WO2019094942A1 - Composition polymère de polyoléfine - Google Patents

Composition polymère de polyoléfine Download PDF

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Publication number
WO2019094942A1
WO2019094942A1 PCT/US2018/060768 US2018060768W WO2019094942A1 WO 2019094942 A1 WO2019094942 A1 WO 2019094942A1 US 2018060768 W US2018060768 W US 2018060768W WO 2019094942 A1 WO2019094942 A1 WO 2019094942A1
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Prior art keywords
compound
polymer
propylene
catalyst component
polymer composition
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PCT/US2018/060768
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English (en)
Inventor
Vladimir P. Marin
Jan Van Egmond
Ahmed HINTOLAY
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W.R. Grace & Co.-Conn.
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Priority claimed from PCT/US2018/057980 external-priority patent/WO2019094216A1/fr
Application filed by W.R. Grace & Co.-Conn. filed Critical W.R. Grace & Co.-Conn.
Priority to CN201880081336.1A priority Critical patent/CN111479871A/zh
Priority to CA3082119A priority patent/CA3082119C/fr
Priority to JP2020544377A priority patent/JP7223017B2/ja
Priority to US16/762,353 priority patent/US11421056B2/en
Priority to KR1020207016270A priority patent/KR102660279B1/ko
Priority to EP18875540.9A priority patent/EP3710527A4/fr
Priority to RU2020119468A priority patent/RU2800539C2/ru
Publication of WO2019094942A1 publication Critical patent/WO2019094942A1/fr
Priority to SA520411959A priority patent/SA520411959B1/ar

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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0204—Ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0209—Esters of carboxylic or carbonic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0212—Alkoxylates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
    • B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • Polyolefins are a class of polymers derived from simple olefins.
  • Known methods of making polyolefins involve the use of Ziegler-Natta polymerization catalysts. These catalysts polymerize olefin monomers using a transition metal halide to provide a polymer with various types of stereochemical configurations.
  • Ziegler-Natta catalyst system comprises a solid catalyst component, constituted by a magnesium halide on which are supported a titanium compound and an internal electron donor compound.
  • internal electron donor compounds can be added during catalyst synthesis.
  • the internal donor can be of various types.
  • Catalyst morphology control is an important aspect of industrial polyolefin plant operation. Catalyst morphology characteristics influence polymer powder properties such as the bulk density, flowability, degassing and particle adhesion. Such properties greatly influence plant operation efficiency.
  • catalyst lifetime or the ability of a catalyst to remain active over prolonged periods of time can also be important in producing polymers with desired characteristics. Catalysts with extended lifetime, for instance, can produce polyolefin polymers and especially impact resistant polyolefin copolymers with improved and more controlled properties.
  • great advances have been made in polyolefin polymerization processes and in formulating new catalyst systems, further improvements are needed. For instance, a need exist for a polymerization process for producing polyolefin polymers with improved polymer flowability and handling.
  • polymer flowability issues are particularly prevalent when producing impact resistant polyolefin polymers that have elastomeric properties.
  • SUMMARY [0008] In general, the present disclosure is directed to producing polyolefin polymers having improved flowability properties that are easier to handle and transport.
  • Polyolefin polymers with improved flow properties for instance, can be produced utilizing a catalyst system that not only has a prolonged and extended lifetime but can also produce polyolefin polymers having improved morphology characteristics that translate into a polymer resin that has better fluid-like properties and is easier to handle. Through the process of the present disclosure, the efficiency of the polymer production process is greatly improved.
  • the present disclosure is directed to a polymer composition
  • a polymer composition comprising a propylene-ethylene copolymer that is in the form of particles.
  • the propylene-ethylene copolymer includes propylene as a primary monomer and contains ethylene in an amount greater than about 5% by weight, such as in an amount greater than about 8% by weight, such as in an amount greater than about 10% by weight, and generally in an amount less than about 45% by weight.
  • the propylene-ethylene copolymer for instance, can be a heterophasic polymer and/or can have elastomeric properties.
  • the propylene-ethylene copolymer particles can be formulated so as to have improved flow properties such that the copolymer displays a Cup Test result of less than about 10 seconds.
  • the copolymer can display a Cup Test Index of 2 or less.
  • the propylene-ethylene copolymer can generally have a melt flow index of greater than about 10 g/10 min, such as greater than about 20 g/10 min, such as greater than about 30 g/10 min, such as greater than about 40 g/10 min, such as greater than about 50 g/10 min and generally less than about 500 g/10 min.
  • the present disclosure is directed to a polymer composition containing a polyolefin polymer, such as a polypropylene polymer.
  • the polypropylene polymer is in the form of particles.
  • the particles can have a D50 particle size of from about 150 microns to about 3000 microns, such as from about 450 microns to about 1000 microns.
  • the particles have a particle morphology such that the particles have a B/L3 of greater than about 0.6, such as greater than about 0.68, such as greater than about 0.7, such as greater than about 0.8 and generally less than about 1.
  • the polymer composition can have a relatively high bulk density.
  • the bulk density can be greater than about 0.415 g/cm 3 , such as from about 0.42 g/cm 3 to about 0.6 g/cm 3.
  • the polymer particles can have a rounded shape and can be devoid of agglomerates. In one embodiment, for instance, the polymer particles may comprise microspheres.
  • Polyolefin polymers as described above, such as propylene-ethylene copolymers and other polypropylene polymers can be formed using various processes. In one embodiment, for instance, the polyolefin polymer is produced in the presence of a catalyst system that includes a solid catalyst component combined with an aluminum compound, at least one selectivity control agent, and optionally an activity limiting agent.
  • the solid catalyst component comprises a reaction product of a magnesium compound with an epoxy compound.
  • the solid catalyst component can further include an organic phosphorous compound, a titanium compound, an organosilicon compound, and an internal electron donor.
  • the solid catalyst component can further include a supportive donor.
  • the supportive donor comprises ethyl benzoate, while the internal electron donor comprises an aryl diester.
  • the solid catalyst component in one embodiment, comprises: a magnesium compound including a halide-containing magnesium compound and a reaction product of a magnesium compound with an epoxy compound; an organic phosphorus compound; a titanium compound; an organosilicon compound containing: Si-O, or O-Si-O groups; an internal electron donor, the internal electron donor comprising an aryl diester, a 1,2-phenylene dibenzoate, a diether, a succinate, an organic acid ester, a polycarboxylic acid ester, a polyhydroxy ester, a heterocyclic polycarboxylic acid ester, an inorganic acid ester, an alicyclic polycarboxylic acid ester, a hydroxy- substituted carboxylic acid ester compound having 2 to 30 carbon atoms, or a compound having at least one ether group and at least one ketone group, or mixtures thereof; wherein the solid catalyst component is free of side reaction products between a carboxylic acid or an anhydride thereof and a magnesium compound or a
  • a catalyst system for use in olefinic polymerization comprising the solid catalyst component produced by the process of any of the above processes, an organoaluminum compound, and optionally, an organosilicon compound.
  • the organoaluminum compound may be an alkyl-aluminum compound.
  • the alkyl-aluminum compound may be a trialkyl aluminum compound such as triethylaluminum, triisobutylaluminum, or tri-n-octylaluminum.
  • a process is provided for polymerizing or
  • FIG.1 shows a microscopic view of the polymer produced with the catalyst component of Example 5 (Comparative).
  • FIG.2 shows a microscopic view of the polymer produced with the catalyst component of Example 7.
  • FIG.3 shows a microscopic view of the polymer produced with the catalyst component of Example 9.
  • FIG.4 shows a microscopic view of the polymer produced with the catalyst component of Example 11.
  • FIG.5 shows a microscopic view of the polymer produced with the catalyst component of Example 13 (Comparative).
  • FIG.6 shows a microscopic view of the polymer produced with the catalyst component of Example 23.
  • FIG.7 shows a microscopic view of the polymer produced with the catalyst component of Example 34.
  • the present disclosure is directed to polyolefin polymers having improved flow properties.
  • the polyolefin polymers can be produced in the form of particles that have fluid-like properties that provide various advantages and benefits.
  • polystyrene resins are produced having improved flow properties by, in one embodiment, carefully controlling the particle morphology during polymerization.
  • the flow properties of the polyolefin polymer can be improved by utilizing a catalyst with an extended catalytic lifetime. Utilizing a catalyst with extended and robust activity has been found to produce polyolefin polymers, particularly polypropylene random copolymers, that have a particle construction that prevents the particles from agglomerating or otherwise sticking together for providing the polymer resin with dramatically improved flow properties.
  • the polyolefin particles of the present disclosure are formed in the presence of a Ziegler-Natta catalyst formed from a magnesium compound, a titanium compound, epoxy, and one or more internal electron donors and/or supportive donors.
  • a polypropylene polymer is formed in accordance with the present disclosure having a controlled particle morphology.
  • the polypropylene particles can be formed having a more rounded or spherical shape in conjunction with a relatively high bulk density that improves the polymer production process and dramatically improves polymer flowability.
  • the polypropylene polymer particles have a D50 particle size of greater than about 400 microns, such as greater than about 500 microns, such as greater than about 600 microns, such as greater than about 700 microns, and generally less than about 1500 microns, such as less than about 1200 microns, such as less than about 1000 microns.
  • the polymer particles can have a rounded shape.
  • the particle morphology is such that the particles have an aspect ratio, such as a B/L3 value of greater than about 0.6, such as greater than about 0.68, such as greater than about 0.7, such as greater than about 0.75, such as greater than about 0.8, and generally less than about 1.
  • the polymer particles can be devoid of agglomerations and can have a substantially spherical shape. In one embodiment, for instance, the polymer particles form microspheres. [0033] In addition to having a rounded shape, the polymer particles can also have a relatively high bulk density.
  • the bulk density of the particles can be greater than about 0.415 g/cm 3 .
  • the bulk density of the polymer particles can be greater than about 0.42 g/cm 3 , such as greater than about 0.44 g/cm 3 , such as greater than about 0.46 g/cm 3 , such as greater than about 0.48 g/cm 3 .
  • the bulk density is generally less than about 0.6 g/cm 3 .
  • the polymer can comprise a homopolymer or copolymer.
  • the copolymer for instance, may comprise a propylene-ethylene random copolymer.
  • the polymer particles are formed in a polymerization process using a catalyst that has a rounded shape and improved morphology.
  • the flowability of elastomeric polypropylene copolymers can be improved using the same or similar catalyst.
  • the propylene random copolymer can be formed using multiple reactors, such as at least two different reactors in order to produce a copolymer having elastomeric properties.
  • the polypropylene random copolymer can be produced that not only easily transfers from a first reactor to a second reactor, but can also be easily handled and removed from the final reactor due to the improvement in flowability.
  • the polypropylene random copolymer may comprise a propylene-ethylene copolymer containing ethylene in an amount greater than about 3% by weight, such as greater than about 5% by weight, such as in an amount greater than about 8% by weight, such as in an amount greater than about 10% by weight, and generally in an amount less than about 45% by weight.
  • the propylene-ethylene random copolymer can be a heterophasic polymer that has elastomeric properties. Such polymers have excellent impact strength resistance but tend to have rather adverse flowability characteristics.
  • Propylene-ethylene copolymers made in accordance with the present disclosure can have flow properties such that the copolymer exhibits a Cup Test result of less than about 10 seconds, such as less than about 9 seconds, such as less than about 8 seconds.
  • the propylene-ethylene copolymer can display a Cup Test Index of 2 or less.
  • the Cup Test is a method that measures powder flowability, especially of high rubber content polypropylene copolymer powders.
  • the propylene-ethylene copolymer can have a melt flow rate of from about 1 g/10 min to about 1000 g/10 min.
  • the copolymer can have a melt flow rate of greater than about 10 g/10 min, such as greater than about 20 g/10 min, such as greater than about 30 g/10 min, such as greater than about 40 g/10 min, such as greater than about 50 g/10 min.
  • the melt flow rate is generally less than about 500 g/10 min, such as less than about 400 g/10 min, such as less than about 300 g/10 min, such as less than about 200 g/10 min.
  • the melt flow rate can be from about 50 g/10 min to about 150 g/10 min.
  • Embodiments of Catalyst Systems Used to Produce Polyolefin Polymers [0038] Described herein are Ziegler-Natta catalyst systems and supports for Ziegler-Natta catalysts and methods of making the same.
  • One aspect of the catalyst systems is a solid catalyst component containing a halide-containing magnesium compound and titanium compound for polymerizing an olefin, where the solid catalyst component has substantially spherical or spheroidal shape.
  • the solid catalyst component can be used to form a competent Ziegler-Natta catalyst in combination with one or more external and/or internal electron donors and an organoaluminum compound.
  • solid catalyst component refers to a pre-catalyst containing a halide-containing magnesium compound and titanium compound, and optionally one or more internal electron donors that are useful for forming a competent Ziegler-Natta catalyst system upon combination with a main group metal alkyl.
  • a solid catalyst component, an electron donor, and an organoaluminum compound (a main group metal alkyl) form a slurry catalyst system, which can contain any suitable liquid such as an inert hydrocarbon medium.
  • inert hydrocarbon media examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof.
  • the slurry medium can be hexane, heptane or mineral oil.
  • the slurry medium can be different from the diluent used in forming the mixture from which the solid catalyst component is precipitated.
  • the herein described solid catalyst supports can be utilized in any suitable Ziegler-Natta polymerization catalyst system.
  • Ziegler-Natta catalyst systems include a reagent or combination of reagents that are functional to catalyze the polymerization of 1-alkenes ( ⁇ -olefins) to form polymers, typically with high isotacticity, when pro- chiral 1-alkenes are polymerized.
  • the term“Ziegler-Natta catalyst” refers to any composition having a transition metal and a main group metal alkyl component capable of supporting catalysis of 1-alkene polymerization.
  • the transition metal component is typically a Group IV metal such as titanium, or vanadium
  • the main group metal alkyl is typically an organoaluminum compound having a carbon-Al bond
  • the electron donor can be any of numerous compounds including aromatic esters, alkoxysilanes, amines and ketones can be used as external donors added to the transition metal component and the main group metal alkyl component or an appropriate internal donor added to the transition metal component and the main group metal alkyl component during synthesis of those components.
  • Described herein are methods of making a solid catalyst component for use in a Ziegler-Natta catalyst, and the methods and catalysts are free of carboxylic acid or anhydrides.
  • the catalysts By being free of the carboxylic acids and/or anhydrides, the catalysts provide high activity due to absence of side products of the reaction between the carboxylic acid and/or anhydride with the magnesium compounds and TiCl 4 , that may otherwise result in the deactivation of active centers in polymerization process.
  • the catalyst/support morphology is a key factor to consider in any commercial polymer production process.
  • To control the catalyst/support morphology variable techniques and processes are used.
  • One such technique is to use a surfactant during the support formation.
  • Surfactants are compounds that lower the surface tension (or interfacial tension) between two liquids or between a liquid and a solid. Surfactants are usually polar organic compounds, and they can be removed from the solid catalyst or can partly stay on the catalyst surface.
  • a process for preparing a solid catalyst component for the production of a polyolefin, such as a polypropylene.
  • the processes include dissolving a halide-containing magnesium compound in a mixture, where the mixture includes epoxy compound, an organic phosphorus compound, and a first hydrocarbon solvent to form a homogenous solution.
  • the homogenous solution is then treated with a first titanium compound in the presence of an organosilicon compound and optionally with a non-phthalate electron donor and/or supportive donor, and, to form a solid precipitate.
  • the solid precipitate is then treated with a second titanium compound in the presence of a non-phthalate electron donor to form the solid catalyst component.
  • the process is to be conducted free of carboxylic acids and anhydrides. Additionally, the dissolving and treating of the homogeneous solution may be performed sequentially or simultaneously.
  • the first and second titanium compounds are, independently, represented as: Ti(OR) g X 4-g where each R is independently a C 1 -C 4 alkyl; X is Br, Cl, or I; and g is 0, 1, 2, 3, or 4.
  • the halide-containing magnesium compound, epoxy compound, and organic phosphorus compound are reacted in the presence of a hydrocarbon solvent.
  • the hydrocarbon solvent can include aromatic or non-aromatic solvents or combinations thereof.
  • the aromatic hydrocarbon solvent is selected from toluene and C2-C20 alkylbenzene.
  • the nonaromatic hydrocarbon solvent is selected from hexane and heptane.
  • the hydrocarbon solvent is a mixture of toluene and hexane.
  • the hydrocarbon solvent is a mixture of ethylbenzene and heptane.
  • a ratio of the non-aromatic solvent to the aromatic solvent is from 10:90 to 90:10 wt% or 30:70 to 70:30 wt% or 40:60 to 65:35 wt% or 50:50 to 45:55 wt%.
  • the halide-containing magnesium compound, epoxy compound, and organic phosphorus compound are reacted in the presence of an organic solvent at a first temperature from about 25 to about 100°C to form a homogenous solution.
  • the first temperature is from about 40 to about 90°C or from about 50 to about 70°C.
  • the molar ratio of the magnesium compound to alkylepoxide is from about 0.1:2 to about 2:0.1 or about 1:0.25 to about 1:4 or about 1:0.9 to about 1:2.2.
  • the molar ratio of the magnesium compound to the Lewis base is from about 1:0.1 to about 1:4 or 0.5:1 to 2.0:1 or 1:0.7 to 1:1.
  • the process for preparing the solid catalyst component may also include addition of an organosilicon compound during, or after, the dissolution of the magnesium compound (Mg-compound) in the organic solvent, along with the epoxy compound.
  • the organosilicon compound may be a silane, a siloxane, or a
  • the organosilicon compound in some embodiments, may be represented as Formula (II): R n Si(OR’) 4-n (II).
  • each R may be H, alkyl, or aryl; each R’ may be H, alkyl, aryl, or -SiR n’ (OR’) 3-n , where n is 0, 1, 2, or 3.
  • the organosilicon is a monomeric or polymeric compound.
  • the organosilicon compound may contain -Si-O-Si- groups inside of one molecule or between others.
  • an organosilicon compound examples include polydialkylsiloxane and/or tetraalkoxysilane. Such compounds may be used individually or as a combination thereof.
  • the organosilicon compound may be used in combination with aluminum alkoxides and a first internal donor.
  • polydimethylsiloxane and/or tetraethoxysilane may be used.
  • the aluminum alkoxide referred to above may be of formula Al(OR’) 3 where each R’ is individually a hydrocarbon with up to 20 carbon atoms.
  • each R’ is individually methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec- butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, etc.
  • the organosilicon compound reacts with the aluminum oxide during the catalyst component preparation, thereby forming compounds containing Al-O-Si-O linkages. Therefore, these compounds can be prepared before the catalyst component synthesis and added directly to the process.
  • the organosilicon compound helps to precipitate the solid catalyst component from the solution. It is believed that the Si-O groups from the
  • organosilicon compound coordinate to Mg atoms of the Mg-compound during the precipitation of solid catalyst component, thereby leading to a desired catalyst component morphology.
  • This type of coordination is usually weak. Therefore, during the treatment of the solid catalyst component with the second Ti-compound and the second non-phthalate internal donor, they displace the organosilicon compound from the Mg compound, providing the high activity catalyst component.
  • the precipitation of the solid catalyst component using Mg compounds in an epoxy medium containing anhydrides or organic acids result in the certain side products containing derivatives formed by interaction of epoxy compounds with anhydrides or organic acids. These derivatives contain carbonyl groups coordinated strongly to Mg- atom and can be present on the final catalyst component, and lead to deactivation the catalyst active centers.
  • the above catalyst systems which are free of organic acids and/or anhydrides, address these deficiencies of the earlier systems.
  • the halide-containing magnesium compound in the homogenous solution is treated with a titanium halide compound to form a solid precipitate.
  • the solution can be heated and a surface modifier can be added to control phase morphology.
  • a non-phthalate electron donor is added.
  • the electron donor changes the viscosity and polarity of the solution that effects on the morphology precipitated particles, in particular, particle size, particle shape and particle density.
  • the process is carried out in the presence of non-phthalate donors.
  • a supportive donor is used that may also be referred to as the first non-phthalate donor.
  • the supportive donor or first non-phthalate donor may be a diether, succinate, diester, oxygen-containing electron donor such as an organic ester, polyester, polyhydroxy ester, heterocyclic polyester, inorganic esters, alicyclic polyester, and hydroxy-substituted esters having 2 to about 30 carbon atoms.
  • Illustrative first non-phthalate donors or supportive donors include methyl formate; ethyl acetate; vinyl acetate; propyl acetate; octyl acetate; cyclohexyl acetate; ethyl propionate; methyl butyrate; ethyl valerate; ethyl stearate; methyl chloroacetate; ethyl dichloroacetate; methyl methacrylate; ethyl crotonate; dibutyl maleate; diethyl butylmalonate; diethyl dibutylmalonate; ethyl cyclohexanecarboxylate; diethyl 1,2- cyclohexanedicarboxylate; di-2-ethylhexyl 1,2-cyclohexanedicarboxylate; methyl benzoate; ethyl benzoate; propyl benzoate; butyl benzoate; butyl
  • diphenyldiethoxysilane diethyl 1,2-cyclohexanecarboxylate; diisobutyl 1,2- cyclohexanecarboxylate; diethyl tetrahydrophthalate and nadic acid; diethyl ester; diethyl naphthalenedicarboxylate; dibutyl naphthlenedicarboxylate; triethyl trimellitate and dibutyl trimellitate; 3,4-furanedicarboxylic acid esters; 1,2- diacetoxybenzene; 1-methyl-2,3-diacetoxybenzene; 2-methyl-2,3-diacetoxybenzene; 2,8-diacetoxynaphthalene; ethylene glycol dipivalate; butanediol pivalate;
  • the first non-phthalate donor is methyl formate, butyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, isobutyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl p-me
  • a catalyst component with different morphology i.e. granular and/or spherical.
  • a catalyst component with granular support may be produced using mono-ester as a first internal donor with an aromatic or hydrocarbon solvent, while spherical type catalyst components may be produced using two or three different internal donors (e.g. mono-ester, dialkyl ether and acrylates) in a mixture of two solvents (aromatic and hydrocarbons).
  • a supportive donor or first internal electron donor is used in conjunction with a second non-phthalate electron donor.
  • Second non- phthalate electron donors may include compounds that are different from the first non-phthalate electron donor and is a compound that is a diether, succinate, oxygen- containing electron donors such as organic ester, polyester, polyhydroxy ester, heterocyclic polyester, inorganic esters, alicyclic polyester, and hydroxy-substituted esters having 2 to about 30 carbon atoms, or a compounding having at least one ether group and at least one ketone group.
  • the second non-phthalate donor is selected from the group consisting of linear of cyclic diethers, and non- phthalate aromatic diesters.
  • the second internal electron donor may be a dibenzoate, a dialkylate, and/or diarylate.
  • Additional illustrative second non-phthalate electron donors may include, alone or in combination with any of the above, compounds represented by the following formulas:
  • each of R 1 through R 34 is independently H, F, Cl, Br, I, OR 33 , alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; q is an integer from 0 to 12, wherein R 33 is a alkyl or heteroalkyl.
  • Other non-phthalate donors may also include those as listed as internal electron donors in U.S.9,045,570, incorporated by reference herein.
  • Examples of the halide-containing magnesium compounds include magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride. In one embodiment, the halide-containing magnesium compound is magnesium chloride.
  • Illustrative of the epoxy compounds include, but are not limited to, glycidyl-containing compounds of the Formula:
  • the alkylepoxide is epichlorohydrin.
  • the epoxy compound is a haloalkylepoxide or a nonhaloalkylepoxide.
  • the epoxy compound is selected from the group consisting of ethylene oxide; propylene oxide; 1,2-epoxybutane; 2,3- epoxybutane; 1,2-epoxyhexane; 1,2-epoxyoctane; 1,2-epoxydecane; 1,2- epoxydodecane; 1,2-epoxytetradecane; 1,2-epoxyhexadecane; 1,2-epoxyoctadecane; 7,8-epoxy-2-methyloctadecane; 2-vinyl oxirane; 2-methyl-2-vinyl oxirane; 1,2-epoxy- 5-hexene; 1,2-epoxy-7-octene; 1-phenyl-2,3-epoxypropane; 1-(1-naphthyl)-2,3- epoxypropane; 1-cyclohexyl-3,4-epoxybutane; 1,3-butadiene dioxide; 1,2,7,8- diep
  • glycidyl 4-methoxyphenyl ether glycidyl 2-phenylphenyl ether; glycidyl 1-naphthyl ether; glycidyl 2-phenylphenyl ether; glycidyl 1-naphthyl ether; glycidyl 4-indolyl ether; glycidyl N-methyl- ⁇ -quinolon-4-yl ether; ethyleneglycol diglycidyl ether; 1,4- butanediol diglycidyl ether; 1,2-diglycidyloxybenzene; 2,2-bis(4- glycidyloxyphenyl)propane; tris(4-glycidyloxyphenyl)methane;
  • poly(oxypropylene)triol triglycidyl ether a glycidic ether of phenol novolac; 1,2- epoxy-4-methoxycyclohexane; 2,3-epoxy-5,6-dimethoxybicyclo[2.2.1]heptane; 4- methoxystyrene oxide; 1-(1,2-epoxybutyl)-2-phenoxybenzene; glycidyl formate; glycidyl acetate; 2,3-epoxybutyl acetate; glycidyl butyrate; glycidyl benzoate;
  • R 1 , R 2 , and R 3 are each independently selected from the group consisting of methyl, ethyl, and linear or branched (C 3 -C 10 ) alkyl groups.
  • the trialkyl phosphate acid ester is tributyl phosphate acid ester.
  • the aromatic hydrocarbon solvent is selected from toluene and C 2 -C 20 alkylbenzene.
  • the nonaromatic hydrocarbon solvent is selected from hexane and heptane.
  • the hydrocarbon solvent is a mixture of toluene and hexane.
  • the hydrocarbon solvent is a mixture of ethylbenzene and heptane.
  • a ratio of the non-aromatic solvent to the aromatic solvent is from 10:90 to 90:10 wt% or 30:70 to 70:30 wt% or 40:60 to 65:35 wt% or 50:50 to 45:55 wt%.
  • the halide-containing magnesium compound, epoxy compound, and organic phosphorus compound are contacted in the presence of an organic solvent at a first temperature from about 25 to about 100°C to form a homogenous solution.
  • the first temperature is from about 40 to about 90°C or from about 50 to about 70°C.
  • the molar ratio of the magnesium compound to alkylepoxide is from about 0.1:2 to about 2:0.1 or about 1:0.25 to about 1:4 or about 1:0.9 to about 1:2.2.
  • the molar ratio of the magnesium compound to the Lewis base is from about 1:0.1 to about 1:4 or 0.5:1 to 2.0:1 or 1:0.7 to 1:1.
  • the homogenous solution can be optionally treated with a halogenating agent.
  • the halogenating agent can be an organic or inorganic compound containing at least one halogen atom that can be transferrable to a magnesium atom.
  • the halogenating agent contains chlorine.
  • the halogenating agent is selected from arynoyl chlorides, alkanoyl chlorides, and alkyl chlorides.
  • the halogenating agent is selected from benzoyl chloride, furoyl chloride, acetyl chloride, linear or branched (C 1 -C 6 ) alkyl chloride, and (C 1 -C 6 ) alkanoyl chloride.
  • the halogenating agent may be phthaloyl chloride. In other embodiments, however, the catalyst composition can be completely phthalate-free.
  • the halogenating agent is selected from HCl, TiCl 4 R n TiCl 4-n , SiCl 4 , R n SiCl 4-n , and R n AlCl 4-n , wherein R represents an alkyl, cycloalkyl, aromatic or alkoxy, and n is a whole number satisfying the formula 0 ⁇ n ⁇ 4.
  • the ratio of halogenating agent to magnesium compound is at least 1:1 mol ratio.
  • the molar ratio of the first titanium compound added to the halide- containing magnesium compound may be from about 3:1 to about 15:1, or from about 5:1 to about 10:1.
  • the magnesium-containing solution formed during the reaction of the halide-containing magnesium compound, epoxy compound, organic phosphorus compound and organosilicon compound can be in the form of dispersions, colloids, emulsions, and other two-phase systems.
  • the homogenous solution can be emulsified using conventional emulsion techniques including one or more of agitation, stirring, mixing, high and/or low shear mixing, mixing nozzles, atomizers, membrane emulsification techniques, milling sonication, vibration, microfluidization, and the like.
  • the magnesium-containing species phase is dispersed within the solvent phase.
  • the size and shape of droplets forming the magnesium phase can be controlled through a combination of adjusting the temperature, adjusting the amount of solvent, adjusting the agitation energy, and including/excluding various additives, including the surface modifier.
  • the temperature during the titanium compounds addition is from about -35 o C to about 15 o C. After phase separation and/or titanium compound addition, the mixture is raised to a higher temperature.
  • the higher temperature is from about 15 °C to about 100 °C. In another embodiment, the temperature is from about 20 °C to about 90 °C or from about 50 °C to about 85 °C or from about 60 °C to 85 °C. In an embodiment, while the mixture is between the lower and higher temperatures, a surface modifier is added to facilitate formation of spherical droplets of the magnesium phase surrounded by the solvent phase. That is, the addition of a surface modifier can assist in controlling the
  • the reaction occurs between the magnesium alkoxide and the titanium halide compound forming the magnesium halide and complexes of the magnesium halide with titanium halide compound and the titanium alkoxide.
  • the newly formed associated groups of the magnesium halide molecules and complexes of the magnesium halide with titanium halide compound and the titanium alkoxide are present in“oil phase-droplets” (higher viscosity liquid than other media (solvent) around).
  • the magnesium halide molecules and complexes of the magnesium halide with titanium halide compound and the titanium alkoxide in the oil phase are crystallized.
  • the crystallization process is usually completed at temperatures of 50-100° C forming the solid intermediate catalyst component.
  • the morphology of the solid intermediate catalyst component (and the catalyst component) depends on many factors including the polarity of solvent, presence of reagents to control precipitation, surfactants, additives and others.
  • the size and shape of droplets forming the magnesium phase can be controlled through a combination of adjusting the temperature, amount of solvent, adjusting the agitation energy, and including/excluding various additives, including the surface modifier and temperature of the precipitation.
  • the catalyst component morphology and catalyst performances are sufficiently controlled by addition of the supportive electron donor (or donors).
  • the supportive electron donor is an organic compound containing an oxygen atom and has the ability to coordinate to magnesium atoms of magnesium in“oil phase-droplets” and allows control of the precipitation process of the solid catalyst component with desired morphology.
  • the supportive electron donor only controls the precipitation process and the catalyst component morphology and is not incorporated into the catalyst component.
  • the supportive electron donor controls the precipitation process and catalyst component morphology and is incorporated in the catalyst component. Therefore, the supportive electron donor and the electron donor can both define the catalyst performance in polymerization process.
  • the supportive electron donors are usually weaker than the electron donors.
  • the combination of the organosilicon compound and the supportive electron donor during the precipitation of the solid catalyst intermediate allow to make the catalyst component with desired granular or spherical shape morphology.
  • the granular catalyst component morphology can be prepared with a raspberry shape, rounded raspberry shape, rounded shape and substantially spherical shape (microspheres) by variation of the organosilicon compounds, supportive electron donors and the conditions of the precipitation of the solid catalyst intermediate.
  • the particle sizes of the catalyst component are from about 5 microns to about 70 microns (on a 50% by volume basis) and depend on the conditions of the precipitation (temperature, agitation speed, solvent and others) and type and amount of the supportive donor.
  • the supportive electron donor is selected from carboxylic monoesters methyl formate, butyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexy acetate, ethyl propionate, methyl butyrate, ethyl butyrate, isobutyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl be
  • Combining the halide-containing magnesium compound, epoxy compound, organic phosphorus compound, titanium halide and hydrocarbon solvent might create an emulsion with two phases: the solvent phase and the magnesium- titanium oil phase and with proper selection of the solvent and reagents.
  • This process can be used to prepare a spherical morphology.
  • Phase separation is accomplished by proper solvent selection.
  • Solvent selection involves considering one or more of physical properties differences in polarity, density, and surface tension among others causing the separation between the solvent and the magnesium phase.
  • Toluene is an organic solvent diluent that has been used for the formation of solid titanium catalyst components; however, use of toluene does not always promote the formation of two phases.
  • the surface modifier include polymer surfactants, such as polyacrylates, polymethacrylates, polyalkyl methacrylates, or any other surfactant that can stabilize and emulsify.
  • surfactants are known in the art, and many surfactants are described in McCutcheon’s“Volume I: Emulsifiers and Detergents”, 2001, North American Edition, published by Manufacturing Confectioner Publishing Co., Glen Rock, N.J., and in particular, pp.1-233 which describes a number of surfactants and is hereby incorporated by reference for the disclosure in this regard.
  • a polyalkyl methacrylate is a polymer that may contain one or more methacrylate monomers, such as at least two different methacrylate monomers, at least three different methacrylate monomers, etc. Moreover, the acrylate and methacrylate polymers may contain monomers other than acrylate and methacrylate monomers, so long as the polymer surfactant contains at least about 40% by weight acrylate and methacrylate monomers. [0081] Examples of monomers that can be polymerized using known
  • polymerization techniques into polymer surfactants include one or more of an acrylate; tert-butyl acrylate; n-hexyl acrylate; methacrylate; methyl methacrylate; ethyl methacrylate; propyl methacrylate; isopropyl methacrylate; n-butyl
  • dimethacrylate triethylene glycol dimethacrylate; polyethylene glycol dimethacrylate; butylene glycol dimethacrylate; trimethylolpropane-3-ethoxylate triacrylate; 1,4- butanediol diacrylate; 1,9-nonanediol diacrylate; neopentyl glycol diacrylate;
  • tripropylene glycol diacrylate tetraethylene glycol diacrylate; heptapropylene glycol diacrylate; trimethylol propane triacrylate; ethoxylated trimethylol propane triacrylate; pentaerythritol triacrylate; trimethylolpropane trimethacrylate;
  • tripropylene glycol diacrylate pentaerythritol tetraacrylate; glyceryl propoxy triacrylate; tris(acryloyloxyethyl)phosphate; 1-acryloxy-3-methacryloxy glycerol; 2- methacryloxy-N-ethyl morpholine; and allyl methacrylate, and the like.
  • the surface modifier is selected from poly((C 1 -C 6 ) alkyl) acrylate, a poly((C 1 -C 6 ) alkyl) methacrylate, and a copolymer of poly((C 1 -C 6 ) alkyl) acrylate and poly((C 1 -C 6 ) alkyl) methacrylate.
  • a ratio of the surface modifier to halide-containing magnesium compound is from 1:10 to 2:1 wt% or from 1:5 to 1:1 wt%.
  • polymer surfactants examples include those under the trade designation VISCOPLEX® available from RohMax Additives, GmbH, including those having product designations 1-254, 1-256 and those under the trade designations CARBOPOL® and PEMULEN® available from Noveon/Lubrizol.
  • the polymer surfactant is typically added in a mixture with an organic solvent. When added as a mixture with an organic solvent, the weight ratio of surfactant to organic solvent is from about 1:20 to about 2:1. In another embodiment, the weight ratio of surfactant to organic solvent is from about 1:10 to about 1:1. In yet another embodiment, the weight ratio of surfactant to organic solvent is from about 1:4 to about 1:2.
  • Treatment with the second titanium compound may include adding the second titanium halide compound and the second electron donor to a solution containing the precipitate to form a solid catalyst composition, and then bringing a temperature of the solid catalyst composition to from 80 °C to 150 °C and further treating with the second titanium compound to form the solid catalyst component.
  • the treatment may include more than one second electron donor.
  • a plurality of electron donors can be used during treatment with the second titanium compound.
  • the second titanium compound treatment includes the steps of filtering out the precipitate, adding the second titanium compound and the second electron donor in a solvent to the precipitate to form a solid catalyst composition, and bringing a temperature of the solid catalyst composition to from 80 °C to 150 °C.
  • the second titanium compound treatment includes the steps of adding the second titanium compound to a solution containing the precipitate; and then bringing a temperature of the solid catalyst composition to from 80 °C to 150 °C and further treating with the second titanium compound and the second electron donor to form the solid catalyst component.
  • Treatment with the second titanium compound may include adding the second titanium halide compound and the second electron donor to a solution containing the precipitate to form a solid catalyst composition, and then bringing a temperature of the solid catalyst composition to from 80 °C to 150 °C and further treating with the second titanium compound to form the solid catalyst component.
  • the second titanium compound treatment includes the steps of filtering out the precipitate, adding the second titanium compound and the second electron donor in a solvent to the precipitate to form a solid catalyst composition, and bringing a temperature of the solid catalyst composition to from 80 °C to 150 °C.
  • the second titanium compound treatment includes the steps of adding the second titanium compound to a solution containing the precipitate; and then bringing a temperature of the solid catalyst composition to from 80 °C to 150 °C and further treating with the second titanium compound and the second electron donor to form the solid catalyst component. [0087] During this treatment, the supportive electron donor partly or fully is removed from the catalyst component and the electron donors adjust the coordination to magnesium halides resulting in increased catalyst activity.
  • a solid catalyst component can be made in accordance with the present disclosure by combining a magnesium halide, such as magnesium chloride with an epoxy compound.
  • the epoxy compound for instance, can be epichlorohydrin.
  • the magnesium halide and the epoxy compound can be combined together at a molar ratio of from about 0.5:1 to about 1:0.5, such as from about 0.8:1.2 to about 1.2:0.8.
  • the magnesium halide and the epoxy compound can be combined together in approximately a 1 to 1 molar ratio.
  • the magnesium halide and epoxy compound can be combined together in the presence of a phosphate such as tributyl phosphate and a solvent such as toluene.
  • an aluminum alkoxide surfactant may be present, such as aluminum alkoxide/isopropoxide.
  • tetraethylorthosilicate can be added to the above composition in addition to a titanium halide such as titaniumtetrachloride to cause a precipitate to form.
  • a titanium halide such as titaniumtetrachloride
  • complexes of the magnesium halide with the monoester, the titanium chloride can form including Cl 3 -Ti-O-CH(CH 2 Cl) 2 .
  • the above precipitate can then be treated with a second internal donor, such as an aryl diester and optionally in the presence with a titanium halide.
  • the resulting solid catalyst component can be washed and used as desired.
  • the resulting solid catalyst component contains a magnesium halide, a titanium halide, the first internal donor or supportive donor, and the second internal donor.
  • the solid catalyst component can contain residual amounts of an aluminum alkoxide, the organosilicon compound and the phosphorus compound. For example, the amount of the aluminum alkoxide and/or the
  • the organosilicon compound present in the final catalyst can be generally greater than about 0.001% by weight, such as greater than about 0.01% by weight, such as greater than about 0.1% by weight and generally less than about 1% by weight, such as less than about 0.5% by weight, such as less than about 0.3% by weight.
  • the solid catalyst component can also contain the phosphorous compound generally in an amount greater than about 0.1% by weight, such as in an amount greater than about 0.2% by weight, such as in an amount greater than about 0.3% by weight, and generally less than about 1% by weight, such as less than about 0.5% by weight.
  • the first internal electron donor may include not only a monoester but also a dialkyl ether.
  • the first internal electron donor can be combined into the catalyst composition with a spherical-promoting surfactant, such as an acrylate surfactant.
  • a spherical-promoting surfactant such as an acrylate surfactant.
  • the surfactant may comprise a polyalkyl methacrylate.
  • the BET surface area of the catalyst can be greater than about 100 m 2 /g, such as greater than about 200 m 2 /g, such as greater than about 300 m 2 /g, such as greater than about 400 m 2 /g and generally less than about 700 m 2 /g, such as less than about 600 m 2 /g.
  • the catalyst system may contain at least one organoaluminum compound in addition to the solid catalyst component. Compounds having at least one aluminum-carbon bond in the molecule can be used as the organoaluminum
  • organoaluminum compounds include those of Formula: AlR n X 3-n wherein, R independently represents a hydrocarbon group usually having 1 to about 20 carbon atoms, X represents a halogen atom, and 0 ⁇ n ⁇ 3.
  • organoaluminum compounds include, but are not limited to, trialkyl aluminums such as triethyl aluminum, tributyl aluminum and trihexyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; and other partially hydrogenated alkyl aluminum such as ethyl aluminum dihydride, and propyl aluminum dihydride.
  • trialkyl aluminums such as triethyl aluminum, tributyl aluminum and
  • the organoaluminum compound can be used in the catalyst system in an amount that the mole ratio of aluminum to titanium (from the solid catalyst component) is from about 5 to about 1. In another embodiment, the mole ratio of aluminum to titanium in the catalyst system is from about 10 to about 700. In yet another embodiment, the mole ratio of aluminum to titanium in the catalyst system is from about 25 to about 400.
  • the catalyst system may contain one or more selectivity control agents (SCA) in addition to the solid catalyst component.
  • the selectivity control agent can comprise one or more organosilicon compounds, such as one or more silane compounds. This organosilicon compound can also function as an external electron donor.
  • the organosilicon compound contains silicon having at least one hydrogen ligand (hydrocarbon group).
  • hydrocarbon groups include alkyl groups, cycloalkyl groups, (cycloalkyl)methylene groups, alkene groups, aromatic groups, and the like.
  • the organosilicon compound is used in the catalyst system in an amount such that the mole ratio of the organoaluminum compound to the organosilicon compound is from about 2 to about 90. In another embodiment, the mole ratio of the organoaluminum compound to the organosilicon compound is from about 5 to about 70. In yet another embodiment, the mole ration of the organoaluminum compound to the organosilicon compound is from about 7 to about 35. [00100] In one embodiment, the organosilicon compound is represented by Formula: R n Si(OR') 4-n
  • each Rand R' independently represent a hydrocarbon group, and n is 0 ⁇ n ⁇ 4.
  • the organosilicon compound include, but are not limited to trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, t- butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t- amylmethyldiethoxysilane, dicyclopentyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolydimethoxysilane, bis-m-tolydimethoxysilane, bis-p-tolydimethoxysilane, bis-p-tolydiethoxys
  • decyltriethoxysilane phenyltrimethoxysilane, ⁇ -chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t- butyltriethoxysilane, nbutyltriethoxysilane, iso-butyltriethoxysilane,
  • phenyltriethoxysilane ⁇ -amniopropyltriethoxysilane, cholotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norboranetriethoxysilane, 2-norboranemethyldimethoxysilane, ethyl silicate, butyl silicate,
  • the organosilicon compound is represented by Formula: SiRR' m (OR") 3-m
  • R independently represents a cyclic hydrocarbon or substituted cyclic hydrocarbon group.
  • R include, but are not limited to cyclopropyl; cyclobutyl; cyclopentyl; 2- methylcyclopentyl; 3-methylcyclopentyl; 2-ethylcyclopentyl; 3-propylcyclopentyl; 3- isopropylcyclopentyl; 3-butylcyclopentyl; 3-tertiary-butyl cyclopentyl; 2,2- dimethylcyclopentyl; 2,3-dimethylcyclopentyl; 2,5-dimethylcyclopentyl; 2,2,5- trimethylcyclopentyl; 2,3,4,5-tetramethylcyclopentyl; 2,2,5,5-tetramethylcyclopentyl; 1-cyclopentylpropyl; 1-methyl-1-cyclopentylethyl; cyclopentenyl;
  • R' and R" are identical or different and each represents a hydrocarbon. Examples of R' and R" are alkyl, cycloalkyl, aryl and aralkyl groups having 3 or more carbon atoms. Furthermore, R and R' may be bridged by an alkyl group, etc.
  • organosilicon compounds are those of formula (VIII) in which R is cyclopentyl group, R' is an alkyl group such as methyl or cyclopentyl group, and R" is an alkyl group, particularly a methyl or ethyl group.
  • R is cyclopentyl group
  • R' is an alkyl group such as methyl or cyclopentyl group
  • R" is an alkyl group, particularly a methyl or ethyl group.
  • SiRR' m (OR) 3-m include, but are not limited to trialkoxysilanes such as
  • cyclopentyltrimethoxysilane 2-methylcyclopentyltrimethoxysilane, 2,3- dimethylcyclopentyltrimethoxysilane, 2,5-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentenyltrimethoxysilane, 3- cyclopentenyltrimethoxysilane, 2,4-cyclopentadienyltrimethoxysilane,
  • dialkoxysilanes such as dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis(3- tertiary-butylcyclopentyl)dimethoxysilane, bis(2,3- dimethylcyclopentyl)dimethoxysilane, bis(2,5-dimethylcyclopentyl)dimethoxysilane, dicyclopentyldiethoxysilane, dicyclobutyldiethoxysilane,
  • cyclopropylcyclobutyldiethoxysilane dicyclopentenyldimethoxysilane, di(3- cyclopentenyl)dimethoxysilane, bis(2,5-dimethyl-3-cyclopentenyl)dimethoxysilane, di-2,4-cyclopentadienyl)dimethoxysilane, bis(2,5-dimethyl-2,4- cyclopentadienyl)dimethoxysilane, bis(l-methyl-1-cyclopentylethyl)dimethoxysilane, cyclopentylcyclopentenyldimethoxysilane,
  • cyclopentylcyclopentadienyldimethoxysilane diindenyldimethoxysilane, bis(1,3- dimethyl-2- indenyl)dimethoxysilane, cyclopentadienylindenyldimethoxysilane, difluorenyldimethoxysilane, cyclopentylfluorenyldimethoxysilane and
  • indenylfluorenyldimethoxysilane indenylfluorenyldimethoxysilane; monoalkoxysilanes such as
  • cyclopentyldiethylmethoxysilane cyclopentyldimethylethoxysilane, bis(2,5- dimethylcyclopentyl)cyclopentylmethoxysilane, dicyclopentylcyclopentenylmethoxysilane,
  • selectivity control agents are present in the catalyst system.
  • selectivity control agents include dimethyldimethoxysilane, n-propyltrimethoxysilane,
  • one or more selectivity control agents may be used in conjunction with an activity limiting agent (ALA).
  • ALA activity limiting agent
  • the activity limiting agent can be an aliphatic ester.
  • the aliphatic ester may be a C 4 -C 30 aliphatic acid ester, may be a mono- or a poly-(two or more) ester, may be straight chain or branched, may be saturated or unsaturated, and any combination thereof.
  • the C 4 -C 30 aliphatic acid ester may also be substituted with one or more Group 14, 15 or 16 heteroatom containing substituents.
  • suitable C 4 -C 30 aliphatic acid esters include C 1- 20 alkyl esters of aliphatic C 4-30 monocarboxylic acids, C 1-20 alkyl esters of aliphatic C 8- 20 monocarboxylic acids, C 1-4 allyl mono- and diesters of aliphatic C 4-20
  • the C 4 -C 30 aliphatic acid ester may be isopropyl myristate, di-n- butyl sebacate, (poly)(alkylene glycol) mono- or diacetates, (poly)(alkylene glycol) mono- or di-myristates, (poly)(alkylene glycol) mono- or di-laurates, (poly)(alkylene glycol) mono- or di-oleates, glyceryl tri(acetate), glyceryl tri-ester of C 2-40 aliphatic carboxylic acids, and mixtures thereof.
  • the C 4 -C 30 aliphatic ester is isopropyl myristate or di-n-butyl sebacate.
  • the ALA is a non-ester composition.
  • a“non-ester composition” is an atom, molecule, or compound that is free of an ester functional group. In other words, the“non-ester composition” does not contain the following functional group.
  • the non-ester composition may be a dialkyl diether compound or an amine compound.
  • the dialkyl diether compound can be represented by the followin formula
  • R 1 R 4 are independently of one another an alkyl, aryl or aralkyl group having up to 20 carbon atoms, which may optionally contain a group 14, 15, 16, or 17 heteroatom, provided that R′ and R 2 may be a hydrogen atom.
  • Nonlimiting examples of suitable dialkyl ether compounds include dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, methyl butyl ether, methyl cyclohexyl ether, 2,2- dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-di-n-butyl- 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-ethyl-2-n-butyl-1,3- dimethoxypropane, 2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dimethyl- 1,3-diethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2- dicyclopentyl-1,3-dimethoxypropane, 2-n-propyl
  • the non-ester composition is an amine compound.
  • suitable amine compounds include 2,6-substituted piperidines such as 2,6-dimethylpiperidine and 2,2,6,6-tetramethylpiperidine and 2,5- substituted piperidines.
  • the piperidine compound is 2,2,6,6- tetramethylpiperidine.
  • ALA ALA
  • all the carboxylate groups are considered effective components.
  • a sebacate molecule contains two carboxylate functional groups is considered to have two effective functional molecules.
  • the activity limiting agent is a C4 to C30 Aliphatic acid ester.
  • the activity limiting agent may comprise a diether or a poly(alkene glycol) ester of a C4 to C30 aliphatic acid.
  • Particular activity limiting agents that may be incorporated into the catalyst system include isopropyl myristate, di-n-butyl sebacate, ethyl 4-ethoxybenzoate, propoxylated (POE) coco fatty acid esters such as containing 10 to 20 mols of POE, a poly(ethylene)glycol coco fatty acid ester, or mixtures thereof.
  • An especially preferred combination of SCA/ALA components is a mixture of an alkoxy silane selected from the group consisting of
  • Preferred SCA/ALA mixtures according to the invention are those comprising from 1 to 99.9, more preferably from 30 to 99, and most preferably from 50 to 98 equivalent percent of one or more ALA compounds, and correspondingly from 99 to 0.1, more preferably from 70 to 1, most preferably from 50 to 2 equivalent percent of one or more alkoxysilane compounds.
  • the normalized polymerization activity at an elevated temperature should be less than that obtainable at 67° C. and less than that obtainable if the alkoxysilane alone were employed alone in the same total SCA molar amount.
  • the total molar quantity of the SCA mixture employed in the present invention based on moles of transition metal is desirably from 0.1 to 500, more desirably from 0.5 to 100 and most preferably from 1.0 to 50.
  • the corresponding molar ratio based on transition metal is desirably from 1 to 10,000, preferably from 2 to 1000, and most preferably from 5 to 100.
  • Catalyst particle morphology is indicative of the polymer particle morphology produced therefrom.
  • the three parameters of polymer particle morphology may be determined using a Camsizer instrument marketed by Horiba Scientific. Camsizer Characteristics: Sphericity 4 ⁇ A
  • P is the measured perimeter/circumference of a particle projection; and A is the measured area covered by a particle projection.
  • P is the measured perimeter/circumference of a particle projection; and A is the measured area covered by a particle projection.
  • SPHT is defined as 1. Otherwise, the value is less than 1.
  • the symmetry is defined as:
  • r 1 und r 2 are distance from the centre of area to the borders in the measuring direction.
  • Symm is less than 1. If the centre of the area is outside the particle, i.e. the Symm is less than 0.5
  • the catalyst morphology characteristics such as aspect ratio (“B/L3”) can be used for characterization of polymer morphology. In some processes, the aspect ratio is higher than 0.6, or higher than 0.7, or higher than 0.8, or higher than 0.90.
  • the particle size of the resulting catalyst component can vary depending upon the process conditions and the desired result.
  • the D 50 particle size can be greater than about 5 microns, such as greater than about 10 microns, such as greater than about 20 microns, such as greater than about 30 microns, such as greater than about 40 microns, such as greater than about 50 microns, such as greater than about 60 microns, and generally less than about 70 microns, such as less than about 50 microns, such as less than about 30 microns, such as less than about 25 microns.
  • Polymerization Processes [00123] Polymerization of olefins can be carried out in the presence of the catalyst systems as prepared and described above. Various different olefins can be
  • catalyst systems of the present disclosure can be used to polymerize ethylene, propylene, and the like.
  • the catalyst systems can also be used to produce homopolymers and copolymers.
  • an olefin monomer, such as propylene is contacted with the catalyst system described above under suitable conditions to form desired polymer products.
  • preliminary polymerization described below is carried out before the main polymerization.
  • polymerization is carried out without preliminary polymerization.
  • the formation of a polypropylene-co-polymer is carried out using at least two
  • the catalyst component of the present disclosure is well suited for use in all different types of polymerization processes.
  • the catalyst component of the present disclosure can be used in bulk loop polymerization processes, gas phase processes, and the like.
  • the catalyst component can also be used in a slurry process.
  • the solid catalyst component is usually employed in combination with at least a portion of the organoaluminum compound. This may be carried out in the presence of part or the whole of the organosilicon compound (external electron donor compound).
  • the concentration of the catalyst system used in the preliminary polymerization may be much higher than that in the reaction system of the main polymerization.
  • the concentration of the solid catalyst component in the preliminary polymerization is usually from about 0.01 to about 200 millimoles, or from about 0.05 to about 100 millimoles, calculated as titanium atoms per liter of an inert hydrocarbon medium described below.
  • the preliminary polymerization is carried out by adding propylene or a mixture of propylene with another olefin and the above catalyst system ingredients to an inert hydrocarbon medium and polymerizing the olefins under mild conditions.
  • the inert hydrocarbon medium include, but are not limited to aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptanes, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; and mixtures thereof.
  • a liquid olefin may be used in place of part or the whole of the inert hydrocarbon medium.
  • the olefin used in the preliminary polymerization may be the same as, or different from, an olefin to be used in the main polymerization.
  • the reaction temperature for the preliminary polymerization is sufficient for the resulting preliminary polymer to not substantially dissolve in the inert hydrocarbon medium. In one embodiment, the temperature is from about -20 oC to about 100 oC. In another embodiment, the temperature is from about -10 oC to about 80 oC. In yet another embodiment, the temperature is from about 0 oC to about 40 oC.
  • a molecular-weight controlling agent such as hydrogen, may be used in the preliminary polymerization.
  • the molecular weight controlling agent is used in such an amount that the polymer obtained by the preliminary polymerization has an intrinsic viscosity, measured in decaliter at 135 oC, of at least about 0.2dl/g, or from about 0.5 to 10 dl/g.
  • the preliminary polymerization is carried out so that from about 0.1 g to about 1,000 g of a polymer is formed per gram of the solid catalyst component of the catalyst system. In another embodiment, the preliminary polymerization is carried out so that from about 0.3 g to about 500 g of a polymer is formed per gram of the solid catalyst component.
  • the efficiency of producing the olefin polymer in the main polymerization may sometimes decrease, and when the resulting olefin polymer is molded into a film or another article, fish eyes tend to occur in the molded article.
  • the preliminary polymerization may be carried out batchwise or continuously. [00132] After the preliminary polymerization conducted as above, or without performing any preliminary polymerization, the main polymerization of the propylene is carried out in the presence of the above-described polymerization catalyst system formed from the solid catalyst component, the organoaluminum compound and the organosilicon compound (external electron donor compound).
  • Examples of other olefins that can be used in the main polymerization with propylene are ⁇ -olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1- butene, 4-methyl-1-pentene, 1- pentene, 1-octene, 1-hexene, 3-methyl-1-pentene, 3- methyl-1-butene, 1-decene, 1-tetradecene, 1-eicosene, and vinylcyclohexane.
  • these ⁇ -olefins may be used individually or in any combination.
  • propylene is homopolymerized, or a mixed olefin containing propylene as a main component is copolymerized.
  • the proportion of propylene as the main component is usually at least about 50 mole %, or at least about 70 mole %.
  • the particles shape of the resulting polymer becomes spherical, and in the case of slurry polymerization, the slurry attains excellent characteristics while in the case of gas phase polymerization, the polymer seed bed attains excellent characteristics.
  • a polymer having a high stereoregularity index can be produced with a high catalytic efficiency by polymerizing an ⁇ -olefin having at least 3 carbon atoms. Accordingly, when producing the propylene copolymer, the resulting copolymer powder or the copolymer becomes easy to handle.
  • a polyunsaturated compound such as conjugated diene or non-conjugated diene may be used as a comonomer.
  • comonomers include styrene, butadiene, acrylonitrile, acrylamide, ⁇ - methyl styrene, chlorostyrene, vinyl toluene, divinyl benzene, diallyphthalate, alkyl methacrylates and alkyl acrylates.
  • the comonomers include thermoplastic and elastomeric monomers. The main polymerization of an olefin is carried out usually in the gaseous or liquid phase. In one embodiment,
  • main polymerization employs a catalyst system containing the solid catalyst component in an amount from about 0.001 to about 0.75 millimoles calculated as Ti atom per liter of the volume of the polymerization zone, the organoaluminum compound in an amount from about 1 to about 2,000 moles per mole of titanium atoms in the solid catalyst component, and the organosilicon compound in an amount from about 0.001 to about 10 moles calculated as Si atoms in the organosilicon compound per mole of the metal atoms in the organoaluminum compound.
  • polymerization employs a catalyst system containing the solid catalyst component in an amount of from 0.005 to about 0.5 milimoles calculated as Ti atom per liter of the volume of the polymerization zone, the organoaluminum compound in an amount from about 5 to about 500 moles per mole of titanium atoms in the solid catalyst component, and the organosilicon compound in an amount from about 0.01 to about 2 moles calculated as Si atoms in the organosilicon compound per mole of the metal atoms in the organoaluminum compound.
  • polymerization employs a catalyst system containing the alkyl benzoate derivative in an amount from about 0.005 to about 1 mole calculated as Si atoms in the organosilicon compound per mole of the metal atoms in the organoaluminum compound.
  • the catalyst system subjected to the preliminary polymerization is used together with the remainder of the catalyst system components.
  • the catalyst system subjected to the preliminary polymerization may contain the preliminary polymerization product.
  • the polymerization temperature is from about 20 oC to about 170 oC. In another embodiment, the polymerization temperature is from about 50 oC to about 165 oC. In one embodiment, the polymerization pressure is typically from atmospheric pressure to about 100 kg/cm 2 . In another embodiment, the polymerization pressure is typically from about 2 kg/cm 2 to about 50 kg/cm 2 .
  • the main polymerization may be carried out batchwise, semi-continuously or continuously.
  • the polymerization may also be carried out in two or more stages under different reaction conditions.
  • the olefin polymer so obtained may be a homopolymer, a random copolymer, a block copolymer or an impact copolymer.
  • the impact copolymer contains an intimate mixture of a polyolefin homopolymer and a polyolefin rubber.
  • polyolefin rubbers include ethylene propylene rubber (EPR) such as ethylene propylene methylene copolymer rubber (EPM) and ethylene propylene diene methylene terpolymer rubber (EPDM).
  • EPR ethylene propylene rubber
  • EPM ethylene propylene methylene copolymer rubber
  • EPDM ethylene propylene diene methylene terpolymer rubber
  • the olefin polymer obtained by using the catalyst system has a very small amount of an amorphous polymer component and therefore a small amount of a hydrocarbon-soluble component. Accordingly, a film molded from the resultant polymer has low surface tackiness.
  • the polyolefin obtained by the polymerization process is excellent in particle size distribution, particle diameter and bulk density, and the copolyolefin obtained has a narrow composition distribution. In an impact copolymer, excellent fluidity, low temperature resistance, and a desired balance between stiffness and elasticity can be obtained.
  • propylene and an ⁇ -olefin having 2 or from about 4 to about 20 carbon atoms are copolymerized in the presence of the catalyst system described above.
  • the catalyst system may be one subjected to the preliminary polymerization described above.
  • propylene and an ethylene rubber are formed in two reactors coupled in series to form an impact polymer.
  • the ⁇ -olefin having 2 carbon atoms is ethylene, and examples of the ⁇ - olefin having about 4 to about 20 carbon atoms are 1-butene, 1-pentene, 4-methyl-1- pentene, 1-octene, 1-hexene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, vinylcyclohexane, 1-tetradecene, and the like.
  • propylene may be copolymerized with two or more such ⁇ -olefins. For example, it is possible to copolymerize propylene with ethylene and 1-butene.
  • propylene is copolymerized with ethylene, 1-butene or ethylene and 1-butene.
  • Copolymerization of propylene and another ⁇ -olefin may be carried out in two stages.
  • the polymerization in a first stage may be the homopolymerization of propylene or the copolymerization of propylene with the other ⁇ -olefin.
  • the amount of the monomers polymerized in the first stage is from about 50 to about 95% by weight. In another embodiment, the amount of the monomers polymerized in the first stage is from about 60 to about 90% by weight.
  • This first stage polymerization may be carried out in two or more stages under the same or different polymerization conditions.
  • the polymerization in a second stage is carried out such that the mole ratio of propylene to the other ⁇ -olefin(s) is from about 10/90 to about 90/10. In another embodiment, the polymerization in a second stage is carried out such that the mole ratio of propylene to the other ⁇ -olefin(s) is from about 20/80 to about 80/20. In yet another embodiment, the polymerization in a second stage is carried out such that the mole ratio of propylene to the other ⁇ -olefin(s) is from about 30/70 to about 70/30. Producing a crystalline polymer or copolymer of another ⁇ - olefin may be provided in the second polymerization stage.
  • the propylene copolymer so obtained may be a random copolymer or the above described block copolymer.
  • the propylene copolymer can contain from about 7 to about 50 mole% of units derived from the ⁇ -olefin having 2 or from about 4 to about 20 carbon atoms.
  • a propylene random copolymer contains from about 7 to about 20 mole % of units derived from the ⁇ -olefin having 2 or from about 4 to about 20 carbon atoms.
  • the propylene block copolymer contains from about 10 to about 50 mole% of units derived from the ⁇ - olefin having 2 or 4-20 carbon atoms.
  • copolymers made with the catalyst system contain from about 50% to about 99% by weight poly- ⁇ -olefins and from about 1% to about 50% by weight comonomers (such as thermoplastic or elastomeric monomers). In another embodiment, copolymers made with the catalyst system contain from about 75% to about 98% by weight poly- ⁇ -olefins and from about 2% to about 25% by weight comonomers.
  • a two stage reactor system such as two fluidized bed reactors in series, can be used to produce a polypropylene copolymer that is heterophasic.
  • a polypropylene homopolymer or polypropylene random copolymer of a first phase is prepared in a first stage reactor.
  • the first phase can comprise a continuous polymer phase in the resulting polymer.
  • An elastomeric propylene copolymer is then produced in a second stage and forms the second phase.
  • the first stage polymerization can be carried out in one or more bulk reactors or in one or more gas phase reactors.
  • the second stage polymerization can be carried out in one or more gas phase reactors.
  • the second stage polymerization is typically carried out directly following the first stage polymerization.
  • the resulting heterophasic copolymer which can comprise a propylene-ethylene copolymer, can have excellent impact resistance properties and have elastomeric properties.
  • the catalyst as described above is particularly well suited for use in producing polypropylene polymers in two stage reactors.
  • the catalyst for instance, has been found to have a dramatically prolonged lifetime and therefore maintains high catalyst activity levels within the second reactor. It is believed that the increased lifetime of a catalyst helps to produce polymer resins with better flow properties.
  • the catalyst efficiency (measured as kilogram of polymer produced per gram of catalyst) of the catalyst system is at least about 30 kg/g/h.
  • the catalyst deficiency can be higher than about 60 kg/g/h, such as greater than about 80 kg/g/h, such as greater than about 100 kg/g/h, such as greater than about 140 kg/g/h.
  • the catalysts/methods discussed above can in some instances lead to the production of poly- ⁇ -olefins having melt flow rates (“MFR”, g/10 minutes) from about 0.01 to about 500 g/10 min, such as from about 0.1 to about 400 g/10 min. In another embodiment, poly- ⁇ -olefins having an MFR from 0.1 to about 300 are produced.
  • MFR melt flow rates
  • PI polydispersity index
  • the polydispersity index can vary depending upon various factors and the desired result.
  • the polydispersity index can generally be greater than about 3, such as greater than about 5, and generally less than about 8, such as less than about 6.
  • the catalysts/methods described above can in some instances lead to the production of poly- ⁇ -olefins having bulk densities (BD) of at least about 0.35 cc/g.
  • poly- ⁇ -olefins having a BD of at least about 0.4 cc/g are produced.
  • polypropylene polymers can be produced having a relatively high bulk density.
  • the bulk density can be greater than 0.415 g/cm 3 , such as greater than 0.42 g/cm 3 , such as greater than 0.44 g/cm 3, such as greater than 0.46 g/cm 3 .
  • the bulk density is generally less than about 0.8 g/cm 3 , such as less than about 0.6 g/cm 3 .
  • the catalysts/methods described above can lead to the production of poly- ⁇ -olefins having a Span of less than 1.0. In some embodiments, the Span is less than 0.6.
  • Embodiments of the present invention can lead to the production of a propylene block copolymer and impact copolymers including polypropylene based impact copolymer having one or more excellent melt-flowability, moldability, desirable balance between rigidity and elasticity, good stereospecific control, good control over polymer particle size, shape, size distribution, and molecular weight distribution, and impact strength with a high catalytic efficiency and/or good operability.
  • Employing the catalyst systems containing the solid catalyst component according to embodiments of the present invention yields catalysts simultaneously having high catalytic efficiency, and one or more of excellent melt-flowability, extrudability, moldability, rigidity, elasticity and impact strength.
  • “D 10 ” represents the size of particles (diameter), wherein 10% of particles are less than that size
  • “D 50 ” represents the size of particles, wherein 50% of particles are less than that size
  • “D 90 ” represents the size of particles, wherein 90% of particles are less than that size.
  • BD is an abbreviation for bulk density, and is reported in units of g/ml or g/cm 3 .
  • To measure bulk density the polymer is dried in an oven at 60°C for one hour and then cooled to room temperature before measurement.
  • a cylindrical measuring cup is used that is 9 1 ⁇ 2 inches in height and has an inside diameter of 1.8 inches.
  • the measuring cup has a volume of 395 ml.
  • a funnel having a 1 inch diameter opening at the bottom is mounted 1 1 ⁇ 2 inches above the measuring cup. The small end of the funnel is covered with a straight edge. 500 ml of polymer sample is loaded into the funnel.
  • CE is an abbreviation for catalyst efficiency and is reported in units of Kg polymer per gram of catalyst (Kg/g) during the polymerization for 1 hour.
  • MFR is an abbreviation for melt flow rate and is reported in units of g/10min. The MFR is measured according to ASTM test number D1238 at 230°C with a 2.16 kg load.
  • the catalyst component particle size analysis was conducted using laser light scattering method by Malvern Mastersizer 3000 instrument. Toluene used as a solvent.
  • the surface area and pore size distribution of the catalyst components were measured by Micrometrics ASAP 2020 instrument. The catalyst component samples were degassed by heating at 60 o C under vacuum for few hours before the measurement.
  • the polydispersity index (PI) and zero shear viscosity for polymer samples were obtained from rheological data by ARES G2 Rheometer. The stabilized polymer sample is pressed on hot press to make plate. The polymer plate is then analyzed on the Rheometer. From the data plot PI and zero shear viscosity are calculated using built in MWD software.
  • the Cup Test is a method to measure polymer powder flowability.
  • the test is particularly well suited to measuring the flowability of high rubber content polypropylene impact copolymers.
  • the test is especially useful when polymer resins are sticky making angle of repose measurements unreliable.
  • the method includes filling a polystyrene 12 oz. coffee cup with the polymer resin powder.
  • the cup is filled with the polymer resin and a flat edge is used to remove excess.
  • the cup is then inverted on a flat surface for 30 minutes.
  • the cup is then removed and a tester observes the shape of the powder and how long it takes to deform and collapse from the initial cup shape.
  • the Cup Test can be measured in seconds for the powder to collapse.
  • the Cup Test also includes a Cup Test Index as specified below:
  • NPDE is an abbreviation for a non-phthalate diaryl ester and can be of the formula:
  • R 1 - R4 selected from substituted or unsubstituted aryl groups
  • R 3 R 4 R 5 R 6 are the same or different alkyl or cycloalkyl having 1 to 20 carbon atoms, heteroatom or combination of them.
  • NPDE1 is 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate.
  • NPDE2 on the other hand, is described in paragraph 52 of U.S. Patent Publication US 2013/0261273, which is incorporated herein by reference.
  • SYLTHERM is a tradename for a polydimethyl siloxane (PDMS) that is commercially available from Dow Chemical.
  • VISCOPLEX is a tradename for a polyalkyl methacrylate available from Evonik.
  • EB is an abbreviation for ethyl benzoate.
  • TBP is an abbreviation for tributyl phosphate.
  • ECH is an abbreviation for epichlorohydrin.
  • TEOS is an abbreviation for tetraethylorthosilicate.
  • Ti, Mg, and D are the weight percentages (wt %) for each of the titanium, magnesium, and internal donor (NPDE), respectively, in the composition.
  • XS is an abbreviation for xylene solubles, and is reported in units of wt%. Bulk Propylene Polymerization
  • catalysts of the examples are used in a method of propylene polymerization the following method was used.
  • the reactor was baked at 100°C under nitrogen flow for 30 minutes prior to the polymerization run.
  • the reactor was cooled to 30-35°C and cocatalyst (1.5 ml of 25 wt% triethylaluminum (TEAl)), C- donor [cyclohexylmethydimethoxysilane] (1 ml), hydrogen (3.5 psi) and liquid propylene (1500 ml) were added in this sequence into the reactor.
  • the catalyst (5-10 mg), loaded as a mineral oil slurry, was pushed into the reactors using high pressure nitrogen.
  • the polymerization was performed for one hour at 70° C. After the polymerization, the reactors were cooled to 22° C, vented to atmospheric pressure, and the polymer collected.
  • catalysts of the examples are used in a method of propylene polymerization the following method was used.
  • the reactor was baked at 100°C under nitrogen flow for 30 minutes prior to the polymerization run.
  • the reactor was cooled to 30°C and propylene was charged (120 g), with cocatalyst (0.27 ml of 25 wt% triethylaluminum (TEAl)), C-donor [cyclohexylmethydimethoxysilane] (0.38 ml), and hydrogen (0.5 g).
  • a reactor was heated to 35° C and the catalyst component (0.5-0.7 mg) was flashed to the reactor with propylene (120 g).
  • the polymerization was performed for one hour at 70° C.
  • Examples 1-3 illustrates preparing the catalyst components using an organosilicon compound without supportive donor and provides the properties of polymer produced using a bulk propylene polymerization scheme.
  • Example 1 demonstrates preparing the catalyst component using tetraethylorthosilicate.
  • the catalyst produced polymer with raspberry shape particle morphology with BD below 0.40g/cc and B/L3 ⁇ 0.7
  • Example 2 demonstrates the catalyst component using two organosilicon compounds (tetraethylorthosilicate and Syltherm PDMS) and Al(OiPr)3.
  • the internal donor was added in two places: in before the solid formed and to the solid component.
  • the mixture was allowed to cool to 25 °C.27 grams of toluene, 1.5 grams of TEOS in 3 grams of toluene, and 0.64 grams of NPDE1were added the reactor.
  • the reactor was chilled to - 25 °C and 65.4 grams of TiCl 4 was added to the reactor.
  • the agitation was set to 300 RPM and ramped to 35°C over 2 hours.
  • the reaction was held at 35 °C for 30 minutes @ 300 RPM.
  • the reaction was heated to 85 °C and held for 30 minutes.
  • the reaction was filtered and 50 mL of toluene was added.
  • the reactor was heated to 40 °C @ 400 RPM and 0.64 grams of NPDE1 was added.
  • Example 3 demonstrates the catalyst component using two organosilicon compounds (tetraethylorthosilicate and Syltherm PDMS) and Al(OiPr)3.
  • the internal donor was added to the solid component..
  • the particle size of catalyst component increased to 14 microns (compared with examples 1 and 2).
  • [00184] 3.3 g of MgCl 2 , 0.25 g Al(O-iPr)3, 20g toluene, 6.7 g TBP, 1.0 g Syltherm(PDMS), 6.43 g of ECH was charged to the reactor. The mixture was heated to 60 °C and held for 8 hours @ 600 RPM agitation speed.
  • the mixture was allowed to cool to 25 °C.27 grams of toluene, 1.5 grams of TEOS in 3 grams of toluene were added to reactor at 600 rpm and 25 °C.
  • the reactor was cooled to -25 °C and 65.2 grams of TiCl 4 was added.
  • the reactor was heated to 35 °C @ 200 RPM for over two hours and held at 35 °C for 30 minutes; heated to 85 °C over 30 minutes and held at 85 °C for 30 minutes and decanted washed 3x with toluene. Cool to 25 °C and let sit over weekend. Filter, add 65 mL of toluene. Heat to 40 °C @ 400 RPM and add 0.64 grams NPDE1.
  • Example 4 (Comparative). This example demonstrates preparing the catalyst component without organosilicon compound. The catalyst produced polymer with irregular morphology with agglomerated polymer particles.
  • Examples 5-13 illustrate preparing the catalyst components using a supportive donor, ethyl benzoate. (EB)
  • Example 5 (Comparative).
  • the catalyst component was made using tetraethylorthosilicate and the supportive donor, ethyl benzoate, and without an epoxy compound to dissolve MgCl 2 .
  • This example demonstrates an irregular polymer morphology with low BD.
  • MgCl 2 (12.0 g) and hexane (130 g) were combined to form an initial reaction mixture.
  • 2-ethylhexanol 50 g
  • stirring 600 rpm
  • FIG.1 is a photograph of the polymer obtained from Example 5
  • Example 6 Granular supported catalyst component prepared with Syltherm and TEOS (as organosilicon compounds) and ethyl benzoate as supportive electron donor.
  • the example demonstrates improvement of the catalyst component with larger particle size 24 microns and high activity catalyst (catalyst efficiency 92 kg/g) and producing polymer with rounded shape.
  • MgCl 2 (13.2 g), Al(OCH(CH3)2)3 (1.0 g), toluene (59.5 g), tri-n- butylphosphate (36.3 g), epichlorohydrin (14.25 g), and Syltherm (6.0 g) are combined and heated to 60 oC with agitation at 600 rpm for 8 hours under a nitrogen atmosphere.
  • toluene (140 g) was added, along with ethyl benzoate (4.5 g) and tetraethylorthosilicate (3 g).
  • the mixture was then cooled to -25 oC and TiCl 4 (261 g) was slowly added under 600 rpm stirring, while maintaining the temperature at -25 oC. After the addition was complete, the temperature was maintained for 1 hour prior to warming to 35 oC over 30 minutes, at which temperature it was held for 30 minutes, then the temperature was raised to 85 oC over 30 minutes, and held for 30 minutes prior to collection of a solid precipitate via filtration. The solid precipitate was washed three times with toluene (200 ml, each wash). [00193] The resulting precipitate was then combined with TiCl 4 in toluene (264 ml; 10 vol%).
  • FIG.2 is a photograph of the polymer produced with the catalyst component obtained from Example 6. Polymer morphology like rounded raspberry shape with large subparticles.
  • Example 7 This example produced a granular supported catalyst illustrating high BD catalyst/PP, with a narrow Span.
  • Example 6 was repeated, however the PDMS was added at 3.0 g, and Al(OCH(CH3)2)3 (0.5 g) and NPDE 1 (2.0g) was added in toluene wash before the final TiCl 4 /Toluene treatment.
  • Example 9 Example 9
  • Example 7 was repeated; however the TEOS was added at 1.50g.
  • Example 10 Illustrates preparation of catalyst component using Syltherm as organosilicon silicon compound. Granular supported catalyst component demonstrating reduction of particle sizes. Example 7 was repeated, however no TEOS was added.
  • FIGs.2 and 3 illustrate the rounded raspberry type morphology of polymers prepared by the catalysts of Examples 7, and 9, respectively, using an epoxy compound to dissolve MgCl 2 , along with varying combinations of organosilicon compounds (polydimethoxysilane (PDMS) and tetraethoxysilane (TEOS)), and ethyl benzoate, demonstrate improvement in catalyst and polymer morphology.
  • the FIGs 2 and 3. show the materials as having a well-defined morphology. The large sub- particles are associated in large particles.
  • the polymers produced with these catalysts exhibit a high density (> 0.40 g/ml) and sphericity (B/L3>0.71) (see tables above).
  • Example 11 illustrate the rounded raspberry type morphology of polymers prepared by the catalysts of Examples 7, and 9, respectively, using an epoxy compound to dissolve MgCl 2 , along with varying combinations of organosilicon compounds (polydimethoxysilane (PDMS) and tetra
  • Example 8 Demonstrates effect of amount of supportive donor on catalyst component particle size.
  • Example 8 was repeated except amount of ethyl benzoate was reduced from 0.34g/gMgCl 2 to 0.26 g/gMgCl 2 which resulted in a reduction of the catalyst component particle size from 18.6 microns to 10.2 microns.
  • Fig.4 the rounded shape of polymer morphology produced by the catalyst from Example 11.
  • Example 12. Demonstrates effect of agitation speed during the
  • Example 11 was repeated except the agitation speed was reduced from 300 rpm to 200 rpm, which resulted in increasing catalyst component particle size from 10.2 microns to 13.6 microns [00202]
  • Example 13 (Comparative). Granular supported catalyst demonstrating reduction of particle sizes and bulk density of the catalyst and polymer. No
  • Example 13 demonstrates that performance of the catalyst component prepared by using an epoxy compound to dissolve the MgCl 2 , and using only ethyl benzoate as a supportive donor without using organosilicon compounds.
  • FIG.5 represents the morphology of polymer produced according to Example 13. Each polymer particle contains numerous small sub-particles. In some polymerization processes, this morphology is not favored because these particles can be easily disintegrated up during the polymerization process.
  • Example 14. (Comparative). Catalyst component made with phthalic anhydride as a precipitation agent.
  • the catalyst component contains bis(1,3-dichloro- iso-propyl) phthalate (1.2%) and phthaloyl chloride (0.3%) as a reaction product of phthalic anhydride with TiCl 4 and Mg-compounds during the catalyst component preparation.
  • the catalyst component shows lower catalyst activity than the catalyst produced under the current claims.
  • the polymer particle morphology is a grape type with B/L3 ⁇ 0.70.
  • MgCl 2 (13.2 g), toluene (190.0 g), tri-n-butylphosphate 26.6 g), ECH (25.6 g) were combined and heated to 60o C with agitation at 600 rpm for 8 hours under a nitrogen atmosphere.
  • Phthalic anhydride was added (4.6 g) at 60o C. The mixture was then cooled to -25o C, at which temperature TiCl 4 (260 g) was slowly added with 600 rpm agitation. The temperature was maintained for 1 hour, followed by raising the temperature to 10o C over 30 minutes, holding for 30 minutes, raising to 85o C over 70 minutes, and holding for 15 minutes before collecting the solid via filtration. The solid was washed three times with toluene (200 ml) for 10 minutes each at the 85o C. The solid was then collected by filtration and washed with toluene (265 ml).
  • Example 14 demonstrates lower catalyst activity than the catalyst prepared without phthalic anhydride.
  • Examples 15-17 illustrate the catalyst component preparation using TEOS as organosilicon compound and ethyl benzoate as a supportive electron donor.
  • Examples 18-23 illustrate the polymerization data in bulk propylene and gas phase reactors producing polymer with substantially spherical shape.
  • Example 16 Add 13.2g MgCl 2 , 0.5g Al(OR)3, 72g toluene , 25.7g ECH, 26.8g TBP, Heat and Agitate at 60C/600rpm/8hr. Cool down to 25C. Leave for next day under N2 Blanket. Add 75.0g toluene, 3.5g EB in 12g toluene, 6.0g TEOS in 8g toluene @ 25C. Cool to -25C @ 600 rpm and add 260.8g TiCl 4 slowly addition. Raise from -25C to 35C over 2hr @ 350 rpm and hold at 35C for
  • Example 15 was repeated with increasing the NPDE1 amount by 10% Table 5
  • Examples 18-23 demonstrate production polymer in bulk and gas phase polymerization reactors with substantially spherical shape of particles with B/L3 of 0.8.
  • Fig.6 shows PP with substantially spherical shape morphology (microspheres) from example 23.
  • Surface area (BET) measurement and porosity of the catalyst components show surface area of around 400 m2/g. Table 7.
  • Examples 24-27 illustrate the relationship of the catalyst performances and relatively ratio of supportive electron donor and internal electron donor.
  • the catalyst isotacticity reduces (%XS) with increasing EB/NPDE1 ratio but the catalyst activity does not change sufficiently.
  • Table 8 Analytical data for catalyst components and corresponding catalyst polymerization data with variable ratio of supportive electron donor and electron donor
  • Example 28 illustrates granular catalyst components prepared with NPDE2 as an internal donor diaryl ester and example 29 presents polymerization data in bulk propylene.
  • the catalyst component was tested in bulk propylene polymerization to evaluate the hydrogen response on MFR. Table 8. Analytical data for catalyst components with NPDE 2
  • Example 29 was conducted at a hydrogen concentration of 5 SL.
  • the hydrogen concentration can be from about 5 SL to about to 40 SL or higher.
  • at lower hydrogen concentrations such as less than about 20 SL, such as less than about 10 SL, polymers are produced having a relatively low melt flow rate.
  • the melt flow rate can be less than about 8 g/10 min, such as less than about 5 g/10 min, such as less than about 3 g/10 min, such as less than about 2 g/10 min, such as less than 1 g/10 min, and generally greater than about 0.01 g/10 min.
  • the melt flow rate can be dramatically increased.
  • the melt flow rate can be greater than about 100 g/10 min, such as greater than about 150 g/10 min, such as greater than about 200 g/10 min, such as greater than about 250 g/10 min, such as greater than about 300 g/10 min, such as greater than about 350 g/10 min, such as greater than about 400 g/10 min, such as greater than about 450 g/10 min, such as greater than about 500 g/10 min, and generally less than about 800 g/10 min.
  • Hydrogen concentration can have some impact on catalyst activity.
  • the catalyst activity can range from about 90 kg/g to about 200 kg/g.
  • a catalyst activity of from about 150 kg/g to about 200 kg/g can reflect a flat kinetic profile.
  • Hydrogen concentration generally does not impact bulk density or particle size.
  • the bulk density can be greater than about 0.3 g/cc, such as greater than about 0.35 g/cc, such as greater than about 0.4 g/cc, and generally less than about 0.5 g/cc, such as less than about 0.45 g/cc.
  • the D50 particle size can generally be from about 500 microns to about 1700 microns, and generally from about 800 microns to about 1400 microns.
  • the B/L3 of the polymer can generally be greater than about 0.6, such as greater than about 0.65 and generally less than about 0.8, such as less than about 0.75.
  • Examples 30-32 illustrate preparing the catalyst components using 1,3 diether (3,3-bis(methoxymethyl)-2,6-dimethylheptane) (DEMH) as an internal donor.
  • DEMH 1,3 diether
  • Example 30 Added 6.6g MgCl 2 , 0.5g Al(O-iPr)3, 48g toluene, 18.2g TBP, 7.1g ECH to reactor. Heated and agitated at 60° C/600rpm/8hr. Cooled down to 25C.
  • Example 31 Example 8 was repeated except the solid precipitation was conducted at 350 rpm agitator speed and 0.80 g of DEMH used as an internal donor with 15% TiCl 4 /toluene treatment.
  • Example 32 Example 32.
  • Example 9 was repeated except the catalyst treatment was conducted with 20% TiCl 4 /toluene.
  • Table 10 Catalyst component characterization (1,3 diether (3,3-bis(methoxymethyl)-2,6- dimethylheptane) (DEMH)
  • Example 33 Demonstration of the preparation and performance of the spherical catalyst component.
  • MgCl 2 (13.2 g), Al(OCH(CH3)2)3 (1.0 g), toluene (59.5 g), tri-n-butylphosphate (“TBP;” 36.3 g), ECH (14.25 g), and Syltherm (6.0 g) are combined and heated to 60 oC with agitation at 600 rpm for 8 hours under a nitrogen atmosphere.
  • the solid was then collected by filtration and washed with a 10 wt% TiCl 4 /toluene solution (265 ml) with agitation at 85o C, followed by addition of NPDE1 (2.0 g) in toluene (5.0 g) with heating at 85o C for 60 minute, and followed by filtration. After filtration, the solid was again washed with the TiCl 4 /toluene solution and NPDE1 (0.5 g) in toluene (2 g), but this time at 95o C. After again filtering, the solid was collected, and washed with the TiCl 4 /toluene solution at 110o C under agitation.
  • Example 34 demonstrates the preparation of a spherical catalyst component made using epoxy compounds to dissolve MgCl 2 , but without the use of an anhydride. Instead, an organosilicon compound, Al(O-iPr)3, and ethyl benzoate were used.
  • the polymer produced with this catalyst (FIG.7) shows high density particles and good sphericity (microspheres).
  • Example 35 Demonstration of the preparation and performance of the spherical catalyst component using TEOS instead Syltherm.
  • Example 34 was repeated, however the Syltherm was replaced with TEOS (5 g) and dibutyl ether (12 g) was used.
  • Example 36 (Comparative). A catalyst was made with EB (no PDMS, no aluminum alkoxide) demonstrating irregular catalyst/polymer morphology, low BD of catalyst/polymer and broad catalyst/PP span. Example 33 was repeated, however no PDMS and Al(OCH(CH3)2)3 were added.
  • Example 35 demonstrates the preparation of a catalyst component, prepared using an epoxy compound to dissolve MgCl 2 , and ethyl benzoate. No organosilicon compounds and Al(O-iPr)3 were used. The polymer produced with the catalyst of Example 35, exhibits low bulk density particles and with an irregular morphology.
  • Table 11 Analytical Data for the spherical solid catalyst components and polymer properties
  • Examples 37-39 demonstrate properties of polypropylene (PI and rheological breadth) produced with catalyst components using different internal donors Table 12 PI and phelogical breadth of PP produced with selected catalysts
  • Example 40-43 The solid catalyst component from example 11 was used for bulk propylene polymerization as described above except a mixture of external donors sold under the designation D6500 were used, which are commercially available from W.R. Grace and Company.
  • D6500 a mixture of external donors sold under the designation
  • the table below demonstrates effect of amount of a mixture of external donors on XS level (catalyst activity) and polymer properties. Table 13
  • Example 44 demonstrates catalyst activity and polyethylene properties produced with solid precipitate from example 15.
  • the polymerization was conducted in hexane in a one-gallon reactor. The reactor was purged at 100 oC under nitrogen for one hour. At room temperature, 0.6 ml of 25- wt% triethylaluminum (TEAL) in heptane was added into the reactor. Then 1500 ml of hexane was added and 10 mg of the catalyst prepared above were added into the reactor. The reactor was pressurized with H2 to 60.0 psig then charged with ethylene to 116 psig.
  • TEAL triethylaluminum
  • Examples 45 and 46 demonstrate the improved lifetime of catalysts made in accordance with the present disclosure.
  • the lifetime of polymerization catalysts can be important for the commercial production of polyolefins. The long lifetime of the catalyst allows to conduct polymerization processes continually in different reactors producing homopolymers and co-polymers with a variety of properties. Many Ziegler-Natta catalysts, in particular non-phthalate donor catalysts, have a limited lifetime. Usually the catalyst activity for these types of catalysts is very high at the beginning of the polymerization process and decreases dramatically thereafter.
  • the reactor was cooled to 30-35°C and cocatalyst (1.5 ml of 25 wt% triethylaluminum (TEAl)), C-donor [cyclohexylmethydimethoxysilane] (1 ml), hydrogen (3.5 psi) and liquid propylene (1500 ml) were added in this sequence into the reactor.
  • the catalyst (5-10 mg), loaded as a mineral oil slurry, was pushed into the reactors using high pressure nitrogen. The polymerization was performed for one or two hours at 70° C. After the polymerization, the reactors were cooled to 22° C, vented to atmospheric pressure, and the polymer collected. [00240] The following results were obtained:
  • the catalysts made according to the present disclosure have excellent catalyst activity during the entire two hour period of polymerization. More particularly, the data illustrates that catalyst systems in accordance with the present disclosure have an extended lifetime such that the catalyst activity during a second hour of polymerization is not less than about 8%, such as not less than about 7% of the catalyst activity of the catalyst system during a first hour of polymerization. Examples 47-51 [00242] The following examples were conducted in order to demonstrate the dramatic and unexpected improvement in the flowability or polymers made according to the present disclosure.
  • the following examples demonstrate the improved flowability properties of elastomeric propylene-ethylene copolymers made in accordance with the present disclosure that contain relatively high amounts of amorphous polyethylene that provide the polymers with elastomeric properties.
  • the examples below had a rubber content of greater than 30% by weight.
  • Such polymer resins typically have very poor flow properties and have a tendency to stick together and form agglomerates.
  • the propylene-ethylene random copolymers were formed using a gas phase polymerization process.
  • the reactor set up included two fluidized bed reactors in series. Polypropylene homopolymer was produced in the first reactor. Non- phthalate catalysts were used to produce the polymers.
  • Example numbers 47 and 48 below are comparative examples.
  • Example numbers 49-51 a catalyst was made in accordance with Example No.8 above except a scale of 20 kg was used. [00244] In the first reactor, the catalyst was used in conjunction with
  • DCPDMS dicyclopentyldimethoxysilane
  • IPM iso- propylmyristate
  • the mixed external election donors included n-propyltrimethoxysilane (NPTMS) as the selectivity control agent and pentyl valerate (PV) as the activity limiting agent.
  • NPTMS n-propyltrimethoxysilane
  • PV pentyl valerate
  • the reactor set up was a two gas phase fluidized-bed UNIPOL reactor system available for license by W.R. Grace & Co. and is described in U.S. Patent No. 4,882,380, which is incorporated herein by reference.
  • the polymer resins were tested according to the Cup Test as described above.
  • the following Table includes operating conditions, product information, and the Cup Test results.

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Abstract

La présente invention concerne de manière générale des polymères de polyoléfine, tels que des homopolymères de polypropylène, et des copolymères de propylène-éthylène qui ont des propriétés d'écoulement améliorées. Dans un mode de réalisation, les polymères peuvent être produits au moyen d'un composant de catalyseur solide qui comprend a) la dissolution d'un composé de magnésium contenant un halogénure dans un mélange, le mélange comprenant un composé époxy, un composé de phosphore organique et un solvant d'hydrocarbure pour former une solution homogène; b) le traitement de la solution homogène avec un composé organosilicié pendant ou après l'étape de dissolution; c) le traitement de la solution homogène avec un premier composé de titane en présence d'un premier donneur d'électrons non-phtalate, et un composé organosilicié, pour former un précipité solide; et d) le traitement du précipité solide avec un second composé de titane en présence d'un second donneur d'électrons non phtalate pour former le composant catalyseur solide, le processus étant exempt d'acides carboxyliques et d'anhydrides.
PCT/US2018/060768 2017-11-13 2018-11-13 Composition polymère de polyoléfine WO2019094942A1 (fr)

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JP2020544377A JP7223017B2 (ja) 2017-11-13 2018-11-13 ポリオレフィンポリマー組成物
US16/762,353 US11421056B2 (en) 2017-11-13 2018-11-13 Polyolefin polymer composition
KR1020207016270A KR102660279B1 (ko) 2017-11-13 2018-11-13 폴리올레핀 중합체 조성물
EP18875540.9A EP3710527A4 (fr) 2017-11-13 2018-11-13 Composition polymère de polyoléfine
RU2020119468A RU2800539C2 (ru) 2017-11-13 2018-11-13 Композиция полиолефинового полимера
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