accordance with the preferred exemplary embodiment of the present invention which is greater than or equal to 25.0 kJ/m2, minimum Charpy notch impact strength according to standard ISO 179/leA at temperature of 20°C, greater than or equal to 7.0 kJ/m2, in accordance with the preferred exemplary embodiment of the present invention which is greater than or equal to 10.0 kJ/m2, and modulus of elasticity in tension according to standard ISO 527-3, which is greater than or equal to 1200 MPa. Also described is a method of producing a heterophase polypropylene polymer composition, use of the composition and an article made by pressure casting.

Emulsive polymerisate containing activators, method for production thereof and use thereof in two- or multi-component systems / 2510405
Described is a core-cladding emulsive polymerisate with an activator included in the core, which is obtained from polymerising a mixture containing: a) 5-99.9 wt % of one or more mono-functional (meth)acrylate monomers with water solubility of < 2 wt % at 20°C; b) 0-70 wt % of one or more monomers that copolymerisable with monomers a); c) 0-20 wt % of one or more compounds that are di- or multi-vinylenically unsaturated; d) 0-20 wt % of one or more polar monomers with water solubility of >2 wt % at 20°C, selected from (meth)acrylic acid and (meth)acrylamide, and c) 0.1-95 wt % of at least one activator. Wherein components a) to e) amount to 100 wt % of polymerisable components of the mixture, characterised by that e1) the activator is a compound of formula I where R1 is methyl; X is a linear alkanediiyl group with 1-18 carbon atoms; R2 denotes a hydrogen atom or a linear or branched alkyl residue with 1-12 carbon atoms; R3, R4, R5, R6 and R7 independently denote a hydrogen atom and that e2) the activator e) is covalently bonded to the emulsive polymerisate. Also described is a method of producing said emulsive polymerisate by "core-cladding" polymerisation in an aqueous emulsion, wherein components a) to e) at the first step are polymerised in form of a core, and then a mixture of components a) to d) are polymerised thereon as cladding in at least an additional step. Components a) to e) for the core and components a) to d) for the cladding are selected such that in the resultant polymerisate, the glass transition temperature of at least one cladding TGS is higher than the glass transition temperature of the core TGK, wherein the glass transition temperature of at least one cladding TGS is higher than 100°C, wherein the glass transition temperature TG is determined according to the EN ISO 11357 standard. Described is a two- or multi-component system with a controlled working life, which is curable at room temperature using a redox system of initiators containing A) 0.8-69.94 wt % emulsive polymerisate according to claims 1-7 or obtained by a method according to claim 8; B) 30-99.14 wt % of one or more ethylenically unsaturated monomers; C) 0.05-30 wt % peroxides; optionally D) 0-60 wt% unsaturated oligomers; E) 0.01-2 wt % polymerisation inhibitor; and optionally F) 0-800 pts.wt auxiliary substances and additives; wherein the sum of components A)+B)+C)+D)+E) is 100 wt %, and the amount of F) relates to 100 pts.wt of the sum A)+B)+C)+D)+E). Wherein component A) and component C) are stored together, and before applying the system, at least one component B) is stored separately from A) and C), wherein the capacity of the separately stored component B) to cause swelling of the polymerisate A) is so high that the activator of the polymerisate A) fixed in the polymer can react with component C), or component A), part of component B) and component DC) are stored together, wherein part of component B) is selected such that the capacity of component B) to cause swelling of the polymerisate A) is so low that the activator of the polymerisate A) fixed in the polymer cannot react with component C). Also described is use of said two- or multi-component system as a component part of substances, such as resins from unsaturated polyesters and vinyl esters or adhesive substances, cast resins, polymer coatings for floors and other reactive coatings, sealants, impregnating compounds, binding compounds, compounds for making artificial marble and other artificial stones, compounds for reactive concrete inserts, tooth filling compounds, porous plastic moulds for ceramic articles.

Emulsive foam material with high content of disperse phase, having low content of non-polymer monomers / 2509090
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Method of producing polyester acrylates / 2509087
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Control of gas phase polymerisation reactor / 2507556
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Method and apparatus for continuous production of polymerisates by radical polymerisation / 2507214
Present invention relates to a method for continuous production of a polymerisate by radical polymerisation. Described is a method for continuous production of a polymerisate by radical polymerisation in a solution, which includes the following steps: (a) preparing at least two liquid streams, each stream including one or more of the following components: a monomer which is suitable for radical polymerisation, which is a monoethylenically unsaturated carboxylic acid or sulphonic acid or a mixture of monomers which contains at least one monoethylenically unsaturated carboxylic acid or sulphonic acid, a regulator selected from solvents with a regulating action, and regulators different therefrom, and an initiator, under the condition that the stream containing an initiator does not contain a regulator; (b) mixing the at least two liquid streams to obtain a reaction mixture, wherein mixing is carried out in one or more steps and at least 10°C below the reaction temperature of subsequent polymerisation and wherein at least the last mixer in the direction of flow before entry into the reaction zone(s) is a micromixer; (c) radical polymerisation of the reaction mixture obtained at step (b), carried out in at least one microstructured reaction zone with a characteristic dimension ranging from 0.1 mm to 8 mm. Also described is an apparatus for continuous production of polymers for carrying out said method. Also described is use of the polymerisate obtained using said method or in said apparatus as a pigment dispersant.

Transparent, colourless, infrared radiation-absorbing compositions containing nanoparticles of non-stoichiometric tungsten oxide / 2506284
Invention relates to transparent and colourless compositions which absorb infrared radiation. The composition contains binder which contains a radiation-curable composition and not more than 500 ppm, relative the total weight of the composition, of particles of non-stoichiometric tungsten oxide of general formula WO2.2-2.999 with average size of primary particles of not more than 300 nm, dispersed in the binder. Also described are films made from the infrared-radiation absorbing composition.

System and method for cationic polymerisation / 2506277
Present invention relates to a system for initiating cationic polymerisation of monomers, a polymerisation method and a polymer obtained using said method. The system for cationic polymerisation in an aqueous reaction medium includes an initiation system, an aqueous reaction medium and an optional dispersant. The initiation system comprises an initiator, an additive, a Lewis acid and an optional diluent. The additive is selected from a group consisting of organic compounds which contain one or more heteroatoms selected from nitrogen, oxygen, sulphur and phosphorus. Water content in the reaction medium ranges from 3.5% to 100%. The cationic polymerisable monomers used are vinyl compounds which are selected from a group consisting of C3-C12-olefins, C4-C12-diolefins, styrenes or derivatives and vinyl esters thereof.

Polymerisation catalysts, methods for production and use thereof and polyolefin products obtained using same / 2509088
Invention relates to catalyst systems for polymerising olefins, which contain a catalytic, high-molecular weight compound and a catalytic, low-molecular weight compound, a method for production thereof, a method of polymerising olefins, an ethylene polymer and an article made from the ethylene polymer. The high-molecular weight catalysts include metallocene catalysts. The second catalyst component has formula I (values of radicals are given in the claim). The second catalyst component is present in an amount of 0.001-5.0 mol % with respect to said first catalyst component. Said first catalyst component enables to obtain a polymer with weight-average molecular weight (Mw) of 40000-200000 g/mol, and the second catalyst component enables to obtain a polymer with Mw higher than 1000000 g/mol. The obtained ethylene polymer has at least one of the following properties: (a) melt strength greater than 6*MI-0.6675, (b) ratio of longitudinal viscosity, measured at rate of extension of 1 s-1, 190°C and exposure time of 4 s, to viscosity predicted based on linear viscoelastic properties for the same temperature and exposure time, greater than 3; (c) activation energy (Ea) less than 7 kcal/mol/K; (d) ratio Mz/Mw greater than the ratio Mw/Mn, where Mz is the z-average molecular weight of said polymer, Mw is the weight-average molecular weight of said polymer, Mn is the number-average molecular weight of said polymer; and (e) Van Gurp-Palmen plot, having a positive slope and having a maximum, wherein the Van Gurp-Palmen plot is a curve of phase shift versus the magnitude of the complex shear modulus, determined based on dynamic rheological properties, more specifically based on frequency sweep in the range of 0.01-100 rad/s at 190°C.

Transition metal based catalyst systems and methods of producing homopolymers of ethylene or copolymers of ethylene and α-olefins using said systems / 2507210
Invention relates to a transition metal compound of chemical formula (1): [Chemical formula 1] In the present formula, M is Group 4 transition; Cp is a cyclopentadienyl ring bonded with M on a η5-type, where the cyclopentadienyl ring can further be substituted with (C1-C20)alkyl or (C6-C30)aryl; Ar is (C6-C14)arylene; R11 and R12 independently denote a hydrogen atom or (C1-C10)alkyl; n is an integer from 0 to 2; R is (C1-C10)alkyl or (C1-C10)alkoxy; and when n equals 2, individual substitutes R can be identical or different; X1 and X2 independently denotes a halogen atom, (C1-C20)alkyl, (C6-C30)aryl(C1-C20)alkyl or (C6-C30)aryloxy; alkyl, arylalkyl, alkoxy, aryloxy groups, radicals Rn, X1 and X2 and arylene groups Ar can be independently substituted with one or more substitutes selected from a group consisting of (C1-C20)alkyl, (C6-C30)aryl and (C1-C20)alkoxy. The invention also discloses a catalyst composition, a method of producing homopolymers of ethylene or copolymers of ethylene with α-olefin, a homopolymer of ethylene or a copolymer of ethylene with α-olefin.

FIELD: chemistry.

SUBSTANCE: claimed invention relates to systems of catalysts of polymerisation of CH₂=CHR olefins, where R represents alkyl, cycloalkyl or aryl radical, containing 1-12 carbon atoms, and to method of gas-phase ethylene (co)polymerisation. Catalyst contains (A) solid component of catalyst, which contains Ti, Mg, halogen and is characterised by porosity (P_F), measured by method of mercury porosimetry and conditioned by pores with radius equal to or smaller than 1 mcm, which constitutes, at least, 0.3 cm³/g, (B) aluminium-alkyl compound and (C) monohalogenated hydrocarbon, in which halogen is bound with secondary carbon atom.

EFFECT: claimed systems of catalysts are characterized by improved activity in polymerisation.

10 cl, 3 tbl, 23 ex

The invention relates to the catalyst polymerization of olefins, including ethylene and its mixtures with olefins CH 2 =CHR, where R represents an alkyl, cycloalkyl or aryl radical containing 1-12 carbon atoms containing solid component of the catalyst, contains Ti, Mg, halogen and demonstrating special physical signs, expressed through a specific range of porosity, aluminiumallee connection and certain specific halogenated alkyl compounds.

Activity during polymerization is a very important factor in any way polymerization. For a given system of catalyst it may depend on the conditions of polymerization, such as temperature, pressure and concentration of regulators polymerization degree. However, after fixing the conditions of polymerization activity is strictly dependent on the system catalyst, and in case of unsatisfactory activity of the quantity of the catalyst, fed to the reactor, should be extended, or shall be extended for the period of his stay. Both solutions degrade the performance of the installation, because increasing the amount of catalyst means an increase in cost per unit of quantity of the obtained polymer, while the increase in time means less productivity of installation.

Given the importance of this, there is a need to increase the activity of the catalyst. In General catalyst Ziegler-Natta receive as a result of the reaction between aluminiumtechnik connection and a firm component of the catalyst containing halide magnesium and connection titanium having at least one link Ti-halogen bonds. Because the catalyst determines how the activity and the properties of the polymer, the catalyst, once selected for industrial production, replaced by another with higher activity, only in case of preservation of a new system of properties of polymer basically unchanged. This is the reason why there is a need modification activity during polymerization of a certain system of catalyst without changing its ability to produce polymer, possessing certain properties.

In particular, the methods of polymerization of ethylene, in which the catalyst unlike catalysts for polypropylene production normally not contain compounds of external donor to increase stereospecificity, try increasing the activity usually involves the use of halogenated hydrocarbon compounds as improvers activity. Such use is described, for example, in the documents USP 5863995 and the EP 703246 A1. Documents WO03/010211 and WO04/03783 relate specifically to the ways of gas-phase polymerization, use the catalyst Ziegler-Natta, aluminijski and full of halogenated hydrocarbons in certain special ratios. In accordance with the description of the catalyst Ziegler-Natta is not attributed to any critical value, and halogenated hydrocarbons can be selected from a very wide range. In the examples of polimerizatsii from the document WO03/010211 use chloroform, and the results are shown in tables 1-3. In all trials example 5-21, which include the use of other polygalacturonic connections, any information on the results is given, which is confirmed by the wording on page 18, lines 9-10, claiming that the increased activity simply "expect".

Another an important feature related to gas-phase polymerization method is the ability of a catalyst to keep a good morphological stability, that is, the ability to withstand conditions of polymerization and not fragmented too small particles that can cause the formation polymer particles that can cause problems with the operation of the installation. This tendency to destruction, in particular, is observed, having received ethylene polymer relatively low molecular mass, expressed through high values of melt flow index. This type of polymer usually get in one of two or more cascade processes of obtaining ethylene polymer, possessing a broad molecular-mass distribution. To obtain such a low-molecular-weight polymer used the increased concentration of the regulator degree of polymerization (usually hydrogen), which has a vast impact on the activity of the catalyst. In these conditions, the agent that improves polymerization must interact with other components of the catalyst so that the resulting system catalyst was able to ensure the production of polymer with high outputs, but if the polymer is identical or increased bulk density in comparison with what can be obtained in no agent, improve activity during polymerization.

So, as to my surprise I found the applicant, the combination of a special type of catalyst and a special type of improver activity has led to improved gas-phase method of polymerization of ethylene.

Therefore, the aim of the present invention is the catalytic Converter system, especially suitable for gas-phase method of polymerization of olefins and containing (A) a solid component of the catalyst containing Ti, Mg, halogen and characterized porosity (P F ), as measured by the method of mercury porosimetry and is caused by then, with a radius equal to 1 micron or less equal to at least 0.3 cm 3 /g () aluminiumallee connection and (C) of mono - or dehalogenating hydrocarbon.

Preferably halogenated hydrocarbon choose from among monopolisierung hydrocarbons. Preferably it is chosen from among monopolisierung of hydrocarbons, in which the halogen associated with the secondary carbon atom. Halogen preferably chosen from chloride and bromide.

Non-limiting examples of the connection (S) are propylchloride, isopropylchloride, butyl chloride, sec-butyl chloride, tert-butyl chloride, 2-hlorbutin, cyclopentolate, cyclohexylamine, 1,2-dichloroethane, 1,6-dichlorohexane, propyl bromide and Isopropylamine, butylbromide, second-butylbromide, tert-butylbromide, isobutylparaben, isopentylamine, tert-interbreed. Among them in particular are preferred isopropylchloride, 2-hlorbutin, cyclopentolate and 2-bromopropane.

Improver activity uses that much to get the molar ratio (B)/(C)that is greater than 3, and preferably in the range 5-20, and preferably in the range 5-13.

Preferably components (a) and (C) uses that much to get the molar ratio between (C) and Ti atoms contained in (A), more than 2.5, preferably more than 3, and preferably greater than 3.5. At gas-phase polymerization one particularly preferred range concluded within 3 to 10, and preferably from more than 3.5 to 7.

Aluminiuim preferably may be selected from derivatives trialkylamine, such as, for example, trimethylaluminum (TMA), triethylamine (TEAL), triisobutylaluminum (CHIBA), tri-n-butylamine, tri-n-hexylamine, tri-n-octylamine. Also can be used alkilaminokarbeny and, in particular, alkilaminokarbeny, such as diethylaluminum (GEAH), diisobutylaluminum, Al-sesquiplane and dimetilaminoboran (DMAH). Can also be used, and in some cases are the preferred and mixtures derived trialkylamine and alkylhalogenides. In accordance with the present invention in particular, it is preferable to use mixtures between TEAL and CHIBA with molar ratios in the range from 0.1 to 10, preferably from 0.5 to 2.5. In the case of mixtures aluminiumtechnik compounds to determine the quantitative relationships ()/() will use the total molar quantity Al.

Preferably component catalyst (A) is characterized by the porosity P F , defined by the method of mercury porosimetry, more than 0.40 cm3 /g, and preferably greater than 0,50 cm3 /g, usually in the range from 0.50 to 0.80 cm 3 /year Total porosity P F can be in the range of 0.50 to 1.50 cm 3 /g), in particular in the range of 0.60 to 1.20 cm 3 /year

The area of the specific surface measured by the BET method, preferably is less than 80, and in particular in the range from 10 to 70 m 2 /year Porosity, measured by BET method, in the General case is in the range from 0.10 to 0.50, preferably from 0.10 to 0.40 cm 3 /year

The number of Ti is usually greater than 1.5%, preferably more than 3%, and preferably equal to or greater than the 3.2% (mass.). It is most preferable is in the range of 3.5 to 8% (mass.).

In one of the preferred aspect component catalyst according to the invention, contains the connection Ti, having at least one link Ti-halogen and recorded on the media, magnesium chloride, which is preferable a magnesium dichloride, and more preferably magnesium dichloride in the active form. In the context of this proposal, the term "magnesium chloride" means compounds of magnesium, which has at least one connection ion chloride and magnesium. As mentioned earlier, a component of the catalyst can also have groups that are distinct from halogen, in any case, in quantities smaller than 0.5 moles per mole of titanium, and preferably less than 0.3.

The component of the catalyst the invention of the value of the mean radius long for porosity, caused by pores with the size up to 1 micron, is in the range from 600 to 1200 E.

The particles of the solid component (A) have essentially spherical morphology, and the average diameter is in the range from 35 to 150 microns, preferably from 40 to 130 microns, and preferably 50 to 130 mm. As particles with essentially spherical morphology, refers to those particles, which is the ratio between the larger axis and less axis is equal to or less than 1.5, and preferably less than 1.3.

Dichloride magnesium in the active form is characterized by x-ray spectra, in which the most intensive line diffraction, which is detected in the spectrum of inactive chloride (constant lattice of 2.56 (E), the intensity decreases and is widened in such extent that it becomes fully or partially fused with a line of reflection observed in position for a permanent crystal lattice (d) 2,95 E. In the case of complete fusion formed a single broad peak will have the maximum of intensity, which is biased towards the corners that are lower than the angles for the most intense lines.

One way suitable for obtaining the above-mentioned spherical components, includes the first stage (a), which connection MgCl 2 .m(R III OH)2 O tH, where 0.3≤m < = 1,7, t is in the range from 0.01 to 0.6, and R III represents an alkyl, cycloalkyl or aryl radical containing 1-12 of carbon atoms enter into a reaction with the mentioned connection titanium, opisyvayutsya formula Ti(OR II ) n X y-n , where n, y, X and R II have the same meaning as described previously.

In this case MgCl 2 .mR OH III is a predecessor of dihalogenides Mg. This type of connection in the General case can be obtained by mixing alcohol and magnesium chloride in the presence of inert hydrocarbon, immiscible with adduct, during operation in conditions of mixing with a melting point of adduct (100-130 C). After this emulsion quickly quenched, thus causing the hardening of the adduct in the form of spherical particles. On representative data retrieval methods spherical adducts reported, for example, in the documents USP 4469648, USP 4399054 and WO98/44009. Another suitable way of sterilisatie is a cooling spray, described, for example, in the documents USP 5100849 and 4829034. Adducts, characterized desirable final level of alcohol content can be obtained directly using the selected number of alcohol at the time of receipt of adduct. However, in case of necessity to get adducts, characterized by high porosity, it will be convenient to first obtain adducts containing more than 1.7 mole of alcohol on one mole of the MgCl 2 , and then expose them to the method of thermal and/or chemical dealcoholisation. The method of thermal dealcoholisation implement in a stream of nitrogen at the temperature within range from 50 to 150 C, up to reduce the level of alcohol content up to values in the range from 0.3 to 1.7. The method of this type is described in the document EP 395083.

Generally, the data subjected to dealcoholisation adducts are also characterized by the porosity (as measured by mercury method), caused by pores having a radius that goes up to 0.1 mm, in the range of 0.15 to 2.5 cm3 /g, preferably from 0.25 to 1.5 cm 3 /year

In response phase (a) the molar ratio Ti/Mg is the stoichiometric or higher; preferably this ratio is greater than 3. Even more preferable is the use of large excess connection titanium. The preferred compounds of titanium are tetrahalogenides titanium, in particular TiCl 4 . Reaction with connection Ti may be held in the result of the suspension of the adduct in the cold TiCl 4 (at 0 C); the mixture is heated up to 80 to 140 C and maintained at this temperature for 0.5-8, preferably from 0.5 to 3 hours. Excess connection titanium can be separated at high temperatures as a result of filtration or sedimentation and sibonisweni.

Despite the lack of hard necessary in a solid component of the catalyst (A) may also contain and electron-electron-connection (internal donor), choose, for instance, from among ethers, esters, amines and ketones. In particular, the internal electron-donating the connection may to be selected from archilovich, cycloalkyl and akrilovyh simple ether and ester polycarboxylic acids, such as esters of acetic acid, phthalic, benzoic acid and succinic acids, in particular n-butylphthalate, diisobutyrate, di-n-octylphthalate, ethyl acetate and ethylbenzoic.

Other donor compounds used in the best variant, are ethers such as tetrahydrofuran and simple 1,3-diesters that describes, in particular, in the documents of the EP 361494, ER and ER.

The above-mentioned components (A)-(C) can be separately submitted to the reactor, where in conditions of polymerization can be used in their activity. Best may be a preliminary introduction to the contact above-mentioned components, not necessarily in the presence of small amounts of olefins over a period of time ranging from 0.1 to 120 minutes, preferably in the range from 1 to 60 minutes. Preliminary introduction to the contact can be carried out in liquid diluent at temperature in the range from 0 to 90 C, preferably in the range from 20 to 70 degrees C.

Thus the obtained system of the catalyst can be used directly at the main way of polymerization, or alternatively it can be pre subjected forprimerates. Stage of forprimerates will usually be preferred in case of implementation of the main way of polymerization in the gas phase. Forprimerates can be carried out using any of olefins CH 2 =CHR, where R is a N or C1-C10 hydrocarbon group. In particular, in particular the preferred forprimerates ethylene, propylene or their mixtures with one or more of giant dipole olefins, these mixes contain up to 20% (mol.) alpha-olefin, leading to obtain amounts of the polymer in the range of approximately-0.1 g per gram of solid component up to approximately 1,000 g per gram of solid component of the catalyst. Stage of forprimerates can be carried out at temperatures in the range from 0 to 80 C, preferably from 5 to 70 C in a liquid or gas phase. Stage of forprimerates can be conducted in the same process line as part of a continuous way of polymerization or separately on a periodic way. In particular, it is preferable to periodic forprimerates catalyst the invention when using propylene to get the number of polymer in the range from 0.5 to 20 g per gram component of the catalyst. Before using on the main stage of polymerization facilitiesbethany component catalyst may be subject to additional processing by the connection of titanium. In this case in particular is preferable to use TiCl 4 . Reaction with connection Ti may be held in the result of the suspension forprimerates component catalyst in liquid connection Ti, optional mixed with liquid diluent; the mixture is heated at 60 to 120 C and maintained at this temperature for 0.5-2 hours.

Gas-phase method can be implemented using a catalyst the invention in any type of polymerization reactor, such as gas-phase reactors with mixed or fluidized bed. In addition, it can also be implemented in the gas-phase reactors with at least two interrelated curing zone, described in documents ER-AND-782587 and ER-AND-1012195, or a combination with reactor stirring or fluidized bed.

The way of the invention may also be implemented in two or more reactors operating in various conditions and not necessarily in the administration, at least partially, polymer, which is produced in the second reactor, recycling the first reactor. Usually two or more of the reactor operated at various concentrations regulator polymerization degree or at different temperatures polymerization, or if there are both differences at the same time. Preferably polymerization is carried out in two or more stages, implemented at various concentrations regulator polymerization degree.

As already mentioned, the catalysts of the present invention are characterized by high activity in the polymerization in respect of (co)polymerization of ethylene.

In addition to the above ethylene Homo - and copolymers of catalysts of the present invention are also suitable for obtaining polyethylene very low-density and very low density (PEOP and PASEP with density less than 0,920 g/cm 3 , reaching 0,880 g/cm 3 ), consisting of copolymers of ethylene and one or more alpha-olefins, containing from 3 to 12 carbon atoms, characterized by the molar level of the content of the links produced from ethylene, more than 80%; elastomeric copolymers of ethylene and propylene and elastomeric terpolymers ethylene and propylene together with small shares of diene, characterized by massive levels of units produced from ethylene, in the range of approximately 30 to 70%.

The following examples are provided for additional descriptions of the present invention of a non-limiting way.

GETTING CHARACTERISTICS

Properties determined in accordance with the following next methods:

Porosity and specific surface area, determined with the use of nitrogen:

determined in accordance with the method BET (used equipment SORPTOMATIC 1900 from the company Carlo Erba).

Porosity and specific surface area defined by the use of mercury:

the measurement is carried out using a device "Porosimeter 2000 series" from the company Carlo Erba.

Flow index MIE (melt index E):

ASTM-D 1238 condition E

Flow index (MIF melt index F):

ASTM-D 1238 condition F

Flow index MIP (index of melt P):

ASTM D 1238 condition P

Bulk density:

DIN 53194

Determination of quantities Mg, Ti

(operat.)

and Al: conducted by the method of emission spectrometry with inductively coupled plasma (ICP) at use of the device "I. C. P. SPECTROMETER ARL Accuris".

The sample was obtained by the analytical otvarivanija in the "melting" platinum crucible" of 0.1 to 0.3 g catalyst and 3 g of a mixture of metaborate/lithium tetraborate, a composition 1/1. The crucible is placed in a weak flame of a Bunsen burner for stage combustion, and then after adding a few drops of the solution of KI is inserted into special equipment "Claisse Fluxy" for complete combustion. The remainder is collected solution HNO 3 with a concentration of 5% (vol/vol.), and then analyzed by the method of COI the next wave length: magnesium 279,08 nm; titanium 368,52 nm; aluminum 394,40 nm.

Determination of the number Cl: was performed using potentiometric titration.

Defining the number of groups OR: the analysis by the method of gas chromatography.

Common testing method polymerization to get HDPE

In the autoclave stainless steel 1.5 liter, degassed in stream N 2 at 70 C, introduced 500 ml anhydrous hexane, a component of the catalyst, 1.8 mol of triethylamine (tea) and a specified number of halogenated hydrocarbon compounds (C). The mixture is mixed, heated up to 75 C, and after that produced the supply 3 bar N 2 and 7 bar ethylene. Polymerization lasted for 2 hours. The ethylene injection conducted by keeping the pressure constant. In conclusion, the pressure in the reactor was stravovani and lessons thus polymer dried in a vacuum at 70 degrees C.

EXAMPLES 1-11 and comparative example 1

Getting solid component (A)

Adduct of magnesium chloride and alcohol containing approximately 3 mol alcohol, received following the method described in example 2 of document USP 4399054, but when working at 2000 rpm instead of 10000 rpm Adduct subjected to thermal treatment in the flow of nitrogen in the temperature range of 50-150°until mass alcohol content of 25%.

In chetyrehosnuju round flask 2 years, purged with nitrogen at 0oC entered 1 l TiCl 4 . After that, when the same temperature with stirring was added 70 g spherical adduct MgCl 2 /EtOH, containing 25% (mass.) ethanol and received exactly as it was described earlier. The temperature for 2 hours was increased to 140 C and kept so for 60 minutes. After that stirring interrupted, solid product was allowed to settle, and the supernatant liquid ciphervalue. Then the solid residue is washed once heptane at 80 C and five times hexane at 25 C and dried in vacuum at 30 C and subjected to analysis.

Thus obtained a solid component of the catalyst (A) was applied for the polymerization of ethylene in accordance with the General method when using the type and number of connections (C)in table 1 together with the results of polymerization.

Examples 12-20 and comparative example 2

Component catalyst (A)obtained as described in example 1, used during polymerization of ethylene, which was conducted in accordance with the General methodology of polymerization, with the difference that the pressure of ethylene amounted to 3 bar, and the pressure of hydrogen was 9 bar. Other specific conditions and results are shown in table 2.

Examples 21-23 and comparative example 3

In the glass reactor of 260 cm 3 , equipped with a mixing device, introduced 351,5 cm 3 hexane at 20 C and while stirring at 20 C 7 g component of the catalyst, obtained as described in example 1. Maintaining internal constant temperature in the reactor was slowly introduced 5.6 cm 3 three-n-octylamine (TOA) in hexane (approximately 370 g/l) and the temperature is brought up to 10 degrees C. Upon completion 10 minutes stirring in the reactor at the same temperature over a period of time 4 hours carefully introduced 10 g propylene. To track the expenditures of propylene in the polymerization reactor and stopped with a presumptive achievement of theoretical degrees of transformation 1 g polymer on one gram of catalyst. After that aggregate content is filtered and three times washed with hexane at a temperature of 20 C (50 g/l). After drying out analysis of the resulting forprimerates catalyst (A) and set the content of 1.1 g polypropylene on one gram of catalyst and 2.6% (mass.) of titanium atoms.

Thus obtained facilitiesbethany a solid component of the catalyst (A) used in the polymerization of ethylene in accordance with the following next technique. Other specific conditions and results are given in table 3.

Used the reactor fluidized bed of stainless steel, having an inner diameter of 200 mm and is equipped with system of circulation of gas, cyclone heat exchanger systems of regulation of temperature and pressure, the supply of ethylene, propane and hydrogen. Gas-phase reactor was purified in the results washing it with nitrogen at 120 C for 12 hours. After that, the pressure in the reactor increased when using propane and were heated up to 75 C. Then received the following composition of the gas: 13,6 bar propane, 1.9 bar ethylene, 9.5 bar hydrogen. Then stir through capacity preliminary introduction to the contact in the reactor has been continuously dosed out jointly with propane as a diluent facilitiesbethany catalyst (1 g/hour), specified in table 3 number of CHIBA/tea (the mixture at a molar ratio of 2:1) in relation to the number catalyst and specified in table 3 number CpCl when calculating the number of atoms Ti. During their stay in the capacity of a preliminary introduction to the contact was 60 minutes. When reaching the stationary state in the reactor of the reactor produced unloading at 5 kg/hour of polyethylene. The amount of content in the reactor is controlled kept equal to 15 kg, which is consistent with the time of stay in the reactor 3 hours. Unloaded polymer continuously dried in the flush of nitrogen. The results are shown in table 3.

1. The catalyst for gas-phase method polymerization of olefins, containing (A) a solid component of the catalyst containing Ti, Mg, halogen and characterized porosity (P F ), measured by the method of mercury porosimetry and is caused by then, with a radius equal to 1 micron or less, part of at least 0.3 cm 3 /g (In) aluminiumallee connection and (C) monopolistically hydrocarbon, in which the halogen associated with the secondary carbon atom.

2. The catalyst of claim 1, wherein the connection (S) halogen choose from chloride and bromide.

3. The catalyst of claim 1, wherein the connection (S) are selected from the group consisting of isopropylchloride, 2-chlorobutane, cyclopenthiazide, 2-bromopropane and cyclohexylurea.

4. The catalyst of claim 1, wherein the component catalyst (A) is characterized by the porosity P F , as defined by the method of mercury porosimetry greater than 0.40 cm 3 /year

5. The catalyst of claim 1, wherein the particles of the component catalyst (A) show an average diameters ranging from 40 to 130 mm.

6. The catalytic Converter system of claim 1 in which the connection (S) used in such quantities as to get the molar ratio (B)/(C)more than 3.

7. The catalytic Converter system of claim 1 in which the components (a) and (C) uses that much to get the molar ratio between (C) and Ti atoms contained in (A), more than 2.5.

8. The catalytic Converter system of claim 1 in which aluminiuim (B) select from derivatives trialkylamine.

9. The catalyst in paragraph 8, in which the quality of the connection (In) is a mixture between triethylaluminum and triisobutylaluminum with molar ratios in the range from 0.1 to 10.

10. Method of gas-phase (co)polymerization of ethylene, implemented in the presence of system of a catalyst under any of the preceding paragraphs.