WO2007134851A1 - Process for preparing a catalyst component for propylene polymerization - Google Patents
Process for preparing a catalyst component for propylene polymerization Download PDFInfo
- Publication number
- WO2007134851A1 WO2007134851A1 PCT/EP2007/004572 EP2007004572W WO2007134851A1 WO 2007134851 A1 WO2007134851 A1 WO 2007134851A1 EP 2007004572 W EP2007004572 W EP 2007004572W WO 2007134851 A1 WO2007134851 A1 WO 2007134851A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- process according
- catalyst component
- polymerization
- catalyst
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Definitions
- the invention is directed to a process for preparing a polymerization catalyst component.
- the invention also relates to a polymerization catalyst system comprising the catalyst component and to a process of making a polyolefin by contacting at least one olefin with a polymerization catalyst system comprising the catalyst component.
- Catalyst systems and their components that are suitable for preparing a polyolefin such as for example polypropylene are generally known, and the essential elements for the preparation of such catalyst components include a solid magnesium-containing compound and a titanium compound supported thereon.
- Such catalysts are generally referred to as Ziegler-Natta catalysts.
- the preparation of such a catalyst component is for instance described in WO96/32427 A1 , which publication discloses a 3-step process wherein, in the first two steps a Mg-containing support of certain morphology is prepared, and subsequently the Mg-containing support is contacted with titanium tetrachloride, and optionally an electron-donating compound.
- An advantage of this catalyst component is that a catalyst system made therewith shows high activity in olefin, especially propylene, polymerization.
- This object is achieved with a process for preparing a polymerization catalyst component comprising the steps of i) contacting a compound R 4 z MgX 2-z wherein R 4 is an organic group, X is a halide, and z is larger than 0 and smaller than 2, with an alkoxy- or aryloxy-containing silane compound to give a solid magnesium-containing compound of formula Mg(OR 1 ) ⁇ CI 2- x wherein x is larger than 0 and smaller than 2, and each R 1 , independently, represents an alkyl group; ii) contacting the solid Mg(OR 1 J x CI 2-X with at least one activating compound selected from the group formed by internal electron donors and compounds of formula M(OR 2 ) v-w (R 3 )w, wherein M can be Ti, Zr, Hf, Al or Si, each R 2 and R 3 , independently, represent an alkyl, alkenyl or aryl group, v is the valency of M and w is smaller than v
- a catalyst system with a higher activity is obtained if before being contacted with the halogen-containing titanium compound, the solid magnesium- containing compound is treated with at least one of the defined activating compounds in the presence of an inert dispersant; that is a higher yield of polyolefin is obtained per gram of catalyst system.
- the higher activity results in lower amounts of catalyst residues present in the polymer made, and in reduced catalyst costs in the polyolefin production.
- a further advantage is that the ethylene sensitivity of a catalyst system comprising said component, for example in copolymerization of propylene and ethylene, can be influenced by varying the activating compound.
- US 5229342 discloses a process including a step of making a solution of a specific magnesium complex by reaction of magnesium metal, titanium tetraethoxide, triethylborate , ferric chloride and ethanol.
- GB 2112402 A discloses a catalyst comprising a solid catalyst component that was obtained by reacting an alkyl magnesium halide or an alkoxy magnesium halide with at least a metal alkoxide, a silane compound, and a halogen-containing Ti-compound; but in a different sequence of steps than in the present invention.
- a solid catalyst component is made by reacting a silica support first with a soluble magnesium chloroalkoxide compound, and then with a titanium compound.
- EP 0921135 A1 discloses to contact a solid catalyst component, which can be prepared from a magnesium, a titanium and an electron donating compound in various ways differing from the present invention, with an alcohol.
- a polymerization catalyst system is prepared from a magnesium chloroalkoxide, but by directly reacting it with titanium tetrachloride in an aromatic hydrocarbon solvent in multiple steps.
- a solid magnesium-containing support is prepared by contacting a compound or a mixture of compounds of formula R 4 z MgX2 -z wherein R 4 is an organic group, X is a halide, and z is larger than 0 and smaller than 2, with an alkoxy- or aryloxy- containing silane compound, as for example described in WO 96/32427 A1 and
- R 4 Z MgX 2-2 also referred to as Grignard compound
- X is preferably chlorine or bromine, more preferably chlorine.
- the organic group R 4 can be an aliphatic or aromatic group, preferably containing from 1 up to 20 carbon atoms.
- R 4 can be an alkyl, aryl, aralkyl, alkoxide, phenoxide, etc., or mixtures thereof. Suitable examples of group R 4 are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, hexyl, cyclohexyl, octyl, phenyl, tolyl, xylyl, mesityl and benzyl. In a preferred embodiment of the invention, R 4 represents an aromatic group, for instance a phenyl group.
- the Grignard compound of formula R 4 z MgX2 -z wherein z is larger than 0 and smaller than 2, is preferably characterized by z being from about 0.5 to 1.5.
- the alkoxy- or aryloxy-containing silane used in step i) is preferably a compound or a mixture of compounds with the general formula Si (OR 5 ) 4-n R 6 n, wherein n can range from 0 up to 4, preferably n is from 0 up to and including 1 , and wherein each R 5 and R 6 groups, independently, represent 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, as defined below for R 2 and R 3 .
- silane-compounds examples include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltributoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, diethyldiphenoxysilane, n-propyltriethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, isobutylisopropyldimethoxylsilane, phenyltrimethoxysilane, diphenyldimethoxysilane, trifluoropropylmethyldimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, dicyclo
- tetraethoxysilane is used as silane-compound in preparing the solid Mg-containing compound in the process according to the invention.
- the silane-compound and the Grignard compound are introduced simultaneously to a mixing device to result in particles of advantageous morphology, especially of the larger particles, as described in WO 01/23441 A1.
- 'morphology' does not only refer to the shape of the particles of the solid Mg-compound and the catalyst made therefrom, but also to the particle size distribution (also characterized as span), its fines content, powder flowability, and the bulk density of the catalyst particles.
- the silane-compound and Grignard compound can be continuously or batch-wise introduced to the mixing device.
- the both compounds are introduced continuously to a mixing device.
- the mixing device can have various forms; it can be a mixing device in which the silane-compound is premixed with the Grignard compound, the mixing device can also be a stirred reactor, in which the reaction between the compounds takes place.
- the compounds are premixed before the mixture is introduced to the reactor for step i).
- 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 i) 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 period of premixing in above indicated reaction step 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 step is not specifically critical, and may for instance range between 0 and 8O 0 C; preferably the temperature is between 10 °C and 50 0 C.
- the reaction between said compounds 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 solid product obtained from the reaction between the silane- compound and the Grignard compound is usually purified by rinsing with an inert solvent, for instance a hydrocarbon solvent with for example 1-20 C-atoms, like pentane, iso-pentane, hexane or heptane.
- an inert solvent for instance a hydrocarbon solvent with for example 1-20 C-atoms, like pentane, iso-pentane, hexane or heptane.
- the solid product can be stored and further used as a suspension in said inert solvent.
- the product may be dried, preferably partly dried, and preferably under mild conditions; e.g. at ambient temperature and pressure.
- the group R 1 generally is an alkyl containing 1-12 carbon atoms.
- the alkyl group may be linear or branched.
- the R 1 group contains 1-8 carbon atoms. More preferably, at least one of the R 1 -groups represents an ethyl group. In a preferred embodiment, each R 1 -group represents an ethyl group.
- the solid magnesium-containing compound is reacted in step ii) with at least one activating compound selected from the group formed by internal electron donors and compounds of formula M(OR 2 ) V-W (R 3 ) W , wherein M can be Ti, Zr, Hf, Al or Si, each R 2 and R 3 , independently, represent an alkyl, alkenyl or aryl group, v is the valency of M and w is smaller than v.
- An internal donor (also referred to as internal electron donor) is within the present application defined as an electron-donating compound that is commonly described as a reactant in the preparation of a solid catalyst component for a (Ziegler-Natta) catalyst system for olefin polymerization; i.e. contacting a magnesium-containing support with a halogen-containing Ti compound and an internal donor.
- Suitable internal electron donors include carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alkoxides, sulphonamides, thioethers, thioesters and other organic compounds containing one or more hetero atoms, such as nitrogen, oxygen, sulphur and/or phosphorus.
- Suitable carboxylic acids may be aliphatic or (partly) aromatic,
- Examples include 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.
- esters of above-mentioned carboxylic acids are formates, for instance, butyl formate; acetates, for instance ethyl acetate and butyl acetate; acrylates, for instance ethyl acrylate, methyl methacrylate and isobutyl methacrylate; benzoates, for instance methylbenzoate and ethylbenzoate; methyl-p-toluate; ethyl-naphthate and phthalates, for instance monomethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diallyl phthalate and/or diphenyl phthalate.
- Suitable carboxylic acid halides 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 linear or branched aliphatic alcohols with 1-
- the alcohol is ethanol or hexanol.
- 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.
- cyclic ethers like tetrahydrofuran (THF), or tri- ethers can be used.
- Suitable examples of other organic compounds containing a heteroatom include 2,2,6,6-tetramethyl piperidine, 2,6-dimethylpiperidine, pyridine, 2-methylpyridine, 4-methylpyridine, imidazole, benzonitrile, aniline, diethylamine, dibutylamine, dimethylacetamide, thiophenol, 2-methyl thiophene, isopropyl mercaptan, diethylthioether, diphenylthioether, tetrahydrofuran, dioxane, dimethylether, diethylether, anisole, acetone, triphenylphosphine, triphenylphosphite, diethylphosphate and/or diphenylphosphate.
- the at least one activating compound can also be of formula M(OR 2 ) V-W (R 3 ) W , wherein M can be Ti, Zr, Hf, Al or Si, each R 2 and R 3 , independently, represent an alkyl, alkenyl or aryl group, v is the valency of M, being either 3 or 4, and and w is smaller than v.
- the R 2 and R 3 groups can be a linear, branched or cyclic alkyl or alkenyl group, suitable groups contain from 1 to 20 carbon atoms, preferably 1-12 or 1-8 carbon atoms. The groups may differ independently, or be the same.
- R 2 and R 3 are ethyl, propyl or butyl; more preferably all groups are ethyl groups.
- R 2 and R 3 can also be aromatic hydrocarbon groups, optionally substituted with e.g. alkyl groups, and can contain for example from 6 to 20 carbon atoms.
- the R 2 and R 3 groups may optionally contain one or more hetero atoms, such as for instance O, N, S or P.
- M in said activating compound is Ti or Si.
- the value of w is 0, the activating compound being for example a titanium tetraalkoxide containing 4-32 C-atoms.
- the four alkoxide groups in the compound may be the same or may differ independently.
- at least one of the alkoxy groups in the compound is an ethoxy group. More preferably the compound is a tetraalkoxide, like titanium tetraethoxide.
- Si-containing compounds suitable as activating compounds are the same as listed above for step i).
- one activating compound can be used, but also a mixture of two or more compounds may be used.
- a combination of a compound of formula M(OR 2 ) v- w(R 3 )w, as defined above, with an internal electron donor is preferred as activating compound, to obtain a catalyst system that for example shows high activity, and of which the ethylene sensitivity can be affected by selecting the internal donor; which is specifically advantageous in preparing copolymers of for example propylene and ethylene.
- a Ti-based compound for example titanium tetraethoxide
- an alcohol like ethanol or hexanol
- an ester compound like ethylacetate, ethylbenzoate or a phthalate ester
- an ether like dibutylether, or with pyridine.
- activating compounds are used in the process according to the invention, their order of addition is not critical, but may affect catalyst performance depending on the compounds used. A skilled person may optimise their addition based on some experiments.
- the compounds can be added together, or sequentially. For example, a carboxylic acid ester may be added before, during or after the treatment with a titanium tetraalkoxyde, or a combination thereof can be applied.
- an internal donor compound is first added to the compound with formula Mg(OR 1 ) x Cl2- x whereafter a compound of formula M(OR 2 ) v-w (R 3 )w is added.
- the activating compounds preferably are added slowly, for instance during a period of 0.1-6, preferably during 0.5-4 hours, most preferably during 1-2.5 hours, each.
- the inert dispersant is preferably a hydrocarbon solvent.
- the dispersant may be for example an aliphatic or aromatic hydrocarbon with 1-20 C-atoms.
- the dispersant is an aliphatic hydrocarbon, more preferably pentane, iso-pentane, hexane or heptane, heptane being most preferred.
- the molar ratio of activating compound to Mg(OR 1 ) x Cl 2-x may range between wide limits and is, for instance, between 0.02 and 1.0.
- the molar ratio is between 0.05 and 0.5, more preferably between 0.06 and 0.4, or even between 0.07 and 0.2.
- the temperature in step ii) can be in the range from -2O 0 C to 7O 0 C, preferably from -10 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.
- at least one of the reaction components is dosed in time, for instance during 0.1 to 6, preferably during 0.5 to 4 hours, more particularly during 1-2.5 hours.
- the obtained solid intermediate product can be further washed, preferably with the solvent also used as inert dispersant; and then stored and further used as a suspension in said inert solvent.
- the product may be dried, preferably partly dried, preferably slowly and under mild conditions; e.g. at ambient temperature and pressure.
- the solid intermediate product obtained is considered to be an adduct of the Mg-containing compound and the at least one activating compound, and is still of controlled morphology.
- This intermediate reaction product is subsequently contacted with a halogen-containing titanium compound in step iii), preferably in the presence of an internal electron donor compound in one or more steps.
- the process according to the invention is characterized in that a solid compound with formula Mg(OR 1 ) x Cl2 -x wherein x is larger than 0 and smaller than 2, and each R 1 , independently, represents an alkyl group with 1-8 carbon atoms, is contacted with a carboxylic acid ester and a titanium tetraalkoxide in the presence of an inert dispersant to give a solid intermediate reaction product, which intermediate reaction product is then contacted with titanium tetrachloride in the presence of an internal donor.
- the Ti/Mg molar ratio in the contact between the intermediate product and halogen-containing titanium compound preferably is between 10 and 100, most preferably, between 10 and 50.
- the intermediate reaction product is preferably contacted with a halogen-containing Ti-compound in the presence of an internal donor.
- Suitable compounds that can be used as internal electron donor are known to the skilled person, and have been defined above.
- the molar ratio of the internal electron 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.
- dibutyl phthalate is used as the internal electron donor, more preferably di-n-butyl phthalate.
- an inert dispersant is preferably used.
- the dispersant preferably is chosen such that virtually all side products formed 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. Examples include toluene, xylene, benzene, heptane, o-chlorotoluene and chlorobenzene.
- the reaction temperature during contacting in step iii) the intermediate product and the halogen-containing titanium compound is preferably between O 0 C and 150 0 C, more preferably between 5O 0 C and 15O 0 C, and most preferably between 6O 0 C and 120 0 C.
- 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 steps may be repeated one or more times.
- a final washing is preferably performed with an aliphatic hydrocarbon to result in a suspended or at least partly dried catalyst component, as described above for the other steps.
- the invention further relates to a polymerization catalyst component obtained with the process according to the invention, and to a polymerization catalyst system comprising the catalyst component.
- the polymerization catalyst system comprises a catalyst component according to the invention and a co-catalyst.
- the catalyst system also comprises an external electron-donating compound, also referred to as external electron donor, or simply external donor.
- external electron donor also referred to as external electron donor, or simply external donor.
- the main function of this external donor compound is to affect the stereoselectivity of the catalyst system in polymerization of olefins having 3 or more carbon atoms, and is for this reason also called selectivity control agent.
- the invention further relates to a process of making a polyolefin by contacting at least one olefin with a polymerization catalyst system comprising the catalyst component obtained with the process according to the invention.
- the preparation of polyolefins takes place by polymerising one or more olefins simultaneously and/or successively in the presence of a catalyst system comprising the catalyst component according to the invention, a co- catalyst and optionally an external donor.
- the polymer obtained contains a low amount of catalyst residues, and has favourable bulk density and particle size distribution.
- the olefins that can be polymerized in the process according to the invention may be mono- and di-olefins 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, to result in a propylene homopolymer or copolymer.
- a propylene copolymer is herein meant to include both so-called random copolymers with relatively low comonomer content, e.g. up to 10 mol%, as well as so-called impact copolymers comprising higher comonomer contents, e.g. from 5 to 80 mol%, more typically from 10 to 60 mol%.
- 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 7 3 , wherein each R 7 independently represents an alkyl group with, for instance, 1-10 C-atoms or an aryl group with, for instance, 6-20 C-atoms.
- R 7 independently represents an alkyl group with, for instance, 1-10 C-atoms or an aryl group with, for instance, 6-20 C-atoms.
- suitable organoaluminium compound are trimethyl aluminium, triethyl aluminium, triisobutyl aluminium, and/or trioctyl aluminium.
- the co-catalyst is triethyl aluminium.
- suitable external donors include the compounds described above as internal donors that can be used in the preparation of the catalyst component.
- external donor also organo-silicon compounds can be used. Mixtures of external donors can also be used.
- organo-silicon compounds that are suitable as external donor are compounds or mixtures of compounds of general formula Si(OR 8 ) 4-n R 9 n , wherein n can be from 0 up to 4, preferably n is 1 or 2, and each R 8 and R 9 , 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, as defined above for R 2 and R 3 .
- suitable compounds include the silane-compounds that can be used as activating compound, as described above.
- the organo-silicon compound used as external donor is n-propyl trimethoxysilane, cyclohexyl methyldimethoxysilane, dicyclopentyl dimethoxysilane, di(iso-propyl) dimethoxysilane or di(iso-butyl) dimethoxysilane.
- the molar ratio of the metal of the co-catalyst relative to titanium in the polymerization catalyst system during the polymerization may vary for instance from 5 to 2000. Preferably this ratio is between 50 and 300.
- the aluminium/external donor molar ratio in the polymerization catalyst system preferably is between 0.1 and 200; more preferably between 1 and 100.
- the polymerization process can be carried out in the gas phase or in the liquid phase (in bulk or slurry).
- a dispersing agent is present in the case of polymerization in a slurry (liquid phase) .
- Suitable dispersing agents include for example n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and liquid propylene.
- polymerization conditions of the process according to the invention 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 further ingredients (like hydrogen) to control polymer molar mass, and other conditions are well known to persons of skill in the art.
- the polymerization temperature may vary within wide limits and is, for example for propylene polymerization, between O 0 C and 12O 0 C, preferably between 4O 0 C and 100 0 C.
- the pressure during (propylene) (co)polymerization is for instance between 0.1 and 6 MPa, preferably between 0.5-3 MPa.
- the molar mass 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 a 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 wherein 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 growing polymer particles. The invention will be further elucidated with the following experiments without being limited hereto.
- reaction product of step I 200 ml, 0.272 mol Mg
- DBE dibutyl ether
- 33.4 ml of TES and 66.6 ml of DBE were cooled to 15 0 C, 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
- 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 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 I 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 titanium tetraethoxide (TET) in 20 ml of heptane was added at 25 0 C for 1 hour.
- TET/Mg 0.2
- reaction product I. C was obtained, suspended in 15 ml of heptane.
- a reactor was brought under nitrogen and 125 ml of titanium tetrachloride was added to it.
- the reactor was heated to 115 0 C and a suspension, containing about 5.5 g of reaction product I. C 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 2.4 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 (125 ml) at 100 0 C for 20 min.
- Example I was repeated, except for the fact that step I.
- Example VII was repeated, except 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 I. C 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., and 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 that step I. D was performed as described below.
- a reactor was brought under nitrogen and a mixture of titanium tetrachloride (50 ml) and toluene (50 ml) was added to it. Then a suspension, containing 5 g of reaction product I. C. 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, but chlorobenzene was used instead of toluene when step I. D was performed. The results are presented in Table 1.
- Example I was repeated, however without activation step I. C. The results are presented in Table 1.
- the mixing device (minimixer) and the feedpipes to it were cooled to 7.5 0 C by means of cold water circulating in the minimixer ' s jacket and round the feedpipes
- the reagents contact time was 20 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 1.2 I reactor, with stirring.
- the reactor was loaded preliminary with 370 ml of DBE and 130 ml chlorobenzene, and heated at 35 0 C. Dosing time was 6 hours.
- the average stirring speed in the reactor was 415 rpm.
- reaction product XIII. B was obtained, suspended in 300 ml of heptane.
- reaction product XIII. C was obtained, suspended in 15 ml of heptane.
- Examples XIV-XXVI Example XIII was repeated, be it that other activating compounds were used in step C, at molar ratio of activator(s) to Mg as listed in Table 2; together with results of propylene polymerization with the catalyst obtained.
- Examples 1 - 14 Gas-phase co-polymerization of propylene and ethylene. Gas phase co-polymerization of ethylene and propylene was carried out in a stainless steel reactor with a volume of 1.8 liter. The polymerization comprised two steps:
- Ti wt% is the weight content in % of titanium in the catalyst component
- Activity kgpp/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 D 1895.
- the particles size distribution of PP powder expressed as span ((d90-d10)/d50) was determined according to ASTM D1921 , method A;
- RC is the rubber content (propylene-ethylene copolymer) in the polymer powder
- RCC2 is the C2 (ethylene) content in the rubber part of the polymer.
- MFI is the melt flow index as measured at 230 0 C with 2.16 kg load.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009511403A JP5529533B2 (en) | 2006-05-24 | 2007-05-23 | Method for preparing catalyst components for propylene polymerization |
US12/227,663 US9512244B2 (en) | 2006-05-24 | 2007-05-23 | Process for preparing a catalyst component for propylene polymerization |
EA200802379A EA013392B1 (en) | 2006-05-24 | 2007-05-23 | Process for preparing a catalyst component for propylene polymerization |
BRPI0711891-0A BRPI0711891B1 (en) | 2006-05-24 | 2007-05-23 | PROCESS FOR PREPARING A CATALYST COMPONENT FOR PROPYLENE POLYMERIZATION |
EP07725472A EP2027164B1 (en) | 2006-05-24 | 2007-05-23 | Process for preparing a catalyst component for propylene polymerization |
CN2007800220993A CN101484480B (en) | 2006-05-24 | 2007-05-23 | Process for preparing a catalyst component for propylene polymerization |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06010720 | 2006-05-24 | ||
EP06010720.8 | 2006-05-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007134851A1 true WO2007134851A1 (en) | 2007-11-29 |
Family
ID=37814425
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/004572 WO2007134851A1 (en) | 2006-05-24 | 2007-05-23 | Process for preparing a catalyst component for propylene polymerization |
Country Status (7)
Country | Link |
---|---|
US (1) | US9512244B2 (en) |
EP (1) | EP2027164B1 (en) |
JP (3) | JP5529533B2 (en) |
CN (1) | CN101484480B (en) |
BR (1) | BRPI0711891B1 (en) |
EA (1) | EA013392B1 (en) |
WO (1) | WO2007134851A1 (en) |
Cited By (64)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101824105B (en) * | 2009-03-04 | 2012-05-30 | 中国石油天然气股份有限公司 | Solid titanium catalytic component and catalyst |
WO2013124063A1 (en) | 2012-02-22 | 2013-08-29 | Saudi Basic Industries Corporation | Catalyst component for the polymerization of olefins |
WO2014001257A1 (en) | 2012-06-29 | 2014-01-03 | Saudi Basic Industries Corporation | Catalyst composition for polymerization of olefins |
WO2014096201A1 (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 |
WO2015022298A1 (en) * | 2013-08-12 | 2015-02-19 | Saudi Basic Industries Corporation | Catalyst system for polymerisation of an olefin |
WO2015091981A2 (en) | 2013-12-20 | 2015-06-25 | Saudi Basic Industries Corporation | Catalyst system for polymerisation of an olefin |
WO2015091982A1 (en) | 2013-12-20 | 2015-06-25 | Saudi Basic Industries Corporation | Catalyst system for polymerisation of an olefin |
WO2015091984A1 (en) * | 2013-12-20 | 2015-06-25 | Saudi Basic Industries Corporation | Procatalyst for polymerization of olefins |
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 |
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 |
WO2016203017A1 (en) | 2015-06-19 | 2016-12-22 | Sabic Global Technologies B.V. | Procatalyst for polymerization of olefins comprising an aminobenzoate internal donor and a 1,3-diether internal donor in a specific ratio |
WO2017050870A1 (en) | 2015-09-22 | 2017-03-30 | Sabic Global Technologies B.V. | Synthesis of substituted amidobenzoate compounds, the compounds obtained and the use thereof as phthalate free internal electron donor for polymerization of olefins |
WO2017093169A1 (en) | 2015-12-02 | 2017-06-08 | Sabic Global Technologies B.V. | A procatalyst for polymerization of olefins |
EP3181625A1 (en) | 2015-12-18 | 2017-06-21 | SABIC Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
WO2018046395A1 (en) | 2016-09-08 | 2018-03-15 | Sabic Global Technologies B.V. | Process of preparing polyolefin with the discontinuous addition of a thermal runaway reducing agent |
US9926391B2 (en) | 2013-12-20 | 2018-03-27 | Saudi Basic Industries Corporation | Catalyst system for polymerization of an olefin |
WO2018059750A1 (en) | 2016-09-29 | 2018-04-05 | Sabic Global Technologies B.V. | Process to prepare procatalyst for polymerization of olefins |
WO2018059955A1 (en) | 2016-09-29 | 2018-04-05 | Sabic Global Technologies B.V. | Process to prepare procatalyst for polymerization of olefins |
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 |
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 |
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 |
US10047218B2 (en) | 2013-12-20 | 2018-08-14 | Saudi Basic Industries Corporation | Polyolefin composition |
US10059656B2 (en) | 2013-12-20 | 2018-08-28 | Sabic Global Technologies B.V. | Catalyst composition for polymerization of olefins |
US10160816B2 (en) | 2014-06-02 | 2018-12-25 | Sabic Global Technologies B.V. | Procatalyst for polymerization of olefins |
US10450388B2 (en) | 2014-12-23 | 2019-10-22 | Sabic Global Technologies B.V. | Process for the preparation of a branched polyolefin |
US10465018B2 (en) | 2014-12-23 | 2019-11-05 | Sabic Global Technologies B.V. | Process for the preparation of a polyolefin having one or multiple end-functionalized branches |
US10472447B2 (en) | 2014-12-17 | 2019-11-12 | Sabic Global Technologies B.V. | Process for the preparation of a graft copolymer comprising a polyolefin main chain and one or a multiple polymer side chains and the products obtained therefrom |
US10519267B2 (en) | 2014-12-17 | 2019-12-31 | Sabic Global Technologies B.V. | Process for the preparation of a graft copolymer comprising a polyolefin main chain and one or a multiple polymer side chains and the products obtained therefrom |
US10526434B2 (en) | 2014-12-17 | 2020-01-07 | Sabic Global Technologies B.V. | Process for the preparation of a block copolymer comprising a first polyolefin block and a second polymer block as well as the products obtained therefrom |
US10533075B2 (en) | 2014-12-17 | 2020-01-14 | Sabic Global Technologies B.V. | Process for the preparation of a block copolymer comprising a first polyolefin block and a second polymer block and the products obtained therefrom |
EP3650494A2 (en) | 2020-02-14 | 2020-05-13 | SABIC Global Technologies B.V. | Matte film comprising heterophasic propylene copolymer composition |
EP3650495A2 (en) | 2020-02-14 | 2020-05-13 | SABIC Global Technologies B.V. | Film comprising heterophasic propylene copolymer composition |
WO2020104306A1 (en) | 2018-11-19 | 2020-05-28 | Sabic Global Technologies B.V. | Food packaging comprising a polymer composition and use of said polymer composition for manufacturing food packaging |
US10696829B2 (en) | 2013-12-20 | 2020-06-30 | Saudi Basic Industries Corporation | Heterophasic propylene copolymer |
US10696756B2 (en) | 2015-08-07 | 2020-06-30 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
US10717826B2 (en) | 2015-12-09 | 2020-07-21 | Sabic Global Technologies B.V. | Process for the preparation of polyolefin-based graft copolymers comprising a first long chain branched polyolefin block and one or multiple polymer side chains |
US10745499B2 (en) | 2015-08-07 | 2020-08-18 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
US10759883B2 (en) | 2015-08-07 | 2020-09-01 | Sabin Global Technologies B.V. | Process for the polymerization of olefins |
US10787545B2 (en) | 2015-12-09 | 2020-09-29 | Sabic Global Technologies B.V. | Process for the preparation of polyolefin-based graft copolymers comprising a first functionalized short chain branched polyolefin block and one or multiple polymer side chains |
US10836847B2 (en) | 2015-12-02 | 2020-11-17 | Sabic Global Technologies B.V. | Procatalyst for polymerization of olefins |
WO2021037590A1 (en) | 2019-08-27 | 2021-03-04 | Sabic Global Technologies B.V. | Heterophasic propylene copolymer composition |
WO2021043784A1 (en) | 2019-09-06 | 2021-03-11 | Sabic Global Technologies B.V. | Healthcare article comprising a random propylene-ethylene copolymer. |
WO2021063930A1 (en) | 2019-10-04 | 2021-04-08 | Sabic Global Technologies B.V. | Process for polymerization of polypropylene using ziegler-natta procatalyst with novel 1,3-diether internal electron donors |
WO2021160773A1 (en) | 2020-02-14 | 2021-08-19 | Sabic Global Technologies B.V. | Film comprising heterophasic propylene copolymer composition |
WO2021191466A1 (en) | 2020-03-27 | 2021-09-30 | Sabic Global Technologies B.V. | Polymer composition having improved impact strength at low temperatures |
US11384166B2 (en) | 2016-09-08 | 2022-07-12 | Sabic Global Technologies B.V. | Process of preparing polyolefin with the discontinuous addition of a thermal runaway reducing agent |
US11478781B2 (en) | 2019-06-19 | 2022-10-25 | Chevron Phillips Chemical Company Lp | Ziegler-Natta catalysts prepared from solid alkoxymagnesium halide supports |
WO2023104940A1 (en) | 2021-12-09 | 2023-06-15 | Sabic Global Technologies B.V. | Catalyst system for polymerization of an olefin |
WO2023117789A1 (en) | 2021-12-21 | 2023-06-29 | Sabic Global Technologies B.V. | High impact polypropylene composition |
WO2023174732A1 (en) | 2022-03-14 | 2023-09-21 | Sabic Global Technologies B.V. | Heterophasic propylene copolymer composition |
WO2023174731A1 (en) | 2022-03-14 | 2023-09-21 | Sabic Global Technologies B.V. | Injection molding process |
WO2023217945A1 (en) | 2022-05-13 | 2023-11-16 | Sabic Global Technologies B.V. | Heterophasic polypropylene composition with low emission |
WO2023217944A1 (en) | 2022-05-13 | 2023-11-16 | Sabic Global Technologies B.V. | Heterophasic polypropylene composition with low shrinkage |
WO2023217946A1 (en) | 2022-05-13 | 2023-11-16 | Sabic Global Technologies B.V. | Heterophasic polypropylene composition with low hexane extractables |
WO2024008770A1 (en) | 2022-07-05 | 2024-01-11 | Sabic Global Technologies B.V. | Catalyst system for polymerization of an olefin |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EA013392B1 (en) * | 2006-05-24 | 2010-04-30 | Сауди Бейсик Индастриз Корпорейшн | Process for preparing a catalyst component for propylene polymerization |
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 |
RU2623228C2 (en) | 2012-09-24 | 2017-06-23 | Индийская Нефтяная Корпорация Лимитэд | Precursor for catalyst, method of its production and application |
EP3653631A1 (en) | 2012-09-24 | 2020-05-20 | INDIAN OIL CORPORATION Ltd. | Processes for the preparation of an olefin polymerization catalyst based on treating solid organomagnesium compounds with titanium moieties |
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 |
EA034784B9 (en) * | 2015-01-21 | 2020-09-09 | Сабик Глоубл Текнолоджиз Б.В. | Procatalyst for polymerization of olefins |
CN109790251B (en) | 2016-09-29 | 2021-11-23 | Sabic环球技术有限责任公司 | Process for preparing procatalyst for olefin polymerization |
EA038511B9 (en) | 2016-09-29 | 2021-10-01 | Сабик Глоубл Текнолоджиз Б.В. | Procatalyst for polymerization of olefins |
EP3519458B1 (en) | 2016-09-29 | 2023-08-09 | SABIC Global Technologies B.V. | Process to prepare procatalyst for polymerization of olefins |
WO2018069379A1 (en) | 2016-10-12 | 2018-04-19 | Sabic Global Technologies B.V. | Process to prepare a solid support for a procatalyst suitable for polymerization of olefins |
EP3526262A1 (en) | 2016-10-12 | 2019-08-21 | SABIC Global Technologies B.V. | Process to prepare a solid support for a procatalyst suitable for polymerization of olefins |
KR101830541B1 (en) * | 2016-11-23 | 2018-02-20 | 한화토탈 주식회사 | Preparation method of catalyst for propylene terpolymer and copolymer using therefrom |
CN110234663B (en) | 2017-03-17 | 2022-03-08 | Sabic环球技术有限责任公司 | Process for producing polyolefin |
EP3596140B1 (en) | 2017-03-17 | 2024-03-20 | SABIC Global Technologies B.V. | Process for preparing a procatalyst for polymerization of olefins |
WO2018167301A1 (en) | 2017-03-17 | 2018-09-20 | Sabic Global Technologies B.V. | Process for the polymerization of a polyolefin |
CN111995704B (en) * | 2019-05-27 | 2022-08-05 | 中国石油天然气股份有限公司 | Propylene polymerization catalyst and preparation method thereof |
CN114728276A (en) * | 2019-11-22 | 2022-07-08 | Sabic环球技术有限责任公司 | Process for preparing procatalyst for olefin polymerization |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4232139A (en) * | 1976-06-02 | 1980-11-04 | Mitsui Petrochemical Industries Ltd. | Process for producing polymers or copolymers of olefins containing at least 3 carbon atoms |
GB2112402A (en) | 1981-12-03 | 1983-07-20 | Nippon Oil Co Ltd | Solid transition metal component of ziegler catalyst |
US4771023A (en) | 1985-06-25 | 1988-09-13 | Sumitomo Chemical Company, Limited | Process for producing olefin polymers and catalyst used therein |
WO1989002446A1 (en) | 1987-09-21 | 1989-03-23 | Quantum Chemical Corporation | Modified silica based catalyst |
US5229342A (en) | 1990-10-18 | 1993-07-20 | Shell Oil Company | Olefin polymerization catalyst |
WO1996032427A1 (en) | 1995-04-10 | 1996-10-17 | Dsm N.V. | Method for the preparation of a catalyst suitable for the polymerisation of an olefine |
EP0921135A1 (en) | 1997-06-26 | 1999-06-09 | Toho Titanium Co., Ltd. | Solid catalytic components and catalysts for polymerization of olefins |
WO2001023441A1 (en) | 1999-09-27 | 2001-04-05 | Dsm N.V. | Process for the preparation of a catalyst component for the polymerization of an olefin |
EP1383808B1 (en) | 2001-05-03 | 2004-12-08 | Akzo Nobel N.V. | Catalyst for propylene polymerization |
WO2006056338A1 (en) * | 2004-11-26 | 2006-06-01 | Saudi Basic Industries Corporation | Process for the preparation of a catalyst component for the polymerization of an olefin |
Family Cites Families (16)
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 |
US4728705A (en) * | 1986-02-28 | 1988-03-01 | Shell Oil Company | Olefin polymerization catalyst composition |
GB8725402D0 (en) | 1987-10-29 | 1987-12-02 | Jefferson R A | Gene fusion |
DE3780260T2 (en) | 1986-11-20 | 1993-02-11 | Mitsubishi Chem Ind | METHOD FOR PRODUCING OLEFIN POLYMERS. |
JPH06102696B2 (en) * | 1987-10-29 | 1994-12-14 | 住友化学工業株式会社 | Method for producing α-olefin polymer |
JP2654687B2 (en) * | 1989-05-17 | 1997-09-17 | 東燃株式会社 | Catalyst component for olefin polymerization |
JP2838310B2 (en) | 1989-05-17 | 1998-12-16 | 三菱化学株式会社 | Method for producing olefin polymer |
US5262573A (en) | 1991-08-06 | 1993-11-16 | Akzo Nv | Halomagnesium hydrocarbyloxide composition and process for preparation |
US5229324A (en) | 1991-12-23 | 1993-07-20 | Texas Instruments Incorporated | Method for forming contacts to p-type HgCdTe semiconductor material using lead and tin |
JP3552342B2 (en) * | 1995-06-23 | 2004-08-11 | 住友化学工業株式会社 | Catalyst for α-olefin polymerization and method for producing α-olefin polymer |
DE69820399T2 (en) * | 1997-05-30 | 2004-10-07 | Mitsui Chemicals Inc | Polypropylene resin composition and injection molded article |
SG87202A1 (en) * | 2000-02-08 | 2002-03-19 | Sumitomo Chemical Co | Process for pruducing solid catalyst component and catalyst alpha-olefin polymerization, and process for producing alpha-olefin polymer |
US6962889B2 (en) * | 2004-01-28 | 2005-11-08 | Engelhard Corporation | Spherical catalyst for olefin polymerization |
EA013392B1 (en) * | 2006-05-24 | 2010-04-30 | Сауди Бейсик Индастриз Корпорейшн | Process for preparing a catalyst component for propylene polymerization |
-
2007
- 2007-05-23 EA EA200802379A patent/EA013392B1/en not_active IP Right Cessation
- 2007-05-23 BR BRPI0711891-0A patent/BRPI0711891B1/en active IP Right Grant
- 2007-05-23 US US12/227,663 patent/US9512244B2/en active Active
- 2007-05-23 CN CN2007800220993A patent/CN101484480B/en active Active
- 2007-05-23 JP JP2009511403A patent/JP5529533B2/en active Active
- 2007-05-23 WO PCT/EP2007/004572 patent/WO2007134851A1/en active Application Filing
- 2007-05-23 EP EP07725472A patent/EP2027164B1/en active Active
-
2013
- 2013-07-04 JP JP2013140513A patent/JP2013189654A/en active Pending
-
2015
- 2015-05-28 JP JP2015108316A patent/JP6073968B2/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4232139A (en) * | 1976-06-02 | 1980-11-04 | Mitsui Petrochemical Industries Ltd. | Process for producing polymers or copolymers of olefins containing at least 3 carbon atoms |
GB2112402A (en) | 1981-12-03 | 1983-07-20 | Nippon Oil Co Ltd | Solid transition metal component of ziegler catalyst |
US4771023A (en) | 1985-06-25 | 1988-09-13 | Sumitomo Chemical Company, Limited | Process for producing olefin polymers and catalyst used therein |
WO1989002446A1 (en) | 1987-09-21 | 1989-03-23 | Quantum Chemical Corporation | Modified silica based catalyst |
US5229342A (en) | 1990-10-18 | 1993-07-20 | Shell Oil Company | Olefin polymerization catalyst |
WO1996032427A1 (en) | 1995-04-10 | 1996-10-17 | Dsm N.V. | Method for the preparation of a catalyst suitable for the polymerisation of an olefine |
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 |
EP0921135A1 (en) | 1997-06-26 | 1999-06-09 | Toho Titanium Co., Ltd. | Solid catalytic components and catalysts for polymerization of olefins |
WO2001023441A1 (en) | 1999-09-27 | 2001-04-05 | Dsm N.V. | Process for the preparation of a catalyst component for the polymerization of an olefin |
EP1383808B1 (en) | 2001-05-03 | 2004-12-08 | Akzo Nobel N.V. | Catalyst for propylene polymerization |
WO2006056338A1 (en) * | 2004-11-26 | 2006-06-01 | Saudi Basic Industries Corporation | Process for the preparation of a catalyst component for the polymerization of an olefin |
Non-Patent Citations (2)
Title |
---|
"Handbook of Chemistry and Physics", 1989, CRC PRESS |
VAN DER VEN: "Polypropylene and other Polyolefins", 1990, ELSEVIER, pages: 8 - 10 |
Cited By (98)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101824105B (en) * | 2009-03-04 | 2012-05-30 | 中国石油天然气股份有限公司 | Solid titanium catalytic component and catalyst |
US9587049B2 (en) | 2012-02-22 | 2017-03-07 | Saudi Basic Industries Corporation | Catalyst component for the polymerization of olefins |
WO2013124063A1 (en) | 2012-02-22 | 2013-08-29 | Saudi Basic Industries Corporation | Catalyst component for the polymerization of olefins |
EA024745B1 (en) * | 2012-02-22 | 2016-10-31 | Сауди Бейсик Индастриз Корпорейшн | Catalyst component for the polymerization of olefins |
WO2014001257A1 (en) | 2012-06-29 | 2014-01-03 | Saudi Basic Industries Corporation | Catalyst composition for polymerization of olefins |
US9688790B2 (en) | 2012-06-29 | 2017-06-27 | Saudi Basic Industries Corporation | Catalyst composition for polymerization of olefins |
WO2014096201A1 (en) | 2012-12-20 | 2014-06-26 | Saudi Basic Industries Corporation | Process for the polymerization of propylene |
US9718902B2 (en) | 2012-12-20 | 2017-08-01 | 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 |
WO2014118164A1 (en) | 2013-01-31 | 2014-08-07 | Saudi Basic Industries Corporation | Catalyst composition for polymerization of olefins |
KR102123473B1 (en) | 2013-01-31 | 2020-06-17 | 사우디 베이식 인더스트리즈 코포레이션 | 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 |
US9587051B2 (en) | 2013-01-31 | 2017-03-07 | Saudi Basic Industries Corporation | Process for preparing a catalyst component for polymerization of olefins |
KR20150113108A (en) * | 2013-01-31 | 2015-10-07 | 사우디 베이식 인더스트리즈 코포레이션 | Process for preparing a catalyst component for polymerization of olefins |
EA025272B1 (en) * | 2013-01-31 | 2016-12-30 | Сауди Бейсик Индастриз Корпорейшн | Process for preparing a catalyst component for polymerization of olefins |
WO2014118165A1 (en) * | 2013-01-31 | 2014-08-07 | Saudi Basic Industries Corporation | Process for preparing a catalyst component for polymerization of olefins |
EA032503B1 (en) * | 2013-08-12 | 2019-06-28 | Сауди Бейсик Индастриз Корпорейшн | Catalyst system for polymerisation of olefins |
KR20160042990A (en) * | 2013-08-12 | 2016-04-20 | 사우디 베이식 인더스트리즈 코포레이션 | Catalyst system for polymerisation of an olefin |
US9701773B2 (en) | 2013-08-12 | 2017-07-11 | Sabic Global Technologies, B.V. | Catalyst system for polymerisation of an OLEFIN |
KR102204379B1 (en) | 2013-08-12 | 2021-01-19 | 사우디 베이식 인더스트리즈 코포레이션 | Catalyst system for polymerisation of an olefin |
WO2015022298A1 (en) * | 2013-08-12 | 2015-02-19 | Saudi Basic Industries Corporation | 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 |
US10059656B2 (en) | 2013-12-20 | 2018-08-28 | Sabic Global Technologies B.V. | Catalyst composition for polymerization of olefins |
US10000591B2 (en) | 2013-12-20 | 2018-06-19 | Saudi Basic Industries Corporation | Catalyst system for polymerization of an olefin |
WO2015091984A1 (en) * | 2013-12-20 | 2015-06-25 | Saudi Basic Industries Corporation | Procatalyst for polymerization of olefins |
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 |
US10696829B2 (en) | 2013-12-20 | 2020-06-30 | Saudi Basic Industries Corporation | Heterophasic propylene copolymer |
CN105940018A (en) * | 2013-12-20 | 2016-09-14 | 沙特基础工业公司 | Procatalyst for polymerization of olefins |
US10047218B2 (en) | 2013-12-20 | 2018-08-14 | Saudi Basic Industries Corporation | Polyolefin composition |
WO2015091981A2 (en) | 2013-12-20 | 2015-06-25 | Saudi Basic Industries Corporation | Catalyst system for polymerisation of an olefin |
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 |
EA028922B1 (en) * | 2013-12-20 | 2018-01-31 | Сауди Бейсик Индастриз Корпорейшн | Procatalyst for polymerization of olefins |
WO2015091982A1 (en) | 2013-12-20 | 2015-06-25 | Saudi Basic Industries Corporation | Catalyst system for polymerisation of an olefin |
US9926391B2 (en) | 2013-12-20 | 2018-03-27 | Saudi Basic Industries Corporation | Catalyst system for polymerization of an olefin |
US10640586B2 (en) | 2013-12-20 | 2020-05-05 | 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 |
US10005859B2 (en) | 2014-06-02 | 2018-06-26 | Sabic Global Technologies B.V. | Procatalyst for polymerization of olefins |
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 |
US9988474B2 (en) | 2014-06-20 | 2018-06-05 | Sabic Global Technologies B.V. | Process for the polymerization of propylene |
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 |
US10472447B2 (en) | 2014-12-17 | 2019-11-12 | Sabic Global Technologies B.V. | Process for the preparation of a graft copolymer comprising a polyolefin main chain and one or a multiple polymer side chains and the products obtained therefrom |
US10533075B2 (en) | 2014-12-17 | 2020-01-14 | Sabic Global Technologies B.V. | Process for the preparation of a block copolymer comprising a first polyolefin block and a second polymer block and the products obtained therefrom |
US10526434B2 (en) | 2014-12-17 | 2020-01-07 | Sabic Global Technologies B.V. | Process for the preparation of a block copolymer comprising a first polyolefin block and a second polymer block as well as the products obtained therefrom |
US10519267B2 (en) | 2014-12-17 | 2019-12-31 | Sabic Global Technologies B.V. | Process for the preparation of a graft copolymer comprising a polyolefin main chain and one or a multiple polymer side chains and the products obtained therefrom |
US10465018B2 (en) | 2014-12-23 | 2019-11-05 | Sabic Global Technologies B.V. | Process for the preparation of a polyolefin having one or multiple end-functionalized branches |
US10450388B2 (en) | 2014-12-23 | 2019-10-22 | Sabic Global Technologies B.V. | Process for the preparation of a branched polyolefin |
WO2016198344A1 (en) | 2015-06-12 | 2016-12-15 | Sabic Global Technologies B.V. | Process for manufacture of low emission polypropylene |
US10435552B2 (en) | 2015-06-12 | 2019-10-08 | Sabic Global Technologies B.V. | Process for manufacture of low emission polypropylene |
US10730971B2 (en) | 2015-06-19 | 2020-08-04 | Sabic Global Technologies B.V. | Procatalyst for polymerization of olefins comprising an aminobenzoate internal donor and a 1,3-diether internal donor in a specific ratio |
WO2016203017A1 (en) | 2015-06-19 | 2016-12-22 | Sabic Global Technologies B.V. | Procatalyst for polymerization of olefins comprising an aminobenzoate internal donor and a 1,3-diether internal donor in a specific ratio |
US10696756B2 (en) | 2015-08-07 | 2020-06-30 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
US10745499B2 (en) | 2015-08-07 | 2020-08-18 | Sabic Global Technologies B.V. | Process for the polymerization of olefins |
US10759883B2 (en) | 2015-08-07 | 2020-09-01 | Sabin Global Technologies B.V. | Process for the polymerization of olefins |
WO2017050870A1 (en) | 2015-09-22 | 2017-03-30 | Sabic Global Technologies B.V. | Synthesis of substituted amidobenzoate compounds, the compounds obtained and the use thereof as phthalate free internal electron donor for polymerization of olefins |
US10611864B2 (en) | 2015-09-22 | 2020-04-07 | Sabic Global Technologies B.V. | Synthesis of substituted amidobenzoate compounds, the compounds obtained and the use thereof as phthalate free internal electron donor for polymerization of olefins |
US10836847B2 (en) | 2015-12-02 | 2020-11-17 | Sabic Global Technologies B.V. | Procatalyst for polymerization of olefins |
WO2017093169A1 (en) | 2015-12-02 | 2017-06-08 | Sabic Global Technologies B.V. | A procatalyst for polymerization of olefins |
US10787545B2 (en) | 2015-12-09 | 2020-09-29 | Sabic Global Technologies B.V. | Process for the preparation of polyolefin-based graft copolymers comprising a first functionalized short chain branched polyolefin block and one or multiple polymer side chains |
US10717826B2 (en) | 2015-12-09 | 2020-07-21 | Sabic Global Technologies B.V. | Process for the preparation of polyolefin-based graft copolymers comprising a first long chain branched polyolefin block and one or multiple polymer side chains |
EP3181625A1 (en) | 2015-12-18 | 2017-06-21 | SABIC Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
US10711125B2 (en) | 2015-12-18 | 2020-07-14 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
US11384166B2 (en) | 2016-09-08 | 2022-07-12 | Sabic Global Technologies B.V. | Process of preparing polyolefin with the discontinuous addition of a thermal runaway reducing agent |
US11773192B2 (en) | 2016-09-08 | 2023-10-03 | Sabic Global Technologies B.V. | Process of preparing polyolefin with the discontinuous addition of a thermal runaway reducing agent |
WO2018046395A1 (en) | 2016-09-08 | 2018-03-15 | Sabic Global Technologies B.V. | Process of preparing polyolefin with the discontinuous addition of a thermal runaway reducing agent |
WO2018059955A1 (en) | 2016-09-29 | 2018-04-05 | Sabic Global Technologies B.V. | Process to prepare procatalyst for polymerization of olefins |
WO2018059750A1 (en) | 2016-09-29 | 2018-04-05 | Sabic Global Technologies B.V. | Process to prepare procatalyst for polymerization of olefins |
EP3333222A1 (en) | 2016-12-12 | 2018-06-13 | SABIC Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
US11149139B2 (en) | 2016-12-12 | 2021-10-19 | Sabic Global Technologies B.V. | Heterophasic propylene copolymer |
WO2018108932A1 (en) | 2016-12-12 | 2018-06-21 | 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 |
WO2018108929A1 (en) | 2016-12-12 | 2018-06-21 | Sabic Global Technologies B.V. | Pellet comprising thermoplastic polymer sheath surrounding glass filaments having reduced emissions |
WO2018108936A1 (en) | 2016-12-12 | 2018-06-21 | Sabic Global Technologies B.V. | Process for manufacture of low emission homopolymer or random polypropylene |
US11603453B2 (en) | 2016-12-12 | 2023-03-14 | 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 |
US10995158B2 (en) | 2016-12-12 | 2021-05-04 | Sabic Global Technologies B.V. | Process for manufacture of low emission heterophasic polypropylene |
WO2018108928A1 (en) | 2016-12-12 | 2018-06-21 | Sabic Global Technologies B.V. | Heterophasic propylene copolymer |
WO2020104306A1 (en) | 2018-11-19 | 2020-05-28 | Sabic Global Technologies B.V. | Food packaging comprising a polymer composition and use of said polymer composition for manufacturing food packaging |
US11478781B2 (en) | 2019-06-19 | 2022-10-25 | Chevron Phillips Chemical Company Lp | Ziegler-Natta catalysts prepared from solid alkoxymagnesium halide supports |
WO2021037590A1 (en) | 2019-08-27 | 2021-03-04 | Sabic Global Technologies B.V. | Heterophasic propylene copolymer composition |
WO2021043784A1 (en) | 2019-09-06 | 2021-03-11 | Sabic Global Technologies B.V. | Healthcare article comprising a random propylene-ethylene copolymer. |
WO2021063930A1 (en) | 2019-10-04 | 2021-04-08 | Sabic Global Technologies B.V. | Process for polymerization of polypropylene using ziegler-natta procatalyst with novel 1,3-diether internal electron donors |
EP3650495A2 (en) | 2020-02-14 | 2020-05-13 | SABIC Global Technologies B.V. | Film comprising heterophasic propylene copolymer composition |
WO2021160773A1 (en) | 2020-02-14 | 2021-08-19 | Sabic Global Technologies B.V. | Film comprising heterophasic propylene copolymer composition |
EP3650494A2 (en) | 2020-02-14 | 2020-05-13 | SABIC Global Technologies B.V. | Matte film comprising heterophasic propylene copolymer composition |
WO2021191466A1 (en) | 2020-03-27 | 2021-09-30 | Sabic Global Technologies B.V. | Polymer composition having improved impact strength at low temperatures |
WO2023104940A1 (en) | 2021-12-09 | 2023-06-15 | Sabic Global Technologies B.V. | Catalyst system for polymerization of an olefin |
WO2023117789A1 (en) | 2021-12-21 | 2023-06-29 | Sabic Global Technologies B.V. | High impact polypropylene composition |
WO2023174732A1 (en) | 2022-03-14 | 2023-09-21 | Sabic Global Technologies B.V. | Heterophasic propylene copolymer composition |
WO2023174731A1 (en) | 2022-03-14 | 2023-09-21 | Sabic Global Technologies B.V. | Injection molding process |
WO2023217945A1 (en) | 2022-05-13 | 2023-11-16 | Sabic Global Technologies B.V. | Heterophasic polypropylene composition with low emission |
WO2023217944A1 (en) | 2022-05-13 | 2023-11-16 | Sabic Global Technologies B.V. | Heterophasic polypropylene composition with low shrinkage |
WO2023217946A1 (en) | 2022-05-13 | 2023-11-16 | Sabic Global Technologies B.V. | Heterophasic polypropylene composition with low hexane extractables |
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 |
---|---|
US9512244B2 (en) | 2016-12-06 |
JP5529533B2 (en) | 2014-06-25 |
CN101484480B (en) | 2011-10-19 |
US20090306315A1 (en) | 2009-12-10 |
BRPI0711891B1 (en) | 2018-05-02 |
JP6073968B2 (en) | 2017-02-01 |
EP2027164B1 (en) | 2012-08-15 |
EA200802379A1 (en) | 2009-06-30 |
EA013392B1 (en) | 2010-04-30 |
BRPI0711891A2 (en) | 2012-01-10 |
EP2027164A1 (en) | 2009-02-25 |
JP2009537675A (en) | 2009-10-29 |
JP2015147944A (en) | 2015-08-20 |
CN101484480A (en) | 2009-07-15 |
JP2013189654A (en) | 2013-09-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9512244B2 (en) | Process for preparing a catalyst component for propylene polymerization | |
US7947788B2 (en) | Process for the preparation of a catalyst component for the polymerization of an olefin | |
US10106632B2 (en) | Process for preparing a catalyst component for polymerization of olefins | |
EP1222214B1 (en) | Process for the preparation of a catalyst component for the polymerization of an olefin | |
US9587049B2 (en) | Catalyst component for the polymerization of olefins | |
EP0830391B1 (en) | Method fo the preparation of a catalyst suitable for the polymerisation of an olefin | |
WO2015193291A1 (en) | Process for the polymerization of propylene | |
US6051666A (en) | Method for preparing a catalyst suitable for polymerizing an olefin | |
WO2023104940A1 (en) | Catalyst system for polymerization of an olefin |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200780022099.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07725472 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009511403 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2644/MUMNP/2008 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007725472 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200802379 Country of ref document: EA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12227663 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: PI0711891 Country of ref document: BR Kind code of ref document: A2 Effective date: 20081121 |