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WO1994011409A1 - Procede de polymerisation d'alpha-olefines - Google Patents

Procede de polymerisation d'alpha-olefines Download PDF

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Publication number
WO1994011409A1
WO1994011409A1 PCT/US1993/010653 US9310653W WO9411409A1 WO 1994011409 A1 WO1994011409 A1 WO 1994011409A1 US 9310653 W US9310653 W US 9310653W WO 9411409 A1 WO9411409 A1 WO 9411409A1
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Prior art keywords
carbon atoms
group
magnesium
compound
methyl
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David Bell Morse
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Shell USA Inc
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Shell Oil Co
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Priority to AU54583/94A priority Critical patent/AU5458394A/en
Priority to EP93925170A priority patent/EP0667875A1/fr
Priority to BR9307390-9A priority patent/BR9307390A/pt
Priority to KR1019950701794A priority patent/KR950704372A/ko
Priority to CA002148596A priority patent/CA2148596A1/fr
Publication of WO1994011409A1 publication Critical patent/WO1994011409A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; 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
    • C08F4/60—Metals; 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
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/656—Pretreating with metals or metal-containing compounds with silicon or compounds thereof
    • C08F4/6562—Pretreating with metals or metal-containing compounds with silicon or compounds thereof and metals of C08F4/64 or compounds thereof
    • 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
    • C08F110/02—Ethene
    • 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
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; 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
    • C08F4/60—Metals; 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
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium

Definitions

  • This invention relates to a process for producing ⁇ - olefin polymers. More particularly, the invention relates to a process that utilizes a novel high activity stereoregular polymerization catalyst system to produce ⁇ -olefin polymers having improved polymer properties.
  • a solid, transition-metal based, olefin polymerization catalyst system including a titanium-containing, magnesium halide-based catalyst component to produce a polymer of an ⁇ -olefin such as ethylene, propylene, and butene-l, is well known in the art.
  • Such polymerization catalyst systems are typically obtained by the combination of a magnesium halide-based catalyst component, an organoaluminum compound and one or more electron donors.
  • the solid titanium-containing catalyst component is referred to herein as "procatalyst", the organoaluminum compound, as “cocatalyst”, and an electron donor compound, which is typically used separately, or used partially or totally complexed with the organoaluminum compound, as “selectivity control agent” (SCA).
  • SCA selectiveivity control agent
  • the electron donor which is incorporated with the titanium-containing compounds serves a different purpose than the electron donor referred to as the selectivity control agent.
  • the compounds which are used as the electron donor are the same as or different from compounds which are used as the selectivity control agent.
  • the above-described stereoregular high activity catalysts are broadly conventional and are described in numerous patents and other references including Nestlerode et al, U. S. Patent 4,728,705, which is incorporated herein by reference.
  • selectivity control agents Although a broad range of compounds are known generally as selectivity control agents, a particular catalyst component may have a specific compound or groups of compounds with which it is specially compatible. For any given procatalyst and/or cocatalyst, discovery of an appropriate type of selectivity control agent can lead to significant increases in catalyst efficiency, hydrogen utilization efficiency as well as an improvement in polymer product properties.
  • selectivity control agents have been disclosed for possible use in polymerization catalysts.
  • One class of such selectivity control agents is the class of organo-silanes.
  • Hoppin et al U.S. Patent 4,990,478, describe branched C 3 - C 10 alkyl-t- butoxydimethoxysilanes.
  • Other aliphatic silanes are described in Hoppin et al, U.S. Patent 4,829,038. Kioka et al, U.S.
  • Patent 5,028,671 describe a catalyst system which incorporates various alkylalkoxysilanes, such as di-n- octadecyldimethoxysilane and di-n-octadecyldiethoxysilane as selectivity control agents.
  • the invention relates to an improved process for the production of homopolymers or copolymers of ⁇ -olefins that have improved polymer properties.
  • the present invention is a process for the production of polymers using a high activity olefin polymerization catalyst system which comprises (a) a titanium halide-containing procatalyst component obtained by halogenating a magnesium compound of the formula MgR'R", wherein R' and R" are alkoxide groups containing from 1 to 10 carbon atoms with a halogenated tetravalent titanium compound in the presence of a polycarboxylic acid ester electron donor, with or without a halohydrocarbon, (b) an organoaluminum cocatalyst component, and (c) an organosilane selectivity control agent having the general formula:
  • R 1 is linear alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 carbon atoms or aralkyl group of 16 to 36 carbon atoms
  • R 2 and R 3 are, independently, methyl or alkyl groups of 13 to 30 carbon atoms, or hydrocarboxyloxy group of 1 to 6 carbon atoms
  • R 4 is hydrocarbyloxy group of 1 to 6 carbon atoms.
  • a typical procatalyst of the invention is prepared by halogenating a magnesium compound of the formula MgR'R", wherein R' is an alkoxide, aryloxide group or hydrocarbyl carbonate and R" is an alkoxide, hydrocarbyl carbonate, aryloxide group or halogen, with a halogenated tetravalent titanium compound in the presence of a halohydrocarbon and an electron donor.
  • the magnesium compound employed in the preparation of the solid catalyst component contains alkoxide, aryloxide, hydrocarbyl carbonate or halogen.
  • the alkoxide when present, contains from 1 to 10 carbon atoms. Alkoxides containing from 1 to 8 carbon atoms are preferable, with alkoxides of 2 to 4 carbon atoms being more preferable.
  • the aryloxide when present, contains from 6 to 10 carbon atoms, with 6 to 8 carbon atoms being preferred.
  • the hydrocarbyl carbonate when present, contains 1 to 10 carbon atoms. When halogen is present, it is present as bromine, fluorine, iodine or chlorine, with chlorine being preferred.
  • Suitable magnesium compounds are magnesium chloride, magnesium bromide, magnesium fluoride, ethoxy magnesium bromide, isobutoxy magnesium chloride, phenoxy magnesium iodide, cumyloxy magnesium bromide, magnesium diethoxide, magnesium isopropoxide, magnesium ethyl carbonate, ethoxy magnesium, magnesium stearate, magnesium laurate, and naphthoxy magnesium chloride.
  • Especially preferred as the magnesium compounds are magnesium dialkoxides.
  • Preferred magnesium compound is magnesium diethoxide.
  • Halogenation of the magnesium compound with the halogenated tetravalent titanium compound is effected by using an excess of the titanium compound. At least 2 moles of the titanium compound are used per mole of the magnesium compound. Preferably from 4 moles to 100 moles of the titanium compound are used per mole of the magnesium compound, and most preferably from 4 moles to 20 moles of the titanium compound are used per mole of the magnesium compound.
  • Halogenation of the magnesium compound with the halogenated tetravalent titanium compound is effected by contacting the compounds at an elevated temperature in the range from about 60°C to about 150°C, preferably from about 70°C to about 120oC. Usually the reaction is allowed to proceed over a period of 0.1 to 6 hours, preferably from about 0.6 to about 3.5 hours.
  • the halogenated product is a solid material which is isolated from the liquid reaction medium by a suitable separation method, such as conventional filtration.
  • the halogenated tetravalent compound employed to halogenate the magnesium compound contains at least two halogen atoms, and preferably contains four halogen atoms.
  • the halogen atoms are chlorine atoms, bromine atoms, iodine atoms or fluorine atoms.
  • the halogenated tetravalent titanium compound has up to two alkoxy or aryloxy groups. Examples of suitable halogenated tetravalent titanium compounds include diethoxytitanium dibromide, isopropoxytitanium triiodide, dihexoxytitanium dichloride, phenoxytitanium trichloride, titanium tetrachloride and titanium tetrabromide.
  • the preferred halogenated tetravalent titanium compound is titanium tetrachloride.
  • Halogenation of the magnesium compound with the halogenated tetravalent titanium compound is conducted in the presence of a halohydrocarbon and an electron donor with or without a halohydrocarbon.
  • a halohydrocarbon and an electron donor with or without a halohydrocarbon.
  • an inert hydrocarbon diluent or solvent may also be present.
  • Suitable halohydrocarbons include aromatic or aliphatic, including cyclic and alicyclic compounds.
  • the halohydrocarbon contains 1 or 2 halogen atoms, although more may be present if desired. It is preferred that the halogen is, independently, chlorine, bromine or fluorine.
  • Suitable aromatic halohydrocarbons are chlorobenzene, bromobenzene, dichlorobenzene, dichlorodibromobenzene, o-chlorotoluene, chlorotoluene, dichlorotoluene, chloronaphthalene.
  • Chlorobenzene, o- chlorotoluene and dichlorobenzene are the preferred halohydrocarbons, with chlorobenzene and o-chlorotoluene being more preferred.
  • the aliphatic halohydrocarbons which can be employed suitably of 1 to 12 carbon atoms. Preferably such halohydrocarbons of 1 to 9 carbon atoms and at least 2 halogen atoms. Most preferably the halogen is present as chlorine.
  • Suitable aliphatic halohydrocarbons include dibromomethane, trichloromethane, 1,2-dichloroethane, trichloroethane, dichlorofluoroethane, hexachloroethane, trichloropropane, chlorobutane, dichlorobutane, chloropentane, trichlorofluorooctane, tetrachloroisooctane, dibromodi-fluorodecane.
  • the preferred aliphatic halohydrocarbons are carbon tetrachloride and trichloroethane.
  • Aromatic halohydrocarbons are preferred, particularly those of 6 to 12 carbon atoms, and especially those of 6 to 10 carbon atoms.
  • Typical electron donors that are incorporated within the procatalyst include esters, particularly aromatic esters, ethers, particularly aromatic ethers, ketones, phenols, amines, amides, imines, nitriles, phosphines, phosphites, stibines, arsines, phosphoramides and alcoholates.
  • Esters of polycarboxylic acids are the preferred electron donors. Particularly preferred are alkyl esters of aromatic polycarboxylic acid.
  • esters of polycarboxylic acid electron donors are diethyl phthalate, diisoamyl phthalate, ethyl p-ethoxybenzoate, methyl p- ethoxybenzoate, diisobutyl phthalate, dimethyl napthalenedicarboxylate, diisobutyl maleate, diisopropyl terephthalate, and diisoamyl phthalate.
  • Diisobutyl phthalate and ethyl-p-ethoxybenzoate are the preferred alkyl ester of an aromatic carboxylic acid.
  • the solid halogenated product After the solid halogenated product has been separated from the liquid reaction medium, it is treated one or more times with additional halogenated tetravalent titanium compound. Preferably, the halogenated product is treated multiple times with separate portions of the halogenated tetravalent titanium compound. Better results are obtained if the halogenated product is treated twice with separate portions of the halogenated tetravalent titanium compound. If desired, the solid halogenated product is treated one or more times with a mixture of halogenated tetravalent titanium compound and a halohydrocarbon.
  • At least 2 moles of the titanium compound are employed per mole of the magnesium compound, and preferably from 4 moles to 100 moles of the titanium compound are employed per mole of the magnesium compound. Most preferably from 4 moles to 20 moles of the titanium compound per mole of the magnesium compound.
  • the solid halogenated product is treated at least once with one or more acid chlorides during the additional treatments with the halogenated tetravalent titanium compound.
  • Suitable acid chlorides include benzoyl chloride and phthaloyl chloride.
  • the preferred acid chloride is phthaloyl chloride.
  • the solid halogenated product After the solid halogenated product has been treated one or more times with additional halogenated tetravalent titanium compound, it is separated from the liquid reaction medium, washed at least once with an inert hydrocarbon of up to 10 carbon atoms to remove unreacted titanium compounds, and dried.
  • an inert hydrocarbon of up to 10 carbon atoms to remove unreacted titanium compounds, and dried.
  • the inert hydrocarbons that are suitable for the invention are isopentane, isooctane, hexane, heptane and cyclohexane.
  • Preferred final washed products have a titanium content of from 0.5 percent by weight to 6.0 percent by weight.
  • a more preferred final wash product has from 1.5 percent by weight to 4.0 percent by weight.
  • the atomic ratio of titanium to magnesium in the final product is between 0.01:1 and 0.2:1.
  • a preferred final product has an atomic ratio of titanium to magnesium from about 0.02:1 to 0.15:1.
  • the cocatalyst is an organoaluminum compound which is typically an alkylaluminum compound.
  • Suitable alkylaluminum compounds include trialkylaluminum compounds, such as triethylaluminum or triisobutylaluminum; dialkylaluminum halides such as diethylaluminum chloride and dipropylaluminum chloride; and dialkylaluminum alkoxides such as diethylaluminum ethoxide.
  • Trialkylaluminum compounds are preferred, with triethylaluminum being the preferred trialkylaluminum compound.
  • organosilane selectivity control agents in the catalyst system contain at least one silicon-oxygen-carbon linkage.
  • Suitable organosilane compounds include compounds having the following general formula: 4
  • R 1 is a linear alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 carbon atoms or aralkyl group of 16 to 36 carbon atoms. It is preferred that R 1 is alkyl group of 16 to 30 carbon atoms, alkaryl group of 19 to 30 carbon atoms or aralkyl group of 19 to 30 carbon atoms. It is further preferred that R 1 is alkyl group of 18 to 28 carbon atoms.
  • R 2 and R 3 are, independently, methyl or alkyl group of 13 to 30 carbon atoms, or hydrocarbyloxy groups of 1 to 6 carbon atoms.
  • R 2 and R 3 are, independently, methyl or alkyl group of 16 to 30 carbon atoms or alkoxy group of 1 to 4 carbon atoms. It is further preferred that R 2 is methyl or alkyl group of 18 to 28 carbon atoms or alkoxy group of 1 to 4 carbon atoms and R 3 is alkoxy group of 1 to 4 carbon atoms. It is preferred that R 4 is alkoxy group of 1 to 4 carbon atoms. R 4 is hydrocarbyloxy group of 1 to 6 carbon atoms. It is further preferred that R 2 , R 3 and R 4 are ethoxy or methoxy groups.
  • organosilane selectivity control agents include n-octadecyltriethoxysilane, n-triacontyl- triethoxysilane, methyl-n-octadecyldimethoxysilane, methyl-n- octadecyldiethoxysilane, n-octadecyltrimethoxysilane, n- triacontyltrimethoxysilane and mixtures thereof.
  • the preferred organosilane selectivity control agents are n-octadecyltriethoxysilane, n-methyloctadecyldimethoxysilane and n- octadecyltrimethoxysilane.
  • the invention also contemplates the use of mixtures of two or more selectivity control agents.
  • the selectivity control agent is provided in a quantity such that the molar ratio of the selectivity control agent to the titanium present in the procatalyst is from about 0.5 to about 80. Molar ratios from about 2 to about 60 are preferred, with molar ratios from about 5 to about 40 being more preferred.
  • the high activity stereoregular polymerization catalyst is utilized to effect polymerization by contacting at least one ⁇ -olefin under polymerization conditions.
  • the procatalyst component, organoaluminum cocatalyst, and selectivity control agent are introduced into the polymerization reactor separately or, if desired, two or all of the components are partially or completely mixed with each other before they are introduced into the reactor.
  • the particular type of polymerization process utilized is not critical to the operation of the present invention and the polymerization processes now regarded as conventional are suitable in the process of the invention.
  • the polymerization is conducted under polymerization conditions as a liquid phase or a gas-phase process employing a fluidized catalyst bed.
  • reaction diluent an added inert liquid diluent or alternatively a liquid diluent which comprises the olefin, such as propylene or 1-butene, undergoing polymerization. If a copolymer is prepared wherein ethylene is one of the monomers, ethylene is introduced by conventional means to a diluent.
  • Typical polymerization conditions include a reaction temperature from about 25°C to about 125°C, with temperatures from about 35°C to about 90°C being preferred, and a pressure sufficient to maintain the reaction mixture in a liquid phase.
  • Such pressures are from about 150 psi to about 1200 psi, with pressures from about 250 psi to about 900 psi are preferred.
  • the liquid phase reaction is operated in a batchwise manner or as a continuous or semi-continuous process. Subsequent to reaction, the polymer product is recovered by conventional procedures. The precise controls of the polymerization conditions and reaction parameters of the liquid phase process are within the skill of the art.
  • the polymerization is conducted in a gas phase process in the presence of a fluidized catalyst bed.
  • gas phase process polymerization process is described in Goeke et al, U.S. Patent 4,379,759, incorporated herein by reference.
  • the gas phase process typically involves charging to reactor an amount of preformed polymer particles, gaseous monomer and separately charge a lesser amount of each catalyst component.
  • Gaseous monomer, such as propylene, is passed through the bed of solid particles at a high rate under conditions of temperature and pressure sufficient to initiate and maintain polymerization. Unreacted olefin is separated and recovered and polymerized olefin particles are separated at a rate substantially equivalent to its production.
  • the process is conducted in a batchwise manner or a continuous or semicontinuous process with constant or intermittent addition of the catalyst components and/or ⁇ -olefin to the polymerization reactor.
  • Typical polymerization temperatures for a gas phase process are from about 30°C to about 120°C and typical pressures are up to about 1000 psi, with pressures from about 100 to about 500 psi being preferred.
  • molecular hydrogen is added to the reaction mixture as a chain transfer agent to regulate the molecular weight of the polymeric product.
  • Hydrogen is typically employed for this purpose in a manner well known to persons skilled in the art. The precise control of reaction conditions, the rate of addition of feed component and molecular hydrogen is broadly within the skill of the art.
  • the present invention is useful in the polymerization of ⁇ -olefins of up to 20 carbon atoms, such as propylene, dodecane, including mixtures thereof. It is preferred that ⁇ - olefins of 3 carbon atoms to 8 carbon atoms, such as propylene, butene-1 and pentene-1 and hexane-1, are polymerized.
  • the polymers produced according to this invention are predominantly isotactic. Polymer yields are high relative to the amount of catalyst employed.
  • the process of the invention produce homopolymers and copolymers including both random and impact copolymers having a relatively high stiffness while having a broad molecular weight distribution and maintaining an oligomers content (determined by the weight fraction of C 21 oligomer) of less than 300 ppm if a homopolymer and less than 600 ppm if a copolymer.
  • the preferred homopolymers of the invention have an oligomers content of less than 150 ppm is preferred. More preferred homopolymers have oligomers content of less than 80 ppm.
  • a reduction in oligomers content is indicative of a reduction in volatiles, e.g. smoke and/or oil, liberated during subsequent processing, e.g. extrusion.
  • TCTMS n-triacontyltrimethoxysilane
  • MNDDMS methyl-n-decyldimethoxysilane
  • NPTMS n-propyltrimethoxysilane
  • DIBDES diisobutyldiethoxysilane
  • DIBDMS (diisobutyldimethoxysilane)
  • the procatalyst was prepared by adding magnesium diethoxide (2.17 g, 19 mmol) to 55 ml of a 50/50 (vol/vol) mixture of TiCl 4 /chlorobenzene. After adding diisobutyl phthalate (0.74 ml, 2.75 mmol), the mixture was heated in an oil bath and stirred at 110°C for 60 minutes. The mixture was filtered hot and the solid portion was slurried in 55 ml of a 50/50 (vol/vol) mixture of TiCl 4 /chlorobenzene.
  • phthaloyl chloride (0.13 ml, 0.90 mmol) was added to the slurry at room temperature.
  • the resulting slurry was stirred at 110°C for 60 minutes, filtered, and the solvent obtained was slurried again in a fresh 50/50 mixture of TiCl 4 /chlorobenzene. After stirring at 110°C for 30 minutes, the mixture was filtered and allowed to cool to room temperature.
  • the procatalyst slurry was washed 6 times with 125 ml portions of isooctane and then dried for 120 minutes, at 25°C, under nitrogen.
  • the amount of silane utilized in the polymerization also varied.
  • the amount of triethylaluminum (0.70 mmoles) and. the amount of the procatalyst slurry (sufficient quantity of procatalyst to provide 0.01 mmoles of titanium) remained constant.
  • the autoclave was then heated to about 67oC and the polymerization was continued at 67°C for one hour.
  • the polypropylene product was recovered from the resulting mixture by conventional methods and the weight of the product was used to calculate the reaction yield in millions of grams of polymer product per gram (MMg/g) of titanium in the procatalyst.
  • the term "Q” was calculated as the quotient of the weight average molecular weight (M w ) and the number average molecular weight (M n ) determined by gel permeation chromatography.
  • M z as defined in "Encyclopedia of Polymer Science and Engineering, 2nd Edition", Vol. 10, pp. 1-19 (1987), incorporated herein by reference, is the z-average molecular weight.
  • R was calculated as the quotient of M z and M w .
  • Melt Flow is determined according to ASTM D-1238-73, condition L.
  • Viscosity Ratiof was determined by cone and plate rheometry (dynamic viscosity measurements) as a ratio of the viscosity of the product at a frequency of 0.1 Hz divided by the viscosity of the product at a frequency of 1.0 Hz. As the viscosity ratio of polymer product increases, the molecular weight distribution increases.
  • the procatalyst was prepared by adding magnesium diethoxide (50 mmol) to 150 ml of a 50/50 (vol/vol) mixture of chlorobenzene/TiCl 4 . After adding ethyl benzoate (16.7 mmol), the mixture was heated in an oil bath and stirred at 110°C for approximately 60 minutes. The resulting slurry was filtered and slurried twice with 150 ml of a fresh 50/50 (vol/vol). Benzoyl chloride (0.4 ml) was added to the final slurry. After stirring at 110°C for approximately 30 minutes, the mixture was filtered. The slurry was washed six times with 150 ml portions of isopentane and then dried for 90 minutes, at 30°C, under nitrogen.
  • propylene was polymerized as, described in Illustrative Embodiment I, section (b), except the selectivity control agent was PEEB.
  • polymer products having a melt flow of about 3.0 dg/min were produced according to the procedures described in Illustrative Embodiment I and the Comparative Example.
  • the polymer products were produced using 0.2 mmol of the specified selectivity control agent ("SCA") and sufficient hydrogen necessary to produce a polymer having a melt flow of about 3.0 dg/min.
  • SCA specified selectivity control agent
  • the catalyst systems of the invention exhibit increased hydrogen utilization efficiency.
  • Viscosity ratio values were taken for the polymers having a melt flow of about 3 dg/min. The values are shown in TABLE III.
  • the catalyst systems of the invention exhibit a higher viscosity ratio and therefore a broader molecular weight distribution than conventional catalyst systems using NPTMS as the selectivity control agent.

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Abstract

Un procédé de polymérisation d'une ou plusieurs α-oléfines possédant jusqu'à 20 atomes de carbone consiste à mettre en contact cette ou ces α-oléfines dans des conditions de polymérisation à l'aide d'un système catalyseur comprenant: (a) un composant pro-catalyseur contenant du magnésium et contenant de l'halogénure de titane; on obtient ce composant en mettant en contact un composé de magnésium de la formule MgR'R', dans laquelle R' et R' représentent, indépendamment, le groupe alcoxyde, le groupe aryloxyde ou halogène, avec un composé de titane tétravalent, halogéné en présence d'un donneur d'électrons d'ester d'acide polycarboxylique avec ou sans halohydrocarbure; (b) un composant co-catalyseur d'organo-aluminum; et (c) un agent de régulation sélective d'organosilane représenté par la formule générale (i) dans laquelle R1 représente un groupe alkyle de 13 à 30 atomes de carbone, un groupe alkaryle de 16 à 36 atomes de carbone ou un groupe aralkyle de 16 à 36 atomes de carbone; R2 et R3 représentent, indépendamment, un groupe méthyle ou alkyle de 13 à 30 atomes de carbone ou un groupe hydrocarbyloxy de 1 à 6 atomes de carbone; et R4 représente un groupe hydrocarbyloxy de 1 à 6 atomes de carbone. Grâce à ce procédé, on obtient une productivité catalytique élevée et des produits polymères qui ont une large répartition de masse moléculaire tout en conservant des propriétés de faible teneur en oligomères.
PCT/US1993/010653 1992-11-06 1993-11-05 Procede de polymerisation d'alpha-olefines Ceased WO1994011409A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU54583/94A AU5458394A (en) 1992-11-06 1993-11-05 Process for polymerizing alpha-olefin
EP93925170A EP0667875A1 (fr) 1992-11-06 1993-11-05 Procede de polymerisation d'alpha-olefines
BR9307390-9A BR9307390A (pt) 1992-11-06 1993-11-05 Processo para polimerização de alfa-olefina
KR1019950701794A KR950704372A (ko) 1992-11-06 1993-11-05 알파-올레핀의 중합 방법(process for polymerizing alpha-olefin)
CA002148596A CA2148596A1 (fr) 1992-11-06 1993-11-05 Methode de polymerisation d'alpha-olefines

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US972,402 1992-11-06

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CA (1) CA2148596A1 (fr)
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US6841502B2 (en) 2002-04-24 2005-01-11 Symyx Technologies, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
EP1270604A4 (fr) * 2000-09-29 2005-02-09 Toho Titanium Co Ltd Catalyseur de polymerisation d'olefines
US7060848B2 (en) 2002-04-24 2006-06-13 Symyx Technologies, Inc. Bridged bi-aromatic catalysts, complexes, and methods of using the same
US7091292B2 (en) 2002-04-24 2006-08-15 Symyx Technologies, Inc. Bridged bi-aromatic catalysts, complexes, and methods of using the same
WO2008142130A1 (fr) * 2007-05-22 2008-11-27 Borealis Technology Oy Système de catalyseur pour des copolymères de polypropylène
WO2011047967A1 (fr) * 2009-10-22 2011-04-28 Basell Polyolefine Gmbh Composants de catalyseurs pour la polymérisation des oléfines et catalyseurs obtenus à partir de ceux-ci

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AU706739B2 (en) * 1994-05-12 1999-06-24 Showa Denko Kabushiki Kaisha A method for the production of propylene-based polymers, catalyst component or polymerization and method for its production
CN1955195B (zh) * 2005-10-26 2010-06-16 中国石油化工股份有限公司 用于烯烃聚合或共聚合的催化剂、制备方法及应用
CN102898556B (zh) * 2011-07-26 2015-06-17 中国石油化工股份有限公司 一种催化剂组分在烯烃聚合中的应用
CN102898558B (zh) * 2011-07-26 2015-06-17 中国石油化工股份有限公司 一种催化剂组分在烯烃聚合中的应用
CN102898555B (zh) * 2011-07-26 2015-06-17 中国石油化工股份有限公司 一种催化剂组分在烯烃聚合中的应用
CN102898557B (zh) * 2011-07-26 2015-06-17 中国石油化工股份有限公司 一种催化剂组分在烯烃聚合中的应用

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EP0455313A1 (fr) * 1987-03-13 1991-11-06 Mitsui Petrochemical Industries, Ltd. Procédé de polymérisation d'oléfines et catalyseur de polymérisation

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EP1270604A4 (fr) * 2000-09-29 2005-02-09 Toho Titanium Co Ltd Catalyseur de polymerisation d'olefines
US7091292B2 (en) 2002-04-24 2006-08-15 Symyx Technologies, Inc. Bridged bi-aromatic catalysts, complexes, and methods of using the same
US6869904B2 (en) 2002-04-24 2005-03-22 Symyx Technologies, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
US6897276B2 (en) 2002-04-24 2005-05-24 Symyx Technologies, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
US7030256B2 (en) 2002-04-24 2006-04-18 Symyx Technologies, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
US7060848B2 (en) 2002-04-24 2006-06-13 Symyx Technologies, Inc. Bridged bi-aromatic catalysts, complexes, and methods of using the same
US6841502B2 (en) 2002-04-24 2005-01-11 Symyx Technologies, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
US7126031B2 (en) 2002-04-24 2006-10-24 Symyx Technologies, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
US7241714B2 (en) 2002-04-24 2007-07-10 Symyx Technologies, Inc. Bridged bi-aromatic catalysts, complexes, and methods of using the same
US7241715B2 (en) 2002-04-24 2007-07-10 Symyx Technologies, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
US7659415B2 (en) 2002-04-24 2010-02-09 Symyx Solutions, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
WO2008142130A1 (fr) * 2007-05-22 2008-11-27 Borealis Technology Oy Système de catalyseur pour des copolymères de polypropylène
RU2436800C2 (ru) * 2007-05-22 2011-12-20 Бореалис Текнолоджи Ой Каталитическая система для получения полипропиленовых сополимеров
WO2011047967A1 (fr) * 2009-10-22 2011-04-28 Basell Polyolefine Gmbh Composants de catalyseurs pour la polymérisation des oléfines et catalyseurs obtenus à partir de ceux-ci

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KR950704372A (ko) 1995-11-20
EP0667875A1 (fr) 1995-08-23
AU5458394A (en) 1994-06-08
CA2148596A1 (fr) 1994-05-26
MX9306919A (es) 1995-01-31
CN1092431A (zh) 1994-09-21
BR9307390A (pt) 1999-08-31

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