Catalyst component and catalyst for olefin polymerization, and use thereof

Abstract

Provided in the present invention are a catalyst component and catalyst for olefin polymerization, and the use thereof. The catalyst component comprises: Mg, Ti, halogen and a kojic acid ester internal electron donor, wherein the kojic acid ester internal electron donor has a structure as represented by formula (I). The catalyst component and the catalyst have high catalytic activity and biological safety, can reduce the total ash content of a polypropylene resin, the residual component of the catalyst and the toxicity of the residual component, and are particularly suitable for the production of medical polypropylene materials.

Description

Catalyst component for olefin polymerization, catalyst and application thereof Technical Field

[0001] The invention relates to a solid catalyst component for olefin polymerization, a preparation method and application thereof, and belongs to the field of polyolefin catalysts. Background Art

[0002] Polypropylene has excellent properties, such as resistance to radiation, high heat, high pressure, physiological degradation, good mechanical properties, and chemical stability, and is increasingly being used in the medical field. Polypropylene is primarily used in the medical field for medical non-woven fabrics, disposable medical products, medical transparent tubes, blood filters, and artificial lungs. Polypropylene is used in the manufacture of disposable medical products, syringe needles, catheters, and other medical products due to its lightweight, unbreakable, high-temperature resistance, non-toxicity, easy processing, low cost, and ability to prevent nosocomial cross-infection during use. However, the hygienic performance indicators of ordinary polypropylene do not meet the standards for the production of medical products, limiting its application.

[0003] One of the difficulties in producing medical clean polypropylene is the extremely high requirements for ash control. The total ash content of polypropylene resin and the residual components of the catalyst are the key indicators to focus on in the production of clean polypropylene. If clean polypropylene is obtained directly in the kettle without using the elution procedure, it is often necessary to use a high-activity catalyst for production. In order to fundamentally improve the properties of the active center of the Ziegler-Natta catalyst (ZN catalyst) to significantly increase the polymerization activity, the addition of internal electron donors during the catalyst preparation process and the addition of external electron donors during the polymerization process will have a great impact on the olefin polymerization behavior and polymer properties. Among them, 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.

[0004] Furthermore, when catalysts prepared using a single internal electron donor fail to meet the specific requirements of polypropylene products, such as requiring high activity, high stereospecificity, and high hydrogen sensitivity, the combination of multiple internal electron donors is an effective approach to address this problem. Specifically, two or more internal electron donors are used simultaneously in the preparation of ZN catalysts, and the overall performance of the ZN catalyst is adjusted by adjusting the content of different internal electron donors in the ZN catalyst. Currently, the internal electron donors commonly used in combination to adjust catalyst performance are mostly organic compounds with reproductive toxicity or unverified safety, such as phthalates, 1,3-diethers, and 1,3-diol esters. Furthermore, combined catalysts typically contain a higher weight percentage of the internal electron donor compound, resulting in higher post-polymerization residues, which is unfavorable for the development of clean medical materials. Medical plastics must possess two fundamental properties: biocompatibility and medical functionality. Furthermore, they must withstand sterilization, be resistant to breakage, and possess appropriate physicochemical and processing properties.

[0005] Therefore, the development of new electron donors has always been a hot topic in the research and development of ZN polypropylene catalysts. The relatively distinctive high-performance internal electron donor compounds in the existing technology mainly include: (1) fatty acid esters 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) glycol ester compounds (such as the compounds disclosed in WO9856834, WO0063261, and WO03022894); (5) compounds with other functional groups (such as the compounds disclosed in CN1105671, CN1242780, and US20060128558), etc. However, in practical applications, the above-mentioned compounds all have certain problems when used as internal electron donors in olefin polymerization catalysts. Although the catalysts using 1,3-diether compounds as internal electron donors have higher activity and better hydrogen modulation sensitivity, the relative molecular weight 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 weight distribution of the synthesized PP is relatively wide, but the disadvantage is that the stereoregularity of PP and the hydrogen modulation 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.

[0006] Currently, the most widely used internal electron donors in polyolefins are phthalates. Catalysts prepared from these compounds offer moderate activity, good stereoselectivity, and are inexpensive. However, as commonly used plasticizers, phthalates pose significant risks to human reproductive health and the environment, creating a significant demand for alternatives. Currently, the use of most phthalates is restricted. To improve the performance of polyolefin catalysts, internal electron donor compounds comprise approximately 5-20% by weight of the solid catalyst. These residual components, as polymerization residues, can negatively impact the cleanliness of polypropylene. In particular, catalysts containing high levels of phthalate internal electron donors can leave residual components with a certain degree of reproductive toxicity in the polypropylene, limiting its medical use. Furthermore, the lower the catalyst activity, the greater the catalyst dosage used during polymerization, the greater the residual content, and the less suitable it is for use in the production of medical polypropylene. Therefore, developing highly active catalysts containing highly biosafe internal electron donors would facilitate the production of medical polypropylene products and promote the development of medical polypropylene materials.

[0007] Summary of the Invention

[0008] In order to solve the above problems, the purpose of the present invention is to provide a catalyst component, catalyst and application thereof for olefin polymerization, which has high catalytic activity and high biosafety, and can reduce the toxicity of catalyst residual components, and is particularly suitable for the production of medical polypropylene materials.

[0009] In order to achieve the above object, the present invention provides a catalyst component for olefin polymerization, which comprises: Mg, Ti, halogen, and a kojic acid ester internal electron donor; wherein the kojic acid ester internal electron donor has a structure shown in Formula I:

[0010] In Formula I, R 1 、R 2 、R 3 and R 4 The same or different, each independently selected from H, halogen, C1-C 20 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 halogen, N, O, S, P and Si; preferably, R 1 、R 2 、R 3 and R 4 Two or more of them are bonded to each other to form a ring.

[0011] According to a specific embodiment of the present invention, preferably, the catalyst component comprises: Mg, Ti, halogen, the kojic acid ester internal electron donor and other internal electron donors, wherein the other internal electron donors include citrate compounds and / or ascorbic acid ester compounds;

[0012] Wherein, the citrate compound has the structure shown in Formula II:

[0013] In formula II, R 5 、R 6 and R 7 The same or different, each independently selected from C1-C 20 Hydrocarbon group; R 8 Selected from hydrogen, C1-C 20 Hydrocarbon, C2-C 21 Preferably, R 5 -R 8 Each contains a heteroatom selected from halogen, N, O, S, P, Ge and Si, or a combination of two or more thereof; preferably, R 5 、R 6 and R 7 Two or more of them are bonded to each other to form a ring;

[0014] The ascorbic acid ester compound has a structure shown in Formula III:

[0015] In formula III, R 9 、R 10 、R 11 and R 12 The same or different, each independently selected from H, R-CO-, wherein R is selected from C1-C 20 Hydrocarbon group; R 9 、R 10 、R 11 and R 12 At least one of them is not H; preferably, R contains heteroatoms selected from halogen, N, O, S, P and Si or a combination of two or more; preferably, R 9 、R 10 、R 11 and R 12 Two or more groups other than H in the molecule are bonded to each other to form a ring.

[0016] According to a specific embodiment of the present invention, preferably, in Formula I, R 1 、R 2 、R 3 and R 4the 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, haloalkyl, alkyl containing heteroatoms, halocycloalkyl, cycloalkyl containing heteroatoms, halophenyl, phenyl containing heteroatoms, haloalkylphenyl, alkylphenyl containing heteroatoms, halophenylalkyl, phenylalkyl containing heteroatoms, haloindenyl, indenyl containing heteroatoms, halobenzyl, benzyl containing heteroatoms, and heterocyclic aromatic substituents; the heteroatoms include one or a combination of two or more of N, O, S, P, and Si.

[0017] According to a specific embodiment of the present invention, preferably, in Formula I, R 1 、R 2 、R 3 and R 4 Each is 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, indenyl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0018] According to a specific embodiment of the present invention, preferably, in Formula I, R 1 and R 2 Selected from C1-C 20 Hydrocarbon group; R 3 and R 4 Both are H.

[0019] According to a specific embodiment of the present invention, preferably, the kojic acid ester internal electron donor includes kojic acid diacetate, kojic acid dipropionate, kojic acid di-n-butyrate, kojic acid diisobutyrate, kojic acid di-n-valerate, kojic acid diisovalerate, kojic acid di-tert-valerate, kojic acid di-n-hexanoate, kojic acid diisohexanoate, kojic acid dicyclopentacarboxylate, kojic acid di-n-heptanoate, kojic acid dicyclohexylcarboxylate, kojic acid dioctanoate, kojic acid dipelargonate, kojic acid didecanoate, kojic acid diundecanoate, kojic acid dilaurate, kojic acid dimyristate, kojic acid dipalmitate, kojic acid distearate Kojic acid ester, kojic acid dibenzoate, kojic acid diphenylacetate, kojic acid diphenylpropionate, kojic acid di-o-chlorobenzoate, kojic acid di-m-chlorobenzoate, kojic acid di-p-toluate, kojic acid di-p-methoxybenzoate, kojic acid m-trimethylbenzoate, kojic acid p-nitrobenzoate, kojic acid p-fluorobenzoate, kojic acid p-trifluoromethylbenzoate, kojic acid dicrotonate, kojic acid di(1-naphthoic acid) ester, kojic acid dinicotinate, kojic acid di(monoethyl succinate), kojic acid dicinnamate, kojic acid di(α-thiophene)carboxylate, and kojic acid difuroate, or a combination of two or more thereof.

[0020] The kojic acid ester compound represented by Formula I can be synthesized by methods including but not limited to the following: Kojic acid is reacted with an acyl chloride in a single step, as shown in Reaction Formula I. Various acyl chlorides can be commercially available, or the corresponding acyl chloride can be prepared by reacting an acid having a corresponding substituent with thionyl chloride;

[0021] According to a specific embodiment of the present invention, preferably, in Formula II, R 5 、R 6 and R 7 Each independently selected from C1-C 20 Straight or branched chain alkyl, C1-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl aryl, C7-C 20 of an aromatic hydrocarbon group.

[0022] According to a specific embodiment of the present invention, preferably, in Formula II, R 5 、R 6 and R 7 The same or different, each independently selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, cyclopentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl to eicosyl, C2-C 20 Alkenyl, C1-C 20 Ester group, C6-C 20 Phenyl, C7-C 20Alkylphenyl, C7-C 20 Phenylalkyl, C 10 -C 20 Indenyl, C7-C 20 benzyl, C3-C 20 Halogenated cycloalkyl, C3-C 20 Heteroatom-containing cycloalkyl, C6-C 20 Halogenated phenyl, C6-C 20 Heteroatom-containing phenyl, C7-C 20 Halogenated alkylphenyl, C7-C 20 Heteroatom-containing alkylphenyl, C7-C 20 Halogenated phenyl alkyl, C7-C 20 Heteroatom-containing phenylalkyl, C 10 -C 20 Halogenated indenyl, C 10 -C 20 Heteroatom-containing indenyl, C7-C 20 Halogenated benzyl, C7-C 20 The heteroatoms include one or more of N, O, S, P, Si, and Ge; preferably, the heteroaromatic substituents include furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, pteridine, and acridine; preferably, R 5 、R 6 and R 7 Bonded to each other to form a ring.

[0023] According to a specific embodiment of the present invention, preferably, in Formula II, R 8 Selected from H, C1-C 20 More preferably, R 8 Selected from C1-C 20 Straight or branched chain alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl aryl and C7-C 20 of an aromatic hydrocarbon group.

[0024] According to a specific embodiment of the present invention, preferably, in Formula II, R 8 Selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, cyclopentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl to eicosyl, C2-C 20 Alkenyl, C1-C 20 Ester group, C6-C 20 Phenyl, C7-C20 Alkylphenyl, C7-C 20 Phenylalkyl, C 10 -C 20 Indenyl, C7-C 20 benzyl, C3-C 20 Halogenated cycloalkyl, C3-C 20 Heteroatom-containing cycloalkyl, C6-C 20 Halogenated phenyl, C6-C 20 Heteroatom-containing phenyl, C7-C 20 Halogenated alkylphenyl, C7-C 20 Heteroatom-containing alkylphenyl, C7-C 20 Halogenated phenyl alkyl, C7-C 20 Heteroatom-containing phenylalkyl, C 10 -C 20 Halogenated indenyl, C 10 -C 20 Heteroatom-containing indenyl, C7-C 20 Halogenated benzyl, C7-C 20 a benzyl or heterocyclic aromatic substituent containing a heteroatom; the heteroatom includes one or a combination of two or more of N, O, S, P, Si, and Ge; preferably, the heterocyclic aromatic substituent includes furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, pteridine, and acridine.

[0025] According to a specific embodiment of the present invention, preferably, the citrate compound includes one or a combination of two or more of citrate, ether citrate, and acyl citrate.

[0026] According to a specific embodiment of the present invention, preferably, the citrate ester includes one or a combination of two or more of trimethyl citrate, triethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate, tri-tert-butyl citrate, triisobutyl citrate, tripentyl citrate, tricyclopentyl citrate, tripeneopentyl citrate, trihexyl citrate, tricyclohexyl citrate, triheptyl citrate, trioctyl citrate, trinonyl citrate, tridecyl citrate, triundecyl citrate to trieicosyl citrate.

[0027] According to a specific embodiment of the present invention, preferably, the ether citrate includes methyl ether trimethyl citrate, methyl ether triethyl citrate, methyl ether tripropyl citrate, methyl ether triisopropyl citrate, methyl ether tributyl citrate, methyl ether tritert-butyl citrate, methyl ether triisobutyl citrate, methyl ether tripentyl citrate, methyl ether tricyclopentyl citrate, methyl ether trineopentyl citrate, methyl ether trihexyl citrate, methyl ether tricyclohexyl citrate, methyl ether triheptyl citrate, methyl ether trioctyl citrate, methyl ether trinonyl citrate, methyl ether tridecyl citrate, methyl ether tri(undecyl) citrate to methyl ether tri(eicosyl) citrate, ethyl ether trimethyl citrate, ethyl ether tricitrate ethyl ether citrate, ethyl ether tripropyl citrate, ethyl ether triisopropyl citrate, ethyl ether tributyl citrate, ethyl ether tri-tert-butyl citrate, ethyl ether triisobutyl citrate, ethyl ether tripentyl citrate, ethyl ether tricyclopentyl citrate, ethyl ether tripeneopentyl citrate, ethyl ether trihexyl citrate, ethyl ether tricyclohexyl citrate, ethyl ether triheptyl citrate, ethyl ether trioctyl citrate, ethyl ether trinonyl citrate, ethyl ether tridecyl citrate, ethyl ether triundecyl citrate to ethyl ether trieicosyl citrate, propyl ether trimethyl citrate to propyl ether trieicosyl citrate, butyl ether trimethyl citrate to butyl ether trieicosyl citrate, or a combination of two or more thereof.

[0028] According to a specific embodiment of the present invention, preferably, the acyl citrate includes acetyl trimethyl citrate, acetyl triethyl citrate, acetyl tripropyl citrate, acetyl triisopropyl citrate, acetyl tributyl citrate, acetyl tri-tert-butyl citrate, acetyl triisobutyl citrate, acetyl tripentyl citrate, acetyl tricyclopentyl citrate, acetyl trineopentyl citrate, acetyl trihexyl citrate, acetyl tricyclohexyl citrate, acetyl triheptyl citrate, acetyl trioctyl citrate, acetyl trinonyl citrate, acetyl tridecyl citrate, acetyl tri(undecyl) citrate to acetyl tri(eicosyl) citrate, n-propionyl trimethyl citrate to n-propionyl tri( trimethyl citrate to trieicosyl citrate, trimethyl isopropyl citrate to trieicosyl citrate, trimethyl n-butyryl citrate to trieicosyl citrate, trimethyl isobutyl citrate to trieicosyl citrate, trimethyl tert-butyryl citrate to trieicosyl citrate, trimethyl n-valeryl citrate to trieicosyl citrate, trimethyl isovaleryl citrate to trieicosyl citrate, trimethyl pivaloyl citrate to trieicosyl pivaloyl citrate, trimethyl cyclopentayl citrate to trieicosyl cyclopentayl citrate, trimethyl hexanoyl citrate to trieicosyl hexanoyl citrate, trimethyl citrate to trieicosyl citrate, cyclohexanecarboxylic acid trimethyl ester to cyclohexanecarboxylic acid trieicosyl ester, heptanoyl citrate trimethyl ester to heptanoyl citrate trieicosyl ester, octanoyl citrate trimethyl ester to octanoyl citrate trieicosyl ester, nonanoyl citrate trimethyl ester to nonanoyl citrate trieicosyl ester, decanoyl citrate trimethyl ester to decanoyl citrate trieicosyl ester, lauroyl citrate trimethyl ester to lauroyl citrate trieicosyl ester, myristoyl citrate trimethyl ester to myristoyl citrate trieicosyl ester, palmitoyl citrate trimethyl ester to palmitoyl citrate trieicosyl ester, stearoyl citrate trimethyl ester to stearoyl citrate trieicosyl ester ) Esters, arachidoyl trimethyl citrate to arachidoyl trieicosyl citrate, benzoyl trimethyl citrate to benzoyl trieicosyl citrate, phenylacetyl trimethyl citrate to phenylacetyl trieicosyl citrate, p-chlorobenzoyl trimethyl citrate to p-chlorobenzoyl trieicosyl citrate, o-chlorobenzoyl trimethyl citrate to o-chlorobenzoyl trieicosyl citrate, m-chlorobenzoyl trimethyl citrate to m-chlorobenzoyl trieicosyl citrate, p-methoxybenzoyl trimethyl citrate to p-methoxybenzoyl trieicosyl citrate, m-fluorobenzoyl trimethyl citrate to m-fluorobenzoyl trieicosyl citrate,p-Fluorobenzoyl trimethyl citrate to p-Fluorobenzoyl trieicosyl citrate, o-Fluorobenzoyl trimethyl citrate to o-Fluorobenzoyl trieicosyl citrate, p-Toluobenzoyl trimethyl citrate to p-Toluobenzoyl trieicosyl citrate, p-Nitrobenzoyl trimethyl citrate to p-Nitrobenzoyl trieicosyl citrate, ethoxyoxalyl trimethyl citrate to ethoxyoxalyl trieicosyl citrate , furoyl trimethyl citrate to furoyl trieicosyl citrate, morpholine trimethyl citrate to morpholine trieicosyl citrate, thenoyl trimethyl citrate to thenoyl trieicosyl citrate, picolinoyl trimethyl citrate to picolinoyl trieicosyl citrate, acryloyl trimethyl citrate to acryloyl trieicosyl citrate, or a combination of two or more thereof. ,

[0029] According to a specific embodiment of the present invention, preferably, the ascorbic acid ester compound includes one or a combination of two or more of an ascorbic acid monoester compound, an ascorbic acid diester compound, and an ascorbic acid tetraester compound;

[0030] The ascorbic acid monoester compound has a structure shown in Formula IV:

[0031] The ascorbic acid diester compound has a structure shown in Formula V:

[0032] The tetraascorbic acid compound has a structure shown in Formula VI:

[0033] In formula IV to formula VI, R 13 to R 19 Each independently selected from C1-C 20 of hydrocarbon groups.

[0034] According to a specific embodiment of the present invention, preferably, R 13 to R 19 Each substituent is independently selected from the following substituents having less than 20 carbon atoms: a straight-chain or branched alkyl group, a cycloalkyl group, an alkenyl group, an ester group, a phenyl group, an alkylphenyl group, a phenylalkyl group, an indenyl group, a benzyl group, a halogenated alkyl group, an alkyl group containing a heteroatom, a halogenated cycloalkyl group, a cycloalkyl group containing a heteroatom, a halogenated phenyl group, a phenyl group containing a heteroatom, a halogenated alkylphenyl group, an alkylphenyl group containing a heteroatom, a halogenated phenylalkyl group, a phenylalkyl group containing a heteroatom, a halogenated indenyl group, an indenyl group containing a heteroatom, a halogenated benzyl group, a benzyl group containing a heteroatom, and a heterocyclic aromatic substituent; the heteroatoms include one or a combination of two or more of N, O, S, P, and Si.

[0035] According to a specific embodiment of the present invention, preferably, R13 to R 19 Each is independently selected from 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, indenyl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0036] According to a specific embodiment of the present invention, preferably, the ascorbic acid monoester compound represented by formula IV is selected from ascorbic acid acetate, ascorbic acid propionate, ascorbic acid n-butyrate, ascorbic acid isobutyrate, ascorbic acid n-valerate, ascorbic acid isovalerate, ascorbic acid tert-valerate, ascorbic acid n-hexanoate, ascorbic acid isocaproate, ascorbic acid cyclopentanecarboxylate, ascorbic acid n-heptanoate, ascorbic acid cyclohexanecarboxylate, ascorbic acid octanoate, ascorbic acid nonanoate, ascorbic acid decanoate, ascorbic acid undecanoate, ascorbic acid laurate, ascorbic acid myristate, ascorbic acid palmitate, ascorbic acid stearate. , ascorbyl benzoate, ascorbyl phenylacetate, ascorbyl phenylpropionate, ascorbyl o-chlorobenzoate, ascorbyl m-chlorobenzoate, ascorbyl p-toluate, ascorbyl p-methoxybenzoate, ascorbyl m-trimethylbenzoate, ascorbyl p-nitrobenzoate, ascorbyl p-fluorobenzoate, ascorbyl p-trifluoromethylbenzoate, ascorbyl crotonate, ascorbyl (1-naphthoic acid) ester, ascorbyl nicotinate, ascorbyl (monoethyl succinate), ascorbyl cinnamate, ascorbyl (α-thiophenecarboxylic acid) ester, ascorbyl furoate, one or a combination of two or more thereof.

[0037] According to a specific embodiment of the present invention, preferably, the ascorbic acid diester compound represented by formula V is selected from ascorbic acid diacetate, ascorbic acid dipropionate, ascorbic acid di-n-butyrate, ascorbic acid diisobutyrate, ascorbic acid di-n-valerate, ascorbic acid diisovalerate, ascorbic acid di-tert-valerate, ascorbic acid di-n-hexanoate, ascorbic acid diisohexanoate, ascorbic acid dicyclopentanecarboxylate, ascorbic acid di-n-heptanoate, ascorbic acid dicyclohexanecarboxylate, ascorbic acid dioctanoate, ascorbic acid dipelargonate, ascorbic acid dicaprate, ascorbic acid diundecanoate, ascorbic acid dilaurate, ascorbic acid dimyristate, ascorbic acid dipalmitate, ascorbic acid dioctanoate ...octanoate, ascorbic acid diundecanoate, ascorbic acid dilaurate, ascorbic acid dimyristate, ascorbic acid dipalmitate, ascorbic acid dioctanoate, ascorbic acid dioctanoate, ascorbic acid diundecanoate, ascorbic acid dioctanoate, ascorbic acid diundecanoate, ascorbic acid dilaurate, ascorbic acid dimyristate, ascorbic acid dipalmitate, ascorbic acid dioctanoate, ascorbic acid dioctanoate, ascorbic acid diundecanoate, ascorbic acid dioctanoate, ascorbic acid diundecanoate, ascorbic acid dioctanoate, ascorbic acid diundecanoate, ascorbic acid dioctanoate, ascorbic acid diundecanoate, ascorbic acid dioc Stearate, ascorbyl dibenzoate, ascorbyl diphenylacetate, ascorbyl diphenylpropionate, ascorbyl di-o-chlorobenzoate, ascorbyl di-m-chlorobenzoate, ascorbyl di-p-toluate, ascorbyl di-p-methoxybenzoate, ascorbyl m-trimethylbenzoate, ascorbyl p-nitrobenzoate, ascorbyl p-fluorobenzoate, ascorbyl p-trifluoromethylbenzoate, ascorbyl dicrotonate, ascorbyl di(1-naphthoic acid) ester, ascorbyl dinicotinate, ascorbyl di(monoethyl succinate), ascorbyl dicinnamate, ascorbyl di(α-thiophenecarboxylic acid) ester, ascorbyl difuroate, or a combination of two or more thereof.

[0038] According to a specific embodiment of the present invention, preferably, the ascorbic acid tetraester compound represented by formula VI is selected from ascorbic acid tetraacetate, ascorbic acid tetrapropionate, ascorbic acid tetra-n-butyrate, ascorbic acid tetraisobutyrate, ascorbic acid tetra-n-pentanoate, ascorbic acid tetraisopentanoate, ascorbic acid tetra-tert-pentanoate, ascorbic acid tetra-n-hexanoate, ascorbic acid tetraisohexanoate, ascorbic acid tetracyclopentacarboxylate, ascorbic acid tetra-n-heptanoate, ascorbic acid tetracyclohexylcarboxylate, ascorbic acid tetraoctanoate, ascorbic acid tetrapelargonate, ascorbic acid tetradecanoate, ascorbic acid tetraundecanoate, ascorbic acid tetralaurate, ascorbic acid tetramyristate, ascorbic acid tetrapalmitate, ascorbic acid tetradecanoate stearate, ascorbyl tetrabenzoate, ascorbyl tetraphenylacetate, ascorbyl tetraphenylpropionate, ascorbyl tetra-o-chlorobenzoate, ascorbyl tetra-m-chlorobenzoate, ascorbyl tetra-p-toluate, ascorbyl tetra-p-methoxybenzoate, ascorbyl m-trimethylbenzoate, ascorbyl p-nitrobenzoate, ascorbyl p-fluorobenzoate, ascorbyl p-trifluoromethylbenzoate, ascorbyl tetracrotonate, ascorbyl tetra(1-naphthoic acid) ester, ascorbyl tetranicotinate, ascorbyl tetra(monoethyl succinate), ascorbyl tetracinnamate, ascorbyl tetra(α-thiophenecarboxylic acid) ester, ascorbyl tetrafuroate, or a combination of two or more thereof.

[0039] The ascorbic acid ester compounds represented by Formula IV, Formula V, and Formula VI can be prepared using ascorbic acid as a raw material through methods such as transesterification, direct esterification, acyl chloride esterification, or enzymatic catalysis. The ascorbic acid esters of the present invention can be prepared using commercially available products or by the following acyl chloride method. As shown in Reaction Formula II, when the four ester groups are the same, only four equivalents of acyl chloride are required in a single step to obtain the ascorbic acid tetraester compound.

[0040] According to a specific embodiment of the present invention, preferably, the molar ratio of the kojic acid ester internal electron donor to other internal electron donors is ≥0.1:1.

[0041] According to a specific embodiment of the present invention, preferably, the composition of the catalyst component comprises a titanium compound, a magnesium compound, the kojic acid ester internal electron donor, or the composition of the catalyst component comprises a titanium compound, a magnesium compound, the kojic acid ester internal electron donor and other internal electron donors; 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 general formula of the titanium compound is TiX N (OR b ) 4-N , where R b C1-C 20 The hydrocarbon group, X is halogen, and N is 1-4.

[0042] 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 a magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; more preferably, it is a hydrocarbonoxy magnesium compound; further preferably, it is an alkoxy magnesium and / or an aryloxy magnesium.

[0043] 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.

[0044] 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; more preferably, the titanium compound is titanium tetrachloride.

[0045] According to a specific embodiment of the present invention, preferably, the molar ratio of the total internal electron donor to the magnesium compound calculated as magnesium element is 0.01-5.0, preferably 0.05-3.0.

[0046] 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:

[0047] Method 1: Magnesium alcoholate or magnesium chloroalcoholate and excess TiCl4 and internal electron donor compound are reacted at a temperature of 80-135°C; preferably, the general formula TiX N (OR b ) 4-N Titanium compounds (where R b C1-C 20 A hydrocarbon group, X is a halogen, N = 1-4; preferably TiCl4) and a general formula of MgCl2·mR a OH adduct (wherein m is a number from 0.1 to 6, preferably from 2 to 4, and R a C1-C 20 The solid catalyst component is prepared by reacting an internal electron donor; wherein the general formula is MgCl2·mR a The OH adduct can be conveniently prepared into spherical form by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, and rapidly quenching the emulsion to solidify the adduct in the form of spherical particles (see the disclosures of US Pat. No. 4,399,054 and US Pat. No. 4,469,648). The spherical adduct obtained in this way can be reacted directly with the titanium compound, or it can be pre-treated by thermally controlled dealcoholation (80-130° C.) to obtain a dealcoholated adduct (wherein the molar number of alcohol is generally less than 3, preferably between 0.1 and 2.5), before being subjected to the subsequent reaction.

[0048] For example, the adduct or dealcoholated adduct is suspended in cold TiCl4 (generally -25-0°C) to react with the titanium compound, and the mixture is heated to 80-130°C and maintained at this temperature for 0.5-2 hours, wherein the treatment with TiCl4 can be carried out once or multiple times, and an internal electron donor compound can be added during the treatment with TiCl4, and this treatment can be repeated once or multiple times;

[0049] Method 2: A magnesium compound is dissolved in a solvent system consisting of an organic epoxy compound, an organic phosphine compound, and an inert diluent to form a uniform solution, which is then mixed with a titanium compound and, in the presence of a precipitation aid, a solid is precipitated. This solid is treated with an internal electron donor compound to load the internal electron donor compound onto the solid, and, if necessary, further treated with titanium tetrahalide and an inert diluent. The precipitation aid is selected from the group consisting of an organic anhydride, an organic acid, an ether, and a ketone. The components, calculated per mole of magnesium halide, include 0.2-10 moles of the organic epoxy compound, 0.1-3 moles of the organic phosphine compound, 0-1.0 moles of the precipitation aid, and 0.5-150 moles of the titanium compound (calculated as moles of titanium element).

[0050] Method three: using TiCl or an aromatic hydrocarbon solution of titanium alkoxide (e.g., toluene, dimethylbenzene, etc.) at -25°C to 0°C to react with a dihydrocarbyl magnesium compound such as magnesium dialkoxide (preferably magnesium diethoxide) or magnesium diaryloxide, and halogenating at 80-130°C. The treatment of the aromatic hydrocarbon solution with TiCl can be repeated once or multiple times, and internal electron donor compounds are added once or in batches in multiple such treatments. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US Pat. No. 5,077,357 can be used for preparation: magnesium ethoxide, titanium tetraethoxide, o-cresol, ethanol, and chlorobenzene are added in sequence and stirred; TiCl / chlorobenzene solution is quickly added to the above-mentioned liquid, heated to be completely dissolved, and then continued to be warmed to a specific temperature; utilizing N bubbling to remove the ethanol reactant and continuing to stir for a certain period of time, then washing once with hot chlorobenzene, twice with isooctane, and then drying with N to obtain the carrier. Or according to another example: TiCl4, tetraethoxytitanium, ethoxymagnesium and o-cresol are added to chlorobenzene in sequence and stirred; ethanol is added and stirred at high temperature for 3 hours after the ethoxymagnesium is dissolved; the mixture is filtered while hot and then washed once with warm chlorobenzene and once with isooctane, and finally dried with nitrogen;

[0051] Method 4: Magnesium dichloride is preactivated according to existing methods and then treated with an excess of TiCl4 at a temperature of about 80-135°C, wherein the solution contains an internal electron donor compound. The TiCl4 treatment is repeated multiple times and the solid is washed with hexane to remove any unreacted TiCl4.

[0052] Method 5: Prepared with reference to the preparation method of the 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 temperature during contact is generally -70°C to 200°C, preferably -30°C to 130°C, and the internal electron donor compound is used during the contact process;

[0053] Method 6: Anhydrous magnesium chloride and an internal electron donor compound are ground together under conditions where magnesium dichloride is activated. The resulting product can be treated one or more times with an excess of TiCl4 at a temperature of 80-130°C and then washed with a hydrocarbon solvent until it is free of chloride ions. A further detailed method is as follows: the product obtained by co-grinding anhydrous magnesium dichloride, a titanium compound, and an internal electron donor compound is treated with a halogenated hydrocarbon such as 1,2-dichloroethane, chlorobenzene, or dichloromethane at a temperature between 40°C and the boiling point of the halogenated hydrocarbon for 1-4 hours, and then the product is typically washed with an inert hydrocarbon solvent such as hexane.

[0054] Method 7: A magnesium compound supported on an inorganic oxide such as SiO2, alumina or porous silica gel is used as a carrier for preparation, which is then activated by a well-known method and then treated with an excess of TiCl4 at a temperature of about 80-135°C, with an internal electron donor compound added during the treatment process.

[0055] The reaction of the above-mentioned catalyst components results in the formation of magnesium halide in an active form. Typical crystalline magnesium halide has a regular structure and can only support a small amount of Ti, resulting in low catalytic activity. To prepare a highly active supported catalyst, the magnesium halide must be activated. Activation methods include physical and / or chemical methods to convert it into microcrystals so that the active centers are supported on the surface, edges, and defects of the magnesium halide. These treated magnesium halide microcrystals suitable for supporting Ti are referred to as "active magnesium halide." In addition to these reactions, other methods are known in the literature for converting compound starting materials other than magnesium halide into an active form of magnesium halide.

[0056] In any of the methods for preparing the catalyst components, the internal electron donor compound can be added directly or prepared in an alternative manner, such as in situ using a suitable precursor that can be converted into the desired internal electron donor compound by, for example, known chemical reactions such as esterification, transesterification, etc. Typically, the internal electron donor compound is used in a molar ratio of 0.01 to 5, preferably 0.05 to 3.0, relative to the moles of MgCl2. Furthermore, the internal electron donor compound can be added simultaneously or separately during the preparation process, in batches or in any order and combination.

[0057] The present invention also provides a catalyst for olefin polymerization, which comprises the above catalyst component and an organic aluminum compound.

[0058] 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 C1-C 20 wherein X is a halogen, and p is an integer of 0≤p≤3.

[0059] According to a specific embodiment of the present invention, preferably, the organoaluminum compound includes one or a combination of two or more of a trialkylaluminum compound, an alkylaluminum halide, an alkylaluminum hydride, an alkylaluminum sesquichloride, and an alkylaluminoxane; more 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; more preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0060] According to a specific embodiment of the present invention, preferably, the molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 1-1000:1, more preferably 50-800.

[0061] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst further includes an external electron donor.

[0062] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0063] 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 C1-C 18 More preferably, R' and R" each contain a heteroatom; more preferably, the heteroatom comprises one or a combination of two or more of N, O, S, P and Si.

[0064] 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, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, 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.

[0065] According to a specific embodiment of the present invention, preferably, the siloxane compound includes di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldiethoxysilane, tert-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane, One or a combination of two or more of cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane and 3,5-dimethylcyclopentyldimethoxysilane.

[0066] 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, and tert-hexyltrimethoxysilane, or a combination of two or more thereof.

[0067] 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, more preferably 0.01-20, and even more preferably 0.01-5.

[0068] The present invention also provides application of the catalyst in olefin polymerization.

[0069] According to a specific embodiment of the present invention, preferably, the olefin includes a linear or branched olefin, such as 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.

[0070] According to a specific embodiment of the present invention, preferably, the polymerization comprises ethylene and / or propylene polymerization.

[0071] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0072] 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, and it is best to add the organoaluminum compound to the polymerization system first, then add the external electron donor, and finally add the catalyst component.

[0073] 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.

[0074] 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 ≤10 MPa, more preferably 0.3-5 MPa.

[0075] Kojic acid ester compounds are food, pharmaceutical, and cosmetic additives that have antibacterial, fresh-keeping, and freckle-removing and whitening effects. During food processing, they can be used as food additives to play preservative, fresh-keeping, and antioxidant roles. They can be used to preserve flowers, vegetables, and fruits, improving the appearance and intrinsic quality of the products and extending their shelf life. Bikojic acid esters are used in cosmetics to remove freckles, are safe to use, and are widely used in the treatment of pigmentation disorders. The present invention includes a variety of kojic acid ester compounds as internal electron donors for the preparation of olefin polymerization catalysts, and the resulting catalysts have high activity and selectivity. Some kojic acid ester compounds are commonly used food and pharmaceutical additives on the market, while other non-commercially available kojic acid ester compounds can be prepared by selecting corresponding acyl chlorides and kojic acid through a one-step reaction. The production cost is low, and the acyl chloride substituents have a wide range of options, which is conducive to optimizing the internal electron donor structure by screening various substituents to further improve the catalyst performance, making them particularly suitable for industrial applications.

[0076] The present invention utilizes kojic acid ester compounds as internal electron donor components in the preparation of olefin polymerization catalysts, resulting in highly active and selective catalysts. Kojic acid esters contain multiple oxygen-containing functional groups, such as ketones, ethers, and esters, on their six-membered ring skeleton. These groups possess multiple electron-donating groups, which positively regulate the catalyst's active center, enhancing catalytic activity and reducing catalyst residue in polypropylene. Kojic acid ester compounds are highly stable and have no side effects on the human body. Ascorbic acid esters are a class of non-toxic, multifunctional nutritional antioxidant preservatives, with several compounds, such as ascorbyl palmitate, being recognized as nutritional antioxidants by the World Health Organization's Joint Committee on Food Additives. Citrate compounds are environmentally friendly and non-toxic plasticizers. The present invention compounds kojic acid ester compounds with citrate compounds and / or ascorbyl ester compounds. All components have high biosafety. Properties such as catalytic activity and molecular weight distribution of the polymerized product can be adjusted by adjusting the different components and proportions of binary or ternary compounds of different internal electron donors. Kojic acid ester compounds can be used as an efficient replacement for reproductively toxic phthalate internal electron donors and are suitable for the production of medical polypropylene products. The high isotacticity and wide molecular weight distribution of the obtained polypropylene products can also be used to further improve the physicochemical and processing properties of medical materials. DETAILED DESCRIPTION

[0077] In order to have a clearer understanding of the technical features, objectives 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 understood as limiting the scope of implementation of the present invention.

[0078] The operations for preparing the catalysts in the following examples were all carried out under the protection of high-purity nitrogen.

[0079] The isotacticity of polymers is determined by the heptane extraction method (extraction with boiling heptane for 6 hours): two grams of dry polymer sample are placed in an extractor and extracted with boiling heptane for 6 hours. The residue is then dried to a constant weight. The ratio of the obtained polymer weight (g) to 2 is the isotacticity.

[0080] The bulk density of the polymer was determined using the JB / T 2412-2008 method.

[0081] The molecular weight distribution of the polymer was determined using a PL-220 gel permeation chromatograph using trichlorobenzene as solvent at 150° C. (standard: polystyrene, flow rate 1.0 mL / min, column: 3xPlgel 10 μm M1Xed-B 300×7.5 nm).

[0082] Some of the citrate compounds described herein are commercially available chemicals and can be purchased and used directly, such as trimethyl citrate, triethyl citrate, tributyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, and the like. Other non-commercially available citrate esters can be prepared by various conventional methods, including single or multiple esterification of citric acid to obtain the corresponding citrate ester, which is then reacted with an acyl chloride to obtain the desired acyl citrate ester. Ether citrate esters can also be prepared by alkylating citrate esters.

[0083] The ascorbyl ester compounds described in the present invention, such as L-ascorbyl palmitate, ascorbyl dipalmitate, ascorbyl tetrapalmitate, etc., are commercially available products. Non-commercially available ascorbyl ester compounds can also be prepared using ascorbic acid as a raw material through main methods such as transesterification, direct esterification, acyl chloride esterification, and enzyme catalysis.

[0084] Preparation Example: Synthesis of Kojic Acid Ester Compounds Represented by Formula I

[0085] 1. The synthesis of kojic acid distearate is as follows:

[0086] 13.5 g of dry kojic acid (0.095 mol) was dissolved in 270 ml of dry pyridine, maintained at 20° C. with vigorous stirring, and stearic acid chloride was rapidly added dropwise at a rate of 10 mL / min. The mixture was cooled with a coolant. After the addition, the temperature was gradually raised to about 30° C., kept warm, and stirred thoroughly for 2 h to obtain a uniform light yellow reactant. The reactant was added to 10 times the volume of distilled water and stirred uniformly. The mixture was centrifuged and the filter cake was washed with a large amount of distilled water until there was no pyridine odor (pyridine wastewater was recycled). The crude filter cake was dissolved in a mixture of 400 mL of ethyl acetate and 10 g of activated carbon, heated to reflux, stirred and decolorized for 20 min, filtered while hot, and the activated carbon was removed to obtain a light yellow solution; the mixture was cooled to room temperature to obtain crystals. The crystals were filtered and washed with cold ethyl acetate 2 to 3 times. The filter cake was fully dried at 70° C. to remove moisture and ethyl acetate to obtain the product kojic acid distearate (a1) in a yield of 80%.

[0087] 2. Other kojic acid ester compounds (a2-a25) were prepared using the above-mentioned route. The starting materials were selected from acyl chlorides and kojic acid with corresponding substituents. The structures and NMR results of compounds a2-a25 are shown in Table 1.

[0088] Table 1 Kojic acid ester compounds represented by formula I

[0089] (1) Kojic acid ester compounds as catalyst components of internal electron donors

[0090] Preparation of catalyst components

[0091] Example 1

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

[0093] In a 500 ml, nitrogen-purged, stirred, five-necked flask, 10 g of MgCl2·2.5C2H5OH microspheres and 150 mL of titanium tetrachloride were added to prepare a suspension. The suspension was then maintained at -15°C for one hour, then slowly heated to 80°C. 3.1 g (5 mmol) of kojic acid distearate was added, and the temperature was further raised to 110°C and held there for one hour. The liquid was then filtered clean. The resulting solid was washed three times with 120 mL of titanium tetrachloride at 110°C and four times with 150 mL of hexane at 60°C. The liquid was filtered off and the suspension was dried to obtain solid catalyst component E1. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 2.

[0094] Example 2-25

[0095] Examples 2-25 each provide a solid catalyst component E2-E25, the preparation process of which is as shown in Example 1, except that kojic acid distearate is replaced by 5 mmol of compounds a2-a25 in Table 1 in sequence.

[0096] Example 26

[0097] This embodiment provides a catalyst component E26, the preparation method of which is as follows:

[0098] To a 500ml, nitrogen-purged, stirred, five-necked flask, 10g of anhydrous magnesium chloride, 150mL of toluene, 17mL of epichlorohydrin, and 16mL of tributyl phosphate were added at room temperature. The temperature was raised to 50°C with stirring and maintained for 2 hours until the solids completely dissolved. Then, 2.40g of phthalic anhydride was added and maintained for another hour. The solution was cooled to -25°C, and 110mL of titanium tetrachloride was added dropwise over 1 hour. The temperature was slowly raised to 80°C, and the solids were gradually washed out during the heating process. 3.1g of kojic acid distearate was added, and the temperature was maintained at 80°C for 1 hour. After filtering, the solution was washed twice with 200mL of toluene. Then, 120mL of toluene and 80mL of titanium tetrachloride were added, and the temperature was continued to rise to 110°C and maintained for 2 hours. The liquid was then filtered and cleaned. The process was repeated once. The liquid was filtered off, and the resulting solid was washed once with 100mL of dichloroethane and four times with hexane. After drying, the solid catalyst component E26 was obtained. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 2.

[0099] Example 27

[0100] This embodiment provides a catalyst component E27, the preparation method of which is as follows:

[0101] In a 500 ml 5-necked flask with a stirrer and fully replaced with nitrogen, 8 g of diethoxymagnesium and 100 mL of toluene were added to prepare a suspension, and 25 mL of titanium tetrachloride was added dropwise at -15°C. After the addition was complete, the temperature was slowly raised to 0°C, and then 50 mL of titanium tetrachloride was added dropwise. The temperature was then slowly raised to 80°C, 3.1 g of kojic acid distearate was added, and the temperature was continued to be raised to 110°C and kept constant for 2 hours. The liquid was then filtered clean and the liquid was filtered off. The resulting solid was washed three times with 100 mL of titanium tetrachloride at 125°C and four times with 120 mL of hexane at 60°C. The liquid was filtered off and dried to obtain the solid catalyst component E27.

[0102] Comparative Example 1

[0103] This comparative example provides a catalyst component D1, which is prepared in the same manner as in Example 1, except that kojic acid distearate is replaced with 5 mmol of di-n-butyl phthalate (DN).

[0104] Comparative Example 2

[0105] This comparative example provides a catalyst component D2, the preparation process of which is the same as that of Example 1, except that kojic acid distearate is replaced by 5 mmol of 9,9-dimethoxyfluorene (FLU).

[0106] Comparative Example 3

[0107] This comparative example provides a catalyst component D3, the preparation process of which is the same as that of Example 1, except that kojic acid distearate is replaced by 5 mmol of acetyl tributyl citrate.

[0108] polymerization

[0109] The solid catalyst component obtained above was used as a component of an olefin polymerization catalyst to carry out polymerization evaluation:

[0110] After fully purging the atmosphere with nitrogen, a 5L stainless steel reactor was charged with 5mL of a 0.5mol / L triethylaluminum hexane solution, 1mL of a 0.1mol / L methylcyclohexyldimethoxysilane hexane solution, and 10mg of the prepared catalyst component. The feed line was then flushed with 10mL of hexane. 2L of hydrogen (under standard conditions) and 2.5L of purified propylene were then added. The reaction was prepolymerized at 25°C for 5 minutes, then heated to 70°C and allowed to polymerize for 1 hour. After the reaction, the reactor was cooled and stirring was stopped. The reaction product was discharged and dried to obtain a polymer. Polymerization data are shown in Table 2.

[0111] Table 2

[0112] The kojic acid ester internal electron donor catalysts of Examples 1-25, under the same preparation conditions, were significantly more active than catalysts using acetyl tributyl citrate (a biosafety additive) as the internal electron donor compound. Furthermore, they were more active than catalysts using the most commonly used phthalate internal electron donor in industry (Polymerization No. 28). This suggests that kojic acid ester compounds can serve as a highly effective alternative to reproductively toxic phthalate internal electron donors. Furthermore, fluorene diether catalysts, due to their high activity, are commonly used in the development of low-ash polyolefin products. The kojic acid ester internal electron donor catalysts of Examples 1-25 of the present invention exhibited comparable activity to that of the fluorene diether catalyst (Polymerization No. 29), with some examples exhibiting even higher activity. Therefore, the kojic acid ester internal electron donors of the present invention are highly biosafe and the resulting catalysts are highly active, making them particularly suitable for the production of medical polypropylene products.

[0113] (2) Kojic acid ester compounds and other internal electron donors are compounded as catalyst components of internal electron donors

[0114] Preparation of catalyst components

[0115] Example 28

[0116] This embodiment provides a catalyst component, and its preparation method is as follows:

[0117] In a 500-ml, nitrogen-purged, stirred, five-necked flask, 10 g of MgCl2·2.5C2H5OH microspheres and 150 mL of titanium tetrachloride were added to prepare a suspension. The suspension was then maintained at -15°C for one hour, then slowly heated to 80°C. 3 mmol of kojic acid distearate (a1) and 3 mmol of tributyl citrate (b1) were added, and the temperature was further raised to 110°C and held there for one hour. The suspension was then filtered clean, and the resulting solid was washed three times with 120 mL of titanium tetrachloride at 110°C and four times with 150 mL of hexane at 60°C. The liquid was filtered off and the suspension was dried to obtain solid catalyst component E28. The polymerization data for this solid catalyst component are shown in Table 3.

[0118] Examples 29-39

[0119] Examples 29-39 each provide a solid catalyst component E29-E39, the preparation process of which is as shown in Example 28, except that 3 mmol of kojic acid distearate (a1) and 3 mmol of tributyl citrate (b1) are replaced in sequence with the two internal electron donor compounds in Table 3, and the feed ratio of the two is 3 mmol:3 mmol.

[0120] Examples 40-47

[0121] Examples 40-47 each provide a solid catalyst component E40-E47, the preparation process of which is as shown in Example 28, except that 3 mmol of kojic acid distearate (a1) and 3 mmol of tributyl citrate (b1) are replaced in sequence with the three internal electron donor compounds in Table 3, and the feed ratio of the three is 2 mmol: 2 mmol: 2 mmol.

[0122] Example 48

[0123] This embodiment provides a solid catalyst component E48, the preparation process of which is as shown in Example 28, except that 3 mmol of kojic acid distearate (a1) and 3 mmol of tributyl citrate (b1) are replaced with kojic acid dibenzoate, acetyl tributyl citrate, and ascorbyl palmitate, and the feed ratio is 1 mmol: 1 mmol: 4 mmol.

[0124] Example 49

[0125] This embodiment provides a solid catalyst component E49, the preparation process of which is as shown in Example 28, except that 3 mmol of kojic acid distearate (a1) and 3 mmol of tributyl citrate (b1) are replaced with kojic acid dibenzoate, acetyl tributyl citrate, and ascorbyl palmitate, and the feed ratio of the three is 1 mmol:4 mmol:1 mmol.

[0126] Example 50

[0127] This embodiment provides a solid catalyst component E50, the preparation process of which is as shown in Example 28, except that 3 mmol of kojic acid distearate (a1) and 3 mmol of tributyl citrate (b1) are replaced with kojic acid dibenzoate, acetyl tributyl citrate, and ascorbyl palmitate, and the feed ratio of the three is 4 mmol:1 mmol:1 mmol.

[0128] Comparative Example 4

[0129] This comparative example provides a catalyst component D4, which is prepared in the same manner as in Example 28, except that 3 mmol of kojic acid distearate and 3 mmol of tributyl citrate are replaced with 6 mmol of di-n-butyl phthalate (DN).

[0130] Comparative Example 5

[0131] This comparative example provides a catalyst component D5, which is prepared in the same manner as in Example 28, except that 3 mmol of kojic acid distearate and 3 mmol of tributyl citrate are replaced with 6 mmol of 9,9-dimethoxyfluorene (FLU).

[0132] Comparative Examples 6-9

[0133] Comparative Examples 6-9 each provide a catalyst component D6-D9, the preparation process of which is the same as that of Example 28, except that 3 mmol of kojic acid distearate and 3 mmol of tributyl citrate are replaced by 6 mmol of kojic acid distearate, kojic acid dibenzoate, acetyl tributyl citrate, and ascorbyl palmitate, respectively.

[0134] polymerization

[0135] Polymerization evaluation using solid catalyst as a component of olefin polymerization catalyst:

[0136] After fully nitrogen-purging a 5L stainless steel reactor, 5mL of a 0.5mol / L triethylaluminum hexane solution, 1mL of a 0.1mol / L methylcyclohexyldimethoxysilane hexane solution, and 10mg of the prepared catalyst component were added. The feed line was then flushed with 10mL of hexane. 2L of hydrogen (under standard conditions) and 2.5L of purified propylene were then added. The reaction was prepolymerized at 25°C for 5 minutes, then heated to 70°C and polymerized for 1 hour at this temperature. After the reaction was complete, the reactor was cooled and stirring was stopped. The reaction product was discharged and dried to obtain a polymer. Polymerization data are shown in Table 3.

[0137] Table 3

[0138]

Note

[0139] b1: tributyl citrate;

[0140] b2: acetyl tributyl citrate;

[0141] b3: benzoyl tributyl citrate;

[0142] b4: L-ascorbyl palmitate;

[0143] b5: ascorbyl dipalmitate;

[0144] b6: Ascorbyl tetrapalmitate.

[0145] Examples 28-39 employ binary compounding of kojic acid ester compounds and citrate compounds or ascorbyl palmitate compounds. Most of the activities are higher than those of the phthalate internal electron donor catalyst (Comparative Example 4), and some are higher than those of the fluorene diether internal electron donor catalyst (Comparative Example 5). The compounding results in high isotacticity and a significantly broadened molecular weight distribution. Examples 40-50 employ ternary compounding of kojic acid ester compounds, citrate compounds, and ascorbyl palmitate compounds. The activities are higher than those of the comparative examples, the molecular weight distribution is further broadened, the isotacticity is higher, the polymer particles are regular, and the bulk density is high.

Claims

1. A catalyst component for olefin polymerization, comprising: Mg, Ti, halogen, kojic acid ester internal electron donors; in, The kojic acid ester 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 of hydrocarbon groups.

2. The catalyst component according to claim 1, wherein R 1 , R 2 , R 3 and R 4 Each of the heteroatoms contains one or a combination of two or more selected from halogen, N, O, S, P and Si.

3. The catalyst component according to claim 1, wherein R 1 , R 2 , R 3 and R 4 Two or more of them are bonded to each other to form a ring.

4. The catalyst component according to claim 1, wherein The composition of the catalyst component comprises: Mg, Ti, halogen, the kojic acid ester internal electron donor and other internal electron donors, wherein the other internal electron donors include citrate compounds and / or ascorbate compounds; Wherein, the citrate compound has a structure shown in Formula II: In formula II, R 5 , R 6 and R 7 The same or different, each independently selected from C1-C 20 The hydrocarbon group; R 8 Selected from hydrogen, C1-C 20 Hydrocarbon, C2-C 21 The acyl group; The ascorbic acid ester compound has a structure shown in Formula III: In Formula III, R 9 , R 10 , R 11 and R 12 are the same or different, each independently selected from H, R-CO-, wherein R is selected from C1-C 20 The hydrocarbon group; R 9 , R 10 , R 11 and R 12 At least one of them is not H.

5. The catalyst component according to claim 4, wherein In formula II, R 5 -R 8 Each of the heteroatoms contains one or a combination of two or more selected from halogen, N, O, S, P, Ge and Si.

6. The catalyst component according to claim 4, wherein In formula II, R 5 , R 6 and R 7 Two or more of them are bonded to each other to form a ring.

7. The catalyst component according to claim 4, wherein In Formula III, R comprises a heteroatom selected from the group consisting of halogen, N, O, S, P and Si, or a combination of two or more thereof.

8. The catalyst component according to claim 4, wherein In Formula III, R 9 , R 10 , R 11 and R 12 Two or more non-H groups in the molecule are bonded to each other to form a ring.

9. 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.

10. The catalyst component according to claim 9, 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.

11. The catalyst component according to claim 10, wherein In Formula I, R 1 and R 2 Selected from C1-C 20 The hydrocarbon group; R 3 and R 4 Both are H.

12. The catalyst component according to claim 1, wherein The kojic acid ester internal electron donor includes kojic acid diacetate, kojic acid dipropionate, kojic acid di-n-butyrate, kojic acid diisobutyrate, kojic acid di-n-valerate, kojic acid diisovalerate, kojic acid di-tert-valerate, kojic acid di-n-hexanoate, kojic acid diisohexanoate, kojic acid dicyclopentacarboxylate, kojic acid di-n-heptanoate, kojic acid dicyclohexylcarboxylate, kojic acid dioctanoate, kojic acid dipelanteate, kojic acid didecanoate, kojic acid di(undecanoic acid) ester, kojic acid dilaurate, kojic acid dimyristate, kojic acid dipalmitate, kojic acid distearate, kojic acid dibenzoate , kojic acid diphenylacetate, kojic acid diphenylpropionate, kojic acid di-o-chlorobenzoate, kojic acid di-m-chlorobenzoate, kojic acid di-p-toluate, kojic acid di-p-methoxybenzoate, kojic acid m-trimethylbenzoate, kojic acid p-nitrobenzoate, kojic acid p-fluorobenzoate, kojic acid p-trifluoromethylbenzoate, kojic acid dicrotonate, kojic acid di(1-naphthoic acid) ester, kojic acid dinicotinate, kojic acid di(monoethyl succinate), kojic acid dicinnamate, kojic acid di(α-thiophene)carboxylate, kojic acid difuroate, or a combination of two or more thereof.

13. The catalyst component according to claim 4, wherein In formula II, R 5 , R 6 and R 7 Each independently selected from C1-C 20 Straight or branched alkyl, C1-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl aryl, C7-C 20 of an aromatic hydrocarbon group.

14. The catalyst component according to claim 13, wherein In formula II, R 5 , R 6 and R 7 the same or different, each independently selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, cyclopentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl to eicosyl, C2-C 20 Alkenyl, C1-C 20 Ester group, C6-C 20 Phenyl, C7-C 20 Alkylphenyl, C7-C 20 Phenylalkyl, C 10 -C 20 Indenyl, C7-C 20 benzyl, C3-C 20 Halogenated cycloalkyl, C3-C 20 Heteroatom-containing cycloalkyl, C6-C 20 Halogenated phenyl, C6-C 20 Heteroatom-containing phenyl, C7-C 20 Halogenated alkylphenyl, C7-C 20 Heteroatom-containing alkylphenyl, C7-C 20 Halogenated phenyl alkyl, C7-C 20 Heteroatom-containing phenylalkyl, C 10 -C 20 The halogenated indenyl, C 10 -C 20 Heteroatom-containing indenyl, C7-C 20 Halogenated benzyl, C7-C 20 A benzyl or heterocyclic aromatic substituent containing a heteroatom; the heteroatom includes one or a combination of two or more of N, O, S, P, Si, and Ge.

15. The catalyst component according to claim 14, wherein The heterocyclic aromatic substituents include furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, pteridine, and acridine.

16. The catalyst component according to claim 14, wherein R 5 , R 6 and R 7 Bonded to each other to form a ring.

17. The catalyst component according to claim 4, wherein In formula II, R 8 Selected from H, C1-C 20 of hydrocarbon groups.

18. The catalyst component according to claim 4, wherein In formula II, R 8 Selected from C1-C 20 Straight or branched alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl aryl and C7-C 20 of an aromatic hydrocarbon group.

19. The catalyst component according to claim 4, wherein In formula II, R 8 is selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, cyclopentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl to eicosyl, C2-C 20 Alkenyl, C1-C 20 Ester group, C6-C 20 Phenyl, C7-C 20 Alkylphenyl, C7-C 20 Phenylalkyl, C 10 -C 20 Indenyl, C7-C 20 benzyl, C3-C 20 Halogenated cycloalkyl, C3-C 20 Heteroatom-containing cycloalkyl, C6-C 20 Halogenated phenyl, C6-C 20 Heteroatom-containing phenyl, C7-C 20 Halogenated alkylphenyl, C7-C 20 Heteroatom-containing alkylphenyl, C7-C 20 Halogenated phenyl alkyl, C7-C 20 Heteroatom-containing phenylalkyl, C 10 -C 20 The halogenated indenyl, C 10 -C 20 Heteroatom-containing indenyl, C7-C 20 Halogenated benzyl, C7-C 20 A benzyl or heterocyclic aromatic substituent containing a heteroatom; the heteroatom includes one or a combination of two or more of N, O, S, P, Si, and Ge.

20. The catalyst component according to claim 4, wherein The ascorbic acid ester compound includes one or a combination of two or more of an ascorbic acid monoester compound, an ascorbic acid diester compound, and an ascorbic acid tetraester compound; The ascorbic acid monoester compound has a structure shown in Formula IV: The ascorbic acid diester compound has a structure shown in Formula V: The tetraascorbic acid compound has a structure shown in Formula VI: In Formula IV to Formula VI, R 13 To R 19 Each independently selected from C1-C 20 of hydrocarbon groups.

21. The catalyst component according to claim 20, wherein R 13 To R 19 Each is independently selected from the following substituents having 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, and heterocyclic aromatic substituents; the heteroatoms include one or a combination of two or more of N, O, S, P, and Si.

22. The catalyst component according to claim 20, wherein R 13 To R 19 each independently selected from 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.

23. The catalyst component according to claim 20, wherein The ascorbic acid monoester compound represented by formula IV is selected from ascorbic acid acetate, ascorbic acid propionate, ascorbic acid n-butyrate, ascorbic acid isobutyrate, ascorbic acid n-valerate, ascorbic acid isovalerate, ascorbic acid tert-valerate, ascorbic acid n-hexanoate, ascorbic acid isocaproate, ascorbic acid cyclopentylcarboxylate, ascorbic acid n-heptanoate, ascorbic acid cyclohexylcarboxylate, ascorbic acid octanoate, ascorbic acid nonanoate, ascorbic acid decanoate, ascorbic acid undecanoate, ascorbic acid laurate, ascorbic acid myristate, ascorbic acid palmitate, ascorbic acid stearate, ascorbic acid benzoate. Ascorbyl ester, ascorbyl phenylacetate, ascorbyl phenylpropionate, ascorbyl o-chlorobenzoate, ascorbyl m-chlorobenzoate, ascorbyl p-toluate, ascorbyl p-methoxybenzoate, ascorbyl m-trimethylbenzoate, ascorbyl p-nitrobenzoate, ascorbyl p-fluorobenzoate, ascorbyl p-trifluoromethylbenzoate, ascorbyl crotonate, ascorbyl (1-naphthoic acid) ester, ascorbyl nicotinate, ascorbyl (monoethyl succinate), ascorbyl cinnamate, ascorbyl (α-thiophene) carboxylate, ascorbyl furoate, or a combination of two or more thereof.

24. The catalyst component according to claim 20, wherein The ascorbic acid diester compound represented by formula V is selected from ascorbic acid diacetate, ascorbic acid dipropionate, ascorbic acid di-n-butyrate, ascorbic acid diisobutyrate, ascorbic acid di-n-valerate, ascorbic acid diisovalerate, ascorbic acid di-tert-valerate, ascorbic acid di-n-hexanoate, ascorbic acid diisohexanoate, ascorbic acid dicyclopentanecarboxylate, ascorbic acid di-n-heptanoate, ascorbic acid dicyclohexylcarboxylate, ascorbic acid dioctanoate, ascorbic acid dipelargonate, ascorbic acid dicaprate, ascorbic acid diundecanoate, ascorbic acid dilaurate, ascorbic acid dimyristate, ascorbic acid dipalmitate, ascorbic acid distearate, ascorbic acid Ascorbic acid dibenzoate, ascorbic acid diphenylacetate, ascorbic acid diphenylpropionate, ascorbic acid di-o-chlorobenzoate, ascorbic acid di-m-chlorobenzoate, ascorbic acid di-p-toluate, ascorbic acid di-p-methoxybenzoate, ascorbic acid m-trimethylbenzoate, ascorbic acid p-nitrobenzoate, ascorbic acid p-fluorobenzoate, ascorbic acid p-trifluoromethylbenzoate, ascorbic acid dicrotonate, ascorbic acid di(1-naphthoic acid) ester, ascorbic acid dinicotinate, ascorbic acid di(monoethyl succinate), ascorbic acid dicinnamate, ascorbic acid di(α-thiophenecarboxylic acid) ester, ascorbic acid difuroate, or a combination of two or more thereof.

25. The catalyst component according to claim 20, wherein The ascorbic acid tetraester compound represented by formula VI is selected from ascorbic acid tetraacetate, ascorbic acid tetrapropionate, ascorbic acid tetra-n-butyrate, ascorbic acid tetraisobutyrate, ascorbic acid tetra-n-valerate, ascorbic acid tetraisovalerate, ascorbic acid tetra-tert-valerate, ascorbic acid tetra-n-hexanoate, ascorbic acid tetraisohexanoate, ascorbic acid tetracyclopentacarboxylate, ascorbic acid tetra-n-heptanoate, ascorbic acid tetracyclohexylcarboxylate, ascorbic acid tetraoctanoate, ascorbic acid tetrapelargonate, ascorbic acid tetradecanoate, ascorbic acid tetra(undecanoate), ascorbic acid tetralaurate, ascorbic acid tetramyristate, ascorbic acid tetrapalmitate, ascorbic acid tetrastearate, ascorbic acid tetra-hexanoate ...hexanoate, ascorbic acid tetra-hexanoate, ascorbic acid tetra-hexanoate, ascorbic acid tetra-hexanoate, ascorbic acid tetra-hexanoate, ascorbic acid tetra-hexanoate, ascorbic acid tetra-hexanoate, ascorbic acid tetra-hexanoate, ascorbic acid tetra-hexanoate, ascorbic acid tetra-hexanoate, ascorbic acid tetra-hexanoate Ascorbic acid tetrabenzoate, ascorbic acid tetraphenylacetate, ascorbic acid tetraphenylpropionate, ascorbic acid tetra-o-chlorobenzoate, ascorbic acid tetra-m-chlorobenzoate, ascorbic acid tetra-p-toluate, ascorbic acid tetra-p-methoxybenzoate, ascorbic acid m-trimethylbenzoate, ascorbic acid p-nitrobenzoate, ascorbic acid p-fluorobenzoate, ascorbic acid p-trifluoromethylbenzoate, ascorbic acid tetracrotonate, ascorbic acid tetra(1-naphthoic acid) ester, ascorbic acid tetranicotinate, ascorbic acid tetra(monoethyl succinate), ascorbic acid tetracinnamate, ascorbic acid tetra(α-thiophene)carboxylate, ascorbic acid tetrafuroate, or a combination of two or more thereof.

26. The catalyst component according to claim 4, wherein The feeding molar ratio of the kojic acid ester internal electron donor to other internal electron donors is ≥0.1:

1.

27. The catalyst component according to any one of claims 1 to 26, wherein The catalyst component comprises a titanium compound, a magnesium compound, the kojic acid ester internal electron donor or, The catalyst component comprises a titanium compound, a magnesium compound, the kojic acid ester internal electron donor and other internal electron donors; 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.

28. The catalyst component according to claim 27, 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 in which at least one halogen atom in a magnesium dihalide molecule is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group.

29. The catalyst component according to claim 28, wherein The magnesium compound is a magnesium alkoxide compound.

30. The catalyst component according to claim 29, wherein The magnesium compound is alkoxy magnesium and / or aryloxy magnesium.

31. The catalyst component according to claim 27, wherein The titanium compound includes one or a combination of two or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide.

32. The catalyst component according to claim 31, wherein 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.

33. The catalyst component according to claim 31, wherein The titanium compound is titanium tetrachloride.

34. The catalyst component according to claim 27, wherein The molar ratio of the sum of the internal electron donors to the magnesium compound is 0.01-5.0, and the magnesium compound is calculated as magnesium element.

35. The catalyst component according to claim 27, wherein The molar ratio of the total internal electron donor to the magnesium compound is 0.05-3.0, and the magnesium compound is calculated as magnesium element.

36. A method for preparing a catalyst component according to any one of claims 1 to 35, wherein the preparation steps comprise: A magnesium compound, a titanium compound and an internal electron donor are brought into contact with each other to obtain the catalyst component.

37. The preparation method according to claim 36, wherein The magnesium compound is magnesium dihalide; or the magnesium compound is a derivative of magnesium dihalide in which at least one halogen atom in the molecule is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; or the magnesium compound is alkoxymagnesium and / or aryloxymagnesium; or the magnesium compound is an alcoholate of magnesium dihalide.

38. The preparation method according to claim 36, wherein The preparation method comprises the following steps: in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters, a liquid magnesium compound is contacted with a liquid titanium compound to precipitate a solid product, and the solid product is contacted with an internal electron donor to obtain the catalyst component.

39. A catalyst for olefin polymerization, comprising the catalyst component according to any one of claims 1 to 35 and an organic aluminum compound.

40. The catalyst according to claim 39, wherein The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C1-C 20 wherein X is a halogen and p is an integer of 0≤p≤3.

41. The catalyst according to claim 40, wherein The organoaluminum compound includes one or a combination of two or more of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

42. The catalyst according to claim 41, wherein 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; and the alkylaluminum sesquichloride includes Al2Et3Cl3.

43. The catalyst according to claim 41, wherein The organic aluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

44. The catalyst according to claim 39, wherein The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:

1.

45. The catalyst according to claim 39, wherein The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 50-800.

46. ​​The catalyst according to claim 39, wherein The raw material composition of the catalyst also includes an external electron donor.

47. The catalyst according to claim 46, wherein The external electron donor is a siloxane compound.

48. The catalyst according to claim 47, 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.

49. The catalyst according to claim 48, wherein R' and R" each contain a heteroatom.

50. The catalyst according to claim 47, wherein The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100.

51. The catalyst according to claim 47, wherein The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.01-20.

52. The catalyst according to claim 47, wherein The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.01-5.

53. Use of the catalyst described in any one of claims 39 to 52 in olefin polymerization.

54. The use according to claim 53, wherein: The olefins include 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.

55. The use according to claim 53, wherein: The polymerization comprises ethylene and / or propylene polymerization.

56. The use according to claim 53, wherein: The polymerization includes homopolymerization or copolymerization.

57. The use according to claim 53, wherein: The polymerization temperature is ≤ 200°C.

58. The use according to claim 53, wherein: The polymerization pressure is ≤10 MPa.

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