Ziegler-Natta catalyst system for ethylene polymerization, its preparation method and application

Abstract

The present invention provides a Ziegler-Natta catalyst system for ethylene polymerization, its preparation method and application. The catalyst system includes a solid phase component and a cocatalyst. The solid phase component includes a porous organic polymer carrier, a magnesium compound and a titanium compound. The porous organic polymer carrier is a copolymer comprising divinylbenzene and a sulfonic acid group-containing functional monomer. Through the design and preparation at the carrier level, the catalyst system of the present invention obtains a Ziegler-Natta catalyst for olefins. During the preparation process, no additional internal electron donor needs to be added, and the catalyst can be used to prepare ultra-high molecular weight polyethylene with a viscosity-average molecular weight up to 7 million.

Description

Technical Field

[0001] The present invention relates to the field of ethylene polymerization, and particularly to a Ziegler-Natta (Z-N) type catalyst system for ethylene polymerization, a preparation method thereof, and an application thereof. Background Art

[0002] Ultra-high molecular weight polyethylene (UHMWPE) generally refers to a linear long-chain polyethylene material with a relative molecular weight of more than 1.5 million (or a viscosity-average molecular weight of more than 1 million). UHMWPE has excellent properties such as high strength, impact resistance, wear resistance, self-lubrication, chemical corrosion resistance, and low-temperature resistance. The main products include fibers, films, pipes, plates, rods, porous materials, and profiled materials, etc., and are widely used in fields such as aerospace, national defense, ocean engineering, petrochemical industry, and new energy materials.

[0003] Currently, the catalysts for preparing UHMWPE mainly include Ziegler-Natta catalysts, metallocene catalysts, and non-metallocene catalysts, such as phenoxyimine (FI) catalysts.

[0004] Ziegler-Natta catalysts (hereinafter referred to as "Z-N catalysts") are one of the most commonly used catalysts for preparing UHMWPE. Due to their advantages such as high catalytic activity, good product regularity, and mild reaction conditions, Z-N type catalysts have been widely used in industrial production. The composition of Z-N catalysts mainly includes a main catalyst, a cocatalyst, a carrier, an electron donor, etc. Among them, the main catalyst is usually a transition metal halide of Group IVB-VIB, and commonly used is titanium tetrachloride (TiCl4). The cocatalyst is usually a metal organic compound of Group IA-IIIA, and commonly used is triethylaluminum (AlEt3). The carrier is usually a magnesium compound, and commonly used is magnesium chloride (MgCl2). According to the different ways of providing electrons, the electron donor can be divided into two categories: internal electron donors and external electron donors. Currently, the main research direction of Z-N catalysts for UHMWPE is still to further optimize their catalytic performance by screening various main components of the catalysts, such as by changing the types of electron donors and carriers.

[0005] There are many disclosed methods for preparing Ziegler-Natta type ultra-high molecular weight polyethylene catalysts. Usually, TiCl4 is supported on compounds such as Mg(OR)2, MgCl2 or MgR2, and then various processes are used to prepare UHMWPE catalysts by reduction with alkylaluminum. An internal electron donor can be added during the process to regulate the electrophilicity of the Ti active center to control the catalyst performance, such as in US Patents US4,447,587, US4,933,393 and US6,114,271, etc. The molecular weight of the polymer can be adjusted by the amount of alcohol added, such as in US4,138,540. In addition, US4,962,167 prepares a UHMWPE catalyst by reacting MgCl2 with a titanium alkoxide compound and then with aluminum trihalide and tetraalkoxysilane. In CN106220768A, an organosilicon compound electron donor is added to the UHMWPE catalyst in the Ti / Mg system. In addition, CN107674134A discloses a method for preparing ultra-high molecular weight polyethylene. This method uses a Ziegler-Natta catalyst, the cocatalyst is a triethylamine solution, and the external electron donor is diphenyldimethoxysilane. Ultra-high molecular weight polyethylene is prepared by selecting specific types of cocatalysts and external electron donors. CN200810051617.0 discloses a Ziegler-Natta catalyst supported on a MgCl2 / mesoporous molecular sieve composite support, which can prepare polyethylene with ultra-high molecular weight.

[0006] In the existing Ziegler-Natta ultra-high molecular weight polyethylene catalyst technology, although the commercialization of ultra-high molecular weight polyethylene has been achieved, the catalyst preparation process is complex, and the catalyst particles are relatively fine, usually requiring control below 5 microns to obtain polymer particles with a suitable particle size for processing. Therefore, the catalyst filtration is difficult, and usually, it is necessary to adopt the method of on-site preparation and continuous addition for treatment. In addition, it is difficult to adjust the molecular weight during the polymerization process of the catalyst system, and the comprehensive performance of the catalyst needs to be improved.

[0007] Metallocene catalysts refer to catalysts composed of complexes of group ⅣB transition metal elements as the main catalyst and alkylaluminoxanes or organoboron compounds as the cocatalyst. Among them, common main catalysts are complexes of titanium and zirconium, common alkylaluminoxanes are methylaluminoxides, and common organoboron compounds are tris(pentafluorophenyl)borane. As ligands of transition metal elements, they need to carry at least one cyclopentadienyl or its derivative group. Metallocene catalysts can precisely control the molecular weight, molecular weight distribution, crystal structure, etc. of the product. Compared with the aforementioned Z-N catalysts, metallocene catalysts have more advantages in terms of reaction activity and can achieve copolymerization with olefins with larger steric hindrance. "Donor-acceptor metallocene catalysts for the production of UHMWPE: Pushing the selectivity for chain growth to its limits" in Angew Chem Int Ed. (2006; 45, pp. 1799-1803) used the metallocene compound [(Flu)Et2PB(Ph)2(Cp)]ZrCl2 to prepare ultra-high molecular weight polyethylene, with a viscosity-average molecular weight reaching 3.9 million. CN101356199A discloses a bisindenyl-substituted bridged metallocene catalyst for ultra-high molecular weight polymers. The bridged metallocene catalyst can be dimethylsilylene-[2-isopropyl-4-(p-isopropylphenyl)indenyl][2-methyl-4-(p-isopropylphenyl)indenyl]zirconium dichloride, dimethylsilylene-bis(2-isopropylindenyl)zirconium dichloride, etc. The molecular weight of the metallocene catalysts reported for ultra-high molecular weight polyethylene is lower than that of Z-N catalysts, and the synthesis of catalyst compounds is complex, and the prices of the catalysts and cocatalysts are expensive, which limits their industrial applications.

[0008] Non-metallocene catalysts generally refer to catalysts that do not contain cyclopentadienyl groups and whose metal centers are organometallic complexes of transition metal elements or some main group metal elements. Among them, transition metal elements are usually metals in Group VIII, such as iron (Fe), cobalt (Co), nickel (Ni), and palladium (Pd). Non-metallocene catalysts can be roughly divided into two categories. One category is non-metallocene-based compounds, and the other category is late transition metal compounds. Their catalytic characteristics are similar to those of metallocene catalysts. The reaction center is single-active, and UHMWPE with a specific molecular weight and main chain structure can be prepared as needed. CN102030844B discloses a supported non-metallocene polyolefin catalyst, which can be used to prepare ultra-low branched ultra-high molecular weight polyethylene. The catalyst is a non-metallocene compound containing a [ONX] tridentate ligand. Typical non-metallocene catalysts such as phenoxyimine (FI) catalysts can usually regulate the molecular weight of ultra-high molecular weight polyethylene through substituents on the compound. CN107936164A discloses a copolymerized UHMWPE, which has a molecular weight equivalent to that of the homopolymerized product, and at the same time has a comparable comonomer content. Moreover, the comonomer content can be adjusted and controlled, the particle morphology is good, the bulk density is high, the activity decay is not obvious, and it can catalyze the homopolymerization of α-olefins without the need to add internal electron donors and external electron donors. The loss of wear resistance and impact strength performance of UHMWPE is relatively low. However, supported non-metallocene catalysts are prone to detachment during the polymerization process, resulting in uneven distribution of polymerization particles and the problem of fouling the reactor.

[0009] Different from the reported inorganic supports, the porous organic polymer (POP) support itself does not introduce impurities, which would otherwise affect the properties of the polymer. There are reports on the POP support loaded with Ziegler-Natta (Z-N) catalysts. Usually, organic supports containing functional groups such as carboxyl, hydroxyl, cyano, and amino groups are used to prepare Z-N catalysts. The molecular weight of the polyethylene products obtained by polymerization is usually less than 300,000. For example, in "Porous polyethylene spheres with nanofiber structure from Ziegler-Natta catalyst supported on porous polymer particles" (2011; 52, pp. 602-605) in Polymer, a POP support loaded with Z-N polyethylene catalyst was prepared using a cyano-functionalized organic support, and its weight-average molecular weight was between 100,000 and 200,000 g / mol. In "Ethylene polymerization on polymer supported Ziegler-Natta catalyst" (2012; 19:9892, pp. 1-13) in J. Polym. Res., a Z-N polyethylene catalyst prepared using a methyl methacrylate-functionalized POP support had a weight-average molecular weight between 200,000 and 300,000 g / mol. In addition, for the metallocene catalysts prepared using organic supports, such as the organic support containing carboxylate groups in US 5,587,439, the molecular weight of the polyethylene products obtained by ethylene polymerization was less than 300,000. Moreover, in "Ultrahigh Molecular Weight Polyethylene Produced by a Bis(phenoxy-imine) Titanium Complex Supported on Latex Particles" (2006; pp. 3103-3113) in Journal of Polymer Science: Part A: Polymer Chemistry, a porous organic support containing pyridine functionality and poly(ethylene oxide) groups was used by the microemulsion polymerization method to load a bis(phenol-imine)titanium (FI-Ti) catalyst compound to obtain an ultrahigh molecular weight polyethylene catalyst. The weight-average molecular weight of the prepared polyethylene was between 2,000,000 and 7,000,000. The active centers of the ultrahigh molecular weight polyethylene catalysts belong to the FI-titanium series, rather than the Z-N catalysts.

[0010] Therefore, there is still a need in the art to further study the Z-N type catalyst system that can be used to prepare ultrahigh molecular weight polyethylene. Summary of the Invention

[0011] The main object of the present invention is to provide a Ziegler-Natta catalyst system for ethylene polymerization, its preparation method and application, so as to overcome the defect that the polyethylene obtained by using the Ziegler-Natta catalyst in the prior art for ethylene polymerization has a relatively low molecular weight and it is difficult to prepare ultra-high molecular weight polyethylene.

[0012] To achieve the above object, the present invention provides a Ziegler-Natta catalyst system for ethylene polymerization, comprising a solid phase component and a cocatalyst. The solid phase component comprises a porous organic polymer carrier, a magnesium compound and a titanium compound, and the porous organic polymer carrier is a copolymer comprising divinylbenzene and a sulfonic acid group-containing functional monomer.

[0013] For the Ziegler-Natta catalyst system for ethylene polymerization of the present invention, based on 100% by mass of the solid phase component, the content of the magnesium compound in the solid phase component in terms of magnesium element is 1-8%, and the content of the titanium compound in the solid phase component in terms of titanium is 1-8%; based on 100 parts by mass of the porous organic polymer carrier, the sulfonic acid group-containing functional monomer accounts for 5-60 parts.

[0014] For the Ziegler-Natta catalyst system for ethylene polymerization of the present invention, the content of the sulfonic acid group-containing functional monomer in the porous organic polymer carrier is 0.5-5 mmol / g of the porous organic polymer carrier.

[0015] For the Ziegler-Natta catalyst system for ethylene polymerization of the present invention, the chemical formula of the sulfonic acid group-containing functional monomer is R2HC=C(R3)R1SO2OH, R2HC=C(R3)R1SO3H or R2HC=C(R3)R1SO2OM, where R1 is an alkylene group or a phenylene group containing 0-6 carbon atoms in the main chain, and the R1 group contains or does not contain chlorine, bromine, fluorine, iodine, an alkyl group, a phenyl group or a naphthalene group; R2 is an H atom, an alkyl group containing 1-6 carbon atoms in the main chain, or a phenyl group, and the R2 group contains or does not contain 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; and M is a metal.

[0016] The Ziegler-Natta catalyst system for ethylene polymerization according to the present invention, wherein the sulfonic acid group-containing functional monomer is at least one of sodium styrene sulfonate, styrene sulfonic acid, sodium m-styrene sulfonate, m-styrene sulfonic acid, o-styrene sulfonic acid, sodium o-styrene sulfonate, 2-methyl-4-sulfonatostyrene, 2-chloro-4-sulfonatostyrene, 2-methyl-4-sulfonic acid styrene, 2-methyl-3-sulfonatostyrene, 2-methyl-3-sulfonic acid styrene, vinyl-4-methylbenzenesulfonic acid, vinyl-4-methylbenzenesulfonate, 2-ethyl-3-sulfonatostyrene, 2-ethyl-3-sulfonic acid styrene, 4,4'-bis(2-sulfonic acid styryl)-1,1'-biphenyl, 2-(2-styryl)benzenesulfonic acid, vinylsulfonic acid, sodium vinylsulfonate, allylsulfonic acid, sodium allylsulfonate, 3-chloroallylsulfonic acid sodium salt, methacrylic acid sulfonic acid, sodium methacrylic acid sulfonate, 1-butenylsulfonic acid, sodium 1-butenylsulfonate, 1-pentenylsulfonic acid, sodium 1-pentenylsulfonate, 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, vinylsulfonic acid, sodium vinylsulfonate, allylsulfonic acid, sodium allylsulfonate, methacrylic acid sulfonic acid, sodium methacrylic acid sulfonate, 1-butenylsulfonic acid, sodium 1-butenylsulfonate, 1-pentenylsulfonic acid, sodium 1-pentenylsulfonate, 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 and hydrates of these compounds.

[0017] The Ziegler-Natta catalyst system for ethylene polymerization according to the present invention, wherein the BET specific surface area of the porous organic polymer carrier of the present invention is 100-600 m 2 / g, and the pore volume is greater than or equal to 0.2 ml / g; the cocatalyst is an alkylaluminum, the cocatalyst is calculated as Al, the titanium compound is calculated as Ti, and the molar ratio of the cocatalyst to the titanium compound is 5-500.

[0018] In order to achieve the above object, the present invention also provides a preparation method of the above Ziegler-Natta catalyst system for ethylene polymerization. The preparation method of the solid phase component includes:

[0019] Reacting the porous organic polymer carrier with the magnesium compound in an inert solvent at a reaction temperature of 0°C to 50°C for a reaction time of 15 to 120 minutes, then filtering the unreacted magnesium compound, adding it to an organic solvent containing a titanium compound, and reacting at a reaction temperature of 0°C to 80°C for a reaction time of 15 to 180 minutes to obtain the solid phase component.

[0020] The preparation method of the Ziegler-Natta catalyst system for ethylene polymerization according to the present invention, wherein the addition amount of the magnesium compound in terms of magnesium is 1 to 30 mmol / g of the porous organic polymer support, and the addition amount of the titanium compound in terms of titanium is 5 to 200 mmol / g of the porous organic polymer support.

[0021] The preparation method of the catalyst system for ethylene polymerization according to the present invention, wherein the preparation method of the porous organic polymer support includes:

[0022] Using divinylbenzene as the basic monomer and copolymerizing with a sulfonic acid group-containing functional monomer by free radical polymerization to obtain the porous organic polymer support.

[0023] In order to achieve the above object, the present invention further provides the application of the above Ziegler-Natta catalyst system for ethylene polymerization in ethylene polymerization or ethylene and α-olefin copolymerization to prepare ultra-high molecular weight polyethylene.

[0024] The beneficial effects of the present invention;

[0025] In the present invention, the Ziegler-Natta catalyst supported on the porous organic polymer support, its pore structure can be adjusted through the pore structure of the support. The catalyst realizes the regulation of the chemical environment of the titanium active center through the design of the functional monomer, forming a POP-SO3...MgCl / TiCl4 / AlEt3 catalyst system, where POP-SO3...MgCl / TiCl4 is the solid catalyst component, and the cocatalyst is added during the polymerization process. After contacting with the POP-SO3...MgCl / TiCl4 solid catalyst, a POP-SO3...MgCl / TiCl4 / AlEt3 catalyst system is formed, and then the Ti active center catalyzes the polymerization of olefins to obtain a polymer product. The preparation method of the POP-SO3...MgCl / TiCl4 / AlEt3 catalyst system of the present invention is simple. Through the design and preparation at the support level, a Ziegler-Natta catalyst for olefins is obtained. No additional internal electron donor needs to be added during the preparation process. The catalyst can prepare ultra-high molecular weight polyethylene with a viscosity-average molecular weight of up to 7 million, having good industrialization prospects. Specific embodiments

[0026] The following details the embodiments of the present invention. These embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation manners and processes are given. However, the protection scope of the present invention is not limited to the following embodiments. For the experimental methods discussed in the following embodiments without specifying specific conditions, they are usually carried out under conventional conditions.

[0027] The present invention discloses a Ziegler-Natta catalyst system for ethylene polymerization, which includes a solid component and a cocatalyst. The solid component includes a porous organic polymer support, a magnesium compound, and a titanium compound. The porous organic polymer support is a copolymer comprising divinylbenzene and a sulfonic acid group-containing functional monomer.

[0028] The catalyst of the present invention designs the functional monomer. The porous organic polymer support is a copolymer comprising divinylbenzene and a sulfonic acid group-containing functional monomer. Thus, the purpose of regulating the chemical environment of the titanium active center can be achieved. The catalyst of the present invention can be used to prepare ultra-high molecular weight polyethylene with a viscosity-average molecular weight of up to 7 million.

[0029] The catalyst system of the present invention belongs to Ziegler-Natta catalysts. The porous organic polymer support is a copolymer obtained by copolymerizing divinylbenzene and a sulfonic acid group-containing functional monomer. In one embodiment, the chemical formula of the sulfonic acid group-containing functional monomer is R2HC=C(R3)R1SO2OH, R2HC=C(R3)R1SO3H or R2HC=C(R3)R1SO2OM. R1 is usually an alkylene group or a phenylene group containing 0-6 carbon atoms in the main chain. R2 is usually 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, alkyl groups, phenyl groups, naphthyl groups, etc. 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.

[0030] When the number of carbon atoms of R1 is 0 and R3 is an H atom, the chemical structural formula of the functional monomer is R2HC=CHSO2OH; when R1 is a phenylene group and R3 is an H atom, the chemical structural formula of the functional monomer is R2HC=CH-PhSO3H; when R2 is a phenyl group, the number of carbon atoms of R1 is 0 and R3 is an H atom, the chemical structural formula of the functional monomer is PhHC=CHSO3H; when the number of carbon atoms in both R1 and R2 is 0 and R3 is an H atom, the chemical structural formula of the functional monomer is H2C=CHSO3H. In addition, the functional monomer can also be selected from metal salts and hydrates of R2HC=C(R3)R1SO2OH, 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.

[0031] In another embodiment, the sulfonic acid group-containing functional monomer of the present invention includes but is not limited to sodium styrene sulfonate, styrene sulfonic acid, sodium m-styrene sulfonate, m-styrene sulfonic acid, o-styrene sulfonic acid, sodium o-styrene sulfonate, 2-methyl-4-sulfonatostyrene, 2-chloro-4-sulfonatostyrene, 2-methyl-4-sulfonic acid styrene, 2-methyl-3-sulfonatostyrene, 2-methyl-3-sulfonic acid styrene, vinyl-4-methylbenzenesulfonic acid, vinyl-4-methylbenzenesulfonate, 2-ethyl-3-sulfonatostyrene, 2-ethyl-3-sulfonic acid styrene, 4,4'-bis(2-sulfonic acid styryl)-1,1'-biphenyl, 2-(2-styryl)benzenesulfonic acid, vinylsulfonic acid, sodium vinylsulfonate, allylsulfonic acid, sodium allylsulfonate, 3-chloroallylsulfonate, methacrylic acid sulfonic acid, sodium methacrylic acid sulfonate, 1-butene sulfonic acid, sodium 1-butene sulfonate, 1-pentene sulfonic acid, sodium 1-pentene 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, vinylsulfonic acid, sodium vinylsulfonate, allylsulfonic acid, sodium allylsulfonate, methacrylic acid sulfonic acid, sodium methacrylic acid sulfonate, 1-butene sulfonic acid, sodium 1-butene sulfonate, 1-pentene sulfonic acid, sodium 1-pentene 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, and their hydrates, etc.

[0032] The present invention uses a sulfonic acid group-containing functional monomer R2HC=C(R3)R1SO2OH or its salt to effectively regulate the chemical environment of the Ti active center, and prepares a POP-SO3H support. By loading magnesium and titanium metals, a Z-N catalyst system POP-SO3H / RMgX / TiCl4 / AlEt3 supported on a POP support is prepared. The catalyst system of the present invention is used for ethylene polymerization, and can obtain ultra-high molecular weight polyethylene with a relative molecular weight Mw reaching 10 million or a viscosity-average molecular weight reaching more than 7 million.

[0033] In the catalyst system of the present invention, the magnesium compound and the titanium compound are common substances in the Z-N catalyst in the art, and the present invention does not make special limitations on them. For example, they are halogen compounds of magnesium and titanium.

[0034] In one embodiment, the magnesium compound of the present invention has the molecular formula RMgX or R6MgR5, where X is a halogen, namely a fluorine, chlorine, bromine, or iodine atom, and the R, R5, and R6 groups can be a linear hydrocarbon or aromatic hydrocarbon group containing 1-8 carbon atoms, such as methyl, ethyl, propyl, butyl, benzene, benzene with a substituted group, or an alkoxy group. R5 and R6 can be the same or different. Further, the magnesium compound of the present invention can be an alkyl magnesium halide Grignard reagent, an alkyl magnesium compound, an alkoxy magnesium halide, etc., such as methyl magnesium chloride, n-butyl magnesium chloride, isobutyl magnesium chloride, tert-butyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-butyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, tert-butyl magnesium iodide, benzyl magnesium iodide, n-butyl magnesium iodide, methyl magnesium fluoride, tert-butyl magnesium fluoride, diethyl magnesium, dibutyl magnesium, ethoxy magnesium chloride, etc. Even further, the magnesium compound of the present invention is an alkyl magnesium chloride Grignard reagent RMgCl.

[0035] In one embodiment, the titanium compound of the present invention is a halide of titanium, such as titanium tetrachloride, titanium trichloride, etc., usually titanium tetrachloride.

[0036] In one embodiment, based on 100% of the mass of the solid component, the content of the magnesium compound in the solid component in terms of magnesium element is 1-8%, preferably 2-6%, and the content of the titanium compound in the solid component in terms of titanium is 1-8%, preferably 2-6%; based on 100 parts by mass of the porous organic polymer carrier, the content of the sulfonic acid group functional monomer is 5-60 parts, preferably 20-50 parts.

[0037] In another embodiment, based on 100% of the mass of the porous organic polymer carrier, the content of the sulfonic acid group functional monomer in the porous organic polymer carrier is 0.5-5 mmol / g of the porous organic polymer carrier, preferably 1-4 mmol / g of the porous organic polymer carrier.

[0038] The cocatalyst of the present invention and its addition amount are well-known technologies 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 is selected from triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-hexyl aluminum, mono-chloro diethyl aluminum, dichloroethyl aluminum; further, the cocatalyst is triethyl aluminum AlEt3. Based on aluminum in the alkyl aluminum and titanium in the titanium compound, the molar ratio of the addition amount of the alkyl aluminum to the amount of the titanium compound used is 5-500.

[0039] The present invention also provides a preparation method of the above Z-N type catalyst system for ethylene polymerization. The preparation method of the solid component includes:

[0040] Treat the porous organic polymer support with a magnesium compound (taking POP-SO3H as an example) to obtain POP-SO3...MgX, and then add a titanium compound to react to obtain the solid component of the Ziegler-Natta catalyst, POP-SO3...MgX / TiCl4.

[0041] Among them, the cocatalyst is added to the reaction system together with the solid component when the catalyst system is used for ethylene polymerization, and the finally formed POP-type ethylene Ziegler-Natta catalyst system is represented by POP-SO3H / RMgX / TiCl4 / AlEt3 in the present invention. At the same time, the cocatalyst can be used as a scavenger for the polymerization reaction system to remove trace moisture in the system.

[0042] In one embodiment, the preparation method of the solid component of the catalyst of the present invention is as follows: React the porous organic polymer support with a magnesium compound in an inert solvent at a reaction temperature of 0 °C to 50 °C for a reaction time of 15 to 120 minutes, then filter the unreacted magnesium compound, add it to an organic solvent containing a titanium compound, and react at a reaction temperature of 0 °C to 80 °C for a reaction time of 15 to 180 minutes to obtain the solid component.

[0043] More specifically, the preparation method of the solid component of the catalyst of the present invention is as follows: After drying the porous organic polymer, add it to an inert solvent under anhydrous and anaerobic operating conditions, add an alkylmagnesium chloride Grignard reagent, react at 0 °C to 50 °C for 15 to 120 minutes, after the reaction is completed, filter the unreacted alkylmagnesium chloride Grignard reagent, add an inert solvent and titanium tetrachloride, adjust the temperature to 0 °C to 80 °C, react for 15 to 180 minutes, and wash the product with an inert solvent to obtain the solid component of the catalyst.

[0044] In one embodiment, the preparation method of the porous organic polymer support of the present invention is as follows: The dispersion polymerization or suspension polymerization process can be adopted, using divinylbenzene as the basic monomer, and copolymerizing with a sulfonic acid group-containing functional monomer by free radical copolymerization to obtain the porous organic polymer support of the present invention. The porous organic polymer support of the present invention can be represented by POP-SO3H or POP-SO3M, where M represents a metal.

[0045] More specifically, the preparation method of the porous organic polymer support of the present invention is as follows: Add divinylbenzene and a sulfonic acid group-containing functional monomer to a dispersion solvent, then add a stabilizer and an initiator, stir and disperse evenly, react at 50-80 °C for 5-12 hours, and then wash, filter, and dry to prepare a sulfonic acid group-containing porous organic polymer support. If the functional monomer used is a sulfonate or its hydrate containing a sulfonic acid group, for the prepared porous organic polymer support, add an acid, such as hydrochloric acid, dilute sulfuric acid, etc., react at 20-80 °C for 0.2-2 hours, wash 1-2 times, and filter and dry to obtain the POP-SO3H support.

[0046] In one embodiment, the above-mentioned dispersion solvent can be a lower alcohol with 1-4 carbon atoms or an alcohol / water mixed solvent system, and the mass ratio of alcohol to water is 5-15:1. The dispersion solvent can be methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, etc. Unless otherwise specified, the following are all mass ratios. A small amount of other solvents, such as ethyl acetate, methyl formate, tetrahydrofuran and other solvents, can be added to the solvent system to adjust the solubility parameter of the solvent system, so as to control the pore structure and morphology of the prepared carrier. The mass ratio of the total amount of monomers added (the total amount of divinylbenzene and sulfonic acid group-containing functional monomers) to the dispersion solvent is 1:5-20, so that the system is evenly dispersed. Among them, the mass ratio of the sulfonic acid group-containing functional monomer to divinylbenzene is 0.2-2:1. The stabilizer is polyvinyl alcohol or polypropylene oxide-polyethylene oxide copolymer. The weight-average molecular weight of the stabilizer is controlled between 6,000 and 100,000, and the addition amount of the stabilizer to the total amount of monomers added is 0.5-3:100. The initiator is a common free radical initiator, including azobisisobutyronitrile AIBN or benzoyl peroxide BPO, and the addition amount of the initiator to the total amount of monomers added is 0.5-3:100. The polymer obtained by the reaction can be washed with a dispersion solvent to remove impurities.

[0047] The monomers used in the preparation of the porous organic polymer carrier of the present invention are divinylbenzene (abbreviated as DVB in English), sulfonic acid group-containing functional monomers (sodium p-styrenesulfonate, sodium vinylsulfonate, allyl sulfonic acid, sodium allylsulfonate or its hydrate, etc.). Commercially available monomers can be used. For example, divinylbenzene can use commercially available monomers with a DVB mass content of 55% or 80%. Divinylbenzene needs to be pretreated before use. After removing the inhibitor, it can be used. There are many methods in the prior art to remove the inhibitor. For example, it can be washed with sodium hydroxide solution and distilled water. Sulfonic acid group-containing functional monomers, such as sodium vinylbenzenesulfonate hydrate and sodium allylsulfonate hydrate, are solid particles and can be used directly.

[0048] In one embodiment, the addition amount of the magnesium compound in terms of magnesium is 1-30 mmol / g of the porous organic polymer carrier, preferably 3-20 mmol / g of the porous organic polymer carrier; in the preparation process of the solid phase component of the present invention, an excessive amount of Ti compound is usually added for the loading of the catalyst; in one embodiment, the addition amount of the titanium compound in terms of titanium is 5-200 mmol / g of the porous organic polymer carrier, preferably 50-150 mmol / g of the porous organic polymer carrier.

[0049] In one embodiment, the specific surface area of the porous organic polymer carrier of the present invention is tested by the BET nitrogen adsorption method using Nova2000e. Preferably, the specific surface area of the carrier is greater than 100 m 2 / g, more preferably in the range of 100-600 m 2between / g; the pore volume is greater than or equal to 0.2 ml / g.

[0050] Thus, the catalyst of the present invention forms a POP-SO3...MgCl / TiCl4 / AlEt3 catalyst system by designing the functional monomer and regulating the chemical environment of the titanium active center. Among them, POP-SO3...MgCl / TiCl4 is the solid catalyst component, and the cocatalyst is added during the polymerization process. After contacting with the POP-SO3...MgCl / TiCl4 solid catalyst, a POP-SO3...MgCl / TiCl4 / AlEt3 catalyst system is formed, and then the Ti active center catalyzes the polymerization of olefins to obtain a polymer product. The preparation method of the POP-SO3...MgCl / TiCl4 / AlEt3 catalyst system of the present invention is simple. Through the design and preparation at the carrier level, a ultra-high molecular weight catalyst is prepared. No additional internal electron donor needs to be added during the catalyst preparation process. The catalyst can prepare ultra-high molecular weight polyethylene with a viscosity-average molecular weight reaching 7 million, and has good industrialization prospects.

[0051] The present invention prepares a Z-N type catalyst system for ethylene polymerization. This catalyst system can be used for ethylene polymerization or copolymerization of ethylene and α-olefins, and can prepare ultra-high molecular weight polyethylene. For example, it is used for propylene-ethylene copolymerization, and the α-olefin can be propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene, etc. The catalyst system of the present invention has good polymerization activity and can polymerize to obtain ultra-high molecular weight polyethylene. The so-called ultra-high molecular weight means that the relative molecular weight Mw can reach 10 million or the viscosity-average molecular weight reaches more than 7 million.

[0052] The catalyst system of the present invention is suitable for gas-phase, bulk or slurry polymerization reactions. The suitable reaction conditions are temperature 30-80 °C and pressure 0.1-2.0 MPa. The solvent suitable for slurry polymerization is an alkane containing 5-10 carbon atoms, and the preferred solvent is hexane.

[0053] The ultra-high molecular weight polyethylene prepared by the present invention has its viscosity-average molecular weight measured by the method in ASTM D4020. The polymer viscosity is tested by an Ubbelohde viscometer, the solvent is decalin, and the test temperature is 135 °C. The polymer viscosity-average molecular weight Mη can be calculated from the intrinsic viscosity η of the polymer through the formula Mη = 5.37×10 4 [η] 1.37 for calculation. The polymer weight-average molecular weight Mw can be calculated through the Margolis formula Mw = 5.37×10 4 [η] 1.49 for calculation.

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

[0055] Example 1

[0056] Treatment of comonomers: Before use, the inhibitor in divinylbenzene was removed with 10% NaOH solution, and then it was washed 3 times with deionized water before use; monomers such as sodium p-styrenesulfonate or sodium p-styrenesulfonate hydrate are solid particles at room temperature and are directly used without post-treatment.

[0057] Preparation of sulfonated porous organic polymer support: In a 5L glass reactor, 1350 ml of ethanol and 150 ml of deionized water were added, and then 100 g of divinylbenzene (Aladdin reagent, 50%) and 35 g of sodium p-styrenesulfonate hydrate (Aladdin reagent, 90%) were added. Stir at room temperature for 5 min, then add 2% of polyvinyl alcohol PVA (PVA, polymerization degree 1750) based on the total mass of the monomers (the total addition amount of divinylbenzene and sodium p-styrenesulfonate hydrate). At 45 °C, stir for 1 h to completely dissolve the stabilizer, add 2.0% (2.7 g) of AIBN based on the total mass of the monomers, raise the temperature to 70 °C, react for 3 hours, then raise the temperature to 80 °C, react for 8 hours, the stirring speed is 350 revolutions per minute, after filtration, 1000 ml of the above ethanol and water mixed solvent was added, and sulfuric acid with a mass ratio of 20% was used to react and acidify at 50 °C for 2 h. After acidification twice, it was filtered and washed 3 times with the alcohol-water mixed solvent, filtered and dried to obtain 118 g of free-flowing porous POP-1. The specific surface area of the support is 291 m 2 / g, and the pore volume is 0.25 ml / g.

[0058] Example 2

[0059] Preparation of Z-N catalyst: In a 250 ml glass reactor, 3 g of the above POP-1 support containing sulfonic acid functional groups was added, 100 ml of toluene was added, stirred, and then 15 ml of 3M methylmagnesium chloride Grignard reagent was added at 35 °C and stirred for 2 h. After filtration, it was washed 2 times with toluene, then 60 ml of toluene was added and the temperature was raised to 50 °C, and 50 ml of TiCl4 was added dropwise and reacted for 3 h. After the reaction was completed, it was filtered and washed 3 times with toluene and hexane respectively, and then dried to obtain free-flowing catalyst solid component particles, denoted as Cat-1, with a Mg content of 4.5% and a Ti content of 3.2%.

[0060] Example 3

[0061] Preparation of Ziegler-Natta catalyst: In a 250 ml glass reactor, 3 g of the above POP-1 support containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, 8 ml of 3 M methylmagnesium chloride Grignard reagent was added at 5 °C, and the mixture was stirred for 2 hours. After filtration, it was washed once with toluene. Then, 50 ml of toluene was added and the temperature was raised to 60 °C. 45 ml of TiCl4 was added dropwise, and the reaction was carried out for 3 hours. After the reaction was completed, it was filtered, washed 3 times each with toluene and hexane, and then dried to obtain free-flowing catalyst solid component particles, denoted as Cat-2, with a Mg content of 3.7% and a Ti content of 4.5%.

[0062] Example 4

[0063] Preparation of Ziegler-Natta catalyst: In a 250 ml glass reactor, 3 g of the above POP-1 support containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, 5 ml of 3 M methylmagnesium chloride Grignard reagent was added at room temperature, and the mixture was stirred for 2 hours. After filtration, it was washed twice with toluene. Then, 40 ml of toluene was added, and 50 ml of TiCl4 was added dropwise at room temperature. The reaction was carried out for 1 hour, and the temperature was raised to 80 °C and the reaction was carried out for 2 hours. After the reaction was completed, it was filtered, washed 3 times each with toluene and hexane, and then dried to obtain free-flowing catalyst solid component particles, denoted as Cat-3, with a Mg content of 2.2% and a Ti content of 2.7%.

[0064] Examples 5 - 10

[0065] Ethylene polymerization for the preparation of ultra-high molecular weight polyethylene

[0066] Example 5: 2.0 liters of dry hexane was added to a 5-liter stainless steel autoclave that had been purged with nitrogen and dried. Then, 10 ml of triethylaluminum TEA (1.0 mol / l) was added, and the stirring speed was 450 revolutions per minute. Then, 32 mg of Cat-1 catalyst was added, and ethylene was introduced to keep the internal pressure of the reaction kettle at 0.6 MPa. Polymerization was carried out at 70 °C and a stirring speed of 450 revolutions per minute for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 633 g of polyethylene product (UHMWPE-1) was obtained, with a bulk density of 0.3 g / ml and a catalyst activity of 4930 kgPE / molTi.bar.h.

[0067] Example 6: 2.0 liters of dry hexane was added to a 5-liter stainless steel autoclave that had been purged with nitrogen and dried. Then, 5 ml of triethylaluminum TEA (1.0 mol / L) was added, and the stirring speed was 450 revolutions per minute. Then, 30 mg of Cat-1 catalyst was added, and ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 80 °C with a stirring speed of 450 revolutions per minute for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 687 g of polyethylene product (UHMWPE-2) was obtained. The bulk density was 0.30 g / ml, and the catalyst activity was 5710 kgPE / molTi.bar.h.

[0068] Example 7: 2.0 liters of dry hexane was added to a 5-liter stainless steel autoclave that had been purged with nitrogen and dried. Then, 5 ml of triethylaluminum TEA (1.0 mol / L) was added, and the stirring speed was 450 revolutions per minute. Then, 30 mg of Cat-2 catalyst was added, and ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 70 °C with a stirring speed of 450 revolutions per minute for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 488 g of polyethylene product (UHMWPE-3) was obtained. The bulk density was 0.32 g / ml, and the catalyst activity was 2880 kgPE / molTi.bar.h.

[0069] Example 8: 2.0 liters of dry hexane was added to a 5-liter stainless steel autoclave that had been purged with nitrogen and dried. Then, 5 ml of triethylaluminum TEA (1.0 mol / L) was added, and the stirring speed was 450 revolutions per minute. Then, 32 mg of the above Cat-2 catalyst was added, and ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 80 °C with a stirring speed of 450 revolutions per minute for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 652 g of polyethylene product (UHMWPE-4) was obtained. The bulk density was 0.30 g / ml, and the catalyst activity was 3610 kgPE / molTi.bar.h.

[0070] Example 9: 2.0 liters of dry hexane was added to a 5-liter stainless steel autoclave that had been purged with nitrogen and dried. Then, 3 ml of triethylaluminum TEA (1.0 mol / L) was added, and the stirring speed was 450 revolutions per minute. Then, 32 mg of Cat-3 catalyst was added, and ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 70 °C with a stirring speed of 450 revolutions per minute for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 412 g of polyethylene product (UHMWPE-5) was obtained. The bulk density was 0.31 g / ml, and the catalyst activity was 3800 kgPE / molTi.bar.h.

[0071] Example 10: 2.0 liters of dry hexane was added to a 5-liter stainless-steel autoclave that had been purged with nitrogen and dried. Then, 3 ml of triethylaluminum (TEA, 1.0 mol / L) was added, and the stirring speed was 450 revolutions per minute. Then, 30 mg of Cat-3 catalyst was added, and ethylene was introduced to maintain the internal pressure of the reactor at 1.0 MPa. Polymerization was carried out at 60 °C with a stirring speed of 450 revolutions per minute for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 482 g of a polyethylene product (UHMWPE-6) was obtained. The bulk density was 0.30 g / ml, and the catalyst activity was 2850 kgPE / molTi.bar.h.

[0072] Table 1 Results of olefin polymerization in Examples 5 - 10

[0073]

[0074] Example 11

[0075] In a 5L glass reactor, 1350 ml of ethanol and 150 ml of deionized water were added. Then, 100 g of divinylbenzene (Aladdin reagent, 80%) and 55 g of sodium p-styrenesulfonate hydrate (Aladdin reagent, 90%) were added. The mixture was stirred at room temperature for 5 min, and then 2% of the total mass of the monomers of poly(propylene oxide)-poly(ethylene oxide) copolymer F127 (BASF, molecular weight 12000) was added. At 45 °C, the mixture was stirred for 1 h to completely dissolve the stabilizer. 2.0% of AIBN based on the total mass of the monomers was added, and the temperature was raised to 70 °C for 3 h. Then, the temperature was raised to 80 °C and reacted for 8 h. The stirring speed was 450 revolutions per minute. After filtration, 100 ml of the above ethanol and water mixed solvent was added, and 10 ml of a 36.5% HCl solution by mass was added. The reaction was carried out at 50 °C for 2 h, filtered, washed 3 times with the alcohol-water mixed solvent, filtered, and dried to obtain 145 g of free-flowing porous POP-2. The specific surface area of the support was 540 m 2 / g, and the pore volume was 0.45 ml / g.

[0076] Example 12

[0077] Preparation of Z-N catalyst: In a 250 ml glass reactor, 3 g of the above POP-2 support containing sulfonic acid functional groups was added, 100 ml of toluene was added, and the mixture was stirred. Then, at 0 °C, 15 ml of 3M methylmagnesium chloride Grignard reagent was added, and the mixture was stirred for 2 h. After filtration, it was washed 2 times with toluene. Then, 50 ml of toluene was added, and the temperature was raised to 50 °C. 50 ml of TiCl4 was added dropwise, and the reaction was carried out for 3 h. After the reaction was completed, it was filtered, washed 3 times each with toluene and hexane, and then dried to obtain free-flowing catalyst solid component particles, denoted as Cat-4, with a Mg content of 4.2% and a Ti content of 2.7%.

[0078] Example 13

[0079] Preparation of Ziegler-Natta catalyst: In a 250 ml glass reactor, add 3 g of POP-2 support, add 100 ml of toluene, stir, then add 8 ml of 3M methylmagnesium chloride Grignard reagent at 35°C, stir for 2 hours, after filtration, wash once with toluene, then add 60 ml of toluene, dropwise add 50 ml of TiCl4 at room temperature, react for 3 hours, after the reaction is completed, filter, wash 3 times each with toluene and hexane, and after drying, obtain free-flowing catalyst solid component particles, denoted as Cat-5, with a Mg content of 4.0% and a Ti content of 2.7%.

[0080] Example 14

[0081] Preparation of Ziegler-Natta catalyst: In a 250 ml glass reactor, add 3 g of POP-2 support, add 100 ml of toluene, stir, then add 5 ml of 3M methylmagnesium chloride Grignard reagent at room temperature, stir for 2 hours, after filtration, wash 2 times with toluene, then add 60 ml of toluene, dropwise add 30 ml of TiCl4 at room temperature, react for 3 hours, after the reaction is completed, filter, wash 3 times each with toluene and hexane, and after drying, obtain free-flowing catalyst solid component particles, denoted as Cat-6, with a Mg content of 3.5% and a Ti content of 3.2%.

[0082] Example 15

[0083] Preparation of Ziegler-Natta catalyst: In a 250 ml glass reactor, add 3 g of the above POP-2-containing support, add 100 ml of toluene, stir, then add 3 ml of 3M methylmagnesium chloride Grignard reagent at 35°C, stir for 2 hours, after filtration, wash 2 times with toluene, then add 60 ml of toluene, heat to 70°C, dropwise add 30 ml of TiCl4, react for 3 hours, after the reaction is completed, filter, wash 3 times each with toluene and hexane, and after drying, obtain free-flowing catalyst solid component particles, denoted as Cat-7, with a Mg content of 2.4% and a Ti content of 2.1%.

[0084] Examples 16 - 22

[0085] Ethylene polymerization for the preparation of ultra-high molecular weight polyethylene

[0086] Example 16: 2.0 liters of dry hexane was added to a 5-liter stainless steel autoclave that had been purged with nitrogen and dried. Then, 10 ml of triethylaluminum TEA (1.0 mol / l) was added, and the stirring speed was 450 revolutions per minute. Subsequently, 30 mg of Cat-4 catalyst was added. Ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 70 °C with a stirring speed of 450 revolutions per minute for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 587 g of polyethylene product (UHMWPE-7) was obtained. The bulk density was 0.35 g / ml, and the catalyst activity was 5780 kgPE / molTi.bar.h.

[0087] Example 17: 2.0 liters of dry hexane was added to a 5-liter stainless steel autoclave that had been purged with nitrogen and dried. Then, 10 ml of triethylaluminum TEA (1.0 mol / l) was added, and the stirring speed was 450 revolutions per minute. Subsequently, 30 mg of Cat-4 catalyst was added. Ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 80 °C with a stirring speed of 450 revolutions per minute for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 675 g of polyethylene product (UHMWPE-8) was obtained. The bulk density was 0.36 g / ml, and the catalyst activity was 6650 kgPE / molTi.bar.h.

[0088] Example 18: 2.0 liters of dry hexane was added to a 5-liter stainless steel autoclave that had been purged with nitrogen and dried. Then, 5 ml of triethylaluminum TEA (1.0 mol / l) was added, and the stirring speed was 450 revolutions per minute. Subsequently, 32 mg of Cat-4 catalyst was added. Ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 60 °C with a stirring speed of 450 revolutions per minute for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 381 g of polyethylene product (UHMWPE-9) was obtained. The bulk density was 0.35 g / ml, and the catalyst activity was 3520 kgPE / molTi.bar.h.

[0089] Example 19: 2.0 liters of dry hexane was added to a 5-liter stainless steel autoclave that had been purged with nitrogen and dried. Then, 3 ml of triethylaluminum TEA (1.0 mol / l) was added, and the stirring speed was 450 revolutions per minute. Subsequently, 32 mg of Cat-4 catalyst was added. Ethylene was introduced to maintain the internal pressure of the autoclave at 1.0 MPa. Polymerization was carried out at 70 °C with a stirring speed of 450 revolutions per minute for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 842 g of polyethylene product (UHMWPE-10) was obtained. The bulk density was 0.36 g / ml, and the catalyst activity was 4670 kgPE / molTi.bar.h.

[0090] Example 20: 2.0 L of dry hexane was added to a 5 L stainless steel autoclave that had been purged with nitrogen and dried. Then, 5 mL of triethylaluminum (TEA, 1.0 mol / L) was added, and the stirring speed was 450 rpm. Then, 32 mg of Cat-5 catalyst was added, and ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 70 °C with a stirring speed of 450 rpm for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 652 g of polyethylene product (UHMWPE-11) was obtained. The bulk density was 0.35 g / mL, and the catalyst activity was 6020 kgPE / molTi.bar.h.

[0091] Example 21: 2.0 L of dry hexane was added to a 5 L stainless steel autoclave that had been purged with nitrogen and dried. Then, 5 mL of triethylaluminum (TEA, 1.0 mol / L) was added, and the stirring speed was 450 rpm. Then, 30 mg of Cat-6 catalyst was added, and ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 70 °C with a stirring speed of 450 rpm for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 584 g of polyethylene product (UHMWPE-12) was obtained. The bulk density was 0.36 g / mL, and the catalyst activity was 4850 kgPE / molTi.bar.h.

[0092] Example 22: 2.0 L of dry hexane was added to a 5 L stainless steel autoclave that had been purged with nitrogen and dried. Then, 3 mL of triethylaluminum (TEA, 1.0 mol / L) was added, and the stirring speed was 450 rpm. Then, 32 mg of Cat-7 catalyst was added, and ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 70 °C with a stirring speed of 450 rpm for 1 hour. The reaction was terminated, cooled to room temperature, and after drying, 389 g of polyethylene product (UHMWPE-13) was obtained. The bulk density was 0.33 g / mL, and the catalyst activity was 4620 kgPE / molTi.bar.h.

[0093] Table 2 Polymerization Results of Olefins in Examples 16 - 22

[0094]

[0095]

[0096] Example 23

[0097] In a 250 ml glass reactor, 130 ml of isobutanol and 14 ml of deionized water were added. Then, 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%) were added. The mixture was stirred at room temperature for 5 min, and then 1% of the total mass of the monomers of poly(propylene oxide)-poly(ethylene oxide) copolymer F127 (BASF, molecular weight 12,000) was added. At 45 °C, the mixture was stirred for 1 h to completely dissolve the stabilizer. 2.0% of AIBN based on the total mass of the monomers was added, and the temperature was raised to 70 °C and reacted for 2 h. Then the temperature was raised to 80 °C and reacted for 5 h. The stirring speed was 350 revolutions per minute. After filtration, 100 ml of the above-mentioned mixed solvent of alcohol and water was added, and 10 ml of 36.5% HCl solution by mass was added. The reaction was carried out at 50 °C for 2 h, filtered, washed 3 times with the mixed solvent of alcohol and water, washed 3 times with the mixed solvent of alcohol and water, filtered and dried to obtain 4.3 g of free-flowing porous POP-3. The specific surface area of the carrier was 228 m 2 / g, and the pore volume was 0.23 ml / g.

[0098] Example 24

[0099] Preparation of Z-N catalyst: In a 250 ml glass reactor, 3 g of the above POP-3 carrier was added, 100 ml of toluene was added and stirred. Then, 15 ml of 3M methylmagnesium chloride Grignard reagent was added at 0 °C and stirred for 2 h. After filtration, it was washed 2 times with toluene. Then 60 ml of toluene was added, the temperature was raised to 50 °C, and 50 ml of TiCl4 was added dropwise and reacted for 3 h. After the reaction was completed, it was filtered, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst solid component particles, denoted as Cat-8, with a Mg content of 4.0% and a Ti content of 2.5%.

[0100] Example 25

[0101] In a 250 ml glass reactor, 126 ml of ethanol and 14 ml of deionized water were added. Then, 4.8 g (about 5.0 ml) of divinylbenzene (Aladdin reagent, 80%) and 2.8 g of sodium p-styrenesulfonate hydrate (Aladdin reagent, 90%) were added. The mixture was stirred at room temperature for 5 min, and then 2% of the total mass of the monomers of polyvinyl alcohol PVA (PVA, polymerization degree 1750) was added. At 45 °C, the mixture was stirred for 1 h to completely dissolve the stabilizer. 2.0% of the total mass of the monomers 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 and reacted for 5 hours. The stirring speed was 350 revolutions per minute. After filtration, 100 ml of the above ethanol and water mixed solvent was added, and 10 ml of HCl solution with a mass ratio of 36.5% was added. The reaction was carried out at 50 °C for 2 h, filtered, washed 3 times with the alcohol-water mixed solvent, filtered and dried to obtain 4.8 g of free-flowing porous POP-4. The specific surface area of the carrier was 450 m 2 / g, and the pore volume was 0.41 ml / g.

[0102] Example 26

[0103] Preparation of Z-N catalyst: In a 250 ml glass reactor, 3 g of the above POP-4 carrier was added, 100 ml of toluene was added and stirred. Then, 15 ml of 3M methylmagnesium chloride Grignard reagent was added at 0 °C and stirred for 2 h. After filtration, it was washed 2 times with toluene. Then 60 ml of toluene was added, the temperature was raised to 50 °C, and 50 ml of TiCl4 was added dropwise and reacted for 3 h. After the reaction was completed, it was filtered, washed 3 times each with toluene and hexane, and dried to obtain free-flowing catalyst solid component particles, denoted as Cat-9, with a Mg content of 4.1% and a Ti content of 2.7%.

[0104] Example 27

[0105] In a 250 ml glass reactor, 126 ml of ethanol and 14 ml of deionized water were added. Then, 4.8 g (about 5.0 ml) of divinylbenzene (Aladdin reagent, 55%) and 1.8 g of 4,4'-bis(2-sulfonatostyryl)-1,1'-biphenyl (Wuhan Jinnuo Chemical Co., Ltd., >95%) were added. The mixture was stirred at room temperature for 5 min, and then 2% of the total mass of the monomers of poly(propylene oxide)-poly(ethylene oxide) copolymer F127 (BASF, molecular weight 12000) was added. At 45 °C, the mixture was stirred for 1 h to completely dissolve the stabilizer. 2.0% of AIBN based on the total mass of the monomers was added, and the temperature was raised to 70 °C. The reaction was carried out for 3 h, and then the temperature was raised to 80 °C. After reacting for 5 h, the stirring speed was 600 revolutions per minute. After filtration, 100 ml of the above ethanol and water mixed solvent was added, and 15 ml of a 10% H2SO4 solution by mass was added. The reaction was carried out at 50 °C for 2 h, washed 3 times with ethanol, filtered, and then washed 3 times with an ethanol-water mixed solvent. After filtration and drying, 4.2 g of free-flowing porous POP-5 was obtained. The specific surface area of the support was 328 m 2 / g, and the pore volume was 0.34 ml / g.

[0106] Example 28

[0107] Preparation of Z-N catalyst: In a 250 ml glass reactor, 3 g of the above POP-5 support was added, 100 ml of toluene was added, and the mixture was stirred. Then, 10 ml of 3M methylmagnesium bromide Grignard reagent was added at room temperature, and the mixture was stirred for 2 h. After filtration, it was washed 2 times with toluene. Then, 60 ml of toluene was added, and the temperature was raised to 60 °C. 40 ml of TiCl4 was added dropwise, and the reaction was carried out for 3 h. After the reaction was completed, it was filtered, washed 3 times with toluene and hexane respectively, and then dried to obtain free-flowing catalyst solid component particles, denoted as Cat-10, with a Mg content of 3.8% and a Ti content of 2.5%.

[0108] Example 29

[0109] In a 250 ml glass reactor, 126 ml of ethanol and 14 ml of deionized water were added. Then, 4.8 g (about 5.0 ml) of divinylbenzene (Aladdin reagent, 80%) and 2.5 g of sodium p-styrenesulfonate hydrate (Aladdin reagent, 90%) were added. The mixture was stirred at room temperature for 5 min, and then 2% of the total mass of the monomers of poly(propylene oxide)-poly(ethylene oxide) copolymer F127 (BASF, molecular weight 12,000) was added. After stirring at room temperature for 1 h to completely dissolve the stabilizer, 2.0% of BPO based on the total mass of the monomers was added. The temperature was raised to 70 °C and the reaction was carried out for 3 h. Then the temperature was raised to 80 °C and the reaction was carried out for 5 h. After that, the stirring speed was 600 revolutions per minute. After filtration, 100 ml of the above-mentioned ethanol and water mixed solvent was added, and 15 ml of a 10% H2SO4 solution by mass ratio was added. The reaction was carried out at 50 °C for 2 h, followed by filtration. The product was washed 3 times with the alcohol-water mixed solvent, and after filtration and drying, 4.6 g of free-flowing porous POP-6 was obtained. The specific surface area of the carrier was 560 m 2 / g, and the pore volume was 0.48 ml / g.

[0110] Example 30

[0111] Preparation of Z-N catalyst: In a 250 ml glass reactor, 3 g of the above POP-6 carrier was added, and 100 ml of toluene was added. After stirring, 15 ml of 3 M methylmagnesium chloride Grignard reagent was added at 0 °C, and the mixture was stirred for 2 h. After filtration, it was washed 2 times with toluene. Then 60 ml of toluene was added, and the temperature was raised to 50 °C. 50 ml of TiCl4 was added dropwise, and the reaction was carried out for 3 h. After the reaction was completed, it was filtered and washed 3 times each with toluene and hexane, and then dried to obtain free-flowing catalyst solid component particles, denoted as Cat-11, with a Mg content of 4.8% and a Ti content of 2.7%.

[0112] Example 31

[0113] In a 250 ml glass reactor, 130 ml of ethanol and 15 ml of deionized water were added, and 2 ml of tetrahydrofuran was added. Then, 5 ml (Aladdin reagent, 55%) (about 4.8 g) of divinylbenzene and 1.9 g of sodium vinylsulfonate (Aladdin reagent, 98%) were added. The mixture was stirred at room temperature for 5 min, and then 2% of the total mass of the monomers of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. At 45 °C, the mixture was stirred for 1 h to completely dissolve the stabilizer. 2.0% (0.132 g) of AIBN based on the total mass of the monomers was added, and the temperature was raised to 70 °C. The reaction was carried out for 2 h, and then the temperature was raised to 80 °C. After the reaction was carried out for 5 h, the stirring speed was 350 revolutions per minute. After filtration, 100 ml of the above-mentioned ethanol and water mixed solvent was added, and 10 ml of a 36.5% HCl solution by mass ratio was added. The reaction was carried out at 50 °C for 2 h, followed by filtration. The product was washed 3 times with the alcohol-water mixed solvent, and after filtration and drying, 3.9 g of free-flowing porous POP-7 was obtained. The specific surface area of the carrier was 187 m2 / g, pore volume 0.38 ml / g.

[0114] Example 32

[0115] Preparation of Z-N catalyst: In a 250 ml glass reactor, add 3 g of the above POP-7 support, add 100 ml of toluene, stir, then add 15 ml of 3 M methylmagnesium chloride Grignard reagent at 0 °C, stir for 2 hours, filter, wash once with toluene, then add 60 ml of toluene, heat up to 50 °C, dropwise add 50 ml of TiCl4, react for 3 hours, after the reaction is completed, filter, wash 3 times each with toluene and hexane, and dry to obtain free-flowing catalyst solid component particles, denoted as Cat-12, with a Mg content of 6.1% and a Ti content of 3.6%.

[0116] Example 33

[0117] In a 250 ml glass reactor, add 126 ml of isobutanol and 14 ml of deionized water, then add 4.8 g (about 5.0 ml) of divinylbenzene (Aladdin reagent, 55%) and 2.0 g of sodium 1-hexenesulfonate (Aladdin reagent, 95%), stir at room temperature for 5 min, then add 2% of the total monomer mass of polyvinyl alcohol PVA (PVA, polymerization degree 1750), stir at 45 °C for 1 h to completely dissolve the stabilizer, add 2.0% of the total monomer mass of AIBN, heat up to 70 °C, react for 3 hours, then raise the temperature to 80 °C, react for 5 hours, stir at a speed of 350 revolutions per minute, filter, add 100 ml of a mixed solvent of ethanol and water, add 10 ml of a 36.5% HCl solution by mass ratio, react at 50 °C for 2 h, filter, wash 3 times with the mixed solvent of alcohol and water, filter and dry to obtain 4.2 g of free-flowing porous POP-8. The specific surface area of the support is 249 m 2 / g, pore volume 0.24 ml / g.

[0118] Example 34

[0119] Preparation of Z-N catalyst: In a 250 ml glass reactor, add 3 g of the above POP-8 support, add 100 ml of toluene, stir, then add 10 ml of 3 M methylmagnesium chloride Grignard reagent at room temperature, stir for 2 hours, filter, wash 2 times with toluene, then add 60 ml of toluene, heat up to 50 °C, dropwise add 50 ml of TiCl4, react for 3 hours, after the reaction is completed, filter, wash 3 times each with toluene and hexane, and dry to obtain free-flowing catalyst solid component particles, denoted as Cat-13, with a Mg content of 3.5% and a Ti content of 4.5%.

[0120] Example 35

[0121] In a 250 ml glass reactor, 126 ml of ethanol and 14 ml of deionized water were added. Then, 4.8 g (about 5.0 ml) of divinylbenzene (Aladdin reagent, 80%) and 2.3 g of sodium methallylsulfonate (Aladdin reagent, 98%) were added. The mixture was stirred at room temperature for 5 min, and then 2% of the total mass of the monomers of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer. 2.0% of the total mass of the monomers of AIBN was added, and the temperature was raised to 70 °C for 3 h. Then the temperature was raised to 80 °C and reacted for 5 h. After that, the stirring speed was 350 revolutions per minute. After filtration, 100 ml of the above-mentioned ethanol and water mixed solvent was added, and 20 ml of a sulfuric acid solution with a mass ratio of 20% was added. The reaction was carried out at 50 °C for 2 h, filtered, washed 3 times with the alcohol-water mixed solvent, and after filtration and drying, 5.4 g of free-flowing porous POP-9 was obtained. The specific surface area of the carrier was 486 m 2 / g, and the pore volume was 0.46 ml / g.

[0122] Example 36

[0123] Preparation of Z-N catalyst: In a 250 ml glass reactor, 3 g of the above POP-9 carrier 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 room temperature and stirred for 2 h. After filtration, it was washed 2 times with toluene. Then 60 ml of toluene was added, and the temperature was raised to 50 °C. 50 ml of TiCl4 was added dropwise and reacted for 3 h. After the reaction was completed, it was filtered, washed 3 times each with toluene and hexane, and after drying, free-flowing catalyst component particles were obtained, denoted as Cat-14, with a Mg content of 3.9% and a Ti content of 2.4%.

[0124] Example 37

[0125] In a 250 ml glass reactor, 126 ml of ethanol and 14 ml of deionized water were added. Then, 4.8 g (about 5.0 ml) of divinylbenzene (Aladdin reagent, 80%) and 3.8 g of sodium methallylsulfonate (Aladdin reagent, 98%) were added. The mixture was stirred at room temperature for 5 min, and then 2% of the total mass of the monomers of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer. 2.0% of the total mass of the monomers of AIBN was added, and the temperature was raised to 70 °C for 3 h. Then the temperature was raised to 80 °C and reacted for 5 h. After that, the stirring speed was 350 revolutions per minute. After filtration, 100 ml of the above-mentioned ethanol and water mixed solvent was added, and 10 ml of an HCl solution with a mass ratio of 36.5% was added. The reaction was carried out at 50 °C for 2 h, filtered, washed 3 times with the alcohol-water mixed solvent, and after filtration and drying, 6.1 g of free-flowing porous POP-10 was obtained. The specific surface area of the carrier was 532 m 2 / g, and the pore volume was 0.51 ml / g.

[0126] Example 38

[0127] Preparation of Z-N catalyst: In a 250 ml glass reactor, add 3 g of the above POP-10 support, add 100 ml of toluene, stir, and then add 15 ml of 3M methylmagnesium chloride Grignard reagent at room temperature, stir for 2 hours, filter, wash twice with toluene, then add 60 ml of toluene, heat up to 50 °C, dropwise add 50 ml of TiCl4, react for 3 hours, after the reaction is completed, filter, wash three times with toluene and hexane respectively, and then dry to obtain free-flowing catalyst solid component particles, denoted as Cat-15, with a Mg content of 4.2% and a Ti content of 2.7%.

[0128] Example 39

[0129] In a 250 ml glass reactor, add 126 ml of ethanol and 20 ml of deionized water, then add 4.8 g (about 5.0 ml) of divinylbenzene (Aladdin reagent, 80%) and 2.0 g of sodium allylsulfonate (Aladdin reagent, 98%), stir at room temperature for 5 min, then add 2% of the total mass of the monomers of polyvinyl alcohol PVA (PVA, polymerization degree 1750), stir at 45 °C for 1 h to completely dissolve the stabilizer, add 2.0% of the total mass of the monomers of AIBN, heat up to 70 °C, react for 3 hours, then raise the temperature to 80 °C, react for 5 hours, with a stirring speed of 350 revolutions per minute, filter, add 100 ml of the above ethanol and water mixed solvent, add 10 ml of HCl solution with a mass ratio of 36.5%, react at 50 °C for 2 h, filter, wash three times with the alcohol-water mixed solvent, filter and dry to obtain 5.5 g of free-flowing porous POP-11. The specific surface area of the support is 382 m 2 / g, and the pore volume is 0.41 ml / g.

[0130] Example 40

[0131] Preparation of Z-N catalyst: In a 250 ml glass reactor, add 3 g of the above POP-11 support, add 100 ml of toluene, stir, and then add 15 ml of 3M methylmagnesium chloride Grignard reagent at room temperature, stir for 2 hours, filter, wash twice with toluene, then add 60 ml of toluene, heat up to 50 °C, dropwise add 50 ml of TiCl4, react for 3 hours, after the reaction is completed, filter, wash three times with toluene and hexane respectively, and then dry to obtain free-flowing catalyst solid component particles, denoted as Cat-16, with a Mg content of 4.0% and a Ti content of 2.7%.

[0132] Example 41

[0133] Preparation of Ziegler-Natta catalyst: In a 250 ml glass reactor, 3 g of POP-6 support was added, 100 ml of toluene was added, and the mixture was stirred. Then, 15 ml of 3 M dibutylmagnesium Grignard reagent was added at 0 °C, and the mixture was stirred for 2 hours. After filtration, it was washed twice with toluene. Then, 60 ml of toluene was added, the temperature was raised to 50 °C, 50 ml of TiCl4 was added dropwise, and the reaction was carried out for 3 hours. After the reaction was completed, it was filtered, washed three times with toluene and hexane respectively, and dried to obtain free-flowing catalyst solid component particles, denoted as Cat-17, with a Mg content of 4.5% and a Ti content of 2.8%.

[0134] Example 42

[0135] Preparation of Ziegler-Natta catalyst: In a 250 ml glass reactor, 3 g of the above POP-6 support 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 room temperature, and the mixture was stirred for 2 hours. After filtration, it was washed twice with toluene. Then, 60 ml of toluene was added, 50 ml of TiCl4 was added dropwise at room temperature, the temperature was raised to 100 °C, and the reaction was carried out for 3 hours. After the reaction was completed, it was filtered, washed three times with toluene and hexane respectively, and dried to obtain free-flowing catalyst solid component particles, denoted as Cat-18, with a Mg content of 5.0% and a Ti content of 2.8%.

[0136] Example 43

[0137] Preparation of Ziegler-Natta catalyst: In a 250 ml glass reactor, 3 g of the above POP-6 support was added, 100 ml of toluene was added, and the mixture was stirred. Then, 15 ml of 3 M benzylmagnesium chloride Grignard reagent was added at room temperature, and the mixture was stirred for 2 hours. After filtration, it was washed twice with toluene. Then, 60 ml of toluene was added, the temperature was raised to 50 °C, 50 ml of TiCl4 was added dropwise, and the reaction was carried out for 2 hours. After the reaction was completed, it was filtered, washed three times with toluene and hexane respectively, and dried to obtain free-flowing catalyst solid component particles, denoted as Cat-19, with a Mg content of 4.0% and a Ti content of 2.0%.

[0138] Catalysts of Examples 44 - 58 were used for ethylene polymerization

[0139] In a polymerization reactor, the prepared catalyst was used for ethylene slurry polymerization to prepare UHMWPE.

[0140] Ethylene homopolymerization: 2.0 liters of dry hexane was added to a 5-liter stainless steel autoclave that had been purged with nitrogen and dried. Then, 5 milliliters of triethylaluminum (TEA, 1.0 mol / L) was added, and the stirring speed was 450 revolutions per minute. Subsequently, 50 milligrams of the above catalyst was added, and ethylene was introduced to maintain the internal pressure of the reaction kettle at 0.6 MPa. Polymerization was carried out at a specific polymerization temperature (50 - 70)°C for 1 hour under stirring at 450 revolutions per minute. The reaction was terminated, cooled to room temperature, and after drying, a polyethylene product was obtained.

[0141] In Example 56, the cat-9 catalyst was used, the polymerization temperature was 60°C, and 0.1 g of hydrogen was added during the polymerization process, with other conditions remaining unchanged.

[0142] Table 3 Results of olefin polymerization in Examples 44 - 58

[0143]

[0144]

[0145] Polymerization conditions in Comparative Example 1: 1 L polymerization reactor, 500 ml of hexane, cat: 43 mg, Al / Ti = 300 (molar ratio), polymerization pressure 5 bar, polymerization time: 2 hours. The titanium content of the catalyst was estimated to be 1.64 mmol / g.

[0146] Polymerization conditions in Comparative Example 2: 100 ml of heptane, cat: 50 mg, Al / Ti = 300 (molar ratio), polymerization pressure 1 bar, polymerization time: 1 hour. The titanium content in the ZN3 catalyst was 2.5%.

[0147] Polymerization conditions in Comparative Example 3: 1 L polymerization reactor, 400 ml of isobutane, cat: 18 mg, Al / Ti = 190 (molar ratio), polymerization pressure 40 bar, polymerization time: 3 hours. The titanium content of the catalyst was 45 μmol Ti / g cat.

[0148] The data in the comparative examples were all from the corresponding references 1, 2, and 3.

[0149] Document 1: "Porous polyethylene spheres with nanofiber structure from Ziegler-Natta catalyst supported on porous polymer particles" in Polymer (2011; Volume 52, pages 602 - 605); Document 2: "Ethylene polymerization on polymer supported Ziegler-Natta catalyst" in J. Polym. Res. (2012; 19:9892, pages 1 - 13). Document 3: "Ultrahigh Molecular Weight Polyethylene Produced by a Bis(phenoxy-imine) Titanium Complex Supported on Latex Particles" in Journal of Polymer Science: Part A: Polymer Chemistry (2006; pages 3103 - 3113).

[0150] As shown in Table 3, the Z-N catalyst supported on the porous organic polymer carrier containing sulfonic acid functional monomer of the present invention is used for ethylene homopolymerization. The weight-average molecular weight of the obtained polyethylene product is between 2 million and 12 million, and the viscosity-average molecular weight can reach more than 7 million, which is higher than that of the FI-Ti catalyst system supported on organic carriers reported in Document 3. The Z-N catalyst supported on the organic carrier containing sulfonic acid functional monomer of the present invention has very high polymerization activity, between 1890 - 6650 kgPE / molTi.bar.h, reaching the activity level of the commercial inorganic carrier supported Z-N ultrahigh molecular weight polyethylene catalyst.

[0151] In addition, the Z-N type UHMWPE catalyst prepared in the present invention can also be used for copolymerization of ethylene and other α-olefins to prepare UHMWPE products.

[0152] Example 59

[0153] Copolymerization of ethylene and α-olefin:

[0154] 2.0 L of dry hexane was added to a 5-L stainless steel autoclave that had been purged with nitrogen and dried. Then, 5 mL of triethylaluminum (TEA, 1.0 mol / L) was added, followed by 30 mL of 1-butene. The stirring speed was 450 rpm. Next, 50 mg of Cat-9 catalyst was added, and ethylene was introduced to maintain the internal pressure of the autoclave at 0.6 MPa. Polymerization was carried out at 60 °C with a stirring speed of 450 rpm for 1 h. The reaction was terminated, cooled to room temperature, and after drying, 387 g of a polyethylene product (UHMWPE-28) was obtained. The bulk density was 0.30 g / mL, and the catalyst activity was 2290 kg PE / mol Ti·bar·h. The intrinsic viscosity η value of the polymer was 32.5, the weight-average molecular weight Mw was 9,610,000 g / mol, and the viscosity-average molecular weight Mη was 6,330,000 g / mol.

[0155] Example 60

[0156] 2.0 L of dry hexane was added to a 5-L stainless steel autoclave that had been purged with nitrogen and dried. Then, 10 mL of triethylaluminum (TEA, 1.0 mol / L) was added, followed by 30 mL of 1-butene. The stirring speed was 450 rpm. Next, 50 mg of Cat-16 catalyst was added, and ethylene was introduced to maintain the internal pressure of the autoclave at 1.0 MPa. Polymerization was carried out at 60 °C with a stirring speed of 450 rpm for 1 h. The reaction was terminated, cooled to room temperature, and after drying, 485 g of a polyethylene product (UHMWPE-29) was obtained. The bulk density was 0.30 g / mL, and the catalyst activity was 2870 kg PE / mol Ti·bar·h. The intrinsic viscosity η value of the polymer was 21.5, the weight-average molecular weight Mw was 5,190,000 g / mol, and the viscosity-average molecular weight Mη was 3,590,000 g / mol.

[0157] 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 can make various corresponding changes and modifications according to the present invention. However, these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A Ziegler-Natta type catalyst system for ethylene polymerization, characterized in that, It includes a solid-phase component and a cocatalyst. The solid-phase component includes a porous organic polymer carrier, a magnesium compound, and a titanium compound. The porous organic polymer carrier is a copolymer including divinylbenzene and a sulfonic acid group-containing functional monomer; Among them, based on the mass of the solid-phase component being 100%, the content of the magnesium compound in the solid-phase component in terms of magnesium element is 1-8%, and the content of the titanium compound in the solid-phase component in terms of titanium is 1-8%; based on 100 parts by mass of the porous organic polymer carrier, the sulfonic acid group-containing functional monomer accounts for 5-60 parts by mass; Among them, the chemical formula of the sulfonic acid group-containing functional monomer is R2HC=C(R3)R1SO3H or R2HC=C(R3)R1SO2OM. R1 is an alkylene group with 0-6 carbon atoms or a phenylene group on the main chain, and the R1 group may or may not contain chlorine, bromine, fluorine, iodine, alkyl, phenyl, or naphthalene substituents; R2 is an H atom, an alkyl group with 1-6 carbon atoms on the main chain, or a phenyl group, and the R2 group may or may not contain chlorine, bromine, fluorine, iodine, alkyl, phenyl, or naphthalene substituents; R3 is an H atom, an alkyl group with 1-6 carbon atoms on the main chain, or a phenyl group; M is a metal; If the sulfonic acid group-containing functional monomer is R2HC=C(R3)R1SO2OM, the porous organic polymer carrier needs to be acidified.

2. The Ziegler-Natta catalyst system for ethylene polymerization according to claim 1, characterized in that, The content of the sulfonic acid group-containing functional monomer in the porous organic polymer carrier is 0.5-5 mmol / g of the porous organic polymer carrier.

3. The Ziegler-Natta catalyst system for ethylene polymerization according to claim 1, characterized in that, The sulfonic acid group-containing functional monomer is at least one of sodium p-styrenesulfonate, p-styrenesulfonic acid, sodium m-styrenesulfonate, m-styrenesulfonic acid, o-styrenesulfonic acid, sodium o-styrenesulfonate, 2-methyl-4-sulfonatostyrene, 2-chloro-4-sulfonatostyrene, 2-methyl-4-sulfonic acid styrene, 2-methyl-3-sulfonatostyrene, 2-methyl-3-sulfonic acid styrene, vinyl-4-methylbenzenesulfonic acid, vinyl-4-methylbenzenesulfonate, 2-ethyl-3-sulfonatostyrene, 2-ethyl-3-sulfonic acid styrene, 4,4'-bis(2-sulfonic acid styryl)-1,1'-biphenyl, 2-(2-styryl)benzenesulfonic acid, vinylsulfonic acid, sodium vinylsulfonate, allylsulfonic acid, sodium allylsulfonate, sodium 3-chloroallylsulfonate, methacrylic acid, sodium methacrylate, 1-butenesulfonic acid, sodium 1-butenesulfonate, 1-pentenesulfonic acid, sodium 1-pentenesulfonate, 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 allylsulfonate, methacrylic acid, sodium methacrylate, 1-butenesulfonic acid, sodium 1-butenesulfonate, 1-pentenesulfonic acid, sodium 1-pentenesulfonate, 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.

4. The Ziegler-Natta catalyst system for ethylene polymerization according to claim 1, wherein The BET specific surface area of the porous organic polymer support is 100 - 600 m 2 / g, and the pore volume is greater than or equal to 0.2 ml / g; the cocatalyst is an alkylaluminum, the cocatalyst is calculated as Al, the titanium compound is calculated as Ti, and the molar ratio of the cocatalyst to the titanium compound is 5 - 500.

5. A method for preparing the Ziegler-Natta catalyst system for ethylene polymerization according to any one of claims 1-4, characterized in that, The preparation method of the solid phase component includes: Reacting the porous organic polymer carrier with the magnesium compound in an inert solvent at a reaction temperature of 0°C to 50°C for a reaction time of 15 to 120 minutes, then filtering the unreacted magnesium compound, adding it to an organic solvent containing a titanium compound, and reacting at a reaction temperature of 0°C to 80°C for a reaction time of 15 to 180 minutes to obtain the solid phase component.

6. The preparation method of the Ziegler-Natta type catalyst system for ethylene polymerization according to claim 5, characterized in that, The addition amount of the magnesium compound in terms of magnesium is 1 to 30 mmol / g of the porous organic polymer carrier, and the addition amount of the titanium compound in terms of titanium is 5 to 200 mmol / g of the porous organic polymer carrier.

7. The preparation method of the catalyst system for ethylene polymerization according to claim 5, characterized in that, The preparation method of the porous organic polymer carrier includes: Using divinylbenzene as the basic monomer and reacting it with a sulfonic acid group-containing functional monomer through free radical copolymerization to obtain the porous organic polymer carrier.

8. Application of the Z-N type catalyst system for ethylene polymerization according to any one of claims 1-4 in ethylene polymerization or ethylene copolymerization with an α-olefin to prepare ultra-high molecular weight polyethylene.

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