solid titanium catalyst component for the production of a polyolefin, method of making the same, and

专利摘要:
SOLID TITANIUM CATALYST COMPONENT FOR THE PRODUCTION OF A POLYOLEFIN, METHOD OF MANUFACTURING THE SAME, AND CATALYST SYSTEM FOR THE POLYMERIZATION OF AN OLEFIN. Spherical magnesium-based catalyst supports and methods of using the same in a Ziegler-Natta catalyst system for polymerizing an olefin are described. Spherical magnesium-based catalyst supports are manufactured by reacting a magnesium halide, a haloalkylpoxide, and a phosphate acid ester in an organic solvent that does not have to contain substantial amounts of tuluene.
公开号:BR112013027847B1
申请号:R112013027847-1
申请日:2012-04-27
公开日:2021-07-06
发明作者:Michael Donald Spencer；Neil O'Reilly
申请人:W. R. Grace & Co. - Conn.；
IPC主号:

专利说明:

TECHNICAL FIELD
[01] Olefin polymerization catalyst systems and methods of making the catalyst systems and olefin polymers and copolymers using the catalyst systems are described. FUNDAMENTALS
[02] Polyolefins are a class of polymers derived from simple olefins. Known methods of making polyolefins involve the use of Ziegler-Natta polymerization catalysts. These catalysts polymerize vinyl monomers using a transition metal halide to provide an isotactic polymer.
[03] Numerous Ziegler-Natta polymerization catalysts exist. Catalysts have different characteristics and/or lead to the production of polyolefins that have different properties. For example, certain catalysts have high activity while other catalysts have low activity. In addition, polyolefins made using Ziegler-Natta polymerization catalysts vary in isotacticity, molecular weight distribution, impact strength, melt fluidity, stiffness, thermal sealability, isotacticity, and others. Since olefin monomers are chained together in the presence of a Ziegler-Natta catalyst system, the product polymer takes on the shape and morphology of the solid components of the Ziegler-Natta catalyst system. The polymeric product which has a controlled and regular morphology can be more easily transported within and between the reactors used for polymer synthesis.
[04] Ziegler-Natta catalysts that have the desired spherical shape can be produced through a precipitation method using an organic magnesium starting material. Replacing the organic magnesium with an inexpensive magnesium halide results in catalyst particles with divergent and spherical morphology. SUMMARY
[05] This description provides polymerization catalyst systems, wherein such systems are formed from a solid titanium catalyst component that incorporates a magnesium-based support that is substantially spherical in shape using magnesium halide starting materials. Spherical magnesium-based catalyst supports are manufactured by reacting a magnesium halide, an alkylepoxide, and a phosphate acid ester in an organic solvent.
[06] One aspect concerns a catalyst system for the polymerization of an olefin. The catalyst system incorporates a solid titanium catalyst component which has a substantially spherical shape and a diameter of from about 5 to about 150 µm (on a 50% volume basis), the solid titanium catalyst component contains a compound of titanium, an internal electron donor, and a magnesium-based support made from a blend containing a magnesium compound, an alkylepoxide, a phosphate acid ester, a titanium halide, and a polymeric surfactant. An organoaluminum compound having at least one aluminum-carbon bond is combined with the solid titanium catalyst support prior to polymerization to complete the catalyst system.
[07] Another aspect relates to a method for fabricating a magnesium-based catalyst support. A magnesium halide, an alkylepoxide, a phosphate acid ester, and an organic solvent are combined to form a mixture. A titanium halide is added to the mixture at a first temperature. The organic solvent is selected such that the mixture separates into at least two phases, a dense phase which contains magnesium components and a light phase which contains the organic solvent, upon addition of the titanium halide. An alkyl methacrylate-based additive is added to the phase-separated mixture at a second temperature higher than the first temperature. On heating the phase-separated mixture to a third temperature, the magnesium-based catalyst support solidifies from the mixture. The magnesium-based catalyst support has a substantially spherical shape and a specific diameter.
[08] Additional aspects refer to the methods and systems to synthesize polyolefins using the catalyst systems described. A Ziegler-Natta catalyst system, as described herein, is contacted with an olefin, optional olefin comonomers, hydrogen gas, a fluid medium, and other optional additives in a suitable reactor. Optionally, a multiple zone circulating reactor can be used that allows different gas phase polymerization conditions to exist on either side of a liquid barrier. The spherical nature of the solid component(s) of the Ziegler-Natta catalyst system aids the movement of catalyst and polymer particles within the reactor and facilitates polymer removal upon completion of polymerization. BRIEF SUMMARY OF DRAWINGS
[09] Figure 1 is a high-level schematic diagram of an olefin polymerization system according to one aspect of the polymerization systems described.
[10] Figure 2 is a schematic diagram of an olefin polymerization reactor according to one aspect of the polymerization systems described.
[11] Figure 3 is a high-level schematic diagram of a system for making impact copolymer according to one aspect of the polymerization systems described.
[12] Figure 4 is a microscopic photograph of a magnesium-based support at 125x magnification according to an aspect of magnesium-based supports described.
[13] Figure 5 is a microscopic photograph of the polymer bead at 500x magnification according to one aspect of the polymerization methods described.
[14] Figure 6 reports the variables A to E for examples 3 to 34. DETAILED DESCRIPTION
[15] Ziegler-Natta catalyst systems and supports for Ziegler-Natta catalysts and methods of making the same are described here. One aspect of catalyst systems is a magnesium-based support for polymerizing an olefin, where the magnesium-based support is substantially spherical in shape. The magnesium-based support can be used to form a competent Ziegler-Natta catalyst in combination with a titanium compound, one or more external and/or internal electron donors, and an organoaluminium compound. The magnesium-based support is comprised within the solid titanium catalyst component. Emulsion techniques can be used to manufacture the solid titanium catalyst component and magnesium-based support.
[16] As used throughout this description, the term "magnesium-based support" refers to a support formed by the precipitation or solidification of a catalyst support from a mixture containing a non-reducible magnesium compound. A magnesium-based support may or may not contain titanium or another group IV metal or metal ion. The term "solid titanium catalyst component" refers to a procatalyst that contains a support based on magnesium, titanium or another group IV metal or metal ion, and optionally one or more internal electron donors that are useful to form a Ziegler-Natta catalyst system competent in combination with a headgroup metal alkyl. In some embodiments, the solid titanium catalyst component is formed directly by precipitation or solidification from a mixture containing a non-reducible magnesium compound and titanium or another Group IV metal or metal ion. In another embodiment, the solid titanium catalyst component is formed by further reacting a magnesium-based support with a titanium compound and optionally one or more internal electron donors.
[17] In a typical way of using the Ziegler-Natta catalyst system, a solid titanium catalyst component, an electron donor, and an organoaluminium compound (a main group metal alkyl) form a slurry catalyst system , which may contain any suitable liquid such as an inert hydrocarbon medium. Examples of inert hydrocarbon media include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. The slurry medium is typically hexane, heptane or mineral oil. The slurry medium may be different from the diluent used in forming the mixture from which the solid titanium catalyst component is precipitated.
[18] The magnesium-based catalyst supports described herein can be used in any suitable Ziegler-Natta polymerization catalyst system. Ziegler-Natta catalyst systems are comprised of a reagent or combination of reagents that are functional to catalyze the polymerization of 1-alkenes (α-olefins) to form polymers, typically with high isotacticity, when prochiral 1-alkenes are polymerized . A Ziegler-Natta catalyst system has a transition metal alkyl component (such as a solid titanium component), a headgroup metal alkyl component, and an electron donor; as used throughout this description, the term "Ziegle-Natta catalyst" refers to any composition that has a transition metal and a headgroup metal alkyl component capable of sustaining the catalysis of 1-alkene polymerization. The transition metal component is typically a group IV metal such as titanium, or vanadium, the main group metal alkyl is typically an organoaluminum compound that has a carbon-Al bond, and the electron donor that can be any one of numerous compounds including aromatic esters, alkoxysilanes, amines and ketones can be used as external donors added to the transition metal component and the main group metal alkyl component or a suitable internal donor added to the transition metal component and the metal alkyl component of the main group during the synthesis of these components. The constituent, structure, and fabrication details of the one or more electron donors and organoaluminium compound components are not critical to the practice of the catalyst systems described, as long as the Ziegler-Natta polymerization catalyst system has a titanium component solid incorporating the magnesium-based support as described herein. Details of the constituent, structure, and fabrication of the Ziegler-Natta polymerization catalyst system can be found, for example, in U.S. Patents and U.S. Patent Publications: 4,771,023; 4,784,983, 4,829,038, 4,861,847, 4,990,479, 5,177,043, 5,194,531, 5,244,989, 5,438,110, 5,489,634, 5,576,259, 5,767,215, 5,773,537, 5,905. 050, 6,323,152, 6,437,061, 6,469112, 6,962,889, 7,135,531, 7,153,803, 7,271,119, 2004/242406, 2004/0242407 and 2007/0021573, all of which are hereby incorporated by reference in this regard.
[19] The magnesium-based support and solid titanium catalyst component are prepared using emulsion techniques. initially, the magnesium-based support is prepared by contacting a non-reducible magnesium compound, an alkyl epoxide, and a Lewis base such as trialkyl phosphate acid ester together in an organic solvent diluent at a first temperature to form one or more magnesium monoalkoxide compounds and/or magnesium dialloalkoxide compounds. For the sake of brevity, these compounds are simply referred to as magnesium haloalkoxide compounds. The combination of these components creates an emulsion with two phases: the solvent phase and the magnesium phase.
[20] Phase separation is accomplished by proper solvent selection. Solvent selection involves considering one or more of the physical property differences in polarity, density, and surface tension among others causing separation between the diluting organic solvent and the magnesium phase. Toluene is a common organic solvent diluent that has been used to form the solid titanium catalyst components; however, the use of toluene does not always promote the formation of two phases. With regard to the magnesium-based supports described herein, it was by chance discovered that the use of hexane as an organic solvent diluent can in some cases result in the formation of a solvent phase and a magnesium phase. The two phases are maintained in the subsequent addition of the titanium compound.
[21] In one embodiment, the blend/emulsion does not include a substantial amount of toluene, although toluene may be blended with other solvents. In another embodiment, the phase-separated mixture/emulsion does not contain more than about 25% by weight of toluene prior to solidification of the magnesium-based catalyst support. It is believed that organic solvents other than hexane may also be useful and accomplish the desired phase separation. In particular, non-aromatic alkane-based solvents are useful such as pentane, hexane, heptane, octane, and cyclohexane.
[22] The magnesium haloalkoxide compound(s) formed in emulsion may then be contacted with a titanium halide compound to form the solid titanium catalyst component (which is thereafter subsequently isolated from the emulsion). The emulsion can be raised to a second temperature higher than the first temperature and a surfactant can be added to control the phase morphology. Then, the emulsion can be raised to a third temperature greater than the second temperature to solidify the solid titanium catalyst component.
[23] Emulsion formation is facilitated using conventional emulsion techniques that include one or more of agitation, stirring, mixing, high and/or low shear mixing, mixing nozzles, atomizers, membrane emulsification techniques, milling , sonification, vibration, microfluidization, and others. While the term emulsion is generally used herein, it is understood that emulsion should encompass dispersions, colloids, emulsions, and other two-phase systems.
[24] In one embodiment, the non-reducible magnesium compound is a magnesium compound that contains halogen. Specific examples of magnesium compounds that have no reducibility include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride.
[25] The alkylepoxide compound is a glycidyl-containing compound that has the structure of Formula I:
where b is from 1 to about 5 and X is selected from F, Cl, Br, I, and methyl. In one embodiment, the alkylepoxide compound is epichlorohydrin. The alkylepoxide compound can be a haloalkylepoxide compound or a non-haloalkylepoxide compound.
[26] A Lewis base is any species that donates unshared pair electrons. Examples of Lewis bases include acidic phosphate esters such as a trialkyl phosphate acid ester. A trialkyl phosphate acid ester can be a compound with the structure of Formula II:

[27] where Ra, Rb, and Rc are independently selected from one or more of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, alkyl groups having from 1 to about 10 carbon atoms, and branched alkyl groups having from about 3 to about 10 carbon atoms. In one embodiment, the trialkyl phosphate acid ester is the tributyl phosphate acid ester.
[28] The non-reducible magnesium compound, alkylepoxide, and Lewis base are contacted in the presence of an organic solvent at a first temperature of about 25 to about 100°C to form a mixture/emulsion. In another embodiment, the first temperature is from about 40 to about 70°C. the molar ratio of magnesium compound to alkylepoxide is from about 0.1:2 to about 2:0.1. The molar ratio of the magnesium compound to the Lewis base is from about 0.7:1.3 to about 1.3:0.7. Without wishing to be bound by any theory, it is believed that a halogen atom is transferred from the magnesium compound to the alkylepoxide to open the epoxide ring and form a kind of magnesium alkoxide which has a bond between the magnesium atom and the atom of oxygen from the newly formed alkoxide group. The Lewis base functions to increase the solubility of the species that contains magnesium present.
[29] After contacting the non-reducible magnesium compound, alkyl epoxide, and Lewis base, a titanium halide is added while keeping the mixture/emulsion at the first temperature or at a different temperature. The molar ratio of the amount of titanium halide added to the magnesium compound is from about 3:1 to about 15:1. Upon addition of the titanium compound, the titanium compound enters the magnesium phase where the titanium compound reacts with the magnesium haloalkoxide compound.
[30] The magnesium phase that includes the magnesium-containing species is dispersed within the solvent phase. The size and shape of the droplets forming the magnesium phase can be controlled through a combination of temperature adjustment, agitation energy adjustment, reaction time adjustment and/or agitation energy time, and including/excluding various additives such as surfactants. After phase separation and/or addition of titanium compound, the mixture is raised to a second temperature higher than the first temperature. In one embodiment, the second temperature is from about 15 to about 30°C. In another embodiment, the second temperature is from about 20 to about 35°C. While the mixture is at the second temperature, a polymeric surfactant is added to facilitate the formation of spherical droplets from the magnesium phase surrounded by the solvent phase. That is, the addition of a polymeric surfactant can help control the morphology of the magnesium phase droplets. The polymeric surfactant is mixed into the mixture over time. In one embodiment, the polymeric surfactant is added and then the mixture is blended for a period of about 30 to about 60 minutes. In another embodiment, the polymeric surfactant is added and then the mixture is blended for a period of about 15 to about 90 minutes.
[31] General examples of surfactants include polymeric surfactants such as polyacrylates, polymethacrylates, polyalkyl methacrylates, or any other surfactant that can stabilize an emulsion. Surfactants are known in the art, and many surfactants are described in McCutcheon's "Volume I: Emulsifiers and Detergents", 2001, North American Edition, published by Manufacturing Confectioner Publishing Co., Glen Rock, N.J., and in particular, pp. 1-233 which describe various surfactants and is hereby incorporated by reference to the description under this aspect. A polyalkyl methacrylate is a polymer that can contain one or more methacrylate monomers, such as at least two different methacrylate monomers, at least three different methacrylate monomers, etc. In addition, the acrylate and methacrylate polymers can contain monomer other than acrylate and methacrylate monomers, provided the polymeric surfactant contains at least about 40% by weight of acrylate and methacrylate monomers.
[32] Examples of monomers that can be polymerized using known polymerization techniques in polymeric surfactants include one or more of acrylate; tert-butyl acrylate; n-hexyl acrylate; methacrylate; methyl methacrylate; ethyl methacrylate; propyl methacrylate; isopropyl methacrylate; n-butyl methacrylate; t-butyl methacrylate; isobutyl methacrylate; pentyl methacrylate; isoamyl methacrylate; n-hexyl methacrylate; isodecyl methacrylate; lauryl methacrylate; stearyl methacrylate; isooctyl acrylate; lauryl acrylate; stearyl acrylate; cyclohexyl acrylate; cyclohexyl methacrylate; methoxy ethyl methacrylate; isobenzyl acrylate; isodecyl acrylate; n-dodecyl acrylate; benzyl acrylate; isobornyl acrylate; isobornyl methacrylate; 2-hydroxyethyl acrylate; 2-hydroxypropyl acrylate; 2-methoxyethyl acrylate; 2-methoxybutyl acrylate; 2-(2-ethoxyethoxy) ethyl acrylate; 2-phenoxyethyl acrylate; tetrahydrofurfuryl acrylate; 2-(2-phenoxyethoxy)ethyl acrylate; methoxylated tripropylene glycol monoacrylate; 1,6-hexanediol diacrylate; ethylene glycol dimethacrylate; diethylene glycol dimethacrylate; triethylene glycol dimethacrylate; polyethylene glycol dimethacrylate; butylene glycol dimethacrylate; trimethylolpropane 3-ethoxylate triacrylate; 1,4-butanediol diacrylate; 1,9-nonanediol diacrylate; neopentyl glycol diacrylate; tripropylene glycol diacrylate; tetraethylene glycol diacrylate; heptapropylene glycol diacrylate; trimethylol propane triacrylate; ethoxylated trimethylol propane triacrylate; pentaerythritol triacrylate; trimethylolpropane trimethacrylate; tripropylene glycol diacrylate; pentaerythritol tetraacrylate; glyceryl propoxy triacrylate; tris(acryloyloxyethyl)phosphate; 1-acryloxy-3-methacryloxy glycerol; 2-methacryloxy-N-ethyl morpholine; and allyl methacrylate and others.
[33] Examples of polymeric surfactants that are commercially available include those under the tradename VISCOPLEX® available from RohMax Additives, GmbH, especially those that have the product designations 1-254, 1-256 and those under the tradenames CARBOPOL® and PEMULEN® available from Noveon/Lubrizol.
[34] The polymeric surfactant is typically added in a mixture with an organic solvent. When added as a mixture with an organic solvent, the volume ratio of surfactant to organic solvent is from about 1:10 to about 2:1. In another embodiment, the volume ratio of surfactant to organic solvent is from about 1:6 to about 1:1. In another embodiment, the volume ratio of surfactant to organic solvent is from about 1:4 to about 1:2.
[35] Magnesium phase droplet morphology can be controlled through a combination of temperature, agitation energy, and type and amount of polymeric surfactant. The magnesium-based support and/or solid titanium catalyst component is solidified from the mixture by changing/elevating the mixture to a third temperature higher than the second temperature. In one embodiment, the third temperature is from about 35 to about 50°C. In another embodiment, the third temperature is from about 40 to about 45°C. The magnesium-based catalyst support and/or solid titanium catalyst component is recovered from the mixture by any suitable means, such as filtration. In one embodiment, the magnesium-based catalyst support and/or solid titanium catalyst component is not recovered using spray drying.
[36] Magnesium-based supports and/or solid titanium catalyst components formed using the methods described herein are substantially spherical in shape. Substantially spherical formed catalyst supports are particles that satisfy the following condition:
where f is greater than about 0.7, A is the cross-sectional area in mm2, and Dmax is the maximum diameter of the cross-sectional area in mm. The f factor is a measure of the degree of sphericity of the catalyst support based on magnesium particles. The closer f is to 1, the closer the shape of the particles is to an ideal spherical shape. In another embodiment, the substantially spherically formed catalyst supports have an f value that is greater than about 0.8. In yet another embodiment, the substantially spherically formed catalyst supports have an f value that is greater than about 0.9.
[37] Magnesium-based supports and/or solid titanium catalyst components formed using the methods described herein are also substantially uniformly spherical in shape. In this regard, in one embodiment, 90% by weight of solid magnesium based supports and/or titanium catalyst components have an f value that is greater than about 0.8. In another embodiment, 90% by weight of solid magnesium based supports and/or titanium catalyst components have an f value that is greater than about 0.9.
[38] When the catalyst support is manufactured using substantially equal molar amounts of a magnesium compound and an epoxy compound, a catalyst system is provided that produces polymer product that has a narrow particle size distribution is obtained. In one embodiment, the particle size range is from about 0.25 to about 1.75. In another embodiment, the particle size range is from about 0.5 to about 1.5. In another embodiment, the particle size range is from about 0.7 to about 1.1. The dimensionless particle size range value is determined by subtracting the D10 size from the D90 size, then dividing by the D50 size. D10 is the diameter where 10% of the particles are smallest, D90 is the diameter where 90% of the particles are smallest, and D50 is the diameter where 50% of the particles are smallest and 50% of the particles are largest.
[39] If the solid titanium catalyst component is not formed using the emulsion process described above (where only the magnesium-based support is manufactured using the emulsion process), the solid titanium catalyst component can be prepared by contacting the magnesium-based catalyst support as described above and a titanium compound. The titanium compound used in preparing the solid titanium catalyst component is, for example, a tetravalent titanium compound represented by Formula III:
wherein each R group independently represents a hydrocarbon group, preferably an alkyl group having from 1 to about 4 carbon atoms, X represents a halogen atom, and 0 < g < 4. Specific examples of the titanium compound include titanium tetralides such as TiCl4, TiBr4 and TiI4; alkoxytitanium trihalides such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(O n-C4H9)Cl3, Ti(OC2H5)Br3 and Ti(O iso-C4H9)Br3; dialkoxytitanium dialects such as Ti(OCH3)2 Cl2, Ti(OC2H5)2Cl2, Ti(On-C4H9)2Cl2 and Ti(OC2H5)2Br2; trialkoxytitanium monohalides such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(On-C4H9)3Cl and Ti(OC2H5)3Br; and tetraalkoxytitaniums such as Ti(OCH3)4, Ti(OC2H5)4, Ti(OC3H7)3Cl, Ti(OC3H7)2Cl2, Ti(OC3H7)Cl3 and Ti(On-C4H9)4.
[40] In one embodiment, the titanium compound is a titanium tetralide. These titanium compounds can be used singly or in a combination of two or more. They can also be used as dilutions in hydrocarbon compounds or halogenated hydrocarbons.
[41] When preparing the solid titanium catalyst component, an optional internal electron donor can be included, or the solid titanium catalyst component can be treated to contain an optional internal electron donor. Internal electron donors can be Lewis acids. A Lewis acid is a chemical species that is an electron-pair acceptor.
[42] Internal electron donors, eg oxygen-containing electron donors such as organic acid esters, polycarboxylic acid esters, polyhydroxy esters, heterocyclic polycarboxylic acid esters, inorganic acid esters, acid esters. alicyclic polycarboxylic acid and hydroxy substituted carboxylic acid ester compounds having from 2 to about 30 carbon atoms such as methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, dibutyl maleate, diethyl butylmalonate, diethyl dibutylmalonate, diethyl cyclohexane carboxylate diethyl 2-cyclohexanedicarboxylate, di-2-ethylhexyl 1,2-cyclohexanedicarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, and octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, dimethyl phthalate diethyl, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, Y-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, ethyl silicate, butyl silicate, vinyltriethoxysilanetriethoxyane, diphenyldiethoxysilane; alicyclic polycarboxylic acid esters such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate and nadic acid, diethyl ester; aromatic polycarboxylic acid esters such as monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, mono-n-butyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, ethyl-n-butyl phthalate, ethyl phthalate di-n-propyl, di-isopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-n-octyl phthalate dineopentyl, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyl trimellitate and dibutyl trimellitate, 3,4-furanedicarboxylic acid esters, 1,2-diacetoxybenzene, 1-methyl-2 ,3-diacetoxybenzene, 2-methyl-2,3-diacetoxy-benzene, 2,8-diacetoxinaphthalene, ethylene glycol dipivalate, butanediol pivalate, benzoylethyl salicylate, acetylisobutyl salicylate and acetylmethyl salicylate.
[43] Long-chain dicarboxylic acid esters such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate and di-2-ethylhexyl sebacate, they can also be used as the polycarboxylic acid esters that can be included in the titanium catalyst component. Among these polyfunctional esters, compounds having the structures given by the above general formulas are preferred. Also preferred are esters formed between phthalic acid, maleic acid or substituted malonic acid and alcohols having at least about 2 carbon atoms, diesters formed between phthalic acid and alcohols having at least about 2 carbon atoms are especially preferred. The monocarboxylic acid esters represented by RCOOR' where R and R' are hydrocarbonyl groups which may have a substituent, and at least one of these is a branched ring or which contains an aliphatic alicyclic group. Specifically, at least one of R and R' can be (CH3)2CH-, C2H5CH(CH3)-, (CH3)2CHCH2-, (CH3)3C-, C2H5CH2-, (CH3)CH2-, cyclohexyl, methylbenzyl, for -xylyl, acrylic, and carbonylbenzyl. If one of R and R' is any of the groups described above, the other can be the above group or another group such as a linear or cyclic group. Specific examples of the monocarboxylic acid esters include the monoesters of dimethylacetic acid, trimethylacetic acid, alpha-methylbutyric acid, beta-methylbutyric acid, methacrylic acid and benzoylacetic acid; and acidic monocarboxylic esters formed with alcohols such as methanol, ethanol, isopropanol, isobutanol and tert-butanol.
[44] Additional useful inner electron donors include inner electron donors that contain at least one ether group and at least one ketone group. That is, the inner electron donor compound contains in its structure at least one group of at least one ketone group.
[45] Examples of internal electron donors that contain at least one ether group and at least one ketone group include the compounds of the following Formula IV.
wherein R 1 , R 2 , R 3 , and R 4 are identical or different, and each represents a substituted or unsubstituted hydrocarbon group. In one embodiment, the substituted or unsubstituted hydrocarbon group includes from 1 to about 30 carbon atoms. In another embodiment, R 1 , R 2 , R 3 , and R 4 are identical or different, and each represents a linear or branched alkyl group containing from 1 to about 18 carbon atoms, a cycloaliphatic group containing from about 3 to about 18 carbon atoms, an aryl group that contains about 6 to about 18 carbon atoms, an alkylaryl group that contains about 7 to about 18 carbon atoms, and an arylalkyl group that contains about from 7 to about 18 carbon atoms. In yet another embodiment, R 1 , C 1 and R 2 are a part of a substituted or unsubstituted cyclic or polycyclic structure that contains from about 5 to about 14 carbon atoms. In yet another embodiment, the cyclic or polycyclic structure has one or more substituents selected from the group consisting of a linear or branched alkyl group containing from 1 to about 18 carbon atoms, a cycloaliphatic group containing from about 3 to about 18 carbon atoms, an aryl group that contains about 6 to about 18 carbon atoms, an alkylaryl group that contains about 7 to about 18 carbon atoms, and an arylalkyl group that contains about from 7 to about 18 carbon atoms.
[46] Specific examples of internal electron donors that contain at least one ether group and at least one ketone group include 9-(alkylcarbonyl)-9'-alkoxymethylfluorene which include 9-(methylcarbonyl)-9'-methoxymethylfluorene, 9- (methylcarbonyl)-9'-ethoxymethylfluorene, 9-(methylcarbonyl)-9'-propoxymethylfluorene, 9-(methylcarbonyl)-9'-butoxy-methylfluorene, 9-(methylcarbonyl)-9'-pentoxymethylfluorene, 9-(ethylcarbonyl)- 9'-methoxymethylfluorene, 9-(ethylcarbonyl)-9'-ethoxymethylfluorene, 9-(ethyl-carbonyl)-9'-propoxymethylfluorene, 9-(ethylcarbonyl)-9'-butoxymethyl-fluorene, 9-(ethylcarbonyl)-9' -pentoxymethylfluorene, 9-(propylcarbonyl)-9'-methoxymethylfluorene, 9-(propylcarbonyl)-9'-ethoxymethylfluorene, 9-(propylcarbonyl)-9'-propoxymethylfluorene, 9-(propylcarbonyl)-9'-butoxy-methylfluorene, 9 -(propylcarbonyl)-9'-pentoxymethylfluorene, 9-(butylcarbonyl)-9'-methoxymethylfluorene, 9-(butylcarbonyl)-9'-ethoxymethyl-fluorene, 9-(butylcarbonyl)-9'-propoxymethylfluorene, 9-(butylcarbonyl) -9'-butoxymethylflu orene, 9-(butylcarbonyl)-9'-pentoxymethylfluorene, 9-(pentylcarbonyl)-9'-methoxymethylfluorene, 9-(pentylcarbonyl)-9'-ethoxymethylfluorene, 9-(pentylcarbonyl)-9'-propoxymethylfluorene, 9- (pentylcarbonyl)-9'-butoxymethylfluorene, 9-(pentylcarbonyl)-9'-pentoxymethylfluorene, 9-(hexylcarbonyl)-9'-methoxymethylfluorene, 9-(hexylcarbonyl)-9'-ethoxymethylfluorene, 9-(hexylcarbonyl)- 9'-propoxymethylfluorene, 9-(hexylcarbonyl)-9'-butoxymethylfluorene, 9-(hexylcarbonyl)-9'-pentoxymethylfluorene, 9-(octylcarbonyl)-9'-methoxymethylfluorene, 9-(octylcarbonyl)-9'-ethoxymethylfluorene , 9-(octylcarbonyl)-9'-propoxymethylfluorene, 9-(octylcarbonyl)-9'-butoxymethylfluorene, 9-(octylcarbonyl)-9'-pentoxymethylfluorene; 9-(i-octylcarbonyl)-9'-methoxymethylfluorene, 9-(i-octylcarbonyl)-9'-ethoxymethylfluorene, 9-(i-octylcarbonyl)-9'-propoxymethylfluorene, 9-(i-octylcarbonyl)-9 '-butoxymethylfluorene, 9-(i-octylcarbonyl)-9'-pentoxymethylfluorene; 9-(i-nonylcarbonyl)-9'-methoxymethylfluorene, 9-(i-nonylcarbonyl)-9'-ethoxymethylfluorene, 9-(i-nonylcarbonyl)-9'-propoxymethylfluorene, 9-(i-nonylcarbonyl)-9 '-butoxymethylfluorene, 9-(i-nonylcarbonyl)-9'-pentoxymethylfluorene; 9-(2-ethylhexylcarbonyl)-9'-methoxymethylfluorene, 9-(2-ethylhexylcarbonyl)-9'-ethoxymethylfluorene, 9-(2-ethylhexylcarbonyl)-9'-propoxymethylfluorene, 9-(2- ethylhexylcarbonyl)-9'-butoxymethylfluorene, 9-(2-ethylhexylcarbonyl)-9'-pentoxymethylfluorene, 9-(phenylketone)-9'-methoxymethylfluorene, 9-(phenyl-ketone-9'-ethoxymethylfluorene, 9- (phenylketone)-9'-propoxymethyl-fluorene, 9-(phenylketone)-9'-butoxymethylfluorene, 9-(phenylketone)-9'-pentoxymethyl-fluorene, 9-(4-methylphenylketone)-9'-methoxymethylfluorene, 9- (3-methylphenylketone)-9'-methoxymethylfluorene, 9-(2-methylphenylketone)-9'-methoxymethylfluorene.
[47] Additional examples include: 1-(ethylcarbonyl)-1'-methoxymethylcyclopentane, 1-(propylcarbonyl)-1'-methoxymethylcyclopentane, 1-(i-propylcarbonyl)-1'-methoxymethylcyclopentane, 1-(butylcarbonyl)-1 '-methoxymethylcyclopentane, 1-(i-butylcarbonyl)-1'-methoxymethylcyclopentane. 1-(pentylcarbonyl)-1'-methoxymethylcyclopentane, 1-(i-pentylcarbonyl)-1'-methoxymethylcyclopentane, 1-(neopentylcarbonyl)-1'-methoxymethylcyclopentane, 1-(hexylcarbonyl)-1'-methoxymethylcyclopentane, 1- (2-ethylhexyl-carbonyl)-1'-methoxymethylcyclopentane, 1-(octylcarbonyl)-1'-methoxymethyl-cyclopentane, 1-(i-octylcarbonyl)-1'-methoxymethylcyclopentane, 1-(i-nonyl-carbonyl)-1 '-methoxymethylcyclopentane, 1-(ethylcarbonyl)-1'-methoxymethyl-2-methylcyclopentane, 1-(propylcarbonyl)-1-methoxymethyl-2-methylcyclopentane, 1-(i-propylcarbonyl)-1'-methoxymethyl-2-methylcyclopentane, 1-(butyl-carbonyl)-1'-methoxymethyl-2-methylcyclopentane, 1-(i-butylcarbonyl)-1'-methoxymethyl-2-methylcyclopentane, 1-(pentylcarbonyl)-1'-methoxymethyl-2-methylcyclopentane, 1 -(i-pentylcarbonyl)-1'-methoxymethyl-2-methylcyclopentane, 1-(neopentylcarbonyl)-1'-methoxymethyl-2-methylcyclopentane, 1-(hexylcarbonyl)-1'-methoxymethyl-2-methylcyclopentane, 1- (2-ethylhexyl-carbonyl)-1'-methoxymethyl-2-methyl cyclopentane, 1-(octylcarbonyl)-1'-methoxymethyl-2-meth yl cyclopentane, 1-(i-octylcarbonyl)-1'-methoxymethyl-2-methyl cyclopentane, 1-(i-nonylcarbonyl)-1'-methoxymethyl-2-methyl cyclopentane, 1-(ethylcarbonyl)-t-methoxymethyl -2,5-dimethylcyclopentane, 1-(propylcarbonyl)-1'-methoxymethyl-2,5-dimethylcyclopentane, 1-(i-propyl-carbonyl)-1'-methoxymethyl-2,5-dimethyl-cyclopentane, 1-( butylcarbonyl)-1'-methoxymethyl-2,5-di-cyclopentane, 1-(i-butylcarbonyl)-1'-methoxymethyl-2,5-dimethylcyclopentane. 1-(pentylcarbonyl)-1'-methoxymethyl-2,5-dimethylcyclopentane, 1-(i-pentylcarbonyl)-1'-methoxymethyl-2,5-dimethylcyclopentane, 1-(neopentylcarbonyl)-1'-methoxymethyl-2 ,5-dimethylcyclopentane, 1-(hexyl-carbonyl)-1'-methoxymethyl-2,5-dimethylcyclopentane, 1-(2-ethylhexylcarbonyl)-1'-methoxymethyl-2,5-dimethyl cyclopentane, 1-(octylcarbonyl)- 1'-methoxymethyl-2,5-dimethyl cyclopentane, 1-(i-octylcarbonyl)-1'-methoxymethyl-2,5-dimethyl cyclopentane, 1-(i-nonylcarbonyl)-1'-methoxymethyl-2,5-dimethyl cyclopentane, 1-(ethylcarbonyl)-1'-methoxymethylcyclohexane, 1-(propylcarbonyl)-1'-methoxymethylcyclohexane, 1-(i-propylcarbonyl)-1'-methoxymethylcyclohexane, 1-(butylcarbonyl)-1'-methoxymethylcyclohexyl, 1- (i-butylcarbonyl)-1'-methoxymethylcyclohexane, 1-(pentylcarbonyl)-1'-methoxy-methylcyclohexane, 1-(i-pentylcarbonyl)-1'-methoxymethylcyclohexane, 1-(neopentylcarbonyl)-1'-methoxymethylcyclohexane,1- (hexylcarbonyl)-11-methoxymethylcyclohexane, 1-(2-ethylhexylcarbonyl)-1'-methoxymethylcyclohexane, 1-(octylcarbonyl)-1'-methoxymethylcyclohexane n, 1-(i-octylcarbonyl)-1'-methoxy-methylcyclohexane, 1-(i-nonylcarbonyl)-1'-methoxymethylcyclohexane, 1-(ethylcarbonyl)-1'-methoxymethyl-2-methylcyclohexane, 1-(propylcarbonyl) -1'-methoxymethyl-2-methylcyclohexane, 1-(i-propanecarbonyl)-1'-methoxymethyl-2-methylcyclohexane, 1-(butylcarbonyl)-1'-methoxymethyl-2-methylcyclohexane, 1-(ibutylcarbonyl)-1' -methoxymethyl-2-methylcyclohexane, 1-(pentylcarbonyl)-1'-methoxymethyl-2-methylcyclohexane, 1-(i-pentylcarbonyl)-1'-methoxymethyl-2-methylcyclohexane, 1-(neopentylcarbonyl)-1'-methoxymethyl- 2-methylcyclohexane, 1-(hexylcarbonyl)-1'-methoxymethyl-2-methylcyclohexane, 1-(2-ethylhexyl-carbonyl)-1'-methoxymethyl-2-methyl cyclohexane, 1-(octylcarbonyl)-1'- methoxymethyl-2-methyl cyclohexane, 1-(i-octylcarbonyl)-1'-methoxymethyl-2-methyl cyclohexane, 1-(i-nonylcarbonyl)-1'-methoxymethyl-2-methyl cyclohexane, 1-(ethylcarbonyl)-1 '-methoxymethyl-2,6-dimethylcyclohexane, 1-(propylcarbonyl)-1'-methoxymethyl-2,6-dimethylcyclohexane, 1-(i-propylcarbonyl)-1'-methoxy-methyl-2,6-dimethylcyclohexane, 1- (butylcarbon yl)-1'-methoxymethyl-2,6-dimethyl-cyclohexane, 1-(i-butylcarbonyl)-t-methoxymethyl-2,6-dimethylcyclohexane, 1-(pentylcarbonyl)-1'-methoxymethyl-2,6-dimethylcyclohexane , 1-(i-pentylcarbonyl)-1'-methoxymethyl-2,6-dimethylcyclohexane, 1-(neopentylcarbonyl)-1'-
[48] methoxymethyl-2,6-dimethylcyclohexane, 1-(hexylcarbonyl)-1'-methoxymethyl-2,6-dimethylcyclohexane, 1-(2-ethylhexylcarbonyl)-t-methoxymethyl-2,6-dimethyl cyclohexane, 1-( octylcarbonyl)-t-methoxymethyl-2,6-dimethyl cyclohexane, 1-(i-octylcarbonyl)-1s-methoxymethyl-2,6-dimethyl cyclohexane, 1-(i-nonylcarbonyl)-1'-methoxymethyl-2,6- dimethyl cyclohexane, 2,5-dimethyl-3-ethylcarbonyl-3'-methoxymethylpentane, 2,5-dimethyl-3-propylcarbonyl-3'-methoxymethylpentane, 2,5-dimethyl-3-propylcarbonyl-3'methoxymethylpentane, 2.5 -dimethyl-3-butyl-carbonyl-3'-methoxymethylpentane, 2,5-dimethyl-3-i-butylcarbonyl-1'-methoxy-methylcyclohexyl. 2,5-dimethyl-3-pentylcarbonyl-3'-methoxymethylpentane, 2,5-dimethyl-3-i-pentylcarbonyl-3'-methoxymethylpentane, 2,5-dimethyl-3-neo-pentylcarbonyl-3'-methoxymethylpentane, 2 ,5-dimethyl-3-hexylcarbonyl-3'-methoxymethylpentane, 2,5-dimethyl-3-2-ethylhexylcarbonyl-3'-methoxymethylpentane, 2,5-dimethyl-3-octylcarbonyl-3'-methoxymethylpentane, 2, 5-dimethyl-3-i-octylcarbonyl-3'-methoxymethylpentane, and 2,5-dimethyl-3-i-nonylcarbonyl-3'-methoxymethylpentane.
[49] In one embodiment, an internal electron donor is one or more selected from dialkyl-4-alkylphthalates which include diisobutyl-4-methylphthalate and di-n-butyl-4-ethylphthalate; diisobutyl cyclophthalate-pentane-1,1-dicarboxylate; and isobutyl 1-(methoxymethyl)cyclophthalatepentanecarboxylate.
[50] Additional useful internal electron donors include 1,8-naphthyl diaryloate compounds that have three aryl groups connected by ester bonds (three aryl groups connected by two ester bonds, such as an aryl compound connected by an ester-bond). naphthyl-aryl ester bond). The 1,8-naphthyl diariolate compounds can be formed by the reaction of a naphthyl alcohol compound with an aryl acid halide compound. Methods of forming an ester product through the reaction of an alcohol and acid anhydride are well known in the art.
[51] While wishing not to be bound by any theory, it is believed that 1,8-naphthyl diaryloate compounds possess a chemical structure that allows them to bind both a titanium compound and a magnesium compound, both of which are typically present in a solid titanium catalyst component of an olefin catalyst polymerization system. 1,8-Naphthyl diaryloate compounds also act as internal electron donors, due to the compounds' electron donating properties, in a solid titanium catalyst component of an olefin catalyst polymerization system.
[52] In one embodiment, the 52.8-aphthyl diaryloate compounds are represented by Chemical Formula V:
where each R is independently hydrogen, halogen, alkyl having 1 to about 8 carbon atoms, phenyl, arylalkyl having 7 to about 18 carbon atoms, or alkylaryl having 7 to about 18 carbon atoms. In another embodiment, each R is independently hydrogen, alkyl that has 1 to about 6 carbon atoms, phenyl, arylalkyl that has 7 to about 12 carbon atoms, or alkylaryl that has 7 to about 12 carbon atoms. carbon.
[53] General examples of the 1,8-naphthyl diaryloate compounds include 1,8-naphthyl di(alkylbenzoates); 1,8-naphthyl di(dialkylbenzoates); 1,8-naphthyl di(trialkylbenzoates); 1,8-naphthyl di(arylbenzoates); 1,8-naphthyl di(halobenzoates); 1,8-naphthyl di(dihalobenzoates); 1,8-naphthyl di(alkylalobenzoates); and others.
[54] Specific examples of the 1,8-naphthyl diaryloate compounds include 1,8-naphthyl dibenzoate; 1,8-naphthyl di-4-methylbenzoate; 1,8-naphthyl di-3-methylbenzoate; 1,8-naphthyl di-2-methylbenzoate; 1,8-naphthyl di-4-ethylbenzoate; 1,8-naphthyl di-4-n-propylbenzoate; 1,8-naphthyl di-4-isopropylbenzoate; 1,8-naphthyl di-4-n-butylbenzoate; 1,8-naphthyl di-4-isobutylbenzoate; 1,8-naphthyl di-4-t-butylbenzoate; 1,8-naphthyl di-4-phenylbenzoate; 1,8-naphthyl di-4-fluorobenzoate; 1,8-naphthyl di-3-fluorobenzoate; 1,8-naphthyl di-2-fluorobenzoate; 1,8-naphthyl di-4-chlorobenzoate; 1,8-naphthyl di-3-chlorobenzoate; 1,8-naphthyl di-2-chlorobenzoate; 1,8-naphthyl di-4-bromobenzoate; 1,8-naphthyl di-3-bromobenzoate; 1,8-naphthyl di-2-bromobenzoate; 1,8-naphthyl di-4-cyclohexylbenzoate; 1,8-naphthyl di-2,3-dimethylbenzoate; 1,8-naphthyl di-2,4-dimethylbenzoate; 1,8-naphthyl di-2,5-dimethylbenzoate; 1,8-naphthyl di-2,6-dimethylbenzoate; 1,8-naphthyl di-3,4-dimethylbenzoate; 1,8-naphthyl di-3,5-dimethylbenzoate; 1,8-naphthyl di-2,3-dichlorobenzoate; 1,8-naphthyl di-2,4-dichlorobenzoate; 1,8-naphthyl di-2,5-dichlorobenzoate; 1,8-naphthyl di-2,6-dichlorobenzoate; 1,8-naphthyl di-3,4-dichlorobenzoate; 1,8-naphthyl di-3,5-dichlorobenzoate; 1,8-naphthyl di-3,5-di-t-butylbenzoate; and others.
[55] Internal electron donors can be used individually or in combination. Where the internal electron donor is used, these cannot be used directly as starting materials, but compounds convertible to electron donors in the course of preparing the titanium catalyst components can also be used as the starting materials.
[56] The solid titanium catalyst component can be formed by contacting the catalyst-supported magnesium, the titanium compound, and the optional internal electron donor through methods used to prepare a highly active titanium catalyst component from a magnesium support, a titanium compound, and an optional electron donor.
[57] Several examples of the method of producing the solid titanium catalyst component are briefly described below. (1) The magnesium-based catalytic support, optionally with the internal electron donor, is reacted with the titanium compound in the liquid phase. (2) Magnesium-based catalytic support and titanium compounds are reacted in the presence of the internal electron donor to precipitate a solid titanium complex. (3) The reaction product obtained in (2) is again reacted with the titanium compound. (4) The reaction product obtained in (1) or (2) is again reacted with the inner electron donor and the titanium compound. (5) The product obtained from (1) to (4) is treated with a halogen, a halogen compound or an aromatic hydrocarbon. (6) A magnesium-based catalytic support is reacted with the optional internal electron donor, the titanium compound and/or a halogen-containing hydrocarbon. (7) The magnesium-based catalytic support is reacted with the titanium compound in the liquid phase, filtered and washed. The reaction product is again reacted with the internal electron donor and the titanium compound, then activated with the additional titanium compound in an organic medium.
[58] When the solid titanium catalyst support is obtained by further reacting the magnesium-based support with a titanium compound, the solid precipitate is washed with an inert diluent and then treated with a titanium compound or a mixture of a titanium compound and an inert diluent. The amount of titanium compound used is from about 1 to about 20 moles, such as from about 2 to about 15 moles, per mole of magnesium halide on the magnesium-based support. The treatment temperature ranges from about 50°C to about 150°C, such as from about 60°C to about 100°C. If a mixture of a titanium compound and inert diluent is used to treat the magnesium-based support, the % by volume of the titanium compound in the treatment solution is from about 10% to about 100%, the rest being one. inert thinner.
[59] Treated solids can be rewashed with an inert diluent to remove ineffective titanium compounds and other impurities. The inert diluent used herein can be hexane, heptane, octane, 1,2-dichloroethane, benzene, toluene, xylenes, and other hydrocarbons.
[60] In one embodiment, particularly the embodiments following example (2) described above, the solid titanium catalyst component has the following chemical composition: titanium, from about 1.5 to about 6.0 % by weight; magnesium, from about 10 to about 20% by weight; halogen, from about 40 to about 70% by weight; internal electron donor, from about 1 to about 25% by weight; and optionally an inert diluent from about 0 to about 15% by weight.
[61] The amounts of ingredients used in preparing the solid titanium catalyst component may vary depending on the method of preparation. In one embodiment, from about 0.01 to about 5 moles of the internal electron donor and from about 0.01 to about 500 moles of the titanium compound are used per mole of magnesium compound used to make the solid titanium catalyst component. In another embodiment, from about 0.05 to about 2 moles of the internal electron donor and from about 0.05 to about 300 moles of the titanium compound are used per mole of magnesium compound used to manufacture the solid titanium catalyst component.
[62] In one embodiment, in the solid titanium catalyst component, the atomic ratio of halogen/titanium is from about 4 to about 200; the internal electron donor/titanium molar ratio is from about 0.01 to about 10; and the atomic ratio of magnesium/titanium is from about 1 to about 100. In another embodiment, in the solid titanium catalyst component, the atomic ratio of halogen/titanium is from about 5 to about 100; the internal electron donor/titanium molar ratio is about 0.2 to about 6; and the atomic magnesium/titanium ratio is from about 2 to about 50.
[63] The resulting solid titanium catalyst component generally contains a magnesium halide of a smaller crystal size than commercial magnesium halides and generally has a specific surface area of at least about 50 m2/g, such as from about 60 to 1000 m2/g, or from about 100 to 800 m2/g. Since the above ingredients are combined to form an integral solid titanium catalyst component structure, the composition of the solid titanium catalyst component does not change substantially upon washing with, for example, hexane.
[64] In one embodiment, in the solid titanium catalyst component, the atomic ratio of halogen/titanium is from about 4 to about 200; the internal electron donor/titanium molar ratio is from about 0.01 to about 10; and the atomic ratio of magnesium/titanium is from about 1 to about 100. In another embodiment, in the solid titanium catalyst component, the atomic ratio of halogen/titanium is from about 5 to about 100; the internal electron donor/titanium molar ratio is about 0.2 to about 6; and the atomic magnesium/titanium ratio is from about 2 to about 50.
[65] The resulting solid titanium catalyst component generally contains a magnesium halide of a smaller crystal size than commercial magnesium halides and generally has a specific surface area of at least about 50 m2/g, such as from about 60 to 1000 m2/g, or from about 100 to 800 m2/g. Since the above ingredients are combined to form an integral solid titanium catalyst component structure, the composition of the solid titanium catalyst component does not change substantially upon washing with, for example, hexane.
[66] Solid titanium catalyst component can be used after being diluted with an inorganic or organic compound such as a silicon compound, an aluminum compound.
[67] The amounts of ingredients used in preparing the solid titanium catalyst component may vary depending on the method of preparation. In one embodiment, from about 0.01 to about 5 moles of the optional internal electron donor and from about 0.01 to about 500 moles of the titanium compound are used per mole of the magnesium compound used to manufacture the solid titanium catalyst component. In another embodiment, from about 0.05 to about 2 moles of the internal electron donor and from about 0.05 to about 300 moles of the titanium compound are used per mole of the magnesium compound used to manufacture the solid titanium catalyst component.
[68] In one embodiment, the size (diameter) of the catalyst support particles is from about 5 µm to about 150 µm (on a 50% volume basis). In another embodiment, the particle size (diameter) of the catalyst support particles is from about 15 µm to about 80 µm (on a 50% volume basis). In another embodiment, the particle size (diameter) of the catalyst support particles is from about 15 µm to about 45 µm (on a 50% volume basis).
[69] The catalyst support particles and the resulting solid titanium component particles have a narrow size distribution. In one embodiment, 75% of the particles are within 25 µm in diameter (on a 50% volume basis). In another embodiment, 75% of the particles are within 15 µm in diameter (on a 50% volume basis). In another embodiment, 75% of the particles are within 10 µm in diameter (on a 50% volume basis).
[70] The resulting solid titanium catalyst component generally contains a magnesium halide of a smaller crystal size than commercial magnesium halides and generally has a specific surface area of at least about 50 m2/g, such as from about 60 to 1000 m2/g, or from about 100 to 800 m2/g. Since the above ingredients are combined to form an integral solid titanium catalyst component structure, the composition of the solid titanium catalyst component does not change substantially upon washing with solvents, e.g., hexane.
[71] The solid titanium catalyst component can be used after being diluted with an inorganic or organic compound such as a silicon compound or an aluminum compound. The catalyst system described also relates to an olefin polymerization catalyst system which contains an antistatic agent, and optionally an organoaluminium compound and/or an organosilicon compound.
[72] The catalyst system can contain at least one organoaluminium compound in addition to the solid titanium catalyst component. Compounds that have at least one aluminum-carbon bond in the molecule can be used as the organoaluminium compound. Examples of organoaluminium compounds include compounds of the following Formulas VI and VII.

[73] In Formula VI, R11 and R12 may be identical or different, and each represents a hydrocarbon group generally having 1 to about 15 carbon atoms, preferably 1 to about 4 carbon atoms; X1 represents a halogen atom, 0<q<3, 0>p<3, 0>n<3 and m+n+p+q=3.
[74] Organoaluminium compounds also include complex alkylated compounds between aluminum and a Group I metal represented by Formula VII:
wherein M1 represents Li, Na or K, and R11 are as depicted above.
[75] Examples of organoaluminium compounds are as follows:
[76] Compounds of the general formula Rr11Al(OR12)3-r wherein R11 is as defined above, and m is preferably a number represented by 1.5>r>3; compounds of the general formula Rr11AlX3-r wherein R11 is as defined above, X1is halogen, and m is preferably a number represented by 0<r<3; the compounds of the general formula Rr11AlH3-r wherein R11 is as defined above, and m is preferably a number represented by 2>r<3; and compounds represented by the general formula Rs11Al(OR12)tXu1 wherein R11 and R12 are as defined, X1is halogen, 0>s<3, O>u<3, s+t+u = 3.
[77] Specific examples of the organoaluminium compounds represented by Formula VI include trialkyl aluminums such as triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum butoxide; aluminum alkyl sesquialkoxides such as sesquietoxides as ethyl aluminum and butyl aluminum sesquibutoxide; partially alkoxylated alkyl aluminums having an average composition represented by R2.511Al(OR12)0.5; dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; aluminum alkyl sesquialides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially halogenated alkyl aluminums, for example, alkyl aluminum dialects such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; other partially hydrogenated alkyl aluminum, for example alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride; and partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxychloride, butyl aluminum butoxychloride and ethyl aluminum ethoxybromide.
[78] Organoaluminum compounds also include those similar to formula VI such as in which two or more aluminum atoms are bonded through an oxygen or nitrogen atom. Examples are (C2H5)2AlOAl(C2H5)2, (C4H9)2AlOAl(C4H9)2,
(C2H5)2AlNAl(C2H5)2C2H5 and methylaluminoxane.
[79] Examples of organoaluminium compounds represented by Formula V include LiAl(C2H5)4 and LiAl(C7H15)4.
[80] The organoaluminium catalyst component compound is used in the catalyst systems described above in an amount such that the mol ratio of aluminum to titanium (of the solid catalyst component) is from about 5 to about 1,000. In another embodiment, the mole ratio of aluminum to titanium in the catalyst system is from about 10 to about 700. In another embodiment, the mole ratio of aluminum to titanium in the catalyst system is from about 25 to about 400.
[81] The organosilicon compound, when used as an external electron donor serving as a component of a Ziegler-Natta catalyst system for olefin polymerization, contributes with the ability to obtain a polymer (at least a portion of which is polyolefin) which has a wide molecular weight distribution and controllable crystalline characteristics while maintaining high performance with respect to catalytic activity and highly isotactic polymer yield.
[82] The Ziegler-Natta catalyst system can be used in the polymerization of olefins in any suitable system/process. Examples of systems for the polymerization of olefins are now described. Referring to Figure 1, a high level schematic diagram of a system 10 for the polymerization of olefins is presented. Inlet 12 is used to introduce catalyst system components into a reactor 14; catalyst system components can include olefins, optional comonomer, hydrogen gas, fluid media, pH adjusters, surfactants, and any other additives. Although only one entry is shown, often many are used. Reactor 14 is any suitable vehicle that can polymerize the olefins. Examples of reactors 14 include a single reactor, a series of two or more reactors, slurry reactors, fixed bed reactors, gas phase reactors, fluidized gas reactors, recirculation reactors, multizone loop reactors, and others. Once polymerization is complete, or as polyolefins are produced, the polymer product is removed from reactor 14 via outlet 16 which leads to a manifold 18. Manifold 18 may include downstream processing such as heating, extrusion, molding, and others.
[83] Referring to Figure 2, a schematic diagram of a multizone loop reactor 20 that can be used as reactor 14 in Figure 1 or reactor 44 in Figure 3 to manufacture the polyolefins is shown. The multi-zone circulating reactor 20 replaces a series of separate reactors with a single reactor recirculation that allows for different gas phase polymerization conditions on both sides due to the use of a liquid barrier. In the multizone circulating reactor 20, a first zone starts out rich in olefin monomer, and optionally one or more comonomers. A second zone is rich in hydrogen gas, and a high velocity gaseous flow splits the free-growing resin particles. The two zones produce resins of different molecular weights and/or monomeric compositions. The polymeric granules grow as they circulate around the recirculation, forming alternating layers of each polymeric fraction in a manner similar to an onion. In this way, the polymer particles/granules take the form of the solid components of the catalyst system. Each polymer particle constitutes an intimate combination of both polymer fractions.
[84] In operation, the polymer particles pass through the fluidizing gas in an upward recirculation location 24 and descend through the liquid monomer in a downward side 26. Same or different monomers (and again optionally one or more comonomer) can be added to both legs of the reactor. The reactor uses the catalyst systems described above.
[85] In the liquid/gas separation zone 30, hydrogen gas is removed to cool and recirculate. The polymeric granules are then packaged on top of the falling side 26, where they then move down. Monomers are introduced as liquids in this section. Conditions at the top of descending site 26 can be varied with different combinations and/or proportions of the monomer in successive passes.
[86] Referring to Figure 3, a high-level schematic diagram of another system 40 for the polymerization of olefins is shown. The system is ideally suited for making the impact copolymer. A reactor 44, such as a single reactor, a series of reactors, or the multizone circulating reactor is paired with a downstream fluidized or gas phase bed reactor 48 which contains the catalyst systems described above for making the impact copolymers with desirable impact to hardness balance or greater softness than those manufactured with conventional catalyst systems. Inlet 42 is used to introduce 44 catalyst system components, olefins, optional comonomer, hydrogen gas, fluid medium, pH adjusters, surfactants, and any other additives into the reactor. Although only one entry is shown, many are often used. Through transfer means 46, polyolefins manufactured in first reactor 44 are sent to second reactor 48. Feed 50 is used to introduce catalyst system components, olefins, optional comonomer, fluid medium, and any other additives. The second reactor 48 may or may not contain a system of catalyst components. Again, although only one entry is shown, many are often used. Once the second polymerization is complete, or as impact copolymers are produced, the polymer product is removed from the second reactor 48 via outlet 52 which leads to a manifold 54. Manifold 54 may include downstream processing, such as heating, extrusion, molding, and others. At least a first reactor 44 and a second reactor 48 contain a catalyst system in accordance with the present description.
[87] When making an impact copolymer, polypropylene can be formed in the first reactor while an ethylene-propylene rubber can be formed in the second reactor. In this polymerization, the ethylene-propylene rubber in the second reactor is formed with the matrix (and particularly within the pores) of the polypropylene formed in the first reactor. Consequently, an intimate blend of an impact copolymer is formed, wherein the polymer product appears as a single polymeric product. Such an intimate blend cannot be manufactured by simply blending a polypropylene product with an ethylene-propylene rubber product.
[88] Although not shown in any of the figures, systems and reactors can be controlled, optionally with feedback based on a continuous or intermittent test, using a processor equipped with optional memory and controllers. For example, a processor can be connected to one or more of the reactors, inputs, outputs, test/measurement systems connected with the reactors, and others to monitor and/or control the polymerization process based on the relevant pre-set data. reactions, and/or based on test/measurement data generated during a reaction. The controller can control valves, flow rates, quantities of materials entering systems, conditions (temperature, reaction time, pH, etc.) of reactions, and more, as instructed by the processor. The processor may contain or be linked to a memory which contains data concerning various aspects of the polymerization process and/or the systems involved in the polymerization process.
[89] The systems also refer to a polymerization process that involves the polymerization or copolymerization of olefins in the presence of the catalyst polymerization system described above. The catalyst system can produce a polymeric product that has a controlled size and shape and/or relatively large. In one embodiment, using the catalyst support, the catalyst system, and/or the methods described herein, the polymer product has substantially an average diameter of about 300 µm or more (on a 50% volume basis) . In another embodiment, the polymer product has an average diameter of about 1000 µm or more (on a 50% volume basis). In yet another embodiment, the polymer product has an average diameter of about 1500 µm or more (on a 50% volume basis). The relatively large size of the polymer product allows the polymer product to contain a high amount of rubber without adversely affecting the flow properties.
[90] The polymerization of olefins is carried out in the presence of the catalyst system described above. Generally speaking, olefins are communicated with the catalyst system described above under suitable conditions to form the desired polymeric products. In one embodiment, the preliminary polymerization described below is carried out prior to the main polymerization. In another embodiment, polymerization is carried out without preliminary polymerization. In another embodiment, the formation of the impact copolymer is carried out using at least two polymerization zones.
[91] The concentration of the solid titanium catalyst component in the preliminary polymerization is generally from about 0.01 to about 200 mM, preferably from about 0.05 to about 100 mM, calculated as titanium atoms per liter of an inert hydrocarbon medium described below. In one embodiment, preliminary polymerization is carried out by adding an olefin and the above catalyst system ingredients to an inert hydrocarbon medium and reacting the olefin under mild conditions.
[92] Specific examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. In the catalyst systems described, a liquid olefin can be used in place of part or all of the inert hydrocarbon medium.
[93] The olefin used in the preliminary polymerization may be the same as, or different from, an olefin to be used in the main polymerization.
[94] The reaction temperature for the preliminary polymerization is low enough for the resulting preliminary polymer not to substantially dissolve in the inert hydrocarbon medium. In one embodiment, the temperature is from about -20°C to about 100°C. In another embodiment, the temperature is from about -10°C to about 80°C. In another embodiment, the temperature is from about 0°C to about 40°C.
[95] Optionally, a molecular weight control agent, such as hydrogen, can be used in the preliminary polymerization. The molecular weight control agent is used in such an amount that the polymer obtained by the preliminary polymerization has an intrinsic viscosity, measured in decalin at 135°C, of at least about 0.2 dl/g, and preferably about 0 .5 to 10 dl/g.
[96] In one embodiment, the preliminary polymerization is desirably carried out so that from about 0.1 g to about 1000 g of a polymer forms per gram of the titanium catalyst component of the catalyst system. In another embodiment, the preliminary polymerization is desirably carried out so that from about 0.3 g to about 500 g of a polymer forms per gram of titanium catalyst component. If the amount of polymer formed by the preliminary polymerization is too large, the production efficiency of the olefin polymer in the main polymerization may sometimes decrease and when the resulting olefin polymer is cast into a film or other article, fish eyes tend to occur in the molded article. Preliminary polymerization can be carried out in portions or continuously.
[97] After the preliminary polymerization conducted as above, or without carrying out any preliminary polymerization, the preliminary polymerization of an olefin is carried out in the presence of the above-described olefin polymerization catalyst system formed from the solid titanium catalyst component containing the organoaluminium compound and the organosilicon compound (external electron donor).
[98] Examples of olefins that can be used in the main polymerization are alpha-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-hexene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, 1-tetradecene, 1-eicosene, and vinylcyclohexane. In the processes described above, alpha-olefins can be used individually or in any combination.
[99] In one embodiment, propylene or 1-butene is homopolymerized, or a blended olefin that contains propylene or 1-butene as a major component is copolymerized. When mixed olefin is used, the proportion of propylene or 1-butene as the main component is generally at least about 50 mol%, preferably at least about 70 mol%.
[100] By carrying out the preliminary polymerization, the catalyst system in the main polymerization can be adjusted in the degree of activity. This adjustment leads to the result of a polymer powder that has good morphology and a high bulk density. Furthermore, when preliminary polymerization is carried out, the particle shape of the resulting polymer becomes more rounded or spherical. In the case of slurry polymerization, the slurry obtains excellent characteristics while in the case of gas phase polymerization, the catalyst bed obtains excellent characteristics. Furthermore, in these embodiments, a polymer having a high isotacticity index can be produced with a high catalytic effectiveness by polymerizing an alpha-olefin having at least about 3 carbon atoms. Therefore, when producing the propylene copolymer, the resulting copolymer powder or copolymer becomes easy to handle.
[101] In homopolymerizing or copolymerizing these olefins, a polyunsaturated compound such as a conjugated diene or an unconjugated diene can be used as a comonomer. Examples of comonomer include styrene, butadiene, acrylonitrile, acrylamide, alpha-methyl styrene, chlorostyrene, vinyl toluene, divinyl benzene, diallyl phthalate, alkyl methacrylates and alkyl acrylates. In one embodiment, the comonomer includes thermoplastic and elastomeric monomer.
[102] In the processes described, the main polymerization of an olefin is generally carried out in the gas phase or liquid phase.
[103] In one embodiment, polymerization (main polymerization) uses a catalyst system that contains the titanium catalyst component in an amount of from about 0.001 to about 0.75 mmol calculated as Ti atom per liter of polymerization zone volume, the organoaluminium compound in an amount of about 1 to about 2000 moles per mole of titanium atoms in the titanium catalyst component, and the organosilicon compound (external donors), if present, in a amount from about 0.001 to about 10 moles calculated as Si atoms in the organosilicon compound per mole of the metal atoms in the organoaluminium compound. In another embodiment, the polymerization uses a catalyst system that contains the titanium catalyst component in an amount of from about 0.005 to about 0.5 mmol calculated as Ti atom per liter of polymerization zone volume, the organoaluminium compound in an amount of about 5 to about 500 moles per mole of titanium atoms in the titanium catalyst component, and the organosilicon compound (external donors), if present, in an amount of about 0. 01 to about 2 moles calculated as Si atoms in the organosilicon compound per mole of the metal atoms in the organoaluminium compound. In another embodiment, the polymerization uses a catalyst system that contains the organosilicon compound (external donors), if present, in an amount of from about 0.05 to about 1 mol calculated as Si atoms in the compound of organosilicon per mole of the metal atoms in the organoaluminium compound.
[104] In one embodiment, the polymerization temperature is from about 20°C to about 200°C. In another embodiment, the polymerization temperature is from about 50°C to about 180°C. In one embodiment, the polymerization pressure is typically around atmospheric pressure at about 100 kg/cm 2 . In another embodiment, the polymerization pressure is typically from about 2 kg/cm2 to about 50 kg/cm2. The main polymerization can be carried out in batches, semi-continuously or continuously. Polymerization can also be carried out in two or more stages under different reaction conditions.
[105] The olefin polymer thus obtained can be a homopolymer, a random copolymer, a block copolymer or an impact copolymer. The impact copolymer contains an intimate blend of a polyolefin homopolymer and a polyolefin rubber. Examples of polyolefin rubbers include ethylene-propylene rubbers (EPR) such as ethylene propylene monomer copolymer rubber (EPM) and ethylene propylene diene monomer terpolymer rubber (EPDM).
[106] The olefin polymer obtained using the catalyst system has a very small amount of an amorphous polymeric component and therefore a small amount of a hydrocarbon-soluble component. Therefore, a film molded from this resulting polymer has low surface adhesion.
[107] The polyolefin obtained through the polymerization process is excellent in particle size distribution, particle diameter and mass density, and the polyolefin obtained has a narrow composition distribution. In an impact copolymer, excellent fluidity, low temperature resistance, and a desired balance between stiffness and elasticity can be achieved.
[108] In one embodiment, propylene and an alpha-olefin having 2 or from about 4 to about 20 carbon atoms are copolymerized in the presence of the catalyst system described above. The catalyst system can be subjected to the preliminary polymerization described above. In another embodiment, propylene and an ethylene rubber are formed in two reactors connected in series to form an impact copolymer.
[109] The alpha-olefin that has 2 carbon atoms is ethylene, and examples of alpha-olefins that have about 4 to about 20 carbon atoms are 1-butene, 1-pentene, 4-methyl-1- pentene, 1-octene, 1-hexene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, vinylcyclohexane, 1-tetradecene, and others.
[110] In main polymerization, propylene can be copolymerized with two or more such alpha-olefins. For example, it is possible to copolymerize propylene with ethylene and 1-butene. In one embodiment, propylene is copolymerized with ethylene, 1-butene, or ethylene and 1-butene.
[111] The block copolymerization of propylene and another alpha-olefin can be performed in two stages. The first stage polymerization can be the homopolymerization of propylene or the copolymerization of propylene with the other alpha-olefin. In one embodiment, the amount of polymerized monomer in the first stage is from about 50 to about 95% by weight. In another embodiment, the amount of monomer polymerized in the first stage is from about 60 to about 90% by weight. In the processes described, this first stage of polymerization can, as necessary, be carried out in two or more stages under the same or different polymerization conditions.
[112] In one embodiment, second-stage polymerization is desirably carried out such that the mole ratio of propylene to the other alpha-olefin is from about 10/90 to about 90/10. In another embodiment, the second stage polymerization is desirably carried out such that the mole ratio of propylene to the other alpha-olefin is from about 20/80 to about 80/20. In yet another embodiment, the second stage polymerization is desirably carried out such that the mole ratio of propylene to the other alpha-olefin is from about 30/70 to about 70/30. The production of a crystalline polymer or copolymer of another alpha-olefin can be provided in the second stage of polymerization.
[113] The propylene copolymer thus obtained can be a random copolymer or the block copolymer described above. This propylene copolymer typically contains from about 7 to about 50 mol% of units derived from alpha-olefin having 2 or from about 4 to about 20 carbon atoms. In one embodiment, a random propylene copolymer contains from about 7 to about 20 mol% of alpha-olefin unit derivatives having 2 or from about 4 to about 20 carbon atoms. In another embodiment, the propylene block copolymer contains from about 10 to about 50 mol% of alpha-olefin-derived units having 2 or 4 to 20 carbon atoms.
[114] In another embodiment, the copolymers made with the catalyst system contain from about 50% to about 99% by weight poly-alpha-olefins and from about 1% to about 50% by weight of comonomer (such as thermoplastic or elastomeric monomers). In another embodiment, the copolymers made with the catalyst system contain from about 75% to about 98% by weight of polyalpha-olefins and from about 2% to about 25% by weight of comonomer.
[115] In one embodiment, the polymer particles formed by the catalyst systems described herein have a diameter of from about 5 to about 150 µm. In another embodiment, the polymer particles have a diameter of from about 18 to about 45 µm. In another embodiment, the polymer particles have a diameter of about 20 to about 50 µm.
[116] It should be understood that where there is no reference to the polyunsaturated compound that can be used, the polymerization method, the amount of the catalyst system and the polymerization conditions, the same descriptions as in the above embodiments apply.
[117] The catalysts/methods of this description can, in some cases, lead to the production of poly-alpha-olefins that include ICPs that have xylene (XS) solubles from about 0.5% to about 10%. In another embodiment, poly-alpha-olefins having xylene (XS) solubles from about 1% to about 6% are produced. In yet another embodiment, poly-alpha-olefins having xylene (XS) solubles from about 2% to about 5% are produced. XS refers to the percent of solid polymer that dissolves in xylene. A low XS % value generally corresponds to a highly isotactic polymer (i.e., higher crystallinity), whereas a high % XS value generally corresponds to a low isotactic polymer.
[118] In one embodiment, the catalyst effectiveness (measured as kilogram of polymer produced per gram of catalyst per hour) of the catalyst system is at least about 10. In another embodiment, the catalyst effectiveness of the catalyst system is at least about 30. In another embodiment, the catalyst efficiency of the catalyst system is at least about 50.
[119] The catalysts/methods described can in some cases lead to the production of polyolefins which include those having a melt flow rate (MFR) of from about 5 to about 250 g (10 min)-1. The MFR rate is measured in accordance with ASTM D 1238 standard.
[120] The catalysts/methods described lead to production that has a relatively narrow molecular weight distribution. In one embodiment, the Mw/Mn of a polypropylene polymer made with the described catalyst system is from about 2 to about 6. In another embodiment, the Mw/Mn of a polypropylene polymer made with the catalyst system described is from about 3 to about 5.
[121] The following examples illustrate the catalyst systems described. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight, all temperatures are in degrees Centigrade, and pressure is at or near atmospheric pressure.
[122] The addition of phthalic anhydride and Viscoplex 1-157 plays a role in dense phase viscosity. The difference in viscosity between the two phases is a factor of the amount of stirring force needed to produce a given particle size.
[123] As chemical reactions are progressing, both viscosity and time are determining factors in the resulting particle size. Example 1
[124] 13.2 g (139 mmol) of magnesium chloride, 14.0 g of epichlorohydrin and 33.6 g of tributyl phosphate were dissolved in 120 g of hexane at 60°C for 5 hours with stirring. Then 3.8 grams of phthalic anhydride (26 mmol) was added and the solution held for an additional 1 hour at 60°C. The solution was cooled to 0°C and then 152 ml (1.38 mol) of TiCl4 was added over 1.5 hours while maintaining stirring and a temperature of 0°C. The mixture was raised to 25°C while maintaining stirring. 5.4 g of VISCOPLEX® (1-254) diluted in 40 grams of hexane were added and the solution held for a period of one hour. Agitation level can be adjusted to control droplet size. Then the mixture was raised to 40°C to solidify the heavy phase droplets and finally to 85°C and 5 ml of di-iso-butyl phthalate (DIBP) was added as an internal electron donor and kept for one hour . The main substance was then filtered and washed with 200 ml of toluene for 10 minutes and repeated. At this point, the magnesium-based catalyst support was collected by particle size using a Malvern instrument and microscopic visualization. A digital image of a microscopic view (at 125x magnification) of the catalyst support from Example 1 is shown in Figure 4.
[125] The magnesium-based catalyst support of Example 1 was activated for use as a solid titanium catalyst component for use in a Ziegler-Natta catalyst system as follows. The magnesium-based support is contacted with 45 g of TiCl4 dissolved in 206.8 g of toluene at 105°C for 25 minutes and repeated three times to activate the Ziegler-Natta catalyst. The Ziegler-Natta catalyst formed is washed four times with 150 ml of hexane at 60°C for 25 to 30 minutes each repetition and subsequently dried under nitrogen. Example 2: Exemplary Polymerization
[126] Ziegler-Natta catalysts are sensitive to air and procedures must be followed to avoid exposure to oxygen. In general, the organoaluminum compound and any optional external electron donor are added to the solid titanium catalyst component just prior to carrying out the polymerization.
[127] The catalyst loading procedure is designed such that the amount of mineral oil or other liquid comprising the catalyst slurry (ie, hexane, mineral oil or other non-polar organic solvent) has a minimal impact on polymerization. The solid catalyst component was suspended with hexane in a glass vessel with a Teflon® regulating valve, where the regulating valve has an inlet to allow continuous purification with nitrogen gas. The glass container serves as a device for charging the catalyst.
[128] First, 1.5 ml of 25% triethyl aluminum (TEA) in hexane or similar non-polar solvent was injected into a 3.4 liter reactor at 35°C, which was devoid of air and moisture through a purification with nitrogen. Second, 1.0 ml of a methylcyclohexyl dimethoxysilane (molar) hexane solution was injected into a 3.4 liter reactor. Similarly, 10 mg of the solid titanium catalyst component in mineral oil (1.0 ml) was added to the 3.4 liter reactor. The reactor is also charged at 4 psi (27.57 kPa) with hydrogen. The reactor is charged with 1500 ml of liquid propylene at 925°C).
[129] The reactor temperature is increased to 70°C in 5 minutes and then held at 70°C for 1 hour. At the end of polymerization, the reactor is vented and cooled down to 20°C. The polypropylene was completely dried in a vacuum oven. A microscopic photograph of the polymeric bead at 500x magnification is shown in Figure 5.
[130] Table 1 indicates the size of the solid titanium catalyst component used in Example 2 to form the catalyst system and the resulting polymer particle size. Table 2 shows the chemical composition of the solid titanium catalyst component used in Example 2 to form the catalyst system, the catalytic activity of the catalyst system, and the physical properties of the resulting polymer. Polymeric Particle.
Table 2: Composition and Catalytic Activity

[131] In Tables 1 and 2, d50 represents the particle size (diameter) in which 50% of the particles are smaller than that size, BD represents the mass density, and the net catalytic activity (CE) indicated in units kgpolymer/(gcat*h) is calculated by dividing the amount of olefin polymer produced (kg) by the mass of the solid titanium catalyst component and scaling the resulting value over a time period of one hour. The amount of polymeric product is determined by subtracting the amount of polymer computed to be formed in the phases then condensed prior to evaporation of the olefin monomers from the total mass of recovered polymer. At any particular point in the polymerization reaction, the instantaneous reaction activity of olefin polymer production varies. Examples 3 to 34: Factors Affecting Catalyst Particle Size.
[132] The following examples demonstrate the production of catalytic solids and the specific factors that can influence the resulting particle size. Examples 3 through 34 were fabricated using the following procedure, with specific values of variables A through E indicated in Figure 6.
[133] A 1 liter Buchi reactor equipped with a 4-blade stirrer with baffles was charged with 13.2 grams of MgCl2, 14.1 grams of epichlorohydrin, 33.6 grams of tributyl phosphate and 120 grams of hexane. The stirred mixture (400 rpm) was heated for 20 minutes to 60°C and held for 5 hours. The mixture was cooled to 0°C until the next step was started. The sample was again heated to 60°C and 4.2 grams of phthalic anhydride was added. After 60 minutes, the solution was cooled to 0°C. TiCl4 (262 grams) in Variable A while shaking at 700 rpm. The slurry temperature was raised to 5°C and held to Variable B. The temperature was raised to Variable C before Viscoplex-154 (6 ml) diluted in 40 grams of hexane was added. After addition of Viscoplex, the slurry was held for Variable D before continuing. The reactor temperature was increased to 85°C over Variable E minutes. DiBP (3 ml) was added to the reaction mixture at 80°C. Once the reaction temperature reached 85°C, the mixture was held for 5 minutes after which the liquid was removed by filtration. The solid was washed twice with 260 ml of toluene.
[134] Figure 6 also indicates the particle size data for each specific example. The analysis of the experimental data indicated in Figure 6 shows that the particle size depends on at least the following factors: - The duration of the TiCl4 addition time; - the length of time after Viscoplex material has been added; - many other factors would contribute differently depending on the swelling in moles of the TiCl4 adduction, and these other factors included: - the maintenance time after the addition of TiCl4; - the temperature at which the Viscoplex material was added; and - the temperature was increased after the Viscoplex delay was complete.
[135] Thus, by controlling any one or more duration of the TiCl4 addition time; the length of time after Viscoplex material is added; the holding time after addition of TiCl4; the temperature at which the Viscoplex material was added; and the rate at which the temperature was increased after the Viscoplex delay was completed, it is possible to increase or decrease the size of the resulting catalytic particle.
[136] As used herein, the terms alkyl and alkoxy refer to a substituent group that has predominantly a hydrocarbon character which includes unsaturated substituents that have carbon-carbon double or triple bonds. The term "alkyl" refers to a substituent group that has a carbon atom directly attached to a head group; the term "alkoxy" refers to a substituent group that has an oxygen atom directly attached to a head group. These include groups that are not only purely hydrocarbon in nature (which contain only carbon and hydrogen), but also groups that contain substituents or heteroatoms that do not change the predominantly hydrocarbon character of the group. Such substituents may include, but are not limited to, halo-, carbonyl-, ester-, hydroxyl-, amine-, ether-, alkoxy-, and nitro groups. These groups can also contain heteroatoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen and particularly oxygen, fluorine, and chlorine. Therefore, while most hydrocarbon quality remains, these groups may contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. In general, no more than about three non-hydrocarbon or heteroatom substituents, and preferably no more than one, will be present for every five carbon atoms in any compound, group or substituent described as "hydrocarbyl" within the context of this specification . The terms alkyl and alkoxy expressly encompass C1-C10 alkyl and alkoxy groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl t-butyl, t-butoxy, ethoxy, propyloxy, t-amyl , s-butyl, isopropyl, octyl, nonyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, cyclopropoxy, cyclobutoxy, cyclopentoxy, and cyclohexoxy as well as any of the foregoing having hydrogen substituted with hydroxyl, amine, or halo groups or atoms. The term aryl expressly includes, but is not limited to, aromatic groups such as phenyl and furanyl, and aromatic groups substituted with alkyl, alkoxy, hydroxyl, amine, and/or halo groups or atoms, where any atom of the aryl substituent is attached to an atom of Si.
[137] With respect to any figure or numeric range for a given feature, a figure or parameter from one range can be combined with another figure or parameter from a different range for the same feature to generate a numeric range.
[138] Other than in the operating examples, or where otherwise indicated, all numbers, values and/or expressions referring to amounts of ingredients, reaction conditions, etc., used in the specification and claims shall be understood to be modified in all examples by the term "about."
[139] While the invention has been explained with respect to certain embodiments, it should be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. therefore, it is to be understood that the invention described herein is intended to cover such modifications as falling within the scope of the appended claims.

权利要求:
Claims (19)
[0001]
1. Solid titanium catalyst component for the production of a polyolefin, characterized in that it comprises: a titanium compound; a magnesium-based support; the solid titanium catalyst component having a sphericity, f, which is greater than 0.7, and an average diameter of 5 to 150 µm (on a 50% volume basis); and the solid titanium catalyst component made by a process which comprises contacting a non-reducible magnesium compound, an alkyl epoxide, a Lewis base, and an organic solvent to form an intermediate; wherein the organic solvent contains up to 25% toluene and at least one non-aromatic alkane-based solvent, wherein the intermediate forms at least two phases subsequent to the addition of a titanium halide at a temperature in the range of -10 °C at 10°C: a phase comprising magnesium compounds and a second phase of organic solvent, followed by the formation of a two-phase emulsion: then raising the emulsion to a second temperature in the range of 35°C to 50°C to solidify the magnesium phase to form a solid titanium catalyst component and separate the solidified titanium solid catalyst component.
[0002]
2. Solid titanium catalyst component according to claim 1, characterized in that a surface-active polymer is added at a temperature of 15 °C to 30 °C when the temperature is raised to said second temperature to solidify the magnesium phase .
[0003]
3. Solid titanium catalyst component according to claim 1, characterized in that the solid titanium catalyst component further comprises an internal electron donor.
[0004]
4. Solid titanium catalyst component according to claim 1, characterized by the fact that the alkylepoxide is epichlorohydrin and the Lewis base is tributyl phosphate acid ester.
[0005]
5. Solid titanium catalyst component according to claim 1, characterized in that the sphericity, f, of the solid titanium catalyst component is greater than 0.8.
[0006]
6. Solid titanium catalyst component according to claim 1, characterized in that the particle size range of the magnesium-based support is from 0.25 to 1.75 when the particle size range is determined by subtraction from D10 size to D90 size, then dividing by D50 size.
[0007]
7. Method of making a solid titanium catalyst component for the production of a polyolefin, characterized in that it comprises: contacting a non-reducible magnesium compound, an alkylepoxide, Lewis base, and an organic solvent to form an intermediate, wherein the organic solvent contains up to 25% toluene and at least one non-aromatic alkane-based solvent, wherein the intermediate forms at least two phases subsequent to the addition of a titanium halide at a first temperature in the range of -10° C to 10°C: a phase comprising at least one magnesium compound and a second organic solvent phase followed by formation of an emulsion of the two phases; then raising the emulsion to a second temperature in the range of 35 °C to 50 °C to solidify the magnesium phase to form a solid titanium catalyst component, and separating the solid titanium catalyst component from the intermediate.
[0008]
8. Method according to claim 7, characterized in that it further comprises controlling the size of the solid titanium catalyst component separated from the intermediate by adjusting the first titanium halide addition temperature and adding a surfactant at a temperature in the range of 15 °C to 30 °C when raising the temperature to the second temperature to solidify the magnesium phase.
[0009]
9. Method according to claim 7, characterized in that it further comprises: stirring the intermediate; and controlling the size of the solid titanium catalyst component separated from the mixture by adjusting the agitation.
[0010]
10. Method according to claim 7, characterized in that the sphericity, f, of the solid titanium catalyst component is greater than 0.8.
[0011]
11. Method according to claim 7, characterized in that the non-aromatic alkane-based organic solvent is selected from the group consisting of pentane, hexane, heptane, octane, and cyclohexane; and the Lewis base comprises a trialkyl phosphate acid ester or a tributyl phosphate acid ester.
[0012]
12. Method according to claim 7, characterized in that the non-reducible magnesium compound is MgCl2, the haloalkylepoxide is epichlorohydrin, the Lewis acid is the acid ester of tributyl phosphate, and the organic solvent is hexane.
[0013]
13. Method according to claim 8, characterized in that the surfactant comprises a polymeric surfactant.
[0014]
14. Method according to claim 7, characterized in that the contact between the non-reducible magnesium compound and the haloalkylepoxide forms an intermediate species that has a magnesium atom attached to a haloalkoxide moiety.
[0015]
15. The method of claim 8, further comprising heating the phase-separated intermediate to a temperature to solidify the magnesium-based catalyst support.
[0016]
16. The method of claim 7, characterized in that it further comprises combining the solid titanium catalyst component with an internal electron donor.
[0017]
17. Method according to claim 16, characterized in that the internal electron donor comprises a phthalate ester.
[0018]
18. Method according to claim 16, characterized in that the inner electron donor comprises a Lewis base.
[0019]
19. Catalyst system for the polymerization of an olefin, characterized in that it comprises: a solid titanium catalyst component having a sphericity, f, and an average diameter of 5 to 150 μm (on a 50% volume basis ), solid titanium catalyst component comprising a titanium halide compound and a magnesium-based support, solid titanium catalyst component manufactured by a process comprising contacting a non-reducible magnesium compound, an alkylepoxide, a Lewis base, and an organic solvent to form an intermediate; wherein the organic solvent contains up to 25% toluene and at least one non-aromatic alkane-based solvent, wherein the intermediate forms at least two phases subsequent to the addition of a titanium halide at a first temperature in the range of -10° C to 10 °C: a phase comprising magnesium compounds and a second phase of organic solvent, followed by formation of a two-phase emulsion: then raise the emulsion to a second temperature in the range of 35 °C to 50 °C to solidify the magnesium phase to form a solid titanium catalyst component and separate the solidified titanium solid catalyst component; and an organoaluminum compound that has at least one aluminum-carbon bond.

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BR112014013067B1|2021-03-02|solid catalyst component, catalyst system for use in olefin polymerization, method for producing a solid catalyst component, and process for polymerizing or copolymerizing an olefin monomer

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JP6062372B2|2017-01-18|Magnesium dichloride / ethanol adduct and catalyst components obtained therefrom

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WO2014128715A2|2014-08-28|An improved magnesium dichloride supported titanium catalyst composition for polyolefin polymerization

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CN104470954B|2017-07-11|Magnesium chloride ethanol adducts and catalytic component therefrom

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KR102153284B1|2020-09-10|Solid catalyst for the production of nucleated polyolefins

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JP2021502469A|2021-01-28|Polyolefin polymer composition

同族专利:

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公开号 | 公开日

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US8685879B2|2014-04-01|

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US20120277090A1|2012-11-01|

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JP2014512451A|2014-05-22|

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EP2701843A1|2014-03-05|

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WO2012149360A1|2012-11-01|

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KR20140027330A|2014-03-06|

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CN103619475A|2014-03-05|

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EP2701843B1|2017-11-29|

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KR101944562B1|2019-01-31|

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BR112013027847A2|2017-01-03|

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JP6152091B2|2017-06-21|

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ES2661105T3|2018-03-27|

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EP2701843A4|2014-10-29|

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CN103619475B|2017-08-04|

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法律状态:
2018-06-12| B25A| Requested transfer of rights approved|Owner name: W.R. GRACE AND CO. - CONN. (US) |

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2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-02| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-02-04| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-09-01| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-07-06| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/04/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/097,210|2011-04-29|

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US13/097,210|US8685879B2|2011-04-29|2011-04-29|Emulsion process for improved large spherical polypropylene catalysts|

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PCT/US2012/035507|WO2012149360A1|2011-04-29|2012-04-27|Emulsion process for improved large spherical polypropylene catalysts|

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