CATALYST COMPONENTS FOR PROPYLENE POLYMERIZATION HAVING IMPROVED CATALYTIC PERFORMANCE - Patent application

Abstract

An isolated solid catalyst component for olefin polymerization. The catalyst component comprises a halide-containing magnesium compound, a halide titanium compound, a support donor comprising a benzoate, an internal electron donor, and an activity control agent (ACA). The ACA comprises: i) a first organosilicon compound containing Si-O groups, present in the catalyst component in an amount of about 0.1 to about 5 weight percent; ii) a C4-C 1,2-diphenylsilane compound in an amount of about 0.1 to about 15 weight percent; 30 Organic esters of fatty acids or C4-C 30 and iii) at least one of a poly(alkene glycol) ester of a fatty acid, and iii) an organoaluminum compound containing an alkyl group, at least a portion of which is chemically bonded to a halide-containing magnesium compound.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 240,300, filed September 2, 2021, which is hereby incorporated by reference in its entirety for all purposes. [Background technology]

[0002] Polyolefins are a class of polymers derived from simple olefins. A known method of making polyolefins involves the use of Ziegler-Natta polymerization catalysts. These catalysts use transition metal halides to polymerize olefin monomers to provide polymers with a wide variety of stereochemical configurations.

[0003] One type of Ziegler-Natta catalyst system includes a solid catalyst component composed of a titanium compound and a magnesium halide on which an internal electron donor compound is supported. The internal electron donor compound is added during the catalyst synthesis to maintain high selectivity for isotactic polymer products. The internal donor can be of various kinds. Traditionally, an external donor compound is also added during the polymerization reaction when a higher degree of crystallinity of the polymer is required.

[0004] During the past 30 years, many supported Ziegler-Natta catalysts have been developed, which give much higher activity in olefin polymerization reactions and much higher content of crystalline isotactic fraction in the polymers they produce. With the development of internal and external electron donor compounds, polyolefin catalyst systems are constantly being reformed.

[0005] One problem encountered with newly developed Ziegler-Natta catalysts, especially non-phthalate catalysts, is that the catalysts instantly result in significantly higher catalytic activity during the polymerization process. High catalytic activity can result in a rapid temperature rise in the center of the catalyst particle. In some applications, the surface area of ​​the catalyst particle is not sufficient to dissipate the heat, causing the particle to break or otherwise decompose.

[0006] Another problem with catalysts having high activity is that they usually exhibit a high level of decay of activity during the polymerization process, which makes it difficult to use such high activity catalysts in multiple reactor polymerization processes for producing certain polymer products, such as impact copolymers.

[0007] To control the catalyst kinetics, some polymerization processes, i.e. slurry phase or bulk phase polymerization processes, are equipped with prepolymerization lines or reactors. In other polymerization processes, such as gas phase processes, the kinetics of the polymerization process can be slightly improved by external donors and activity limiting agents. However, greater improvements in the control of polymerization kinetics are needed. Summary of the Invention

[0008] The present disclosure is generally directed to an isolated solid catalyst component for olefin polymerization. The catalyst component includes a halide-containing magnesium compound, a titanium halide compound, a support donor including a benzoate, an internal electron donor, and an activity control agent (ACA). The ACA includes at least one of i) a first organosilicon compound containing a Si-O group, present in the catalyst component in an amount of about 0.1 to about 5 wt%, ii) an organic ester of a C4-C30 fatty acid or a poly(alkene glycol) ester of a C4-C30 fatty acid in an amount of about 0.1 wt% to about 15 wt%, and iii) an organoaluminum compound containing an alkyl group. At least a portion of the ACA is chemically bonded to the halide-containing magnesium compound.

[0009] The present disclosure is also directed to a process for making an isolated solid catalyst component, comprising: a) preparing a magnesium alkoxide, Mg(OR) n X 2-n Or magnesium alcoholate MgX2·mR'OH Ti(OR'') g X 4-g wherein X is Br, Cl, or I, n is 1, 2, m is 0.5-10, g is 0, 1, 2, 3, or 4, and R, R', and R'' are independently C1-C10 alkyl, the catalyst precursor containing a supporting electron donor and an internal electron donor; and b) forming a catalyst precursor component by reacting, in a hydrocarbon solvent, i) with a compound of the formula: R2nSi(OR3) 4-n wherein R2 is H, alkyl, or aryl, each R3 is alkyl, or aryl, and n is 0, 1, 2, or 3, with at least one of ii) an organic ester from a C4 to C30 fatty acid ester or a poly(alkene glycol) ester of a C4 to C30 fatty acid, and iii) an alkylaluminum compound; and c) isolating the solid catalyst component.

[0010] A process for producing olefin polymers is also provided. The process includes polymerizing olefins in the presence of a solid catalyst component. The solid catalyst component includes the reaction product of a) a halide-containing magnesium compound, b) a titanium halide compound, c) at least one internal electron donor, and d) an activity control agent (ACA). The ACA includes at least one of i) a first organosilicon compound containing Si-O groups, present in the catalyst component in an amount of about 0.1 to about 5 wt%, ii) an organic ester of a C4-C30 fatty acid or a poly(alkene glycol) ester of a C4-C30 fatty acid in an amount of about 0.1 wt% to about 15 wt%, and iii) an organoaluminum compound containing an alkyl group. At least a portion of the ACA is chemically bonded to the halide-containing magnesium compound.

[0011] Other features and aspects of the disclosure are discussed in more detail below. [Brief description of the drawings]

[0012] The present disclosure may be better understood with reference to the following drawings. [Figure 1] 1 is a chart comparing the FTIR spectrum of a catalyst component containing ACA made according to the present disclosure with a catalyst component without ACA. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Before describing some exemplary embodiments, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description as the invention is capable of other embodiments and of being practiced or carried out in various ways.

[0014] In general, the present disclosure is directed to a catalyst component for producing polyolefin polymers, particularly polypropylene, polyethylene, and copolymers thereof, and a method for making such a catalyst component. The present disclosure is also directed to a method for polymerizing olefins using the catalyst component. In general, the catalyst component of the present disclosure is a reaction product of a halide-containing magnesium compound, a halide titanium compound, a monobenzoate-supported electron donor, at least one internal electron donor, and an activity control agent (ACA) comprising (a) an organosilicon compound containing a Si-O group, (b) an organic ester of a C4-C30 fatty acid or a poly(alkene glycol) ester of a C4-C30 fatty acid, (c) an organoaluminum compound containing an alkyl group, or any combination thereof.

[0015] The present inventors have discovered that treating a catalyst precursor containing a monobenzoate supported donor and an internal donor supported on a magnesium halide compound with ACA prior to polymerization unexpectedly results in high levels of incorporation of ACA into the catalyst component, partial removal of the supported donor from the catalyst component, and a change in the coordination of the internal donor on the magnesium halide support surface due to bonding between the ACA and the halide-containing magnesium compound.

[0016] In addition, the inventors have unexpectedly discovered that the resulting catalyst components exhibit improved lifetime and relatively flat polymerization kinetics, which provides significant advantages when the catalyst components are used in multiple reactor polymerization systems, such as systems for producing impact copolymers. For example, the level of catalyst activity remains more constant over a relatively long period of time, such as more than one hour, instead of being very high at the beginning of the polymerization and then decreasing rapidly. Some multiple reactor polymerization processes require the catalyst to remain active for multiple hours, so the more stable kinetics of the catalyst components described herein are desirable.

[0017] The inventors further discovered that catalyst life can be controlled by varying the coordination of the internal donor on the magnesium halide surface using varying activation conditions and varying amounts of internal donor.

[0018] One measure of catalyst life is to compare the catalytic activity over the first hour of polymerization with the catalytic activity over the second hour of polymerization. High catalytic activity during the first hour of polymerization followed by much lower catalytic activity during the second hour is evidence that the catalyst has a short life. If the activity level during the second hour is similar to the activity level during the first hour, the catalyst generally has a longer life. In certain polymerization processes, such as multiple reactor processes carried out over multiple hours, it is more desirable to have a longer catalytic life even if the activity level is slightly lower initially. In this regard, the catalyst components described herein exhibit a relatively long life as measured by comparing the catalytic activity over the first hour of polymerization with the catalytic activity during the second hour of polymerization. For example, the change in catalytic activity from the first hour to the second hour is generally about 30% or less, such as less than about 25%, such as less than about 20%, such as less than about 15%, such as less than about 10%, such as less than about 5%. In some embodiments, the catalytic activity is greater in the second hour than in the first hour.

[0019] Typically, catalysts contain three to five major types of active centers that differ in activity and other polymerization characteristics. Highly active catalytic centers usually have a short lifetime. Therefore, to improve polymerization kinetics, it is necessary to have multi-site active catalytic centers with narrow catalytic activity. Without intending to be limited by theory, it is believed that the improvement in catalyst lifetime is related to changing the internal donor coordination on the magnesium halide support by increasing the concentration of weakly coordinated complexes with magnesium halide. It is believed that the weakly coordinated internal donors can be easily removed by cocatalysts such as triethylaluminum (TEAl) in the early stages of the polymerization process, resulting in a reduction of highly active catalytic centers at the beginning of the polymerization process, thus extending the catalyst lifetime.

[0020] In addition, in some polymerization processes using active catalysts, the polymerization temperature may rise at certain spots in the reactor, resulting in uncontrolled polymerization and plugging of the polymerization reactor. Catalysts containing ACA may reduce the catalyst activity at high polymerization temperatures (i.e., they are self-extinguishing) and improve the polymerization process. For example, in some embodiments, the catalyst activity at 90°C may be at least about 10% lower, such as about 12% to about 20% lower, than the catalyst activity at 80°C when determined over a 30 minute period.

[0021] Improved catalysts can also produce polymers with improved morphology, such as improved bulk density, particle shape, and sphericity, which leads to better commercial processability. For example, in high productivity commercial processes, it is desirable to produce spherical polymer particles with high bulk density and without breakage.

[0022] In this regard, the polymer powders made according to the present disclosure may have an average particle size of more than about 5 microns, such as more than about 50 microns, such as more than about 100 microns, such as more than about 300 microns, such as more than about 500 microns. The average particle size of the polymer particles may generally be less than about 3,000 microns, such as less than about 2,000 microns, such as less than about 1,600 microns. As mentioned above, the polymer particles may be substantially spherical. For example, the polymer particles may have a B / L3 of more than about 0.65, such as more than about 0.7, such as more than about 0.75, such as even more than about 0.8, generally less than 1. In addition, the polymer particles may have a sphericity (SPHT) of more than about 0.80, such as more than about 0.85, such as more than about 0.9, such as more than about 0.95, generally less than 1.

[0023] Due to the particle morphology, the polymer resin made according to the present disclosure can also have increased bulk density and therefore good flow properties. The bulk density of the polymer particles can be, for example, greater than about 0.35 g / cc, for example greater than about 0.38 g / cc, for example greater than about 0.4 g / cc, for example greater than about 0.41 g / cc. The bulk density is generally less than about 0.55 g / cc, for example less than about 0.50 g / cc.

[0024] High catalyst activity levels can be achieved using the catalyst components of the present disclosure, for example, the average catalyst activity over the first 2 hours of polymerization can be greater than 40 kg / g / h, such as greater than 50 kg / g / h, for example greater than 60 kg / g / h, such as greater than 70 kg / g / h, for example greater than 80 kg / g / h, for example even greater than 90 kg / g / h.

[0025] Advantageously, the catalyst components are prepared outside the polymerization reactor and therefore may be stored and used in dry form or in hydrocarbon solvents or mineral oils.

[0026] In one embodiment, the method of preparing the catalyst component of the present disclosure includes forming a catalyst precursor containing a magnesium compound, a titanium compound, a support donor, and an internal electron donor. The catalyst precursor is then reacted with (a) an organosilicon compound containing Si-O groups, (b) a C4-C 30 Organic esters from fatty acid esters or C4-C 30 (c) an organoaluminum compound containing an alkyl group, or any combination thereof. In another embodiment, the active control agent is added during the incorporation of the internal donor.

[0027] A. Catalyst Precursor When the catalyst precursor is formed prior to the incorporation of the activity control agent, the catalyst precursor generally comprises a magnesium compound and a titanium compound in combination with a supporting electron donor and at least one internal electron donor.

[0028] In one embodiment, the catalyst precursor has the formula MgdTi(OR e )fX, wherein R e is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR', R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms, and each OR eThe groups are the same or different, X is independently chlorine, bromine, or iodine, d is 0.5-56, or 2-4, f is 2-116, or 5-15, and g is 0.5-116, or 1-3. The catalyst precursor component may be prepared by controlled precipitation, removing alcohol from the reaction mixture used in its preparation. In one embodiment, the reaction medium comprises a mixture of an aromatic liquid, particularly a chlorinated aromatic compound, such as chlorobenzene, with an alkanol, such as ethanol. Suitable halogenating agents include titanium tetrabromide, titanium alkoxides, titanium tetrachloride, or titanium trichloride. Removal of the alkanol from the solution used for halogenation results in precipitation of the solid catalyst precursor.

[0029] For example, in one embodiment, the catalyst precursor component comprises the reaction product of a magnesium alkoxide, such as magnesium ethylene oxide, with a mixture of o-cresol, titanium ethoxide, titanium tetrachloride, and ethanol in the presence of an internal electron donor. During the process, in one embodiment, the support electron donor is formed as a by-product and incorporated into the catalyst. Additionally, the support donor may be formed in situ as a by-product by reaction of the internal donor with the reaction mixture.

[0030] In another embodiment, the catalyst precursor component is formed from a magnesium alcoholate, a titanium halide, a supporting electron donor, and an internal electron donor. For example, in one embodiment, the solid magnesium alcoholate is treated with a titanium halide to remove the alcohol. The internal donor and the supporting donor can be added at different steps in the process to change the properties of the solid catalyst component.

[0031] For example, the catalyst precursor can be an alcohol adduct of anhydrous magnesium halide. Anhydrous magnesium halide adducts are generally defined as MgX2-nROH, where n ranges from 0.5 to 10, preferably 2.5 to 4.0, and most preferably 2.8 to 3.5 moles of total alcohol. ROH is a linear or branched C1 to C4 alcohol, or a mixture of alcohols. Preferably, ROH is ethanol or a mixture of ethanol and a higher alcohol. When ROH is a mixture, the molar ratio of ethanol to higher alcohol is at least 80:20, preferably 90:10, and most preferably at least 95:5.

[0032] In one embodiment, the substantially spherical MgCl-nEtOH adduct may be formed by a spray crystallization process.

[0033] In another embodiment, the catalyst precursor is formed by dissolving a halide-containing magnesium compound in a mixture, the mixture including an epoxy compound, an organophosphorus compound, and a hydrocarbon solvent to form a homogeneous solution. The homogeneous solution can then be treated with a support donor in the presence of an organosilicon compound and a hydrocarbon solvent. A titanium halide compound can then be added to form a solid precipitate. The precipitate can then be combined with a hydrocarbon solvent to form a mixture. An internal electron donor in a hydrocarbon solvent can then be added to the mixture. The resulting solid can then be filtered and further treated with a titanium halide to form a catalyst precursor.

[0034] In certain embodiments, the halide-containing magnesium compound, the epoxy compound, and the organophosphorus 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 about 40 to about 90° C. or about 50 to about 70° C. In certain embodiments, the molar ratio of the magnesium compound to the alkyl epoxide is about 0.1:2 to about 2:0.1, or about 1:0.25 to about 1:4, or about 1:0.9 to about 1:2.2. In certain embodiments, the molar ratio of the magnesium compound to the Lewis base is about 1:0.1 to about 1:4, or 0.5:1 to 2.0:1, or 1:0.7 to 1:1. Without being bound by any theory, it is believed that the halogen atom migrates from the magnesium compound to the epoxy compound, opening the epoxide ring and forming an alkoxide magnesium species having a bond between the magnesium atom and the oxygen atom of the newly formed alkoxide group. During this process, the organophosphorus compound coordinates to the Mg atom of the halide-containing magnesium compound, increasing the solubility of the magnesium-containing species present.

[0035] The organosilicon compound can be added together with the epoxy compound during or after dissolving the magnesium compound in the organic solvent.The organosilicon compound can be silane, siloxane, or polysiloxane.The organosilicon compound can be represented in some embodiments by the following formula (II): R n Si(OR') 4-n (II) In formula (II), each R can be H, alkyl, or aryl, and each R' can be H, alkyl, aryl, or -SiRn'(OR')3-n, where n is 0, 1, 2, or 3.

[0036] In some embodiments, the organosilicon is a monomeric or polymeric compound. The organosilicon compound may contain -Si-O-Si- groups in one molecule or between other molecules. Other illustrative examples of organosilicon compounds include polydialkylsiloxanes and / or tetraalkoxysilanes. Such compounds may be used individually or in combination. The organosilicon compound may be used in combination with an aluminum alkoxide and a first internal donor. In some embodiments, polydimethylsiloxanes and / or tetraethoxysilanes may be used.

[0037] The titanium halide compound used to form the catalyst precursor is Ti(OR). g X 4-g wherein each R is independently selected from C1 to C 10 alkyl, X is Br, Cl, or I, and g is 0, 1, 2, 3, or 4, for example, TiCl4.

[0038] The hydrocarbon solvent used to generate the catalyst precursor may include aromatic or non-aromatic solvents or combinations thereof. In certain embodiments, the aromatic hydrocarbon solvent is toluene and C2-C4 20 In certain embodiments, the non-aromatic hydrocarbon solvent is selected from hexane and heptane.

[0039] Exemplary epoxy compounds include, but are not limited to, glycidyl-containing compounds of the formula:

[0040] [ka] where "a" is 1, 2, 3, 4, or 5; X is F, Cl, Br, I, or methyl; R a is 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.

[0041] According to some embodiments, the epoxy compound is ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 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, cyclooctene oxide, α-pinene oxide, 2,3-epoxynorbornane, limonene oxide, cyclodecane epoxide, 2,3,5,6-diepoxynorbornane Lunan, styrene oxide, 3-methylstyrene oxide, 1,2-epoxybutylbenzene, 1,2-epoxyoctylbenzene, stilbene oxide, 3-vinylstyrene 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, epifluoro hydrin, 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, glycidyl methyl ether glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, ethyl 3,4-epoxybutyl ether, glycidyl phenyl ether, glycidyl 4-tert-butylphenyl ether, glycidyl 4-chlorophenyl ether, glycidyl 4-methoxyphenyl ether, glycidyl 2-phenylphenyl ether, glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, glycidyl 1-naphthyl ether, glycidyl 4-indolyl ether, glycidyl N-methyl-α- Quinolone-4-yl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,2-diglycidyloxybenzene, 2,2-bis(4-glycidyloxyphenyl)propane, tris(4-glycidyloxyphenyl)methane, poly(oxypropylene)triol triglycidyl ether, glycidyl ether of phenol novolac, 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), copolymers of glycidyl acrylate with another monomer, copolymers 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-glycidyl-methylacetamide, N,N-ethylglycidylpropionamide, N,N-glycidylmethylbenzamide, N-(4,5-epoxypentyl)-N-methyl-benzamide, N,N-diglycylaniline, bis(4-diglycidylaminophenyl)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.

[0042] As an example of an organophosphorus compound, a phosphate ester such as a trialkyl phosphate ester may be used. Such a compound may be represented by the following formula:

[0043] [ka] In the formula, R1, R2, and R3 are each independently methyl, ethyl, and straight or branched chain (C3 to C 10 ) alkyl groups. In one embodiment, the trialkyl phosphate is tributyl phosphate.

[0044] As mentioned above, at least one internal electron donor is present during the synthesis of the catalyst precursor. The internal electron donor is a compound added or otherwise formed during the formation of the catalyst precursor, which donates at least one pair of electrons to one or more metals present in the resulting catalyst support. A support donor is also present. The support donor is a reagent added during the support synthesis and / or formed during the process of building the catalyst precursor, which, like the internal electron donor, binds to the magnesium surface and remains in the catalyst precursor. The support donor is usually smaller (less bulky) than the internal electron donor and is weakly coordinated with the catalyst support.

[0045] The catalyst components can be converted to solid catalysts by halogenation. Halogenation involves contacting the catalyst components with a halogenating agent in the presence of a supporting electron donor and / or an internal electron donor. Halogenation converts the magnesium moieties present in the catalyst components to a magnesium halide support on which titanium halides (such as titanium halide) are deposited. Without wishing to be bound by any particular theory, it is believed that during halogenation, the internal electron donor (1) adjusts the location of titanium on the magnesium-based support, (2) promotes the conversion of the magnesium and titanium moieties to their respective halides, and (3) adjusts the crystal size of the magnesium halide support during the conversion.

[0046] In certain embodiments, the halogenating agent has the formula Ti(OR e ) f X h wherein R e and X are defined as above, f is an integer from 0 to 3, h is an integer from 1 to 4, and f+h is 4. In one embodiment, the halogenating agent is TiCl4. In a further embodiment, the halogenation is carried out in the presence of a chlorinated or non-chlorinated aromatic liquid, such as dichlorobenzene, o-chlorotoluene, chlorobenzene, benzene, toluene, or xylene. In yet another embodiment, the halogenation is carried out by use of a mixture of a halogenating agent and a chlorinated aromatic liquid, the mixture comprising 40 to 60 volume percent of the halogenating agent, such as TiCl4.

[0047] The reaction mixture may be heated during halogenation. The catalyst precursor and halogenating agent are initially contacted at a temperature below about 10° C., such as below about 0° C., such as below about −10° C., such as below about −20° C. The initial temperature is generally above about −50° C., such as above about −40° C. After contacting the catalyst precursor with the halogenating agent, the mixture may be held at the initial temperature for a period of time, such as 1 hour, and then heated at a rate of 0.1-10.0° C. / min, or at a rate of 1.0-5.0° C. / min. The internal electron donor may be added later, after the initial contact period between the halogenating agent and the catalyst components. The temperature of the halogenation is from 20° C. to 150° C. (or any value or subrange therebetween), or from 0° C. to 120° C.

[0048] The manner of adding the halogenation agent, supporting electron donor, and internal electron donor may be varied when synthesizing the catalyst precursor. In an embodiment, the catalyst precursor is first contacted with a mixture containing the halogenation agent and the chlorinated aromatic compound. The resulting mixture may be stirred and heated as needed. The supporting electron donor and / or the internal electron donor are then added to the same reaction mixture without isolating or recovering the precursor. The aforementioned process may be carried out in a single reactor with the addition of the various components controlled by an automatic process control.

[0049] In one embodiment, the catalyst component is contacted with an internal electron donor prior to reacting with the halogenating agent.

[0050] The contact time of the catalyst component with the supported electron donor and / or the internal electron donor is at least 10 minutes, or at least 15 minutes, or at least 20 minutes, or at least 1 hour, at a temperature of at least -30°C, or at least -20°C, or at least 10°C up to 150°C, or up to 120°C, or up to 115°C, or up to 110°C.

[0051] In one embodiment, the catalyst components, the supporting electron donor, the internal electron donor, and the halogenating agent are added simultaneously or substantially simultaneously. The halogenating procedure may be repeated one, two, three or more times as necessary.

[0052] The monobenzoate support donor contained in the catalyst precursor has the formula:

[0053] [ka] wherein R' comprises an alkyl group, a cyclic group, an aryl group having 1 to 20 carbon atoms, a heteroatom, or a combination thereof, and R'' comprises one or more substituents, each of which may independently comprise hydrogen, an alkyl group, a cyclic group, an aryl group having 1 to 20 carbon atoms, a heteroatom, or a combination thereof. Exemplary monobenzoate support donors include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl p-methoxybenzoate, methyl p-methylbenzoate, ethyl pt-butylbenzoate, ethyl naphthoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, or ethyl ethoxybenzoate.

[0054] A variety of different types of internal electron donors can be incorporated into the solid catalyst component. In one embodiment, the internal electron donor is an aryl diester, such as a phenylene substituted diester. In one embodiment, the internal electron donor can have the following chemical structure:

[0055] [ka] In the formula, R 50 , R 51 , R 52 , R 53 , R 54 , and R 55each is independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and q is an integer from 0 to 12.

[0056] In one embodiment, the internal electron donor may have one of the following chemical structures:

[0057] [ka] In the formula, R 60 ~R 73 each is independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and q is an integer from 0 to 12.

[0058] In one embodiment, the internal electron donor may have the following chemical structure:

[0059] [ka] wherein R1 to R4 are the same or different, and each R1 to R4 is selected from the group consisting of hydrogen, a substituted hydrocarboyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarobyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof; at least one of R1 to R4 is not hydrogen; E1 and E2 are the same or different, and are selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, including a cycloalkyl group having 5 to 10 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a substituted aryl group having 6 to 20 carbon atoms, or an inert functional group having 1 to 20 carbon atoms and optionally containing a heteroatom; X1 and X2 are each O, S, an alkyl group, or NR5, and R5 is a hydrocarbyl group having 1 to 20 carbon atoms or hydrogen.

[0060] In one embodiment, R1 and R4 are each a saturated or unsaturated hydrocarbyl group having 1 to 20 carbon atoms, at least one of R2 and R3 is hydrogen, at least one of R2 and R3 includes a substituted or unsubstituted hydrocarbyl group having 5 to 15 carbon atoms, the hydrocarbyl group having a branched or linear structure or includes a cycloalkyl group, an aryl group, and a substituted aryl group having 5 to 15 carbon atoms, for example, 7 to 15 carbon atoms, E1 and E2 are the same or different and are selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a substituted aryl group having 6 to 20 carbon atoms, or an inert functional group having 1 to 20 carbon atoms and optionally containing a heteroatom, X1 and X2 are each O, S, an alkyl group, or NR5, and R5 is a hydrocarbyl group having 1 to 20 carbon atoms or is hydrogen.

[0061] In one embodiment, R1 and R4 are the same or very similar. In one embodiment, for example, R1 and R4 are linear hydrocarbyl groups. For example, R1 and R4 can include C1-C8 alkyl groups, C2-C8 alkenyl groups, or mixtures thereof. For example, in one embodiment, R1 and R4 can both include alkyl groups having the same carbon chain length or where the carbon chain length varies by about 3 carbon atoms or less, for example about 2 carbon atoms or less.

[0062] In one embodiment, R4 is a methyl group and R1 is a methyl group, an ethyl group, a propyl group, or a butyl group, or vice versa. In another alternative embodiment, R1 and R4 are both methyl groups, R1 and R4 are both ethyl groups, R1 and R4 are both propyl groups, or R1 and R4 are both butyl groups.

[0063] In relation to the R1 and R4 groups above, in one embodiment, at least one of R2 or R3 is a larger or bulkier substituent than the R1 and R4 groups. The other of R2 or R3 can be hydrogen. The larger or bulkier group located at R2 or R3 can be, for example, a hydrocarbyl group having a branched or straight chain structure, or can include a cycloalkyl group having 5 to 15 carbon atoms. The cycloalkyl group can be, for example, a cyclopenyl group, a cyclohexyl group, a cycloheptyl group, or a cyclooctyl group. When either R2 or R3 has a branched or straight chain structure, the other R2 or R3 can be a butyl group, a pentyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, or the like. For example, R2 or R3 can be a t-butyl group, a 3-pentyl group, or a 2-pentyl group.

[0064] Further examples of internal electron donors made according to the present disclosure are shown below (Formulas I-XII): In each of the following structures, R1-R4 may be substituted with any of the groups in any of the combinations described above.

[0065] [ka] In formula (I), R to R 15 may be the same or different. 15 Each of may be selected from hydrogen, substituted hydrocarbyl groups having 1 to 20 carbon atoms, and unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, alkoxyl groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof.

[0066] [ka] In formula (II), X1 and X2 can be oxygen, sulfur, or nitrogen-containing groups. In one embodiment, for example, X1 is oxygen and X2 is sulfur. R5a and R 5b R can be independently an alkyl group or an aryl group. 5a and R 5b In other embodiments, may individually be a C1 to C8 alkyl group.

[0067] [ka] In formula (III), R 16 and R 17 are independently hydrogen or C1-C 20 X1 and X2 are hydrocarbyl groups. In the above formula, X1 and X2 can be oxygen, sulfur, or nitrogen groups. Alternatively, one or both of X1 and X2 can be a hydrocarbyl group, such as an alkyl group containing 1 to 3 carbon atoms. X3 can be a -OR group or a -NR'R'' group, where R, R', or R'' are C1 to C2 groups, optionally containing heteroatoms independently selected from halogen, phosphorus, sulfur, nitrogen, or oxygen. 20 is a hydrocarbyl group. In one embodiment, X1 is a carbon atom and X3 is an ethyl group.

[0068] [ka] In formula IV, R 5ccan be an alkyl group or an aryl group. For example, R 5c can be a C1 to C8 alkyl group.

[0069] [ka]

[0070] [ka] In the above formula, R 18 can be hydrogen or a hydrocarbyl group containing from about 1 to about 8 carbon atoms.

[0071] [ka]

[0072] [ka] In the above formula, R 19 , R 20 , and R 21 R can be the same or different and can be selected from hydrocarbyl groups having from about 1 to about 15 carbon atoms, optionally containing heteroatoms selected from halogen, phosphorus, sulfur, nitrogen, or oxygen. 20 and R 21 can be the same or different and can be fused together to form one or more cyclic groups.

[0073] As used herein, the terms "hydrocarbyl" and "hydrocarbon" refer to substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, fused, or acyclic species, and combinations thereof. Non-limiting examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, alkylaryl, and alkynyl groups.

[0074] As used herein, the terms "substituted hydrocarbyl" and "substituted hydrocarbon" refer to a hydrocarbyl group substituted with one or more non-hydrocarbyl substituents. A non-limiting example of a non-hydrocarbyl substituent is a heteroatom. As used herein, "heteroatom" refers to an atom other than carbon or hydrogen. A heteroatom can be a non-carbon atom from Groups IV, V, VI, and VII of the periodic table. Non-limiting examples of heteroatoms include halogens (F, Cl, Br, I), N, O, P, B, S, and Si. Substituted hydrocarbyl groups also include halohydrocarbyl groups and silicon-containing hydrocarbyl groups. As used herein, the term "halohydrocarbyl" group refers to a hydrocarbyl group substituted with one or more halogen atoms. As used herein, the term "silicon-containing hydrocarbyl group" is a hydrocarbyl group substituted with one or more silicon atoms. The silicon atom may or may not be in the carbon chain.

[0075] The support donor is generally present in the catalyst component in an amount of about 0.5% by weight to about 7% by weight, such as about 2% by weight to about 6% by weight, for example about 3% by weight to about 5.5% by weight. A portion of the support donor is generally removed from the catalyst component when the activity control agent is added. For example, when an activity control agent is incorporated into the catalyst component, about 1% by weight to about 20% by weight, for example about 4% by weight to about 16% by weight of the monobenzoate support donor may be lost compared to the amount of monobenzoate present in the catalyst precursor.

[0076] The internal donor is generally present in the catalyst component in an amount of from about 3% to about 25% by weight, such as from about 5% to about 12% by weight, for example from about 8% to about 17% by weight, for example from about 10% to about 15% by weight, for example from about 12% to about 14% by weight.

[0077] The catalyst component generally contains titanium in an amount of about 1% by weight to about 10% by weight, for example, about 1.5% by weight to about 5% by weight, for example, about 2% by weight to about 4% by weight, for example, about 2.5% by weight to about 3.5% by weight. The catalyst component generally contains magnesium in an amount of about 10% by weight to about 20% by weight, for example, about 15% by weight to about 18% by weight.

[0078] B. Activity control agents The catalyst components further contain an activity control agent. The activity control agent can be added to the catalyst precursor by mixing the catalyst precursor with the activity control agent in a hydrocarbon solvent. The catalyst components can then be filtered off.

[0079] For example, in one embodiment, the catalyst precursor is contacted with the activity control agent in a hydrocarbon solvent at a temperature of about 10° C. to about 40° C., e.g., about 15° C. to about 35° C., e.g., about 20° C. to about 30° C. 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 C2-C20 alkylbenzenes. In certain embodiments, the non-aromatic hydrocarbon solvent is a cycloalkyl compound, such as hexane.

[0080] The activity control agent may be added in an amount of about 0.01 to about 1.0 mole per mole of Ti, such as about 0.05 to about 0.7 mole per mole of Ti, such as about 0.08 to about 0.6 mole per mole of Ti, such as about 0.1 to about 0.5 mole per mole of Ti. The activity control agent is generally present in the catalyst component in an amount of about 0.1% to about 20% by weight of the catalyst component.

[0081] The activity control agent is (a) an organosilicon compound containing a Si-O group, (b) a C4-C 30 The organic ester may be an organic ester from a fatty acid ester or a poly(alkene glycol) ester of a C4 to C30 fatty acid, (c) an organoaluminum compound containing an alkyl group, or a combination thereof.

[0082] The inventors have discovered that when the activity control agent is added to the catalyst precursor, the activity control agent becomes chemically bound to the halide-containing magnesium compound. In binding to the halide-containing magnesium compound, the ACA causes partial removal of the support donor and causes a change in the coordination between the internal donor and the halide-containing magnesium support.

[0083] The organosilicon compound containing Si-O groups may be represented by the following chemical formula: R n Si(OR') 4-n wherein each R and R' independently represents a hydrocarbon group, such as hydrogen, an alkyl, or an aryl group, and n is 0≦n<4.

[0084] Specific examples of the organosilicon compound include, but are not limited to, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclopentyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tridimethoxysilane, bis-m-dimethoxysilane, bis-p-tridimethoxysilane, bis-p-tridiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, Silanes include decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, gamma-amniopropyltriethoxysilane, cholotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethylsilicate, butylsilicate, trimethylphenoxysilane, and methyltriallyloxysilane.

[0085] In one embodiment, the catalyst component contains an organosilicon compound containing Si-O groups in an amount of from about 0.1% to about 5% by weight, such as from about 0.2% to about 4% by weight, e.g., from about 0.15% to about 2% by weight, of the catalyst component.

[0086] In another embodiment, the ACA is a C 30 Fatty acid ester. Suitable C4-C 30 Non-limiting examples of aliphatic acid esters include aliphatic C 4~30 Monocarboxylic acid C 1~20 Alkyl ester, aliphatic C 8~20 Monocarboxylic acid C 1~20 Alkyl ester, aliphatic C 4~20 C of monocarboxylic and dicarboxylic acids 1~4 Alkyl mono- and diesters, aliphatic C 8~20 C of monocarboxylic and dicarboxylic acids 1~4 Alkyl esters, and C 2~100 (Poly)glycol or C 2~100 (Poly)glycol ether C 4~20 Mono- or polycarboxylate derivatives are included. In one embodiment, C4-C 30 The fatty acid esters can be isopropyl myristate, pentyl valerate, and / or di-n-butyl sebacate.

[0087] In another embodiment, the active control agent is a poly(alkylene glycol) ester. Non-limiting examples of suitable poly(alkylene glycol) esters include 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), C 2~40 glyceryl tri-esters of aliphatic carboxylic acids, and any combination thereof. In certain embodiments, the poly(alkylene glycol) portion of the poly(alkylene glycol) ester is poly(ethylene glycol).

[0088] When used, C4~C 30 Fatty acid ester or C4-C 30The poly(alkylene glycol) ester of a fatty acid is present in the catalyst component in an amount of from about 0.1% to about 15% by weight, such as from about 0.5% to about 14% by weight, for example, from about 1% to about 12% by weight.

[0089] In one embodiment, the active control agent is an organoaluminum compound containing an alkyl group. Examples of such organoaluminum compounds include those of the formula: AlR n X 3-n In the formula, R independently represents a hydrocarbon group having usually 1 to about 20 carbon atoms, X represents a halogen atom, and <n≦3である。

[0090] Specific examples of organoaluminum compounds include, but are not limited to, trialkylaluminums such as triethylaluminum, tributylaluminum, and trihexylaluminum; trialkenylaluminums such as triisoprenylaluminum; dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, and diethylaluminum bromide; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride, and dibutylaluminum hydride; and other partially hydrided alkylaluminums such as ethylaluminum dihydride, and propylaluminum dihydride.

[0091] When an organoaluminum compound is used, the organoaluminum compound is generally present in the catalyst component in an amount of about 0.1% by weight to about 5% by weight, for example, about 0.15% by weight to about 2% by weight, for example, about 0.2% by weight to about 1.5% by weight.

[0092] C. Polymerization The olefin polymerization process according to the present disclosure is carried out in the presence of a catalyst system comprising a solid catalyst component as described herein, a cocatalyst such as an organoaluminum compound, and optionally an external electron donor such as an organosilicon compound. Generally speaking, an olefin, CH2=CHR, where R is hydrogen or a hydrocarbon radical having 1 to 12 atoms, is contacted with the catalyst system under conditions suitable to form a polymeric product. The term polymerization as used in this disclosure may include copolymerization, such as random or multi-stage copolymerization, used to produce heterophasic copolymers. The polymerization process may be carried out according to known techniques, for example, gas phase in a fluidized or stirred bed reactor, slurry polymerization using an inert hydrocarbon solvent as diluent, or slurry polymerization using liquid monomers as reactants and diluents. The polymerization process may also be a combination or hybrid process, for example, a bulk propylene liquid loop reactor connected to a gas phase reactor. The polymerization is generally carried out at a temperature of 20-120°C, more preferably at about 50-90°C.

[0093] In one embodiment, the catalyst components or a portion of the catalyst components are pre-contacted before being fed to the polymerization reactor zone. The pre-contact step is typically carried out at higher concentration and lower temperature conditions than the polymerization reactor zone. In another embodiment, the solid catalyst components can be fed separately to the reactor and contacted with the cocatalyst and external electron donor under polymerization conditions. The organoaluminum cocatalyst is preferably used in a molar amount of about 1-1000, preferably about 100-600, more preferably about 45-300, relative to the moles of titanium in the procatalyst. The external electron donor is preferably used in a molar amount of about 0.005-1.0, more preferably about 0.01-0.5, relative to the moles of organoaluminum cocatalyst. At high levels of external electron donor, the ability to further reduce amorphous polypropylene as measured by xylene solubles may be reduced, decreasing catalyst activity. The procatalysts of the present disclosure can reach low xylene solubles levels before reaching a point where reduction feeding the external electron donor is reduced. In some cases, very low XS of 1% or less is achievable.

[0094] In some embodiments, a prepolymerization step (prepolymerization) is carried out before the main polymerization. In another embodiment, the main polymerization is carried out without a prepolymerization step. When using prepolymerization, the prepolymerization may be carried out batchwise, followed by feeding the prepolymerization catalyst to the polymerization process. Alternatively, the catalyst may be fed to a continuous polymerization process, and the prepolymerization step may be carried out as part of the process. The prepolymerization temperature is preferably in the range of -20 to +100°C, more preferably -20 to +80°C, and most preferably 0 to +40°C. By carrying out a prepolymerization step, it is possible to improve the catalyst activity, stereoselectivity, particle fragmentation, and the resulting polymer morphology.

[0095] Hydrogen is typically added as a chain transfer agent to control polymer molecular weight. Different polymerization processes have different limitations on the amount of hydrogen that can be added to lower polymer molecular weight. The procatalysts of the present disclosure have increased sensitivity to hydrogen, thus improving the molecular weight control ability of the process and expanding the types of polymers that can be produced.

[0096] The present disclosure may be better understood with reference to the following examples. EXAMPLES

[0097] The following parameters are defined as follows:

[0098] Catalyst particle morphology is indicative of the polymer particle morphology produced therefrom. Three parameters of polymer particle morphology (sphericity, symmetry, and aspect ratio) can be determined using the Camsizer instrument. Camsizer features: Sphericity

[0099]

number

[0100] Symmetry is defined as follows:

[0101]

number

[0102]

number

[0103] Aspect Ratio:

[0104]

number

[0105] Catalyst morphology features such as aspect ratio ("B / L3") can be used to characterize polymer morphology.

[0106] "D 10 " represents the diameter of a particle below which 10% of the particles are. 50 " represents the size of a particle below which 50% of the particles are, and "D 90 " represents the size of a particle below which 90% of the particles are. "Span" represents the particle size distribution. This value can be calculated according to the following formula: Span=(D 90 -D 10 ) / D 50

[0107] BD is an abbreviation for bulk density and is reported in g / ml.

[0108] CE is an abbreviation for catalyst efficiency and is reported in units of Kg of polymer per gram of catalyst (Kg / g) during one hour of polymerization.

[0109] MFR is an abbreviation for melt flow rate and is reported in g / 10 min. MFR is measured according to ASTM test D1238 T.

[0110] EB is an abbreviation for ethyl benzoate.

[0111] Ti, Mg, and D are the weight percent (wt %) of each of the titanium, magnesium, and internal donor in the composition, respectively.

[0112] XS is an abbreviation for xylene soluble and is reported in weight percent.

[0113] sl is the abbreviation for standard liter.

[0114] Example 1. Preparation of catalyst component (1) (comparative). MgCl2 (13.2 g), toluene (59.5 g), tri-n-butyl phosphate (36.3 g), and epichlorohydrin (14.25 g) were combined and heated to 60° C. under nitrogen atmosphere with stirring at 600 rpm for 8 hours. After cooling to room temperature, toluene (140 g) was added along with ethyl benzoate (3.5 g) and tetraethyl orthosilicate (6 g). The mixture was then cooled to −25° C., and TiCl4 (261 g) was added slowly under stirring at 600 rpm while maintaining the temperature at −25° C. After the addition was complete, the temperature was maintained for 1 hour, then warmed to 35° C. over 30 minutes and held at that temperature for 30 minutes, then the temperature was increased to 85° C. over 30 minutes and held for 30 minutes, after which the solid precipitate was collected by filtration. The solid precipitate was washed three times with toluene (200 ml each wash). The resulting precipitate was then combined with toluene (264 ml). The mixture was heated to 105° C. under stirring, followed by the addition of an internal electron donor (2.4 g) in toluene (10 g). The internal electron donor was tert-butyl (3-methyl-5-t-butylcatechol dibenzoate) (CDB-1).

[0115] Heating at 105°C was continued for 1 hour and the solid was collected by filtration. The process involved combining with TiCl4 in toluene and heating at 105°C and again at 110°C to form catalyst component (1). Catalyst component (1) was washed four times with hexane (200 ml each wash) and stirred at 60-65°C for 10 minutes for each wash.

[0116] Example 2. Preparation of catalyst component (2). 2.00 grams of dried catalyst component (1) was added to a 50 mL vial with a stir bar. 20 grams of hexane and 0.295 g of 10% dicyclopentyldimethoxysilane (D donor) were added at ambient temperature. The mixture was stirred at ambient temperature for 1 hour. The liquid was filtered and the solid was washed three times with hexane. The solid was dried to form catalyst component (2).

[0117] Example 3. Preparation of catalyst component (3). 1.00 grams of dried catalyst component (1) was added to a 50 mL vial with a stir bar. 20 grams of hexane and 4.29 g of 10% D donor were added at ambient temperature. The mixture was stirred at ambient temperature for 1 hour. The liquid was filtered and the solid was washed with hexane three times. The solid was dried to form catalyst component (3). The compositions of catalyst components 1-3 are provided in Table 1.

[0118] [Table 1]

[0119] As shown, the amount of ethyl benzoate is reduced in Examples 2 and 3 compared to the untreated catalyst component (1) due to the substitution of the D donor on the MgCl2 surface of the catalyst component. Increasing the amount of D donor in Example 3 resulted in a greater reduction in ethyl benzoate. The amount of the internal donor CDB-1 was unchanged.

[0120] Examples 8-16 illustrate the preparation and composition of catalyst components containing CDB-2 as the internal donor, ethyl benzoate as the supporting donor, and either dicyclopentyldimethoxysilane (D donor) or cyclohexylmethyldimethoxysilane (C donor) as the ACA. The examples show the change in catalyst component composition after treatment with ACA. For example, ACA partially replaces the supporting electron donor while keeping the amount of internal electron donor CDB-2 the same compared to the catalyst component of Comparative Example 4.

[0121] Examples 4-7. Preparation of catalyst components (4-7) (comparative). Catalyst components 4, 5, 6, and 7 were prepared based on Example 1, except that CDB-2 was used as the internal donor (2.5-3.0 g) and the TiCl4 treatment conditions were varied. CDB-2 is a catechol dibenzoate described in paragraph 52 of U.S. Patent Application Publication No. 2013 / 0261273, which is incorporated herein by reference.

[0122] Example 8. Preparation of catalytic component (8). Catalytic component (4) was treated under the conditions described in Example 2 with a D donor in an amount of 0.1 mole per mole of Ti.

[0123] Example 9. Preparation of catalytic component (9). Catalyst component (4) was treated with D donor in an amount of 0.5 moles per mole of Ti under the conditions described in Example 2. The compositions of catalytic components 4, 8, and 9 are provided in Table 2.

[0124] [Table 2]

[0125] Example 10. Preparation of catalytic component (10). Catalytic component (5) was treated under the conditions described in Example 2 with a D donor in an amount of 0.1 mole per mole of Ti.

[0126] Example 11. Preparation of catalytic component (11). Catalyst component (5) was treated with D donor in an amount of 0.2 moles per mole of Ti under the conditions described in Example 2. The compositions of catalytic components 5, 10, and 11 are provided in Table 3.

[0127] [Table 3]

[0128] Example 12. Preparation of catalytic component (12). Catalytic component (6) was treated under the conditions described in Example 2 with a D donor in an amount of 0.1 mole per mole of Ti.

[0129] Example 13. Preparation of catalytic component (13). Catalyst component (6) was treated with cyclohexylmethyldimethoxysilane (C donor) in an amount of 0.1 mole per mole of Ti under the conditions described in Example 2. The compositions of catalytic components 6, 12, and 13 are provided in Table 4.

[0130] [Table 4]

[0131] Example 14. Preparation of catalytic component (14). Catalytic component (7) was treated under the conditions described in Example 2 with a D donor in an amount of 0.1 mole per mole of Ti.

[0132] Example 15. Preparation of catalytic component (15). Catalytic component (7) was treated under the conditions described in Example 2 with a D donor in an amount of 0.15 moles per mole of Ti.

[0133] Example 16. Preparation of catalytic component (16). Catalyst component (7) was treated with a C donor in an amount of 0.1 mole per mole of Ti under the conditions described in Example 2. The compositions of catalytic components 7, 14, 15, and 16 are provided in Table 5.

[0134] [Table 5]

[0135] Example 17. Preparation of catalytic component (17) (comparison). Catalyst component (17) was prepared according to Example 1, with the addition of the second electron donor diether (3,3-bis(methoxymethyl)-2,6-dimethylheptane) (DEMH) and a reduction in the amount of CDB-1.

[0136] Example 18. Preparation of catalyst component (18). Catalyst component (17) was reacted with a D donor under the conditions described in Example 2.

[0137] [Table 6]

[0138] Example 19. Catalyst component (19) (comparative). CONSISTA® catalyst component Grace available from WR was used as catalyst component 19.

[0139] Example 20. Preparation of catalytic component (20). Catalytic component (19) was treated with a D donor under the conditions described in Example 2.

[0140] Bulk Propylene Polymerization Polypropylene was produced using the catalyst components of the above examples. The following procedure was used: Prior to carrying out the polymerization, the reactor was baked out at 100°C for 30 minutes under nitrogen flow. The reactor was cooled to 30-35°C and the cocatalyst (1.5ml of 25wt% triethylaluminum (TEAl)), C donor (cyclohexylmethydimethoxysilane) (1ml), hydrogen (3.5psi) and liquid propylene (1500ml) were added to the reactor in that order. The catalyst (5-10mg) loaded as a mineral oil slurry was forced into the reactor using high pressure nitrogen. The polymerization was carried out at 70°C for 1 hour. After polymerization, the reactor was cooled to 22°C, vented to atmospheric pressure and the polymer was collected.

[0141] Bulk polymerization results from the first and second hours of polymerization were used to compare the catalytic performance of treated and untreated catalysts. The catalytic activity at the first and second hours of polymerization was calculated based on the product polymer collected during each hour.

[0142] The examples in Tables 7-11 demonstrate the performance of the catalyst components in propylene polymerization. The performance of the catalyst components is compared to comparative examples prepared without ACA. The catalyst activity was measured during the first and second hours of polymerization. The results in the tables show that the catalyst activity of the catalyst containing ACA decreases in the first hour of polymerization compared to the comparative catalyst components, but remains high and stable through the second hour of polymerization. The reduction in activity of the catalyst containing ACA is variable and depends on the catalyst components and the nature of the ACA used. A stronger effect of D donors on catalyst life was observed compared to C donors. The amount of ACA used in the preparation of each catalyst component affects the catalyst activity. For example, the catalyst activity in both the first and second hours decreases as the amount of ACA increases.

[0143] The observed improvement in catalyst lifetime can be explained by the fact that the coordination of ACA on the MgCl2 surface of the catalyst changes the coordination of the internal donors around the Ti active centers, partially deactivating the highly active catalytic centers and resulting in a longer catalyst lifetime during the second hour of the polymerization process.

[0144] [Table 7]

[0145] [Table 8]

[0146] [Table 9]

[0147] [Table 10]

[0148] [Table 11]

[0149] Example 34. Preparation of aluminum-containing catalyst components (catalyst components 21-27). Catalyst component (4) was treated with various amounts of Et3Al and D donor. The amount of ACA used and the composition of the resulting catalyst are shown in Table 12. As shown, the amount of support donor (ethyl benzoate) was reduced compared to catalyst component (4), and the catalyst component contains aluminum.

[0150] [Table 12]

[0151] Examples 35-41. Polymerization with aluminum-containing catalyst components. Catalyst components 21-27 were tested in the same manner as in Examples 21-33. The results are shown in Table 13.

[0152] Examples 35-39 demonstrate catalytic performance with catalyst components containing different amounts of Al, resulting in different distributions of catalytic activity between the first and second hours of polymerization. These examples show better distribution of catalytic activity and improved polymer morphology (bulk density and sphericity data) compared to Comparative Example 23.

[0153] Examples 40 and 41 demonstrate the catalytic performance with catalyst components (26) and (27) containing two ACAs (D donor and TEAl).

[0154] [Table 13]

[0155] Examples 42-58. Two types of spherical catalyst components containing ACA were prepared and tested. The first type, used in Examples 42-50, was prepared with a support prepared using an emulsion method as described in US Patent Application Publication No. 2020 / 0283553. Catalyst components 29-31 used a support in combination with ACA and CDB-2 as an internal donor.

[0156] Example 42. Spherical catalyst component (28) (comparison). The spherical catalyst component (28) was prepared based on magnesium alkoxide as described in US Patent Application Publication No. 2020 / 0283553.

[0157] Example 43. Preparation of spherical catalyst component (29). Catalyst component (28) was treated with a D donor as described in Example 2 with Ti / D=0.1.

[0158] Example 44. Preparation of spherical catalyst component (30). Catalyst component (28) was treated with a D donor as described in Example 2 with Ti / D=0.2.

[0159] Example 45. Preparation of spherical catalyst component (31). Catalyst component (28) was treated with Et3Al (Ti / Al=0.5). The compositions of catalyst components 28-31 are provided in Table 14.

[0160] Examples 46-48. Examples 47 and 48 demonstrate bulk propylene polymerization with spherical catalyst components (29) and (31). The examples show improved bulk density of polymer particles produced with these catalysts compared to Example 46. Results are provided in Table 15.

[0161] [Table 14]

[0162] [Table 15]

[0163] Examples 49 and 50. In Example 50, catalyst component (31) was tested using a "stress test" in which the catalyst was injected into a polymerization reactor at 60° C. to compare the catalyst performance without a prepolymerization step. The bulk density of the polymer particles produced under these conditions is compared with catalyst component (28) (Comparative Example 49).

[0164] [Table 16]

[0165] The second type of spherical catalyst used in Examples 51-58 was prepared based on spherical MgCl2nEtOH support containing CDB-2 as the internal donor.

[0166] Example 51. Spherical catalyst component (32) (comparison). The spherical catalyst component (32) was prepared based on spherical MgCl2n nEtOH and CDB-2, as described in PCT International Publication No. WO 2021 / 055430, which is incorporated herein by reference.

[0167] Example 52. Preparation of spherical catalyst components (33) and (34). Catalyst component (33): Catalyst component 32 was treated with D donor (Ti / D=1.0 / 0.2) as described in Example 2. Catalyst component (34): Catalyst component 32 was treated with Et3Al (Ti / Al=1.0 / 0.8) in hexane at ambient temperature for 1 hour. The solid was washed with hexane and dried. Catalyst components (33) and (34) were tested in standard bulk propylene polymerizations (Table 17) including precontacting and prepolymerization steps, and under the above-mentioned "stress" test (Table 18). The catalytic performance was compared with that of comparative catalyst component (32) that does not contain ACA.

[0168] Examples 54, 55, 57, and 58 demonstrate the improvement in bulk density and sphericity of polymers produced with catalyst components made with D donors and Et3Al.

[0169] [Table 17]

[0170] [Table 18]

[0171] Examples 59-63. A different ACA, isopropyl myristate (IPM), was used.

[0172] Example 59. Preparation of catalyst component (35). Example 1 was repeated with the addition of isopropyl myristate (IPM) (3.0 g), followed by the addition of CDB-1.

[0173] Example 60. Preparation of catalyst component (36). Example 1 was repeated, adding isopropyl myristate (IPM) (3.0 g) at the final stage of the TiCl4 treatment.

[0174] Example 61. Preparation of catalyst component (37). Example 4 was repeated, adding isopropyl myristate (IPM) (3.0 g) at the final stage of the TiCl4 treatment.

[0175] Example 62. Preparation of catalyst component (38). Catalyst component (6) (3.00 g) was treated with IPM (0.525 g) in hexane at ambient temperature for 1 hour. The solid was washed with hexane and dried.

[0176] Example 63. Preparation of catalyst component (39). Catalyst component (27) (1.00 g) was treated with D donor in hexane (0.143 g of a 10% solution in hexane) at ambient temperature for 1 hour. The solid was washed with hexane and dried.

[0177] Examples 64-66. Catalyst components (35)-(39) were tested in bulk propylene polymerization to evaluate the catalytic activity in the first and second hours of polymerization. Examples 64 and 65 demonstrate polymerization with catalyst components (35) and (36) containing CDB-1 and ethyl benzoate prepared with IPM as ACA. The impregnation method of IPM was found to affect the catalytic activity during the first and second hours of polymerization. For example, Example 65 shows a dramatic improvement in polymerization kinetics, with a higher catalytic activity in the second hour than in the first hour. Example 21 can be used as a comparative example, where a higher catalytic activity is observed in the first hour of polymerization.

[0178] Catalyst components (37) and (38) containing CDB-2, ethyl benzoate, and IPM prepared by different methods exhibit different polymerization behaviors. Example 66 with catalyst component (34) demonstrates higher catalytic activity in the first and second hours of polymerization compared to Comparative Example 29, with nearly flat kinetics.

[0179] Catalyst component (39) was prepared with two ACAs (D donor and IPM). Example 58 demonstrates the polymerization behavior of catalyst component (39), showing a reduction in catalytic activity but maintaining a higher catalytic activity in the second hour of polymerization than in the first hour, which provides benefits for a multi-reactor polymerization process.

[0180] [Table 19]

[0181] [Table 20]

[0182] Catalyst components containing ACA for controlling catalyst activity at high polymerization temperatures are described in Examples 69 to 70. The reduction in catalyst activity (self-extinguishing) at high polymerization temperatures is an important catalyst feature to prevent uncontrolled polymerization and plugging of polymerization reactors.

[0183] It has been found that the ACAs described herein, such as organic esters of C4-C30 fatty acids, poly(alkene glycol) esters of C4-C30 fatty acids, organosilicon compounds, and alkylaluminum compounds, can also provide self-extinguishing properties. The ACAs can be used alone or in combination to achieve this effect. For example, as shown below, C4-C30 fatty acids or poly(alkene glycol) esters of C4-C30 fatty acids can be used alone as ACAs to demonstrate self-extinguishing properties.

[0184] Examples of the preparation of catalyst components containing isopropyl myristate are described in Examples 35-39.

[0185] Catalyst component 40 containing pentyl valerate (PV) is prepared by the same procedure as catalyst component 35, except that PV (0.23 g per g MgCl2) is used instead of IPM.

[0186] Catalyst components containing benzoate-supported donors and internal donors exhibit some self-extinguishing (reduced catalyst activity at high polymerization temperatures). However, it has been observed that the combination of benzoate-supported donors, internal donors, and ACA in the catalyst component increases the self-extinguishing property of the catalyst.

[0187] To test the self-extinguishing property, polymerizations were carried out in a bulk propylene polymerization reactor for 30 minutes at 70, 80, and 90° C. The ratio of catalyst activity at 90° C. and 80° C. was used to compare the self-extinguishing property of the catalysts.

[0188] Examples 69-70 illustrate the catalyst component behavior at high polymerization temperatures (Table 19). Example 69 uses catalyst component 1, and Example 70 uses catalyst component 40, which contains PV as ACA. Example 70 shows a higher reduction (15%) in catalyst activity at 90°C compared to Example 69.

[0189] [Table 21]

[0190] Example 71. Donor coordination in treated and untreated catalysts. The effect of incorporating ACA on donor coordination was studied by comparing the FTIR spectra of catalyst components with and without ACA. Figure 1 illustrates the effect of D-donor on the coordination of CDB-2 donor. The broad peak in the 1700 cm-1 region is associated with the C=O group from CDB-2 donor and ethyl benzoate. To understand the specific difference in the coordination of the internal donor, the peak was deconvoluted into several peaks of different assigned complexes (donor / Q4- and donor / Q5-MgCl2) on the MgCl2 surface (Table 20).

[0191] The ratio of CDB-2 Q5 / Q4-MgCl2 complex and the maximum frequency of C=O groups in the FTIR spectra were analyzed for their effect on the catalyst lifetime (distribution of catalyst activity between the 1st and 2nd hours of the polymerization process).

[0192] It was found that an increase in the Q5 / Q4 ratio (increasing the concentration of the weaker complex) resulted in an increase in the catalyst activity in the second hour of polymerization.

[0193] [Table 22]

[0194] While certain embodiments have been illustrated and described, it should be understood that changes and modifications may be made therein by those skilled in the art without departing from the technology in its broader aspects as defined in the following claims.

[0195] The embodiments illustratively described herein may be suitably practiced in the absence of any element(s), limitation(s) not specifically disclosed herein. Thus, for example, terms such as "comprising", "including", "containing" and the like should be read expansively and without limitation. In addition, the terms and expressions used herein are used as terms of description and not of limitation, and in the use of such terms and expressions, there is no intention to exclude any equivalents of the shown and described features or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. In addition, the phrase "consisting essentially of" will be understood to include those elements specifically recited, as well as those additional elements that do not materially affect the basic and novel features of the claimed technology. The phrase "consisting of" excludes any elements not specified.

[0196] The present disclosure is not limited with respect to the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope of the present invention. In addition to those recited herein, functionally equivalent methods and compositions within the scope of the present disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that the present disclosure is not limited to particular methods, reagents, compounds, compositions, or biological systems, which may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0197] Additionally, when features or aspects of the disclosure are described in terms of a Markush group, one of skill in the art will recognize that the disclosure is also thereby described in terms of any individual members or subgroups of members of the Markush group.

[0198] As will be understood by those skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein encompass any and all possible subranges and combinations thereof. It can be easily recognized that any recited range fully describes and allows for the same range to be subdivided into at least two, three, four, five, ten, etc. As a non-limiting example, each range discussed herein can be easily subdivided into a lower third, a middle third, and an upper third, etc. Also, as will be understood by those skilled in the art, all terms such as "up to," "at least," "greater than," "less than," etc. refer to ranges that include the recited numbers and can then be subdivided into the subranges discussed above. Finally, as will be understood by those skilled in the art, a range includes each individual member.

[0199] All publications, patent applications, issued patents, and other documents referenced herein are incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in the descriptions incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0200] Other embodiments are within the scope of the following claims.

Claims

1. 1. An isolated solid catalyst component for olefin polymerization, said component comprising: a halide-containing magnesium compound; a titanium halide compound; a support donor comprising a benzoate; an internal electron donor; an activity control agent (ACA), a first organosilicon compound containing Si—O groups present in said catalyst component in an amount of from about 0.1 to about 5 weight percent; C in an amount of about 0.1% to about 15% by weight ４ ~C ３０ Organic esters of fatty acids or C ４ ~C ３０ poly(alkene glycol) esters of fatty acids, and the reaction product of an alkyl group-containing organoaluminum compound with an activity control agent (ACA), A solid catalyst component wherein at least a portion of said ACA is chemically bonded to said halide-containing magnesium compound.

2. the supporting electron donor is present in the catalyst component in an amount of from about 0.5% to about 7% by weight; 10. The solid catalyst component of claim 1, wherein the internal electron donor is present in the catalyst component in an amount of from about 3% to about 25% by weight.

3. 10. The solid catalyst component of claim 1, wherein the internal electron donor comprises a diester, a diether, a succinate, or any combination thereof.

4. 2. The solid catalyst component of claim 1, wherein the halide-containing magnesium compound comprises magnesium chloride.

5. the first organosilicon compound is a silane, siloxane, or polysiloxane having the following chemical structure: R ｎ Si(OR’) ４－ｎ During the ceremony, each R is H, alkyl, or aryl; Each R' is H, alkyl, aryl, or SiR ｎ’ (OR') ３－ｎ and 2. The solid catalyst component according to claim 1, wherein n is 0, 1, 2, or 3.

6. The internal electron donor is represented by the formula: 【Chemical 1】 During the ceremony, R １５ ~R ２０ each is independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; q is an integer from 0 to 12; or The internal electron donor is represented by one of the following formulas: 【Chemistry 2】 In the formula, R １ ~R ４ are the same or different, and each R １ ~R ４ is selected from the group consisting of hydrogen, substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof; R １ ~R ４ At least one of the atoms is not hydrogen, E １ and E ２ are the same or different, and each E １ and E ２ is selected from the group consisting of substituted hydrocarbyl groups having 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof; X １ and X ２ are each O, S, an alkyl group, or NR ５ and R ５ is a hydrocarbyl group having 1 to 20 carbon atoms or hydrogen; 【Chemistry 3】 During the ceremony, R ６０ ~R ６５ each is independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; or 【Chemistry 4】 In the formula, R ６６ ~R ７３ each is independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl group; or The supporting electron donor has the formula: 【Chemistry 5】 wherein R' comprises an alkyl group, a cyclic group, an aryl group having 1 to 20 carbon atoms, a heteroatom, or a combination thereof; and R'' comprises one or more substituents, each of which may independently comprise hydrogen, an alkyl group, a cyclic group, an aryl group having 1 to 20 carbon atoms, a heteroatom, or a combination thereof. The solid catalyst component according to claim 1 .

7. further comprising a second organosilicon compound different from the first organosilicon compound; the second organosilicon compound comprises tetraethyl orthosilicate and / or polydimethylsiloxane; the first organosilicon compound comprises dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, n-propyltrimethoxysilane, trimethoxysilane, or any combination thereof; The solid catalyst component according to claim 1 .

8. the ACA comprises an organosilicon compound and no organoaluminum component is contained in the catalyst component; or the ACA comprises a combination of a) dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, n-propyltrimethoxysilane, and / or trimethoxysilane, and b) an organoaluminum compound containing an alkyl group; or the ACA comprises an organoaluminum compound, and no organosilicon compounds other than polydialkylsiloxanes and / or tetraalkoxysilanes are present in the catalyst component; or the ACA comprises an organic ester of an aliphatic C4 to C30 mono- or di-carboxylic acid; The solid catalyst component according to claim 1 .

9. 9. The solid catalyst component according to claim 8, wherein the organic ester is selected from the group consisting of isopropyl myristate, di-n-butyl sebacate, (poly)(alkylene glycol), mono- or di-myristate, pentyl valerate, and combinations thereof.

10. 2. The solid catalyst component of claim 1, wherein the ACA comprises a combination of a) dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, n-propyltrimethoxysilane, and / or trimethoxysilane and b) an organic ester selected from the group consisting of isopropyl myristate, di-n-butyl sebacate, (poly)(alkylene glycol), mono- or di-myristate, pentyl valerate, and combinations thereof.

11. 10. The solid catalyst component of claim 1, wherein the solid catalyst component does not contain a polyolefin.

12. 10. The solid catalyst component of claim 1, wherein the catalyst component exhibits a catalytic activity at 90°C that is at least about 10% lower than the catalytic activity exhibited at 80°C under otherwise identical conditions, as determined by polymerizing propylene in a bulk propylene reactor over a period of 30 minutes.

13. 1. A process for producing a solid catalyst component, said process comprising: Magnesium alkoxide Mg(OR) ｎ X ２－ｎ or magnesium alcoholate MgX ２ mR'OH Ti(OR'') ｇ X ４－ｇ wherein X is Br, Cl, or I, n is 1 or 2, m is 0.5 to 10, g is 0, 1, 2, 3, or 4, and R, R', and R'' are independently C1 to C10 alkyl, and the catalyst precursor contains a supporting electron donor and an internal electron donor; The catalyst precursor components are mixed in a hydrocarbon solvent, The following formula: ２ nSi(OR ３ ) ４－ｎ a first organosilicon compound having the formula: ２ is H, alkyl, or aryl, and each R ３ is alkyl or aryl, and n is 0, 1, 2, or 3; an organic ester of a C4 to C30 fatty acid ester or a poly(alkene glycol) ester of a C4 to C30 fatty acid; reacting the aluminum compound with at least one of alkylaluminum compounds; and isolating said solid catalyst component.

14. 14. The process of claim 13, further comprising isolating and / or drying the catalyst precursor compound prior to the step of reacting the catalyst precursor.

15. 1. A process for producing an olefin polymer, said process comprising polymerizing an olefin in the presence of an isolated solid catalyst component, said solid catalyst component comprising: a halide-containing magnesium compound; a titanium halide compound; at least one internal electron donor; an activity control agent (ACA), a first organosilicon compound containing Si—O groups present in said catalyst component in an amount of from about 0.1 to about 5 weight percent; an organic ester of a C4 to C30 fatty acid or a poly(alkene glycol) ester of a C4 to C30 fatty acid in an amount of about 0.1% to about 15% by weight; and the reaction product of an alkyl group-containing organoaluminum compound with an activity control agent (ACA), A process wherein at least a portion of said ACA is chemically bound to said halide-containing magnesium compound, and said solid catalyst component is not prepared in a polymerization reactor.

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