US20180326407A1 - Olefin polymerization catalyst components and process for the production of olefin polymers therewith - Google Patents

Olefin polymerization catalyst components and process for the production of olefin polymers therewith Download PDF

Info

Publication number
US20180326407A1
US20180326407A1 US15/590,559 US201715590559A US2018326407A1 US 20180326407 A1 US20180326407 A1 US 20180326407A1 US 201715590559 A US201715590559 A US 201715590559A US 2018326407 A1 US2018326407 A1 US 2018326407A1
Authority
US
United States
Prior art keywords
dimethoxypropane
bis
methoxymethyl
component
internal electron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US15/590,559
Other versions
US10124324B1 (en
Inventor
Gapgoung Kong
Lei Zhang
Demin Xu
Yiqun Fang
Chih-Jian Chen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Formosa Plastics Corp USA
Original Assignee
Formosa Plastics Corp USA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Formosa Plastics Corp USA filed Critical Formosa Plastics Corp USA
Priority to US15/590,559 priority Critical patent/US10124324B1/en
Assigned to FORMOSA PLASTICS CORPORATION, USA reassignment FORMOSA PLASTICS CORPORATION, USA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHEN, CHIH-JIAN, FANG, YIQUN, KONG, GAPGOUNG, XU, DEMIN, ZHANG, LEI
Application granted granted Critical
Publication of US10124324B1 publication Critical patent/US10124324B1/en
Publication of US20180326407A1 publication Critical patent/US20180326407A1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J35/0006—
    • 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
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0881—Titanium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • 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

  • This invention relates (1) to Ziegler-Natta catalyst components for olefin polymerization employing specific forms of amide compounds as an element of the solid catalyst composition in conjunction with one or more internal donor compounds, (2) to methods of making such polymerization catalyst systems, and (3) to polymerization processes for producing polyolefins, particularly polypropylene, that exhibit substantially higher stereo-regularity and activity.
  • Ziegler-Natta catalyst systems for polyolefin polymerization are well known in the art. Commonly, these systems are composed of a solid Ziegler-Natta catalyst component and a co-catalyst component, usually an organoaluminum compound, and/or an external electron donor to be used in conjunction.
  • the Ziegler-Natta catalyst components have included magnesium, halide, titanium and internal electron donor compounds which have been widely employed to increase the activity and stereo-specificity of polymerization catalyst system.
  • Common internal electron donor compounds which are incorporated in the solid Ziegler-Natta catalyst component during preparation of such component, are known in the art and include ethers, ketones, amines, alcohols, heterocyclic organic compounds, phenols, phosphines, and silanes. It is well known in the art that polymerization activity, as well as stereoregularity, molecular weight, and molecular weight distribution of the resulting polymer depend on the molecular structure of the internal electron donor employed. Therefore, in order to improve the polymerization process and the properties of the resulting polymer, there has been an effort and desire to develop various internal electron donors. Examples of such internal electron donor compounds and their use as a component of the catalyst system are described in U.S. Pat. Nos.
  • an external electron donor In the utilization of Ziegler-Natta type catalysts for polymerizations involving propylene or other olefins for which isotacticity is a possibility, it may be desirable to utilize an external electron donor, and acceptable external electron donors include organic compounds containing O, Si, N, S, and/or P. Such compounds include organic acids, organic acid esters, organic acid anhydrides, ethers, ketones, alcohols, aldehydes, silanes, amides, urea, amines, amine oxides, thiols, various phosphorus acid esters and amides, etc.
  • Preferred external electron donors are organosilicon compounds containing Si—O—C and/or Si—N—C bonds, having silicon as the central atom.
  • U.S. Pat. No. 6,323,150 describes the use of a propylene polymerization catalyst which contains a reduced amount of phthalate as an internal electron donor.
  • the resultant polypropylene product was found to exhibit low isotacticity and productivity.
  • This reference further taught a polymerization catalyst consisting of a polyether compound combined with the phthalate derivative as internal electron donors. The resultant polypropylene product exhibits lower isotacticity than that of a catalyst containing only the phthalate derivative.
  • U.S. Pat. No. 7,491,781 teaches the use of an internal electron donor in a propylene polymerization catalyst component which does not contain a phthalate derivative.
  • the resultant propylene polymerization catalyst produced polypropylene with lower isotacticity than that of a catalyst containing a phthalate derivative.
  • U.S. Pat. No. 7,276,463 teaches the use of compound containing a C( ⁇ O)N bond, such as amide or urea, as an external donor in the polymerization process, in combination with a silicon compound and an organoaluminum compound that enables the production of olefin polymer with improved stereo-regularity.
  • urea was never employed as an element of a solid catalyst composition in the catalyst preparation process, and never enabled production of phthalate-free catalyst system with stereo-regularity that is equal to or better than phthalate catalyst systems.
  • U.S. Patent Publ. No. 2016/0115260 A1 teaches the use of an oxalic acid amide compound as a modifier in the composition of solid catalyst components to improve stereo-regularity that enables the production of phthalate-free catalyst system with stereo-regularity that is equal to or better than phthalate catalyst systems.
  • R is an aliphatic hydrocarbon having 1 to 20 carbon atoms that may or may not contain a carbonyl or carbonyl ester group, wherein R 1 is an alkyl group having 1 to 20 carbon atoms, wherein R and R 1 may be linked to form a cyclic ring, and R 2 is hydrogen, alkyl group having 1 to 20 carbon atom, phenyl, carbonyl or alkoxy carbonyl.
  • urea compound employed as an element of solid Ziegler-Natta catalyst components in conjunction with one or more internal donors, for the production of polyolefins, particularly polypropylene are disclosed.
  • the urea compounds of the present invention may be used in combination with one or more internal electron donors that are typically employed in Ziegler-Natta polypropylene catalyst systems such as 1,3-diethers, malonates, succinates, phthalic acid esters, esters of aliphatic or aromatic diols, or their derivatives.
  • the amide compounds that may be employed as an element of a solid catalyst composition are represented by Formula I:
  • R is an aliphatic hydrocarbon having 1 to 20 carbon atoms that may or may not contain carbonyl or a carbonyl ester group, wherein R 1 is alkyl group having 1 to 20 carbon atoms, wherein R and R 1 may be linked to form a cyclic ring, and R 2 is hydrogen, alkyl group having 1 to 20 carbon atom, phenyl, carbonyl, or alkoxy carbonyl.
  • Preferred embodiments of the amide compounds of Formula I include, but not limited to cyclic amide compounds, such as: n-methyl-2-piperidone, n-ethyl-2-piperidone, n-propyl-2-piperidone, n-butyl-2-piperidone, n-phenyl-2-piperidone, 2-piperidone, 2-pyrrolidinone, n-methyl-2-pyrrolidinone, n-ethyl-2-pyrrolidinone, n-propyl-2-pyrrolidinone, n-butyl-2-pyrrolidinone, n-phenyl-2-pyrrolidinone, n-methyl-caprolactam, or their derivatives.
  • cyclic amide compounds such as: n-methyl-2-piperidone, n-ethyl-2-piperidone, n-propyl-2-piperidone, n-butyl-2-piperidone, n-phenyl-2-piperidone, 2-
  • preferred embodiments of Formula I include cyclic amide compounds containing carbonyl ester groups, such as: 3-ethoxycarbonyl-2-piperidone, 3-methoxycarbonyl-2-piperidone, 3-propoxycarbonyl-2-piperidone, 3-phenoxycarbonyl-2-piperidone, n-tert-butoxycarbonyl-2-piperidone, n-ethoxycarbonyl-2-piperidone, n-propoxycarbonyl-2-piperidone, n-phenoxycarbonyl-2-piperidone, or their derivatives.
  • carbonyl ester groups such as: 3-ethoxycarbonyl-2-piperidone, 3-methoxycarbonyl-2-piperidone, 3-propoxycarbonyl-2-piperidone, 3-phenoxycarbonyl-2-piperidone, n-tert-butoxycarbonyl-2-piperidone, n-ethoxycarbonyl-2-piperidone, n-propoxycarbonyl-2-piperidone, n-phenoxycarbony
  • Suitable amide compounds of Formula I include, but are not limited to, non-cyclic amide compounds, such as n,n-dimethylpropionamide, n,n-dimethylisobutyramide, n,n-dimethylacetamide, n,n-dimethylpentanamide, n,n-dimethylhexanamide n,n-diethylpropionamide, n-ethyl-n-(3-methyl phenyl)propionamide, n,n-dimethyl-benzamide, or their derivatives.
  • non-cyclic amide compounds such as n,n-dimethylpropionamide, n,n-dimethylisobutyramide, n,n-dimethylacetamide, n,n-dimethylpentanamide, n,n-dimethylhexanamide n,n-diethylpropionamide, n-ethyl-n-(3-methyl phenyl)propionamide,
  • Acceptable Ziegler-Natta type catalyst systems that may be used in accordance with the present invention comprise (a) a solid Ziegler-Natta type catalyst component containing urea compound as a modifier in conjunction with internal donors, (b) a co-catalyst component, and optionally (c) one or more external electron donors.
  • Preferred solid Ziegler-Natta type catalyst component (a) include solid catalyst components comprising a titanium compound having at least a Ti-halogen bond and an amide compound in combination with internal electron donor compound supported on an anhydrous magnesium-dihalide support.
  • Acceptable internal electron donor compounds for the preparation of solid Ziegler-Natta type catalyst component (a) are not generally limited and include, but are not limited to, one or more internal electron donors that are typically employed in Ziegler-Natta polypropylene catalyst system, such as 1,3-diethers, malonates, succinates, phthalic acid esters, esters of aliphatic or aromatic diols, or their derivatives.
  • phthalic acid esters that may be used in conjunction with Formula I compounds include, but are not limited to: diethylphthalate, di-n-propylphthalate, di-n-butylphthalate, di-n-pentylphthalate, di-i-pentylphthalate, bis(2-ethylhexyl)phthalate, ethylisobutylphthalate, ethyl-n-butylphthalate, di-n-hexylphthalate, di-isobutylphthalate.
  • 1,3-diethers that may be used in conjunction with Formula I compounds include, but are not limited to: 2-(2-ethylhexyl)1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl
  • malonates that may be used in conjunction with Formula I compounds include, but are not limited to: diethyl2-isopropylmalonate, diethyl2-phenylmalonate, dineopentyl 2-isopropylmalonate, diisobutyl 2-isopropylmalonate, di-n-butyl 2-isopropylmalonate, diethyl 2-dodecylmalonate, diethyl 2-t-butylmalonate, diethyl 2-(2-pentyl)malonate, diethyl 2-cyclohexylmalonate, dineopentyl 2-t-butylmalonate, dineopentyl 2-isobutylmalonate, diethyl 2-cyclohexylmethylmalonate, dimethyl 2-cyclohexylmethylmalonate, diethyl 2,2-dibenzylmalonate, diethyl 2-isobutyl-2-cyclohexylmalon
  • succinates that may be used in conjunction with Formula I compounds include, but are not limited to: diethyl 2,3-bis(trimethylsilyl)succinate, diethyl 2,3-bis(2-ethylbutyl)succinate, diethyl 2,3-dibenzylsuccinate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diethyl 2,3-bis(cyclohexylmethyl)succinate, diethyl 2,3-diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate, diethyl 2,3-dicyclopentylsuccinate, diethyl 2,3-dicyclohexylsuccinate.
  • esters of aliphatic or aromatic diols that may be used in conjunction with Formula I compounds include, but are not limited to: 1,3-propylene-glycol dibenzoate, 2-methyl-1,3-propylene-glycol dibenzoate, 2-ethyl-1,3-propylene-glycol dibenzoate, 2-propyl-1,3-propylene-glycol dibenzoate, 2-butyl-1,3-propylene-glycol dibenzoate, 2,2-dimethyl-1,3-propylene-glycol dibenzoate, (R)-1-phenyl-1,3-propylene-glycol dibenzoate, (S)-1-phenyl-1,3-propylene-glycol dibenzoate, 1,3-diphenyl-1,3-propylene-glycol dibenzoate, 2-methyl-1,3-diphenyl-1,3-propylene-glycol dibenzoate, 1,3-diphenyl-1,3-
  • Acceptable anhydrous magnesium dihalides forming the support of the solid Ziegler-Natta type catalyst component (a) are the magnesium dihalides in active form that are well known in the art. Such magnesium dihalides may be preactivated, may be activated in situ during the titanation, may be formed in-situ from a magnesium compound, which is capable of forming magnesium dihalide when treated with a suitable halogen-containing transition metal compound, and then activated.
  • Preferred magnesium dihalides are magnesium dichloride and magnesium dibromide.
  • the water content of the dihalides is generally less than 1% by weight.
  • the solid Ziegler-Natta type catalyst component (a) may be made by various methods.
  • One such method consists of co-grinding the magnesium dihalide and the internal electron donor compound until the product shows a surface area higher than 20 m 2 /g and thereafter reacting the ground product with the Ti compound.
  • Other methods of preparing solid Ziegler-Natta type catalyst component (a) are disclosed in U.S. Pat. Nos. 4,220,554; 4,294,721; 4,315,835; 4,330,649; 4,439,540; 4,816,433; and 4,978,648. These methods are incorporated herein by reference.
  • the molar ratio between the magnesium dihalide and the halogenated titanium compound is between 1 and 500
  • the molar ratio between said halogenated titanium compound and the internal electron donor is between 0.1 and 50
  • the molar ratio between said internal electron donor and the oxalic acid diamide modifier is between 0.1 and 100.
  • Preferred co-catalyst component (b) includes aluminum alkyl compounds, which can be represented by the formula II;
  • R n represents an alkyl group having 1 to 6 carbon atoms
  • Q represents a hydrogen or a halogen atom
  • n represents a real number that satisfies 0 ⁇ n ⁇ 3.
  • Acceptable aluminum alkyl compounds include aluminum trialkyls, such as aluminum triethyl, aluminum triisobutyl, and aluminum triisopropyl.
  • Other acceptable aluminum alkyl compounds include aluminum-dialkyl hydrides, such as aluminum-diethyl hydrides.
  • Other acceptable co-catalyst component (b) includes compounds containing two or more aluminum atoms linked to each other through hetero-atoms, such as:
  • Acceptable external electron donor component (c) is organic compounds containing O, Si, N, S, and/or P. Such compounds include organic acids, organic acid esters, organic acid anhydrides, ethers, ketones, alcohols, aldehydes, silanes, amides, amines, amine oxides, thiols, various phosphorus acid esters and amides, etc.
  • Preferred component (c) is organosilicon compounds containing Si—O—C and/or Si—N—C bonds.
  • organosilicon compounds are, without limitation, trimethylmethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, isobutyltriethoxysilane, vinyltrimethoxysilane, dicyclohexyldimethoxysilane, 3-tert-Butyl-2-isobutyl-2methoxy-[1,3,2]oxazasilolidine, 3-tert-Butyl-2-cyclopentyl-2-methoxy-[1,3,2]oxazasilolidine, 2-Bicyclo[2.2.1]hept-5-en-2-yl-3-tert-butyl-2-methoxy-[1,3,2]oxazasilolidine, 3-tert-Butyl-2,2-diethoxy-[1,3,2]oxazasilol
  • the olefin polymerization processes that may be used in accordance with the present invention are not generally limited.
  • the catalyst components (a), (b) and (c), when employed, may be added to the polymerization reactor simultaneously or sequentially. It is preferred to mix components (b) and (c) first and then contact the resultant mixture with component (a) prior to the polymerization.
  • the olefin monomer may be added prior to, with, or after the addition of the Ziegler-Natta type catalyst system to the polymerization reactor. It is preferred to add the olefin monomer after the addition of the Ziegler-Natta type catalyst system.
  • the molecular weight of the polymers may be controlled in a known manner, preferably by using hydrogen. With the catalysts produced according to the present invention, molecular weight may be suitably controlled with hydrogen when the polymerization is carried out at relatively low temperatures, e.g., from about 30° C. to about 105° C. This control of molecular weight may be evidenced by a measurable positive change of the Melt Flow Rate.
  • the polymerization reactions may be carried out in slurry, liquid or gas phase processes, or in a combination of liquid and gas phase processes using separate reactors, all of which may be done either by batch or continuously.
  • the polyolefin may be directly obtained from gas phase process, or obtained by isolation and recovery of solvent from the slurry process, according to conventionally known methods.
  • polymerization conditions for production of polyolefins by the method of this invention such as the polymerization temperature, polymerization time, polymerization pressure, monomer concentration, etc.
  • the polymerization temperature is generally from 40-90° C. and the polymerization pressure is generally 1 atmosphere or higher.
  • the Ziegler-Natta type catalyst systems of the present invention may be pre-contacted with small quantities of olefin monomer, well known in the art as prepolymerization, in a hydrocarbon solvent at a temperature of 60° C. or lower for a time sufficient to produce a quantity of polymer from 0.5 to 3 times the weight of the catalyst. If such a prepolymerization is done in liquid or gaseous monomer, the quantity of resultant polymer is generally up to 1000 times the catalyst weight.
  • the Ziegler-Natta type catalyst systems of the present invention are useful in the polymerization of olefins, including but not limited to homopolymerization and copolymerization of alpha olefins.
  • Suitable ⁇ -olefins that may be used in a polymerization process in accordance with the present invention include olefins of the general formula CH 2 ⁇ CHR, where R is H or C 1-10 straight or branched alkyl, such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1 and octene-1.
  • Ziegler-Natta type catalyst systems of the present invention may be employed in processes in which ethylene is polymerized, it is more desirable to employ the Ziegler-Natta type catalyst systems of the present invention in processes in which polypropylene or higher olefins are polymerized. Processes involving the homopolymerization or copolymerization of propylene are preferred.
  • Heptane Insolubles (% HI): The weight percent (wt %) of residuals of polypropylene sample after extracted with boiling heptane for 8 hours.
  • MI Melt Flow rate
  • T m ASTM D-3417, determined by DSC (Manufacturer: TA Instrument, Inc.; Model: DSC Q1000).
  • Mn and Mw The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) of polymers were obtained by gel permeation chromatography on Water 2000GPCV system using Polymer Labs Plgel 10 um MIXED-B LS 300 ⁇ 7.5 mm columns and 1,2,4-trichlorobenzene (TCB) as mobile phase. The mobile phase was set at 0.9 ml/min, and temperature was set at 145° C. Polymer samples were heated at 150° C. for two hours. Injection volume was 200 microliters. External standard calibration of polystyrene standards was used to calculate the molecular weight.
  • P-donor Diisopropyldimethoxysilane
  • D-donor dicyclopentyldimethoxysilane
  • the solid was washed twice with 100 ml of anhydrous toluene at 90° C., and then 80 ml of fresh anhydrous toluene and 20 ml TiCl 4 was added to the filtered solid. Temperature of the mixture was heated to 110° C., and stirred for 2 hours. The solid was precipitated and supernatant liquid was decanted and residual solid was washed with heptane 7 times at 70° C. The final catalyst was collected and dried under vacuum to obtain a solid catalyst component (A1).
  • Propylene polymerization was conducted in a bench scale 2-liter reactor per the following procedure.
  • the reactor was first preheated to at least 100° C. with a nitrogen purge to remove residual moisture and oxygen.
  • the reactor was thereafter cooled to 50° C. Under nitrogen, 1 liter dry heptane was introduced into the reactor.
  • When reactor temperature was about 50° C. 4.3 ml of triethylaluminum (0.58M, in hexanes), 0.8-1.6 ml of dicyclopentyl(dimethoxy)silane (D-donor) (0.5 M in heptane), and then 30 mg of the solid catalyst component (A1) prepared above were added to the reactor.
  • the temperature of the reactor was heated to 50° C. and 8 psi hydrogen in a 150 ml vessel was flushed into the reactor with propylene.
  • the reactor temperature was then raised to 70° C.
  • the total reactor pressure was raised to and controlled at 90 psig by continually introducing propylene into the reactor and the polymerization was allowed to proceed for 1 hour. After polymerization, the reactor was vented to reduce the pressure to 0 psig and the reactor temperature was cooled to 50° C.
  • a solid catalyst component (A2) was prepared in the same manner as in Example 1, except that 2.0 mmol of n-tert-buthoxycarbonyl-2-piperidone was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A2) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1 & 2.
  • a solid catalyst component (A3) was prepared in the same manner as in Example 1, except that 2.0 mmol of n-methylpiperidone was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A3) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1 & 2.
  • a solid catalyst component (A4) was prepared in the same manner as in Example 1, except that 2.0 mmol of n,n-dimethylpropionamide was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A4) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1 & 2.
  • a solid catalyst component (A5) was prepared in the same manner as in Example 1, except that 2.0 mmol of 2-piperidone was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A5) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1 & 2.
  • a solid catalyst component (A6) was prepared in the same manner as in Example 1, except that 2.0 mmol of 2-pyrrolidinone was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A6) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1&2.
  • a solid catalyst component (C1) was prepared in the same manner as in Example 1, except that 10.0 mmol of 9,9-bis(methoxymethyl)fluorene was used instead of diisobutylphthalate. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A8) was charged instead of solid catalyst component (C2). The results are summarized in TABLE 1 & 2.
  • the resulting solid was filtered and washed twice with 100 ml of anhydrous toluene at 90° C., and then 80 ml of fresh anhydrous toluene and 20 ml TiCl 4 was added to the filtered solid. Temperature of the mixture was heated to 110° C., and stirred for 2 hours. The solid was filtered and residual solid was washed with heptane 7 times at 70° C. The final catalyst was collected and dried under vacuum to obtain a solid catalyst component (A7).
  • a solid catalyst component (C2) was prepared in the same manner as in Example 7, except that of 3-ethoxycarbonyl-2-piperidone was not added.
  • the catalyst component (Ex. 1-Ex. 6) employing amide compounds in combination with internal donors of 1,3-diether (9,9-bis(methoxymethyl)fluorene) as an element of catalyst composition, produce polypropylene with an isotacticity and activities much higher than the comparative catalyst components (C1) that does not contain the urea element in its solid catalyst composition.
  • Catalyst component A1-A6 containing amide element in its catalyst composition produced polypropylene of 98.1-98.6% HI (Example 1-Example 6) with activities of 2883-4280 gPP/gcat in the presence of 0.4 mmol P donor, which is much higher than % HI 97.2% with activity of 3533 gPP/gcat by comparative catalyst components (C1) that does not contain amide element in its solid catalyst composition.
  • catalyst component A7 containing the amide element produced polypropylene with % HI of 99.6 (Example 7), which is much higher than 99.1% for the comparative catalyst component C2, which does not contain an amide element in its solid catalyst composition.

Landscapes

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

Abstract

The present invention relates to a Ziegler-Natta catalyst component for olefin polymerization containing an amide element in combination with one or more internal electron donors. The catalyst components, according to the present invention, are able to produce polypropylene polymers with higher stereo-regularity. The present invention also provides a phthalate-free catalyst system capable of producing polypropylene with an isotacticity that is equal to or higher than catalyst systems containing phthalate derivatives.

Description

    BACKGROUND 1. Field of the Invention
  • This invention relates (1) to Ziegler-Natta catalyst components for olefin polymerization employing specific forms of amide compounds as an element of the solid catalyst composition in conjunction with one or more internal donor compounds, (2) to methods of making such polymerization catalyst systems, and (3) to polymerization processes for producing polyolefins, particularly polypropylene, that exhibit substantially higher stereo-regularity and activity.
    • 2. Description of the Related Art
  • Ziegler-Natta catalyst systems for polyolefin polymerization are well known in the art. Commonly, these systems are composed of a solid Ziegler-Natta catalyst component and a co-catalyst component, usually an organoaluminum compound, and/or an external electron donor to be used in conjunction. The Ziegler-Natta catalyst components have included magnesium, halide, titanium and internal electron donor compounds which have been widely employed to increase the activity and stereo-specificity of polymerization catalyst system.
  • Common internal electron donor compounds, which are incorporated in the solid Ziegler-Natta catalyst component during preparation of such component, are known in the art and include ethers, ketones, amines, alcohols, heterocyclic organic compounds, phenols, phosphines, and silanes. It is well known in the art that polymerization activity, as well as stereoregularity, molecular weight, and molecular weight distribution of the resulting polymer depend on the molecular structure of the internal electron donor employed. Therefore, in order to improve the polymerization process and the properties of the resulting polymer, there has been an effort and desire to develop various internal electron donors. Examples of such internal electron donor compounds and their use as a component of the catalyst system are described in U.S. Pat. Nos. 4,107,414; 4,186,107; 4,226,963; 4,347,160; 4,382,019; 4,435,550; 4,465,782; 4,522,930; 4,530,912; 4,532,313; 4,560,671; 4,657,882; 5,208,302; 5,902,765; 5,948,872; 6,048,818; 6,121,483; 6,281,301; 6,294,497; 6,313,238; 6,395,670; 6,436,864; 6,605,562; 6,716,939; 6,770,586; 6,818,583; 6,825,309; 7,022,640; 7,049,377; 7,202,314; 7,208,435; 7,223,712; 7,351,778; 7,371,802; 7,491,781; 7,544,748; 7,674,741; 7,674,943; 7,888,437; 7,888,438; 7,935,766; 7,964,678; 8,003,558; 8,003,559; 8,088,872; 8,211,819; 8,222,357; 8,227,370; 8,236,908; 8,247,341; 8,263,520; 8,263,692; 8,288,304; 8,288,585; 8,288,606; 8,318,626; 8,383,540; 8,536,290; 8,569,195; 8,575,283; 8,604,146; 8,633,126; 8,692,927; 8,664,142; 8,680,222; 8,716,514; and 8,742,040, which are incorporated by reference herein.
  • In the utilization of Ziegler-Natta type catalysts for polymerizations involving propylene or other olefins for which isotacticity is a possibility, it may be desirable to utilize an external electron donor, and acceptable external electron donors include organic compounds containing O, Si, N, S, and/or P. Such compounds include organic acids, organic acid esters, organic acid anhydrides, ethers, ketones, alcohols, aldehydes, silanes, amides, urea, amines, amine oxides, thiols, various phosphorus acid esters and amides, etc. Preferred external electron donors are organosilicon compounds containing Si—O—C and/or Si—N—C bonds, having silicon as the central atom. Such compounds are described in U.S. Pat. Nos. 4,472,524; 4,473,660; 4,560,671; 4,581,342; 4,657,882; 5,106,807; 5,407,883; 5,684,173; 6,228,961; 6,362,124; 6,552,136; 6,689,849; 7,009,015; 7,244,794; 7,276,463; 7,619,049; 7,790,819; 8,247,504; 8,648,001; and 8,614,162, which are incorporated by reference herein. U.S. Pat. No. 6,271,310 listed urea as a potential external donor that may be used for propylene polymerization.
  • Most commercial propylene polymerization catalysts currently employ alkyl phthalate esters as an internal electron donor. But still there is a need to further improve stereo-regularity of catalyst components employing alkyl phthalate esters as an internal donor for the application of polypropylene polymer to impact copolymer area. Moreover, certain environmental issues have been recently raised concerning the continued use of phthalate derivatives in human contact applications. As a result, the employment of a phthalate-free propylene polymerization catalyst or a catalyst system that employs a reduced amount of phthalate is now necessary for the production of polypropylene to remedy these issues.
  • U.S. Pat. No. 6,323,150 describes the use of a propylene polymerization catalyst which contains a reduced amount of phthalate as an internal electron donor. However, the resultant polypropylene product was found to exhibit low isotacticity and productivity. This reference further taught a polymerization catalyst consisting of a polyether compound combined with the phthalate derivative as internal electron donors. The resultant polypropylene product exhibits lower isotacticity than that of a catalyst containing only the phthalate derivative.
  • U.S. Pat. No. 7,491,781 teaches the use of an internal electron donor in a propylene polymerization catalyst component which does not contain a phthalate derivative. However the resultant propylene polymerization catalyst produced polypropylene with lower isotacticity than that of a catalyst containing a phthalate derivative.
  • U.S. Pat. No. 7,276,463 teaches the use of compound containing a C(═O)N bond, such as amide or urea, as an external donor in the polymerization process, in combination with a silicon compound and an organoaluminum compound that enables the production of olefin polymer with improved stereo-regularity. However urea was never employed as an element of a solid catalyst composition in the catalyst preparation process, and never enabled production of phthalate-free catalyst system with stereo-regularity that is equal to or better than phthalate catalyst systems.
  • Recently, U.S. Patent Publ. No. 2016/0115260 A1 teaches the use of an oxalic acid amide compound as a modifier in the composition of solid catalyst components to improve stereo-regularity that enables the production of phthalate-free catalyst system with stereo-regularity that is equal to or better than phthalate catalyst systems.
  • As such, there is still a need of development for a catalyst system that can produce polypropylene with further higher isotacticity, hydrogen response, and activity. Even more desirable is the development of phthalate free catalyst system producing polypropylene with even higher isotacticity and activity.
    • SUMMARY OF THE INVENTION
  • It is therefore an object of present invention to provide a method of preparing Ziegler-Natta catalyst components for producing polypropylene with enhanced isotacticity and activity, where the catalyst components comprise magnesium, titanium, halide, one or more internal electron donors, and an amide compound selected from the compound represented by Formula I:
  • Figure US20180326407A1-20181115-C00001
  • wherein R is an aliphatic hydrocarbon having 1 to 20 carbon atoms that may or may not contain a carbonyl or carbonyl ester group, wherein R1 is an alkyl group having 1 to 20 carbon atoms, wherein R and R1 may be linked to form a cyclic ring, and R2 is hydrogen, alkyl group having 1 to 20 carbon atom, phenyl, carbonyl or alkoxy carbonyl.
    • DESCRIPTION OF PREFERRED EMBODIMENTS
  • In accordance with certain embodiments of the present invention, a class of urea compound employed as an element of solid Ziegler-Natta catalyst components in conjunction with one or more internal donors, for the production of polyolefins, particularly polypropylene, are disclosed. The urea compounds of the present invention may be used in combination with one or more internal electron donors that are typically employed in Ziegler-Natta polypropylene catalyst systems such as 1,3-diethers, malonates, succinates, phthalic acid esters, esters of aliphatic or aromatic diols, or their derivatives.
  • According to certain aspects of the present invention, the amide compounds that may be employed as an element of a solid catalyst composition are represented by Formula I:
  • Figure US20180326407A1-20181115-C00002
  • wherein R is an aliphatic hydrocarbon having 1 to 20 carbon atoms that may or may not contain carbonyl or a carbonyl ester group, wherein R1 is alkyl group having 1 to 20 carbon atoms, wherein R and R1 may be linked to form a cyclic ring, and R2 is hydrogen, alkyl group having 1 to 20 carbon atom, phenyl, carbonyl, or alkoxy carbonyl.
  • Preferred embodiments of the amide compounds of Formula I include, but not limited to cyclic amide compounds, such as: n-methyl-2-piperidone, n-ethyl-2-piperidone, n-propyl-2-piperidone, n-butyl-2-piperidone, n-phenyl-2-piperidone, 2-piperidone, 2-pyrrolidinone, n-methyl-2-pyrrolidinone, n-ethyl-2-pyrrolidinone, n-propyl-2-pyrrolidinone, n-butyl-2-pyrrolidinone, n-phenyl-2-pyrrolidinone, n-methyl-caprolactam, or their derivatives. Also, preferred embodiments of Formula I include cyclic amide compounds containing carbonyl ester groups, such as: 3-ethoxycarbonyl-2-piperidone, 3-methoxycarbonyl-2-piperidone, 3-propoxycarbonyl-2-piperidone, 3-phenoxycarbonyl-2-piperidone, n-tert-butoxycarbonyl-2-piperidone, n-ethoxycarbonyl-2-piperidone, n-propoxycarbonyl-2-piperidone, n-phenoxycarbonyl-2-piperidone, or their derivatives.
  • Other suitable amide compounds of Formula I include, but are not limited to, non-cyclic amide compounds, such as n,n-dimethylpropionamide, n,n-dimethylisobutyramide, n,n-dimethylacetamide, n,n-dimethylpentanamide, n,n-dimethylhexanamide n,n-diethylpropionamide, n-ethyl-n-(3-methyl phenyl)propionamide, n,n-dimethyl-benzamide, or their derivatives.
  • Acceptable Ziegler-Natta type catalyst systems that may be used in accordance with the present invention comprise (a) a solid Ziegler-Natta type catalyst component containing urea compound as a modifier in conjunction with internal donors, (b) a co-catalyst component, and optionally (c) one or more external electron donors. Preferred solid Ziegler-Natta type catalyst component (a) include solid catalyst components comprising a titanium compound having at least a Ti-halogen bond and an amide compound in combination with internal electron donor compound supported on an anhydrous magnesium-dihalide support.
  • Acceptable internal electron donor compounds for the preparation of solid Ziegler-Natta type catalyst component (a) are not generally limited and include, but are not limited to, one or more internal electron donors that are typically employed in Ziegler-Natta polypropylene catalyst system, such as 1,3-diethers, malonates, succinates, phthalic acid esters, esters of aliphatic or aromatic diols, or their derivatives.
  • Examples of phthalic acid esters that may be used in conjunction with Formula I compounds include, but are not limited to: diethylphthalate, di-n-propylphthalate, di-n-butylphthalate, di-n-pentylphthalate, di-i-pentylphthalate, bis(2-ethylhexyl)phthalate, ethylisobutylphthalate, ethyl-n-butylphthalate, di-n-hexylphthalate, di-isobutylphthalate.
  • Examples of 1,3-diethers that may be used in conjunction with Formula I compounds include, but are not limited to: 2-(2-ethylhexyl)1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene, 1,1-bis(methoxymethyl)-7-trimethyisilylindene; 1,1-bis(methoxymethyl)-7-trifluoromethylindene, 1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene, 1,1-bis(methoxymethyl)-7-methylindene, 1,1-bis(methoxymethyl)-1H-benz[e]indene, 1,1-bis(methoxymethyl)-1H-2-methylbenz[e]indene, 9,9-bis(methoxymethyl)fluorene, 9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene, 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene, 9,9-bis(methoxymethyl)-2,3-benzofluorene, 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene, 9,9-bis(methoxymethyl)-2,7-diisopropylfluorene, 9,9-bis(methoxymethyl)-1,8-dichlorofluorene, 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene, 9,9-bis(methoxymethyl)-1,8-difluorofluorene, 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene, 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene, 9,9-bis(methoxymethyl)-4-tert-butylfluorene.
  • Examples of malonates that may be used in conjunction with Formula I compounds include, but are not limited to: diethyl2-isopropylmalonate, diethyl2-phenylmalonate, dineopentyl 2-isopropylmalonate, diisobutyl 2-isopropylmalonate, di-n-butyl 2-isopropylmalonate, diethyl 2-dodecylmalonate, diethyl 2-t-butylmalonate, diethyl 2-(2-pentyl)malonate, diethyl 2-cyclohexylmalonate, dineopentyl 2-t-butylmalonate, dineopentyl 2-isobutylmalonate, diethyl 2-cyclohexylmethylmalonate, dimethyl 2-cyclohexylmethylmalonate, diethyl 2,2-dibenzylmalonate, diethyl 2-isobutyl-2-cyclohexylmalonate, dimethyl 2-n-butyl-2-isobutylmalonate, diethyl 2-n-butyl-2-isobutylmalonate, diethyl 2-isopropyl-2-n-butylmalonate, diethyl 2-methyl-2-isopropylmalonate, diethyl 2-isopropyl-2-isobutylmalonate, diethyl 2-methyl-2-isobutylmalonate, diethyl 2-isobutyl-2-benzylmalonate, diethyldiisobutylmalonate.
  • Examples of succinates that may be used in conjunction with Formula I compounds include, but are not limited to: diethyl 2,3-bis(trimethylsilyl)succinate, diethyl 2,3-bis(2-ethylbutyl)succinate, diethyl 2,3-dibenzylsuccinate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diethyl 2,3-bis(cyclohexylmethyl)succinate, diethyl 2,3-diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate, diethyl 2,3-dicyclopentylsuccinate, diethyl 2,3-dicyclohexylsuccinate.
  • Examples of esters of aliphatic or aromatic diols that may be used in conjunction with Formula I compounds include, but are not limited to: 1,3-propylene-glycol dibenzoate, 2-methyl-1,3-propylene-glycol dibenzoate, 2-ethyl-1,3-propylene-glycol dibenzoate, 2-propyl-1,3-propylene-glycol dibenzoate, 2-butyl-1,3-propylene-glycol dibenzoate, 2,2-dimethyl-1,3-propylene-glycol dibenzoate, (R)-1-phenyl-1,3-propylene-glycol dibenzoate, (S)-1-phenyl-1,3-propylene-glycol dibenzoate, 1,3-diphenyl-1,3-propylene-glycol dibenzoate, 2-methyl-1,3-diphenyl-1,3-propylene-glycol dibenzoate, 1,3-diphenyl-1,3-propylene-glycol dipropionate, 2-methyl-1,3-diphenyl-1,3-propylene-glycol dipropionate, 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol dibenzoate, 3-propyl-2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, (2S,4S)-(+)-2,4-pentanediol dibenzoate, (2R,4R)-(+)-2,4-pentanediol dibenzoate, 2,4-pentanediol di(p-chlorobenzoate), 2,4-pentanediol di(m-chlorobenzoate), 2,4-pentanediol di(p-bromobenzoate), 2,4-pentanediol di(o-bromobenzoate), 2,4-pentanediol di(p-methylbenzoate) 2,4-pentanediol di(p-tert-butylbenzoate), 2,4-pentanediol di(p-butylbenzoate), 2,4-pentanediol dicinnamate, 2-methyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol di(p-chlorobenzoate), 2-methyl-1,3-pentanediol di(p-methylbenzoate), 2-butyl-1,3-pentanediol di(p-methylbenzoate), 2-methyl-1,3-pentanediol di(p-tert-butylbenzoate)
  • Acceptable anhydrous magnesium dihalides forming the support of the solid Ziegler-Natta type catalyst component (a) are the magnesium dihalides in active form that are well known in the art. Such magnesium dihalides may be preactivated, may be activated in situ during the titanation, may be formed in-situ from a magnesium compound, which is capable of forming magnesium dihalide when treated with a suitable halogen-containing transition metal compound, and then activated. Preferred magnesium dihalides are magnesium dichloride and magnesium dibromide. The water content of the dihalides is generally less than 1% by weight.
  • The solid Ziegler-Natta type catalyst component (a) may be made by various methods. One such method consists of co-grinding the magnesium dihalide and the internal electron donor compound until the product shows a surface area higher than 20 m2/g and thereafter reacting the ground product with the Ti compound. Other methods of preparing solid Ziegler-Natta type catalyst component (a) are disclosed in U.S. Pat. Nos. 4,220,554; 4,294,721; 4,315,835; 4,330,649; 4,439,540; 4,816,433; and 4,978,648. These methods are incorporated herein by reference.
  • In a typical modified solid Ziegler-Natta type catalyst component (a), the molar ratio between the magnesium dihalide and the halogenated titanium compound is between 1 and 500, the molar ratio between said halogenated titanium compound and the internal electron donor is between 0.1 and 50, and the molar ratio between said internal electron donor and the oxalic acid diamide modifier is between 0.1 and 100.
  • Preferred co-catalyst component (b) includes aluminum alkyl compounds, which can be represented by the formula II;

  • RnAlQ3-n   [Formula II]
  • wherein Rn represents an alkyl group having 1 to 6 carbon atoms, Q represents a hydrogen or a halogen atom, and n represents a real number that satisfies 0<n≤3. Acceptable aluminum alkyl compounds include aluminum trialkyls, such as aluminum triethyl, aluminum triisobutyl, and aluminum triisopropyl. Other acceptable aluminum alkyl compounds include aluminum-dialkyl hydrides, such as aluminum-diethyl hydrides. Other acceptable co-catalyst component (b) includes compounds containing two or more aluminum atoms linked to each other through hetero-atoms, such as:

  • (C2H5)2Al—O-A(C2H5)2

  • (C2H5)2Al—N(C6H5)—Al(C2H5)2; and

  • (C2H5)2Al—O—SO2—O—Al(C2H5)2.
  • Acceptable external electron donor component (c) is organic compounds containing O, Si, N, S, and/or P. Such compounds include organic acids, organic acid esters, organic acid anhydrides, ethers, ketones, alcohols, aldehydes, silanes, amides, amines, amine oxides, thiols, various phosphorus acid esters and amides, etc. Preferred component (c) is organosilicon compounds containing Si—O—C and/or Si—N—C bonds. Specific examples of such organosilicon compounds are, without limitation, trimethylmethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, isobutyltriethoxysilane, vinyltrimethoxysilane, dicyclohexyldimethoxysilane, 3-tert-Butyl-2-isobutyl-2methoxy-[1,3,2]oxazasilolidine, 3-tert-Butyl-2-cyclopentyl-2-methoxy-[1,3,2]oxazasilolidine, 2-Bicyclo[2.2.1]hept-5-en-2-yl-3-tert-butyl-2-methoxy-[1,3,2]oxazasilolidine, 3-tert-Butyl-2,2-diethoxy-[1,3,2]oxazasilolidine, 4,9-Di-tert-butyl-1,6-dioxa-4,9-diaza-5-sila-spiro[4.4]nonane, and bis(perhydroisoquinolino)dimethoxysilane. Mixtures of organic electron donors may also be used. Finally, the oxalic acid diamides of the present invention may also be employed as an external electronic donor.
  • The olefin polymerization processes that may be used in accordance with the present invention are not generally limited. For example, the catalyst components (a), (b) and (c), when employed, may be added to the polymerization reactor simultaneously or sequentially. It is preferred to mix components (b) and (c) first and then contact the resultant mixture with component (a) prior to the polymerization.
  • The olefin monomer may be added prior to, with, or after the addition of the Ziegler-Natta type catalyst system to the polymerization reactor. It is preferred to add the olefin monomer after the addition of the Ziegler-Natta type catalyst system. The molecular weight of the polymers may be controlled in a known manner, preferably by using hydrogen. With the catalysts produced according to the present invention, molecular weight may be suitably controlled with hydrogen when the polymerization is carried out at relatively low temperatures, e.g., from about 30° C. to about 105° C. This control of molecular weight may be evidenced by a measurable positive change of the Melt Flow Rate.
  • The polymerization reactions may be carried out in slurry, liquid or gas phase processes, or in a combination of liquid and gas phase processes using separate reactors, all of which may be done either by batch or continuously. The polyolefin may be directly obtained from gas phase process, or obtained by isolation and recovery of solvent from the slurry process, according to conventionally known methods.
  • There are no particular restrictions on the polymerization conditions for production of polyolefins by the method of this invention, such as the polymerization temperature, polymerization time, polymerization pressure, monomer concentration, etc. The polymerization temperature is generally from 40-90° C. and the polymerization pressure is generally 1 atmosphere or higher.
  • The Ziegler-Natta type catalyst systems of the present invention may be pre-contacted with small quantities of olefin monomer, well known in the art as prepolymerization, in a hydrocarbon solvent at a temperature of 60° C. or lower for a time sufficient to produce a quantity of polymer from 0.5 to 3 times the weight of the catalyst. If such a prepolymerization is done in liquid or gaseous monomer, the quantity of resultant polymer is generally up to 1000 times the catalyst weight.
  • The Ziegler-Natta type catalyst systems of the present invention are useful in the polymerization of olefins, including but not limited to homopolymerization and copolymerization of alpha olefins. Suitable α-olefins that may be used in a polymerization process in accordance with the present invention include olefins of the general formula CH2═CHR, where R is H or C1-10 straight or branched alkyl, such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1 and octene-1. While the Ziegler-Natta type catalyst systems of the present invention may be employed in processes in which ethylene is polymerized, it is more desirable to employ the Ziegler-Natta type catalyst systems of the present invention in processes in which polypropylene or higher olefins are polymerized. Processes involving the homopolymerization or copolymerization of propylene are preferred.
    • EXAMPLES
  • In order to provide a better understanding of the foregoing, the following non-limiting examples are offered. Although the examples may be directed to specific embodiments, they are not to be viewed as limiting the invention in any specific respect. The activity values (AC) are based upon grams of polymer produced per gram of solid catalyst component used.
  • The following analytical methods are used to characterize the polymer.
  • Heptane Insolubles (% HI): The weight percent (wt %) of residuals of polypropylene sample after extracted with boiling heptane for 8 hours.
  • Melt Flow rate (MI): ASTM D-1238, determined at 230° C. under the load of 2.16 kg.
  • Tm: ASTM D-3417, determined by DSC (Manufacturer: TA Instrument, Inc.; Model: DSC Q1000).
  • Determination of Isotactic Pentads Content: Place 400 mg of polymer sample into 10 mm NMR tube. 1.7 g TCE-d2 and 1.7 g o-DCB were added into the tube. 13C NMR spectra were acquired on a Bruker AVANCE 400 NMR (100.61 MHz, 90° pulse, 12 s delay between pulse). About 5000 transients were stored for each spectrum; mmmm pentad peak (21.09 ppm) was used as reference. The microstructure analysis was carried out as described in literature (Macromolecules, 1994, 27, 4521-4524, by V. Busico, et al.).
  • Molecular weight (Mn and Mw): The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) of polymers were obtained by gel permeation chromatography on Water 2000GPCV system using Polymer Labs Plgel 10 um MIXED-B LS 300×7.5 mm columns and 1,2,4-trichlorobenzene (TCB) as mobile phase. The mobile phase was set at 0.9 ml/min, and temperature was set at 145° C. Polymer samples were heated at 150° C. for two hours. Injection volume was 200 microliters. External standard calibration of polystyrene standards was used to calculate the molecular weight.
  • Magnesium ethoxide (98%), anhydrous toluene (99.8%), TiCl4 (99.9%), anhydrous n-heptane (99%), diisobutyl phthalate (99%), cyclohexyl(dimethoxy)methylsilane (C-donor, ≥99%) and triethylaluminum (93%) were all purchased from Sigma-Aldrich Co. of Milwaukee, Wis., USA.
  • Diisopropyldimethoxysilane (P-donor) and dicyclopentyldimethoxysilane (D-donor) were purchased from Gelest, Inc. of Morrisville, Pa., USA.
  • Unless otherwise indicated, all reactions were conducted under an inert atmosphere.
    • Example 1 (A) The Preparation of a Solid Catalyst Component
  • To a three-neck 250 ml flask equipped magnetic bar, which is thoroughly purged with anhydrous nitrogen, 7.5 g of magnesium ethoxide, and 70 ml of anhydrous toluene was introduced to form a suspension. 20 ml of TiCl4 was added. The temperature of the mixture was gradually raised to 90° C., and 7.0 mmol of 9,9-bis(methoxymethyl)fluorene and 2.0 mmol of 3-ethoxycarbonyl-2-piperidone were charged. The temperature of the mixture was increased to 110° C., and maintained for 2 hours with stirring. The resulting solid was precipitated and supernatant liquid was decanted. The solid was washed twice with 100 ml of anhydrous toluene at 90° C., and then 80 ml of fresh anhydrous toluene and 20 ml TiCl4 was added to the filtered solid. Temperature of the mixture was heated to 110° C., and stirred for 2 hours. The solid was precipitated and supernatant liquid was decanted and residual solid was washed with heptane 7 times at 70° C. The final catalyst was collected and dried under vacuum to obtain a solid catalyst component (A1).
    • (B) Propylene Slurry Polymerization
  • Propylene polymerization was conducted in a bench scale 2-liter reactor per the following procedure. The reactor was first preheated to at least 100° C. with a nitrogen purge to remove residual moisture and oxygen. The reactor was thereafter cooled to 50° C. Under nitrogen, 1 liter dry heptane was introduced into the reactor. When reactor temperature was about 50° C., 4.3 ml of triethylaluminum (0.58M, in hexanes), 0.8-1.6 ml of dicyclopentyl(dimethoxy)silane (D-donor) (0.5 M in heptane), and then 30 mg of the solid catalyst component (A1) prepared above were added to the reactor. The temperature of the reactor was heated to 50° C. and 8 psi hydrogen in a 150 ml vessel was flushed into the reactor with propylene.
  • The reactor temperature was then raised to 70° C. The total reactor pressure was raised to and controlled at 90 psig by continually introducing propylene into the reactor and the polymerization was allowed to proceed for 1 hour. After polymerization, the reactor was vented to reduce the pressure to 0 psig and the reactor temperature was cooled to 50° C.
  • The reactor was then opened. 500 ml methanol was added to the reactor and the resulting mixture was stirred for 5 minutes then filtered to obtain the polymer product. The obtained polymer was vacuum dried at 80° C. for 6 hours. The polymer was evaluated for melt flow rate (MFR), and heptane insoluble (% HI). The activity of catalyst (AC) was also measured. The results are summarized in TABLE 1 & 2.
    • Example 2
  • A solid catalyst component (A2) was prepared in the same manner as in Example 1, except that 2.0 mmol of n-tert-buthoxycarbonyl-2-piperidone was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A2) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1 & 2.
    • Example 3
  • A solid catalyst component (A3) was prepared in the same manner as in Example 1, except that 2.0 mmol of n-methylpiperidone was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A3) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1 & 2.
    • Example 4
  • A solid catalyst component (A4) was prepared in the same manner as in Example 1, except that 2.0 mmol of n,n-dimethylpropionamide was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A4) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1 & 2.
    • Example 5
  • A solid catalyst component (A5) was prepared in the same manner as in Example 1, except that 2.0 mmol of 2-piperidone was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A5) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1 & 2.
    • Example 6
  • A solid catalyst component (A6) was prepared in the same manner as in Example 1, except that 2.0 mmol of 2-pyrrolidinone was used instead of 3-ethoxycarbonyl-2-piperidone. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A6) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1&2.
    • Comparative Example 1
  • A solid catalyst component (C1) was prepared in the same manner as in Example 1, except that 10.0 mmol of 9,9-bis(methoxymethyl)fluorene was used instead of diisobutylphthalate. Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A8) was charged instead of solid catalyst component (C2). The results are summarized in TABLE 1 & 2.
    • Example 7 (A) The Preparation of a Solid Catalyst Component
  • To a three-neck 250 ml flask equipped with fritted filter disc and mechanical stirrer, which is thoroughly purged with anhydrous nitrogen, 9.2 g of magnesium ethoxide, and 80 ml of anhydrous toluene was introduced to form a suspension. 20 ml of TiCl4 was added through a stainless steel cannula. The temperature of the mixture was gradually raised to 90° C., and 10.0 mmol of diisobutylphthalate and 2.0 mmol of 3-ethoxycarbonyl-2-piperidone were charged. The temperature of the mixture was increased to 110° C., and maintained for 2 hours with stirring. The resulting solid was filtered and washed twice with 100 ml of anhydrous toluene at 90° C., and then 80 ml of fresh anhydrous toluene and 20 ml TiCl4 was added to the filtered solid. Temperature of the mixture was heated to 110° C., and stirred for 2 hours. The solid was filtered and residual solid was washed with heptane 7 times at 70° C. The final catalyst was collected and dried under vacuum to obtain a solid catalyst component (A7).
    • (B) Propylene Slurry Polymerization
  • Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (A7) was charged instead of solid catalyst component (A1).
  • The results are summarized in TABLE 1 & 2.
    • Comparative Example 2 (A) The Preparation of a Solid Catalyst Component (C2)
  • A solid catalyst component (C2) was prepared in the same manner as in Example 7, except that of 3-ethoxycarbonyl-2-piperidone was not added.
    • (B) Propylene Slurry Polymerization
  • Propylene polymerization was carried out in the same manner as described in Example 1, except that solid catalyst component (C2) was charged instead of solid catalyst component (A1). The results are summarized in TABLE 1 & 2.
  • TABLE 1
    Amide element & internal donor composition
    in solid Catalyst Components
    Catalyst Internal
    Example components Donor (mmol) amide element (mmol)
    Ex. 1 A1 1,3-diether** 3-ethoxycarbonyl-2-
    (7.0) piperidone (2.0)
    Ex. 2 A2 1,3-diether** n-tert-butoxycarbonyl-2-
    (7.0) piperidone (2.0)
    Ex. 3 A3 1,3-diether** n-methyl-2-piperidone
    (7.0) (2.0)
    Ex. 4 A4 1,3-diether** n,n-dimethylpropionamide
    (7.0) (2.0)
    Ex. 5 A5 1,3-diether** 2-piperidone
    (7.0) (2.0)
    Ex. 6 A6 1,3-diether** 2-pyrrolidinone
    (7.0) (2.0)
    Comp. Ex 1 C1 1,3-diether** Without amide element
    (7.0)
    Ex. 7 A7 DiBP* (10.0) 3-ethoxycarbonyl-2-
    piperidone (2.0)
    Comp. Ex 2 C2 DiBP* (10.0) Without amide element
    *DiBP = Diisobutylphthalate
    **1,3 diether = 9,9-bis(methoxymethyl)fluorene
  • TABLE 2
    Polymerization Summary
    Ext.
    Donor H2 MFR Activity HI
    Example Catalyst (mmol) (psi) (g/10 min) (g/g cat.) (%)
    Ex. 1 A1 P (0.4) 8 11.8 3470 98.6
    Ex 2 A2 P (0.4) 8 9.7 3566 98.5
    Ex. 3 A3 P (0.4) 8 9.6 3010 98.6
    Ex. 4 A4 P (0.4) 8 7.6 4280 98.4
    Ex. 5 A5 P (0.4) 8 9.4 2883 98.4
    Ex. 6 A6 P (0.4) 8 10.5 2903 98.1
    Comp. Ex 1 C1 P (0.4) 8 7.0 3533 97.2
    Ex 7. A7 D (0.4) 8 1.3 7614 99.6
    Comp. Ex 2 C2 D (0.4) 8 1.2 6907 99.1
  • As shown from the above results, the catalyst component (Ex. 1-Ex. 6) according to present invention employing amide compounds in combination with internal donors of 1,3-diether (9,9-bis(methoxymethyl)fluorene) as an element of catalyst composition, produce polypropylene with an isotacticity and activities much higher than the comparative catalyst components (C1) that does not contain the urea element in its solid catalyst composition. For example, for a given loading of 7.0 mmol of 1,3-diether (9,9-bis(methoxymethyl)fluorene), Catalyst component A1-A6 containing amide element in its catalyst composition produced polypropylene of 98.1-98.6% HI (Example 1-Example 6) with activities of 2883-4280 gPP/gcat in the presence of 0.4 mmol P donor, which is much higher than % HI 97.2% with activity of 3533 gPP/gcat by comparative catalyst components (C1) that does not contain amide element in its solid catalyst composition.
  • The same trend has been observed in combination with diisobutylphthalate donors. For example, in the preparation equipped with mechanical stirrer and fritted filter disc and higher loading of 10.0 mmol of diisobutylphthalate, catalyst component A7 containing the amide element produced polypropylene with % HI of 99.6 (Example 7), which is much higher than 99.1% for the comparative catalyst component C2, which does not contain an amide element in its solid catalyst composition.
  • As such, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number falling within the range is specifically disclosed. Moreover, the indefinite articles “a” or “an”, as used in the claims, are defined herein to mean one or more than one of the element that it introduces.

Claims (37)

1. A solid catalyst component for the polymerization or co-polymerization of alpha-olefins comprising: titanium, magnesium, halogen, one or more internal electron donors, and one or more amide compounds selected from the compound represented by the formula:
Figure US20180326407A1-20181115-C00003
wherein R is an aliphatic hydrocarbon having 1 to 20 carbon atoms and contains a carbonyl or carbonyl ester group;
wherein R1 is alkyl group having 1 to 20 carbon atoms; and
wherein R2 is hydrogen, alkyl group having 1 to 20 carbon atom, phenyl, carbonyl or alkoxy carbonyl.
2. (canceled)
3. The component of claim 1, wherein the one or more amide compounds are selected from cyclic amide compounds, wherein two or more of R, R1, and R2 are linked to form one or more saturated or unsaturated monocyclic or polycyclic rings.
4. The component of claim 1, wherein the one or more amide compounds are non-cyclic amide compounds.
5. The component of claim 1, wherein the one or more amide compounds are selected from 3-ethoxycarbonyl-2-piperidone, n-methyl-2-piperidone, 2-piperidone, 2-pyrrolidinone, n-tert-butoxycarbonyl-2-piperidone, n-methyl-2-pyridone, 1-cyclohexyl-2-pyrrolidone, 1-benzyl-2-piperidone, 1-phenyl-2-pyrrolidinone, n,n-dimethylpropionamide, n,n-dimethylisobutyramide, n,n-dimethylacetamide, n,n-dimethylpentanamide, n,n-dimethylhexanamide, and their derivatives.
6. The component of claim 1, wherein at least one of the one or more internal electron donors is selected from a 1,3 diether compound.
7. The component of claim 6, wherein the 1,3 diether compound is selected from 9,9-bis(methoxymethyl)fluorene; 9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene; 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene; 9,9-bis(methoxymethyl)-2,3-benzofluorene; 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene; 9,9-bis(methoxymethyl)-2,7-diisopropylfluorene; 9,9-bis(methoxymethyl)-1,8-dichlorofluorene; 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene; 9,9-bis(methoxymethyl)-1,8-difluorofluorene; 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene; 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene; and 9,9-bis(methoxymethyl)-4-tert-butylfluorene.
8. The component of claim 6, wherein the 1,3 diether compound is selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypropane, 2-cumyl-1,3-diethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl) 1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxy propane, 2,2-fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-t-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane; 2-isopropyl 2-isopentyl-1,3-dimethoxypropane; and 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,
9. The component of claim 1, wherein at least one of the one or more internal electron donors is selected from esters of phthalic acid.
10. The component of claim 1, wherein at least one of the one or more internal electron donors is selected from malonate compounds.
11. The component of claim 1, wherein at least one of the one or more internal electron donors is selected from esters of succinic acid compounds.
12. The component of claim 1, wherein at least of the one or more internal electron donors is selected from esters of diol compounds.
13. A catalyst system for the polymerization or co-polymerization of alpha-olefins comprising:
a) a solid catalyst component according to claim 1; and
b) a co-catalyst component comprising an organoaluminum compound represented by the general formula: RnAlQ3-n, wherein R represents an alkyl group having 1 to 6 carbon atoms, Q represents a hydrogen or a halogen atom, and n represents a real number that satisfies 0<n≤3.
14. The catalyst system of claim 13, further comprising: (c) one or more external electron donor components.
15. (canceled)
16. The catalyst system of claim 13, wherein the one or more amide compounds of the solid catalyst component are selected from cyclic amide compounds, wherein two or more of R, R1, and R2 are linked to form one or more saturated or unsaturated monocyclic or polycyclic rings.
17. The catalyst system of claim 13, wherein the one or more amide compounds of the solid catalyst component are non-cyclic amide compounds.
18. The catalyst system of claim 13, wherein at least one of the one or more internal electron donors of the solid catalyst component is selected from a 1,3 diether compound.
19. The catalyst system of claim 13, wherein at least one of the one or more internal electron donors of the solid catalyst component is selected from esters of phthalic acid.
20. The catalyst system of claim 13, wherein at least one of the one or more internal electron donors of the solid catalyst component is selected from malonate compounds.
21. The catalyst system of claim 13, wherein at least one of the one or more internal electron donors of the solid catalyst component is selected from esters of succinic acid compounds.
22. The catalyst system of claim 13, wherein at least one of the one or more internal electron donors of the solid catalyst component is selected from esters of diol compounds.
23. A solid catalyst component for the polymerization or co-polymerization of alpha-olefins comprising: titanium, magnesium, halogen, one or more internal electron donors, and one or more amide compounds selected from 3-ethoxycarbonyl-2-piperidone, n-methyl-2-piperidone, 2-piperidone, 2-pyrrolidinone, n-tert-butoxycarbonyl-2-piperidone, n-methyl-2-pyridone, 1-cyclohexyl-2-pyrrolidone, 1-benzyl-2-piperidone, 1-phenyl-2-pyrrolidinone, n,n-dimethylpropionamide, n,n-dimethylisobutyramide, n,n-dimethylacetamide, n,n-dimethylpentanamide, n,n-dimethylhexanamide, and their derivatives.
24. The component of claim 23, wherein at least one of the one or more internal electron donors is selected from a 1,3 diether compound.
25. The component of claim 24, wherein the 1,3 diether compound is selected from 9,9-bis(methoxymethyl)fluorene; 9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene; 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene; 9,9-bis(methoxymethyl)-2,3-benzofluorene; 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene; 9,9-bis(methoxymethyl)-2,7-diisopropylfluorene; 9,9-bis(methoxymethyl)-1,8-dichlorofluorene; 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene; 9,9-bis(methoxymethyl)-1,8-difluorofluorene; 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene; 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene; or 9,9-bis(methoxymethyl)-4-tert-butylfluorene.
26. The component of claim 24, wherein the 1,3 diether compound is selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypropane, 2-cumyl-1,3-diethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl) 1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxy propane, 2,2-fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-t-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane; 2-isopropyl 2-isopentyl-1,3-dimethoxypropane; aor 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,
27. The component of claim 23, wherein at least one of the one or more internal electron donors is selected from esters of phthalic acid.
28. The component of claim 23, wherein at least one of the one or more internal electron donors is selected from malonate compounds.
29. The component of claim 23, wherein at least one of the one or more internal electron donors is selected from esters of succinic acid compounds.
30. The component of claim 23, wherein at least of the one or more internal electron donors is selected from esters of diol compounds.
31. A catalyst system for the polymerization or co-polymerization of alpha-olefins comprising:
a) a solid catalyst component according to claim 23; and
b) a co-catalyst component comprising an organoaluminum compound represented by the general formula: RnAlQ3-n, wherein R represents an alkyl group having 1 to 6 carbon atoms, Q represents a hydrogen or a halogen atom, and n represents a real number that satisfies 0<n≤3.
32. The catalyst system of claim 31, further comprising: (c) one or more external electron donor components.
33. The catalyst system of claim 31, wherein at least one of the one or more internal electron donors of the solid catalyst component is selected from a 1,3 diether compound.
34. The catalyst system of claim 31, wherein at least one of the one or more internal electron donors of the solid catalyst component is selected from esters of phthalic acid.
35. The catalyst system of claim 31, wherein at least one of the one or more internal electron donors of the solid catalyst component is selected from malonate compounds.
36. The catalyst system of claim 31, wherein at least one of the one or more internal electron donors of the solid catalyst component is selected from esters of succinic acid compounds.
37. The catalyst system of claim 31, wherein at least one of the one or more internal electron donors of the solid catalyst component is selected from esters of diol compounds.
US15/590,559 2017-05-09 2017-05-09 Olefin polymerization catalyst components and process for the production of olefin polymers therewith Active US10124324B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/590,559 US10124324B1 (en) 2017-05-09 2017-05-09 Olefin polymerization catalyst components and process for the production of olefin polymers therewith

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US15/590,559 US10124324B1 (en) 2017-05-09 2017-05-09 Olefin polymerization catalyst components and process for the production of olefin polymers therewith

Publications (2)

Publication Number Publication Date
US10124324B1 US10124324B1 (en) 2018-11-13
US20180326407A1 true US20180326407A1 (en) 2018-11-15

Family

ID=64050700

Family Applications (1)

Application Number Title Priority Date Filing Date
US15/590,559 Active US10124324B1 (en) 2017-05-09 2017-05-09 Olefin polymerization catalyst components and process for the production of olefin polymers therewith

Country Status (1)

Country Link
US (1) US10124324B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021105373A1 (en) * 2019-11-29 2021-06-03 Thai Polyethylene Co., Ltd. Catalyst composition for the polymerization of olefins

Family Cites Families (92)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4226963A (en) 1971-06-25 1980-10-07 Montedison S.P.A. Process for the stereoregular polymerization of alpha-olephins
US4107414A (en) 1971-06-25 1978-08-15 Montecatini Edison S.P.A. Process for the stereoregular polymerization of alpha olefins
GB1603724A (en) 1977-05-25 1981-11-25 Montedison Spa Components and catalysts for the polymerisation of alpha-olefins
IT1114822B (en) 1977-07-04 1986-01-27 Montedison Spa COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS
US4186107A (en) 1978-04-14 1980-01-29 Hercules Incorporated Solid catalyst component for olefin polymerization
JPS56811A (en) 1979-06-18 1981-01-07 Mitsui Petrochem Ind Ltd Preparation of olefin polymer or copolymer
US4347160A (en) 1980-06-27 1982-08-31 Stauffer Chemical Company Titanium halide catalyst system
JPS57153005A (en) 1981-03-19 1982-09-21 Ube Ind Ltd Polymerization of alpha-olefin
US4530912A (en) 1981-06-04 1985-07-23 Chemplex Company Polymerization catalyst and method
EP0072129B2 (en) 1981-08-07 1990-02-28 Imperial Chemical Industries Plc Supported transition metal composition
US4382019A (en) 1981-09-10 1983-05-03 Stauffer Chemical Company Purified catalyst support
IT1190683B (en) 1982-02-12 1988-02-24 Montedison Spa COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE
IT1190681B (en) 1982-02-12 1988-02-24 Montedison Spa COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE
IT1190682B (en) 1982-02-12 1988-02-24 Montedison Spa CATALYSTS FOR THE POLYMERIZATION OF OLEFINE
US4532313A (en) 1982-10-13 1985-07-30 Himont Incorporated Method for preparing an improved catalyst support, Ziegler-Natta catalyst utilizing said support and polymerization of 1-olefins utilizing said catalyst
US4560671A (en) 1983-07-01 1985-12-24 Union Carbide Corporation Olefin polymerization catalysts adapted for gas phase processes
US4581342A (en) 1984-11-26 1986-04-08 Standard Oil Company (Indiana) Supported olefin polymerization catalyst
US4657882A (en) 1984-11-26 1987-04-14 Amoco Corporation Supported olefin polymerization catalyst produced from a magnesium alkyl/organophosphoryl complex
JPH06104693B2 (en) 1986-01-06 1994-12-21 東邦チタニウム株式会社 Catalyst for olefin polymerization
IT1227259B (en) 1988-09-30 1991-03-28 Himont Inc CATALYSTS FOR THE POLYMERIZATION OF OLEFINE.
US5208302A (en) 1989-07-11 1993-05-04 Showa Denko K.K. Catalyst, process for preparation of same and process for polymerization of olefins using same
US5726262A (en) 1990-04-13 1998-03-10 Mitsui Petrochemical Industries, Ltd. Solid titanium catalyst component for olefin polymerization, olefin polymerization catalyst, prepolymerized polyolefin-containing catalyst and method of olefin polymerization
US5105807A (en) 1991-02-26 1992-04-21 Alternative Medical Products, Inc. Device and methods for securing nasal tubing
JP2879391B2 (en) 1992-04-14 1999-04-05 昭和電工株式会社 Olefin polymerization catalyst and method for producing olefin polymer
US5684173A (en) 1994-04-28 1997-11-04 Toho Titanium Co., Ltd. Organosilicon compound and ziegler-natta catalyst containing the same
DE69506980T2 (en) 1994-09-28 1999-06-02 Showa Denko Kk 3-alkoxypropionic acid ester derivative, olefin polymerization catalyst and process for producing a polyolefin
US7049377B1 (en) 1995-02-21 2006-05-23 Basell Poliolefine Italia S.R.L. 1,3-diethers and components and catalysts for the polymerization of olefins, containing said diethers
FR2738826B1 (en) 1995-09-20 1997-10-17 Atochem Elf Sa ALCOXYSILACYCLOALCANES, THEIR PREPARATION PROCESS AND THEIR USE FOR THE POLYMERIZATION OF OLEFINS
JP3143057B2 (en) 1996-02-16 2001-03-07 日本ポリオレフィン株式会社 Solid catalyst component for olefin polymerization, method for producing the same, and method for producing polyolefin
DE69817337T2 (en) 1997-04-17 2004-06-24 Chisso K.K. POLYPROPYLENE COMPOSITION AND METHOD FOR THE PRODUCTION THEREOF
IT1292108B1 (en) 1997-06-09 1999-01-25 Montell North America Inc COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE
IT1292109B1 (en) 1997-06-09 1999-01-25 Montell North America Inc COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE
IT1292107B1 (en) 1997-06-09 1999-01-25 Montell North America Inc COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE
TW539690B (en) 1997-08-11 2003-07-01 Mitsui Chemicals Inc Process for preparing solid titanium catalyst component, olefin polymerization catalyst, and olefin polymerization process
DE69914278T2 (en) 1998-05-06 2004-11-18 Basell Poliolefine Italia S.P.A. CATALYST COMPONENTS FOR OLEFIN POLYMERIZATION
HUP0104266A2 (en) 1998-11-04 2002-03-28 Montell Technology Company Bv. Components and catalyts for the polymerization of olefins
SG80673A1 (en) 1999-02-25 2001-05-22 Sumitomo Chemical Co Catalyst component, catalyst for olefin polymerization, process for producing olefin polymer and use of organosilicon compound
JP4717219B2 (en) 1999-04-15 2011-07-06 バセル テクノロジー カンパニー ビー．ブイ． Components and catalysts for olefin polymerization
JP2000336112A (en) 1999-06-01 2000-12-05 Idemitsu Petrochem Co Ltd Organic silicon compound, catalyst for production of olefin polymer and production of olefin polymer
US6436864B1 (en) 1999-10-06 2002-08-20 Sri International Unsaturated nitrogenous compounds as electron donors for use with ziegler-natta catalysts
JP4758583B2 (en) 1999-12-22 2011-08-31 バセル テクノロジー カンパニー ビー．ブイ． Alpha-olefin polymerization catalyst system containing aromatic silane compound
WO2001057099A1 (en) 2000-02-02 2001-08-09 Basell Technology Company B.V. Components and catalysts for the polymerization of olefins
CN1271093C (en) 2000-04-24 2006-08-23 出光兴产株式会社 Catalyst for bulk polymerization, catalyst for gas phase polymerization, polymerization method using the catalyst, and olefin polymer obtained therefrom
DE60134611D1 (en) 2000-04-24 2008-08-14 Toho Titanium Co Ltd SOLID CATALYST COMPONENT AND CATALYST FOR OLEFIN POLYMERIZATION
ES2312484T3 (en) 2000-10-13 2009-03-01 Basell Poliolefine Italia S.R.L. CATALYTIC COMPONENTS FOR POLYMERIZATION OF OLEFINS.
JP4295084B2 (en) 2001-06-13 2009-07-15 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ Components and catalysts for (co) polymerization of olefins
TWI253451B (en) 2002-08-29 2006-04-21 Toho Catalyst Co Ltd Solid catalyst component, catalyst for polymerization of olefins, and polymerizing method of olefins
EP1548035A4 (en) 2002-09-11 2006-08-09 Japan Polypropylene Corp CATALYST FOR POLYMERIZING a-OLEFIN AND PRODUCTION METHOD OF a-OLEFIN POLYMER USING THE SAME
DE60330252D1 (en) 2002-09-16 2010-01-07 Basell Poliolefine Srl COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINES
JP4624986B2 (en) 2003-03-26 2011-02-02 イネオス・ユーエスエイ・エルエルシー Olefin polymerization catalyst containing cycloalkanedicarboxylate as electron donor
JP4653755B2 (en) 2003-10-28 2011-03-16 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ Components and catalysts for olefin polymerization
JP4795334B2 (en) 2004-04-02 2011-10-19 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ Catalyst components and catalysts for the polymerization of olefins
US7351778B2 (en) 2004-04-30 2008-04-01 China Petroleum & Chemical Corporation Catalyst component for olefin polymerization and catalyst comprising the same
DE602005017489D1 (en) 2004-06-16 2009-12-17 Basell Poliolefine Srl COMPONENTS AND CATALYSTS FOR OLEFIN POLYMERIZATION
HUE025490T2 (en) 2005-01-19 2016-04-28 Mitsui Chemicals Inc Process for producing olefin polymer
US7888438B2 (en) 2005-01-19 2011-02-15 Mitsui Chemicals, Inc. Catalyst for olefin polymerization and process for olefin polymerization
CN1670043A (en) 2005-03-07 2005-09-21 营口市向阳催化剂有限责任公司 Catalyst for polymerization of olefins and its preparation and polymerization method
US8288606B2 (en) 2005-03-08 2012-10-16 Ineos Usa Llc Propylene polymer catalyst donor component
US7491781B2 (en) 2005-03-08 2009-02-17 Ineos Usa Llc Propylene polymer catalyst donor component
KR100523474B1 (en) 2005-03-29 2005-10-24 삼성토탈 주식회사 Method for producing propylene polymer having a very high melt-flowability
KR101234427B1 (en) 2005-05-31 2013-02-18 도호 티타늄 가부시키가이샤 Aminosilane compounds, catalyst components and catalysts for olefin polymerization, and process for production of olefin polymers with the same
BRPI0615149B1 (en) 2005-08-08 2017-06-27 Toho Titanium Co., Ltd. COMPONENT OF A CATALYST FOR POLYMERIZATION OF OLEFIN, CATALYST FOR POLYMERIZATION OF OLEFIN, AND PROCESS FOR PRODUCTION IN POLYMER OF OLEFIN
US20080207972A1 (en) 2006-03-01 2008-08-28 Ineos Usa Llc Propylene polymer catalyst donor component
EP1849807A1 (en) 2006-04-24 2007-10-31 Total Petrochemicals Research Feluy Catalyst composition for the copolymerization of propylene
MY155648A (en) 2007-11-27 2015-11-13 Mitsui Chemicals Inc Solid titanium catalyst component, olefin polymerization catalyst, and olefin polymerization process
RU2489447C2 (en) * 2007-12-21 2013-08-10 ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи Self-limiting catalyst composition with bidentate internal donor
US8003559B2 (en) 2008-05-13 2011-08-23 Basf Corporation Internal donor for olefin polymerization catalysts
US8003558B2 (en) 2008-07-29 2011-08-23 Basf Corporation Internal donor for olefin polymerization catalysts
US8088872B2 (en) 2008-11-25 2012-01-03 Dow Global Technologies Llc Procatalyst composition including silyl ester internal donor and method
EP2350143B1 (en) 2008-11-25 2016-02-17 W.R. Grace & CO. - CONN. Procatalyst composition multiple internal donor having silyl ester and method
CN102325804A (en) 2008-12-29 2012-01-18 陶氏环球技术有限责任公司 Comprise the catalyst composition of giving body based on phosphorus
PL2373702T3 (en) 2008-12-31 2018-07-31 W.R. Grace & Co.-Conn. Procatalyst composition with substituted 1,2-phenylene aromatic diester internal donor and method
WO2010078479A1 (en) 2008-12-31 2010-07-08 Dow Global Technologies Inc. Random propylene copolymer compositions, articles and process
US7619049B1 (en) 2009-04-13 2009-11-17 Formosa Plastics Corporation, U.S.A. Cyclic organosilicon compounds as electron donors for polyolefin catalysts
US7790819B1 (en) 2009-04-13 2010-09-07 Formosa Plastics Corporation, U.S.A. Bicyclic organosilicon compounds as electron donors for polyolefin catalysts
US8247341B2 (en) 2009-04-17 2012-08-21 Dow Global Technologies Llc Procatalyst composition with silyl glutarate and method
WO2010123775A1 (en) 2009-04-23 2010-10-28 Dow Global Technologies Inc. Procatalyst composition with adamantane and method
SG181482A1 (en) 2009-12-02 2012-07-30 Dow Global Technologies Llc Two atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture
MY158466A (en) 2009-12-02 2016-10-14 Grace W R & Co Three and four atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture
KR101114073B1 (en) 2009-12-08 2012-02-22 삼성토탈 주식회사 A method for preparation of a solid catalyst for polymerization of propylene
US8211819B2 (en) 2009-12-21 2012-07-03 Basf Corporation Internal and external donor compounds for olefin polymerization catalysts
US8569195B2 (en) 2010-02-24 2013-10-29 Basf Corporation Internal and external donor compounds for olefin polymerization catalysts II
US8318626B2 (en) 2010-03-01 2012-11-27 Basf Corporation Internal and external donor compounds for olefin polymerization catalysts III
US8236908B2 (en) 2010-04-28 2012-08-07 Sumitomo Chemical Company, Limited Components and catalysts for the polymerization of olefins
US8227370B2 (en) 2010-11-10 2012-07-24 Basf Corporation High activity catalyst component for olefin polymerization and method of using the same
US8604146B2 (en) 2010-12-21 2013-12-10 Dow Global Technologies Llc Catalyst composition with alkoxyalkyl ester internal electron donor and polymer from same
US8536290B2 (en) 2010-12-21 2013-09-17 Dow Global Technologies Llc Procatalyst composition with alkoxyalkyl 2-propenoate internal electron donor and polymer from same
US8383540B2 (en) * 2010-12-21 2013-02-26 Dow Global Technologies Llc Catalyst composition with halo-malonate internal electron donor and polymer from same
US8692927B2 (en) 2011-01-19 2014-04-08 Hand Held Products, Inc. Imaging terminal having focus control
US8575283B1 (en) 2012-06-28 2013-11-05 Formosa Plastics Corporation, U.S.A. Heterocyclic organic compounds as electron donors for polyolefin catalysts
US9481741B2 (en) * 2012-11-26 2016-11-01 Lummus Novolen Technology Gmbh High performance Ziegler-Natta catalyst systems, process for producing such supported catalysts and use thereof
US9593184B2 (en) 2014-10-28 2017-03-14 Formosa Plastics Corporation, Usa Oxalic acid diamides as modifiers for polyolefin catalysts

Also Published As

Publication number Publication date
US10124324B1 (en) 2018-11-13

Similar Documents

Publication Publication Date Title
US10442874B2 (en) Heterocyclic organic compounds as electron donors for polyolefin catalysts
JP6130436B2 (en) Olefin polymerization catalyst composition
US9951157B2 (en) Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor
JP6248120B2 (en) High performance Ziegler-Natta catalyst system, process for producing such supported catalyst and use thereof
WO2015135903A1 (en) Catalyst components for the polymerization of olefins
US20230092187A1 (en) Olefin polymerization catalyst component having carbonate compounds
CN107428995B (en) Oxalic acid diamides as modifiers for polyolefin catalysts
US9815920B1 (en) Olefin polymerization catalyst components and process for the production of olefin polymers therewith
US20070191558A1 (en) Olefin polymerization procatalyst compositions and method of preparation
US9777084B2 (en) Catalyst system for olefin polymerization and method for producing olefin polymer
US10124324B1 (en) Olefin polymerization catalyst components and process for the production of olefin polymers therewith
US10822438B2 (en) Catalyst system for enhanced stereo-specificity of olefin polymerization and method for producing olefin polymer
US20230091516A1 (en) Olefin polymerization Ziegler-Natta catalyst components and process for the production of olefin polymers therewith
WO2023080938A1 (en) Catalyst components for the preparation of highly isotactactic polypropylene polymer with broad molecular weight distribution
WO2024035392A1 (en) Carbonate compounds as activity limiting agents in ziegler-natta catalyst compositions for olefin polymerization
KR20240076546A (en) A method for preparation of propylene copolymer improved in coplymerization
WO2021105373A1 (en) Catalyst composition for the polymerization of olefins

Legal Events

Date Code Title Description
AS Assignment

Owner name: FORMOSA PLASTICS CORPORATION, USA, NEW JERSEY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KONG, GAPGOUNG;ZHANG, LEI;XU, DEMIN;AND OTHERS;SIGNING DATES FROM 20181002 TO 20181003;REEL/FRAME:047104/0428

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4