A catalyst component for the polymerization of olefins, a catalyst and use thereof

Abstract

The application provides a catalyst component for olefin polymerization, a catalyst and application thereof; the composition of the catalyst component comprises: Mg, Ti, halogen, 2,6-disubstituted oxymethyl-4-pyrone internal electron donor; wherein the 2,6-disubstituted oxymethyl-4-pyrone internal electron donor has the structure shown in formula I: the catalytic activity of the catalyst component and the catalyst is high, is generally higher than that of an o-phthalate internal electron donor catalyst and a diether internal electron donor catalyst 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.

Description

TECHNICAL FIELD

[0001] The present application relates to a solid catalyst component for olefin polymerization, belonging to the field of polyolefin catalysts. BACKGROUND

[0002] At present, Ziegler-Natta catalysts (Z-N catalysts) still dominate in the production of polyolefins. Most of the development of Z-N catalysts aims at the development of high-activity and highly stereospecific catalysts and the improvement of the copolymerization ability of the catalysts. Moreover, due to the high catalytic efficiency of traditional Z-N catalysts (transition metal compounds such as titanium chemically bonded on a magnesium-containing carrier), the comprehensive performance of the produced polymers is good, and the cost is low. At present, most of the catalysts for producing polypropylene in the world are still based on Z-N catalytic systems, and the characteristics are high activity, high stereoregularity, long service life and product structure customization. From the development process of Z-N catalysts, it can be seen that as early as the first generation of catalysts appeared, it was found that the addition of a third component (mostly electron donors, also known as Lewis bases, among which, the addition in the catalyst preparation process is called internal electron donor, and the addition in the polymerization process is called external electron donor) can greatly affect the olefin polymerization behavior and the properties of the polymers. Changing the internal electron donor in the catalyst can maximize the change in the properties of the active centers of the catalyst, thereby maximizing the change in the performance of the catalyst. Therefore, the development of new electron donors has always been a hot spot in the research and development of Z-N polypropylene catalysts.

[0003] The high-performance internal electron donor compounds with relatively distinctive features in the prior art mainly include: (1) fatty acid ester and aromatic acid ester compounds, mainly represented by phthalate compounds; (2) diether compounds (such as the compounds disclosed in EP0361493 and EP0728724); (3) succinate compounds (such as the compounds disclosed in WO9856834, WO0063261 and WO03022894); (4) diol ester compounds (such as the compounds disclosed in WO9856834, WO0063261 and WO03022894); (5) other functional group compounds (such as the compounds disclosed in CN1105671, CN1242780 and US20060128558); and the like. However, in actual application, the above-mentioned compounds as internal electron donors for olefin polymerization catalysts all have certain problems. Although the catalysts using 1,3-diether compounds as internal electron donors have high activity and good hydrogen regulation 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 succinate compounds as internal electron donors have the advantage that the relative molecular mass distribution of the synthesized PP is wide, but the stereoregularity of the PP and the hydrogen regulation sensitivity of the catalyst need to be improved. The activity of the diol ester catalyst system as a whole is not as ideal as that of the diether system.

[0004] The most widely used polyolefin internal electron donor in the industry at present is phthalate compounds, and the catalyst prepared therefrom has moderate activity, good stereoselectivity and low price. However, phthalate compounds are commonly used plasticizers, which have great harm to human reproductive health and environment, and thus have great demand for substitution. At present, the use of most phthalate compounds has been limited. Therefore, it is one of the common research and development goals in the field of polyolefin catalysts in recent years to develop a new type of internal electron donor with good activity, good stereodirecting property, good comprehensive performance and low cost, to replace the widely used phthalate internal electron donor compounds in the prior art and apply it to the preparation of high-efficiency Ziegler-Natta catalyst. SUMMARY

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

[0006] In order to achieve the above purpose, the present application 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 the structure shown in formula I:

[0007]

[0008] In formula I, R 1 , R 2 , R 3 and R 4 are the same or different, and each is independently selected from H, halogen, C1-C 20 hydrocarbon group; preferably, R 1 , R 2 , R 3 and R 4 respectively contain one or more than two combinations of heteroatoms selected from N, O, S, P, Si and halogen; more preferably, two or more of R 1 , R 2 , R 3 and R 4 are bonded to each other to form a ring.

[0009] According to a specific embodiment of the present application, preferably, in formula I, R 1 , R 2 , R 3 and R 4the same or different, each independently selected from the group consisting of H, halogen, the following substituents within 20 carbon atoms: straight chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, haloalkyl, heteroatom-containing alkyl, halocycloalkyl, heteroatom-containing cycloalkyl, halophenyl, heteroatom-containing phenyl, haloalkylphenyl, heteroatom-containing alkylphenyl, halophenylalkyl, heteroatom-containing phenylalkyl, haloindenyl, heteroatom-containing indenyl, halobenzyl, heteroatom-containing benzyl, heterocyclic aryl substituents; said heteroatoms include one or a combination of more than one of N, O, S, P, Si.

[0010] According to a specific embodiment of the present application, preferably, in formula I, R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of H, halogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 straight chain or branched alkyl of C 20 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, furanyl, pyrrolyl, thienyl, indenyl; more preferably, said alkenyl includes propenyl, butenyl, pentenyl, hexenyl.

[0011] According to a specific embodiment of the present application, preferably, the 2,6-disubstituted oxymethyl-4-pyrone internal electron donor includes one or more than two combinations of 2,6-dimethoxymethyl-4-pyrone, 2,6-diethyloxymethyl-4-pyrone, 2,6-dipropoxymethyl-4-pyrone, 2,6-dibutoxymethyl-4-pyrone, 2,6-dipentoxymethyl-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-dibenzyl-oxymethyl-4-pyrone, 2,6-di(m-chlorophenyl)oxymethyl-4-pyrone, 2,6-di(o-chlorophenyl)oxymethyl-4-pyrone, 2,6-di(p-chlorophenyl)oxymethyl-4-pyrone, 2,6-di(p-methylphenyl)oxymethyl-4-pyrone, 2,6-di(p-methoxyphenyl)oxymethyl-4-pyrone, 2,6-difuryloxymethyl-4-pyrone, 2,6-dipropenyloxymethyl-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.

[0012] According to a specific embodiment of the present application, 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, C1-C 20 hydrocarbon group; preferably, R 5 , R 6 , R 7 and R 8 respectively contain one or more than two combinations of heteroatoms selected from N, O, S, P, Si and halogen; preferably, R 5 , R 6 , R 7 and R 8two or more of the substituents in the above formula are linked to each other to form a ring.

[0015] According to a specific embodiment of the present application, preferably, the 2,6-disubstituted oxymethyl-4-pyrone internal electron donor includes one or more than two of 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-di(pentadecanoyl)oxymethyl-4-pyrone, 2,6-di(heptadecanoyl)oxymethyl-4-pyrone, 2,6-dibenzoyloxymethyl-4-pyrone, 2,6-di(m-chlorobenzoyl)oxymethyl-4-pyrone, 2,6-di(p-methylbenzoyl)oxymethyl-4-pyrone, 2,6-di(o-chlorobenzoyl)oxymethyl-4-pyrone, 2,6-di(p-chlorobenzoyl)oxymethyl-4-pyrone, 2,6-di(p-methoxybenzoyl)oxymethyl-4-pyrone, 2,6-di(p-nitrobenzoyl)oxymethyl-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, 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-valeryloxymethyl-4-pyrone, and 2-benzoyloxymethyl-6-p-methylbenzoyloxymethyl-4-pyrone.

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

[0017] The synthesis route is shown in reaction formula I, diethyl oxalate is reacted with a corresponding ketone and then 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-pyrone compounds, which can be directly used as an internal electron donor without separation. The proportion of each component in the mixture can be adjusted by the addition proportion of the two alcohols in the reactants, and the proportion of each component can be determined by chromatography-mass spectrometry technology, nuclear magnetic resonance, etc.

[0018] Reaction Formula I:

[0019]

[0020] Reaction Formula II:

[0021]

[0022] The 2,6-disubstituted carbonyloxymethyl-4-pyrone shown in Formula II can be synthesized by a preparation method including but not limited to the following:

[0023] The synthesis route is shown in Reaction Formula III. After diethyl oxalate reacts with a corresponding ketone and is then reduced, a substituted 2,6-dimethanol-4-pyrone compound is obtained. Then, the compound reacts with an acyl chloride compound to obtain a 2,6-disubstituted carbonyloxymethyl-4-pyrone compound, or reacts 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. Without separation, the mixture is directly used as an internal electron donor. The proportion of each component in the mixture can be adjusted by the addition proportion of the two acyl chloride compounds in the reactants. The proportion of each component can be determined by chromatography-mass spectrometry technology, nuclear magnetic resonance, and the like.

[0024] Reaction Formula III:

[0025]

[0026] Reaction Formula IV:

[0027]

[0028] According to a specific embodiment of the present application, preferably, the composition of the catalyst component comprises a titanium compound, a magnesium compound, and an internal electron donor shown in Formula I; the precursor of the magnesium compound is selected from one or more than two combinations of 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 alcoholate, wherein m is 0.1-6, 0≤n≤2, X is halogen, R a is a C1-C 20 hydrocarbon group; the general formula of the titanium compound is TiX N (OR b ) 4-N , wherein R b is a C1-C20 hydrocarbyl group, X is halogen, and N is 1-4.

[0029] According to a specific embodiment of the present application, preferably, the magnesium compound is an alcoholate of a 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 a magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarboxy group or a halogenated hydrocarboxy group; preferably, a magnesium hydrocarboxy compound; more preferably, an alkyl magnesium and / or an aryl magnesium.

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

[0031] According to a specific embodiment of the present application, preferably, the titanium alkyl halide comprises one or a combination of two or more of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

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

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

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

[0035] Method 1: reacting an alcoholate of magnesium or a chlorohydrate of magnesium with an excess of TiCl4 and an internal electron donor compound at a temperature of 80°C-135°C; preferably, a titanium compound represented by the general formula TiX N (OR b ) 4-N (wherein R b is a C1-C 20 hydrocarbyl group, X is halogen, and N is 1-4; preferably, TiCl4) and an adduct represented by the general formula MgCl2-mR a OH (wherein m is a number of 0.1-6, preferably 2-4, and R a is a C1-C 20 hydrocarbyl group) and an internal electron donor; wherein the solid catalyst component is prepared. aThe adduct of OH can be suitably made spherical by mixing the alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, rapidly quenching the emulsion so that the adduct solidifies in the form of spherical particles (cf. the disclosures of US 4399054 and US 4469648). The spherical adduct obtained in this way can be reacted directly with the titanium compound, or it can be previously subjected to a thermally controlled dealcoholation (80°C-130°C) to obtain a dealcoholated adduct (in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5), followed by the subsequent reaction;

[0036] For example, the reaction with the titanium compound is carried out by suspending the adduct or dealcoholated adduct in cold TiCl4(generally -25°C-0°C), heating the mixture of the two to 80°C-130°C and maintaining it at this temperature for 0.5-2 hours, where the treatment with TiCl4can be carried out once or more times and the internal donor compound can be added during the treatment with TiCl4, which can be repeated once or more times;

[0037] Method 2: the magnesium compound is dissolved in a solvent system consisting of an organic epoxide compound, an organic phosphine compound and an inert diluent, a homogeneous solution is formed and then mixed with the titanium compound, in the presence of a co-precipitant, a solid is precipitated; this solid is treated with the internal donor compound, so that the internal donor compound is supported on the solid, and if necessary, further treated with titanium tetrahalide and an inert diluent; the co-precipitant is one of an organic acid anhydride, an organic acid, an ether, a ketone. The components are used in amounts of 0.2-10 mol of organic epoxide compound, 0.1-3 mol of organic phosphine compound, 0-1.0 mol of co-precipitant, and 0.5-150 mol (in terms of titanium element) of Ti compound per mole of magnesium halide;

[0038] Method three: reaction of TiCl4or an aromatic solution of a hydrocarbyloxytitanium compound (e.g. toluene, xylene, etc.) at -25 to 0°C with a dihydrocarbyloxymagnesium compound such as a dialkoxy magnesium (preferably diethoxy magnesium) or diaryloxy magnesium and halogenation at 80 to 130°C. The treatment with TiCl4in an aromatic can be repeated one or more times and the internal donor compound can be added in one or more portions during the course of the treatment. For example, the preparation of a titanium containing solid catalyst component can be carried out as disclosed in US 5 077 357 by adding ethyl magnesium chloride, titanium tetraethoxide, o-cresol, ethanol and chlorobenzene in this order with stirring; the TiCl4in chlorobenzene solution is added rapidly to the above liquid, after complete dissolution by warming, the temperature is increased to a specific temperature; after the ethanol reactant is removed by bubbling N2through the solution, the stirring is continued for a certain period of time, then a washing with hot chlorobenzene is carried out once, a washing with isooctane is carried out twice and then the product is dried with N2;

[0039] Method four: the pre-activation of magnesium dichloride is carried out according to the prior art and then the product is treated with an excess of TiCl4at a temperature of about 80 to 135°C in the presence of an internal donor compound in solution. The treatment with TiCl4is carried out several times and the solid is washed with hexane to remove any unreacted TiCl4;

[0040] Method five: the preparation of a titanium containing solid catalyst component can be carried out as disclosed in CN 1208045 by contacting a liquid magnesium compound and a liquid titanium compound at a low temperature in the presence of a compound selected from the group consisting of alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters, the temperature of the contacting is generally from -70°C to 200°C, preferably from -30°C to 130°C, and the contacting is carried out in the presence of an internal donor compound;

[0041] Method six: anhydrous magnesium chloride and an internal donor compound are ground together under conditions of activation of the magnesium dichloride, the product thus obtained can be treated with an excess of TiCl4at a temperature of 80 to 130°C for one or more times and the product is washed with a hydrocarbon solvent until it is free of chloride ions. In further detail: the product obtained by co-grinding anhydrous magnesium dichloride, a titanium compound and an internal donor compound is treated with a halogenated hydrocarbon such as 1,2-dichloroethane, chlorobenzene, dichloromethane, etc. at a temperature between 40°C and the boiling point of the halogenated hydrocarbon for a period of time of 1 to 4 hours and then the product is washed with an inert hydrocarbon solvent such as hexane, etc;

[0042] Method seven: the catalyst component is prepared using a magnesium compound supported on inorganic oxides such as SiO2, alumina or porous silica gel, then activated by well-known methods and treated with excess TiCl4at a temperature of from about 80°C to about 135°C, adding an internal electron donor compound during the treatment.

[0043] The reactions of the above catalyst components result in the formation of magnesium halide in an active form; the crystalline magnesium halide is generally regular and has a low Ti loading, thus having low catalytic activity; to prepare a supported catalyst with high activity, the magnesium halide must be subjected to an activation treatment; the activation treatment consists in making it microcrystalline by physical and / or chemical methods, so that the active centres are available on the surface, edges and defects of the magnesium halide; the microcrystalline magnesium halide thus treated, which is suitable for loading with Ti, is "active magnesium halide". In addition to these reactions, other methods are known from the literature for obtaining active magnesium halide starting from compounds other than magnesium halide.

[0044] In any of the methods for preparing the catalyst component, the above internal electron donor compound can be added directly as such or by alternative means, for example by using a suitable precursor which is converted in situ in the desired internal electron donor compound, for example by known chemical reactions such as esterification, transesterification and the like. Generally, the internal electron donor compound is used in a molar ratio of from 0.01 to 5:1, preferably from 0.05 to 3.0:1, with respect to the number of moles of MgCl2; furthermore, the internal electron donor compound can be added in one batch or in several batches, simultaneously or separately, in any order and in any combination.

[0045] The present application also provides a catalyst for the polymerization of olefins, which comprises the above catalyst component and an organic aluminium compound.

[0046] According to a specific embodiment of the present application, preferably, the organic aluminium compound has the general formula AlR c p X (3-p) wherein R c is hydrogen or a C1-C 20 hydrocarbon group, X is halogen and p is an integer from 0 to 3.

[0047] According to a specific embodiment of the present application, preferably, the organic aluminium compound comprises one or a combination of two or more of a trialkyl aluminium compound, an alkyl aluminium halide, an alkyl aluminium hydride, an alkyl aluminium sesquichloride, an alkyl aluminium oxide.

[0048] According to a specific embodiment of the present application, preferably, the trialkyl aluminum compound comprises one or more than two combinations of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, trioctyl aluminum; the alkyl aluminum halide comprises AlEt2Cl; the alkyl aluminum sesquichloride comprises Al2Et3Cl3; more preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0049] According to a specific embodiment of the present application, preferably, the molar ratio of the organoaluminum 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 application, preferably, the raw material composition of the catalyst further comprises an external electron donor.

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

[0052] According to a specific embodiment of the present application, preferably, 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 hydrocarbon group, and t is an integer of 0≤t≤3.

[0053] According to a specific embodiment of the present application, preferably, R’ and R” each comprises a heteroatom.

[0054] According to a specific embodiment of the present application, preferably, the heteroatom comprises one or more than two combinations of N, O, S, P, Si.

[0055] According to a particular embodiment of the application, preferably, the siloxane compound comprises 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-t-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-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-propyldimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethyl-ethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, t-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,one or more than two of 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3- methylcyclohexylcyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4- methylcyclohexylcyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,5- dimethylcyclohexylcyclohexyldimethoxysilane, di(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, tetrabutoxysilane.

[0056] According to a specific embodiment of the present application, preferably, the siloxane compound comprises one or more than two of di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldiethoxysilane, tert- butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3- methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclopentyldimethoxysilane.

[0057] According to a specific embodiment of the present application, preferably, the siloxane compound comprises one or more than two of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2- ethylpiperidinyl dimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyl dimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, tert-hexyltrimethoxysilane.

[0058] According to a specific embodiment of the present application, 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 present application also provides the use of the above-mentioned catalyst in the polymerization of olefins.

[0060] According to a specific embodiment of the present application, preferably, the olefin includes one or a combination of two or more of linear or branched olefins, 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, and vinylcyclohexene.

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

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

[0063] According to a specific embodiment of the present application, preferably, in the catalytic process, the order of adding the components in the catalyst is arbitrary, and it is preferable that the organic aluminum 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 application, preferably, in the above application, the polymerization process can be carried out with or without a solvent; the olefin monomer can be in a gas phase or a liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (the polymerization can also be carried out without a molecular weight regulator); both continuous polymerization and batch polymerization processes 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 application, preferably, the temperature of the polymerization is ≤200℃, more preferably 20-100℃, and further preferably 40-80℃; the pressure of the polymerization is ≤10MPa, more preferably 0.3-5MPa.

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

[0067] The present application provides a catalyst component with 2,6-disubstituted oxymethyl-4-pyrone as an internal electron donor, wherein one type of preferred internal electron donor is 2,6-disubstituted oxymethyl-4-pyrone. The internal electron donor compound contained in the catalyst component contains ketone, polyether, or ketone, ether, ester, etc. oxygen-containing functional groups in the six-membered ring structure, and its stereochemical configuration and steric hindrance are conducive to the formation of functional groups participating in the active center. The catalyst prepared by the internal electron donor compound of the same series with different substituents has a higher activity than the catalyst with the most commonly used phthalate internal electron donor in industry, and is 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. The 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, objectives and beneficial effects of the present application, the technical solutions of the present application are described in detail as follows, but it should not be understood as a limitation to the implementable scope of the present application.

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

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

[0071] The determination of the molecular weight distribution of the polymer is determined by PL-220 gel permeation chromatography with trichlorobenzene as the solvent at 150°C (standard sample: polystyrene, flow rate 1.0 mL / min, column: 3xPlgel 10um M1Xed-B300x7.5nm).

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

[0073] 1. Synthesis of 2,6-dimethoxymethyl-4-pyrone, the steps are as follows:

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

[0075] (2) In a 1 L three-necked flask, 4-pyrone-2,6-dicarboxylic acid (6.6 g), ethanol (120 mL), concentrated sulfuric acid (0.72 mL) were added, heated to reflux for 2 h, then cooled to room temperature; the reaction solution was poured into saturated sodium bicarbonate solution, extracted with ethyl acetate twice (120 mL x 2), the organic phase was combined, washed with saturated brine (120 mL x 1), concentrated, recrystallized, then dissolved in 120 mL of anhydrous methanol, sodium borohydride (3.8 g) was added gradually, cooled to -20 °C in an ice-salt bath, stirred for 1 h, then the solvent was removed, the orange residue was dissolved in water (120 mL), then neutralized with 10% H2SO4 aqueous solution, 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, recrystallized from ethanol / petroleum ether (v / v = 2:1) to obtain light brown powder 2,6-dimethanol-4-pyrone.

[0076] (3) In a 250 mL three-necked flask, 2,6-dimethanol-4-pyrone (7.8 g, 0.05 mol), toluene (90 mL), tetra-n-butylammonium hydrogen sulfate (0.283 g, 0.8335 mmol), 50% NaOH aqueous solution (45.5 g, 0.57 mol) were added, cooled to 0 °C in an ice-salt bath, dimethyl sulfate / toluene (8.5 g / 20 mL) was added dropwise, the temperature was raised to 10 °C after 0.5 h, stirred for 5 h; the temperature was raised to room temperature, stirred overnight, water (80 mL) was added, stirred for 20 min, then extracted with water twice (50 mL x 2), the organic phase was filtered, the filtrate was evaporated to dryness, then dried with an oil pump to obtain a solid, which was recrystallized from ethanol to obtain 2,6-dimethoxymethyl-4-pyrone (al). Its NMR data are shown in Table 1.

[0077] 2, Other 2,6-disubstituted oxymethyl-4-pyrone compounds (a2-a13) were synthesized by the above route, or other existing synthesis routes, for example, starting from oxalic acid or diethyl oxalate, addition reaction with acetone or other ketones, then reduction, and etherification with one or two alcohols to obtain the corresponding 2,6-disubstituted oxymethyl-4-pyrone product; when reacted 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 of formula II

[0079] 1, Synthesis of 2,6-dipropionyloxymethyl-4-pyrone, the steps are as follows:

[0080] The synthesis of 2,6-dimethyloxymethyl-4-pyrone is described above; in a 250 mL flask, 2,6-dimethyloxymethyl-4-pyrone (15.5 g, 0.1 mol), dimethylpyridine (4.9 g), triethylamine (36 mL), THF (100 mL) were added and stirred to form a homogeneous solution. The solution was cooled to 10 °C and a solution of propionyl chloride (20 mL) in THF (50 mL) was added dropwise at a temperature of 10-20 °C. After the addition was completed, the solution was stirred for 10 min and then warmed to reflux overnight. The solution was cooled to room temperature, filtered, and the filtrate was concentrated to near dryness. The residue was dissolved in dichloromethane (200 mL) and the solution was filtered. The filtrate was combined with the aqueous solution and the two phases were separated. The organic phase was washed with HCl solution (100 mL, 1 mol / L), saturated NaHCO3solution (100 mL), and saturated brine (100 mL), dried over anhydrous Na2SO4, filtered, and concentrated to dryness to give a crude product. The product, 2,6-dipropionyloxymethyl-4-pyrone (a14), was obtained by recrystallization.

[0081] 2. Other 2,6-disubstituted carbonyloxymethyl-4-pyrone compounds (a15-a26) were synthesized using the above route (or other existing synthetic routes) starting from oxalic acid or diethyl oxalate, which was added to ketone such as acetone or other ketones, followed by reduction and esterification with one or two acyl chlorides to give the corresponding 2,6-disubstituted carbonyloxymethyl-4-pyrone products. When two acyl chlorides were used, a mixture of three products was obtained, which was used directly 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 of Formula I

[0084]

[0085]

[0086]

[0087] Table 2. 2,6-disubstituted acyloxymethyl-4-pyrone compounds of Formula II

[0088]

[0089]

[0090] Preparation of catalyst components

[0091] Example 1

[0092] This example provides a catalyst component prepared as follows:

[0093] Into a 500 ml 5 neck flask with stirring, nitrogen sparging, and a temperature probe, was added 10 g of MgCl2.2.5C2H5OH microspheres and 150 mL of titanium tetrachloride to make a suspension. The suspension was maintained at -15 °C for 1 hour, then slowly warmed to 80 °C. 2,6-dimethoxymethyl-4-pyrone (2.8 g, 15 mmol) was added and the temperature was increased to 110 °C and held for 1 hour. The liquid was then filtered off and the resulting solid was washed with 120 mL of titanium tetrachloride at 125 °C for 3 times. Then it was washed with 150 mL of hexane at 60 °C for 4 times. Finally the liquid was filtered off and the solid catalyst component E1 was obtained. The titanium content, internal donor content, and polymerization data for this solid catalyst component are shown in Table 3.

[0094] Examples 2-26

[0095] Examples 2-26 each provide a catalyst component E2-E26 prepared as shown in Example 1, except that 2,6-dimethoxymethyl-4-pyrone was replaced in order by 15 mmol of the compound a2-a26 in Table 1 and Table 2, respectively.

[0096] Example 27

[0097] This example provides a catalyst component prepared as follows:

[0098] Into a 500 ml 5 neck flask with stirring, nitrogen sparging, and a temperature probe, was added 10 g of MgCl2.2.5C2H5OH microspheres and 150 mL of titanium tetrachloride to make a suspension. The suspension was maintained at -15 °C for 1 hour, then slowly warmed to 80 °C. 2,6-dimethoxymethyl-4-pyrone (2.8 g, 15 mmol) was added and the temperature was increased to 110 °C and held for 1 hour. The liquid was then filtered off and the resulting solid was washed with 120 mL of titanium tetrachloride at 125 °C for 3 times. Then it was washed with 150 mL of hexane at 60 °C for 4 times. Finally the liquid was filtered off and the solid catalyst component E1 was obtained. The titanium content, internal donor content, and polymerization data for this solid catalyst component are shown in Table 3.

[0099] Example 28

[0100] This example provides a catalyst component prepared as follows:

[0101] In a 500 mL 5-neck flask with stirring, thoroughly replaced with nitrogen, was added 8 g of diethoxy magnesium and 100 mL of toluene to make a suspension. At -15 °C, 25 mL of titanium tetrachloride was added dropwise. After the addition was complete, the temperature was slowly increased to 0 °C, and then 50 mL of titanium tetrachloride was added dropwise. The temperature was then slowly increased to 80 °C, and then 15 mmol of 2,6-dimethoxymethyl-4-pyrone was added. The temperature was then increased to 110 °C and held for 2 hours. The liquid was then filtered off, and the resulting solid was washed with 100 mL of titanium tetrachloride at 125 °C for 3 times, and then with 120 mL of hexane at 60 °C for 4 times. The liquid was filtered off and dried to obtain the solid catalyst component E28. The titanium content, internal donor content, and polymerization data for this solid catalyst component are shown in Table 3.

[0102] Example 29

[0103] This example provides a catalyst component prepared as follows:

[0104] In a 500 mL 5-neck flask with stirring, thoroughly replaced with nitrogen, was added 8 g of diethoxy magnesium and 100 mL of toluene to make a suspension. At -15 °C, 25 mL of titanium tetrachloride was added dropwise. After the addition was complete, the temperature was slowly increased to 0 °C, and then 50 mL of titanium tetrachloride was added dropwise. The temperature was then slowly increased to 80 °C, and then 15 mmol of 2,6-dimethoxymethyl-4-pyrone was added. The temperature was then increased to 110 °C and held for 2 hours. The liquid was then filtered off, and the resulting solid was washed with 100 mL of titanium tetrachloride at 125 °C for 3 times, and then with 120 mL of hexane at 60 °C for 4 times. The liquid was filtered off and dried to obtain the solid catalyst component E28. The titanium content, internal donor content, and polymerization data for this solid catalyst component are shown in Table 3.

[0105] Example 30

[0106] This example provides a catalyst component prepared as follows:

[0107] A suspension was prepared by adding 8 g of diethoxy magnesium and 100 mL of toluene in a 500 mL 5 neck flask with stirring and nitrogen sparging. 25 mL of titanium tetrachloride was added dropwise at -15 °C. After the addition was complete, the temperature was slowly increased to 0 °C and 50 mL of titanium tetrachloride was added dropwise. The temperature was then slowly increased to 80 °C and 15 mmol of 2,6-dipropionyloxymethyl-4-pyrone was added. The temperature was then increased to 110 °C and held for 2 hours. The liquid was then filtered off and the solid was washed with 100 mL of titanium tetrachloride at 125 °C for 3 times and then with 120 mL of hexane at 60 °C for 4 times. The liquid was filtered off and the solid was dried to give the solid catalyst component E30. The titanium content, internal 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 which was prepared in the same manner as Example 1 except that 2,6-dimethoxymethyl-4-pyrone was replaced with 15 mmol of di-n-butyl phthalate (DN).

[0110] Comparative Example 2

[0111] This comparative example provides a catalyst component D2 which was prepared in the same manner as Example 1 except that 2,6-dimethoxymethyl-4-pyrone was replaced with 15 mmol of 9,9-dimethoxyfluorene (FLU).

[0112] Polymerization

[0113] The above obtained catalyst components were used as components of olefin polymerization catalysts for polymerization evaluation:

[0114] A 5 L stainless steel autoclave was purged with nitrogen and 5 mL of a 0.5 mol / L triethylaluminum hexane solution, 1 mL of a 0.1 mol / L methylcyclohexyldimethoxysilane hexane solution and 10 mg of the prepared catalyst component were added. The feed line was then flushed with 10 mL of hexane. 2 L (standard state) of hydrogen and 2.5 L of refined propylene were then added. The reaction was controlled at 25 °C for 5 minutes of prepolymerization, and then the temperature was increased to 70 °C. The polymerization reaction was carried out at this temperature for 1 hour. After the reaction was completed, the reactor was cooled and the stirring was stopped. The reaction product was discharged and dried to obtain the polymer. The polymerization data are shown in Table 3.

[0115] Table 3

[0116]

[0117]

[0118] As shown in Table 3, the catalyst components of Examples 1-26 containing different 2,6-disubstituted oxymethyl-4-pyrone or 2,6-disubstituted carbonyloxymethyl-4-pyrone internal electron donors have higher activity than the catalysts of Comparative Example 1 containing phthalate internal electron donors and the catalysts of Comparative Example 2 containing diether internal electron donors under the same preparation conditions, and have good stereoselectivity, high isotacticity of the obtained polymers, and narrow overall molecular weight distribution. The 2,6-disubstituted oxymethyl-4-pyrone has a significantly narrowed molecular weight distribution due to the presence of a polyether structure, and the obtained polymers have regular particle size and high bulk density. Examples 27-30 are catalyst components prepared using different preparation methods and 2,6-disubstituted oxymethyl-4-pyrone or 2,6-disubstituted carbonyloxymethyl-4-pyrone, and also show excellent performance of high activity, high stereoselectivity, and narrow molecular weight distribution of the polymers.

Claims

1. A catalyst component for olefin polymerization, comprising: Mg, Ti, halogens, and 2,6-disubstituted oxymethyl-4-pyranone internal electron donors; wherein The 2,6-disubstituted oxymethyl-4-pyranone internal electron donor has the structure shown in Formula I: 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, a C1-C 20 hydrocarbon group, or a C1-C 20 group containing one or more heteroatoms selected from N, O and halogen; Optionally, two or more of R 1 , R 2 , R 3 , and R 4 are bonded to each other to form a ring.

2. The catalyst component of claim 1 wherein, In Formula I, R 1 , R 2 , R 3 , and R 4 are the same or different, each independently selected from H, halogen, the following substituents of up to 20 carbon atoms: straight chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, haloalkyl, heteroatom-containing alkyl, halocycloalkyl, heteroatom-containing cycloalkyl, halophenyl, heteroatom-containing phenyl, haloalkylphenyl, heteroatom-containing alkylphenyl, halophenylalkyl, heteroatom-containing phenylalkyl, haloindenyl, heteroatom-containing indenyl, halobenzyl, heteroatom-containing benzyl, heterocyclic aryl substituents; the heteroatoms including one or both of N, O.

3. The catalyst component of claim 2 wherein, In formula I, R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of H, halogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 straight-chain or branched alkyl groups having up to 20 carbon atoms, the following substituents having up to 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 derivatives thereof, phenethyl and derivatives thereof, furanyl, pyrrolyl, indenyl.

4. The catalyst component of claim 1 wherein, The 2,6-disubstituted oxymethyl-4-pyranone internal electron donors include 2,6-dimethoxymethyl-4-pyranone, 2,6-diethyloxymethyl-4-pyranone, 2,6-dipropyloxymethyl-4-pyranone, 2,6-dibutyloxymethyl-4-pyranone, 2,6-dipentyloxymethyl-4-pyranone, 2,6-dihexyloxymethyl-4-pyranone, and 2,6-diheptyloxymethyl-4-pyranone. 2,6-Dioctyloxymethyl-4-pyranone, 2,6-Di(dodecyl)oxymethyl-4-pyranone, 2,6-Di(tetradecyl)oxymethyl-4-pyranone, 2,6-Di(hexadecyl)oxymethyl-4-pyranone, 2,6-Diphenyloxymethyl-4-pyranone, 2,6-Diphenylmethyloxymethyl-4-pyranone, 2,6-Di-m-chlorophenyloxymethyl-4-pyranone, 2,6-di-o-chlorophenyl Oxymethyl-4-pyranone, 2,6-di-p-chlorophenyloxymethyl-4-pyranone, 2,6-di-p-methylphenyloxymethyl-4-pyranone, 2,6-di-p-methoxyphenyloxymethyl-4-pyranone, 2,6-difuranyloxymethyl-4-pyranone, 2,6-dipropenyloxymethyl-4-pyranone, 2,6-dimethoxymethyl-3,5-dimethyl-4-pyranone, 2,6-dimethoxymethyl-3-methyl- One or more of the following: 5-ethyl-4-pyranone, 2,6-dimethoxymethyl-3,5-diethyl-4-pyranone, 2,6-dimethoxymethyl-3,5-dibutyl-4-pyranone, 2,6-dimethoxymethyl-3-ethyl-5-butyl-4-pyranone, 2,6-dimethoxymethyl-3-methyl-5-butyl-4-pyranone, and 2-methoxymethyl-6-ethyloxymethyl-4-pyranone.

5. The catalyst component of claim 1 wherein, The 2,6-disubstituted oxymethyl-4-pyranone internal electron donor has the structure shown in Formula II: 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, a C1-C 20 hydrocarbon group, or a C1-C 20 group containing one or more heteroatoms selected from N, O and halogen; optionally, two or more of R 5 , R 6 , R 7 and R 8 are bonded to each other to form a ring.

6. The catalyst component of claim 5 wherein, The 2,6-disubstituted oxymethyl-4-pyrone internal electron donor includes one or more than two combinations of 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-di(pentadecanoyl)oxymethyl-4-pyrone, 2,6-di(hexadecanoyl)oxymethyl-4-pyrone, 2,6-dibenzoyloxymethyl-4-pyrone, 2,6-di(m-chlorobenzoyl)oxymethyl-4-pyrone, 2,6-di(p-methylbenzoyl)oxymethyl-4-pyrone, 2,6-di(o-chlorobenzoyl)oxymethyl-4-pyrone, 2,6-di(p-chlorobenzoyl)oxymethyl-4-pyrone, 2,6-di(p-methoxybenzoyl)oxymethyl-4-pyrone, 2,6-di(p-nitrobenzoyl)oxymethyl-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, 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-valeryloxymethyl-4-pyrone, 2-benzoyloxymethyl-6-p-methylbenzoyloxymethyl-4-pyrone.

7. The catalyst component according to any of claims 1 to 6 wherein, The composition of the catalyst component includes a titanium compound, a magnesium compound, and an internal electron donor represented by 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 One or more combinations of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halides, and titanium alkoxides, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 hydrocarbon group; The general formula of the titanium compound is TiX N (OR b ) 4-N , wherein R b is a C1-C 20 hydrocarbon group, X is halogen, and N is 1-4.

8. The catalyst component of claim 7 wherein, The magnesium compound is an alcohol compound of a dihalogenated magnesium. Alternatively, the magnesium compound is a liquid magnesium compound. Alternatively, the magnesium compound is a derivative of the dihalogenated magnesium molecule in which at least one halogen atom is replaced by a hydrocarbyloxy group or a halogenated hydrocarbyloxy group.

9. The catalyst component of claim 8 wherein, The magnesium compound is a hydrocarbyloxymagnesium compound.

10. The catalyst component of claim 9 wherein, The magnesium compound is an alkoxy magnesium and / or an aryloxy magnesium.

11. The catalyst component of claim 7 wherein, The titanium compound includes one or more than two combinations of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and an alkoxy halogenated titanium.

12. The catalyst component of claim 11 wherein, The alkoxy halogenated titanium includes one or more than two combinations of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

13. The catalyst component of claim 11 wherein, The titanium compound is titanium tetrachloride.

14. The catalyst component of claim 7 wherein, The molar ratio of the internal electron donor represented by Formula I to the magnesium compound is 0.01-5.0:1, the magnesium compound is calculated as magnesium element.

15. The catalyst component of claim 14 wherein, The molar ratio of the internal electron donor represented by Formula I to the magnesium compound is 0.05-3.0:

1.

16. A catalyst for olefin polymerization, the composition of which comprises the catalyst component of any one of claims 1-15 and an organic aluminum compound.

17. The catalyst of claim 16, wherein, The general formula of the organic aluminum compound is AlR c p X (3-p) wherein R c is hydrogen or a C1-C 20 hydrocarbon group, X is halogen, and p is an integer of 0≤p≤3.

18. The catalyst of claim 17, wherein, The organic aluminum compound comprises one or a combination of two or more of a trialkyl aluminum compound, an alkyl aluminum halide, an alkyl aluminum hydride, an alkyl aluminum sesquichloride, and an alkyl aluminum alkoxide.

19. The catalyst of claim 18, wherein, The trialkyl aluminum compound comprises one or a combination of two or more of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, and trioctyl aluminum; the alkyl aluminum halide comprises AlEt2Cl; and the alkyl aluminum sesquichloride comprises Al2Et3Cl3.

20. The catalyst of claim 18, wherein, The organic aluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

21. The catalyst of claim 16, wherein, The molar ratio of the organic aluminum compound to titanium atoms in the catalyst component is 1-1000:

1.

22. The catalyst of claim 21, wherein, The molar ratio of the organic aluminum compound to titanium atoms in the catalyst component is 50-800:

1.

23. The catalyst of claim 16, wherein, The raw material composition of the catalyst further comprises an external electron donor.

24. The catalyst of claim 23, wherein, The external electron donor is a siloxane compound.

25. The catalyst of claim 24, wherein, The general formula of the siloxane compound is R' t Si(OR'') 4-t wherein R' and R'' are each independently selected from a C1-C 18 hydrocarbon group, and t is an integer of 0 ≤ t ≤ 3.

26. The catalyst of claim 23, wherein, The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100:

1.

27. The catalyst of claim 26, wherein, The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.01-20:

1.

28. The catalyst of claim 27, wherein, The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.01-5:

1.

29. Use of the catalyst of any one of claims 16-28 in olefin polymerization, the olefin comprising 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.

30. The use according to claim 29, wherein, The polymerization comprises polymerization of ethylene and / or propylene.

31. The use according to claim 30, wherein, The polymerization comprises homopolymerization or copolymerization.

32. The use of claim 29, wherein, The temperature of the polymerization is ≤200℃, and the pressure of the polymerization is ≤10 MPa.

33. The use according to claim 32, wherein, The temperature of the polymerization is 20-100℃, and the pressure of the polymerization is 0.3-5 MPa.

34. The use of claim 33, wherein, The temperature of the polymerization is 40-80℃.

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