Organic carrier-supported polypropylene catalyst system and its preparation method and application

Abstract

The present invention discloses an organic carrier-supported polypropylene catalyst system, its preparation method, and application. The catalyst system 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 of divinylbenzene and a sulfonic acid functional monomer. The catalyst of the present invention is used for propylene polymerization, and the resulting polypropylene has both high chain regularity and a wide molecular weight distribution.

Description

Technical Field

[0001] The present invention relates to the field of propylene polymerization, and in particular to an organic carrier-supported polypropylene catalyst system and a preparation method and application thereof. Background Art

[0002] Since the discovery of ZN catalyst 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 its production and consumption will continue to grow.

[0003] Currently, industrial polypropylene catalysts are primarily ZN-type catalysts and metallocene catalysts, primarily used to produce highly isotactic polypropylene. In addition, metallocene and post-metallocene catalysts are used to produce small amounts of syndiotactic polypropylene, atactic polypropylene, and propylene-based elastomers. For industrial polypropylene production equipment, such as those using slurry, bulk, or gas-phase polymerization processes, the catalyst must be loaded to control the morphology of the resulting polymer and avoid problems such as reactor agglomeration and blockage.

[0004] Existing industrial catalysts primarily utilize inorganic supports for ZN catalysts and metallocene catalysts. These supports primarily include silica, magnesium chloride, magnesium ethoxide, and molecular sieves. For example, MgCl2-supported polypropylene catalysts typically include the following components: MgCl2 / TiCl4 / internal electron donor (ID) / silane-based 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 diether-based internal electron donors. Inorganic support-supported polypropylene catalysts typically exhibit high polymerization activity, better control of polymer morphology, and high bulk density. However, inorganic supports often introduce additional impurities (beyond the Mg and Ti catalyst components), making the development of highly clean polypropylene products difficult.

[0005] Unlike reported inorganic supports, organic polymer supports themselves do not introduce impurities that would affect polymer performance. Furthermore, organic supports have controllable pore structures, high specific surface areas, stable thermal properties, and are easily functionalized. Through support design and functionalization, high-performance or distinctive polyolefin catalysts can be prepared. There are public reports on porous organic supports supporting ZN catalysts, typically using organic supports containing functional groups such as carboxylic acid, hydroxyl, cyano, and amino groups. For example, U.S. Patent No. 4,623,707 uses an organic support prepared from a chloromethylated styrene monomer to prepare a ZN catalyst. For example, in “Porous polyethylene spheres with nanofiber structure from Ziegler-Natta catalyst supported on porous polymer particles” (2011; Vol. 52, pp. 602-605), a cyano-functionalized organic support was used to prepare a POP support-supported ZN polyethylene catalyst. 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 POP support functionalized with methyl methacrylate. In Catalyst Letters, "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), a ZN catalyst was prepared using a copolymer of methacrylic acid and 1-octene as a support for the preparation of polyethylene with a broad molecular weight distribution. In addition, metallocene catalysts prepared using organic supports, such as those prepared using an organic support containing carboxylate groups in US Pat. No. 5,587,439, reported that these organic polymer-supported ZN catalysts are generally suitable for polyethylene catalysts, with few reports of their use in propylene polymerization. This is mainly because the ZN catalyst system supported by the above organic carrier has low propylene polymerization activity. Even after the internal electron donor ID is used to regulate the regularity of the polypropylene molecular chain, although its isotacticity and propylene polymerization activity are improved, it cannot meet the requirements of commercial application.

[0006] Therefore, there is a need in the art to further study organic-supported catalysts for propylene polymerization. Summary of the Invention

[0007] The main purpose of the present invention is to provide an organic carrier-supported polypropylene catalyst system and its preparation method and application. When the catalyst is used for propylene polymerization, the polypropylene product has both high chain regularity and wide molecular weight distribution.

[0008] In order to achieve the above-mentioned object, the present invention provides an organic carrier-supported polypropylene catalyst system, comprising a solid phase component, a co-catalyst and an external electron donor, wherein the solid phase component comprises a porous organic polymer carrier, a magnesium compound, a titanium compound and an internal electron donor, and the porous organic polymer carrier is a copolymer comprising divinylbenzene and a sulfonic acid functional monomer.

[0009] The organic carrier-supported polypropylene catalyst system of the present invention comprises 60 to 85 parts by weight of the porous organic polymer carrier in the solid phase component, 1 to 8 parts by weight of the magnesium compound in the solid phase component calculated as magnesium element, 1 to 8 parts by weight of the titanium compound in the solid phase component calculated as titanium element, and 1 to 10 parts by weight of the internal electron donor in the solid phase component; and based on 100% by weight of the porous organic polymer carrier, the sulfonic acid group-containing functional monomer accounts for 5 to 60% of the total weight.

[0010] The organic carrier-supported polypropylene catalyst system of the present invention comprises: a porous organic polymer carrier having a sulfonic acid functional monomer content of 0.5 to 5 mmol / g; and a porous organic polymer carrier comprising a copolymer of divinylbenzene, a sulfonic acid functional monomer, and a third monomer, wherein the third monomer is at least one of styrene, an alkyl-substituted styrene, and a chloromethyl-substituted styrene.

[0011] The organic carrier-supported polypropylene catalyst system of the present invention comprises the following: the chemical formula of the sulfonic acid functional monomer is R2HC=C(R3)R1SO2OH, R2HC=C(R3)R1SO3H or R2HC=C(R3)R1SO2OM; R1 is an alkylene group or a phenylene group having 0-6 carbon atoms on the main chain; the R1 group may contain chlorine, bromine, fluorine, iodine, an alkyl group, a phenyl group or naphthalene; R2 is an H atom, an alkyl group or a phenyl group having 1-6 carbon atoms on the main chain; the R2 group may contain chlorine, bromine, fluorine, iodine, an alkyl group, a phenyl group or a naphthyl group; R3 is an H atom, an alkyl group or a phenyl group having 1-6 carbon atoms on the main chain; and M is a metal.

[0012] The organic carrier-supported polypropylene catalyst system of the present invention, wherein the sulfonic acid group-containing functional monomer is sodium p-styrenesulfonate, p-styrenesulfonic acid, sodium m-styrenesulfonate, m-styrenesulfonic acid, o-styrenesulfonic acid, sodium o-styrenesulfonate, 2-methyl-4-sodium sulfonate styrene, 2-chloro-4-sodium sulfonate styrene, 2-methyl-4-sulfonate styrene, 2-methyl-3-sodium sulfonate styrene, 2-methyl-3-sulfonate styrene, vinyl-4-methylbenzenesulfonic acid, sodium vinyl-4-methylbenzenesulfonate, 2-ethyl-3-sodium sulfonate styrene, 2-ethyl-3-sulfonate styrene, 4,4'-bis(2-sulfonatostyryl)-1,1'-biphenyl, 2-(2-styryl)benzenesulfonic acid, vinyl sulfonic acid, sodium vinyl sulfonate, propenylsulfonic acid, sodium propenylsulfonate, sodium 3-chloropropenylsulfonate, methylpropenylsulfonic acid, methyl Sodium propylene sulfonate, 1-butenyl sulfonic acid, sodium 1-butenyl sulfonate, 1-pentenyl sulfonic acid, sodium 1-pentenyl sulfonate, 1-hexene sulfonic acid, sodium 1-hexene sulfonate, 1-heptene sulfonic acid, sodium 1-heptene sulfonate, 1-octene sulfonic acid, sodium 1-octene sulfonate, 1-decene sulfonic acid, sodium 1-decene sulfonate, 2-acrylamido-2-methyl-1-propane sulfonic acid, vinyl sulfonic acid, sodium vinyl sulfonate, allyl sulfonic acid, sodium allylpropane sulfonate, At least one of methacrylic acid, sodium methacrylic acid, 1-butenylsulfonic acid, sodium 1-butenylsulfonate, 1-pentenylsulfonic acid, sodium 1-pentenylsulfonate, 1-hexenesulfonic acid, sodium 1-hexenesulfonate, 1-heptenesulfonic acid, sodium 1-heptenesulfonate, 1-octenesulfonic acid, sodium 1-octenesulfonate, 1-decenesulfonic acid, sodium 1-decenesulfonate, 2-acrylamido-2-methyl-1-propanesulfonic acid, and hydrates of these compounds.

[0013] The organic carrier-supported polypropylene catalyst system of the present invention, wherein the BET specific surface area of ​​the porous organic polymer carrier of the present invention is 100-600m 2 / g, and a pore volume greater than or equal to 0.2 ml / g; the co-catalyst is an alkyl aluminum, the co-catalyst is calculated as Al, the titanium compound is calculated as Ti, and the molar ratio of the co-catalyst to the titanium compound is 5-500; the internal electron donor is at least one of a diester internal electron donor, a diphenol ester internal electron donor, a glycol ester internal electron donor, a succinate internal electron donor, and a diether internal electron donor; and the external electron donor is a silane compound.

[0014] In order to achieve the above object, the present invention also provides a method for preparing the above organic carrier-supported polypropylene catalyst system, wherein the method for preparing the solid phase component of the catalyst comprises:

[0015] The porous organic polymer support and the magnesium compound are reacted in an inert solvent at a reaction temperature of 0°C to 50°C and a reaction time of 15 to 120 minutes. The unreacted magnesium compound is then filtered and added to an organic solvent containing a titanium compound to react at a reaction temperature of 0°C to 80°C and a reaction time of 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.

[0016] The method for preparing an organic carrier-supported polypropylene catalyst system of the present invention comprises the following steps: the magnesium compound is added in an amount of 1 to 30 mmol per gram of the porous organic polymer carrier, the titanium compound is added in an amount of 5 to 200 mmol per gram of the porous organic polymer carrier, and the ratio of the internal electron donor to the porous organic polymer carrier is 0.02 to 0.3 g per gram of the porous organic polymer carrier.

[0017] The method for preparing the organic carrier-supported polypropylene catalyst system of the present invention, wherein the method for preparing the porous organic polymer carrier comprises:

[0018] The porous organic polymer carrier is prepared by free radical copolymerization of divinylbenzene as a basic monomer and a sulfonic acid functional monomer.

[0019] In order to achieve the above object, the present invention further provides the use of the above organic carrier-supported polypropylene catalyst system in propylene polymerization or copolymerization of propylene and α-olefin.

[0020] Beneficial effects of the present invention:

[0021] The ZN polypropylene catalyst supported on a porous organic polymer carrier of the present invention has a pore structure that can be adjusted by the carrier's pore structure. By designing functional monomers, the catalyst regulates the chemical environment of the titanium active center, forming a solid-phase component of an organic-support-supported POP-SO3H / RMgX / TiCl4 / ID (internal electron donor) polypropylene catalyst. The synergistic effect between the sulfonic acid groups on the carrier and the internal electron donor ID enhances the stereospecificity of the catalyst's Ti active center, thereby resulting in a wider molecular weight distribution for the resulting polypropylene. During propylene polymerization, the ZN-type catalyst solid-phase component requires the addition of an external electron donor and a co-catalyst. The catalyst exhibits excellent polymerization activity and a high polymer isotacticity, exceeding 98%. TREF fractionation results indicate that the resulting homopolymerized polypropylene has a higher elution temperature (i.e., this segment has higher chain regularity), exceeding 123°C (compared to the elution temperature of other commercial homopolymerized PP, which is generally around 122°C). Furthermore, the product exhibits a broad molecular weight distribution, ranging from 8 to 15. Conventional ZN-type polypropylene catalysts typically struggle to produce polypropylene with both high chain regularity and a broad molecular weight distribution. The organic carrier-supported ZN polypropylene catalyst has good industrial prospects, and the catalyst system has advantages in developing homopolymer products with high rigidity and toughness balance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is the temperature rise elution fractionation (Tref) curve of the polypropylene prepared in the embodiment of the present invention.

[0023] Figure 2 The GPC molecular weight and distribution curve of the polypropylene prepared in the embodiment of the present invention. DETAILED DESCRIPTION

[0024] The following is a detailed description of the embodiments of the present invention. These embodiments are implemented based on the technical solutions of the present invention, and detailed implementation methods and processes are given. However, the scope of protection of the present invention is not limited to the following embodiments. The experimental methods for which specific conditions are not specified in the following embodiments are generally based on conventional conditions.

[0025] The present invention provides an organic carrier-supported polypropylene catalyst system, comprising a solid phase component, a co-catalyst and an external electron donor, wherein the solid phase component comprises a porous organic polymer carrier, a magnesium compound, a titanium compound and an internal electron donor, and the porous organic polymer carrier is a copolymer comprising divinylbenzene and a sulfonic acid group-containing functional monomer.

[0026] The present invention utilizes the synergistic effect of sulfonic acid functional monomers and an internal electron donor to impart excellent stereospecificity to the catalyst and a broad molecular weight distribution to the resulting polymer chains. Experimental results show that when the catalyst system (POP-SO3...MgX / TiCl4 solid catalyst component) is used to catalyze propylene polymerization without the internal electron donor, the resulting polypropylene exhibits a broad molecular weight distribution and a certain degree of stereospecificity. However, when the internal electron donor is added, the synergistic effect of the sulfonic acid functional monomers and the internal electron donor significantly enhances the catalyst's polymerization activity and the stereospecificity of the active centers, while also maintaining a relatively broad molecular weight distribution for the resulting polypropylene product.

[0027] However, when the catalyst is used for propylene polymerization, the cocatalyst will complex with the internal electron donor, causing the Ti atoms and the internal electron donor to lose stability and reoccupy the random active sites complexed by the internal electron donor, resulting in a decrease in the catalyst's directional ability. The present invention adds an external electron donor to preferentially bind the external electron donor to the cocatalyst, preventing the internal electron donor from falling off, reducing the amount of internal electron donor removed by the cocatalyst, ensuring the stability of the stereoactive centers in the catalyst, and thus making the prepared polymer have higher isotacticity.

[0028] The catalyst system of the present invention is a ZN catalyst. The porous organic polymer support is a copolymer obtained by copolymerizing divinylbenzene and a sulfonic acid functional monomer. In one embodiment, the sulfonic acid functional monomer has the formula R2HC=C(R3)R1SO2OH, R2HC=C(R3)R1SO3H, or R2HC=C(R3)R1SO2OM. R1 is typically an alkylene group or a phenylene group containing 0-6 carbon atoms in the main chain, and R2 is typically an H atom, an alkyl group containing 1-6 carbon atoms in the main chain, or a phenyl group. The R1 and R2 groups may also contain other substituents such as chlorine, bromine, fluorine, iodine, an alkyl group, a phenyl group, or a naphthyl group. R3 is an H atom, an alkyl group containing 1-6 carbon atoms in the main chain, or a phenyl group. M is a metal. In one embodiment, M is an alkali metal or an alkaline earth metal; in another embodiment, M is Na, Mg, or Al.

[0029] When the number of carbon atoms in R1 is 0 and R3 is an H atom, the chemical formula of the functional monomer is R2HC=CHSO2OH; when R1 is a phenylene group and R3 is an H atom, the chemical formula of the functional monomer is R2HC=CH-PhSO3H; when R2 is a phenyl group, the number of carbon atoms in R1 is 0 and R3 is an H atom, the chemical formula of the functional monomer is PhHC=CHSO3H; when the number of carbon atoms in R1 and R2 is 0 and R3 is an H atom, the chemical formula of the functional monomer is H2C=CHSO3H. In addition, the functional monomer can also be selected from R2HC=C(R3)R1SO2OH metal salts and their hydrates, such as sodium salts and their hydrates, Mg, Al salts, etc. and their hydrates, such as R2HC=CHR1SO2ONa.xH2O. After preparing the POP porous organic support, the POP-SO3H support is obtained by acidification.

[0030] In another embodiment, the sulfonic acid functional monomer of the present invention includes but is not limited to sodium p-styrenesulfonate, p-styrenesulfonic acid, sodium m-styrenesulfonate, m-styrenesulfonic acid, o-styrenesulfonic acid, sodium o-styrenesulfonate, 2-methyl-4-sodium sulfonate styrene, 2-chloro-4-sodium sulfonate styrene, 2-methyl-4-sulfonate styrene, 2-methyl-3-sodium sulfonate styrene, 2-methyl-3-sulfonate styrene, vinyl-4-methylbenzenesulfonic acid, sodium vinyl-4-methylbenzenesulfonate, 2-ethyl-3-sodium sulfonate styrene, 2-ethyl-3-sulfonate styrene, 4,4'-bis(2-sulfonatostyryl)-1,1'-biphenyl, 2-(2-styryl)benzenesulfonic acid, vinyl sulfonic acid, sodium vinyl sulfonate, propenylsulfonic acid, sodium propenylsulfonate, sodium 3-chloropropenylsulfonate, methylpropenylsulfonic acid, methylpropenylsulfonic acid, Sodium 1-butenesulfonate, 1-butenesulfonic acid, sodium 1-butenesulfonate, 1-pentenylsulfonic acid, sodium 1-pentenylsulfonate, 1-hexenesulfonic acid, sodium 1-hexenesulfonate, 1-heptenesulfonic acid, sodium 1-heptenesulfonate, 1-octenesulfonic acid, sodium 1-octenesulfonate, 1-decenesulfonic acid, sodium 1-decenesulfonate, 2-acrylamido-2-methyl-1-propanesulfonic acid, vinylsulfonic acid, sodium vinylsulfonate, allylsulfonic acid, allylpropanesulfonic acid Sodium sulfonate, methacrylic acid, sodium methacrylic acid, 1-butenylsulfonic acid, sodium 1-butenylsulfonate, 1-pentenylsulfonic acid, sodium 1-pentenylsulfonate, 1-hexenesulfonic acid, sodium 1-hexenesulfonate, 1-heptenesulfonic acid, sodium 1-heptenesulfonate, 1-octenesulfonic acid, sodium 1-octenesulfonate, 1-decenesulfonic acid, sodium 1-decenesulfonate, 2-acrylamido-2-methyl-1-propanesulfonic acid and hydrates thereof, etc.

[0031] In one embodiment, the sulfonic acid functional monomer accounts for 5-60% of the porous organic polymer support by mass, based on 100% of the porous organic polymer support. In another embodiment, the sulfonic acid functional monomer in the porous organic polymer support is present in an amount of 0.5 to 5 mmoles per gram of the porous organic polymer support, preferably 1 to 4 mmoles per gram of the porous organic polymer support. In yet another embodiment, the porous organic polymer of the present invention further comprises a third monomer, i.e., the porous organic polymer support is a copolymer obtained by copolymerizing divinylbenzene, the sulfonic acid functional monomer, and the third monomer. In yet another embodiment, the third monomer is selected from at least one of styrene, alkyl-substituted styrene, and chloromethyl-substituted styrene.

[0032] In the catalyst system of the present invention, the magnesium compound and the titanium compound are commonly used in ZN catalysts in the art and are not particularly limited in the present invention, for example, halogen compounds of magnesium and titanium.

[0033] In one embodiment, the magnesium compound of the present invention has the molecular formula RMgX or R6MgR5, wherein X is a halogen, i.e., a fluorine, chlorine, bromine, or iodine atom, and the R, R5, and R6 groups can be chain hydrocarbons or aromatic hydrocarbon groups containing 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, benzene, benzene containing a substituted group, or alkoxy, and R5 and R6 can be the same or different. Furthermore, the magnesium compound of the present invention can be an alkyl halide magnesium Grignard reagent, an alkyl magnesium compound, an alkoxy magnesium halide, and the like, such as methylmagnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, tert-butylmagnesium chloride, benzylmagnesium chloride, ethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, n-butylmagnesium bromide, benzylmagnesium bromide, methylmagnesium iodide, tert-butylmagnesium iodide, benzylmagnesium iodide, n-butylmagnesium iodide, methylmagnesium fluoride, tert-butylmagnesium fluoride, diethylmagnesium, diethylmagnesium, ethoxymagnesium chloride, and the like. Furthermore, the magnesium compound of the present invention is an alkyl magnesium chloride Grignard reagent RMgCl.

[0034] In one embodiment, the titanium compound of the present invention is a titanium halide, such as titanium tetrachloride, titanium trichloride, etc., typically titanium tetrachloride.

[0035] 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. The internal electron donor includes, but is not limited to, the following internal electron donors, such as diisobutyl phthalate (DIBP), di-n-butyl phthalate (DNBP), 9,9-dimethoxyfluorene, 2,3-diisobutyl diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzyl ester (IAIPPDB), 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether (IAIPDMP), and the like.

[0036] In one embodiment, the mass of the porous organic polymer support in the solid phase component is 60 to 85 parts, the mass of the magnesium compound in the solid phase component calculated as magnesium element is 1 to 8 parts, the mass of the titanium compound in the solid phase component calculated as titanium element is 1 to 8 parts, and the mass of the internal electron donor in the solid phase component is 1 to 10 parts.

[0037] In one embodiment, the external electron donor is a silane compound, that is, a silane-type external electron donor, and the silane-type external electron donor includes but is not limited to cyclohexylmethyldimethylsilane (C external donor), dicyclopentenyldimethoxysilane (D external donor), diisopropyldimethoxysilane (P external donor), diisobutyldimethoxysilane (B external donor), and tetraethoxysilane (TEOS).

[0038] In another embodiment, the external electron donor is added in an amount according to a Si / Ti molar ratio of typically 1-30, wherein Si is the molar number of the silane-based external electron donor added as Si, and Ti is the molar number of the titanium compound added to the catalyst as Ti.

[0039] The cocatalyst of the present invention and its addition amount are well known to those skilled in the art. In one embodiment, the cocatalyst of the present invention is an alkyl aluminum compound. In another embodiment, the alkyl aluminum compound has 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 yet another embodiment, the cocatalyst is selected from triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-hexyl aluminum, diethyl aluminum monochloride, and ethyl aluminum dichloride; further, the cocatalyst is triethyl aluminum AlEt3. The alkyl aluminum is calculated as aluminum, and the titanium compound is calculated as titanium. The molar ratio of the amount of the alkyl aluminum added to the amount of the titanium compound used is 10-500.

[0040] The present invention also provides a method for preparing the above-mentioned organic carrier-supported polypropylene catalyst system, wherein the method for preparing the solid phase component of the catalyst comprises:

[0041] The porous organic polymer carrier and the magnesium compound are reacted in an inert solvent at a reaction temperature of 0°C to 50°C and a reaction time of 15 to 120 minutes. The unreacted magnesium compound is then filtered and added to an organic solvent containing a titanium compound to react at a reaction temperature of 0°C to 80°C and a reaction time of 15 to 180 minutes. An internal electron donor is then added and the reaction is carried out at 20-120°C to obtain a solid phase component.

[0042] Among them, a porous organic polymer support (taking POP-SO3H as an example) is treated with a magnesium-containing compound to obtain POP-SO3...MgX, and then a titanium compound is added to react to obtain POP-SO3...MgX / TiCl4, and then an internal electron donor ID is added to obtain a ZN-type POP-SO3...MgX / TiCl4 / ID polypropylene catalyst solid phase component.

[0043] The cocatalyst and external electron donor are added to the reaction system along with the solid phase components when the catalyst system is used for propylene polymerization, ultimately forming a POP-type polypropylene catalyst system. The cocatalyst can also serve as an impurity remover for the polymerization reaction system, removing trace amounts of water from the system.

[0044] In one embodiment, the preparation method of the solid phase component of the catalyst of the present invention is as follows: after the porous organic polymer support containing the sulfonic acid functional monomer is dried, it is added to an inert solvent under anhydrous and oxygen-free operating conditions, and then a magnesium compound is added, and the reaction is carried out at 0°C to 50°C for 15 to 120 minutes. After the reaction is completed, the unreacted magnesium compound is filtered, and then an inert solvent and a titanium compound are added, the temperature is adjusted to 0°C to 80°C, and the reaction is carried out for 15 to 180 minutes. Then, an internal electron donor is added at 20-120°C, and the reaction is carried out for 15 to 180 minutes. The product is then washed with an inert solvent to obtain the solid phase component of the catalyst.

[0045] The porous organic polymer support of the present invention is typically prepared using free radical polymerization, and can be prepared using processes such as dispersion polymerization, suspension polymerization, and emulsion polymerization. The functional monomer content in the support is determined by the amount of divinylbenzene and the sulfonic acid group-containing functional monomer added, resulting in a sulfonic acid group-functionalized organic support. For example, a dispersion polymerization process can be used to prepare a narrowly dispersed, highly fluid sulfonic acid-functionalized organic support, designated POP-SO3H.

[0046] In one embodiment, the porous organic polymer support of the present invention is prepared by free radical copolymerization of divinylbenzene as a base monomer with a sulfonic acid functional monomer using a dispersion polymerization or suspension polymerization process. The porous organic polymer support of the present invention can be represented by POP-SO3H or POP-SO3M, where M represents a metal.

[0047] More specifically, the method for preparing the porous organic polymer support of the present invention comprises adding divinylbenzene and a sulfonic acid group-containing functional monomer to a dispersing solvent, followed by adding a stabilizer and an initiator. After stirring and dispersing the mixture uniformly, the mixture is reacted at 50-80°C for 5-12 hours, followed by washing, filtering, and drying to produce the porous organic polymer support containing sulfonic acid groups. If the functional monomer used is a sulfonic acid group-containing sulfonate or a hydrate thereof, the prepared porous organic polymer support is then reacted with an acid, such as hydrochloric acid or dilute sulfuric acid, at 20-80°C for 0.2-2 hours, washed once or twice, and filtered and dried to produce the POP-SO3H support.

[0048] In one embodiment, the dispersing solvent can be a lower alcohol containing 1-4 carbon atoms or an alcohol / water mixed solvent system, with a mass ratio of alcohol to water of 5-15:1. The dispersing solvent can be methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, etc. Unless otherwise specified, all ratios are by mass. A small amount of additional solvents, such as ethyl acetate, methyl formate, tetrahydrofuran, etc., can be added to the solvent system to adjust the solubility parameter of the solvent system, thereby controlling the pore structure and morphology of the prepared carrier. The mass ratio of the total monomer addition (divinylbenzene and sulfonic acid functional monomer) to the dispersing solvent is 1:5-20, ensuring uniform dispersion of the system. The mass ratio of the sulfonic acid functional monomer to divinylbenzene is 0.2-2:1. The stabilizer is polyvinyl alcohol or a polypropylene oxide-polyethylene oxide copolymer. The weight-average molecular weight of the stabilizer is controlled between 6,000 and 100,000, and the ratio of the stabilizer addition to the total monomer addition is 0.5-3:100. The initiator is a common free radical initiator, including azobisisobutyronitrile (AIBN) or dibenzoyl peroxide (BPO). The ratio of the initiator to the total amount of monomer added is 0.5-3:100. The polymer obtained by the reaction can be washed with a dispersing solvent to remove impurities.

[0049] The monomers used in the preparation of the porous organic polymer carrier of the present invention are divinylbenzene (DVB) and sulfonic acid functional monomers (such as sodium p-styrenesulfonate, sodium vinylsulfonate, propylene sulfonic acid, sodium propylenesulfonate, or its hydrate). Commercially available monomers can be used. For example, divinylbenzene can be a commercial monomer containing 55% or 80% DVB by weight. Divinylbenzene requires pretreatment before use to remove the polymerization inhibitor. Numerous methods are available in the art for removing polymerization inhibitors, such as washing with sodium hydroxide solution and distilled water. Sulfonic acid functional monomers, such as sodium vinylbenzenesulfonate hydrate and sodium propylenesulfonate hydrate, are solid particles and can be used directly.

[0050] In one embodiment, the magnesium compound is added in an amount of 1 to 30 mmol per gram of the porous organic polymer support, preferably 3 to 20 mmol per gram of the porous organic polymer support, calculated as magnesium. In the solid phase component preparation process of the present invention, an excess of Ti compound is usually added to load the catalyst. In one embodiment, the titanium compound is added in an amount of 5 to 200 mmol per gram of the porous organic polymer support, preferably 50-150 mmol per gram of the porous organic polymer support, calculated as titanium. The ratio of the internal electron donor to the porous organic polymer support is 0.02-0.3 g per gram of the porous organic polymer support.

[0051] In one embodiment, the specific surface area of ​​the porous organic polymer carrier of the present invention is measured by using the BET nitrogen adsorption method using Nova2000e. Preferably, the specific surface area of ​​the carrier is greater than 100 m 2 / g, more preferably 100-600m 2 / g; pore volume is greater than or equal to 0.2ml / g.

[0052] The porous organic polymer-supported ZN polypropylene catalyst system of the present invention is suitable for gas-phase, bulk or slurry polymerization reactions, and the suitable reaction conditions are a temperature of 30 to 80°C and a pressure of 0.1 to 2.0 MPa. Suitable solvents for slurry polymerization are alkanes containing 5 to 10 carbon atoms, and the preferred solvent is hexane. In bulk polymerization, the polymerization pressure is generally 2.8 to 4.0 MPa, and the polymerization temperature is generally 68 to 72°C. Hydrogen is usually used during the polymerization process to adjust the polymer molecular weight or polymer melt index. The porous organic polymer-supported ZN polypropylene catalyst system of the present invention can be used for propylene homopolymerization and copolymerization of propylene with ethylene and other α-olefins. The α-olefins can be butene, isobutylene, pentene, hexene, octene, 4-methyl-1-pentene, etc.

[0053] The catalyst system of the present invention, starting from the carrier, selects a functional monomer containing a sulfonic acid group, R2HC=C(R3)R1SO2OH, through the design and optimization of functional monomers, thereby preparing a porous organic polymer POP-SO3H carrier suitable for polypropylene catalysts. The carrier is then modified to load an active component containing a magnesium / titanium compound onto the carrier, and an internal electron donor is further loaded onto the catalyst, thereby preparing a porous organic polymer (POP) carrier-supported ZN-type polypropylene catalyst system, POP-SO3H / RMgX / TiCl4 / ID (internal electron donor) solid phase component. The synergistic effect of the sulfonic acid groups on the carrier and the internal electron donor ID enhances the stereospecificity of the catalyst and allows the production of polypropylene with a broad molecular weight distribution. During propylene polymerization, the catalyst solid phase component requires the addition of an external electron donor and a cocatalyst, resulting in a catalyst with good polymerization activity and a high polymer isotacticity of over 98%. TREF fractionation results indicate that the homopolymerized polypropylene has a higher chain regularity. Furthermore, the product has a broad molecular weight distribution, ranging from 8 to 15.

[0054] The technical solution of the present invention will be further described in detail below through specific examples. Unless otherwise specified, the percentages "%" below are all weight percentages.

[0055] The molecular weight and distribution of the polypropylene prepared by propylene polymerization in the present invention are obtained by gel permeation chromatography (GPC) of Polymer Char. The isotacticity of the polymer is obtained by n-heptane extraction test results. In addition, the regularity and distribution of the polymer molecular chains are evaluated by temperature rise elution fractionation (TREF) test of Polymer Char. The main fractions are room temperature soluble part and high temperature elution part. For homopolypropylene, the room temperature soluble part is atactic polypropylene. As the elution temperature increases, the chain regularity of the eluted polypropylene molecular chains increases.

[0056] Example 1

[0057] Treatment of comonomers: Before using divinylbenzene, remove the polymerization inhibitor with 10% NaOH solution, and then wash it with deionized water three times before use; monomers such as sodium p-styrene sulfonate or sodium p-styrene sulfonate hydrate are solid particles at room temperature and are used directly without post-treatment.

[0058] Preparation of sulfonated porous organic polymer support: In a 5L glass reactor, 1350ml of ethanol, 150ml of deionized water and 150ml of tetrahydrofuran were added, and then 100g of divinylbenzene (Aladdin reagent, 50%) and 40g of sodium p-styrenesulfonate hydrate (Aladdin reagent, 90%) were added. Stir at room temperature for 5 minutes, then add polyvinyl alcohol PVA (PVA, degree of polymerization 1750) 2% of the total weight of the monomers (the total amount of divinylbenzene and sodium p-styrenesulfonate hydrate), stir at 45 ° C for 1 hour to completely dissolve the stabilizer, add AIBN 2.0% of the total weight of the monomers, heat to 70 ° C, react for 3 hours, then raise the temperature to 80 ° C, react for 12 hours, stir at 350 rpm, filter, add 1000 ml of a mixed solvent of ethanol and water (9:1 volume ratio), use 20% sulfuric acid by mass, react at 50 ° C for 2 hours, acidify twice, filter, wash three times with the above-mentioned alcohol-water mixed solvent, filter and dry to obtain 128g of free-flowing porous POP-1. The carrier has a specific surface area of ​​450m 2 / g, pore volume 0.43ml / g.

[0059] Example 2

[0060] Preparation of ZN catalyst: In a 250ml glass reactor, 3g of the above-mentioned POP-1 carrier containing sulfonic acid functional groups was added, 100ml of toluene was added and stirred, then 15ml of 3M methylmagnesium chloride Grignard reagent was added at room temperature, stirred for 2 hours, filtered, washed twice with toluene, then 50ml of toluene was added, 50ml of TiCl4 was added dropwise at room temperature, reacted for 2 hours, warmed to 80°C, then 0.45g of diisobutyl phthalate (DIBP) internal electron donor was added, reacted for 3 hours, filtered after completion of the reaction, then washed three times with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-1, with a Mg content of 4.5%, a titanium content of 3.2%, and an internal electron donor DIBP content of 5.8%.

[0061] Example 3

[0062] Preparation of ZN catalyst: In a 250ml glass reactor, 3g of the above-mentioned POP-1 carrier containing sulfonic acid functional groups was added, 100ml of toluene was added and stirred, then 10ml of 3M methylmagnesium chloride Grignard reagent was added at 35°C, stirred for 2 hours, filtered, washed once with toluene, then heated to 50°C, 50ml of TiCl4 was added dropwise, reacted for 2 hours, then heated to 80°C, and then 0.40g of diisobutyl phthalate DIBP internal electron donor was added and reacted for 3 hours. After completion of the reaction, the catalyst was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-2, with a Mg content of 3.7%, a titanium content of 4.5%, and an internal electron donor content of 5.4%.

[0063] Example 4

[0064] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-1 support containing sulfonic acid functional groups was added, 100 ml of toluene was added and stirred, then 5 ml of 3 M methylmagnesium chloride Grignard reagent was added at 5 ° C, stirred for 2 hours, filtered, washed twice with toluene, then 30 ml of toluene was added, 50 ml of TiCl4 was added dropwise at room temperature, reacted for 1 hour, heated to 80 ° C, and then 0.35 g of DIBP internal electron donor was added and reacted for 2 hours. After completion of the reaction, the catalyst was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-3, with a Mg content of 2.1%, a titanium content of 2.4%, and an internal electron donor content of 4.2%.

[0065] Example 5

[0066] Preparation of ZN catalyst: In a 250ml glass reactor, 3g of the above-mentioned POP-1 carrier containing sulfonic acid functional groups was added, 100ml of toluene was added and stirred, then 8ml of 3M benzylmagnesium bromide Grignard reagent was added at room temperature, stirred for 2 hours, filtered, washed twice with toluene, then 50ml of toluene was added, 50ml of TiCl4 was added dropwise at room temperature, reacted for 1 hour, heated to 80°C, then 0.40g of di-n-butyl phthalate DNBP internal electron donor was added, reacted for 2 hours, filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-4, with a Mg content of 2.6%, a titanium content of 3.1%, and an internal electron donor content of 3.8%.

[0067] Example 6

[0068] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-1 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, 15 ml of 3 M methyl magnesium chloride Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, then the temperature was raised to 50 ° C. 50 ml of TiCl4 was added dropwise and the reaction was carried out for 2 hours. Then the temperature was raised to 80 ° C. 0.40 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 with toluene and hexane respectively, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-5, with a Mg content of 3.8%, a titanium content of 2.8%, and an internal electron donor content of 5.4%.

[0069] Example 7

[0070] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-1 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, 10 ml of 3 M methyl magnesium chloride Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, then 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. 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 with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-6, with a Mg content of 3.2%, a titanium content of 2.4%, and an internal electron donor content of 5.6%.

[0071] Example 8

[0072] Preparation of ZN catalyst: In a 250ml glass reactor, 3g of the above-mentioned POP-1 carrier containing sulfonic acid functional groups was added, 100ml of toluene was added and stirred, then 15ml of 3M methylmagnesium chloride Grignard reagent was added at 0°C, stirred for 2 hours, filtered, washed twice with toluene, then heated to 50°C, 30ml of TiCl4 was added dropwise, reacted for 2 hours, then heated to 80°C, 0.40g of 2-isopropyl-2-isopentyl-1,3-propylene glycol diphenyl ester (IAIPPDB) was added, reacted for 3 hours, after completion of the reaction, filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-7, with a Mg content of 3.4%, a titanium content of 2.2%, and an internal electron donor content of 5.2%.

[0073] Comparative Example 9

[0074] Preparation of ZN catalyst: In a 250ml glass reactor, 3g of the above-mentioned POP-1 carrier containing sulfonic acid functional groups was added, 100ml of toluene was added, and the mixture was stirred. Then, 15ml of 3M methylmagnesium chloride Grignard reagent was added at 35°C and stirred for 2 hours. After filtering, the mixture was washed twice with toluene. Then, 50ml of TiCl4 was added dropwise at room temperature, the temperature was raised to 80°C, and the reaction was carried out for 3 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, designated Cat-8, with a Mg content of 4.0% and a titanium content of 2.8%.

[0075] Comparative Example 10

[0076] Preparation of inorganic carrier-supported ZN polypropylene catalyst: In a 250 ml glass reactor, 3 g of spherical ethoxymagnesium support (Japan Soda Co., Ltd.) was added, 100 ml of toluene was added, stirred, and then 50 ml of TiCl4 was slowly added dropwise at 0 ° C. The addition rate was controlled to control the temperature at 0-5 ° C. After the addition was complete, the temperature was raised to 60 ° C, 0.30 g of DIBP internal electron donor was added, the temperature was raised to 100 ° C for 1 hour, and then 0.20 g of 9,9-dimethoxyfluorene internal electron donor was added. The reaction was carried out at 110 ° C for 2 hours, filtered, and then 100 ml of fresh TiCl4 was added. The reaction was carried out at 110 ° C for 2 hours. After the reaction was completed, it was filtered, washed with toluene and hexane 3 times each, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-9, with a titanium content of 3.2%, a DIBP internal electron donor content of 3.6%, and a 9,9-dimethoxyfluorene internal electron donor content of 2.1%.

[0077] Comparative Example 11

[0078] Preparation of inorganic carrier-supported ZN polypropylene catalyst: In a 250ml glass reactor, add 3g of spherical magnesium chloride support and 100ml of toluene, stir, then slowly add 50ml of TiCl4 at 0℃, control the addition speed, and control the temperature at 0-5℃. After the addition is complete, heat to 80℃, add 0.30g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate internal electron donor, heat to 100℃ and react for 1 hour, then add 0.20g The 9,9-dimethoxyfluorene internal electron donor was reacted at 110°C for 2 hours, filtered, and then 100 ml of fresh TiCl4 was added and reacted at 110°C for 2 hours. After the reaction was completed, it was filtered, washed with toluene and hexane 3 times each, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-10, with a titanium content of 2.8%, a 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate internal electron donor content of 3.4%, and a 9,9-dimethoxyfluorene internal electron donor content of 2.2%.

[0079] Examples 12-22 Propylene Polymerization

[0080] Example 12: To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added with stirring at 600 rpm. 120 mg of Cat-1 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (external C) were then added. 0.5 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1028 g of a polypropylene product (PP-1) with a bulk density of 0.36 g / ml and a catalyst activity of 8567 gPP / gcat.h.

[0081] Example 13: To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added with stirring at 600 rpm. 120 mg of Cat-2 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (C external supply) were then added. 0.5 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1380 g of a polypropylene product (PP-2) with a bulk density of 0.35 g / ml and a catalyst activity of 11500 gPP / gcat.h.

[0082] Example 14: To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added with stirring at 600 rpm. 120 mg of Cat-3 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (external C) were then added. 0.5 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 986 g of a polypropylene product (PP-3) with a bulk density of 0.36 g / ml and a catalyst activity of 8217 gPP / gcat.h.

[0083] Example 15: To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added with stirring at 600 rpm. 120 mg of Cat-4 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (external C) were then added. 0.5 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1150 g of a polypropylene product (PP-4) with a bulk density of 0.36 g / ml and a catalyst activity of 9583 gPP / gcat.h.

[0084] Example 16: To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added with stirring at 600 rpm. 80 mg of Cat-5 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (external C) were then added. 0.5 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the reactor was cooled to room temperature, and dried to obtain 1362 g of a polypropylene product (PP-5) with a bulk density of 0.38 g / ml and a catalyst activity of 17025 gPP / gcat.h.

[0085] Example 17: To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added with stirring at 600 rpm. 80 mg of Cat-6 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (external C) were then added. 0.5 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the reactor was cooled to room temperature, and dried to obtain 1254 g of a polypropylene product (PP-6) with a bulk density of 0.38 g / ml and a catalyst activity of 15675 gPP / gcat.h.

[0086] Example 18: To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added with stirring at 600 rpm. 80 mg of Cat-7 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (external C) were then added. 0.5 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the reactor was cooled to room temperature, and dried to obtain 1235 g of a polypropylene product (PP-7) with a bulk density of 0.37 g / ml and a catalyst activity of 15438 gPP / gcat.h.

[0087] Example 19: To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added with stirring at 600 rpm. 120 mg of Cat-3 catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (D externally supplied) were then added. 1.0 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1025 g of a polypropylene product (PP-8) with a bulk density of 0.36 g / ml and a catalyst activity of 8542 gPP / gcat.h.

[0088] 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 with a stirring rate of 600 rpm. 200 mg of the comparative catalyst Cat-8 and 0.3 ml of cyclohexylmethyldimethylsilane (external C) were then added. 0.5 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 545 g of a polypropylene product (PP-9) with a bulk density of 0.37 g / ml and a catalyst activity of 2725 gPP / gcat.h.

[0089] 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 with a stirring rate of 600 rpm. 60 mg of the comparative catalyst Cat-9 and 0.3 ml of cyclohexylmethyldimethylsilane (C externally supplied) were then added. 1 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1280 g of a polypropylene product (PP-10) with a bulk density of 0.37 g / ml and a catalyst activity of 21333 gPP / gcat.h.

[0090] 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 with a stirring rate of 600 rpm. 60 mg of comparative catalyst Cat-10 and 0.3 ml of cyclohexylmethyldimethylsilane (external C) were then added. 0.5 g of hydrogen was added, the temperature was raised to 70° C., and the polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1456 g of a polypropylene product (PP-11) with a bulk density of 0.42 g / ml and a catalyst activity of 24267 gPP / gcat.h.

[0091] Table 1 Olefin polymerization results of catalysts of Examples 12-22

[0092]

[0093]

[0094] Example 23

[0095] In a 5L glass reactor, 1350ml of ethanol and 150ml of deionized water were added, followed by 100g of divinylbenzene (Aladdin reagent, 80%) and 55g of sodium p-styrenesulfonate hydrate (Aladdin reagent, 90%). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% of the monomer weight of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12000) and stirring at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% of the monomer weight of AIBN was added, the temperature was raised to 70°C, and the reaction was continued for 3 hours. The temperature was then raised to 80°C. After 8 hours of reaction, the stirring speed was increased to 350 rpm. After filtration, 100ml of the above-mentioned ethanol and water mixed solvent was added, and 10ml of 36.5% by mass HCl solution was added. The mixture was reacted at 50°C for 2 hours, filtered, and washed three times with the alcohol-water mixed solvent. After filtration and drying, 145g of free-flowing porous POP-2 was obtained. The carrier has a specific surface area of ​​540m 2 / g, pore volume 0.45ml / g.

[0096] Example 24

[0097] Preparation of ZN catalyst: In a 250ml glass reactor, 3g of the above-mentioned POP-2 carrier containing sulfonic acid functional groups was added, 100ml of toluene was added and stirred, then 15ml of 3M methylmagnesium chloride Grignard reagent was added at room temperature, stirred for 2 hours, filtered, washed once with toluene, then 50ml of toluene was added, 50ml of TiCl4 was added dropwise at room temperature, reacted for 2 hours, warmed to 80°C, then 0.40g of diisobutyl phthalate (DIBP) internal electron donor was added, reacted for 3 hours, filtered after completion of the reaction, then washed three times with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-11, with a Mg content of 4.3%, a titanium content of 3.1%, and an internal electron donor DIBP content of 4.8%.

[0098] Example 25

[0099] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-2 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added and stirred, and then 10 ml of 3M methylmagnesium chloride Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, then heated to 50 ° C., 50 ml of TiCl4 was added dropwise, and the reaction was carried out for 2 hours. 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 with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-12, with a Mg content of 3.2%, a titanium content of 3.0%, and an internal electron donor content of 5.4%.

[0100] Example 26

[0101] In a 250 ml glass reactor, 130 ml of isobutanol and 14 ml of deionized water were added, followed by 4.8 g (about 5.0 ml) of 55% divinylbenzene (Aladdin reagent, 55%) and 3.0 g of 2-Methyl-3-sulfonic acid styrene (95%) was stirred at room temperature for 5 minutes, and then 2% of the monomer weight of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The stabilizer was completely dissolved by stirring at 45°C for 1 hour. 2.0% of the monomer weight of AIBN was added. The temperature was raised to 70°C and reacted for 2 hours. The temperature was then raised to 80°C and reacted for 5 hours. The stirring speed was 350 rpm. After filtering, 100 ml of the above-mentioned alcohol and water mixed solvent was added, and 10 ml of 36.5% by weight HCl solution was added. The mixture was reacted at 50°C for 2 hours, filtered, washed three times with an alcohol-water mixed solvent, washed three times with an alcohol-water mixed solvent, filtered, and dried to obtain 4.3 g of free-flowing porous POP-3. The carrier has a specific surface area of ​​228 m 2 / g, pore volume 0.23ml / g.

[0102] Example 27

[0103] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-3 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added and stirred, and then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, and then 50 ml of toluene was added. 30 ml of TiCl4 was added dropwise at room temperature and reacted for 2 hours. The temperature was raised to 80 ° C. Then, 0.40 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate internal electron donor was added and reacted for 3 hours. After the reaction was completed, the mixture was filtered and then washed 3 times with toluene and hexane respectively. After drying, free-flowing catalyst solid phase component particles were obtained, which were recorded as Cat-13, with a Mg content of 3.8%, a titanium content of 3.1%, and a 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate internal electron donor content of 4.5%.

[0104] Example 28

[0105] In a 250ml glass reactor, 126ml of ethanol and 14ml of deionized water were added, followed by 4.8g (about 5.0ml) of divinylbenzene (Aladdin reagent, 80%) and 2.8g of sodium p-styrenesulfonate hydrate (Aladdin reagent, 90%). The mixture was stirred at room temperature for 5min, followed by the addition of 2% monomer weight of polyvinyl alcohol (PVA, degree of polymerization 1750) and stirring at 45°C for 1h to completely dissolve the stabilizer. 2.0% monomer weight of AIBN was added, the temperature was raised to 70°C, and the reaction was continued for 3 hours. The temperature was then raised to 80°C. After 5 hours of reaction, the stirring speed was set at 350 rpm. After filtration, 100ml of the above-mentioned ethanol and water mixed solvent was added, and 10ml of 36.5% by mass HCl solution was added. The mixture was reacted at 50°C for 2h, filtered, and washed three times with an alcohol-water mixed solvent. After filtration and drying, 4.8g of free-flowing porous POP-4 was obtained. The carrier has a specific surface area of ​​450m 2 / g, pore volume 0.41ml / g.

[0106] Example 29

[0107] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-4 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, 10 ml of 3 M methyl magnesium chloride Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, then the temperature was raised to 50 ° C. 50 ml of TiCl4 was added dropwise and the reaction was carried out for 2 hours. 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 with toluene and hexane respectively, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-14, with a Mg content of 3.2%, a titanium content of 3.2%, and an internal electron donor content of 5.6%.

[0108] Example 30

[0109] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-4 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, 15 ml of 3 M methylmagnesium chloride Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, then the temperature was raised to 50 ° C. 50 ml of TiCl4 was added dropwise and the reaction was carried out for 2 hours. Then the temperature was raised to 80 ° C. 0.45 g of 9,9-dimethoxyfluorene was added and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times with toluene and hexane respectively, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-15, with a Mg content of 4.5%, a titanium content of 3.0%, and an internal electron donor content of 4.6%.

[0110] Example 31

[0111] In a 250 ml glass reactor, 126 ml of ethanol and 14 ml of deionized water were added, followed by 4.8 g (about 5.0 ml) of divinylbenzene (Aladdin reagent, 55%) and 1.8 g of 4,4'-bis(2-sulfonic acid styryl)-1,1'-biphenyl (Wuhan Jinnuo Chemical Co., Ltd., >95%) was stirred at room temperature for 5 minutes, and then 2% of the monomer mass of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. At 45 ° C, it was stirred for 1 hour to completely dissolve the stabilizer. 2.0% of the monomer mass of AIBN was added, and the temperature was raised to 70 ° C and reacted for 3 hours. Then the temperature was raised to 80 ° C. After reacting for 5 hours, the stirring speed was 600 rpm. After filtration, 100 ml of the above-mentioned ethanol and water mixed solvent was added, and 15 ml of 10% H2SO4 solution by mass was added. The mixture was reacted at 50 ° C for 2 hours, washed with ethanol three times, filtered, and washed with an alcohol-water mixed solvent three times. After filtration and drying, 4.2 g of free-flowing porous POP-5 was obtained. The carrier has a specific surface area of ​​328 m 2 / g, pore volume 0.34ml / g.

[0112] Example 32

[0113] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-5 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added and stirred, and then 10 ml of 3M methylmagnesium chloride Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, then the temperature was raised to 50 ° C. 50 ml of TiCl4 was added dropwise and the reaction was carried out for 2 hours. Then the temperature was raised to 80 ° C. 0.40 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 with toluene and hexane respectively, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-16, with a Mg content of 3.8%, a titanium content of 2.8%, and an internal electron donor content of 5.2%.

[0114] Example 33

[0115] In a 250ml glass reactor, 126ml of ethanol and 14ml of deionized water were added, followed by the addition of 4.8g (about 5.0ml) of divinylbenzene (Aladdin reagent, 80%) and 2.5g of sodium p-styrenesulfonate hydrate (Aladdin reagent, 90%), and the mixture was stirred at room temperature for 5min. Then, 2% of the monomer mass of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12000) was added and stirred at room temperature for 1h to completely dissolve the stabilizer. 2.0% of the monomer mass of BPO was added, the temperature was raised to 70°C, and the reaction was continued for 3 hours. The temperature was then raised to 80°C. After the reaction was continued for 5 hours, the stirring speed was 600 rpm, and after filtration, 100ml of the above-mentioned ethanol and water mixed solvent was added, and 15ml of a 10% by mass H2SO4 solution was added. The mixture was reacted at 50°C for 2h, filtered, and washed three times with an alcohol-water mixed solvent. After filtration and drying, 4.6g of free-flowing porous POP-6 was obtained. The specific surface area of ​​the carrier is 560m 2 / g, pore volume 0.48ml / g.

[0116] Example 34

[0117] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-6 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, 15 ml of 3 M methyl magnesium chloride Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, then the temperature was raised to 50 ° C. 50 ml of TiCl4 was added dropwise and the reaction was carried out for 2 hours. 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 with toluene and hexane respectively, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-17, with a Mg content of 5.2%, a titanium content of 2.7%, and an internal electron donor content of 4.6%.

[0118] Example 35

[0119] In a 250ml glass reactor, 130ml of ethanol and 15ml of deionized water were added, followed by 2ml of tetrahydrofuran, followed by 5ml of (Aladdin reagent, 55%) (approximately 4.8g) of divinylbenzene and 1.9g of sodium vinyl sulfonate (Aladdin reagent, 98%). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% by weight of polyvinyl alcohol (PVA, DP 1750) and stirring at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% (0.132g) by weight of AIBN was then added, and the temperature was raised to 70°C for 2 hours. The temperature was then raised to 80°C for 5 hours, with stirring at 350 rpm. After filtration, 100ml of the aforementioned ethanol-water mixture was added, followed by 10ml of a 36.5% by weight HCl solution, and the mixture was reacted at 50°C for 2 hours. The mixture was filtered, washed three times with the alcohol-water mixture, filtered, and dried to obtain 3.9g of free-flowing porous POP-7. The specific surface area of ​​the carrier is 187m 2 / g, pore volume 0.38ml / g.

[0120] Example 36

[0121] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-7 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, 10 ml of 3 M methyl magnesium chloride Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, then the temperature was raised to 50 ° C. 50 ml of TiCl4 was added dropwise and the reaction was carried out for 2 hours. 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 with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-18, with a Mg content of 3.5%, a titanium content of 2.7%, and an internal electron donor content of 6.4%.

[0122] Example 37

[0123] In a 250ml glass reactor, 126ml of isobutanol and 14ml of deionized water were added, followed by 4.8g (about 5.0ml) of divinylbenzene (Aladdin reagent, 55%) and 2.0g of sodium 1-hexenesulfonate (Aladdin reagent, 95%). The mixture was stirred at room temperature for 5min, and then 2% of the monomer weight of polyvinyl alcohol (PVA, degree of polymerization 1750) was added. The stabilizer was completely dissolved at 45°C and stirred for 1h. 2.0% of the monomer weight of AIBN was added, the temperature was raised to 70°C, and the reaction was continued for 3 hours. The temperature was then raised to 80°C. After 5 hours of reaction, the stirring speed was set at 350 rpm. After filtration, 100ml of a mixed solvent of ethanol and water was added, and 10ml of a 36.5% by mass HCl solution was added. The mixture was reacted at 50°C for 2h, filtered, and washed three times with a mixed solvent of alcohol and water. After filtration and drying, 4.2g of free-flowing porous POP-8 was obtained. The carrier has a specific surface area of ​​249m 2 / g, pore volume 0.24ml / g.

[0124] Example 38

[0125] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-8 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added and stirred, and then 10 ml of 3M methylmagnesium chloride Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, it was washed twice with toluene, then the temperature was raised to 50 ° C. 50 ml of TiCl4 was added dropwise and reacted for 2 hours. Then the temperature was raised to 80 ° C. 0.45 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate was added and reacted for 3 hours. After the reaction was completed, it was filtered and washed 3 times with toluene and hexane respectively. After drying, free-flowing catalyst solid phase component particles were obtained, which were recorded as Cat-19 with a Mg content of 3.7%, a titanium content of 3.2%, and an internal electron donor content of 5.6%.

[0126] Example 39

[0127] In a 250ml glass reactor, 126ml of ethanol and 14ml of deionized water were added, followed by 4.8g (about 5.0ml) of divinylbenzene (Aladdin reagent, 80%) and 2.3g of sodium methyl propylene sulfonate (Aladdin reagent, 98%). The mixture was stirred at room temperature for 5min, and then 2% of the monomer weight of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The stabilizer was completely dissolved at 45°C and stirred for 1h. 2.0% of the monomer weight of AIBN was added, the temperature was raised to 70°C, and the reaction was continued for 3 hours. The temperature was then raised to 80°C. After 5 hours of reaction, the stirring speed was set at 350 rpm. After filtration, 100ml of the above-mentioned ethanol and water mixed solvent was added, and 20ml of a 20% by mass sulfuric acid solution was added. The mixture was reacted at 50°C for 2h, filtered, and washed three times with an alcohol-water mixed solvent. After filtration and drying, 5.4g of free-flowing porous POP-9 was obtained. The carrier has a specific surface area of ​​486m 2 / g, pore volume 0.46ml / g.

[0128] Example 40

[0129] Preparation of ZN catalyst: In a 250ml glass reactor, 3g of the above-mentioned POP-9 carrier containing sulfonic acid functional groups was added, 100ml of toluene was added and stirred, then 10ml of 3M butyl magnesium chloride Grignard reagent was added at 35°C, stirred for 2 hours, filtered, washed twice with toluene, then heated to 50°C, 60ml of TiCl4 was added dropwise, reacted for 2 hours, then heated to 80°C, 0.45g of di-n-butyl phthalate was added, reacted for 3 hours, after completion of the reaction, filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-20, with a Mg content of 3.7%, a titanium content of 3.2%, and an internal electron donor content of 7.4%.

[0130] Example 41

[0131] In a 250ml glass reactor, 126ml of ethanol and 14ml of deionized water were added, followed by 4.8g (about 5.0ml) of divinylbenzene (Aladdin reagent, 80%) and 3.8g of sodium methyl propylene sulfonate (Aladdin reagent, 98%). The mixture was stirred at room temperature for 5min, and then 2% of the monomer weight of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The stabilizer was completely dissolved at 45°C and stirred for 1h. 2.0% of the monomer weight of AIBN was added, and the temperature was raised to 70°C and reacted for 3 hours. The temperature was then raised to 80°C and reacted for 5 hours. The stirring speed was 350 rpm, and after filtration, 100ml of the above-mentioned ethanol and water mixed solvent was added, and 10ml of 36.5% by mass HCl solution was added. The mixture was reacted at 50°C for 2h, filtered, and washed three times with an alcohol-water mixed solvent. After filtration and drying, 6.1g of free-flowing porous POP-10 was obtained. The carrier has a specific surface area of ​​532m 2 / g, pore volume 0.51ml / g.

[0132] Example 42

[0133] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-10 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, 15 ml of 3 M benzylmagnesium bromide Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, then the temperature was raised to 50 ° C. 50 ml of TiCl4 was added dropwise and the reaction was carried out for 2 hours. Then the temperature was raised to 80 ° C. 0.45 g of 9,9-dimethoxyfluorene was added and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times with toluene and hexane respectively, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-21, with a Mg content of 4.5%, a titanium content of 2.8%, and an internal electron donor content of 4.6%.

[0134] Example 43

[0135] In a 250ml glass reactor, 126ml of ethanol and 20ml of deionized water were added, followed by 4.8g (about 5.0ml) of divinylbenzene (Aladdin reagent, 80%) and 2.0g of sodium allyl sulfonate (Aladdin reagent, 98%). The mixture was stirred at room temperature for 5min, and then 2% of the monomer weight of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The stabilizer was completely dissolved at 45°C and stirred for 1h. 2.0% of the monomer weight of AIBN was added, the temperature was raised to 70°C, and the reaction was continued for 3 hours. The temperature was then raised to 80°C. After 5 hours of reaction, the stirring speed was set at 350 rpm. After filtration, 100ml of the above-mentioned ethanol and water mixed solvent was added, and 10ml of 36.5% by mass HCl solution was added. The mixture was reacted at 50°C for 2h, filtered, and washed three times with the alcohol-water mixed solvent. After filtration and drying, 5.5g of free-flowing porous POP-11 was obtained. The carrier has a specific surface area of ​​382m 2 / g, pore volume 0.41ml / g.

[0136] Example 44

[0137] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-11 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added and stirred, then 15 ml of 3 M dibutyl magnesium grignard reagent was added at room temperature, stirred for 2 hours, filtered, washed twice with toluene, then 50 ml of toluene was added, 50 ml of TiCl4 was added dropwise at room temperature, reacted for 2 hours, heated to 80 ° C, then 0.45 g of diisobutyl phthalate DIBP internal electron donor was added, reacted for 3 hours, filtered after completion of the reaction, then washed three times with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-22, with a Mg content of 4.3%, a titanium content of 3.1%, and an internal electron donor DIBP content of 4.8%.

[0138] Example 45

[0139] Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the above-mentioned POP-11 carrier containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, 10 ml of 3 M methyl magnesium chloride Grignard reagent was added at 35 ° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene, then the temperature was raised to 50 ° C. 50 ml of TiCl4 was added dropwise and the reaction was carried out for 2 hours. 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 with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, recorded as Cat-23, with a Mg content of 3.1%, a titanium content of 3.3%, and an internal electron donor content of 5.2%.

[0140] Comparative Example 46

[0141] Preparation of ZN catalyst: In a 250ml glass reactor, 3g of the above-mentioned POP-11 carrier containing sulfonic acid functional groups was added, 100ml of toluene was added, and the mixture was stirred. Then, 15ml of 3M methylmagnesium chloride Grignard reagent was added at 35°C and stirred for 2 hours. After filtering, the mixture was washed twice with toluene. Then, 50ml of TiCl4 was added dropwise at room temperature, the temperature was raised to 80°C, and the reaction was carried out for 3 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst solid phase component particles, designated Cat-24, with a Mg content of 4.2% and a titanium content of 2.8%.

[0142] Comparative Example 47

[0143] Preparation of inorganic carrier-supported ZN polypropylene catalyst: In a 250ml glass reactor, 3g of spherical magnesium chloride support and 100ml of toluene were added and stirred. Then, 50ml of TiCl4 was slowly added dropwise at 0°C. The addition rate was controlled to keep the temperature between 0-5°C. After the addition was complete, the temperature was raised to 80°C, 0.45g of diisobutyl phthalate (DIBP) internal electron donor was added, filtered, and then 100ml of fresh TiCl4 was added. The reaction was carried out at 110°C for 2 hours. After the reaction was complete, the catalyst was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-25, with a titanium content of 3.2% and an internal electron donor content of 6.8%.

[0144] Examples 48-63 Catalysts for Propylene Polymerization

[0145] In a polymerization reactor, propylene bulk polymerization is carried out using the prepared catalyst to prepare a polypropylene product.

[0146] Propylene homopolymerization: In a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 80 mg of the above-prepared catalyst and 0.3 ml of cyclohexylmethyldimethylsilane (C external supply) were added. 0.5 g of hydrogen was added, the temperature was raised to 70° C., and the mixture was polymerized at 600 rpm for 1 hour. The pressure was released, the mixture was cooled to room temperature, and dried to obtain a polypropylene product.

[0147] In Example 61, cat-15 catalyst was used, 0.3 ml of dicyclopentenyldimethoxysilane D external electron donor was added, and other conditions remained unchanged.

[0148] Table 2 Propylene polymerization results of catalysts of Examples 48-63

[0149]

[0150]

[0151] As shown in Table 3, the porous organic polymer-supported ZN polypropylene catalyst POP-SO3H / RMgX / TiCl4 / ID (internal electron donor) exhibits excellent polymerization activity, with homopolymerization activity exceeding 15,000 gPP / gcat.h. While lower than that of catalysts supported on conventional inorganic MgCl2 supports, its activity is significantly improved over existing organic polymer supports, meeting the standards of existing industrial catalysts. Importantly, the synergistic effect of the sulfonic acid groups on the support and the internal electron donor ID gives the Ti active centers in the prepared catalyst enhanced stereospecificity, resulting in a wider molecular weight distribution for the resulting polypropylene. Experiments have shown that, when the internal electron donor-free catalyst POP-SO3H / RMgX / TiCl4 is used, the polymer produced has a very broad molecular weight distribution, exceeding 22 (Comparative Example 62). The addition of an internal electron donor further enhances the stereospecificity of the catalyst, achieving a polymer isotacticity exceeding 98%. TREF fractionation results indicate that the homopolypropylene exhibits a higher elution temperature (i.e., the chain segments exhibit higher chain regularity), exceeding 123°C (other commercial homopolypropylene typically exhibit elution temperatures around 122°C). Furthermore, the catalyst maintains a broad molecular weight distribution, ranging from 8 to 15. Conventional ZN-type polypropylene catalysts generally have difficulty producing polypropylene with both high chain regularity and a wide molecular weight distribution. Even with the addition of a compounded internal electron donor, i.e., two internal electron donors (compared to Example 22), Example 21 exhibits a relatively high polymer isotacticity but a relatively narrow molecular weight distribution. In Example 22, although the polymer achieves a relatively wide molecular weight distribution, the chain regularity of the highly isotactic molecular chains in its TREF fractionation (high-temperature elution peak) is still lower than that of the catalyst of the present invention. Generally speaking, internal electron donors determine polymer stereoregularity (molecular chain regularity, of which isotacticity is a part), molecular weight distribution, hydrogen sensitivity, polymerization activity, and the like, and are a very important component of polypropylene catalysts. Comparative Example 22 uses two internal electron donors, diphenol esters and fluorene diethers (compared to Example 21, it can be seen that fluorene diethers, as internal electron donors, have relatively high isotacticity but a relatively narrow molecular weight distribution), indicating that compounded internal electron donors are required to achieve a wide molecular weight distribution and high chain regularity. Example 14 only needs to use the most commonly used DIBP internal electron donor to achieve the effect of Comparative Example 22. If a diphenol ester internal electron donor is used, as in Example 16, the polymer can achieve ultra-high chain tacticity and a wide molecular weight distribution using the same diphenol ester internal electron donor.

[0152] Compared with existing catalysts, the POP-SO3H / RMgX / TiCl4 / ID catalyst disclosed in the present invention has a simple preparation method. Its active center has both a wide molecular weight distribution and high stereospecificity, giving it good industrial prospects. In particular, this catalyst system has advantages in developing homopolymer products with high rigidity and toughness balance.

[0153] Figure 1 is the temperature rise elution fractionation (Tref) curve of the polypropylene prepared in the embodiment of the present invention, further, Figure 1 The following are the temperature rise elution fractionation (Tref) curves for the polypropylene prepared in Example 16, Comparative Example 22, and Comparative Example 61. These curves typically have two main peaks: one is the room-temperature soluble peak, representing the atactic polypropylene component; the other is the high-temperature elution peak. Higher elution temperatures indicate more regular polypropylene chains, fewer defects, and stronger crystallization ability. Larger peak areas indicate higher content of these components. As can be seen from the curves, the polypropylene represented by the TREF fractionation curve in Example 16 has the lowest atactic content, while its high-temperature elution peak has the highest elution temperature, indicating the highest regularity of these subchains.

[0154] Figure 2 The GPC molecular weight and distribution curve of the polypropylene prepared in the embodiment of the present invention are shown in FIG. Figure 2 The following are GPC molecular weight and distribution curves for the polypropylenes prepared in Example 16, Comparative Example 21, Comparative Example 22, and Comparative Example 61. In these curves, Comparative Example 61 (without the addition of an internal electron donor) and Example 16 both exhibit broad molecular weight distributions. While the molecular weight distribution of Comparative Example 22 is broadened by the addition of a compounded internal electron donor, its polymer molecular chain regularity (TREF curve) is lower than that of Example 16. Comparative Example 21 exhibits a narrower molecular weight distribution.

[0155] Furthermore, the ZN-type polypropylene catalyst prepared by this invention can also be used for the copolymerization of propylene and ethylene to produce copolymerized polypropylene products. The catalyst has good copolymerization ability. When ethylene monomer is added, the catalyst activity is significantly increased, and the polymer molecular weight distribution is relatively broad.

[0156] Example 64

[0157] Propylene-Ethylene Copolymerization: A 10-L dried propylene polymerization reactor was charged with 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L). The reactor was stirred at 600 rpm. Then, 60 mg of the Cat-3 catalyst prepared above and 0.3 ml of cyclohexylmethyldimethylsilane (external C) were added. 0.5 g of hydrogen and 30 g of ethylene monomer were added. The reactor was heated to 70°C and stirred at 600 rpm for 1 hour. The reactor was then depressurized, cooled to room temperature, and dried to yield 1,350 g of polypropylene. The catalyst polymerization activity was 22,500 g PP / gcat.h, and the polymer had a weight-average molecular weight (Mw) of 632,500 and a molecular weight distribution (MDD) of 9.2.

[0158] Example 65

[0159] Propylene-ethylene copolymerization: A 10-liter dried propylene polymerization reactor was charged with 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L). The reactor was stirred at 600 rpm. Then, 60 mg of the Cat-23 catalyst prepared above and 0.3 ml of cyclohexylmethyldimethylsilane (external C) were added. 0.5 g of hydrogen and 30 g of ethylene monomer were added. The reactor was heated to 70°C and stirred at 600 rpm for 1 hour. The reactor was then depressurized, cooled to room temperature, and dried to yield 1,242 g of polypropylene. The catalyst polymerization activity was 22,500 gPP / gcat.h, and the polymer had a weight-average molecular weight (Mw) of 583,000 and a molecular weight distribution (MDD) of 11.5.

[0160] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims of the present invention.

Claims

1. An organic carrier-supported polypropylene catalyst system, characterized in that: The invention comprises a solid phase component, a co-catalyst and an external electron donor, wherein the solid phase component comprises a porous organic polymer carrier, a magnesium compound, a titanium compound and an internal electron donor, and the porous organic polymer carrier is a copolymer comprising divinylbenzene and a sulfonic acid functional monomer; The porous organic polymer support in the solid phase component accounts for 60 to 85 parts by weight, the magnesium compound in the solid phase component accounts for 1 to 8 parts by weight as magnesium element, the titanium compound in the solid phase component accounts for 1 to 8 parts by weight as titanium element, and the internal electron donor in the solid phase component accounts for 1 to 10 parts by weight; based on 100% of the mass of the porous organic polymer support, the sulfonic acid group-containing functional monomer accounts for 5 to 60%; The chemical formula of the sulfonic acid functional monomer is R2HC=C(R3)R1SO3H or R2HC=C(R3)R1SO2OM, R1 is an alkylene group or phenylene group containing 0-6 carbon atoms on the main chain, and the R1 group may contain chlorine, bromine, fluorine, iodine, alkyl, phenyl or naphthalene substituents; R2 is an H atom, an alkyl group or phenyl group containing 1-6 carbon atoms on the main chain, and the R2 group may contain chlorine, bromine, fluorine, iodine, alkyl, phenyl or naphthyl substituents; R3 is an H atom, an alkyl group or phenyl group containing 1-6 carbon atoms on the main chain; M is a metal; If the sulfonic acid group-containing functional monomer is R2HC=C(R3)R1SO2OM, the porous organic polymer support needs to be acidified.

2. The organic carrier-supported polypropylene catalyst system according to claim 1, characterized in that: The content of the sulfonic acid functional monomer in the porous organic polymer carrier is 0.5 to 5 mmol / g of the porous organic polymer carrier; the porous organic polymer carrier is a copolymer of divinylbenzene, a sulfonic acid functional monomer and a third monomer, and the third monomer is at least one of styrene, alkyl-substituted styrene and chloromethyl-substituted styrene.

3. The organic carrier-supported polypropylene catalyst system according to claim 1, characterized in that: The sulfonic acid group-containing functional monomer is sodium p-styrenesulfonate, p-styrenesulfonic acid, sodium m-styrenesulfonate, m-styrenesulfonic acid, o-styrenesulfonic acid, sodium o-styrenesulfonate, 2-methyl-4-sodium sulfonate styrene, 2-chloro-4-sodium sulfonate styrene, 2-methyl-4-sulfonate styrene, 2-methyl-3-sodium sulfonate styrene, 2-methyl-3-sulfonate styrene, vinyl-4-methylbenzenesulfonic acid, sodium vinyl-4-methylbenzenesulfonate, 2-ethyl-3-sodium sulfonate styrene, 2-ethyl-3-sulfonate styrene, 4,4'-bis(2-sulfonatostyryl)-1,1'-biphenyl, 2-(2-styryl)benzenesulfonic acid, vinylsulfonic acid, sodium vinylsulfonate, propenylsulfonic acid, sodium propenylsulfonate, sodium 3-chloropropenylsulfonate, methylpropenylsulfonic acid, sodium methylpropenylsulfonate, 1-butenylsulfonate Acid, sodium 1-butenesulfonate, 1-pentenylsulfonic acid, sodium 1-pentenylsulfonate, 1-hexenesulfonic acid, sodium 1-hexenesulfonate, 1-heptenesulfonic acid, sodium 1-heptenesulfonate, 1-octenesulfonic acid, sodium 1-octenesulfonate, 1-decenesulfonic acid, sodium 1-decenesulfonate, 2-acrylamido-2-methyl-1-propanesulfonic acid, vinylsulfonic acid, sodium vinylsulfonate, allylsulfonic acid, sodium allylpropanesulfonate, methacrylic acid , sodium methacrylic acid, 1-butenylsulfonic acid, sodium 1-butenylsulfonate, 1-pentenylsulfonic acid, sodium 1-pentenylsulfonate, 1-hexenesulfonic acid, sodium 1-hexenesulfonate, 1-heptenesulfonic acid, sodium 1-heptenesulfonate, 1-octenesulfonic acid, sodium 1-octenesulfonate, 1-decenesulfonic acid, sodium 1-decenesulfonate, 2-acrylamido-2-methyl-1-propanesulfonic acid and at least one of hydrates of these compounds.

4. The organic carrier-supported polypropylene catalyst system according to claim 1, characterized in that: The BET surface area of ​​the porous organic polymer support is 100-600 m 2 / g, the pore volume is greater than or equal to 0.2ml / g; the co-catalyst is an alkyl aluminum, the co-catalyst is calculated as Al, the titanium compound is calculated as Ti, and the molar ratio of the co-catalyst to the titanium compound is 5-500; the internal electron donor is at least one of a diester internal electron donor and a diether internal electron donor; and the external electron donor is a silane compound.

5. The organic carrier-supported polypropylene catalyst system according to claim 1, characterized in that: The internal electron donor is at least one of a diphenol ester internal electron donor, a glycol ester internal electron donor, a succinate internal electron donor, and a diether internal electron donor.

6. The method for preparing the organic carrier-supported polypropylene catalyst system according to any one of claims 1 to 5, characterized in that: The preparation method of the solid phase component comprises: The porous organic polymer support and the magnesium compound are reacted in an inert solvent at a reaction temperature of 0°C to 50°C and a reaction time of 15 to 120 minutes. The unreacted magnesium compound is then filtered and added to an organic solvent containing a titanium compound to react at a reaction temperature of 0°C to 80°C and a reaction time of 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.

7. The method for preparing an organic carrier-supported polypropylene catalyst system according to claim 6, characterized in that: The amount of the magnesium compound added as magnesium is 1 to 30 mmol per gram of the porous organic polymer carrier, the amount of the titanium compound added as titanium is 5 to 200 mmol per gram of the porous organic polymer carrier, and the ratio of the internal electron donor to the porous organic polymer carrier is 0.02 to 0.3 g per gram of the porous organic polymer carrier.

8. The method for preparing an organic carrier-supported polypropylene catalyst system according to claim 6, characterized in that: The preparation method of the porous organic polymer carrier comprises: The porous organic polymer carrier is prepared by free radical copolymerization of divinylbenzene as a basic monomer and a sulfonic acid functional monomer.

9. Use of the organic carrier-supported polypropylene catalyst system according to any one of claims 1 to 5 in propylene polymerization or copolymerization of propylene and α-olefin.

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