RU2793854C2 - Catalyst components for propylene polymerization - Google Patents

Abstract

FIELD: polymers.

SUBSTANCE: invention relates to a process for preparing solid catalyst components, catalyst systems formed from catalyst components, and polymerization processes using the described catalyst systems. Proposed are a solid catalytic component for the polymerization of olefins with a particle size of 5 to 70 mcm based on 50% of volume containing a halogenated magnesium compound and a reaction product of a magnesium compound with an epoxy compound, an organic phosphorus compound, a titanium compound, an organosilicon compound, a non-phthalate internal electron donor, which contains an aryl diester, a simple diester, or a mixture thereof, and a supporting donor that differs from the internal donor and does not contain by-products of the interaction of a carboxylic acid and its anhydride with magnesium and titanium compounds, a catalytic system containing the specified solid catalyst component, an organoaluminium compound and a selectivity control agent, a method for polymerizing an olefin in the presence of a solid catalyst component and an organoaluminium compound, a method for producing a solid catalyst component, including dissolving a magnesium compound in a mixture of an epoxy compound, organic phosphorus compound and hydrocarbon solvent followed by successive treatments with two titanium compounds, where the first compound is in the presence of an organosilicon compound, and the second in the presence of a non-phthalate electron donor and at least one selectivity agent.

EFFECT: obtaining an improved Ziegler-Natta catalyst, which has a higher and/or longer activity during polymerization, and is also capable of producing polymer particles with improved morphology.

25 cl, 7 dwg, 15 tbl, 44 ex

Description

RELATED APPLICATIONS

[0001] This application claims priority over U.S. Provisional Applications No. 62/585,137, filed 11/13/2017, and PCT/US2018/057980, filed October 29, 2018, the contents of which are hereby incorporated by reference in their entirety.

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

[0002] The present invention relates to a process for the production of polymerization catalyst components, catalyst systems formed from catalyst components, and methods for producing catalyst systems and olefin polymers and copolymers using the described catalyst systems. More specifically, it refers to cases in which the catalyst components are phthalate-free.

BACKGROUND OF THE INVENTION

[0003] Polyolefins are a class of polymers derived from simple olefins. Known methods for producing polyolefins include the use of Ziegler-Natta polymerization catalysts. These catalysts polymerize olefin monomers using a transition metal halide to produce a polymer with various types of stereochemical configurations.

[0004] One type of Ziegler-Natta catalyst system comprises a solid component, a magnesium halide catalyst component supported by a titanium compound and an internal electron donor compound. To maintain high selectivity for the isotactic polymer product, internal electron donor compounds must be added during catalyst synthesis. The internal donor can be of various types. If a higher degree of crystallinity of the polymer is desired, an external donor compound is usually also added during the polymerization reaction.

[0005] In the past 30 years, many supported Ziegler-Natta catalysts have been developed that provide much higher activity in olefin polymerization reactions and much higher crystalline isotactic fractions in the polymers they produce. With the development of internal and external electron donor compounds, polyolefin catalyst systems are continuously updated.

[0006] Catalyst morphology control is an important aspect of the operation of a commercial polyolefin plant. Morphological characteristics of the catalyst include particle size and particle size distribution, particle shape and surface texture.

[0007] the Morphological characteristics of the catalysts affect the properties of polymer powders, such as bulk density, fluidity, degassing and particle adhesion. Such properties significantly affect the efficiency of the installation. For example, inappropriate catalyst morphology can cause polymer morphology control to fail, which can lead to serious plant failures such as clogging or delamination.

[0008] For these reasons, MgCl ₂ supported catalysts with good morphology control (desired particle size and shape, narrow particle size distribution, high bulk density and low adhesion) are desirable.

[0009] The general production scheme for MgCl ₂ supported catalysts includes a method of making an MgCl ₂ support, TiCU impregnation with a Lewis base and an internal MgCl ₂ surface donor. One way to prepare catalysts supported by MgCl ₂ is the reaction of (OR)Cl or Mg(OR) ₂ with an excess of TiCl ₄ diluted in aromatic or halogenated solvents. In such a case, the MgCl ₂ support is formed by the reaction between the magnesium compound and TiCl ₄ and the internal donor is added during or after the solid support is deposited.

[0010] In another method, the alkoxymagnesium complex is first reacted with an electron donor precursor and then with TiCl ₄ . In this method, the electron donor precursor is converted to the desired internal donor upon formation of MgCl ₂ .

[0011] In another method, solid MgCl ₂ is used to prepare an MgCl ₂ catalyst. Solid MgCl ₂ is dissolved in suitable solvents such as ethyl alcohol. The solution is then treated with TiCl ₄ to precipitate the supported catalyst on the MgCl ₂ carrier. For example, MgCl ₂ can be dissolved in hot ethanol and precipitated in cold hexane in the presence of tetraethylorthosilicate (TEOS).

[0012] U.S. Patent Nos. 6,376,417; 4,784,983; and 4,861,847 describe a catalyst system for use in the polymerization of olefins, obtained by dissolving a magnesium halide in a solvent system consisting of an organic compound, an organic phosphorus compound, and an inert diluent to form a homogeneous solution; mixing the homogeneous solution with titanium halide to form a mixture; precipitation of a solid from the mixture in the presence of an auxiliary precipitating agent; treating the solid with a polycarboxylic ester to apply the ester to the solid; and treating the applied ester with a titanium halide and an inert diluent. US Patent No. 9,714,302 requires the use of carboxylic acids, anhydrides and phthalates in the preparation of solid catalysts. However, there remains a need in the art for an improved Ziegler-Natta catalyst that has higher and/or longer activity during polymerization. There is also a need for a catalyst capable of producing polymer particles with improved morphology.

SUMMARY OF THE INVENTION

[0013] In one aspect, a process is provided for preparing a solid catalyst component for producing a polyolefin, such as polypropylene, the process comprising:

a) dissolving a magnesium halide compound in the mixture, wherein the mixture includes an epoxy compound, an organic phosphorus compound, and a hydrocarbon solvent to form a homogeneous solution;

b) treating the homogeneous solution with a first titanium compound in the presence of an organosilicon compound to form a solid precipitate;

c) treating the solid precipitate with a second titanium compound in the presence of a non-phthalate electron donor to form a solid catalyst component;

and:

the method should not use carboxylic acids and anhydrides;

the first titanium compound and the second titanium compound are independently represented by the formula:

Ti(OR)gX4-g;

each R is independently C1-C4 alkyl;

X is Br, CI or I; And

g is 0, 1, 2 or 3 and

the organosilicon compound contains O-Si-0 and/or Si-O-Si groups.

[0014] The epoxy compound may include a glycidyl-containing compound represented by the Formula:

and:

a is 1, 2, 3, 4 or 5;

X is alkyl, F, CI, Br, I; And

R ^a is H, alkyl, aryl or cyclyl.

[0015] In any of the above embodiments, X is methyl, ethyl, F, CI, Br, or I. In other embodiments, the epoxy compound is selected from the group consisting of: ethylene oxide; propylene oxide; 1,2-epoxybutane; 2,3-epoxybutane; 1,2-epoxyhexane; 1,2-epoxyoctane; 1,2-epoxydecane; 1,2-epoxydecane; 1,2-epoxytetradecane; 1,2-epoxyhexadecane; 1,2-epoxyoctadecane; 7,8-epoxy-2-methyloctadecane; 2-vinyloxirane; 2-methyl-2-vinyloxirane; 1,2-epoxy-5-hexene; 1,2-epoxy-7-octene; 1-phenyl-2,3-epoxypropane; 1-(1-naphthyl)-2,3-epoxypropane; 1-cyclohexyl-3,4-epoxybutane; 1,3-butadiene dioxide; 1,2,7,8-diepoxyoctane; cyclopentene oxide; cyclooctenoxide; α-pinene oxide; 2,3-epoxynorbornane; limonene oxide; cyclodecane epoxide; 2,3,5,6-diepoxynorbornane; styrene oxide; 3-methylstyrene oxide; 1,2-epoxybutylbenzene; 1,2-epoxyoctylbenzene; stilbene oxide; 3-vinyl styrene oxide; 1-(1-methyl-1,2-epoxyethyl)-3-(1-methylvinylbenzene); 1,4-bis(1,2-epoxypropyl)benzene; 1,3-bis(1,2-epoxy-1-methylethyl)benzene; 1,4-bis(1,2-epoxy-1-methylethyl)benzene; epifluorohydrin; epichlorohydrin; epibromohydrin; hexafluoropropylene oxide; 1,2-epoxy-4-fluorobutane; 1-(2,3-epoxypropyl)-4-fluorobenzene; 1-(3,4-epoxybutyl)-2-fluorobenzene; 1-(2,3-epoxypropyl)-4-chlorobenzene; 1-(3,4-epoxybutyl)-3-chlorobenzene; 4-fluoro-1,2-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-1-cyclohexanone;2,3-epoxy-5-oxobicyclo[2.2.1]heptane; 3-acetylstyrene oxide; 4-(1,2-epoxypropyl)benzophenone; simple glycidyl methyl ether; simple butylglycidyl ether; simple 2-ethylhexylglycidyl ether; simple allylglycidyl ether; simple ethyl-3,4-epoxybutyl ether; simple glycidylphenyl ether; simple glycidyl-4-tert-butylphenyl ether; simple glycidyl-4-chlorophenyl ether; simple glycidyl-4-methoxyphenyl ether; simple glycidyl-2-phenylphenyl ether; simple glycidyl-1-naphthyl ether; simple glycidyl-2-phenylphenyl ether; simple glycidyl-1-naphthyl ether; a simple glycidyl-4-indolyl ether; a simple glycidyl-N-methyl-α-quinolon-4-yl ether; simple ethylene glycol diglycidyl ether; simple 1,4-butanediol diglycidyl ether; 1,2-diglycidyloxybenzene; 2,2-bis(4-glycidyloxyphenyl)propane; tris(4-glycidyloxyphenyl)methane; simple poly(oxypropylene)trioltriglycidyl ether; phenol novolac glycidic ether; 1,2-epoxy-4-methoxycyclohexane; 2,3-epoxy-5,6-dimethoxybicyclo[2.2.1]heptane; 4-methoxystyrene oxide; 1-(1,2-epoxybutyl)-2-phenoxybenzene; glycidyl formate; glycidyl acetate; 2,3-epoxybutyl acetate; glycidyl butyrate; glycidyl benzoate; diglycidyl terephthalate; poly(glycidyl acrylate); poly(glycidyl methacrylate); a copolymer of glycidyl acrylate with another monomer; a copolymer of glycidyl methacrylate with another monomer; 1,2-epoxy-4-methoxycarbonylcyclohexane; 2,3-epoxy-5-butoxycarbonylbicyclo[2.2.1]heptane; ethyl 4-(1,2-epoxyethyl)benzoate; methyl 3-(1,2-epoxybutyl)benzoate; methyl 3-(1,2-epoxybutyl)-5-phenylbenzoate; N,N-glycidylmethylacetamide; N,N-ethylglycidylpropionamide; N,N-glycidylmethylbenzamide; N-(4,5-epoxypentyl)-N-methyl-benzamide; Ν,Ν-diglycidylaniline; bis(4-diglycyldilaminophenyl)methane; poly(N,N-glycidylmethylacrylamide); 1,2-epoxy-3-(diphenylcarbamoyl)cyclohexane; 2,3-epoxy-6-(dimethylcarbamoyl)bicyclo[2.2.1]heptane; 2-(dimethylcarbamoyl)styrene oxide; 4-(1,2-epoxybutyl)-4-(dimethylcarbamoyl)biphenyl; 4-cyano-1,2-epoxybutane; 1-(3-cyanophenyl)-2,3-epoxybutane; 2-cyanostyrene oxide; and 6-cyano-1-(1,2-epoxy-2-phenylethyl)naphthalene.

[0016] In any of the above embodiments, steps a) and b) can be carried out in the presence of a simple di-(C ₁ -C ₁₂ )-alkyl ether.

[0017] In the above embodiments, the method may also include adding an organosilicon compound during or after dissolving the Mg compound in an organic solvent including the organosilicon compound in step a). Exemplary silicone compounds include, but are not limited to, silane, siloxane, or polysiloxane. In some embodiments, the silicone compound may be represented by Formula (II):

In formula (II), each R may be H, alkyl or aryl; each R' may be H, alkyl, aryl or -SiR _n' (OR') _3-n where n is 0, 1, 2 or 3.

[0018] In some embodiments, the silicone compound is a monomeric or polymeric compound. The organosilicon compound may contain -Si-O-Si- groups within one molecule or between other molecules. Other exemplary silicone compounds include polydialkylsiloxane and/or tetraalkoxysilane. Such compounds may be used singly or in combination. The silicone compound can be used in combination with aluminum alkoxides and a first internal donor. In some embodiments, polydimethylsiloxane and/or tetraethoxysilane can be used. The aluminum alkoxide mentioned above may have the formula Al(OR') ₃ where each R' individually is a hydrocarbon having up to 20 carbon atoms. This may include cases in which each R' is individually methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, etc.

[0019] As described above, the process can take place in the presence of non-phthalate electron donors. In one embodiment, the method may take place in the presence of a maintenance donor. In one embodiment, the method is run in the presence of a maintenance donor (which may also be a first non-phthalate electron donor) and in the presence of a second non-phthalate electron donor.

[0020] The maintenance donor or first non-phthalate donor may include diester, succinate, oxygen containing electron donors such as organic acid ester, polycarboxylic acid ester, polyhydroxy ester, heterocyclic polycarboxylic acid esters, inorganic acid ester, ester an alicyclic polycarboxylic acid; and a hydroxy-substituted carboxylic acid ester compound having from 2 to about 30 carbon atoms. For example, the first non-phthalate donor may include methyl formate; ethyl acetate; vinyl acetate; propyl acetate; octyl acetate; cyclohexyl acetate; ethyl propionate; methyl butyrate; ethyl valerate; ethyl stearate; methyl chloroacetate; ethyl dichloroacetate; methyl methacrylate; ethyl crotonate; dibutyl maleate; diethylbutylmalonate; diethyldibutylmalonate; ethylcyclohexanecarboxylate; diethyl 1,2-cyclohexanedicarboxylate; di-2-ethylhexyl 1,2-cyclohexanedicarboxylate; methyl benzoate; ethyl benzoate; propyl benzoate; butyl benzoate; octyl benzoate; cyclohexyl benzoate; phenyl benzoate; benzyl benzoate; methyltoluate; ethyltoluate; amyltoluate; ethyl ethyl benzoate; methylanisate; ethylanisate; ethylethoxybenzoate, γ-butyrolactone; δ-valerolactone; coumarin; phthalide; ethylene carbonate; ethyl silicate; butyl silicate; vinyltriethoxysilane; phenyltriethoxysilane; diphenyltriethoxysilane; diethyl 1,2-cyclohexanecarboxylate; diisobutyl 1,2-cyclohexanecarboxylate; diethyltetrahydrophthalate and nadic acid; diethyl ester; diethylnaphthalenedicarboxylate; dibutylnaphatlindicarboxylate; triethyl trimellitate and dibutyl trimellitate; esters of 3,4-furandicarboxylic acid; 1,2-diacetoxybenzene; 1-methyl-2,3-diacetoxybenzene; 2-methyl-2,3-diacetoxybenzene; 2,8-diacetoxynaphthalene; ethylene glycol dipivalate; butanediol pivalate; benzoylethyl salicylate; acetyl isobutyl salicylate; acetylmethyl salicylate; diethyl adipate; diisobutyl adipate; diisopropyl sebacate; di-n-butyl sebacate; di-n-octylsebacate; or di-2-ethylhexyl sebacate.

[0021] In some of the above embodiments, the maintenance donor or the first non-phthalate donor may be selected from the group consisting of methyl formate, butyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, isobutyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl p-methoxybenzoate, methyl p-methyl benzoate, ethyl p-tert-butyl benzoate, ethyl naphthoate, methyl toluate, ethyltoluate, amyltoluate, ethylethylbenzoate, methylanisate, ethylanisate and ethylethoxybenzoate.

[0022] In any of the above embodiments, the second non-phthalate electron donor may include a compound other than the maintenance donor and is a compound that is diester, succinate, oxygenated electron donors such as an organic acid ester, a polycarboxylic acid ester , a polyhydroxy ester, a heterocyclic polycarboxylic acid ester, an inorganic acid ester, an alicyclic polycarboxylic acid ester, a hydroxy-substituted carboxylic acid ester compound having from 2 to about 30 carbon atoms, or a compound having at least one ether group and at least one ketone group.

[0023] In many of the above embodiments, the second non-phthalate donor may be selected from the group consisting of linear or cyclic diesters and non-phthalate aromatic diesters. For example, in one embodiment, the second electron donor may comprise an aryl ester. In one specific embodiment, the electron donor may contain a substituted 1,2-phenylenedibenzoate. Various electron donors may include compounds represented by the following formulas:

, или

, or

where each of the elements from R ¹ to R ³⁴ independently represents H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl or heteroarylalkyl; and q is an integer from 0 to 12.

[0024] In any of the above embodiments, treatment of the homogeneous solution with the first titanium compound is carried out in the presence of an organic ester and an organosilicon compound; organic ester and aluminum alkoxide; or an organic ester, an organosilicon compound and an aluminum alkoxy oxide; with the formation of a solid precipitate.

[0025] In any of the above embodiments, the hydrocarbon solvent comprises an aromatic solvent, a non-aromatic solvent, or a mixture of any two or more of them.

[0026] In any of the above embodiments, the implementation of the hydrocarbon solvent contains (C ₁ -C ₂₀ -alkyl)benzene, hexane, heptane, or a mixture of any two or more of them. For example, the hydrocarbon solvent may include toluene, hexane, heptane, or a mixture of any two or more of these.

[0027] In any of the above embodiments, step c) comprises treatment with a first titanium compound, a second titanium compound, or a mixture thereof, which is carried out at a temperature of from about -25°C to about 150°C.

[0028] In any of the above embodiments, the magnesium halide compound is selected from the group consisting of magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, and a mixture of any two or more of them.

[0029] In any of the above embodiments, the organic phosphorus compound is:

where each of R ₁ , R ₂ , and R ₃ is independently C ₁ -C ₁₀ alkyl.

[0030] In the above embodiments, di-(C ₁ -C ₁₂ )alkyl ether can be selected from the group consisting of: dimethyl ether, diethyl ether, dipropyl ether, di-n-butyl ether, butyl propyl ether, diamyl ether, diisoamyl ether , dihexyl ether, and mixtures of any two or more of them.

[0031] In any of the above embodiments, the organosilicon compound may be a siloxane or a polysiloxane represented by Formula:

and:

each R is H, alkyl or aryl;

each R' is H, alkyl, aryl or SiR _n' (OR') _3-n ; And

n is 0, 1, 2, or 3.

[0032] The present invention also relates to a solid catalyst component. The solid catalyst component in one embodiment comprises:

A magnesium compound including a magnesium halide compound and a reaction product of a magnesium compound with an epoxy compound;

organic compound of phosphorus;

titanium compound;

an organosilicon compound containing: Si-O or O-Si-O groups;

an internal electron donor, wherein the internal electron donor contains an aryl diester, 1,2-phenylenedibenzoate, a diester, a succinate, an organic acid ester, a polycarboxylic acid ester, a polyhydroxy ester, a heterocyclic polycarboxylic acid ester, an inorganic acid ester, a an alicyclic polycarboxylic acid ester, a hydroxy-substituted carboxylic acid ester compound having 2 to 30 carbon atoms, or a compound having at least one ether group and at least one ketone group, or a mixture thereof;

wherein the solid catalyst component does not contain by-products of the reaction between the carboxylic acid or its anhydride and a magnesium or titanium compound, and

while the solid catalyst component has a particle size of from about 5 microns to about 70 microns (based on 50% by volume).

[0033] In another aspect, a catalyst system is provided for use in the polymerization of olefins, wherein the catalyst system comprises a solid catalyst component produced by any of the above methods, an organoaluminum compound, and optionally an organosilicon compound.

[0034] In any of the above embodiments of the catalyst system, the organoaluminum compound may be an alkylaluminum compound. For example, it may be a trialkylaluminum compound such as triethylaluminum, triisobutylaluminum, or tri-n-octylaluminum.

[0035] In another aspect, a process for polymerizing or

copolymerization of a polypropylene monomer, the method may include contacting an olefin monomer or a mixture of olefin monomers with any of the above catalyst systems to form an olefin monomer homopolymer or a copolymer of a mixture of olefin monomers.

[0036] A process for polymerizing or copolymerizing an olefin monomer, the method comprising contacting a polypropylene monomer or a mixture of polypropylene with at least one other olefin monomer with a catalyst system as described herein to form a polypropylene or a copolymer of polypropylene and olefin monomers.

BRIEF DESCRIPTION OF THE FIGURES

[0037] FIG. 1 shows a microscopic view of a polymer produced with the catalyst component of Example 5 (comparative).

[0038] FIG. 2 shows a microscopic view of a polymer produced with the catalyst component of Example 7.

[0039] FIG. 3 shows a microscopic view of a polymer produced with the catalyst component of Example 9.

[0040] FIG. 4 shows a microscopic view of a polymer produced with the catalyst component of Example 11.

[0041] FIG. 5 shows a microscopic view of a polymer produced with the catalyst component of Example 13 (comparative).

[0042] FIG. 6 shows a microscopic view of a polymer produced with the catalyst component of Example 23.

[0043] FIG. 7 shows a microscopic view of a polymer produced with the catalyst component of Example 34.

DETAILED DESCRIPTION

[0044] Before describing a few embodiments, it should be understood that the invention is not limited to the design features or method steps set forth in the following description. Other embodiments of the invention are possible, and the invention may be practiced or carried out in various ways.

[0045] Reference in the description to "one embodiment", "certain embodiments", "one or more embodiments", or "an embodiment" means that a particular feature, structure, material or characteristic described in connection with an embodiment, included in at least one embodiment. Thus, the appearance of phrases such as "in one or more embodiments", "in certain embodiments", "in one embodiment" or "in an embodiment" in various places in this specification does not necessarily refer to the same embodiment. implementation. In addition, specific features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0046] While references herein refer to specific embodiments, it should be understood that these embodiments are only illustrative of the principles and uses of the present invention. Those skilled in the art will appreciate that various modifications and changes may be made to the methods and apparatus of the present invention without departing from the spirit and scope of the present invention. Thus, the present invention is intended to include modifications and alterations that fall within the scope of the appended claims and their equivalents.

[0047] This document describes Ziegler-Natta catalyst systems and supports for Ziegler-Natta catalysts, as well as methods for their manufacture. One aspect of the catalyst systems is a solid catalyst containing a magnesium halide compound and a titanium compound for olefin polymerization, wherein the solid catalyst component is substantially spherical or spheroidal in shape. The solid catalyst component can be used to form an effective Ziegler-Natta catalyst in combination with one or more external and/or internal electron donors and an organoaluminum compound.

[0048] As used herein, the term "solid catalyst component" refers to a pre-catalyst containing a magnesium halide compound and a titanium compound, and optionally one or more internal electron donors, that are used in forming an efficient Ziegler-Natta catalyst system in combination with main group metal alkyl.

[0049] In a typical Ziegler-Natta catalyst system application, the solid catalyst component, the electron donor, and the organoaluminum compound (main group metal alkyl) form a slurry catalyst system that may contain any suitable liquid, such as an inert hydrocarbon medium. Examples of inert hydrocarbon media include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and their mixtures. The suspension medium may be hexane, heptane or mineral oil. The slurry medium may be different from the diluent used in forming the mixture from which the solid catalyst component is deposited.

[0050] The solid catalyst supports described herein can be used in any suitable Ziegler-Natta polymerization catalyst system. Ziegler-Natta catalyst systems include a reactant or combination of reactants that are capable of catalyzing the polymerization of 1-alkenes (α-olefins) to form polymers, typically with high isotacticity, when polymerizing prochiral 1-alkenes. The term “Ziegler-Natta catalyst” refers to any composition having a transition metal and a main group metal alkyl component capable of supporting the catalysis of 1-alkene polymerization. The transition metal component is typically a Group IV metal such as titanium or vanadium, the main group alkyl alkyl is typically an organoaluminum compound having a carbon-Al bond, and the electron donor can be any of a variety of compounds including complex aromatic ethers, alkoxysilanes, amines and ketones, which can be used as external donors added to the transition metal component and the main group metal alkyl component or a suitable internal donor added to the transition metal component and the main group metal alkyl component in the synthesis of these components.

[0051] This document describes methods for preparing a solid catalyst component for use in a Ziegler-Natta catalyst, wherein the methods and catalysts do not contain carboxylic acid or anhydrides. Due to the absence of carboxylic acids and/or anhydrides, the catalysts provide high activity due to the absence of by-products of the reaction between the carboxylic acid and/or anhydride with magnesium compounds and TiCl ₄ , which may otherwise lead to deactivation of active sites during polymerization.

[0052] Catalyst/support morphology is a key factor to consider in any commercial polymer production process. Various techniques and methods are used to control the catalyst/support morphology. One such technique is the use of a surfactant in the formation of the support. Surfactants are compounds that reduce surface tension (or interfacial tension) between two liquids or between a liquid and a solid. Surfactants are typically polar organic compounds and may be removed from the solid catalyst or may partially remain on the surface of the catalyst. Surfactants can also act as a maintenance internal donor interacting with the main internal donor or act as a negative component deactivating the catalytic active site during polymerization.

[0053] In a first aspect, a process is provided for preparing a solid catalyst component for the production of a polyolefin, such as polypropylene. The methods include dissolving a magnesium halide compound in a mixture, wherein the mixture includes an epoxy compound, an organic phosphorus compound, and a first hydrocarbon solvent to form a homogeneous solution. The homogeneous solution is then treated with a first titanium compound in the presence of an organosilicon compound and optionally a non-phthalate electron donor and/or a support donor to form a solid precipitate. The solid precipitate is then treated with a second titanium compound in the presence of a non-phthalate electron donor to form a solid catalyst component. The method should not use carboxylic acids and anhydrides. In addition, the dissolution and processing of a homogeneous solution can be performed sequentially or simultaneously. Finally, the first and second titanium compounds are independently represented as:

Ti(OR) _g X _4-g

where each R is independently C ₁ -C ₄ alkyl; X is Br, CI or I; and g is 0, 1, 2, 3, or 4.

[0054] A magnesium halogen compound, an epoxy compound, and an organic phosphorus compound are reacted in the presence of a hydrocarbon solvent. The hydrocarbon solvent may include aromatic or non-aromatic solvents, or combinations thereof. In certain embodiments, the aromatic hydrocarbon solvent is selected from toluene and C ₂ -C ₂₀ alkylbenzene. In certain embodiments, the non-aromatic hydrocarbon solvent is selected from hexane and heptane. In an embodiment, the hydrocarbon solvent is a mixture of toluene and hexane. In another embodiment, the hydrocarbon solvent is a mixture of ethylbenzene and heptane. In certain embodiments, the ratio of non-aromatic solvent to aromatic solvent is from 10:90 to 90:10 wt.%, or from 30:70 to 70:30 wt.%, or from 40:60 to 65:35 wt.%, or from 50:50 to 45:55 wt%.

[0055] In a particular embodiment, the magnesium halide compound, the epoxy compound, and the organic compound are reacted in the presence of an organic solvent at a first temperature of about 25 to about 100°C to form a homogeneous solution. In another embodiment, the first temperature is from about 40 to about 90°C, or from about 50 to about 70°C. In a particular embodiment, the molar ratio of the magnesium compound to the alkyl epoxide is from about 0.1:2 to about 2:0.1, or from about 1:0.25 to about 1:4, or from about 1:0.9 to about 1: 2.2. In a certain embodiment, the Lewis molar ratio of magnesium compound to base is from about 1:0.1 to about 1:4, or from 0.5:1 to 2.0:1, or from 1:0.7 to 1:1 . 1. Without wishing to be bound by any theory, it is believed that a halogen atom is transferred from the magnesium compound to the epoxy compound to open the epoxy ring and form magnesium alkoxide compounds having a bond between the magnesium atom and the oxygen atom of the newly formed alkoxide group. During this process, the organic phosphorus compound forms a coordination bond with the Mg atom of the magnesium halogen compound and increases the solubility of the magnesium compounds present.

[0056] The method for producing a solid catalyst component may also include adding an organosilicon compound during or after dissolving the magnesium compound (Mg compound) in the organic solvent along with the epoxy compound. The silicone compound may be a silane, siloxane or polysiloxane. The organosilicon compound, in some embodiments, may be represented as formula (II):

In formula (II), each R may be H, alkyl or aryl; each R' may be H, alkyl, aryl or -SiR _n' (OR') _3-n where n is 0, 1, 2 or 3.

[0057] In some embodiments, the silicone compound is a monomeric or polymeric compound. The organosilicon compound may contain -Si-O-Si- groups within one molecule or between other molecules. Other exemplary silicone compounds include polydialkylsiloxane and/or tetraalkoxysilane. Such compounds may be used singly or in combination. The silicone compound can be used in combination with aluminum alkoxides and a first internal donor. In some embodiments, polydimethylsiloxane and/or tetraethoxysilane can be used.

[0058] The aluminum alkoxide mentioned above may have the formula Al(OR') ₃ where each R' individually is a hydrocarbon having up to 20 carbon atoms. This may include variants where each R' is individually methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, etc. It is believed that the organosilicon compound reacts with alumina to form a catalyst component, thus forming compounds containing Al-O-Si-O bonds. Therefore, these compounds can be obtained before the synthesis of the catalyst component and added directly to the process.

[0059] The organosilicon compound facilitates the precipitation of the solid catalyst component from solution. It is believed that the Si-O groups from the organosilicon compound form a coordination bond with the atoms of the Mg compound upon precipitation of the solid catalyst component, thus providing the desired morphology of the catalyst component. This type of coordination bond is usually weak. Therefore, when the solid catalyst component is treated with the second Ti compound and the second non-phthalate internal donor, they replace the organosilicon compound from the Mg compound, providing a catalyst component with high activity.

[0060] It is known that the precipitation of a solid catalyst component using Mg compounds in an epoxy medium containing anhydrides or organic acids leads to the formation of certain by-products containing derivatives formed as a result of the interaction of epoxy compounds with anhydrides or organic acids. These derivatives contain carbonyl groups strongly coordinated to the Mg- atom and may be present on the final catalyst component and lead to the deactivation of the active sites of the catalyst. The present catalyst systems, free of organic acids and/or anhydrides, overcome these shortcomings of earlier systems.

[0061] A magnesium halide compound in a homogeneous solution is treated with a titanium halide compound to form a solid precipitate. The temperature of the solution may be raised to a second temperature greater than the first temperature and a surface modifier may be added to control the phase morphology. In addition, when treated with a titanium halide compound, a non-phthalate electron donor is added. The first electron donor changes the viscosity and polarity of the solution, which affects the morphology of the deposited particles, in particular the particle size, particle shape and particle density.

[0062] As noted above, the method is carried out in the presence of non-phthalate donors. In one embodiment, a maintenance donor is used, which may also be referred to as a first non-phthalate donor. The supporting donor or first non-phthalate donor may be a diester, a succinate, a diester, an oxygenated electron donor such as an organic ester, a polyester, a polyhydroxy ester, a heterocyclic polyester, inorganic esters, an alicyclic polyester, and hydroxy-substituted esters having 2 to about 30 carbon atoms.

[0063] Exemplary first non-phthalate donors or maintenance donors include methyl formate; ethyl acetate; vinyl acetate; propyl acetate; octyl acetate; cyclohexyl acetate; ethyl propionate; methyl butyrate; ethyl valerate; ethyl stearate; methyl chloroacetate; ethyl dichloroacetate; methyl methacrylate; ethyl crotonate; dibutyl maleate; diethylbutylmalonate; diethyldibutylmalonate; ethylcyclohexanecarboxylate; diethyl 1,2-cyclohexanedicarboxylate; di-2-ethylhexyl 1,2-cyclohexanedicarboxylate; methyl benzoate; ethyl benzoate; propyl benzoate; butyl benzoate; octyl benzoate; cyclohexyl benzoate; phenyl benzoate; benzyl benzoate; methyltoluate; ethyltoluate; amyltoluate; ethyl ethyl benzoate; methylanisate; ethylanisate; ethylethoxybenzoate, γ-butyrolactone; δ-valerolactone; coumarin; phthalide; ethylene carbonate; ethyl silicate; butyl silicate; vinyltriethoxysilane; phenyltriethoxysilane; diphenyltriethoxysilane; diethyl 1,2-cyclohexanecarboxylate; diisobutyl 1,2-cyclohexanecarboxylate; diethyltetrahydrophthalate and nadic acid; diethyl ester; diethylnaphthalenedicarboxylate; dibutylnaphatlindicarboxylate; triethyl trimellitate and dibutyl trimellitate; esters of 3,4-furandicarboxylic acid; 1,2-diacetoxybenzene; 1-methyl-2,3-diacetoxybenzene; 2-methyl-2,3-diacetoxybenzene; 2,8-diacetoxynaphthalene; ethylene glycol dipivalate; butanediol pivalate; benzoylethyl salicylate; acetyl isobutyl salicylate; acetylmethyl salicylate; diethyl adipate; diisobutyl adipate; diisopropyl sebacate; di-n-butyl sebacate; di-n-octylsebacate; or di-2-ethylhexyl sebacate. In some embodiments, the first non-phthalate donor is methyl formate, butyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, isobutyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate, methyl methacrylate, ethyl crotonate, ethyl cyclohexamethylenecarboxylate , propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl p-methoxybenzoate, methyl p-methyl benzoate, ethyl p-tert-butyl benzoate, ethyl naphthoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methylanisate, ethylanisate, and ethyl ethoxybenzoate.

[0064] A combination of different support donors or first internal donors and solvents can be used to produce a catalyst component with a different morphology: i.e. granular and/or spherical. In particular, a granular-supported catalyst component can be produced using a monoester as the first internal donor with an aromatic or hydrocarbon solvent, and spherical-type catalyst components can be produced using two or three different internal donors (e.g., monoesters, dialkyl ether, and acrylates) in a mixture of two solvents (aromatic and hydrocarbons).

[0065] In one embodiment, a maintenance donor or first internal electron donor is used in conjunction with a second non-phthalate electron donor. The second non-phthalate electron donor may include compounds other than the first non-phthalate electron donor and is a diester, succinate, oxygenated electron donor compound such as an organic ester, polyester, polyhydroxy ester, heterocyclic polyester, inorganic esters, an alicyclic polyester; and hydroxy-substituted esters having from 2 to about 30 carbon atoms, or a compound having at least one ether group and at least one ketone group. In some embodiments, the second non-phthalate donor is selected from the group consisting of linear or cyclic diesters and non-phthalate aromatic diesters. In another embodiment, the second internal electron donor may be a dibenzoate, dialkylate and/or diarylate.

[0066] Additional exemplary second non-phthalate electron donors may include, alone or in combination with any of the above, compounds represented by the following formulas:

, или

, or

where each of the elements from R ¹ to R ³⁴ independently represents H, F, Cl, Br, I, OR ³³ , alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl or heteroarylalkyl; q is an integer from 0 to 12, wherein R ³³ is alkyl or heteroalkyl. Other non-phthalate donors may also include those listed as internal electron donors in US 9,045,570, incorporated herein by reference.

[0067] Examples of the magnesium halide compound include magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride. In one embodiment, the magnesium halogen compound is magnesium chloride.

[0068] Examples of epoxy compounds include, but are not limited to, glycidyl-containing compounds of the formula:

where "a" represents 1, 2, 3, 4 or 5, X represents F, Cl, Br, I or methyl, and R ^a represents H, alkyl, aryl or cyclyl. In one embodiment, the alkyl epoxide is epichlorohydrin. In some embodiments, the epoxy compound is a haloalkyl epoxide or a non-haloalkyl epoxide.

[0069] In some embodiments, the epoxy compound is selected from the group consisting of ethylene oxide; propylene oxide; 1,2-epoxybutane; 2,3-epoxybutane; 1,2-epoxyhexane; 1,2-epoxyoctane; 1,2-epoxydecane; 1,2-epoxydecane; 1,2-epoxytetradecane; 1,2-epoxyhexadecane; 1,2-epoxyoctadecane; 7,8-epoxy-2-methyloctadecane; 2-vinyloxirane; 2-methyl-2-vinyloxirane; 1,2-epoxy-5-hexene; 1,2-epoxy-7-octene; 1-phenyl-2,3-epoxypropane; 1-(1-naphthyl)-2,3-epoxypropane; 1-cyclohexyl-3,4-epoxybutane; 1,3-butadiene dioxide; 1,2,7,8-diepoxyoctane; cyclopentene oxide; cyclooctenoxide; α-pinene oxide; 2,3-epoxynorbornane; limonene oxide; cyclodecane epoxide; 2,3,5,6-diepoxynorbornane; styrene oxide; 3-methylstyrene oxide; 1,2-epoxybutylbenzene; 1,2-epoxyoctylbenzene; stilbene oxide; 3-vinyl styrene oxide; 1-(1-methyl1,2-epoxyethyl)-3-(1-methylvinylbenzene); 1,4-bis(1,2-epoxypropyl)benzene; 1,3-bis(1,2-epoxy-1-methylethyl)benzene; 1,4-bis(1,2-epoxy-1-methylethyl)benzene; epifluorohydrin; epichlorohydrin; epibromohydrin; hexafluoropropylene oxide; 1,2-epoxy-4-fluorobutane; 1-(2,3-epoxypropyl)-4-fluorobenzene; 1-(3,4-epoxybutyl)-2-fluorobenzene; 1-(2,3-epoxypropyl)-4-chlorobenzene; 1-(3,4-epoxybutyl)-3-chlorobenzene; 4-fluoro-1,2-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-1-cyclohexanone;2,3-epoxy-5-oxobicyclo[2.2.1]heptane; 3-(acetylcarbamoyl)styrene oxide; 4-(1,2-epoxypropyl)benzophenone; simple glycidyl methyl ether; simple butylglycidyl ether; simple 2-ethylhexylglycidyl ether; simple allylglycidyl ether; simple ethyl-3,4-epoxybutyl ether; simple glycidylphenyl ether; simple glycidyl-4-tert-butylphenyl ether; simple glycidyl-4-chlorophenyl ether; simple glycidyl-4-methoxyphenyl ether; simple glycidyl-2-phenylphenyl ether; simple glycidyl-1-naphthyl ether; simple glycidyl-2-phenylphenyl ether; simple glycidyl-1-naphthyl ether; a simple glycidyl-4-indolyl ether; a simple glycidyl-N-methyl-α-quinolon-4-yl ether; simple ethylene glycol diglycidyl ether; simple 1,4-butanediol diglycidyl ether; 1,2-diglycidyloxybenzene; 2,2-bis(4-glycidyloxyphenyl)propane; tris(4-glycidyloxyphenyl)methane; simple poly(oxypropylene)trioltriglycidyl ether; phenol novolac glycidic ether; 1,2-epoxy-4-methoxycyclohexane; 2,3-epoxy-5,6-dimethoxybicyclo[2.2.1]heptane; 4-methoxystyrene oxide; 1-(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; 1,2-epoxy-4-methoxycarbonylcyclohexane; 2,3-epoxy-5-butoxycarbonylbicyclo[2.2.1]heptane; ethyl 4-(1,2-epoxyethyl)benzoate; methyl 3-(1,2-epoxybutyl)benzoate; methyl 3-(1,2-epoxybutyl)-5-phenylbenzoate; N,N-glycidylmethylacetamide; Ν,N-ethylglycidylpropionamide; N,N-glycidylmethylbenzamide; N-(4,5-epoxypentyl)-N-methyl-benzamide; N,N-diglycylaniline; bis(4-diglycyldilaminophenyl)methane; poly(N,N-glycidylmethylacrylamide); 1,2-epoxy-3-(diphenylcarbamoyl)cyclohexane; 2,3-epoxy-6-(dimethylcarbamoyl)bicyclo[2.2.1]heptane; 2-(dimethylcarbamoyl)styrene oxide; 4-(1,2-epoxybutyl)-4-(dimethylcarbamoyl)biphenyl; 4-cyano-1,2-epoxybutane; 1-(3-cyanophenyl)-2,3-epoxybutane; 2-cyanostyrene oxide; and 6-cyano-1-(1,2-epoxy-2-phenylethyl)naphthalene.

[0070] Phosphoric acid esters such as trialkyl phosphate ester can be mentioned as an example of an organic phosphorus compound. Such compounds can be represented by the formula:

where R ₁ , R ₂ , and R ₃ are independently selected from the group consisting of methyl, ethyl, and linear or branched alkyl groups (C ₃ -C ₁₀ ). In one embodiment, the trialkyl phosphate ester is a tributyl phosphate ester.

[0071] A magnesium halogen compound, an epoxy compound, and an organic phosphorus compound are contacted in the presence of a hydrocarbon solvent. The hydrocarbon solvent may include aromatic or non-aromatic solvents, or combinations thereof. In certain embodiments, the aromatic hydrocarbon solvent is selected from toluene and C ₂ -C ₂₀ alkylbenzene. In certain embodiments, the non-aromatic hydrocarbon solvent is selected from hexane and heptane. In an embodiment, the hydrocarbon solvent is a mixture of toluene and hexane. In another embodiment, the hydrocarbon solvent is a mixture of ethylbenzene and heptane. In certain embodiments, the ratio of non-aromatic solvent to aromatic solvent is 10:90 to 90:10 wt%, or 30:70 to 70:30 wt%, or 40:60 to 65:35 wt%, magnesium compound , epoxy compound and organic compound or from 50:50 to 45:55 wt.%.

[0072] In a particular embodiment, the phosphorus halide is contacted in the presence of an organic solvent at a first temperature of about 25 to about 100°C to form a homogeneous solution. In another embodiment, the first temperature is from about 40 to about 90°C, or from about 50 to about 70°C. In a certain embodiment, the molar ratio of the magnesium compound to the alkyl epoxide is from about 0.1:2 to about 2:0.1, or from about 1:0.25 to about 1:4, or from about 1:0.9 to about 1: 2.2. In a certain embodiment, the Lewis molar ratio of magnesium compound to base is from about 1:0.1 to about 1:4, or from 0.5:1 to 2.0:1, or from 1:0.7 to 1:1 . Without wishing to be bound by any theory, it is believed that the halogen atom is transferred from the magnesium compound to the epoxy compound to open the epoxy ring and form magnesium alkoxide compounds having a bond between the magnesium atom and the oxygen atom of the newly formed alkoxide group. The organic phosphorus compound functions to increase the solubility of the magnesium-containing compounds present.

[0073] Once formed, the homogeneous solution may optionally be treated with a halogenating agent. The halogenating agent may be an organic or inorganic compound containing at least one halogen atom from which transfer to a magnesium atom may take place. In specific embodiments, the implementation of the halogenating agent contains chlorine. In particular embodiments, the halogenating agent is selected from arinoyl chlorides, alkanoyl chlorides, and alkyl chlorides. In certain embodiments, the halogenating agent is selected from benzoyl chloride, furoyl chloride, acetyl chloride, linear or branched alkyl chloride (C ₁ -C ₆ ), and alkanoyl chloride (C ₁ -C ₆ ). In one embodiment, the halogenating agent may be phthaloyl chloride. In other embodiments, however, the catalyst composition may be completely phthalate-free. In other embodiments, the halogenating agent is selected from HCl, TiCl ₄ R _n TiCl _4-n , SiCl ₄ , R _n SiCl _4-n and R _n AlCl _4-n , where R is an alkyl, cycloalkyl, aromatic, or alkoxy group, and n is an integer satisfying the formula 0<n<4. In certain embodiments, the ratio of halogenating agent to magnesium compound is at least 1:1 mol.

[0074] The molar ratio of the first titanium compound added to the magnesium halide compound may be from about 3:1 to about 15:1, or from about 5:1 to about 10:1.

[0075] The magnesium-containing solution formed by the reaction of a mashnium halide compound, an epoxy compound, an organic phosphorus compound, and an organosilicon compound may be in the form of dispersions, colloids, emulsions, and other two-phase systems. The homogeneous solution can be emulsified using conventional emulsification methods, including one or more of the following: agitation and/or agitation and/or mixing and/or low and/or high shear mixing and/or use of mixing nozzles and/or atomizers and/or membrane emulsification techniques and/or ultrasonic grinding and/or vibration and/or microfluidization, and the like.

[0076] The magnesium-containing compound phase is dispersed in the solvent phase. The size and shape of the droplets forming the magnesium phase can be controlled through a combination of temperature control, solvent amount adjustment, agitation energy adjustment, and inclusion/exclusion of various surface modifier additives. The temperature when adding titanium compounds is from about -35°C to about 15°C. After phase separation and/or addition of a titanium compound, the temperature of the mixture rises to higher values. In one embodiment, the higher temperature is from about 15°C to about 100°C. In another embodiment, the temperature is from about 20°C to about 90°C, or from about 50°C to about 85°C, or from about 60°C to 85°C. In one embodiment, at a mixture temperature between a lower and a higher temperature, a surface modifier is added to facilitate the formation of spherical magnesium phase droplets surrounded by a solvent phase. In other words, the addition of a surface modifier can help control the morphology of the droplets of the magnesium phase.

[0077] When a titanium halide compound is added to a magnesium solution that contains linked magnesium alkoxide molecules or groups of molecules with a coordinating organic phosphorus compound, an organosilicon compound, and solvent molecules, a reaction occurs between the magnesium alkoxide and the titanium halide compound to form magnesium halide and halide complexes magnesium with a titanium halide compound and titanium alkoxide.

[0078] At the beginning of the reaction (typically at low temperature: (-35 to -20°C)) the newly formed associated groups of magnesium halide molecules and complexes of magnesium halide with the titanium halide compound and titalkoxide are present in the "oil phase droplets" (liquid with a higher viscosity than other environments (solvents)). As the reaction continues (the reaction temperature rises to 0-40°C), crystallization of magnesium halide molecules and complexes of magnesium halide with a titanium halide compound and titanium alkoxide occurs in the oil phase. The crystallization process is usually completed at a temperature of 50-100°C, forming a solid intermediate catalyst component.

[0079] The morphology of the solid intermediate catalyst component (and catalyst component) (particle size and shape) depends on many factors, including solvent polarity, the presence of precipitation control agents, surfactants, additives, and others.

[0080] In particular, the size and shape of the droplets forming the magnesium phase can be controlled through a combination of temperature adjustment, solvent amount, stirring energy adjustment, and inclusion/exclusion of various surface modifier additives and precipitation temperature.

[0081] The morphology of the catalyst component and the characteristics of the catalyst are sufficiently controlled by the addition of a supporting electron donor (or donors). The supporting electron donor is an organic compound containing an oxygen atom and capable of forming a coordination bond with the magnesium atom in the "oil phase drops", and allowing control over the deposition of a solid catalyst component with the desired morphology.

[0082] In one embodiment, the supporting electron donor controls only the deposition process and the morphology of the catalyst component and is not included in the catalyst component.

[0083] In another embodiment, the supporting electron donor controls the deposition process and the morphology of the catalyst component and is included in the catalyst component. Therefore, both the supporting electron donor and the electron donor determine the performance of the catalyst during polymerization. Supporting electron donors are usually weaker than electron donors.

[0084] The combination of the organosilicon compound and the supporting electron donor during the deposition of the solid catalyst intermediate allows the creation of a catalyst component with the desired granular or spherical shape morphology.

[0085] The morphology of the granular catalyst component can be obtained with a raspberry-like shape, a rounded raspberry-like shape, a rounded shape, and a substantially spherical shape by varying the organosilicon compounds supporting electron donors and the precipitation conditions of the solid intermediate catalyst. The particle size of the catalyst component is from about 5 microns to about 70 microns (based on 50% by volume) and depends on the precipitation conditions (temperature, stirring speed, solvent, etc.) and the type and amount of supporting donor.

[0086] The supporting electron donor is selected from carboxyl monoesters, methyl formate, butyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, isobutyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate, methyl cyclotone, ethyl methacrylate methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl p-methoxybenzoate, methyl p-methyl benzoate, ethyl p-tert-butyl benzoate, ethyl naphthoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methylanisate, ethylanisate and ethylethoxybenzoate.

[0087] The combination of a magnesium halide compound, an epoxy compound, an organic phosphorus compound, a titanium halide, and a hydrocarbon solvent can create an emulsion with two phases: a solvent phase and a magnesium titanium oil phase; and with proper choice of solvent and reagents. This method can be used to obtain a catalyst component with a spherical morphology. Phase separation is accomplished by selecting the appropriate solvent. The choice of solvent includes consideration of one or more differences in the physical properties of polarity, density, and surface tension, among others causing a separation between the solvent and the magnesium phase. Toluene is an organic solvent diluent that is configured to form solid titanium catalyst components; however, the use of toluene does not always promote the formation of two phases. In addition, it has been found that other alkylbenzene compounds, hexane and heptane as solvent, or a mixture of aromatics and hydrocarbons can be used, resulting in the formation of a solvent phase and a magnesium phase. The two phases are retained after the subsequent addition of the titanium compound. The combination of two or more different support donors allows the production of a spherical type solid catalyst component.

[0088] A simple di-(C ₁ -C ₁₂ )-alkyl ether with a combination of acrylates (surface modifier) is used as a supporting electron donor to obtain a spherical type catalyst component.

[0089] General examples of a surface modifier include polymeric surfactants such as polyacrylates, polymethacrylates, polyalkyl methacrylates, or any other surfactant that can effect stabilization and emulsification. Surfactants are known in the art, and many surfactants are described in McCutcheon's "Volume I: Emulsifiers and Detergents", 2001, North American Edition, Manufacturing Confectioner Publishing Co., Glen Rock, NJ, and in particular, on page 1-233, which describes a number of surfactants and is therefore incorporated herein by reference. 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, and the like. Moreover, the acrylate and methacrylate polymers may contain monomers other than acrylate and methacrylate monomers, as long as the polymeric surfactant contains at least about 40% by weight of acrylate and methacrylate monomers.

[0090] Examples of monomers that can be polymerized using known polymerization techniques into polymeric surfactants include one or more of the following: acrylate; tert-butyl acrylate; n-hexyl acrylate; methacrylate; methyl methacrylate; ethyl methacrylate; propyl methacrylate; isopropyl methacrylate; n-butyl methacrylate; t-butyl methacrylate; isobutyl methacrylate; pentyl methacrylate; isoamyl methacrylate; n-hexyl methacrylate; isodecyl methacrylate; lauryl methacrylate; stearyl methacrylate; isooctyl acrylate; lauryl acrylate; stearyl acrylate; cyclohexyl acrylate; cyclohexyl methacrylate; methoxyethyl acrylate; isobenzylacrylate; isodecyl acrylate; n-dodecyl acrylate; benzyl acrylate; isobornyl acrylate; isobornyl acrylate; isobornyl methacrylate; 2-hydroxyethyl acrylate; 2-hydroxypropylacrylate; 2-methoxyethyl acrylate; 2-methoxybutyl acrylate; 2-(2-ethoxyethoxy)ethyl acrylate; 2-phenoxyethyl acrylate; tetrahydrofurfuryl acrylate; 2-(2-phenoxyethoxy)ethyl acrylate; methoxylated tripropylene glycol monoacrylate; 1,6-hexanediol diacrylate; ethylene glycol dimethacrylate; diethylene glycol dimethacrylate; triethylene glycol dimethacrylate; polyethylene glycol dimethacrylate; butylene glycol dimethacrylate; trimethylolpropane-3-ethoxylate triacrylate; 1,4-butanediol diacrylate; 1,9-nonanediol diacrylate; neopentyl glycol diacrylate; tripropylene glycol diacrylate; tetraethylene glycol diacrylate; heptapropylene glycol diacrylate; trimethylol propane triacrylate; ethoxylated trimethylol propane triacrylate; pentaerythritol triacrylate; triethylopropane trimethacrylate; tripropylene glycol diacrylate; pentaerythritol tetraacrylate; glyceryl propoxy triacrylate; tris(acryloyloxyethyl)phosphate; 1-acryloxy-3-methacryloxyglycerol; 2-methacryloxy-N-ethylmorpholine; and allyl methacrylate, etc.

[0091] In certain embodiments, the surface modifier is selected from poly((C ₁ -C ₆ )alkyl)acrylate, poly((C ₁ -C ₆ )alkyl)methacrylate, and poly((C ₁ -C ₆ )alkyl) copolymer acrylate; and poly((C ₁ -C ₆ )alkyl)methacrylate. In embodiments, the ratio of surface modifier to magnesium halide compound is 1:10 to 2:1 wt%, or 1:5 to 1:1 wt%.

[0092] Examples of commercially available polymeric surfactants include those bearing the trade designation VISCOPLEX® and marketed by RohMax Additives, GmbH, including those with product designations 1-254, 1-256, and those with the trade designations CARBOPOL® and PEMULEN® marketed by Noveon/Lubrizol.

[0093] The polymeric surfactant is typically added in admixture with an organic solvent. When added as a mixture with an organic solvent, the weight ratio of surfactant to organic solvent is from about 1:20 to about 2:1. In another embodiment, the weight ratio of surfactant to organic solvent is from about 1:10 to about 1:1. In yet another embodiment, the weight ratio of surfactant to organic solvent is from about 1:4 to about 1:2.

[0094] Treatment with a second titanium compound may include adding a second titanium halide compound and a second electron donor to a solution containing a precipitate to form a solid catalyst composition, and then bringing the temperature of the solid catalyst composition to between 80°C and 150°C and further processing with the second titanium compound to form a solid catalyst component. In one embodiment, the treatment may include more than one second electron donor. For example, when treated with a second titanium compound, a plurality of electron donors may occur. In another embodiment, treatment with a second titanium compound includes the steps of filtering off the precipitate, adding the second titanium compound and a second electron donor in the solvent to the precipitate to form a solid catalyst composition, and bringing the temperature of the solid catalyst composition to between 80°C and 150°C. In another embodiment, the treatment with the second titanium compound comprises the steps of adding the second titanium compound to the solution containing the precipitate; and then bringing the temperature of the composition of the solid catalyst to values from 80°C to 150°C and further processing with a second titanium compound and a second electron donor to form a solid catalyst component.

[0095] Treatment with a second titanium compound may include adding a second titanium halide compound and a second electron donor to a solution containing a precipitate to form a solid catalyst composition, and then bringing the temperature of the solid catalyst composition to between 80°C and 150°C and further processing with the second compound to form a solid catalyst component. In another titanium, filtering off the precipitate, adding a second titanium compound and a second electron donor in the solvent to the precipitate to form a solid catalyst composition, and adjusting the temperature of the solid catalyst composition to between 80°C and 150°C. In another embodiment, the treatment with the second titanium compound includes the steps of adding the second titanium compound to the solution containing the precipitate; and then bringing the temperature of the composition of the solid catalyst to values from 80°C to 150°C and further processing with a second titanium compound and a second electron donor to form a solid catalyst component.

[0096] With this treatment, the supporting electron donor is partially or completely removed from the catalyst component, and the electron donors regulate the coordination bond with magnesium halides, which leads to an increase in catalytic activity.

[0097] In one embodiment, for example, a solid catalyst can be made in accordance with the present invention by combining a magnesium halide, such as magnesium chloride, with an epoxy compound. The epoxy compound, for example, may be epichlorohydrin. The magnesium halide and epoxy compound may be combined in a molar ratio of from about 0.5:1 to about 1:0.5, for example, from about 0.8:1.2 to about 1.2:0.8. In one embodiment, for example, the magnesium halide and the epoxy compound can be combined in a molar ratio of about 1 to 1. The magnesium halide and the epoxy compound can be combined in the presence of a phosphate, such as tributyl phosphate, and a solvent, such as toluene. In addition, an aluminum alkoxide surfactant such as aluminum alkoxide/isopropoxide may be present.

[0098] In the above composition, a monoester such as ethyl benzoate and a silicate such as tetraethylorthosilicate can be added in addition to titanium halide such as titanium tetrachloride to form a precipitate. In one embodiment, magnesium halide complexes with the monoester, titanium chloride, can be formed, including Cl ₃ -Ti-O-CH(CH ₂ Cl) ₂ .

[0099] The above precipitate may then be treated with a second internal donor, such as an aryl diester, and optionally in the presence of a titanium halide. The resulting solid catalyst component can be washed and used as desired.

[00100] In general, the resulting catalyst component contains a magnesium halide, a titanium halide, a first internal donor or support donor, and a second internal donor. In addition, the solid catalyst component may contain a residual amount of aluminum alkoxide, organosilicon compound and phosphorus compound. For example, the amount of aluminum alkoxide and/or silicone present in the final catalyst can typically be greater than about 0.001% by weight, such as greater than about 0.01% by weight, such as greater than about 0.1% by weight, and substantially less than about 1% by weight, such as less than about 0.5% by weight, such as less than about 0.3% by weight. The solid catalyst component may also contain a phosphorus compound, typically in an amount greater than about 0.1% by weight, such as greater than about 0.2% by weight, such as greater than about 0.3% by weight, and substantially less than about 1% by weight, such as less than about 0.5% by weight.

[00101] In an alternative embodiment, especially to form spherical particles, the first internal electron donor may include not only a monoester but also a dialkyl ether. In addition, the first internal electron donor may be combined in the catalyst composition with a spherical stimulating surfactant such as an acrylate surfactant. In one embodiment, for example, the surfactant may comprise a polyalkyl methacrylate.

[00102] The solid catalyst component of the present invention is produced with many useful properties and characteristics. For example, in one embodiment, the catalyst component can be made with a relatively large surface area. For example, the BET catalyst surface area may be greater than about 100 m ² /g, such as greater than about 200 m ² /g, such as greater than about 300 m ² /g, such as greater than about 400 m ² /g, and typically less than about 700 m ² /g, such as less than about 600 m ² /g.

[00103] A solid catalyst component can then be used with an inorganic or organic compound, such as a silicone compound or an aluminum compound.

[00104] In addition to the solid catalyst component, the catalyst system may contain at least one organoaluminum compound. As an organoaluminum compound, compounds can be used whose molecules contain at least one aluminum-carbon bond. Examples of organoaluminum compounds include compounds having the formula:

AlR _n X ₃ -n

where, R is independently a hydrocarbon group typically having from 1 to about 20 carbon atoms, X is a halogen atom, and 0<n<3.

[00105] Specific examples of organoaluminum compounds include, but are not limited to, various forms of trialkylaluminum such as triethylaluminum, tributylaluminum, and trihexylaluminum; various forms of trialkenyl aluminum such as triisoprenyl aluminum; 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 forms of partially hydrogenated alkylaluminum such as ethylaluminum dihydride and propylaluminum dihydride.

[00106] The organoaluminum compound may be used in the catalyst system in an amount such that the mole ratio of aluminum to titanium (from the solid catalyst component) is from about 5 to about 1. In another embodiment, the molar 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.

[00107] In addition to the solid catalyst component, the catalyst system may contain one or more selectivity control agents (SCAs). In one embodiment, the selectivity control agent may contain one or more silicone compounds, such as one or more silane compounds. The organosilicon compound can also function 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.

[00108] An organosilicon compound used as an external electron donor, which serves as one component of the Ziegler-Natta catalyst system for olefin polymerization, improves the ability to obtain a polymer (at least part of which is a polyolefin) having a controlled molecular weight distribution and controlled crystallinity and while maintaining high efficiency in relation to catalytic activity.

[00109] The organosilicon compound is used in the catalyst system in an amount such that the mole ratio of organoaluminum compound to organosilicon compound is from about 2 to about 90. In another embodiment, the molar ratio of organoaluminum compound to organosilicon compound is from about 5 to about 70. In still another in one embodiment, the molar ratio of organoaluminum to organosilicon is from about 7 to about 35.

[00110] In one embodiment, the organosilicon compound is represented by the formula:

R _n Si(OR') _4-n

where each R and R independently represent a hydrocarbon group, and n is 0<n<4.

[00111] Конкретные примеры кремнийорганического соединения включают, помимо прочего, триметилметоксисилан, триметилэтоксисилан, диметилдиметоксисилан, диметилдиэтоксисилан, диизопропилдиметоксисилан, диизобутилдиметоксисилан, трет-бутилметилдиметоксисилан, трет-бутилметилдиэтоксисилан, трет-амилметилдиэтоксисилан, дициклопентилдиметоксисилан, дифенилдиметоксисилан, фенилметилдиметоксисилан, дифенилдиэтоксисилан, бис-о-толидиметоксисилан, бис-м-толидиметоксисилан, бис-п-толидиметоксисилан, бис-п-толидиэтоксисилан, бисэтилфенилдиметоксисилан, дициклогексилдиметоксисилан, циклогексилметилдиметоксисилан, циклогексилметилдиэтоксисилан, этилтриметоксисилан, этилтриэтоксисилан, винилтриметоксисилан, метилтриметоксисилан, н-пропилтриэтоксисилан, децилтриметоксисилан, децилтриэтоксисилан, фенилтриметоксисилан, γ-хлорпропилтриметоксисилан, метилтриэтоксисилан, этилтриэтоксисилан, винилтриэтоксисилан, трет-бутилтриэтоксисилан, н-бутилтриэтоксисилан, изобутилтриэтоксисилан, фенилтриэтоксисилан, γ-аминопропилтриэтоксисилан, хлортриэтоксисилан, этилтриизопропоксисилан, винилтрибутоксисилан, циклогексилтриметоксисилан, циклогексилтриэтоксисилан, 2-норборнантриметоксисилан, 2-норборнантриэтоксисилан, 2-норборнанметилдиметоксисилан, этилсиликат, бутилсиликат, триметилфеноксисилан и метилтриаллилоксисилан.

[00112] In another embodiment, the silicone compound is represented by the formula:

where 0≤m<3, for example, 0≤m<2; and R is independently a cyclic hydrocarbon or substituted cyclic hydrocarbon group. Specific examples of the R group 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; 1,3-cyclopentadienyl; 2,4-cyclopentadienyl; 1,4-cyclopentadienyl; 2-methyl-1,3-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; 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 groups; cyclohexyl; methylcyclohexyl; ethylcyclohexyl; propylcyclohexyl; isopropylcyclohexyl; n-butylcyclohexyl; tert-butylcyclohexyl; dimethylcyclohexyl; and trimethylcyclohexyl.

[00113] In the formula: SiRR' _m (OR") _3-m , R' and R" are identical or different, and each is a hydrocarbon. For example, R' and R" are alkyl, cycloalkyl, aryl and aralkyl groups having 3 or more carbon atoms. In addition, R and R' may be bridged by an alkyl group, etc. General examples of organosilicon compounds are compounds of formula (IV) 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, in particular a methyl or ethyl group.

[00114] Specific examples of organosilicon compounds of the formula SiRR' _m (OR") _3-m 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-cyclopentyl) 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(1-methyl-1-cyclopentylethyl)dimethoxysilane, cyclopentylcyclopentenyldimethoxysilane, cyclopentylcyclopentadienyldimethoxysilane, diindenyldimethoxysilane, bis(1,3-dimethyl-2-indenyl) dimethoxysilane, cyclopentadienylindenyldimethoxysilane, difluorenyldimethoxysilane, cyclopentylfluorenyldimethoxysilane and indenylfluorenyldimethoxysilane; моноалкоксисиланы, такие как трициклопентилметоксисилан, трициклопентенилметоксисилан, трициклопентадиенилметоксисилан, трициклопентилэтоксисилан, дициклопентилметилметоксисилан, дициклопентилэтилметоксисилан, дициклопентилметилэтоксисилан, циклопентилдиметилметоксисилан, циклопентилдиэтилметоксисилан, циклопентилдиметилэтоксисилан, бис(2,5-диметилциклопентил)циклопентилметоксисилан, дициклопентилциклопентенилметоксисилан, дициклопентилциклопентадиенилметоксисилан и диинденилциклопентилметоксисилан; and ethylenebis-cyclopentyldimethoxysilane.

[00115] In one embodiment, one or more selectivity control agents are present in the catalyst system. Particularly preferred selectivity control agents include dimethyldimethoxysilane, n-propyltrimethoxysilane, methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane, n-propyltriethoxysilane, bis(perhydroisoquinoline)dimethoxysilane, 2,2,6,6-tetramethylpiperidine, or mixtures thereof.

[00116] In one embodiment, one or more selectivity control agents can be used in combination with an activity limiting agent (ALA). The activity limiting agent may be an aliphatic ester. The aliphatic ester may be a C ₄ -C ₃₀ aliphatic acid ester, may be a mono or polyester (di or more) ester, may be straight or branched chain, may be saturated or unsaturated, and may be any combination of them. The C ₄ -C ₃₀ fatty acid ester may also be substituted with one or more heteroatom-containing substituents from group 14, 15, or 16. Non-limiting examples of suitable C ₄ -C ₃₀ fatty acid esters include C _1-20 alkyl esters of aliphatic C _4-30 monocarboxylic acids, C _1-20 alkyl esters of aliphatic C _8-20 monocarboxylic acids, C _1-4 allyl mono- and diesters of aliphatic C _4-20 monocarboxylic acids and dicarboxylic acids, alkyl diesters aliphatic C _5-20 monocarboxylic acids and dicarboxylic acids; and C _4-20 alkyl mono- or polycarboxylate derivatives of C _2-100 (poly) glycol or C _2-100 (poly) glycol ethers. In a further embodiment, the C ₄ -C ₃₀ aliphatic acid ester can be isopropyl, myristate, di-n-butyl sebacate, (poly)(alkylene glycol) mono- or diacetates, (poly)(alkylene glycol) mono- or di-myristates, (poly)(alkylene glycol) mono- or di-laurates, (poly)(alkylene glycol) mono- or di-oleates, glyceryl tri(acetate), glyceryl triesters of _C2-10 aliphatic carboxylic acids, and _mixtures thereof. In a further embodiment, the C ₄ -C ₃₀ aliphatic ester is isopropyl myristate or di-n-butyl sebacate.

[00117] In one embodiment, ALA is a non-ester composition. As used herein, a "non-ester composition" is an atom, molecule, or compound that does not contain an ester functional group. In other words, the "non-ester composition" must not contain the following functional group.

[00118] In one embodiment, the non-ester composition may be a dialkyl diester compound or an amine compound. The dialkyl diester compound may be represented by the following formula,

[00119] where R ¹ R ⁴ independently of each other represent an alkyl, aryl or aralkyl group having up to 20 carbon atoms, which may optionally contain a heteroatom from group 14, 15, 16 or 17, provided that R' and R ² may represent a hydrogen atom. Non-limiting examples of suitable dialkyl diester compounds include dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, methyl butyl ether, methylcyclohexyl ether, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1 ,3-dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-ethyl-2-n-butyl-1,3-dimethoxypropane, 2 -n-propyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3 -dimethoxypropane, 2-n-propyl-2-cyclohexyl-1,3-diethoxypropane and 9,9-bis(methoxymethyl)fluorene. In a further embodiment, the dialkyl diester compound is 2,2-diisobutyl-1,3-dimethoxypropane.

[00120] In one embodiment, the non-ester composition is an amine compound. Non-limiting examples of suitable amine compounds include 2,6-substituted piperidines such as 2,6-dimethylpiperidine and 2,2,6,6-tetramethylpiperidine, as well as 2,5-substituted piperidines. In a further embodiment, the piperidine compound is 2,2,6,6-tetramethylpiperidine.

[00121] For ALA that contains more than one carboxylate group, all carboxylate groups are considered effective components. For example, a sebacate molecule containing two carboxylate functional groups is considered to be two effective functional molecules.

[00122] As described above, in one embodiment, the activity limiting agent is a C4-C30 aliphatic acid ester. In an alternative embodiment, the activity limiting agent may comprise a diester or polymer of an alkylene glycol ester of a C4-C30 aliphatic acid. Specific activity limiting agents that may be included in the catalyst system include isopropyl myristate, di-n-butyl sebacate, ethyl 4-ethoxybenzoate, propoxylated (POE) coconut oil fatty acid esters, for example, containing 10 to 20 moles of POE, ester of poly(ethylene)glycol and fatty acids of coconut oil.

[00123] A particularly preferred combination of SCA/ALA components is a mixture of an alkoxysilane selected from the group consisting of dicyclopentyldimethoxysilane, methylcyclohexyldimethoxysilane and n-propyltrimethoxysilane with an ester that is isopropyl myristate, vi(n-butyl)sebacate, (poly)(ethylene glycol )monolaurate, (poly)(alkene glycol) dioleate, (poly)(ethylene glycol)methyl ether laurate, glyceryl tri(acetate), or a mixture thereof.

[00124] Preferred SCA/ALA mixtures in accordance with the invention are mixtures containing from 1 to 99.9, more preferably from 30 to 99, and most preferably from 50 to 98 equivalent percent of one or more ALA compounds, and, accordingly, from 99 to 0.1, more preferably 70 to 1, most preferably 50 to 2 equivalent percent of one or more alkoxysilane compounds. Regardless of the above range of components, one skilled in the art will appreciate that the normalized polymerization activity at elevated temperature should be lower than that obtained at 67°C and lower than that obtained if alkoxysilane alone were used in the same total molar amount of SCA.

[00125] The total molar amount of the SCA mixture used in the present invention, based on the moles of the transition metal, is preferably 0.1 to 500, more preferably 0.5 to 100, and most preferably 1.0 to 50. With respect to amount of ALA, the corresponding transition metal molar ratio is preferably 1 to 10,000, preferably 2 to 1,000, and most preferably 5 to 100.

[00126] The morphology of the catalyst particles indicates the morphology of the polymer particles produced from them. Three polymer particle morphology parameters (sphericity, symmetry and aspect ratio) can be determined using the Camsizer instrument.

Features of Camsizer:

Where:

P is the measured perimeter/circumference of the projection of the particle; And

A is the measured area covered by the projection of the particle.

P is the measured perimeter/circumference of the projection of the particle; And

A is the measured area covered by the projection of the particle.

[00127] For an ideal sphere, SPHT is defined as 1. Otherwise, this value is less than 1.

[00128] Symmetry is defined as:

то Symm меньше 0,5where r ₁ and r ₂ represent the distance from the center of the region to the boundaries in the measurement direction. For asymmetric particles, Symm is less than 1. If the center of the region is outside the particle, i.e.

then Symm is less than 0.5

[00129] x _Ma =r ₁ +r2, "Symm" is the minimum value of the measured set of symmetry values from different directions.

[00130] Aspect ratio:

where x _{c min} and x _{Fe max} from the measured set of x _c and x _Fe values.

[00131] Catalyst morphological characteristics, such as aspect ratio ("B/L3"), can be used to determine polymer morphological characteristics. In some methods, the aspect ratio is greater than 0.6, or greater than 0.7, or greater than 0.8, or greater than 0.90.

[00132] The particle size of the resulting catalyst component may vary depending on process conditions and the desired result. In general, the D ₅₀ particle size may be greater than about 5 microns, such as greater than about 10 microns, such as greater than about 20 microns, such as greater than about 30 microns, such as greater than about 40 microns, such as greater than less than about 50 microns, such as greater than about 60 microns, and typically less than about 70 microns, such as less than about 50 microns, such as less than about 30 microns, such as less than about 25 microns.

[00133] The polymerization of olefins can be carried out in the presence of the catalyst systems prepared and described above. In accordance with the present invention can carry out the polymerization of various olefins. For example, the catalyst systems of the present invention can be used to polymerize ethylene, propylene, and the like. Catalyst systems can also be used to produce homopolymers and copolymers. In general, an olefin monomer such as propylene is contacted with the catalyst system described above under suitable conditions to form the desired polymer products. In one embodiment, the main polymerization is preceded by a prepolymerization, described below. In another embodiment, polymerization is carried out without prepolymerization. In yet another embodiment, the formation of the polypropylene copolymer is carried out using at least two polymerization zones.

[00134] A particular advantage is that the catalyst component of the present invention is well suited for use in all of the various polymerization processes. For example, the catalyst component of the present invention can be used in serpentine-type bulk polymerization processes, gas phase processes, and the like. The catalyst component can also be used in a slurry process.

[00135] During prepolymerization, the solid catalyst component is typically used in combination with at least a portion of the organoaluminum compound. This can be done in the presence of some or all of the organosilicon compound (external electron donor compound). The concentration of the catalyst system used in the prepolymerization can be much higher than in the reaction system for the main polymerization.

[00136] In prepolymerization, the concentration of solid catalyst components is typically from about 0.01 to about 200 millimoles, preferably from about 0.05 to about 100 millimoles, when calculated in titanium atoms per liter of inert hydrocarbon medium, described below. In one embodiment, the prepolymerization is carried out by adding propylene or a mixture of propylene with another olefin and the aforementioned catalyst system ingredients to an inert hydrocarbon medium and polymerizing the olefin under mild conditions.

[00137] 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 their mixtures. In certain embodiments, a liquid olefin may be used instead of part or all of the inert hydrocarbon medium.

[00138] The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

[00139] The reaction temperature in the prepolymerization should be sufficient so that the resulting prepolymer is substantially insoluble 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.

[00140] A molecular weight control agent, such as hydrogen, can optionally be used during the prepolymerization. The molecular weight control agent is used in such an amount that the polymer obtained during the prepolymerization has an intrinsic viscosity, measured in decalitres at a temperature of 135 °C, of at least about 0.2 dl/g or from about 0.5 to 10 dl /G.

[00141] In one embodiment, the prepolymerization is carried out so as to obtain from about 0.1 g to about 1000 g of polymer per gram of solid catalyst component of the catalyst system. In another embodiment, the prepolymerization is carried out so as to obtain from about 0.3 g to about 500 g of polymer per gram of solid catalyst component. If too much polymer is produced during the prepolymerization, the efficiency of producing an olefin polymer during the main polymerization may in some cases be reduced, and during casting of the resulting olefin polymer into a film or other product, fisheye defects often form in the cast product. The prepolymerization can be carried out in a batch or continuous mode.

[00142] After carrying out the prepolymerization as described above, or without carrying out the prepolymerization, the main polymerization of propylene is carried out in the presence of the above-described polymerization catalyst system formed from a solid catalyst component, an organoaluminum compound, and an organosilicon compound (external electron donor compound).

[00143] Examples of olefins that can be used in the base polymerization with polypropylene are α-olefins having from 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-hexene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, 1-tetradecene, 1-eicosene and vinylcyclohexane. In illustrative methods, these α-olefins can be used alone or in any combination.

[00144] In one embodiment, propylene is homopolymerized or an olefin mixture containing propylene as a major component is copolymerized. When using a mixture of olefins, the proportion of propylene as the main component is usually at least about 50 mol.% or at least about 70 mol.%.

[00145] The implementation of pre-polymerization allows you to control the degree of activity of the catalyst system for the main polymerization. This optimization typically results in a polymer powder having a high bulk density. In addition, when prepolymerization is carried out, the particle shape of the resulting polymer becomes spherical, and in the case of slurry polymerization, the slurry has excellent performance, while in the case of gas phase polymerization, the seed polymer layer has excellent performance. In addition, in these embodiments, a polymer with a high isotactic index can be produced with high catalytic efficiency by polymerizing an α-olefin having at least 3 carbon atoms. Accordingly, when producing a propylene copolymer, the resulting copolymer powder or copolymer is easy to process.

[00146] In the copolymerization of propylene, a polyunsaturated compound such as a conjugated diene or a non-conjugated diene can be used as the comonomer. Examples of comonomers include styrene, butadiene, acrylonitrile, acrylamide, α-methylstyrene, chlorostyrene, vinyltoluene, divinylbenzene, diallyl phthalate, alkyl methacrylates, and alkyl acrylates. In one embodiment, the comonomers include thermoplastic and elastomeric monomers. The main polymerization of the olefin is carried out, as a rule, in the gaseous or liquid phase. In one embodiment, the polymerization (basic polymerization) uses a catalyst system containing a solid catalyst component in an amount of from about 0.001 to about 0.75 millimoles, calculated as the number of Ti atoms per liter of polymerization zone volume, an organoaluminum compound in an amount of from about 1 to about 2000 moles per mole of titanium atoms in the solid catalyst component and organosilicon compound in an amount of from about 0.001 to about 10 moles, calculated as the number of Si atoms in the organosilicon compound per mole of metal atoms in the organoaluminum compound. In another embodiment, a catalyst system is used for polymerization containing a solid catalyst component in an amount of from about 0.005 to about 0.5 millimoles, calculated as the number of Ti atoms per liter of volume of the polymerization zone, an organoaluminum compound in an amount of from about 5 to about 500 mols per mol titanium atoms in the solid catalyst component; and an organosilicon compound in an amount of from about 0.01 to about 2 moles, calculated as the number of Si atoms in the organosilicon compound per mole of metal atoms in the organoaluminum compound. In another embodiment, the polymerization uses a catalyst system containing an alkyl benzoate derivative in an amount of from about 0.005 to about 1 mole, calculated as the number of moles of Si atoms in the organosilicon compound per mole of metal atoms in the organoaluminum compound.

[00147] When partially using an organoaluminum compound and an organosilicon compound for prepolymerization, the prepolymerized catalyst system is used along with the remaining components of the catalyst system. The prepolymerized catalyst system may contain a prepolymerized product.

[00148] The use of hydrogen during polymerization assists and assists in controlling the molecular weight of the resulting polymer, and the resulting polymer can have a high melt flow rate (MFR). 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.

[00149] In one embodiment, the polymerization temperature is from about 20°C to about 170°C. In another embodiment, the polymerization temperature is from about 50°C to about 165°C. In one embodiment, the polymerization pressure typically ranges from atmospheric pressure to about 100 kg/cm ² . In another embodiment, the polymerization pressure is typically from about 2 kg/cm ² to about 50 kg/cm ² . The main polymerization can be carried out in batch, semi-continuous or continuous mode. The polymerization can also be carried out in two or more stages under different reaction conditions.

[00150] The olefin polymer thus obtained may be a homopolymer, a random copolymer, a block copolymer, or an impact copolymer. The impact copolymer contains a carefully blended blend of polyolefin homopolymer and polyolefin rubber. Examples of polyolefin rubbers include ethylene-propylene rubber (EPR) such as ethylene-propylene-methylene (EPM) rubber and ethylene-propylene-diene-methylene terpolymer (EPDM) rubber.

[00151] The olefin polymer obtained using this catalyst system contains a very small amount of an amorphous polymer component and, therefore, a small amount of a component soluble in a hydrocarbon solvent. Accordingly, the film cast from the resulting polymer has a low surface tack.

[00152] The polyolefin obtained during polymerization is characterized by excellent particle size distribution, particle diameter and bulk density, and the resulting copolyolefin has a narrow composition distribution. The impact copolymer may have excellent flowability, low temperature resistance, and a desirable balance between stiffness and elasticity.

[00153] In one embodiment, propylene and an α-olefin having 2 or about 4 to about 20 carbon atoms are copolymerized in the presence of the catalyst system described above. The catalyst system may be a prepolymerized system as described above. In another embodiment, propylene and ethylene rubber are formed in two or more reactors connected in series to form an impact polymer.

[00154] An α-olefin having 2 carbon atoms is ethylene, and examples of an α-olefin having from about 4 to about 20 carbon atoms are 1-butene, 1-pentene, 4-methyl-1-pentene, 1-octene, 1-hexene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, vinylcyclohexane, 1-tetradecene, etc.

[00155] In base polymerization, propylene can form a copolymer with two or more of the same α-olefins. For example, propylene can be copolymerized with ethylene and 1-butene. In one embodiment, propylene forms a copolymer with ethylene, 1-butene, or ethylene and 1-butene.

[00156] The block copolymerization of propylene and another α-olefin can be carried out in two stages. In the first step, the polymerization may be a homopolymerization of propylene or a copolymerization of propylene with another α-olefin. In one embodiment, the amount of monomers polymerized in the first stage is from about 50% to about 95% by weight. In another embodiment, the amount of monomers polymerized in the first stage is from about 60% to about 90% by weight. Said first polymerization step may be carried out in two or more steps under the same or different polymerization conditions.

[00157] In one embodiment, the polymerization in the second stage is carried out so that the mole ratio of propylene and other(s) α-olefin(s) ranged from about 10/90 to about 90/10. In another embodiment, the polymerization in the second stage is carried out so that the molar ratio of propylene and other(s) α-olefin(s) ranged from about 20/80 to about 80/20. In another embodiment, the polymerization in the second stage is carried out so that the molar ratio of propylene and other(s) α-olefin(s) ranged from about 30/70 to about 70/30. In the second polymerization step, a crystalline polymer or copolymer of another α-olefin can be obtained.

[00158] The propylene copolymer thus obtained may be a random copolymer or a block copolymer as described above. This propylene copolymer may contain from about 7 to about 50 mole % of units derived from an α-olefin having 2 or from about 4 to about 20 carbon atoms. In one embodiment, the propylene random copolymer contains from about 7 to about 20 mole % units derived from an α-olefin having 2 or about 4 to about 20 carbon atoms. In another embodiment, the block copolymer of propylene contains from about 10 to about 50 mol.% units derived from α-olefin having 2 or 4-20 carbon atoms.

[00159] In another embodiment, the copolymers made with this catalyst system contain from about 50% to about 99% by weight of poly-α-olefins and from about 1% to about 50% by weight of comonomers (such as thermoplastic or elastomeric monomers). In another embodiment, the copolymers produced with this catalyst system contain from about 75% to about 98% by weight of poly-α-olefins and from about 2% to about 25% by weight of comonomers.

[00160] It should be understood that in cases where there is no mention of a polyunsaturated compound that can be used, a polymerization method, an amount of a catalyst system, and polymerization conditions, the same description as in the above embodiment applies.

[00161] In one embodiment, the catalyst efficiency (measured in kilograms of polymer produced per gram of catalyst) of the catalyst system is at least about 30 kg/g/h. Catalyst inefficiency, for example, may be greater than about 60 kg/g/h, such as greater than about 80 kg/g/h, such as greater than about 100 kg/g/h, such as greater than about 140 kg/g /h

[00162] The catalysts/methods described above may, in some instances, result in the production of poly-α-olefins having a melt flow rate ("MFR", g/10 min) of from about 0.01 to about 500 g/10 min, e.g. from about 0.1 to about 400 g/10 min. MFR is measured in accordance with the ASTM standard. In another embodiment, poly-α-olefins are produced with an MFR of 0.1 to about 300.

[00163] In addition to the melt flow rate, the polydispersity index (pi) may vary depending on various factors and the desired result. The polydispersity index may generally be greater than about 3, such as greater than about 5, and typically less than about 8, such as less than about 6.

[00164] In some instances, the catalysts/methods described above can result in the production of poly-α-olefins having a bulk density (BD) of at least about 0.35 ^cc /g. In another embodiment, poly-α-olefins are produced having a BD of at least about 0.4 ^cc /g. In another embodiment, poly-α-olefins are produced having a BD of 0.35-0.5 cm ³ /g, or from 0.38-0.46 cm ³ /g.

[00165] The catalysts/methods described above can produce poly-α-olefins having a range of less than 1.0. In some embodiments, the range is less than 0.6.

[00166] Embodiments of the present invention can produce propylene block copolymers and impact copolymers comprising a polypropylene-based impact copolymer having one or more excellent properties in terms of melt flow, formability, desired balance between stiffness and elasticity, good stereospecificity control, good control over polymer particle size, shape, size distribution and molecular weight distribution, as well as impact resistance and high catalytic efficiency and/or good performance. The use of catalyst systems containing a solid catalyst component in accordance with embodiments of the present invention imparts catalysts both high catalytic efficiency and one or more of excellent melt flow, extrudability, formability, balance of stiffness and elasticity, and impact strength.

[00167] The following examples illustrate embodiments of the present invention. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight, all temperatures are in degrees Celsius, and pressure is at or near atmospheric pressure.

EXAMPLES

Abbreviations and definitions

[00168] “D ₁₀ ” is the particle size (diameter) at which 10% of the particles are less than this size, “D50” is the particle size at which 50% of the particles are less than this size, and “D ₉₀ ” is the particle size , at which 90% of the particles are smaller than this size. "Range" is the particle size distribution of the particles. The value can be calculated according to the following formula:

"PP" in front of any D or range value indicates the D value or range value for polypropylene made using these catalysts.

[00169] The abbreviation BD stands for bulk density and is indicated in units of g/ml.

[00170] The abbreviation CE stands for catalytic efficiency and is indicated in units of kg of polymer per gram of catalyst (kg/g) when polymerized for 1 hour.

[00171] The abbreviation MFR stands for melt flow rate and is indicated in units of g/10 min. MFR is measured in accordance with ASTM D1238.T.

[00172] Particle size analysis of the catalyst component was performed using a laser light scattering method using a Malvern Mastersizer 3000 instrument. Toluene was used as a solvent.

[00173] The surface area and pore size distribution of the catalyst components was measured using a Micrometrics ASAP 2020 instrument. Samples of the catalyst components were degassed by heating at 60° C. under vacuum for several hours prior to measurement.

[00174] Polydispersity index (PI) and zero shear viscosity for polymer samples were obtained from rheological data using an ARES G2 rheometer. The stabilized polymer sample is pressed on a hot press to create a plate. The polymer plate is then analyzed on a rheometer. On the PI data graph, the zero shear viscosity is calculated using the built-in MWD software.

[00175] The abbreviation NPDE stands for non-phthalate diaryl ester and may have the following formula:

where R ¹ - R 4 are selected from substituted or unsubstituted aryl groups, R ³ R ⁴ R ⁵ R ⁶ are the same or different alkyl or cycloalkyl having from 1 to 20 carbon atoms, a heteroatom, or a combination thereof. As used herein, NPDE1 is 3-methyl-5-tert-butyl-1,2-phenylenedibenzoate. NPDE2, on the other hand, is described in paragraph 52 of US 2013/0261273, which is incorporated herein by reference.

[00176] SYLTHERM is the trade name for polydimethylsiloxane (PDMS) marketed by Dow Chemical.

[00177] VISCOPLEX is a trade name for polyalkyl methacrylate supplied by Evonik.

[00178] The abbreviation EB stands for ethyl benzoate.

[00179] The abbreviation TBP stands for tributyl phosphate.

[00180] The abbreviation ECH stands for epichlorohydrin.

[00181] The abbreviation TEOS stands for tetraethyl orthosilicate.

[00182] Ti, Mg, and D are the weight percentage (wt.%) for titanium, magnesium and internal donor (NPDE), respectively, in the composition.

[00183] The abbreviation XS stands for xylene solubles and is indicated in units of mass%.

Block polymerization of propylene

[00184] In cases where the catalysts of the examples were used in the propylene polymerization process, the following method was used. The reactor was calcined at 100°C under nitrogen flow for 30 minutes before the polymerization cycle. The reactor was cooled to 30-35°C and the cocatalyst (1.5 ml 25 wt% triethylaluminum (TEAl)), C-donor, [cyclohexylmethyldimethoxysilane] (1 ml), hydrogen (3.5 psig) was added to the reactor. inch) and liquid propylene (1500 ml) in this sequence. The catalyst (5-10 mg) loaded as a mineral oil slurry was fed into the reactors with high pressure nitrogen. Polymerization was carried out for one hour at a temperature of 70°C. After polymerization, the reactors were cooled to 22°C, vented to atmospheric pressure, and the polymer was collected.

Gas-phase polymerization of polymer

[00185] In cases where the catalysts of the examples were used in the propylene polymerization process, the following method was used. The reactor was calcined at a temperature of 100°C in a stream of nitrogen for 30 minutes before the polymerization cycle. The reactor was cooled to 30° C., and propylene (120 g) with co-catalyst (0.27 ml of 25 wt.% triethylaluminum (TEA1)), C-donor, [cyclohexylmethyldimethoxysilane] (0.38 ml) and hydrogen (0.5 G). The reactor was heated to 35° C. and the catalyst component (0.5-0.7 mg) was transferred to the reactor with propylene (120 g). The polymerization was carried out for one hour at a temperature of 70°C. After polymerization, the reactors were cooled to 22°C, vented to atmospheric pressure, and the polymer was collected.

[00186] Examples 1-3 illustrate the preparation of catalyst components using an organosilicon compound without a supporting donor and provide the properties of a polymer produced using a propylene block polymerization scheme.

[00187] Example 1 demonstrates the preparation of a catalyst component using tetraethylorthosilicate. The catalyst produced a polymer with a raspberry-like particle morphology with a BD below 0.40 g/cm3 and a B/L3<0.7.

[00188] The reactor was charged with 3.3 g MgCl ₂ , 20 g toluene, 6.7 g TBP, 6.43 g ECH. The mixture was heated to a temperature of 60°C and kept for 8 hours at a stirring speed of 600 rpm. The mixture was left to cool to a temperature of 25°C. 27 grams of toluene and 1.5 grams of tetraethyl orthogilicate in 3 grams of toluene were added to the reactor at 25°C. The reactor was cooled down to -25°C and 65.2 grams of TiCl ₄ was added. After the addition, the stirring speed was reduced to 200 rpm, and the reaction mixture was heated to a temperature of 35°C for more than two hours and held for 30 minutes, heated to a temperature of 85°C for 30 minutes and held for 30 minutes. Filtration was done. The reaction mixture was washed with 50 ml of toluene 3 times. Added 65 ml of toluene and heated the reactor to a temperature of 40°C at 400 rpm. Added 0.64 grams of NPDE1 and heated the reactor to a temperature of 105°C and held for one hour. Filtration was done. Added 65 ml of 10% TiCl ₄ and raised the temperature to 105 °C for one hour. Filtration was done. Added 65 ml of 10% TiCl ₄ and raised the temperature to 110°C for 30 minutes and 3 times produced filtration. The solid was washed with 50 ml of hexanes at 65° C. and 400 rpm 3 times. The catalyst component was discharged as a hexane slurry. Analytical data and characteristics of the catalyst are presented below.

[00189] Example 2 demonstrates a catalyst component using two silicone compounds (tetraethylorthosilicate and Syltherm PDMS) and Al(OiPr)3. The internal donor was added in two places: before the formation of the solid and in the solid component. The catalyst produced a polymer with a round crimson type morphology and improved bulk density (BD=0.44 g/cm ³ ).

[00190] The reactor was charged with 3.3 g MgCl ₂ for subscript correction, 0.25 g Al(O-iPr) 3 , 20 g toluene, 9.1 g TBP, 1.0 g Syltherm(PDMS), 3, 55 g ECH. The mixture was heated to a temperature of 60°C and kept for 8 hours at a stirring speed of 600 rpm. The mixture was allowed to cool to a temperature of 25°C. 27 grams of toluene, 1.5 grams of TEOS in 3 grams of toluene, and 0.64 grams of NPDE1 were added to the reactor. The reactor was cooled to -25°C and 65.4 grams of TiCl ₄ was added to the reactor. For stirring, 300 rpm was set and gradual heating was carried out to a temperature of 35°C for 2 hours. The reaction mixture was kept at 35° C. for 30 minutes at 300 rpm. The reaction mixture was heated to 85°C and kept for 30 minutes. The reaction mixture was filtered and 50 ml of toluene was added. The reactor was heated to 40° C. at 400 rpm and 0.64 grams of PDE1 was added. The reactor continued to be heated to a temperature of 105°C and kept for 1 hour, then left for settling and decanting. Added 65 ml of 10% TiCl ₄ carried out heating to a temperature of 105°C and kept for 1 hour. The reaction mixture was allowed to settle and decanted. Added 65 ml of 10% TiCl ₄ carried out heating to a temperature of 110°C and kept for 1 hour. The reaction mixture was allowed to settle and decanted. Added 50 ml of hexane and stirred for 5 minutes at a jacket temperature of 65°C. The reaction mixture was allowed to settle and decanted. Hexane was then added and the product was discharged as a hexane slurry.

[00191] Example 3 demonstrates a catalyst component using two silicone compounds (tetraethylorthosilicate and Syltherm PDMS) and Al(OiPr)3. An internal donor was added to the solid component. The particle size of the catalyst component was increased to 14 μm (compared to examples 1 and 2).

[00192] The reactor was charged with 3.3 g MgCl ₂ , 0.25 g Al(O-iPr) 3 , 20 g toluene, 6.7 g TBP, 1.0 g Syltherm(PDMS) 6.43 g ECH. The mixture was heated to a temperature of 60°C and kept for 8 hours at a stirring speed of 600 rpm. The mixture was left to cool to a temperature of 25°C. 27 grams of toluene, 1.5 grams of TEOS in 3 grams of toluene were added to the reactor at 600 rpm and 25°C. The reactor was cooled to a temperature of -25°C and added to 65.2 grams of TiCl ₄ . The reactor was heated to a temperature of 35°C at 200 rpm for more than two hours and kept at a temperature of 35°C for 30 minutes; heated to a temperature of 85°C for 30 minutes and kept at a temperature of 85°C for 30 minutes, decanted, washed 3 times with toluene. Cooled to a temperature of 25°C and left to stand for the weekend. Filtration was carried out, 65 ml of toluene was added. Heated to a temperature of 40°C at 400 rpm and added 0.64 grams of PDE1. Heated to a temperature of 105°C for one hour. Filtration was done. Added 65 ml of 10% TiCl ₄ heated to a temperature of 105°C, kept for one hour. Filtration was done. Added 65 ml of 10% TiCl ₄ heated to a temperature of 110°C, kept for one hour. Filtration was done. Washed with 50 ml of hexanes three times at a jacket temperature of 65°C, stirred for 5 minutes between washes. Unloaded in the form of a suspension of hexane.

[00193] Example 4 (comparative). This example demonstrates the preparation of a catalyst component without silicone. The catalyst produced an irregular morphology polymer with agglomerated polymer particles.

[00194] Reactor 14A was charged with 3.3 g MgCl ₂ , 1.15 g Al(O-iPr) 3 , 20 g toluene, 6.7 g TBP, 6.43 g ECH. The mixture was heated to a temperature of 60°C and kept for 8 hours at a stirring speed of 600 rpm. The mixture was left to cool to a temperature of 25°C. 30 grams of toluene was added to the reactor at a temperature of 25° C. and at a speed of 600 rpm. The reactor was cooled to a temperature of 25°C and added to 65.2 grams of TiCl ₄ . After the addition, the stirring speed was reduced to 200, and the reaction mixture was heated to a temperature of 35°C for two hours. Withstood for 30 minutes. Heated to a temperature of 85 °C for 30 minutes. Withstood for 30 minutes. Filtration was done. The reaction mixture was washed with 50 ml of toluene, 3 times, JT 80°C, 400 rpm. Filtration was done. Added 65 ml of toluene and heated the reactor to a temperature of 40°C at 400 rpm. 0.64 grams of NPDE1 was added and the reactor was heated to 105°C and held for one hour. Filtration was done. Added 65 ml of 10% TiCl ₄ and raised the temperature to 105°C for one hour. Filtration was done. Added 65 ml of 10% TiCl ₄ and raised the temperature to 110°C for 30 minutes and 3 times produced filtration. The reactor was washed with 50 ml of hexanes at a temperature of 65°C and a speed of 400 rpm 3 times. The product was discharged as a hexane slurry.

Table 1. Catalyst components obtained using two organosilicon compounds and Al(OiPr)3

Example Present Component D10 D50 D90 Range Ti% Mg% NPDE1% Example 1 TEOS 5.81 9.84 14.9 0.928 3.79 17.34 9.83 Example 2 Al(OiPr)3, Syltherm, TEOS, NPDE1 5.02 8.94 13.8 0.982 3.94 15.76 17.08 Example 3 Al(OiPr)3, Syltherm, TEOS, 9.67 14.5 21.5 0.817 4.19 17.64 9.73 Example 4 (comparative) Only Al-O 3.85 7.12 13.5 1.356 2.818 18.48 7.41

Table 2. Properties of catalysts and polymers (catalyst components obtained using two organosilicon compounds and Al(OiPr)3)

catalytic component CE kg/g MFR, (g/10 min) XS,% BD, g/cm3 pp D10 pp D50 pp D90 pp Range B/L3 Note on PP morphology Example 1 65 1.46 3.1 0.397 353 590 1120 13 0.66 Raspberry-like shape Example 2 91.2 0.25 1.88 0.443 319 495 915 1.204 0.681 Round crimson shape Example 3 54.4 1.84 2.22 0.394 319 617 1081 1.235 0.682 Grape-like shape Example 4 (comparative) 51.4 2.86 4.07 0.237 612 1393 2085 1.057 0.624 Irregular morphology

Examples 5-13 illustrate the preparation of catalyst components using a supporting donor, ethyl benzoate. (EB)

TABLE 3. Catalyst Components Produced Using Organosilicon Compounds and Supporting Donors

Example Comments D10 (µm) D50 (µm) D90 (µm) Range Ti% Mg% NPDE1, % Example 5 (comparative) No epoxy 6.0 10.5 18.3 1.173 3.6 16.16 16.17 Example 6 Syltherm/TEOS=2/1; EB/MgCl ₂ =0.34 14.9 24.0 37.2 0.929 3.36 17.62 13.5 Example 7 Syltherm/TEOS=1/1; EB/MgCl ₂ =0.34 9.4 18.0 26.6 0.960 3.26 15.21 11.7 Example 8 TEOS; EB/MgCl ₂ =0.34 12.7 18.6 26.1 0.720 3.71 16.37 14.2 Example 9 (19724-17) Syltherm/TEOS=1/2; EB/MgCl ₂ =0.34 8.7 14.1 19.8 0.788 3.53 16.25 11.7 Example 10 19724-14 Syltherm; EB/MgCl ₂ =0.34 3.1 10.5 17.2 1.338 2.96 16.4 11.3 Example 11 (19724-67) batch 4 TEOS; EB / MgCl ₂ \u003d 0.26, rpm 300 6.4 10.2 14.9 0.842 3.16 17.36 10.4 Example 12 TEOS; EB / MgCl ₂ \u003d 0.26, rpm 200 8.6 13.6 20.7 0.889 3.01 8.56 10.9 Example 13 Silicone free, EB 6.9 11.9 18.8 996 3.06 7.19 11.1 Example 14 (comparative) Silicone Free, Phthalic Anhydride 9.8 20.2 33.5 173 2.52 8.70 10.46

Table 4 Properties of catalysts and polymers (catalyst components obtained using organosilicon compounds and using supporting donors) (block polymerization of propylene)

catalytic component CE kg/g MFR, (g/10 min) XS,% BD, g/ml PP D50 (µm) PP range B/L3 Morphology of PP Example 5 (comparative) 70.9 0.23 2.89 0.321 449 1.178 0.672 Irregular, agglomerated small particles Example 6 91.7 0.10 2.29 0.383 1087 0.573 0.706 Round crimson shape Example 7 82.9 0.26 2.28 0.418 836 0.435 0.720 Round crimson shape Example 8 81.1 0.17 2.40 0.424 899 0.433 0.738 round shape Example 9 84.3 0.17 3.14 0.454 705 0.704 0.707 Round crimson shape Example 10 83.1 0.12 2.23 0.421 970 0.992 0.625 Raspberry-like shape Example 11 81.9 0.34 2.44 0.447 492 0.754 0.719 round shape Example 12 79.4 0.2 2.00 0.425 643 0.736 0.713 Round crimson shape Example 13 (comparative) 75.4 0.07 1.83 0.410 644 0.626 0.699 Grape-like shape with small subparticles Example 14 (comparative) 53.9 0.10 0.127 0.404 772 0.764 - Grape type

[00195] Example 5 (comparative). The catalytic component is made using tetraethyl orthosilicate and supporting donor, ethyl benzoate and no epoxy compound to dissolve MgCl ₂ . This example demonstrates the irregular morphology of a low BD polymer.

[00196] MgCl ₂ (12.0 g) and hexane (130 g) were combined to form the initial reaction mixture. To the mixture was then added 2-ethylhexanol (50 g) with stirring (600 rpm), and then the temperature was increased to 120°C. This temperature was then maintained for 4 hours. Tetraethylorthosilicate (1.75 g in 2.0 g hexane) was then added to the reaction mixture, and the reaction mixture was held for 20 minutes, followed by cooling to -25°C. TiCl ₄ (150 ml) was added at low temperature over 1.5 hours, after which the temperature was raised to room temperature. At room temperature was added ethyl benzoate (2 g in 2 g of hexane) and the mixture was heated to a temperature of 100°C. Then NPDE1 (3.0 g in 5 g toluene) was added and the reaction mixture was kept at 100° C. for 1 hour. The solid was then collected by filtration and washed with toluene (3 times 200 ml at 85°C with 10 minutes stirring while maintaining the temperature before filtering again). After resuspending the solid in toluene, additional NPDE1 (2.0 g in 5.0 g toluene) was added at 40° C., the solid was collected by filtration and washed with hexane. Then, the process of adding NPDE1, heating at 110°C (0.5 hours) and filtering was repeated, and the process of washing with hexane and filtering was repeated three times. Finally, the solid product was washed (4 times with 300 ml of hexane at 65°C) and the solid was discharged into a hexane slurry.

[00197] FIG. 1 is a photograph of the polymer obtained in example 5 (comparative). The images shown are SEM images of polypropylene particles produced with the catalysts of the respective examples. Because the polymer particles replicate the catalyst particles, we can compare the catalyst morphology in each example. Catalyst and polymer morphology is a key factor to be considered in commercial polymer production processes. Polymerization processes require good polymer flow to transfer polymer from one reactor to another. The process must proceed without the production of fine polymer particles leading to clogging of the polymerization reactor. Therefore, for any polymerization process, a strong and uniform catalyst morphology and a high polymer bulk density are preferred.

[00198] As illustrated in FIG. 1, the morphology of the polymer produced in Example 5 (comparative) includes small subparticles. The bulk density of the polymer is very low at 0.321 g/ml. The catalyst and polymer of this example are not preferred and may lead to plugging of the reactor with generated fines.

[00199] Example 6 . A granular supported catalyst component made using Syltherm and TEOS (as silicone compounds) and ethyl benzoate as the supporting electron donor. This example demonstrates the improvement of a catalyst component with a larger particle size of 24 μm and a high activity catalyst (catalytic efficiency of 92 kg/g) and the production of a polymer with a rounded shape.

[00200] Combined MgCl ₂ (13.2 g), Al(OCH(CH3)2)3 (1.0 g), toluene (59.5 g), tri-n-butyl phosphate (36.3 g), epichlorohydrin (14.25 g) and Syltherm (6.0 g) and heated to 60°C with stirring at 600 rpm for 8 hours under nitrogen. After cooling to room temperature, toluene (140 g) was added along with ethyl benzoate (4.5 g) and tetraethyl orthosilicate (3 g). The mixture was then cooled to a temperature of -25°C and slowly added TiCl ₄ (261 g) with stirring at 600 rpm, while maintaining a temperature of -25°C. After the addition was completed, the temperature was maintained for 1 hour before heating to 35°C for 30 minutes, held at this temperature for 30 minutes, then raised the temperature to 85°C for 30 minutes, held for 30 minutes before collecting the solid sediment by filtration. The solid precipitate was washed three times with toluene (200 ml, each wash).

[00201] The resulting precipitate was then combined with TiCl ₄ in toluene (264 ml; 10 vol.%). This mixture was heated with stirring to a temperature of 85°C, followed by the addition of NPDE 1 (2.0 g) in toluene (10 g). Heating at 85° C. was continued for 1 hour before collecting the solid by filtration. This method of combining with TiCl ₄ in toluene, heating, adding NPDE 1 was repeated at 95°C and again at 110°C before washing the final product four times with hexane (200 ml, each wash) and stirring at 60-65°C for 10 minutes for each wash. The catalyst component was then discharged as a hexane slurry. In FIG. 2 is a photograph of a polymer produced with the catalyst component of Example 6. Polymer morphology similar to a round raspberry-like shape with large subparticles.

[00202] Example 7 . In this example, a granular supported catalyst was produced showing a high BD catalyst/PP with a narrow range. Example 6 was repeated, however 3.0 g of PDMS was added and Al(OCH(CH3)2)3 (0.5 g) and NPDE 1 (2.0 g) were added while washing with toluene before finishing with TiCl ₄ /toluene.

[00203] Example 8 . Example 7 was repeated, however, TEOS was added in an amount of 6.0 g and no Syltherm was added. In this example, a granular supported catalyst was produced which produced a polymer with a round shape morphology (B/L3=0.74)

[00204] Example 9 . In this example, a granular supported catalyst was produced showing an improvement in catalyst and polymer morphology and showing a high BD catalyst/PP with a narrow Range. The polymer is illustrated in Figure 3. Example 7 was repeated; however, TEOS was added in an amount of 1.50 g.

[00205] Example 10 . Illustrates the preparation of a catalyst component using Syltherm as the organosilicon silicon compound. Granular supported catalyst component showing particle size reduction. Example 7 was repeated, however TEOS was not added.

[00206] FIG. 2 and 3 illustrate the morphology of the round raspberry-like polymers prepared with the catalysts of Examples 7 and 9 respectively, the use of an epoxy compound to dissolve MgCl ₂ along with various combinations of organosilicon compounds (polydimethoxysilane (PDMS) and tetraethoxysilane (TEOS)) and ethyl benzoate demonstrate an improvement in morphology catalyst and polymer. In FIG. 2 and 3 show materials that have a distinct morphology. Large subparticles are bound in large particles. The polymers produced with these catalysts show high density (>0.40 g/ml) and sphericity (B/L3>0.71) (see tables above).

[00207] Example 11 . Demonstrates the effect of the amount of support donor on the particle size of the catalyst component. Example 8 was repeated except that the amount of ethyl benzoate was reduced from 0.34 g/g MgCl ₂ to 0.26 g/g MgCl ₂ resulting in a reduction in the particle size of the catalyst component from 18.6 µm to 10.2 µm.

[00208] FIG. 4 shows the round shape of the morphology of the polymer produced by the catalyst of Example 11.

[00209] Example 12 . Demonstrates the effect of agitation rate during catalytic component deposition on the size of the catalyst component portion. Example 11 was repeated, except that the agitation speed was reduced from 300 rpm to 200 rpm, resulting in an increase in the particle size of the catalyst component from 10.2 µm to 13.6 µm.

[00210] Example 13 . (comparative) Granular supported catalyst showing reduction in particle size and bulk density of catalyst and polymer. Al(OCH(CH3)2)3, Syltherm or TEOS were not used. Example 7 was repeated, however Al(OCH(CH3)2)3, PDMS or TEOS was not added. Example 13 demonstrates the performance of a catalyst component made using an epoxy compound to dissolve MgCl ₂ and using only ethyl benzoate as a support donor without the use of organosilicon compounds. In FIG. 5 shows the morphology of the polymer produced according to example 13. Each polymer particle contains numerous small sub-particles. In some polymerization processes, this morphology is not preferred as these particles can easily disintegrate during polymerization.

[00211] Example 14 . (comparative) Catalyst component made using phthalic anhydride as a precipitating agent. The catalytic component contains bis(1,3-dichloro-iso-propyl)phthalate (1.2%) and phthaloyl chloride (0.3%) as a product of the reaction of phthalic anhydride with TiCl ₄ and Mg compounds in the preparation of the catalytic component. The catalyst component exhibits lower catalytic activity than the catalyst produced in accordance with the current claims. The morphology of the polymer particles is grape type with B/L3<0.70.

[00212] Combined MgCl ₂ (13.2 g), toluene (190.0 g), tri-n-butyl phosphate (26.6 g), ECH (25.6 g) and heated to a temperature of 60°C with stirring at 600 rpm for 8 hours under nitrogen atmosphere. Phthalic anhydride (4.6 g) was added at 60°C. The mixture was then cooled to -25° C., at which temperature TiCl ₄ (260 g) was added slowly with stirring at 600 rpm. The temperature was maintained for 1 hour followed by raising the temperature to 10°C over 30 minutes, holding for 30 minutes, raising to 85°C over 70 minutes and holding for 15 minutes before collecting the solid by filtration. The solid was washed three times with toluene (200 ml), each time for 10 minutes at 85°C. The solid was then collected by filtration and washed with toluene (265 ml). After filtration, a solution of TiCl ₄ /toluene and NPDE 1 (3.0 g) in toluene (2 g) was added and heated to 105°C. After re-filtration, the solid was collected and washed with a solution of TiCl ₄ /toluene at a temperature of 110°C with stirring. Finally, the solid was washed with hexane (200 ml) four times with stirring at a temperature of 60-65°C, while the catalyst was discharged as a suspension of hexane. The catalyst from example 14 shows a lower catalytic activity than the catalyst obtained without phthalic anhydride.

[00213] Examples 15-17 illustrate the preparation of a catalyst component using TEOS as the silicone compound and ethyl benzoate as the supporting electron donor. Examples 18-23 illustrate polymerization data in bulk propylene and gas phase reactors producing substantially spherical polymer.

[00214] Example 15 . Example 11 was repeated on a scale of MgCl ₂ =20 kg

[00215] Example 16 . 13.2 g MgCl ₂ , 0.5 g Al(OR) 3 , 72 g toluene, 25.7 g ECH, 26.8 g TBP were added, heated and stirred at 60°C/600 rpm/8 h. Cooled to a temperature of 25°C. Left the next day under a layer of N2. 75.0 g of toluene, 3.5 g of EB in 12 g of toluene, 6.0 g of TEOS in 8 g of toluene were added at a temperature of 25°C. Cooled to -25° C. at 600 rpm and 260.8 g TiCl ₄ was slowly added. Raise the temperature from -25°C to 35°C over 2 hours at 350 rpm and hold at 35°C for 30 min/350 rpm. Raised the temperature from 35°C to 85°C over 30 min and kept at 85°C for 30 min at 350 rpm, filtered. It was washed with 200 ml of toluene/3 times/10 min and 200 ml of toluene was added, left under N2 until the next day and filtered. 265 ml of toluene was added, heated, 1.25 g of NPDE1 was added, heated to 105°C, ₄₀₀ rpm, 1 h. °C/400 rpm/1 h and filter. From Act 2 to Act 4, 265 ml 10% TiCl ₄ /toluene was added, heated to 110°C/400 rpm/30 minutes and filtered, washed with 200 ml hexane at 65°C JT/4 times/10 minutes and discharged as a suspension of hexane

[00216] Example 17 Example 15 was repeated with a 10% increase in NPDE1.

Table 5

Catalyst Component Notes D10 D50 D90 Range Ti% Mg% NPDE1% Example 15 TEOS, EB (scale 20 kg MgCl ₂ ) 8.8 11.6 15.4 0.570 3.04 16.85 10.68 Example 16 ECH/MgCl ₂ =2 (mol); TEOS, EB 11.5 17.5 26.4 0.851 2.95 16.88 10.54 Example 17 TEOS, EB (scale 20 kg MgCl ₂ ) 6.19 11.4 18.1 1.044 2.56 16.64 10.37

Table 6

Example catalytic component Polymerization condition CE kg/g MFR, (g/10 min) XS (%) BD, g/cm3 pp D10 pp D50 pp D90 pp Range B/L3 pp morphology Example 18 From example 15 block 70.6 1.36 2.40 0.463 490 717 1698 1.685 0.706 round shape Example 19 From example 15 gas phase 64.3 4.20 2.15 0.436 443 511 672 0.447 0.797 Essentially spherical shape Example 20 From example 16 block 93.6 0.26 2.25 0.432 706 848 1107 0.473 0.762 round shape Example 21 From example 16 gas phase 63.9 1.70 1.94 0.389 645 756 919 0.363 0.82 Essentially spherical shape Example 22 From example 17 block 90.1 0.33 2.04 0.435 446 558 843 0.711 0.763 Essentially spherical shape Example 23 From example 17 gas phase 60.6 1.4 1.89 0.414 423 508 716 0.575 0.763 Essentially spherical shape

[00217] Examples 18-23 demonstrate polymer production in a bulk and gas-phase polymerization reactor with essentially spherical particles with a B/L3 of 0.8. In FIG. 6 shows the substantially spherical PP morphology from Example 23.

[00218] Surface area (BET) and porosity measurements of the catalyst components show a surface area of approximately 400 m ² /g.

Table 7. Surface area (BET)

catalytic component S
A, BET, ^m2 /g A
ds PV, ^cm3 /g Des
PV, ^cm3 /g A
dsPD, A D
es PD, A Example 23 395.0 0.2714 0.2719 27.4841 27.5313

[00219] Examples 24-27 illustrate the relationship of catalyst characteristics and the relative ratio of sustaining electron donor to internal electron donor. The isotacticity of the catalyst decreases (%XS) with increasing EB/NPDE1 ratio, but the catalytic activity does not change sufficiently.

Table 8-1. Analytical Data for Catalyst Components and Corresponding Polymerization Data for Catalysts with Varying Supporting Electron Donor to Electron Donor Ratio

Example NPDE1/MgCl2, wt. Ti,% Mg% NPDE1, % EB, % CE kg/g MFR, (g/10 min) XS,% Example 24 0.227 3.37 18.62 13.06 6.03 102.3 0.16 2.21 Example 25 0.182 3.37 16.93 10.70 7.46 93.7 0.14 2.53 Example 26 0.152 3.57 17.15 9.34 8.50 91.6 0.35 3.07 Example 27 0.121 3.62 16.7 7.73 9.90 96.3 0.35 3.87

[00220] The catalyst components in examples 24-27 were produced as in example 8, except that the amount of NPDE1 was used as in table 8-1. The particle size of the catalyst components is 32 μm (produced at a stirring speed of 200 rpm during the deposition of the support).

[00221] Example 28 illustrates granular catalyst components made using NPDE2 as the internal donor diaryl ester, and Example 29 shows polymerization data in bulk propylene.

Example 28 Example 8 was repeated except that NPDE2 was used as the internal electron donor (NPDE2/MgCl ₂ = 0.18 wt.)

[00222] The catalyst component was tested in block polymerization of propylene to evaluate the hydrogen response to MFR.

Table 8-2. Analytical data for catalytic components with NPDE 2

Conditions D10 D50 D90 Range Ti% Mg% D% Example 28 NPDE2, TEOS 11.2 18.8 28.9 0.940 3.53 17.12 No data

Table 9 Polymerization Data Using the Catalyst Component of Example 28

catalytic component H2, SL CE kg/g MFR, (g/10 min) XS,% BD, g/cm3 pp D10 pp D50 pp D90 pp Range B/L3 Example 29 From example 28 5 94.7 1.5 3.36 0.424 762 986 1604 0.854 0.696

[00223] As shown above, Example 29 was run at a hydrogen concentration of 5 SL. In general, the hydrogen concentration may be from about 5 SL to about 40 SL or higher. In general, at lower hydrogen concentrations, eg, less than about 20 SL, eg, less than about 10 SL, polymers are produced having a relatively low melt flow rate. For example, the melt flow rate may be less than about 8 g/10 min, such as less than about 5 g/10 min, such as less than about 3 g/10 min, such as less than about 2 g/10 min, such as less than than about 1 g/10 min, and typically more than about 0.01 g/10 min. At higher amounts of hydrogen, eg, greater than about 30 SL, eg, from about 30 SL to about 50 SL, the melt flow rate can increase significantly. For example, the melt flow rate may be greater than about 100 g/10 min, such as greater than about 150 g/10 min, such as greater than about 200 g/10 min, such as greater than about 250 g/10 min, such as , more than about 300 g/10 min, for example, more than about 350 g/10 min, for example, more than about 400 g/10 min, for example, more than about 450 g/10 min, for example, more than about 500 g /10 min, and usually less than about 800 g/10 min.

[00224] The concentration of hydrogen may have some effect on catalytic activity. In general, catalytic activity may range from about 90 kg/g to about 200 kg/g. Catalytic activity from about 150 kg/g to about 200 kg/g may reflect a flat kinetic profile.

[00225] The concentration of hydrogen generally does not affect bulk density or particle size. For example, the bulk density may be greater than about 0.3 g/cm ³ , such as greater than about 0.35 g/cm ³ , such as greater than about 0.4 g/ ^cm g/cm ³ , for example less than about 0.45 g/cm ³ . The particle size D50 can typically be from about 500 microns to about 1700 microns, and typically from about 800 microns to about 1400 microns. The B/L3 of the polymer can typically be greater than about 0.6, such as greater than about 0.65, and typically less than about 0.8, such as less than about 0.75.

[00226] Examples 30-32 illustrate the preparation of catalyst components using 1,3-diester(3,3-bis(methoxymethyl)-2,6-dimethylheptane) (DEMH) as an internal donor.

[00227] In Example 30, 6.6 g MgCl ₂ , 0.5 g Al(O-iPr) 3 , 48 g toluene, 18.2 g TBP, 7.1 g ECH were added to the reactor. Produced heating and stirring at a temperature of 60°C/600 rpm/8 hours Cooled to a temperature of 25°C. 35 g of toluene, 2.25 g of ethyl benzoate in 5 g of toluene, 3.0 g of TEOS in 5 g of toluene and 0.75 g of DEMH in 5 g of toluene were added at a temperature of 25°C. Cooled to -25° C. at 600 rpm and 130.4 g TiCl ₄ was slowly added. Heated from -25°C to 35°C for 2 hours at 250 rpm and held at 35°C for 30 min/250 rpm. Heated from 35°C to 85°C for 30 min, kept for 1 hour and filtered. Washed with 100 ml of toluene/3 times/10 min. Added 132 ml 10% TiCl ₄ /toluene, added (1.25 g DEMH in 5 g toluene at 40°C, heated at 80°C for 1 h, filtered. Added 132 ml 10% TiCl ₄ /t. and produced heating at 105° C. for 1 hour.The treatment was repeated at 110° C. for 30 minutes three more times.The solid was washed with hexane and discharged as a hexane slurry.

[00228] Example 31 Example 8 was repeated, except that the solid precipitation was carried out at a stirring speed of 350 rpm and 0.80 g DEMH was used as an internal donor treated with 15% TiCl ₄ /toluene.

[00229] Example 32 Example 9 was repeated except that the catalyst treatment was carried out using 20% TiCl ₄ /toluene.

Table 10. Characteristics of the catalyst component 1,3-diester(3,3-bis(methoxymethyl)-2,6-dimethylheptane) (DEMH)

D50 Range Ti% Mg% DEM H, % CE kg/g MFR, (g/10 min) XS (%) BD, g/
cm3 pp D50 pp Range B/L3 Morphology of PP Example 30 18.4 1.014 19.2 76.2 8.5 1.24 0.407 835 0.620 0.736 Essentially spherical shape Example 31 10.8 0.525 2.66 18.03 12.2 74.6 6.8 0.424 710 1.244 0.672 Round crimson shape Example 32 eleven 0.547 2.92 17.84 12.9 98.0 5.1 2.83 0.437 616 1.268 0.688 Round crimson shape

[00230] Example 33 Demonstration of the preparation and performance of a spherical catalyst component. MgCl ₂ (13.2 g), Al(OCH(CH3)2)3 (1.0 g), toluene (59.5 g), tri-n-butyl phosphate ("TBP;" 36.3 g), ECH (14.25 g) and Syltherm (6.0 g) were combined and heated to 60°C with stirring at 600 rpm for 8 hours under nitrogen. After cooling to room temperature, hexane (59.0 g), dibutyl ether (8 g in 13 g hexane), Viscoplex (6.0 g) in hexane (40 g) and EB (4.5 g) in hexane (5 d) and cooled to 0°C, at this temperature, TiCl ₄ (288 g) was slowly added with stirring at 600 rpm. The temperature was maintained for 1 hour followed by raising the temperature to 10°C over 30 minutes, holding for 30 minutes, raising to 85°C over 70 minutes and holding for 15 minutes before collecting the solid by filtration. The solid was washed three times with toluene (200 ml), each time for 10 minutes at 85°C. The solid was then collected by filtration and washed with a solution of 10 wt.% TiCl ₄ /toluene (265 ml) with stirring at a temperature of 85°C, followed by the addition of NPDE1 (2.0 g) in toluene (5.0 g) with heating at a temperature 85°C for 60 minutes and followed by filtration. After filtration, the solid was again washed with a solution of TiCU/toluene and NPDE1 (0.5 g) in toluene (2 g), but this time at 95°C. After re-filtration, the solid was collected and washed with a solution of TiCU/toluene at a temperature of 110°C with stirring. Finally, the solid was washed with hexane (200 ml) four times with stirring at a temperature of 60-65°C, while the catalyst was discharged as a suspension of hexane.

[00231] Example 34 demonstrates the preparation of a spherical catalyst component performed using epoxy compounds to dissolve MgCl ₂ but without the use of an anhydride. Instead, an organosilicon compound, Al(O-iPr)3, and ethyl benzoate were used. The polymer produced with this catalyst (FIG. 7) exhibits high particle density and good sphericity.

[00232] Example 35 Demonstration of the preparation and performance of a spherical catalyst component using TEOS instead of Syltherm. Example 34 was repeated, however Syltherm was changed to TEOS (5 g) and dibutyl ether (12 g) was used.

[00233] Example 36 (comparative). A catalyst (no PDMS, no aluminum alkoxide) was performed with EB showing irregular catalyst/polymer morphology, low catalyst/polymer BD and wide catalyst/PP range. Example 33 was repeated, however PDMS and Al(OCH(CH3)2)3 were not added. Example 35 demonstrates the preparation of a catalyst component produced using an epoxy compound to dissolve MgCl ₂ and ethyl benzoate. Silicone compounds and Al(O-iPr)3 were not used. The polymer produced using the catalyst of Example 35 exhibits particles with low bulk density and irregular morphology.

[00234] Table 11. Analytical Data for Properties of Spherical Solid Catalyst Components and Polymers

Example 34 35 36 (comp.) D10 (µm) 12.6 16.9 8.6 D50 (µm) 20.7 27.2 28.8 D90 (µm) 34.7 44.2 60.2 Range 1.069 1.004 1.792 Ti% 1.77 2.31 2.65 Mg% 16.23 18.50 17.23 NPDE1,% 12.9 12.5 11.3 CE kg/g 66.4 58.6 67.1 MFR, (g/10 min) 0.12 0.73 0.22 XS,% 1.12 1.49 1.60 BD, g/ml 0.439 0.390 0.387 PPD50 (µm) 827 1098 957 PP range 0.912 0.808 1.325

[00235] Since the morphology of the polymer is an exact copy of the morphology of the catalyst, the same trends in the morphology of the catalyst are expected. The morphology of the catalyst and polymer is a key factor to consider in any commercial polymer production process. It is known that some polymerization processes require good polymer flow or polymer transfer from one reactor to another.

[00236] The catalysts/methods provide for the production of poly-α-olefins having a variable molecular weight distribution. The polydispersity index (PI) is tightly related to the molecular weight distribution of the polymer.

[00237] Examples 37-39 demonstrate the properties of polypropylene (PI and rheological width) produced using catalyst components using various internal donors.

Table 12 PI and Rheological Width of PP Produced Using Selected Catalysts

Example Catalyst Internal donor PI Rheological width Example 37 Example 8 catalyst NPDE1 5.2559 0.2754 Example 38 Example 8 catalyst NPDE1 6.1586 0.2892 Example 39 Example 31 catalyst DEMH 3.8113 0.3912

[00238] Example 40-43 . The solid catalyst component from Example 11 was used for block polymerization of propylene as described above, except that a blend of external donors marketed under the designation D6500, available from WR Grace and Company, was used. The table below shows the effect of the amount of external donor mixture on the XS level (catalytic activity) and polymer properties.

Table 13

Example catalytic component Donor (ml) Corr. CE kg/g B/D MFR, (g/10 min) XS,% PP D50, µm Range b/13 Example 40 Example 15 0.39 108.8 0.411 2.46 5.53 1698 1.042 0.596 Example 41 Example 15 0.78 96.8 0.439 0.73 3.27 716 1.094 0.695 Example 42 Example 15 1.17 85.6 0.446 0.91 2.25 562 0.859 0.751 Example 43 Example 15 1.56 91.6 0.429 1.25 1.99 563 0.917 0.751

[00239] Solid catalyst components or solid precipitates can be used for the ethylene polymerization process. Example 44 demonstrates the catalytic activity and properties of polyethylene produced using the solid residue from Example 15. Polymerization of ethylene was carried out in hexane in a one gallon reactor. The reactor was purged at 100° C. with nitrogen for one hour. At room temperature, 0.6 ml of a 25 wt% solution of triethylaluminum (TEAL) in heptane was added to the reactor. Then, 1500 ml of hexane was added, and 10 mg of the catalyst obtained above was added to the reactor. The reactor was pressurized with H2 to 60.0 psig and then charged with ethylene to 116 psig. The reactor was heated to 80°C and maintained at this temperature for two hours. After heating was completed, the reactor was depressurized and the polymer recovered.

Table 14. Ethylene polymerization using a solid component

Example D50 Ti,% Mg, % CE, kg/n BD, g/ cm3 MFI2 MFI10 MFI22 MFI ratio PE D50 Range Example 44 12 4.45 15.84 35.2 0.303 1.918 17.205 72.484 37.791 330 0.883

[00240] While certain embodiments have been illustrated and described, it should be understood that changes and modifications may be made by those skilled in the art within the scope of the technology in its broader aspects as defined in the following claims.

[00241] The invention illustratively described herein may be appropriately practiced in the absence of any element or elements, limitation or limitations that have not been expressly described herein. Thus, for example, the terms "comprising", "including",

"comprising", etc., should be interpreted broadly and without limitation. In addition, the terms and expressions used herein are used as a description and not a limitation, and it is not intended to use such terms and expressions to exclude, in whole or in part, any equivalents of the features given and described herein, but it is recognized that various modifications are possible within the scope of the claimed technology. In addition, it should be understood that the phrase "consisting essentially of" includes both specifically specified elements, and those additional elements that do not significantly affect the main and new characteristics of the claimed technology. The phrase "consisting of" excludes any unspecified elements.

[00242] The present description is not limited to the specific embodiments described herein. Those skilled in the art will appreciate that many modifications and changes are possible without departing from its spirit and scope. Functionally equivalent methods and compositions that are within the scope of the present disclosure, in addition to those listed herein, will become apparent to those skilled in the art upon review of the above descriptions. Such modifications and changes are intended to be included within the scope of the appended claims. The present invention is limited solely by the appended claims, as well as the full range of equivalents to which such claims apply. It is to be understood that this description is not limited to specific methods, reagents, compounds, compositions, or biological systems, which, of course, may vary. In addition, it should be understood that the terms used herein are used only for the purpose of describing specific embodiments of the present invention and they are not restrictive.

[00243] In addition, if features or aspects of the present description are described in terms of Markush groups, it will be apparent to those skilled in the art that the present description is thus also described in terms of any individual member or subgroup of members of the Markush group.

[00244] As will be apparent to one of skill in the art, for any and all purposes, especially such as providing a written description, all ranges described herein also cover all of their possible subranges and combinations of subranges. Any range listed can be easily recognized as being sufficiently described and as a range that can be broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. In a non-limiting example, each range described in this document, can be easily broken down into lower third, middle third and upper third, etc. As will be apparent to one skilled in the art, all terms such as "up to", "at least", "more than", "less than" and the like include the specified number and refer to ranges that can be further sub-ranged as described above. Finally, as will be apparent to those skilled in the art, the range includes every single element.

[00245] All publications, patent applications, granted patents, and other documents referred to in this specification are incorporated herein by reference as if each individual publication, patent application, patent granted, or other document were specifically and individually incorporated herein by reference in its entirety. Definitions that are contained in the text incorporated herein by reference are excluded to the extent that they conflict with the definitions given in this specification.

Claims (81)

1. Solid catalyst component for the polymerization of olefins, containing: a magnesium compound including a magnesium halide compound and a reaction product of a magnesium compound with an epoxy compound; organic compound of phosphorus; titanium compound; organosilicon compound; a non-phthalate internal electron donor, wherein the internal electron donor comprises an aryl diester, a diester, or a mixture thereof; a support donor, wherein the support donor is different from the internal electron donor, wherein the support donor comprises a monoester alone or in combination with a dialkyl ether or acrylate, wherein the internal electron donor contains a diaryl ester; wherein the solid catalyst component does not contain by-products of the reaction between the carboxylic acid or its anhydride and a magnesium or titanium compound, and the solid catalyst component has a particle size of from about 5 microns to about 70 microns (based on 50% by volume); where at the same time epoxy compound is represented by the formula:

and: a is 1, 2, 3, 4 or 5; X is alkyl, F, Cl, Br, I; And R ^a is H, alkyl, aryl or cyclyl; an organic compound of phosphorus is represented by the formula

where each of R ₁ , R ₂ and R ₃ independently represents alkyl C ₁ -C ₁₀ ; the titanium compound is represented by the formula: Ti(OR) _g X _4-g , where each R is independently C ₁ -C ₄ alkyl; X is Br, Cl or I; And g is 0, 1, 2 or 3; the organosilicon compound is a silane, siloxane or polysiloxane represented by Formula (II): R _n Si(OR') _4-n (II), and: each R is H, alkyl or aryl; each R' is H, alkyl, aryl or SiR _n' (OR') _3-n ; And n is 0, 1, 2, or 3. 2. The solid catalyst component of claim 1 further comprising an aluminum compound. 3. The solid catalyst component according to claim 1 or 2, wherein the solid catalyst component has a BET surface area of from about 100 m ² /g to about 500 m ² /g. 4. The solid catalyst component according to any one of the preceding claims, characterized in that the solid catalyst component does not include any by-products of the reaction between the organic acid and the magnesium compound or the titanium compound. 5. An olefin polymerization catalyst system comprising the solid catalyst component of any one of the preceding claims in combination with an organoaluminum compound and at least one selectivity control agent. 6. Catalyst system according to claim 5, further comprising an activity limiting agent. 7. Catalyst system according to claim 6, characterized in that the activity limiting agent comprises a C ₄ -C ₃₀ aliphatic acid ester, a diester, or a polymer of alkylene glycol aliphatic acid C ₄ -C ₃₀ ester. 8. Catalytic system according to paragraphs. 5, 6 or 7, characterized in that the selectivity control agent contains dimethyldimethoxysilane, n-propyltrimethoxysilane, methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane, n-propyltriethoxysilane, bis(perhydroisoquinoline)dimethoxysilane, 2,2,6,6-tetramethylpiperidine or mixtures thereof. 9. Solid catalyst component according to any one of paragraphs. 1-4, characterized in that the magnesium halogen compound is selected from the group consisting of magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride and a mixture of any two or more of them. 10. Method of polymerization, including: polymerization of an olefin in the presence of a solid catalyst component according to any one of paragraphs. 1-4, an organoaluminum compound and optionally an external electron donor. 11. A polymerization process according to claim 10, characterized in that the olefin is polymerized in the presence of also at least one selectivity control agent containing a silane compound, and optionally in the presence of an activity limiting agent. 12. The polymerization process according to claim 11, wherein the activity limiting agent is present during the polymerization and comprises a C ₄ -C ₃₀ fatty acid ester, a diester or a C ₄ -C ₃₀ fatty acid alkyl ester polymer or alkyl ester polymer. 13. The method of polymerization according to paragraphs. 10, 11 or 12, characterized in that the polymer particles are obtained with a particle morphology such that the particles have an aspect ratio B/L3 of more than about 0.6, for example, more than about 0.7, for example, more than about 0, 8. 14. A method for producing a solid catalyst component for the polymerization of an olefin, the method comprising: a) dissolving a magnesium halide compound in the mixture, wherein the mixture includes an epoxy compound, an organic phosphorus compound, and a hydrocarbon solvent to form a homogeneous solution; b) treating the homogeneous solution with a first titanium compound in the presence of an organosilicon compound to form a solid precipitate; c) treating the solid precipitate with a second titanium compound in the presence of a non-phthalate electron donor to form a solid catalyst component; and: the method does not use carboxylic acids and anhydrides; the first titanium compound and the second titanium compound are independently represented by the formula: Ti(OR) _g X _4-g ; each R is independently C ₁ -C ₄ alkyl; X is Br, Cl or I; And g is 0, 1, 2 or 3; And the organosilicon compound is a silane, siloxane or polysiloxane represented by Formula (II):

R _n Si(OR') _4-n (II), and: each R is H, alkyl or aryl; each R' is H, alkyl, aryl or SiR _n' (OR') _3-n ; And n is 0, 1, 2 or 3; an organic compound of phosphorus is represented by the formula:

where each of R ₁ , R ₂ , and R ₃ independently represents alkyl C ₁ -C ₁₀ ; epoxy compound is a compound represented by the formula:

and: a is 1, 2, 3, 4 or 5; X is alkyl, F, Cl, Br, I; And R ^a is H, alkyl, aryl or cyclyl; And the non-phthalate electron donor contains an aryl diester, a diester, or a mixture thereof. 15. The method of claim 14, further comprising the step of treating the homogeneous solution with a support donor, wherein the support donor comprises a diester, a succinate, an aryl monoester, a polycarboxylic acid ester, a polyhydroxy ester, a heterocyclic polycarboxylic acid ester, an inorganic acid ester, an ester of an alicyclic polycarboxylic acid, a hydroxy-substituted carboxylic acid ester compound having from 2 to 30 carbon atoms, an acrylate, or mixtures thereof. 16. The method according to claim 14 or 15, further comprising the step of forming a homogeneous solution in the presence of aluminum alkoxide. 17. The method according to p. 16, characterized in that the aluminum alkoxide has the formula Al(OR') ₃ , while each R' individually represents a C ₁ -C ₂₀ hydrocarbon. 18. The method according to paragraphs. 14-16 or 17, characterized in that the non-phthalate electron donor is added before or after the formation of a solid precipitate. 19. The method according to p. 14, characterized in that the epoxy compound is selected from the group consisting of: ethylene oxide; propylene oxide; 1,2-epoxybutane; 1,2-epoxyhexane; 1,2-epoxyoctane; 1,2-epoxydecane; 1,2-epoxydecane; 1,2-epoxytetradecane; 1,2-epoxyhexadecane; 1,2-epoxyoctadecane; 7,8-epoxy-2-methyloctadecane; 1-cyclohexyl-3,4-epoxybutane; epifluorohydrin; epichlorohydrin; and epibromhydrin. 20. The method according to any one of paragraphs. 14-19, characterized in that the magnesium halide compound is selected from the group consisting of magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, and a mixture of any two or more of them. 21. The method according to p. 14, characterized in that the organosilicon compound is a polydialkylsiloxane, tetraalkoxysilane, or a mixture of any two or more of them. 22. The method according to p. 17, characterized in that the aluminum alkoxide is aluminum isopropoxide. 23. The method according to claim 15, characterized in that the supporting donor contains methyl formate, butyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, isobutyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate, methyl methacrylate, ethyl crotonate , ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl p-methoxybenzoate, methyl p-methyl benzoate, ethyl p-tert-butyl benzoate, ethyl naphthoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methylanisate , ethylanisate and ethylethoxybenzoate. 24. The method of polymerization or copolymerization of an olefin monomer, the method includes contacting the olefin monomer with a catalyst component obtained by the method according to any one of paragraphs. 14-23 to form a polyolefin polymer in the presence of an organoaluminum compound and at least one selectivity control agent containing a silane compound alone or in combination with an activity limiting agent. 25. The polymerization process of claim 24, wherein the polymer particles are obtained with a particle morphology such that the particles have a B/L3 aspect ratio of greater than about 0.6, such as greater than about 0.7, such as greater than approximately 0.8.

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