Solid components for producing olefin polymerization catalysts, methods for producing the same, and their applications.

Abstract

The present disclosure relates to a solid component for producing an olefin polymerization catalyst, its production method, and its use. The solid component contains (i) a magnesium compound represented by the following formula (1), (ii) a Lewis base (LB), and (iii) optionally a metal component other than magnesium, where LB is a compound represented by the general formula (II) or an amide compound represented by the general formula (II'). The solid component produced in the present invention has a good particle morphology, and a catalyst produced by using the solid component as a support is less likely to be crushed and has better stereostructure orientation in olefin polymerization, particularly propylene polymerization or copolymerization. [Formula 1] JPEG2023546624000060.jpg41169

Description

Detailed description of the invention

[0001] [Cross-reference of related applications] This application claims priority and interest in the following Chinese patent application numbers: CN202011156589.6, CN202011157579.4, CN202011157613.8 and CN202011157626.5 (filed October 26, 2020), which are incorporated herein by reference in their entirety.

[0002] [Technical Field] The present invention relates to a solid component for producing a polyolefin catalyst (also known as a support), a method for producing the same, and the use of the same in the production of a polyolefin catalyst.

[0003] [Background technology] Most catalysts used in olefin polymerization are produced by supporting titanium halides on activated anhydrous magnesium chloride. In this method, anhydrous α-MgCl2 is reacted with an alcohol to form an adduct, and titanium halides are supported on this adduct to produce the solid component of the olefin polymerization catalyst. Magnesium chloride-alcohol adducts can be produced by methods such as spray drying, spray cooling, high-pressure extrusion, high-speed stirring, emulsifiers, and super-gravity rotating beds. For example, US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304, US6323152, CN1463990, and CN1580136 disclose methods for producing magnesium chloride-alcohol adducts.

[0004] Furthermore, studies have shown that adding a small amount of electron donor compound to a two-component support manufacturing system consisting of a magnesium chloride-alcohol adduct leads to the production of a multi-component support of MgCl2·mEtOH·nLB, thereby improving the polymerization performance of the catalyst. For example, patent CN101050245 teaches the addition of a phthalate compound, CN101544710 teaches the addition of a C,C-dihydrocarbyl oxyhydrocarbon compound, CN101550205 teaches the addition of a polyether compound, CN101486776 teaches the addition of a polyester compound, CN101215344 teaches the addition of an o-alkoxybenzoate compound, and CN102796127 teaches the addition of an alkoxybenzoyl compound or a hydroxybenzoyl compound. US2008 / 0293897 teaches the addition of a Lewis base compound other than water during the production of a magnesium chloride-alcohol adduct support, thereby increasing the polymerization activity of the final catalyst. Lewis base compounds include ethers, esters, and RX. m The compound may have a structural formula (wherein R is an alkyl group with 1 to 20 carbon atoms, and X has the structure of -NH2, -NHR, or -OH).

[0005] Activated magnesium chloride supports can also be produced by using magnesium alkoxide as a raw material. CN1016422B discloses a method for producing the solid component of a Zn catalyst. The solid component of the Zn catalyst is produced by reacting a water-soluble dialkylmagnesium with a transition metal halide in the presence of a transition metal alkoxide, and then precipitating the solid component with a liquid hydrocarbon. The alkoxy group in the magnesium dialkoxide used here is a linear alkoxy group containing 6 to 12 carbon atoms or a branched alkoxy group containing 5 to 12 carbon atoms, so that a water-soluble magnesium alkoxide solution can be formed in the liquid hydrocarbon. However, obtaining such magnesium alkoxides is difficult. CN1177868C discloses a method for producing an olefin polymerization catalyst precursor. The precursor of the olefin polymerization catalyst is produced by reacting a magnesium alkoxide with a titanium alkoxide in the presence of a clipping agent to form a solid complex. The magnesium alkoxide is magnesium diethoxide, and the titanium alkoxide is titanium tetraethoxide. CN101056894A discloses a catalyst for propylene polymerization. The catalyst is produced by reacting a magnesium dialkoxide with a titanium halide compound or a silane halide compound and an internal electron donor in the presence of an organic solvent. The magnesium dialkoxide has the general formula Mg(OR)2, where R is a C1-C6 alkyl group, and is produced by reacting magnesium metal with an alcohol. CN101190953A discloses a method for producing the solid component of an olefin polymerization catalyst, comprising reacting a magnesium-containing complex of the general formula ClMg(OR)·n(ROH) with an electron donor compound and a titanium tetrahalide, respectively, in the presence of an inert hydrocarbon. The magnesium-containing complex is produced by reacting metallic magnesium powder with an alcohol, where R is a C1-C5 alkyl group and n is 0.1-1.0.

[0006] Patent application CN200910235565 discloses a compound that can be used as an olefin polymerization catalyst support and a method for producing the same. The method involves heating magnesium halide, an alcohol compound, and an inert dispersion medium to form a magnesium halide-alcohol adduct solution, and then reacting this solution with an oxirane-type compound to form a spherical support. Patent application CN2013104913936 teaches that the addition of a polymer dispersion stabilizer in the above-described support production process can yield solid particles with good particle morphology and a narrow particle size distribution without the addition of an inert dispersion medium, thereby improving single-pot yield and reducing solvent recovery costs. Based on this, patent applications CN111072804A, CN111072811A, CN107915792A, CN107915793A, CN107915795A, CN109400763A, CN109400778A, and CN11072803A successively disclose the addition of metal halides such as zinc halide, chromium halide, manganese halide, iron halide, and alkali metal halides in the carrier manufacturing process described above in order to improve the particle morphology and polymerization properties of the carrier.

[0007] Solid components / supports useful for producing olefin polymerization catalysts that exhibit desirable properties such as good particle morphology are still needed.

[0008] [Summary of the Invention] The object of the present invention is to provide a solid component that can be used as a support for the production of olefin polymerization catalysts, particularly propylene polymerization or copolymerization catalysts, and is useful for the production of polyolefin catalysts. The solid component / support according to the present invention exhibits good particle morphology without the problem of support particle aggregation that is impaired by prior art, for example. Furthermore, when used for olefin polymerization, particularly propylene polymerization or copolymerization, catalysts produced using the solid component as a support exhibit high polymerization activity and stereospecificity and / or good hydrogen modulation sensitivity.

[0009] A further object of the present invention is to provide a method for producing a solid component useful for the production of a polyolefin catalyst. The method according to the present invention has a simple production process and low energy consumption in the production process.

[0010] A further object of the present invention is to provide a polyolefin catalyst component. The polyolefin catalyst component includes a reaction product of the carrier / solid component according to the present invention, a titanium compound, and an internal electron donor compound.

[0011] A further object of the present invention is to provide a polyolefin catalyst system.

[0012] A further object of the present invention is to provide a method for olefin polymerization.

[0013] Hereinafter, other features and advantages of the present invention will be described in detail.

[0014] 〔Brief Description of the Drawings〕 Figure 1A is an optical micrograph of the morphology of the solid component particles produced in Example 1 (magnification 160 times).

[0015] Figure 1B is an optical micrograph of the morphology of the solid component particles produced in Example 1 (magnification 400 times).

[0016] Figure 2 is an optical micrograph of the morphology of the solid component particles produced in Example 4 (magnification 160 times).

[0017] Figure 3A is an optical micrograph of the morphology of the solid component produced in Comparative Example 1 (magnification 160 times).

[0018] Figure 3B is an optical micrograph of the morphology of the solid component produced in Comparative Example 1 (magnification 400 times).

[0019] Figure 4 is an optical micrograph of the morphology of the solid catalyst component particles produced in Example 1.

[0020] Figure 5 is an optical micrograph of the morphology of the catalyst component produced in Comparative Example 1.

[0021] Figure 6A is an optical micrograph of the morphology of the carrier particles produced in Example 14 at a magnification of 160 times.

[0022] Figure 6B is an electron micrograph of the carrier particles produced in Example 14.

[0023] Figure 7 is an optical micrograph of the morphology of the catalyst component produced in Example 24.

[0024] Figure 8A is an optical micrograph of the morphology of the carrier particles produced in Example 27 at a magnification of 160 times.

[0025] Figure 8B is an optical micrograph of the morphology of the carrier particles produced in Example 27 at a magnification of 400 times.

[0026] Figure 8C is an electron micrograph of the carrier particles produced in Example 27.

[0027] 〔Summary of the Invention〕 In a first aspect, the present invention provides a solid component useful for the production of a polyolefin catalyst: (i) a magnesium compound represented by the following formula:

[0028]

Chemical formula

[0029] In the formula, R1 is a linear or branched alkyl having C1 to C 12 ; R2 and R3 are the same or different and are hydrogen or an unsubstituted or halogenated linear or branched alkyl having C1 to C5; X is a halogen; m is 0.1 to 1.9; n is 0.1 to 1.9; and m + n = 2; and (ii) a Lewis base (LB); and (iii) optionally, other metallic components other than magnesium, preferably one or both of iron and copper, and preferably the content of the other metallic component in terms of metal in the solid component is 0 to 1% by weight; and, Here, the Lewis base is a compound represented by general formula (II),

[0030] [ka]

[0031] In the formula, R5 and R7 are either the same or different, and are hydrogen, or unsubstituted or hydroxyl-substituted C1-C8 linear or branched alkyl groups; R6 is a C1-C8 linear or branched alkylene, or The Lewis base is an amide compound represented by the general formula (II'),

[0032] [ka]

[0033] In the formula, R 10 R is a hydrogen atom, an amino acid, or a linear or branched alkyl group of C1-C8. 11 and R 12 They are either the same or different, and are hydrogen or C1-C8 linear or branched alkyl groups.

[0034] In this disclosure, the terms “solid components useful for the production of polyolefin catalysts” and “carriers (or simply “carriers”) useful for the production of polyolefin catalysts” are used interchangeably.

[0035] In some embodiments, the carrier according to the present invention comprises a composition represented by general formula (I), general formula (I'), or general formula (I''), or has a composition represented by general formula (I), general formula (I'), or general formula (I''):

[0036] [ka]

[0037] In equation (I'), R1 is C1~C 12 It is a linear or branched alkyl group; R2 and R3 are the same or different, and are hydrogen, or unsubstituted or halogenated linear or branched alkyl groups of C1-C5; X and Y independently represent halogens; m is 0.1-1.9; n is 0.1-1.9; m+n=2; 0 <i≦2;0<j≦2;0<k≦2;i+j+k=3;0<p≦0.1;および0<z<0.1であり; In equation (I) above, R1 is C1 to C 12 It is a linear or branched alkyl group; R2 and R3 are the same or different, and are hydrogen, or unsubstituted or halogenated linear or branched alkyl groups of C1-C5; X is a halogen; m is 0.1-1.9; n is 0.1-1.9; m+n=2; 0 <z<0.5であり; In equation (I′′), R1 is C1~C 12 It is a linear or branched alkyl group; R2 and R3 are the same or different, and are hydrogenated or unsubstituted or halogenated linear or branched alkyl groups of C1-C5; X and Y independently represent halogens; m is 0.1-1.9; n is 0.1-1.9; m+n=2; 0≦a<2, 0 <b≦2、a+b=2であり;0<q<0.1であり;および0≦z<0.1であり; LB is a compound represented by general formula (II),

[0038] [ka]

[0039] In the formula, R5 and R7 are the same or different and are hydrogen or a C1-C8 linear or branched alkyl group which is unsubstituted or substituted with a hydroxyl group; R6 is a C1-C8 linear or branched alkylene.

[0040] As can be understood by those skilled in the art, the above general formula (I) represents

[0041]

Chemical formula

[0042] a composition consisting of a magnesium compound represented by and LB in a predetermined molar ratio. Similarly, the general formula (I') represents

[0043]

Chemical formula

[0044] a composition consisting of and LB in a predetermined molar ratio. Similarly, the general formula (I'') represents

[0045]

Chemical formula

[0046] a composition consisting of and LB in a predetermined molar ratio.

[0047] In some embodiments, the carrier according to the present invention comprises or has a composition represented by the general formula (I'''):

[0048]

Chemical formula

[0049] In the formula, R1 is C1-C 12is a linear or branched alkyl; R2 and R3 are the same or different and are hydrogen or an unsubstituted or halogenated C1-C5 linear or branched alkyl; X is halogen; m is 0.1-1.9; n is 0.1-1.9; m + n = 2; 0 < z < 0.5; LB is an amide compound represented by the general formula (II′),

[0050]

Chemical formula

[0051] wherein R 10 is hydrogen, amino, or a C1-C8 linear or branched alkyl, and R 11 and R 12 are the same or different and are hydrogen or a C1-C8 linear or branched alkyl.

[0052] As can be understood by those skilled in the art, the above general formula (I′′′) represents a composition consisting of a magnesium compound represented by

[0053]

Chemical formula

[0054] and LB at a predetermined mol ratio.

[0055] In some embodiments of the present disclosure, R1 is a C1-C8 linear or branched alkyl. Preferably, R1 is selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl, and 2-ethylhexyl.

[0056] In some embodiments of this disclosure, R2 and R3 are each independently hydrogen, a C1-C3 linear or branched alkyl group, or a halogenated C1-C3 linear or branched alkyl group. Preferably, R2 and R3 are each independently methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, or bromoethyl.

[0057] In some embodiments of this disclosure, R5 and R7 are C1-C5 linear or branched alkyl groups, and R6 is a C1-C5 linear or branched alkylene group. In some embodiments, R5 and R7 are independently hydrogen, methyl, ethyl, isopropyl, n-propyl, tert-butyl, or isobutyl. In some embodiments, R6 is methylene, ethylene, or propylene.

[0058] In some embodiments of this disclosure, the compound represented by the general formula (II) useful in this disclosure is one or more selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, and N-methyldiethanolamine.

[0059] In some embodiments of this disclosure, R 10 R is a hydrogen atom, an amino acid, or a linear or branched alkyl group of C1-C5. 11 and R 12 This is hydrogen, or a linear or branched alkyl group of C1-C5.

[0060] In some embodiments of this disclosure, the amide compound represented by the general formula (II′) useful in this disclosure is one or more selected from the group consisting of formamide, acetamide, propionamide, N-methylacetamide, N,N-dimethylacetamide, and carbonamide.

[0061] In the context of this application, the halogen is selected from the group consisting of fluorine, chlorine, bromine, and iodine, and is preferably chlorine.

[0062] According to the present invention, the carrier may further contain other metallic components besides magnesium, such as transition metal components. Preferably, the other metallic components are iron and copper, or both.

[0063] According to some embodiments of the present invention, the content of other metallic components in the solid component is 0-1% by weight.

[0064] According to some embodiments of the present invention, the carrier is spherical. As used herein, the term "spherical" means that the carrier has a spherical particle form, without requiring the carrier to have a perfectly spherical shape.

[0065] In some embodiments, the carrier has an average particle size of 10 to 100 μm, preferably 30 to 70 μm, and a particle size distribution smaller than 1.2, preferably 0.7 to 0.9.

[0066] In a second embodiment, the present invention provides a method for producing a support for a polyolefin catalyst: (a) Magnesium halide represented by the general formula MgX2, and any Metal halides The process involves reacting an alcohol compound represented by the general formula R1OH with a compound represented by the general formula (II) or (II') to produce a solution.

[0067] [ka]

[0068] In the formula, X is a halogen; R1 is C1~C 12R5 and R7 are linear or branched alkyl groups; R5 and R7 are the same or different, and are C1-C8 linear or branched alkyl groups with hydrogen, or unsubstituted or hydroxyl group substituted; R6 is a C1-C8 linear or branched alkylene group; R 10 is hydrogen, amino, or a linear or branched alkyl group of C1-C8; and R 11 and R 12 They are either identical or different, and are hydrogen, or C1-C8 linear or branched alkyl groups; (b) A step of directly producing spherical solid particles by reacting the solution produced in step (a) with an epoxy compound; (c) A step of recovering the spherical solid particles produced in step (b); and the above.

[0069] Here, the phrase "directly generating spherical solid particles" has the following meanings: (1) The solid particles precipitate by a chemical reaction, that is, in the manufacturing process, the solid particles precipitate directly from the original system by a chemical reaction, without the need to precipitate the solid particles from the reactants by other means such as vaporization of the solvent or changing the system temperature (e.g., spray drying, reduction of system temperature); (2) The acquisition of solid particle shape (typically spherical) can be achieved without the need to introduce an inert carrier material with good particle morphology (e.g., SiO2, metal oxide, etc.) into the product.

[0070] In a more specific aspect of this embodiment, high: (a) Magnesium halide represented by the general formula MgX2, any magnesium halide represented by the structural formula FeY2 Metal halides , or any structure represented by the structural formula CuYc Metal halides A step of preparing a solution by reacting an alcohol compound represented by the general formula R1OH with a compound represented by the following general formula (II),

[0071] [ka]

[0072] In the formula, R1 is C1~C 12 R5 and R7 are linear or branched alkyl groups, where R5 and R7 are the same or different, and are hydrogen, or unsubstituted or hydroxyl-substituted C1-C8 linear or branched alkyl groups; R6 is a C1-C8 linear or branched alkylene, where X and Y are halogens, C=1 or C=2, preferably C=1; and (b) A step of reacting the solution produced in step (a) with an epoxy compound to directly produce spherical solid particles; (c) A step of recovering the spherical solid particles produced in step (b); and the above.

[0073] In another, more specific embodiment of this aspect, the method is: (a) A step of preparing a solution by reacting magnesium halide represented by the general formula MgX2 with an alcohol compound represented by the general formula R1OH and an amide compound represented by the following general formula (II'),

[0074] [ka]

[0075] In the formula, R1 is C1~C 12 It is a linear or branched alkyl group, R 10 R is hydrogen, amino, or a linear or branched alkyl group of C1-C8. 11 and R 12 are either identical or different, and are hydrogen, or C1-C8 linear or branched alkyl groups, where X is a halogen; and (b) A step of directly producing solid particles by reacting the solution produced in step (a) with an epoxy compound; (c) A step of recovering the solid particles produced in step (b); and the above.

[0076] In some embodiments of this model, R1 is a linear or branched alkyl group of C1 to C8, preferably a linear or branched alkyl group of C1 to C6. According to some specific embodiments, R1 is selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl, and 2-ethylhexyl. According to some preferred embodiments of the present invention, the R1OH compound used in step (a) may be one or more alcohol compounds. Specific examples of alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethyl-1-hexanol.

[0077] In some embodiments of this model, R5 and R7 are hydrogen or C1-C5 linear or branched alkyl groups, and R6 is C1-C5 linear or branched alkylene groups. In some embodiments, R5 and R7 are hydrogen or methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, etc. In some embodiments, R6 is methylene, ethylene, propylene, etc. According to some embodiments of the present invention, the compound represented by general formula (II) is one or more selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, and N-methyldiethanolamine.

[0078] In some embodiments of this model, R 10 R is hydrogen, amino, or a linear or branched alkyl group of C1-C5. 11 and R 12 This is hydrogen, or a linear or branched alkyl group of C1-C5. According to some embodiments of the present invention, the amide compound is one or more selected from the group consisting of formamide, acetamide, propionamide, N-methylacetamide, N,N-dimethylacetamide, and carbonamide.

[0079] In some embodiments of this model, the epoxy compound is preferably represented by general formula (III),

[0080] [ka]

[0081] In the formula, R2 and R3 are either the same or different, and are hydrogen, or an unsubstituted or halogenated C1-C5 linear or branched alkyl group. Preferably, R2 and R3 are each independently hydrogen, a C1-C3 linear or branched alkyl group, or a halogenated C1-C3 linear or branched alkyl group. Preferably, R2 and R3 are each independently methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, or bromoethyl.

[0082] In some embodiments of this design, in step (a), a polymeric dispersion stabilizer is added during the preparation of the solution, the weight-average molecular weight of which is greater than 1000, preferably greater than 3000.

[0083] In some embodiments of this model, the magnesium halide of general formula MgX2 used in step (a) is one or more of magnesium chloride, magnesium bromide, and magnesium diiodide.

[0084] In some embodiments of this model, a metal halide, preferably a reducing metal halide, may be added in step (a). For example, the metal halide may have the structural formula MY a A metal halide can be selected from those having the following properties, where M is a transition metal, Y is a halogen, and a is 1 or 2. In some specific embodiments, M is copper and a=1. In other specific embodiments, M is iron and a=2. Preferred metal halides are CuCl and FeCl2.

[0085] In some embodiments of this model, the metal halide optionally used in step (a) is one or more selected from the group consisting of ferrous chloride, ferrous bromide, ferrous iodide, and their hydrates, such as ferrous chloride tetrahydrate, preferably ferrous chloride and its hydrate.

[0086] In some embodiments of this model, the metal halide optionally used in step (a) is a copper halide, preferably a cuprous halide, most preferably a cuprous chloride. When a cuprous halide is used in the above-described manufacturing method, it has been found that the mixture formed in step (a) is a suspension because the cuprous halide is insoluble (or slightly soluble) in the reaction system. Surprisingly, the particle size of the final carrier particles can be significantly affected by the amount of metal halide added within a certain range.

[0087] In some embodiments of this model, the manufactured carrier has an average particle size of 10 to 100 μm, preferably 30 to 70 μm.

[0088] In some embodiments of this model, the manufactured carrier has a particle size distribution smaller than 1.2, preferably between 0.7 and 0.9.

[0089] In some embodiments of this invention, the preparation of the solution in step (a) is carried out at a temperature of 30 to 160°C, preferably 40 to 120°C. According to some embodiments of the present invention, the amount of R1OH compound added is in the range of 3 to 30 mol, preferably 4 to 25 mol, per mol of magnesium. According to some embodiments of the present invention, the molar ratio of the compound represented by general formula (II) or (II') to magnesium halide is 1:200 to 1:10, preferably 1:200 to 1:2, for example 1:100 to 1:5, preferably 1:50 to 1:50. According to some preferred embodiments of the present invention, step (a) is carried out in a sealed container. According to some preferred embodiments of the present invention, in step (a), the order in which the raw materials are added during the preparation of the solution is not specified.

[0090] In some embodiments of this model, the amount of metal halide added is in the range of 0.001 to 0.1 mol, preferably 0.003 to 0.08 mol, per mol of magnesium.

[0091] According to some embodiments of the present invention, the inert dispersion medium may or may not be added during the preparation of the solution in step (a). The inert dispersion medium may be one or a mixture of liquid aliphatic compounds, aromatic compounds, or alicyclic hydrocarbons and silicone oils. The ratio (volume ratio) of the amount of inert dispersion medium added to the amount of R1OH compound added is 0 to 5:1, preferably 0 to 2:1.

[0092] According to some preferred embodiments of the present invention, examples of the MgX2 compound used in step (a) include, but are not limited to, magnesium chloride, magnesium dibromide, and magnesium diiodide. Of these, magnesium chloride is preferred. The MgX2 compounds can be used separately or in combination.

[0093] According to some preferred embodiments of the present invention, trace amounts of water in the individual raw materials added in step (a) can participate in the reaction to produce a solution.

[0094] According to some preferred embodiments of the present invention, specific examples of epoxy compounds used in step (b) include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epoxychlorobutane, epoxybromopropane, and epoxybromobutane.

[0095] According to some preferred embodiments of the present invention, the reaction temperature in step (b) is in the range of 30 to 160°C, preferably 40 to 120°C.

[0096] According to some preferred embodiments of the present invention, the amount of ethylene oxide type compound added in step (b) is 1 to 10 mol, preferably 2 to 6 mol, per mol of magnesium.

[0097] To obtain particles having a better particle morphology, it is preferable to add at least one polymeric dispersion stabilizer during the preparation of the solution in step (a), wherein the weight-average molecular weight of the polymeric dispersion stabilizer is greater than 1000, preferably greater than 3000, for example up to 2,000,000, or up to 1,000,000. In particular, the polymer dispersion stabilizer may be at least one selected from polyacrylate, styrene-maleic anhydride copolymer, polystyrene sulfonate, naphthalene sulfonic acid-formaldehyde condensation product, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer-modified polyethyleneimine, poly(1-dodecyl-4-vinylpyridinium bromide), poly(vinylbenzyltrimethylammonium salt), poly(vinyl alcohol), polyacrylamide, ethylene oxide-propylene oxide block copolymer, polyvinylpyrrolidone, poly(vinylpyrrolidone-co-vinyl acetate), poly(ethylene glycol), alkylphenyl polyoxyethylene ether, and poly(alkyl methacrylate), preferably at least one of polyvinylpyrrolidone, poly(vinylpyrrolidone-co-vinyl acetate), and poly(ethylene glycol).

[0098] According to some preferred embodiments of the present invention, the amount of polymeric dispersion stabilizer is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total amount of the magnesium compound and the R1OH compound.

[0099] According to the present invention, the manufacturing method further comprises step (c) of recovering the obtained solid particles. Recovery of the solid in step (c) means obtaining solid particles by using known solid-liquid separation techniques such as filtration, decanting, centrifugation, and other operations, and also includes washing and drying the obtained spherical carrier particles with a hydrocarbon solvent. The inert hydrocarbon solvent is preferably a straight-chain or branched-chain liquid alkane having a carbon chain length of more than 4, or an aromatic hydrocarbon such as hexane, heptane, octane, decane, or toluene.

[0100] In a preferred embodiment, a method for producing a carrier is: (1) In a sealed container, in the presence of at least one polymer dispersion stabilizer, a mixture of magnesium halide (MgX2), an organic alcohol (R1OH), any metal halide with structural formula FeY2 or any metal halide with structural formula CuYc, and a compound of general formula (II) is reacted at 30 to 160°C, preferably 40 to 120°C, for 0.1 to 5 hours, preferably 0.5 to 2 hours to produce a solution; (2) Reacting the above solution with an alkylene oxide compound represented by formula (III) at 30 to 160°C, preferably 40 to 120°C, for 0.1 to 5 hours, preferably 0.2 to 1 hour, to directly precipitate solid particles; (3) The method includes recovering solid particles by solid-liquid separation technology to obtain a spherical carrier.

[0101] In a more preferred embodiment, a method for manufacturing a carrier is: (1) In a sealed container, a mixture of magnesium halide, organic alcohol, any metal halide of structural formula FeY2 or any metal halide of structural formula CuYc, a compound of general formula (II), and at least one polymer dispersion stabilizer is heated to a temperature of 30 to 160°C, preferably 40 to 120°C, while stirring, and the mixture is reacted for 0.1 to 5 hours, preferably 0.5 to 2 hours, to produce a mixed solution, where the amount of organic alcohol is 3 to 30 mol, preferably 4 to 25 mol, and the general formula ( The amount of compound II) is 0.005 to 0.1 mol, preferably 0.005 to 0.05 mol, per mol of magnesium; the amount of the metal halide with structural formula FeY2 or the metal halide with structural formula CuYc is preferably 0.01 to 0.1 mol, more preferably 0.01 to 0.05 mol, per mol of magnesium; and the amount of polymeric dispersion stabilizer is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, relative to the combined amount of magnesium halide and organic alcohol. (2) Add the alkylene oxide compound represented by formula (III) to the above mixed solution while stirring, and react at 30 to 160°C, preferably 40 to 120°C, for 0.1 to 5 hours, preferably 0.2 to 1 hour to directly produce solid particles, wherein the amount of alkylene oxide compound used is 1 to 10 moles, preferably 2 to 6 moles, per mole of magnesium; (3) The method includes recovering solid particles by solid-liquid separation technology to obtain a spherical carrier.

[0102] In a preferred embodiment, a method for producing a solid component is: (1) Prepare a solution by reacting a mixture of magnesium halide (MgX2), an organic alcohol (R1OH), and a compound of general formula (II') in a sealed container in the presence of at least one polymeric dispersion stabilizer at 30 to 160°C, preferably 40 to 120°C, for 0.1 to 5 hours, preferably 0.5 to 2 hours; (2) React the above solution with the alkylene oxide compound represented by formula (III) at 30 to 160°C, preferably 40 to 120°C, for 0.1 to 5 hours, preferably 0.2 to 1 hour, to directly precipitate solid particles; (3) The method includes recovering solid particles by solid-liquid separation technology to obtain a spherical carrier.

[0103] In a preferred embodiment, in step (1) above, MY a Metal halogens having the structure are also added.

[0104] In a more preferred embodiment, a method for producing a spherical carrier is: (1) In a sealed container, a mixture of magnesium halide, an organic alcohol, a compound of general formula (II'), and at least one polymeric dispersion stabilizer is heated to 30-160°C, preferably 40-120°C, while stirring, and the mixture is reacted for 0.1-5 hours, preferably 0.5-2 hours, to produce a mixed solution, wherein the amount of organic alcohol is 3-30 mol, preferably 4-25 mol, the amount of compound of general formula (II') is 0.01-0.5 mol, preferably 0.02-0.3 mol, per 1 mol of magnesium, and the amount of polymeric dispersion stabilizer is 0.1-10% by weight, preferably 0.2-5% by weight, relative to the combined amount of magnesium halide and organic alcohol, and in this step, MY a If a metal halide is optionally added and used in the structure, it should be added in an amount of 0.01 to 0.1 mol, preferably 0.01 to 0.05 mol, per mol of magnesium; (2) Add the alkylene oxide compound represented by formula (III) to the above mixed solution while stirring, and react at 30 to 160°C, preferably 40 to 120°C for 0.1 to 5 hours, preferably 0.2 to 1 hour to directly produce solid particles, wherein the amount of alkylene oxide compound used is 1 to 10 moles, preferably 2 to 6 moles, per mole of magnesium; (3) The method includes recovering solid particles by solid-liquid separation technology to obtain a spherical carrier.

[0105] In the above preferred embodiment, the recovery of solid particles can be carried out by solid-liquid separation techniques known in the art, such as filtration, decanting, or centrifugation. Furthermore, step (3) may further include washing and drying the obtained spherical carrier particles with an inert hydrocarbon solvent. The inert hydrocarbon solvent is preferably a straight-chain or branched-chain liquid alkane or aromatic hydrocarbon having a carbon chain length of more than four carbon atoms, such as hexane, heptane, octane, decane, or toluene.

[0106] The present invention further provides a solid component produced by the above-described manufacturing method. According to some embodiments of the present invention, the solid component is spherical and has an average particle size of 10 to 100 μm, preferably 30 to 70 μm, and a particle size distribution less than 1.2, preferably 0.7 to 0.9.

[0107] The present invention further provides a catalyst component for olefin polymerization. The catalyst component comprises a reaction product of a carrier / solid component and / or a solid component produced by the production method described herein, a titanium compound, and an internal electron donor compound. The synthesis of the catalyst component can be carried out by known synthesis methods, for example, a method by directly reacting spherical magnesium-containing composition particles with titanium halide, as described in Chinese Patent CN1091748; or a method by first reacting a spherical magnesium-containing composition with an alkoxy titanium compound having the structural formula Ti(OR)4 to obtain an intermediate product, and then reacting the intermediate product with titanium halide, as described in Chinese Patent Application CN201310469927. In the above-described methods for producing the catalyst, it is common to optionally add several internal electron donor compounds known in the art, depending on the actual application.

[0108] The present invention further provides a catalyst system for olefin polymerization comprising a catalyst component, an alkylaluminum compound, and an optional external electron donor compound.

[0109] The present invention further provides a method for olefin polymerization, comprising contacting one or more olefins with a catalyst system under olefin polymerization conditions. In one embodiment of the present invention, the olefin is CH2=CHR, where R is hydrogen or a C1-C7 alkyl group. Preferably, the olefin is one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene.

[0110] The present invention has some or all of the following advantages: (1) the particle morphology of the solid component having the composition described in the present invention is improved, thereby reducing particle aggregation; (2) when used in the polymerization of olefins, particularly the polymerization or copolymerization of propylene, the catalyst produced by using the solid component of the present invention as a support has high stereospecificity; (3) the catalyst produced by using the solid component of the present invention as a support has high strength and is less prone to breakage; (4) the particle size of the support can be adjusted without changing the stirring speed by adding reducing metal halides and electron donor compounds having a specific structure to the reaction system, in particular, a support having a small particle size (<40 μm) without changing the stirring speed; and (5) the method for producing the support is stable.

[0111] [Examples] The following embodiments are provided to further illustrate the present invention and are not intended to limit the scope of the invention.

[0112] Test method: 1. Polymer melt index: Measured according to ASTM D1238-99 at 230°C and a load of 2.16 kg.

[0113] 2. Polymer isotacticity: Measured by heptane extraction (heptane boiling extraction for 6 hours) as follows: 2 g of dried polymer sample was extracted by boiling heptane in an extractor for 6 hours. The residual material was then dried to a certain weight, and the ratio of the weight of residual polymer (g) to 2 (g) was considered as isotacticity.

[0114] 3. Particle Size Distribution: The average particle size and particle size distribution of the carrier particles were measured using a Masters Sizer Model 2000 Particle sizer (Malvern Instruments), with n-hexane as the dispersion medium. The span of the particle size distribution value is (D90-D10) / D50.

[0115] 4. The external morphology of the supports for the olefin polymerization catalysts was observed at 160x or 400x magnification using an Eclipse E200 optical microscope purchased from Nikon, or using an XL-30 field emission environmental scanning electron microscope from FEI, USA.

[0116] 5. Metal element content in the support: Measured using an Agilent ICP-MS 7500CX inductively coupled plasma mass spectrometer (Agilent, USA), where the support was dissolved in concentrated nitric acid and then allowed to stand for 12 hours before measurement.

[0117] 6. Catalyst activity = weight of polymer obtained / weight of catalyst used.

[0118] 7. 1 ¹H-NMR measurements are performed using a Bruker AVANCE300 nuclear magnetic resonance spectrometer from Switzerland. Approximately 100 mg of the sample to be tested is placed in a 2 mL sample bottle in a glove box with a stream of dry nitrogen. Then, 1 mL of deuterated toluene and 100 μL of tri-n-butyl phosphate or triisobutyl phosphate are added to the sample bottle. The sample bottle is sealed with a sealing film and sonicated in a 60°C water bath for 0.5 hours, after which it is allowed to stand for several minutes. Next, approximately 1 / 10 of the clear liquid is placed in the NMR tube. Additional deuterated toluene is added to the NMR tube until the total volume of liquid in the NMR tube is 0.5 mL, and the sample is prepared for testing.

[0119] 8. Electron donor content in the support: Measured using a TraceGC Ultra chromatograph and DSQ II mass spectrometer from Thermo Fisher, Inc., USA. The column was an HP-5 capillary column with a column length of 30 m, methanol was used as the solvent for the sample, the heating rate was 10°C / min, and the evaporation temperature was 200°C.

[0120] A-1. Manufacturing of spherical carriers Example 1 In a 1.0 L reaction vessel, 1.6 g of polyvinylpyrrolidone (PVP, weight-average molecular weight 58000), 2.8 mol of ethanol, 0.2 mol of magnesium chloride, and 0.015 mol of formamide were sequentially added, and the temperature was raised to 70°C while stirring (450 rpm). After 1 hour of constant-temperature reaction, 0.6 mol of epichlorohydrin was added, and the temperature was maintained for 0.5 hours before filtration. The solid was washed five times with hexane and dried under vacuum to obtain solid component particles. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the composition of the solid component particles was determined to be:

[0121] [ka]

[0122] It was found that...

[0123] The solid component particles have a particle size distribution of D50 = 63.5 μm and span = 0.67, and the particle morphology is shown in Figure 1A (160x magnification) and Figure 1B (400x magnification).

[0124] Example 2 The manufacturing method was the same as described in Example 1, except that the amount of formamide was 0.03 mol and the reaction temperature was 80°C. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the composition of the solid component particles was determined to be:

[0125] [ka]

[0126] It was found that...

[0127] The solid component particles have a particle size distribution with D50 = 45.2 μm and span = 0.65.

[0128] Example 3 The manufacturing method was the same as described in Example 1, except that the amount of formamide was 0.005 mol. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the composition of the solid component particles was determined to be:

[0129] [ka]

[0130] It was found that...

[0131] The carrier has a particle size distribution of D50 = 78.5 μm and span = 0.67.

[0132] Example 4 The manufacturing method was the same as that described in Example 1, except that 2 mmol of ferrous chloride was added. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, it was found that the solid component particles had the same main composition as in Example 1 and contained 0.046 wt% Fe.

[0133] The solid component particles have a particle size distribution of D50 = 61.4 μm and span = 0.69, and the particle morphology is shown in Figure 2.

[0134] Example 5 The manufacturing method was the same as that described in Example 4, except that the amount of ferrous chloride added was 9 mmol. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, it was found that the solid component particles had the same main composition as in Example 1 and contained 0.59% by weight of Fe.

[0135] The solid component particles have a particle size distribution with D50 = 47.1 μm and span = 0.76.

[0136] Example 6 The manufacturing method was the same as that described in Example 1, except that 5 mmol of cuprous chloride was further added. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, it was found that the solid component particles had the same main composition as in Example 1 and contained 0.038 wt% Cu.

[0137] The solid component particles have a particle size distribution with D50 = 53.1 μm and span = 0.68.

[0138] Example 7 The manufacturing method was the same as that described in Example 1, except that 0.015 mol of formamide was replaced with 0.02 mol of N,N-dimethylacetamide. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the main composition of the solid component particles was determined to be:

[0139] [ka]

[0140] It was found that...

[0141] The solid component particles have a particle size distribution with D50 = 65.1 μm and span = 0.65.

[0142] Example 8 The manufacturing method was the same as that described in Example 1, except that 0.015 mol of formamide was replaced with 0.02 mol of N-methylacetamide. Characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography revealed the main composition of the solid component particles to be:

[0143] [ka]

[0144] It was found that...

[0145] The solid component particles have a particle size distribution with D50 = 57.8 μm and span = 0.67.

[0146] Example 9 The manufacturing method was the same as that described in Example 1, except that the amount of formamide added was changed to 0.04 mol and the reaction temperature was set to 60°C. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the composition of the solid component particles was determined to be:

[0147] [ka]

[0148] It was found that...

[0149] The solid component particles have a particle size distribution with D50 = 43.6 μm and span = 0.66.

[0150] Example 10 The manufacturing method was the same as that described in Example 1, except that 0.015 mol of formamide was replaced with 0.01 mol of carvonamide. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the composition of the solid component particles was determined to be:

[0151] [ka]

[0152] It was found that...

[0153] The solid component particles have a particle size distribution with D50 = 65.3 μm and span = 0.65.

[0154] B-1. Production of spherical catalyst components Example 11 (1) Preparation of intermediate reaction products In a 300 mL glass reaction flask, under a nitrogen atmosphere, 10 g of solid component particles prepared in Example 1 were dispersed in 100 mL of hexane while mechanically stirring. The mixture was cooled to -10°C and maintained for 0.5 hours. Next, 2.5 mL of tetraethyl titanate (TET) (corresponding to a molar ratio of TET / Mg = 0.2) was added, and the temperature was gradually raised to 60°C and maintained for 0.5 hours. The liquid was filtered, the solid was washed three times with hexane, and then dried under vacuum to obtain the intermediate product.

[0155] (2) Production of catalyst components Under an inert atmosphere, 100 mL of titanium tetrachloride was added to a 300 mL glass reaction flask, cooled to -20°C, and 8 g of the intermediate product prepared above was added. The temperature was raised to 110°C, and 1.5 mL of diisobutyl phthalate was added during the heating process. The liquid was filtered, the solid was washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain spherical catalyst components.

[0156] (3) Polymerization of propylene Liquid-phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (with a concentration of 0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (with a concentration of 0.1 mmol / mL), and 9 mg of the above spherical catalyst component were continuously added to the autoclave. The autoclave was closed, and a fixed amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70°C and the reaction was allowed to proceed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the material was discharged, and the resulting propylene homopolymer was dried and weighed. The results are shown in Table 1.

[0157] Example 12 The procedure of Example 11 was repeated, except that the solid component particles used were those produced in Example 6.

[0158] Example 13 The procedure of Example 10 was repeated, except that the solid component particles used were those produced in Example 7.

[0159] Comparative Example 1 The production of the spherical carrier was the same as described for Example 1, except that the amide compound of general formula (II) was not added. The morphology of the solid component particles is shown in Figure 3A (160x magnification) and Figure 3B (400x magnification), and it can be seen from the figures that some solid component particles adhere to each other to form irregular particles.

[0160] As described in Example 11, catalyst production and polymerization of propylene were carried out, and the polymerization results are shown in Table 1.

[0161] From the particle size distribution of the solid components described above and the results shown in the attached drawings, it can be seen that the present invention improves the particle morphology of the carrier and further reduces particle aggregation by adding an amide compound represented by general formula (II) during the manufacturing of the carrier.

[0162] [Table 1]

[0163] The results in Table 1 show that the addition of amide compounds during the production of the support can improve the stereospecificity of the catalyst and has little effect on the polymerization activity of the catalyst.

[0164] A photograph of the catalyst component of Example 1 is shown in Figure 4, and a photograph of the catalyst component of Comparative Example 1 is shown in Figure 5. From the figures, it can be seen that the catalyst produced using solid component particles to which the compound of general formula (II) is added as a support shows less damage.

[0165] A-2. Manufacturing of spherical carriers Example 14 In a 1.0 L reaction vessel, 1.6 g of polyvinylpyrrolidone (PVP, weight-average molecular weight 58000), 2.8 mol of ethanol, 0.2 mol of magnesium chloride, 2 mmol of ferrous chloride, and 2 mmol of triethanolamine were sequentially added, and the temperature was raised to 70°C while stirring (450 rpm). After a constant temperature reaction for 1 hour, 0.6 mol of epichlorohydrin was added, the temperature was maintained for 0.5 hours, and then the mixture was filtered. The solid was washed five times with hexane and dried under vacuum to obtain solid component particles. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following structure.

[0166] [ka]

[0167] The carrier has a particle size distribution of D50 = 71.1 μm and span = 0.65, and the particle morphology is shown in Figure 6(A) (optical microscope image, 160x magnification) and Figure 6(B) (electron microscope image).

[0168] Example 15 The manufacturing method was the same as described in Example 14, except that the amount of ferrous chloride added was 4 mmol. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following structure.

[0169] [ka]

[0170] The carrier has a particle size distribution of D50 = 68.2 μm and span = 0.67.

[0171] Example 16 The manufacturing method was the same as that described in Example 14, except that the amount of ferrous chloride added was 8 mmol. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following structure.

[0172] [ka]

[0173] The carrier has a particle size distribution of D50 = 39.8 μm and span = 0.68.

[0174] Example 17 The manufacturing method was the same as described in Example 14, except that the reaction temperature was 80°C. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following structure.

[0175] [ka]

[0176] The carrier has a particle size distribution of D50 = 72.2 μm and span = 0.65.

[0177] Example 18 The manufacturing method was the same as described in Example 14, except that the reaction temperature was 60°C.

[0178] The carrier has a particle size distribution of D50 = 38.8 μm and span = 0.66.

[0179] Example 19 The manufacturing method was the same as described in Example 18, except that the amount of ferrous chloride added was 5 mmol. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following structure.

[0180] [ka]

[0181] The carrier has a particle size distribution of D50 = 35.4 μm and span = 0.66.

[0182] Example 20 The manufacturing method was the same as described in Example 14, except that the amount of ferrous chloride tetrahydrate added was 0.1 g.

[0183] The carrier has a particle size distribution of D50 = 81.6 μm and span = 0.59.

[0184] Example 21 The manufacturing method was the same as described in Example 20, except that the amount of ethanol added was 2.4 mol.

[0185] The carrier has a particle size distribution of D50 = 73.5 μm and span = 0.67.

[0186] Example 22 The manufacturing method was the same as described in Example 14, except that 2 mmol of triethanolamine was replaced with 4 mmol of N,N-dimethylethanolamine. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following structure.

[0187] [ka]

[0188] The carrier has a particle size distribution of D50 = 69.5 μm and span = 0.64.

[0189] Example 23 The manufacturing method was the same as described in Example 16, except that the amount of triethanolamine added was 0.01 mol. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following structure.

[0190] [ka]

[0191] The carrier has a particle size distribution of D50 = 53.2 μm and span = 0.68.

[0192] B-2. Production of spherical catalyst components Example 24 (1) Preparation of intermediate reaction products In a 300 mL glass reaction flask, under a nitrogen atmosphere, 10 g of the carrier prepared in Example 14 was dispersed in 100 mL of hexane while mechanically stirring, and the mixture was cooled to -10°C and maintained for 0.5 hours. Next, 2.5 mL of tetraethyl titanate (TET) (corresponding to a molar ratio of TET / Mg = 0.2) was added, and the temperature was gradually raised to 60°C and maintained for 0.5 hours. The liquid was filtered, the solid was washed three times with hexane, and then dried under vacuum to obtain the intermediate product.

[0193] (2) Production of catalyst components In a 300 mL glass reaction flask, 100 mL of titanium tetrachloride was added under an inert atmosphere, cooled to -20°C, and 8 g of the intermediate product prepared in (1) above was added. The temperature was raised to 110°C, and 1.5 mL of diisobutyl phthalate was added during the heating process. The liquid was filtered, the solid was washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain spherical catalyst components.

[0194] (3) Polymerization of propylene Liquid-phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (with a concentration of 0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (with a concentration of 0.1 mmol / mL), and 9 mg of the aforementioned spherical catalyst component were continuously added to the autoclave. The autoclave was closed, and a fixed amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70°C and the reaction was allowed to proceed for 1 hour. Then, the temperature was lowered, the pressure was released, the material was discharged, and the resulting propylene homopolymer was dried and weighed. The results are shown in Table 2.

[0195] Example 25 (1) Preparation of intermediate reaction products In a 300 mL glass reaction flask, under a nitrogen atmosphere, 10 g of the carrier prepared in Example 15 was dispersed in 100 mL of hexane while mechanically stirring, and the mixture was cooled to -10°C and maintained for 0.5 hours. Next, 2.5 mL of tetraethyl titanate (TET) (corresponding to a molar ratio of TET / Mg = 0.2) was added, and the temperature was gradually raised to 60°C and maintained for 0.5 hours. The liquid was filtered, the solid was washed three times with hexane, and then dried under vacuum to obtain the intermediate product.

[0196] (2) Production of catalyst components Under an inert atmosphere, 100 mL of titanium tetrachloride was added to a 300 mL glass reaction flask, cooled to -20°C, and 8 g of the intermediate product prepared in (1) above was added. The temperature was raised to 110°C, and 1.5 mL of diisobutyl phthalate was added during the heating process. The liquid was filtered, the solid was washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain spherical catalyst components.

[0197] (3) Polymerization of propylene Liquid-phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (with a concentration of 0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (with a concentration of 0.1 mmol / mL), and 9 mg of the above spherical catalyst component were continuously added to the autoclave. The autoclave was closed, and a fixed amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70°C and the reaction was allowed to proceed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the material was discharged, and the resulting propylene homopolymer was dried and weighed. The results are shown in Table 2.

[0198] Example 26 (1) Preparation of intermediate reaction products In a 300 mL glass reaction flask, under a nitrogen atmosphere, 10 g of the carrier prepared in Example 21 was dispersed in 100 mL of hexane while mechanically stirring, and the mixture was cooled to -10°C and maintained for 0.5 hours. Next, 2.5 mL of tetraethyl titanate (TET) (corresponding to a molar ratio of TET / Mg = 0.2) was added, and the temperature was gradually raised to 60°C and maintained for 0.5 hours. The liquid was filtered, the solid was washed three times with hexane, and then dried under vacuum to obtain the intermediate product.

[0199] (2) Production of catalyst components Under an inert atmosphere, 100 mL of titanium tetrachloride was added to a 300 mL glass reaction flask, cooled to -20°C, and 8 g of the intermediate product prepared in (1) above was added. The temperature was raised to 110°C, and 1.5 mL of diisobutyl phthalate was added during the heating process. The liquid was filtered, the solid was washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain spherical catalyst components.

[0200] (3) Polymerization of propylene Liquid-phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (with a concentration of 0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (with a concentration of 0.1 mmol / mL), and 9 mg of the above spherical catalyst component were continuously added to the autoclave. The autoclave was closed, and a fixed amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70°C and the reaction was allowed to proceed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the material was discharged, and the resulting propylene homopolymer was dried and weighed. The results are shown in Table 2.

[0201] Comparative Example 2 The manufacturing method was the same as described in Example 19, except that ferrous chloride and the compound of formula (II) were not added, and the stirring speed was increased to 1600 rpm. The carrier has a particle size distribution of D50 = 35.4 μm and span = 0.9.

[0202] Comparative Example 3 The manufacturing method was the same as described in Example 14, except that 2 mmol of ferrous chloride was replaced with 3 mmol of ferric chloride. The carrier had a particle size distribution of D50 = 76.5 μm and span = 0.68. It was observed that some of the carrier particles aggregated to form irregular particles.

[0203] Comparative Example 4 The manufacturing method was the same as that described in Example 14, except that 2 mmol of ferrous chloride was replaced with 6 mmol of ferric chloride. The carrier has a particle size distribution of D50 = 72.5 μm and span = 0.67.

[0204] Comparative Example 5 The manufacturing method was the same as described in Example 14, except that triethanolamine was not added. The carrier had a particle size distribution of D50 = 71.0 μm and span = 0.67. The carrier was observed to have a rough surface and a small amount of aggregation.

[0205] From the particle size distribution of the carrier described above and the results shown in the attached drawings, it can be seen that, according to the present invention, adding ferrous chloride during the production of the carrier significantly improves the particle morphology of the carrier and reduces particle aggregation. Furthermore, the greater the amount of ferrous chloride added, the smaller the particle size of the carrier becomes (see Examples 14-16), and carriers with small particle sizes can be obtained even under low-speed stirring (see Example 19). When ferrous chloride is not added, even when the stirring speed is increased to 1600 rpm, the particle size of the carrier is still 35 μm, and the particle size distribution is clearly broadened (see Comparative Example 2). Comparative Examples 3 and 4 show that the effect of adding ferric chloride on adjusting the particle size of the carrier particles is not clear. Comparative Example 5 shows that ferrous chloride has a clear improvement effect on the particle morphology of the carrier only when used in combination with a compound of general formula (II).

[0206] [Table 2]

[0207] A photograph of the catalyst of Example 24 is shown in Figure 7, and a photograph of the catalyst component of Comparative Example 1 is shown in Figure 5.

[0208] The results from Table 2 and Figures 7 and 5 show that when the catalyst component produced from the spherical support according to the present invention is used in the polymerization of propylene, it exhibits high polymerization activity and stereospecificity, and at the same time, the catalyst is free of cracks on its surface and suffers little fracture.

[0209] A-3. Manufacturing of spherical carriers Example 27 In a 1.0 L reaction vessel, 1.6 g of polyvinylpyrrolidone (PVP, weight-average molecular weight 58000), 2.8 mol of ethanol, 0.2 mol of magnesium chloride, and 2 mmol of triethanolamine were sequentially added, and the temperature was raised to 70°C while stirring (450 rpm). After a constant temperature reaction for 1 hour, 0.6 mol of epichlorohydrin was added, the temperature was maintained for 0.5 hours, and then the mixture was filtered. The solid was washed five times with hexane and dried in vacuum to obtain solid component particles. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following composition.

[0210] [ka]

[0211] The carrier has a particle size distribution of D50 = 59.9 μm and span = 0.66, and the particle morphology is shown in Figure 8(A) (optical microscope image, 160x), Figure 8(B) (optical microscope image, 400x), and Figure 8(C) (electron microscope image).

[0212] Example 28 The manufacturing method was the same as described in Example 27, except that the amount of triethanolamine added was 4 mmol. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following composition.

[0213] [ka]

[0214] The carrier has a particle size distribution with D50 = 66 μm and span = 0.65.

[0215] Example 29 The manufacturing method was the same as described in Example 27, except that the added amount of triethanolamine was 6 mmol. Through the characterization evaluation by nuclear magnetic resonance, elemental analysis, and gas chromatography, it was found that the carrier had the following composition.

[0216]

Chemical formula

[0217] The carrier has a particle size distribution with D50 = 86 μm and span = 0.73.

[0218] Example 30 The manufacturing method was the same as described in Example 27, except that 2 mmol of triethanolamine was replaced with 4 mmol of N,N-dimethylethanolamine. Through the characterization evaluation by nuclear magnetic resonance, elemental analysis, and gas chromatography, it was found that the carrier had the following composition.

[0219]

Chemical formula

[0220] The carrier has a particle size distribution with D50 = 58.6 μm and span = 0.65. <了

[0221] Example 31 The manufacturing method was the same as described in Example 27, except that 2 mmol of triethanolamine was replaced with 2 mmol of diethanolamine. Through the characterization evaluation by nuclear magnetic resonance, elemental analysis, and gas chromatography, it was found that the carrier had the following composition.

[0222] [ka]

[0223] The carrier has a particle size distribution of D50 = 58.6 μm and span = 0.65.

[0224] B-3. ​​Production of spherical catalyst components Example 32 (1) Preparation of intermediate reaction products In a 300 mL glass reaction flask, under a nitrogen atmosphere, 10 g of the carrier prepared in Example 27 was dispersed in 100 mL of hexane while mechanically stirring, and the mixture was cooled to -10°C and maintained for 0.5 hours. Next, 2.5 mL of tetraethyl titanate (TET) (corresponding to a molar ratio of TET / Mg = 0.2) was added, and the temperature was gradually raised to 60°C and maintained for 0.5 hours. The liquid was filtered, the solid was washed three times with hexane, and then dried under vacuum to obtain the intermediate product.

[0225] (2) Production of catalyst components Under an inert atmosphere, 100 mL of titanium tetrachloride was added to a 300 mL glass reaction flask, cooled to -20°C, and 8 g of the intermediate product prepared in (1) above was added. The temperature was raised to 110°C, and 1.5 mL of diisobutyl phthalate was added during the heating process. The liquid was filtered, the solid was washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain spherical catalyst components.

[0226] (3) Polymerization of propylene Liquid-phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (with a concentration of 0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (with a concentration of 0.1 mmol / mL), and 9 mg of the above spherical catalyst component were continuously added to the autoclave. The autoclave was closed, and a fixed amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70°C and the reaction was allowed to proceed for 1 hour. Then, the temperature was lowered, the pressure was relieved, the material was discharged, and the resulting propylene homopolymer was dried and weighed. The results are shown in Table 3.

[0227] Example 33 (1) Preparation of intermediate reaction products In a 300 mL glass reaction flask, under a nitrogen atmosphere, 10 g of the carrier prepared in Example 30 was dispersed in 100 mL of hexane while mechanically stirring, and the mixture was cooled to -10°C and maintained for 0.5 hours. Next, 2.5 mL of tetraethyl titanate (TET) (corresponding to a molar ratio of TET / Mg = 0.2) was added, and the temperature was gradually raised to 60°C and maintained for 0.5 hours. The liquid was filtered, the solid was washed three times with hexane, and then dried under vacuum to obtain the intermediate product.

[0228] (2) Production of catalyst components Under an inert atmosphere, 100 mL of titanium tetrachloride was added to a 300 mL glass reaction flask, cooled to -20°C, and 8 g of the intermediate product prepared in (1) above was added. The temperature was raised to 110°C, and 1.5 mL of diisobutyl phthalate was added during the heating process. The liquid was filtered, the solid was washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain spherical catalyst components.

[0229] (3) Polymerization of propylene The liquid-phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (having a concentration of 0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (having a concentration of 0.1 mmol / mL), and 9 mg of the above spherical catalyst component were continuously added to the autoclave. The autoclave was closed, and a certain amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70 °C and reacted for 1 hour. Then, the temperature was lowered, the pressure was relieved, the material was discharged, and the obtained propylene homopolymer was dried and weighed. The results are shown in Table 3.

[0230] From the particle size distribution of the carrier and the results of the attached drawings, according to the present invention, by adding the compound represented by the general formula (II) during the production of the carrier, the particle form of the carrier can be improved. Therefore, the particles have a smooth surface, and thus it can be seen that the aggregation of the particles can be further reduced.

[0231]

Table 3

[0232] From the results in Table 3, it can be seen that by adding an alcoholamine compound during the production of the carrier, the hydrogen modulation sensitivity of the catalyst can be improved.

[0233] A-4. Production of Carrier for Polyolefin Catalyst Example 34 In a 1.0 L reaction vessel, 1.6 g of polyvinylpyrrolidone (PVP, weight-average molecular weight 58000), 2.8 mol of ethanol, 0.2 mol of magnesium chloride, 3 mmol of cuprous chloride, and 2 mmol of triethanolamine were sequentially added, and the temperature was raised to 70°C while stirring (stirring speed 450 rpm). After a constant temperature reaction for 1 hour, 0.6 mol of epichlorohydrin was added, and the temperature was maintained for 0.5 hours before filtration. The solid was washed five times with hexane and dried under vacuum to obtain solid component particles. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following composition.

[0234] [ka]

[0235] The carrier has a particle size distribution of D50 = 68.2 μm and span = 0.64.

[0236] Example 35 The manufacturing method was the same as described in Example 34, except that the amount of cuprous chloride added was 6 mmol. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following composition.

[0237] [ka]

[0238] The carrier has a particle size distribution of D50 = 54.8 μm and span = 0.64.

[0239] Example 36 The manufacturing method was the same as described in Example 34, except that the amount of cuprous chloride added was 0.01 mol. The carrier has a particle size distribution of D50 = 45.4 μm and span = 0.64.

[0240] Example 37 The manufacturing method was the same as described in Example 36, except that the reaction temperature was 60°C. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following composition.

[0241] [ka]

[0242] The carrier has a particle size distribution of D50 = 31 μm and span = 0.64.

[0243] Example 38 The manufacturing method was the same as described in Example 36, except that the amount of ethanol added was 2.4 mol and the amount of cuprous chloride added was 0.01 mol. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following composition.

[0244] [ka]

[0245] The carrier has a particle size distribution of D50 = 36.2 μm and span = 0.64.

[0246] Example 39 The manufacturing method was the same as described in Example 35, except that the amount of triethanolamine added was 0.01 mol. Characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography revealed that the support had the following composition:

[0247] [ka]

[0248] The carrier has a particle size distribution of D50 = 57.8 μm and span = 0.7.

[0249] Example 40 The manufacturing method was the same as described in Example 34, except that 2 mmol of triethanolamine was replaced with 4 mmol of N,N-dimethylethanolamine. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following composition.

[0250] [ka]

[0251] The carrier has a particle size distribution of D50 = 52.8 μm and span = 0.64.

[0252] Example 41 The manufacturing method was the same as described in Example 37, except that the stirring speed was 1200 rpm.

[0253] The carrier has a particle size distribution of D50 = 24.5 μm and span = 0.64.

[0254] Example 42 The manufacturing method was the same as described in Example 34, except that triethanolamine was not added. Through characterization by nuclear magnetic resonance, elemental analysis, and gas chromatography, the support was found to have the following composition.

[0255] [ka]

[0256] The carrier has a particle size distribution of D50 = 60.4 μm and span = 0.63.

[0257] Example 43 The manufacturing method was the same as described in Example 42, except that the amount of cuprous chloride was 6 mmol and triethanolamine was not added.

[0258] The carrier has a particle size distribution of D50 = 57.2 μm and span = 0.64.

[0259] Example 44 The manufacturing method was the same as described in Example 43, except that the amount of cuprous chloride was 12 mmol and triethanolamine was not added.

[0260] The carrier has a particle size distribution of D50 = 35.3 μm and span = 0.67.

[0261] Example 45 The manufacturing method was the same as described in Example 34, except that cuprous chloride was replaced with cupric chloride.

[0262] [ka]

[0263] The carrier has a particle size distribution of D50 = 62.5 μm and span = 0.69.

[0264] Example 46 The manufacturing method was the same as described in Example 45, except that the amount of cupric chloride added was 6 mmol.

[0265] The carrier has a particle size distribution of D50 = 60.2 μm and span = 0.68.

[0266] B-4. Production of spherical catalyst components Example 47 (1) Preparation of intermediate reaction products In a 300 mL glass reaction flask, under a nitrogen atmosphere, 10 g of the carrier prepared in Example 34 was dispersed in 100 mL of hexane while mechanically stirring, and the mixture was cooled to -10°C and maintained for 0.5 hours. Next, 2.5 mL of tetraethyl titanate (TET) (corresponding to a molar ratio of TET / Mg = 0.2) was added, and the temperature was gradually raised to 60°C and maintained at that temperature for 0.5 hours. The liquid was filtered, the solid was washed three times with hexane, and then dried under vacuum to obtain the intermediate product.

[0267] (2) Production of catalyst components Under an inert atmosphere, 100 mL of titanium tetrachloride was added to a 300 mL glass reaction flask, cooled to -20°C, and 8 g of the intermediate product prepared in (1) above was added. The temperature was raised to 110°C, and 1.5 mL of diisobutyl phthalate was added during the heating process. The liquid was filtered, the solid was washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain spherical catalyst components.

[0268] (3) Polymerization of propylene Liquid-phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (with a concentration of 0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (with a concentration of 0.1 mmol / mL), and 9 mg of the above spherical catalyst component were continuously added to the autoclave. The autoclave was closed, and a fixed amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70°C and the reaction was allowed to proceed for 1 hour. Then, the temperature was lowered, the pressure was released, the material was discharged, and the resulting propylene homopolymer was dried and weighed. The results are shown in Table 4.

[0269] Example 48 (1) Preparation of intermediate reaction products In a 300 mL glass reaction flask, under a nitrogen atmosphere, 10 g of the carrier prepared in Example 40 was dispersed in 100 mL of hexane while mechanically stirring, and the mixture was cooled to -10°C and maintained for 0.5 hours. Next, 2.5 mL of tetraethyl titanate (TET) (corresponding to a molar ratio of TET / Mg = 0.2) was added, and the temperature was gradually raised to 60°C and maintained at that temperature for 0.5 hours. The liquid was filtered, the solid was washed three times with hexane, and then dried under vacuum to obtain the intermediate product.

[0270] (2) Production of catalyst components Under an inert atmosphere, 100 mL of titanium tetrachloride was added to a 300 mL glass reaction flask, cooled to -20°C, and 8 g of the intermediate product prepared in (1) above was added. The temperature was raised to 110°C, and 1.5 mL of diisobutyl phthalate was added during the heating process. The liquid was filtered, the solid was washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain spherical catalyst components.

[0271] (3) Polymerization of propylene Liquid-phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (with a concentration of 0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (with a concentration of 0.1 mmol / mL), and 9 mg of the above spherical catalyst component were continuously added to the autoclave. The autoclave was closed, and a fixed amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70°C and the reaction was allowed to proceed for 1 hour. Then, the temperature was lowered, the pressure was released, the material was discharged, and the resulting propylene homopolymer was dried and weighed. The results are shown in Table 4.

[0272] Example 49 (1) Preparation of intermediate reaction products In a 300 mL glass reaction flask, under a nitrogen atmosphere, 10 g of the carrier prepared in Example 42 was dispersed in 100 mL of hexane while mechanically stirring, and the mixture was cooled to -10°C and maintained for 0.5 hours. Next, 2.5 mL of tetraethyl titanate (TET) (corresponding to a molar ratio of TET / Mg = 0.2) was added, and the temperature was gradually raised to 60°C and maintained at that temperature for 0.5 hours. The liquid was filtered, the solid was washed three times with hexane, and then dried under vacuum to obtain the intermediate product.

[0273] (2) Production of catalyst components Under an inert atmosphere, 100 mL of titanium tetrachloride was added to a 300 mL glass reaction flask, cooled to -20°C, and 8 g of the intermediate product prepared in (1) above was added. The temperature was raised to 110°C, and 1.5 mL of diisobutyl phthalate was added during the heating process. The liquid was filtered, the solid was washed twice with titanium tetrachloride and three times with hexane, and dried under vacuum to obtain spherical catalyst components.

[0274] (3) Polymerization of propylene Liquid-phase bulk polymerization of propylene was carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (with a concentration of 0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (with a concentration of 0.1 mmol / mL), and 9 mg of the above spherical catalyst component were continuously added to the autoclave. The autoclave was closed, and a fixed amount of hydrogen (standard volume) and 2.3 L of liquid propylene were added thereto. The temperature was raised to 70°C and the reaction was allowed to proceed for 1 hour. Then, the temperature was lowered, the pressure was released, the material was discharged, and the resulting propylene homopolymer was dried and weighed. The results are shown in Table 4.

[0275] From the particle size distribution of the carrier described above and the results shown in the attached drawings, it can be seen that, according to the present invention, adding cuprous chloride during the production of the carrier significantly improves the particle morphology of the carrier and reduces particle aggregation. Furthermore, the more cuprous chloride is added, the smaller the particle size of the carrier becomes (see Examples 34-36, 42-44). In particular, when cuprous chloride is used in combination with an amine compound represented by general formula (II), the surface of the carrier becomes smoother, the sphericity of the carrier is better, the particle size adjustment effect is more pronounced, and carriers with small particle sizes can be obtained even under low-speed stirring (see Example 37). By increasing the stirring speed, the particle size of the carrier can be further reduced to 25 μm, and a narrow particle size distribution can be obtained (see Example 41). When cuprous chloride is not added, even when the stirring speed is increased to 1600 rpm, the particle size of the carrier is still 35 μm, and the particle size distribution is clearly broader (see Comparative Example 2). Examples 45 and 46 demonstrate that the effect of adding cuprous chloride on adjusting the particle size of carrier particles is non-obvious.

[0276] [Table 4]

[0277] The results in Table 4 show that the addition of alcoholamine compounds during the production of the support can improve the hydrogen modulation sensitivity of the catalyst and does not substantially affect the polymerization activity of the catalyst.

[0278] The above examples are for illustrative purposes only and do not limit the present invention. While the present invention has been described with reference to typical examples, it should be understood that the terminology used herein is descriptive and interpretive, not restrictive. The present invention may be modified within the scope of the claims of the present invention, without departing from the spirit of the invention. The present invention as described herein relates to specific methods, materials, and examples, but is not intended to be limited to the specific examples disclosed herein; rather, the present invention extends to all other methods and uses having the same function. [Brief explanation of the drawing]

[0279] [Figure 1A] Figure 1A is an optical microscope image (magnification 160x) of the morphology of the solid component particles produced in Example 1. [Figure 1B] Figure 1B is an optical microscope image (400x magnification) of the morphology of the solid component particles produced in Example 1. [Figure 2] Figure 2 is an optical microscope image (magnification 160x) of the morphology of the solid component particles produced in Example 4. [Figure 3A] Figure 3A is an optical microscope image (magnification 160x) of the morphology of the solid component produced in Comparative Example 1. [Figure 3B] Figure 3B is an optical microscope image (400x magnification) of the morphology of the solid component produced in Comparative Example 1. [Figure 4] Figure 4 is an optical microscope image of the morphology of the solid catalyst component particles produced in Example 1. [Figure 5] Figure 5 is an optical microscope image of the morphology of the catalyst component produced in Comparative Example 1. [Figure 6A] Figure 6A is an optical microscope image at 160x magnification of the morphology of the carrier particles produced in Example 14. [Figure 6B] Figure 6B is an electron microscope image of the carrier particles produced in Example 14. [Figure 7] Figure 7 is an optical microscope image of the morphology of the catalyst component produced in Example 24. [Figure 8A] Figure 8A is an optical microscope image at 160x magnification of the morphology of the carrier particles produced in Example 27. [Figure 8B] Figure 8B is an optical microscope image of the carrier particles produced in Example 27 at 400x magnification. [Figure 8C] Figure 8C is an electron microscope image of the carrier particles produced in Example 27.

Claims

1. (i) Magnesium compounds represented by the following formula (1): 【Chemistry 1】 In the formula, R １ is C １ ~C １２ It is a linear or branched alkyl group; R ２ and R ３ They are either identical or different, and contain hydrogen, or unsubstituted or halogenated C １ ~C ５ It is a linear or branched alkyl group; X is a halogen; m is 0.1 to 1.9; n is 0.1 to 1.9; m + n = 2; and (ii) Lewis base (LB); and, (iii) optionally, other metallic components other than magnesium; and, Here, the Lewis base is a compound represented by general formula (II), 【Chemistry 2】 In the formula, R ５ and R ７ are the same or different, and are hydrogen, or a linear or branched C １ to C ８ alkyl that is unsubstituted or substituted with a hydroxyl group; R ６ is a linear or branched C １ to C ８ alkylene, or The Lewis base is an amide compound represented by the general formula (II'), 【Transformation 3】 In the formula, R １０ is hydrogen, amino acid, or C １ ~C ８ It is a linear or branched alkyl group, R １１ and R １２ They are either the same or different, and hydrogen or C １ ~C ８ A support for a polyolefin catalyst, which is a linear or branched alkyl group.

2. The support for the polyolefin catalyst according to claim 1, wherein the other metal component besides magnesium is either iron and / or copper.

3. The polyolefin catalyst carrier according to claim 1, wherein the content of metal components other than magnesium in the solid component, in terms of metal content, is 0 to 1% by weight.

4. Compositions represented by general formulas (I), (I'), or (I''): 【Chemistry 4】 In the above formula (I'), R １ C １ ~C １２ It is a linear or branched alkyl group; R ２ and R ３ They are the same or different, and are hydrogen, or unsubstituted or halogenated C １ ~C ５ It is a linear or branched alkyl group; X and Y independently represent a halogen; m is between 0.1 and 1.9; n is between 0.1 and 1.9; m + n = 2; 0 < i ≤ 2; 0 < j ≤ 2; 0 < k ≤ 2; i + j + k = 3; 0 < p ≤ 0.1; and 0 < z < 0.1; In the above formula (I), R １ C １ ~C １２ It is a linear or branched alkyl group; R ２ and R ３ They are either identical or different, and contain hydrogen, or unsubstituted or halogenated C １ ~C ５ It is a linear or branched alkyl group; X is a halogen; m is 0.1 to 1.9; n is 0.1 to 1.9; m + n = 2; 0 < z < 0.5; In the above formula (I''), R １ is C １ ~C １２ It is a linear or branched alkyl group; R ２ and R ３ They are either identical or different, and contain hydrogen, or unsubstituted or halogenated C １ ~C ５ It is a linear or branched alkyl group; X and Y independently represent a halogen; m is between 0.1 and 1.9; n is between 0.1 and 1.9; m + n = 2; 0 ≤ a < 2, 0 < b ≤ 2, a + b = 2; 0 < q < 0.1; and 0 ≤ z < 0.1; In the aforementioned general formulas (I), (I'), and (I''), LB is a compound represented by general formula (II), 【Transformation 5】 In the formula, R ５ and R ７ They are either identical or different, and are hydrogen, or unsubstituted or hydroxyl-substituted C １ ~C ８ It is a linear or branched alkyl group; R ６ C １ ~C ８ A support for a polyolefin catalyst according to claim 1, comprising: a linear or branched alkylene.

5. The following features: In the above general formula (I), the above general formula (I'), or the above general formula (I''), R １ is C １ ~C ８ It is a linear or branched alkyl group; and, In the above general formula (I), the above general formula (I'), or the above general formula (I''), R ２ and R ３ Each of them is independently of hydrogen and C １ ~C ３ Linear or branched alkyl groups, or halogenated C １ ~C ３ It is a linear or branched alkyl group; and, In the above general formula (II), R ５ and R ７ is hydrogen, or C １ ~C ５ It is a linear or branched alkyl group, R ６ C １ ~C ５ It is a linear or branched alkylene; and, Each of the aforementioned halogens is selected from the group consisting of chlorine, bromine, and iodine; The polyolefin catalyst carrier according to claim 4, wherein the compound represented by the general formula (II) is one or more of ethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, and N-methyldiethanolamine; and at least one of the above.

6. The following features: In the above general formula (I), the above general formula (I'), or the above general formula (I''), R １ This is selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl, and 2-ethylhexyl; In the above general formula (I), the above general formula (I'), or the above general formula (I''), R ２ and R ３ The support for the polyolefin catalyst according to claim 4, wherein each of is independently hydrogen, methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, or bromoethyl; and has at least one of the above.

7. The support for the polyolefin catalyst according to claim 4, characterized in that the support has an average particle size of 10 to 100 μm as measured by a laser particle size analyzer, and a particle size distribution smaller than 1.2 as measured by a laser particle size analyzer.

8. The support for the polyolefin catalyst according to claim 4, characterized in that the support has an average particle size of 30 to 70 μm as measured by a laser particle size analyzer, and a particle size distribution of 0.7 to 0.9 as measured by a laser particle size analyzer.

9. The composition represented by the following general formula (I'''): 【Transformation 6】 In the formula, R １ is C １ ~C １２ It is a linear or branched alkyl group; R ２ and R ３ They are either identical or different, and contain hydrogen, or unsubstituted or halogenated C １ ~C ５ It is a linear or branched alkyl group; X is a halogen; m is 0.1 to 1.9; n is 0.1 to 1.9; m + n = 2; 0 < z < 0.5; and LB is an amide compound represented by the following general formula (II'); 【Transformation 7】 In the formula, R １０ is hydrogen, amino acid, or C １ ~C ８ It is a linear or branched alkyl group; R １１ and R １２ They are either the same or different, and hydrogen or C １ ~C ８ A support for a polyolefin catalyst according to claim 1, comprising: a linear or branched alkyl group.

10. The following features: In the above general formula (I'''), R １ C １ ~C ８ It is a linear or branched alkyl group; and, In the general formula (I'''), R ２ and R ３ are each independently hydrogen, a linear or branched alkyl having from C １ to C ３ or a halogenated linear or branched alkyl having from C １ to C ３ ; and In the general formula (I''), R １０ is hydrogen, amino, or a linear or branched alkyl having C １ to C ５ , and R １１ and R １２ are hydrogen or a linear or branched alkyl having C １ to C ５ ; and Each of the aforementioned halogens is selected from the group consisting of chlorine, bromine, and iodine; The amide compound is one or more of formamide, acetamide, propionamide, N-methylacetamide, N,N-dimethylacetamide, and carvonamide; The carrier according to claim 9, wherein the carrier is spherical and has an average particle size of 10 to 100 μm as measured by a laser particle size analyzer, and a particle size distribution smaller than 1.2 as measured by a laser particle size analyzer; and has at least one of these.

11. The following features: In the above general formula (I'''), R １ This is selected from the group consisting of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl, and 2-ethylhexyl; In the above general formula (I'''), R ２ and R ３ These are independently methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, and bromoethyl; and, The carrier according to claim 9, wherein the carrier is spherical and has an average particle size of 30 to 70 μm as measured by a laser particle size analyzer, and a particle size distribution of 0.7 to 0.9 as measured by a laser particle size analyzer; and has at least one of these.

12. The carrier according to claim 9, further comprising other metal components besides magnesium.

13. The carrier according to claim 9, wherein the other metal component besides magnesium is iron and / or copper.

14. The carrier according to claim 9, wherein the content of other metal components in the solid component, in terms of metal, is 0 to 1% by weight.

15. The following steps: (a) General formula MgX ２ A magnesium halide represented by the general formula R, any metal halide, and a magnesium halide represented by the general formula R １ A process of preparing a solution by reacting an alcohol compound represented by OH with a compound represented by general formula (II) or (II'), 【Transformation 8】 In the formula, X is a halogen; R １ is C １ ~C １２ It is a linear or branched alkyl group; R ５ and R ７ They are either the same or different, and are hydrogen, or unsubstituted or hydroxyl-substituted C １ ~C ８ It is a linear or branched alkyl group; R ６ C １ ~C ８ It is a linear or branched alkylene; R １０ is hydrogen, amino acid, or C １ ~C ８ It is a linear or branched alkyl group; and R １１ and R １２ They are either the same or different, and hydrogen or C １ ~C ８ It is a linear or branched alkyl group; and (b) A step of reacting the solution produced in step (a) with an epoxy compound to directly produce spherical solid particles; A method for producing a polyolefin catalyst carrier, comprising: (c) a step of recovering the spherical solid particles produced in step (b); and

16. The following steps: (a) The general formula MgX ２ The magnesium halide represented by the structural formula FeY ２ Any metal halide represented by or any metal halide represented by structural formula CuYc, and the general formula R １ A process of preparing a solution by reacting an alcohol compound represented by OH with a compound represented by the following general formula (II), 【Chemistry 9】 In the formula, R １ is C １ ~C １２ It is a linear or branched alkyl group, R ５ and R ７ They are either the same or different, and are hydrogen, or unsubstituted or hydroxyl-substituted C １ ~C ８ It is a linear or branched alkyl group; R ６ is C １ ~C ８ A linear or branched alkylene, where X and Y are halogens and C = 1 or 2; (b) A step of reacting the solution produced in step (a) with an epoxy compound to directly produce spherical solid particles; (c) A step of recovering the spherical solid particles produced in step (b); The method according to claim 15, including the method described in claim 15.

17. The epoxy compound is represented by the following general formula (III), 【Chemistry 10】 In the formula, R ２ and R ３ They are either identical or different, and contain hydrogen, or unsubstituted or halogenated C １ ~C ５ The method according to claim 16, which represents a linear or branched alkyl group.

18. The following features: The general formula R １ In OH, R １ is C １ ~C ８ It is a linear or branched alkyl group; and, In the above general formula (II), R ５ and R ７ is hydrogen, or C １ ~C ５ It is a linear or branched alkyl group, R ６ is C １ ~C ５ It is a linear or branched alkylene; and, In the above general formula (III), R ２ and R ３ These are, independently, hydrogen and C １ ~C ３ Linear or branched alkyl groups, or halogenated C １ ~C ３ It is a linear or branched alkyl group; and, In step (a), a polymeric dispersion stabilizer is added to the solution during the manufacturing process, and the weight-average molecular weight of the polymeric dispersion stabilizer is greater than 1000; The magnesium halide is one or more of magnesium chloride, magnesium dibromide, and magnesium diiodide; The aforementioned structural formula FeY ２ Alternatively, the metal halide represented by CuYc is one or more of ferrous chloride, ferrous chloride tetrahydrate, ferrous bromide, and ferrous iodide; and, The carrier has an average particle size of 10 to 100 μm, as measured by a laser particle size analyzer; and, The carrier has a particle size distribution smaller than 1.2 as measured by a laser particle size analyzer; In step (a), the preparation of the solution is carried out at a temperature of 30 to 160°C; The aforementioned R １ The amount of OH compound added is 3 to 30 mol per 1 mol of magnesium; and, The molar ratio of the compound represented by the general formula (II) to the magnesium halide is 1:100 to 1:5; and, The aforementioned structural formula FeY ２ The amount of the metal halide, represented by CuYc, added is 0.001 to 0.1 mol per 1 mol of magnesium; In step (b), the reaction temperature is 30 to 160°C; The method according to claim 17, wherein in step (b), the amount of epoxy compound added is 1 to 10 mol per mol of magnesium; and at least one of these.

19. The following features: The general formula R １ In OH, R １ is C １ ~C ６ It is a linear or branched alkyl group; and, In step (a), a polymeric dispersion stabilizer is added to the solution during the manufacturing process, and the weight-average molecular weight of the polymeric dispersion stabilizer is greater than 3000; and, The aforementioned structural formula FeY ２ Alternatively, the metal halide represented by CuYc is one or more of ferrous chloride and its hydrate; The carrier has an average particle size of 30 to 70 μm, as measured by a laser particle size analyzer; and, The carrier has a particle size distribution of 0.7 to 0.9 as measured by a laser particle size analyzer; In step (a), the preparation of the solution is carried out at a temperature of 40 to 120°C; The aforementioned R １ The amount of OH compound added is 4 to 25 mol per 1 mol of magnesium; and, The molar ratio of the compound represented by the general formula (II) to the magnesium halide is 1:50 to 1:5; and, The aforementioned structural formula FeY ２ The amount of the metal halide, represented by CuYc, added is 0.003 to 0.08 mol per 1 mol of magnesium; In step (b), the reaction temperature is 40 to 120°C; The method according to claim 16, wherein in step (b), the amount of epoxy compound added is 2 to 6 mol per 1 mol of magnesium; and at least one of these.

20. The following steps: (a) The general formula MgX ２ Magnesium halide represented by the general formula R １ A step of preparing a solution by reacting the alcohol compound represented by OH with the amide compound represented by the following general formula (II'), 【Chemistry 11】 In the formula, R １ is C １ ~C １２ It is a linear or branched alkyl group, R １０ is hydrogen, amino acid, or C １ ~C ８ It is a linear or branched alkyl group, R １１ and R １２ They are either the same or different, and hydrogen or C １ ~C ８ It is a linear or branched alkyl group, where X is a halogen; and The method according to claim 15, comprising the step of reacting the solution produced in step (a) with an epoxy compound to directly produce spherical solid particles;

21. The epoxy compound is represented by general formula (III), 【Chemistry 12】 In the formula, R ２ and R ３ They are either identical or different, and contain hydrogen, or unsubstituted or halogenated C １ ~C ５ The method according to claim 20, wherein the alkyl group is linear or branched.

22. The following features: The general formula R １ In OH, R １ C １ ~C ８ It is a linear or branched alkyl group; and, In the above general formula (II'), R １０ is hydrogen, amino acid, or C １ ~C ５ It is a linear or branched alkyl group, R １１ and R １２ is hydrogen, or C １ ~C ５ It is a linear or branched alkyl group; and, In the above general formula (III), R ２ and R ３ These are, independently, hydrogen and C １ ~C ３ Linear or branched alkyl groups, or halogenated C １ ~C ３ It is a linear or branched alkyl group; and, In step (a), a reducing metal halide is added to the solution during the manufacturing process, and formula MY ａ The metal halide having the following characteristics, where Y is a halogen, M is one or more of iron and copper, a is 1 or 2, and the amount of the metal halide added is 0.001 to 0.1 mol per 1 mol of magnesium; In step (a), a polymeric dispersion stabilizer is added to the solution during the manufacturing process, and the weight-average molecular weight of the polymeric dispersion stabilizer is greater than 1000; In step (a), the preparation of the solution is carried out at a temperature of 30 to 160°C; In step (a), the R １ The amount of OH compound added should be 3 to 30 mol per 1 mol of magnesium; The molar ratio of the compound represented by the general formula (II') to the magnesium halide is 1:100 to 1:5; and, (b) In step (b), the reaction temperature is 30 to 160°C; In step (b), the amount of epoxy compound added is 1 to 10 mol per 1 mol of magnesium; The method according to claim 21, wherein the spherical solid particles have an average particle size of 10 to 100 μm as measured by a laser particle size analyzer, and a particle size distribution smaller than 1.2 as measured by a laser particle size analyzer; and at least one of these.

23. The following features: In step (a), a reducing metal halide is added to the solution during the manufacturing process, and the metal halide is CuCl and FeCl ２ The amount of the metal halide added is selected from the group consisting of the following, and the amount of the metal halide added is 0.003 to 0.08 mol per 1 mol of magnesium; In step (a), a polymeric dispersion stabilizer is added to the solution during the manufacturing process, and the weight-average molecular weight of the polymeric dispersion stabilizer is greater than 3000; In step (a), the preparation of the solution is carried out at a temperature of 40 to 120°C; In step (a), the R １ The amount of OH compound added should be 4 to 25 mol per 1 mol of magnesium; The molar ratio of the compound represented by the general formula (II') to the magnesium halide is 1:50 to 1:5; and, (b) In step (b), the reaction temperature is 40 to 120°C; In step (b), the amount of epoxy compound added is 2 to 6 mol per 1 mol of magnesium; The method according to claim 20, wherein the spherical solid particles have an average particle size of 30 to 70 μm as measured by a laser particle size analyzer, and a particle size distribution of 0.7 to 0.9 as measured by a laser particle size analyzer; and at least one of these.

24. A catalyst component for olefin polymerization comprising a carrier according to any one of claims 1 to 14, a reaction product of a titanium compound and an internal electron donor compound.

25. A catalyst system for olefin polymerization comprising the catalyst component described in claim 24, an alkylaluminum compound, and optionally an external electron donor compound.

26. A method for olefin polymerization, comprising: contacting one or more olefins with the catalyst system described in claim 25 under olefin polymerization conditions to produce a polyolefin; and recovering the obtained polyolefin.

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