Catalyst component for olefin polymerization, catalyst and application thereof

Abstract

The invention provides a catalyst component for olefin polymerization, a catalyst and application thereof. The catalyst component is prepared from the following components: Mg, Ti, halogen and a 2, 6-disubstituted oxymethyl-4-pyrone internal electron donor, wherein the 2, 6-disubstituted oxymethyl-4-pyrone internal electron donor has a structure as shown in a formula I: # imgabs0, the catalytic activity of the catalyst component and the catalyst is high and is generally higher than that of phthalate and diether internal electron donor catalysts commonly used in industry, and a polymer obtained through catalytic polymerization is regular in particle size, high in stacking density and good in stability. The isotacticity is high, and the overall molecular weight distribution is narrower.

Description

Technical Field

[0001] The invention relates to a solid catalyst component for olefin polymerization, belonging to the field of polyolefin catalysts. Background Art

[0002] At present, Ziegler-Natta catalysts (ZN catalysts) still occupy a dominant position in polyolefin production. The development focus of most ZN catalysts is on the development of highly active and highly stereospecific catalysts and improving the copolymerization ability of catalysts. In addition, due to the high catalytic efficiency of traditional ZN catalysts (transition metal compounds such as titanium chemically bonded to a magnesium-containing carrier), the polymer produced has good comprehensive performance and low cost. At present, most catalysts for producing polypropylene in the world are still based on ZN catalytic systems, which are characterized by high activity, high stereoregularity, long life and customized product structure. From the development process of ZN catalysts, it can be seen that as early as the emergence of the first generation of catalysts, it was found that adding a third component (mostly electron donors, also known as Lewis bases, among which those added during the catalyst preparation process are called internal electron donors, and those added during the polymerization process are called external electron donors) will have a great influence on the polymerization behavior of olefins and the properties of polymers; changing the internal electron donor in the catalyst can change the properties of the catalyst active center to the greatest extent possible, thereby changing the performance of the catalyst to the greatest extent. Therefore, the development of new electron donors has always been a hot spot in the research and development of ZN polypropylene catalysts.

[0003] The relatively distinctive high-performance internal electron donor compounds in the prior art mainly include: (1) fatty acid esters and aromatic acid ester compounds, mainly represented by phthalate compounds; (2) diether compounds (for example, compounds disclosed in EP0361493 and EP0728724); (3) succinate compounds (for example, compounds disclosed in WO9856834, WO0063261, and WO03022894); (4) glycol ester compounds (for example, compounds disclosed in WO9856834, WO0063261, and WO03022894); (5) compounds with other functional groups (for example, compounds disclosed in CN1105671, CN1242780, and US20060128558), etc. However, in practical applications, the above compounds have certain problems as internal electron donors for olefin polymerization catalysts. Although the catalysts using 1,3-diether compounds as internal electron donors have higher activity and good hydrogen tuning sensitivity, the relative molecular mass distribution of the produced PP is narrow, which is not conducive to the development of different grades of PP; the advantage of using succinate compounds as internal electron donors is that the relative molecular mass distribution of the synthesized PP is relatively wide, but the disadvantage is that the stereoregularity of PP and the hydrogen tuning sensitivity of the catalyst need to be improved; and the overall activity of the diol ester catalytic system is not as ideal as the diether system.

[0004] At present, the most widely used polyolefin internal electron donor in industry is phthalate compounds, which have medium catalyst activity, good stereoselectivity and low price. However, phthalate compounds, as commonly used plasticizers, have great harm to human reproductive health and the environment, and there is a great demand for replacement. At present, the use of most phthalate substances has been restricted. Therefore, it is one of the common research and development goals in the field of polyolefin catalysts in recent years to develop a new electron donor with excellent activity, good stereospecificity, good comprehensive performance and low cost to replace the phthalate electron donor compounds widely used in the prior art and apply them to the preparation of efficient Ziegler-Natta catalysts. Summary of the invention

[0005] In order to solve the above problems, the purpose of the present invention is to provide a catalyst component, a catalyst and its application for olefin polymerization. The catalyst component and the catalyst have high catalytic activity, which is generally higher than the phthalate ester and diether internal electron donor catalysts commonly used in industry, and the polymer obtained by catalytic polymerization has regular particle size, high bulk density, high isotacticity and narrow overall molecular weight distribution.

[0006] In order to achieve the above object, the present invention provides a catalyst component for olefin polymerization, which comprises: Mg, Ti, halogen, and 2,6-disubstituted oxymethyl-4-pyrone internal electron donor; wherein the 2,6-disubstituted oxymethyl-4-pyrone internal electron donor has a structure shown in Formula I:

[0007]

[0008] In Formula I, R 1 , R 2 , R 3 and R 4 are the same or different, each independently selected from H, halogen, C 1 -C 20 Preferably, R 1 , R 2 , R 3 and R 4 Each of the above mentioned heteroatoms contains one or more heteroatoms selected from N, O, S, P, Si and halogen; more preferably, R 1 , R 2 , R 3 and R 4 Two or more of them are bonded to each other to form a ring.

[0009] According to a specific embodiment of the present invention, preferably, in Formula I, R 1 , R 2 , R 3 and R4 the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated alkyl, alkyl containing heteroatoms, halogenated cycloalkyl, cycloalkyl containing heteroatoms, halogenated phenyl, phenyl containing heteroatoms, halogenated alkylphenyl, alkylphenyl containing heteroatoms, halogenated phenylalkyl, phenylalkyl containing heteroatoms, halogenated indenyl, indenyl containing heteroatoms, halogenated benzyl, benzyl containing heteroatoms, heterocyclic aromatic substituents; the heteroatoms include one or a combination of two or more of N, O, S, P, and Si.

[0010] According to a specific embodiment of the present invention, preferably, in Formula I, R 1 , R 2 , R 3 and R 4 are each independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 The straight chain or branched alkyl group of 20 carbon atoms or the following substituents within 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furyl, pyrrolyl, thienyl and indenyl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl and hexenyl.

[0011] According to a specific embodiment of the present invention, preferably, the 2,6-disubstituted oxymethyl-4-pyrone internal electron donor includes 2,6-dimethoxymethyl-4-pyrone, 2,6-diethyloxymethyl-4-pyrone, 2,6-dipropyloxymethyl-4-pyrone, 2,6-dibutyloxymethyl-4-pyrone, 2,6-dipentyloxymethyl-4-pyrone, 2,6-dihexyloxymethyl-4-pyrone, 2,6 -Diheptyloxymethyl-4-pyrone, 2,6-dioctyloxymethyl-4-pyrone, 2,6-di(dodecyl)oxymethyl-4-pyrone, 2,6-di(tetradecyl)oxymethyl-4-pyrone, 2,6-di(hexadecyl)oxymethyl-4-pyrone, 2,6-diphenyloxymethyl-4-pyrone, 2,6-dibenzyloxymethyl-4-pyrone, 2,6-di-m-chlorophenyloxymethyl-4-pyrone, 2,6-di-o-chlorophenyloxymethyl-4-pyrone, 2,6-di-p-chlorophenyloxymethyl-4-pyrone, 2,6-di-p-methylphenyloxymethyl-4-pyrone, 2,6-di-p-methoxyphenyloxymethyl-4-pyrone, 2,6-difuranyloxymethyl-4-pyrone, 2,6-dipropyleneoxymethyl-4-pyrone, 2,6-dimethoxymethyl-3,5-dimethyl-4-pyrone, 2,6-dimethoxymethyl- 3-methyl-5-ethyl-4-pyrone, 2,6-dimethoxymethyl-3,5-diethyl-4-pyrone, 2,6-dimethoxymethyl-3,5-dibutyl-4-pyrone, 2,6-dimethoxymethyl-3-ethyl-5-butyl-4-pyrone, 2,6-dimethoxymethyl-3-methyl-5-butyl-4-pyrone, 2-methoxymethyl-6-ethyloxymethyl-4-pyrone, or a combination of two or more thereof.

[0012] According to a specific embodiment of the present invention, preferably, the 2,6-disubstituted oxymethyl-4-pyrone internal electron donor has a structure shown in Formula II:

[0013]

[0014] In formula II, R 5 , R 6 , R 7 and R 8 are the same or different, each independently selected from H, halogen, C 1 -C 20 Preferably, R 5 , R 6 , R 7 and R 8 Each of the heteroatoms comprises one or a combination of two or more selected from N, O, S, P, Si and halogen; preferably, R 5 , R 6 , R 7 and R8 Two or more of them are bonded to each other to form a ring.

[0015] According to a specific embodiment of the present invention, preferably, the 2,6-disubstituted oxymethyl-4-pyrone internal electron donor includes 2,6-dipropionyloxymethyl-4-pyrone, 2,6-dibutyryloxymethyl-4-pyrone, 2,6-divaleryloxymethyl-4-pyrone, 2,6-dihexanoyloxymethyl-4-pyrone, 2,6-dicyclohexanecarbonyloxymethyl-4-pyrone, 2,6-dinonanoyloxymethyl-4-pyrone, 2,6-di(tridecane) Acyloxymethyl-4-pyrone, 2,6-dipentadecanoyloxymethyl-4-pyrone, 2,6-diheptadecanoyloxymethyl-4-pyrone, 2,6-dibenzoyloxymethyl-4-pyrone, 2,6-di-m-chlorobenzoyloxymethyl-4-pyrone, 2,6-di-p-toluoyloxymethyl-4-pyrone, 2,6-di-o-chlorobenzoyloxymethyl-4-pyrone, 2,6-di-p-chlorobenzoyloxymethyl-4-pyrone, 2,6-di-p-chlorobenzoyloxymethyl-4-pyrone, p-Anisyloxybenzoyloxymethyl-4-pyrone, 2,6-di-p-nitrobenzoyloxymethyl-4-pyrone, 2,6-dibenzoyloxymethyl-3,5-dimethyl-4-pyrone, 2,6-dibenzoyloxymethyl-3,5-diethyl-4-pyrone, 2,6-dibenzoyloxymethyl-3,5-dipropyl-4-pyrone, 2,6-dibenzoyloxymethyl-3,5-dibutyl-4-pyrone, 2,6-dibenzoyloxymethyl-3-methyl The invention can be selected from the group consisting of 2,6-dibenzoyloxymethyl-3-ethyl-5-butyl-4-pyrone, 2,6-dibenzoyloxymethyl-3-methyl-5-butyl-4-pyrone, 2,6-dibenzoyloxymethyl-3-methyl-5-phenyl-4-pyrone, 2-propionyloxymethyl-6-pentanoyloxymethyl-4-pyrone and 2-benzoyloxymethyl-6-p-methylbenzoyloxymethyl-4-pyrone, or a combination of two or more thereof.

[0016] The 2,6-disubstituted oxymethyl-4-pyrone compounds shown in formula I can be synthesized by the following preparation methods including but not limited to:

[0017] The synthetic route is shown in reaction formula I. Diethyl oxalate reacts with the corresponding ketone and then is reduced to obtain a substituted 2,6-dimethanol-4-pyrone compound, which is then reacted with another alcohol to obtain a 2,6-disubstituted oxymethyl-4-pyrone compound, or reacted with a mixture of two alcohols (as shown in reaction formula II) to obtain a mixture of three 2,6-disubstituted oxymethyl-4-pyrones, which can be directly used as internal electron donors without separation. The ratio of each component in the mixture can be adjusted by the addition ratio of the two alcohols in the reactants, and the ratio of each component can be characterized and determined by analytical methods such as chromatography-mass spectrometry technology and nuclear magnetic resonance.

[0018] Reaction formula Ⅰ:

[0019]

[0020] Reaction formula II:

[0021]

[0022] The 2,6-disubstituted carbonyloxymethyl-4-pyrone represented by formula II can be synthesized by the following preparation methods including but not limited to:

[0023] The synthetic route is shown in reaction formula III. Diethyl oxalate reacts with the corresponding ketone and then is reduced to obtain a substituted 2,6-dimethanol-4-pyrone compound, which is then reacted with an acyl chloride compound to obtain a 2,6-disubstituted carbonyloxymethyl-4-pyrone compound, or reacted with a mixture of two acyl chloride compounds (as shown in reaction formula IV) to obtain a mixture of three 2,6-disubstituted carbonyloxymethyl-4-pyrone compounds, which are directly used as internal electron donors without separation. The ratio of each component in the mixture can be adjusted by the addition ratio of the two acyl chloride compounds in the reactants, and the ratio of each component can be characterized and determined by analytical methods such as chromatography-mass spectrometry technology and nuclear magnetic resonance.

[0024] Reaction formula III:

[0025]

[0026] Reaction formula IV:

[0027]

[0028] According to a specific embodiment of the present invention, preferably, the catalyst component comprises a titanium compound, a magnesium compound, and an internal electron donor as shown in formula I; the precursor of the magnesium compound is selected from X n Mg(OR a ) 2-n MgCl 2 ·mR a OH, R a 2-n MgX n MgCl 2 / SiO 2 MgCl 2 / Al 2 O 3 , a mixture of magnesium halide and titanium alkoxide, or a combination of two or more thereof, wherein m is 0.1-6, 0≤n≤2, X is a halogen, R a C 1 -C 20 The general formula of the titanium compound is TiX N (OR b ) 4-N , where R b C 1 -C 20 The hydrocarbon group is: X is halogen, and N is 1-4.

[0029] According to a specific embodiment of the present invention, preferably, the magnesium compound is an alcoholate of magnesium dihalide; or, the magnesium compound is a liquid magnesium compound (a magnesium compound dissolved in a liquid); or, the magnesium compound is a derivative of the magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; preferably, it is a hydrocarbonoxy magnesium compound; more preferably, it is an alkoxy magnesium and / or an aryloxy magnesium.

[0030] According to a specific embodiment of the present invention, preferably, the titanium compound includes one or a combination of two or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide.

[0031] According to a specific embodiment of the present invention, preferably, the alkyl titanium halide includes one or a combination of two or more of methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride.

[0032] According to a specific embodiment of the present invention, preferably, the titanium compound is titanium tetrachloride.

[0033] According to a specific embodiment of the present invention, preferably, the molar ratio of the internal electron donor represented by formula I to the magnesium compound calculated as magnesium element is 0.01-5.0:1, preferably 0.05-3.0:1.

[0034] The present invention does not particularly limit the preparation method of the above-mentioned solid catalyst component, which can be carried out according to the following methods:

[0035] Method 1: Magnesium alcoholate or magnesium chloroalcoholate and excess TiCl 4 and an internal electron donor compound, reacting at a temperature of 80°C to 135°C; preferably, the general formula TiX N (OR b ) 4-N Titanium compounds (where R b C 1 -C 20 A hydrocarbon group, X is a halogen, N = 1-4; preferably TiCl 4 ) and the general formula is MgCl 2 ·mR a OH adduct (wherein m is a number of 0.1-6, preferably 2-4, and R a C 1 -C 20 The solid catalyst component is prepared by reacting an internal electron donor with a hydrocarbon group; wherein the general formula is MgCl 2 ·mR a The adduct of OH can be suitably made into spherical shape by the following method: in the presence of an inert hydrocarbon immiscible with the adduct, alcohol and magnesium chloride are mixed, and the emulsion is rapidly quenched, thereby solidifying the adduct in the form of spherical particles (refer to the disclosures of US4399054 and US4469648). The spherical adduct obtained in this way can be directly reacted with the titanium compound, or it can be previously subjected to heat-controlled dealcoholation (80°C-130°C) to obtain a dealcoholated adduct (wherein the molar number of alcohol is generally less than 3, preferably between 0.1-2.5), and then subjected to the subsequent reaction;

[0036] For example, the adduct or dealcoholate adduct is suspended in cold TiCl 4 (generally -25°C-0°C) to react with the titanium compound, heating the mixture to 80°C-130°C and maintaining it at this temperature for 0.5-2 hours, wherein the TiCl 4 The treatment can be performed once or multiple times, and the TiCl 4 An internal electron donor compound may be added during the treatment, and the treatment may be repeated one or more times;

[0037] Method 2: Dissolve the magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphine compound and an inert diluent to form a uniform solution, and then mix it with a titanium compound, and precipitate a solid in the presence of a precipitation aid; the solid is treated with an internal electron donor compound to load the internal electron donor compound on the solid, and if necessary, further treated with titanium tetrahalide and an inert diluent; the precipitation aid is one of an organic anhydride, an organic acid, an ether, and a ketone. The components are calculated per mole of magnesium halide, and the organic epoxy compound is 0.2-10 mol, the organic phosphine compound is 0.1-3 mol, the precipitation aid is 0-1.0 mol, and the Ti compound is 0.5-150 mol (calculated as mole of titanium element);

[0038] Method 3: Using TiCl 4 or an aromatic hydrocarbon solution of titanium alkoxide (e.g. toluene, xylene, etc.) is reacted with a dihydrocarbyl magnesium compound such as dialkoxy magnesium (preferably diethoxy magnesium) or diaryloxy magnesium at -25-0°C and halogenated at 80-130°C. The TiCl 4 The treatment with the aromatic hydrocarbon solution can be repeated once or multiple times, and the internal electron donor compound can be added once or in batches during multiple such treatments. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357 can be referred to: ethoxymagnesium, tetraethoxytitanium, o-cresol, ethanol and chlorobenzene are added in sequence and stirred; TiCl 4 / chlorobenzene solution is quickly added to the above liquid, and the temperature is raised until it is completely dissolved, and then the temperature is continued to be raised to a specific temperature; using N 2 After bubbling away the ethanol reactant, continue stirring for a certain period of time, then wash once with hot chlorobenzene, wash twice with isooctane, and then N 2 The carrier can be obtained by drying. Or according to another example: TiCl 4 , tetraethoxytitanium, ethoxymagnesium and o-cresol are added to chlorobenzene and stirred; ethanol is added and stirred for 3 hours at high temperature after the ethoxymagnesium is dissolved; hot filtering is then washed once with warm chlorobenzene, once with isooctane, and finally N 2 dry;

[0039] Method 4: Pre-activate magnesium dichloride according to the existing method, and then use excess TiCl 4 treatment, wherein an internal electron donor compound is contained in the solution. 4 The solid was treated several times and washed with hexane to remove any unreacted TiCl 4 ;

[0040] Method 5: Prepare with reference to the preparation method of titanium-containing solid catalyst component disclosed in CN1208045: first, a liquid magnesium compound and a liquid titanium compound are contacted at low temperature in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate a solid, the contact temperature is generally -70°C to 200°C, preferably -30°C to 130°C, and an internal electron donor compound is used during the contact process;

[0041] Method 6: Grind anhydrous magnesium chloride and an internal electron donor compound together under conditions where magnesium dichloride is activated. The product obtained can be treated with excess TiCl 4 The method is further described as follows: the product obtained by co-grinding magnesium dichloride, a titanium compound and an internal electron donor compound in an anhydrous state is treated with a halogenated hydrocarbon such as 1,2-dichloroethane, chlorobenzene, dichloromethane, etc., the treatment being carried out at a temperature between 40°C and the boiling point of the halogenated hydrocarbon for 1-4 hours, and then the product is usually washed with an inert hydrocarbon solvent such as hexane;

[0042] Method 7: Using SiO 2 The magnesium compound supported on inorganic oxides such as MgO, alumina or porous silica gel is used as a carrier, and then activated by a well-known method, and then an excess of TiCl 4 treatment, during which an internal electron donor compound is added.

[0043] The reaction of the above catalyst components leads to the formation of magnesium halide in an active form; general crystalline magnesium halide has a regular structure and can carry very little Ti, so the catalytic activity is low. To prepare a highly active supported catalyst, the magnesium halide must be activated; the activation treatment method includes using physical and / or chemical methods to make it into microcrystals so that the active center is loaded on the surface, edge and defect of the magnesium halide. The treated magnesium halide microcrystal suitable for loading Ti is "active magnesium halide". In addition to these reactions, other methods are also known in the literature to make compound starting materials other than magnesium halide form magnesium halide in an active form.

[0044] In any of the methods for preparing the catalyst components, the internal electron donor compound can be added directly as such or prepared in an alternative manner, such as by using a suitable precursor in situ, which can be converted into the desired internal electron donor compound, for example, by known chemical reactions such as esterification, transesterification, etc. 2In terms of molar number, the internal electron donor compound is used in a molar ratio of 0.01-5:1, preferably 0.05-3.0:1; in addition, the internal electron donor compound can be added simultaneously or separately in the preparation process in one batch or in batches, in any order and in any combination.

[0045] The present invention also provides a catalyst for olefin polymerization, which comprises the above catalyst component and an organic aluminum compound.

[0046] According to a specific embodiment of the present invention, preferably, the general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C 1 -C 20 wherein X is a halogen and p is an integer of 0≤p≤3.

[0047] According to a specific embodiment of the present invention, preferably, the organoaluminum compound includes one or a combination of two or more of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

[0048] According to a specific embodiment of the present invention, preferably, the trialkylaluminum compound includes one or a combination of two or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt 2 Cl; the alkylaluminum sesquichloride includes Al 2 E 3 Cl 3 More preferably, the organoaluminum compound is AlEt 2 Cl and Al 2 E 3 Cl 3 mixture.

[0049] According to a specific embodiment of the present invention, preferably, the molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:1, more preferably 50-800:1.

[0050] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst also includes an external electron donor.

[0051] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0052] According to a specific embodiment of the present invention, preferably, the general formula of the siloxane compound is R' t Si(OR”) 4-t, wherein R' and R" are each independently selected from C 1 -C 18 A hydrocarbon group, t is an integer of 0≤t≤3.

[0053] According to a specific embodiment of the present invention, preferably, R' and R" each contain a heteroatom.

[0054] According to a specific embodiment of the present invention, preferably, the heteroatom includes one or a combination of two or more of N, O, S, P and Si.

[0055] According to a specific embodiment of the present invention, preferably, the siloxane compound includes trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane silane, di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di(2-ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyl Dimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, amylmethyldimethoxysilane, amylmethyldiethoxysilane, amylethyldimethoxysilane, amylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyl trimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, bis(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or a combination of two or more thereof.

[0056] According to a specific embodiment of the present invention, preferably, the siloxane compound includes di-n-propyl dimethoxysilane, diisopropyl dimethoxysilane, di-n-butyl dimethoxysilane, diisobutyl dimethoxysilane, di-tert-butyl dimethoxysilane, di-n-butyl diethoxysilane, tert-butyl trimethoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, cyclohexyl methyl dimethoxysilane, cyclohexyl ethyl diethoxysilane, One or a combination of two or more of cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane and 3,5-dimethylcyclopentyldimethoxysilane.

[0057] According to a specific embodiment of the present invention, preferably, the siloxane compound includes cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyl-methoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, tert-hexyltrimethoxysilane, or a combination of two or more thereof.

[0058] According to a specific embodiment of the present invention, preferably, the molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100:1, more preferably 0.01-20:1, and further preferably 0.01-5:1.

[0059] The invention also provides application of the catalyst in olefin polymerization.

[0060] According to a specific embodiment of the present invention, preferably, the olefin includes a linear or branched olefin, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, vinylcyclohexene, one or a combination of two or more thereof.

[0061] According to a specific embodiment of the present invention, preferably, the polymerization comprises ethylene and / or propylene polymerization.

[0062] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0063] According to a specific embodiment of the present invention, preferably, during the catalytic process, the order of adding the components in the catalyst is arbitrary, preferably the organoaluminum compound is first added to the polymerization system, then the external electron donor is added, and finally the catalyst component is added.

[0064] According to a specific embodiment of the present invention, preferably, in the above application, the polymerization process can be carried out with or without a solvent; the olefin monomer can be in gas phase or liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (polymerization can also be carried out without a molecular weight regulator); continuous polymerization or batch polymerization process can be applied, and the polymerization reaction can be carried out in one step, two steps or multiple steps.

[0065] According to a specific embodiment of the present invention, preferably, the polymerization temperature is ≤200°C, more preferably 20-100°C, and further preferably 40-80°C; the polymerization pressure is ≤10MPa, more preferably 0.3-5MPa.

[0066] The present invention has the following beneficial effects:

[0067] The invention provides a catalyst component with 2,6-disubstituted oxymethyl-4-pyrone as an internal electron donor, wherein a preferred internal electron donor is 2,6-disubstituted carbonyloxymethyl-4-pyrone, and the internal electron donor compound contained in the catalyst component contains ketone, polyether or ketone, ether, ester and other oxygen-containing functional groups on a six-membered ring structure, and the stereo configuration and steric hindrance of the internal electron donor compound are conducive to the functional group participating in the formation of an active center; the catalyst prepared by using the internal electron donor compounds with multiple different substituents in the same series generally has higher activity than the catalyst of the most commonly used phthalate internal electron donor in industry, and higher than the high-activity diether catalyst, and has good stereoselectivity, high isotacticity of the polymer obtained by catalysis, and narrow overall molecular weight distribution, wherein 2,6-disubstituted oxymethyl-4-pyrone has a significantly narrowed molecular weight distribution due to the polyether structure, which is close to the molecular weight distribution of polypropylene obtained by diether. DETAILED DESCRIPTION

[0068] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0069] The isotacticity of a polymer is determined by the heptane extraction method (extraction with boiling heptane for 6 hours): two grams of a dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is then dried to a constant weight, and the ratio of the obtained polymer weight (g) to 2 is the isotacticity.

[0070] The bulk density of the polymer was determined using the JB / T 2412-2008 method.

[0071] The molecular weight distribution of the polymer was determined by a PL-220 gel permeation chromatograph using trichlorobenzene as solvent at 150°C (standard sample: polystyrene, flow rate 1.0 mL / min, column: 3×Plgel 10um M1Xed-B300×7.5nm).

[0072] Preparation Example: Synthesis of 2,6-disubstituted oxymethyl-4-pyrone compounds represented by formula I

[0073] 1. The synthesis of 2,6-dimethoxymethyl-4-pyrone is as follows:

[0074] (1) Sodium (14.2 g, 0.6 mol) was dissolved in anhydrous ethanol (200 mL) to obtain a solution for use; anhydrous acetone (17.4 g, 22.8 mL, 0.3 mol) and diethyl oxalate (93 g, 86.5 mL, 0.64 mol) were added to the above-obtained solution within 15 minutes to form a yellow precipitate; the reaction mixture was kept at 60°C for one hour, HCl (aq. 37%, 120 mL) and water (60 mL) were added, and the solution was stirred at 50°C for 20 hours, after which water and ethanol were removed under reduced pressure, and then water (170 mL) and HCl (aq. 37%, 30 mL) were added to the mixture and stirred until silica gel TLC (eluent: 3 / 7 (v / v), 10% NaCl aqueous solution / ethanol) showed only one spot. After cooling to room temperature, the crystals were filtered out, washed with water, and then washed with cold acetone. The crude product was recrystallized to obtain white powder 4-pyrone-2,6-dicarboxylic acid;

[0075] (2) In a 1L three-necked flask, add 4-pyrone-2,6-dicarboxylic acid (6.6 g), ethanol (120 mL), and concentrated sulfuric acid (0.72 mL). After heating under reflux for 2 hours, cool to room temperature; pour the reaction solution into a saturated sodium bicarbonate solution, extract twice with ethyl acetate (120 mL × 2), combine the organic phases, wash with saturated brine (120 mL × 1), concentrate and recrystallize, dissolve in 120 mL of anhydrous methanol, gradually add sodium borohydride (3.8 g), cool to -20°C in an ice-salt bath, stir for 1 hour, remove the solvent, dissolve the orange residue with water (120 ml), and then add 10% H 2 SO 4 The aqueous solution was neutralized and evaporated to dryness to obtain an orange solid product, which was dissolved in ethanol / ethyl acetate (v / v=9:1, 170 ml) and the reaction mixture was filtered and recrystallized from ethanol / petroleum ether (v / v=2:1) ​​to obtain a light brown powder 2,6-dimethanol-4-pyrone.

[0076] (3) 2,6-dimethylol-4-pyrone (7.8 g, 0.05 mol), toluene (90 ml), tetrabutylammonium hydrogen sulfate (0.283 g, 0.8335 mmol), 50% NaOH aqueous solution (45.5 g, 0.57 mol) were added to a 250 mL three-necked flask, cooled to 0°C in an ice-salt bath, and dimethyl sulfate / toluene (8.5 g / 20 ml) was added dropwise. After 0.5 h of dropwise addition, the temperature was raised to 10°C and stirred for 5 h; the temperature was raised to room temperature and stirred overnight, and water (80 ml) was added, stirred for 20 min, and the liquid was separated by extraction. The organic phase was washed with water twice (50 ml × 2), the organic phase was filtered, the filtrate was evaporated to dryness, and the oil pump was used to dryness to obtain a solid, which was recrystallized from ethanol to obtain 2,6-dimethoxymethyl-4-pyrone (a1). Its NMR data are shown in Table 1.

[0077] 2. Other 2,6-disubstituted oxymethyl-4-pyrone compounds (a2-a13) are synthesized by the above-mentioned route, or by other existing synthetic routes, for example, the starting material is selected from oxalic acid or diethyl oxalate, and then reduced after addition reaction with acetone or other ketones, and then etherified with one or two alcohols to obtain the corresponding 2,6-disubstituted oxymethyl-4-pyrone products; when reacting with two alcohols, a mixture of three products is obtained, which can be directly used as an internal electron donor composition without separation. The structures and NMR results of other 2,6-disubstituted oxymethyl-4-pyrone compounds (a2-a13) are shown in Table 1.

[0078] Synthesis of 2,6-disubstituted carbonyloxymethyl-4-pyrone compounds represented by formula II

[0079] 1. The synthesis of 2,6-dipropionyloxymethyl-4-pyrone is as follows:

[0080] The synthesis steps of 2,6-dimethanol-4-pyrone are shown in the above-mentioned synthesis method of 2,6-dimethanol-4-pyrone; 2,6-dimethanol-4-pyrone (15.5 g, 0.1 mol), dimethylpyridine (4.9 g), triethylamine (36 mL), and THF (100 mL) were added to a 250 mL five-necked flask, stirred to form a homogeneous solution, cooled to 10°C, controlled at 10-20°C, and a solution of propionyl chloride (20 mL) in THF (50 mL) was added dropwise. After the addition was complete, the mixture was stirred for 10 min, and then the temperature was raised to reflux for overnight reaction; cooled to room temperature, filtered, and the filtrate was concentrated to near dryness. A dichloromethane (200 mL) solution was added to the residue, and an aqueous solution was added to the filter cake. The aqueous solution and the dichloromethane phase were combined and separated; the organic phase was washed with HCl solution (100 mL, 1 mol / L), saturated sodium bicarbonate solution (100 mL), and saturated brine (100 mL), respectively, and then anhydrous Na 2 SO 4 The residue was dried, filtered and concentrated to dryness to obtain a crude product, which was then recrystallized to obtain the product 2,6-dipropionyloxymethyl (a14).

[0081] 2. Other 2,6-disubstituted carbonyloxymethyl-4-pyrone compounds (a15-a26) adopt the above-mentioned route (other existing synthetic routes may also be adopted), the starting material is selected from oxalic acid or diethyl oxalate, and after addition reaction with acetone or other ketones, it is reduced, and then reacted with one or two acyl chlorides for esterification to obtain the corresponding 2,6-disubstituted carbonyloxymethyl-4-pyrone products; when reacting with two acyl chlorides, a mixture of three products is obtained, which can be directly used as an internal electron donor composition without separation. The structures and NMR results of other 2,6-disubstituted carbonyloxymethyl-4-pyrone compounds (a15-a26) are shown in Table 2.

[0082]

[0083] Table 1 2,6-disubstituted oxymethyl-4-pyrone compounds represented by formula I

[0084]

[0085]

[0086]

[0087] Table 2 2,6-disubstituted acyloxymethyl-4-pyrone compounds represented by formula II

[0088]

[0089]

[0090] Preparation of catalyst components

[0091] Example 1

[0092] This embodiment provides a catalyst component, and the preparation method thereof is as follows:

[0093] In a 500 ml 5-necked flask with stirring and fully replaced with nitrogen, add 10 g MgCl 2 2.5C 2 H 5 OH microspheres and 150mL titanium tetrachloride were used to prepare a suspension, then maintained at -15°C for 1 hour, slowly heated to 80°C, 2,6-dimethoxymethyl-4-pyrone (2.8g, 15mmol) was added, and the temperature was continued to rise to 110°C for 1 hour, and the liquid was filtered clean, the liquid was filtered off, and the obtained solid was washed 3 times with 120mL titanium tetrachloride at 125°C. Then it was washed 4 times with 150mL hexane at 60°C, and finally the liquid was filtered off and dried to obtain the solid catalyst component E1. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 3.

[0094] Example 2-26

[0095] Examples 2-26 each provide a catalyst component E2-E26, the preparation process of which is as shown in Example 1, except that 2,6-dimethoxymethyl-4-pyrone is replaced with 15 mmol of compounds a2-a26 in Tables 1 and 2, respectively, in sequence.

[0096] Embodiment 27

[0097] This embodiment provides a catalyst component, and the preparation method thereof is as follows:

[0098] In a 500 ml 5-necked flask fully replaced with nitrogen and with stirring, 10 g of anhydrous magnesium chloride, 150 mL of toluene, 17 mL of epichlorohydrin and 16 mL of tributyl phosphate were added at room temperature, and the temperature was raised to 50°C with stirring and maintained for 2 hours. The solid was completely dissolved, and then 2.40 g of phthalic anhydride was added and maintained for another hour; the solution was cooled to -25°C, 110 mL of titanium tetrachloride was added dropwise within 1 hour, and the temperature was slowly raised to 80°C. During the heating process, the solid was gradually washed out, 15 mmol of 2,6-dimethoxymethyl-4-pyrone was added, and the temperature was maintained at 80°C for 1 hour; after filtering, it was washed twice with 200 mL of toluene, and then 120 mL of toluene and 80 mL of titanium tetrachloride were added, and the temperature was continued to rise to 110°C and kept constant for 2 hours, and then the liquid was filtered clean, and the treatment was repeated once, and the liquid was filtered off. The obtained solid was washed once with 100 mL of dichloroethane and 4 times with hexane, and the solid catalyst component E27 was obtained after drying. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 3.

[0099] Embodiment 28

[0100] This embodiment provides a catalyst component, and the preparation method thereof is as follows:

[0101] In a 500ml 5-necked flask with nitrogen fully replaced and stirred, 8g of diethoxymagnesium and 100mL of toluene were added to prepare a suspension, 25mL of titanium tetrachloride was added dropwise at -15°C, the temperature was slowly raised to 0°C after the addition was completed, and 50mL of titanium tetrachloride was added dropwise, and then the temperature was slowly raised to 80°C, 15mmol of 2,6-dimethoxymethyl-4-pyrone was added, and the temperature was continued to rise to 110°C and kept constant for 2 hours, and then the liquid was filtered clean, the liquid was filtered off, and the obtained solid was washed 3 times with 100mL of titanium tetrachloride at 125°C, and then washed 4 times with 120mL of hexane at 60°C, the liquid was filtered off and dried to obtain a solid catalyst component E28. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 3.

[0102] Embodiment 29

[0103] This embodiment provides a catalyst component, and the preparation method thereof is as follows:

[0104] In a 500ml 5-necked flask with nitrogen fully replaced and stirred, add 10g anhydrous magnesium chloride, 150mL toluene, 17mL epichlorohydrin and 16mL tributyl phosphate at room temperature, heat to 50℃ with stirring and maintain for 2 hours until the solid is completely dissolved, then add 2.40g phthalic anhydride and maintain for another hour; cool the solution to -25℃, add 110mL titanium tetrachloride dropwise within 1 hour, slowly heat to 80℃, gradually wash out the solid during the heating process, add 15mmo 2,6-dipropionyloxymethyl-4-pyrone, maintained at 80°C for 1 hour; after filtration, washed twice with 200mL toluene, then added 120mL toluene and 80mL titanium tetrachloride, continued to heat to 110°C, kept constant for 2 hours, then filtered the liquid clean, repeated the treatment once, filtered the liquid, the obtained solid was washed once with 100mL dichloroethane, washed 4 times with hexane, and dried to obtain solid catalyst component E29. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 3.

[0105] Embodiment 30

[0106] This embodiment provides a catalyst component, and the preparation method thereof is as follows:

[0107] In a 500ml 5-necked flask with nitrogen fully replaced and stirred, 8g of diethoxymagnesium and 100mL of toluene were added to prepare a suspension, 25mL of titanium tetrachloride was added dropwise at -15°C, and after the addition was completed, the temperature was slowly raised to 0°C, and then 50mL of titanium tetrachloride was added dropwise, and then the temperature was slowly raised to 80°C, 15mmol of 2,6-dipropionyloxymethyl-4-pyrone was added, and the temperature was continued to rise to 110°C and kept constant for 2 hours, and then the liquid was filtered clean, the liquid was filtered off, and the obtained solid was washed 3 times with 100mL of titanium tetrachloride at 125°C, and then washed 4 times with 120mL of hexane at 60°C, the liquid was filtered off and dried to obtain a solid catalyst component E30. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 3.

[0108] Comparative Example 1

[0109] This comparative example provides a catalyst component D1, and its preparation process is the same as that of Example 1, except that 2,6-dimethoxymethyl-4-pyrone is replaced by 15 mmol of di-n-butyl phthalate (DN).

[0110] Comparative Example 2

[0111] This comparative example provides a catalyst component D2, and its preparation process is the same as that of Example 1, except that 2,6-dimethoxymethyl-4-pyrone is replaced by 15 mmol of 9,9-dimethoxyfluorene (FLU).

[0112] polymerization

[0113] The above-obtained catalyst component was used as a component of an olefin polymerization catalyst to carry out polymerization evaluation:

[0114] After nitrogen is fully replaced in a 5L stainless steel reactor, 5mL of 0.5mol / L triethylaluminum hexane solution and 1mL of 0.1mol / L methylcyclohexyldimethoxysilane hexane solution and 10mg of the prepared catalyst component are added, and then 10mL of hexane is added to flush the feed line, and then 2L (under standard conditions) of hydrogen and 2.5L of refined propylene are added, and the reaction is controlled to prepolymerize at 25°C for 5 minutes, and the temperature is raised to 70°C, and the polymerization reaction is carried out at this temperature for 1 hour. After the reaction is completed, the reactor is cooled and stirring is stopped, the reaction product is discharged, and the polymer is obtained by drying. The polymerization data is shown in Table 3.

[0115] Table 3

[0116]

[0117]

[0118] As can be seen from Table 3, the catalyst components containing different 2,6-disubstituted oxymethyl-4-pyrone or 2,6-disubstituted carbonyloxymethyl-4-pyrone compounds as internal electron donors in Examples 1-26 are all more active than the catalyst containing phthalate internal electron donors in Comparative Example 1, and are higher than the diether catalyst in Comparative Example 2 under the same preparation conditions, and have good stereoselectivity, high isotacticity of the obtained polymer, and a narrow overall molecular weight distribution. Among them, 2,6-disubstituted oxymethyl-4-pyrone has a significantly narrowed molecular weight distribution due to its polyether structure, and the obtained polymer has a regular particle size and a high bulk density. Examples 27-30 are catalyst components prepared by using 2,6-disubstituted oxymethyl-4-pyrone or 2,6-disubstituted carbonyloxymethyl-4-pyrone using different preparation methods, and also show excellent properties of high activity, high stereoselectivity, and a narrow polymer molecular weight distribution.

Claims

1. A catalyst component for olefin polymerization, comprising: Mg, Ti, halogen, 2,6-disubstituted oxymethyl-4-pyrone internal electron donors; in, The 2,6-disubstituted oxymethyl-4-pyrone internal electron donor has a structure shown in Formula I: In Formula I, R 1 , R 2 , R 3 and R 4 are the same or different, each independently selected from H, halogen, C1-C 20 The hydrocarbon group; Preferably, R 1 , R 2 , R 3 and R 4 Each of the heteroatoms comprises one or a combination of two or more selected from N, O, S, P, Si and halogen; Preferably, R 1 , R 2 , R 3 and R 4 Two or more of them are bonded to each other to form a ring.

2. The catalyst component according to claim 1, wherein In Formula I, R 1 , R 2 , R 3 and R 4 the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated alkyl, alkyl containing heteroatoms, halogenated cycloalkyl, cycloalkyl containing heteroatoms, halogenated phenyl, phenyl containing heteroatoms, halogenated alkylphenyl, alkylphenyl containing heteroatoms, halogenated phenylalkyl, phenylalkyl containing heteroatoms, halogenated indenyl, indenyl containing heteroatoms, halogenated benzyl, benzyl containing heteroatoms, heterocyclic aromatic substituents; the heteroatoms include one or a combination of two or more of N, O, S, P, and Si.

3. The catalyst component according to claim 2, wherein In Formula I, R 1 , R 2 , R 3 and R 4 are each independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 The straight-chain or branched alkyl group of 20 carbon atoms or the following substituents within 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furyl, pyrrolyl, thienyl and indenyl.

4. The catalyst component according to claim 1, wherein The 2,6-disubstituted oxymethyl-4-pyrone internal electron donors include 2,6-dimethoxymethyl-4-pyrone, 2,6-diethyloxymethyl-4-pyrone, 2,6-dipropyloxymethyl-4-pyrone, 2,6-dibutyloxymethyl-4-pyrone, 2,6-dipentyloxymethyl-4-pyrone, 2,6-dihexyloxymethyl-4-pyrone, 2,6-diheptyloxymethyl-4-pyrone. , 2,6-dioctyloxymethyl-4-pyrone, 2,6-di(dodecyl)oxymethyl-4-pyrone, 2,6-di(tetradecyl)oxymethyl-4-pyrone, 2,6-di(hexadecyl)oxymethyl-4-pyrone, 2,6-diphenyloxymethyl-4-pyrone, 2,6-diphenyloxymethyl-4-pyrone, 2,6-di(m-chlorophenyl)oxymethyl-4-pyrone, 2,6-di(o-chlorophenyl)oxymethyl-4-pyrone Oxymethyl-4-pyrone, 2,6-di-p-chlorophenyloxymethyl-4-pyrone, 2,6-di-p-methylphenyloxymethyl-4-pyrone, 2,6-di-p-methoxyphenyloxymethyl-4-pyrone, 2,6-difuryloxymethyl-4-pyrone, 2,6-dipropyleneoxymethyl-4-pyrone, 2,6-dimethoxymethyl-3,5-dimethyl-4-pyrone, 2,6-dimethoxymethyl-3-methyl- 5-ethyl-4-pyrone, 2,6-dimethoxymethyl-3,5-diethyl-4-pyrone, 2,6-dimethoxymethyl-3,5-dibutyl-4-pyrone, 2,6-dimethoxymethyl-3-ethyl-5-butyl-4-pyrone, 2,6-dimethoxymethyl-3-methyl-5-butyl-4-pyrone, 2-methoxymethyl-6-ethyloxymethyl-4-pyrone, or a combination of two or more thereof.

5. The catalyst component according to claim 1, wherein The 2,6-disubstituted oxymethyl-4-pyrone internal electron donor has a structure shown in Formula II: In formula II, R 5 , R 6 , R 7 and R 8 are the same or different, each independently selected from H, halogen, C1-C 20 Preferably, R 5 , R 6 , R 7 and R 8 Each of the heteroatoms comprises one or a combination of two or more selected from N, O, S, P, Si and halogen; preferably, R 5 , R 6 , R 7 and R 8 Two or more of them are bonded to each other to form a ring.

6. The catalyst component according to claim 5, wherein The 2,6-disubstituted oxymethyl-4-pyrone internal electron donors include 2,6-dipropionyloxymethyl-4-pyrone, 2,6-dibutyryloxymethyl-4-pyrone, 2,6-divaleryloxymethyl-4-pyrone, 2,6-dihexanoyloxymethyl-4-pyrone, 2,6-dicyclohexanoyloxymethyl-4-pyrone, 2,6-dinonanoyloxymethyl-4-pyrone, 2,6-di(tridecanoyl)oxymethyl-4-pyrone, 2 ,6-dipentadecanoyloxymethyl-4-pyrone, 2,6-di(heptadecanoyl)oxymethyl-4-pyrone, 2,6-dibenzoyloxymethyl-4-pyrone, 2,6-di-m-chlorobenzoyloxymethyl-4-pyrone, 2,6-di-p-toluoyloxymethyl-4-pyrone, 2,6-di-o-chlorobenzoyloxymethyl-4-pyrone, 2,6-di-p-chlorobenzoyloxymethyl-4-pyrone, 2,6-di-p-chlorobenzoyloxymethyl-4-pyrone, 2,6-di-p-methoxybenzoyloxy 2,6-dibenzoyloxymethyl-4-pyrone, 2,6-dibenzoyloxymethyl-3,5-dimethyl-4-pyrone, 2,6-dibenzoyloxymethyl-3,5-diethyl-4-pyrone, 2,6-dibenzoyloxymethyl-3,5-dipropyl-4-pyrone, 2,6-dibenzoyloxymethyl-3,5-dibutyl-4-pyrone, 2,6-dibenzoyloxymethyl-3-methyl-5-ethyl-4-pyrone, The invention can be selected from the group consisting of 2,6-dibenzoyloxymethyl-3-ethyl-5-butyl-4-pyrone, 2,6-dibenzoyloxymethyl-3-methyl-5-butyl-4-pyrone, 2,6-dibenzoyloxymethyl-3-methyl-5-phenyl-4-pyrone, 2-propionyloxymethyl-6-pentanoyloxymethyl-4-pyrone, and 2-benzoyloxymethyl-6-p-methylbenzoyloxymethyl-4-pyrone, or a combination of two or more thereof.

7. The catalyst component according to any one of claims 1 to 6, wherein The catalyst component comprises a titanium compound, a magnesium compound, and an internal electron donor as shown in formula I; The precursor of the magnesium compound is selected from X n Mg(OR a ) 2-n 、MgCl2·mR a OH, R a 2-n MgX n , MgCl2 / SiO2, MgCl2 / Al2O3, a mixture of magnesium halide and titanium alkoxide, or a combination of two or more thereof, wherein m is 0.1-6, 0≤n≤2, X is a halogen, R a C1-C 20 The hydrocarbon group; The general formula of the titanium compound is TiX N (OR b ) 4-N , where R b C1-C 20 The hydrocarbon group is: X is halogen, and N is 1-4.

8. The catalyst component according to claim 7, wherein The magnesium compound is an alcoholate of magnesium dihalide; Alternatively, the magnesium compound is a liquid magnesium compound; Alternatively, the magnesium compound is a derivative of a magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; preferably, it is a hydrocarbonoxy magnesium compound; more preferably, it is an alkoxy magnesium and / or an aryloxy magnesium.

9. The catalyst component according to claim 7, wherein The titanium compound includes one or a combination of two or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide; Preferably, the alkyl titanium halide includes one or a combination of two or more of methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride; Preferably, the titanium compound is titanium tetrachloride.

10. The catalyst component according to claim 7, wherein The molar ratio of the internal electron donor shown in formula I to the magnesium compound is 0.01-5.0:1, preferably 0.05-3.0:1, and the magnesium compound is calculated as magnesium element.

11. A catalyst for olefin polymerization, comprising the catalyst component according to any one of claims 1 to 10 and an organic aluminum compound.

12. The catalyst according to claim 11, wherein The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C1-C 20 A hydrocarbon group, X is a halogen, and p is an integer of 0≤p≤3; Preferably, the organoaluminum compound comprises one or a combination of two or more of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes; Preferably, the trialkylaluminum compound includes one or a combination of two or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; the alkylaluminum sesquichloride includes Al2Et3Cl3; Preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

13. The catalyst according to claim 11, wherein The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:1, preferably 50-800:

1.

14. The catalyst according to claim 11, wherein The raw material composition of the catalyst also includes an external electron donor.

15. The catalyst according to claim 14, wherein The external electron donor is a siloxane compound.

16. The catalyst according to claim 15, wherein The general formula of the siloxane compound is R' t Si(OR”) 4-t , wherein R' and R" are each independently selected from C1-C 18 A hydrocarbon group, t is an integer of 0≤t≤3; Preferably, R' and R" each contain a heteroatom; Preferably, the heteroatom includes one or a combination of two or more of N, O, S, P and Si.

17. The catalyst according to claim 14, wherein The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100:1, preferably 0.01-20:1, and more preferably 0.01-5:

1.

18. Use of the catalyst according to any one of claims 11 to 17 in olefin polymerization; Preferably, the olefin includes one or a combination of two or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene; Preferably, the polymerization comprises ethylene and / or propylene polymerization; Preferably, the polymerization comprises homopolymerization or copolymerization.

19. The use according to claim 18, wherein: The polymerization temperature is ≤200°C, preferably 20-100°C, more preferably 40-80°C; The polymerization pressure is ≤10 MPa, preferably 0.3-5 MPa.

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