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

Abstract

The present application provides a catalyst component for olefin polymerization, a catalyst and its application and a method for olefin polymerization, characterized in that the catalyst component comprises titanium, magnesium, halogen and an internal electron donor compound, the internal electron donor compound comprises an ether ester compound represented by formula (I); in formula (I), R 1 is selected from C1-C 18 alkyl, C6-C 30 aryl with or without substituent, C 7‑ C 30 aralkyl and C5-C 30 cycloalkyl with or without substituent; R 2 is selected from C1-C 18 alkyl, C6-C 30 aryl with or without substituent, C 30 C 5‑ aralkyl and C5-C 30 cycloalkyl with or without substituent; R 1 and R 2 are each independently selected from at least one of C1-C 18 alkyl, C1-C 18 alkoxy and halogen. The catalyst component and catalyst of the present application have good catalytic activity and high polymer isotacticity when used for olefin polymerization, especially propylene polymerization.

Description

Technical Field

[0001] This invention relates to the field of olefin polymerization catalyst technology, and particularly to a catalyst component, catalyst, and its application in olefin polymerization, and a method for olefin polymerization. Background Technology

[0002] As is well known, solid catalyst components with magnesium, titanium, halogens and internal electron donors as the main components can be used to catalyze the polymerization of olefins (CH2=CHR), especially in the polymerization of α-olefins containing 3 or more carbon atoms, which can obtain polymers with high stereoregularity in high yield. Among them, internal electron donor compounds are one of the essential components of catalyst components, and the discovery and application of new internal electron donor compounds have led to the continuous upgrading of polyolefin catalysts.

[0003] Currently, various internal electron-donating compounds with different structures have been disclosed, such as monocarboxylic acid esters or polycarboxylic acid esters, acid anhydrides, monoethers or polyethers, ketones, alcohols, amines and their derivatives, etc. Among them, aromatic dicarboxylic acid esters are more commonly used, such as diisobutyl phthalate or di-n-butyl phthalate. Catalysts containing phthalate diesters have low catalytic activity, and the resulting polymers have a narrow molecular weight distribution. External electron donors are required during polymerization to achieve high catalytic activity and obtain polymers with high isotacticity.

[0004] In the 1990s, Himont disclosed a class of 1,3-diether internal electron-donating compounds in CN1041752A. Using catalysts containing 1,3-diether internal electron donors, highly isotactic polypropylene can be polymerized with high catalytic activity; however, the resulting polymer has a narrow molecular weight distribution, which is detrimental to polymer processing. Furthermore, 1,3-diether compounds are prepared by O-alkylation of the corresponding 1,3-diols. The synthesis of the intermediate 1,3-diol involved in the preparation process is complex and yields are low. The O-alkylation reaction conditions are harsh, requiring the use of strong bases such as potassium tert-butoxide or sodium hydride for dehydrogenation, and the O-alkylating agent iodomethane is a highly toxic chemical. Summary of the Invention

[0005] To address the technical problems existing in the prior art, this invention provides a catalyst component, a catalyst, its application, and a method for olefin polymerization. The catalyst component and catalyst of this invention have excellent comprehensive performance, exhibiting high catalytic activity and good stereoregularity in the polymer, thus showing good application prospects. The catalyst component or catalyst of this invention is particularly suitable for propylene polymerization.

[0006] The objective of this invention is mainly achieved through the following technical solutions.

[0007] In a first aspect, the present invention provides a catalyst component for olefin polymerization, said catalyst component comprising titanium, magnesium, halogen, and an internal electron donor compound, wherein the internal electron donor compound comprises an ether ester compound represented by formula (I).

[0008]

[0009] In equation (I), R 1 Selected from C1-C 18 Alkyl, with or without substituents, C6-C 30 aryl, C with or without substituents 7- C 30 Aryl groups and C5-C groups with or without substituents 30 Cycloalkyl.

[0010] R 2 Selected from C1-C 18 Alkyl, with or without substituents, C6-C 30 aryl, with or without substituents, C7-C 30 Aryl groups and C groups with or without substituents 5- C 30 Cycloalkyl.

[0011] R 1 and R 2 In this context, each substituent is independently selected from C1-C1. 18 Alkyl, C1-C 18 Alkyl groups and halogens.

[0012] In a second aspect, the present invention provides a catalyst for olefin polymerization, the catalyst comprising the catalyst component described in the first aspect, an organoaluminum compound, and optionally an external electron donor compound as reaction products.

[0013] Thirdly, the present invention provides a prepolymerization catalyst for olefin polymerization, the prepolymerization catalyst comprising a prepolymer containing an olefin polymer obtained by prepolymerization reaction of the catalyst described in the second aspect with an olefin.

[0014] Fourthly, the present invention provides the application of the catalyst component described in the first aspect or the catalyst described in the second aspect in olefin polymerization reactions.

[0015] Fifthly, the present invention provides a method for olefin polymerization, the method comprising: contacting an olefin with the catalyst component described in the first aspect or the catalyst described in the second aspect under olefin polymerization conditions to carry out a polymerization reaction.

[0016] The catalyst component, catalyst, and their application, and the method for olefin polymerization involved in this invention have the following advantages:

[0017] This invention provides a novel catalyst component and a catalyst and prepolymerization catalyst prepared using the ether ester compound shown in formula (I) as an internal electron donor. These catalysts exhibit excellent overall performance, demonstrating high catalytic activity (above 165 gPP / (gCat·2h)) in olefin polymerization, particularly propylene polymerization, and producing polymers with high isotacticity (above 96.5%), showing promising application prospects. Furthermore, the preparation method of the ether ester compound is simple, the reaction conditions are mild, the operation is simple and safe, and the raw materials are inexpensive and readily available. Detailed Implementation

[0018] Through research, the inventors discovered that using ether ester compounds with specific structures as internal electron donors to prepare catalyst components for olefin polymerization results in polymer products with high isotactic indexes, and the catalyst components also exhibit high polymerization activity.

[0019] In a first aspect, the present invention provides a catalyst component for olefin polymerization, the catalyst component comprising titanium, magnesium, halogen, and an internal electron donor compound, wherein the internal electron donor compound comprises an ether ester compound represented by formula (I).

[0020]

[0021] In equation (I), R 1 Selected from C1-C 18 Alkyl, with or without substituents, C6-C 30 aryl, C with or without substituents 7- C 30 Aryl groups and C5-C groups with or without substituents 30 cycloalkyl;

[0022] R 2 Selected from C1-C 18 Alkyl, with or without substituents, C6-C 30 aryl, with or without substituents, C7-C 30 Aryl groups and C groups with or without substituents 5- C 30 Cycloalkyl.

[0023] R 1 and R 2 In this context, each substituent is independently selected from C1-C1. 18 Alkyl, C1-C 18 Alkyl groups and halogens.

[0024] In a preferred embodiment of the present invention, R 1 Selected from C1-C12 Alkyl, with or without substituents, C6-C 20 aryl, with or without substituents, C7-C 20 Aryl groups and C5-C groups with or without substituents 20 Cycloalkyl; preferably selected from C1-C6 alkyl groups, with or without substituents, C6-C6 10 aryl, with or without substituents, C7-C 10 Aryl groups and C5-C groups with or without substituents 10 Cycloalkyl; more preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 1-ethylpropyl, phenyl with or without substituents, naphthyl with or without substituents, benzyl with or without substituents, phenethyl with or without substituents, and cyclohexyl with or without substituents.

[0025] In a preferred embodiment of the present invention, R 2 Selected from C1-C 12 Alkyl, with or without substituents, C6-C 20 aryl, with or without substituents, C7-C 20 Aryl groups and C5-C groups with or without substituents 20 Cycloalkyl; preferably selected from C1-C6 alkyl groups, with or without substituents, C6-C6 10 aryl, with or without substituents, C7-C 10 Aryl groups and C5-C groups with or without substituents 10 Cycloalkyl; more preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 1-ethylpropyl, phenyl with or without substituents, naphthyl with or without substituents, benzyl with or without substituents, phenethyl with or without substituents, and cyclohexyl with or without substituents.

[0026] In a preferred embodiment of the present invention, each substituent is independently selected from at least one of C1-C6 alkyl, C1-C6 alkoxy, and halogen; preferably, each substituent is independently selected from at least one of C1-C4 alkyl, C1-C4 alkoxy, chlorine, and bromine; more preferably, each substituent is independently selected from at least one of methyl, ethyl, tert-butyl, methoxy, ethoxy, and chlorine.

[0027] In a preferred embodiment of the present invention, the ether ester compound represented by formula (I) is selected from 2,2-bis(methoxymethyl)-1,3-propanediol diacetate, 3-acetoxy-2,2-bis(methoxymethyl)propyl propionate, 3-acetoxy-2,2-bis(methoxymethyl)propyl butyrate, 3-acetoxy-2,2-bis(methoxymethyl)propyl isobutyrate, 3-acetoxy-2,2-bis(methoxymethyl)propyl valerate, 3-acetoxy-2,2-bis(methoxymethyl)propyl 2-methylbutyrate, 3-acetoxy-2,2-bis(methoxymethyl)propyl hexanoate, 3-acetoxy-2,2-bis(methoxymethyl)propyl 2-ethylbutyrate, 3-acetoxy-2,2-bis(methoxymethyl)propyl benzoate, 4 3-Acetoxy-2,2-bis(methoxymethyl)propyl methylbenzoate, 3-Acetoxy-2,2-bis(methoxymethyl)propyl 4-tert-butylbenzoate, 3-Acetoxy-2,2-bis(methoxymethyl)propyl 3-phenylpropionic acid, 3-Acetoxy-2,2-bis(methoxymethyl)propyl cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol dipropionate, 3-Methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl butyrate, 3-Methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl isobutyrate, 3-Methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl valerate, 3-Methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl valerate, 3-Methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl 2-methylbutyrate 3-Methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of hexanoic acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of 2-ethylbutyric acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of benzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of 4-methylbenzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of 4-tert-butylbenzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of 3-phenylpropionic acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of cyclohexanecarboxylic acid, 3-methoxy-2-(methoxymethyl) 2-[(propionyloxy)methyl]propyl ester, 2,2-bis(methoxymethyl)-1,3-propanediol dibutyrate, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl butyrate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl valerate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl 2-methylbutyrate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl hexanoate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl 2-ethylbutyrate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl benzoate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl benzoate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl 4-methylbenzoate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl 4-tert-butylbenzoate2-Di(methoxymethyl)propyl ester, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl ester of butyrate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl ester of cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol of bis(2-methylpropionic acid), 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl ester of valerate, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl ester of 2-methylbutyrate, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl ester of hexanoate, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl ester of 2-ethylbutyrate, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl ester of benzoate. 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl 4-methylbenzoic acid, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl 4-tert-butylbenzoic acid, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl 3-phenylpropionic acid, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol divalerate, 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl valerate, 3-methoxy-2-(methoxymethyl)-2-[(valerate)methyl]propyl hexanoate, 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl valerate, benzoic acid 3-Methoxy-2-(methoxymethyl)-2-[(valeroyloxy)methyl]propyl ester, 3-methoxy-2-(methoxymethyl)-2-[(valeroyloxy)methyl]propyl ester of 4-methylbenzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(valeroyloxy)methyl]propyl ester of 4-tert-butylbenzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionoyloxy)methyl]propyl ester of valeric acid, 3-methoxy-2-(methoxymethyl)-2-[(valeroyloxy)methyl]propyl ester of cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol of bis(2-methylbutyric acid), 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl ester of hexanoic acid, 2-methyl 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl butyrate, 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl benzoate, 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl 4-methylbenzoate, 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl 4-tert-butylbenzoate, 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl 2-methylbutyrate, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-Propanediol, 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl hexanoate, 3-hexanoyloxy-2,2-bis(methoxymethyl)propyl benzoate, 3-hexanoyloxy-2,2-bis(methoxymethyl)propyl 4-methylbenzoate, 3-hexanoyloxy-2,2-bis(methoxymethyl)propyl 4-tert-butylbenzoate, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl hexanoate, 3-hexanoyloxy-2,2-bis(methoxymethyl)propyl cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol bis(2-ethylbutyric acid), 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)-1,3-propanediol benzoate 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl 4-methylbenzoic acid, 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl 4-tert-butylbenzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl 2-ethylbutyric acid, 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol dibenzoic acid, 3-(benzoyloxy)-2,2-bis(methoxymethyl)propyl 4-methylbenzoic acid, 4-tert-butylbenzoic acid 3-(benzoyloxy)-2,2-bis(methoxymethyl)propyl formate, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl benzoate, 3-(cyclohexaneformyloxy)-2,2-bis(methoxymethyl)propyl benzoate, bis(4-methylbenzoic acid)2,2-bis(methoxymethyl)-1,3-propanediol, 3-(4-tert-butylbenzoyloxy)-2,2-bis(methoxymethyl)propyl benzoate, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl benzoate, 3-(cyclohexaneformyloxy)-2 At least one of the following: 2-bis(methoxymethyl)propyl ester, bis(4-tert-butylbenzoic acid)2,2-bis(methoxymethyl)-1,3-propanediol, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl ester of 4-tert-butylbenzoic acid, 3-(cyclohexaneformyloxy)-2,2-bis(methoxymethyl)propyl ester, bis(3-phenylpropionic acid)2,2-bis(methoxymethyl)-1,3-propanediol, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl ester of cyclohexanecarboxylic acid, and 2,2-bis(methoxymethyl)-1,3-propanediol of dicyclohexanecarboxylic acid.

[0028] In this invention, the method for preparing the ether ester compound represented by formula (I) includes:

[0029] Step (1): In a first solvent, 2,2-bis(methoxymethyl)-1,3-propanediol, a first acid-binding agent and the acyl halide shown in formula (III) are mixed to carry out a first esterification reaction to obtain a reaction mixture containing a monoester compound.

[0030] Step (2): In the second solvent, the reaction mixture containing the monoester compound obtained in step (1), the second acid-binding agent and the acyl halide shown in formula (IV) are mixed to carry out a second esterification reaction to obtain the ether ester compound shown in formula (I).

[0031] In formulas (III) and (IV), X is a halogen, preferably Cl;

[0032] Wherein, R in equation (III) 1 R in equation (I) described in the first aspect 1 Similarly, R in equation (IV) 2 R in equation (I) described in the first aspect 2 same.

[0033] In this invention, the reaction progress of the first esterification reaction in step (1) and the second esterification reaction in step (2) can be monitored using methods commonly used in the art, such as TLC (thin-layer chromatography), which will not be described in detail here.

[0034] In this invention, the chemical formula of the 2,2-bis(methoxymethyl)-1,3-propanediol is shown in formula (II).

[0035]

[0036] In a preferred embodiment of the present invention, in step (1), the mixing method includes: first mixing 2,2-bis(methoxymethyl)-1,3-propanediol and a first acid-binding agent, and then adding the acyl halide shown in formula (III) for mixing.

[0037] In a preferred embodiment of the present invention, an acyl halide of formula (III) is added at 10-20°C; preferably, the acyl halide of formula (III) is added in the form of a solution, wherein the solvent in the acyl halide solution of formula (III) is the same as the first solvent. It can be understood that the first solvent contains the solvent in the acyl halide solution of formula (III).

[0038] In a preferred embodiment of the present invention, in step (2), the mixing method includes: first mixing the reaction mixture containing the monoester compound obtained in step (1) with the second acid-binding agent, and then adding the acyl halide shown in formula (IV) for mixing.

[0039] In a preferred embodiment of the present invention, an acyl halide of formula (IV) is added at 10-20°C; preferably, the acyl halide of formula (IV) is added in the form of a solution, wherein the solvent in the acyl halide solution of formula (IV) is the same as the second solvent. It can be understood that the second solvent contains the solvent in the acyl halide solution of formula (IV).

[0040] In a preferred embodiment of the present invention, the molar ratio of the first acid-binding agent to the 2,2-bis(methoxymethyl)-1,3-propanediol is (1.3-1.7):1. And / or, the molar ratio of the second acid-binding agent to the 2,2-bis(methoxymethyl)-1,3-propanediol is (1.3-1.7):1.

[0041] In a preferred embodiment of the present invention, the first acid-binding agent and the second acid-binding agent are each independently selected from at least one of triethylamine, pyridine, ethylenediamine, piperidine and quinoline, preferably triethylamine.

[0042] In a preferred embodiment of the present invention, the first acid-binding agent is the same as the second acid-binding agent.

[0043] In a preferred embodiment of the present invention, the first solvent and the second solvent are each independently selected from at least one of tetrahydrofuran, diethyl ether, acetonitrile, benzene and toluene, preferably tetrahydrofuran.

[0044] In a preferred embodiment of the present invention, the first solvent is the same as the second solvent.

[0045] In a preferred embodiment of the present invention, the amount of the first solvent used is 1-5 ml relative to 1 mmol of 2,2-bis(methoxymethyl)-1,3-propanediol.

[0046] In a preferred embodiment of the present invention, the amount of the second solvent is 1-5 ml relative to 1 mmol of 2,2-bis(methoxymethyl)-1,3-propanediol.

[0047] In a preferred embodiment of the present invention, the molar ratio of 2,2-bis(methoxymethyl)-1,3-propanediol to the acyl halide of formula (III) is 1:(0.8-1.2); and / or, the molar ratio of 2,2-bis(methoxymethyl)-1,3-propanediol to the acyl halide of formula (IV) is 1:(0.8-1.2).

[0048] In a preferred embodiment of the present invention, the conditions for the first esterification reaction include: a reaction temperature of 15-80°C, preferably 50-75°C; and a reaction time of 4-12 h, preferably 6-10 h.

[0049] In a preferred embodiment of the present invention, the conditions for the first esterification reaction include: a reaction temperature of 15-80°C, preferably 50-75°C; and a reaction time of 4-12 h, preferably 6-10 h.

[0050] In a preferred embodiment of the present invention, the first esterification reaction and the second esterification reaction are each carried out independently under a protective atmosphere; preferably, the protective atmosphere is selected from nitrogen or an inert gas; more preferably, the inert gas includes at least one of helium, neon and argon.

[0051] As an example, the ether ester compounds of the present invention can be obtained by the following two-step esterification reaction:

[0052] Step (1): In a first solvent (such as THF), 2,2-bis(methoxymethyl)-1,3-propanediol (Formula II), a first acid-binding agent (such as Et3N) and an acyl halide (Formula (III)) are mixed and subjected to a first esterification reaction to obtain a reaction mixture containing a monoester compound;

[0053] In step (2), the reaction mixture containing the monoester compound obtained in step (1), the second acid-binding agent, and the acyl halide (formula (IV)) are mixed in a second solvent (such as THF) and subjected to a second esterification reaction to obtain the ether ester compound as shown in formula (I).

[0054]

[0055] Preferably, the preparation method includes:

[0056] Step (1): Under a protective atmosphere (e.g., nitrogen and / or inert gas), the 2,2-bis(methoxymethyl)-1,3-propanediol, the first acid-binding agent and the first solvent are mixed, and a solution containing the acyl halide (formula (III)) is added dropwise at 10-20°C. The mixture is then refluxed at the solvent reflux temperature (reaction temperature of the first esterification reaction) for 4-12 hours to obtain a reaction mixture containing a monoester compound.

[0057] Step (2): Under a protective atmosphere (e.g., nitrogen and / or inert gas), the reaction mixture containing the monoester compound obtained in step (1), the second acid-binding agent, and the second solvent are mixed, and a solution containing the acyl halide (formula (IV)) is added dropwise at 10-20°C. The mixture is then refluxed at the solvent reflux temperature (reaction temperature of the second esterification reaction) for 4-12 hours (second esterification reaction).

[0058] In a preferred embodiment of the present invention, R 1 and R 2Similarly, steps (1) and (2) can be combined into one step. That is, in a solvent, 2,2-bis(methoxymethyl)-1,3-propanediol, an acid-binding agent, and an acyl halide are mixed and subjected to an esterification reaction to obtain an ether ester compound represented by formula (I). The solvent includes a first solvent and a second solvent; the acid-binding agent includes a first acid-binding agent and a second acid-binding agent; the acyl halide includes the acyl halide represented by formula (III) and the acyl halide represented by formula (IV); the ratio of the amounts of 2,2-bis(methoxymethyl)-1,3-propanediol, the first solvent, the second solvent, the first acid-binding agent, the second acid-binding agent, the acyl halide represented by formula (III), and the acyl halide represented by formula (IV) is as described above. The conditions for the esterification reaction can be selected from either the aforementioned first esterification reaction conditions or the second esterification reaction conditions.

[0059] In this invention, the magnesium, titanium, and internal electron-donating compound in the catalyst component are in conventional amounts in the art. The magnesium and titanium in the catalyst component are calculated as elemental magnesium and elemental titanium, respectively. The catalyst component contains 3-25 wt% (e.g., 3 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or any two or any range of any two values) of the ether ester compound represented by formula (I), and 1-8 wt% (e.g., 1 wt%, 2 wt%, 3 wt%) of the ether ester compound represented by formula (I). The mixture contains 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, and any two ranges or any range of any two values ​​of titanium, and 8-30 wt% (e.g., 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, and any two ranges or any range of any two values ​​of magnesium); preferably, it contains 5-25 wt% of the ether ester compound represented by formula (I), 1-6 wt% of titanium and 10-25 wt% of magnesium.

[0060] In a preferred embodiment of the present invention, the magnesium in the catalyst component is derived from a magnesium compound; preferably, the magnesium compound includes at least one of magnesium dihalide, magnesium alkoxy, alkyl magnesium, magnesium dihalide hydrate, magnesium dihalide ethanolate, derivatives of magnesium dihalide in which the halogen atom is substituted with a hydroxyl group, and derivatives of magnesium dihalide in which the halogen atom is substituted with a halogenated hydroxyl group; preferably, the hydroxyl group in the derivatives of magnesium dihalide in which the halogen atom is substituted with a hydroxyl group is C1-C. 10 Hydroxyl groups.

[0061] In a preferred embodiment of the present invention, the magnesium compound is magnesium dihalide or an alcoholic compound of magnesium dihalide; more preferably, the magnesium compound includes at least one selected from magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcoholic compound of magnesium dichloride, an alcoholic compound of magnesium dibromide, and an alcoholic compound of magnesium diiodide.

[0062] In a preferred embodiment of the present invention, the titanium in the catalyst component is derived from a titanium compound; the titanium compound includes compounds with the general formula TiX. m (OR1) 4-m At least one of the compounds, the TiX m (OR1) 4-m R1 in the equation is C1-C 20 The hydrocarbon group, where X is a halogen, 1≤m≤4; preferably, R1 is a C1-C4 hydrocarbon group, preferably a C1-C4 alkyl group.

[0063] In a preferred embodiment of the present invention, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy, preferably titanium tetrachloride.

[0064] In this invention, the catalyst component can be prepared by the following method: First, the magnesium compound is dissolved in a solvent system containing an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a homogeneous solution, which is then mixed with the titanium compound, and a solid is precipitated in the presence of a precipitation aid; then, the ether ester compound shown in formula (I) is attached to the solid, and if necessary, the solid is further treated with titanium tetrahalide and an inert diluent.

[0065] The magnesium compound, titanium compound, and ether ester compound of formula (I) are as previously described. The organic epoxy compound, organophosphorus compound, and precipitation aid are disclosed in CN85100997A, the relevant content of which is incorporated herein by reference.

[0066] The organic epoxy compound includes at least one of aliphatic olefins, dienes, halogenated aliphatic olefins, oxides of dienes, glycidyl ethers, and internal ethers with 2-8 carbon atoms; preferably, it includes at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran.

[0067] The organophosphorus compound includes at least one of orthophosphoric acid, a hydrocarbon ester of phosphorous acid, and a halohydrocarbon ester, preferably including at least one of trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, triphenyl orthophosphoric acid, trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, and triphenyl phosphoric acid.

[0068] The precipitation aid comprises at least one of organic anhydrides, organic acids, ethers, ketones, and esters; preferably, it comprises at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, diethyl ether, propyl ether, butyl ether, pentyl ether, succinate, malonate, glutarate, 2,4-pentanediol ester, and 3,5-heptanediol ester.

[0069] In this invention, relative to 1 mole of magnesium compound, the amount of the organic epoxy compound is 0.2-10 moles, the amount of the organic phosphorus compound is 0.1-3 moles, the amount of the precipitation aid is 0-1.0 moles, the amount of the titanium compound is 0.5-150 moles, and the amount of the internal electron donor compound is 0.01-1.0 moles.

[0070] In this invention, the catalyst component can also be prepared by other methods, specifically including the methods listed below.

[0071] Method 1: The catalyst component was prepared according to the method disclosed in CN1506384A. First, a magnesium compound and an organic alcohol compound were mixed with an inert solvent at a molar ratio of 2-5, and the mixture was heated to 120-150°C and reacted for 1-5 hours at a magnesium / anhydride molar ratio of 5-10. Then, the alcohol compound cooled to room temperature was added to a titanium compound solution pre-cooled to -15 to -40°C at a titanium / magnesium molar ratio of 20-50, and the mixture was heated to 90-110°C. The internal electron donor compound was added at a magnesium / internal electron donor molar ratio of 2-10 and reacted at 100-130°C for 1-3 hours. The solid particles were then separated by filtration. Next, the solid particles were added to the titanium compound solution at a titanium / magnesium molar ratio of 20-50, stirred, and reacted at 100-130°C for 1.5-3 hours. The solid particles were then separated by filtration. Finally, the solid particles were washed with an inert solvent at 50-80°C and dried to obtain the catalyst component.

[0072] Method 2: A catalyst component is prepared by reacting the titanium compound of the present invention, specifically TiCl4, with an adduct of the general formula MgCl2·pROH. In MgCl2·pROH, p is a number from 0.1 to 6, preferably 2 to 3.5, and R is a hydrocarbon group having 1 to 18 carbon atoms. The adduct can be suitably prepared into spherical form by mixing an alcohol (ROH) and MgCl2 in the presence of an inert hydrocarbon immiscible with the adduct, followed by rapid cooling of the emulsion, thereby solidifying the adduct into spherical particles. The resulting adduct can then react directly with the titanium compound, or it can be pre-treated with a thermally controlled dealcoholization process (80–130°C) before reacting with the titanium compound to obtain an adduct, wherein the molar number of the alcohol is generally less than 3, preferably between 0.1 and 2.7. The reaction with the titanium compound can be carried out by suspending the adduct (de-alcoholized or the adduct itself) in cold TiCl4 (typically 0°C) and then heating the mixture to 80–130°C and maintaining it at this temperature for 0.1–2 hours. The TiCl4 treatment can be performed once or multiple times. During the TiCl4 treatment, the internal electron donor compound can be added, and this treatment can also be repeated once or multiple times.

[0073] Method 3: The catalyst component was prepared according to the method disclosed in CN1091748A. The magnesium chloride alcohol melt was dispersed in a dispersant system of white oil and silicone oil by high-speed stirring to form an emulsion. This emulsion was then discharged into a cooling liquid and rapidly cooled and solidified to form magnesium chloride alcohol microspheres. The cooling liquid was an inert hydrocarbon solvent with a low boiling point, such as petroleum ether, pentane, hexane, or heptane. The obtained magnesium chloride alcohol microspheres were washed and dried to form a spherical carrier. The molar ratio of alcohol to magnesium chloride was 2–3, preferably 2–2.5. The carrier particle size was 10–300 micrometers, preferably 30–150 micrometers.

[0074] The spherical support was treated with an excess of titanium tetrachloride at low temperature, with the temperature gradually increased. During the treatment, the internal electron donor compound was added. After treatment, the sample was washed multiple times with an inert solvent and dried to obtain a solid powdered spherical catalyst component. The molar ratio of titanium tetrachloride to magnesium chloride was 20–200, preferably 30–60; the initial treatment temperature was -30–0℃, preferably -25–-20℃; and the final treatment temperature was 80–136℃, preferably 100–130℃.

[0075] Method 4: Add dialkoxymagnesium to an aromatic hydrocarbon compound and stir to form a suspension; treat the suspension with tetravalent titanium chloride at -20 to 100°C and react at 0 to 130°C. During this process, add the internal electron donor compound at -20 to 130°C to react. The resulting solid is washed with the aromatic hydrocarbon compound; then, at 0 to 130°C, treat again with tetravalent titanium chloride in an aromatic hydrocarbon solvent, and finally wash with an inert solvent and dry to obtain the solid catalyst component. The tetravalent titanium chloride is used at 0.5 to 100 mol per mole of dialkoxymagnesium, and the electron donor is used at 0.01 to 10 mol per mole.

[0076] Method 5: Halogenation of dialkoxymagnesium compounds such as magnesium dialkoxy or magnesium diaryloxy with TiCl4 or its aromatic solution at 80–130 °C. The treatment with TiCl4 or its aromatic solution can be repeated once or multiple times, and the internal electron donor compound is added during one or more such treatments.

[0077] Method Six: The catalyst component is prepared according to the method disclosed in US4540679A. First, magnesium alkoxide and carbon dioxide are reacted to obtain a hydrocarbon-based magnesium carbonate support. Then, a transition metal compound (preferably a tetravalent titanium compound) and the hydrocarbon-based magnesium carbonate support are reacted with the internal electron donor compound in a certain ratio in an inert solvent, wherein the molar ratio of the transition metal element to magnesium element is at least 0.5:1, and the amount of the internal electron donor compound is at most 1.0 mol / g titanium atom. The inert solvent must be purified to remove substances that can poison the catalyst, such as water, oxygen, and carbon dioxide. The reaction is carried out at -10 to 170°C for several minutes to several hours.

[0078] Another method for preparing solid catalyst components is to form an emulsion of the magnesium compound, an internal electron donor, etc. in a diluent, add the titanium compound to fix it to obtain a spherical solid, and then process it to obtain a solid catalyst component.

[0079] In any of the above preparation methods, the internal electron donor compound can be added in the form of a compound or in other ways, such as by obtaining it in situ using a suitable precursor of the internal electron donor compound, which can be converted into the desired electron donor compound through, for example, a known chemical reaction such as esterification.

[0080] In a second aspect, the present invention provides a catalyst for olefin polymerization, the catalyst comprising the catalyst component described in the first aspect, an organoaluminum compound, and optionally an external electron donor compound as reaction products.

[0081] In this invention, the catalyst components, organoaluminum compounds and optional external electron donor compounds are mixed and reacted under conventional conditions.

[0082] In a preferred embodiment of the present invention, the external electron donor compound comprises an organosilicon compound, wherein the general formula of the organosilicon compound is R. 2’ k Si(OR 3’ ) 4-k , 0≤k≤3, k is an integer; R 2’ Selected from at least one of alkyl, cycloalkyl, aryl, haloalkyl, amino, substituted amino, halogen, and hydrogen; R 3’ It is selected from at least one of alkyl, cycloalkyl, aryl and haloalkyl groups.

[0083] In a preferred embodiment of the present invention, the organosilicon compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, and methyltert-butyldimethoxysilane; preferably cyclohexylmethyldimethoxysilane and / or diphenyldimethoxysilane.

[0084] In a preferred embodiment of the present invention, the organoaluminum compound is an alkylaluminum compound; preferably, the alkylaluminum compound has the general formula AlR. n X 3-n R is hydrogen or C1-C 20 The hydrocarbon group is preferably hydrogen or C1-C8 alkyl, where X is a halogen and 1 ≤ n ≤ 3.

[0085] In a preferred embodiment of the present invention, the alkyl aluminum compound is selected from at least one of triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisooctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride; preferably triethylaluminum and / or triisobutylaluminum.

[0086] In a preferred embodiment of the present invention, the molar ratio of aluminum in the alkyl aluminum compound to titanium in the catalyst component is 5-5000:1, preferably 20-500:1.

[0087] In a preferred embodiment of the present invention, the molar ratio of silicon in the external electron donor compound to titanium in the catalyst component is 0.1-500:1, preferably 3-100:1.

[0088] Thirdly, the present invention provides a prepolymerization catalyst for olefin polymerization, the prepolymerization catalyst comprising a prepolymer containing an olefin polymer obtained by prepolymerization reaction of the catalyst described in the second aspect with an olefin.

[0089] In a preferred embodiment of the present invention, 0.1-1000g of olefin polymer is obtained relative to 1g of the catalyst component, preferably 0.5-20g of olefin polymer.

[0090] Fourthly, the present invention provides the application of the catalyst component described in the first aspect or the catalyst described in the second aspect in olefin polymerization reactions.

[0091] Fifthly, the present invention provides a method for olefin polymerization, the method comprising: contacting an olefin with the catalyst component described in the first aspect or the catalyst described in the second aspect under olefin polymerization conditions to carry out a polymerization reaction.

[0092] In a preferred embodiment of the present invention, the olefin comprises an olefin as shown in the general formula CH2=CHR, wherein R is hydrogen, C1-C 12 Alkyl or C1-C 12 The aryl group, preferably C1-C 12 Alkyl, more preferably C1-C6 alkyl.

[0093] In a preferred embodiment of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, preferably ethylene and / or propylene.

[0094] In this invention, the polymerization reaction employs conventional polymerization methods, such as slurry polymerization or gas-phase fluidized bed polymerization. Specifically, the polymerization reaction is carried out under the protection of an inert gas, in a liquid monomer or an inert solvent containing the monomer, or in the gas phase, or through a combined gas-liquid phase polymerization process.

[0095] In this invention, the polymerization reaction temperature is 0–150°C, preferably 60–90°C. The polymerization reaction pressure is atmospheric pressure or higher, preferably 0.01–10 MPa, more preferably 0.01–6 MPa, and even more preferably 0.1–4 MPa. All pressures in this invention refer to gauge pressure. Furthermore, the types and amounts of inert gases and solvents used in the olefin polymerization process are well known to those skilled in the art and will not be described further here.

[0096] The olefin polymerization of the present invention can be homopolymerization of a single olefin or copolymerization of multiple olefins. For example, copolymerization of ethylene or propylene with α-olefins (such as propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene).

[0097] In a preferred embodiment of the present invention, the method for olefin polymerization further includes a prepolymerization reaction in which the olefin and the catalyst component or catalyst are contacted before the polymerization reaction. In this invention, the term "prepolymerization" refers to polymerization with a lower degree of conversion.

[0098] In a preferred embodiment of the present invention, the prepolymerization ratio is: relative to 1g of catalyst component, 0.1-1000g of olefin polymer is obtained, preferably 0.5-20g of olefin polymer is obtained.

[0099] In this invention, the olefin used for prepolymerization may be the same as or different from the olefin used in the polymerization reaction; preferably, the olefin used for prepolymerization is selected from ethylene or propylene.

[0100] In a preferred embodiment of the present invention, ethylene or propylene is prepolymerized with an α-olefin; preferably, the amount of the α-olefin is 0.1-20 mol% of the amount of ethylene or propylene.

[0101] Preferably, the conversion degree of the catalyst component participating in the prepolymerization is 0.2-500 g polymer / g catalyst component.

[0102] In a preferred embodiment of the present invention, the prepolymerization is carried out in the liquid phase or the gas phase, and the conditions of the prepolymerization reaction include: the prepolymerization temperature is -20 to 80°C, preferably 0 to 50°C; the prepolymerization pressure is 0.01 to 10 MPa, preferably 0.01 to 6 MPa.

[0103] In this invention, the prepolymerization can be performed online as a step in the olefin polymerization method, or it can be performed independently in a batch operation, preferably independently in a batch operation.

[0104] In a preferred embodiment of the present invention, the prepolymerization is selected by preparing a polymer of 0.5–20 g / g solid catalyst component through a batch operation.

[0105] The following detailed description of preferred embodiments of the present invention illustrates the principles of the invention and is not intended to limit the scope of the invention.

[0106] Test methods

[0107] 1) Polymer isotactic index: The isotactic index is determined by heptane extraction. 2g of dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is dried to constant weight. The ratio of the polymer weight (g) to 2 (g) is the isotactic index.

[0108] 2) Nuclear magnetic resonance (NMR) measurement: 1H-NMR was measured using a Bruke dmx300 NMR spectrometer (300 MHz, solvent CDCl3, TMS as internal standard, measurement temperature 300 K).

[0109] Preparation Example 1

[0110] In the first step, under a nitrogen atmosphere, 20 mmol of 2,2-bis(methoxymethyl)-1,3-propanediol, 30 mmol of triethylamine, and 20 ml of tetrahydrofuran (THF) were added to a 250 ml three-necked flask. The mixture was stirred and cooled in an ice bath at 10-20 °C. 10 ml of THF solution containing 20 mmol of 2-ethylbutyryl chloride was added dropwise. After the addition was complete, the ice bath was removed, and the mixture was allowed to warm naturally to room temperature. Then, it was heated to the reflux temperature of THF (65-67 °C) and refluxed. The reaction was monitored using TLC. After 8 hours, the reaction was monitored to be complete. The mixture was then cooled to room temperature to obtain the first reaction mixture.

[0111] In the second step, under a nitrogen atmosphere, 30 mmol of triethylamine and 20 ml of tetrahydrofuran (THF) were added to the first reaction solution obtained in the first step. The mixture was stirred and cooled in an ice bath at 10-20°C. Then, 10 ml of THF solution containing 20 mmol of butyryl chloride was added dropwise. After the addition was complete, the ice bath was removed, and the mixture was allowed to warm naturally to room temperature. Then, it was heated to the reflux temperature of THF (65-67°C) and refluxed. The reaction was monitored using TLC. After 8.2 hours, the reaction was confirmed to be complete. The mixture was then cooled to room temperature to obtain the second reaction mixture.

[0112] The second reaction mixture was washed with 30 mL of water, and the organic phase was separated by liquid-liquid extraction. The aqueous phase was extracted twice with 25 mL of diethyl ether each time. The extracted organic phase was combined with the previously washed and separated organic phase. The combined organic phase was washed with 60 mL of 1N HCl, then with 50 mL of saturated NaHCO3 solution, and then with 50 mL of water. The washed organic phase was dried over anhydrous Na2SO4, concentrated under vacuum to remove the solvent, and purified by column chromatography to obtain the target ether ester compound D1 [2-ethylbutyric acid 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl ester].

[0113] The structure of the synthesized ether ester compound D1 was confirmed by 1H NMR, as follows:

[0114] ¹H NMR (300MHz, CDCl₃, TMS as internal standard, δ / ppm): 4.09–4.11 (m, 4H), 3.36 (s, 4H), 3.30 (s, 6H), 2.29 (t, 2H), 2.17–2.25 (m, 1H), 1.52–1.69 (m, 6H), 0.95 (t, 3H), 0.89 (t, 6H).

[0115]

[0116] Preparation Example 2

[0117] Under a nitrogen atmosphere, 20 mmol of 2,2-bis(methoxymethyl)-1,3-propanediol, 60 mmol of triethylamine, and 40 ml of tetrahydrofuran (THF) were added to a 250 ml three-necked flask. The mixture was stirred and cooled in an ice bath at 10-20 °C. 20 ml of THF solution containing 40 mmol of benzoyl chloride was added dropwise. After the addition was complete, the ice bath was removed, and the mixture was allowed to warm naturally to room temperature. Then, it was heated to the reflux temperature of THF (65-67 °C) and refluxed. The reaction was monitored using TLC. After 8.5 h, the reaction was monitored again. The mixture was then cooled to room temperature to obtain the reaction mixture.

[0118] The reaction mixture was washed with 30 mL of water, and the organic phase was separated by liquid-liquid extraction. The aqueous phase was extracted twice with 25 mL of diethyl ether each time. The extracted organic phase was combined with the previously washed and separated organic phase. The combined organic phase was washed with 60 mL of 1N HCl, then with 50 mL of saturated NaHCO3 solution, and then with 50 mL of water. The washed organic phase was dried over anhydrous Na2SO4, concentrated under vacuum to remove the solvent, and purified by column chromatography to obtain the target ether ester compound D2 [2,2-bis(methoxymethyl)-1,3-propanediol benzoate].

[0119] The structure of the synthesized ether ester compound D2 was confirmed by 1H NMR, as follows:

[0120] ¹H NMR (300MHz, CDCl₃, TMS as internal standard, δ / ppm): 7.39-8.03 (m, 10H), 4.48 (s, 4H), 3.56 (s, 4H), 3.34 (s, 6H).

[0121]

[0122] Preparation Examples 3-10

[0123] The preparation method is the same as in Preparation Example 2, except that benzoyl chloride is replaced with R. 1 and R 2 As shown in Table 1, the acyl chlorides yielded the ether ester compounds D3-D10 shown in Table 1.

[0124] Its structure was confirmed by 1H NMR, as shown in Table 1.

[0125] Preparation Examples 11-15

[0126] The preparation method is the same as in Preparation Example 1, except that 2-ethylbutyryl chloride is replaced with R. 1 As shown in Table 1, equal amounts of acyl chloride were used to replace butyryl chloride with R. 2 Equal amounts of acyl chlorides as shown in Table 1 were used to obtain the ether ester compounds D11-D15 shown in Table 1.

[0127] Its structure was confirmed by 1H NMR, as shown in Table 1.

[0128] Example 1

[0129] Step (1) Preparation of catalyst components

[0130] Nitrogen gas was introduced into the reactor to create a nitrogen atmosphere. Magnesium chloride 4.8 g, toluene 95 mL, epichlorohydrin 4 mL, and tributyl phosphate (TBP) 12.5 mL were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 2.5 h.

[0131] After the solid has completely dissolved, add 1.4 g of phthalic anhydride, cool the solution to -25°C, add 56 mL of TiCl4 dropwise over 1 hour, maintain this temperature for 1 hour, and then slowly raise the temperature to 80°C. During the heating process, the solid gradually precipitates out.

[0132] Then, 6 mmol of ether ester compound D1 was added, and the mixture was kept at 80 °C for 1 h. After hot filtration, the resulting solid precipitate was washed twice with 150 mL of toluene. Then, 60 mL of toluene and 40 mL of TiCl4 were added to the washed solid precipitate, the temperature was raised to 110 °C, and the mixture was kept at 2 h before filtration. Then, 60 mL of toluene and 40 mL of TiCl4 were added to the resulting solid precipitate again, the temperature was raised to 110 °C, and the mixture was kept at 2 h before filtration. Then, 70 mL of toluene was added to the resulting solid precipitate, and the mixture was washed at 110 °C. The washing was repeated three times, with each washing time being 10 min. Then, 60 mL of hexane was added to the washed solid precipitate, and the mixture was washed at room temperature. The washing was repeated twice, and then the mixture was dried under vacuum to obtain the solid catalyst component (Ti element content 3 wt%).

[0133] Step (2) Propylene polymerization experiment

[0134] A dry 250 mL three-necked flask was first purged with nitrogen, then completely purged with propylene. 100 mL of heptane was added, and the mixture was heated to 70 °C. Under normal pressure, 2.0 mmol of AlEt3 (triethylaluminum) and 0.1 mmol of methylcyclohexyldimethoxysilane (CHMMS) were added to achieve an Al:Si (mol) ratio of 20:1. At this temperature, 10 mg of catalyst was added, and the polymerization reaction was initiated. This temperature was maintained for 2 hours, and the reaction was terminated with ethanol. The polymer was washed with anhydrous ethanol and dried under vacuum to obtain the final polymer.

[0135] The isotactic index of the prepared polymer and the catalytic activity data of the catalyst are shown in Table 2.

[0136] Example 2-15

[0137] The experiment was conducted according to the method of Example 1, except that in the preparation of the catalyst components in step (1), the ether ester compound D1 was replaced with the same amount of ether ester compounds D2-D15 as shown in Table 1.

[0138] The isotactic index of the prepared polymer and the catalytic activity data of the catalyst are shown in Table 2.

[0139] Example 16

[0140] The method is the same as in Example 15, except that in step (2) propylene polymerization experiment, 0.05 mmol methylcyclohexyldimethoxysilane is replaced with 0.05 mmol tetramethoxysilane.

[0141] The isotactic index of the prepared polymer and the catalytic activity data of the catalyst are shown in Table 2.

[0142] Example 17

[0143] The method is the same as in Example 15, except that in step (2) of the propylene polymerization experiment, the dry 250 mL three-necked flask was first purged with nitrogen, then fully purged with propylene, and then 100 mL of heptane was added. The mixture was heated to 70 °C, and 2.0 mmol of AlEt3 (triethylaluminum) and 0.01 mmol of methylcyclohexyldimethoxysilane (CHMMS) were added under normal pressure to make Al:Si (mol) = 200:1. At this temperature, 10 mg of catalyst component was added to carry out the polymerization reaction, and this temperature was maintained for 2 h. The reaction was terminated with ethanol. The polymer was washed with anhydrous ethanol and dried under vacuum to obtain the polymer.

[0144] The isotactic index of the prepared polymer and the catalytic activity data of the catalyst are shown in Table 2.

[0145] Comparative Example 1

[0146] The method is the same as in Example 15, except that in step (1) of preparing the catalyst component, the ether ester compound (D-1) is replaced with di-n-butyl phthalate (DNBP).

[0147] The isotactic index of the prepared polymer and the catalytic activity data of the catalyst are shown in Table 2.

[0148] Table 1

[0149]

[0150]

[0151]

[0152]

[0153]

[0154] Table 2

[0155]

[0156]

[0157] As can be seen from Table 2, the catalyst components and catalysts prepared using the ether ester compounds of the present invention as internal electron donors exhibit good catalytic activity (reaching above 165 gPP / (gCat·2h)) and a high polymer isotactic index (reaching above 96.5%) when used for olefin polymerization.

[0158] Compared to Example 16, which uses a combination of cyclohexylmethyldimethoxysilane and tetramethoxysilane as an external electron donor, the catalyst prepared in Example 15 of this invention using cyclohexylmethyldimethoxysilane as an external electron donor has higher catalytic activity and polymer isotactic index.

[0159] Compared to Example 17, where the amounts of alkylaluminum, organosilane external electron donors, and internal electron donors in the catalyst are not within the preferred range, Example 15 of the present invention uses a catalyst prepared with preferred component amounts for olefin polymerization, which has a higher polymer isotactic index and also has higher polymerization activity.

[0160] Compared to Comparative Example 1, which uses DNBP as the internal electron donor, the catalyst prepared in Example 15 of this invention using ether ester compound D1 as the internal electron donor exhibits higher catalytic activity and polymer isotactic index.

[0161] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A catalyst component for olefin polymerization, characterized in that, The catalyst components include titanium, magnesium, halogens, and an internal electron donor compound, wherein the internal electron donor compound includes ether ester compounds represented by formula (I). In equation (I), R 1 Selected from C1-C 18 Alkyl, with or without substituents, C6-C 30 aryl, C with or without substituents 7- C 30 Aryl groups and C5-C groups with or without substituents 30 cycloalkyl; R 2 Selected from C1-C 18 Alkyl, with or without substituents, C6-C 30 aryl, with or without substituents, C7-C 30 Aryl groups and C groups with or without substituents 5- C 30 cycloalkyl; R 1 and R 2 In this context, each substituent is independently selected from C1-C1. 18 Alkyl, C1-C 18 At least one of alkoxy groups and halogens.

2. The catalyst component according to claim 1, characterized in that, R 1 Selected from C1-C 12 Alkyl, with or without substituents, C6-C 20 aryl, with or without substituents, C7-C 20 Aryl groups and C5-C groups with or without substituents 20 Cycloalkyl; preferably selected from C1-C6 alkyl groups, with or without substituents, C6-C 10 aryl, with or without substituents, C7-C 10 Aryl groups and C5-C groups with or without substituents 10 Cycloalkyl; more preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 1-ethylpropyl, phenyl with or without substituents, naphthyl with or without substituents, benzyl with or without substituents, phenethyl with or without substituents, and cyclohexyl with or without substituents; And / or, R 2 Selected from C1-C 12 Alkyl, with or without substituents, C6-C 20 aryl, with or without substituents, C7-C 20 Aryl groups and C5-C groups with or without substituents 20 Cycloalkyl; preferably selected from C1-C6 alkyl groups, with or without substituents, C6-C 10 aryl, with or without substituents, C7-C 10 Aryl groups and C5-C groups with or without substituents 10 Cycloalkyl; more preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 1-ethylpropyl, phenyl with or without substituents, naphthyl with or without substituents, benzyl with or without substituents, phenethyl with or without substituents, and cyclohexyl with or without substituents; And / or, each of the substituents is independently selected from at least one of C1-C6 alkyl, C1-C6 alkoxy and halogen; preferably, each of the substituents is independently selected from at least one of C1-C4 alkyl, C1-C4 alkoxy, chlorine and bromine; more preferably, each of the substituents is independently selected from at least one of methyl, ethyl, tert-butyl, methoxy, ethoxy and chlorine.

3. The catalyst component according to claim 1 or 2, characterized in that, The ether ester compounds represented by formula (I) are selected from 2,2-bis(methoxymethyl)-1,3-propanediol diacetate, 3-acetoxy-2,2-bis(methoxymethyl)propyl propionate, 3-acetoxy-2,2-bis(methoxymethyl)propyl butyrate, 3-acetoxy-2,2-bis(methoxymethyl)propyl isobutyrate, 3-acetoxy-2,2-bis(methoxymethyl)propyl valerate, 3-acetoxy-2,2-bis(methoxymethyl)propyl 2-methylbutyrate, 3-acetoxy-2,2-bis(methoxymethyl)propyl hexanoate, 3-acetoxy-2,2-bis(methoxymethyl)propyl 2-ethylbutyrate, 3-acetoxy-2,2-bis(methoxymethyl)propyl benzoate, and 3-acetoxy-2,2-bis(methoxymethyl)propyl 4-methylbenzoate. Acyloxy-2,2-bis(methoxymethyl)propyl ester, 3-acetoxy-2,2-bis(methoxymethyl)propyl 4-tert-butylbenzoic acid, 3-acetoxy-2,2-bis(methoxymethyl)propyl 3-phenylpropionic acid, 3-acetoxy-2,2-bis(methoxymethyl)propyl cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol dipropionate, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl butyrate, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl isobutyrate, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl valerate, 3-methoxy-2-(methoxymethyl)-2-[( [Propionyloxy)methyl]propyl ester, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl hexanoate, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of 2-ethylbutyric acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of benzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of 4-methylbenzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of 4-tert-butylbenzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of 3-phenylpropionic acid, 3-methoxy-2-(methoxymethyl)-2-[(propionyloxy)methyl]propyl ester of cyclohexanecarboxylic acid, 3-methoxy-2-(methoxymethyl)-2- [(propionyloxy)methyl]propyl ester, 2,2-bis(methoxymethyl)-1,3-propanediol dibutyrate, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl butyrate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl valerate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl 2-methylbutyrate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl hexanoate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl 2-ethylbutyrate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl benzoate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl benzoate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl 4-methylbenzoate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl 4-tert-butylbenzoate2-Di(methoxymethyl)propyl ester, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl ester of butyrate, 3-(butyryloxy)-2,2-bis(methoxymethyl)propyl ester of cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol of bis(2-methylpropionic acid), 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl ester of valerate, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl ester of 2-methylbutyrate, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl ester of hexanoate, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl ester of 2-ethylbutyrate, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl ester of benzoate. 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl 4-methylbenzoic acid, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl 4-tert-butylbenzoic acid, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl 3-phenylpropionic acid, 3-(isobutyryloxy)-2,2-bis(methoxymethyl)propyl cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol divalerate, 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl valerate, 3-methoxy-2-(methoxymethyl)-2-[(valerate)methyl]propyl hexanoate, 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl valerate, benzoic acid 3-Methoxy-2-(methoxymethyl)-2-[(valeroyloxy)methyl]propyl ester, 3-methoxy-2-(methoxymethyl)-2-[(valeroyloxy)methyl]propyl ester of 4-methylbenzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(valeroyloxy)methyl]propyl ester of 4-tert-butylbenzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionoyloxy)methyl]propyl ester of valeric acid, 3-methoxy-2-(methoxymethyl)-2-[(valeroyloxy)methyl]propyl ester of cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol of bis(2-methylbutyric acid), 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl ester of hexanoic acid, 2-methyl 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl butyrate, 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl benzoate, 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl 4-methylbenzoate, 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl 4-tert-butylbenzoate, 3-methoxy-2-(methoxymethyl)-2-[(2-methylbutyryloxy)methyl]propyl 2-methylbutyrate, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-Propanediol, 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl hexanoate, 3-hexanoyloxy-2,2-bis(methoxymethyl)propyl benzoate, 3-hexanoyloxy-2,2-bis(methoxymethyl)propyl 4-methylbenzoate, 3-hexanoyloxy-2,2-bis(methoxymethyl)propyl 4-tert-butylbenzoate, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl hexanoate, 3-hexanoyloxy-2,2-bis(methoxymethyl)propyl cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol bis(2-ethylbutyric acid), 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)-1,3-propanediol benzoate 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl 4-methylbenzoic acid, 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl 4-tert-butylbenzoic acid, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl 2-ethylbutyric acid, 3-(2-ethylbutyryloxy)-2,2-bis(methoxymethyl)propyl cyclohexanecarboxylic acid, 2,2-bis(methoxymethyl)-1,3-propanediol dibenzoic acid, 3-(benzoyloxy)-2,2-bis(methoxymethyl)propyl 4-methylbenzoic acid, 4-tert-butylbenzoic acid 3-(benzoyloxy)-2,2-bis(methoxymethyl)propyl formate, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl benzoate, 3-(cyclohexaneformyloxy)-2,2-bis(methoxymethyl)propyl benzoate, bis(4-methylbenzoic acid)2,2-bis(methoxymethyl)-1,3-propanediol, 3-(4-tert-butylbenzoyloxy)-2,2-bis(methoxymethyl)propyl benzoate, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl benzoate, 3-(cyclohexaneformyloxy)-2 At least one of the following: 2-bis(methoxymethyl)propyl ester, bis(4-tert-butylbenzoic acid)2,2-bis(methoxymethyl)-1,3-propanediol, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl ester of 4-tert-butylbenzoic acid, 3-(cyclohexaneformyloxy)-2,2-bis(methoxymethyl)propyl ester, bis(3-phenylpropionic acid)2,2-bis(methoxymethyl)-1,3-propanediol, 3-methoxy-2-(methoxymethyl)-2-[(3-phenylpropionyloxy)methyl]propyl ester of cyclohexanecarboxylic acid, and 2,2-bis(methoxymethyl)-1,3-propanediol of dicyclohexanecarboxylic acid.

4. The catalyst component according to any one of claims 1-3, characterized in that, The catalyst component contains 3-25 wt% of an ether ester compound of formula (I), 1-8 wt% of titanium, and 8-30 wt% of magnesium; preferably, it contains 5-25 wt% of an ether ester compound of formula (I), 1-6 wt% of titanium, and 10-25 wt% of magnesium.

5. The catalyst component according to any one of claims 1-4, characterized in that, The magnesium in the catalyst component is derived from magnesium compounds; Preferably, the magnesium compound includes at least one of magnesium dihalide, magnesium alkoxy, alkyl magnesium, magnesium dihalide hydrate, magnesium dihalide alcohol, derivatives of magnesium dihalide in which the halogen atom is replaced by an alkyl group, and derivatives of magnesium dihalide in which the halogen atom is replaced by a halogenated alkyl group. Preferably, the hydroxyl groups in the magnesium dihalide derivatives in which the halogen atoms are substituted with hydroxyl groups are C1-C. 10 hydroxyl groups; Preferably, the magnesium compound includes at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcoholysis of magnesium dichloride, an alcoholysis of magnesium dibromide, and an alcoholysis of magnesium diiodide.

6. The catalyst component according to any one of claims 1-5, characterized in that, The titanium in the catalyst component is derived from titanium compounds; And / or, the titanium compound comprises the general formula TiX m (OR1) 4-m At least one of the compounds, the TiX m (OR1) 4-m R1 in the equation is C1-C 20 The hydrocarbon group, where X is a halogen, 1≤m≤4; More preferably, R1 is a C1-C4 hydrocarbon group, preferably a C1-C4 alkyl group; Preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloroethoxy.

7. A catalyst for olefin polymerization, characterized in that, The catalyst comprises the catalyst component according to any one of claims 1-6, the reaction product of an organoaluminum compound and an optional external electron donor compound; Preferably, the external electron donor compound comprises an organosilicon compound, the organosilicon compound having the general formula R. 2’ k Si(OR 3’ ) 4-k , 0≤k≤3, where k is an integer; R 2’ It is selected from at least one of alkyl, cycloalkyl, aryl, haloalkyl, amino, substituted amino, halogen and hydrogen; R 3’ It is selected from at least one of alkyl, cycloalkyl, aryl, and haloalkyl groups; Preferably, the organosilicon compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, and methyltert-butyldimethoxysilane; And / or, the organoaluminum compound is an alkylaluminum compound; Preferably, the alkylaluminum compound has the general formula AlR n X 3-n R is hydrogen or C1-C 20 Hydrocarbon group, preferably hydrogen or C1-C8 alkyl, X is a halogen, 1≤n≤3; Preferably, the alkylaluminum compound is selected from at least one of triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisooctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloro, diisobutylaluminum monochloro, sesquiethylaluminum chloride, and diethylaluminum dichloro. And / or, the molar ratio of aluminum in the alkylaluminum compound to titanium in the catalyst component is 5-5000:1, preferably 20-500:1; And / or, the molar ratio of silicon in the external electron donor compound to titanium in the catalyst component is 0.1-500:1, preferably 3-100:

1.

8. A prepolymerization catalyst for olefin polymerization, characterized in that, The prepolymerization catalyst includes a prepolymer containing an olefin polymer obtained by prepolymerization reaction of the catalyst of claim 7 with an olefin; Relative to 1g of the catalyst component, 0.1-1000g of olefin polymer is obtained, preferably 0.5-20g of olefin polymer.

9. The use of the catalyst component according to any one of claims 1-6 or the catalyst according to claim 7 in olefin polymerization reactions.

10. A method for olefin polymerization, characterized in that, The method includes: contacting an olefin with any one of the catalyst components of claims 1-6 or the catalyst of claim 7 under olefin polymerization conditions to carry out a polymerization reaction; Preferably, the method further includes: prepolymerizing the olefin and the catalyst component or catalyst by contacting them before carrying out the polymerization reaction; Preferably, the olefin comprises an olefin as shown in the general formula CH2=CHR, wherein R is hydrogen, C1-C2, C2 ... 12 Alkyl or C1-C 12 aryl; More preferably, R is a C1-C6 alkyl group; More preferably, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, and more preferably ethylene and / or propylene; And / or, the conditions for the polymerization of the olefin include: a polymerization temperature of 0 to 150°C, preferably 60 to 90°C; and a polymerization pressure of 0.01 to 10 MPa, preferably 0.01 to 6 MPa. And / or, the conditions for the olefin prepolymerization reaction include: a polymerization temperature of -20 to 80°C, preferably 0 to 50°C; and a polymerization pressure of 0.01 to 10 MPa, preferably 0.01 to 6 MPa.

Images