Polypropylene catalyst, its preparation method and application

Abstract

The application provides a polypropylene catalyst and a preparation method and application thereof. The catalyst comprises a solid phase component, a cocatalyst and an external electron donor. The solid phase component comprises a porous organic polymer carrier, a magnesium compound, a titanium compound and an internal electron donor. The porous organic polymer carrier is a copolymer comprising divinylbenzene and an unsaturated carboxylic acid hydroxy ester. The catalyst is used for propylene polymerization, and the prepared polypropylene has high chain regularity and a wide molecular weight distribution.

Description

Technical Field

[0001] This invention relates to an olefin polymerization catalyst, and more specifically, to a polypropylene catalyst, its preparation method, and its application. Background Technology

[0002] Since the discovery of Zn catalysts in the 1950s, with the innovation of polyolefin production technology and catalysts, the production and demand of polyolefins have continued to grow. Polypropylene is one of the fastest-growing synthetic resins, and it is expected that the production and consumption of polypropylene will continue to grow in the future.

[0003] Currently, industrial polypropylene catalysts mainly consist of Zn-type catalysts and metallocene catalysts, primarily producing high-isotactic polypropylene. In addition, small quantities of syndiotactic polypropylene, atactic polypropylene, and propylene-based elastomers are produced using metallocene catalysts and post-metallocene catalysts. For industrial polypropylene production plants employing slurry polymerization, bulk polymerization, or gas-phase polymerization processes, catalyst loading is necessary to control the morphology of the polymer and prevent reactor agglomeration or blockage.

[0004] Currently, industrially produced catalysts primarily utilize inorganic supports for supporting Zn and metallocene catalysts. Inorganic supports mainly consist of silica, magnesium chloride, magnesium ethoxylate, and molecular sieves. For example, MgCl2-supported polypropylene catalysts typically include the following components: MgCl2 / TiCl4 / internal electron donor (ID) / silane external electron donor (ED). Common internal electron donors include phthalates such as diisobutyl phthalate (DIBP) and di-n-butyl phthalate (DNBP), phenolic esters, succinates, and diethers. Inorganic-supported polypropylene catalysts generally exhibit high polymerization activity, well-controlled polymer morphology, and high bulk density. However, inorganic supports typically introduce additional impurities (besides the Mg and Ti catalyst components), making it difficult to develop high-purity polypropylene products. Organic polymer supports differ from the reported inorganic supports; POP supports themselves do not introduce impurities that affect polymer performance. In addition, organic supports have controllable pore structure, high specific surface area, stable thermal performance, and are easy to functionalize; high-performance or unique polyolefin catalysts can be prepared through the design and functionalization of supports.

[0005] Zn catalysts supported on porous organic supports have been publicly reported. Typically, organic supports containing functional groups such as carboxylic acid, hydroxyl, cyano, and amino groups are used for the preparation of Zn catalysts. For example, US Patent 4,623,707 uses an organic support prepared from chloromethylated styrene monomers to prepare a Zn catalyst. In the polymer paper "Porous polyethylene spheres with nanofiber structure from Ziegler-Natta catalyst supported on porous polymer particles" (2011; Vol. 52, pp. 602-605), a Zn polyethylene catalyst supported on a POP support was prepared using a cyano-functionalized organic support. In J. Polym. Res., "Ethylene polymerization on polymer supported Ziegler-Natta catalyst" (2012; 19:9892, pp. 1-13), a Zn polyethylene catalyst was prepared using a methyl methacrylate-functionalized POP support. The Catalyst Letter, "Immobilization of Titanium Tetrachloride on Mixed Support of MgCl2 xEB / Poly (methyl acrylate-co-1-octene): Catalyst for Synthesis of Broad MWD Polyethylene" (2009; 132; 87-93), describes the preparation of a Zn catalyst using a copolymer of methacrylic acid and 1-octene as a support for the synthesis of broad molecular weight polyethylene. Furthermore, metallocene catalysts prepared using organic supports, such as those described in US 5,587,439 which utilizes organic supports containing carboxylic acid ester groups, have also been used. However, these organic polymer-supported Zn catalysts are generally suitable for polyethylene polymerization, with few reports on their application in propylene polymerization. This is primarily because the aforementioned organically supported Zn catalyst systems exhibit low activity when directly used for propylene polymerization; additionally, an internal electron donor (ID) is required to regulate the regularity of the polypropylene molecular chain. Although this improves isotacticity and propylene polymerization activity, it still falls short of the requirements for commercial applications.

[0006] Chinese patent CN104530267A and the patent titled "Metal oxide as a template in the preparation of porous poly(2-hydroxyethylmethylacrylate-co-divinylbenzene) parts as a metallocene catalyst support" (RSC Advances, 2016, Vol. 6) disclose a method for preparing a porous organic polymer support. This method employs dispersion polymerization (precipitation polymerization) using nano-metal oxide as a template and copolymerizing hydroxyalkyl methacrylate with divinylbenzene to obtain a porous organic polymer support with uniform and narrow particle size distribution. The prepared metallocene catalyst exhibits high activity but has not yet been used in the preparation of Zn polypropylene catalysts. US patent US6750303B discloses a method for preparing a catalyst support using suspension polymerization. This method uses hydroxyethyl methacrylate as a functional monomer and styrene and divinylbenzene as comonomers to prepare an organic support containing hydroxyethyl methacrylate as a functional monomer. The metallocene catalyst obtained with this support exhibits higher activity than the silica gel-supported catalyst, but it has also not been used in the preparation of Zn polypropylene catalysts.

[0007] Therefore, further research is needed in this field on ZN-type catalyst systems that can be used for propylene polymerization. Summary of the Invention

[0008] The main objective of this invention is to provide a polypropylene catalyst, its preparation method, and its application, in order to overcome the defects of low catalytic activity and low molecular chain regularity of ZN-type catalysts used for propylene in the prior art.

[0009] To achieve the above objectives, the present invention provides a polypropylene catalyst comprising a solid phase component, a co-catalyst, and an external electron donor. The solid phase component comprises a porous organic polymer support, a magnesium compound, a titanium compound, and an internal electron donor. The porous organic polymer support is a copolymer comprising divinylbenzene and an unsaturated carboxylic acid hydroxy ester.

[0010] The polypropylene catalyst of the present invention is a Zn catalyst; the solid phase component contains 1-8 parts by mass of magnesium compound (based on elemental magnesium), 1-8 parts by mass of titanium compound (based on titanium), 1-10 parts by mass of internal electron donor, and 60-85 parts by mass of porous organic polymer support; based on 100% by mass of porous organic polymer support, the content of unsaturated carboxylic acid hydroxy ester is 5-60%.

[0011] The polypropylene catalyst of the present invention, wherein the content of unsaturated carboxylic acid hydroxy ester monomer in the porous organic polymer support is 0.5-5 mmol / g porous organic polymer support.

[0012] The polypropylene catalyst of the present invention comprises the following: the unsaturated carboxylic acid hydroxy ester has the chemical formula R3HC=C(R4)R2CO2R1OH, wherein R1 is an alkylene or phenylene group containing 1-6 carbon atoms in the main chain, and the R1 group may or may not have substituents, the substituents being at least one of chlorine, bromine, fluorine, iodine, alkyl, phenyl, and naphthyl; R2 is an alkylene or phenylene group containing 0-6 carbon atoms in the main chain, and the R2 group may or may not have substituents, the substituents being at least one of chlorine, bromine, fluorine, iodine, alkyl, phenyl, and naphthyl; R3 is an alkyl, phenyl, or hydrogen group containing 1-6 carbon atoms in the main chain, and the R3 group may or may not have substituents, the substituents being at least one of chlorine, bromine, fluorine, iodine, alkyl, phenyl, and naphthyl; and R4 is an alkyl, phenyl, or hydrogen group containing 1-6 carbon atoms in the main chain.

[0013] The polypropylene catalyst of this invention, wherein the unsaturated carboxylic acid hydroxy ester is methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-chlorohydroxymethyl methacrylate, 4-vinylbenzoic acid hydroxymethyl ester, 4-vinylbenzoic acid hydroxyethyl ester, 4-vinylbenzoic acid hydroxypropyl ester, stilbene-4-carboxylic acid hydroxymethyl ester, stilbene-4-carboxylic acid hydroxyethyl ester, stilbene-4-carboxylic acid hydroxypropyl ester, 2-hexenoic acid hydroxymethyl ester, 2-hexenoic acid hydroxyethyl ester, 2-hexenoic acid-2-hydroxypropyl ester, styrylformate hydroxymethyl ester, styrylformate hydroxyethyl ester, styrylformate-2- The first of the following: hydroxypropyl ester, 2-hydroxy-4-(1-propenyl)phenol carboxylate, 2-hydroxy-4-(1-propenyl)phenol acetate, 2-hydroxy-4-(1-propenyl)phenol propionate, 2-hydroxy-4-(1-propenyl)phenol benzoate, 4-(1-propenyl)benzoic acid hydroxypropyl ester, 4-(1-propenyl)benzoic acid hydroxyethyl ester, 4-(1-propenyl)benzoic acid hydroxymethyl ester, 2-hydroxy-4-vinylphenol carboxylate, 2-hydroxy-4-vinylphenol acetate, 2-hydroxy-4-vinylphenol propionate, 2-hydroxy-4-vinylphenol monochloroacetate, 2-hydroxy-4-vinylphenol trichloroacetate, and 2-hydroxy-4-vinylphenol trifluoroacetate.

[0014] The polypropylene catalyst of the present invention further comprises a third monomer, wherein the porous organic polymer is selected from at least one of styrene, alkyl-substituted styrene, and chloromethyl-substituted styrene; the internal electron donor is at least one of diester internal electron donor, diphenol ester internal electron donor, glycol ester internal electron donor, succinate internal electron donor, and diether internal electron donor; and the external electron donor is a silane external electron donor.

[0015] To achieve the above objectives, the present invention also provides a method for preparing the aforementioned polypropylene catalyst, wherein the method for preparing the catalyst solid phase component includes:

[0016] The porous organic polymer support and the magnesium compound are reacted in an inert solvent at a temperature of 0°C to 50°C for 15 to 120 minutes. The unreacted magnesium compound is then filtered and added to an organic solvent containing a titanium compound for further reaction at a temperature of 0°C to 80°C for 15 to 180 minutes. An internal electron donor is then added, and the reaction is carried out at 20-120°C to obtain the solid phase component.

[0017] The method for preparing the polypropylene catalyst of the present invention includes a method in which the amount of magnesium compound added, calculated as magnesium, is 1 to 30 mmol / g porous organic polymer support, and the amount of titanium compound added, calculated as titanium, is 5 to 200 mmol / g porous organic polymer support.

[0018] The method for preparing the catalyst system for propylene polymerization according to the present invention, wherein the method for preparing the porous organic polymer support includes:

[0019] The porous organic polymer carrier was prepared by free radical copolymerization using divinylbenzene as the basic monomer and unsaturated carboxylic acid hydroxy esters as functional monomers.

[0020] To achieve the above objectives, the present invention further provides the application of the aforementioned polypropylene catalyst in propylene polymerization or copolymerization of propylene with α-olefins.

[0021] The beneficial effects of this invention are:

[0022] The ZN polypropylene catalyst supported on a porous organic polymer support in this invention has a pore structure that can be adjusted by the pore structure of the support. The catalyst, through the design of functional monomers, regulates the chemical environment of the titanium active center, forming a POP-CO2R1O...MgCl / TiCl4 / ID (internal electron donor) polypropylene catalyst solid component supported on a porous organic polymer support. Through the synergistic effect of the unsaturated carboxylic acid hydroxy ester on the support and the internal electron donor ID, the Ti active center of the catalyst has better stereotactic ability, resulting in a wider molecular weight distribution of the obtained polypropylene.

[0023] During propylene polymerization, the solid component of the ZN-type catalyst requires the addition of silane-based external electron donors and triethylaluminum co-catalysts. The catalyst exhibits good polymerization activity, with high polymer isotacticity, reaching over 98%. TREF classification results show that its homopolymer polypropylene has a higher elution temperature (i.e., this segment has higher chain regularity), reaching 124℃ (the elution temperature of other commercial homopolymer PP is generally around 122℃). In addition, the product has a wide molecular weight distribution, ranging from 8 to 15 (conventional ZN-type polypropylene catalysts usually cannot produce polypropylene with both high chain regularity and a wide molecular weight distribution). This makes the organically supported ZN polypropylene catalyst a promising candidate for industrialization, especially in developing high-rigidity and high-toughness balanced homopolymer products. Attached Figure Description

[0024] Figure 1 The Tref curve is shown for the polypropylene prepared in the embodiments of the present invention.

[0025] Figure 2 The molecular weight and distribution curve of the polypropylene GPC prepared in the embodiments of the present invention are shown. Detailed Implementation

[0026] The following provides a detailed description of the embodiments of the present invention. These embodiments are implemented based on the technical solution of the present invention and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0027] This invention provides a polypropylene catalyst comprising a solid phase component, a co-catalyst, and an external electron donor. The solid phase component comprises a porous organic polymer support, a magnesium compound, a titanium compound, and an internal electron donor. The porous organic polymer support is a copolymer comprising divinylbenzene and an unsaturated carboxylic acid hydroxy ester.

[0028] This invention utilizes the synergistic effect of unsaturated carboxylic acid hydroxy esters on a porous organic polymer support and internal electron donors (IDs) to simultaneously enhance the stereotactic ability of the catalyst and prepare polypropylene with a wide molecular weight distribution.

[0029] Typically, during propylene polymerization, the co-catalyst can complex with the internal electron donor, causing the Ti atoms to become unstable and reoccupy the random active sites complexed with the internal electron donor, resulting in a decrease in the catalyst's orientation ability. The catalyst of this invention incorporates an external electron donor, which preferentially binds to the co-catalyst, preventing the internal electron donor from detaching and reducing the amount of internal electron donor removed by the co-catalyst, thus ensuring the stability of the stereoactive centers. Therefore, the polypropylene prepared by the catalyst of this invention exhibits high isotacticity.

[0030] The catalyst of this invention belongs to the ZN catalyst category. The porous organic polymer support is a copolymer obtained by copolymerizing divinylbenzene and unsaturated carboxylic acid hydroxy esters. The unsaturated carboxylic acid hydroxy esters are functional monomers, including unsaturated carboxylic acid hydroxyalkyl esters and unsaturated carboxylic acid phenol esters. In one embodiment, the chemical formula of the unsaturated carboxylic acid hydroxy ester is R3HC=C(R4)R2CO2R1OH, wherein R1 is an alkylene or phenylene group containing 1-6 carbon atoms in the main chain, and the R1 group may or may not have substituents, the substituents being at least one of chlorine, bromine, fluorine, iodine, alkyl, phenyl, and naphthyl; R2 is an alkylene or phenylene group containing 0-6 carbon atoms in the main chain, and the R2 group may or may not have substituents, the substituents being at least one of chlorine, bromine, fluorine, iodine, alkyl, phenyl, and naphthyl; R3 is an alkyl, phenyl, or hydrogen group containing 1-6 carbon atoms in the main chain, and the R3 group may or may not have substituents, the substituents being at least one of chlorine, bromine, fluorine, iodine, alkyl, phenyl, and naphthyl; and R4 is an alkyl, phenyl, or hydrogen group containing 1-6 carbon atoms in the main chain.

[0031] When R2 has 0 carbon atoms and R4 is methyl, the chemical structure of the functional monomer is R3HC=C(CH3)CO2R1OH; further, if R3 is H, the chemical structure of the functional monomer is H2C=C(CH3)CO2R1OH. When R2 is phenylene and R4 is H, the chemical structure of the functional monomer is R3HC=CH-Ph-CO2R1OH. When R3 is phenyl, R2 has 0 carbon atoms, and R4 is hydrogen, the chemical structure of the functional monomer is Ph-HC=CHCO2R1OH. When R1 is phenyl and R4 is hydrogen, the chemical structure of the functional monomer is R3HC=CHR2CO2PhOH. Usually, the ester group and the phenolic hydroxyl group are ortho-positioned to the phenyl group. The functional monomer of unsaturated carboxylic acid hydroxy esters can also have the chemical structure R2CO2R1(OH)R4C=CHR3, such as 2-hydroxy-4-(1-propenyl)phenol benzoate.

[0032] In another embodiment, the unsaturated carboxylic acid hydroxy esters of the present invention include, but are not limited to, methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-chlorohydroxymethyl methacrylate, 4-vinylbenzoic acid hydroxymethyl ester, 4-vinylbenzoic acid hydroxyethyl ester, 4-vinylbenzoic acid hydroxypropyl ester, stilbene-4-carboxylic acid hydroxymethyl ester, stilbene-4-carboxylic acid hydroxyethyl ester, stilbene-4-carboxylic acid hydroxypropyl ester, 2-hexenoic acid hydroxymethyl ester, 2-hexenoic acid hydroxyethyl ester, 2-hexenoic acid-2-hydroxypropyl ester, styrylformate hydroxymethyl ester, styrylformate hydroxyethyl ester, styrylformate-2- The first of the following: hydroxypropyl ester, 2-hydroxy-4-(1-propenyl)phenol carboxylate, 2-hydroxy-4-(1-propenyl)phenol acetate, 2-hydroxy-4-(1-propenyl)phenol propionate, 2-hydroxy-4-(1-propenyl)phenol benzoate, 4-(1-propenyl)benzoic acid hydroxypropyl ester, 4-(1-propenyl)benzoic acid hydroxyethyl ester, 4-(1-propenyl)benzoic acid hydroxymethyl ester, 2-hydroxy-4-vinylphenol carboxylate, 2-hydroxy-4-vinylphenol acetate, 2-hydroxy-4-vinylphenol propionate, 2-hydroxy-4-vinylphenol monochloroacetate, 2-hydroxy-4-vinylphenol trichloroacetate, and 2-hydroxy-4-vinylphenol trifluoroacetate.

[0033] In one embodiment, the porous organic polymer of the present invention further includes a third monomer, namely a copolymer obtained by copolymerizing divinylbenzene, an unsaturated carboxylic acid hydroxy ester, and the third monomer, with the porous organic polymer carrier as the copolymer. In another embodiment, the third monomer is selected from at least one of styrene, alkyl-substituted styrene, and chloromethyl-substituted styrene.

[0034] In the catalyst system of this invention, magnesium and titanium compounds are commonly used substances in Zn catalysts in the art, and this invention does not impose any particular limitation on them. For example, halogen compounds of magnesium and titanium.

[0035] In one embodiment, the magnesium compound of the present invention has the molecular formula RMgX or R6MgR5, wherein X is a halogen, i.e., fluorine, chlorine, bromine, or iodine atom, and the R, R5, and R6 groups can be chain hydrocarbons or aromatic hydrocarbon groups containing 1-8 carbon atoms, such as methyl, ethyl, propyl, butyl, benzene, benzene containing substituted groups, or alkoxy groups. R5 and R6 can be the same or different. Further, the magnesium compound of the present invention can be an alkyl halide magnesium Grignard reagent, an alkyl magnesium compound, an alkoxy magnesium halide, etc., such as methyl magnesium chloride, n-butyl magnesium chloride, isobutyl magnesium chloride, tert-butyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-butyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, tert-butyl magnesium iodide, benzyl magnesium iodide, n-butyl magnesium iodide, methyl magnesium fluoride, tert-butyl magnesium fluoride, diethyl magnesium, diethyl magnesium, dibutyl magnesium, ethoxy magnesium chloride, etc. Furthermore, the magnesium compound of the present invention is an alkyl chloromagnesium Grignard reagent RMgCl.

[0036] In one embodiment, the titanium compound of the present invention is a titanium halide, such as titanium tetrachloride, titanium trichloride, etc., typically titanium tetrachloride.

[0037] In one embodiment, the internal electron donor ID of the present invention is a diester, diphenol ester, glycol ester, succinate, or diether internal electron donor. Internal electron donors include, but are not limited to, the following: diisobutyl phthalate (DIBP), di-n-butyl phthalate (DNBP), 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropyl succinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl methyl ester (IAIPPDB), 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether (IAIPDMP), etc.

[0038] In one embodiment, the external electron donor of the present invention is a silane-based external electron donor, such as including but not limited to cyclohexylmethyldimethylsilane (C external electron donor), dicyclopentenedimethoxysilane (D external electron donor), diisopropyldimethoxysilane (P external electron donor), diisobutyldimethoxysilane (B external electron donor), and tetraethoxysilane (TEOS).

[0039] The co-catalyst and its dosage in this invention are well-known to those skilled in the art. In one embodiment, the co-catalyst is an alkylaluminum with the general formula AlR3, where R is an alkane group containing 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. In another embodiment, the alkylaluminum is selected from triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, and diethylaluminum chloride; further, the co-catalyst is triethylaluminum AlEt3. The alkylaluminum is calculated as aluminum, and the titanium compound is calculated as titanium, with a molar ratio of alkylaluminum to titanium compound of 5-500.

[0040] In one embodiment, the solid phase component contains 1-8 parts by mass of magnesium compound, preferably 2-6 parts by mass of magnesium element; the solid phase component contains 1-8 parts by mass of titanium compound, preferably 2-6 parts by mass of titanium element; the solid phase component contains 1-10 parts by mass of internal electron donor, preferably 2-8 parts by mass; and the porous organic polymer support contains 60-85 parts by mass. Based on 100% by mass of the porous organic polymer support, the content of unsaturated carboxylic acid hydroxy ester is 5-60%.

[0041] In another embodiment, the content of unsaturated carboxylic acid hydroxy ester comonomer in the porous organic polymer carrier is 0.5-5 mmol / g porous organic polymer carrier, preferably 1-4 mmol / g porous organic polymer carrier. The content of functional monomer is usually controlled during the carrier preparation process by adjusting the ratio of functional monomer to divinylbenzene (DVB) monomer.

[0042] This invention also provides a method for preparing the above-mentioned polypropylene catalyst, wherein the method for preparing the catalyst solid phase component includes:

[0043] A porous organic polymer support is reacted with a magnesium compound in an inert solvent at a temperature of 0°C to 50°C for 15 to 120 minutes. The unreacted magnesium compound is then filtered and added to an organic solvent containing a titanium compound for further reaction at a temperature of 0°C to 80°C for 15 to 180 minutes. An internal electron donor is then added, and the reaction is carried out at 20-120°C to obtain the solid phase component.

[0044] In this process, after the porous organic polymer support is contacted with the magnesium-containing compound, POP-CO2R1O...MgX is obtained. Then, the titanium-containing compound reacts with POP-CO2R1O...MgX to form a POP-CO2R1O...MgX / TiCl4 solid phase component. Then, an internal electron donor ID is added to obtain a ZN-type POP-CO2R1O...MgX / TiCl4 / ID polypropylene catalyst solid phase component.

[0045] In one embodiment, the preparation method of the catalyst solid phase component includes: drying a porous organic polymer containing functional monomers of unsaturated carboxylic acid hydroxy esters, adding it to an inert solvent under anhydrous and oxygen-free operating conditions, adding an alkyl magnesium chloride Grignard reagent, reacting at 0°C to 50°C for 15 to 120 minutes, filtering out the unreacted alkyl magnesium chloride Grignard reagent after the reaction is complete, adding an inert solvent and titanium tetrachloride, adjusting the temperature to 0°C to 80°C, reacting for 15 to 180 minutes, then adding an internal electron donor at 20-120°C, reacting for 15 to 180 minutes, and finally washing the product with an inert solvent to obtain the supported ZN polypropylene catalyst solid phase component.

[0046] The Zn polypropylene catalyst supported on a porous organic polymer support provided by this invention exhibits excellent stereoregulation and a wide molecular weight distribution in the prepared solid catalyst through the synergistic effect of the POP-CO2R1OH groups on the porous organic polymer support and the added internal electron donor. Experimental results show that the polypropylene obtained from the catalyst system without the added internal electron donor (POP-CO2R1O...MgX / TiCl4 solid catalyst component) has a wide molecular weight distribution and a certain stereoregulation. When the aforementioned internal electron donor is added, the synergistic effect between the unsaturated carboxylic acid hydroxy ester and the internal electron donor not only greatly improves the polymerization activity and stereoregulation of the active center of the catalyst, but also maintains a relatively wide molecular weight distribution in the polypropylene product.

[0047] This invention does not impose any particular limitations on inert solvents or organic solvents, such as hydrocarbon solvents.

[0048] In one embodiment, the ratio of the amount of magnesium compound added (in moles of magnesium Mg) to the amount of support is 1-30 mmol / g support, preferably 3-20 mmol / g support. An excess of titanium compound, such as TiCl4, is typically included for catalyst loading, and the amount of titanium compound added (in moles of titanium Ti) is generally 5 mmol / g support to 200 mmol / g support, preferably 50 mmol / g support to 150 mmol / g support. The ratio of the internal electron donor to the support is 0.02 g / g support to 0.3 g / g support.

[0049] The porous organic polymer carrier of this invention is typically prepared using free radical polymerization, such as dispersion polymerization, suspension polymerization, or emulsion polymerization. In one embodiment, the preparation method of this invention is as follows: using dispersion polymerization or suspension polymerization, with divinylbenzene as the basic monomer and unsaturated carboxylic acid hydroxy esters as functional monomers, the porous organic polymer carrier of this invention is prepared by free radical copolymerization. The porous organic polymer carrier of this invention can be represented as POP-CO2R1OH.

[0050] In one embodiment, the method for preparing the porous organic polymer carrier of the present invention is as follows: divinylbenzene and unsaturated carboxylic acid hydroxy ester are added to a dispersion solvent, then a stabilizer and an initiator are added, the mixture is stirred and dispersed evenly, and then reacted at 50-80°C for 5-12 hours. After filtration, washing and drying, the porous organic polymer carrier is obtained.

[0051] The dispersing solvent can be a lower alcohol, ester, or alcohol / water mixture system with 1-4 carbon atoms, with an alcohol to water mass ratio of 5-15:1. Dispersing solvents can include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, ethyl acetate, methyl acetate, ethyl formate, methyl formate, etc. Small amounts of other solvents, such as ethyl acetate, methyl formate, tetrahydrofuran, etc., can be added to the solvent system to adjust the solubility parameters, thereby controlling the pore structure and morphology of the prepared support. The total amount of divinylbenzene and unsaturated carboxylic acid hydroxy ester added is in a mass ratio of 1:5-20 to the dispersing solvent to ensure uniform dispersion. The mass ratio of unsaturated carboxylic acid hydroxy ester to divinylbenzene is 0.2-2:1. The stabilizer is polyvinyl alcohol or polypropylene oxide-ethylene oxide copolymer. The weight-average molecular weight of the stabilizer is controlled between 6,000 and 100,000, and the mass ratio of the stabilizer added to the total amount of divinylbenzene and unsaturated carboxylic acid hydroxy esters is 0.5-3:100. Common free radical initiators are used, including azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO), and the ratio of the initiator added to the total amount of divinylbenzene and unsaturated carboxylic acid hydroxy esters is 0.5-3:100. Washing refers to washing the polymer obtained from the reaction with a dispersing solvent to remove impurities.

[0052] The monomers divinylbenzene and unsaturated carboxylic acid hydroxy esters used in this invention can be commercially available. For example, divinylbenzene (abbreviated as DVB) can be a commercially available monomer with a DVB content of 55% or 80%. The monomers require pretreatment before use: Divinylbenzene needs pretreatment to remove the polymerization inhibitor before use. There are many existing methods for removing the polymerization inhibitor, such as washing with sodium hydroxide solution and distilled water. Unsaturated carboxylic acid hydroxy esters such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate can all be commercially available monomers. The polymerization inhibitor can be removed by neutral alumina particles before use.

[0053] In one embodiment, the specific surface area of ​​the porous organic polymer carrier of the present invention is tested using the BET nitrogen adsorption method on a Nova 2000e, and preferably the specific surface area of ​​the carrier is greater than 100 m². 2 / g, more preferably 100-600m 2 Between / g; pore volume greater than 0.2ml / g.

[0054] Therefore, this invention provides a polypropylene catalyst that can be used for propylene polymerization or copolymerization of propylene with α-olefins, wherein the α-olefins can be butene, isobutene, pentene, hexene, octene, 4-methyl-1-pentene, etc. The catalyst is suitable for gas-phase, bulk, or slurry polymerization reactions, with suitable reaction conditions of temperature 30–80°C and pressure 0.1–2.0 MPa. For slurry polymerization, a suitable solvent is an alkane containing 5–10 carbon atoms, with hexane being the preferred solvent. During bulk polymerization, the polymerization pressure is generally 2.8–4.0 MPa, and the polymerization temperature is generally 68–72°C. Hydrogen is typically used during the polymerization process to adjust the polymer molecular weight or melt index.

[0055] This invention relates to a Zn-based polypropylene catalyst, in which an alkylaluminum compound is added as a co-catalyst during polymerization. Furthermore, the added alkylaluminum compound can also serve as a purifying agent for the polymerization reaction system. Typically, the alkylaluminum compound used in the polypropylene catalyst system is triethylaluminum (AlEt3). The amount of alkylaluminum added is usually between 10 and 500, based on an Al / Ti molar ratio, where Al represents the molar number of triethylaluminum or alkylaluminum, and Ti represents the molar number of Ti in the titanium compound added to the catalyst.

[0056] During the polymerization process, an external electron donor is also required. The amount of external electron donor added is usually between 1 and 30 according to the Si / Ti molar ratio, where Si is the number of moles of Si in the added silane-based external electron donor, and Ti is the number of moles of Ti in the added titanium compound of the catalyst.

[0057] When the catalyst of this invention is used in propylene polymerization, the polypropylene product exhibits both high chain regularity and a wide molecular weight distribution.

[0058] This invention relates to a ZN-type polypropylene catalyst. Starting from the support level, through the design and optimization of functional monomers, the functional monomer R3HC=C(R4)R2CO2R1OH containing unsaturated carboxylic acid hydroxy esters is selected to prepare a porous organic polymer POP-CO2R1OH support suitable for polypropylene catalysts. Then, by modifying the support, magnesium / titanium compound active components are loaded onto the support, and an internal electron donor is further loaded onto the catalyst, thereby preparing the solid phase component POP-CO2R1OH / RMgX / TiCl4 / ID (internal electron donor) of the ZN-type polypropylene catalyst supported on a porous organic polymer (POP) support. Through the synergistic effect of the unsaturated carboxylic acid hydroxy esters on the support and the internal electron donor ID, the stereoregulation ability of the catalyst is improved, and polypropylene with a wide molecular weight distribution is prepared. During propylene polymerization, the solid component of this catalyst needs to be supplemented with silane-based external electron donors and triethylaluminum co-catalysts, which gives the catalyst good polymerization activity and high polymer isotacticity, reaching over 98%. TREF classification results show that its homopolymer polypropylene has higher chain regularity. In addition, the product has a wide molecular weight distribution, with molecular weights ranging from 8 to 15.

[0059] The technical solution of the present invention will be further described in detail below through specific embodiments. Unless otherwise specified, all percentages "%" below refer to mass percentages.

[0060] In this invention, the molecular weight and distribution of polypropylene prepared by propylene polymerization were obtained by gel permeation chromatography (GPC) by PolymerCharts; the isotacticity of the polymer was obtained by n-heptane elution test; the regularity and distribution of the polymer molecular chains were evaluated by temperature rise elution fractionation (TREF) test by PolymerCharts. The main fractionation consists of a room-temperature soluble fraction and a high-temperature eluted fraction. For homopolymer polypropylene, the room-temperature soluble fraction is atactic polypropylene. As the elution temperature increases, the chain regularity of the eluted polypropylene molecular chains increases.

[0061] Example 1

[0062] Treatment of comonomers: Before use, divinylbenzene should be treated with a 10% NaOH solution to remove the polymerization inhibitor, and then washed three times with deionized water. For functional monomers containing unsaturated carboxylic acid hydroxy esters, the monomers can be passed through 200-mesh neutral alumina particles to remove the polymerization inhibitor before use. The carrier preparation can be carried out with reference to Chinese patent CN104558260B.

[0063] Preparation of porous organic polymer carriers containing unsaturated carboxylic acid hydroxy ester groups: In a 5L glass reactor, 1350ml of ethanol, 150ml of deionized water, and 10ml of tetrahydrofuran were added, followed by 100g of divinylbenzene (Aladdin reagent, 80%) and 40g of hydroxypropyl methacrylate. The mixture was stirred at room temperature for 10 min, then 2% (2.7 g) of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45°C for 1 h to completely dissolve the stabilizer. Then, 2.0% (2.7 g) of azobisisobutyronitrile (AIBN) was added, and the temperature was raised to 70°C. The reaction was carried out for 2 h, then the temperature was raised to 80°C and the reaction was carried out for 10 h. The stirring speed was 350 rpm. After filtration, 1 L of the above-mentioned ethanol and water mixture was added, and the mixture was washed three times at 50°C. After filtration and drying, 102 g of free-flowing porous organic polymer carrier POP-1 was obtained, with a specific surface area of ​​423 m². 2 / g, pore volume 0.325ml / g, bulk density 0.27g / ml.

[0064] Example 2

[0065] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of the above-mentioned POP-1 support containing hydroxypropyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methylmagnesium chloride Grignard reagent was added at room temperature. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. Then, 50 ml of toluene was added, and 50 ml of TiCl4 was added dropwise at room temperature. The reaction was carried out for 2 hours, and the temperature was raised to 80 °C. Then, 0.45 g of diisobutyl phthalate (DIBP) internal electron donor was added, and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst solid phase particles, denoted as Cat-1, with a Mg content of 6.1%, a titanium content of 2.8%, and an DIBP internal electron donor content of 6.3%.

[0066] Example 3

[0067] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of the above-mentioned POP-1 support containing hydroxypropyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 8 ml of 3M methylmagnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 60 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of diisobutyl phthalate (DIBP) internal electron donor was added, and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst solid phase particles, denoted as Cat-2, with a Mg content of 3.6%, a titanium content of 4.8%, and an internal electron donor content of 5.6%.

[0068] Example 4

[0069] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of the above-mentioned POP-1 support containing hydroxypropyl methacrylate functional groups was added, along with 100 ml of toluene. The mixture was stirred, and then 5 ml of 3M methylmagnesium chloride Grignard reagent was added at room temperature. The mixture was stirred for 2 hours, filtered, and washed once with toluene. Then, 30 ml of toluene was added, and 60 ml of TiCl4 was added dropwise at room temperature. The reaction was carried out for 1 hour, and the temperature was raised to 80 °C. Then, 0.35 g of DIBP internal electron donor was added, and the reaction was carried out for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst solid phase particles, denoted as Cat-3, with a Mg content of 2.0%, a titanium content of 4.3%, and an internal electron donor content of 4.6%.

[0070] Example 5

[0071] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of the above-mentioned POP-1 support containing hydroxypropyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 8 ml of 3M benzyl magnesium bromide Grignard reagent was added at room temperature. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. Then, 50 ml of toluene was added, and 35 ml of TiCl4 was added dropwise at 50 °C. The reaction was carried out for 1 hour, and the temperature was raised to 80 °C. Then, 0.35 g of DIBP internal electron donor was added, and the reaction was carried out for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst solid phase particles, denoted as Cat-4, with a Mg content of 2.8%, a titanium content of 2.1%, and an internal electron donor content of 4.7%.

[0072] Example 6

[0073] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-1 support containing the above-mentioned hydroxypropyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methylmagnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 50 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.50 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst solid phase particles, denoted as Cat-5, with a Mg content of 4.1%, a titanium content of 3.2%, and an internal electron donor content of 6.3%.

[0074] Example 7

[0075] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-1 support containing the above-mentioned hydroxypropyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst solid phase particles, denoted as Cat-6, with a Mg content of 3.1%, a titanium content of 2.7%, and an internal electron donor content of 5.4%.

[0076] Example 8

[0077] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-1 support containing the above-mentioned hydroxypropyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.40 g of 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl methyl ester (IAIPPDB) was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst solid phase particles, denoted as Cat-7, with a Mg content of 3.4%, a titanium content of 2.1%, and an internal electron donor content of 4.8%.

[0078] Comparative Example 9

[0079] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of the above-mentioned POP-1 support with hydroxypropyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methylmagnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. Then, 50 ml of TiCl4 was added dropwise at room temperature, and the temperature was raised to 80 °C. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst solid phase particles, denoted as Cat-8, with a Mg content of 4.0% and a titanium content of 2.8%.

[0080] Comparative Example 10

[0081] Preparation of Zn-supported polypropylene catalyst on an inorganic support: In a 250 ml glass reactor, 3 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) was added, along with 100 ml of toluene. The mixture was stirred, and then 50 ml of TiCl4 was slowly added dropwise at 0 °C, controlling the dropping rate to maintain the temperature between 0 and 5 °C. After the addition was complete, the temperature was raised to 60 °C, and 0.30 g of DIBP internal electron donor was added. The temperature was raised to 100 °C and reacted for 1 hour. Then, 0.20 g of 9,9-dimethoxyfluorene internal electron donor was added, and the reaction was carried out at 110 °C for 2 hours. After filtration, 100 ml of fresh TiCl4 was added, and the reaction was carried out at 110 °C for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-9. The titanium content was 3.2%, the DIBP internal electron donor content was 3.6%, and the 9,9-dimethoxyfluorene internal electron donor content was 2.1%.

[0082] Comparative Example 11

[0083] Preparation of Zn-supported polypropylene catalyst on an inorganic support: In a 250 ml glass reactor, 3 g of spherical magnesium chloride support was added, followed by 100 ml of toluene. The mixture was stirred, and then 50 ml of TiCl4 was slowly added dropwise at 0°C, controlling the dropping rate to maintain the temperature between 0-5°C. After the addition was complete, the temperature was raised to 80°C, and 0.30 g of 3-methyl-5-tert-butyl-1,2-benzenedibenzoate (an internal electron donor) was added. The temperature was raised to 100°C and the reaction was carried out for 1 hour. Then, 0.20 g of... The 9,9-dimethoxyfluorene internal electron donor was reacted at 110°C for 2 hours. After filtration, 100 ml of fresh TiCl4 was added, and the reaction was carried out at 110°C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-10. The titanium content was 2.8%, the 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate internal electron donor content was 3.4%, and the 9,9-dimethoxyfluorene internal electron donor content was 2.2%.

[0084] Examples 12-22 Propylene Polymerization

[0085] Example 12: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 120 mg of Cat-1 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (C external electron donor) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 988 g of polypropylene product (PP-1) with a bulk density of 0.38 g / ml and a catalyst activity of 8233 gPP / gcat.h.

[0086] Example 13: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 120 mg of Cat-2 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1040 g of polypropylene product (PP-2) with a bulk density of 0.38 g / ml and a catalyst activity of 8667 gPP / gcat.h.

[0087] Example 14: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 120 mg of Cat-3 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (externally supplied C) were added. 0.5 g of hydrogen was added. The temperature was raised to 70 °C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 981 g of polypropylene product (PP-3) with a bulk density of 0.37 g / ml and a catalyst activity of 8175 gPP / gcat.h.

[0088] Example 15: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 120 mg of Cat-4 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 945 g of polypropylene product (PP-4) with a bulk density of 0.37 g / ml and a catalyst activity of 7875 gPP / gcat.h.

[0089] Example 16: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 80 mg of Cat-5 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1024 g of polypropylene product (PP-5) with a bulk density of 0.38 g / ml and a catalyst activity of 12800 gPP / gcat.h.

[0090] Example 17: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 80 mg of Cat-6 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1120 g of polypropylene product (PP-6) with a bulk density of 0.38 g / ml and a catalyst activity of 14000 gPP / gcat.h.

[0091] Example 18: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 80 mg of Cat-7 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (externally supplied C) were added. 0.5 g of hydrogen was added. The temperature was raised to 70 °C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 827 g of polypropylene product (PP-7) with a bulk density of 0.37 g / ml and a catalyst activity of 10338 gPP / gcat.h.

[0092] Example 19: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 120 mg of Cat-3 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (externally supplied) were added. 1.0 g of hydrogen was added. The temperature was raised to 70 °C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1028 g of polypropylene product (PP-8) with a bulk density of 0.36 g / ml and a catalyst activity of 8567 gPP / gcat.h.

[0093] Comparative Example 20: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 200 mg of the comparative catalyst Cat-8 and 0.3 ml of cyclohexylmethyldimethylsilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 325 g of polypropylene product (PP-9) with a bulk density of 0.33 g / ml and a catalyst activity of 1625 gPP / gcat.h.

[0094] Comparative Example 21: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 60 mg of the comparative catalyst Cat-9 and 0.3 ml of cyclohexylmethyldimethylsilane (externally supplied C) were added. 1 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1280 g of polypropylene product (PP-10) with a bulk density of 0.37 g / ml and a catalyst activity of 21333 gPP / gcat.h.

[0095] Comparative Example 22: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 60 mg of the comparative catalyst Cat-10 and 0.3 ml of cyclohexylmethyldimethylsilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1456 g of polypropylene product (PP-11) with a bulk density of 0.42 g / ml and a catalyst activity of 24267 gPP / gcat.h.

[0096] Table 1 Results of olefin polymerization catalysts in Examples 12-22

[0097]

[0098] Example 23

[0099] Preparation of a porous organic polymer carrier containing unsaturated carboxylic acid hydroxy ester groups: In a 5L glass reactor, 1500ml of ethanol was added, followed by 100g of divinylbenzene (Aladdin reagent, 80%) and 35g of hydroxyethyl methacrylate. The mixture was stirred at room temperature for 5 minutes, then 2% (by total monomer mass) of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45℃ for 1 hour to completely dissolve the stabilizer. Then, 2.0% (by total monomer mass) of AIBN was added, and the temperature was raised to 70℃. The reaction was carried out for 2 hours, then the temperature was raised to 80℃ and the reaction was continued for 8 hours. The stirring speed was maintained at 350 rpm. After filtration, 1000ml of the above-mentioned ethanol and water mixture was added, and the mixture was washed at 50℃. The mixture was filtered three times and dried to obtain 97g of free-flowing porous organic polymer carrier POP-2 with a specific surface area of ​​325m². 2 / g, pore volume 0.248ml / g, bulk density 0.24g / ml.

[0100] Example 24

[0101] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-2 support containing the above-mentioned hydroxyethyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 30 °C, and 50 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 90 °C. 0.45 g of diisobutyl phthalate (DIBP) internal electron donor was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-11. The catalyst contained 3.2% Mg, 2.8% titanium, and 6.4% internal electron donor.

[0102] Example 25

[0103] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-2 support containing the above-mentioned hydroxyethyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methylmagnesium chloride Grignard reagent was added at 5°C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50°C, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80°C. 0.42 g of 9,9-dimethoxyfluorene internal electron donor was added, and the reaction was carried out for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-12. The catalyst contained 4.5% Mg, 3.0% titanium, and 5.6% internal electron donor.

[0104] Example 26

[0105] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-2 support containing the above-mentioned hydroxyethyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 12 ml of 3M benzyl magnesium bromide Grignard reagent was added at 0 °C. The mixture was stirred for 2 hours, filtered, and washed once with toluene. The temperature was then raised to 50 °C, and 35 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 70 °C. 0.45 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added. The reaction was carried out for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-13. The catalyst contained 3.8% Mg, 3.1% titanium, and 5.6% internal electron donors.

[0106] Example 27

[0107] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-2 support containing the above-mentioned hydroxyethyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 50 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-14. The catalyst had a Mg content of 4.5%, a titanium content of 3.0%, and an internal electron donor content of 5.4%.

[0108] Example 28

[0109] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-2 support containing the above-mentioned hydroxyethyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether (IAIPDMP) was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-15. The catalyst contained 4.2% Mg, 3.4% titanium, and 5.3% internal electron donors.

[0110] Example 29

[0111] Preparation of a porous organic polymer carrier containing carboxylic acid hydroxyalkyl ester groups: In a 5L glass reactor, 1350ml of ethanol and 150ml of deionized water were added, followed by 100g of divinylbenzene (Aladdin reagent, 55%) and 50g of hydroxyethyl methacrylate. The mixture was stirred at room temperature for 15min, then 2% (3.0g) of polyvinyl alcohol (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45℃ for 1h to completely dissolve the stabilizer. Then, 2.0% (3.0g) of AIBN was added, and the temperature was raised to 70℃. The reaction was carried out for 2h, then the temperature was raised to 80℃ and the reaction was carried out for 8h. The stirring speed was 350 rpm. After filtration, 1L of the above-mentioned ethanol and water mixture was added, and the mixture was washed three times at 50℃. After filtration and drying, 105g of free-flowing porous organic polymer carrier POP-3 was obtained, with a specific surface area of ​​176m². 2 / g, pore volume 0.285ml / g, bulk density 0.21g / ml.

[0112] Example 30

[0113] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-3 support containing the above-mentioned hydroxyethyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at 0 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-16. The catalyst contained 2.8% Mg, 2.4% titanium, and 4.5% internal electron donors.

[0114] Example 31

[0115] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-3 support containing the above-mentioned hydroxyethyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M butylmagnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. 30 ml of toluene was added, and the temperature was raised to 50 °C. 30 ml of TiCl4 was added dropwise, and the reaction was carried out for 2 hours. Then, the temperature was raised to 80 °C, and 0.40 g of 9,9-dimethoxyfluorene internal electron donor was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-17. The catalyst had a Mg content of 4.2%, a titanium content of 3.1%, and an internal electron donor content of 4.7%.

[0116] Example 32

[0117] In a 250 ml glass reactor, 130 ml of ethyl acetate was added, followed by 4.8 g (approximately 5.0 ml) of divinylbenzene (Aladdin reagent, 80%) and 2.0 g of hydroxyethyl 4-vinylbenzoate (>97%, Aladdin reagent). The mixture was stirred at room temperature for 15 min. Then, 2% monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer. 2.0% monomer mass of AIBN was added, and the temperature was raised to 70 °C. The reaction was carried out for 3 h, then the temperature was raised to 80 °C and the reaction was carried out for 5 h. The stirring speed was 300 rpm. After filtration, the mixture was washed three times with an ethanol / water mixture (volume ratio: 1:1). After filtration and drying, 4.2 g of free-flowing porous POP-4 was obtained, with a carrier specific surface area of ​​248 m². 2 / g, pore volume 0.683ml / g, bulk density 0.27g / ml.

[0118] Example 33

[0119] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-4 support containing the above-mentioned hydroxyethyl benzoate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 50 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-18. The catalyst contained 3.8% Mg, 3.5% titanium, and 5.8% internal electron donors.

[0120] Example 34

[0121] In a 250 ml glass reactor, 130 ml of ethanol and 20 ml of deionized water were added, followed by 4.8 g (approximately 5.0 ml) of divinylbenzene (Aladdin reagent, 55%) and 2.4 g of methyl 4-vinylbenzoate (>90%). The mixture was stirred at room temperature for 5 min, then 2% monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer, followed by 2.0% monomer mass of AIBN. The temperature was raised to 70 °C and reacted for 3 h, then the temperature was raised to 80 °C and reacted for 5 h. The stirring speed was 600 rpm. The mixture was washed three times with ethanol, filtered, and then washed three times with an alcohol-water mixed solvent. After filtration and drying, 4.0 g of free-flowing porous POP-5 was obtained, with a carrier specific surface area of ​​289 m². 2 / g, pore volume 0.311ml / g, bulk density 0.24g / ml.

[0122] Example 35

[0123] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-5 support containing the above-mentioned hydroxymethyl benzoate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M dibutylmagnesium was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 50 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-19. The catalyst contained 4.5% Mg, 2.7% titanium, and 4.9% internal electron donors.

[0124] Example 36

[0125] In a 250 ml glass reactor, 130 ml of ethyl acetate was added, followed by 4.8 g (approximately 5.0 ml) of divinylbenzene (Aladdin reagent, 55%) and 3.2 g of hydroxyethyl styrene formate (Aladdin reagent, >97%). The mixture was stirred at room temperature for 5 min, then 2% monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer, followed by 2.0% monomer mass of AIBN. The temperature was raised to 70 °C and reacted for 3 h, then the temperature was raised to 80 °C and reacted for 5 h. The stirring speed was 600 rpm. The mixture was washed three times with ethanol, filtered, and dried to obtain 3.5 g of free-flowing porous POP-6 with a carrier specific surface area of ​​149 m². 2 / g, pore volume 0.473ml / g, bulk density 0.22g / ml.

[0126] Example 37

[0127] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-6 support containing the above-mentioned hydroxyethyl formate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 1 hour, filtered, washed twice with toluene, and then 50 ml of toluene was added. The temperature was then raised to 50 °C, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 1 hour, and then the temperature was raised to 80 °C. 0.42 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added, and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-20. The catalyst had a Mg content of 3.8%, a titanium content of 2.8%, and an internal electron donor content of 5.3%.

[0128] Example 38

[0129] In a 250 ml glass reactor, 130 ml of ethanol and 20 ml of deionized water were added, followed by 4.8 g (approximately 5.0 ml) of divinylbenzene (Aladdin reagent, 80%) and 2.4 g of 3-chloro-2-hydroxypropyl methacrylate (Aladdin reagent, >95%). The mixture was stirred at room temperature for 5 min, then 2% monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer, followed by 2.0% monomer mass of AIBN. The temperature was raised to 70 °C and reacted for 3 h, then the temperature was raised to 80 °C and reacted for 5 h. The stirring speed was 600 rpm. The mixture was washed three times with ethanol, filtered, and dried to obtain 4.8 g of free-flowing porous POP-7 with a carrier specific surface area of ​​338 m². 2 / g, pore volume 0.352ml / g, bulk density 0.27g / ml.

[0130] Example 39

[0131] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-7 support containing the above-mentioned 3-chloro-2-hydroxypropyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 8 ml of 3M methylmagnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-21. The catalyst had a Mg content of 3.2%, a titanium content of 2.4%, and an internal electron donor content of 4.5%.

[0132] Example 40

[0133] In a 250 ml glass reactor, 130 ml of isobutanol was added, followed by 4.8 g (approximately 5.0 ml) of divinylbenzene (Aladdin reagent, 55%) and 2.4 g of stilbene-4-carboxylic acid hydroxyethyl ester (Aladdin reagent, >95%). The mixture was stirred at room temperature for 5 min, then 3% monomer weight of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer. 3.0% monomer weight of BPO was then added, and the temperature was raised to 70 °C and reacted for 3 h. The temperature was then raised to 80 °C and reacted for 5 h. The stirring speed was 350 rpm. The mixture was washed three times with ethanol, filtered, and dried to obtain 4.5 g of free-flowing porous POP-8 with a carrier specific surface area of ​​223 m². 2 / g, pore volume 0.324ml / g, bulk density 0.26g / ml.

[0134] Example 41

[0135] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-8 support containing the above-mentioned stilbene-4-carboxylic acid hydroxyethyl ester functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-22. The catalyst contained 4.2% Mg, 3.1% titanium, and 5.6% internal electron donors.

[0136] Example 42

[0137] In a 250 ml glass reactor, 130 ml of ethanol and 20 ml of deionized water were added, followed by 4.8 g (approximately 5.0 ml) of divinylbenzene (Aladdin reagent, 80%) and 1.8 g of hydroxyethyl 4-(1-propenyl)benzoate (Aladdin reagent, >95%). The mixture was stirred at room temperature for 5 min, then 2% monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer, followed by 2.0% monomer mass of AIBN. The temperature was raised to 70 °C and reacted for 3 h, then the temperature was raised to 80 °C and reacted for 5 h. The stirring speed was 450 rpm. The mixture was washed three times with ethanol, filtered, and dried to obtain 4.0 g of free-flowing porous POP-9 with a carrier specific surface area of ​​287 m². 2 / g, pore volume 0.254ml / g, bulk density 0.24g / ml.

[0138] Example 43

[0139] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of POP-9 support containing the above-mentioned hydroxyethyl benzoate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 35 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.40 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-23. The catalyst contained 4.2% Mg, 3.1% titanium, and 5.6% internal electron donors.

[0140] Example 44

[0141] In a 250 ml glass reactor, 130 ml of ethanol and 20 ml of deionized water were added, followed by 4.8 g (approximately 5.0 ml) of divinylbenzene (Aladdin reagent, 80%) and 2.1 g of 2-hydroxy-4-(1-propenyl)phenol acetate (Aladdin reagent, >95%). The mixture was stirred at room temperature for 5 min, then 2% monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer, followed by 2.0% monomer mass of AIBN. The temperature was raised to 70 °C and reacted for 3 h, then the temperature was raised to 80 °C and reacted for 5 h. The stirring speed was 600 rpm. The mixture was washed three times with ethanol, filtered, and dried to obtain 4.3 g of free-flowing porous POP-10 with a carrier specific surface area of ​​287 m². 2 / g, pore volume 0.384ml / g, bulk density 0.27g / ml.

[0142] Example 45

[0143] Zn catalyst preparation: In a 250 ml glass reactor, 3 g of the above-mentioned POP-10 support was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M benzyl magnesium bromide Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 50 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added, and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-24. The catalyst contained 4.0% Mg, 3.5% titanium, and 6.1% internal electron donors.

[0144] Example 46

[0145] Zn catalyst preparation: In a 250 ml glass reactor, 3 g of the above-mentioned POP-10 support was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M dibutylmagnesium Grignard reagent was added at 0 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 50 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.45 g of 9,9-dimethoxyfluorene internal electron donor was added, and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-25. The catalyst contained 4.3% Mg, 3.8% titanium, and 5.4% internal electron donor.

[0146] Comparative Example 47

[0147] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of the above-mentioned POP-2 support containing hydroxyethyl methacrylate functional group was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. Then, 30 ml of TiCl4 was added dropwise at room temperature, and the temperature was raised to 80 °C. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-26. The catalyst contained 4.5% Mg and 3.8% titanium.

[0148] Comparative Example 48

[0149] Preparation of Zn-supported polypropylene catalyst on an inorganic support: In a 250 ml glass reactor, 3 g of spherical magnesium chloride support and 100 ml of toluene were added and stirred. Then, 50 ml of TiCl4 was slowly added dropwise at 0 °C, controlling the dropping rate to keep the temperature between 0 and 5 °C. After the addition was complete, the temperature was raised to 80 °C, and 0.45 g of diisobutyl phthalate (DIBP) internal electron donor was added. After filtration, 100 ml of fresh TiCl4 was added, and the reaction was carried out at 110 °C for 2 hours. After the reaction was complete, the catalyst was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-27, with a titanium content of 3.2% and an internal electron donor content of 6.8%.

[0150] Examples 49-66 Catalysts for Propylene Polymerization

[0151] In a polymerization reactor, propylene bulk polymerization is carried out using the prepared catalyst to produce polypropylene products.

[0152] Propylene homopolymerization: 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The stirring speed was 600 rpm. Then, 80 mg of the catalyst prepared above and 0.3 ml of cyclohexylmethyldimethylsilane (C externally supplied) were added. 0.5 g of hydrogen was added. The temperature was raised to 70 °C and the mixture was polymerized for 1 hour under stirring at 600 rpm. The pressure was released, the mixture was cooled to room temperature, and dried to obtain the polypropylene product.

[0153] In Example 64, the cat-23 catalyst was used, and 0.3 ml of dicyclopentene dimethoxysilane D external electron donor was added, while other conditions remained unchanged.

[0154] Table 2 Results of propylene polymerization using catalysts from Examples 49-66

[0155]

[0156]

[0157]

[0158] As shown in Table 3, the ZN polypropylene catalyst POP-CO2R1O...MgCl / TiCl4 / ID (internal electron donor) solid component supported on a porous organic polymer support in this invention exhibits good polymerization activity, with homopolymerization activity reaching over 13000 gPP / gcat.h. Although this is lower than that of catalysts supported on traditional inorganic MgCl2 supports, its activity is significantly improved compared to existing organic polymer supports, meeting the requirements of current industrial catalysts. Importantly, it was unexpectedly discovered through experiments that the Ti active centers of the prepared catalyst possess better stereoorientation ability due to the synergistic effect of the unsaturated carboxylic acid hydroxyl ester groups on the support and the internal electron donor ID, resulting in a wider molecular weight distribution of the obtained polypropylene. Experiments show that without the addition of an internal electron donor catalyst, POP-CO2R1O...MgCl / TiCl4, the prepared polymer has a very wide molecular weight distribution (comparative examples 20 and 63), reaching over 20. By adding an internal electron donor, the stereoregulation ability of the catalyst is further improved, and the isotacticity of the polymer can reach over 98%. TREF classification results show that its homopolymer polypropylene has a higher elution temperature (i.e., this part of the chain segment has higher chain regularity), reaching 124℃ (the elution temperature of other commercial homopolymer PP is generally around 122℃). In addition, the catalyst maintains the characteristic of a wide molecular weight distribution, with a molecular weight distribution between 8 and 15. Conventional Zn-type polypropylene catalysts typically struggle to produce polypropylene with both high chain regularity and a wide molecular weight distribution. Even with the addition of internal electron donors (e.g., two types, as in Comparative Example 22), while Comparative Example 21 uses a combination of fluorene diethers and DIBP as internal electron donors, although the polymer exhibits high isotacticity, its molecular weight distribution is narrow. In Comparative Example 22, although the polymer achieves a wider molecular weight distribution, the chain regularity of the highly isotactic molecular chains in its TREF fraction (high-temperature elution peak) is still lower than that of the catalyst in this invention. Generally, internal electron donors determine the stereoregularity (molecular chain regularity, of which isotacticity is a component), molecular weight distribution, hydrogen sensitivity, and polymerization activity of the polymer, making them a crucial component of polypropylene catalysts. Comparative Example 22, using a combination of bisphenol A and fluorene diethers as internal electron donors (as seen in Comparative Example 21, fluorene diethers exhibit high isotacticity as internal electron donors, but a narrow molecular weight distribution), achieves both a wide molecular weight distribution and high chain regularity. The present invention (as in Example 14) only requires the most commonly used DIBP internal electron donor to achieve the same effect as Comparative Example 22, and the results are even better. If a bisphenol ester internal electron donor is used, as in Example 52, the polymer can achieve ultra-high chain stereoregularity and a wide molecular weight distribution using the same bisphenol ester internal electron donor.

[0159] The POP-CO2R1OH / RMgX / TiCl4 / ID solid catalyst component disclosed in this invention has a simple preparation method compared with existing catalysts. Its active center has both a wide molecular weight distribution and high stereotacticity, which makes it have good industrialization prospects. In particular, this catalyst system has advantages in developing high rigidity and toughness balanced homopolymer products.

[0160] Figure 1 The Tref curve is shown for the polypropylene prepared in this embodiment of the invention. Further, Figure 1 The Tref (Temperature Rise Eluent) curves are for the polypropylene prepared in Examples 52, 22, and 65. These curves typically have two main peaks: one is a room-temperature soluble peak, representing atactic polypropylene; the other is a high-temperature elution peak. Higher elution temperatures indicate more regular polypropylene molecular chains, fewer defects, stronger crystallinity, and larger peak areas, indicating a higher content of this component. The curves show that the Tref fraction curve of Example 52 indicates the lowest content of atactic polypropylene and the highest elution temperature of its high-temperature elution peak, indicating the highest regularity of this component's molecular chains.

[0161] Figure 2 The molecular weight and distribution curves of the polypropylene GPC prepared in this embodiment of the invention are shown. Further, Figure 2 The GPC molecular weight and distribution curves of polypropylene prepared in Examples 52, 63, Comparative Examples 21, 22, and 65 are shown. In these curves, Comparative Example 65 (without additional internal electron donor), Examples 52, and 63 all exhibit relatively broad molecular weight distributions; Comparative Example 22 (with the addition of a compound internal electron donor) further broadens the molecular weight distribution. Comparative Example 21 exhibits a relatively narrow molecular weight distribution.

[0162] Furthermore, the ZN-type polypropylene catalyst prepared in this invention can also be used for copolymerization of propylene and ethylene to prepare copolymerized polypropylene products. The catalyst exhibits good copolymerization ability; when ethylene monomer is added, the catalyst activity increases significantly, and the polymer molecular weight distribution is broad.

[0163] Example 67

[0164] Propylene-ethylene copolymerization: 2.0 kg of liquid propylene and 10 mL of triethylaluminum (TEA) (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, followed by 60 mg of the prepared Cat-13 catalyst and 0.3 mL of cyclohexylmethyldimethylsilane (externally supplied by C). 0.5 g of hydrogen and 30 g of ethylene monomer were added. The mixture was heated to 70 °C and polymerized at 600 rpm for 1 hour. The pressure was released, the mixture was cooled to room temperature, and dried to obtain 1098 g of polypropylene product. The catalyst polymerization activity was 18300 gPP / gcat.h, the polymer weight-average molecular weight (Mw) was 532,500, and the molecular weight distribution was 9.7.

[0165] Example 68

[0166] Propylene-ethylene copolymerization: 2.0 kg of liquid propylene and 10 mL of triethylaluminum (TEA) (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, followed by 60 mg of the prepared Cat-23 catalyst and 0.3 mL of cyclohexylmethyldimethylsilane (externally supplied by C). 0.5 g of hydrogen and 30 g of ethylene monomer were added. The mixture was heated to 70 °C and polymerized at 600 rpm for 1 hour. The pressure was released, the mixture was cooled to room temperature, and dried to obtain 991 g of polypropylene product. The catalyst polymerization activity was 16517 gPP / gcat.h, the polymer weight-average molecular weight (Mw) was 623,000, and the molecular weight distribution was 12.3.

[0167] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A polypropylene catalyst, characterized in that, The polypropylene catalyst is a Zn catalyst, comprising a solid phase component, a co-catalyst, and an external electron donor. The solid phase component comprises a porous organic polymer support, a magnesium compound, a titanium compound, and an internal electron donor. The porous organic polymer support is a copolymer comprising divinylbenzene and an unsaturated carboxylic acid hydroxy ester. The content of the unsaturated carboxylic acid hydroxy ester is 5-60%, based on the mass of the porous organic polymer carrier being 100%.

2. The polypropylene catalyst according to claim 1, characterized in that, The polypropylene catalyst is a ZN catalyst; the mass of the magnesium compound in the solid phase component is 1-8 parts based on magnesium element, the mass of the titanium compound in the solid phase component is 1-8 parts based on titanium, the mass of the internal electron donor in the solid phase component is 1-10 parts, and the mass of the porous organic polymer support is 60-85 parts.

3. The polypropylene catalyst according to claim 1, characterized in that, The content of unsaturated carboxylic acid hydroxy ester monomers in the porous organic polymer carrier is 0.5–5 mmol / g porous organic polymer carrier.

4. The polypropylene catalyst according to claim 1, characterized in that, The chemical formula of the unsaturated carboxylic acid hydroxy ester is R3HC=C(R4)R2CO2R1OH, wherein R1 is an alkylene or phenylene group containing 1-6 carbon atoms in the main chain, and the R1 group may or may not have substituents, the substituents being at least one of chlorine, bromine, fluorine, iodine, alkyl, phenyl, and naphthyl; R2 is an alkylene or phenylene group containing 0-6 carbon atoms in the main chain, and the R2 group may or may not have substituents, the substituents being at least one of chlorine, bromine, fluorine, iodine, alkyl, phenyl, and naphthyl; R3 is an alkyl, phenyl, or hydrogen group containing 1-6 carbon atoms in the main chain, and the R3 group may or may not have substituents, the substituents being at least one of chlorine, bromine, fluorine, iodine, alkyl, phenyl, and naphthyl; R4 is an alkyl, phenyl, or hydrogen group containing 1-6 carbon atoms in the main chain.

5. The polypropylene catalyst according to claim 4, characterized in that, The unsaturated carboxylic acid hydroxy esters are methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-chlorohydroxymethyl methacrylate, 4-vinylbenzoic acid hydroxymethyl ester, 4-vinylbenzoic acid hydroxyethyl ester, 4-vinylbenzoic acid hydroxypropyl ester, stilbene-4-carboxylic acid hydroxymethyl ester, stilbene-4-carboxylic acid hydroxyethyl ester, stilbene-4-carboxylic acid hydroxypropyl ester, 2-hexenoic acid hydroxymethyl ester, 2-hexenoic acid hydroxyethyl ester, 2-hexenoic acid 2-hydroxypropyl ester, styrylformic acid hydroxymethyl ester, styrylformic acid hydroxyethyl ester, styrylformic acid 2-hydroxypropyl ester, 2-hydroxy... The ester of at least one of the following: 4-(1-propenyl)phenol carboxylate, 2-hydroxy-4-(1-propenyl)phenol acetate, 2-hydroxy-4-(1-propenyl)phenol propionate, 2-hydroxy-4-(1-propenyl)phenol benzoate, 4-(1-propenyl)benzoic acid hydroxypropyl ester, 4-(1-propenyl)benzoic acid hydroxyethyl ester, 4-(1-propenyl)benzoic acid hydroxymethyl ester, 2-hydroxy-4-vinylphenol carboxylate, 2-hydroxy-4-vinylphenol acetate, 2-hydroxy-4-vinylphenol propionate, 2-hydroxy-4-vinylphenol monochloroacetate, 2-hydroxy-4-vinylphenol trichloroacetate, and 2-hydroxy-4-vinylphenol trifluoroacetate.

6. The polypropylene catalyst according to claim 1, characterized in that, The porous organic polymer further includes a third monomer, which is selected from at least one of styrene, alkyl-substituted styrene, and chloromethyl-substituted styrene; the internal electron donor is at least one of diester internal electron donor and diether internal electron donor; and the external electron donor is a silane external electron donor.

7. The polypropylene catalyst according to claim 6, characterized in that, The diester internal electron donor is at least one of the following: a diphenol ester internal electron donor, a diol ester internal electron donor, and a succinate ester internal electron donor.

8. The method for preparing the polypropylene catalyst according to any one of claims 1-7, characterized in that, The method for preparing the solid phase component includes: The porous organic polymer support and the magnesium compound are reacted in an inert solvent at a temperature of 0°C to 50°C for 15 to 120 minutes. The unreacted magnesium compound is then filtered and added to an organic solvent containing a titanium compound for further reaction at a temperature of 0°C to 80°C for 15 to 180 minutes. An internal electron donor is then added, and the reaction is carried out at 20-120°C to obtain the solid phase component.

9. The method for preparing the polypropylene catalyst according to claim 8, characterized in that, The amount of magnesium compound added, calculated as magnesium, is 1 to 30 mmol / g porous organic polymer carrier, and the amount of titanium compound added, calculated as titanium, is 5 to 200 mmol / g porous organic polymer carrier.

10. The method for preparing the catalyst system for propylene polymerization according to claim 8, characterized in that, The method for preparing the porous organic polymer support includes: The porous organic polymer carrier was prepared by free radical copolymerization using divinylbenzene as the basic monomer and unsaturated carboxylic acid hydroxy esters as functional monomers.

11. The use of the polypropylene catalyst according to any one of claims 1-7 in propylene polymerization or copolymerization of propylene and α-olefins, characterized in that, The molecular weight distribution of the prepared polymer is between 8 and 15.

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