Catalyst component and catalyst system for olefin polymerization and application thereof

Abstract

The present invention relates to a catalyst component and a catalyst system for olefin polymerization and applications thereof, the catalyst component contains a magnesium element, halogen, a titanium element, a regulator a and an internal electron donor compound b, the regulator a is at least one of 1, 2-diether compounds represented by formula (I-1) and formula (I-2), and the internal electron donor compound b is at least one of 1, 2-diether compounds represented by formula (I-1) and formula (I-2). The internal electron donor compound b is a diether compound as shown in a formula (II), and the catalyst component and the catalyst system can maintain relatively high activity and can be used for producing a polymer which has the characteristics of reduced crystallinity and easily adjusted stereoregularity.

Description

Technical Field

[0001] This invention relates to a catalyst component and catalyst system for olefin polymerization and their applications, and more specifically, to a catalyst component and catalyst system that can maintain high activity while being used to produce polymers characterized by reduced crystallinity and easily adjustable stereoregularity and their applications. Background Technology

[0002] Ziegler-Natter catalysts typically consist of magnesium, titanium, halogens, and Lewis bases as basic components. They exhibit high polymerization activity and stereotactic orientation in olefin polymerization, particularly propylene polymerization. Lewis bases are organic compounds containing oxygen, nitrogen, phosphorus, silicon, etc., and are generally considered electron-donating compounds. Their composition and structure play a decisive role in important indicators such as the catalyst's polymerization activity, the isotactic index of the polymer, molecular weight, and molecular weight distribution. Different methods of adding the same Lewis base also significantly affect the catalyst's performance.

[0003] Catalysts containing different internal electron donors exhibit different properties. For example, some catalysts possess high polymerization activity, some have good hydrogen regulation sensitivity, and some catalysts produce polyolefin resins with a wide molecular weight distribution. To obtain polyolefins with more comprehensive properties, researchers are making efforts in resin modification and continuously experimenting with the composition of Lewis bases in catalysts.

[0004] To date, Ziegler-Natta type polyolefin catalysts have seen the development of several distinctive industrial-grade Lewis base internal electron donor compounds, including dicarboxylic acid esters, 1,3-diethers, succinates, and glycol esters. Compared to similar catalysts, catalysts using 1,3-diethers as internal electron donors exhibit higher activity and stereotactic orientation, leading to their widespread application. However, as the isotacticity and crystallinity of polypropylene increase, problems arise such as low elasticity, poor toughness, low-temperature embrittlement, and difficulties in processing and molding. In practical applications, it is sometimes necessary to modify these catalysts by incorporating materials with good toughness, such as rubber, polyethylene, and atactic polypropylene, to obtain certain specific properties.

[0005] In the production of certain products, such as BOPP-specific materials, the crystallinity of the product is directly related to the selection of the process window during stretching and film formation, as well as the stiffness, toughness, and transparency of the resulting film. Therefore, the isotacticity of the propylene homopolymer and the xylene-soluble content must be within a certain range, thus requiring the catalyst to have adjustable stereoconfiguration. If the electron donor concentration is too high, it will significantly reduce the metering pump flow rate, resulting in a stroke of less than 30%. Conversely, if the electron donor concentration is too low, the stroke will exceed 50%, leading to inaccurate metering. Therefore, finding a method to prepare propylene polymerization catalysts that can adjust and control the stereoconfiguration of polypropylene molecular chains within a wide range, which is beneficial for developing different grades of polypropylene products, has always been a goal pursued by industry players.

[0006] The applicant unexpectedly discovered that by introducing 1,2-diether compounds as regulators into the catalyst components for propylene polymerization, the prepared catalyst exhibits good polymerization activity without raising concerns about phthalate toxicity. The stereoregularity of the catalyst is adjustable over a wider range, and by changing the amount of external electron donor, the produced polymer exhibits characteristics such as reduced crystallinity, easily adjustable xylene-soluble content, and isotacticity. In industrial production, the stereoregularity of polymers at different polymerization stages is often controlled by changing the main catalyst or adding different external electron donors at different stages to obtain the target product. Therefore, the easily adjustable stereoregularity of the catalyst and the crystallinity of the polymer are beneficial for developing different grades of polypropylene products without changing the main catalyst. This is particularly advantageous for developing film packaging products, as it provides both good rigidity and film-forming properties, further promoting the industrial application of the catalyst. Summary of the Invention

[0007] In view of the aforementioned state of the prior art, the inventors of this invention have developed a catalyst system that, by adding 1,2-diether compounds as modifiers to promote the formation of more and greater numbers of non-oriented active center species, can increase the adjustable range of stereoregularity while simultaneously producing polymers with characteristics such as reduced crystallinity, easily adjustable xylene-soluble content, and adjustable isotacticity by changing the amount of external electron donor. Based on this, the present invention provides a catalyst component and catalyst system, as well as its application, that can maintain high activity while being used to produce polymers characterized by reduced crystallinity and easily adjustable stereoregularity.

[0008] A first aspect of the present invention provides a catalyst component for olefin polymerization, the catalyst component comprising magnesium, halogen, titanium, a regulator a, and an internal electron donor compound b, wherein the regulator a is at least one of 1,2-diether compounds represented by formula (I-1) and (I-2), and the internal electron donor compound b is a diether compound represented by formula (II).

[0009]

[0010] In formulas (I-1) and (I-2), R1 and R2 may be the same or different, and each is independently selected from alkyl or alkylene groups of C1-C30, aryl groups of C6-C30 with or without substituents, and aralkyl groups of C7-C30 with or without substituents, except that they are not hydrogen. R1 and R2 may optionally be bonded together to form an epoxy group containing one -O- or two -O-.

[0011] In formulas (I-1) and (I-2), R3, R4, R5 and R6 may be the same or different, and each is independently selected from hydrogen, halogen, C1-C30 alkyl or alkylene, C2-C30 alkenyl, C6-C30 aryl with or without substituents, C7-C30 aralkyl with or without substituents or alkoxy of formula -OR1 or OR2. R3, R4, R5 and R6 may optionally be bonded to form a ring, and R3, R4, R5 and R6 may optionally be bonded to R1 and / or R2 to form a ring.

[0012] In formula (II), R1', R2', R3', R4', R5', and R6' may be the same or different, and each independently represents one of hydrogen, halogen, a C1-C20 straight-chain or branched alkyl group, a C3-C20 substituted or unsubstituted cycloalkyl group, a C6-C20 substituted or unsubstituted aryl group, or a C7-C20 substituted or unsubstituted aralkyl group; or, two or more of R1', R2', R3', R4', R5', and R6' are bonded together to form a ring; R7' and R8' are each independently one of a C1-C20 straight-chain or branched alkyl group, a C3-C20 substituted or unsubstituted cycloalkyl group, a C6-C20 substituted or unsubstituted aryl group, or a C7-C20 substituted or unsubstituted aralkyl group.

[0013] The optional bonding of R1 and R2 to form an epoxy group containing one -O- or two -O- means that R1 and R2 may or may not be bonded. When bonded, an epoxy group containing one -O- or two -O- is formed. The epoxy group containing one -O- refers to a group that forms a monocyclic ether, and the epoxy group containing two -O- refers to a group that forms a dicyclic ether.

[0014] The optional bonding of R3, R4, R5, and R6 to form a ring means that any two or more groups selected from R3, R4, R5, and R6 are bonded together to form a ring structure; alternatively, they may not be bonded.

[0015] Optionally, R3, R4, R5, and R6 can be bonded to R1 and / or R2 to form a loop. This means that one or more of R3, R4, R5, and R6 can be bonded to one or both of R1 and R2. In the case of bonding, a loop structure is formed, or they can be left unbonded.

[0016] RⅢ and RⅣ can be optionally bonded to form a ring, meaning that RⅢ and RⅣ can be bonded to form a ring structure; or they can be left unbonded.

[0017] In this invention, the term "alkyl" includes straight-chain alkyl, branched-chain alkyl, and cycloalkyl. For example, C1-C30 alkyl includes C1-C30 straight-chain alkyl, C3-C30 branched-chain alkyl, and C3-C30 cycloalkyl.

[0018] An aryl group refers to an aryl group to which a single bond is located. When an aryl group is substituted with an alkyl group, it can also be called an alkylaryl group. Taking R1 in formula (I-2) as an example, which is selected from C6-C30 aryl groups with or without substituents, it means that the "C6-C30 aryl group with or without substituents" is connected to the -O- in formula (I-2) through a single bond located on the aromatic group. When an aryl group is substituted with an alkyl group, the "C6-C30 aryl group with or without substituents" can be selected from C7-C30 alkylaryl groups with or without substituents.

[0019] During the research process, the inventors were surprised to find that when the addition of the regulator a in the catalyst component can ensure that the catalyst maintains excellent performance, the xylene soluble content and isotacticity of the polymer can be easily adjusted by changing the amount of external electron donor. The stereotactic orientation ability of the catalyst can be adjusted within a wider range while also reducing crystallinity. Since the solid component of the catalyst does not use phthalate compounds, the resulting polypropylene product does not contain plasticizers.

[0020] In some embodiments of the catalyst components described in this invention, the halogen is selected from one or more of bromine, chlorine, and iodine.

[0021] According to some embodiments of the catalyst components of the present invention, R1 and R2 of formula (I-1) and formula (I-2) are each independently selected from one of halogen, C1-C10 alkyl or alkylene groups, and C1-C10 alkoxy groups; preferably, R1 and R2 of formula (I-1) and formula (I-2) are each selected from one of C1-C5 straight-chain or branched alkyl or alkylene groups, more preferably from one or more of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, and isopentyl groups in which one hydrogen atom is replaced by a chemical bond.

[0022] In some preferred embodiments of the catalyst components according to the present invention, R3, R4, R5 and R6 of formula (I-1) and formula (I-2) are each independently selected from hydrogen, halogen, C1-C10 alkyl or alkylene, C2-C10 alkenyl, C1-C10 alkoxy, C6-C30 aryl with or without substituents, C7-C30 aralkyl with or without substituents or alkoxy of formula -OR1 or OR2.

[0023] Preferably, when two or more groups from R3, R4, R5, and R6 are linked to form a ring, or when R3, R4, R5, and R6 are bonded to R1 and / or R2 to form a ring, the 1,2-diether compound has one or more epoxy groups containing one -O- or two -O- groups; or, the 1,2-diether compound has a polycyclic structure containing at least one benzene ring, wherein the ring fused to the benzene ring is saturated or unsaturated; wherein, more preferably, the polycyclic structure has multiple alkoxy groups, the number of which is not less than 2. The number of carbon atoms in the group is 1-10; or, when two or more groups in R3, R4, R5 and R6 are not bonded to form a ring, R3, R4, R5 and R6 in formula (I-1) and formula (I-2) are each selected from C1-C5 straight-chain or branched alkyl or alkoxy, C6-C30 aryl with or without substituents, more preferably the following groups or oxygen-containing groups containing the following groups: hydrogen, methyl, ethyl, vinyl, propenyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, phenyl.

[0024] In a more preferred embodiment of the catalyst component according to the present invention, the regulator a is selected from at least one of the following subclasses: polyalkoxybenzene, polyalkoxytoluene, dialkoxynaphthalene, dialkoxyanthracene, dioxane compounds, tetrahydrofuran compounds, tetrahydrofurfuryl ether compounds, and dialkoxyethane, more preferably selected from 1,2-dimethoxybenzene, 1,2-diethoxybenzene, 1,2-dipropoxybenzene, 1,2-dibutoxybenzene, and 1,2-dimethoxybenzene. Naphthalene, 1,2-diethoxynaphthalene, 1,2-dimethoxyanthracene, 1,2-diethoxyanthracene, 2,3-dimethoxytoluene, 3,4-dimethoxytoluene, 3,4-dimethoxystyrene, 3,4-dimethoxy-1-propenylbenzene, 1,2,3-trimethoxybenzene, 3,4,5-trimethoxytoluene, 1,3-benzodioxane, 1,4-benzodioxane, 1,3-dioxane, 1,2- One or more of dimethoxypropane, 1-tert-butoxy-2-ethoxyethane, 1-tert-butoxy-2-methoxyethane, 1,2-diethoxyethane, 1,2-dimethoxyethane, 1,2-dibutoxyethane, 1,2-dipropoxyethane, 1,2-diisopropoxyethane, 1,2-diphenoxyethane, and tetrahydrofurfuryl ether; more preferably, the regulator a is selected from 1,2-dimethoxybenzene, 1,2-diethoxybenzene, 1 One or more of the following: 2-dimethoxynaphthalene, 2,3-dimethoxytoluene, 3,4-dimethoxytoluene, 3,4-dimethoxy-1-propenylbenzene, 1,2,3-trimethoxybenzene, 3,4,5-trimethoxytoluene, 1,4-benzodioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-diphenoxyethane, 1,2-dipropoxyethane, 2,5-dimethoxytetrahydrofuran, and tetrahydrofurfuryl ether. In this invention, regulator a can be obtained by synthesis or commercial purchase.

[0025] According to an embodiment of the catalyst component of the present invention, the internal electron donor compound b is a diether compound represented by formula (II).

[0026] According to a preferred embodiment of the catalyst component of the present invention, the internal electron donor compound b is a 1,3-diether compound represented by formula (III):

[0027]

[0028] According to a preferred embodiment of the catalyst component of the present invention, in Formula III, R9' and R10' may be the same or different, and each is independently one of hydrogen, halogen, C1-C18 straight-chain or branched alkyl, C3-C18 substituted or unsubstituted cycloalkyl, C6-C18 substituted or unsubstituted aryl, and C7-C18 substituted or unsubstituted aralkyl; or, R9' and R10' are bonded to each other to form a ring; R11' and R12' may be the same or different, and each is independently a C1-C10 straight-chain or branched alkyl.

[0029] According to the present invention, examples of the diether compounds may include, but are not limited to: 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1 3-Dimethoxypropane, 2,2-Dicyclopentyl-1,3-dimethoxypropane, 2,2-Diethyl-1,3-dimethoxypropane, 2,2-Dipropyl-1,3-dimethoxypropane, 2,2-Diisopropyl-1,3-dimethoxypropane, 2,2-Dibutyl-1,3-dimethoxypropane, 2-Methyl-2-propyl-1,3-dimethoxypropane, 2-Methyl-2-benzyl-1,3-dimethoxypropane, 2-Methyl-2-ethyl-1,3-dimethoxypropane, 2-Methyl-2-isopropyl-1,3-dimethoxypropane, 2-Methyl-2-phenyl-1,3-dimethoxypropane, 2-Methyl-2-cyclohexyl-1,3- Dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1 3-Dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 9,9-dimethoxymethylfluorene.

[0030] In the most preferred embodiment, the internal electron donor compound b is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-dimethoxymethylfluorene.

[0031] According to a preferred embodiment of the catalyst component of the present invention, the catalyst component comprises a reaction product of a magnesium compound, an organic epoxy compound, an organic phosphorus compound, a titanium compound, a precipitation aid, a regulator a, and an internal electron donor compound b.

[0032] As a specific embodiment of the present invention, the content of magnesium, based on the total weight of the catalyst components, is 5-30 wt%, preferably 8-25 wt%, more preferably 10-23 wt%; and / or, the content of titanium is 0.5-10 wt%, preferably 1-8 wt%; and / or, the content of regulator a is 0.5-25 wt%, preferably 1-20 wt%; and / or, the content of internal electron donor compound b is 0.5-25 wt%, preferably 1-20 wt%. Within the preferred content ranges of the present invention, the olefin polymerization catalyst containing the catalyst components of the present invention for preparing polyolefins exhibits better adjustability in terms of stereoregulation.

[0033] According to a preferred embodiment of the catalyst composition of the present invention, the molar ratio of the magnesium compound, the titanium compound and the internal electron donor compound b is 1:(0.5-150):(0.02-0.4).

[0034] According to a preferred embodiment of the catalyst component of the present invention, the molar ratio of the regulator a to the internal electron donor compound b is (1-100):(100-1), preferably (1-50):(50-1), more preferably (1-20):(20-1), and even more preferably (0.1-10):1, preferably (0.3-8):1.

[0035] According to a preferred embodiment of the present invention, when the molar ratio of the content of the modulator a to the internal electron donor compound b is (0.1-10):1, and more preferably (0.3-8):1, it has better adjustable stereotactic orientation ability while maintaining excellent activity.

[0036] Preferably, the magnesium compound is selected from magnesium dihalides, magnesium alkoxy compounds, alkyl magnesium compounds, hydrates or alcohols of magnesium dihalides, or their derivatives. The magnesium dihalide derivative is a derivative in which one halogen atom in the magnesium dihalide molecular formula is replaced by an alkoxy or haloalkoxy group. The magnesium compound is preferably selected from magnesium dihalides or their alcohols, and more preferably from at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, and their alcohols. Preferably, the organic epoxy compound is selected from at least one oxide of compounds with 2 to 8 carbon atoms: aliphatic olefins, dienes, halogenated aliphatic olefins; preferably from at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran.

[0037] Preferably, the organophosphorus compound is selected from the hydrocarbon ester or halohydrocarbon ester of phosphoric acid or phosphorous acid; more preferably, it is selected from at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, and triphenyl phosphite.

[0038] Preferably, the titanium compound has the general formula TiX. m (OR1) 4-m , formula TiX m (OR1) 4-m R1 is a C1-C20 hydrocarbon group, X is a halogen, 1≤m≤4; the titanium compound is preferably selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy; more preferably titanium tetrachloride;

[0039] Preferably, the precipitation aid can be selected from oxygen-containing compounds, more preferably from at least one of acid anhydride compounds and diester compounds, and more preferably from acid anhydride and malonic acid ester diester compounds. Specifically, it can be selected from acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, di-dipentyl diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, di-dihexyl diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, etc.

[0040] According to some embodiments of the preparation method of the present invention, the solvent used to prepare the catalyst component can be a mixture capable of dissolving magnesium compounds, organic epoxy compounds, organic phosphorus compounds, regulator a and internal electron donor compound b. Preferably, the solvent is selected from one or more of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane and decane.

[0041] A second aspect of the present invention provides a method for preparing the above-mentioned catalyst component for preparing polyolefins, comprising: reacting a raw material including a magnesium compound, an organic epoxy compound, an organic phosphorus compound, a titanium compound, a precipitation aid, and a regulator a with an internal electron donor compound b to obtain the catalyst component; preferably, including but not limited to the following methods:

[0042] Step 1: The magnesium compound, organophosphorus compound, organoepoxide compound, and optional modifier a are brought into a first contact in a solvent to obtain a first mixture;

[0043] Step 2: In the presence of a precipitation aid, the first mixture, the titanium compound, and optionally the modifier a and the internal electron donor compound b are brought into a second contact to obtain a second mixture;

[0044] Step 3: Optionally, the second mixture is brought into a third contact with regulator a, washed, and dried;

[0045] Wherein, at least one of steps 1, 2 and 3 uses regulator a, preferably at least one of steps 1 and 2 uses regulator a;

[0046] Wherein, the regulator a is at least one of the 1,2-diether compounds shown in formula (I-1) and formula (I-2), and the internal electron donor compound b is a diether compound shown in formula (II).

[0047] As described in the first aspect, in formulas (I-1) and (I-2), R1 and R2 may be the same or different, and each is independently selected from C1-C30 alkyl, C6-C30 aryl with or without substituents, and C7-C30 aralkyl with or without substituents, except that they are not hydrogen; R3, R4, R5 and R6 may be the same or different, and each is independently selected from hydrogen, halogen, C1-C30 alkyl, C6-C30 aryl with or without substituents, C7-C30 aralkyl with or without substituents, or alkoxy of formula -OR1 or OR2; R3, R4, R5 and R6 may optionally be bonded to form cycloalkyl or phenyl-containing rings;

[0048] In formula (I), R1 and R2 may be the same or different, and each is independently selected from C1-C30 alkyl, C6-C30 aryl with or without substituents, and C7-C30 aralkyl with or without substituents, except that they are not hydrogen; R3, R4, R5 and R6 may be the same or different, and each is independently selected from hydrogen, halogen, C1-C30 alkyl, C6-C30 aryl with or without substituents, C7-C30 aralkyl with or without substituents, or alkoxy of formula -OR1 or OR2, which may combine to form cycloalkyl or benzene rings except that they are hydrogen;

[0049] In formula (II), R1', R2', R3', R4', R5', and R6' may be the same or different, and each independently represents one of hydrogen, halogen, a C1-C20 straight-chain or branched alkyl group, a C3-C20 substituted or unsubstituted cycloalkyl group, a C6-C20 substituted or unsubstituted aryl group, or a C7-C20 substituted or unsubstituted aralkyl group; or, two or more of R1', R2', R3', R4', R5', and R6' are bonded together to form a ring; R7' and R8' are each independently one of a C1-C20 straight-chain or branched alkyl group, a C3-C20 substituted or unsubstituted cycloalkyl group, a C6-C20 substituted or unsubstituted aryl group, or a C7-C20 substituted or unsubstituted aralkyl group.

[0050] In this invention, the term "alkyl" includes straight-chain alkyl, branched-chain alkyl, and cycloalkyl. For example, C1-C30 alkyl includes C1-C30 straight-chain alkyl, C3-C30 branched-chain alkyl, and C3-C30 cycloalkyl.

[0051] According to a preferred embodiment of the method for preparing the catalyst component of the present invention, regulator a is preferably used in at least one of steps 1 and 2.

[0052] The preferred methods for the above-mentioned regulator a and internal electron donor compound b are the same as those described in the first aspect, and will not be repeated here.

[0053] Preferably, the magnesium compound is selected from magnesium dihalides, magnesium alkoxy compounds, alkyl magnesium compounds, hydrates or alcohols of magnesium dihalides, or their derivatives. The derivatives of magnesium dihalides are those in which one halogen atom in the magnesium dihalide molecular formula is replaced by an alkoxy or haloalkoxy group. The magnesium compound is preferably selected from magnesium dihalides or their alcohols, and more preferably from magnesium dichloride, magnesium dibromide, magnesium diiodide, and their alcohols.

[0054] Preferably, the organic epoxy compound is selected from at least one oxide of compounds having 2 to 8 carbon atoms: aliphatic olefins, dienes, and halogenated aliphatic olefins; for example, it can be at least one of glycidyl ether, internal ether, butadiene oxide, and butadiene dioxide, more preferably selected from at least one of ethylene oxide, propylene oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran;

[0055] Preferably, the organophosphorus compound is selected from the hydrocarbon ester or halohydrocarbon ester of phosphoric acid or phosphorous acid; more preferably, it is selected from at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, and triphenyl phosphite.

[0056] Preferably, the titanium compound has the general formula TiX. m (OR1) 4-m (III), where R1 is a C1-C20 hydrocarbon group, X is a halogen, and 1≤m≤4; the titanium compound is preferably selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy; more preferably titanium tetrachloride;

[0057] Preferably, the precipitation aid can be selected from oxygen-containing compounds, more preferably from at least one of acid anhydride compounds and diester compounds, and even more preferably from acid anhydride compounds and malondiester compounds. Specifically, it can be selected from acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, di-isobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, di-isobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, di-isobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, etc.

[0058] According to some embodiments of the preparation method of the present invention, the solvent may be one or more compounds capable of dissolving magnesium compounds, organic epoxy compounds, organophosphorus compounds, regulator a and internal electron donor compound b. Preferably, the solvent is selected from one or more of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane and decane.

[0059] According to some embodiments of the preparation method of the present invention, the amount of organophosphorus compound used is 0.1-5 mol per mole of magnesium compound, the amount of organoepoxide compound used is 0.2-10 mol per mole of magnesium compound, the amount of precipitation aid used is 0.025-1 mol per mole of titanium compound used is 0.5-30 mol per mole of titanium compound used is 0.0001-5 mol per mole of regulator a used is 0.0001-5 mol per mole of internal electron donor compound b used is 0.0001-5 mol per mole of magnesium compound used is preferred. The amount of organophosphorus compound used is 0.3-3 mol per mole of magnesium compound used is preferred, the amount of organoepoxide compound used is preferred, the amount of precipitation aid used is preferred, the amount of titanium compound used is preferred, the amount of regulator a used is preferred, and the amount of internal electron donor compound b used is preferred, all relative to each mole of magnesium compound used is preferred. For example, if only 0.05 moles of regulator a are used in step 1, then the total amount of regulator a used is 0.05 moles.

[0060] According to some embodiments of the preparation method of the present invention, the conditions for the first contact include: a temperature of 10-100°C, preferably 30-80°C, and a time of 0.05-6 hours, preferably 0.1-2 hours.

[0061] According to some embodiments of the preparation method of the present invention, the conditions for the second contact include: -30 to 60°C, preferably -30 to 20°C, and a time of 0.1 to 5 hours, preferably 0.2 to 4 hours.

[0062] According to some embodiments of the preparation method of the present invention, the conditions for the third contact include: a temperature of 30-200°C, preferably 60-120°C, and a time of 0.5-8 hours, preferably 1-6 hours.

[0063] The catalyst component preparation method provided by this invention preferably follows the above-described method, but the preparation method of the catalyst component involved in this invention is not limited thereto. Preferably, the preparation method of the catalyst component can refer to the following steps: a magnesium compound is dissolved in a solvent system composed of regulator a, an organic epoxy compound, an organic phosphorus compound, and an inert diluent to form a homogeneous solution, which is then mixed with a titanium compound. A solid is then precipitated in the presence of a precipitation aid. Finally, this solid is treated with an internal electron donor compound b, which allows the internal electron donor compound b to be attached to the solid. If necessary, the solid is further treated with titanium tetrahalide and an inert diluent. See CN85100997A for details.

[0064] A third aspect of the present invention provides a catalyst system for olefin polymerization, comprising reaction products of the following components:

[0065] a. The catalyst components described above, or the catalyst components prepared by the above preparation method;

[0066] b. Alkyl aluminum compounds, with the general formula AlR' n X' 3-n In the general formula, R' is hydrogen or a C1-C20 hydrocarbon group, X' is a halogen, and 0 < n ≤ 3;

[0067] c. Optionally, external electrons are provided.

[0068] In this invention, the alkyl aluminum compound may be selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride, preferably at least one of triethylaluminum and triisobutylaluminum.

[0069] According to the present invention, "optionally, external electron donor" means that an external electron donor may or may not be added as needed. For applications requiring highly stereoregular olefin polymers, an external electron donor must be added. The external electron donor can be conventionally selected according to existing technology, for example, it can be selected from the general formula (R... 3 ) k Si(OR 4 ) 4-k The organosilicon compounds shown have the formula 0≤k≤3, R 3 Selected from halogens, hydrogen atoms, and C1-C20 alkyl, cycloalkyl, aryl, haloalkyl, or amino groups, R 4 It is a C1-C20 alkyl, cycloalkyl, aryl, haloalkyl, or amino group.

[0070] Specific examples of external electron donors include, but are not limited to: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, and methyltert-butyldimethoxysilane; preferably cyclohexylmethyldimethoxysilane and diphenyldimethoxysilane.

[0071] In this invention, the molar ratio of component a to component b, calculated as titanium:aluminum, is 1:(5-1000), preferably 1:(25-100); the molar ratio of component c to component a, calculated as external electron donor:titanium, is (0-500):1, preferably (25-100):1. When the external electron donor of component c is the aforementioned organosilicon compound, the molar ratio of component c to component a, calculated as silicon:titanium, is (0-500):1, preferably (25-100):1.

[0072] As a specific embodiment of the present invention, the preparation method of the olefin polymerization catalyst includes the following steps: alkyl aluminum compound and optional external electron donor compound are respectively mixed with catalyst components for olefin polymerization and then reacted, or alkyl aluminum compound and optional external electron donor are first mixed and then mixed with catalyst components for olefin polymerization and reacted.

[0073] According to a fourth aspect of the present invention, the present invention provides the application of the catalyst component prepared by the above-described preparation method, or the application of the above-described catalyst component or catalyst in olefin polymerization, preferably in propylene polymerization.

[0074] The catalyst component or catalyst of the present invention can be used directly in the propylene polymerization reaction, or it can be used in the propylene polymerization reaction after prepolymerization.

[0075] Prepolymerization involves prepolymerizing the above-mentioned catalyst component or catalyst with olefin (propylene) to obtain a prepolymer. The prepolymerization ratio of the prepolymer is 0.1-1000g olefin polymer / g catalyst component, preferably 0.2-500g olefin polymer / g catalyst component.

[0076] Prepolymerization can be carried out in a liquid or gas phase at temperatures ranging from -20 to 80°C, preferably 0 to 50°C. The prepolymerization step can be performed online as part of a continuous polymerization process or independently in a batch operation.

[0077] According to some embodiments of the application described in this invention, the polymerization of olefins can be carried out in the liquid phase of a solution of monomers in an inert solvent, in the gas phase, or by a combined gas-liquid phase polymerization process. The polymerization temperature can be 0-150°C, preferably 60-100°C. The polymerization reaction pressure is 0.01-10 MPa, preferably 0.5-5 MPa. The polymerization reaction time is 0.1-5 hours, preferably 0.5-3 hours.

[0078] Advantages of the present invention

[0079] During their research, the inventors surprisingly discovered that the addition of regulator a to the catalyst component ensured excellent catalyst performance while easily adjusting the xylene-soluble content and isotacticity of the polymer by changing the amount of external electron donor. This increased the adjustable range of the catalyst's stereoregularity while simultaneously reducing crystallinity. Since the solid component of the catalyst does not use phthalate compounds, the resulting polypropylene product is free of plasticizers. The catalyst component and catalyst system of this invention maintain high activity while being suitable for producing polymers characterized by both reduced crystallinity and easily adjustable stereoregularity.

[0080] Within the preferred content range of this invention, olefin polymerization catalysts containing the catalyst components of this invention for preparing polyolefins have better adjustable stereoregulation capabilities. Detailed Implementation

[0081] The substances and parameters not limited in this invention can be selected according to existing technology, which is a conventional technical means in this field.

[0082] The following examples further illustrate how the objectives, technical solutions, and advantages of the present invention can be more readily understood. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of the invention.

[0083] In the following examples and comparative examples, the data were obtained using the following test methods:

[0084] 1. Polymer isotacticity (II, wt%): determined by heptane extraction method (boiling heptane extraction for 6 hours): 2 g of dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is dried to constant weight. The ratio of the polymer weight (g) obtained to 2 is the isotacticity.

[0085] 2. The melt flow index (MFR, g / 10min) of the polymer was determined using a CEAST 6932 melt flow index tester from Italy, in accordance with GB / T 3682.1-2018 standard.

[0086] 3. Electron-donator content in the catalyst: The electron-donator content in the catalyst was determined using a Waters 600E high-performance liquid chromatograph. First, the sample was pretreated with an ethyl acetate-dilute hydrochloric acid solution to extract the electron-donator compound. The compound was then separated by HPLC, and its peak area was measured. Correction was performed using an external standard curve, and the percentage content of the electron-donator compound in the sample was calculated. This was then converted to the molar ratio of electron donors.

[0087] 4. Calculation method and formula of AC ((kgPP / gCat): weight of powder obtained from polymerization / (weight of catalyst × polymerization time).

[0088] 5. Determination of xylene-soluble content (XS, wt%) and intrinsic viscosity (IV) ratio of soluble content to polypropylene in propylene homopolymer: The tests were performed using a PolymerCharts CRYST-EX instrument. Trichlorobenzene solvent was used, and the mixture was heated to 150°C, held at that temperature for 90 min, and then sampled for testing. The temperature was then lowered to 35°C, held at that temperature for 70 min, and then sampled for testing again.

[0089] 6. Crystallinity of propylene homopolymer (XC, wt%): Differential scanning calorimetry (DSC) was used for testing. Specifically, a PE diamond DSC differential scanning calorimeter was used, and the sample amount was 4-5 mg. The specific steps were as follows: First, the sample was heated to 200°C at a rate of 10°C / min and held for 5 min to eliminate the thermal history. Then, the sample was cooled to 50°C at a rate of 10°C / min and held at 50°C for 1 min. After that, the sample was heated to 200°C again at a rate of 10°C / min. The melting temperature and melting enthalpy were determined from the DSC curve recorded after the reheating. The crystallinity Xc was calculated according to formula (1). The results are shown in Table 2.

[0090]

[0091] Wherein, ΔHm is the enthalpy of melting per unit mass of the sample, ΔHαθ is the enthalpy of melting of 100% crystallinity polypropylene, and ΔHα θ The value is taken as 209 J / g.

[0092] Example 1

[0093] Preparation of solid catalyst component a: Under nitrogen protection, 4.8 g of magnesium chloride, 98 mL of toluene, 4 mL of epichlorohydrin, 12.5 mL of tributyl phosphate, and regulator a (2,3-dimethoxytoluene) were sequentially added to a 300 mL reactor equipped with a stirrer. The mixture was heated to 50 °C with stirring and maintained for 2.5 h. Then, 1.4 g of phthalic anhydride was added, and the temperature was maintained for another h. The solution was cooled to below -25 °C, and 56 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly raised to 80 °C, and a solid precipitate formed. Then, internal electron donor compound b (2-isopropyl-2-isopentyl-1,3-dimethoxypropane) was added to the solid, and the temperature was maintained for 1 h. After filtration, the solid precipitate was washed twice with 70 mL of toluene to obtain a solid precipitate. Then, a TiCl4 / toluene solution was added to the precipitate, and the temperature was raised to 110 °C and maintained for 1 h. The mixture was then filtered. This process was repeated four times. The filtered precipitate was washed three times with 70 mL of toluene at 110 °C for 10 min each time, and then washed twice with 60 mL of hexane to obtain the solid catalyst component. The molar ratios of regulator a and internal electron donor compound b in the catalyst components obtained in each example are shown in Table 1.

[0094] Example 1A

[0095] This example illustrates the application of the catalyst component used in Example 1 for preparing polyolefins in propylene polymerization.

[0096] Propylene polymerization experiment 1: The solid catalyst components obtained above were subjected to propylene polymerization. The propylene polymerization procedure was as follows: In a 5L stainless steel reactor, after complete replacement with gaseous propylene, 5 mL of a 0.5 mol / L hexane solution of triethylaluminum and 5 mL of a 0.1 mol / L hexane solution of methylcyclohexyldimethoxysilane (CHMMS, external electron donor) were added, followed by 8-10 mg of the catalyst component prepared in Example 1 and 1.2L of hydrogen gas. 2.3L of liquid propylene was then introduced, and the temperature was raised to 70°C and maintained at this temperature for 1 hour. The temperature was then lowered, the pressure was released, and the olefin polymerization product was obtained. The catalyst activity (AC1) was calculated by weighing, and the isotacticity II1, melt index MFR1, xylene soluble content XS1, and crystallinity XC1 were tested. The specific results are detailed in Table 2.

[0097] Propylene polymerization experiment 2: The solid catalyst components obtained above were subjected to propylene polymerization. The propylene polymerization procedure was as follows: In a 5L stainless steel reactor, after complete replacement with gaseous propylene, 5 mL of a 0.5 mol / L hexane solution of triethylaluminum and 0.125 mL of a 0.1 mol / L hexane solution of methylcyclohexyldimethoxysilane (CHMMS, external electron donor) were added, followed by 8–10 mg of the catalyst component prepared in Example 1 and 1.2L of hydrogen gas. 2.3L of liquid propylene was then introduced, and the temperature was raised to 70°C and maintained at this temperature for 1 hour. The temperature was then lowered, the pressure was released, and the olefin polymerization product was obtained. The catalyst activity (AC2) was calculated by weighing, and the isotacticity II2, melt index MFR2, xylene soluble content XS2, XS2 / IV, and crystallinity XC2 were tested. The specific results are detailed in Table 2.

[0098] Example 2

[0099] The method was followed in Example 1, except that 9,9-dimethoxymethylfluorene was used instead of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. The test data for the content of each substance are shown in Table 1.

[0100] Example 2A

[0101] The olefin polymerization product was prepared according to the method of Example 1A, except that the catalyst component for preparing polyolefins prepared in Example 2 was used. The catalyst activities AC1 and AC2, isotacticity II1 and II2, melt index MFR1 and MFR2, xylene soluble content XS1 and XS2, XS2 / IV, and crystallinity XC1 and XC2 were tested. The specific results are shown in Table 2.

[0102] Example 3

[0103] The method of Example 1 was followed, except that 3,4-dimethoxy-1-propenylbenzene was used instead of 2,3-dimethoxytoluene. The test data of the content of each substance are shown in Table 1.

[0104] Example 3A

[0105] The olefin polymerization product was prepared according to the method of Example 1A, except that the catalyst component for preparing polyolefins prepared in Example 3 was used. The catalyst activities AC1 and AC2, isotacticity II1 and II2, melt index MFR1 and MFR2, xylene soluble content XS1 and XS2, XS2 / IV, and crystallinity XC1 and XC2 were tested. The specific results are shown in Table 2.

[0106] Example 4

[0107] The method of Example 2 was followed, except that 3,4,5-trimethoxytoluene was used instead of 2,3-dimethoxytoluene. The test data of the content of each substance are shown in Table 1.

[0108] Example 4A

[0109] The olefin polymerization product was prepared according to the method of Example 1A, except that the catalyst component for preparing polyolefins prepared in Example 4 was used. The catalyst activities AC1 and AC2, isotacticity II1 and II2, melt index MFR1 and MFR2, xylene soluble content XS1 and XS2, XS2 / IV, and crystallinity XC1 and XC2 were tested. The specific results are shown in Table 2.

[0110] Example 5

[0111] Preparation of solid catalyst component a: Under nitrogen protection, 4.8 g of magnesium chloride, 98 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate were sequentially added to a 300 mL reactor equipped with a stirrer. The mixture was heated to 50 °C with stirring and maintained for 2.5 h. Then, 1.4 g of phthalic anhydride was added, and the temperature was maintained for another h. The solution was cooled to below -25 °C, and 56 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly raised to 80 °C, and a solid precipitate was formed. Then, regulator a (2,5-dimethoxytetrahydrofuran) and internal electron donor compound b (9,9-dimethoxymethylfluorene) were added to the solid, and the temperature was maintained for 1 h. After filtration, the solid precipitate was washed twice with 70 mL of toluene to obtain a solid precipitate. Then, a TiCl4 / toluene solution was added to the precipitate, and the temperature was raised to 110 °C and maintained for 1 h. The mixture was then filtered. This process was repeated four times. The filtered precipitate was washed three times with 70 mL of toluene at 110 °C for 10 min each time, and then washed twice with 60 mL of hexane. The molar ratios of solid catalyst component regulator a and internal electron donor compound b are shown in Table 1.

[0112] Example 5A

[0113] The olefin polymerization product was prepared according to the method of Example 1A, except that the catalyst component for preparing polyolefins prepared in Example 5 was used. The catalyst activities AC1 and AC2, isotacticity II1 and II2, melt index MFR1 and MFR2, xylene soluble content XS1 and XS2, XS2 / IV, and crystallinity XC1 and XC2 were tested. The specific results are shown in Table 2.

[0114] Example 6

[0115] The method of Example 5 was followed, except that 1,2-diethoxyethane was used instead of 1,2-dimethoxybenzene, and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was used instead of 9,9-dimethoxymethylfluorene. The test data of the content of each substance are shown in Table 1.

[0116] Example 6A

[0117] The olefin polymerization product was prepared according to the method of Example 1A, except that the catalyst component for preparing polyolefins prepared in Example 6 was used. The catalyst activities AC1 and AC2, isotacticity II1 and II2, melt index MFR1 and MFR2, xylene soluble content XS1 and XS2, XS2 / IV, and crystallinity XC1 and XC2 were tested. The specific results are shown in Table 2.

[0118] Example 7

[0119] Preparation of solid catalyst component a: Under nitrogen protection, 4.8 g of magnesium chloride, 98 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate were sequentially added to a 300 mL reactor equipped with a stirrer. The mixture was heated to 50 °C with stirring and maintained for 2.5 h. Then, 1.4 g of phthalic anhydride was added, and the temperature was maintained for another h. The solution was cooled to below -25 °C, and 56 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly raised to 80 °C, and a solid precipitate was formed. Then, an internal electron donor compound b (9,9-dimethoxymethylfluorene) was added to the solid, and the temperature was maintained for 1 h. After filtration, the solid precipitate was washed twice with 70 mL of toluene to obtain a solid precipitate. Then, a TiCl4 / toluene solution was added to the precipitate, and the temperature was raised to 110 °C and maintained for 1 h. The mixture was then filtered. This process was repeated three times. Finally, TiCl4 / toluene solution and regulator a (1,4-benzodioxane) were added, the temperature was raised to 110℃ and maintained for 1 h, and then filtered. The precipitate was washed three times with 70 mL of toluene at 110℃ for 10 min each time, and then washed twice with 60 mL of hexane. The molar ratios of regulator a and internal electron donor compound b of the solid catalyst component are shown in Table 1.

[0120] Example 7A

[0121] The olefin polymerization product was prepared according to the method of Example 1A, except that the catalyst component used in Example 7 for the preparation of polyolefins was used. The catalyst activities AC1 and AC2, isotacticity II1 and II2, melt index MFR1 and MFR2, xylene soluble content XS1 and XS2, XS2 / IV, and crystallinity XC1 and XC2 were tested. The specific results are shown in Table 2.

[0122] Comparative Example 1

[0123] The method of Example 2 was followed, except that regulator a (2,3-dimethoxytoluene) was not used. The test data of the content of each substance are shown in Table 1.

[0124] Comparative Example 1A

[0125] The olefin polymerization product was prepared according to the method of Example 1A, except that the catalyst component prepared in Comparative Example 1 for the preparation of polyolefins was used. The catalyst activities AC1 and AC2, isotacticity II1 and II2, melt index MFR1 and MFR2, xylene soluble content XS1 and XS2, XS2 / IV, and crystallinity XC1 and XC2 were tested. The specific results are shown in Table 2.

[0126] Comparative Example 2

[0127] The method of Example 1 was followed, except that modifier a (1,2-dimethoxybenzene) was not used. The test data of the content of each substance are shown in Table 1.

[0128] Comparative Example 2B

[0129] The olefin polymerization product was prepared according to the method of Example 1A, except that the catalyst component prepared in Comparative Example 2 for the preparation of polyolefins was used. The catalyst activities AC1 and AC2, isotacticity II1 and II2, melt index MFR1 and MFR2, xylene soluble content XS1 and XS2, XS2 / IV, and crystallinity XC1 and XC2 were tested. The specific results are shown in Table 2.

[0130] Comparative Example 3

[0131] The method of Example 2 was followed, except that dicyclohexane ether was used instead of 2,3-dimethoxytoluene. The test data of the content of each substance are shown in Table 1.

[0132] Comparative Example 3B

[0133] The olefin polymerization product was prepared according to the method of Example 1A, except that the catalyst component prepared in Comparative Example 3 for the preparation of polyolefins was used. The catalyst activities AC1 and AC2, isotacticity II1 and II2, melt index MFR1 and MFR2, xylene soluble content XS1 and XS2, XS2 / IV, and crystallinity XC1 and XC2 were tested. The specific results are shown in Table 2.

[0134]

[0135]

[0136] The catalyst components and catalyst system of the present invention can maintain high activity while being used to produce polymers characterized by reduced crystallinity and easily adjustable stereoregularity.

[0137] The results from Examples 1-7 and Comparative Examples 1-3 show that the introduction of 1,2-diether compounds as regulators and diether compounds as internal electron donors in the catalyst components for preparing polyolefins of the present invention results in catalysts with good polymerization activity without involving the toxicity issues of phthalates. When the amount of external electron donor is high, the isotactic index of the propylene homopolymer remains above 98%; however, after reducing the amount of external electron donor, the isotactic index of the polymers obtained in Examples 1A-7A is significantly reduced, and the xylene-soluble content is significantly increased. This indicates that by changing the amount of external electron donor, the stereotactic orientation ability of the catalyst can be adjusted within a wider range, and the polymers produced by changing the amount of external electron donor also have the characteristics of reduced crystallinity, easily adjustable xylene-soluble content, and isotacticity. The ability of catalysts to stereotactic orientation and the crystallinity of polymers are easily adjustable, which is beneficial for developing different grades of polypropylene products without changing the main catalyst. This is especially true when developing film packaging products, as it can provide both good rigidity and good film-forming properties, and is more conducive to the industrial application of the catalyst.

[0138] Furthermore, the solid component of the catalyst does not use phthalate compounds, so the resulting polypropylene products are free of plasticizers and have broad market application prospects in food-grade fields such as food and beverage container processing and disposable packaging. In particular, it can avoid situations that do not comply with the regulations of relevant exporting countries.

[0139] The above description of the embodiments is provided to enable those skilled in the art to understand and apply the present invention. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the embodiments described herein, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A catalyst component comprising magnesium, titanium, halogen, modifier a, and internal electron donor compound b; The regulator a is at least one of the 1,2-diether compounds shown in formula (I-1) and formula (I-2), and the internal electron donor compound b is a diether compound shown in formula (II). In formulas (I-1) and (I-2), R1 and R2 may be the same or different, and each is independently selected from alkyl or alkylene groups of C1-C30, aryl groups of C6-C30 with or without substituents, and aralkyl groups of C7-C30 with or without substituents, except that they are not hydrogen. R1 and R2 may optionally be bonded together to form an epoxy group containing one -O- or two -O-. In formulas (I-1) and (I-2), R3, R4, R5 and R6 may be the same or different, and each is independently selected from hydrogen, halogen, C1-C30 alkyl or alkylene, C2-C30 alkenyl, C6-C30 aryl with or without substituents, C7-C30 aralkyl with or without substituents or alkoxy of formula -OR1 or OR2. R3, R4, R5 and R6 may optionally be bonded to form a ring, and R3, R4, R5 and R6 may optionally be bonded to R1 and / or R2 to form a ring. In formula (II), R1', R2', R3', R4', R5', and R6' may be the same or different, and each independently represents one of hydrogen, halogen, a C1-C20 straight-chain or branched alkyl group, a C3-C20 substituted or unsubstituted cycloalkyl group, a C6-C20 substituted or unsubstituted aryl group, or a C7-C20 substituted or unsubstituted aralkyl group; or, two or more of R1', R2', R3', R4', R5', and R6' are bonded together to form a ring; R7' and R8' are each independently one of a C1-C20 straight-chain or branched alkyl group, a C3-C20 substituted or unsubstituted cycloalkyl group, a C6-C20 substituted or unsubstituted aryl group, or a C7-C20 substituted or unsubstituted aralkyl group.

2. The catalyst component according to claim 1, characterized in that, The halogen is selected from one or more of bromine, chlorine, and iodine; and / or, In formulas (I-1) and (I-2), R1 and R2 are each independently selected from one of halogen, C1-C10 alkyl or alkylene groups, and C1-C10 alkoxy groups; preferably, in formulas (I-1) and (I-2), R1 and R2 are each selected from one of C1-C5 straight-chain or branched alkyl or alkylene groups, more preferably from one or more of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, and isopentyl groups where one hydrogen atom is chemically replaced; and / or, R3, R4, R5 and R6 of formula (I-1) and formula (I-2) are each independently selected from hydrogen, halogen, C1-C10 alkyl or alkylene, C2-C10 alkenyl, C1-C10 alkoxy, C6-C30 aryl with or without substituents, C7-C30 aralkyl with or without substituents or alkoxy of formula -OR1 or OR2; Preferably, when two or more groups from R3, R4, R5, and R6 are linked to form a ring, or when R3, R4, R5, and R6 are bonded to R1 and / or R2 to form a ring, the 1,2-diether compound has one or more epoxy groups containing one -O- or two -O- groups; or, the 1,2-diether compound has a polycyclic structure containing at least one benzene ring, wherein the ring fused to the benzene ring is saturated or unsaturated; wherein, more preferably, the polycyclic structure has multiple alkoxy groups, the number of which is not less than 2. The number of carbon atoms in the group is 1-10; or, when two or more groups in R3, R4, R5 and R6 are not bonded to form a ring, R3, R4, R5 and R6 in formula (I-1) and formula (I-2) are each selected from C1-C5 straight-chain or branched alkyl or alkoxy, C6-C30 aryl with or without substituents, more preferably the following groups or oxygen-containing groups containing the following groups: hydrogen, methyl, ethyl, vinyl, propenyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, phenyl; More preferably, the regulator a is selected from 1,2-dimethoxybenzene, 1,2-diethoxybenzene, 1,2-dipropoxybenzene, 1,2-dibutoxybenzene, 1,2-dimethoxynaphthalene, 1,2-diethoxynaphthalene, 1,2-dimethoxyanthracene, 1,2-diethoxyanthracene, 2,3-dimethoxytoluene, 3,4-dimethoxytoluene, 3,4-dimethoxystyrene, 3,4-dimethoxy-1-propenylbenzene, 1,2,3-trimethoxybenzene, 3,4,5-trimethoxytoluene, etc. One or more of the following: oxytoluene, 1,3-benzodioxane, 1,4-benzodioxane, 1,3-dioxane, 1,4-dioxane, 1,2-dimethoxypropane, 1-tert-butoxy-2-ethoxyethane, 1-tert-butoxy-2-methoxyethane, 1,2-diethoxyethane, 1,2-dimethoxyethane, 1,2-dibutoxyethane, 1,2-dipropoxyethane, 1,2-diisopropoxyethane, 1,2-diphenoxyethane, and tetrahydrofurfuryl ether.

3. The catalyst component according to claim 1, characterized in that, The internal electron donor compound b is a 1,3-diether compound represented by formula (Ⅲ); In formula (Ⅲ), R9' and R10' may be the same or different, and each is independently one of hydrogen, halogen, C1-C18 straight-chain or branched alkyl, C3-C18 substituted or unsubstituted cycloalkyl, C6-C18 substituted or unsubstituted aryl, and C7-C18 substituted or unsubstituted aralkyl; or, R9' and R10' are bonded together to form a ring; R11' and R12' may be the same or different, and each is independently a C1-C10 straight-chain or branched alkyl; preferably, The 1,3-diether compounds are selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2 2-Dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2 -Bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane One or more of the following: alkyl, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, and 9,9-dimethoxymethylfluorene.

4. The catalyst component according to claim 1, characterized in that, The catalyst component comprises a magnesium compound, an organic epoxy compound, an organic phosphorus compound, a titanium compound, a precipitation aid, a regulator a, and the reaction product of an internal electron donor compound b; preferably, The molar ratio of the magnesium compound, the titanium compound, and the internal electron donor compound b is 1:(0.5-150):(0.02-0.4).

5. The catalyst component according to any one of claims 1-4, characterized in that, Based on a total weight of 100 wt% of the catalyst components, the magnesium content is 5-30 wt%, preferably 8-25 wt%, more preferably 10-23 wt%; and / or, the titanium content is 0.5-10 wt%, preferably 1-8 wt%; and / or, the modifier a content is 0.5-25 wt%, preferably 1-20 wt%; and / or, the internal electron donor compound b content is 0.5-25 wt%, preferably 1-20 wt%; and / or, The molar ratio of regulator a to internal electron donor compound b is (1-100):(100-1), preferably (1-50):(50-1), further preferably (1-20):(20-1), even more preferably (0.1-10):1, and most preferably (0.3-8):

1.

6. A method for preparing the catalyst component according to any one of claims 1-5, comprising: The catalyst component is prepared by reacting a raw material comprising a magnesium compound, an organic epoxy compound, an organic phosphorus compound, a titanium compound, a precipitation aid, a regulator a, and an internal electron donor compound b.

7. The preparation method according to claim 6, characterized in that, include: Step 1: The magnesium compound, organophosphorus compound, organoepoxide compound, and optional modifier a are brought into a first contact in a solvent to obtain a first mixture; Step 2: In the presence of a precipitation aid, the first mixture, the titanium compound, and optionally the modifier a and the internal electron donor compound b are brought into a second contact to obtain a second mixture; Step 3: Optionally, the second mixture is brought into a third contact with regulator a, washed, and dried; In this process, at least one of steps 1, 2, and 3 uses regulator a; Preferably, regulator a is used in at least one of steps 1 and 2.

8. The preparation method according to claim 6, characterized in that, The magnesium compound is selected from magnesium dihalides, magnesium alkoxy compounds, alkyl magnesium compounds, hydrates or alcohols of magnesium dihalides, or their derivatives. The magnesium dihalide derivatives are those in which one halogen atom in the magnesium dihalide molecular formula is replaced by an alkoxy or haloalkoxy group. The magnesium compound is preferably selected from magnesium dihalides or their alcohols, and more preferably from at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, and their alcohols; and / or, The organic epoxy compound is selected from at least one oxide of compounds having 2 to 8 carbon atoms: aliphatic olefins, dienes, and halogenated aliphatic olefins; preferably selected from at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran; and / or, The organophosphorus compound is selected from hydrocarbon esters or halohydrocarbon esters of orthophosphoric acid or phosphorous acid; preferably from at least one of trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, triphenyl orthophosphoric acid, trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, and triphenyl phosphoric acid; and / or, The general formula of the titanium compound is TiX. m (OR1) 4-m TiX m (OR1) 4-m R1 is a C1-C20 hydrocarbon group, X is a halogen, 1≤m≤4; the titanium compound is preferably selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy; preferably titanium tetrachloride; and / or, The precipitation aid is selected from oxygen-containing compounds, preferably from at least one of acid anhydride compounds and diester compounds, more preferably from at least one of acid anhydride compounds and malonate diester compounds; more preferably from at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, di-n-butylmalonate, di-tert-butylmalonate, di-tert-butylmalonate, di-tert-butylmalonate, di-tert-butylmalonate, di-tert-butylmalonate, di-tert-butylmalonate, di-tert-butylmalonate; and / or, The solvent is selected from one or more compounds capable of dissolving magnesium compounds, organic epoxy compounds, organophosphorus compounds, regulator a and internal electron donor compound b. Preferably, the solvent is selected from one or more of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane and decane.

9. The preparation method according to any one of claims 6-8, characterized in that, Relative to each mole of magnesium compound, the amount of organophosphorus compound is 0.1-5 moles, the amount of organoepoxide compound is 0.2-10 moles, the amount of precipitation aid is 0.025-1 mole, the amount of titanium compound is 0.5-30 moles, the total amount of regulator a is 0.0001-5 moles, and the amount of internal electron donor compound b is 0.0001-5 moles; preferably, relative to each mole of magnesium compound, the amount of organophosphorus compound is 0.3-3 moles, the amount of organoepoxide compound is 0.5-4 moles, the amount of precipitation aid is 0.05-0.5 moles, the amount of titanium compound is 1-20 moles, the amount of regulator a is 0.01-1 mole, and the amount of internal electron donor compound b is 0.01-1 mole; and / or, The molar ratio of regulator a to internal electron donor compound b is (1-100):(100-1), preferably (1-50):(50-1), further preferably (1-20):(20-1), even more preferably (0.1-10):1, and most preferably (0.3-8):

1.

10. An olefin polymerization catalyst system, the catalyst comprising the following components: a. The catalyst component according to any one of claims 1-5, or the catalyst component prepared by the preparation method according to any one of claims 6-9; b. Alkyl aluminum compounds, with the general formula AlR' n X' 3-n In the general formula, R' is hydrogen or a C1-C20 hydrocarbon group, X' is a halogen, and 0 < n ≤ 3; c. Optionally, an external electron donor; preferably, an external electron donor. The alkylaluminum compound is selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride, preferably at least one of triethylaluminum and triisobutylaluminum; and / or; The external electron donor is selected from general formula (R) 3 ) k Si(OR 4 ) 4-k The organosilicon compounds shown have the formula 0≤k≤3, R 3 Selected from halogens, hydrogen atoms, and C1-C20 alkyl, cycloalkyl, aryl, haloalkyl, or amino groups, R 4 It is a C1-C20 alkyl, cycloalkyl, aryl, haloalkyl, or amino group; and / or, The molar ratio of component a to component b, calculated as titanium:aluminum, is 1:(5-1000), preferably 1:(25-100); the molar ratio of component c to component a, calculated as electron donor:titanium, is (0-500):1, preferably (25-100):

1.

11. The application of a catalyst component according to any one of claims 1-5, a catalyst component prepared by any one of claims 6-9, or a catalyst system according to claim 10 in olefin polymerization, preferably in propylene polymerization.

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