WO2016168108A1 - Olefin polymerization catalyst component with auxiliary internal electron donor - Google Patents

Abstract

A process for preparing a solid catalyst component for use in olefinic polymerization, the process including contacting in a first solvent, a solid magnesium compound, and a first titanium compound to form a solid component and liquid component; contacting the solid component with an internal electron donor and an auxiliary internal electron donor; contacting the solid component with a second titanium compound in second solvent to form the solid catalyst component; and washing the solid catalyst component with hydrocarbon or chlorinated hydrocarbon solvent with or without a titanium compound; wherein: the solid magnesium compound is at least one of a magnesium halide, a magnesium alkoxide, a magnesium halide complex with an alcohol, a magnesium alkoxide complex with an alcohol; the auxiliary internal electron donor is an acyl halide; and the internal electron donor is a ester, an ether, a ketone, or a combination of any two or more thereof.

Description

OLEFIN POLYMERIZATION CATALYST COMPONENT WITH AUXILIARY INTERNAL ELECTRON DONOR

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims benefit of U.S. Provisional Patent Application Number 62/146,749, filed on April 13, 2015, the entirety of which is incorporated herein by reference.

FIELD

[0002] The present technology is generally related to polyolefin catalysts. More specifically, the technology is related to a process for the preparation of MgCl₂-supported olefin polymerization catalysts.

SUMMARY

[0003] In one aspect, a process is provided for preparing a solid catalyst component for use in olefinic polymerization The process includes contacting in a first solvent, a solid magnesium compound, and a first titanium compound to form a solid component and liquid component; contacting the solid component with an internal electron donor and an auxiliary internal electron donor; contacting the solid component with a second titanium compound in second solvent to form the solid catalyst component; and washing the solid catalyst component with hydrocarbon or chlorinated hydrocarbon solvent with or without a titanium compound. In the process, the solid magnesium compound is at least one of a magnesium halide, a magnesium alkoxide, and their complexes with alcohols, and a third titanium compound; the auxiliary internal electron donor is an acyl halide; and the internal electron donor is a ester, an ether, a ketone, or a combination of any two or more thereof. In some embodiments, the contacting the solid component with the internal electron donor and the auxiliary internal electron donor and the contacting the solid component with the second titanium compound in the second solvent to form the solid catalyst component occur sequentially, while in other embodiments they occur simultaneously.

[0004] In any of the above embodiments, the acyl halide may be a compound represented as: RC(0)C1, and R is alkyl, alkenyl, or aryl. In any of the above embodiments, the acyl halide is:

where R¹ is H or C(0)X; R², R³, R⁴, and R⁵ are individually H, alkyl, aryl, or any two adjacent members thereof may join together to for an aliphatic cyclic group or fused aromatic ring; and X is CI or Br.

[0005] In any of the above embodiments, the solid magnesium compound may be prepared by a process that includes dissolving a halide-containing magnesium compound in a mixture including an alkylepoxide; an organic phosphorous compound; a carboxylic acid, a carboxylic anhydride, or both a carboxylic acid and a carboxylic anhydride; and an initial solvent to form a homogenous solution; and treating the homogenous solution with an initial titanium halide compound to form the solid magnesium compound.

[0006] In another aspect, the solid catalyst component prepared by any of the processes described above is provided.

[0007] In another aspect, the washed solid catalyst component is prepared by any of the processes described above is provided.

[0008] In another aspect, a process of polymerizing or copolymerizing an olefin is provided. The process may include contacting the washed solid catalyst component according to any of the above embodiments with an organoaluminum activating agent and the olefin.

[0009] In another aspect, a catalyst system for use in olefinic polymerization is provided. The system includes a solid magnesium-based component having an internal electron donor, an auxiliary internal electron donor, and a titanium material; and an organoaluminum;

wherein the solid magnesium-based component is at least one of a magnesium halide, a magnesium alkoxide, and their complexes with alcohols, and a third titanium compound; the auxiliary internal electron donor is an acyl halide; and the internal electron donor is a ester, an ether, a ketone, or a combination of any two or more thereof. [0010] In another aspect, a catalyst system for use in olefinic polymerization is provided. The system includes a solid magnesium component as produced according to the methods above, an electron donor, an auxiliary internal electron donor, and an organoaluminum compound. In some embodiments the organoaluminum compound may be an alkyl aluminum compound. In any of the above embodiments, the alkyl-aluminum compound may be a trialkyl aluminum compound. In any of the above embodiments, the trialkyl aluminum compound may be triethylaluminum, triisobutylaluminum, or tri-n-octylaluminum.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] FIG. 1 is an infra-red spectrum of a solid component before and after reaction with triethylaluminum (15 min) (v(C=0) range), according to the examples. FIG. 1 demonstrates that removal of phthaloyl chloride (auxiliary electron donor) from the catalyst after triethylaluminum treatment.

DETAILED DESCRIPTION

[0012] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other

embodiment(s).

[0013] As used herein, "about" will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are 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.

[0014] The use of the terms "a" and "an" and "the" and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the

specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0015] In general, "substituted" refers to an alkyl, alkenyl, aryl, or ether group, as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non-hydrogen or non-carbon atoms. Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom. Thus, a substituted group will be 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 substituent groups include: halogens (i.e., F, CI, Br, and I); hydroxyls; alkoxy, alkenoxy, alkynoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxyls; esters; urethanes; oximes; hydroxylamines; alkoxyamines; aralkoxyamines; thiols; sulfides; sulfoxides; sulfones; sulfonyls; sulfonamides; amines; N-oxides; hydrazines; hydrazides; hydrazones; azides; amides; ureas; amidines; guanidines; enamines; imides; isocyanates; isothiocyanates; cyanates; thiocyanates; imines; nitro groups; nitriles (i.e., CN); and the like.

[0016] As used herein, "alkyl" groups include straight chain and branched alkyl groups having from 1 to about 20 carbon atoms, and typically from 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms. As employed herein, "alkyl groups" include cycloalkyl groups as defined below. Alkyl groups may be substituted or unsubstituted.

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, and isopentyl groups. Representative substituted alkyl groups may be substituted one or more times with, for example, amino, thio, hydroxy, cyano, alkoxy, and/or halo groups such as F, CI, Br, and I groups. As used herein the term haloalkyl is an alkyl group having one or more halo groups. In some embodiments, haloalkyl refers to a per-haloalkyl group.

[0017] As used herein, "aryl", or "aromatic," groups are cyclic aromatic hydrocarbons that do 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. In some embodiments, aryl groups contain 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups. The phrase "aryl groups" includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like). Aryl groups may be substituted or unsubstituted.

[0018] It has been found that olefin polymerization support catalysts may be prepared using both an internal electron donor and an auxiliary internal electron donor. The auxiliary internal electron donors modify the surface of the polymerization support by blocking atactic sites, while not preventing the internal electron donor from attaching to the active center. The auxiliary internal electron donor is then present on the support until activation by an organoaluminum compound. The combination of both the internal electron donor and the auxiliary internal electron donor provides for enhanced performance evidenced by higher catalyst tacticity and hydrogen response.

[0019] In one aspect, a process is provided for preparing a solid catalyst component for use in olefinic polymerization. The process includes contacting in a first solvent, a solid

magnesium compound, and a first titanium compound to form a solid component and liquid component, contacting the solid component with an internal electron donor and an auxiliary internal electron donor, contacting the solid component with a second titanium compound in second solvent to form the solid catalyst component; and washing the solid catalyst component with hydrocarbon or chlorinated hydrocarbon solvent with or without a titanium compound. In the process, the solid magnesium compound is at least one of a magnesium halide, a magnesium alkoxide, or their complexes with alcohols. In the process, the auxiliary internal electron donor may be an acyl halide, while the internal electron donor is a ester, an ether, a ketone, or a combination of any two or more thereof. In the process, the contacting of the solid component with the internal electron donor and the auxiliary internal electron donor is conducted at a temperature of from about 80°C to about 150°C.

[0020] The contacting of the internal electron donor and the auxiliary electron donor with the solid component may occur in different orderings. For example, the contacting of the solid component with the internal electron donor and the auxiliary internal electron donor and the contacting the solid component with the second titanium compound in the second solvent to form the solid catalyst component occur simultaneously. In some embodiments, the contacting of the solid component with the internal electron donor and the auxiliary internal electron donor and the contacting the solid component with the second titanium compound in the second solvent to form the solid catalyst component occur sequentially. Accordingly, the second titanium compound may be contacted prior to or after the internal donors. In yet other embodiments, the contacting of the solid component with the internal electron donor occurs prior to contacting the solid with the auxiliary internal electron donor, or vice versa.

[0021] The titanium compounds used in the preparation of the solid catalyst component may include, for example, a tetravalent titanium compound represented by Formula (I):

[0022] In Formula (I), R represents a hydrocarbon group, such as an alkyl group having 1 to about 20 carbon atoms, X represents a halogen atom, and 0<g<4. Specific examples of the titanium compound include, but are not limited to, titanium tetrahalides such as TiCl₄, TiBr₄, and Til₄; alkoxytitanium trihalides such as Ti(OCH₃)Cl₃, Ti(OC₂H₅)Cl₃, Ti(0-n-C₄H₉)Cl₃, Ti(OC₂H₅)Br₃, and Ti(0-i-C₄H₉)Br₃; dialkoxytitanium dihalides such as Ti(OCH₃)₂Cl₂, Ti(OC₂H5)₂Cl2, Ti(0-n-C₄H9)₂Cl₂ and Ti(OC₂H5)₂Br2; trialkoxytitanium monohalides such as Ti(OCH₃)₃Cl, Ti(OC₂H₅)₃Cl, Ti(0-n-C₄H₉)₃Cl and Ti(OC₂H₅)₃Br; and tetraalkoxytitaniums such as Ti(OCH₃) , Ti(OC₂H₅) and Ti(0-n-C₄H₉) . In some embodiments, the halogen containing titanium compounds, such as titanium tetrahalides, are used. These titanium compounds may be used individually or in solutions of hydrocarbon compounds or halogenated hydrocarbons.

[0023] The magnesium compounds used in the preparation of the solid catalyst component include, for example, a magnesium compound having no reducibility. In one embodiment, the magnesium compound having no reducibility is a halogen-containing magnesium compound. Specific examples of the magnesium compound having no reducibility 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 compounds such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n- octoxy magnesium and 2-ethylhexoxy magnesium; aryloxy magnesium compounds such as phenoxy magnesium and dimethyl phenoxy magnesium; and carboxylic acid salts of magnesium such as magnesium laurate and magnesium stearate. These magnesium compounds may be in the liquid or solid state. In one aspect, halogen containing magnesium compounds, such as magnesium chloride, alkoxy magnesium chlorides and aryloxy magnesium chlorides, are employed.

[0024] Illustrative magnesium compounds include, but are not limited to, magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, phenoxy magnesium chloride, methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n- octoxy magnesium, 2-ethyloxy magnesium, phenoxy magnesium, dimethylphenoxy magnesium, magnesium laurate, and magnesium stearate. In some embodiments, the magnesium compound is MgCl₂.

[0025] Examples of internal electron donors include oxygen-containing internal 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-l,2-cyclohexanedicarboxylate, di-2- isononyl-l,2-cyclohexanedicarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, naphthalene- 1,8-diyl dibenzoate, di-butyl phthalate, diisononyl phthalate, di-2-ethylhexyl phthalate, 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-l,3- dimethoxypropane, 2,2-diisobutyl- 1 ,3 -dimethoxypropane, 2,2-diisopentyl- 1,3- dimethoxypropane, and 2-isopropyl-2-cyclohexyl-l,3-dimethoxypropane.

[0026] The internal electron donor compounds may be used individually, or in combination. In employing the internal electron donor compounds, they do not have to be used directly as starting materials, but compounds convertible to internal electron donors in the course of preparing the solid catalyst components may also be used as the starting materials. [0027] In any of the above embodiments, the auxiliary internal electron donor may be an acyl halide. Illustrative acyl halides may be a compound represented as: RC(0)C1, and R is alkyl, alkenyl, or aryl. In any of the above embodiments, the acyl halide is:

where R¹ is H or C(0)X; R², R³, R⁴, and R⁵ are individually H, alkyl, aryl, or any two adjacent members thereof may join together to for an aliphatic cyclic group or fused aromatic ring; and X is CI or Br. In some embodiments, the acyl halide is represented as:

; and

R¹ is C(0)X. Illustrative acyl halides for use as the auxiliary electron donor include, but are not limited to phthaloyl chloride, benzoyl chloride, 1-naphthoyl chloride 2-naphthoyl chloride, furoyl chloride, ethanoyl chloride, propanoyl chloride, butanoyl chloride, hexanoyl chloride, and cyclohexanoyl chloride.

[0028] The solid catalyst component can be made by contacting a magnesium compound and a titanium compound with an internal electron donor compound.

[0029] Generally speaking, a magnesium compound solution is made by mixing a

magnesium compound with a material to aid in dissolution of the magnesium compound in the presence of a solvent including at least one of an alcohol, an epoxy compound, or a phosphorus compound, and an optional inert diluent to form a homogenous solution. A first titanium compound may then be added to the homogenous solution. The homogeneous solution is then heated, during which process a solid magnesium support begins to precipitate from solution. At this stage the present disclosure describes alternative processes for contacting the magnesium support with an activating species as described herein and internal donor, and optinally an auxiliary internal donor. In one embodiment, the donor(s) may be added to the homogenous solution after heating. In another embodiment, the donor(s) may be added upon precipitation of the solid magnesium support, prior to isolation of the support. In yet another embodiment, the solid magnesium support may be isolated from the solution from which it was precipitated, followed by exposure to the donor(s). In yet another embodiment, the solid magnesium support may be isolated from the solution from which it was

precipitated, followed by exposure to the activating species followed by, or concurrently with, the donor(s).

[0030] In one embodiment, the solid catalyst component is made by contacting a magnesium compound and a titanium compound in the presence of an internal electron donor compound. In another embodiment, the solid catalyst component is made by forming a magnesium-based catalyst support optionally with a titanium compound and optionally with an internal electron donor compound and contacting the magnesium-based catalyst support with the titanium compound and the internal electron donor compound. In yet another embodiment, the solid catalyst component is made by contacting a magnesium compound solution with a titanium compound to form a mixture, then contacting the mixture with an internal electron donor. In still yet another embodiment, the solid catalyst component is made by contacting a magnesium compound solution with a titanium compound to form a mixture, then contacting the mixture with an internal electron compound, then contacting the mixture again with the internal electron donor compound. Such repeated contact with the internal electron donor compound can occur once, twice, three times, four times or more, successively or with other acts performed between contacts with additional doses of the internal electron donor compounds. The auxiliary internal electron donor may be added with the internal electron donor at any of the stages described above, or the auxiliary internal electron donor may be added separately from the internal electron donor, but at the stages described.

[0031] The epoxy compounds can include compounds having at least one epoxy group in the form of monomers, dimmers, oligomers and polymers. Examples of epoxy compounds include, but are not limited to aliphatic epoxy compounds, alicyclic epoxy compounds, aromatic epoxy compounds, or the like. Examples of aliphatic epoxy compounds 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, or the like. Examples of alicyclic epoxy compounds include, but are not limited to halogenated alicyclic epoxy compounds, alicyclic epoxy compounds having a keto group, alicyclic epoxy compounds having an ether bond, alicyclic epoxy compounds having an ester bond, alicyclic epoxy compounds having a tertiary amino group, alicyclic epoxy compounds having a cyano group, or the like.

Examples of aromatic epoxy compounds 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, or the like.

[0032] Illustrative epoxy compounds include, but are not limited to, ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxyhexane, 1,2-epoxy octane, 1,2- epoxy decane, 1,2-epoxy dodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2- epoxyoctadecane, 7,8-epoxy-2-methyloctadecane, 2-vinyl oxirane, 2-methyl-2-vinyl oxirane,

1.2- epoxy-5-hexene, l,2-epoxy-7-octene, l-phenyl-2,3 -epoxypropane, l-(l-naphthyl)-2,3- epoxypropane, l-cyclohexyl-3,4-epoxybutane, 1,3 -butadiene dioxide, 1,2,7,8-di epoxy octane, cyclopentene oxide, cyclooctene oxide, alpha-pinene oxide, 2,3-epoxynorbornane, limonene oxide, cyclodecane epoxide, 2,3,5,6-diepoxynorbornane, styrene oxide, 3 -methyl sty rene oxide, 1,2-epoxybutylbenzene, 1,2-epoxy octylbenzene, stilbene oxide, 3 -vinyl styrene oxide, 1 -(1 -methyl- 1 ,2-epoxyethyl)-3 -( 1 -methylvinyl benzene), 1 ,4-bis(l ,2-epoxypropyl)benzene,

1.3- bis(l,2-epoxy-l-methylethyl)benzene, l,4-bis(l,2-epoxy-l-methylethyl)benzene, epifluorohydrin, epichlorohydrin, epibromohydrin, hexafluoropropylene oxide, l,2-epoxy-4- fluorobutane, l-(2,3-epoxypropyl)-4-fluorobenzene, l-(3,4-epoxybutyl)-2-fluorobenzene, 1- (2,3-epoxypropyl)-4-chlorobenzene, l-(3,4-epoxybutyl)-3-chlorobenzene, 4-fluoro-l,2- cyclohexene oxide, 6-chloro-2,3-epoxybicyclo[2.2.1]heptane, 4-fluorostyrene oxide, 1-(1,2- epoxypropyl)-3-trifluorobenzene, 3 -acetyl- 1,2-epoxypropane, 4-benzoyl- 1,2-epoxybutane, 4- (4-benzoyl)phenyl- 1,2-epoxybutane, 4,4'-bis(3,4-epoxybutyl)benzophenone, 3,4-epoxy-l- cyclohexanone, 2,3-epoxy-5-oxobicyclo[2.2.1]heptane, 3 -acetyl styrene oxide, 4-(l,2- epoxypropyl)benzophenone, glycidyl methyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, ethyl 3,4-epoxybutyl ether, glycidyl phenyl ether, glycidyl 4-tert-butylphenyl ether, glycidyl 4-chlorophenyl ether, glycidyl 4-methoxyphenyl ether, glycidyl 2-phenylphenyl ether, glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, glycidyl 1-naphthyl ether, glycidyl 4-indolyl ether, glycidyl N-methyl-alpha-quinolon-4-yl ether, theyleneglycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,2- diglycidyloxybenzene, 2,2-bis(4-glycidyloxyphenyl)propane, tris(4- glycidyloxyphenyl)methane, poly(oxypropylene)triol triglycidyl ether, a glycidic ether of phenol novolac, l,2-epoxy-4-methoxycyclohexane, 2,3-epoxy-5,6- dimethoxybicyclo[2.2.1]heptane, 4-methoxystyrene oxide, l-(l,2-epoxybutyl)-2- phenoxybenzene, glycidyl formate, glycidyl acetate, 2,3-epoxybutyl acetate, glycidyl butyrate, glycidyl benzoate, diglycidyl terephthalate, poly(glycidyl acrylate), poly(glycidyl methacrylate), a copolymer of glycidyl acrylate with another monomer, a copolymer of glycidyl methacrylate with another monomer, l,2-epoxy-4-methoxycarbonylcyclohexane, 2,3-epoxy-5-butoxycarbonylbicyclo[2.2.1]heptane, ethyl 4-(l,2-epoxyethyl)benzoate, emthyl 3-(l,2-epoxybutyl)benzoate, methyl 3-(l,2-epoxybutyl)-5-pheylbenzoate, N,N-glycidyl- methylacetamide, N,N-ethylglycidylpropionamide, Ν,Ν-glycidylmethylbenzamide, N-(4,5- epoxypentyl)-N-methyl-benzamide, Ν,Ν-diglycylaniline, bis(4- diglycidylaminophenyl)methane, poly(N,N-glycidylmethylacrylamide), l,2-epoxy-3- (diphenylcarbamoyl)cyclohexane, 2,3-epoxy-6-(dimethylcarbamoyl)bicycle[2.2. ljheptane, 2- (dimethylcarbamoyl)styrene oxide, 4-(l,2-epoxybutyl)-4'-(dimethylcarbamoyl)biphenyl, 4- cyano-l,2-epoxybutane, l-(3-cyanophenyl)-2,3-epoxybutane, 2-cyanostyrene oxide, and 6- cyano- 1 -(1 ,2-epoxy-2-phenylethyl)naphthalene.

[0033] Specific examples of epoxy compounds include, but are not limited to

epifluorohydrin, epichlorohydrin, epibromohydrin, hexafluoropropylene oxide, l,2-epoxy-4- fluorobutane, l-(2,3-epoxypropyl)-4-fluorobenzene, l-(3,4-epoxybutyl)-2-fluorobenzene, 1- (2,3-epoxypropyl)-4-chlorobenzene, l-(3,4-epoxybutyl)-3-chlorobenzene, or the like.

Specific examples of halogenated alicyclic epoxy compounds include 4-fluoro-l,2- cyclohexene oxide, 6-chloro-2,3epoxybicyclo[2,2, ljheptane, or the like. Specific examples of halogenated aromatic epoxy compounds include 4-fluorostyrene oxide, 1-(1,2- epoxypropyl)-3-trifluorobenzene, or the like.

[0034] The phosphorus compounds can include, but are not limited to hydrocarbyl esters and halohydrocarbyl esters of ortho-phosphoric acid and phosphorous acid. Specific examples include, but are not limited to trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and triphenyl phosphite.

[0035] To aid in sufficiently dissolving the magnesium compound, an inert diluent is optionally added in the solvent mixture. The inert diluent can typically be aromatic hydrocarbons or alkanes, as long as it can facilitate the 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, heptanes, and the like. These inert diluents may be used alone or in combination.

[0036] In embodiments of making the solid catalyst component, the magnesium compound solution is mixed with a titanium compound such as liquid titanium tetrahalide to form a solid precipitate in the optional presence of an auxiliary precipitant. The auxiliary precipitant may be added before, during or after the precipitation of the solids and loaded on the solids.

[0037] Materials that may be added to the magnesium compound and the titanium compound to aid in dissolution of the magnesium compound can include carboxylic acids, carboxylic acid anhydrides, ethers, ketones, or mixture thereof. Specific examples include, but are not limited to acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, 1,2,4,5-benzene tetracarboxylic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, and dipentyl ether. In some embodiments, the internal electron donor is phthalic anhydride.

[0038] The process of solids precipitation can be carried out by at least one of three methods. One method involves mixing a titanium compound such as liquid titanium tetrahalide with a magnesium compound solution at a temperature from about -30 ⁰ C to about 10° C, and precipitating the solids while the temperature is raised slowly to a range of about 30° C to about 120° C, such as from about 60° C to about 100° C. The second method involves adding a titanium compound dropwise into a magnesium compound solution at low or room temperature to precipitate out solids immediately. The third method involves adding a first titanium compound dropwise into a magnesium compound solution and mixing a second titanium compound with the magnesium compound solution. In these methods, an internal electron donor compound can be present in the reaction system.

[0039] In one embodiment, when the solid catalyst component is formed, a surfactant can be used. The surfactant can contribute to many of the beneficial properties of the solid catalyst component and catalyst system. General examples of surfactants include polymer surfactants, such as polyacrylates, polymethacrylates, polyalkyl methacrylates, and the like. A polyalkyl methacrylate is a polymer that may contain one or more methacrylate monomers, such as at least two different methacrylate monomers, at least three different methacrylate monomers, etc. Moreover, the acrylate and methacrylate polymers may contain monomers other than acrylate and methacrylate monomers, so long as the polymer surfactant contains at least about 40% by weight acrylate and methacrylate monomers.

[0040] In one embodiment, non-ionic surfactants and/or anionic surfactants can be used. Examples of non-ionic surfactants and/or anionic surfactants include, but are not limited to phosphate esters, alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates, linear alkyl benzene sulfonates, alkylphenols, ethoxylated alcohols, carboxylic esters, fatty alcohols, fatty esters, fatty aldehydes, fatty ketones, fatty acid nitriles, benzene, naphthalene, anthracene, succinic anhydride, phthalic anhydrides, rosin, terpene, phenol, or the like. In fact, a number of anhydride surfactants are effective. In some instances, the absence of an anhydride surfactant causes the formation of very small catalyst support particles while the over-use creates straw shaped material sometimes referred to as needles.

[0041] A solid catalyst precursor can be formed in the following way. In a solvent such as toluene, a magnesium and titanium containing solution is formed following the addition of a halogenating agent such as TiCl₄ into a magnesium based solution at relatively cooler temperatures, such as -25° C until about 0° C. An oil phase is then formed, which can be dispersed into the hydrocarbon phase that is stable until about 40° C. The resultant magnesium material becomes a semi-solid at this point and the particle morphology is now determined. The semi-solid converts to a solid between about 40° C and about 80° C.

[0042] To facilitate obtaining uniform solid particles, the process of precipitation can be carried out slowly. When the second method of adding titanium halide dropwise at low or room temperature is applied, the process may take place over a period from about 1 hour to about 6 hours. When the first method of raising the temperature in a slow manner is applied, the rate of temperature increase can range from about 4° C to about 125° C per hour.

[0043] The solid precipitate may be first separated from the mixture. In the separated solid precipitate may be entrained a variety of complexes and byproducts, so that further treatment may in some instances be necessary. In one embodiment, the solid precipitate is washed to substantially remove the byproducts from the solid precipitate. This may then be followed by addition of an internal donor(s) and an optional auxiliary donor(s). Further, activation of the materials is then undertaken to prepare the catalytic materials.

[0044] The solid precipitate can be washed with an inert diluent or with a mixture of a titanium compound and an inert diluent. The titanium compound used in this treatment can be identical to or different from the titanium compound used for forming the solid precipitate. The wash step is conducted at a temperature below 90° C. (Specifically from about 20 to about 85° C) The wash temperature is lower than the temperature for the treatment step (activation step) in order to remove effectively all side products from previous steps before conducting the activation step. The wash step prior to the activation step improves catalyst production and catalyst morphology. In the wash step, a solvent, or a mixture of solvents may be used, or altneratively different concentrations of TiCl₄ in inert solvent can be used. The concentration can be from about 5 to about 50 vol % TiCl₄ in the inert solvent, such as toluene. Optionally, the wash step can include an internal electron donor compound. It was found that different concentrations of TiCl₄ during the wash step effects the catalyst isotacticity and can be used to vary the isotacticity of the resulting polymer.

[0045] The washed solid precipitant is treated with a titanium compound or a mixture of a titanium compound and an inert diluent. The titanium compound used in this treatment can be identical to or different from the titanium compound used for forming the solid precipitate. 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 compound in the support. The treatment temperature ranges from about 90° C to about 150° C, such as from about 90° C to about 100° C. If a mixture of titanium tetrahalide and an inert diluent is used to treat the solid

precipitate, the volume % of titanium tetrahalide in the treating solution is from about 5% to about 100%, the rest being the inert diluent. By treating the solid precipitate with the titanium compound and optionally an inert diluent, the byproducts in the solid precipitate can be removed from the treated solid precipitate. In one embodiment, the solid precipitate is treated with the titanium compound and optionally an inert diluent about two times or more and five times or less.

[0046] The treated solids can be further washed with an inert diluent to remove ineffective titanium compounds and other byproducts. The inert diluent herein used can be hexane, heptane, octane, 1,2-dichloroethane, benzene, toluene, ethyl benzene, xylene, and other hydrocarbons.

[0047] By washing the solid precipitate with an inert diluent, a free titanium compound in the solid precipitate can be removed from the solid precipitate. As a result, the resultant solid precipitate does not substantially contain a free titanium compound. In one embodiment, the solid precipitate is treated repeatedly with an inert diluent until the filtrate contains about 100 ppm or less of titanium. In another embodiment, the solid precipitate is treated repeatedly with an inert diluent until the filtrate contains about 50 ppm or less of titanium. In yet another embodiment, the solid precipitate is treated with an inert diluent until the filtrate contains about 10 ppm or less of titanium. In some embodiments, the solid precipitate is treated with an inert diluent about three times or more and seven times or less.

[0048] The amounts of the ingredients used in preparing the solid catalyst component may vary depending upon the method of preparation. In one embodiment, from about 0.01 to about 5 moles of the internal electron donor compound and the auxiliary internal electron donor, and from about 0.01 to about 500 moles of the titanium compounds are used per mole of the magnesium compound used to make the solid catalyst component. In another embodiment, from about 0.05 to about 2 moles of the internal electron donor compound, and the auxiliary internal electron donor, and from about 0.05 to about 300 moles of the titanium compounds are used per mole of the magnesium compound used to make the solid catalyst component.

[0049] In one embodiment, in the solid catalyst component, the atomic ratio of

halogen/titanium is from about 4 to about 200; the internal electron donor/titanium mole ratio is from about 0.01 to about 10; and the magnesium/titanium atomic ratio is from about 1 to about 100. In another embodiment, in the solid catalyst component, the atomic ratio of halogen/titanium is from about 5 to about 100; the internal electron donor/titanium mole ratio is from about 0.2 to about 6; and the magnesium/titanium atomic ratio is from about 2 to about 50. [0050] The resulting solid catalyst component generally contains a magnesium halide of a smaller crystal size than commercial magnesium halides and usually has a specific surface area of at least about 5 m²/g, such as from about 10 to about 1,000 m²/g, or from about 100 to about 800 m²/g. Using the wash step with TiCl₄/solvent mixture results in increasing the specific surface area and pore volume, which might increase the catalyst activity. Since the above ingredients are unified to form an integral structure of the solid catalyst component, the composition of the solid catalyst component does not substantially change by washing with, for example, hexane.

[0051] The solid catalyst component may be used after being diluted with an inorganic or organic compound such as a silicon compound, an aluminum compound, or the like.

[0052] The catalyst system may contain at least one organoaluminum compound in addition to the solid catalyst component. Compounds having at least one aluminum-carbon bond in the molecule can be used as the organoaluminum compound. Examples of organoaluminum compounds include compounds of Formula (III):

AlR_nX_3-n (HI).

[0053] In Formula (III), R independently represents a hydrocarbon group usually having 1 to about 20 carbon atoms, X represents halogen atoms, and 0<n<3.

[0054] Specific examples of the organoaluminum compounds represented by formula (III) include, but are not limited to trialkyl aluminums such as triethyl aluminum, tributyl aluminum and trihexyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkyl aluminum sesquihalides such as ethyl aluminum

sesqui chloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; and other partially hydrogenated alkyl aluminum such as ethyl aluminum dihydride and propyl aluminum dihydride.

[0055] The organoaluminum compound can be used in the catalyst system in an amount that the mole ratio of aluminum to titanium (from the solid catalyst component) is from about 5 to about 1. In another embodiment, the mole ratio of aluminum to titanium in the catalyst system is from about 10 to about 700. In yet another embodiment, the mole ratio of aluminum to titanium in the catalyst system is from about 25 to about 400.

[0056] The catalyst system may contain at least one organosilicon compound in addition to the solid catalyst component. This organosilicon compound is sometimes termed as an external electron donor. The organosilicon compound contains silicon having at least one hydrogen ligand (hydrocarbon group). General examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, (cycloalkyl)methylene groups, alkene groups, aromatic groups, and the like.

[0057] The organosilicon compound, when used as an external electron donor serving as one component of a Ziegler-Natta catalyst system for olefin polymerization, contributes to the ability to obtain a polymer (at least a portion of which is polyolefin) having a controllable molecular weight distribution and controllable crystallinity while retaining high performance with respect to catalytic activity.

[0058] The organosilicon compound is used in the catalyst system in an amount such that the mole ratio of the organoaluminum compound to the organosilicon compound is from about 2 to about 90. In another embodiment, the mole ratio of the organoaluminum compound to the organosilicon compound is from about 5 to about 70. In yet another embodiment, the mole ration of the organoaluminum compound to the organosilicon compound is from about 7 to about 35. In one embodiment, the organosilicon compound is represented as Formula (IV):

[0059] In Formula (IV), each R and R' is independently represent a hydrocarbon group, and n is 0<n<4.

[0060] Specific examples of the organosilicon compound 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-tolydimethoxysilane, bis-m-tolydimethoxysilane, bis-p- tolydimethoxysilane, bis-p-tolydiethoxysilane, bisethylphenyldimethoxysilane,

dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane,

decyltrimethoxysilane, decy ltriethoxysilane, phenyltrimethoxysilane, gamma-chloropropy ltrimethoxysi lane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t- butyltriethoxysilane, nbutyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, gammaamniopropyltriethoxysilane, cholotriethoxysilane, ethyltriisopropoxysilane, vinyltirbutoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2- norbornanetrimethoxysilane, 2-norboranetriethoxysilane, 2- norboranemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, and methyltriallyloxysilane.

[0061] In another embodiment, the organosilicon compound is represented by Formula (V):

[0062] In Formula (V), 0<m<3, such as 0<m<2; and 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-tetiary butyl cyclopentyl; 2,2-dimethylcyclopentyl; 2,3- dimethylcyclopentyl; 2,5-dimethylcyclopentyl; 2,2,5-trimethylcyclopentyl; 2,3,4,5- tetramethylcyclopentyl; 2,2,5, 5-tetramethylcyclopentyl; 1-cyclopentylpropyl; 1-methyl-l- cyclopentylethyl; cyclopentenyl; 2-cyclopentenyl; 3-cyclopentenyl; 2-methyl-l- 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; 1,3-cyclopentadienyl; 2,4- cyclopentadienyl; 1,4-cyclopentadienyl; 2-methyl-l,3-cyclopentadienyl; 2-methyl-2,4- cyclopentadienyl; 3-methyl-2,4-cyclopentadienyl; 2-ethyl-2,4-cyclopentadienyl; 2,2- dimethyl-2,4-cyclopentadienyl; 2,3-dimethyl-2,4-cyclopentadienyl; 2,5-dimethyl-2,4- cyclopentadienyl; 2,3,4,5-tetramethyl-2,4-cyclopentadienyl; indenyl; 2-methylindenyl; 2- ethylindenyl; 2-indenyl; l-methyl-2-indenyl; l,3-dimethyl-2-indenyl; indanyl; 2- methylindanyl; 2-indanyl; l,3-dimethyl-2-indanyl; 4,5,6,7-tetrahydroindenyl; 4,5,6,7- tetrahydro-2-indenyl; 4,5,6,7-tetrahydro-l-methyl-2-indenyl; 4,5,6,7-tetrahydro-l,3- dimethyl-2-indenyl; fluorenyl groups; cyclohexyl; methylcyclohexyls; ethylcylcohexyls; propylcyclohexyls; isopropylcyclohexyls; n-butylcyclohexyls; tertiary-butyl cyclohexyls; dimethylcyclohexyls; and trimethylcyclohexyls.

[0063] In formula (V), R' and R" are identical or different and each represents a

hydrocarbon. Examples of R' and R" are alkyl, cycloalkyl, aryl and aralkyl groups having 3 or more carbon atoms. Furthermore, R and R' may be bridged by an alkyl group, etc.

General examples of organosilicon compounds are those of formula (V) in which R is cyclopentyl group, R' is an alkyl group such as methyl or cyclopentyl group, and R" is an alkyl group, particularly a methyl or ethyl group.

[0064] 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-tertiary butylcyclopentyl)dimethoxysilane, bis(2,3- dimethylcyclopentyl)dimethoxysilane, bis(2,5-dimethylcyclopentyl)dimethoxysilane, dicyclopentyldiethoxysilane, dicyclobutyldiethoxysilane,

cyclopropylcyclobutyldiethoxysilane, dicyclopentenyldimethoxysilane, di(3- cyclopentenyl)dimethoxysilane, bis(2,5-dimethyl-3-cyclopentenyl)dimethoxysilane, di-2,4- cyclopentadienyl)dimethoxysilane, bis(2,5-dimethyl-2,4-cyclopentadienyl)dimethoxysilane, bis(l-methyl-l-cyclopentylethyl)dimethoxysilane, cyclopentylcyclopentenyldimethoxysilane, cyclopentylcyclopentadienyldimethoxysilane, diindenyldimethoxysilane, bis(l,3-dimethyl-2- indenyl)dimethoxysilane, cyclopentadienylindenyldimethoxysilane,

difluorenyldimethoxysilane, cyclopentylfluorenyldimethoxysilane and

indenylfluorenyldimethoxysilane; monoalkoxysilanes such as tricyclopentylmethoxysilane, tricyclopentenylmethoxysilane, tricyclopentadienylmethoxysilane,

tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane,

dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane,

cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane,

cyclopentyldimethylethoxysilane, bis(2,5-dimethy lcyclopentyl)cyclopentylmethoxysilane, dicyclopentyl cyclopentenylmethoxysilane, dicyclopentylcyclopentenadienylmethoxysilane and diindenylcyclopentylmethoxysilane; and ethylenebis-cyclopentyldimethoxysilane.

[0065] Polymerization of olefins can be carried out in the presence of the catalyst system described above. Generally speaking, olefins are contacted with the catalyst system described above under suitable conditions to form desired polymer products. In one embodiment, preliminary polymerization described below is carried out before the main polymerization. In another embodiment, polymerization is carried out without preliminary polymerization. In yet another embodiment, the formation of copolymer is carried out using at least two polymerization zones.

[0066] In preliminary polymerization, the solid catalyst component is usually employed in combination with at least a portion of the organoaluminum compound. This may be carried out in the presence of part or the whole of the organosilicon compound (external electron donor compound). The concentration of the catalyst system used in the preliminary polymerization may be much higher than that in the reaction system of the main

polymerization.

[0067] In preliminary polymerization, the concentration of the solid catalyst component in the preliminary polymerization is usually from about 0.01 to about 200 millimoles, or from about 0.05 to about 100 millimoles, calculated as titanium atoms per liter of an inert hydrocarbon medium described below. In one embodiment, the preliminary polymerization is carried out by adding an olefin and the above catalyst system ingredients to an inert hydrocarbon medium and polymerizing the olefin under mild conditions.

[0068] Specific examples of the inert hydrocarbon medium include, but are not limited to aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptanes, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; and mixtures thereof. In certain embodiments, a liquid olefin may be used in place of part or the whole of the inert hydrocarbon medium.

[0069] The olefin used in the preliminary polymerization may be the same as, or different from, an olefin to be used in the main polymerization. [0070] The reaction temperature for the preliminary polymerization is sufficient for the resulting preliminary polymer to not substantially dissolve in the inert hydrocarbon medium. In one embodiment, the temperature is from about -20° C to about 100° C. In another embodiment, the temperature is from about -10° C to about 80° C. In yet another

embodiment, the temperature is from about 0° C to about 40° C.

[0071] Optionally, a molecular-weight controlling agent, such, as hydrogen, may be used in the preliminary polymerization. The molecular weight controlling agent is used in such an amount that the polymer obtained by the preliminary polymerization has an intrinsic viscosity, measured in decaliter at 135° C, of at least about 0.2 dl/g, or from about 0.5 to 10 dl/g.

[0072] In one embodiment, the preliminary polymerization is carried out so that from about 0.1 g to about 1,000 g of a polymer is formed per gram of the solid catalyst component of the catalyst system. In another embodiment, the preliminary polymerization is carried out so that from about 0.3 g to about 500 g of a polymer is formed per gram of the solid catalyst component. If the amount of the polymer formed by the preliminary polymerization is too large, the efficiency of producing the olefin polymer in the main polymerization may sometimes decrease, and when the resulting olefin polymer is molded into a film or another article, fish eyes tend to occur in the molded article. The preliminary polymerization may be carried out batchwise or continuously.

[0073] After the preliminary polymerization conducted as above, or without performing any preliminary polymerization, the main polymerization of an olefin is carried out in the presence of the above-described olefin polymerization catalyst system formed from the solid catalyst component, the organoaluminum compound and the organosilicon compound (external electron donor compound).

[0074] 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-l-pentene, 1- pentene, 1-octene, 1-hexene, 3 -methyl- 1-pentene, 3 -methyl- 1-butene, 1-decene, 1- tetradecene, 1-eicosene, and vinylcyclohexane. In exemplary processes, these alpha-olefins may be used individually or in any combination.

[0075] In one embodiment, ethylene, propylene, or 1-butene is homopolymerized. In other embodiments, co-polymers may be formed from any two or more of ethylene, propylene, or 1-butene. When the mixed olefin is used, the proportion of propylene or 1-butene as the main component is usually at least about 50 mole %, or at least about 70 mole %.

[0076] By performing the preliminary polymerization, the catalyst system in the main polymerization can be adjusted in the degree of activity. This adjustment tends to result in a powdery polymer having a high bulk density. Furthermore, when the preliminary

polymerization is carried out, the particles shape of the resulting polymer becomes spherical, and in the case of slurry polymerization, the slurry attains excellent characteristics while in the case of gas phase polymerization, the polymer seed bed attains excellent characteristics. Furthermore, in these embodiments, a polymer having a high stereoregularity index can be produced with a high catalytic efficiency by polymerizing an alpha-olefin having at least 3 carbon atoms. Accordingly, when producing the propylene copolymer, the resulting copolymer powder or the copolymer becomes easy to handle.

[0077] In the homopolymerization of these olefins, a polyunsaturated compound such as conjugated diene or non-conjugated diene may be used as a comonomer. Examples of comonomers include styrene, butadiene, acrylonitrile, acrylamide, alpha-methyl styrene, chlorostyrene, vinyl toluene, divinyl benzene, diallyphthalate, alkyl methacrylates and alkyl acrylates. In one embodiment, the comonomers include thermoplastic and elastomeric monomers. The main polymerization of an olefin is carried out usually in the gaseous or liquid phase. In one embodiment, polymerization (main polymerization) employs a catalyst system containing the solid catalyst component in an amount from about 0.001 to about 0.75 millimoles calculated as Ti atom per liter of the volume of the polymerization zone, the organoaluminum compound in an amount from about 1 to about 2,000 moles per mole of titanium atoms in the solid catalyst component, and the organosilicon compound in an amount from about 0.001 to about 10 moles calculated as Si atoms in the organosilicon compound per mole of the metal atoms in the organoaluminum compound. In another embodiment, polymerization employs a catalyst system containing the solid catalyst component in an amount of from 0.005 to about 0.5 milimoles calculated as Ti atom per liter of the volume of the polymerization zone, the organoaluminum compound in an amount from about 5 to about 500 moles per mole of titanium atoms in the solid catalyst component, and the organosilicon compound in an amount from about 0.01 to about 2 moles calculated as Si atoms in the organosilicon compound per mole of the metal atoms in the organoaluminum compound. In yet another embodiment, polymerization employs a catalyst system containing the alkyl benzoate derivative in an amount from about 0.005 to about 1 mole calculated as Si atoms in the organosilicon compound per mole of the metal atoms in the organoaluminum compound.

[0078] When the organoaluminum compound and the organosilicon compound are used partially in the preliminary polymerization, the catalyst system subjected to the preliminary polymerization is used together with the remainder of the catalyst system components. The catalyst system subjected to the preliminary polymerization may contain the preliminary polymerization product.

[0079] The use of hydrogen at the time of polymerization promotes and contributes to control of the molecular weight of the resulting polymer, and the polymer obtained may have a high melt flow rate. In this case, the stereoregularity index of the resulting polymer and the activity of the catalyst system can be increased according to the above methods.

[0080] In one embodiment, the polymerization temperature is from about 20 degree C to about 200° C. In another embodiment, the polymerization temperature is from about 50 degree C to about 180° C. In one embodiment, the polymerization pressure is typically from atmospheric pressure to about 100 kg/cm². In another embodiment, the polymerization pressure is typically from about 2 kg/cm² to about 50 kg/cm². The main polymerization may be carried out batchwise, semi-continuously or continuously. The polymerization may also be carried out in two or more stages under different reaction conditions.

[0081] The olefin polymer so obtained may be a homopolymer, a random copolymer, a block copolymer or an impact copolymer. The impact copolymer contains an intimate mixture of a polyolefin homopolymer and a polyolefin rubber. Examples of polyolefin rubbers include ethylene propylene rubber (EPR) such as ethylene propylene methylene copolymer rubber (EPM) and ethylene propylene diene methylene terpolymer rubber (EPDM).

[0082] The olefin polymer obtained by using the catalyst system has a very small amount of an amorphous polymer component and therefore a small amount of a hydrocarbon-soluble component. Accordingly, a film molded from the resultant polymer has low surface tackiness.

[0083] The polyolefin obtained by the polymerization process is excellent in particle size distribution, particle diameter and bulk density, and the copolyolefin obtained has a narrow composition distribution. In an impact copolymer, excellent fluidity, low temperature resistance, and a desired balance between stiffness and elasticity can be obtained.

[0084] In some embodiments, the solvents include at least one of alcohol, epoxy compound, or phosphorus compound. In further embodiments, the solvents may further include other inert solvents. In further embodiments, the epoxy compound includes at least one of aliphatic epoxy compounds, alicyclic epoxy compounds, or aromatic epoxy compounds. In yet further embodiments, the epoxy compound includes at least one of 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, halogenated alicyclic epoxy compounds, alicyclic epoxy compounds having a keto group, alicyclic epoxy compounds having an ether bond, alicyclic epoxy compounds having an ester bond, alicyclic epoxy compounds having a tertiary amino group, alicyclic epoxy compounds having a cyano group, halogenated aromatic epoxy compounds, aromatic epoxy compounds having a keto group, aromatic epoxy compounds having an ester bond, aromatic epoxy compounds having a tertiary amino group, or aromatic epoxy compounds having a cyano group.

[0085] U.S. Patent Nos. 4,784,983; 4,861,847; and 6,376,417 disclose a catalyst system for olefinic polymerization comprising magnesium chloride, TiCl₄ and external donor phthalates. The catalyst is prepared by dissolving MgCl₂ in a solvent mixture of an epoxy compound, a phosphorus compound, phthalic anhydride, and inert solvent. The mixture is added TiCl₄ to form a precipitate. The precipitate is then treated with a phthalates to load the phthalate on the solid. The precipitate is then separated from the mixture and treated again with TiCl₄ or a solution containing TiCl₄.

[0086] The auxiliary internal donor may be added to the support with or without an internal electron donor. The support was formed by following steps: MgCl₂, an epoxy compound, a phosphorus compound, and a phthalic anhydride were dissolved in an inert solvent. Addition of TiCl₄ caused formation of a precipitate. The auxiliary internal donor modifies the surface of the MgCl₂, thereby blocking atactic sites, and the auxiliary internal donor does not prevent the internal donor from attaching to the MgCl₂ TiCl₄ active centers. The auxiliary internal donor is present in the catalyst until activated by tri ethyl aluminum. Due to the presence of a halogen leaving group, the auxiliary internal donor may be easily removed from the catalyst surface during the catalyst component activation by tri ethyl aluminum. The result of the combination of the auxiliary internal donor together with the internal donor is that the catalyst improves the performances related to catalyst tacticity, and hydrogen response.

[0087] The present invention, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention.

EXAMPLES

[0088] Example 1 (Comparative). Anhydrous magnesium dichloride (6.6 g), toluene (115 g), epichlorohydrin (ECH, 7.0 g), and tributyl phosphate (17.2 g), were introduced into a reactor. The mixture was heated to 60°C for 5 hours with stirring. Phthalic anhydride (2.0 g) was added to the reactor, and the resulting solution was then stirred for an additional 1 hour at 60°C. After stirring, the solution was further cooled to -25°C. Titanium tetrachloride (TiCl₄; 130 g) was added dropwise over 1 hour. The solution was heated to 85°C, and a solid product precipitated from solution. The solid product was washed with toluene (100 ml), forming a solid intermediate support. 10 vol% TiCl₄ in toluene (133 ml) was added to the reactor and heated at 110°C for 1 hour. This step was then repeated. The solid was then washed with hexane (4 times, 150 ml) and dried in vacuo.

[0089] Accordingly, Example 1 shows what has been known in the art. As shown in Table 1, when used to produce polypropylene (PP), the catalyst of this example has a lower catalyst efficiency (CE) of 14.8 kg/g, and higher xylene extractables of 9.06%.

[0090] Example 2 (Comparative). The intermediate support (9.5 g) from Example 1, and 10 vol% TiCl₄ in toluene (133 ml) were charged to reactor. The reactor and contents were heated to 95°C and phthaloyl chloride (3.0 g) was added at 95°C, followed by stirring for 1 hour. After filtering liquid off of the solid, the solid was treated with 10 vol% TiCl₄ in toluene (133 ml) at 110°C for 30 min (3 times). The solid was then washed with hexane (4 times, 150 ml) and dried in vacuo.

[0091] In this example, also comparative, phthaloyl chloride is added with the initial

TiCl₄/toluene treatment. As shown in Table 1, the catalytic efficiency improves to 21.5 kg/g, and the xyxlene extractables decrease to 5.26%. [0092] Example 3 (Comparative). The intermediate support (9.5 g) from Example 1 and toluene (133 ml) were added to the reactor. Naphthalene- 1,8-diyl dibenzoate (0.70 g) was added at 80°C and the mixture was heated at 105°C for 1 hour. After filtering the liquid from the solid, the solid was treated with 10 vol% TiCl₄ in toluene (133 ml) at 105°C for 1 h, and then at 110°C for 30 min (3 times). The solid was then washed with hexane (4 times, 150 ml) and dried in vacuo.

[0093] In this example, also comparative, the naphthalene- 1,8-diyl dibenzoate a known donor material for magnesium chloride catalysts is used prior to the treatment with TiCl₄/toluene. In comparison to Examples 1 and 2, the catalytic efficiency increases to 50.4 kg/g, and there is a further decrease in the xylene extactables to 2.91%.

[0094] Example 4. The procedure was repeated as in Example 3, except phthaloyl chloride (1.0 g) was added to the reactor prior to addition of the naphthalene- 1,8-diyl dibenzoate.

[0095] This example shows the surprising benefits of the combination of the donor material (naphthalene- 1,8-diyl dibenzoate) with the auxiliary donor (phthaloyl chloride). The catalytic efficiency is maintained at a high level of 47.9 kg/g, however, the xylene extractables {i.e. the atactic polymer, or low molecular weight oligomers) are reduced by 50% to 2.0%. Other auxiliary donors in combination with the primary donor show similar results.

[0096] Summary to this point. Example 1 demonstrates that the support itself does not provide for the stereospecific polymerization of propylene. Addition of the auxiliary donor to the support improves the MgCl₂ surface by blocking atactic sites, but does not significantly effect the catalyst activity. The internal donor (such as, naphthalene- 1,8-diyl dibenzoate) typically generates isotactic polymerization sites on the MgCl₂-TiCl₄ catalyst support providing the high catalytic activity for polymerization process. Atactic sites may be present in the catalyst resulting in undesirable polymer properties (soluble atactic and low molecular weight polymer fractions). The combination of the auxiliary donor and the internal donor provides for a synergistic effect of the catalyst performance by blocking atactic sites and modifying the isotactic sites due to the competition between coordination on MgCl₂/TiCl₄ catalyst surface, and the ability to be removed by alkyl aluminum and external donors. As a result the catalyst properties of the catalyst are improved with regard to isotacticity and hydrogen response on the polymer molecular weight (MFI). [0097] Example 5. The procedure was repeated as in Example 3, except benzoyl chloride (2.0 g) was added to the reactor during heating at 105°C.

[0098] Example 6. The procedure was repeated as in Example 3, except 2-furoyl chloride (2.0 g) was added to the reactor at during heating at 105°C.

[0099] Example 7. (Comparative) Anhydrous magnesium chloride (6.6 g), toluene (95 g), epichlorohydrin (13.3 g), and tributyl phosphate (13.4 g) were introduced to a reactor. The mixture was heated at 60°C for 5 hours with stirring. Phthalic anhydride (1.70 g) was added to the reactor, and then the resulting solution was stirred for an additional 1 hour at 60°C. The solution was cooled to -25°C. Titanium tetrachloride (130 g) was added dropwise over 1 hour. The solution was heated to 85°C and held at temperature for 1 hour, as a solid product precipitated from solution. The solid was collected by filtration, and was washed with toluene.

[0100] Toluene (133 ml) was added to the reactor. Naphthalene-l,8-diyl dibenzoate (0.70 g) was added at 80°C and the mixture was heated at 105°C for 1 hour. After filtering the liquid from the solid, the solid was treated with a 10 vol% TiCl₄ in toluene solution (133 ml) at 105°C for 1 hours, at then at 110°C for an additional 30 min ( 3 times). The solid was then washed with hexane (4 times, 150 ml) and dried in vacuo.

[0101] Example 8. Example 7 was repeated, except phthaloyl chloride (2.0 g) was added with the TiCl₄ in toluene and heating at 105°C.

[0102] Example 9. Example 7 was repeated, except phthaloyl chloride (1.0 g) was added prior to addition of the naphthalene- 1,8-diyl dibenzoate.

[0103] Example 10. Example 8 was repeated, except phthaloyl chloride (1.0 g) was added with the TiCl₄ in toluene and heating at 105°C.

[0104] Example 11 (Comparative). Anhydrous magnesium chloride (6.6 g), toluene (95 g), epichlorohydrin (13.3 g), and tributyl phosphate (13.4 g), were introduced to a reactor. The mixture was heated at 60°C for 5 hours with stirring. Phthalic anhydride (1.70 g) was added to the reactor, and the solution was stirred for an additional 1 hour at 60°C. The solution was cooled to -25°C. Titanium tetrachloride (130 g) was added dropwise over 1 hour. The solution was heated to 85°C, during which time a solid product precipitated from solution. The mixture was then maintained at 85°C for 1 hour. The solid was collected by filtration and washed with toluene.

[0105] After filtering the liquid from the solid, the solid was treated with a 10 vol% TiCl₄ and toluene solution (133 ml) and di-n-butyl phthalate (D BP, 2.5g) at 105°C for 1 h, followed by hearing at 110°C for 30 min ( 3 times). The solid was then washed with hexane (4 times, 150 ml) and dried in vacuo.

[0106] Example 12. Example 11 was repeated, except phthaloyl chloride (3.0 g ) was added prior to the addition of the dibutyl phthalate (DNBP).

[0107] Propylene Polymerization Examples (all examples except B, D and F ). Triethyl aluminum (1.5 ml at 25 wt% in heptane), cyclohexylmethyldimethoxysilane (76.8 mmol) and 10 mg of the solid catalyst component (from the above Examples 1-12) dispersed into mineral oil (1 ml), was introduced to a N₂-purged, 3.4 L stainless steel autoclave. The autoclave was charged with 4 standard L of H₂. The autoclave was then filled with 1500 ml of liquid propylene, and the temperature was raised to 70°C. The temperature was maintained at 70°C for 1 hour, over which time the propylene polymerized. After 1 hour, the reactor was cooled to 35°C, and the polymer removed from the reactor. The polymerization in Examples B, D and F was conducted using 40 standard L of H₂.

[0108] The tables illustrate the improvement in xylene soluble (XS) material with high hydrogen response for the catalyst made with phthaloyl chloride and naphthalene- 1,8-diyl dibenzoate.

Table 1 : Analytical Data for the solid catalyst components and polymer properties.

the particle size of the catalyst.

² CE is the Catalytic Efficiency.

XS is the Xylene Solubles that are extractactable from the catalyst.

⁴ MFI is the Melt Flow Index.

⁵ D₅₀ PP is the particle size of the produced polypropylene.

⁶ Internal donor - naphthalene- 1,8-diyl dibenzoate

⁷ Phthaloyl Chloride

Table 2: Benefit of combination of phthalyol chloride and donor on MFI and XS

SL is Standard Liter

Table 2 illustrates the hydrogen response on MFI using the reference catalyst and the catalysts prepared with various auxiliary donors. Increasing the hydrogen concentration from 4 SL to 40 SL the MFI increases more strongly for catalysts containing the auxiliary electron donors.

Polymerization with catalyst containing DNBP and phthaloyl chloride

[0109] FIG. 1 is an overlay of two infra-red spectra. The spectra are of the catalyst after preparation, but prior to activation with tri ethyl aluminum (TEA1). Peaks are shown at about 1750 cm^"1 and from about 1800 cm^"1 to 1875 cm^"1 that are indicative of phthaloyl chloride. After treatment with TEA1 for polymerization reactions, the phthaloyl chloride reacts with the aluminum, allowing for a second donor, such as a silane or siloxane to attach to the surface of the catalyst. The removal of the phthaloyl chloride from the catalyst is evidenced by the loss of the peaks at about 1750 cm^"1 and from about 1800 cm to 1875 cm^"1.

ILLUSTRATIVE EMBODIMENTS

[0110] Para. A. A process for preparing a solid catalyst component for use in olefinic polymerization, the process comprising: contacting in a first solvent, a solid magnesium compound, and a first titanium compound to form a solution; heating the solution to form a solid component and liquid component; contacting the solution or the solid component with an internal electron donor and an auxiliary internal electron donor; contacting the solid component with a second titanium compound in second solvent to form the solid catalyst component; and washing the solid catalyst component with hydrocarbon or chlorinated hydrocarbon solvent, optionally containing a third titanium compound;

wherein: the solid magnesium compound is at least one of a magnesium halide, a magnesium alkoxide, a magnesium halide complex with an alcohol, a magnesium alkoxide complex with an alcohol; the auxiliary internal electron donor is an acyl halide; and the internal electron donor is a ester, an ether, a ketone, or a combination of any two or more thereof.

[0111] Para. B. The process of para. A, wherein the contacting the solid component with the internal electron donor and the auxiliary internal electron donor is conducted at a temperature of from about 70°C to about 150°C.

[0112] Para. C. The process of para. B, wherein the contacting the solid component with the internal electron donor and the auxiliary internal electron donor and the contacting the solid component with the second titanium compound in the second solvent to form the solid catalyst component occur simultaneously. [0113] Para. D. The process of para. B or C, wherein the contacting the solid component with the internal electron donor and the auxiliary internal electron donor and the contacting the solid component with the second titanium compound in the second solvent to form the solid catalyst component occur sequentially.

[0114] Para. E. The process of any one of paras. B, C, or D, wherein the contacting the solid component with the internal electron donor occurs prior to contacting the solid with the auxiliary internal electron donor.

[0115] Para. F. The process of any one of paras. A-E, wherein the second titanium compound, and optional third titanium compounds are a titanium halide; and the second solvent is an aromatic solvent, a halogenated hydrocarbon solvent, or the liquid component.

[0116] Para. G. The process of any one of paras. A-F, wherein the acyl halide is a compound represented as: RC(0)C1, and R is alkyl, alkenyl, or aryl.

[0117] Para. H. The process of any one of paras. A-G, wherein the acyl halide is

wherein: R¹ is H or C(0)X; R², R³, R⁴, R⁵ are individually H, alkyl, aryl, or any two adjacent members thereof may join together to for an aliphatic cyclic group or fused aromatic ring; and X is CI or Br.

[0118] Para. I. The process of any one of paras. A-H, wherein the acyl halide is

; and

R¹ is C(0)X.

[0119] Para. J. The process of any one of paras. A-I, wherein the acyl halide is phthaloyl chloride, benzoyl chloride, furoyl chloride, 1-naphthoyl chloride, 2-naphthoyl chloride, furoyl chloride, ethanoyl chloride, propanoyl chloride, butanoyl chloride, hexanoyl chloride, or cyclohexanoyl chloride.

[0120] Para. K. The process of any one of paras. A- J, wherein the first titanium

compounds is a titanium halide, a titanium alkoxide, or a titanium alkoxychloride.

[0121] Para. L. The process of any one of paras. A-K, wherein the first, and second titanium compounds are titanium halides.

[0122] Para. M. The process of para. L, wherein the titanium halide is T1CI3 or T1CI4.

[0123] Para. N. The process of any one of paras. A-M, wherein the first solvent and second solvent comprise toluene or ethyl benzene.

[0124] Para. O. The process of any one of paras. A-N, wherein the second titanium compound is present in the second solvent at a concentration of about 5 wt% to about 80 wt%.

[0125] Para. P. The process of any one of paras. A-O, wherein the magnesium compound comprises magnesium dichloride, magnesium dibromide, magnesium diiodide,

magnesium difluoride, methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, phenoxy magnesium chloride, methylphenoxy magnesium chloride, magnesium laurate, or magnesium stearate. [0126] Para. Q. The process of any one of paras. A-P, wherein the magnesium compound is MgCl₂.

[0127] Para. R. The process of any one of paras. A-Q, wherein the solid magnesium compound is prepared by a process comprising: dissolving a halide-containing magnesium compound in a mixture comprising an alkylepoxide; an organic phosphorous compound; a carboxylic acid, a carboxylic anhydride, or both a carboxylic acid and a carboxylic anhydride; and an initial solvent to form a homogenous solution; and treating the homogenous solution with an initial titanium halide compound to form the solid magnesium compound.

[0128] Para. S. The process of para. R, wherein the carboxylic acid or carboxylic anhydride is at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, or methacrylic acid; and the acyl halide is phthaloyl chloride, benzoyl chloride, furoyl chloride, 1-naphthoyl chloride, 2-naphthoyl chloride, furoyl chloride, ethanoyl chloride, propanoyl chloride, butanoyl chloride, hexanoyl chloride, or cyclohexanoyl chloride.

[0129] Para. T. The process of para. R or S, wherein treating the homogenous solution with the initial titanium halide compound is conducted in the presence of a surface modifier.

[0130] Para. U. The process of para. T, wherein the surface modifier comprises an acrylate or a polyacrylate.

[0131] Para. V. The process of para. T or U, wherein the surface modifier is at least one of a poly((Ci-C₆) alkyl) acrylate, a poly((Ci-C₆) alkyl) methacrylate, or a copolymer of poly((Ci-C₆) alkyl) acrylate and poly((Ci-C₆) alkyl) methacrylate.

[0132] Para. W. The process of any one of paras. A-V, wherein the ester is a phthalate or a 1,8-naphthyl dibenzoate.

[0133] Para. X. The process of any one of paras. R-W, wherein the organophosphorous compound is represented as:

wherein R¹, R², and R³ are each independently Ci-Cio alkyl.

[0134] Para. Y. The process of any one of paras. R-W, wherein the epoxyalkyl compound is represented as:

n is 1, 2, 3, 4, or 5; and X is F, CI, Br, I, or methyl.

[0135] Para. Z. The solid catalyst component prepared by the process of para. A.

[0136] Para. AA. A process of polymerizing or copolymerizing an olefin, the process comprising contacting the washed solid catalyst component prepared by the process of para. A with an organoaluminum activating agent and the olefin.

[0137] Para. BB. The process of para. BB, wherein the organoaluminum activating agent is triethylaluminum.

[0138] Para. CC. The process of para. AA or BB, wherein the olefin is ethylene, propylene, 1-butylene, 1 -methyl- 1-pentene, 1-hexene, and 1-octene.

[0139] Para. DD. A catalyst system for use in olefinic polymerization, the system comprising: a solid magnesium-based component having an internal electron donor, an auxiliary internal electron donor, and a titanium material; and an organoaluminum;

wherein: the solid magnesium-based component is at least one of a magnesium halide, a magnesium alkoxide, and their complexes with alcohols, and a third titanium compound; the auxiliary internal electron donor is an acyl halide; and the internal electron donor is a ester, an ether, a ketone, or a combination of any two or more thereof.

[0140] Para. EE. A catalyst system for use in olefinic polymerization, the system comprising: a solid component produced according to the method of paras. R-Y, an electron donor, an auxiliary internal electron donor, and an organoaluminum compound. [0141] Para. FF. The catalyst system according to para. EE, wherein the organoaluminum compound is an alkyl aluminum compound.

[0142] Para. GG. The catalyst system according to para. EE or FF, wherein the alkyl- aluminum compound is a trialkyl aluminum compound.

[0143] Para. ΉΗ. The catalyst system according to para. EE, FF, or GG, wherein the trialkyl aluminum compound is triethylaluminum, triisobutylaluminum, or tri-n- octylaluminum.

[0144] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0145] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase "consisting essentially of will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of excludes any element not specified.

[0146] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art.

Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds compositions or biological systems, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0147] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0148] As will be understood by one 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 thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as "up to," "at least," "greater than," "less than," and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0149] All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated 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 that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0150] Other embodiments are set forth in the following claims.

Claims

WHAT IS CLAIMED IS:

A process for preparing a solid catalyst component for use in olefinic

polymerization, the process comprising:

contacting in a first solvent, a solid magnesium compound, and a first titanium compound to form a solution;

heating the solution to form a solid component and liquid component; contacting the solid component with an internal electron donor, and an auxiliary internal electron donor;

contacting the solution or the solid component with a second titanium

compound in second solvent to form the solid catalyst component; and

washing the solid catalyst component with hydrocarbon or chlorinated hydrocarbon solvent, optionally containing a thirdtitanium compound;

wherein:

the solid magnesium compound is at least one of a magnesium halide, a magnesium alkoxide, a magnesium halide complex with an alcohol, a magnesium alkoxide complex with an alcohol;

the auxiliary internal electron donor is an acyl halide; and

the internal electron donor is a ester, an ether, a ketone, or a combination of any two or more thereof.

The process of Claim 1, wherein the contacting the solid component with the internal electron donor and the auxiliary internal electron donor is conducted at a temperature of from about 70°C to about 150°C.

The process of Claim 1, wherein the contacting the solid component with the internal electron donor and the auxiliary internal electron donor and the contacting the solid component with the second titanium compound in the second solvent to form the solid catalyst component occur simultaneously.

The process of Claim 1, wherein the contacting the solid component with the internal electron donor and the auxiliary internal electron donor and the contacting the solid component with the second titanium compound in the second solvent to form the solid catalyst component occur sequentially.

The process of Claim 1, wherein the contacting the solid component with the internal electron donor occurs prior to contacting the solid with the auxiliary internal electron donor.

The process of Claim 1, wherein the second titanium compound is a titanium halide; and the second solvent is an aromatic solvent, a halogenated hydrocarbon solvent, or the liquid component.

The process of Claim 1, wherein the acyl halide is a compound represented as: RC(0)C1, and R is alkyl, alkenyl, or aryl.

The rocess of Claim 7, wherein the acyl halide is:

wherein:

R¹ is H or C(0)X;

R², R³, R⁴, R⁵ are individually H, alkyl, aryl, or any two adjacent members thereof may join together to for an aliphatic cyclic group or fused aromatic ring; and

X is CI or Br.

9. The process of Claim 8, wherein the acyl halide is

R¹ is C(0)X.

10. The process of Claim 7, wherein the acyl halide is phthaloyl chloride, benzoyl chloride, furoyl chloride, 1-naphthoyl chloride, 2-naphthoyl chloride, furoyl chloride, ethanoyl chloride, propanoyl chloride, butanoyl chloride, hexanoyl chloride, or cyclohexanoyl chloride.

11. The process of Claim 1, wherein the first titanium compound is a titanium halide, a titanium alkoxide, or a titanium alkoxychloride.

12. The process of Claim 1, wherein the first, and second titanium compounds are titanium halides.

13. The process of Claim 12, wherein the titanium halide is TiCl₃ or TiCl₄.

14. The process of Claim 1, wherein the first solvent and second solvent comprise toluene or ethyl benzene.

15. The process of Claim 1, wherein the second titanium compound is present in the second solvent at a concentration of about 5 wt% to about 80 wt%.

The process of Claim 1, wherein the magnesium compound comprises magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium difluoride, methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, phenoxy magnesium chloride, methylphenoxy magnesium chloride, magnesium laurate, or magnesium stearate.

17. The process of Claim 1, wherein the magnesium compound is MgCl₂.

18. The process of Claim 1, wherein the solid magnesium compound is prepared by a process comprising:

dissolving a halide-containing magnesium compound in a mixture

comprising an alkylepoxide; an organic phosphorous compound; a carboxylic acid, a carboxylic anhydride, or both a carboxylic acid and a carboxylic anhydride; and an initial solvent to form a homogenous solution; and

treating the homogenous solution with an initial titanium halide compound to form the solid magnesium compound.

19. The process of Claim 18, wherein the carboxylic acid or carboxylic anhydride is at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, or methacrylic acid.

20. The process of Claim 19, the wherein the acyl halide is phthaloyl chloride, benzoyl chloride, furoyl chloride, 1-naphthoyl chloride, 2-naphthoyl chloride, furoyl chloride, ethanoyl chloride, propanoyl chloride, butanoyl chloride, hexanoyl chloride, or cyclohexanoyl chloride.

21. The process of Claim 18, wherein treating the homogenous solution with the initial titanium halide compound is conducted in the presence of a surface modifier.

22. The process of Claim 21, wherein the surface modifier comprises an acrylate or a polyacrylate.

23. The process of claim 21, wherein the surface modifier is at least one of a poly((Ci- C₆) alkyl) acrylate, a poly((Ci-C₆) alkyl) methacrylate, or a copolymer of poly((Ci- C₆) alkyl) acrylate and poly((Ci-C₆) alkyl) methacrylate.

24. The process of Claim 1, 19, or 20, wherein the ester is a phthalate or a 1,8-naphthyl dibenzoate.

25. The process of Claim 18, wherein the organophosphorous compound is represented as: O

R'O p OR

wherein R¹, R², and R³ are each independently Ci-Ci₀ alkyl.

The process Claim 18, wherein the epoxyalkyl compound is represented as:

n is 1, 2, 3, 4, or 5; and

X is F, CI, Br, I, or methyl.

27. The solid catalyst component prepared by the process of Claim 1. 28. A process of polymerizing or copolymerizing an olefin, the process comprising contacting the washed solid catalyst component prepared by the process of Claim 1 with an organoaluminum activating agent and the olefin.

29. The process of Claim 28, wherein the organoaluminum activating agent is

tri ethyl aluminum . 30. The process of Claim 28, wherein the olefin is ethylene, propylene, 1-butylene, 1- methyl-l-pentene, 1 iexene, and 1-octene. 31. A catalyst system for use in olefinic polymerization, the system comprising:

a solid magnesium-based component having an internal electron donor, an auxiliary internal electron donor, and a titanium material; and an organoaluminum;

wherein:

the solid magnesium-based component is at least one of a magnesium

halide, a magnesium alkoxide, and their complexes with alcohols, and a third titanium compound;

the auxiliary internal electron donor is an acyl halide; and

the internal electron donor is a ester, an ether, a ketone, or a combination of any two or more thereof.

32. A catalyst system for use in olefinic polymerization, the system comprising:

a solid component produced according to the method of Claim 18, an

electron donor, an auxiliary internal electron donor, and an organoaluminum compound.

33. The catalyst system according to Claim 32, wherein the organoaluminum

compound is an alkyl aluminum compound.

34. The catalyst system according to Claim 33, wherein the alkyl-aluminum compound is a trialkyl aluminum compound.

35. The catalyst system according to Claim 34, wherein the trialkyl aluminum

compound is triethylaluminum, triisobutyl aluminum, or tri-n-octylaluminum.