Solid catalyst component for the polymerization of olefins, process for its preparation, catalyst and use thereof

Abstract

The present application belongs to the technical field of olefin polymerization, and relates to a solid catalyst component for olefin polymerization, a preparation method of the solid catalyst component, a catalyst and application. The solid catalyst component contains a product obtained by reacting a magnesium source, a titanium source and an internal electron donor; the internal electron donor comprises butane diacid monoester compounds and diether compounds, and the preparation method comprises the following steps: contacting the magnesium source with the titanium source, and adding the internal electron donor at one or more time periods before, during and after the contacting reaction of the magnesium source with the titanium source. The present application has the following advantages: the internal electron donor containing butane diacid monoester compounds and diether compounds is used, and phthalate compounds are not used, so that the catalyst is a non-plasticizer catalyst; the catalyst of the present application has high stereoregularity, and has good hydrogen regulation sensitivity; the prepared high melt index polymer can maintain a high isotacticity, and the product can have good processing performance and mechanical properties.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of olefin polymerization, and more particularly relates to a solid catalyst component for olefin polymerization, a preparation method of the solid catalyst component, a catalyst comprising the solid catalyst component, and an application of the catalyst in an olefin polymerization reaction. BACKGROUND

[0002] The internal electron donor compound as an important component of the Ziegler-Natta catalyst plays a decisive role in polymerization activity, hydrogen sensitivity, polymer isotacticity, polymer molecular weight and molecular weight distribution, etc. With the development of the electron donor compound, the polyolefin catalyst is constantly updated. There are many compounds that can be used as internal electron donors of the Ziegler-Natta catalyst: polycarboxylic acids, carboxylic acid esters, acid anhydrides, ketones, ethers and their derivatives, among which the commonly used in industry are dibasic aromatic carboxylic acid esters such as di-n-butyl phthalate or diisobutyl phthalate (US6365685B1, US20010020073A1) and the like.

[0003] Although the phthalate diester catalyst as an internal electron donor has been widely used, the residual phthalate diester in the polypropylene product during the use of the catalyst can affect human fertility, and countries have successively formulated corresponding regulations to limit the use of plastic products with excessive phthalate content. Therefore, in the development process of the olefin polymerization catalyst, the use of phthalate diester compounds in the preparation process should be avoided.

[0004] In addition, the stereospecificity of the catalyst determines the isotacticity of the polymer. The higher the isotacticity of the polymer, the higher the degree of regularity and crystallinity, and the mechanical properties such as hardness, stiffness, modulus, breaking and yield strength of the product are increased, and the melting point, thermal stability, aging resistance and radiation resistance are also improved. In order to develop high-performance polyolefin products, the stereospecificity of the catalyst should be further improved. SUMMARY

[0005] The present inventors have unexpectedly found that the catalyst using a combination of succinic monoester compounds and diether compounds as internal electron donors has high stereospecificity and good hydrogen sensitivity, and the high melt index polymer prepared thereby can maintain high isotacticity, and the product can have good processing performance and mechanical properties. Based on this finding, the present application is proposed.

[0006] In order to achieve the purpose of the present application, the first aspect of the present application provides a solid catalyst component for olefin polymerization, which comprises a product obtained by reacting a magnesium source, a titanium source and an internal electron donor;

[0007] The internal electron donor comprises a monoester of succinic acid and a diether compound.

[0008] The second aspect of the present application provides a preparation method of the solid catalyst component for olefin polymerization, comprising the following steps:

[0009] The magnesium source is contacted with the titanium source, and the internal electron donor is added at one or more time periods before, during and after the contacting reaction of the magnesium source with the titanium source.

[0010] The third aspect of the present application provides a catalyst for olefin polymerization, which comprises:

[0011] (i) the solid catalyst component;

[0012] (ii) at least one aluminum alkyl compound; and

[0013] (iii) an optional external electron donor compound.

[0014] The fourth aspect of the present application provides the use of the catalyst for olefin polymerization in an olefin polymerization reaction.

[0015] The present application has the following advantages:

[0016] (1) The internal electron donor comprises a monoester of succinic acid and a diether compound, and phthalate compounds are not used, so that the catalyst is a non-plasticizer catalyst.

[0017] (2) The catalyst of the present application has high stereoregularity and good hydrogen sensitivity, and the high melt index polymer prepared can maintain high isotacticity, and the product can have good processing performance and mechanical properties.

[0018] Other features and advantages of the present application will be described in detail in the following specific embodiments. DETAILED DESCRIPTION

[0019] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0020] In order to achieve the purpose of the present application, the first aspect of the present application provides a solid catalyst component for olefin polymerization, which comprises a product obtained by reacting a magnesium source, a titanium source and an internal electron donor;

[0021] The internal electron donor comprises a monoester of succinic acid and a diether compound.

[0022] According to the present application, preferably, the total content of the monoester succinic acid compound and the diether compound is 70 to 100% by weight, more preferably 80 to 100% by weight, based on the content of the internal electron donor.

[0023] According to the present application, preferably, the monoester succinic acid compound is at least one selected from the group consisting of compounds represented by formula (1):

[0024]

[0025] In formula (1), R1is a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl or alkylaryl group having 7 to 12 carbon atoms, and R2to R5are each independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl or alkylaryl group having 7 to 12 carbon atoms. 20 20 20 20 20 20 20 20 20 20 20 20

[0026] Further preferably, the monoester succinic acid compound is at least one selected from the group consisting of 4-methoxy-4-oxobutanoic acid, 4-ethoxy-4-oxobutanoic acid, 4-propoxy-4-oxobutanoic acid, 4-t-butoxy-4-oxobutanoic acid, and 4-benzyl-4-oxobutanoic acid.

[0027] According to one embodiment of the present application, the monoester succinic acid compound is 4-t-butoxy-4-oxobutanoic acid.

[0028] The present application is not particularly limited to the type of the diether compound, and can be any of various diether compounds that are conventionally used as an internal electron donor for an olefin polymerization catalyst. Preferably, the diether compound is at least one selected from the group consisting of diether compounds represented by formula (2):

[0029]

[0030] In formula (2), R Ⅰ , R Ⅱ , R Ⅲ , R Ⅳ , R Ⅴ , and R​​​​​​​​​​​​Ⅵ Whether they are the same or different, they are each independently selected from hydrogen, halogen atoms, and C1-C atoms. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 Aryl groups and C7-C 20 One of the alkylaryl groups, R Ⅰ -R Ⅵ The groups can be bonded together to form a ring; while R Ⅶ and R Ⅷ They can also be the same or different, each independently selected from C1-C. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 One of the aryl groups.

[0031] In particular preferably, the diether compound is selected from at least one of 2-(2- ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3- dimethoxypropane, 2-sec-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, 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-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-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3- dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2- sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2- cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, and 9,9-dimethoxymethylfluorene.

[0032] Most preferably, the diether compound is 2-isopropyl-2-isopentyl-1,3- dimethoxypropane and / or 9,9-dimethoxymethylfluorene.

[0033] According to the present application, the amount of succinic monoester compound can be 0.05-1.5 moles, preferably 0.15-1 mole, per mole of diether compound, both of which can be better coordinated with the above-mentioned preferred amount, the catalyst has high stereospecificity, and at the same time has good hydrogen sensitivity.

[0034] According to the present application, the molar ratio of the magnesium source in terms of magnesium element, the titanium source in terms of titanium element and the internal electron donor is 1:15-180:0.1-1, preferably 1:18-150:0.15-0.9.

[0035] In the present application, the content of magnesium element in the catalyst component is 3-16 parts by weight, preferably 4-15 parts by weight, and further preferably 5-14 parts by weight, per part by weight of titanium element; the content of internal electron donor is 2-16 parts by weight, preferably 3-15 parts by weight, and further preferably 4-12 parts by weight.

[0036] In the present application, the magnesium source can be various magnesium-containing compounds that can be used in olefin polymerization catalysts, for example, the magnesium source can be magnesium halide, magnesium alcoholate, magnesium halogen alcoholate or halide magnesium adduct carrier, etc. The magnesium halide can be magnesium chloride and / or magnesium bromide, for example. The magnesium alcoholate can be magnesium diethoxide, for example. The magnesium halogen alcoholate can be chloroethoxy magnesium, for example. The types of halide magnesium adduct carrier are well known to those skilled in the art, for example, the halide magnesium adduct carriers disclosed in patent documents CN1091748, CN101050245, CN101486722, CN102796132B, CN102796129B and CN102796128B, and the relevant contents disclosed in these patent documents are all incorporated into the present application by reference.

[0037] According to the present application, the titanium source can be a conventional choice in the art, for example, the titanium source can be a titanium compound of the general formula Ti(OR′) 3-a Z a and / or Ti(OR′) 4-b Z b , wherein R' is a C1-C20 alkyl group, Z is F, Cl, Br or I, a is an integer of 1-3, and b is an integer of 1-4. Preferably, the titanium source is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxy titanium chloride, dibutoxy titanium dichloride, butoxy titanium trichloride, triethoxy titanium chloride, diethoxy titanium dichloride, ethoxy titanium trichloride and titanium trichloride.

[0038] The second aspect of the present application provides a preparation method of the solid catalyst component for olefin polymerization, comprising the following steps:

[0039] The magnesium source is contacted with the titanium source, and an internal electron donor is added at one or more time periods before, during and after the contacting of the magnesium source with the titanium source, followed by one or more treatments with the titanium source, and washing with an inert solvent to obtain the solid catalyst component.

[0040] The catalyst component for the polymerization of olefins according to the present application can be prepared by conventional methods, for example, the preparation method of the catalyst component includes: contacting a magnesium source with a titanium source, and adding an internal electron donor at one or more time periods before, during and after the contacting of the magnesium source with the titanium source, the components of the internal electron donor can be added separately or simultaneously, and the internal electron donor comprises a monoester of succinic acid and a diether compound.

[0041] Preferably, the reaction of the magnesium source with the titanium source can be carried out in the following manner: the titanium source is cooled to below 0°C (preferably -5 to -25°C), then the magnesium source is added, and the mixture is stirred at this temperature for 15-50 minutes, after which the temperature is gradually increased to the reaction temperature (i.e. about 60-130°C), and maintained at this reaction temperature for 0.2-10 hours, preferably 0.5-6 hours. In the preparation method of the catalyst component for the polymerization of olefins, the internal electron donor is added at one or more time periods before, during or after the reaction of the magnesium source with the titanium source. The time period before the reaction of the magnesium source with the titanium source refers to the time period after the magnesium source is added to the reactor and before the temperature is increased to the reaction temperature.

[0042] The third aspect of the present application provides a catalyst for the polymerization of olefins, which comprises:

[0043] (i) the solid catalyst component described above;

[0044] (ii) at least one alkyl aluminum compound; and

[0045] (iii) optionally, an external electron donor compound.

[0046] In the present application, the alkyl aluminum compound can be various alkyl aluminum compounds conventionally used in the art, for example, the general formula of the alkyl aluminum can be AlR n X 3-n wherein R is a C1-C8 alkyl group, the hydrogen on the alkyl group is optionally substituted with a halogen atom, X is a halogen, and n is an integer of 0 < n < 3.

[0047] Specific examples of the C1-C8 alkyl group can include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, n-heptyl, n-octyl, and the halogen can be fluorine, chlorine, bromine, iodine.

[0048] Specifically, the alkylaluminum compound can be selected from one or more of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, di-n-butylaluminum chloride, di-n-hexylaluminum chloride, ethylaluminum dichloride, isobutylaluminum dichloride, n-butylaluminum dichloride, and n-hexylaluminum dichloride.

[0049] According to the present application, the alkylaluminum compound can be used in an amount conventional in the art. The molar ratio of aluminum in the alkylaluminum compound to titanium in the catalyst component can be 1-2000: 1, preferably 20-500: 1, and more preferably 30-300: 1.

[0050] In the present application, the external electron donor can be any of various external electron donors conventionally used in the art. For example, the external electron donor can be selected from at least one of carboxylic acids, carboxylic anhydrides, carboxylic esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, and organosilicon compounds.

[0051] Preferably, the external electron donor is selected from silicon compounds containing at least one Si-OR 19 bond, and having a general formula of (R 17 ) x (R 18 ) y Si(OR 19 ) z , R 17 , R 18 , and R 19 are C1-C 18 hydrocarbon groups, optionally containing a heteroatom, x and y are each independently an integer of 0-2, z is an integer of 1-3, and the sum of x, y, and z is 4. R 17 , R 18 are preferably C3-C 10 alkyl groups, cycloalkyl groups, optionally containing a heteroatom; and R 19 is preferably a C1-C 10 alkyl group, optionally containing a heteroatom.

[0052] Specifically, the external electron donor can be selected from at least one of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyl dimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane.

[0053] According to the present application, the amount of the external electron donor can be the conventional amount in the art. The molar ratio of the external electron donor to the aluminum in the alkyl aluminum compound can be 1:1-300, preferably 1:2-100.

[0054] The fourth aspect of the present application provides the use of the catalyst for olefin polymerization in an olefin polymerization reaction.

[0055] When the catalyst of the present application is used in an olefin polymerization reaction, the catalyst component, the alkyl aluminum compound, and the optional external electron donor can be added to the polymerization reactor separately, or mixed and then added to the polymerization reactor, or pre-polymerized with olefin and then added to the polymerization reactor.

[0056] In the present application, the specific type of olefin, the method and conditions of the olefin polymerization reaction can be selected according to the prior art.

[0057] The catalyst of the present application is particularly suitable for the homo- and co-polymerization of olefins of the general formula CH2=CHR 1 , wherein R 1 is hydrogen, C1-C6 alkyl, or C6-C 12 aryl.

[0058] According to the present application, the polymerization of the olefin can be carried out according to the prior art, specifically, under the protection of inert gas, in liquid monomer or inert solvent containing polymerizable monomer, or in gas phase, or by combined polymerization process in gas-liquid phase. The temperature of the polymerization reaction can generally be 0-150℃, preferably 60-90℃. The pressure of the polymerization reaction can be normal pressure or higher, for example, 0.01-10MPa, preferably 0.01-5MPa, more preferably 0.1-4Mpa, the pressure of the present application refers to the gauge pressure. During the polymerization, hydrogen can be added to the reaction system as a polymer molecular weight regulator to adjust the molecular weight and melt index of the polymer. In addition, the type and amount of the inert gas and solvent used in the polymerization of the olefin are known to those skilled in the art, and will not be described here.

[0059] The parameters not defined in the present application are conventional technical means in the art.

[0060] The present application will be further described below with reference to examples, but the scope of the present application is not limited to these examples.

[0061] In the present application, the melt index of the polymer is measured according to GB3682-2000 at 230℃ under a load of 2.16kg.

[0062] The isotacticity of the polymer in the present application is determined by heptane extraction method (6 hours of boiling extraction with heptane), i.e. 2 g of dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. After that, the residue is dried to constant weight, and the ratio of the weight of the obtained polymer (g) to 2 is the isotacticity.

[0063] Examples 1-5 are used to illustrate the catalyst component and catalyst for olefin polymerization and application of the present application.

[0064] Example 1

[0065] (1) Preparation of catalyst component

[0066] In a 300 mL glass reaction bottle, 80 mL of titanium tetrachloride is added and cooled to -20°C, 36 mmol of magnesium halide carrier (prepared according to the method disclosed in Example 1 of CN1267508C) is added, and then warmed to 112°C, and 2 mmol of 4-tert-butoxy-4-oxobutyric acid and 7.5 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are added during the warming process. After maintaining at 110°C for 30 min, the liquid is filtered off, washed with titanium tetrachloride, and then washed with hexane. After vacuum drying, the catalyst component Cat-1 for olefin polymerization is obtained.

[0067] (2) Propylene liquid bulk polymerization

[0068] The propylene liquid bulk polymerization is carried out in a 5 L stainless steel autoclave. Under nitrogen protection, 5 mL of triethylaluminum hexane solution (concentration of 0.5 mmol / mL), 1 mL of cyclohexylmethyldimethoxysilane (CHMMS) hexane solution (concentration of 0.1 mmol / mL), and 8 mg of the above-mentioned catalyst component Cat-1 for olefin polymerization are sequentially added to the autoclave. The autoclave is closed, hydrogen is added, and 2.3 L of liquid propylene is added. The temperature is raised to 70°C, and after 1 hour of reaction, the temperature is lowered, the pressure is released, and the product is discharged. The obtained propylene homopolymer is dried and weighed, and analyzed. When the amount of hydrogen is 1.5 NL, the polymerization activity of the catalyst is 49.2 kgPP / gcat. The test results of the isotacticity and melt index of the polymer are shown in Table 1.

[0069] Example 2

[0070] The catalyst component is prepared and the propylene liquid bulk polymerization is carried out according to the method of Example 1, except that the amounts of 4-tert-butoxy-4-oxobutyric acid and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane added during the warming process are 3.2 mmol and 6.8 mmol, respectively, to obtain the catalyst component Cat-2 for olefin polymerization.

[0071] The obtained propylene homopolymer was dried, weighed and analyzed. When the amount of hydrogen was 1.5 NL, the polymerization activity of the catalyst was 51.3 kgPP / gcat. The test results of the isotacticity and melt index of the polymer are shown in Table 1.

[0072] Example 3

[0073] The catalyst component was prepared according to the method of Example 1 and propylene liquid bulk polymerization was carried out, except that 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was not added during the temperature rising process, and the amounts of 4-tert-butoxy-4-oxobutanoic acid and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane added were 4.6 mmol and 4.7 mmol, respectively, to obtain a catalyst component Cat-3 for olefin polymerization.

[0074] The obtained propylene homopolymer was dried, weighed and analyzed. When the amount of hydrogen was 1.5 NL, the polymerization activity of the catalyst was 45.7 kgPP / gcat. The test results of the isotacticity and melt index of the polymer are shown in Table 1.

[0075] Example 4

[0076] The catalyst component was prepared according to the method of Example 1 and propylene liquid bulk polymerization was carried out, except that the amounts of 4-tert-butoxy-4-oxobutanoic acid and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane added during the temperature rising process were 1 mmol and 8 mmol, respectively, to obtain a catalyst component Cat-4 for olefin polymerization.

[0077] The obtained propylene homopolymer was dried, weighed and analyzed. When the amount of hydrogen was 1.5 NL, the polymerization activity of the catalyst was 47.6 kgPP / gcat. The test results of the isotacticity and melt index of the polymer are shown in Table 1.

[0078] Example 5

[0079] The catalyst component was prepared according to the method of Example 1 and propylene liquid bulk polymerization was carried out, except that the amounts of 4-tert-butoxy-4-oxobutanoic acid and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane added during the temperature rising process were 5 mmol and 4.1 mmol, respectively, to obtain a catalyst component Cat-5 for olefin polymerization.

[0080] The obtained propylene homopolymer was dried, weighed and analyzed. When the amount of hydrogen was 1.5 NL, the polymerization activity of the catalyst was 43.8 kgPP / gcat. The test results of the isotacticity and melt index of the polymer are shown in Table 1.

[0081] Example 6

[0082] The catalyst component was prepared according to the method of Example 1 and propylene liquid bulk polymerization was carried out, except that the amounts of 4-tert-butoxy-4-oxobutanoic acid and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane added during the temperature rising process were 5.8 mmol and 2.9 mmol, respectively, to obtain a catalyst component Cat-6 for olefin polymerization.

[0083] The obtained propylene homopolymer was dried, weighed and analyzed. When the amount of hydrogen was 1.5 NL, the polymerization activity of the catalyst was 35.9 kgPP / gcat. The test results of the polymer isotacticity and melt index are shown in Table 1.

[0084] Comparative Example 1

[0085] The catalyst component was prepared according to the method of Example 1 and propylene liquid bulk polymerization was carried out, except that during the preparation of the catalyst component, 4-tert-butoxy-4-oxobutanoic acid was not added, and only 9.5 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added, to obtain a catalyst component DCat-1 for olefin polymerization; the obtained propylene homopolymer was dried, weighed and analyzed. When the amount of hydrogen was 1.5 NL, the polymerization activity of the catalyst was 46.3 kgPP / gcat. The test results of the polymer isotacticity and melt index are shown in Table 1.

[0086] Comparative Example 2

[0087] The catalyst component was prepared according to the method of Example 1 and propylene liquid bulk polymerization was carried out, except that during the preparation of the catalyst component, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was not added, and only 9.5 mmol of 4-tert-butoxy-4-oxobutanoic acid was added, to obtain a catalyst component DCat-2 for olefin polymerization; the obtained propylene homopolymer was dried, weighed and analyzed. When the amount of hydrogen was 1.5 NL, the polymerization activity of the catalyst was 16.9 kgPP / gcat. The test results of the polymer isotacticity and melt index are shown in Table 1.

[0088] Table 1

[0089]

[0090]

[0091] As can be seen from Table 1, when the internal electron donor contains a certain proportion of butane diester compounds and diether compounds, the catalyst has high hydrogen sensitivity and stereoregularity, especially high stereoregularity, and the catalyst component of the present application does not contain phthalate compounds (plasticizer).

[0092] Embodiments of the application have been described above, as well as examples. None of the above description is exhaustive or complete with respect to the practice of the disclosed embodiments. Many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the before disclosure.

[0093] The endpoints of the ranges and any values described herein are not limited to the precise values recited as exactly that endpoint point, but rather are intended to cover values approximating that range or that point. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within the range. For values having a range, the endpoints of the ranges are included within

Claims

1. A solid catalyst component for olefin polymerization, characterized in that, The solid catalyst component contains a magnesium source, a titanium source, and a product obtained from the reaction of an internal electron donor. The internal electron donor is a succinic acid monoester compound and a diether compound; the amount of the succinic acid monoester compound is 0.05-1.5 moles per mole of the diether compound. The succinic acid monoester compound is selected from at least one of the compounds shown in formula (1): Equation (1) In equation (1), R1 is C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 The aryl or alkylaryl group, where R2 to R5 are each independently selected from hydrogen, C1-C6. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 aryl or alkylaryl; the C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 The aryl or alkylaryl groups may optionally contain heteroatoms, and the R2 to R5 atoms attached to the same carbon atom may be bonded to form a ring; The diether compound is selected from at least one of the diether compounds shown in formula (2): Equation (2) In equation (2), R Ⅰ R Ⅱ R Ⅲ R Ⅳ R Ⅴ and R Ⅵ Whether they are the same or different, they are each independently selected from hydrogen, halogen atoms, and C1-C atoms. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 Aryl groups and C7-C 20 One of the alkylaryl groups, R Ⅰ -R Ⅵ The groups can be bonded together to form a ring; R Ⅶ and R Ⅷ Whether the two are the same or different, they are each independently selected from C1-C. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 One of the aryl groups; The molar ratio of magnesium source (calculated as magnesium element), titanium source (calculated as titanium element), and internal electron donor is 1:15-180:0.1-1.

2. The solid catalyst component for olefin polymerization according to claim 1, wherein, The succinic acid monoester compound is selected from at least one of 4-methoxy-4-oxobutyric acid, 4-ethoxy-4-oxobutyric acid, 4-propoxy-4-oxobutyric acid, 4-tert-butoxy-4-oxobutyric acid and 4-benzyl-4-oxobutyric acid.

3. The solid catalyst component for olefin polymerization according to claim 1, wherein, The diether compounds are selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-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, 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-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 At least one of the following: alkyl, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, and 9,9-dimethoxymethylfluorene.

4. The solid catalyst component for olefin polymerization according to claim 3, wherein, The diether compound is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-dimethoxymethylfluorene.

5. The solid catalyst component for olefin polymerization according to claim 1, wherein, The amount of succinic acid monoester compound used is 0.15-1 moles per mole of diether compound.

6. The solid catalyst component for olefin polymerization according to claim 1, wherein, The magnesium source is at least one of magnesium halide, magnesium alcohol, magnesium halide alcohol, and magnesium halide adduct carrier. The titanium source is of the general formula Ti(OR′). 3-a Z a And Ti(OR′) 4-b Z b At least one of the compounds shown, wherein R′ is C1-C 20 Alkyl group, Z is halogen, a is an integer from 1 to 3, and b is an integer from 1 to 4.

7. The solid catalyst component for olefin polymerization according to claim 6, wherein, R′ is C1-C 12 Alkyl groups.

8. The solid catalyst component for olefin polymerization according to claim 7, wherein, R′ is a C1-C6 alkyl group.

9. The solid catalyst component for olefin polymerization according to claim 1, wherein, The molar ratio of magnesium source (calculated as magnesium element), titanium source (calculated as titanium element), and internal electron donor is 1:18-150:0.15-0.

9.

10. A method for preparing the solid catalyst component for olefin polymerization according to any one of claims 1-9, characterized in that, Includes the following steps: A magnesium source and a titanium source are brought into contact and reacted. An internal electron donor is added before, during, and after the contact and reaction of the magnesium source and the titanium source. The mixture is then treated once or multiple times with a titanium source and washed with an inert solvent to obtain the solid catalyst component.

11. A catalyst for olefin polymerization, characterized in that, The catalyst contains: (i) The solid catalyst component according to any one of claims 1-9; (ii) at least one alkylaluminum compound; as well as (iii) Optional external electron donor compounds.

12. The catalyst for olefin polymerization according to claim 11, wherein, The alkylaluminum compound is selected from at least one of the compounds represented by AlR n X 3-n , wherein R is an alkyl group having 1 to 8 carbon atoms, the hydrogen on the alkyl group is optionally substituted by a halogen atom, X is a halogen, and n is an integer of 0 < n ≤ 3; The external electron donor is selected from at least one of carboxylic acids, carboxylic anhydrides, carboxylic esters, ketones, ethers, alcohols, organophosphorus compounds, and organosilicon compounds.

13. The catalyst for olefin polymerization according to claim 12, wherein, The alkylaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, di-n-butylaluminum chloride, di-n-hexylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, di-n-butylaluminum chloride, and di-n-hexylaluminum chloride.

14. The catalyst for olefin polymerization according to claim 12, wherein, The external electron donor is selected from those containing at least one Si-OR 19 The key and the general formula is (R) 17 ) x (R 18 ) y Si(OR 19 ) z Silicon compounds, wherein R 17 R 18 and R 19 For C1-C 18 The hydrocarbon group, optionally containing heteroatoms, x and y are each independent integers from 0 to 2, z is an integer from 1 to 3, and the sum of x, y, and z is 4.

15. The catalyst for olefin polymerization according to claim 14, wherein, R 17 R 18 For C3-C 10 Alkyl or cycloalkyl groups, optionally containing heteroatoms.

16. The catalyst for olefin polymerization according to claim 14, wherein, R 19 For C1-C 10 Alkyl groups, optionally containing heteroatoms.

17. The catalyst for olefin polymerization according to claim 11, wherein, The molar ratio of the solid catalyst component (calculated as titanium) to the alkylaluminum compound (calculated as aluminum) is 1:1-2000; the molar ratio of the external electron donor to the alkylaluminum compound (calculated as aluminum) is 1:1-300.

18. The catalyst for olefin polymerization according to claim 17, wherein, The molar ratio of the solid catalyst component (calculated as titanium) to the alkylaluminum compound (calculated as aluminum) is 1:20-500.

19. The catalyst for olefin polymerization according to claim 18, wherein, The molar ratio of the solid catalyst component (calculated as titanium) to the alkylaluminum compound (calculated as aluminum) is 1:30-300.

20. The catalyst for olefin polymerization according to claim 17, wherein, The molar ratio of the external electron donor to the alkylaluminum compound (calculated as aluminum) is 1:2-100.

21. The use of the catalyst for olefin polymerization according to any one of claims 11-20 in an olefin polymerization reaction.

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