Activated catalyst component for olefin polymerization

Abstract

An activated solid catalyst component formed from a magnesium compound, a titanium compound, an organosilicon compound, a supported electron donor, and at least one internal electron donor is disclosed. The solid catalyst component is activated to contain titanium and carbon bonds by reaction with an activator such as an aluminum compound. In one embodiment, a small amount of polymer is polymerized with the catalyst component during activation. The activated catalyst component is stable and, when formed, can be subsequently used to produce various polyolefin polymers. The reaction rate of the activated catalyst component is controlled to prevent the catalyst from overheating and decomposing during initial polymerization.

Description

Technical Field

[0001] (Related Application) This application claims priority based on, and hereby incorporates by reference in its entirety, U.S. Provisional Patent Application No. 62 / 846,130, filed May 10, 2019.

Background Art

[0002] Polyolefins are a classification of polymers derived from simple olefins. Well-known methods for producing polyolefins involve the use of Ziegler-Natta type polymerization catalysts. These catalysts polymerize olefin monomers using transition metal halides and provide polymers with various types of stereochemical configurations.

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

[0004] Over the past 30 years, many supported Ziegler-Natta catalysts have been developed that give much higher activity in olefin polymerization reactions and result in much higher contents of crystalline isotactic segments in the polymers made by those catalysts. With the development of internal and external electron donor compounds, polyolefin catalyst systems have been continuously improved.

[0005] One of the problems seen with newly developed Ziegler-Natta catalysts, particularly non-phthalate catalysts, is that the catalyst can bring about a significantly high catalytic activity immediately after the polymerization process. A high catalytic activity can lead to a rapid temperature rise at the center of the catalyst particles. In some applications, the surface area of the catalyst particles is insufficient to dissipate heat and break down or decompose the particles.

[0006] To control the kinetics of the catalyst, some polymerization processes, namely slurry-phase polymerization processes or bulk-phase polymerization processes, are equipped with a prepolymerization line or reactor. In these processes, a polyolefin prepolymerization step is carried out before the catalyst enters the main polymerization reactor. During prepolymerization, a small amount of olefin monomer is polymerized into polyolefin under mild conditions and at a low reaction rate. As a result, a small amount of polyolefin polymer is produced and combined with the catalyst particles without damaging the catalyst particles. Then, the prepolymerized catalyst is fed into the main reaction chamber to produce polyolefin polymer under normal reaction conditions. It has been found that the prepolymerization step controls the initial catalyst dynamics to prevent catalyst damage.

[0007] Using a prepolymerization reactor offers various advantages, but many of the polyolefin polymerization processes do not have a prepolymerization reactor and are not suitable for designing changes to include a prepolymerization step. For example, many gas-phase polyolefin reactors do not include a prepolymerization reactor and are not well-suited for including one. These processes are particularly problematic in that the catalyst particles are directly injected into a high-temperature fluidized bed. Thus, one of the problems frequently occurring in many gas-phase reactors is, in particular, the ability to control the catalyst reaction rate and activity at the start of the polymerization process. Summary of the Invention Problems to be Solved by the Invention

[0008] In view of the above, heretofore, catalyst manufacturers have attempted to prepolymerize or activate the catalyst before shipping it to customers for use in the polymerization process. However, little success has been achieved in prepolymerizing the catalyst outside the polymerization process. For example, when the catalyst is activated for later use in the polymerization process, the catalyst may become unstable. For example, when the prepolymerized catalyst is used later, the catalyst activity may deteriorate or decrease dramatically. Therefore, in the past, storing or shipping the prepolymerized catalyst at low temperatures has made distribution and storage more complicated and increased the cost of using the catalyst.

[0009] In view of the above, there is a need for a prepolymerized Ziegler-Natta catalyst that is stable at ambient temperature over a long period of time. An improved prepolymerized or activated catalyst for use in a gas-phase polyolefin polymerization process is needed that initially controls the reaction rate to prevent catalyst destruction and decomposition while obtaining sufficient activity so as not to increase the total polymerization reaction time.

[0010] The present disclosure generally relates to non-phthalate, highly active, activated catalyst components for polyolefin production that improve the control of reaction kinetics. The polymers produced from the activated catalyst components can improve flow characteristics and processability. Such improvements can result from improvements in the polymer morphology. The activated solid catalyst components of the present disclosure are Ziegler-Natta catalysts that not only provide high catalyst activity without causing an initial exotherm that would cause catalyst destruction, but have also been found to extend catalyst life. Surprisingly, the activated solid catalyst components of the present disclosure have been found to exhibit stability over several months without changing the catalyst activity and to exhibit an improvement in the catalyst morphology that converts to an improved polymer morphology.

[0011] For example, in one embodiment, the present disclosure relates to an activated solid catalyst component for olefin polymerization. The activated solid catalyst component comprises a reaction product consisting of: (a) a magnesium compound containing a halide; (b) A titanium compound present in the catalyst component in an oxidation state of +3; other titanium compounds having an oxidation state of +2 and / or +4 may also be present; (c) An organosilicon compound containing an Si-O group; (d) An alkylaluminum compound; and (e) Optionally, at least one internal electron donor containing a carrier donor, wherein the at least one internal electron donor is present in the catalyst component in an amount of about 0.05 wt% to about 15 wt% in one embodiment and in an amount of about 1 wt% to about 20 wt% in another embodiment.

[0012] The activated solid catalyst component further comprises a polymer formed from an α-olefin of the following formula: CH2=CHR1 wherein R1 contains hydrogen or a C1-C7 alkyl group and is present in the catalyst component in an amount of about 0.3 g to about 200 g of polymer per gram of catalyst component.

[0013] The polyolefin formed from the activated solid catalyst component may be, for example, polyethylene or polypropylene and can be incorporated into the catalyst particles. For example, in one embodiment, the prepolymerized polyolefin polymer can at least partially coat the catalyst particles.

[0014] The magnesium compound containing a halide includes magnesium chloride. The organosilicon compound may be a silane, siloxane or polysiloxane having the following chemical structure: R n Si(OR’) 4-n wherein 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.

[0015] The supported electron donor can, in one embodiment, contain benzoic acid. Benzoic acid can have the following formula: [Chemical formula]

[0016] In the formula, R’ includes an alkyl group, a cyclic group, an aryl group having 1 to 20 carbon atoms, a heteroatom, or a combination thereof. In the formula, R’’ includes one or more substituents, and each substituent can individually include hydrogen, an alkyl group, a cyclic group, an aryl group having 1 to 20 carbon atoms, a heteroatom, or a combination thereof.

[0017] The internal electron donor can have the following formula: [Chemical formula] In the formula, R1 to R4 are the same or different, and each of R1 to R4 is selected from the group consisting of hydrogen, a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl 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. In the formula, E1 and E2 are the same or different and are selected from the group consisting of a cycloalkyl group having 5 to 10 carbon atoms, a substituted alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, a substituted aryl having 6 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms and containing, as appropriate, an inert functional group containing a heteroatom. In the formula, 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; or

[0018] In one aspect, the internal electron donor can have one of the following formulas. [Chemical formula] In the formula, R 15 ~R 20 each of which 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

Chemical formula

[0019] Generally, the catalyst component is activated by combining the catalyst component with an alkyl-aluminum compound which may contain triethylaluminum. After activation, the solid catalyst component contains titanium and carbon bonds. In one embodiment, the molar ratio between aluminum and titanium is about 0.1 to 200, for example, about 0.5 to 20, and the silicon to titanium molar ratio is about 0.05 to 10, for example, about 0.1 to 6, so that the activated solid catalyst component is formulated. The resulting activated solid catalyst may be in particulate form with an average particle size of about 5 microns to about 300 microns, for example, about 5 microns to about 70 microns.

[0020] In one embodiment, the activated solid catalyst component can further contain an organophosphorus compound. The organophosphorus compound includes, for example, phosphate esters. The activated solid catalyst component can also contain an activity inhibitor. This activity inhibitor includes C4 - C30 aliphatic acid esters, diethers, or poly(alkene glycol) esters of C4 - C30 aliphatic acids. Examples of the activity inhibitor include isopropyl myristate, pentyl valerate, or mixtures thereof.

[0021] The present disclosure also targets a process for generating an activated solid catalyst. This process, in one embodiment, includes the following: a. Reacting magnesium alkoxide (Mg(OR)nX 2-n ) or magnesium alcoholate (MgX2mR’OH) with Ti(OR)gX 4-g to form a catalyst precursor, where X is Br, Cl or I; n is 1 or 2; m is from 0.5 to 10; g is 0, 1, 2, 3 or 4; and further, R, R’, R’’ are each, independently, a C1-C10 alkyl such as a C1-C4 alkyl, and the catalyst precursor contains a supported electron donor and an internal electron donor; b. Reacting the product obtained from (a) with a trialkylaluminum compound in the presence of an organosilicon compound having the formula R2nSi(OR3’)4-n, where R2 is H, alkyl or aryl; each R 3 is alkyl or aryl; and n is 0, 1, 2 or 3; c. Reacting the product obtained in (b) with an olefin having the formula CH2=CHR’, where R’ = H or a C1-C7 alkyl group, polymerizing the olefin to form a polymer coating on the solid catalyst component particles, and the olefin polymer is present in an amount of less than 50 g per 1 g of the activated solid catalyst component; d. Isolating the activated catalyst component.

[0022] In one embodiment, the catalyst precursor is an alcohol adduct of magnesium chloride anhydrous. The magnesium chloride anhydrous adduct is generally defined as MgCl2-nROH, where n is the total alcohol in the molar range of 1.5 to 6.0, preferably 2.5 to 4.0, and most preferably 2.8 to 3.5. ROH is a C1-C4 alcohol, linear or branched, 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 the higher alcohol is at least 80:20, preferably 90:10, and most preferably at least 95:5.

[0023] In one embodiment, a substantially spherical MgCl2-nEtOH adduct can be formed by a spray crystallization process. In one embodiment, the spherical MgCl2 precursor has an average particle size (Malvern d 50 ) of about 15 to 150 microns, preferably 20 to 100 microns, and most preferably 35 to 85 microns.

[0024] The present disclosure further targets a process for producing an olefin polymer. This process includes polymerizing an olefin in the presence of an activated solid catalyst component in a gas phase polymerization reactor for the production of homopolymers and copolymers. The activated solid catalyst component may be as described above. The polymers produced by this process have improved morphology. Specifically, the polymers produced by this activated catalyst have a very high bulk density (greater than about 0.45 g / cc, for example, greater than about 0.50 g / cc) and excellent flow characteristics. In addition, the polymer particles are substantially spherical. For example, the particles may have a B / L3 greater than about 0.65, for example, greater than about 0.7, for example, greater than about 0.77. The polyolefin particles may include polypropylene particles. Further, the polyolefin particles may have a bulk density greater than about 0.4 g / cc, for example, greater than about 0.5 g / cc, and generally less than about 0.8 g / cc.

[0025] Other characteristics and aspects of the present disclosure will be discussed in more detail below.

Brief Description of the Drawings

[0026] The complete and valid disclosure of the present disclosure is described in more detail in the remaining part of this specification, including reference to the accompanying drawings.

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Embodiments for Carrying Out the Invention

[0033] Before describing some representative embodiments, it should be understood that the present invention is not limited to the detailed parts of the structures or process steps described in the following description. The present invention can be implemented in other embodiments and can be practiced or executed in various ways.

[0034] Generally, the present disclosure is directed to catalyst systems for producing polyolefin polymers, particularly polypropylene polymers. The present disclosure is also directed to methods for polymerizing and copolymerizing olefins using such catalyst systems. Generally, the catalyst systems of the present disclosure are directed to the use of activated solid catalyst components. This solid catalyst component is "activated" by exposure to an activator, such as an aluminum compound, which forms a titanium and carbon bond within the catalyst component that can function as an active site for catalyzing the production of polyolefin polymers from olefin monomers. In one embodiment, the activated solid catalyst component is activated in the presence of a small amount of α-olefin monomer to form a prepolymerized activated solid catalyst component.

[0035] This activated catalyst component comprises a Ziegler-Natta catalyst and is prepared by synthesizing a magnesium compound, such as magnesium chloride or magnesium alkoxide, and a titanium compound in the presence of a supported electron donor and at least one internal electron donor. The supported electron donor may be, for example, an alkyl benzoate, and the internal electron donor may be an aryl diester. The formed catalyst support is then synthesized with an alkylaluminum compound in the presence of an organosilicon compound to activate the solid catalyst component. There may also be present an α-olefin that polymerizes and is incorporated into the activated solid catalyst component. The formed olefin polymer may be present in the catalyst component, for example, in an amount of from about 0.3 g to about 50 g of polymer per gram of catalyst component.

[0036] The prepolymerized activated solid catalyst component of the present disclosure can provide various advantages and benefits. For example, the activated solid catalyst component exhibits high catalytic activity exceeding 60 g / kg, but the activated catalyst component does not overheat when supplied to a polymerization reactor in the presence of an olefin monomer and under normal operating conditions. For example, the activated solid catalyst of the present disclosure has been found to efficiently polymerize propylene monomers even in a gas-phase reactor without causing breakage due to lack of heat transfer control. Furthermore, unexpectedly, this activated solid catalyst has also been shown to be very stable. This activated catalyst component can be stable for at least 3 months, for example, 5 months or more without losing any significant catalytic activity when stored under ambient conditions. Therefore, the catalyst manufacturer can activate the solid catalyst component and transport the activated solid catalyst component to the polymer manufacturer for injection into a prepolymerization reactor or a polymerization reactor without a prepolymerization reactor or line. In this regard, the activated solid catalyst of the present disclosure is particularly suitable for use in a gas-phase reactor, and the catalyst component can be directly injected into a high-temperature fluidized bed to produce a polyolefin polymer.

[0037] Furthermore, unexpectedly, it has also been revealed that the activated solid catalyst of the present disclosure produces, unexpectedly, a polyolefin polymer with improved morphology due to its catalyst morphology. Examples of the morphological characteristics of the catalyst and the polymer include average particle size, particle size distribution, particle shape, and surface texture. The morphological characteristics of the catalyst can directly affect the morphology of the polymer particles produced from the catalyst. The polyolefin polymer made from the activated solid catalyst can be produced, for example, as substantially spherical particles having an optimal particle size and a relatively narrow particle size distribution. The polymer particles are improved and can have a relatively high bulk density. Due to the improved polymer morphology, the polymer particles are much easier to handle. The polymer particles have excellent fluidity and are easy to process. For example, the polymer particles are easy to remove from the reactor, easy to transport, and easier to package and transport. In addition, the improvement of the particle characteristics also prevents contamination in the reactor device.

[0038] For example, the polymer particles made according to the present disclosure can have an average particle size of greater than about 5 microns, such as greater than about 10 microns, greater than about 20 microns, greater than about 30 microns, greater than about 40 microns. Generally, the average particle size of the polymer particles can be less than about 300 microns, such as less than about 200 microns, such as less than about 120 microns, such as less than about 70 microns. As described above, the polymer particles can be substantially spherical. For example, the polymer particles can have a B / L3 greater than about 0.65, such as greater than about 0.7, such as greater than about 0.75, such as even greater than about 0.77, and generally less than 1. This particle morphology results in an increase in the bulk density of the polymer resin made according to the present disclosure, and thus good flow characteristics are obtained. The bulk density of the polymer particles can be greater than about 0.4 g / cc, such as greater than about 0.45 g / cc, such as greater than about 0.5 g / cc. The bulk density is generally less than about 0.58 g / cc.

[0039] The method for preparing the activated solid catalyst component of the present disclosure generally includes treating a non-phthalic acid, Ziegler-Natta catalyst component with an activator such as an aluminum compound in the presence of an organosilicon compound, a selectivity control agent that can optionally include an activity limiting agent, or an external electron donor, and subsequently adding a controlled amount of an olefin monomer, such as propylene.

[0040] The catalyst platform activated according to the present disclosure can vary depending on the specific embodiment and the desired result. Generally, the catalyst precursor platform or catalyst component includes a magnesium compound and a titanium compound synthesized with a supported electron donor and at least one internal electron donor.

[0041] In one embodiment, the catalyst precursor component is a mixed magnesium / titanium compound that can have the following formula MgdTi(OR e )fX g wherein R e is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR’, where R’ is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms, and each OR eThe bases are the same or different, X is independently chlorine, bromine, or iodine, preferably chlorine, d is from 0.5 to 56, or from 2 to 4, f is from 2 to 116 or from 5 to 15, and g is from 0.5 to 116, or from 1 to 3. The catalyst precursor component is prepared by controlled precipitation by removing it from the reaction mixture used in the preparation of the alcohol. In one embodiment, the reaction medium comprises a mixture of an aromatic liquid, in particular a chlorinated aromatic compound such as chlorobenzene, and an alkanol such as ethanol. Suitable halogenating agents include titanium tetrabromide, titanium alkoxide, titanium tetrachloride or titanium trichloride. Removal of the alkanol from the solution used in the halogenation causes the solid catalyst precursor component to precipitate.

[0042] For example, in one embodiment, the catalyst precursor component comprises a reaction product consisting of a magnesium alkoxide such as magnesium ethylene oxide together with a mixture of o-cresol, titanium ethoxide, titanium tetrachloride, and ethanol in the presence of an internal electron donor. In one embodiment, during this process, a supported electron donor can be formed as a by-product and incorporated into the catalyst. The supported electron donor may include an alkyl benzoate such as ethyl benzoate. The supported electron donor can be incorporated into the deactivated catalyst component in an amount of from about 0.01 wt% to about 5 wt%, such as from about 0.5 wt% to about 5 wt%, such as from about 1 wt% to about 4 wt%. Additionally, the supported donor can be formed in situ as a by-product by reaction of the internal donor with the reaction mixture.

[0043] In another embodiment, the catalyst precursor component can be formed from a magnesium alcoholate, a titanium halide, a supported 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 and supported donors can be added in various steps of the process to vary the properties of the solid catalyst component.

[0044] For example, the catalyst precursor can be an alcohol adduct of magnesium chloride anhydride. The magnesium chloride anhydride adduct is generally defined as MgCl2-nROH, where n is the total alcohol in the range of 1.5 to 6.0, preferably 2.5 to 4.0, and most preferably 2.8 to 3.5 moles. ROH is a C1-C4 alcohol, linear or branched, 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 the higher alcohol is at least 80:20, preferably 90:10, and most preferably at least 95:5.

[0045] In one embodiment, a substantially spherical MgCl2-nEtOH adduct can be formed by a spray crystallization process. In one embodiment, the spherical MgCl2 precursor has an average particle size (Malvern d 50 ) of about 15 to 150 microns, preferably 20 to 100 microns, and most preferably 35 to 85 microns.

[0046] In another embodiment, the catalyst precursor component can be formed from a magnesium moiety, a titanium moiety, an epoxy compound, an organic phosphorus compound, an organosilicon compound, a supported electron donor, and an internal electron donor. For example, in one embodiment, the halide-containing magnesium compound can be dissolved in a mixture containing an epoxy compound, an organic phosphorus compound, and a hydrocarbon solvent. In the presence of an organosilicon compound, a supported electron donor, and an internal electron donor, the resulting alkoxide solution can be treated with a titanium compound to form a solid precipitate. Next, the solid precipitate can be treated with a further amount of the titanium compound. The titanium compound used to form the catalyst can have the following chemical formula, Ti(OR) g X 4-g Each R is independently a C1-C4 alkyl, X is Br, Cl, or I, and g is 0, 1, 2, 3, or 4.

[0047] In some embodiments, the organosilicon is a monomer or polymer compound. The organosilicon compound may contain -Si-O-Si- groups within one molecule or between other molecules. Other examples of organosilicon compounds include polydialkylsiloxane and / or tetraalkoxysilane. Such compounds may be used individually or in combinations thereof. The organosilicon compound may be used in combination with a supported electron donor and an internal electron donor.

[0048] Examples of magnesium compounds containing halides include magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride. In one embodiment, the magnesium compound containing halides is magnesium chloride.

[0049] Exemplary epoxy compounds include, but are not limited to, glycidyl-containing compounds of the following formula:

Chemical formula

[0050] wherein, "a" is 1, 2, 3, 4, or 5, X is F, Cl, Br, I, or methyl, and R a is H, alkyl, aryl, or cyclil. In one embodiment, the alkyl epoxide is epichlorohydrin. In some embodiments, the epoxy compound is a haloalkyl epoxide or a non-haloalkyl epoxide.

[0051] 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-butadienedioxide, 1,2,7,8-diepoxyoctane, cyclopentene oxide, cyclooctene oxide, α-pinene oxide, 2,3-epoxynorbornane, limonene oxide, cyclodecane epoxide, 2,3,5,6-diepoxynorboman, 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, 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, glycidyl methyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, ethyl 3,4-epoxybutyl ether, glycidyl phenyl ether, glycidyl 4-tert-butylphenyl ether, glycidyl 4-chlorophenyl ether, glycidyl 4-methoxyphenyl ether, glycidyl 2-phenylphenyl ether, glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, glycidyl 1-naphthyl ether, glycidyl 4-indolyl ether, glycidyl N-methyl-α-quinolin-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 novolak, 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), copolymer of glycidyl acrylate and another monomer, copolymer of glycidyl methacrylate and another monomer, 1,2-epoxy-4-methoxycarbonylcyclohexane, 2,3-epoxy-5-butoxycarbonylbicyclo[2.2.1] It is selected from the group consisting of 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.

[0052] As an example of the organophosphorus compound, a phosphate ester such as a trialkyl phosphate ester may be used. Such a compound can be represented by the formula [Chemical formula] In the formula, R1, R2, and R3 are each independently selected from the group consisting of methyl, ethyl, and a linear or branched (C3-C 10 ) alkyl group. In one embodiment, the trialkyl phosphate ester is tributyl phosphate ester.

[0053] The catalyst component may be converted into a solid catalyst by halogenation. Halogenation includes contacting the catalyst component with a halogenating agent in the presence of a supported electron donor and / or an internal electron donor. By halogenation, the magnesium moiety present in the catalyst component is converted into a magnesium halide support on which a titanium moiety (such as titanium halide) is deposited. Without being bound by any particular theory, during halogenation, the internal electron donor is thought to (1) regulate the position of titanium on the magnesium-based support, (2) facilitate the conversion of the magnesium and titanium moieties into their respective halides, and (3) adjust the crystal size of the magnesium halide support during conversion.

[0054] As described above, during the synthesis of the catalyst support, at least one internal electron donor is present. The internal electron donor is added during the formation of the catalyst composition that donates at least one electron pair to one or more metals present in the finally formed catalyst support, or is a compound that would otherwise be formed. In one embodiment, during the synthesis of the catalyst support, at least two internal electron donors are present. A supported donor may also be present. The supported donor is a reagent that is added during the synthesis of the support and / or is formed during the process of bonding to the magnesium surface and remaining in the catalyst support in the same manner as the internal electron donor to constitute the catalyst. The supported donor is usually smaller (less bulky) and has a weaker coordination with the catalyst support than the internal electron donor. In this regard, although not certain, it is considered that the supported donor is partially removed from the catalyst support when contacted with an activator such as an aluminum compound. It is considered that the supported donor is preferentially removed from the catalyst support during activation so that more of the other internal electron donors remain in the catalyst composition. For example, this electron donor, which can be an aryl diester, can be used to leave more of the internal electron donor. Due to the presence of the supported donor, the aryl diester remains bound to the catalyst support, so it is considered that the catalyst during activation and prepolymerization maintains a relatively high level of catalytic activity for some time and the finally obtained prepolymer catalyst can be stored before use. Therefore, the supported donor acts like an internal electron donor but is removed more from the catalyst support during the activation of the catalyst compared to the internal electron donor. Thus, the supported donor is a secondary internal electron donor that protects the primary internal electron donor. Furthermore, the supported donor is considered to be incorporated into the catalyst support during synthesis and is partially removed from the catalyst support without affecting the metals contained in the catalyst support at all. During the activation of the catalyst components with alkylaluminum, the supported electron donor is considered to be at least partially replaced by an external electron donor such as RnSi(OR’)4-n, resulting in a stable active catalyst component over a long period of time.

[0055] The morphology of the catalyst constituent components and the catalyst performance are sufficiently controlled by the addition of a supported electron donor (or donor). The supported electron donor is an organic compound containing an oxygen atom, which can coordinate with the magnesium atoms of magnesium in the "oil phase droplets" and enables the precipitation process of the solid catalyst component to be controlled in a desired form.

[0056] In one embodiment, the supported electron donor only controls the precipitation process and the morphology of the catalyst constituent components and is not incorporated into the catalyst constituent components.

[0057] In other embodiments, the supported electron donor controls the precipitation process and the morphology of the catalyst constituent components and is incorporated into the catalyst constituent components. Therefore, both the supported electron donor and the electron donor define the catalyst performance in the polymerization process. The supported electron donor is usually weaker than the electron donor.

[0058] By combining an organosilicon compound and a supported electron donor during the precipitation of the solid catalyst intermediate, it is possible to produce the catalyst constituent components in a desired granular or spherical form.

[0059] The morphology of the granular catalyst constituent components can be prepared in a raspberry shape, a rounded raspberry shape, a rounded shape, and a substantially spherical shape depending on the deformed form of the organosilicon compound, the supported electron donor, and the precipitation conditions of the solid catalyst intermediate. The particle size of the catalyst constituent components is from about 5 microns to about 70 microns (50% by volume) and is determined by the precipitation conditions (temperature, stirring speed, solvent, etc.) and the type and amount of the supported donor.

[0060] In one embodiment, the halogenating agent is titanium halide of the formula Ti(OR e ) f X h wherein R eAnd X is as defined above, f is an integer from 0 to 3, h is an integer from 1 to 4, and f + h is 4. In certain embodiments, the halogenating agent is TiCl4. In further embodiments, 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 using a mixture of a halogenating agent and a chlorinated aromatic liquid that contains 40 to 60 volume percent of the halogenating agent, such as TiCl4.

[0061] The reaction mixture can be heated during halogenation. The catalyst component and the halogenating agent are first contacted at a temperature of less than about 10 °C, such as less than about 0 °C, such as less than about -10 °C, such as less than about -20 °C, such as less than about -30 °C. The initial temperature is generally greater than about -50 °C, such as greater than about -40 °C. Next, the mixture is heated at a rate of 0.1 to 10.0 °C / min, or 1.0 to 5.0 °C / min. The internal electron donor may be added after the initial contact period between the halogenating agent and the catalyst component. The temperature of the halogenation is 20 °C to 150 °C, (or any value or some range therebetween), or 0 °C to 120 °C. The halogenation may continue for a period of 5 to 60 minutes, or 10 to 50 minutes, in the substantial absence of the internal electron donor.

[0062] The method of contacting the catalyst component, the halogenating agent, the supported electron donor, and the internal electron donor can be varied during the synthesis of the catalyst precursor or during the activation process with alkylaluminum. In certain embodiments, the catalyst component is first contacted with a mixture containing a halogenating agent and a chlorinated aromatic compound. The resulting mixture may be stirred and, if desired, heated. Next, the internal electron donor is added to the same reaction mixture without isolating or recovering the precursor. The foregoing process may be carried out in a single reactor with the addition of various components controlled by automated process control.

[0063] In one embodiment, the catalyst component is contacted with the internal electron donor before reacting with the halogenating agent.

[0064] The time for contacting the catalyst component with the supported electron donor and / or the internal electron donor is from a temperature of at least -30°C, or at least -20°C, or at least 10°C to a temperature of at most 150°C, or at most 120°C, or at most 115°C, or at most 110°C for at least 10 minutes, or at least 15 minutes, or at least 20 minutes, or at least 1 hour.

[0065] In one embodiment, the catalyst component, the supported electron donor, the internal electron donor, and the halogenating agent are added simultaneously or substantially simultaneously. The halogenation procedure may be repeated once, twice, three times, or more as desired.

[0066] After the aforementioned halogenation procedure, the resulting solid catalyst composition is separated from the reaction medium used in the final process, for example by filtration, to produce a wet filter cake. Next, the wet filter cake may be rinsed or washed with a diluent to remove unreacted TiCl4, and if desired, dried to remove the residual liquid. Typically, the resulting solid catalyst composition is washed one or more times with a "washing liquid" which is a liquid hydrocarbon, such as an aliphatic hydrocarbon like isopentane, isooctane, isohexane, hexane, pentane, or octane. The solid catalyst composition can then be separated, dried, or slurried in a hydrocarbon, particularly a relatively heavy hydrocarbon such as mineral oil, for further storage or use.

[0067] Various different types of supported electron donors and internal electron donors may be incorporated into the solid catalyst component of the present disclosure. Examples of supported electron 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, diethyl butylmalonate, diethyl dibutylmalonate, cyclohexanecarbonylethyl, 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, methyl toluylate, ethyl toluylate, amyl toluylate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, ethyl silicate, butyl silicate, vinyltriethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate and nadic acid, diethyl ester, diethyl naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyl trimellitate and dibutyl trimellitate, 3,4-furandicarboxylic acid ester, 1,2-diacetoxybenzene, 1-methyl-2,3-diacetoxybenzene, 2-methyl-2,3-diacetoxybenzene, 2,8-diacetoxynaphthalene, ethylene glycol dipivalate, butanediol pivalate, benzoylethyl salicylate, acetylisobutyl salicylate, acetylsalicylate, diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, or di-2-ethylhexyl sebacate.In some embodiments, the first non-phthalic acid 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 cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl p-methoxybenzoate, methyl p-methylbenzoate, ethyl p-t-butylbenzoate, ethyl naphthoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, or ethyl ethoxybenzoate.

[0068] In one embodiment, the supported electron donor has the following formula:

Chemical formula

[0069] Various different types of internal electron donors can be incorporated into the solid catalyst component. In one embodiment, the internal electron donor is an aryldiester such as a phenylene-substituted diester. In one embodiment, the internal electron donor may have the following chemical structure:

Chemical formula

[0070] In one embodiment, the internal electron donor may have one of the following chemical structures,

Chemical formula

Chemical formula

[0071] In one embodiment, the internal electron donor may have the following chemical structure,

Chemical formula

[0072] In the formula, R1 to R4 are the same or different, and each of R1 to R4 is selected from the group consisting of hydrogen, a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl 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, and E1 and E2 are the same or different and are selected from the group consisting of a cycloalkyl group having 5 to 10 carbon atoms, a substituted alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, a substituted aryl having 6 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms and containing, as appropriate, an inert functional group containing a heteroatom. In the formula, 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.

[0073] As used herein, the terms "hydrocarbyl" and "hydrocarbon" refer to substituents containing only hydrogen atoms 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 groups, cycloalkyl groups, alkenyl groups, alkadienyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, aralkyl groups, alkylaryl groups, and alkynyl groups.

[0074] As used herein, the terms "substituted hydrocarbyl" and "substituted hydrocarbon" refer to hydrocarbyl groups substituted with one or more non-hydrocarbyl substituents. Non-limiting examples of non-hydrocarbyl substituents are heteroatoms. As used herein, "heteroatom" refers to an atom other than carbon or hydrogen. The heteroatom can be a non-carbon atom belonging to Groups IV, V, VI, and VII of the periodic table. Non-limiting examples of heteroatoms include halogen (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" refers to a hydrocarbyl group substituted with one or more silicon atoms. The silicon atom(s) may or may not be in the carbon chain.

[0075] When forming the solid catalyst component of the present disclosure, the organosilicon compound may be used in various ways. For example, the organosilicon compound can be used during the precipitation of the catalyst support or can be incorporated into the catalyst support as it is. In addition, the organosilicon compound can be brought into contact with the catalyst together with an activator.

[0076] In one embodiment, when forming the catalyst support, an organosilicon compound can be used and combined with a magnesium compound, a titanium compound, a supported electron donor, and at least one internal electron donor. In one embodiment, the organosilicon compound is incorporated into the catalyst component in an amount such that the molar ratio of silicon to titanium is about 0.05 to about 10, for example about 0.1 to about 6.

[0077] In one embodiment, the organosilicon compound is represented by the following formula: RnSi(OR’) 4-n wherein R and R 1 each represent a hydrocarbon group individually, and n satisfies 0 ≦ n < 4.

[0078] 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-tridyldimethoxysilane, bis-m-tridyldimethoxysilane, bis-p-tridyldimethoxysilane, bis-p-tridiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, and methyltriallyloxysilane.

[0079] In another embodiment, the organosilicon compound is represented by the following formula. SiRR’ m (OR’’) 3-m In the formula, 0 ≤ m < 3, for example, 0 ≤ m < 2, and R independently represents a cyclic hydrocarbon group or a substituted cyclic hydrocarbon group. Specific examples of the R group include 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,Examples include, but are not limited to, 3-dimethyl-2-indenyl, fluorenyl group, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, isopropylcyclohexyl, n-butylcyclohexyl, tertiary butylcyclohexyl, dimethylcyclohexyl, and trimethylcyclohexyl.,

[0080] Formula SiRR’ m (OR’’) 3-m In the formula SiRR’(OR’’), R’ and R’’ are the same or different and each represents a hydrocarbon. Examples of R’ and R’’ are alkyl, cycloalkyl, aryl, and aralkyl groups having 3 or more carbon atoms. Further, R and R’ may be bridged by an alkyl group or the like. General examples of the organosilicon compound include an organosilicon compound in which R is a cyclopentyl group, R’ is an alkyl group such as a methyl group or a cyclopentyl group, and R’’ is an alkyl group, particularly a methyl group or an ethyl group.,

[0081] Formula SiRR’ m (OR’’) 3-mSpecific examples of the organosilicon compound include trialkoxysilanes such as cyclopropyltrimethoxysilane, cyclobutyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, 2,5-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane, 2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane, and fluorenyltrimethoxysilane; dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis(3-tert-butylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, bis(2,5-dimethylcyclopentyl)dimethoxysilane, dicyclopentyldiethoxysilane, dicyclobutyldiethoxysilane, cyclopropylcyclobutyldiethoxysilane, dicyclopentenyl dimethoxysilane, 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, cyclopentylcyclopentenyl dimethoxysilane, cyclopentylcyclopentadienyl dimethoxysilane, diindenyl dimethoxysilane, bis(1,3-dimethyl-2-indenyl)dimethoxysilane, cyclopentadienylindene dimethoxysilane, difluorenyl dimethoxysilane, cyclopentylfluorenyl dimethoxysilane, and indenylfluorenyl dimethoxysilane; tricyclopentylmethoxysilane, tricyclopentenylmethoxysilane, tricyclopentadienylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, bis(2,Monoalkoxysilanes such as (5-dimethylcyclopentyl)cyclopentylmethoxysilane, dicyclopentylcyclopentenylmethoxysilane, dicyclopentylcyclopentadienylmethoxysilane, and diindenylcyclopentylmethoxysilane, and ethylenebis-cyclopentyldimethoxysilane are included, but not limited thereto.,

[0082] According to the present disclosure, when the catalyst precursor component is formed, the catalyst component contacts an activator that generates an activated solid catalyst component. The activator can convert titanium bonds such as titanium and chloride bonds into titanium and carbon bonds, for example. Next, the titanium and carbon bonds can function as active sites that initiate a polymerization process using olefin monomers. In one embodiment, the activator is a hydrocarbyl aluminum compound represented by the formula R3Al, wherein each R is an alkyl, cycloalkyl, aryl, or hydride radical, at least one R is a hydrocarbyl radical, and two or three R radicals can be bonded to a cyclic radical that forms a heterocyclic structure. Each R may be the same or different, and each R that is a hydrocarbyl radical has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. In a further embodiment, each alkyl radical may be linear or branched, and such hydrocarbyl radicals may be mixed radicals, i.e., the radicals may contain alkyl groups, aryl groups, and / or cycloalkyl groups. Non-limiting examples of suitable radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-methylpentyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, n-nonyl, n-decyl, isodecyl, n-undecyl, n-dodecyl.

[0083] Non-limiting examples of suitable hydrocarbyl aluminum compounds are triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride, di-n-hexylaluminum hydride, isobutylaluminum dihydride, n-hexylaluminum dihydride, diisobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, tri-n-dodecylaluminum.

[0084] In one embodiment, triethylaluminum is used. The molar ratio of aluminum to titanium is from about 0.1 to about 200, or from about 0.5 to about 20.

[0085] As described above, the organosilicon compound can be incorporated into the catalyst support and can also be used in combination with an activator. For example, an aluminum compound as described above may be added to the catalyst component together with the organosilicon compound, or can be added to the catalyst component after the organosilicon compound is added. The organosilicon compound can be any of the above organosilicon compounds.

[0086] According to the present disclosure, the activated solid catalyst component also undergoes a prepolymerization step in which a relatively small amount of polymer is formed and incorporated into the catalyst particles. In this regard, the activated solid catalyst component is synthesized with an olefin monomer. For example, the olefin monomer can be an α-olefin of the following formula, CH2=CHR1 wherein R1 includes hydrogen or a C1-C7 alkyl group.

[0087] In one embodiment, the olefin monomer includes propylene. The prepolymerization process can generally be carried out at a temperature above about -20°C, for example above about -10°C, for example above about 0°C, and further generally at a temperature below about 60°C, for example generally below about 50°C, for example generally below about 40°C, for example generally below about 30°C.

[0088] In one embodiment, the prepolymerization process is carried out in suspension. For example, in one embodiment, an activated solid catalyst can be combined with an inert hydrocarbon medium. The liquid phase can be, for example, an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and / or kerosene. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane can also be used. Aromatic hydrocarbons can also be used in slurry polymerization. Aromatic hydrocarbons include benzene, toluene, xylene, and mixtures thereof. In one embodiment, for example, the hydrocarbon liquid is hexane.

[0089] The activated solid catalyst component is combined with the hydrocarbon liquid and contacted with a controlled amount of olefin monomer while adjusting the temperature. The reaction temperature for prepolymerization is, for example, a temperature sufficient for the resulting prepolymer not to dissolve in the hydrocarbon medium and at the same time sufficient for the polymerization reaction to occur. The temperature can be from about 0 °C to about 20 °C. When an organosilicon compound is used during activation, the organosilicon compound can be added in the presence of an activator or after the activator has been added. In either case, the organosilicon compound is added before contacting with the olefin monomer. Alternatively, no organosilicon compound is used during activation.

[0090] Optionally, in prepolymerization, a molecular weight regulator such as hydrogen can also be added to the suspension.

[0091] According to the present disclosure, the amount of polymer formed is controlled such that the prepolymerization reaction conditions result in less than about 50 g, for example less than about 40 g, for example less than about 30 g, for example less than about 20 g of polymer per 1 g of catalyst component. The amount of polymer formed is generally more than about 1 g, for example more than about 5 g, for example more than about 10 g per 1 g of catalyst component.

[0092] The finally obtained activated and prepolymerized solid catalyst can be washed with hydrocarbons and isolated in dry form or in suspension in hydrocarbons or mineral oils.

[0093] The finally obtained activated and prepolymerized solid catalyst particles are substantially spherical and, when used in the production of polyolefin polymers, lead to an improvement in the polymer form.

[0094] The prepolymerized and activated solid catalyst components of the present disclosure have been found to provide various advantages and benefits that are thought to result from the various components used to produce the above-described catalyst particles. For example, although not certain, it is thought that by maximizing the amount of internal electron donor incorporated into the catalyst component, the supported electron donor promotes the formation of the solid catalyst component. For example, it is thought that at least a portion of the supported electron donor is removed from the catalyst component and preferentially replaced by the internal electron donor during catalyst formation. In addition, the insertion of an organosilicon compound into the pores on the surface of the magnesium compound formed after removing the supported electron donor during treatment with an aluminum compound results in a very stable and active catalyst component that can produce a polymer with improved polymer form.

[0095] As described above, the prepolymerized activated solid catalyst components of the present disclosure are extremely stable and can be stored for several months under ambient conditions without loss of catalytic activity. Although not certain, the stability is thought to be related to the incorporation of the supported electron donor, internal electron donor, and organosilicon compound into the activated solid catalyst component. Furthermore, the polymer formed on the catalyst particles is thought to generate stable activated polymerization centers that are extremely suitable for use in subsequent polymerization processes.

[0096] The relative amounts of the components can also bring benefits regarding catalytic activity and stability. For example, increasing the amount of the aluminum compound can lead to a decrease in the amount of the internal electron donor incorporated into the catalyst component, resulting in not only a decrease in catalytic activity but also a decrease in stereoselectivity. On the other hand, the organosilicon compound can protect the internal electron donor incorporated into the catalyst component and prevent extraction. Generally, higher activity can be obtained by increasing the concentration of the internal electron donor on the activated catalyst component. Both the supported electron donor and the organosilicon compound can act to maintain the internal electron donor at a high concentration.

[0097] When the activated solid catalyst of the present disclosure is prepared, the catalyst can be stored and then used in a polyolefin polymerization process. For example, the activated solid catalyst component of the present disclosure can be synthesized with other components to generate a catalyst system for polyolefin polymers such as polypropylene polymers. The catalyst system used to produce polyolefin polymers can include the activated solid catalyst component of the present disclosure in combination with a greater amount of the above aluminum compound and / or a greater amount of the above organosilicon compound. Further, the catalyst system may include an activity limiting agent (ALA). As used herein, an "activity limiting agent" ("ALA") is a material that reduces catalytic activity at high temperatures (i.e., temperatures above about 85°C). The ALA suppresses or otherwise prevents malfunctions in the polymerization reactor and ensures the continuation of the polymerization process. Typically, the activity of a Ziegler-Natta catalyst increases as the temperature of the reactor rises. A Ziegler-Natta catalyst also typically maintains high activity at a temperature close to the melting point of the polymer produced. The heat generated by the exothermic polymerization reaction may form polymer particle aggregates, ultimately interrupting the polymer production process. The ALA reduces (or prevents) the catalytic activity upon temperature increase, thereby preventing malfunctions in the reactor, reducing (or preventing) particle aggregation, and ensuring the continuation of the polymerization process. The ALA can also be added to the catalyst component during activation with an alkylaluminum compound.

[0098] The activity limiting agent may be a carboxylic acid ester. The aliphatic carboxylic acid ester may be C4-C 30It may be an aliphatic acid ester, may be mono- or poly- (two or more) esters, may be linear or branched, may be saturated or unsaturated, and may be any combination thereof. C4-C 30 The aliphatic acid ester may also be substituted with substituents containing one or more heteroatoms of Group 14, Group 15, or Group 16. Suitable C4-C 30 Non-limiting examples of aliphatic acid esters include aliphatic C 4-30 alkyl esters of monocarboxylic acids, aliphatic C 1-20 alkyl esters of monocarboxylic acids, aliphatic C 8-20 alkyl esters of monocarboxylic acids, aliphatic C 1-20 alkyl esters, aliphatic C 4-20 allyl mono- and diesters of monocarboxylic and dicarboxylic acids, aliphatic C 1-4 alkyl esters of monocarboxylic and dicarboxylic acids, and C 8-20 alkyl esters of monocarboxylic and dicarboxylic acids, as well as C 1-4 (poly) glycol or C 2-100 (poly) glycol ether C 2-100 (poly) glycol ether C 4-20 mono- or polycarboxylate derivatives of. In a further embodiment, C4-C 30 The aliphatic acid ester may be laurate, myristate, palmitate, stearate, oleate, sebacate, mono- or diacetic (poly) (alkylene glycol), mono- or dimyristic (poly) (alkylene glycol), mono- or dilauric (poly) (alkylene glycol), mono- or dioleic (poly) (alkylene glycol), glyceryl triacetate, C 2-40 glyceryl triesters of aliphatic carboxylic acids, and mixtures thereof. In a further embodiment, C4-C 30 The aliphatic ester is isopropyl myristate, di-n-butyl sebacate, and / or octyl acetate.

[0099] The catalyst system of the present disclosure can be used in all kinds of polymerization processes. For example, the catalyst system can be used in bulk polymerization processes and gas phase processes. In each process, one or more olefin monomers are contacted with the catalyst system under polymerization conditions.

[0100] One or more olefin monomers can be introduced into a polymerization reactor and reacted with a catalyst system to form a polymer such as a fluidized bed of polymer particles. Non-limiting examples of suitable olefin monomers include ethylene, propylene, C 4-20 α-olefins such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, etc.; C 4-20 diolefins such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB), and dicyclopentadiene; C including styrene, o-, m-, and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnaphthalene 8-40 vinyl aromatic compounds; and halogen-substituted C 8-40 vinyl aromatic compounds such as chlorostyrene and fluorostyrene.

[0101] As used herein, "polymerization conditions" are the temperature and pressure parameters within a polymerization reactor that are suitable for promoting polymerization between a catalyst composition and an olefin to form a desired polymer. The polymerization process may be a gas-phase polymerization process, a slurry polymerization process, or a bulk polymerization process operating in one or more reactors.

[0102] In one embodiment, the polymerization occurs by gas-phase polymerization. As used herein, "gas-phase polymerization" means that an upwardly flowing fluidization medium containing one or more monomers passes through a fluidized bed of polymer particles maintained in a fluidized state by the fluidization medium in the presence of a catalyst. "Fluidization", "fluidized", or "fluidizing" refers to a gas-solid contacting method in which a bed of finely divided polymer particles is lifted and agitated by an upward gas flow. Fluidization occurs in the bed of particles when the upward flow of fluid through the interstitial spaces of the bed of particles reaches a pressure difference and an increment in frictional resistance that exceeds the particle weight. Thus, a "fluidized bed" is a plurality of polymer particles suspended in a fluidized state by a fluidization medium flow. The "fluidization medium" is one or more olefin gases, optionally a carrier gas (such as H2 or N2), and optionally a liquid (such as a hydrocarbon), which travels upward through the gas-phase reactor.

[0103] A typical gas-phase polymerization reactor (or gas-phase reactor) includes a vessel (i.e., the reactor), a fluidized bed, a distributor plate, inlet and outlet pipes, a compressor, a recycle gas cooler or heat exchanger, and a product discharge system. The vessel includes a reaction zone and a velocity reduction zone, each of which is located above the distributor plate. The bed is located within the reaction zone. In certain embodiments, the fluidization medium includes propylene gas and other gases such as at least one olefin and / or a carrier gas such as hydrogen or nitrogen.

[0104] In one embodiment, the contacting is effected by feeding a catalyst composition to the polymerization reactor and introducing an olefin into the polymerization reactor.

[0105] A variety of different types of polymers can be produced using the catalyst systems of the present disclosure. For example, polypropylene homopolymers, polypropylene copolymers, and polypropylene terpolymers can be produced using the present catalyst systems. The present catalyst systems can also be used to produce impact polymers having elastomeric properties.

[0106] Impact-resistant polymers having rubbery or elastomeric properties are typically made in two reactor systems where it is desirable for the catalyst to maintain a high level of activity. In one embodiment, for example, the polymerization is carried out in two reactors connected in series. A propylene homopolymer or propylene copolymer can be formed in the first reactor to form an active propylene-based polymer. Subsequently, the active propylene-based polymer from the first polymerization reactor is introduced into the second polymerization reactor and contacted with at least one second comonomer in the second reactor under second polymerization conditions to form a propylene impact copolymer. In one embodiment, the process includes contacting the active propylene-based polymer with propylene and ethylene in the second polymerization reactor under polymerization conditions to form a discontinuous phase of a propylene / ethylene copolymer.

[0107] As described above, the first-phase polymer can include a polypropylene homopolymer. However, in alternative embodiments, the first-phase polymer may include a random copolymer of polypropylene.

[0108] The random copolymer can be, for example, a copolymer of propylene and an alpha-olefin such as ethylene. The polypropylene random copolymer forms a matrix polymer in the polypropylene composition and contains the alpha-olefin in an amount of less than about 12 wt%, for example less than about 5 wt%, for example less than about 4 wt%, and generally more than about 0.5 wt%, for example more than about 1 wt%, for example more than about 1.5 wt%, for example more than about 2 wt%.

[0109] The second-phase polymer is a copolymer of propylene and an alpha-olefin. However, the second-phase polymer has elastomeric or rubbery properties. For this reason, the second-phase polymer can significantly improve the impact resistance of the polymer.

[0110] The second-phase polymer that forms a dispersed phase in the polymer composition generally contains α-olefin or ethylene in an amount of more than about 10% by weight, for example more than about 20% by weight, for example more than about 40% by weight, and generally less than about 65% by weight, for example less than about 45% by weight, based on the weight of the second-phase polymer (of the rubber part).

[0111] As described above, in addition to producing polymers with improved morphology, the catalyst system of the present disclosure can produce various different polymers having spherical particles and a relatively high bulk density. Furthermore, the catalyst system of the present disclosure has been found to be particularly suitable for use in a reactor system not only because of its high catalytic activity but also because of its long catalyst life.

[0112] The present disclosure can be better understood with reference to the following examples.

Examples

[0113] Definition

[0114] The following parameters are defined as follows.

[0115] The morphology of the catalyst particles indicates the morphology of the polymer particles produced therefrom. Three parameters (sphericity, symmetry, and aspect ratio) of the polymer particle morphology can be determined using a CamSizer instrument. CamSizer characteristics:

Number

[0116] In the case of an ideal sphere, SPHT is defined to be 1. Otherwise, the value is less than 1.

[0117] Symmetry is defined as follows.

Mathematics

Mathematics

[0118] X Ma = r1 + r2, or "Symm" is the minimum value of the set of symmetry values measured from different directions.

[0119] Aspect ratio:

Mathematics

[0120] Catalyst morphological characteristics such as aspect ratio ("B / L3") can be used for the characterization of polymer morphology.

[0121] "D 10 " represents the size (diameter) of the particles such that 10% of the particles are smaller than that size, "D 50 " represents the size of the particles such that 50% of the particles are smaller than that size, and "D 90 " represents the size of the particles such that 90% of the particles are smaller than that size. "Span" represents the particle size distribution. The value can be calculated according to the following formula. Span = (D 90 - D 10 ) / D 50 "PP" before any of the D or span values indicates the D value or span value of the polypropylene prepared with the indicated catalyst.

[0122] BD is the abbreviation of bulk density and is reported in the unit of g / mL.

[0123] CE is the abbreviation of catalyst efficiency and is reported in the unit of Kg polymer per gram of catalyst (Kg / g) during 1 hour of polymerization.

[0124] MFR is the abbreviation of melt flow rate and is reported in the unit of g / 10 min. MFR is measured according to ASTM test D1238 T.

[0125] Laser light scattering method by Malvern Mastersizer 3000 instrument was used to perform catalyst component particle size analysis. Toluene was used as the solvent.

[0126] IED is the abbreviation of internal electron donor.

[0127] EB is the abbreviation of ethyl benzoate.

[0128] TBP is the abbreviation of tributyl phosphate.

[0129] ECH is the abbreviation of epichlorohydrin.

[0130] TEOS is the abbreviation of tetraethyl orthosilicate.

[0131] Ti, Mg, and D are the weight percentages (wt%) for titanium, magnesium, and internal donor respectively in the composition.

[0132] XS is the abbreviation of xylene soluble and is reported in the unit of wt%.

[0133] Bulk propylene polymerization

[0134] The catalyst of the example was used in the propylene polymerization method. The following method was used. The reactor was calcined at 100 °C for 30 minutes while flowing nitrogen prior to carrying out the polymerization. The reactor was cooled to 30 - 35 °C, and a cocatalyst (1.5 mL of 25 wt% triethylaluminum (TEAl)), a carbon donor [cyclohexylmethyldimethoxysilane] (1 mL), hydrogen (3.5 psi), and liquid propylene (1500 mL) were added into the reactor in this order. The catalyst (5 - 10 mg) filled as a mineral oil slurry was pushed into the reactor using high-pressure nitrogen. Polymerization was carried out at 70 °C for 1 hour. After the polymerization, the reactor was cooled to 22 °C and degassed until atmospheric pressure was reached to recover the polymer.

[0135] The catalyst of the example was used in the gas-phase propylene polymerization method. The following method was used. The reactor was calcined at 100 °C for 30 minutes while flowing nitrogen prior to carrying out the polymerization. The reactor was cooled to 30 °C, and filled with propylene (150 g) together with a cocatalyst (0.27 ml of 25 wt% triethylaluminum (TEAl)), a carbon 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 charged into the reactor together with propylene (150 g). Polymerization was carried out at 70 °C for 1 hour. After the polymerization, the reactor was cooled to 22 °C and degassed until atmospheric pressure was reached to recover the polymer. The catalytic activity of the activated catalyst component was calculated based on the content of the primary catalyst component.

[0136] Example 1

[0137] MgCl2 (13.2 g), Al(OCH(CH3)2)3 (1.0 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 a nitrogen atmosphere while stirring at 600 rpm for 8 hours. When cooled to room temperature, toluene (140 g) was added together with ethyl benzoate (3.5 g) and tetraethyl orthosilicate (6 g). The mixture was then cooled to -25 °C, and TiCl4 (261 g) was slowly added with 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, held at that temperature for 30 minutes, then the temperature was raised to 85 °C over 30 minutes and held for 30 minutes, and then the solid precipitate was recovered by filtration. The solid precipitate was washed three times with toluene (200 mL each wash). The finally obtained precipitate was then synthesized in toluene (264 ml). This mixture was heated to 105 °C with stirring, and subsequently an internal electron donor (2.0 g) was added in toluene (10 g). The internal electron donor has the following formula: [Chemical formula]

[0138] In the formula, R 1 ~R 4 is selected from hydrogen or an alkyl group, and R 3 , R 4 , R 5 , R 6 are the same or different alkyl or cycloalkyl having 1 to 20 carbon atoms, heteroatoms, or a combination thereof. In this example, one of the R groups was methyl and another R group was tert-butyl (3-methyl-5-t-butylcatechol dibenzoate) (CDB-1).

[0139] Heating at 105 °C was continued for 1 hour, and then the solid was recovered by filtration. This process included synthesizing with TiCl4 in toluene, heating at 105 °C, heating again at 110 °C, and then washing the final product 4 times with hexane (200 ml each time), and further stirring at 60 - 65 °C for 10 minutes for each washing. Next, the catalyst components were discharged as a hexane slurry.

[0140] Examples 2 - 4 show the composition and catalytic behavior of the activated catalyst components prepared without prepolymer. The catalyst components of Example 1 were treated according to Table 1. The activation of the catalyst components was carried out with various amounts of external donor D (Examples 2 and 3). Example 4 was carried out in the presence of a second electron donor, diether (3,3 - bis(methoxymethyl)-2,6 - dimethylheptane) (DEMH). Examples 2 - 4 show relatively different recovery amounts of the internal electron donor and EB and different catalytic behaviors during the activation process.

[0141] As can be seen in Figure 1, from the activated catalyst of Example 4, a high - polymer BD (0.46 g / cc) containing polymer particles in a rounded solid shape was produced.

[0142]

Table 1

[0143]

Table 2

[0144] By activating the non - phthalic acid catalyst components of Example 1, activated catalyst components containing polypropylene of Examples 5 - 7 were prepared.

[0145] Example 5. The catalyst of Example 1 (27.0 g of hexane suspension on a dry basis of 5.0 g) was added to the reactor. 250 ml of hexane was added. 2.1 g of a D donor (dicyclopentyldimethoxysilane) (in 2 g of hexane) was added. The reactor temperature was set at 10 °C. 21 g of 10% TEAL in heptane was added to the reactor. The reactor was heated to 30 °C and maintained at 250 rpm for 120 minutes. The reactor was cooled to 5 °C and TEAL (7 g of 10% TEAL in heptane) was added. After several minutes, propylene (10 g) was added over 40 minutes. The reactor temperature was raised to 30 °C. The solid was washed with hexane and then dried.

[0146] Example 6. Example 5 was repeated, except that AlEt3 was added all at once.

[0147] Example 7. Example 6 was repeated, except that the amount of AlEt3 was reduced according to Table 3.

[0148] Example 8. Example 7 was repeated, except that the amounts of AlEt3 and the external donor were reduced according to Table 3. The external donor was a carbon donor.

[0149] Example 9 shows the composition and catalyst properties of a non-phthalic acid catalyst component prepared in the same manner as Example 1 except for varying the time.

[0150] Example 10 shows the preparation of an activated catalyst component, the composition of the activated catalyst component, and the catalyst properties. Example 8 was repeated, except that the non-phthalic acid ester-based catalyst component of Example 9 was used and the amounts of AlEt3 and the carbon donor were used as recorded in Table 3.

[0151] The properties of the activated catalyst components according to Examples 5 to 8 and 10 are shown in Table 3. The activated catalyst component contains about 2 g of prepolymer per gram of catalyst component. The particle size of the activated catalyst component increased up to several microns compared to the particle size of the catalyst component.

[0152] The activating catalyst components according to Examples 5 to 9 and 10 produced polymers with a high bulk density and an improved polymer morphology. The shape of the polymer particles was found to be substantially spherical. The activating catalyst component according to Example 10 was tested in bulk and gas-phase propylene polymerization. The activating catalyst component showed high catalytic activity and produced polymers with a very high bulk density (BD = 0.50 g / cc for bulk propylene polymerization and 0.45 g / cc in a gas-phase reactor). SEM images of the polymer particles are shown in Figures 2 and 3.

[0153] The amounts of the internal electron donor ("IED") and EB in the activating catalyst component differ under the activation conditions. The supported electron donor was found to be substantially removed during the activation process. At the same time, most of the amount of IED still remained in the activating catalyst component. It was also found that the catalytic activity of the activating catalyst component is related to the residual amount in the activating catalyst component.

Table 3

[0154]

Table 4

[0155]

Table 5

[0156]

Table 6

[0157] By using the same polymerization process as described, polymers with high bulk density and improved polymer morphology were produced from the activated catalyst components according to Examples 5 to 9 and 10. The shape of the polymer particles was found to be substantially spherical. The activated catalyst component of Example 10 was tested in bulk and gas-phase propylene polymerization. The activated catalyst component showed high catalytic activity and produced polymers with very high bulk density (BD = 0.50 g / cc for bulk propylene polymerization and 0.45 g / cc in the gas-phase reactor). SEM images of the polymer particles are shown in Figures 3 and 4.

[0158] Examples 12 to 24 show the performance of activated catalyst components prepared based on different catalyst platforms. Example 11 (comparative example) shows the polymerization behavior of a catalyst component (CONSICONSIST601) that is not activated initially.

[0159] Examples 12 to 24.

[0160] An Mo suspension of the CONSISTA® catalyst component, available from W.R. Grace Company (41.0 g at 17.1% solids) was added to the reactor. The solid was washed with hexane and hexane (about 200 ml) was added to the reactor. The mixture was stirred at 400 rpm and the temperature of the reactor was cooled to 0 °C. AlEt3 (6.90 g in a 25% solution) was added. Immediately, a carbon donor (3.44 g in a 10% carbon donor) was added. After stirring for several minutes, propylene was slowly added for 30 - 60 minutes. The temperature of the reactor was raised to 30 °C and maintained for several minutes. The reactor was cooled to 0 °C. Gaseous propylene was added to the reactor for 60 - 90 minutes. The temperature of the reactor was raised from 0 °C to 30 °C and maintained at 30 °C for 1 hour. After removing the solvent, the solid was washed with hexane and dried to form the activated catalyst component. A portion of the suspension of the activated catalyst component was treated with CO2 (Condition 1), and another portion of the suspension was left untreated (Condition 2). In some examples, the activated catalyst component was washed with TiCl4 (Condition 3). The amount of propylene in the examples was variable and is listed in the following table.

[0161]

Table 7

[0162] Regarding the aging effect, this activated catalyst component was evaluated. The activated catalyst component was held in mineral oil at 20 - 22 °C and tested for polymerization. This catalyst component was found to be stable for several months without impairing the catalytic activity.

[0163]

Table 8

[0164] The catalytic stability (lifetime) of the activated catalyst component was determined using propylene polymerization over 1 hour and 2 hours. From the examples, it was demonstrated that using this activated catalyst component improves the catalyst lifetime.

[0165]

Table 9

Table 10

[0166] This activated catalyst component has high catalytic activity and shows improvement in the BD of the produced polymer. This catalyst component is stable for several months without impairing the catalytic activity. The more stable activated catalyst component had a lower prepolymerization ratio.

[0167] This activated catalyst component showed improvement in kinetics compared to the comparative control.

[0168] Examples 28 - 33

[0169] Examples 28 to 33 describe an activated catalyst component composition prepared with another internal donor. CDB-2 internal donor and EB as a supported donor were used in the preparation of the highly active activated catalyst component (Table 11). CDB-2 is catechol dibenzoic acid as described in paragraph 52 of US Patent Publication No. 2013 / 0261273, which is incorporated herein by reference. The activated catalyst component was prepared by the general procedure described in Examples 5 to 7. Example 27 (comparative example) presents a non-activated catalyst component prepared with CDB-2 as the internal electron donor under the general procedure described in Example 1.

Table 11

Table 12

[0170] Examples 42 to 44

[0171] Examples 42 to 44 show data on gas-phase propylene polymerization with the activated catalyst component containing the CDB-2 internal donor. Example 41 is a comparative example testing the non-activated catalyst in a gas-phase reactor (Table 11). Examples 42 to 44 show that the activated catalyst component has high catalytic activity in gas-phase propylene polymerization under different polymerization conditions (Table 13).

Table 13

Table 14

[0172] Examples 45 to 49

[0173] Examples 46 to 49 show the production of ethylene-propylene impact copolymers (ICP) with the activated catalyst component and the properties of the polymers produced with these catalysts. The impact copolymer was produced in a gas-phase reactor in two steps. The first step was the production of homopolymer PP as described above. After evacuating the reactor 30 minutes after propylene polymerization, it was filled with an ethylene-propylene mixture and the production was continued for 60 minutes. A carbon donor (cyclohexylmethyldimethoxysilane), a D donor (dicyclopentyldimethoxysilane), and an ALA-activity limiting agent were used as external donors (Table 15). The composition of the ethylene-propylene comonomer was analyzed by the FTIR method. Et% - the total ethylene content (wt%) in the polymer, Ec% - the ethylene content (wt%) in the rubber-type polymer, Fc% - the rubber content (wt%) in the polymer (Table 16).

Table 15

Table 16

[0174] Examples 50 - 53

[0175] Examples 50 - 53 show the oxidation state of titanium atoms in the activated catalyst component prepared by the general procedure described in Examples 5 - 8 using CDB-1 and CDB-2 internal donors. During the catalyst treatment with TEA1, the titanium atoms are Ti from TiCl4 4+ to Ti 3+ and Ti 2+It was reduced to Ti(+3) species. The Ti(+3) species are dominant in the activated catalyst component, and the relative amount of Ti(+3) varies depending on the activation conditions (Table 17). The amount of decrease in the titanium species was measured by the titration method described in J.Mol.Cata.A-Chem, 2001, 172, 89-95.

Table 17

[0176] These and other modifications and variations to the present invention may be made by those skilled in the art without departing from the spirit and scope of the invention as more specifically set forth in the appended claims. Additionally, it should be understood that aspects of the various embodiments may be exchanged both in whole or in part. Further, those skilled in the art will understand that the foregoing description is by way of example only and is not intended to limit the invention as further described in the appended claims. The present invention includes the following aspects. [1] An activated non-phthalic acid solid catalyst component for olefin polymerization, comprising: (a) a magnesium compound containing a halide, (b) a titanium compound containing titanium in at least +3 and +2 oxidation states, (c) an organosilicon compound containing an Si-O group, (d) an alkylaluminum compound, (e) a supported electron donor containing monobenzoic acid, wherein the supported electron donor is present in the catalyst component in an amount of about 0.01 wt% to about 5 wt%, (f) at least one internal electron donor, wherein the at least one internal electron donor is present in the catalyst component in an amount of about 1 wt% to about 15 wt%, a reaction product of the at least one internal electron donor, and a polymer formed from an α-olefin of the formula: CH 2 =CHR 1 wherein R 1 comprises hydrogen or a C1-C7 alkyl group and is present in the catalyst component in an amount of about 0.3 g to about 200 g per gram of the catalyst component, an activated non-phthalic acid solid catalyst component. [2] The activated solid catalyst component according to 1, wherein the at least one internal electron donor contains an aryldiester. [3] The activated solid catalyst component according to 1 or 2, wherein the α-olefin comprises ethylene or propylene. [4] The activated solid catalyst component according to 1, 2 or 3, wherein the magnesium compound containing a halide comprises magnesium chloride. [5] The activated solid catalyst component according to 1, 2, 3 or 4, wherein the olefin polymer is present in an amount of about 20 g or less per gram of the activated solid catalyst component. [6] The organosilicon compound has the following chemical structure: RnSi(OR’) 4-n wherein each R is H, alkyl, or aryl, each R’ is H, alkyl, aryl, or SiRn(OR’)3-n, n is 0, 1, 2, or 3, and is a silane, siloxane or polysiloxane having the above formula, the activated solid catalyst component according to any one of 1-5. [7] The internal electron donor is represented by the following formula:

Chem.

Chem.

Chem.

Chem.

Chem.

[10] The titanium compound contains titanium having an oxidation state of +2 to +4, and the titanium in the +3 oxidation state is present in an amount of more than 60%, for example more than 65%, for example more than 70%, and the titanium in the +4 oxidation state is present in an amount of 0.01% to 20%, and further, the titanium in the +2 oxidation state is present in an amount of 1% to 20%. The activated solid catalyst component according to any one of 1 to 9.

[11] The catalyst component has an average particle size of about 5 microns to about 300 microns, for example about 5 microns to about 70 microns. The activated solid catalyst component according to any one of 1 to 10.

[12] The solid catalyst component further contains an organic phosphorus compound. The activated solid catalyst component according to any one of 1 to 11.

[13] The organic phosphorus compound contains a phosphate ester. The activated solid catalyst component according to 12.

[14] The activated solid catalyst component includes catalyst particles, and the polymer formed from the α-olefin forms at least a partial coating on the catalyst particles. The activated solid catalyst component according to any one of 1 to 13.

[15] Further includes an activity inhibitor. The activated solid catalyst component according to any one of 1 to 14.

[16] The activity inhibitor includes a C4-C30 aliphatic acid ester, a diether, or a poly(alkene glycol) ester of a C4-C30 aliphatic acid. The activated solid catalyst component according to 15.

[17] The supported electron donor is present in the catalyst component in an amount of about 0.01 wt% to about 3 wt%, and the at least one internal electron donor is present in the catalyst component in an amount of about 3 wt% to about 10 wt%. The activated solid catalyst component according to any one of 1 to 16.

[18] The solid catalyst component is activated in that the solid catalyst component contains a titanium-carbon bond. The activated solid catalyst component according to any one of 1 to 17.

[19] The supported electron donor includes ethyl benzoate. The activated solid catalyst component according to 9.

[20] The activated solid catalyst component contains aluminum and titanium in a molar ratio of about 0.1 to about 200, for example about 0.1 to about 20, and contains silicon and titanium in a molar ratio of about 0.05 to about 10, for example about 0.1 to about 10. The activated solid catalyst component according to any one of 1 to 19.

[21] The solid catalyst component is formed and then fed to a polymerization reactor to form the activated solid catalyst having the related polymer. The activated solid catalyst component according to any one of 1 to 20.

[22] A process for producing an activated solid catalyst component, a. Magnesium alkoxide Mg(OR) n X 2-n or magnesium alcoholate MgX 2 mROH and Ti(OR'')gX4-g are reacted to form a catalyst precursor component, where 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 further, R, R', R'' are independently C1-C10 alkyl, and the catalyst precursor contains a supported electron donor and an internal electron donor, b. In the presence of an organosilicon compound of the formula R 2 nSi(OR 3 )4-n, the product obtained from (a) is reacted with a trialkylaluminum compound, where in the formula, R 2 is H, alkyl or aryl, each R 3 is H, alkyl or aryl, and n is 0, 1, 2 or 3, c. The product obtained in (b) is reacted with an olefin of the formula CH2=CHR', where in the formula, R' = H or a C1-C7 alkyl group, and the olefin is polymerized to form a polymer coating on the solid catalyst component particles, and the olefin polymer is present in an amount of less than 200 g per 1 g of the activated solid catalyst component, d. Isolating the activated solid catalyst component, including a process.

[23] The activity inhibitor is added in step b), and the activity inhibitor contains a C4-C30 aliphatic acid ester, a diether, or a poly(alkylene glycol) ester of a C4-C30 aliphatic acid is added. The process according to 22.

[24] The internal electron donor is represented by one of the following formulas

change

change

change

[25] A process for producing an olefin polymer, comprising polymerizing an olefin in a gas-phase polymerization reactor in the presence of an activated solid catalyst component, wherein the activated solid catalyst component is (a) a magnesium compound containing a halide, (b) a titanium compound having titanium in at least +3 and +2 oxidation states, (c) an organosilicon compound containing an Si—O group, (d) an alkylaluminum compound, (e) a supported electron donor containing monobenzoic acid, wherein the supported electron donor is present in the catalyst component in an amount of about 0.01 wt% to about 5 wt%, the supported electron donor. (f) At least one internal electron donor, wherein the internal electron donor comprises an aryl diester, and the at least one internal electron donor is present in the catalyst component in an amount of about 1 wt% to about 15 wt%, and (g) A polymer formed from an α-olefin of the formula: CH 2 =CHR 1 wherein R 1 is hydrogen or comprises a C1-C7 alkyl group, and the α-olefin polymer forms a coating on the catalyst particles and is present in the catalyst component in an amount of about 0.3 g to about 200 g per gram of catalyst particles, The activated solid catalyst component is prepared outside the polymerization reactor and fed into the reactor,

[26] The process according to item 25, wherein the olefin is polymerized in a fluidized bed.

[27] The process according to item 25, wherein the olefin is polymerized in a stirred gas reactor.

[28] The process according to item 25, 26 or 27, wherein the solid catalyst component is fed into the reactor in combination with the olefin to produce an olefin polymer.

[29] The process according to any one of items 25 to 28, wherein the process produces a polypropylene homopolymer or a polypropylene copolymer.

[30] The polymer produced by the process has a B / L3 greater than about 0.75 and a bulk density greater than about 0.4 g / cc, for example about 0.45 g / cc to about 0.6 g / cc, according to item 29.

[31] The polymer produced by the process has a fluidity greater than about 3.5 g / sec, for example about 4 g / sec, as measured by a funnel with an outlet diameter of 8.0 mm, according to item 29 or 30.

[32] The polymer produced by the process is a propylene-ethylene impact copolymer containing ethylene in an amount greater than about 30 wt% of the rubber portion, for example about 40 wt% to 65 wt% of the rubber portion, according to item 29, 30 or 31.

Claims

1. An activated non-phthalic acid solid catalyst component for olefin polymerization, comprising: (a) a magnesium compound containing a halide; (b) a titanium compound containing titanium in at least +3 and +2 oxidation states; (c) an organosilicon compound containing an Si-O group; (d) an alkylaluminum compound; (e) a supported electron donor containing monobenzoic acid, wherein the supported electron donor is present in the catalyst component in an amount of about 0.01 wt% to about 5 wt%; (f) at least one internal electron donor represented by one of the following formulas: 【Chemical 1】 wherein, R １ to R ４ are the same or different, and each of R １ to R ４ is selected from the group consisting of hydrogen, a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbons, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof, and at least one of R １ to R ４ is not hydrogen, E １ and E ２ are the same or different, and each of E １ and E ２ is selected from the group consisting of a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbons, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof, wherein X １ and X ２ are each O, and wherein R ５ is a hydrocarbyl group having 1 to 20 carbon atoms or hydrogen, or [Chemical Formula 2] wherein each of R １ to R ６ is independently H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; or 【Chemical Formula 3】 R ７ to R １４ each independently is H, F, Cl, Br, I, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an aralkyl group, a heterocyclyl group, a heterocyclylalkyl group, a heteroaryl group, or a heteroarylalkyl group, at least one internal electron donor present in the catalyst component in an amount of about 1 wt% to about 15 wt%, and a reaction product thereof; and Formula: CH ２ =CHR １ A polymer formed from an α-olefin of the formula, wherein R １ contains hydrogen or a C1-C7 alkyl group and is present in the catalyst component in an amount of about 0.3 g to about 200 g per gram of the catalyst component, the polymer, an activated non-phthalic acid solid catalyst component.

2. The activated solid catalyst component according to claim 1, wherein the α-olefin contains ethylene or propylene.

3. The activated solid catalyst component according to claim 1 or 2, wherein the magnesium compound containing a halide contains magnesium chloride.

4. The activated solid catalyst component according to claim 1, 2 or 3, wherein the olefin polymer is present in an amount of about 20 g or less per gram of the activated solid catalyst component.

5. The organosilicon compound has the following chemical structure: R ｎ Si(OR') ４－ｎ wherein 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, and is a silane, siloxane or polysiloxane. The activated solid catalyst component according to any one of claims 1 to 4.

6. The supported electron donor has the following formula: 【Chemical Formula 4】 wherein R' contains an alkyl group, a cyclic group, a heteroatom, or a combination thereof, R'' contains one or more substituents, and each substituent independently contains hydrogen, an alkyl group, a cyclic group, a heteroatom, or a combination thereof. The activated solid catalyst component according to any one of claims 1 to 5.

7. The titanium compound contains titanium having an oxidation state of +2 to +4, wherein titanium in the +3 oxidation state is present in an amount of more than 60%, for example more than 65%, for example more than 70%, and titanium in the +4 oxidation state is present in an amount of 0.01% to 20%, and further, titanium in the +2 oxidation state is present in an amount of 1% to 20%. The activated solid catalyst component according to any one of claims 1 to 6.

8. The activated solid catalyst component according to any one of claims 1 to 7, wherein the catalyst component has an average particle size of about 5 microns to about 300 microns, for example about 5 microns to about 70 microns.

9. The activated solid catalyst component according to any one of claims 1 to 8, wherein the solid catalyst component further comprises an organophosphorus compound.

10. The activated solid catalyst component according to claim 9, wherein the organophosphorus compound comprises a phosphate ester.

11. The activated solid catalyst component according to any one of claims 1 to 10, wherein the activated solid catalyst component comprises catalyst particles, and the polymer formed from the α-olefin forms at least a partial coating on the catalyst particles.

12. The activated solid catalyst component according to any one of claims 1 to 11, further comprising an activity inhibitor.

13. The activated solid catalyst component according to claim 12, wherein the activity inhibitor comprises a C4-C30 aliphatic acid ester, a diether, or a poly(alkylene glycol) ester of a C4-C30 aliphatic acid.

14. The activated solid catalyst component according to any one of claims 1 to 13, wherein the supported electron donor is present in the catalyst component in an amount of about 0.01 wt% to about 3 wt%, and the at least one internal electron donor is present in the catalyst component in an amount of about 3 wt% to about 10 wt%.

15. The activated solid catalyst component according to any one of claims 1 to 14, wherein the solid catalyst component is activated in that it contains titanium and a carbon bond.

16. The activated solid catalyst component according to claim 6, wherein the supported electron donor comprises ethyl benzoate.

17. The activated solid catalyst component according to any one of claims 1 to 16, wherein the activated solid catalyst component contains aluminum and titanium in a molar ratio of about 0.1 to about 200, for example about 0.1 to about 20, and contains silicon and titanium in a molar ratio of about 0.05 to about 10, for example about 0.1 to about 10.

18. The activated solid catalyst component according to any one of claims 1 to 17, wherein the solid catalyst component is formed and then fed to a polymerization reactor to form the activated solid catalyst having the associated polymer.

19. A process for producing an activated non-phthalic acid solid catalyst component, a. Magnesium alkoxide Mg(OR) ｎ X ２－ｎ or magnesium alcoholate MgX ２ mR'OH and Ti(OR'') ｇ X ４－ｇ are reacted to form a catalyst precursor component, where 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 further, Mg(OR) ｎ X ２－ｎ , MgX ２ mR'OH or Ti(OR'') ｇ X ４－ｇ R, R', R'' in are independently C1 - C10 alkyl, and the catalyst precursor contains a supported electron donor and an internal electron donor containing monobenzoic acid, b. In the presence of an organosilicon compound of the following formula R ２ｎ Si(OR ３ ) ４－ｎ reacting the product obtained from (a) with a trialkylaluminum compound, wherein R ２ is H, alkyl, or aryl, each R ３ is alkyl or aryl, and n is 0, 1, 2, or 3, c. Reacting the product obtained in (b) with an olefin of the formula CH ２ =CHR', wherein R' in CH ２ =CHR' is H or a C1-C7 alkyl group, polymerizing the olefin to form a polymer coating on the solid catalyst component particles, and the olefin polymer is present in an amount of less than 200 g per 1 g of the activated solid catalyst component, and d. isolating the activated solid catalyst component, wherein the internal electron donor is represented by one of the following formulas: 【Chemical Formula 5】 wherein, R １ to R ４ are the same or different, and each of R １ to R ４ is selected from the group consisting of hydrogen, a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbons, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof, and at least one of R １ to R ４ is not hydrogen, and E １ and E ２ are the same or different, and each of E １ and E ２ is selected from the group consisting of a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbons, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof. wherein, X １ and X ２ are each O, and wherein R ５ is a hydrocarbyl group having 1 to 20 carbon atoms or is hydrogen, or 【Chemical Formula 6】 In the formula, R １ ~R ６ each independently represents H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl, or 【Chemical Formula 7】 R ７ to R １４ each of which is independently H, F, Cl, Br, I, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an aralkyl group, a heterocyclyl group, a heterocyclylalkyl group, a heteroaryl group, or a heteroarylalkyl group, Process.

20. The activity limiting agent is added in step b), and the activity limiting agent comprises a C4-C30 aliphatic acid ester, a diether, or a poly(alkene glycol) ester of a C4-C30 aliphatic acid is added, the process according to claim 19.

21. The supported electron donor has the following formula: 【Chemical 8】 wherein R' comprises an alkyl group, a cyclic group, a heteroatom, or a combination thereof, and R'' comprises one or more substituents, each substituent independently comprising hydrogen, an alkyl group, a cyclic group, a heteroatom, or a combination thereof. The process according to claim 19 or 20, having.

22. A process for producing an olefin polymer, comprising polymerizing an olefin in a gas phase polymerization reactor in the presence of an activated non-phthalic acid solid catalyst component, said activated solid catalyst component comprising (a) a magnesium compound containing a halide, (b) a titanium compound having titanium in at least +3 and +2 oxidation states, (c) an organosilicon compound containing an Si-O group, (d) an alkylaluminum compound, (e) a supported electron donor containing monobenzoic acid, said supported electron donor being present in said catalyst component in an amount of about 0.01 wt% to about 5 wt%, (f) at least one internal electron donor present in said catalyst component in an amount of about 1 wt% to about 15 wt%, and (g) formula: CH ２ =CHR １ A polymer formed from an α-olefin of the formula, wherein R １ is hydrogen or contains a C1-C7 alkyl group, and the α-olefin polymer forms a coating on the catalyst particles and is present in the catalyst component in an amount of about 0.3 g to about 200 g per gram of catalyst particles, the polymer, said activated solid catalyst component is prepared outside said polymerization reactor and supplied to said reactor, said at least one internal electron donor has the following formula: 【Chemical Formula 9】 Wherein, R １ to R ４ are the same or different, and each of R １ to R ４ is selected from the group consisting of hydrogen, a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl 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, and at least one of R １ to R ４ is not hydrogen, and E １ and E ２ are the same or different, and each of E １ and E ２ is selected from the group consisting of a substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl 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. wherein, X １ and X ２ are each O, and wherein R ５ is a hydrocarbyl group having 1 to 20 carbon atoms or is hydrogen, or 【Chemical Formula 10】 In the formula, R １ to R ６ each independently represents H, F, Cl, Br, I, alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl, or 【Chemical 11】 R ７ to R １４ each independently is H, F, Cl, Br, I, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aryl group, an aralkyl group, a heterocyclyl group, a heterocyclylalkyl group, a heteroaryl group, or a heteroarylalkyl group, represented by one of the process.

23. The process according to claim 22, wherein the olefin is polymerized in a fluidized bed.

24. The process according to claim 22, wherein the olefin is polymerized in a stirred gas reactor.

25. The process according to claim 22, 23 or 24, wherein said solid catalyst component is supplied to said reactor in combination with said olefin to produce an olefin polymer.

26. The process according to any one of claims 22 to 25, wherein the process produces a polypropylene homopolymer or a polypropylene copolymer.

27. The polymer produced by the process has a B / L3 greater than 0.75 and a bulk density greater than 0.4 g / cc, for example about 0.45 g / cc to about 0.6 g / cc, the process according to claim 26.

28. The polymer produced by the process according to claim 26 or 27 has a fluidity of more than 3.5 g / sec, for example about 4 g / sec, as measured with a funnel having an outlet diameter of 8.0 mm. **Claim 29** The polymer produced by the process according to claim 26, 27 or 28 is a propylene-ethylene impact copolymer containing ethylene in an amount of more than 30% by weight, for example about 40% to 65% by weight, of the rubber part.

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