Olefin polymerization catalysts containing internal electron donors such as magnesium, titanium, epoxy compounds and 1,2-phenylenedibenzoate-based compounds

Abstract

A method for preparing a solid catalyst component for olefin polymerization includes the steps of forming a homogeneous solution by reacting a halide-containing magnesium compound with an epoxy compound in a hydrocarbon solvent, adding at least one non-phthalate internal donor to the homogeneous solution to form a first mixture, treating the first mixture with a first titanium compound to form a solid precipitate, and separating the solid precipitate from the first mixture to form a solid catalyst component.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 305,172, filed January 31, 2022, which is incorporated by reference in its entirety herein for all purposes. Field

[0002] The present technology relates generally to polyolefin catalyst systems. More specifically, the present technology relates to solid catalyst components for olefin polymerization that include a halide-containing magnesium, a titanium compound, and an internal electron donor. [Background technology]

[0002]

[0003] Polyolefins are a class of polymers derived from simple olefins. Known methods for making polyolefins include the use of Ziegler-Natta polymerization catalysts. These catalysts use transition metal halides to polymerize vinyl monomers to give polymers with a highly isotactic stereochemical configuration.

[0003]

[0004] Essentially, two types of Ziegler-Natta catalyst systems are used in conventional processes for the polymerization or copolymerization of olefins. The first, in its broadest definition, is TiCl 2 , which is an aluminum alkyl used in conjunction with an aluminum compound such as diethylaluminum chloride (DEAC). 4 TiCl obtained by reduction of 3 The system comprises a catalyst component. Despite the moderate properties of the polymer in terms of isotacticity, the catalyst is characterized by a very low activity which leads to the presence of large amounts of catalyst residues in the polymer.

[0004]

[0005] The second type of catalyst system includes a solid precatalyst component having a magnesium dihalide supported titanium compound and an internal electron donor compound. In order to maintain high selectivity to isotactic polymer products, various internal electron donor compounds must be added during the precatalyst synthesis. Prior to the polymerization reaction, the oxidation state of the titanium compound is reduced in the presence of an aluminum alkyl to form the catalyst. Conventionally, when higher crystallinity of the polymer is required, an external donor compound may also be added during the polymerization reaction. Both the internal and external electron donor compounds are important components of the catalyst system.

[0005]

[0006] Typically, magnesium Ziegler-Natta catalysts are prepared by mixing magnesium compounds (e.g., MgCl 2 ) with a haloepoxy compound (e.g., epichlorohydrin) to form a solution (see, e.g., U.S. Pat. Nos. 9,593,182 and 8,344,079). 4 ) is added followed by an internal donor to form a solid catalyst component. However, this process tends to produce irregularly shaped catalyst particles or powders that result in poorly shaped polymers or more difficult catalysts to use. In other words, the resulting morphology of these types of catalysts, and the resulting polymers, is difficult to control. To address this, surface compounds can be added to the magnesium solution, but this tends to produce powders that can have a negative impact on industrial polymerization processes. Other methods for forming magnesium-based Ziegler-Natta catalysts are needed. Summary of the Invention

[0006]

[0007] In one embodiment, a solid catalyst component for olefin polymerization is provided, comprising a magnesium halide-containing, titanium compound, and an internal electron donor, wherein the solid catalyst component is prepared from a homogeneous reaction mixture containing the magnesium halide-containing, an epoxy compound, and an internal electron donor, to which titanium halide is added to form the solid catalyst component. The magnesium halide-containing is Mg(OR'). x X' 2-x wherein each R' is independently halogen or C optionally substituted with halogen. 3 -C 20 C optionally substituted with cycloalkyl 1 -C 20 alkyl; X' is Br, Cl, or I; x is 0, 1, or 2; the internal electron donor is a non-phthalate internal electron donor; the internal electron donor is present in an amount of from about 3 wt.% to about 25 wt.% based on the total solids weight of the solid catalyst component; the titanium compound is Ti(OR) g X 4-g Each R is independently represented by C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, or C 6 -C 30 aryl; X is Br, Cl, or I; g is 0, 1, 2, 3, or 4; titanium is present in an amount of from 1 wt % to about 6 wt %, based on the total solids weight of the solid catalyst component; and the solid catalyst component has a particle size of from about 3 microns to about 100 microns (on a 50% by volume basis).

[0007]

[0008] In another aspect, a method for preparing a solid catalyst component for olefin polymerization is provided, comprising the steps of forming a homogeneous solution by reacting a halide-containing magnesium compound with an epoxy compound in a hydrocarbon solvent, contacting at least one internal donor with the homogeneous solution to form a first mixture, treating the first mixture with a first titanium compound to form a solid precipitate, and separating the solid precipitate from the first mixture to form the solid catalyst component.

[0008]

[0009] In another aspect, there is provided a catalyst system for use in the polymerization of olefins, comprising a solid catalyst component produced by the process described herein, an organoaluminum compound, and optionally an organosilicon compound and / or an organic external donor compound containing oxygen or nitrogen atoms.

[0009]

[0010] In another aspect, a method for polymerizing or copolymerizing an olefinic monomer is provided, comprising contacting the olefinic monomer with the catalyst components described herein in the presence of at least one selectivity control agent comprising an organoaluminum compound and a silane compound, alone or together with an activity limiting agent, to form a polyolefin polymer. [Brief description of the drawings]

[0010] [Figure 1]

[0011] FIG. 2 shows an SEM image of the polymer particles produced in Example 1. [Diagram 2]

[0012] FIG. 1 shows an optical image of the polymer produced in Example 6. [Diagram 3]

[0013] FIG. 1 shows an SEM image of the polymer produced in Example 9. [Figure 4]

[0014] FIG. 1 shows an SEM image of the PP polymer produced in Example 14 (comparative). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011]

[0015] Various embodiments are described herein below. It should be noted that the specific embodiments are not intended to be exhaustive or limiting to the broader aspects described herein. An aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and may be implemented in any other embodiment.

[0012]

[0016] As used herein, "about" will be understood by those of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If any term is used that is not clear to persons of ordinary skill in the art given the context in which it is used, "about" will mean up to plus or minus 10% of the particular term.

[0013]

[0017] The use of the terms "a" and "an" and "the" and similar referents in describing elements (particularly in the claims that follow) should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand notation for referring individually to each and every value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein is intended merely to make the embodiments more clear, and does not impose limitations on the scope of the claims unless otherwise stated. No language in this specification should be construed as indicating any element not recited in the claims as required.

[0014]

[0018] In general, "substituted" refers to an alkyl, alkenyl, aryl, or ether group (e.g., an alkyl group) as defined below, in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to a non-hydrogen or non-carbon atom. Substituted groups also include groups in which one or more bonds to a carbon or hydrogen atom are replaced by one or more bonds, including double or triple bonds to a heteroatom. Thus, a substituted group is substituted with one or more substituents unless otherwise specified. In some embodiments, a substituted group is substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples of substituents include halogens (i.e., F, Cl, Br, and I); hydroxyl; alkoxy, alkenoxy, alkynoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyl (oxo); carboxyl; ester; urethane; oxime; hydroxylamine; alkoxyamine; aralkoxyamine; thiol; sulfide; sulfoxide; sulfone; sulfonyl; sulfonamide; amine; N-oxide; hydrazine; hydrazide; hydrazone; azide; amide; urea; amidine; guanidine; enamine; imide; isocyanate; isothiocyanate; cyanate; thiocyanate; imine; nitro group; nitrile (i.e., CN); and the like.

[0015]

[0019] As used herein, "alkyl" groups include straight-chain and branched alkyl groups having 1 to about 20 carbon atoms, typically 1 to 12 carbons or, in some embodiments, 1 to 8 carbon atoms. As used herein, "alkyl group" includes cycloalkyl groups, as defined below. Alkyl groups can be substituted or unsubstituted. Alkyl groups can be substituted singly or multiply. Alkyl groups can be substituted two or more times. Examples of straight-chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, neopentyl, isopentyl groups, and 1-cyclopentyl-4-methylpentyl. Representative substituted alkyl groups can be substituted singly or multiply with, for example, amino, thio, hydroxy, cyano, alkoxy, and / or halo groups, such as F, Cl, Br, and I groups. As used herein, the term haloalkyl is an alkyl group having one or more halo groups. In some embodiments, the haloalkyl refers to a perhaloalkyl group.

[0016]

[0020] Cycloalkyl groups are cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, cycloalkyl groups have 3 to 8 ring members, while in other embodiments the number of ring carbon atoms ranges from 3 to 5, 6, or 7. Cycloalkyl groups can be substituted or unsubstituted. Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, as well as fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings substituted with straight or branched chain alkyl groups as defined above. Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to, 2,2-; 2,3-; 2,4-; 2,5-; or 2,6-disubstituted cyclohexyl groups or mono-, di-, or tri-substituted norbornyl or cycloheptyl groups, which may be substituted, for example, with alkyl, alkoxy, amino, thio, hydroxy, cyano, and / or halo groups.

[0017]

[0021] Alkenyl groups are straight, branched, or cyclic alkyl groups having from 2 to about 20 carbon atoms and further containing at least one double bond. In some embodiments, alkenyl groups have from 1 to 12 carbons, or typically from 1 to 8 carbon atoms. Alkenyl groups can be substituted or unsubstituted. Alkenyl groups include, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl groups, among others. Alkenyl groups can be substituted in the same manner as alkyl groups. Divalent alkenyl groups, i.e., alkenyl groups with two points of attachment, include, but are not limited to, CH-CH=CH 2 , C=CH 2 , or C=CHCH 3 Includes.

[0018]

[0022] As used herein, an "aryl", or "aromatic" group is a cyclic, aromatic hydrocarbon that does not contain heteroatoms. Aryl groups include monocyclic, bicyclic, and polycyclic ring systems. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenylenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups. An aryl group with one or more alkyl groups can also be referred to as an alkaryl group. In some embodiments, aryl groups contain 6-14 carbons, and in others 6-12 or even 6-10 carbon atoms in the ring portion of the group. The phrase "aryl group" includes groups that contain fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, etc.). Aryl groups can be substituted or unsubstituted.

[0019]

[0023] Heterocyclyl or heterocycle refers to both aromatic and non-aromatic ring compounds, including monocyclic, bicyclic, and polycyclic ring compounds, containing three or more ring members, one or more of which are heteroatoms, such as, but not limited to, N, O, and S. Examples of heterocyclyl groups include, but are not limited to, unsaturated 3-8 membered rings containing 1-4 nitrogen atoms, such as, but not limited to, pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridinyl, dihydropyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazolyl (e.g., 4H-1,2,4-triazolyl, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl, etc.), tetrazolyl (e.g., 1H-tetrazolyl, 2H-tetrazolyl, etc.), aryl, ... tetrazolyl, etc.); saturated 3-8 membered rings containing 1-4 nitrogen atoms, such as, but not limited to, pyrrolidinyl, imidazolidinyl, piperidinyl, piperazinyl; fused unsaturated heterocyclic groups containing 1-4 nitrogen atoms, such as, but not limited to, indolyl, isoindolyl, indolinyl, indolizinyl, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl; unsaturated 3-8 membered rings containing 1-2 oxygen atoms and 1-3 nitrogen atoms, such as, but not limited to, oxazolyl, isoxazolyl, oxadiazolyl (e.g., 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, etc.); ... unsaturated fused heterocyclic groups containing 1-2 oxygen atoms and 1-3 nitrogen atoms, such as benzoxazolyl, benzoxadiazolyl, benzoxazinyl (e.g., 2H-1,4-benzoxazinyl, etc.); unsaturated 3-8 membered rings containing 1-3 sulfur atoms and 1-3 nitrogen atoms, such as, but not limited to, thiazolyl, isothiazolyl, thiadiazolyl (e.g., 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, etc.); saturated 3-8 membered rings containing 1-2 sulfur atoms and 1-3 nitrogen atoms, such as, but not limited to, thiazolodinyl;Saturated and unsaturated 3-8 membered rings containing 1-2 sulfur atoms, such as, but not limited to, thienyl, dihydrodithiinyl, dihydrodithionyl, tetrahydrothiophene, tetrahydrothiopyran; unsaturated fused heterocyclic rings containing 1-2 sulfur atoms and 1-3 nitrogen atoms, such as, but not limited to, benzothiazolyl, benzothiadiazolyl, benzothiazinyl (e.g., 2H-1,4-benzothiazinyl, etc.), dihydrobenzothiazinyl (e.g., 2H-3,4-dihydrobenzothiazinyl, etc.); unsaturated 3-8 membered rings containing oxygen atoms, such as, but not limited to, unsaturated fused heterocyclic rings containing 1-2 oxygen atoms, such as benzodioxolyl (e.g., 1,3-benzodioxoyl, etc.); unsaturated 3-8 membered rings containing an oxygen atom and 1-2 sulfur atoms, such as, but not limited to, dihydrooxathiinyl; saturated 3-8 membered rings containing 1-2 oxygen atoms and 1-2 sulfur atoms, such as 1,4-oxathiane; unsaturated fused rings containing 1-2 sulfur atoms, such as benzothienyl, benzodithiinyl;and unsaturated fused heterocyclic rings containing oxygen and one to two oxygen atoms, such as benzoxathiinyl. Heterocyclyl groups also include those described above in which one or more S atoms in the ring are double-bonded to one or two oxygen atoms (sulfoxides and sulfones). For example, heterocyclyl groups include tetrahydrothiophene oxide and tetrahydrothiophene 1,1-dioxide. Typical heterocyclyl groups contain 5 or 6 ring members. Thus, for example, heterocyclyl groups include morpholinyl, piperazinyl, piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, thiophenyl, thiomorpholinyl, thiomorpholinyl where the S atom of thiomorpholinyl is bonded to one or more O atoms, pyrrolyl, pyridinyl homopiperazinyl, oxazolidin-2-onyl, pyrrolidin-2-onyl, oxazolyl, quinuclidinyl, thiazolyl, isoxazolyl, furanyl, dibenzylfuranyl, and tetrahydrofuranyl. The heterocyclyl or heterocycle may be substituted.;

[0020]

[0024] Heteroaryl groups are aromatic ring compounds containing five or more ring members, one or more of which are heteroatoms such as, but not limited to, N, O, and S. Heteroaryl groups include, but are not limited to, groups such as pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, dibenzofuranyl, indolyl, azaindolyl (pyrrolopyridinyl), indazolyl, benzimidazolyl, imidazopyridinyl (azabenzimidazolyl), pyrazolopyridinyl, triazolopyridinyl, benzotriazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Heteroaryl groups include fused ring compounds in which all rings are aromatic, such as indolyl groups, and also fused ring compounds in which only one ring is aromatic, such as 2,3-dihydroindolyl groups. Although the phrase "heteroaryl group" includes fused ring compounds, the phrase does not include heteroaryl groups in which another group, such as an alkyl group, is attached to one of the ring members. Rather, heteroaryl groups that contain such substitutions are referred to as "substituted heteroaryl groups." Representative substituted heteroaryl groups may be substituted one or more with a variety of substituents, such as those listed above.

[0021]

[0025] As used herein, the prefix "halo" refers to a halogen (i.e., F, Cl, Br, or I) bonded to the group that is modified by the "halo" prefix. For example, a haloaryl is a halogenated aryl group.

[0022]

[0026] Groups described herein that have more than one point of attachment in the compounds of the present technology (i.e., divalent, trivalent, or polyvalent) are designated using the suffix "ene." For example, a divalent alkyl group is an alkylene group, a divalent aryl group is an arylene group, a divalent heteroaryl group is a divalent heteroarylene group, etc.

[0023]

[0027] Described herein is a method for preparing a solid catalyst system for olefin polymerization. The method involves the incorporation of an internal donor prior to the addition of titanium to a magnesium chloride solution. The method includes the incorporation of a magnesium compound (e.g., MgCl 2 ) is dissolved in a solvent mixture containing an organic epoxy compound, an organic phosphorus compound, and an optional inert diluent to form a homogeneous solution. To this homogeneous solution is then added an internal donor (which is also a surface active compound and a structure-directing molecule). Thereafter, a titanium species (e.g., TiCl 4 ) is added to precipitate the solid catalyst component. In subsequent steps or washes, at least one additional internal donor and / or other titanium species may be used, but the solid catalyst component is often suitable for use as is. Thus, the processes described herein are faster and more economical, and provide improved morphology (catalyst particle size) and catalyst performance (catalyst activity, catalyst stereoregularity, and hydrogen reaction).

[0024]

[0028] As a general matter, the magnesium-containing solution formed during the reaction of magnesium compounds with epoxy compounds is treated with an internal donor. The electron donor is an organic compound containing an oxygen atom that has the ability to coordinate with the magnesium atom and allow control of the precipitation process of the solid catalyst component in the desired morphology. The combination of organosilicon compounds, acrylates, and / or other surfactants in the magnesium-containing solution allows for further morphology control morphology of the catalyst component. It is also noted that the magnesium-containing solution can be in the form of a dispersion, colloid, emulsion, or other two-phase system. The homogeneous solution can be emulsified using conventional emulsion techniques, including one or more of stirring, agitation, mixing, high and / or low shear mixing, mixing nozzles, sprayers, membrane emulsification techniques, milling sonication, vibration, microfluidization, and the like.

[0025]

[0029] In one aspect, a method for forming a solid catalyst component for olefin polymerization is provided. The method includes forming a homogeneous solution of a halide-containing magnesium compound, an epoxy compound, a phosphorus compound, and a non-phthalate internal electron donor. A titanium halide is then added to the homogeneous solution to form a solid catalyst component. In other words, the process for preparing a solid catalyst component for olefin polymerization includes forming a homogeneous solution by reacting a halide-containing magnesium compound with an epoxy compound in a hydrocarbon solvent; adding at least one non-phthalate internal donor to the homogeneous solution to form a first mixture; treating the first mixture with a first titanium compound to form a solid precipitate; and separating the solid precipitate from the first mixture to form a solid catalyst component. In some embodiments, the step of treating with the first titanium compound further includes treating with a further internal donor, which may be a non-phthalate internal donor or a conventional donor. In some embodiments, the step of treating further includes treating the solid precipitate with a second titanium compound to form a solid catalyst component. In a further embodiment, the treating step further comprises treating the solid precipitate with a second titanium compound and a second internal electron donor to form a solid catalyst component.

[0026]

[0030] During the addition of the first titanium halide compound to the magnesium solution containing the associated molecules or molecular groups of magnesium compounds in solution together with the coordinated organic compound, a reaction takes place between the magnesium compounds in solution and the titanium halide compounds to form magnesium halides and complexes of magnesium halide and titanium halide compounds and titanium alkoxides. At the beginning of this reaction (usually at low temperatures; i.e. -35 to -20°C) the newly formed associated groups of magnesium halide molecules and complexes of magnesium halide and titanium halide compounds are present as "oil phase-droplets" (liquid with a higher viscosity than the other surrounding medium (solvent)). During the reaction, the temperature rises to 0-40°C, where the magnesium halide molecules and complexes of magnesium halide and titanium halide compounds in the oil phase and titanium alkoxides crystallize. The crystallization process is usually completed at temperatures of 50-100°C, thereby forming a solid catalyst component.

[0027]

[0031] The morphology (i.e., as measured by particle size and shape) of the solid catalyst component depends on many factors such as the polarity of the solvent, the presence of precipitation controlling agents, surfactants, additives, etc. In particular, the size and shape of the droplets formed in the magnesium phase can be controlled by a combination of temperature control, amount of solvent, stirring energy, and the inclusion (or exclusion) of various additives including surface modifiers and the temperature of precipitation.

[0028]

[0032] The type of internal donor used in the precipitation process also affects the morphology of the catalyst component. The catalyst component morphology and catalytic performance can be fully controlled by the addition of electron donors. The electron donor controls the precipitation process and the catalyst component morphology and is incorporated into the catalyst component. Therefore, the electron donor also determines the catalyst performance in the polymerization process.

[0029]

[0033] The morphology of the particulate catalyst component can be prepared in raspberry (i.e., drupelet) shape, rounded raspberry shape, rounded shape, and substantially spherical shape by varying the internal donor or additive added in the process.1 -C 12 ) - alkyl ether (i.e., surface modifier) can be used together with an internal donor to prepare a spherical type catalyst component. After formation, the magnesem - containing solution can optionally be treated with a halogenating agent. The halogenating agent can be an organic or inorganic compound containing at least one halogen atom that can be transferable to a magnesium atom. In certain embodiments, the halogenating agent contains chlorine. In certain embodiments, the halogenating agent is selected from aroyl chlorides, alkanoyl chlorides, and alkyl chlorides. In certain specific embodiments, the halogenating agent is benzoyl chloride, phthaloyl chloride, acetyl chloride, linear or branched (C 2 -C 6 ) alkyl, and (C 2 -C 6 ) alkanoyl chloride. In other embodiments, the halogenating agent is selected from aroyl chlorides, alkanoyl chlorides, and alkyl chlorides, HCl, TiCl 4 , R n TiCl 4-n , CCl 4 , R n SiC1 4-n , and R n A1C1 3-n , where R represents alkyl, cycloalkyl, aromatic, or alkoxy, n is an integer satisfying the formula 0 < n < 4, and the ratio of the halogenating agent to the magnesium compound is at least 1:1 on a molar basis.

[0030]

[0034] The magnesium compound used in the preparation of the solid pre-catalyst component may include, for example, a magnesium compound that is not reducible. In one embodiment, the magnesium compound that is not reducible is a magnesium compound that contains a halogen. Specific examples of the magnesium halide-containing compounds that are not reducible include, but are not limited to, magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, and octoxy magnesium chloride; aryloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, and 2-ethylhexoxy magnesium; aryloxy magnesium such as phenoxy magnesium and dimethylphenoxy magnesium; and magnesium carboxylates such as magnesium laurate and magnesium stearate. These magnesium compounds may be in liquid or solid state. In some embodiments, the magnesium halide-containing compounds are Mg(OR') x X' 2-x where each R' is independently a C optionally substituted with halogen. 1 -C 20 C optionally substituted with alkyl or halogen 3 -C 20 cycloalkylalkyl, where X′ is Br, Cl, or I, and x is 0, 1, or 2.

[0031]

[0035] As noted above, the internal electron donor can be a non-phthalate electron donor. For example, the internal electron donor can be of the formula:

[0032] [ka]

[0033] In the formula, R 15 ~R 20 are each independently H, a heteroatom, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and q is an integer from 0 to 12. 15 ~R 20 are independently F, Cl, Br, I, , NR 2 46 , SiR 80 3 , alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; q is an integer from 0 to 12, and each R 46 are independently H, C 1 -C 20 Alkyl, C 6 -C 20 aryl or alkylaryl. 80 is individually alkyl, cycloalkyl, alkoxy, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl.

[0034]

[0036] As mentioned above, the solid catalyst component may contain at least one additional internal electron donor. In some embodiments, the at least one additional internal electron donor comprises an aryl diester, a diether, a succinate, an organic acid ester, a polycarboxylic acid ester, a polyhydroxy ester, a heterocyclic polycarboxylic acid ester, a compound having at least one ether group and at least one ketone group, or a mixture of any two or more of these. In some embodiments, the at least one additional internal electron donor comprises an aryl diester, an acylated catechol, a catechol containing carbonic acid, or an alkoxyalkyl ether. In some embodiments, the at least one additional internal electron donor comprises an aryl diester.

[0035]

[0037] In some embodiments, the internal electron donor or at least one additional internal electron donor (which may be different from the internal electron donor) has the following formula:

[0036] [ka]

[0037] [In the formula, R 40 -R 43 each independently represents H, a heteroatom, an alkyl, a cycloalkyl, a cycloalkylalkyl, an aryl, an aralkyl, an alkylaryl, or -OR 44 is selected from, where R 44 is C 1 -C 20 Alkyl, C 6 -C 20 Aryl, C 6 -C 20 Aralkyl, or C 6 -C 20 R is alkylaryl; 36 and R 37 each independently represents F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, alkylaryl, -OR 45 , or -NR 2 46 Selected from; R 45 is C 1 -C 20 Alkyl, C 6 -C 20 aryl, or alkylaryl; X 1 and X 2 are O, S, or NR, respectively. 47 ;R 47 is H, C 1 -C 20 Alkyl, C 6 -C 20 Aryl, C 6 -C 20 aralkyl; or

[0038] [ka]

[0039] [In the formula, R 38 , R 39 , R 40 , R 41 , R 42 , and R 43 are each independently H, a heteroatom, alkyl, cycloalkyl, cycloalkylalkyl, aryl, alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; or

[0040] [ka]

[0041] [In the formula, R 50 ~R 57 each independently is H, a heteroatom, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl. The internal electron donor may be present in an amount of from about 3 wt % to about 25 wt %, based on the total solids weight of the solid catalyst component.

[0042] As mentioned above, the homogeneous solution includes an epoxy compound. The epoxy compound may include a compound having at least one epoxy group in the form of a monomer, dimer, oligomer, or polymer. Examples of epoxy compounds may include, but are not limited to, aliphatic epoxy compounds, cycloaliphatic epoxy compounds, aromatic epoxy compounds, and the like. Examples of aliphatic epoxy compounds may include, but are not limited to, halogenated aliphatic epoxy compounds, aliphatic epoxy compounds having a keto group, aliphatic epoxy compounds having an ether bond, aliphatic epoxy compounds having an ester bond, aliphatic epoxy compounds having a tertiary amino group, aliphatic epoxy compounds having a cyano group, and the like. Examples of cyclic epoxy compounds may include, but are not limited to, halogenated cycloaliphatic epoxy compounds, cycloaliphatic epoxy compounds having a keto group, aliphatic epoxy compounds having an ether bond, aliphatic epoxy compounds having an ester bond, aliphatic epoxy compounds having a tertiary amino group, aliphatic epoxy compounds having a cyano group, and the like. Examples of aromatic epoxy compounds may include, but are not limited to, halogenated aromatic epoxy compounds, aromatic epoxy compounds having a keto group, aromatic epoxy compounds having an ether bond, aromatic epoxy compounds having an ester bond, aromatic epoxy compounds having a tertiary amino group, aromatic epoxy compounds having a cyano group, and the like.

[0043] Illustrative epoxy compounds have the formula:

[0044] [ka]

[0045] [wherein a is 1, 2, 3, 4, or 5; X″ is alkyl, F, Cl, Br, or I; R 30 is alkyl, aryl, or cyclyl. In some embodiments, X″ is methyl, ethyl, F, Cl, Br, or I.

[0046] Specific examples of epoxy compounds may include, but are not limited to, epifluorohydrin, epichlorohydrin, epibromohydrin, hexafluoropropylene oxide, 1,2-epoxy-4-fluorobutane, 1-(2,3-epoxypropyl)-4-fluorobenzene, 1-(3,4-epoxybutyl)-2-fluorobenzene, epoxypropyl)-4-chlorobenzene, 1-(3,4-epoxybutyl)-3-chlorobenzene, etc. Specific examples of halogenated cycloaliphatic epoxy compounds include 4-fluoro-1,2-cyclohexene oxide, 6-chloro-2,3 epoxybicyclo[2,2,1]heptane, etc. Specific examples of halogenated aromatic epoxy compounds may include 4-fluorostyrene oxide, 1-(1,2-epoxypropyl)-3-trifluorobenzene, etc.

[0047] In some embodiments, the reaction mixture may include an organophosphorus compound. In some embodiments, the organophosphorus compound is

[0048] [ka]

[0049] where R 58 , R 59 , and R 60 are each independently C 1 -C 10 Illustrative organophosphorus compounds can include, but are not limited to, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and triphenyl phosphite.

[0050]

[0042] The homogeneous solution may also optionally contain an organosilicon compound as a surfactant. The organosilicon compound may contain silicon with at least one hydrogen ligand (hydrocarbon group). Common examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, (cycloalkyl)methylene groups, alkene groups, aromatic groups, and the like.

[0051] In one embodiment, the organosilicon compound has the formula (IV): R n Si(OR') 4-n (IV) In formula (IV), each R and R' independently represents a hydrocarbon group, and n is 0≦n≦4. In other embodiments, the organosilane is a silane or a polysiloxane.

[0052] Specific examples of organosilicon compounds of formula (IV) include, but are not limited to, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclopentyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, , bis-o-tridimethoxysilane, bis-m-tridimethoxysilane, bis-p-tridimethoxysilane, bis-p-tridiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyl(decy l) Triethoxysilane, phenyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, gammaaminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norboranetriethoxysilane, 2-norboranemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, and methyltriallyloxysilane.

[0053] In another embodiment, the organosilicon compound has the formula (V): SiRR' m (OR") 3-m (V) In formula (V), 0≦m<3, for example 0≦m<2; R independently represents a cyclic hydrocarbon or substituted cyclic hydrocarbon group. Specific examples of the group R include, but are not limited to, cyclopropyl; cyclobutyl; cyclopentyl; 2-methylcyclopentyl; 3-methylcyclopentyl; 2-ethylcyclopentyl; 3-propylcyclopentyl; 3-isopropylcyclopentyl; 3-butylcyclopentyl; 3-tert-butylcyclopentyl; 2,2-dimethylcyclopentyl; 2,3-dimethylcyclopentyl; 2,5-dimethylcyclopentyl; 2,2,5-trimethylcyclopentyl; 2,3,4,5-tetramethylcyclopentyl; 2,2, 5,5-Tetramethylcyclopentyl;1-Cyclopentylpropyl;1-Methyl-1-cyclopentylethyl;Cyclopentenyl;2-Cyclopentenyl;3-Cyclopentenyl;2-Methyl-1-cyclopentenyl;2-Methyl-3-cyclopentenyl;3-Methyl-3-cyclopentenyl;2-Ethyl-3-cyclopentenyl;2,2-Dimethyl-3-cyclopentenyl;2,5-Dimethyl-3-cyclopentenyl;2,3,4,5-Tetramethyl-3-cyclopentenyl;2,2,5,5-Tetramethyl-3-cyclopentenyl 2,3-Dimethyl-2,4-cyclopentadienyl;2,3-Dimethyl-2,4-cyclopentadienyl;2,5-Dimethyl-2,4-cyclopentadienyl;2,3,4,5-Tetramethyl-2,4-cyclopenta Dienyl;Indenyl;2-Methylindenyl;2-Ethylindenyl;2-Indenyl;1-Methyl-2-indenyl;1,3-Dimethyl-2-indenyl;Indanyl;2-Methylindanyl;2-Indanyl;1,3-Dimethyl-2-indanyl;4,5,6,7-Tetrahydroindenyl;4,5,6,7-Tetrahydro-2-indenyl;4,5,6,7-Tetrahydro-1-methyl-2-indenyl;4,5,6,7-Tetrahydro-1,3-dimethyl-2-indenyl;Fluorenyl;Cyclohexyl;Includes methylcyclohexyl; ethylcyclo(cylco)hexyl; propylcyclohexyl; isopropylcyclohexyl; n-butylcyclohexyl; tert-butylcyclohexyl; dimethylcyclohexyl; and trimethylcyclohexyl.

[0054] In formula (V), R' and R" may be the same or different and each represents a hydrocarbon. Examples of R' and R" are alkyl, cycloalkyl, aryl and aralkyl groups having 3 or more carbon atoms, and R and R' may be bridged by alkyl groups, etc. Common examples of organosilicon compounds are those of formula (V) in which R is a cyclopentyl group, R' is an alkyl group, such as a methyl or cyclopentyl group, and R" is an alkyl group, especially a methyl or ethyl group.

[0055] Specific examples of organosilicon compounds of formula (V) include, but are not limited to, trialkoxysilanes such as cyclopropyltrimethoxysilane, cyclobutyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, 2,5-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane, 2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane and fluorenyltrimethoxysilane; dialkoxysilanes such as dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis(3-tert-butylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, bis(2,5-dimethylcyclopentyl)dimethoxysilane, butyl)dimethoxysilane, dicyclopentyldiethoxysilane, dicyclobutyldiethoxysilane, cyclopropylcyclobutyldiethoxysilane, dicyclopentenyldimethoxysilane, di(3-cyclopentenyl)dimethoxysilane, bis(2,5-dimethyl-3-cyclopentenyl)dimethoxysilane, di-2,4-cyclopentadienyl)dimethoxysilane, bis(2,5-dimethyl-2,4-cyclopentadienyl)dimethoxysilane, bis(1-methyl-1-cyclopentylethyl)dimethoxysilane, cyclopentylcyclopentenyldimethoxysilane, cyclopentylcyclopentadienyldimethoxysilane, diindenyldimethoxysilane, bis(1,3-dimethyl-2-indenyl)dimethoxysilane, cyclopentadienylindenyldimethoxysilane, difluorenyldimethoxysilane, cyclopentylfluorenyldimethoxysilane and indenylfluorenyldimethoxysilane;Monoalkoxysilanes, such as tricyclopentyl methoxysilane, tricyclopentenyl methoxysilane, tricyclopentadienyl methoxysilane, tricyclopentyl ethoxysilane, dicyclopentyl methyl methoxysilane, dicyclopentyl ethyl methoxysilane, dicyclopentyl methyl ethoxysilane, cyclopentyl dimethyl methoxysilane, cyclopentyl diethyl methoxysilane, cyclopentyl dimethyl ethoxysilane, bis(2,5-dimethyl cyclopentyl)cyclopentyl methoxysilane, dicyclopentyl cyclopentenyl methoxysilane, dicyclopentyl cyclopentadienyl methoxysilane and diindenyl cyclopentyl methoxysilane; and ethylene bis-cyclopentyl dimethoxysilane.

[0056]

[0048] With regard to the solvent in which the homogeneous solution is formed, suitable solvents include, but are not limited to, hydrocarbon or halogenated hydrocarbon solvents. In some embodiments, the hydrocarbon solvent is an aromatic or aliphatic hydrocarbon. In further embodiments, the hydrocarbon solvent is selected from the group consisting of toluene, ethylbenzene, pentane, hexane, and heptane. In certain embodiments, the solvent further comprises a siloxane solvent. In further specific embodiments, the siloxane solvent is dimethylpolysiloxane.

[0057]

[0049] In order to dissolve the magnesium compound sufficiently, an inert diluent may be added to the solvent mixture. The inert diluent can generally be an aromatic hydrocarbon or an alkane, provided that it can facilitate dissolution of the magnesium compound. Examples of aromatic hydrocarbons include, but are not limited to, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, chlorotoluene, and derivatives thereof. Examples of alkanes include linear, branched, or cyclic alkanes having about 3 to about 30 carbons, such as butane, pentane, hexane, cyclohexane, heptane, and the like. These inert diluents may be used alone or in combination.

[0058] In some embodiments, the titanium compounds used in the method may be the same or different and may be Ti(OR). g X 4-g where each R is independently C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, or C 6 -C 30 aryl; X is Br, Cl, or I; and g is 0, 1, 2, 3, or 4. Titanium is present in an amount of from 1 wt % to about 6 wt %, based on the total solids weight of the solid catalyst component. The preferred titanium compound is TiCl 4 It is.

[0059]

[0051] In some embodiments, the treating step is carried out at a temperature between -35°C and 30°C during the addition of the first titanium compound, and at a temperature between 30°C and 150°C after the addition is complete. In some embodiments, the solid catalyst component formed in the process has a particle size of about 3 microns to about 100 microns (50% by volume basis). In some embodiments, the solid catalyst component contains at least one additional internal electron donor.

[0060] In some embodiments, the non-phthalate internal electron donor has the formula:

[0061] [ka]

[0062] In this formula, R 15 ~R 20 are each independently H, a heteroatom, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and q is an integer from 0 to 12. 15 ~R 20 are independently F, Cl, Br, I, , NR2 46 , SiR 80 3 , alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; q is an integer from 0 to 12, and each R 46 are independently H, C 1 -C 20 Alkyl, C 6 -C 20 aryl or alkylaryl. 80 is individually alkyl, cycloalkyl, alkoxy, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl.

[0063] In some embodiments, the non-phthalate internal electron donor has the formula:

[0064] [ka]

[0065] [In the formula, R 40 -R 43 each independently represents H, a heteroatom, an alkyl, a cycloalkyl, a cycloalkylalkyl, an aryl, an aralkyl, an alkylaryl, or -OR 44 where R 44 is C 1 -C 20 Alkyl, C 6 -C 20 Aryl, C 6 -C 20 Aralkyl, or C 6 -C 20 R is alkylaryl; 36 and R 37 each independently represents F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, alkylaryl, -OR 45 , or -NR 246 Selected from; R 45 is C 1 -C 20 Alkyl, C 6 -C 20 aryl, or alkylaryl; each R 46 are independently H, C 1 -C 20 Alkyl, C 6 -C 20 aryl or alkylaryl; X 1 and X 2 are O, S, or NR, respectively. 47 ;R 47 is H, C 1 -C 20 Alkyl, C 6 -C 20 Aryl, C 6 -C 20 aralkyl; or

[0066] [ka]

[0067] [In the formula, R 38 , R 39 , R 40 , R 41 , R 42 , and R 43 are each independently H, a heteroatom, alkyl, cycloalkyl, cycloalkylalkyl, aryl, alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; or

[0068] [ka]

[0069] [In the formula, R 50 ~R 57each is independently H, a heteroatom, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl. It is represented by one of the following:

[0070] In some embodiments, R 40 ~R 43 are each independently H, F, Cl, Br, I, a heteroatom, or NR 2 46 , alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, alkylaryl, or -OR 44 Each R 46 are independently H, C 1 -C 20 Alkyl, C 6 -C 20 In some embodiments, R 38 , R 39 , R 40 , R 41 , R 42 , and R 43 are each independently H, F, Cl, Br, I, a heteroatom, or NR 2 46 , alkyl, cycloalkyl, cycloalkylalkyl, aryl, alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; each R 46 are independently H, C 1 -C 20 Alkyl, C 6 -C 20 In some embodiments, R 50 ~R 57 Each of the is independently H, F, Cl, Br, I, NR 2 46 , SiR 80 3, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; each R 46 are independently H, C 1 -C 20 Alkyl, C 6 -C 20 aryl or alkylaryl, each R 80 is individually alkyl, alkoxy, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl.

[0071]

[0056] Examples of other electron donors include oxygen-containing electron donors such as organic acid esters. Specific examples include, but are not limited to, diethyl ethylmalonate, diethyl propylmalonate, diethyl isopropylmalonate, diethyl butylmalonate, diethyl 1,2-cyclohexanedicarboxylate, di-2-ethylhexyl 1,2-cyclohexanedicarboxylate, di-2-isononyl 1,2-cyclohexanedicarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, and ethyl benzoate. , methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl succinate, dipropyl succinate, diisopropyl succinate, dibutyl succinate, diisobutyl succinate, dioctyl succinate, diisononyl succinate, and diether compounds such as 9,9-bis(methoxymethyl)fluorine, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisopentyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane.

[0072] In one embodiment, surfactants may be used when the solid catalyst component is formed. Surfactants may contribute many of the beneficial properties of the solid catalyst component and catalyst system. Common examples of surface modifiers include polymeric surfactants, such as polyacrylates, polymethacrylates, polyalkyl methacrylates, or any other surfactant capable of stabilizing and emulsifying. Surfactants are known in the art, and numerous surfactants are described in McCutcheon's "Volume I: Emulsifiers and Detergents", 2001, North American Edition, published by Manufacturing Confectioner Publishing Co., Glen Rock, NJ, and incorporated herein by reference for disclosure therein, particularly pages 1-233. Polyalkyl methacrylates are polymers that may contain one or more methacrylate monomers, such as at least two different methacrylate monomers, at least three different methacrylate monomers, and the like. Additionally, the acrylate and methacrylate polymers may contain monomers other than acrylate and methacrylate monomers, so long as the polymeric surfactant contains at least about 40% by weight of acrylate and methacrylate monomers.

[0073]

[0058] Examples of monomers which can be polymerized into the polymeric surfactant using known polymerization techniques include one or more of acrylates; tert-butyl acrylate; n-hexyl acrylate; methacrylates; 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;Methoxyethyl acrylate;Isobenzyl acrylate;Isodecyl acrylate;N-Dodecyl acrylate;Benzyl acrylate;Isobornyl acrylate;Isobornyl acrylate;Isobornyl methacrylate;2-Hydroxyethyl acrylate;2-Hydroxypropyl acrylate;2-Methoxyethyl acrylate;2-Methoxybutyl acrylate;2-(2-Ethoxyethoxy)ethyl acrylate;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;Trimethylolpropane triacrylate;Ethoxylated trimethylolpropane triacrylate;Pentaerythritol triacrylate;Trimethylolpropane trimethacrylate;Tripropylene glycol diacrylate;Pentaerythritol tetraacrylate;Glyceryl propoxy triacrylate;Tris(acryloyloxyethyl)phosphate; 1-acryloxy-3-methacryloxyglycerol; 2-methacryloxy-N-ethylmorpholine; and allyl methacrylate, etc.;

[0074] In certain embodiments, the surface modifier is poly((C 1 -C 6 ) alkyl) acrylate, poly((C 1 -C 6 ) alkyl) methacrylates, and poly((C 1 -C 6 )alkyl)acrylate and poly((C 1 -C 6 ) alkyl) methacrylate copolymers. In some embodiments, the ratio of surface modifier to halide-containing magnesium compound is 1:10 to 2:1 wt % or 1:5 to 1:1 wt %. Examples of commercially available polymeric surfactants include those available from RohMax Additives, GmbH under the trade name VISCOPLEX®, such as those having product numbers 1-254, 1-256, and those available from Noveon / Lubrizol under the trade names CARBOPOL® and PEMULEN®.

[0075]

[0060] In another aspect, there is provided a catalyst system for use in the polymerization of olefins, comprising a solid catalyst component produced by the process described herein, an organoaluminum compound, and optionally an organosilicon compound or an organic external donor compound containing oxygen or nitrogen atoms.

[0076] In some embodiments, the organoaluminum compound is an alkyl-aluminum compound. In some embodiments, the alkyl-aluminum compound is a trialkylaluminum compound. In some embodiments, the trialkylaluminum compound includes triethylaluminum, triisobutylaluminum, or tri-n-octylaluminum. Illustrative examples of organoaluminum compounds include, but are not limited to, trialkylaluminum, such as triethylaluminum, tributylaluminum, and trihexylaluminum; trialkenylaluminum, such as triisoprenylaluminum; dialkylaluminum halides, such as diethylaluminum chloride, dibutylaluminum chloride, and diethylaluminum bromide; alkylaluminum sesquihalides, such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; dialkylaluminum hydrides, such as diethylaluminum hydride and dibutylaluminum hydride; and other partially hydrogenated alkylaluminum, such as ethylaluminum dihydrogenate and propylaluminum dihydrogenate.

[0077] The organoaluminum compound may be used in the catalyst system in an amount such that the molar ratio of aluminum to titanium (from the solid precatalyst component) is from about 5 to about 1,000. In another embodiment, the molar ratio of aluminum to titanium in the catalyst system may be from about 10 to about 700. In yet another embodiment, the molar ratio of aluminum to titanium in the catalyst system may be from about 25 to about 400.

[0078] In addition to the solid catalyst components, the catalyst system may contain at least one organosilicon compound added after precipitation of the catalyst by addition of titanium. This organosilicon compound is sometimes called an external electron donor and may be any of the organosilicon compounds described above.

[0079]

[0064] When used as an external electron donor that functions as one component of a Ziegler-Natta catalyst system for the polymerization of olefins, organosilicon compounds contribute to the ability to obtain polymers (at least a portion of which is a polyolefin) having controllable molecular weight distribution and controllable crystallinity while retaining high performance in terms of catalytic activity.

[0080] The organosilicon compound may be used in the catalyst system as an external donor in an amount such that the molar ratio of the organoaluminum compound to the organosilicon compound is from about 2 to about 90. In another embodiment, the molar ratio of the organoaluminum compound to the organosilicon compound is from about 5 to about 70. In yet another embodiment, the molar ratio of the organoaluminum compound to the organosilicon compound is from about 7 to about 35.

[0081]

[0066] In another aspect, a method for polymerizing or copolymerizing an olefinic monomer is provided, comprising contacting the olefinic monomer with the catalyst component described herein in the presence of at least one selectivity control agent comprising an organoaluminum compound and a silane compound, alone or in combination with an activity limiting agent, to form a polyolefin polymer.

[0082] In some embodiments, the polymerizing or copolymerizing step occurs in the presence of at least one selectivity control agent comprising a silane compound alone or in combination with an activity limiting agent. Without being bound by theory, the use of an electron donor compound is believed to result in improved performance characteristics of the resulting catalyst, such as higher / improved catalytic activity, higher / improved hydrogen reaction, polymer fractionation values, and 13 and the ability to produce polyolefins with desired / controllable crystallinity as measured by C NMR analysis and desired / controllable molecular weight as measured by melt flow index and high temperature size exclusion chromatography (HSEC).

[0083] The polymerization of olefins may be carried out in the presence of the catalyst system described above. Generally speaking, the olefin is contacted with the catalyst system described above under conditions suitable to form the desired polymer product. In one embodiment, the main polymerization is preceded by a preliminary polymerization as described below. In another embodiment, the polymerization is carried out without a preliminary polymerization. In yet another embodiment, the formation of the copolymer is carried out using at least two polymerization zones.

[0084] The invention thus generally described will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the invention. EXAMPLES

[0085] General Catalyst Preparation. In general, the methods for preparing the catalyst components described herein involve the use of MgCl 2 The process involves dissolving TiCl in a mixture of epichlorohydrin (ECH), tributyl phosphate (TBP), and toluene at 60 °C to form a homogeneous solution. An internal donor (which is also a surface active compound and a structure directing molecule) is added to the homogeneous solution at room temperature. The mixture is then cooled to -25 °C and TiCl 4 TiCl is added. 4 After the addition is complete, the reaction mixture is heated to 85-110° C. The solid is washed with toluene to form the catalyst component, which contains titanium, magnesium, and an internal donor.

[0086] General Polymerization Process. The following is typical when the catalysts of the examples are used in a process for propylene polymerization. The reactor is cooled to 30-35° C. and the cocatalyst (1.5 ml of 25 wt % triethylaluminum ("TEAl")), silane (i.e., cyclohexylmethyl(methy)dimethoxysilane; 1 ml), H 2(10 standard liters ("SL")), and liquid propylene (1500 ml) were added to the reactor in the order mentioned. The catalyst components (5-10 mg) were then charged to the reactor as a mineral oil slurry under pressurized nitrogen. Polymerization was then carried out for 1 hour at 70°C. After polymerization, the reactor was cooled to 22°C, vented to atmospheric pressure, and the polymer was collected.

[0087] Example 1 3.3 g MgCl 2 , 30 g toluene, 9.1 g TBP, 3.55 g ECH were charged to the reactor. The mixture was heated to 60°C and maintained at 600 RPM stirring speed for 8 hours to form a homogenous solution. The mixture was cooled to 25°C and 28 grams toluene and 1.125 g ID1 in 5 g toluene were added to the reactor. The reactor was cooled to -25°C and 65.4 grams TiCl 4 was added to the reactor. Agitation was set to 250 RPM and the temperature was increased to 35°C over 2 hours where it was held with stirring for 30 minutes. The reaction was then heated to 85°C and held for 30 minutes. The reaction mixture was filtered and the solid was collected, washed three times with hexane and dried. ID1 used in this example is 4-cyclohexyl-3,6-dimethyl-1,2-phenylene dibenzoate:

[0088] [ka]

[0089] The catalyst component exhibited high catalytic activity (CE=64.2 kg / g) and high bulk density ("BD") conversion (0.429 g / cc).

[0090] Example 2 The catalyst components were mixed in 65 mL of 10% TiCl 4 Example 1 was repeated except that the catalyst was treated with 105° C. for 1 hour and 110° C. for 30 minutes (3x). The result of this treatment is that the catalyst component activity is increased to 78.6 kg / g.

[0091] Example 3 3.3 g MgCl 2The reactor was charged with 30 g of toluene, 9.1 g of TBP, and 3.55 g of ECH. The mixture was heated to 60° C. for 8 hours with an agitation speed of 600 RPM. After the mixture was cooled to 25° C., toluene (22 g) and ID2 (1.125 g in 5 g of toluene) were added to the reactor. The reaction was then cooled to −25° C. and TiCl 4 (65.4 g) was added to the reactor with a stirring speed of 600 rpm. The reaction mixture was then heated to 35° C. over a period of 2 hours with a stirring speed of 250 rpm, where the temperature was held for 30 minutes, and then heated to 85° C. and held for 30 minutes. The solid precipitate was collected by filtration and washed three times with toluene (50 ml). The solid precipitate was dissolved in 65 mL of 10% TiCl in toluene. 4 10% TiCl in 65 mL of toluene at 105 °C for 1 h. 4 The final solid was washed with hexane (three times) and dried. In this example, ID2 is 4-cycloheptyl-3,6-dimethyl-1,2-phenylenedibenzoate:

[0092] [ka]

[0093] The catalyst component used in this example exhibits an average particle size (62.8 microns), high activity (103.6 kg / g), and high hydrogen reaction (MFR=655.6 g / 10 min at 35 SL).

[0094] Example 4

[0076] Using ID3, the solid precipitate was dissolved in 10% TiCl in toluene. 4 Example 3 was repeated, except that the reaction was carried out at 110° C. for 1 hour with ID3, where ID3 is 1,1′-[5-(1,1-dimethylethyl)-3-methyl-1,2-phenylene]bis(3-chlorobenzoate):

[0095] [ka]

[0096] The catalyst component exhibited an average particle size of about 10.8 microns.

[0097] Example 5 Example 4 was repeated using ID4, 3,6-dimethyl-1,2-phenylenedibenzoate:

[0098] [ka]

[0099] The catalyst component exhibits an average particle size of 21 microns and produces a high melt flow rate (MFR) polypropylene (PP) of 342 g / 10 min at 35 SL.

[0100] Example 6 Example 4 was repeated except that ID5 was used. The resulting catalyst component particles averaged 16.9 microns and this catalyst component produced a high MFR (582.7 g / 10 min at 35 SL) PP. ID5 is 5-(tert-butyl)-3-methyl-1,2-phenylenediphenyl bis(carbonate):

[0101] [ka]

[0102] The following Examples 7 and 8 describe the preparation of a catalyst component from ID1 and a polyacrylate compound (Viscoplex®-154). 4 The addition of a polyacrylate compound in the reaction mixture prior to addition results in a reduction in the particle size of the catalyst components and an increase in the stereoregularity of the resulting catalyst. 4 / Additional treatment of the catalyst components with toluene (10% vol.) was included, which resulted in increased catalyst activity and catalyst tactisity compared to Example 7.

[0103] Example 7 Example 1 was repeated except that 0.5 g of Viscoplex-126 was added after ID1. The catalyst showed an activity of 52.6 kg / g and produced a PP with XS=3.39%.

[0104] Example 8 Example 2 was repeated except that 0.5 g of Viscoplex-126 was added after ID1. The catalyst showed an activity of 77.6 kg / g and produced PP with XS=2.66%.

[0105] Example 9

[0082] TiCl 4 Prior to the addition of 1.25 g of ID1 and 0.25 g of Viscoplex-126, 0.5 g of ID1 was added to the reaction mixture. 4 Example 8 was repeated except that the toluene was added at 105° C. during the treatment.

[0106] This describes the preparation of catalyst components with two configurations of the internal donor ID1: (1) addition of ID1 to the reaction mixture before precipitation and (2) addition of ID1 after precipitation. The results show an increase in catalyst activity, catalyst stereoregularity, and polymer morphology (bulk density).

[0107] Example 10 3.3 g MgCl 2 , 0.25g Al(O-iPr) 3 A reactor was charged with 20 g toluene, 9.1 g TBP, 1.0 g Syltherm™ (polydimethylsiloxane; “PDMS”), and 3.55 g ECH. The mixture was heated to 60° C. and held at a stirring speed of 600 RPM for 8 hours, followed by cooling to 25° C. Then, 27 g toluene, 1.5 grams TEOS in 3 g toluene, and 2.66 g ID6 (24% solution) were added to the reactor. The reactor was cooled to −25° C., and 65.4 g TiCl 4was added to the reactor. Agitation was set at 300 RPM. The reaction mixture was heated to 35°C over 2 hours and then the temperature was held with stirring for 30 minutes. The reaction was then further heated to 85°C and held for 30 minutes. The solid product precipitated and after decantation of the supernatant, 50 mL of toluene was added. The reactor was heated to 40°C at 400 RPM and 2.66 g of ID6 (24% solution) was added. The reactor was further heated to 105°C and held for 1 hour, then allowed to settle and decanted. The solid was dissolved in 65 mL of 10% TiCl 4 at 105 °C and 65 mL of 10% TiCl 4 The mixture was treated with 1,1'-[5-(1,1-dimethylethyl)-3-methyl-1,2-phenylene]dibenzoate for 1 hour at 110°C. The final solid was collected and washed with hexane before drying. ID6 is (1,1'-[5-(1,1-dimethylethyl)-3-methyl-1,2-phenylene]dibenzoate):

[0108] [ka]

[0109] The internal donor was added before and after precipitation was completed. The catalyst exhibited high activity (91.2 kg / g) and produced PP with high bulk density (0.443 g / cc).

[0110] Example 11

[0085] TiCl 4 Example 10 was repeated except that the internal donor ID1 (0.791 g), TEOS (0.500 g) and Viscoplex®-261 (0.500 g) were added prior to the addition.

[0111] Example 12

[0086] TiCl 4 / Example 11 was repeated at 105 and 110°C without the toluene treatment.

[0112] Example 13 Example 10 was repeated except that ID1 (1.00 g) and TEOS (0.750 g) were used without precipitation at 105 and 110°C.

[0113] Example 14 (Comparative) Example 2 was repeated without the addition of internal donor ID2 in the precipitation step. Instead, the internal donor (ID6, 0.66 g) was added to 10% TiCl 4 / Toluene was added to the solid support during the treatment. This comparative example shows the preparation of the catalyst component without the addition of an internal donor during the precipitation process. The corresponding catalyst produces PP particles with irregular morphology and low bulk density (0.237 g / cc). See Figure 4.

[0114] Example 15 (Comparative) Comparative Example 1 was repeated, except that phthalic anhydride (PA, 0.60 g) was added to the homogeneous solution. This comparative example illustrates the preparation of a catalyst component containing PA as a surfactant. The catalyst component contains the phthalate impurities diisopropyl chlorophthalate (DICPP) (1.23%), phthaloyl chloride (PhCl) (0.35%).

[0115] Example 16 Testing. The solid catalyst components or solid precipitates can be used in ethylene polymerization processes. Table 1 shows the catalyst activity and polyethylene properties produced from the solid precipitates of Examples 10-13. Polymerizations were carried out in hexane in a 1 gallon reactor. The reactor was purged under nitrogen at 100° C. for 1 hour. At room temperature, 0.6 ml of 25-wt% triethylaluminum (TEAL) in heptane was added to the reactor. Then 1500 ml of hexane was added and 10 mg of the above prepared catalyst was added to the reactor. The reactor was cooled to 100° C. for 1 hour and then cooled to 100° C. for 1 hour. 2 After pressurization (6SL or 30SL), ethylene was charged to 116 psig. The reactor was heated to 80° C. and held at 80° C. for 2 hours. At the end of the hold, the reactor was vented and the polymer was recovered.

[0116] [Table 1]

[0117]

[0091] Examples 1-6 show the preparation of catalyst components with different internal donors and the catalytic behavior in propylene polymerization. The examples show the effect of the internal donor on catalyst morphology (catalyst particle size) and catalyst performance (Table 2; catalyst activity, catalyst stereoregularity and hydrogen reaction).

[0118] [Table 2]

[0119] [Table 3]

[0120] Abbreviations and Definitions

[0093] "D 10 " represents the particle size (diameter), where 10% of the particles are less than that size, and "D 50 " represents the particle size, where 50% of the particles are below that size, and "D 90 " represents a particle size where 90% of the particles are below that size.

[0121]

[0094] "Span" represents the particle size distribution. Its value is expressed by the following formula: Span=(D 90 -D 10 ) / D 50 It can be calculated according to:

[0122] "PP" before a D or Span value indicates the D or Span value for polypropylene prepared with the indicated catalyst.

[0096] "BD" is an abbreviation for bulk density and is reported in g / ml.

[0123] "CE" is an abbreviation for catalyst efficiency and is reported in units of Kg polymer per gram of catalyst per hour of polymerization (Kg / g). "MFR" is an abbreviation for melt flow rate and is reported in g / 10 min (unless otherwise indicated). MFR is measured according to ASTM standard D1238.T.

[0124] SYLTHERM® is the trade name for polydimethylsiloxane (PDMS) available from Dow Chemical.

[0100] VISCOPLEX® is the trade name for polyalkyl methacrylates available from Evonik.

[0125]

[0101] EB is an abbreviation for ethyl benzoate.

[0102] TBP is an abbreviation for tributyl phosphate.

[0103] ECH is an abbreviation for epichlorohydrin.

[0126]

[0104] TEOS is an abbreviation for tetraethyl orthosilicate.

[0105] XS is an abbreviation for xylene soluble and is reported in wt % (unless otherwise indicated).

[0127]

[0106] Although certain particular embodiments have been illustrated and described, it is to be understood that changes and modifications can be made in accordance with ordinary skill in the art without departing from the broader aspects of the science and technology defined in the following claims.

[0128]

[0107] The embodiments illustratively described herein may suitably be practiced without any element or elements, limitations not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," etc., should be read broadly and without limitation. Furthermore, the terms and expressions used herein are used as terms of description and not of limitation, and in using such terms and expressions, there is no intention to exclude any equivalents of the features shown and described or portions thereof, and it is recognized that various modifications are possible within the scope of the technology described in the claims. In addition, the phrase "consisting essentially of" is understood to include the elements specifically recited and additional elements that do not materially affect the basic and novel characteristics of the technology described in the claims. The phrase "consisting of" excludes any elements not specified.

[0129]

[0108] The present disclosure is not limited with respect to the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope of the present disclosure. From the above description, functionally equivalent methods and compositions within the scope of the present disclosure in addition to those enumerated herein will be apparent to those skilled in the art. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure should be limited only by the appended claims and the full scope of equivalents encompassed by such claims. It should be understood that the present disclosure is not limited to specific methods, reagents, compounds, compositions, or biological systems, which may of course vary. It should also be understood that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to be limiting.

[0130]

[0109] Furthermore, when features or aspects of the present disclosure are described in terms of a Markush group, those skilled in the art will recognize that the present disclosure is also described as every individual member or subgroup member of that Markush group.

[0131]

[0110] As will be appreciated by those skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges. Any listed range can be readily recognized as fully delineated and allowing for the same range to be divided into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range described herein can be readily divided into a lower third, a middle third, and an upper third, etc. Also, as will be appreciated by those skilled in the art, all words such as "up to," "at least," "greater than," "less than," etc., include the recited numbers and refer to ranges that can then be divided into subranges as described above. Finally, as will be appreciated by those skilled in the art, a range includes each individual member.

[0132]

[0111] All publications, patent applications, issued patents, and other documents mentioned in this specification are incorporated herein by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in the text incorporated by reference are excluded to the extent that they conflict with definitions in this disclosure.

[0133]

[0112] Other embodiments are set forth in the following claims.

Claims

1. 1. A method for preparing a solid catalyst component for olefin polymerization, comprising the steps of: forming a magnesium solution by reacting a halide-containing magnesium compound with an epoxy compound in a hydrocarbon solvent; adding at least one non-phthalate internal electron donor to a magnesium solution to form a first mixture; treating the first mixture with a first titanium compound to form a solid precipitate; separating the solid precipitate from the first mixture to form a solid catalyst component; A method comprising:

2. 10. The method of claim 1, wherein the treating step further comprises treating the solid precipitate with a second titanium compound to form a solid catalyst component.

3. 10. The method of claim 1, wherein the treating step further comprises treating the solid precipitate with a second titanium compound and a second internal electron donor to form a solid catalyst component.

4. 10. The method of claim 1, wherein the magnesium solution further comprises an organosilicon compound.

5. The organosilicon compound is R ｎ Si(OR') ４－ｎ 5. The method of claim 4, wherein R is alkyl or aryl; and R' is alkyl or aryl.

6. The method of claim 4 wherein the organosilicon compound is a polysiloxane.

7. 10. The method of claim 1, wherein the magnesium solution further comprises a halogenating agent containing at least one halogen atom capable of transferring to the magnesium.

8. The halogenating agent is an aryloyl chloride, an alkanoyl chloride, an alkyl chloride, HCl, TiCl ４ , R ｎ TiCl ４－ｎ , CCl ４ , R ｎ SiCl ４－ｎ , and R ｎ AlCl ３－ｎ 8. The method of claim 7, wherein R represents alkyl, cycloalkyl, aryl, or alkoxy, n is an integer satisfying the formula 0<n<4, and the ratio of halogenating agent to magnesium compound is at least 1:1 on a molar basis.

9. The method of claim 1 , wherein the magnesium solution further comprises an organophosphorus compound.

10. 10. The method of claim 1, wherein the magnesium solution further comprises an organosilicon compound, a polyacrylate, an organophosphorus compound, or a mixture of any two or more thereof.

11. The first and (if present) second titanium compounds are Ti(OR) ｇ X ４－ｇ wherein each R is independently C １ -C ２０ Alkyl, C ３ -C ２０ cycloalkyl, or C ６ -C ３０ is aryl, X is Br, Cl, or I; g is 0, 1, 2, 3, or 4. The method of claim 2 , wherein the

12. 10. The method of claim 1, wherein the solid catalyst component exhibits an average particle size (50% by volume basis) of about 3 microns to about 100 microns.

13. The internal electron donor is 【Chemistry 1】 [In the formula, R １５ ~R ２０ are each independently H, a heteroatom, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and q is an integer from 0 to 12. The method of claim 1 , wherein:

14. The internal electron donor has the formula: 【Chemistry 2】 [In the formula, R ４０ ~R ４３ are each independently H, a heteroatom, an alkyl, a cycloalkyl, a cycloalkylalkyl, an aryl, an aralkyl, an alkylaryl, or —OR ４４ where R is selected from ４４ is C １ -C ２０ Alkyl, C ６ -C ２０ Aryl, C ６ -C ２０ Aralkyl, or C ６ -C ２０ is alkylaryl, R ３６ and R ３７ are each independently F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, alkylaryl, -OR ４５ , or -NR ２ ４６ is selected from R ４５ is C １ -C ２０ Alkyl, C ６ -C ２０ aryl, or alkylaryl; X １ and X ２ are O, S, or NR, respectively. ４７ and R ４７ is H, C １ -C ２０ Alkyl, C ６ -C ２０ Aryl, C ６ -C ２０ aralkyl], or 【Transformation 3】 [In the formula, R ３８ , R ３９ , R ４０ , R ４１ , R ４２ , and R ４３ are each independently H, a heteroatom, alkyl, cycloalkyl, cycloalkylalkyl, aryl, alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; or 【Chemistry 4】 [Wherein, each R ５０ ~R ５７ are each independently H, a heteroatom, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heterocyclic alkyl or aryl, heteroaryl, or heteroarylalkyl. The method of claim 1 , wherein the method is represented by one of:

15. A solid catalyst component for olefin polymerization, comprising a halide-containing magnesium, titanium compound, and an internal electron donor, A solid catalyst component is prepared from a homogeneous reaction mixture containing a magnesium halide, an epoxy compound, and an internal electron donor, and a titanium halide is added to the mixture to form the solid catalyst component; The halide-containing magnesium Mg(OR’) ｘ X’ ２－ｘ is represented by Each R' is independently a C optionally substituted with halogen. １ -C ２０ C optionally substituted with alkyl or halogen ３ -C ２０ is cycloalkylalkyl, X' is Br, Cl, or I; x is 0, 1 or 2; the internal electron donor is a non-phthalate internal electron donor; the internal electron donor is present in an amount of from about 3 wt % to about 25 wt %, based on the total solids weight of the solid catalyst component; Titanium compounds are Ti(OR) ｇ X ４－ｇ is represented by Each R is independently C １ -C ２０ Alkyl, C ３ -C ２０ cycloalkyl, or C ６ -C ３０ is aryl, X is Br, Cl, or I; g is 0, 1, 2, 3, or 4; titanium is present in an amount of from 1 wt % to about 6 wt %, based on the total solids weight of the solid catalyst component; the solid catalyst component has a particle size (50% by volume) of about 3 microns to about 100 microns; Solid catalyst component.

16. 10. A catalyst system for use in the polymerization of olefins, comprising a solid catalyst component produced by the process of claim 1, an organoaluminum compound, and optionally an organosilicon compound and / or an organic external donor compound containing oxygen or nitrogen atoms.

17. 17. The catalyst system of claim 16, wherein the organoaluminum compound is an alkyl-aluminum compound.

18. 18. The catalyst system of claim 17, wherein the alkyl-aluminum compound is a trialkylaluminum compound.

19. 19. The catalyst system of claim 18, wherein the trialkylaluminum compound comprises triethylaluminum, triisobutylaluminum, or tri-n-octylaluminum.

20. 20. A method for polymerizing or copolymerizing an olefinic monomer, the method comprising contacting the olefinic monomer with the catalyst system of any one of claims 16 to 19 to form a polyolefin polymer.

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