Catalyst components for olefin polymerization, their preparation method, and use.

Abstract

This invention relates to an olefin polymerization catalyst, and discloses a catalyst component for olefin polymerization, a method for preparing the same, and its use. The catalyst component of this invention comprises magnesium, titanium, a halogen, and an electron donor, the electron donor comprising furan compounds and diether compounds. When this catalyst component is used in olefin polymerization, the molecular weight distribution of the prepared polymer with a low melt index is broader than that of the polymer with a high melt index.

Description

Detailed description of the invention

[0001] [Cross-reference of related applications] This application claims the benefits of Chinese patent applications 202310721613.3 and 202310722783.3, filed on 16 June 2023, the contents of which are incorporated herein by reference.

[0002] [Technical Field] This invention belongs to the field of olefin polymerization catalysts, and more specifically, relates to catalyst components for olefin polymerization, as well as methods for preparing and using the same.

[0003] [Background technology] As is well known, Zn catalysts have been continuously developed since their introduction and have become the main catalysts for industrial olefin polymerization reactions.

[0004] As internal electron donors that facilitate the development of Zn catalysts, the process has progressed from monobasic acid ester compounds, such as ethyl benzoate and p-ethoxybenzoate, which are third-generation Zn catalysts, to dibasic acid ester compounds such as di(iso)butyl phthalate, which are fourth-generation Zn catalysts. Phthalate compounds (plasticizers) are currently the most commonly used internal electron donors in polypropylene catalysts, and research suggests that they can cause serious damage to the growth, development, and reproductive systems of animals, and may have similar effects on humans. In the United States, the European Union, and other countries and regions, such compounds are being successively designated as hazardous chemicals, and their use (especially in toys for infants and young children) is being severely restricted. Therefore, the development of high-performance catalysts that do not contain phthalate compounds is urgently needed.

[0005] High-flow polypropylene is one of the major future development directions for polypropylene due to its excellent processing properties. Generally, obtaining olefin polymers with high melt flow rates requires reducing the polymer's molecular weight by adding large amounts of hydrogen during polymerization. However, the upper limit of the amount of hydrogen that can be added is limited by the pressure resistance of the polymerization reactor. Adding more hydrogen requires lowering the partial pressure of the polymerization olefin gas, which reduces productivity. Furthermore, polymers obtained using conventional olefin polymerization catalysts have problems with insufficient processing properties for low-flow polymers and with a large amount of precipitates in high-flow polymers.

[0006] [Summary of the Invention] [Problems the invention aims to solve] The object of the present invention is to provide an olefin polymerization catalyst. When this olefin polymerization catalyst is used in olefin polymerization, the polymer prepared has a molecular weight distribution that narrows as the melt index increases. As a result, polymers with a low melt index have good processing properties, while polymers with a high melt index produce relatively few precipitates, thereby achieving both good processing properties and environmental protection. Furthermore, the catalyst components of the present invention do not contain phthalate compounds (plasticizers).

[0007] [Means for solving the problem] A first aspect of the present invention provides a catalyst component for olefin polymerization, wherein the catalyst component comprises a magnesium element, a titanium element, a halogen, and an electron donor, the electron donor comprises a furan compound and a diether compound, and the furan compound is at least one selected from furan compounds represented by formula (I). [ka] (In equation (I), R1 and R3 are, independently, hydrogen, C1~C 20 Linear or branched alkyl groups, C3-C 20cycloalkyl, C6-C 20 aryl, C7-C 20 aralkyl, or C7-C 20 alkaryl selected from, and R2 and R4 are each independently C1-C 10 linear or branched alkyl, C3-C 10 cycloalkyl, C6-C 10 aryl, C7-C 10 aralkyl, or C7-C 10 alkaryl selected from.)

[0008] A second aspect of the present invention is a method for preparing a catalyst component for olefin polymerization, the method comprising the step of mixing a magnesium source, a titanium source, and an electron donor, wherein the electron donor includes a furan-based compound and a diether-based compound, and the furan-based compound includes at least one selected from furan-based compounds represented by formula (I).[[ID=2!]]

Chemical formula

[0009] A third aspect of the present invention is a catalyst system for olefin polymerization, the catalyst system comprising (1) A catalyst component described in the first aspect and / or a catalyst component prepared by the method described in the second aspect, (2) At least one alkylaluminum, (3) A catalyst system for olefin polymerization is provided, comprising any other electron donor.

[0010] A fourth aspect of the present invention provides the use of the catalyst component described in the first aspect, and / or the catalyst component prepared by the method described in the second aspect, and / or the catalyst system described in the third aspect in olefin polymerization.

[0011] A fifth aspect of the present invention provides an olefin polymerization method, the olefin polymerization method comprising the step of carrying out an olefin polymerization reaction in the presence of a catalyst component described in the first aspect and / or a catalyst component prepared by the method described in the second aspect and / or a catalyst system described in the third aspect.

[0012] [Effects of the invention] The present invention achieves the following beneficial effects through the above-described technical solutions. (1) Polymers prepared under low-hydrogen polymerization conditions using the catalyst component of the present invention, which is composed of a furan compound and a diether compound represented by formula (I) as electron donors, have a relatively broad molecular weight distribution and can effectively improve processing properties. Polymers prepared under high-hydrogen polymerization conditions have a molecular weight distribution that narrows with increasing hydrogen, thus reducing the content of small molecules in polymers with high melt index, which is advantageous for reducing precipitate content. Furthermore, products with high melt index themselves have relatively excellent processing properties. In addition, when used in olefin polymerization, the catalyst component has a good balance between hydrogen responsiveness and stereospecificity. (2) The catalyst component of the present invention, which uses a magnesium-containing solid component containing sulfur as a support and incorporates a furan compound and a diether compound as an electron donor, preferably has a relatively narrow particle size distribution. When used in olefin polymerization, this catalyst component not only has a good balance between hydrogen responsiveness and stereospecificity, but the molecular weight distribution of the prepared polymer narrows with increasing melt index, and furthermore, the polymer has a relatively low fine powder content.

[0013] [Modes for carrying out the invention] The endpoints and any values ​​of the ranges disclosed herein are not limited to such precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to them. In the case of numerical ranges, one or more new numerical ranges can be obtained by combining the endpoint values ​​of each range, the endpoint values ​​of each range and individual dot values, and individual dot values, and these numerical ranges are deemed to be specifically disclosed herein.

[0014] In the present invention, unless otherwise specified, "electron donor" usually refers to an internal electron donor in the relevant field, and "other electron donor" usually refers to an external electron donor in the relevant field.

[0015] A first aspect of the present invention provides a catalyst component for olefin polymerization, wherein the catalyst component comprises a magnesium element, a titanium element, a halogen, and an electron donor, the electron donor comprises a furan compound and a diether compound, and the furan compound is at least one selected from furan compounds represented by formula (I). [ka] (In equation (I), R1 and R3 are, independently, hydrogen, C1~C 20 Linear alkyl groups, C3~C 20 Branched alkyl, C3~C 20 Cycloalkyl, C6~C 20aryl, C7~C 20 Aralkill of C7~C 20 Selected from the alkalis, R2 and R4 are independently C1~C 10 Linear alkyl groups, C3~C 10 Branched alkyl, C3~C 10 Cycloalkyl, C6~C 10 aryl, C7~C 10 Aralkill of C7~C 10 (Selected from the alkalis.)

[0016] According to the present invention, in formula (I), R1 and R3 may each be independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, and preferably, in formula (I), R1 and R3 are each independently selected from hydrogen, a C1-C6 linear alkyl group, or a C3-C6 branched alkyl group.

[0017] According to the present invention, in formula (I), R2 and R4 may each be independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, preferably in formula (I), R2 and R4 are each independently selected from a linear alkyl group of C1 to C6 or a branched alkyl group of C3 to C6, and more preferably selected from a linear alkyl group of C1 to C3.

[0018] The inventors unexpectedly discovered that when a diether compound and a furan compound represented by formula (I) of this application are used as an electron donor in combination, a synergistic effect can be achieved. When this is used in olefin polymerization, the molecular weight distribution of the prepared polymer narrows with increasing melt index, thereby achieving both good processing properties and environmental protection. Furthermore, the catalyst component has a good balance between hydrogen responsiveness and stereospecificity.

[0019] According to the present invention, preferably, in the catalyst component, the content of the furan compound per mole of the diether compound is 0.01 to 2 moles. For example, in the catalyst component, the content of the furan compound per mole of the diether compound may be in the range of 0.01 moles, 0.05 moles, 0.06 moles, 0.07 moles, 0.08 moles, 0.09 moles, 0.1 moles, 0.15 moles, 0.2 moles, 0.25 moles, 0.3 moles, 0.35 moles, 0.4 moles, 0.45 moles, 0.5 moles, 0.6 moles, 0.7 moles, 0.8 moles, 0.9 moles, 1 mole, 1.1 moles, 1.2 moles, 1.5 moles, 2 moles, and any two of the above values. More preferably, in the catalyst component, the content of the furan compound per mole of the diether compound is 0.03 to 1.2 moles, and even more preferably 0.05 to 0.4 moles. When the molar ratio of the diether compound to the furan compound in the catalyst component is within the above-mentioned more preferable range, the synergistic effect of these two electron donors becomes more pronounced, further improving hydrogen responsiveness and stereospecificity, and narrowing the molecular weight distribution of the polymer under high hydrogen conditions.

[0020] According to the present invention, preferably, based on the total weight of the electron donor, the total content of the furan-based compound and the diether-based compound in the electron donor is 70% to 100% by weight, more preferably 80% to 100% by weight, and even more preferably 90% to 100% by weight.

[0021] According to the present invention, preferably, the furan compound is at least one selected from the furan compounds represented by formula (I-1). [ka] (In equation (I-1), R1, R2, R3, and R4 are as described in equation (I), so they will not be explained in detail here.)

[0022] According to the present invention, preferably, the furan compound is at least one selected from (3R,3aR,6S,6aR)-3-methoxy-6-propoxyhexahydrofloo[3,2-b]furan, (3R,3aR,6S,6aR)-3-methoxy-6-ethoxyhexahydrofloo[3,2-b]furan, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofloo[3,2-b]furan, and (3R,3aR,6S,6aR)-3,6-diethoxyhexahydrofloo[3,2-b]furan. More preferably, the furan compound is (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydroflu[3,2-b]furan.

[0023] According to the present invention, the diether compound may be a diether compound of various electron donors that can be used as catalysts for olefin polymerization, and preferably, the diether compound is at least one selected from the diether compounds represented by formula (II). [ka] (In equation (II), R I , R II , R III , R IV , R V and R VI They are either identical or different, and each is independently of hydrogen, halogen atoms, and C1-C 20 Linear alkyl groups, C3~C 20 Branched alkyl, C3~C 20 Cycloalkyl, C6~C 20 aryl, C7~C 20 Aralkill of C7~C 20 Selected from the alkalis, R I ~R VI The groups may be arbitrarily bonded to each other to form a ring, R VII and R VIII They are either identical or different, and each is independent of C1~C 20Linear alkyl groups, C3~C 20 Branched alkyl, C3~C 20 Cycloalkyl, C6~C 20 aryl, C7~C 20 Alkali, or C7~C 20 (Selected from the Aralquil.)

[0024] According to the present invention, preferably in formula (II), R I , R II , R III , R IV , R V and R VI These are, independently, hydrogen, C1~C 20 Linear alkyl groups, C3~C 20 Selected from branched alkyl groups, or R III , R IV These are bonded to form a fluorene ring. More preferably, in formula (II), R I , R II , R III , R IV , R V and R VI Each of these is independently selected from hydrogen, a C1-C7 linear alkyl group, and a C3-C7 branched alkyl group.

[0025] According to the present invention, preferably in formula (II), R III , R IV When bonded to form a fluorene ring, the diether compound has the structure of formula (II-1). [ka] (In equation (II-1), R I , R II , R V , R VI , R VII and R VIII This is as shown in equation (II).

[0026] According to the present invention, preferably in formula (II), R VII and RVIII Each of these is independently selected from a linear alkyl group of C1-C5 and a branched alkyl group of C3-C5.

[0027] According to the present invention, preferably the diether compound is 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane Methoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl 2-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3 -Dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,The diether compound is at least one selected from 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene. More preferably, the diether compound is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-bis(methoxymethyl)fluorene.

[0028] In the catalyst component of the present invention, the magnesium content may be 2 to 18 parts by weight, preferably 3 to 16 parts by weight, per 1 part by weight of titanium.

[0029] In the catalyst component of the present invention, the content of the electron donor per 1 part by weight of titanium element may be 2 to 17 parts by weight, preferably 3 to 15 parts by weight.

[0030] According to the present invention, the catalyst component may further contain halogens, and the halogen in the catalyst component may be at least one of fluorine, chlorine, bromine, and iodine. The halogen in the catalyst component may be a halogen contained in magnesium and / or titanium.

[0031] According to the present invention, the source of the magnesium element may be any magnesium-containing compound capable of preparing a polyolefin catalyst component, preferably at least one selected from magnesium halides (e.g., magnesium chloride and / or magnesium bromide), magnesium alcohols (e.g., diethoxymagnesium), magnesium haloalcoates (e.g., ethoxymagnesium chloride), magnesium alcohol adducts, magnesium halide adducts (e.g., magnesium halide adducts disclosed in patent applications CN1091748, CN101050245, CN101486722, CN102796132B, CN102796129B and CN102796128B, etc., all relevant information disclosed in these patent applications is incorporated into the present invention by reference), and magnesium-containing solid components.

[0032] In the present invention, the magnesium halide alcohol adduct may be, for example, at least one of the structures represented by formula (IV). MgX2 m'R7OH formula (IV) In formula (IV), X is a halogen, preferably chlorine or bromine, m' is 1 to 5, and R7 is a C1 to C6 linear or branched alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, or hexyl.

[0033] In the present invention, the magnesium-containing solid component may be, for example, at least one of the structures represented by formula (III). [ka] (In formula (III), R1 is a C1-C6 linear or branched alkyl group, R2 and R3 are the same or different, independently of hydrogen or a C1-C5 linear or branched alkyl group, where hydrogen in the alkyl group may optionally be substituted with a halogen atom, X is a halogen, preferably chlorine or bromine, m is 0.1-1.9, n is 0.1-1.9, m+n=2, 0 <q≦0.5である。)

[0034] According to the present invention, preferably, the magnesium-containing solid component has an average particle diameter of 12 to 30 μm, a particle size distribution of less than 1.2, and more preferably 0.2 to 0.8. In the present invention, the average particle diameter and particle size distribution of the olefin polymerization catalyst support (magnesium-containing solid component) can be measured using a Master Sizer 2000 laser particle size analyzer (manufactured by Malvern Instruments Ltd).

[0035] The raw materials for synthesizing the magnesium-containing solid component include a sulfur source and a general formula MgX 2 Y includes magnesium halides, compounds with the general formula R4OH, and ethylene oxide compounds, with the general formula MgX 2 In Y, X 2 Y is a halogen, and Y is a halogen or an alkyl group of C1-C6, an alkoxy group of C1-C5, or a C6-C6 group. 10 The aryl, or C6~C 10 The aryloxy compound is represented by the general formula R4OH, where R4 is a C1-C8 alkyl or a C3-C8 cycloalkyl, and the structure of the ethylene oxide compound is shown by formula (V). [ka] (In formula (V), R5 and R6 are independently hydrogen, a C1-C5 alkyl group, or a C1-C5 haloalkyl group.)

[0036] According to the present invention, the sulfur source is sulfur without water of crystallization or sulfur containing water of crystallization, sulfur or sulfur bromide, sulfur chloride or sulfur iodide, preferably sulfur and / or sulfur chloride, more preferably α-sulfur and / or β-sulfur.

[0037] According to the present invention, in the general formula MgX 2 Y, X 2 is preferably chlorine or bromine, and Y is preferably chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 aryl, or C6-C 10 aryloxy. The C1-C5 alkyl may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, or neopentyl. The C1-C5 alkoxy may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy. The C6-C 10 aryl may be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, or naphthyl. The C6-C 10 aryloxy may be, for example, phenoxy or naphthoxy.

[0038] The magnesium halide of the general formula MgX 2 Y may be one kind of magnesium halide or a mixture of plural kinds of magnesium halides. Specific examples of the magnesium halide of the general formula MgX 2 Y include, but are not limited to, one or more of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride, and n-butoxymagnesium chloride. From the viewpoint of easy availability of raw materials, magnesium chloride is preferred. <00,00324> According to the present invention, in the general formula R4OH, R4 is preferably an alkyl having 1 to 8 carbon atoms, and the alkyl having 1 to 8 carbon atoms is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, or isooctyl. Specific examples of the compound having the general formula R4OH may be one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol, but are not limited thereto.

[0040] According to the present invention, in the ethylene oxide-based compound whose structure is represented by the formula (V), R5 and R6 are preferably each independently hydrogen, an alkyl having 1 to 3 carbon atoms, or a haloalkyl having 1 to 3 carbon atoms. Specific examples of the ethylene oxide-based compound may be one or more of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epoxychlorobutane, epoxybromopropane, and epoxybromobutane, but are not limited thereto.

[0041] According to the present invention, the water contained in the magnesium-containing solid component is derived from trace amounts of water contained in the synthesis raw materials and the reaction medium.

[0042] The method for preparing the magnesium-containing solid component of the present invention includes the following steps. (a) A sulfur source, magnesium halide having the general formula MgX 2 Y, a compound having the general formula R4OH, and an arbitrary inert liquid medium are mixed and heated to obtain a liquid mixture. (b) The liquid mixture obtained in step (a) is emulsified, and the emulsified product is brought into contact with an ethylene oxide-based compound and reacted. <着

[0043] In the general formula MgX 2 Y, X 2R is a halogen, Y is a halogen or a C1-C6 alkyl, and in the general formula R4OH, R4 is a C1-C8 alkyl or a C3-C8 cycloalkyl, and the structure of the ethylene oxide compound is shown by formula (V). [ka] Here, the general formula is MgX 2 The types of magnesium halide (Y), compounds with the general formula R4OH, sulfur sources, and ethylene oxide compounds are described above and will not be explained in detail here.

[0044] According to the present invention, the general formula is MgX 2 Based on 1 mol of magnesium halide Y, the amount of sulfur source used is 0.0001 to 0.1 mol, the amount of compound with general formula R4OH used is 4 to 30 mol, and the amount of ethylene oxide compound represented by the structure of formula (V) used is 1 to 10 mol, preferably with general formula MgX 2 Based on 1 mole of magnesium halide (Y), the amount of compound with the general formula R4OH used is 6 to 20 moles, and the amount of ethylene oxide compound represented by the structure of formula (V) used is 2 to 6 moles.

[0045] According to the present invention, even trace amounts of water in the above-mentioned reactants can participate in the formation reaction of the magnesium-containing solid component.

[0046] According to the present invention, a surfactant may be added to the liquid mixture of step (a) and used, and the surfactant is selected from polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyacrylic acid, polyacrylate, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer-modified polyethyleneimine, polymer of 1-dodeca-4-ethylenepyridine bromide, polyvinylbenzyltrimethylamine salt, polyvinyl alcohol, polyacrylamide, polyethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether, and polyalkyl methacrylate compounds, or a combination thereof, and preferably one of polyvinylpyrrolidone, polyvinylpyrrolidone vinyl acetate copolymer, and polyethylene glycol, or a combination thereof.

[0047] According to the present invention, in step (a), a sulfur source and a general formula of MgX 2 The conditions for heating a mixture of magnesium halide Y, a compound with the general formula R4OH, and any inert liquid medium are not particularly limited, and the heating conditions are as follows: 2 The magnesium halide Y should be melted and react sufficiently with the sulfur source. Generally, the heating conditions may include a temperature of 80 to 120°C and a duration of 0.5 to 5 hours, preferably a temperature of 80 to 100°C and a duration of 0.5 to 3 hours.

[0048] According to the present invention, the amount of the inert liquid medium used is given by a general formula of MgX 2 Y may be selected depending on the amount of magnesium halide used. Generally, the general formula is MgX 2Based on 1 mole of magnesium halide Y, the amount of the inert liquid medium used may be 0.8 to 10 L, preferably 2 to 8 L. The inert liquid medium may be any liquid medium commonly used in the art that does not chemically interact with the reactants and reaction products. For example, the inert liquid medium may be a silicone oil and / or an inert liquid hydrocarbon solvent. Specifically, the inert liquid medium may be one or more of kerosene, paraffin oil, petrolatum oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methylphenyl silicone oil. White oil is particularly preferred as the inert liquid medium in the present invention.

[0049] According to the present invention, the liquid mixture obtained in step (a) may be emulsified by various methods known to those skilled in the art. For example, the liquid mixture can be emulsified by low-speed shearing or high-speed shearing. The stirring speed for low-speed shearing is typically 400 to 800 revolutions per minute. The high-speed shearing method is known to those skilled in the art and includes, for example, the high-speed stirring method disclosed in CN1151183C (i.e., stirring the solution containing the liquid magnesium halide adduct at a speed of 2000 to 5000 revolutions per minute). Furthermore, the liquid mixture can also be emulsified by referring to the methods disclosed in the following patents. Disclosed in CN1267508C is a method for rotating and dispersing a solution containing a liquid magnesium halide adduct on a supergravity bed (rotation speed of 100 to 3000 revolutions per minute), disclosed in CN1463990A is a method for outputting a solution containing a liquid magnesium halide adduct to an emulsifier at a speed of 1500 to 8000 revolutions per minute, and disclosed in US6020279 is a method for emulsifying a solution containing a liquid magnesium halide adduct by a spray method.

[0050] According to the present invention, in step (b), the conditions for contacting and reacting the emulsion product with the ethylene oxide compound may be any of the conventional conditions that can form an olefin polymerization catalyst support. For example, the conditions for the contact reaction may be a temperature of 50 to 120°C and a time of 20 to 60 minutes, preferably a temperature of 60 to 100°C and a time of 20 to 50 minutes.

[0051] According to the present invention, step (b) may further include a step of solid-liquid separation of the product obtained by the contact reaction, washing and drying the solid phase product. The solid-liquid separation may be any existing method capable of achieving separation of the solid and liquid phases, such as suction filtration, pressure filtration, or centrifugation, and preferably the solid-liquid separation method is pressure filtration. The present invention does not particularly limit the conditions of pressure filtration, as long as the separation of the solid and liquid phases is achieved as completely as possible. The washing can be performed by washing the obtained solid phase product in a manner known to those skilled in the art, for example, the obtained solid phase product can be washed with an inert hydrocarbon solvent (e.g., pentane, hexane, heptane, petroleum ether, and gasoline). In the present invention, the drying conditions are not particularly limited, but for example, the drying temperature may be 20 to 70°C and the drying time may be 0.5 to 10 hours. According to the present invention, the drying can be performed under atmospheric pressure or reduced pressure.

[0052] Preferably, the magnesium-containing solid component particles obtained in the above process for preparing the magnesium-containing solid component are washed with an inert hydrocarbon solvent (e.g., hexane, heptane, octane, decane, toluene, etc.) and dried, and used in a later step to prepare the catalyst component for olefin polymerization.

[0053] According to the present invention, the source of the titanium element may be any titanium-containing compound capable of preparing a polyolefin catalyst component, and preferably the source of the titanium element is a compound with the general formula Ti(OR') 3-a Z a and / or Ti(OR') 4-b Zb Selected from titanium compounds, where R' is C1~C 20 alkyl, preferably C1-C 14 The aliphatic hydrocarbon is preferably a C1-C8 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc., Z is F, Cl, Br or I, a is an integer from 1 to 3, and b is an integer from 0 to 4, preferably an integer from 1 to 4. More preferably, the titanium element is derived from one or more selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxytitanium chloride, dibutoxytitanium dichloride, butoxytitanium trichloride, triethoxytitanium chloride, diethoxytitanium dichloride, ethoxytitanium trichloride, and titanium trichloride.

[0054] According to one specific embodiment of the present invention, the present invention also provides a catalyst component for olefin polymerization, the catalyst component comprising a reaction product of a magnesium source, a titanium source, and an electron donor, the electron donor comprising a furan compound and a diether compound.

[0055] According to one specific embodiment of the present invention, the present invention also provides a catalyst component for olefin polymerization, the catalyst component comprising a reaction product of the following components: (1) Magnesium-containing solid components (2) at least one titanium-containing compound (titanium source), and (3) Electron donor Here, the electron donor comprises a furan compound and a diether compound, and the magnesium-containing solid component is at least one of the structures shown in formula (III).

[0056] A second aspect of the present invention provides a method for preparing a catalyst component for olefin polymerization, the method comprising the step of mixing a magnesium source, a titanium source, and an electron donor, wherein the electron donor comprises a furan compound and a diether compound, and the furan compound is at least one selected from the furan compounds represented by formula (I). [ka] (In equation (I), R1 and R3 are, independently, hydrogen, C1~C 20 Linear alkyl groups, C3~C 20 Branched alkyl, C3~C 20 Cycloalkyl, C6~C 20 aryl, C7~C 20 Aralkill of C7~C 20 Selected from the alkalis, R2 and R4 are independently C1~C 10 Linear alkyl groups, C3~C 10 Branched alkyl, C3~C 10 Cycloalkyl, C6~C 10 aryl, C7~C 10 Aralkill of C7~C 10 (Selected from the alkalis.)

[0057] The catalyst components for olefin polymerization of the present invention can be prepared by conventional methods. For example, the mixing method includes contacting and reacting a magnesium source and a titanium source, and adding an electron donor before, during, and after the contact reaction between the magnesium source and the titanium source, wherein each component of the electron donor may be added separately or simultaneously. The electron donor includes furan compounds and diether compounds. Specifically, the reaction between the magnesium source and the titanium source can be carried out in the same manner as in the prior art, for example, by cooling the titanium source to below 0°C (preferably -5 to -30°C), then adding the magnesium source, stirring and mixing at this temperature for 10 to 60 minutes, then raising the temperature to the reaction temperature (i.e., about 60 to 130°C), and maintaining this reaction temperature for 0.5 to 10 hours, preferably 0.5 to 5 hours. The period until the magnesium source and titanium source react refers to the period from when the magnesium source is added to the reactor until the temperature is raised to the reaction temperature.

[0058] According to one particularly preferred embodiment of the present invention, a method for preparing a catalyst component for olefin polymerization includes the steps of: adding a titanium source (e.g., titanium halide) to a reaction vessel and cooling to -30°C to 0°C; then adding a magnesium source to the reaction vessel and stirring and mixing at this temperature for 10 to 60 minutes; then raising the temperature to 0 to 130°C (preferably 80°C to 130°C); adding an electron donor during the heating process; and holding at 0 to 130°C (preferably 80°C to 130°C) for 10 to 900 minutes (preferably 20 to 240 minutes) before filtering off the liquid; and then washing with a titanium source (e.g., titanium halide), then washing with a non-polar solvent (e.g., hexane) and drying to obtain a catalyst component.

[0059] In the present invention, the types of furan compounds and diether compounds used in the method for preparing catalyst components for olefin polymerization are as described in the first embodiment and will not be described in detail here.

[0060] In the present invention, the types of magnesium and titanium sources used in the method for preparing catalyst components for olefin polymerization are as described in the first embodiment regarding the origin of the magnesium element and the origin of the titanium element, and therefore will not be described in detail here.

[0061] According to the present invention, in a method for preparing catalyst components for olefin polymerization, the amount of furan compound used per mole of diether compound may be 0.1 to 3 moles. For example, the amount of furan compound used per mole of diether compound may be in the range of 0.1 mole, 0.2 mole, 0.3 mole, 0.4 mole, 0.5 mole, 0.6 mole, 0.7 mole, 0.8 mole, 0.9 mole, 1 mole, 1.1 mole, 1.2 mole, 1.3 mole, 1.4 mole, 1.5 mole, 1.6 mole, 1.7 mole, 1.8 mole, 1.9 mole, 2 mole, 2.1 mole, 2.5 mole, 3 mole, and any two of the above values. Preferably, the amount of furan compound used per mole of diether compound is 0.1 to 2 moles, more preferably 0.15 to 1.8 moles. When the molar ratio of the diether compound to the furan compound in the catalyst component is within the above preferred range, the synergistic effect of these two electron donors becomes more pronounced, further improving hydrogen sensitivity and stereospecificity, and potentially yielding polymers with higher melt index and a narrower molecular weight distribution. The amount of furan compound used per mole of diether compound may be 0.1 to 1.5 moles, 0.15 to 1.5 moles, 0.15 to 1.2 moles, 0.15 to 1 mole, or 0.2 to 1 mole.

[0062] In the present invention, in a method for preparing a catalyst component for olefin polymerization, the molar ratio of the amount of magnesium source used in terms of magnesium element to the amount of titanium source used in terms of titanium element may be in the range of 1:5, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:200, 1:220, and any two of the above values. Preferably, in a method for preparing a catalyst component for olefin polymerization, the molar ratio of the amount of magnesium source used in terms of magnesium element to the amount of titanium source used in terms of titanium element is 1:5 to 220, more preferably 1:15 to 180, and even more preferably 1:18 to 150.

[0063] In the present invention, in a method for preparing a catalyst component for olefin polymerization, the molar ratio of the amount of magnesium source to the amount of electron donor used, in terms of magnesium element, may be in the range of 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1:1, 1:1.2, and any two of the above values. Preferably, in a method for preparing a catalyst component for olefin polymerization, the molar ratio of the amount of magnesium source to the amount of electron donor used, in terms of magnesium element, may be 1:0.05 to 1.2, more preferably 1:0.1 to 1, and even more preferably 1:0.15 to 0.9.

[0064] According to the present invention, preferably in a method for preparing a catalyst component for olefin polymerization, the molar ratio of the amount of magnesium source (calculated on a magnesium element basis), the titanium source (calculated on a titanium element basis), and the electron donor used may be 1:15 to 180:0.1 to 1, and more preferably 1:18 to 150:0.15 to 0.9.

[0065] According to one specific embodiment of the present invention, the present invention also provides a method for preparing a catalyst component for olefin polymerization, the method comprising the steps of contacting and reacting a magnesium-containing solid component with a titanium compound and adding an electron donor containing a furan compound and a diether compound. In the process of preparing the catalyst component of the present invention, the amount of the titanium compound used per mole of magnesium may be 5 to 220 moles, preferably 10 to 200 moles, and the amount of the electron donor used per mole of magnesium may be 0.05 to 1.2 moles, preferably 0.07 to 1.0 moles, and more preferably 0.1 to 0.8 moles.

[0066] A third aspect of the present invention provides a catalyst system for olefin polymerization, the catalyst system is (1) A catalyst component described in the first aspect and / or a catalyst component prepared by the method described in the second aspect, (2) at least one alkylaluminum, and (3) any other electron donor, and is included.

[0067] According to the present invention, the amount of the alkylaluminum used may be the normal amount used in the art. Preferably, the molar ratio of the alkylaluminum in terms of aluminum element to the catalyst component in terms of titanium element may be 1 to 2000:1, more preferably 20 to 500:1, and still more preferably 30 to 300:1.

[0068] According to the present invention, the amount of the other electron donor used may be the normal amount used in the art. Preferably, the molar ratio of the other electron donor to the alkylaluminum compound in terms of aluminum element may be 1:1 to 300, more preferably 1:2 to 100.

[0069] According to the present invention, the alkylaluminum may be various alkylaluminums generally used in the art. For example, the general formula of the alkylaluminum may be AlR’’ n1 X’ 3-n1 where R’’ is C1-C8 alkyl, hydrogen in the alkyl is optionally substituted by a halogen atom, X’ is a halogen, and n1 is an integer of 0 < n1 ≦ 3. Specific examples of the C1-C8 alkyl may include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, n-heptyl, n-octyl, and the halogen may be fluorine, chlorine, bromine, or iodine.

[0070] According to the present invention, preferably, the alkylaluminum is one or more selected from triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum monolide, diisobutylaluminum monolide, di-n-butylaluminum monolide, di-n-hexylaluminum monolide, ethylaluminum dichloride, isobutylaluminum dichloride, n-butylaluminum dichloride, and n-hexylaluminum dichloride.

[0071] According to the present invention, the other electron donor may be any of the various external electron donors commonly used in the art, for example, the other electron donor may be at least one selected from carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, and organosilicon compounds.

[0072] Preferably, the other electron donor is at least one Si-OR 19 It includes a bond and the general formula is (R 17 ) x (R 18 ) y Si(OR 19 ) z A silicon compound is selected from which R is, 17 , R 18 and R 19 These are, independently, C1~C 18 It is a hydrocarbon that optionally contains heteroatoms, where x and y are each independent integers between 0 and 2, z is an integer between 1 and 3, and the sum of x, y, and z is 4. 17 , R 18 Preferably C3~C 10 alkyl, C3~C 10 It is a cycloalkyl group, optionally containing a heteroatom, and R 19 Preferably C1~C 10The alkyl group optionally contains a heteroatom. More preferably, the other electron donor is at least one selected from cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methylt-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, and (1,1,1-,trifluoro-2-propyl)-methyldimethoxysilane.

[0073] According to the present invention, in the process of preparing a catalyst system for olefin polymerization, alkylaluminum and any other electron donor may be mixed with the catalyst component for olefin polymerization before being reacted, or the alkylaluminum compound and any other electron donor may be mixed with the catalyst component for olefin polymerization before being reacted.

[0074] A fourth aspect of the present invention provides the use of the catalyst component described in the first aspect, and / or the catalyst component prepared by the method described in the second aspect, and / or the catalyst system described in the third aspect in olefin polymerization.

[0075] When the catalyst system of the present invention is used in an olefin polymerization reaction, the catalyst component, alkylaluminum, and any other electron donor may be added to the polymerization reactor individually, or they may be mixed and then added to the polymerization reactor, or the olefin may be prepolymerized by a prepolymerization method known in the industry and then added to the polymerization reactor. According to one preferred embodiment of the present invention, the catalyst component, alkylaluminum, and any other electron donor are contacted and reacted in advance and before the polymerization reaction, preferably the catalyst and propylene and / or other α-olefin monomers are prepolymerized. The temperature of the prepolymerization reaction may be 5 to 40°C, and preferably 10 to 30°C.

[0076] In the present invention, the specific type of olefin, the polymerization reaction method and conditions for the olefin may all be selected according to the prior art.

[0077] A fifth aspect of the present invention provides an olefin polymerization method, which comprises the step of carrying out an olefin polymerization reaction in the presence of a catalyst component described in the first aspect and / or a catalyst component prepared by the method described in the second aspect and / or a catalyst system described in the third aspect.

[0078] According to the present invention, preferably, the olefin is at least one selected from compounds represented by the formula CH2=CHR''', where R''' is hydrogen, C1-C6 alkyl, C6-C 12 This is the arrow.

[0079] According to the present invention, the polymerization reaction of the olefin may be carried out according to conventional methods, specifically, under the protection of an inert gas, in a liquid-phase monomer or polymerization monomer-containing inert solvent or in the gas phase, or by a polymerization process with a combination in the gas-liquid phase. The temperature of the polymerization reaction may generally be 0 to 150°C, preferably 60 to 90°C. The pressure of the polymerization reaction may be atmospheric pressure or higher, for example, 0.01 to 10 MPa, preferably 0.01 to 5 MPa, more preferably 0.1 to 4 MPa, and all pressures in the present invention refer to gauge pressure. During the polymerization process, hydrogen can be added to the reaction system as a polymer molecular weight modifier to adjust the molecular weight and melt index of the polymer. Furthermore, the types and amounts of the inert gas and solvent used in the polymerization reaction of the olefin are known to those skilled in the art and will not be described in detail here. According to the present invention, the catalyst component and the olefin may be subjected to a prepolymerization reaction before the polymerization reaction. The temperature of the prepolymerization reaction is 5 to 40°C, preferably 10 to 30°C.

[0080] Parameters not limited by this invention are all conventional techniques in the art.

[0081] The present invention will be described in detail below with reference to examples.

[0082] Unless otherwise specified, all raw materials used in the examples and comparative examples are disclosed in the prior art and can be purchased directly or prepared according to the preparation methods disclosed in the prior art.

[0083] The titanium content in the catalyst component of the present invention can be measured by colorimetric method. Specifically, 0.2 to 0.5 g of the sample is dissolved in 50 mL of 2N H2SO4, the upper suspended matter is filtered, and the clear solution is collected and colorimetric analysis is performed. Using the 2N H2SO4 solution as a blank, the cuvette thickness is set to 1 cm, and its absorbance E1 is measured at a wavelength of 410 μm. Then, one drop of 30 wt% H2O2 is added, and after shaking well, the absorbance E2 is measured. The titanium content Ti (%) is calculated according to the following formula. Ti%=[(E2-E1)×100) / (K·L·W·100)]×100% Here, W is the weight of the sample (g), L is the thickness of the cuvette (cm), K is the specific extinction coefficient (K=15.52), E1 is the absorbance of the blank, and E2 is the absorbance of the sample.

[0084] The magnesium content in the catalyst component of the present invention can be measured by EDTA titration. Specifically, 0.2 to 0.5 g of the sample is placed in a 250 mL Erlenmeyer flask, dissolved in 20 to 30 mL of 2N H2SO4 solution, 20 mL of triethanolamine (1+2) standard solution is added, and the pH is adjusted to 10 by adding 20% ​​by weight NaOH solution. The mixture is shaken, 10 mL of pH=10 buffer is added, 6 drops of 30% H2O2 and 30 to 50 mL of distilled water are added, a small amount of chromium black T indicator is added and the mixture is shaken well. The mixture is titrated with 0.02 N EDTA solution, and the endpoint is reached when the color changes from purple-red to blue (the purple light disappears). The magnesium content Mg(%) is then calculated according to the following formula. Mg(%)=[(VE·NE×24.31) / (G·1000)]×100% Here, G is the mass of the sample (g), VE is the amount of EDTA consumed (mL), NE is the equivalent volume of the EDTA solution, and 24.31 is the atomic weight of magnesium.

[0085] In this invention, the content of furan compounds in the catalyst component is measured by weighing the catalyst component, dissolving it in methanol, and then filtering it through a membrane. The content of furan compounds in the catalyst component of this invention is measured using an Agilent 7890A-5975C gas chromatography-mass spectrometer. Chromatography conditions: HP-5 MS UI gas chromatography column (30 m × 0.25 mm × 0.25 μm), programmed heating: held at 35°C for 3 min, then heated to 250°C at 10°C / min and held for 3 min. Carrier gas: He, flow rate: 1.0 mL / min, split injection, split ratio: 50:1, inlet temperature: 250°C, transfer line temperature: 250°C. Mass spectrometry conditions: quadrupole mass spectrometer, EI ion source, electron energy: 70 eV, ion source temperature: 200°C, acquisition mode: full scan, mass range: m / z: 20~400.

[0086] In this invention, after weighing the catalyst components, they are acid-decomposed with dilute hydrochloric acid, then extracted with cyclohexane, and finally the content of diether compounds in the catalyst components is measured. The content of diether compounds in the catalyst components of this invention is measured using an Agilent 7890 gas chromatograph. Chromatography column: HP-INNO WAX (60 m × 0.530 mm × 1 μm), internal standard method, internal standard: amyl ester.

[0087] The molecular weight distribution (Mw / Mn) of the polymer in this invention is measured using a PL-GPC220 gel permeation chromatograph manufactured by Polymer Laboratories, UK, with trichlorobenzene as the solvent, a measurement temperature of 150°C, polystyrene as the standard substance, a flow rate of 1.0 ml / min, and a 3×Plgel 10mMlXED-B 300×7.5 nm column.

[0088] The melt index of the polymer in this invention is measured in accordance with GB3682-2000 at 230°C and under a load of 2.16 kg.

[0089] The isotactic index of the polymer in this invention is measured by heptane extraction. The average particle size and particle size distribution of the catalyst component and its support in this invention are measured using a Masters Sizer 2000 particle size analyzer (manufactured by Malvern Instruments Ltd).

[0090] The polymer fine powder content in this invention is measured using a MICROTRAC MRB camsizer P4. The data in the table represent the polymer content of less than 100 mesh (mesh / inch) after sieving with a standard sieve, i.e., the polymer content that passes through a 150 μm sieve.

[0091] The following Example A describes a method for preparing a catalyst component and a polymer preparation process, using a magnesium halide alcohol adduct as a support and furan compounds and diether compounds as electron donors.

[0092] Example 1A (1) Preparation of catalyst components In a 300 mL glass reaction flask, 90 mL of titanium tetrachloride was added and cooled to -20°C. 38 mmol of magnesium dichloride alcohol adduct (structural formula: MgCl2·2.6C2H5OH) was added as a magnesium element equivalent, and the mixture was stirred at this temperature for 40 mins. The temperature was then raised to 112°C, and during the heating process, 2.6 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan and 8 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added. After holding at 110°C for 30 mins, the liquid was filtered off, washed with titanium tetrachloride, then washed with hexane, and vacuum dried to obtain the catalyst component Cat-1A for olefin polymerization. The molar ratio of furan compounds to diether compounds in the catalyst component is shown in Table 1. The measurement results showed that in catalyst component Cat-1A, the magnesium content was 5.65 parts by weight and the electron donor content was 5.55 parts by weight per 1 part by weight of titanium. (2) Liquid-phase bulk polymerization of propylene Liquid-phase bulk polymerization of propylene was carried out in a 5L stainless steel high-pressure reaction vessel. Under nitrogen protection, 2 mL of a hexane solution of triethylaluminum (concentration 0.5 mmol / mL), 0.4 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (concentration 0.1 mmol / mL), and 9 mg of the catalyst component Cat-1A for olefin polymerization were sequentially added to the reaction vessel. The high-pressure reaction vessel was turned off, and hydrogen gas (the amount of hydrogen gas used is shown in Table 1) and 2.3 L of liquid propylene were added. The temperature was raised to 70°C, and after 1 hour of reaction, the temperature was lowered, the pressure was released, the material was removed, the resulting propylene homopolymer was dried, weighed, and analyzed, and the results are shown in Table 1.

[0093] Example 2A In the heating process, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was omitted, and the amounts of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofluoro[3,2-b]furan and 9,9-bis(methoxymethyl)fluorene added were set to 5 mmol and 7.5 mmol, respectively. The catalyst component was then prepared according to the method of Example 1A, and liquid-phase bulk polymerization of propylene was carried out to obtain catalyst component Cat-2A for olefin polymerization. Measurement results showed that in catalyst component Cat-2A, the magnesium content was 5.22 parts by weight and the electron donor content was 5.63 parts by weight per 1 part by weight of titanium.

[0094] Example 3A In addition to adding 7 mmol and 6 mmol, respectively, of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane in the heating process, the catalyst component was prepared according to the method of Example 1A, and liquid-phase bulk polymerization of propylene was carried out to obtain catalyst component Cat-3A for olefin polymerization. Measurement results showed that in catalyst component Cat-3A, the magnesium content was 5.20 parts by weight and the electron donor content was 4.71 parts by weight per 1 part by weight of titanium element.

[0095] Example 4A In addition to adding 2 mmol and 8 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, respectively, during the heating process, the catalyst component was prepared according to the method of Example 1A, and liquid-phase bulk polymerization of propylene was carried out to obtain the catalyst component Cat-4A for olefin polymerization. Measurement results showed that in catalyst component Cat-4A, the magnesium content was 5.74 parts by weight and the electron donor content was 5.48 parts by weight per 1 part by weight of titanium.

[0096] Example 5A In addition to adding 8.7 mmol and 3.2 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, respectively, during the heating process, the catalyst component was prepared according to the method of Example 1A, and liquid-phase bulk polymerization of propylene was carried out to obtain the catalyst component Cat-5A for olefin polymerization. Measurement results showed that in catalyst component Cat-5A, the magnesium content was 4.67 parts by weight and the electron donor content was 3.62 parts by weight per 1 part by weight of titanium.

[0097] Example 6A (1) Preparation of catalyst components 80 mL of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to -15°C. 38 mmol of magnesium dichloride alcohol adduct (structural formula: MgCl2·2,6C2H5OH) support was added (in terms of magnesium element), and the mixture was stirred at this temperature for 30 minutes. The temperature was then raised to 115°C, and during the heating process, 3 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofluoro[3,2-b]furan and 8.2 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added. After holding at 115°C for 45 minutes, the liquid was filtered off, washed with titanium tetrachloride, then washed with hexane, and vacuum dried to obtain the catalyst component Cat-6A for olefin polymerization. Measurements showed that in catalyst component Cat-6A, the magnesium content was 6.19 parts by weight and the electron donor content was 6.63 parts by weight per 1 part by weight of titanium element. (2) Liquid-phase bulk polymerization of propylene was the same as in Example 1A.

[0098] Comparative Example 1A In the catalyst component preparation process, in addition to adding only 11 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane without adding (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan, the catalyst component was prepared according to the method of Example 1A, and liquid-phase bulk polymerization of propylene was carried out to obtain the catalyst component DCat-1A for olefin polymerization.

[0099] Comparative example 2A In addition to adding only 11 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan and omitting 2-isopropyl-2-isopentyl-1,3-dimethoxypropane in the catalyst component preparation process, the catalyst component was prepared according to the method of Example 1A, and liquid-phase bulk polymerization of propylene was carried out to obtain the catalyst component DCat-2A for olefin polymerization.

[0100] Comparative example 3A In addition to replacing 2-isopropyl-2-isopentyl-1,3-dimethoxypropane with equimolar 4-ethyl-3,5-heptanediol dibenzoate in the catalyst component preparation process, the catalyst component was prepared according to the method of Example 1A, and liquid-phase bulk polymerization of propylene was carried out to obtain the catalyst component DCat-3A for olefin polymerization.

[0101] [Table 1] Note: n フラン:ジエーテル This represents the molar ratio of furan compounds to diether compounds.

[0102] Table 1 shows that when the electron donor contains furan compounds and diether compounds in a certain proportion, the catalyst has high hydrogen responsiveness and stereospecificity, with a good balance between them, and the molecular weight distribution of the prepared polymer with a low melt index is broader than that of the polymer with a high melt index, indicating that the catalyst component of the present invention does not contain phthalate compounds (plasticizers).

[0103] The following preparation examples and Example B describe a method for preparing catalyst components using a magnesium-containing solid component as a support and furan compounds and diether compounds as electron donors, as well as a process for preparing polymers.

[0104] Preparation Example 1: Magnesium-containing solid component (catalyst support) This preparation example illustrates the olefin polymerization catalyst support provided in the present invention and the method for preparing the same. In a 0.6 L reaction vessel, 0.08 mol of magnesium chloride, 0.96 mol of ethanol, 1 g of α-sulfur, and 0.5 g of PVP (polyvinylpyrrolidone) as a surfactant were added, and the mixture was heated to 90°C while stirring. After allowing the reaction to proceed for 2 hours, 0.48 mol of epichlorohydrin was added, and after half an hour of reaction, the mixture was filtered under pressure. The filtered product was washed five times with hexane and vacuum dried to obtain olefin polymerization catalyst support Z1. The average particle diameter (D50) of the olefin polymerization catalyst support Z1 is 15 μm, and the particle size distribution ((D90-D10) / D50) is 0.6. Observation with an optical microscope revealed that the olefin polymerization catalyst support Z1 had a relatively regular particle morphology, a smooth surface, was basically spherical, and had a relatively concentrated particle size distribution with almost no irregular particles present. Based on characterization by gas chromatography-mass spectrometry, elemental analysis, and NMR, the structural formula of Z1 is as follows. [ka]

[0105] Preparation Example 2: Magnesium-containing solid component (catalyst support) This preparation example illustrates the olefin polymerization catalyst support provided in the present invention and the method for preparing the same. In a 0.6 L reaction vessel, 300 mL of white oil, 0.08 mol of magnesium chloride, 0.48 mol of ethanol, 0.3 g of β-sulfur, and 1 g of PVP (polyvinylpyrrolidone) as a surfactant were added, and the mixture was heated to 100°C while stirring. After allowing the reaction to proceed for 1 hour, 0.16 mol of epichlorohydrin was added, and the reaction was continued at 100°C for another 20 minutes. The mixture was then filtered under pressure, the filtered product was washed five times with hexane, and finally the product was vacuum dried to obtain olefin polymerization catalyst support Z2. The olefin polymerization catalyst support Z2 had an average particle diameter (D50) of 18 μm and a particle size distribution ((D90-D10) / D50) of 0.7. Observation with an optical microscope revealed that the olefin polymerization catalyst support Z2 had a relatively regular particle morphology, a smooth surface, was basically spherical, and had a relatively concentrated particle size distribution with almost no irregular particles present. Based on evaluation of its properties by gas chromatography-mass spectrometry, elemental analysis, and NMR, the structural formula of Z2 is as follows. [ka]

[0106] Example 1B (1) Preparation of catalyst components 80 mL of titanium tetrachloride was added to a 300 mL glass reaction flask and cooled to -20°C. 8 g of the above solid component Z1 was added, and the mixture was stirred at this temperature for 40 mins before being heated to 115°C. During the heating process, 2.3 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan and 8.9 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added. After holding at 110°C for 1 hour, the liquid was filtered off, washed with titanium tetrachloride, then washed with hexane, and vacuum dried to obtain the solid catalyst component Cat-1B. The molar ratio of furan compounds to diether compounds in the catalyst component is shown in Table 2. Measurements revealed that in catalyst component Cat-1B, the magnesium content was 5.06 parts by weight and the electron donor content was 5.87 parts by weight per 1 part by weight of titanium. (2) Liquid-phase bulk polymerization of propylene Liquid-phase bulk polymerization of propylene was carried out in a 5L stainless steel high-pressure reaction vessel. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (concentration 0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (concentration 0.1 mmol / mL), and 7.5 mg of the above-mentioned solid catalyst Cat-1B were sequentially added to the reaction vessel. The high-pressure reaction vessel was turned off, and hydrogen gas (the amount of hydrogen gas used is shown in Table 2) and 2.3 L of liquid propylene were added. The temperature was raised to 70°C, and after 1 hour of reaction, the temperature was lowered, the pressure was released, the material was removed, the resulting propylene homopolymer was dried, weighed, and analyzed, and the results are shown in Table 3.

[0107] Example 2B The solid component to be added was Z2. In addition to adding 3.2 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydroflu[3,2-b]furan and 7.0 mmol of 9,9-bis(methoxymethyl)fluorene during the heating process, the catalyst component was prepared according to the method of Example 1B, and liquid-phase bulk polymerization of propylene was carried out to obtain the solid catalyst component Cat-2B. Measurement results showed that in catalyst component Cat-2B, the magnesium content was 4.85 parts by weight and the electron donor content was 5.53 parts by weight per 1 part by weight of titanium.

[0108] Example 3B The solid component to be added was Z2. In addition to adding 4.7 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan and 6.5 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane during the heating process, the catalyst component was prepared according to the method of Example 1B, and liquid-phase bulk polymerization of propylene was carried out to obtain the solid catalyst component Cat-3B. Measurement results showed that in catalyst component Cat-3B, the magnesium content was 4.63 parts by weight and the electron donor content was 4.45 parts by weight per 1 part by weight of titanium.

[0109] Example 4B In addition to adding 5.8 mmol and 6.3 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, respectively, during the heating process, the catalyst components were prepared according to the method of Example 1B, and liquid-phase bulk polymerization of propylene was carried out to obtain the catalyst component Cat-4B for olefin polymerization. Measurement results showed that in catalyst component Cat-4B, the magnesium content was 4.78 parts by weight and the electron donor content was 4.64 parts by weight per 1 part by weight of titanium.

[0110] Example 5B In addition to adding 7.5 mmol and 4.2 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, respectively, during the heating process, the catalyst component was prepared according to the method of Example 1B, and liquid-phase bulk polymerization of propylene was carried out to obtain the catalyst component Cat-5B for olefin polymerization. Measurement results showed that in the catalyst component, the content of magnesium element was 4.64 parts by weight and the content of electron donor was 4.22 parts by weight per 1 part by weight of titanium element.

[0111] Comparative example 1B In the catalyst component preparation process, 8 g of magnesium halide support (prepared according to the method disclosed in Example 1 of CN1267508C) was added instead of solid component Z1, and the (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofl[3,2-b]furan was replaced with the same molar amount of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. In addition, the catalyst component was prepared according to the method of Example 1B, and liquid-phase bulk polymerization of propylene was carried out to obtain the catalyst component DCat-1B for olefin polymerization.

[0112] Comparative Example 2B In the catalyst component preparation process, 8 g of magnesium halide support (prepared according to the method disclosed in Example 1 of CN1267508C) was added instead of solid component Z1, and the 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was replaced with the same molar amount of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofluoro[3,2-b]furan. In addition, the catalyst component was prepared according to the method of Example 1B, and liquid-phase bulk polymerization of propylene was carried out to obtain the catalyst component DCat-2B for olefin polymerization.

[0113] [Table 2] Note: Span represents the width of the particle size distribution, and Span = (D90 - D10) / D50, n フラン:ジエーテル This represents the molar ratio of furan compounds to diether compounds.

[0114] [Table 3]

[0115] From the results of the examples and comparative examples in Tables 2-3, it was found that the particle size distribution of the catalyst component of the present invention is narrow, and when the catalyst component of the present invention is used, the catalyst simultaneously has high hydrogen responsiveness and stereospecificity and high polymerization activity, the prepared polypropylene has a low content of fine powder, and furthermore, the molecular weight distribution of the prepared polymer with a low melt index is wider than that of the polymer with a high melt index, and furthermore, the catalyst component of the present invention does not contain phthalate compounds (plasticizers).

[0116] Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, several simple modifications can be made to the technical solutions of the present invention and can be combined in any other suitable way that includes each technical feature, and these simple modifications and combinations should also be considered as part of the disclosure of the present invention and all fall within the scope of protection of the present invention.

Claims

1. A catalyst component for olefin polymerization, characterized by comprising a magnesium element, a titanium element, a halogen, and an electron donor, wherein the electron donor comprises a furan compound and a diether compound, and the furan compound is at least one selected from the furan compounds represented by formula (I). 【Chemistry 1】 (In formula (I), R1 and R3 are each independently hydrogen, C １ to C ２０ linear alkyl, C ３ to C ２０ branched alkyl, C ３ to C ２０ cycloalkyl, C ６ to C ２０ aryl, C ７ to C ２０ aralkyl, or C ７ to C ２０ alkaryl, and are selected; R2 and R4 are each independently C １ to C １０ linear alkyl, C ３ to C １０ [[ID=三十二]]branched alkyl, C ３ to C １０ cycloalkyl, C ６ to C １０ aryl, C ７ to C １０ aralkyl, or C ７ to C １０ alkaryl, and are selected.

2. The content of the furan compound per mole of the diether compound is 0.01 to 2 moles, preferably 0.03 to 1.2 moles. And / or, R2 and R4 are each independently of C １ ~C ３ The catalyst component according to claim 1, selected from linear alkyl groups.

3. The furan compound is at least one selected from the furan compounds represented by formula (I-1), 【Chemistry 2】 (Here, in formula (I-1), R1, R2, R3, and R4 are as described in claim 1 or 2.) Preferably, the furan compound is at least one selected from (3R,3aR,6S,6aR)-3-methoxy-6-propoxyhexahydrofloo[3,2-b]furan, (3R,3aR,6S,6aR)-3-methoxy-6-ethoxyhexahydrofloo[3,2-b]furan, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofloo[3,2-b]furan, (3R,3aR,6S,6aR)-3,6-diethoxyhexahydrofloo[3,2-b]furan, and (3R,3aR,6S,6aR)-3,6-dipropoxyhexahydrofloo[3,2-b]furan, the catalyst component according to claim 1 or 2.

4. The catalyst component according to any one of claims 1 to 3, wherein the diether compound is at least one selected from the diether compounds represented by formula (II). 【Transformation 3】 (In equation (II), R Ｉ , R ＩＩ , R ＩＩＩ , R ＩＶ , R Ｖ and R ＶＩ They are either identical or different, and each is independently a hydrogen atom, a halogen atom, and C. １ ~C ２０ Linear alkyl, C ３ ~C ２０ branched alkyl, C ３ ~C ２０ Cycloalkyl, C ６ ~C ２０ Ariel, C ７ ~C ２０ Aralkill of C ７ ~C ２０ Selected from the alkalil, R Ｉ ~R ＶＩ The groups may be arbitrarily bonded to each other to form a ring, R ＶＩＩ and R ＶＩＩＩ They are either identical or different, and each is independent of C １ ~C ２０ Linear alkyl, C ３ ~C ２０ branched alkyl, C ３ ~C ２０ Cycloalkyl, C ６ ~C ２０ Ariel, C ７ ~C ２０ Alkali, or C ７ ~C ２０ (Selected from the Aralkir.)

5. R Ｉ , R ＩＩ , R ＩＩＩ , R ＩＶ , R Ｖ and R ＶＩ These are, independently, hydrogen and C １ ~C ２０ Linear alkyl, C ３ ~C ２０ Selected from branched alkyl groups, and / or, R ＩＩＩ , R ＩＶ They are bonded together to form a fluorene ring, and / or, R ＶＩＩ and R ＶＩＩＩ Each of them is independent of C １ ~C ５ Linear alkyl, C ３ ~C ５ The catalyst component according to claim 4, selected from branched alkyl groups.

6. The aforementioned diether compounds are 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, and 2-(diphenylmethyl 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2 -Methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimeth Xypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,The catalyst component according to any one of claims 1 to 5, which is at least one selected from 3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene.

7. The magnesium content is 2 to 18 parts by weight, preferably 3 to 16 parts by weight, per 1 part by weight of titanium, and the electron donor content is 2 to 17 parts by weight, preferably 3 to 15 parts by weight. and / or, the origin of the magnesium element is at least one selected from magnesium halides, magnesium alkoxides, magnesium haloalkoxides, magnesium alcohol adducts, magnesium halide adducts, and magnesium-containing solid components, according to any one of claims 1 to 6.

8. The origin of the aforementioned titanium element is that its general formula is Ti(OR'). ３－ａ Z ａ and / or Ti (OR') ４－ｂ Z ｂ Selected from titanium compounds, where R' is C １ ~C ２０ It is an alkyl group, where Z is F, Cl, Br, or I, a is an integer from 1 to 3, and b is an integer from 1 to 4. Preferably, the origin of the titanium element is one or more selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxytitanium chloride, dibutoxytitanium dichloride, butoxytitanium trichloride, triethoxytitanium chloride, diethoxytitanium dichloride, ethoxytitanium trichloride, and titanium trichloride, the catalyst component according to any one of claims 1 to 7.

9. A method for preparing catalyst components for olefin polymerization, The method comprises the step of mixing a magnesium source, a titanium source, and an electron donor, wherein the electron donor comprises a furan compound and a diether compound, and the furan compound is at least one selected from the furan compounds represented by formula (I). 【Chemistry 4】 (In formula (I), R1 and R3 are each independently hydrogen, C １ -C ２０ linear alkyl, C ３ -C ２０ branched alkyl, C ３ -C ２０ cycloalkyl, C ６ -C ２０ aryl, C ７ -C ２０ aralkyl, or C ７ -C ２０ alkaryl selected from, R2 and R4 are each independently, C １ -C １０ linear alkyl, C ３ -C １０ branched alkyl, C ３ -C １０ cycloalkyl, C ６ -C １０ aryl, C ７ -C １０ aralkyl, or C ７ -C １０ alkaryl selected from.)

10. The method according to claim 9, wherein the amount of furan compound used per mole of diether compound is 0.1 to 3 moles, more preferably 0.1 to 2 moles, and even more preferably 0.15 to 1.8 moles.

11. (1) A catalyst component according to any one of claims 1 to 8, and / or a catalyst component prepared by the method of claim 9 or 10, (2) at least one alkylaluminum, (3) A catalyst system for olefin polymerization, characterized by comprising any other electron donor.

12. The molar ratio of the alkylaluminum in terms of aluminum element to the catalyst component in terms of titanium element is 1 to 2000:1, preferably 20 to 500:1, and more preferably 30 to 300:

1. The catalyst system according to claim 11, and / or, the molar ratio of the other electron donor to the alkylaluminum compound in terms of aluminum element is 1:1 to 300, preferably 1:2 to 100.

13. The general formula for the alkylaluminum is AlR'' ｎ１ X １ ３－ｎ１ And here, R'' is C １ ~C ８ It is an alkyl group, and the hydrogen atoms in the alkyl group are optionally substituted with halogen atoms, X １ is a halogen, and n1 is an integer such that 0 < n1 ≤ 3. Preferably, the alkylaluminum is one or more selected from triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum monolide, diisobutylaluminum monolide, di-n-butylaluminum monolide, di-n-hexylaluminum monolide, ethylaluminum dichloride, isobutylaluminum dichloride, n-butylaluminum dichloride, and n-hexylaluminum dichloride, the catalyst system according to claim 11 or 12.

14. The other electron donor is at least one selected from carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, and organosilicon compounds. Preferably, the catalyst system according to any one of claims 11 to 13, wherein the other electron donor is at least one selected from cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methylt-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane.

15. Use in olefin polymerization of a catalyst component according to any one of claims 1 to 8, and / or a catalyst component prepared by the method of claim 9 or 10, and / or a catalyst system according to any one of claims 11 to 14.

16. An olefin polymerization method, the olefin polymerization method comprising the step of carrying out an olefin polymerization reaction in the presence of a catalyst component according to any one of claims 1 to 8 and / or a catalyst component prepared by the method according to claim 9 or 10 and / or a catalyst system according to any one of claims 11 to 14, Preferably, the olefin is of the formula CH ２ = At least one compound selected from the compounds represented by CHR''', where R''' is hydrogen, C １ ~C ６ alkyl, C ６ ~C １２ It is an allele, Preferably, the conditions for the polymerization reaction include a temperature of 0 to 150°C, preferably 60 to 90°C, and a pressure of 0.01 to 10 MPa, preferably 0.01 to 5 MPa, characterized in that it is an olefin polymerization method.

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