WO2006056338A1 - Process for the preparation of a catalyst component for the polymerization of an olefin - Google Patents

Process for the preparation of a catalyst component for the polymerization of an olefin Download PDF

Info

Publication number
WO2006056338A1
WO2006056338A1 PCT/EP2005/012202 EP2005012202W WO2006056338A1 WO 2006056338 A1 WO2006056338 A1 WO 2006056338A1 EP 2005012202 W EP2005012202 W EP 2005012202W WO 2006056338 A1 WO2006056338 A1 WO 2006056338A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
reaction product
catalyst
oaik
compound
Prior art date
Application number
PCT/EP2005/012202
Other languages
French (fr)
Inventor
Yves Johann Elizabeth Ramjoie
Sergei Andreevich Sergeev
Mark Vlaar
Vladimir Aleksandrovich Zakharov
Gennadii Dimitrievich Bukatov
Original Assignee
Saudi Basic Industries Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saudi Basic Industries Corporation filed Critical Saudi Basic Industries Corporation
Priority to US11/791,592 priority Critical patent/US7947788B2/en
Priority to DE602005027615T priority patent/DE602005027615D1/en
Priority to KR1020077014239A priority patent/KR101221304B1/en
Priority to JP2007541767A priority patent/JP2008521944A/en
Priority to AT05812344T priority patent/ATE506377T1/en
Priority to EP05812344A priority patent/EP1838741B1/en
Priority to EA200701144A priority patent/EA011828B1/en
Priority to MX2007006290A priority patent/MX2007006290A/en
Priority to BRPI0517871A priority patent/BRPI0517871B1/en
Priority to CN200580040424XA priority patent/CN101065404B/en
Priority to PL05812344T priority patent/PL1838741T3/en
Publication of WO2006056338A1 publication Critical patent/WO2006056338A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652Pretreating with metals or metal-containing compounds
    • C08F4/658Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in a single group of groups C08F4/653 - C08F4/657
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652Pretreating with metals or metal-containing compounds
    • C08F4/654Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04Monomers containing three or four carbon atoms
    • C08F110/06Propene

Definitions

  • the invention is directed to a process for the preparation of a polymerization catalyst component.
  • the invention also relates to a polymerization catalyst comprising the catalyst component and furthermore the invention relates to the polymerization of an olefin in the presence of a polymerization catalyst comprising the catalyst component.
  • Catalyst components for the preparation of a polyolefin such as for example polypropylene are generally known and the essential elements for the preparation of such catalyst components are a magnesium-containing compound and a titanium compound supported thereon.
  • the preparation of such catalyst components is for instance described in WO-A-96/32427.
  • This publication discloses a 3-step process wherein, in the first two steps a Mg-containing support is prepared, and subsequently the Mg-containing support is contacted with titanium tetrachloride. The catalyst yield obtained with this process is relatively low.
  • the process according to the invention is characterized in that a compound with formula Mg(OAIk) x Cl y wherein x is larger than 0 and smaller than 2, y equals 2-x and each AIk, independently, represents an alkyl group, is contacted with a titanium tetraalkoxide and/or an alcohol in the presence of an inert dispersant to give an intermediate reaction product and wherein the intermediate reaction product is contacted with titanium tetrachloride in the presence of an internal donor.
  • the solid magnesium containing support having the formula Mg(OAIk) x CI x
  • the solid magnesium containing support having the formula Mg(OAIk) x CI x
  • Ti (OAIk) 4 and/or an alcohol AIkOH in the presence of an inert dispersant.
  • the obtained higher activity of the catalyst component means a higher yield of the polyolefin per gram of catalyst.
  • the higher activity reduces the catalyst costs in the polyolefin production.
  • the alkyl group AIk of Mg(OAIk) x CI y is an alkyl group with 1-8 carbon atoms.
  • the alkyl group may be linear or branched.
  • At least one of the Alk-groups represents an ethyl group.
  • each Alk-group represents an ethyl group.
  • the titanium tetraalkoxide contains 4-32 C-atoms.
  • the alkoxide group of the titanium tetraalkoxide may be either linear or branched.
  • the four alkoxide groups may be the same or differ independently.
  • These titanium tetraalkoxide compounds may be used alone or in combination.
  • At least one of the alkoxy groups in the titanium tetraalkoxide is an ethoxy group. More preferably the titanium tetraalkoxide is titanium tetraethoxide.
  • Suitable alcohols include for instance a linear or branched alcohol with 1-8 C-atoms.
  • the alcohols may be used alone or in combination.
  • the alcohol is ethanol.
  • the inert dispersant is a hydrocarbon solvent.
  • the solvent may be for example an aliphatic or aromatic hydrocarbon with 1-20 C-atoms.
  • the dispersant is heptane.
  • the molar ratio titanium tetraalkoxide to Mg(OAIk) x CI y may range between wide limits and is, for instance, between 0.02 and 0.5 . Preferably the molar ratio is between 0.07 and 0.2.
  • the molar ratio alcohol to Mg(OAIk) x CI y is between 0.02 and 0.5 . More preferably this ratio is between 0.07 and 0.2.
  • the temperature during the treatment of the compound with formula Mg(OAIk) x Cl y with the titanium tetraalkoxide and/or alcohol is in the range from -1O 0 C to 5O 0 C, more preferably in the range from -5 0 C to 4O 0 C and most preferably in the range between O 0 C and 3O 0 C.
  • the process according to the invention is characterized in that a compound with formula Mg(OAIk) x CI y wherein x is larger than 0 and smaller than 2, y equals 2-x and each AIk, independently, represents an alkyl group with 1-8 carbon atoms, is contacted with a titanium tetraalkoxide in the presence of an inert dispersant to give an intermediate reaction product and wherein the intermediate reaction product is contacted with titanium tetrachloride in the presence of an internal donor.
  • a compound with formula Mg(OAIk) x CI y wherein x is larger than 0 and smaller than 2, y equals 2-x and each AIk, independently, represents an alkyl group with 1-8 carbon atoms
  • an alcohol may be added before, during or after the treatment with Ti(OAIk) 4 , or a combination thereof.
  • the alcohol is first added to the compound with formula Mg(OAIk) x CIy whereafter the tetraalkoxide is added.
  • the alcohol and the tetraalkoxide preferably are added slowly, for instance during 0.5-4 hours, most preferably during 1-2.5 hours, each.
  • the TiCI 4 /Mg molar ratio in the contact between the intermediate product and titanium tetrachloride preferably is between 10 and 100, most preferably, between 10 and 50.
  • Suitable internal donors include carboxylic acids, carboxylic acid anhydrides, esters of carboxylic acids, halide carboxylic acids, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates, sulphonamides, thioethers, thioesters and other organic compounds containing a hetero atom, such as nitrogen, oxygen, sulphur and/or phosphorus.
  • the molar ratio of the internal donor relative to the magnesium during the treatment of the intermediate product with the titanium tetrachloride may vary between wide limits, for instance between 0.05 and 0.75. Preferably this molar ratio is between 0.1 and 0.4.
  • carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, isobutanoic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tartaric acid, cyclohexanoic monocarboxylic acid, cis-1 ,2-cyclohexanoic dicarboxylic acid, phenylcarboxylic acid, toluenecarboxylic acid, naphthalene carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and/or trimellitic acid.
  • suitable carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, isobutanoic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tartaric acid, cyclohexanoic monocarboxylic acid, cis-1 ,2-cyclohexanoic dicarboxylic acid, phenylcarboxylic acid, tol
  • Anhydrides of the aforementioned carboxylic acids can be mentioned as examples of carboxylic acid anhydrides, such as for example acetic acid anhydride, butyric acid anhydride and methacrylic acid anhydride.
  • esters of carboxylic acids are formates, for instance, butyl formate; acetates, for instance ethyl acetate and butyl acetate; - A -
  • acrylates for instance ethyl acrylate, methyl methacrylate and isobutyl methacrylate; benzoates, for instance methylbenzoate and ethylbenzoate; methyl-p-toluate; ethyl-D- naphthoate and phthalates, for instance monomethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diallyl phthalate and/or diphenyl phthalate.
  • Suitable halide carboxylic acids are the halides of the carboxylic acids mentioned above, for instance acetyl chloride, acetyl bromide, propionyl chloride, butanoyl chloride, butanoyl iodide, benzoyl bromide, p-toluyl chloride and/or phthaloyl dichloride.
  • Suitable alcohols are methanol, ethanol, butanol, isobutanol, xylenol and benzyl alcohol.
  • Suitable ethers are diethyl ether, dibutyl ether, diisoamyl ether, anisole and ethylphenyl ether, 2,2-diisobutyl-1 ,3-dimethoxypropane, 2,2- dicyclopentyl-1 ,3-dimethoxypropane, 2-ethyl-2-butyl-1 ,3-dimethoxypropane, 2- isopropyl-2-isopentyl-1 ,3-dimethoxypropane and/or 9,9-bis(methoxymethyl) fluorene.
  • tri-ethers can be used.
  • Examples of other organic compounds containing a heteroatom are 2,2,6,6-tetramethyl piperidine, 2,6-dimethylpiperidine, 2-methylpyridine, A- methylpyridine, imidazole, benzonitrile, aniline, diethylamine, dibutylamine, thiophenol, 2-methyl thiophene, isopropyl mercaptan, diethylthioether, diphenylthioether, tetrahydrofuran, dioxane, dimethylether, diethylether, anisole, acetone, triphenylphosphine, triphenylphosphite, diethylphosphate and/or diphenylphosphate.
  • the internal donor is dibutyl phthalate. Most preferably the internal donor is di-n-butyl phtalate.
  • an inert dispersant may be selected for example from the groups of aliphatic or aromatic hydrocarbon compounds with, for instance, 4-20 C-atoms.
  • the dispersant preferably is chosen such that virtually all side products are dissolved in the dispersant.
  • Suitable dispersants include for example aliphatic and aromatic hydrocarbons and halogenated aromatic solvents with for instance 4-20 C-atoms. Suitable examples are toluene, xylene, benzene, heptane and chlorobenzene.
  • the reaction temperature during the contact between the intermediate product and the titanium tetrachloride is preferably between 5O 0 C and 150 0 C, most preferably between 6O 0 C and 12O 0 C. At higher or lower temperatures the activity of the catalyst component prepared according to the process of the invention becomes lower.
  • the obtained reaction product is purified, usually with an inert aliphatic or aromatic hydrocarbon or halogenated aromatic compound, to obtain the catalyst component of the invention. If desired, the reaction and subsequent purification may be repeated one or more times.
  • the preparation of the magnesium containing support having the formula Mg(OAIk) x CI y is well known in the art and several methods are for instance described in US patent 5,262,573 and references cited therein.
  • such a magnesium containing support is prepared for instance as described in WO-A-96/32427 and WO-A-01/23441 wherein the magnesium containing support is obtained by: a) a Grignard formation step wherein metallic magnesium is contacted with an organic halide RX, where R is an organic group, preferably an aromatic group, containing for instance up to 20 carbon atoms and X is a halide, whereupon the resulting dissolved first reaction product is separated from the solid residual products and whereafter, b) an alkoxy group or aryloxy group containing silane compound is contacted with the obtained first reaction product whereupon the precipitate formed is purified.
  • a stirred reactor is used.
  • the Grignard formation step in the process for the preparation of the catalyst component of the invention is carried out by contacting metallic magnesium with an organic halide RX.
  • RX is an organic group preferably containing from 1 up to 20 carbon atoms and X preferably is chlorine or bromine.
  • organic group R examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, hexyl, octyl, phenyl, tolyl, xylyl, mesityl and benzyl. Combinations of two or more organic halides RX can also be used.
  • R represents an aromatic group, for instance a phenyl group.
  • RX represents chlorobenzene.
  • the magnesium and the organic halide RX can be reacted with each other without the use of a separate dispersant; the organic halide RX is then used in excess.
  • the organic halide RX and the magnesium can also be brought into contact with one another in the presence of an inert dispersant.
  • suitable dispersants include aliphatic, alicyclic or aromatic dispersants containing from 4 up to 20 carbon atoms.
  • chlorobenzene serves as dispersant as well as organic halide RX.
  • an ether is present in the reaction mixture.
  • Suitable ethers include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, diallyl ether, tetrahydrofuran (THF) and anisole.
  • the ether is dibutyl ether and/or diisoamyl ether.
  • the organic halide/ether ratio acts upon the activity of the catalyst component. More generally it acts upon the polymerization performance and the catalyst morphology.
  • the volume ratio organic halide to ether may vary within wide limits, for example between 75:25 and 35:65.
  • the organic halide/ether ratio for instance the chlorobenzene/dibutyl ether ratio
  • decreases the bulk density of the polyolefine powder prepared with the aid of the catalyst component becomes lower and when the organic halide/ether ratio increases, the amount of the dissolved first reaction product becomes lower.
  • the ratio at which the best results are obtained depends on the specific reactants and conditions chosen and can easily be determined by the skilled person. For instance when chlorobenzene and dibutylether were used the best results were obtained when the chlorobenzene/dibutyl ether volume ratio was between 70:30 and 50:50.
  • iodine and/or alkyl halides can be added to cause the reaction between the metallic magnesium and the organic halide RX to proceed at a higher rate.
  • suitable alkyl halides are butyl chloride, butyl bromide and 1 ,2-dibromoethane.
  • the organic halide RX is an alkyl halide, iodine or 1 ,2-dibromoethane is preferably used.
  • the reaction temperature for the Grignard formation step may range for instance between 2O 0 C and 15O 0 C and the reaction times may range for instance between 0.5 and 20 hours.
  • the dissolved first reaction product is separated from the solid residual products.
  • step b) the silane compound and first reaction product are introduced simultaneously to a mixing device in order to improve the morphology of the catalyst particles, especially of the larger catalyst particles, as described in WO-A- 01/23441.
  • 'morphology' does not only refer to the shape of the catalyst particles, but also to the particle size distribution, its fine content, powder flowability and the bulk density of the catalyst particles.
  • the polyolefin powder produced in the polymerization by using a catalyst component has the same morphology as the catalyst component (the so-called "replica effect"; see for instance S. van der Ven, Polypropylene and other Polyolefins, Elsevier 1990, p. 8-10).
  • the silane compound and first reaction product can be continuously or batch-wise introduced to the mixing device.
  • the silane compound and the first reaction product are introduced continuously to the mixing device.
  • the mixing device can have various forms; the mixing device can be a mixing device in which the silane compound is premixed with the first reaction product, the mixing device can also be the reactor in which the reaction between the silane compound and the first reaction product takes place.
  • the silane compound and the first reaction product are premixed before the mixture is introduced to the reactor for step b).
  • a catalyst component is formed with a morphology that leads to polymer particles with the best morphology (high bulk density, narrow particle size distribution, (virtually) no fines, excellent flowability).
  • the Si/Mg molar ratio during step b) may vary within wide limits for instance from 0.2 to 20.
  • the Si/Mg molar ratio is from 0.4 to 1.0.
  • the alkoxy group or aryloxy group containing silane is a compound or a mixture of compounds with the general formula SiR 1 n OR 2 4 .n, wherein n is 0, 1 , 2 or 3, preferably n is 0 or 1 , each R 1 , independently, represents an alkyl, alkenyl or aryl group, optionally containing one or more hetero atoms for instance O, N, S or P, with, for instance, 1-20 C-atoms, and each R 2 , independently, represents an alkyl or aryl group, optionally containing one or more hetero atoms for instance O, N, S or P, with, for instance, 1-20 C-atoms.
  • the silane is tetraethoxysilane.
  • the period of premixing may vary between wide limits, for instance 0.1 to 300 seconds. Preferably premixing is performed during 1 to 50 seconds.
  • the temperature during the premixing is not critical and may for instance range between 0 and 80 0 C; preferably the temperature is between 10 0 C and 50 0 C.
  • the reaction between the silane compound and the first reaction product may, for instance, take place at a temperature between -2O 0 C and 100 0 C; preferably at a temperature of from O 0 C to 8O 0 C.
  • the product obtained with the reaction between the silane compound and the first reaction product is usually purified by rinsing with an inert solvent, for instance a hydrocarbon solvent with for instance 1-20 C-atoms. It is very suitable to be used as starting material in the process of the present invention for the preparation of a catalyst compound.
  • an inert solvent for instance a hydrocarbon solvent with for instance 1-20 C-atoms. It is very suitable to be used as starting material in the process of the present invention for the preparation of a catalyst compound.
  • the invention is also directed to a polymerization catalyst comprising the catalyst component according to the invention and a co catalyst.
  • the catalyst composition also comprises an external donor.
  • the preparation of polyolefines takes place by polymerising one or more olefins simultaneously or successively in the presence of a catalyst comprising the catalyst component according to the invention, a co catalyst and optionally an external donor.
  • the olefins may be for example mono- and diolefins containing from 2 to 10 carbon atoms, such as for example ethylene, propylene, butylene, hexene, octane and/or butadiene.
  • the olefin is propylene or a mixture of propylene and ethylene.
  • the co catalyst is an organometallic compound containing a metal from group 1 , 2, 12 or 13 of the Periodic System of the Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989-1990).
  • the co catalyst is an organoaluminium compound.
  • the organoaluminium compound may be, for instance, a compound having the formula AIR 3 3 , wherein each R 3 independently represents an alkyl group with, for instance, 1-10 C-atoms or an aryl group with, for instance, 4-20 C-atoms.
  • Suitable examples of an organoaluminium compound are trimethyl aluminium, triethyl aluminium, ethyl-di-methyl aluminium, triisobutyl aluminium, methyl-ethyl-butyl aluminium and/or trioctyl aluminium.
  • the co catalyst is triethyl aluminium.
  • organo-silicon compounds that are suitable as external donor are compounds or mixtures of compounds with the general formula SiR 4 n OR 5 4 .n, wherein n is 0, 1 or 3, preferably n is 1 or 2, each R 4 , independently, represents an alkyl, alkenyl or aryl group, optionally containing one or more hetero atoms for instance O, N, S or P, with, for instance, 1-20 C-atoms, and each R 5 , independently, represents an alkyl or aryl group, optionally containing one or more hetero atoms for instance O, N, S or P, with, for instance, 1-20 C-atoms, for instance tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltributoxysi
  • the organo-silicon compound is n-propyltrimethoxysilane, cyclohexylmethyldimethoxysilane, di(iso-propyl)dimethoxysilane or di(iso- butyl)dimethoxysilane.
  • the molar ratio of the metal in the co catalyst relative to the Ti during the polymerization may vary for instance from 5 to 2000. Preferably this ratio is between 50 and 300.
  • the aluminium/ donor molar ratio in the polymerization mixture preferably is between 0.1 and 200; more preferably between 1 and 100.
  • the polymerization can be carried out in the gas phase or in the liquid phase (bulk or slurry).
  • a dispersing agent is present in the case of polymerization in the liquid phase.
  • Suitable dispersing agents include for instance n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and liquid propylene.
  • polymerization conditions such as for example the polymerization temperature and time, monomer pressure, avoidance of contamination of catalyst, choice of polymerization medium in slurry processes, the use of ingredients (like hydrogen) to control polymer molecular weights, and other conditions are well known to persons of skill in the art.
  • the polymerization temperature may very within wide limits and is, for instance, between 0° C and 120 0 C, preferably between 4O 0 C and 100° C.
  • the pressure during the polymerization is for instance between 0.1 and 6 MPa, preferably between 0.5-3 MPa.
  • the molecular weight of the polyolefine obtained during the polymerization can be controlled by adding during the polymerization hydrogen or any other agent known to be suitable for the purpose.
  • the polymerization can be carried out in continuous mode or batch wise. Slurry-, bulk-, and gas-phase polymerization processes, multistage processes of each of these types of polymerization processes, or combinations of the different types of polymerization processes in a multistage process are contemplated herein.
  • the polymerization process is a single stage gas phase process or a multistage, for instance a 2-stage, gas phase process where in each stage a gas-phase process is used.
  • gas-phase polymerization processes include both stirred bed reactors and fluidized bed reactor systems; such processes are well known in the art.
  • Typical gas phase ⁇ -olefin polymerization reactor systems comprise a reactor vessel to which ⁇ -olefin monomer(s) and a catalyst system can be added and which contain an agitated bed of forming polymer particles.
  • EP-A-398698 discloses a process for producing an olefin polymer by polymerizing an olefin in the presence of a catalyst comprising a solid catalyst component obtained by reacting with heating Mg (OR 1 ) n (OR 2 ) 2 - n , a titanium compound and a silicon compound Si(OR 4 ) 4 and subjecting the resultant reaction product to contact with TiX m (OR 5 ) 4 . m and an electron donating compound.
  • the process according to the present invention is different because of amongst others EP-A-398698 uses Mg (OR 1 ) n (OR 2 ) 2 -n and a silicon compound Si(OR 4 ) 4 whereas in the process according to the present invention the chlorine containing compound Mg(OAIk) x CI y is applied and no silicon compound is present in the reaction between the compound with formula Mg(OAIk) x CIy with a titanium tetraalkoxide and/or an alcohol in the presence of an inert dispersant.
  • US-A-5229342 discloses the production of a solution of a magnesium complex Mg 3 Ti(OR m )((B(OR 4 )) n by reaction of magnesium metal, titanium tetraethoxide, triethylborate , ferric chloride and ethanol.
  • US-A-5229342 discloses amongst others as essential different features the use of the metal magnesium instead of Mg(OAIk) x Cl y , a product in solution instead of a solid product and a boron containing compound Mg 3 T ⁇ (OR m )((B(OR 4 )) n instead of the chlorine containing compound Mg(OAIk) x Cl y • aTi(OAIk) 4 .
  • reaction product of step I 200 ml, 0.272 mol Mg
  • DBE dibutyl ether
  • TES tetraethoxysilane
  • DBE dibutyl ether
  • the reagents contact time was 13 s in the minimixer and the connecting tube between the minimixer and the reactor.
  • the stirring speed in the minimixer was 1000 rpm.
  • the mixture formed in the minimixer was introduced to a 0.7 I reactor, with stirring.
  • the reactor was loaded preliminary with 100 ml of DBE, and cooled to 5 0 C. Dosing time was 1 hour.
  • the stirring speed in the reactor was 200 rpm.
  • reaction mixture was kept at 5 0 C for 0.5 hour, then heated up to 6O 0 C and kept at this temperature for 1 hour. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting. The solid substance was washed three times using 300 ml of heptane. As a result, a pale yellow solid substance, reaction product I. B, was obtained, suspended in 110 ml of heptane.
  • reaction product III was obtained, suspended in 15 ml of heptane.
  • the supernatant was removed by decanting, after which the solid product was washed with chlorobenzene (125 ml) at 100 0 C for 20 min. Then the washing solution was removed by decanting, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 115 0 C for 30 min, after which the solid substance was allowed to settle, and the last treatment was repeated once again. The solid substance obtained was washed five times using 150 ml of heptane at 6O 0 C, after which the catalyst component, suspended in heptane, was obtained.
  • Example I was repeated, except for the fact that step I. C was performed as described below.
  • a 250 ml glass flask equipped with a mechanical agitator is filled with a slurry of 5 g of reaction product I. B dispersed in 60 ml of heptane.
  • Example VIII Example IV was repeated, except for the fact that step I.C was performed as described below.
  • reaction product I. B dispersed in 60 ml of heptane.
  • Example IV was repeated, except for the fact that step I. C was performed as described below.
  • Example I was repeated, however without activation step I. C. The results are presented in Table 1.
  • Example VII was repeated, except for the fact that step I. D was performed as described below.
  • a reactor was brought under nitrogen and titanium tetrachloride (87.5 ml) was added to it.
  • the reactor was heated to 115 0 C and a suspension, containing 5 g of reaction product III in 15 ml of heptane, was added to it under stirring. Then the reaction mixture was kept at 115 0 C for 15 min and 2 ml of dibutyl phthalate was added to reactor. Then the reaction mixture was kept at 115 0 C for 105 min. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which the solid product was washed with chlorobenzene (87.5 ml) at 10O 0 C for 20 min.
  • Example VII was repeated, except for the fact that step D was performed as described below.
  • a reactor was brought under nitrogen and mixture of titanium tetrachloride (50 ml) and toluene (50 ml) was added to it. Then a suspension, containing 5 g of reaction product LC. in 15 ml of heptane, was added to it under stirring at 25 0 C. The reactor was heated to 115 0 C, the reaction mixture was kept at 115 0 C for 15 min and 1.65 ml of dibutyl phthalate was added to reactor. Then the reaction mixture was kept at 115 0 C for 1 hour. Then the stirring was stopped and the solid substance was allowed to settle.
  • Example Xl was repeated, except for the fact that chlorobenzene was used instead of toluene when step LD was performed. The results are presented in Table 1. Table 1
  • - Ti is the weight content in % of titanium in the catalyst component
  • Activity kgp P /g cat is the amount of polypropylene obtained per gram of catalyst component .
  • the weight percentage of atactic polypropylene was determined as follows: 100 ml of the filtrate (y ml) obtained in separating the polypropylene powder (x g) and the heptane was dried over a steam bath and then under vacuum at 60 0 C. That yielded z g of a PP.
  • the total amount of a PP (q g) is: (y/ 100)*z.
  • the weight percentage of a PP is: (q/(q+x))*100%.
  • the bulk density (BD) of the polypropylene powder was determined according to ASTM D1895.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention is directed to a process for the preparation of a catalyst component wherein a compound with formula Mg(OAlk)xCly wherein x is larger than and smaller than 2, y equals 2-x and each Alk, independently represents an alkyl group, is contacted with a titanium tetraalkoxide and/or an alcohol in the presence of an inert dispersant to give an intermediate reaction product and wherein the intermediate reaction product is contacted with titanium tetrachloride in the presence of an internal donor. The invention also relates to a polymerization catalyst comprising the catalyst component and furthermore the invention relates to the polymerization of an olefin in the presence of the polymerization catalyst comprising the catalyst component.

Description

PROCESS FOR THE PREPARATION QF A CATALYST COMPONENT FOR THE
POLYMERIZATION OF AN OLEFIN
The invention is directed to a process for the preparation of a polymerization catalyst component. The invention also relates to a polymerization catalyst comprising the catalyst component and furthermore the invention relates to the polymerization of an olefin in the presence of a polymerization catalyst comprising the catalyst component.
Catalyst components for the preparation of a polyolefin such as for example polypropylene are generally known and the essential elements for the preparation of such catalyst components are a magnesium-containing compound and a titanium compound supported thereon. The preparation of such catalyst components is for instance described in WO-A-96/32427. This publication discloses a 3-step process wherein, in the first two steps a Mg-containing support is prepared, and subsequently the Mg-containing support is contacted with titanium tetrachloride. The catalyst yield obtained with this process is relatively low.
It is the object of the invention to provide a process for the preparation of a polymerization catalyst component and furthermore to provide a polymerization catalyst comprising this catalyst component to obtain a higher catalyst yield during the polymerization of an olefin while maintaining other required characteristics such as for example a high bulk density and a narrow span.
The process according to the invention is characterized in that a compound with formula Mg(OAIk)xCly wherein x is larger than 0 and smaller than 2, y equals 2-x and each AIk, independently, represents an alkyl group, is contacted with a titanium tetraalkoxide and/or an alcohol in the presence of an inert dispersant to give an intermediate reaction product and wherein the intermediate reaction product is contacted with titanium tetrachloride in the presence of an internal donor.
It is an advantage of the process according to the present invention that a catalyst with a higher activity is obtained if before being contacted with the titanium tetrachloride, the solid magnesium containing support, having the formula Mg(OAIk)xCIx, is treated with titanium tetraalkoxide Ti (OAIk)4 and/or an alcohol AIkOH in the presence of an inert dispersant. The obtained higher activity of the catalyst component means a higher yield of the polyolefin per gram of catalyst. The higher activity reduces the catalyst costs in the polyolefin production. Generally, the alkyl group AIk of Mg(OAIk)xCIy is an alkyl group with 1-8 carbon atoms. The alkyl group may be linear or branched.
Preferably at least one of the Alk-groups represents an ethyl group.
More preferably each Alk-group represents an ethyl group.
Preferably, the titanium tetraalkoxide contains 4-32 C-atoms. The alkoxide group of the titanium tetraalkoxide may be either linear or branched. The four alkoxide groups may be the same or differ independently. These titanium tetraalkoxide compounds may be used alone or in combination.
Preferably, at least one of the alkoxy groups in the titanium tetraalkoxide is an ethoxy group. More preferably the titanium tetraalkoxide is titanium tetraethoxide.
Suitable alcohols include for instance a linear or branched alcohol with 1-8 C-atoms. The alcohols may be used alone or in combination.
According to a preferred embodiment of the invention the alcohol is ethanol. Preferably the inert dispersant is a hydrocarbon solvent. The solvent may be for example an aliphatic or aromatic hydrocarbon with 1-20 C-atoms.
According to a preferred embodiment of the invention the dispersant is heptane.
The molar ratio titanium tetraalkoxide to Mg(OAIk)xCIy may range between wide limits and is, for instance, between 0.02 and 0.5 . Preferably the molar ratio is between 0.07 and 0.2.
Preferably, the molar ratio alcohol to Mg(OAIk)xCIy is between 0.02 and 0.5 . More preferably this ratio is between 0.07 and 0.2.
Preferably the temperature during the treatment of the compound with formula Mg(OAIk)xCly with the titanium tetraalkoxide and/or alcohol is in the range from -1O0C to 5O0C, more preferably in the range from -50C to 4O0C and most preferably in the range between O0C and 3O0C.
Preferably at least one of the reaction components is dosed in time, for instance during 0.5 to 4 hours, particularly during 1-2.5 hours. According to a preferred embodiment of the invention the process according to the invention is characterized in that a compound with formula Mg(OAIk)xCIy wherein x is larger than 0 and smaller than 2, y equals 2-x and each AIk, independently, represents an alkyl group with 1-8 carbon atoms, is contacted with a titanium tetraalkoxide in the presence of an inert dispersant to give an intermediate reaction product and wherein the intermediate reaction product is contacted with titanium tetrachloride in the presence of an internal donor.
Starting from a solid product (Mg(OAIk)xCIy) of controlled morphology an intermediate solid reaction product (Mg(OAIk)xCIy • aTi(OAIk)4 is obtained after treatment with Ti(OaIk)4 according to the equation Mg(OAIk)xCly + TiOAIk4 -> Mg(OAIk)xCIy • aTi(OAIk)4. wherein a depends on the selected molar ratio as described in the following. This intermediate reaction product is subsequently contacted with titanium tetrachloride in the presence of an internal donor.
If desired an alcohol may be added before, during or after the treatment with Ti(OAIk)4, or a combination thereof. In a preferred embodiment of the invention the alcohol is first added to the compound with formula Mg(OAIk)xCIy whereafter the tetraalkoxide is added. The alcohol and the tetraalkoxide preferably are added slowly, for instance during 0.5-4 hours, most preferably during 1-2.5 hours, each.
The TiCI4/Mg molar ratio in the contact between the intermediate product and titanium tetrachloride preferably is between 10 and 100, most preferably, between 10 and 50.
Examples of suitable internal donors include carboxylic acids, carboxylic acid anhydrides, esters of carboxylic acids, halide carboxylic acids, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates, sulphonamides, thioethers, thioesters and other organic compounds containing a hetero atom, such as nitrogen, oxygen, sulphur and/or phosphorus.
The molar ratio of the internal donor relative to the magnesium during the treatment of the intermediate product with the titanium tetrachloride may vary between wide limits, for instance between 0.05 and 0.75. Preferably this molar ratio is between 0.1 and 0.4.
Examples of suitable carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, isobutanoic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tartaric acid, cyclohexanoic monocarboxylic acid, cis-1 ,2-cyclohexanoic dicarboxylic acid, phenylcarboxylic acid, toluenecarboxylic acid, naphthalene carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and/or trimellitic acid.
Anhydrides of the aforementioned carboxylic acids can be mentioned as examples of carboxylic acid anhydrides, such as for example acetic acid anhydride, butyric acid anhydride and methacrylic acid anhydride.
Suitable examples of esters of carboxylic acids are formates, for instance, butyl formate; acetates, for instance ethyl acetate and butyl acetate; - A -
acrylates, for instance ethyl acrylate, methyl methacrylate and isobutyl methacrylate; benzoates, for instance methylbenzoate and ethylbenzoate; methyl-p-toluate; ethyl-D- naphthoate and phthalates, for instance monomethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diallyl phthalate and/or diphenyl phthalate. Examples of suitable halide carboxylic acids are the halides of the carboxylic acids mentioned above, for instance acetyl chloride, acetyl bromide, propionyl chloride, butanoyl chloride, butanoyl iodide, benzoyl bromide, p-toluyl chloride and/or phthaloyl dichloride.
Examples of suitable alcohols are methanol, ethanol, butanol, isobutanol, xylenol and benzyl alcohol.
Examples of suitable ethers are diethyl ether, dibutyl ether, diisoamyl ether, anisole and ethylphenyl ether, 2,2-diisobutyl-1 ,3-dimethoxypropane, 2,2- dicyclopentyl-1 ,3-dimethoxypropane, 2-ethyl-2-butyl-1 ,3-dimethoxypropane, 2- isopropyl-2-isopentyl-1 ,3-dimethoxypropane and/or 9,9-bis(methoxymethyl) fluorene. Also, tri-ethers can be used.
Examples of other organic compounds containing a heteroatom are 2,2,6,6-tetramethyl piperidine, 2,6-dimethylpiperidine, 2-methylpyridine, A- methylpyridine, imidazole, benzonitrile, aniline, diethylamine, dibutylamine, thiophenol, 2-methyl thiophene, isopropyl mercaptan, diethylthioether, diphenylthioether, tetrahydrofuran, dioxane, dimethylether, diethylether, anisole, acetone, triphenylphosphine, triphenylphosphite, diethylphosphate and/or diphenylphosphate. Preferably the internal donor is dibutyl phthalate. Most preferably the internal donor is di-n-butyl phtalate. In the contact between the intermediate product and the titanium tetrachloride use is preferably made of an inert dispersant. The dispersant may be selected for example from the groups of aliphatic or aromatic hydrocarbon compounds with, for instance, 4-20 C-atoms. The dispersant preferably is chosen such that virtually all side products are dissolved in the dispersant. Suitable dispersants include for example aliphatic and aromatic hydrocarbons and halogenated aromatic solvents with for instance 4-20 C-atoms. Suitable examples are toluene, xylene, benzene, heptane and chlorobenzene.
The reaction temperature during the contact between the intermediate product and the titanium tetrachloride is preferably between 5O0C and 1500C, most preferably between 6O0C and 12O0C. At higher or lower temperatures the activity of the catalyst component prepared according to the process of the invention becomes lower. The obtained reaction product is purified, usually with an inert aliphatic or aromatic hydrocarbon or halogenated aromatic compound, to obtain the catalyst component of the invention. If desired, the reaction and subsequent purification may be repeated one or more times. The preparation of the magnesium containing support having the formula Mg(OAIk)xCIy is well known in the art and several methods are for instance described in US patent 5,262,573 and references cited therein.
In a preferred embodiment such a magnesium containing support is prepared for instance as described in WO-A-96/32427 and WO-A-01/23441 wherein the magnesium containing support is obtained by: a) a Grignard formation step wherein metallic magnesium is contacted with an organic halide RX, where R is an organic group, preferably an aromatic group, containing for instance up to 20 carbon atoms and X is a halide, whereupon the resulting dissolved first reaction product is separated from the solid residual products and whereafter, b) an alkoxy group or aryloxy group containing silane compound is contacted with the obtained first reaction product whereupon the precipitate formed is purified. Preferably in step b), a stirred reactor is used.
The Grignard formation step in the process for the preparation of the catalyst component of the invention is carried out by contacting metallic magnesium with an organic halide RX.
All forms of metallic magnesium may be used. Preferably use is made of finely divided metallic magnesium, for example magnesium powder. To obtain a fast reaction it is preferable to heat the magnesium under nitrogen prior to use. In the organic halide RX, R is an organic group preferably containing from 1 up to 20 carbon atoms and X preferably is chlorine or bromine.
Examples of the organic group R are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, hexyl, octyl, phenyl, tolyl, xylyl, mesityl and benzyl. Combinations of two or more organic halides RX can also be used. Preferably R represents an aromatic group, for instance a phenyl group. Preferably RX represents chlorobenzene.
The magnesium and the organic halide RX can be reacted with each other without the use of a separate dispersant; the organic halide RX is then used in excess. The organic halide RX and the magnesium can also be brought into contact with one another in the presence of an inert dispersant. Examples of suitable dispersants include aliphatic, alicyclic or aromatic dispersants containing from 4 up to 20 carbon atoms.
Preferably, an excess of chlorobenzene is used as the organic halide RX. Thus, the chlorobenzene serves as dispersant as well as organic halide RX.
Preferably, in the Grignard formation step also an ether is present in the reaction mixture.
Examples of suitable ethers include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, diallyl ether, tetrahydrofuran (THF) and anisole.
Preferably, the ether is dibutyl ether and/or diisoamyl ether. The organic halide/ether ratio acts upon the activity of the catalyst component. More generally it acts upon the polymerization performance and the catalyst morphology. The volume ratio organic halide to ether, for instance the ratio chlorobenzene/dibutyl ether, may vary within wide limits, for example between 75:25 and 35:65. When the organic halide/ether ratio, for instance the chlorobenzene/dibutyl ether ratio, decreases, the bulk density of the polyolefine powder prepared with the aid of the catalyst component becomes lower and when the organic halide/ether ratio increases, the amount of the dissolved first reaction product becomes lower. The ratio at which the best results are obtained depends on the specific reactants and conditions chosen and can easily be determined by the skilled person. For instance when chlorobenzene and dibutylether were used the best results were obtained when the chlorobenzene/dibutyl ether volume ratio was between 70:30 and 50:50.
Small amounts of iodine and/or alkyl halides can be added to cause the reaction between the metallic magnesium and the organic halide RX to proceed at a higher rate. Examples of suitable alkyl halides are butyl chloride, butyl bromide and 1 ,2-dibromoethane. When the organic halide RX is an alkyl halide, iodine or 1 ,2-dibromoethane is preferably used.
The reaction temperature for the Grignard formation step may range for instance between 2O0C and 15O0C and the reaction times may range for instance between 0.5 and 20 hours.
After the Grignard formation is completed, the dissolved first reaction product is separated from the solid residual products.
Preferably in step b) the silane compound and first reaction product are introduced simultaneously to a mixing device in order to improve the morphology of the catalyst particles, especially of the larger catalyst particles, as described in WO-A- 01/23441. Here, 'morphology' does not only refer to the shape of the catalyst particles, but also to the particle size distribution, its fine content, powder flowability and the bulk density of the catalyst particles. Moreover, it is well known that the polyolefin powder produced in the polymerization by using a catalyst component has the same morphology as the catalyst component (the so-called "replica effect"; see for instance S. van der Ven, Polypropylene and other Polyolefins, Elsevier 1990, p. 8-10). Accordingly almost round polymer particles are obtained with a length/diameter ratio (l/d) smaller than 2 and good powder flowability. "Simultaneous introduction" means the introduction of the first reaction product and the silane compound in such a way that the molar ratio Mg/Si does not substantially vary during the introduction of these compounds to the mixing device.
The silane compound and first reaction product can be continuously or batch-wise introduced to the mixing device. Preferably, the silane compound and the first reaction product are introduced continuously to the mixing device.
The mixing device can have various forms; the mixing device can be a mixing device in which the silane compound is premixed with the first reaction product, the mixing device can also be the reactor in which the reaction between the silane compound and the first reaction product takes place.
Preferably, the silane compound and the first reaction product are premixed before the mixture is introduced to the reactor for step b). In this way a catalyst component is formed with a morphology that leads to polymer particles with the best morphology (high bulk density, narrow particle size distribution, (virtually) no fines, excellent flowability).
The Si/Mg molar ratio during step b) may vary within wide limits for instance from 0.2 to 20. Preferably, the Si/Mg molar ratio is from 0.4 to 1.0.
Preferably the alkoxy group or aryloxy group containing silane is a compound or a mixture of compounds with the general formula SiR1 nOR2 4.n, wherein n is 0, 1 , 2 or 3, preferably n is 0 or 1 , each R1, independently, represents an alkyl, alkenyl or aryl group, optionally containing one or more hetero atoms for instance O, N, S or P, with, for instance, 1-20 C-atoms, and each R2, independently, represents an alkyl or aryl group, optionally containing one or more hetero atoms for instance O, N, S or P, with, for instance, 1-20 C-atoms. Preferably, the silane is tetraethoxysilane. The period of premixing may vary between wide limits, for instance 0.1 to 300 seconds. Preferably premixing is performed during 1 to 50 seconds.
The temperature during the premixing is not critical and may for instance range between 0 and 800C; preferably the temperature is between 10 0C and 500C.
The reaction between the silane compound and the first reaction product may, for instance, take place at a temperature between -2O0C and 1000C; preferably at a temperature of from O0C to 8O0C.
The product obtained with the reaction between the silane compound and the first reaction product, is usually purified by rinsing with an inert solvent, for instance a hydrocarbon solvent with for instance 1-20 C-atoms. It is very suitable to be used as starting material in the process of the present invention for the preparation of a catalyst compound.
The invention is also directed to a polymerization catalyst comprising the catalyst component according to the invention and a co catalyst. Preferably, the catalyst composition also comprises an external donor.
The preparation of polyolefines takes place by polymerising one or more olefins simultaneously or successively in the presence of a catalyst comprising the catalyst component according to the invention, a co catalyst and optionally an external donor.
It is an advantage of the present invention that the amount of metal residues in the obtained polymer is reduced.
The olefins may be for example mono- and diolefins containing from 2 to 10 carbon atoms, such as for example ethylene, propylene, butylene, hexene, octane and/or butadiene.
According a preferred embodiment of the invention the olefin is propylene or a mixture of propylene and ethylene.
Generally, the co catalyst is an organometallic compound containing a metal from group 1 , 2, 12 or 13 of the Periodic System of the Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989-1990).
Preferably, the co catalyst is an organoaluminium compound. The organoaluminium compound may be, for instance, a compound having the formula AIR3 3, wherein each R3 independently represents an alkyl group with, for instance, 1-10 C-atoms or an aryl group with, for instance, 4-20 C-atoms. Suitable examples of an organoaluminium compound are trimethyl aluminium, triethyl aluminium, ethyl-di-methyl aluminium, triisobutyl aluminium, methyl-ethyl-butyl aluminium and/or trioctyl aluminium.
According to a preferred embodiment of the invention the co catalyst is triethyl aluminium.
Examples of possible external donors are for instance the compounds described above as the internal donors that can be used in the preparation of the catalyst component. As external donor also organo-silicon compounds can be used. Mixtures of external donors can also be used. Examples of organo-silicon compounds that are suitable as external donor are compounds or mixtures of compounds with the general formula SiR4 nOR5 4.n, wherein n is 0, 1 or 3, preferably n is 1 or 2, each R4, independently, represents an alkyl, alkenyl or aryl group, optionally containing one or more hetero atoms for instance O, N, S or P, with, for instance, 1-20 C-atoms, and each R5, independently, represents an alkyl or aryl group, optionally containing one or more hetero atoms for instance O, N, S or P, with, for instance, 1-20 C-atoms, for instance tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltributoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, diethyldiphenoxysilane, n-propyltriethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, cyclohexylmethyldimethoxysilane, icyclopentyldimethoxysilane, isobutylisopropyldimethoxylsilane, phenyltrimethoxysilane, diphenyldimethoxysilane, trifluoropropylmethyldimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, dicyclohexyldimethoxysilane, dinorbornyldimethoxysilane, di(n-propyl)dimethoxysilane, di(iso-propyl)dimethoxysilane, di(n-butyl)dimethoxysilane and/or di(iso- butyl)dimethoxysilane.
Preferably the organo-silicon compound is n-propyltrimethoxysilane, cyclohexylmethyldimethoxysilane, di(iso-propyl)dimethoxysilane or di(iso- butyl)dimethoxysilane.
The molar ratio of the metal in the co catalyst relative to the Ti during the polymerization may vary for instance from 5 to 2000. Preferably this ratio is between 50 and 300.
The aluminium/ donor molar ratio in the polymerization mixture preferably is between 0.1 and 200; more preferably between 1 and 100.
The polymerization can be carried out in the gas phase or in the liquid phase (bulk or slurry). In the case of polymerization in the liquid phase a dispersing agent is present. Suitable dispersing agents include for instance n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and liquid propylene.
The polymerization conditions such as for example the polymerization temperature and time, monomer pressure, avoidance of contamination of catalyst, choice of polymerization medium in slurry processes, the use of ingredients (like hydrogen) to control polymer molecular weights, and other conditions are well known to persons of skill in the art.
The polymerization temperature may very within wide limits and is, for instance, between 0° C and 1200 C, preferably between 4O0C and 100° C.
The pressure during the polymerization is for instance between 0.1 and 6 MPa, preferably between 0.5-3 MPa.
The molecular weight of the polyolefine obtained during the polymerization can be controlled by adding during the polymerization hydrogen or any other agent known to be suitable for the purpose.
The polymerization can be carried out in continuous mode or batch wise. Slurry-, bulk-, and gas-phase polymerization processes, multistage processes of each of these types of polymerization processes, or combinations of the different types of polymerization processes in a multistage process are contemplated herein. Preferably the polymerization process is a single stage gas phase process or a multistage, for instance a 2-stage, gas phase process where in each stage a gas-phase process is used.
Examples of gas-phase polymerization processes include both stirred bed reactors and fluidized bed reactor systems; such processes are well known in the art. Typical gas phase α-olefin polymerization reactor systems comprise a reactor vessel to which α-olefin monomer(s) and a catalyst system can be added and which contain an agitated bed of forming polymer particles.
EP-A-398698 discloses a process for producing an olefin polymer by polymerizing an olefin in the presence of a catalyst comprising a solid catalyst component obtained by reacting with heating Mg (OR1)n (OR2)2-n, a titanium compound and a silicon compound Si(OR4)4 and subjecting the resultant reaction product to contact with TiXm(OR5)4.m and an electron donating compound. The process according to the present invention is different because of amongst others EP-A-398698 uses Mg (OR1)n (OR2)2-n and a silicon compound Si(OR4)4 whereas in the process according to the present invention the chlorine containing compound Mg(OAIk)xCIy is applied and no silicon compound is present in the reaction between the compound with formula Mg(OAIk)xCIy with a titanium tetraalkoxide and/or an alcohol in the presence of an inert dispersant. US-A-5229342 discloses the production of a solution of a magnesium complex Mg3Ti(ORm)((B(OR4))n by reaction of magnesium metal, titanium tetraethoxide, triethylborate , ferric chloride and ethanol. In contrast to the process according to the present invention US-A-5229342 discloses amongst others as essential different features the use of the metal magnesium instead of Mg(OAIk)xCly , a product in solution instead of a solid product and a boron containing compound Mg3Tϊ(ORm)((B(OR4))n instead of the chlorine containing compound Mg(OAIk)xCly • aTi(OAIk)4.
The invention will be further elucidated with examples without being limited hereto.
Examples
Example I
I. A. Ghgnard formation step A flask, fitted with a reflux condenser and a funnel, was filled with magnesium powder (24.3 g, 1 mol). The flask was brought under nitrogen. The magnesium was heated at 800C for 1 hour, after which a mixture of dibutyl ether (170 ml) and chlorobenzene (60 ml) was added. Then iodine (0.03 g) and n-chlorobutane (3 ml) were successively added to the reaction mixture. After the colour of the iodine had disappeared, the temperature was raised to 970C and chlorobenzene (220 ml) was slowly added for 2.5 hours. The dark reaction mixture that was formed in the process was stirred for another 8 hours at 970C. Then the stirring and heating were stopped and the solid material was allowed to settle for 48 hours. By decanting the solution above the precipitate, a solution of phenylmagnesiumchloride (PhxMgCI2.x, reaction product I.A.) with a concentration of 1.36 mol Mg/I has been obtained. This solution was used in the further catalyst preparation.
I. B. Preparation of the compound with formula Mg(OAIk)xCIy
The solution of reaction product of step I (200 ml, 0.272 mol Mg) and 100 ml of a solution of tetraethoxysilane (TES) in dibutyl ether (DBE), (33.4 ml of TES and 66.6 ml of DBE), were cooled to 150C, and then were dosed simultaneously to a mixing device of 0.45 ml volume supplied with a stirrer and jacket. Thereafter the premixed reaction product I. A and the TES-solution were introduced to a reactor. The mixing device (minimixer) was cooled to 1O0C by means of cold water circulating in the minimixer' s jacket. The reagents contact time was 13 s in the minimixer and the connecting tube between the minimixer and the reactor. The stirring speed in the minimixer was 1000 rpm.The mixture formed in the minimixer was introduced to a 0.7 I reactor, with stirring. The reactor was loaded preliminary with 100 ml of DBE, and cooled to 50C. Dosing time was 1 hour. The stirring speed in the reactor was 200 rpm.
On the dosing completion the reaction mixture was kept at 50C for 0.5 hour, then heated up to 6O0C and kept at this temperature for 1 hour. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting. The solid substance was washed three times using 300 ml of heptane. As a result, a pale yellow solid substance, reaction product I. B, was obtained, suspended in 110 ml of heptane.
I .C. Activation with titanium tetraalkoxide
In an inert nitrogen atmosphere at O0C a 250 ml glass flask equipped with a mechanical agitator was filled with a slurry of 5 g of reaction product I. B dispersed in 60 ml of heptane. Subsequently a solution of 1.57 ml titaniumtetraethoxide
(TET) in 20 ml of heptane was added at 250C for 1 hour. The ratio TET/Mg=0.2
The slurry was slowly allowed to warm up to 3O0C for 90 min and kept at that temperature for another 2 hours. Finally the supernatant liquid was decanted from the solid substance (~ 5.5 g) which was washed once with 90 ml of heptane at 300C. As a result, reaction product III was obtained, suspended in 15 ml of heptane.
I .D. Preparation of the catalyst component A reactor was brought under nitrogen and 125 ml of titanium tetrachloride was added to it. The reactor was heated to 1 150C and a suspension, containing ~5.5 g of reaction product III in 15 ml of heptane, was added to it under stirring. Then the reaction mixture was kept at 1150C for 15 min and 2.4 ml of dibutyl phthalate was added to reactor. Then the reaction mixture was kept at 1150C for 105 min. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which the solid product was washed with chlorobenzene (125 ml) at 1000C for 20 min. Then the washing solution was removed by decanting, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 1150C for 30 min, after which the solid substance was allowed to settle, and the last treatment was repeated once again. The solid substance obtained was washed five times using 150 ml of heptane at 6O0C, after which the catalyst component, suspended in heptane, was obtained.
I.E. Polymerization of propylene
Polymerization of propylene was carried out in a stainless steel reactor (with a volume of 0.7 I) in heptane (300 ml) at a temperature of 7O0C, total pressure 0.7 MPa and hydrogen presence (55 ml) for 1 hour in the presence of a catalyst comprising the catalyst component according to step I. D, triethylaluminium and propyltrimethoxysilane. The concentration of the catalyst component was 0.033 g/l; the concentration of triethylaluminium was 4.0 mmol/l and the concentration of propyltrimethoxysilane was 0.4 mmol/l.
Data on the catalyst performance during the propylene polymerization are presented in Table 1. The particles of the polymer powder obtained had a round shape.
Example Il
Example I was repeated, except for the fact that 0.79 ml of titaniumtetraethoxide (Ti/Mg =0.1) was used in step I. C. The results are presented in Table 1.
Example III
Example I was repeated, except for the fact that 0.39 ml of titaniumtetraethoxide (Ti/Mg=0.05) was used in step I. C. The results are presented in Table 1.
Example IV
Example I was repeated, except for the fact that step I. C was performed as described below. In an inert nitrogen atmosphere at O0C a 250 ml glass flask equipped with a mechanical agitator is filled with a slurry of 5 g of reaction product I. B dispersed in 60 ml of heptane. Subsequently a solution of 0.33 ml ethanol (EtOH/Mg=0.15) in 20 ml heptane is dosed under stirring during 1 hour. After keeping the reaction mixture at O0C for 30 minutes, a solution of 1.18 ml titaniumtetraethoxide (TET/Mg=0.15) in 20 ml of heptane was added at O0C for 1 hour. The slurry was slowly allowed to warm up to 3O0C for 90 min and kept at that temperature for another 2 hours. Finally the supernatant liquid is decanted from the solid reaction product (~ 5.5 g) which was washed once with 90 ml of heptane at 3O0C.
The results are presented in Table 1.
Example V
Example IV was repeated, except for the fact that 0.28 ml of ethanol (EtOH/Mg=0.125) and 0.79 ml of titanium tetraethoxide (Ti/Mg=0.1 ) were used in step I.C. The results are presented in Table 1.
Example Vl
Example IV was repeated, except for the fact that 0.22 ml of ethanol (EtOH/Mg =0.1) and 0.99 ml of titanium tetraethoxide (Ti/Mg=0.125) were used in step I.C.
The results are presented in Table 1.
Example VII
Example IV was repeated, except for the fact that 0.22 ml of ethanol (EtOH/Mg =0.1) and 0.79 ml of titanium tetraethoxide (Ti/Mg=0.1 ) were used in step I.C.
The results are presented in Table 1.
Example VIII Example IV was repeated, except for the fact that step I.C was performed as described below.
In an inert nitrogen atmosphere at 2O0C a 250 ml glass flask equipped with a mechanical agitator is filled with a slurry of 5 g of reaction product I. B. dispersed in 60 ml of heptane. Subsequently a solution of 0.22 ml ethanol (EtOH/Mg=0.1) in 20 ml heptane is dosed under stirring during 1 hour. After keeping the reaction mixture at 2O0C for 30 minutes, a solution of 0.79 ml titaniumtetraethoxide (TET/Mg=0.1 ) in 20 ml of heptane was added for 1 hour. The slurry was slowly allowed to warm up to 3O0C for 90 min and kept at that temperature for another 2 hours. Finally the supernatant liquid is decanted from the solid reaction product which was washed once with 90 ml of heptane at 3O0C.
The results are presented in Table 1.
Example IX
Example IV was repeated, except for the fact that step I. C was performed as described below.
In an inert nitrogen atmosphere at O0C a 250 ml glass flask equipped with a mechanical agitator is filled with a slurry of 5 g of reaction product I. B dispersed in 60 ml of heptane. Subsequently a solution of 0.22 ml ethanol (EtOH/Mg=0.1) and 0.99 ml titaniumtetraethoxide (TET/Mg=0.125) in 20 ml heptane is dosed under stirring during 1 hour. The slurry was slowly allowed to warm up to 3O0C for 90 min and kept at that temperature for another 2 hours. Finally the supernatant liquid is decanted from the from the solid reaction product (~ 5.5 g) which was washed once with 90 ml of heptane at 3O0C.
The results are presented in Table 1.
Comparative Example A.
Example I was repeated, however without activation step I. C. The results are presented in Table 1.
Example X
Example VII was repeated, except for the fact that step I. D was performed as described below.
A reactor was brought under nitrogen and titanium tetrachloride (87.5 ml) was added to it. The reactor was heated to 1150C and a suspension, containing 5 g of reaction product III in 15 ml of heptane, was added to it under stirring. Then the reaction mixture was kept at 1150C for 15 min and 2 ml of dibutyl phthalate was added to reactor. Then the reaction mixture was kept at 1150C for 105 min. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which the solid product was washed with chlorobenzene (87.5 ml) at 10O0C for 20 min. Then the washing solution was removed by decanting, after which a mixture of titanium tetrachloride (44 ml) and chlorobenzene (44 ml) was added. The reaction mixture was kept at 1150C for 30 min, after which the solid substance was allowed to settle, and the last treatment was repeated once again. The solid substance obtained was washed five times using 150 ml of heptane at 6O0C, after which the catalyst component, suspended in heptane, was obtained.
The results are presented in Table 1.
Example Xl
Example VII was repeated, except for the fact that step D was performed as described below.
A reactor was brought under nitrogen and mixture of titanium tetrachloride (50 ml) and toluene (50 ml) was added to it. Then a suspension, containing 5 g of reaction product LC. in 15 ml of heptane, was added to it under stirring at 250C. The reactor was heated to 1150C, the reaction mixture was kept at 1150C for 15 min and 1.65 ml of dibutyl phthalate was added to reactor. Then the reaction mixture was kept at 1150C for 1 hour. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decanting, after which the solid product was washed with toluene (100 ml) at 1000C for 20 min. Then the washing solution was removed by decanting, after which a mixture of titanium tetrachloride (50 ml) and toluene (50 ml) was added. The reaction mixture was kept at 1150C for 30 min, after which the solid substance was allowed to settle, and the last treatment was repeated once again. The solid substance obtained was washed five times using 150 ml of heptane at 6O0C, after which the catalyst component, suspended in heptane, was obtained. The results are presented in Table 1.
Example XII
Example Xl was repeated, except for the fact that chlorobenzene was used instead of toluene when step LD was performed. The results are presented in Table 1. Table 1
Figure imgf000018_0001
Abbreviations and measuring methods:
- Ti is the weight content in % of titanium in the catalyst component
- Activity kgpP/gcat is the amount of polypropylene obtained per gram of catalyst component .
- The weight percentage of atactic polypropylene (aPP) was determined as follows: 100 ml of the filtrate (y ml) obtained in separating the polypropylene powder (x g) and the heptane was dried over a steam bath and then under vacuum at 60 0C. That yielded z g of aPP. The total amount of aPP (q g) is: (y/ 100)*z.
The weight percentage of aPP is: (q/(q+x))*100%.
- The bulk density (BD) of the polypropylene powder was determined according to ASTM D1895.
- The span of PP powder was determined according to ASTM D1921 , method A.

Claims

I . A process for the preparation of a polymerization catalyst component wherein a compound with formula Mg(OAIk)xCIy wherein x is larger than 0 and smaller than 2, y equals 2-x and each AIk, independently, represents an alkyl group, is contacted with a titanium tetraalkoxide and/or an alcohol in the presence of an inert dispersant to give an intermediate reaction product and wherein the intermediate reaction product is contacted with titanium tetrachloride in the presence of an internal donor.
2. A process according to Claim 1 wherein a compound with formula
Mg(OAIk)xCIy wherein x is larger than 0 and smaller than 2, y equals 2-x and each AIk, independently, represents an alkyl group, is contacted with a titanium tetraalkoxide in the presence of an inert dispersant to give an intermediate reaction product and wherein the intermediate reaction product is contacted with titanium tetrachloride in the presence of an internal donor.
3. A process according to any one of Claims 1-2 wherein at least one of the AIk- groups represents an ethyl group.
4. A process according to any one of Claims 1-3, wherein at least one of the alkoxide groups in titanium tetraalkoxide represents an ethyl group.
5. A process according to Claim 4, wherein the titanium alkoxide is titanium tetraethoxide.
6. A process according to any one of Claims 1-5, wherein the dispersant is heptane.
7. A process according to any one of Claims 1-6, wherein the temperature is in the range of -100C to 5O0C.
8. A process according to any one of Claims 1-7, wherein the molar ratio titanium tetraalkoxide to Mg(OAIk)xCIy is between 0.02 and 0.5.
9. A process according to any one of Claims 1-8, wherein the alcohol is ethanol.
10. A process according to any one of Claim 1-9, wherein the molar ratio alcohol to Mg(OAIk)xCIy is between 0.02 and 0.5.
I I . A process according to any one of Claims 1-10, wherein a compound with formula Mg(OAIk)xCIy is prepared in a process wherein a metallic magnesium is contacted with an organic halide RX, where R is an organic group containing up to 20 carbon atoms and X is a halide to form a first reaction product, whereupon the resulting dissolved first reaction product is separated from the solid residual products and whereafter, an alkoxy group or aryloxy group containing silane compound is added to the first reaction product, whereupon the precipitate formed is purified to obtain the compound with formula Mg(OAIk)xCly.
12. A process according to Claim 11 , wherein the mixing device is a static mixer
13. A polymerization catalyst comprising the catalyst component obtained with the process according to any one of Claims 1-12 and a co catalyst.
14. The catalyst according to Claim 13 wherein the co catalyst is an organometallic compound containing a metal from group 1 , 2, 12 or 13 of the Periodic System of the Elements.
15. A process for the polymerization of one or more olefins in the presence of the catalyst according to any one of Claims 13-14.
16. A process according to Claim 15 characterized in that the olefin is propylene or a mixture of propylene and ethylene.
PCT/EP2005/012202 2004-11-26 2005-11-11 Process for the preparation of a catalyst component for the polymerization of an olefin WO2006056338A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US11/791,592 US7947788B2 (en) 2004-11-26 2005-11-11 Process for the preparation of a catalyst component for the polymerization of an olefin
DE602005027615T DE602005027615D1 (en) 2004-11-26 2005-11-11 PROCESS FOR PREPARING A CATALYST COMPONENT FOR POLYMERIZING AN OLEFIN
KR1020077014239A KR101221304B1 (en) 2004-11-26 2005-11-11 Process for the preparation of a catalyst component for the polymerization of an olefin
JP2007541767A JP2008521944A (en) 2004-11-26 2005-11-11 Process for the preparation of catalyst components for the polymerization of olefins
AT05812344T ATE506377T1 (en) 2004-11-26 2005-11-11 METHOD FOR PRODUCING A CATALYST COMPONENT FOR POLYMERIZING AN OLEFIN
EP05812344A EP1838741B1 (en) 2004-11-26 2005-11-11 Process for the preparation of a catalyst component for the polymerization of an olefin
EA200701144A EA011828B1 (en) 2004-11-26 2005-11-11 Process for the preparation of a catalyst component for the polymerization of an olefin
MX2007006290A MX2007006290A (en) 2004-11-26 2005-11-11 Process for the preparation of a catalyst component for the polymerization of an olefin.
BRPI0517871A BRPI0517871B1 (en) 2004-11-26 2005-11-11 polymerization catalyst, and process for preparing a component thereof
CN200580040424XA CN101065404B (en) 2004-11-26 2005-11-11 Process for the preparation of a catalyst component for the polymerization of an olefin
PL05812344T PL1838741T3 (en) 2004-11-26 2005-11-11 Process for the preparation of a catalyst component for the polymerization of an olefin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP04078224A EP1661917A1 (en) 2004-11-26 2004-11-26 Process for the preparation of a catalyst component for the polymerization of an olefin
EP04078224.5 2004-11-26

Publications (1)

Publication Number Publication Date
WO2006056338A1 true WO2006056338A1 (en) 2006-06-01

Family

ID=34928687

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/012202 WO2006056338A1 (en) 2004-11-26 2005-11-11 Process for the preparation of a catalyst component for the polymerization of an olefin

Country Status (13)

Country Link
US (1) US7947788B2 (en)
EP (2) EP1661917A1 (en)
JP (1) JP2008521944A (en)
KR (1) KR101221304B1 (en)
CN (1) CN101065404B (en)
AT (1) ATE506377T1 (en)
BR (1) BRPI0517871B1 (en)
DE (1) DE602005027615D1 (en)
EA (1) EA011828B1 (en)
ES (1) ES2365350T3 (en)
MX (1) MX2007006290A (en)
PL (1) PL1838741T3 (en)
WO (1) WO2006056338A1 (en)

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007134851A1 (en) * 2006-05-24 2007-11-29 Saudi Basic Industries Corporation Process for preparing a catalyst component for propylene polymerization
WO2013124063A1 (en) 2012-02-22 2013-08-29 Saudi Basic Industries Corporation Catalyst component for the polymerization of olefins
US20140178617A1 (en) * 2012-12-20 2014-06-26 Saudi Basic Industries Corporation Process for the polymerization of propylene
WO2014118164A1 (en) 2013-01-31 2014-08-07 Saudi Basic Industries Corporation Catalyst composition for polymerization of olefins
EP2837634A1 (en) 2013-08-12 2015-02-18 Saudi Basic Industries Corporation Catalyst system for polymerisation of an olefin
WO2015091940A1 (en) 2013-12-20 2015-06-25 Saudi Basic Industries Corporation Catalyst system for polymerisation of an olefin
WO2015091966A1 (en) 2013-12-20 2015-06-25 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
WO2015091982A1 (en) 2013-12-20 2015-06-25 Saudi Basic Industries Corporation Catalyst system for polymerisation of an olefin
WO2015185489A1 (en) 2014-06-02 2015-12-10 Sabic Global Technologies B.V. Procatalyst for polymerization of olefins
WO2015192910A1 (en) 2014-06-20 2015-12-23 Sabic Global Technologies B.V. Process for the polymerization of propylene
WO2016198344A1 (en) 2015-06-12 2016-12-15 Sabic Global Technologies B.V. Process for manufacture of low emission polypropylene
US9701773B2 (en) 2013-08-12 2017-07-11 Sabic Global Technologies, B.V. Catalyst system for polymerisation of an OLEFIN
US9868799B2 (en) 2013-12-20 2018-01-16 Saudi Basic Industries Corporation Procatalyst for polymerization of olefins
US9926391B2 (en) 2013-12-20 2018-03-27 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
US9944731B2 (en) 2013-12-20 2018-04-17 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
US9988474B2 (en) 2014-06-20 2018-06-05 Sabic Global Technologies B.V. Process for the polymerization of propylene
EP3333222A1 (en) 2016-12-12 2018-06-13 SABIC Global Technologies B.V. Composition comprising heterophasic propylene copolymer
US10000591B2 (en) 2013-12-20 2018-06-19 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
WO2018108929A1 (en) 2016-12-12 2018-06-21 Sabic Global Technologies B.V. Pellet comprising thermoplastic polymer sheath surrounding glass filaments having reduced emissions
WO2018108935A1 (en) 2016-12-12 2018-06-21 Sabic Global Technologies B.V. Process for manufacture of low emission heterophasic polypropylene
WO2018108936A1 (en) 2016-12-12 2018-06-21 Sabic Global Technologies B.V. Process for manufacture of low emission homopolymer or random polypropylene
WO2018108928A1 (en) 2016-12-12 2018-06-21 Sabic Global Technologies B.V. Heterophasic propylene copolymer
CN108368192A (en) * 2015-12-18 2018-08-03 日本聚丙烯株式会社 The manufacturing method of alpha-olefine polymerization solid catalyst component and the manufacturing method for using its alpha-olefine polymers
US10047218B2 (en) 2013-12-20 2018-08-14 Saudi Basic Industries Corporation Polyolefin composition
WO2018167155A1 (en) 2017-03-17 2018-09-20 Sabic Global Technologies B.V. Process of making polyolefins
US10160816B2 (en) 2014-06-02 2018-12-25 Sabic Global Technologies B.V. Procatalyst for polymerization of olefins
US10696829B2 (en) 2013-12-20 2020-06-30 Saudi Basic Industries Corporation Heterophasic propylene copolymer
US11254758B2 (en) 2017-03-17 2022-02-22 Sabic Global Technologies B.V. Process for preparing a procatalyst for polymerization of olefins
US11261266B2 (en) 2017-03-17 2022-03-01 Sabic Global Technologies B.V. Process for the polymerization of a polyolefin
WO2023104940A1 (en) 2021-12-09 2023-06-15 Sabic Global Technologies B.V. Catalyst system for polymerization of an olefin
WO2024008770A1 (en) 2022-07-05 2024-01-11 Sabic Global Technologies B.V. Catalyst system for polymerization of an olefin

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101970508B (en) 2008-03-14 2013-03-27 沙特基础工业公司 A catalyst system and a process for the production of polyethylene in the presence of this catalyst system
CN102099386B (en) * 2008-07-18 2014-08-20 沙特基础工业公司 Process for the production of polyethylene
EP2284199A1 (en) 2009-08-14 2011-02-16 Saudi Basic Industries Corporation A catalyst system and a process for the production of polyethylene
CN102276635B (en) * 2010-06-12 2014-05-28 中国石油化工股份有限公司 Preparation method for alkoxy magnesium chloride
EP2679609A1 (en) * 2012-06-28 2014-01-01 Lummus Novolen Technology Gmbh Sterically demanding dialkoxydialkylsilanes as external donors for ziegler catalysts for the polymerization of propylene
CN104583244B (en) * 2012-09-24 2017-10-24 印度石油有限公司 Catalyst for olefines polymerizing and preparation method thereof
CN103819585B (en) * 2012-11-16 2016-05-25 中国石油化工股份有限公司 A kind of catalytic component for olefinic polymerization, catalyst and application
CN113621098B (en) 2020-05-09 2022-11-04 中国石油天然气股份有限公司 Propylene polymerization catalyst, propylene polymerization catalyst system, preparation and application thereof
EP4251661A1 (en) 2020-11-27 2023-10-04 SABIC Global Technologies B.V. Process to prepare a solid support for a procatalyst for polymerization of olefins

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0398698A2 (en) * 1989-05-17 1990-11-22 Mitsubishi Chemical Corporation Process for producing olefin polymer
US5229342A (en) * 1990-10-18 1993-07-20 Shell Oil Company Olefin polymerization catalyst
WO1996032426A1 (en) * 1995-04-10 1996-10-17 Dsm N.V. Method for the preparation of a catalyst suitable for the polymerisation of an olefine

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1603724A (en) * 1977-05-25 1981-11-25 Montedison Spa Components and catalysts for the polymerisation of alpha-olefins
JPS5440293A (en) * 1977-09-05 1979-03-29 Mitsubishi Petrochem Co Ltd Olefin polymerization catalyst component
JPS54120288A (en) * 1978-03-10 1979-09-18 Mitsubishi Petrochem Co Ltd Olefin polymerization catalyst component
JPH06102696B2 (en) * 1987-10-29 1994-12-14 住友化学工業株式会社 Method for producing α-olefin polymer
US5262573A (en) * 1991-08-06 1993-11-16 Akzo Nv Halomagnesium hydrocarbyloxide composition and process for preparation
JP3529894B2 (en) * 1994-05-19 2004-05-24 三井化学株式会社 Solid titanium catalyst component for olefin polymerization, olefin polymerization catalyst containing the same, and olefin polymerization method
EP1086961A1 (en) * 1999-09-27 2001-03-28 Dsm N.V. Process for the preparation of a catalyst component for the polymerisation of an olefin
US20030022786A1 (en) * 2001-05-03 2003-01-30 Epstein Ronald A. Catalyst for propylene polymerization
CN1257919C (en) * 2001-11-20 2006-05-31 弗纳技术股份有限公司 Polyolefin cafalyst, preparing method thereof, use method and polymer obtained therewith

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0398698A2 (en) * 1989-05-17 1990-11-22 Mitsubishi Chemical Corporation Process for producing olefin polymer
US5229342A (en) * 1990-10-18 1993-07-20 Shell Oil Company Olefin polymerization catalyst
WO1996032426A1 (en) * 1995-04-10 1996-10-17 Dsm N.V. Method for the preparation of a catalyst suitable for the polymerisation of an olefine

Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9512244B2 (en) 2006-05-24 2016-12-06 Saudi Basic Industries Corporation Process for preparing a catalyst component for propylene polymerization
EA013392B1 (en) * 2006-05-24 2010-04-30 Сауди Бейсик Индастриз Корпорейшн Process for preparing a catalyst component for propylene polymerization
WO2007134851A1 (en) * 2006-05-24 2007-11-29 Saudi Basic Industries Corporation Process for preparing a catalyst component for propylene polymerization
WO2013124063A1 (en) 2012-02-22 2013-08-29 Saudi Basic Industries Corporation Catalyst component for the polymerization of olefins
US9587049B2 (en) 2012-02-22 2017-03-07 Saudi Basic Industries Corporation Catalyst component for the polymerization of olefins
US9718902B2 (en) 2012-12-20 2017-08-01 Saudi Basic Industries Corporation Process for the polymerization of propylene
US20140178617A1 (en) * 2012-12-20 2014-06-26 Saudi Basic Industries Corporation Process for the polymerization of propylene
US10202505B2 (en) 2012-12-20 2019-02-12 Saudi Basic Industries Corporation Polypropylene and articles thereof
WO2014096201A1 (en) 2012-12-20 2014-06-26 Saudi Basic Industries Corporation Process for the polymerization of propylene
US9587051B2 (en) 2013-01-31 2017-03-07 Saudi Basic Industries Corporation Process for preparing a catalyst component for polymerization of olefins
US10106632B2 (en) 2013-01-31 2018-10-23 Saudi Basic Industries Corporation Process for preparing a catalyst component for polymerization of olefins
US9663596B2 (en) 2013-01-31 2017-05-30 Saudi Basic Industries Corporation Catalyst composition for polymerization of olefins
WO2014118164A1 (en) 2013-01-31 2014-08-07 Saudi Basic Industries Corporation Catalyst composition for polymerization of olefins
US9701773B2 (en) 2013-08-12 2017-07-11 Sabic Global Technologies, B.V. Catalyst system for polymerisation of an OLEFIN
EP2837634A1 (en) 2013-08-12 2015-02-18 Saudi Basic Industries Corporation Catalyst system for polymerisation of an olefin
US10640586B2 (en) 2013-12-20 2020-05-05 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
US10696829B2 (en) 2013-12-20 2020-06-30 Saudi Basic Industries Corporation Heterophasic propylene copolymer
WO2015091982A1 (en) 2013-12-20 2015-06-25 Saudi Basic Industries Corporation Catalyst system for polymerisation of an olefin
US10047218B2 (en) 2013-12-20 2018-08-14 Saudi Basic Industries Corporation Polyolefin composition
US9868799B2 (en) 2013-12-20 2018-01-16 Saudi Basic Industries Corporation Procatalyst for polymerization of olefins
US9873753B2 (en) 2013-12-20 2018-01-23 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
US9926391B2 (en) 2013-12-20 2018-03-27 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
US9944734B2 (en) 2013-12-20 2018-04-17 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
US9944731B2 (en) 2013-12-20 2018-04-17 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
WO2015091966A1 (en) 2013-12-20 2015-06-25 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
WO2015091940A1 (en) 2013-12-20 2015-06-25 Saudi Basic Industries Corporation Catalyst system for polymerisation of an olefin
US10000591B2 (en) 2013-12-20 2018-06-19 Saudi Basic Industries Corporation Catalyst system for polymerization of an olefin
US10160816B2 (en) 2014-06-02 2018-12-25 Sabic Global Technologies B.V. Procatalyst for polymerization of olefins
WO2015185489A1 (en) 2014-06-02 2015-12-10 Sabic Global Technologies B.V. Procatalyst for polymerization of olefins
US10005859B2 (en) 2014-06-02 2018-06-26 Sabic Global Technologies B.V. Procatalyst for polymerization of olefins
US10106631B2 (en) 2014-06-20 2018-10-23 Sabic Global Technologies B.V. Process for the polymerization of propylene
WO2015192910A1 (en) 2014-06-20 2015-12-23 Sabic Global Technologies B.V. Process for the polymerization of propylene
US9988474B2 (en) 2014-06-20 2018-06-05 Sabic Global Technologies B.V. Process for the polymerization of propylene
US10435552B2 (en) 2015-06-12 2019-10-08 Sabic Global Technologies B.V. Process for manufacture of low emission polypropylene
WO2016198344A1 (en) 2015-06-12 2016-12-15 Sabic Global Technologies B.V. Process for manufacture of low emission polypropylene
CN108368192B (en) * 2015-12-18 2020-09-11 日本聚丙烯株式会社 Method for producing solid catalyst component for alpha-olefin polymerization and method for producing alpha-olefin polymer using same
CN108368192A (en) * 2015-12-18 2018-08-03 日本聚丙烯株式会社 The manufacturing method of alpha-olefine polymerization solid catalyst component and the manufacturing method for using its alpha-olefine polymers
WO2018108929A1 (en) 2016-12-12 2018-06-21 Sabic Global Technologies B.V. Pellet comprising thermoplastic polymer sheath surrounding glass filaments having reduced emissions
US11603453B2 (en) 2016-12-12 2023-03-14 SABIC Global Technologies B.V Composition comprising heterophasic propylene copolymer
US11608432B2 (en) 2016-12-12 2023-03-21 Sabic Global Technologies B.V. Pellet comprising thermoplastic polymer sheath surrounding glass filaments having reduced emissions
WO2018108935A1 (en) 2016-12-12 2018-06-21 Sabic Global Technologies B.V. Process for manufacture of low emission heterophasic polypropylene
WO2018108932A1 (en) 2016-12-12 2018-06-21 Sabic Global Technologies B.V. Composition comprising heterophasic propylene copolymer
WO2018108928A1 (en) 2016-12-12 2018-06-21 Sabic Global Technologies B.V. Heterophasic propylene copolymer
WO2018108936A1 (en) 2016-12-12 2018-06-21 Sabic Global Technologies B.V. Process for manufacture of low emission homopolymer or random polypropylene
US10995158B2 (en) 2016-12-12 2021-05-04 Sabic Global Technologies B.V. Process for manufacture of low emission heterophasic polypropylene
US11149139B2 (en) 2016-12-12 2021-10-19 Sabic Global Technologies B.V. Heterophasic propylene copolymer
EP3333222A1 (en) 2016-12-12 2018-06-13 SABIC Global Technologies B.V. Composition comprising heterophasic propylene copolymer
US11542349B2 (en) 2016-12-12 2023-01-03 SABIC Global Technologies B.V Process for manufacture of low emission homopolymer or random polypropylene
US11261266B2 (en) 2017-03-17 2022-03-01 Sabic Global Technologies B.V. Process for the polymerization of a polyolefin
US11254758B2 (en) 2017-03-17 2022-02-22 Sabic Global Technologies B.V. Process for preparing a procatalyst for polymerization of olefins
US11186653B2 (en) 2017-03-17 2021-11-30 Sabic Global Technologies B.V. Process of making polyolefins
WO2018167155A1 (en) 2017-03-17 2018-09-20 Sabic Global Technologies B.V. Process of making polyolefins
WO2023104940A1 (en) 2021-12-09 2023-06-15 Sabic Global Technologies B.V. Catalyst system for polymerization of an olefin
WO2024008770A1 (en) 2022-07-05 2024-01-11 Sabic Global Technologies B.V. Catalyst system for polymerization of an olefin

Also Published As

Publication number Publication date
JP2008521944A (en) 2008-06-26
EA011828B1 (en) 2009-06-30
EP1838741B1 (en) 2011-04-20
US7947788B2 (en) 2011-05-24
BRPI0517871B1 (en) 2017-01-17
US20080312389A1 (en) 2008-12-18
ATE506377T1 (en) 2011-05-15
EP1838741A1 (en) 2007-10-03
DE602005027615D1 (en) 2011-06-01
KR101221304B1 (en) 2013-01-10
EP1661917A1 (en) 2006-05-31
KR20070092237A (en) 2007-09-12
PL1838741T3 (en) 2011-09-30
EA200701144A1 (en) 2007-10-26
BRPI0517871A (en) 2008-10-21
ES2365350T3 (en) 2011-09-30
CN101065404B (en) 2010-06-09
CN101065404A (en) 2007-10-31
MX2007006290A (en) 2007-10-19

Similar Documents

Publication Publication Date Title
US7947788B2 (en) Process for the preparation of a catalyst component for the polymerization of an olefin
EP1222214B1 (en) Process for the preparation of a catalyst component for the polymerization of an olefin
JP6073968B2 (en) Method for preparing catalyst components for propylene polymerization
EP0830391B1 (en) Method fo the preparation of a catalyst suitable for the polymerisation of an olefin
EP3083718B1 (en) Procatalyst for polymerization of olefins
EP3149056B1 (en) Procatalyst for polymerization of olefins
EP3083724B1 (en) Catalyst system for polymerization of an olefin
US6051666A (en) Method for preparing a catalyst suitable for polymerizing an olefin
RU2152404C1 (en) Method of producing catalyst used for olefin polymerization

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KN KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 3761/DELNP/2007

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: MX/a/2007/006290

Country of ref document: MX

Ref document number: 200580040424.X

Country of ref document: CN

Ref document number: 2007541767

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2005812344

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1020077014239

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 200701144

Country of ref document: EA

WWP Wipo information: published in national office

Ref document number: 2005812344

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 11791592

Country of ref document: US

ENP Entry into the national phase

Ref document number: PI0517871

Country of ref document: BR