An organic polymer carrier, Z-N catalyst and preparation method and application thereof

Abstract

The application provides an organic polymer carrier, a Z-N catalyst and a preparation method and application thereof. The organic polymer carrier is obtained by copolymerization of monomers including divinylbenzene and unsaturated 1,3-propylene glycol ether monomers; wherein the unsaturated 1,3-propylene glycol ether monomer has a structure shown in formula I: the catalyst has good olefin insertion, stereodirectional capacity, catalyst activity and narrow molecular weight distribution and the like.

Description

Technical Field

[0001] This invention belongs to the field of catalysts, specifically relating to an organically supported ZN catalyst and its preparation method. Background Technology

[0002] Currently, industrial polypropylene catalysts mainly consist of Zn-type catalysts and metallocene catalysts, primarily producing high-isotactic polypropylene. In addition, small quantities of syndiotactic polypropylene, atactic polypropylene, and propylene-based elastomers are produced using metallocene catalysts and post-metallocene catalysts. For industrial polypropylene production plants employing slurry polymerization, bulk polymerization, or gas-phase polymerization processes, catalyst loading is necessary to control the morphology of the generated polymer and prevent reactor agglomeration or blockage.

[0003] Currently, industrially produced catalysts primarily utilize inorganic supports for supporting Zn and metallocene catalysts. Inorganic supports mainly consist of silica, magnesium chloride, ethoxymagnesium, and molecular sieves. For Zn catalysts, commonly used supports include ethoxymagnesium and anhydrous magnesium chloride, which, after reacting with TiCl4, become MgCl2-supported Zn catalysts. During catalyst preparation, electron donors or Lewis bases are typically added to regulate the microchemical environment of the catalyst's metal active sites, thereby modulating the catalyst's performance. 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 phthalate-based internal electron donors (such as diisobutyl phthalate (DIBP) and di-n-butyl phthalate (DNBP)), phenolic ester-based internal electron donors, succinate-based internal electron donors, and diether-based internal electron donors. The addition of internal electron donors or Lewis bases to the catalyst system provides a unique electronic and steric environment for the MgCl2 / TiCl4 surface, thus significantly influencing the catalyst's activity, stereoregularity, hydrogen sensitivity, and the molecular weight and distribution of the products. Furthermore, it can regulate the grain size of the MgCl2 surface and the content and distribution of Ti active centers. Over the past thirty years, most research in the development of high-performance polypropylene catalysts has focused on the design and screening of novel internal electron donors. The journal *Polymer Research*, in its article "Progress in MgCl2 supported Ziegler-Natta catalyzed polyolefin products and applications" (Vol. 28, 2021, 45), reviewed the internal electron donors used in polyolefin catalysts, including succinates (US20140200316), 1,3-diesters, diethers (US7022640), bicyclic alkane diacids, bicyclic olefin diacids (US20140005345), and silicon-containing compounds (US8088872B2). Different internal electron donors resulted in varying polymerization activities, stereoregularity, hydrogen sensitivity, and molecular weight distribution of the polypropylene catalysts. Among these, the ZN polypropylene catalyst (CN105408371A), using 1,3-diethers as the internal electron donor, exhibited products with high isotacticity and a narrow molecular weight distribution.

[0004] Inorganic supported polypropylene catalysts typically exhibit high polymerization activity, well-controlled polymer morphology, and high bulk density. However, inorganic supports often introduce additional impurities (besides Mg and Ti active centers), limiting their application in the development of high-purity polypropylene products. Organic polymer supports differ from reported inorganic supports; POP supports themselves do not introduce impurities that affect polymer performance. Furthermore, organic supports offer controllable pore structures, high specific surface areas, stable thermal properties, and ease of functionalization; high-performance or specialty polyolefin catalysts can be prepared through support design and functionalization. Porous organic supports supporting Zn catalysts have been publicly reported, typically using organic supports containing carboxylic acid, hydroxyl, cyano, or amino functional groups. However, since organic supported olefin catalysts are primarily used for polyethylene polymerization, reports on their application in propylene polymerization are scarce. For example, the paper "Sulfonatedporous organic polymer supported ZN polypropylene catalysts with high stereoregularity and broad molecular weight distribution" in Microporous and Mesoporous Materials (Vol. 343, 2022, 112151) reports a ZN catalyst supported on a POP support prepared using a styrene sulfonic acid functional monomer. The product catalyzed by this catalyst has a broad molecular weight distribution with a distribution value above 11. When an additional bisphenol ester is added as an internal electron donor, the isotacticity reaches over 98%. Summary of the Invention

[0005] To address the aforementioned problems, the present invention aims to provide an organic polymer support, a Zn catalyst, its preparation method, and its applications. This catalyst exhibits excellent olefin insertion, stereoregulation ability, catalytic activity, and narrow molecular weight distribution.

[0006] To achieve the above objectives, the present invention provides an organic polymer carrier obtained by copolymerization of monomers comprising divinylbenzene and unsaturated 1,3-propanediol ether monomers; wherein the unsaturated 1,3-propanediol ether monomers have the structure shown in Formula I:

[0007]

[0008] In Formula I, R1, R2, and R3 are each independently selected from hydrogen, chlorine, fluorine, bromine, hydroxyl, C1-C6 straight-chain alkyl groups and their derivatives, C1-C6 branched alkyl groups and their derivatives, cycloalkyl groups and their derivatives, and aromatic groups and their derivatives; x is 0-3, and when x is 0, the carbon atom of the double bond attached to R3 directly bonds to the carbon atom attached to R4; R4 is ... and 10 Straight-chain alkyl groups and their derivatives, C1-C 10 Branched alkyl groups and their derivatives, cycloalkyl groups and their derivatives, aromatic groups and their derivatives, alkoxy groups; R5 and R6 are each independently selected from C1-C6. 10 Straight-chain hydrocarbon groups and their derivatives, C1-C 10 Branched hydrocarbon groups and their derivatives, cycloalkyl groups and their derivatives, aromatic groups and their derivatives; preferably, R1 and R4 are linked together to form a ring.

[0009] According to a specific embodiment of the present invention, preferably, in Formula I, R1, R2, and R3 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, phenyl, chlorine, bromine, and hydroxyl; R4 is selected from hydrogen, methyl, n-propyl, isopropyl, phenyl, fluorine, chlorine, bromine, 3-trifluoromethyl, isobutyl, hydroxyl, benzoxy, 4-tert-butylphenyl, and tert-butyl; R5 and R6 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, and n-hexyl. , n-Octyl, phenyl, benzyl, 4-tert-butylphenyl, 2-methylhexyl, 2-ethylpentyl, 2-ethylhexyl, allyl, 2-methylallyl, 4-pentenyl, 5-hexenyl, 3-methyl-3-pentenyl, 2-ethyl-2-propenyl, 3-ethyl-3-butenyl, 6-heptenyl, 5-methyl-5-hexenyl, 7-octenyl, 4-methyl-4-pentenyl, 4-ethyl-4-pentenyl, 5-ethyl-5-hexenyl, hydroxyethyl, hydroxypropyl; x is 0, 1 or 2.

[0010] According to a specific embodiment of the present invention, preferably, in Formula I, R1, R2, and R3 are each independently selected from hydrogen, methyl, bromine, and chlorine; R4 is selected from hydrogen, methyl, isopropyl, chlorine, bromine, and isobutyl; R5 and R6 are each independently selected from methyl, ethyl, isopropyl, isobutyl, phenyl, benzyl, and 4-tert-butylphenyl; and x is 1.

[0011] According to a specific embodiment of the present invention, preferably, the unsaturated 1,3-propanediol ether monomer is selected from 2-allyl-1,3-propanediol dimethyl ether, 2-allyl-1,3-propanediol diethyl ether, 2-allyl-1,3-propanediol di-n-propyl ether, 2-allyl-1,3-propanediol diisopropyl ether, 2-allyl-1,3-propanediol di-n-butyl ether, 2-allyl-1,3-propanediol diisobutyl ether, 2-allyl-1,3-propanediol diphenyl ether, 2-(1-methylallyl)-1,3-propanediol dimethyl ether, 2-(1-methylallyl)-1,3-propanediol diethyl ether, 2-(1-methylallyl)-1,3-propanediol di-n-propyl ether, and 2-(1-methylallyl)-1,3-malonic acid. Diisopropyl ether, 2-(1-methylallyl)-1,3-propanediol di-n-butyl ether, 2-(1-methylallyl)-1,3-propanediol diisobutyl ether, 2-(1-methylallyl)-1,3-propanediol diphenyl ether, 2-allyl-2-propyl-1,3-propanediol dimethyl ether, 2-allyl-2-propyl-1,3-propanediol diethyl ether, 2-allyl-2-propyl-1,3-propanediol diisopropyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-propyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-butyl ether, 2-allyl-2-propyl-1,3-propanediol diisobutyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-pentyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-pentyl ether, 2-allyl-2-propyl-1 3-Propanediol di-n-hexyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-octyl ether, 2-allyl-2-propyl-1,3-propanediol di(2-methylpentyl) ether, 2-allyl-2-propyl-1,3-propanediol di(2-methylhexyl) ether, 2-allyl-2-propyl-1,3-propanediol di(2-ethylpentyl) ether, 2-allyl-2-propyl-1,3-propanediol di(2-ethylhexyl) ether, 2-allyl-2-propyl-1,3-propanediol di(2-ethylhexyl) ether, 2-allyl-2-propyl-1,3-propanediol diallyl ether, 2-allyl-2-propyl-1,3-propanediol di(2-methylallyl) ether, 2-allyl-2-propyl-1,3-propanediol di(4-pentenyl) ether, 2-allyl-2-propyl-1,3- Propylene glycol di(5-hexenyl) ether, 2-allyl-2-propyl-1,3-propanediol di(3-methyl-3-pentenyl) ether, 2-allyl-2-propyl-1,3-propanediol di(2-ethyl-2-propenyl) ether, 2-allyl-2-propyl-1,3-propanediol di(3-ethyl-3-butenyl) ether, 2-allyl-2-propyl-1,3-propanediol di(6-heptenyl) ether, 2-allyl-2-propyl-1,3-propanediol di(5-methyl-5-hexenyl) ether, 2-allyl-2-propyl-1,3-propanediol di(7-octenyl) ether, 2-allyl-2-propyl-1,3-propanediol di(4-methyl-4-pentenyl) ether, 2-allyl-2-propyl-1,3-propanediol di(4-methyl-4-pentenyl) ether, 2-allyl-2-propyl-1,3-Propanediol di(4-ethyl-4-pentenyl) ether, 2-allyl-2-propyl-1,3-propanediol di(5-ethyl-5-hexenyl) ether, 2-allyl-2-propyl-1,3-propanediol diphenyl ether, 2-allyl-2-methyl-1,3-propanediol dibenzyl ether, 2-allyl-2-methyl-1,3-propanediol dimethyl ether, 2-allyl-2-methyl-1,3-propanediol diethyl ether, 2-allyl-2-methyl-1,3-propanediol di-n-propyl ether, 2-allyl-2-methyl-1,3-propanediol diisopropyl ether, 2-allyl-2-methyl-1,3-propanediol di-n-butyl ether, 2-allyl-2-methyl-1,3-propanediol diiso ... 3-Propanediol di-n-pentyl ether, 2-allyl-2-methyl-1,3-propanediol di-n-hexyl ether, 2-allyl-2-methyl-1,3-propanediol di-n-octyl ether, 2-allyl-2-methyl-1,3-propanediol di(2-methylpentyl) ether, 2-allyl-2-methyl-1,3-propanediol di(2-methylhexyl) ether, 2-allyl-2-methyl-1,3-propanediol di(2-ethylpentyl) ether, 2-allyl-2-methyl-1,3-propanediol di(2-ethylhexyl) ether, 2-allyl-2-methyl-1,3-propanediol diphenyl ether, 2-allyl-2-isopropyl-1,3-propanediol dimethyl ether, 2-allyl-2-isopropyl-1,3-propanediol diethyl ether, 2-allyl-2- Isopropyl-1,3-propanediol di-n-propyl ether, 2-allyl-2-isopropyl-1,3-propanediol diisopropyl ether, 2-allyl-2-isopropyl-1,3-propanediol di-n-butyl ether, 2-allyl-2-isopropyl-1,3-propanediol diisobutyl ether, 2-allyl-2-isopropyl-1,3-propanediol di-n-pentyl ether, 2-allyl-2-isopropyl- 1,3-Propanediol dihexyl ether, 2-allyl-2-isopropyl-1,3-propanediol diphenyl ether, 2-allyl-2-isopropyl-1,3-propanediol dibenzyl ether, 2-(3-cyclopentenyl)-1,3-propanediol dimethyl ether, 2-(3-cyclopentenyl)-1,3-propanediol diethyl ether, 2-(3-cyclopentenyl)-1,3-propanediol diisopropyl ether Ethers, 2-(3-cyclopentenyl)-1,3-propanediol di-n-butyl ether, 2-(3-cyclopentenyl)-1,3-propanediol diisobutyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propanediol dimethyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propanediol diethyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propanediol diisopropyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propanediol di-n-butyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propanediol diphenyl ether, 2-allyl-2-phenyl-1,3-propanediol dimethyl ether, 2-allyl-2-phenyl-1,3-propanediol diethyl ...3-Propanediol diisopropyl ether, 2-Allyl-2-phenyl-1,3-propanediol diphenyl ether, 2-Allyl-2-phenyl-1,3-propanediol dibenzyl ether, 2-(1-chlorovinyl)-2-propyl-1,3-propanediol dimethyl ether, 2-(1-hydroxyallyl)-2-propyl-1,3-propanediol dimethyl ether, 2-Allyl-2-propyl-1,3-propanediol dihydroxyethyl ether, 2-Allyl-2-propyl-1,3-propanediol dihydroxypropyl ether, 2-Allyl-2-chloro-1,3-propanediol diethyl ether, 2-Allyl-2-chloro-1,3-propanediol diisopropyl ether, 2-Allyl-2-chloro-1,3-propanediol diisobutyl ether, 2-Allyl-2-chloro-1,3-propanediol di-n- ... propyl-2-fluoro-1,3-propanediol diethyl ether, 2-allyl-2-fluoro-1,3-propanediol diisopropyl ether, 2-allyl-2-fluoro-1,3-propanediol diisobutyl ether, 2-allyl-2-fluoro-1,3-propanediol di-n-butyl ether, 2-allyl-2-bromo-1,3-propanediol diisopropyl ether, 2-allyl-2-bromo-1,3-propanediol di(4-tert-butylphenyl) ether, 2-allyl-2-(3-trifluoromethyl)-1,3-propanediol diethyl ether, 2-allyl-2-(3-trifluoromethyl-propyl)-1,3-propanediol di-n-butyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-propanediol dimethyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol dimethyl ether Diethyl ether of alcohol, 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diisopropyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol di-n-butyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diphenyl ether, 2-allyl-2-hydroxy-1,3-propanediol dimethyl ether, 2-allyl-2-hydroxy-1,3-propanediol diethyl ether, 2-allyl-2-hydroxy-1,3-propanediol diisobutyl ether, 2-allyl-2-hydroxy-1,3-propanediol dipentyl ether, 2-allyl-2-hydroxy-1,3-propanediol diphenyl ether, 2-allyl-2-phenyl-1,3-propanediol diisobutyl ... 3-Propanediol dipentyl ether, 2-allyl-2-benzoxy-1,3-propanediol dimethyl ether, 2-allyl-2-benzoxy-1,3-propanediol diethyl ether, 2-allyl-2-benzoxy-1,3-propanediol diisopropyl ether, 2-allyl-2-benzoxy-1,3-propanediol diisobutyl ether, 2-allyl-2-benzoxy-1,3-propanediol di-n-butyl ether, 2-allyl-2-benzoxy-1,3-propanediol diphenyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,3-propanediol dimethyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,3-propanediol diethyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,3-propanediol diethyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,One or more of the following: 3-propanediol di-n-butyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,3-propanediol diphenyl ether, 2-(1-chloroallyl)-2-tert-butyl-1,3-propanediol diphenyl ether, 2-(1-chloroallyl)-2-isobutyl-1,3-propanediol diisopropyl ether, and 2-allyl-2-methoxy-1,3-propanediol diisopropyl ether.

[0012] According to a specific embodiment of the present invention, preferably, based on the organic polymer carrier mass of 100%, the mass fraction of the unsaturated 1,3-propanediol ether monomer is 20-60%; the content of functional monomers in the carrier is determined by the amount of divinylbenzene and unsaturated 1,3-propanediol ether functional monomers added.

[0013] The present invention also provides a method for preparing the above-mentioned organic polymer carrier, which includes the following steps: using a monomer comprising the divinylbenzene, the unsaturated 1,3-propanediol ether monomer and an additional monomer as raw materials, the organic polymer carrier is obtained by copolymerization; the mass ratio of the additional monomer to divinylbenzene is 0-1:1; the mass ratio of the unsaturated 1,3-propanediol ether monomer to divinylbenzene is 0.2-2:1.

[0014] According to a specific embodiment of the present invention, preferably, in the above preparation method, the organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization.

[0015] According to a specific embodiment of the present invention, preferably, the organic polymer carrier is prepared by the dispersion polymerization method, which includes the following steps: adding divinylbenzene, unsaturated 1,3-propanediol ether monomers, and additional monomers to a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, and reacting at 50-80°C for 5-12 hours to obtain the organic polymer carrier, denoted as POP-(ROR)2; more preferably, the obtained organic polymer carrier can be further washed with a dispersion solvent to remove impurities and dried; the obtained organic carrier has a narrow dispersion and good flowability.

[0016] According to a specific embodiment of the present invention, preferably, in the above preparation method, the additional monomer includes one or more of styrene, alkyl-substituted styrene, chloromethyl-substituted styrene, methacrylic acid, methacrylate, and hydroxyalkyl methacrylate, such as hydroxyethyl methacrylate.

[0017] According to a specific embodiment of the present invention, preferably, in the above preparation method, the dispersing solvent includes a C1-C4 alcohol or a mixed solvent of a C1-C4 alcohol and water; in the mixed solvent, the mass ratio of alcohol to water is 5-15:1.

[0018] According to a specific embodiment of the present invention, preferably, in the above preparation method, the C1-C4 alcohol includes one or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol.

[0019] According to a specific embodiment of the present invention, preferably, in the above preparation method, the dispersing solvent further includes an additional solvent, more preferably, the additional solvent includes one or more of ethyl acetate, methyl formate, butyl acetate, and tetrahydrofuran, which can further adjust the solubility parameters of the solvent system, thereby controlling the pore structure and morphology of the prepared carrier.

[0020] According to a specific embodiment of the present invention, preferably, in the above preparation method, the mass ratio of the total amount of monomer added to the mass of the dispersing solvent is 1:5-20, so that the system is uniformly dispersed.

[0021] According to a specific embodiment of the present invention, preferably, in the above preparation method, the stabilizer is polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer.

[0022] According to a specific embodiment of the present invention, preferably, in the above preparation method, the weight-average molecular weight of the stabilizer is 1000-100000.

[0023] According to a specific embodiment of the present invention, preferably, in the above preparation method, the mass ratio of the amount of stabilizer added to the total amount of monomer added is 0.5-5:100.

[0024] According to a specific embodiment of the present invention, preferably, in the above preparation method, the initiator is azobisisobutyronitrile (AIBN) and / or benzoyl peroxide (BPO).

[0025] According to a specific embodiment of the present invention, preferably, in the above preparation method, the mass ratio of the amount of initiator added to the total amount of monomer added is 0.5-3:100.

[0026] According to a specific embodiment of the present invention, preferably, in the above preparation method, the divinylbenzene is a pretreated divinylbenzene, and the pretreatment is to remove the polymerization inhibitor.

[0027] The present invention also provides a ZN catalyst, wherein the raw material composition, calculated as 100% by mass of the ZN catalyst, includes 60-85 wt% of the organic polymer support, 1-5 wt% of magnesium compound calculated as magnesium element, 1-5 wt% of titanium compound calculated as titanium element, and 0-5 wt% of internal electron donor.

[0028] According to a specific embodiment of the present invention, preferably, the content of the organic polymer carrier is 65-80 wt%, the content of magnesium is 2-5 wt%, and the content of titanium is 2-5 wt%.

[0029] According to a specific embodiment of the present invention, preferably, the magnesium compound is RMgX or R'MgR"; wherein R, R', and R" are each independently selected from C1-C8 alkyl groups and their derivatives, aryl groups and their derivatives, alkoxy groups and their derivatives, and X is fluorine, chlorine, bromine, or iodine.

[0030] According to a specific embodiment of the present invention, preferably, R, R', and R'" are each independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl, and substituted phenyl.

[0031] According to a specific embodiment of the present invention, preferably, the magnesium compound is one or a combination of two or more of alkyl magnesium halide compounds, alkyl magnesium compounds, and alkoxy magnesium halide compounds, more preferably an alkyl chloride magnesium compound.

[0032] According to a specific embodiment of the present invention, preferably, the magnesium compound includes one or more of the following: 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, dipropyl magnesium, dibutyl magnesium, and ethoxy magnesium chloride; after the magnesium compound is contacted with the organic polymer carrier, a porous organic carrier treated with magnesium compound is prepared, denoted as POP-(ROR)2...MgX.

[0033] According to a specific embodiment of the present invention, preferably, the titanium compound is titanium tetrachloride; the porous organic support (POP-(ROR)2...MgX) treated with the magnesium compound is further reacted with titanium tetrachloride to obtain the ZN catalyst, denoted as POP-(ROR)2...MgX / TiCl4.

[0034] The ZN catalyst of the present invention may selectively incorporate an additional internal electron donor (ID), and the resulting ZN catalyst is denoted as POP-(ROR)2...MgX / TiCl4 / ID; according to a specific embodiment of the present invention, preferably, the internal electron donor is one or a combination of two or more of diester compounds, diphenol ester compounds, diol ester compounds, succinate compounds, and diether compounds.

[0035] According to a specific embodiment of the present invention, preferably, the internal electron donor includes one or a combination of two or more of the following: diisobutyl phthalate (DIBP), di-n-butyl phthalate (DNBP), 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl methyl ester (IAIPPDB), and 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether (IAIPDMP).

[0036] This invention also provides a method for preparing the above-mentioned ZN catalyst, which includes the following steps:

[0037] Under anhydrous and oxygen-free conditions, the organic polymer support is added to an inert solvent, followed by the magnesium compound. After reacting at 0℃-50℃ for 15-120 minutes, the unreacted magnesium compound is filtered out. Then, an inert solvent and titanium tetrachloride are added, and the reaction is carried out at 0℃-80℃ for 15-180 minutes. Finally, the internal electron donor is added, and the reaction is carried out at 50℃-120℃ for 15-180 minutes. The mixture is then washed with an inert solvent to obtain the ZN catalyst.

[0038] In the ZN catalyst of the present invention, the content of the functional monomer (unsaturated 1,3-propanediol ether monomer) of the organic polymer support is generally 0.5 mmol / g support to 5 mmol / g support, preferably 1 mmol / g support to 4 mmol / g support; the content of the functional monomer is usually controlled during the preparation of the support by the ratio of the functional monomer to the divinylbenzene (DVB) monomer; the ratio of the amount of magnesium compound reagent added (based on the molar amount of magnesium Mg) to the amount of support is 1 mmol / g support to 30 mmol / g support, preferably 3 mmol / g support to 20 mmol / g support; an excess of Ti metal compound, such as TiCl4, is usually included for catalyst loading, and the amount of Ti metal compound added (based on the molar amount of titanium Ti) is generally 5 mmol / g support to 200 mmol / g support, preferably 50 mmol / g support to 150 mmol / g support; the ratio of the additional internal electron donor to the support is 0 to 0.3 g internal electron donor / g support.

[0039] The present invention also provides a ZN catalyst system, which comprises the ZN catalyst, an external electron donor, and a co-catalyst.

[0040] According to a specific embodiment of the present invention, preferably, the external electron donor includes a silane-based external electron donor.

[0041] According to a specific embodiment of the present invention, preferably, the silane-based external electron donor includes one or more combinations of cyclohexylmethyldimethoxysilane (C external donor), dicyclopentenedimethoxysilane (D external donor), diisopropyldimethoxysilane (P external donor), diisobutyldimethoxysilane (B external donor), and tetraethoxysilane (TEOS).

[0042] According to a specific embodiment of the present invention, preferably, the molar ratio of silicon in the silane-based external electron donor to titanium in the ZN catalyst is 1-50.

[0043] According to a specific embodiment of the present invention, preferably, the co-catalyst comprises an alkyl aluminum compound, wherein the alkyl aluminum compound is Al(R”’)3, and R”’ is a C1-C6 alkyl group; in addition, the alkyl aluminum compound can also be used as a purifying agent for the polymerization reaction system.

[0044] According to a specific embodiment of the present invention, preferably, R”' is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl.

[0045] According to a specific embodiment of the present invention, preferably, the co-catalyst is triethylaluminum.

[0046] According to a specific embodiment of the present invention, preferably, the molar ratio of aluminum in the alkylaluminum compound to titanium in the ZN catalyst is 10-500.

[0047] The present invention also provides the application of the above-mentioned ZN catalyst or the above-mentioned ZN catalyst system in olefin polymerization.

[0048] According to a specific embodiment of the present invention, preferably, the olefin polymerization is ethylene or propylene homopolymerization, propylene-ethylene copolymerization, or α-olefin copolymerization.

[0049] According to a specific embodiment of the present invention, preferably, the α-olefin includes one or more of butene, isobutene, pentene, hexene, octene, and 4-methyl-1-pentene.

[0050] According to a specific embodiment of the present invention, preferably, the olefin polymerization is gas-phase polymerization, bulk polymerization or slurry polymerization.

[0051] According to a specific embodiment of the present invention, preferably, the reaction temperature of the slurry polymerization is 30-80℃ and the reaction pressure is 0.1-2.0 MPa.

[0052] According to a specific embodiment of the present invention, preferably, the solvent for the slurry polymerization is C5-C. 10 The alkane, more preferably hexane.

[0053] According to a specific embodiment of the present invention, preferably, the reaction pressure of the bulk polymerization is 2.8-4.0 MPa, and the reaction temperature is 68-72°C. Hydrogen is typically used during the polymerization process to adjust the polymer molecular weight or melt index.

[0054] The organic polymer support prepared in this invention uses unsaturated 1,3-propanediol ether monomers suitable for free radical polymerization. By selecting a solvent system with appropriate solubility parameters, dispersion polymerization is employed to prepare a POP support with excellent specific surface area, pore volume, bulk density, and flowability. Due to the addition of the 1,3-propanediol ether functional groups in the support POP-(ROR)2, the microchemical environment of the Ti and Mg active centers is controlled, resulting in a catalyst with excellent olefin insertion, stereoregulation ability, catalyst activity, and narrow molecular weight distribution. Furthermore, the catalyst exhibits good olefin copolymerization properties. During catalyst preparation, the addition of an internal electron donor is not required (alternative addition is optional). During propylene polymerization, the addition of a silane-based external electron donor and a triethylaluminum co-catalyst results in a catalyst with good polymerization activity and a high polymer isotacticity, reaching over 98%. Additionally, the product has a narrow molecular weight distribution, ranging from 4 to 7.

[0055] The organic polymer-supported Zn olefin polymerization catalyst system of this invention requires the addition of an external electron donor during polymerization, and the two must be properly matched to achieve the excellent performance of high catalytic activity and high orientation. Typically, the co-catalyst AlEt3 can complex with the internal electron donor, causing the Ti atoms to become unstable and reoccupy the random active sites complexed by the internal electron donor, resulting in a decrease in the catalyst's orientation. Adding an external electron donor allows it to preferentially bind to AlEt3, preventing the internal electron donor from detaching and reducing the amount of internal electron-donating compound removed by AlEt3, thus ensuring the stability of the stereoactive center. Therefore, additional external electron donors are needed during polymerization to ensure that the prepared polymer has high isotacticity. Detailed Implementation

[0056] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0057] In this invention, divinylbenzene (DVB) can be a commercially available monomer with a DVB content of 55% or 80%. The monomer must be pretreated before use to remove the polymerization inhibitor. There are many existing methods for removing the polymerization inhibitor. For example, divinylbenzene and styrene can be washed with NaOH solution and distilled water. Additional monomers such as hydroxyethyl methacrylate can be used to remove the polymerization inhibitor using a neutral alumina column before use.

[0058] There are many methods for preparing unsaturated 1,3-propanediol ethers in this invention. It can be prepared by reacting unsaturated propylene glycol with the corresponding chloroalkanes, according to existing technology (see reference: Effect of multi-ethers and conventional alkoxysilanes as external donors on the 4th generation Ziegler-Natta catalysts for propylene polymerization, Mirjahanmardi S. et al., Polymer Science, Series B, 2016, Vol. 58, No. 6, pp. 619–628).

[0059] The specific surface area of ​​the organic polymer carrier prepared by this invention was tested using the BET nitrogen adsorption method on a Nova 2000e, and the specific surface area of ​​the carrier prepared by this invention was controlled to be greater than 100 m². 2 / g, usually controlled between 100-600m 2 The pore volume is greater than 0.2 ml / g, with a value between / g.

[0060] The molecular weight and distribution of the polymers prepared by olefin polymerization in this invention were obtained by gel permeation chromatography (GPC) using PolymerCharts; the isotacticity of the polymers was obtained by n-heptane extraction testing (referencing standard GB / T 2412-2008). The content of internal electron donors could be determined by extraction and gas chromatography.

[0061] Preparation of unsaturated 1,3-propanediol ether functional monomers

[0062] Preparation Example 1

[0063] This preparation example provides a 2-allyl-2-methyl-1,3-propanediol dimethyl ether monomer, which is prepared by the following steps:

[0064] All reactions were carried out under dry nitrogen protection. 3.4 g of 2-allyl-2-methyl-1,3-propanediol (CAS: 25462-37-7) was dissolved in 80 ml of tetrahydrofuran solvent in a 250 ml reactor. In another 250 ml reactor, 5.2 g of NaH and 60 ml of THF were added and stirred until homogeneous. The temperature was maintained at 0°C. Then, the THF solution containing 2-allyl-2-methyl-1,3-propanediol was slowly added dropwise to the reactor. After the addition was complete, the reaction was carried out at room temperature (25°C) for 2 hours. The reaction temperature was then lowered to 0°C, and 7.5 g of iodomethane was added. The reaction was carried out at 35°C for 3 hours. After the reaction was complete, the reaction solution was washed with deionized water, and the reactants were extracted with diethyl ether, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure to obtain 2-allyl-2-methyl-1,3-propanediol dimethyl ether in 85% yield.

[0065] Preparation Example 2

[0066] This preparation example provides a 2-allyl-2-methyl-1,3-propanediol diphenyl ether monomer, which is prepared by the following steps:

[0067] 3.8 g of 2-allyl-2-methyl-1,3-propanediol was dissolved in 80 ml of tetrahydrofuran solvent in a 250 ml reactor. In another 250 ml reactor, 5.2 g of NaH and 60 ml of THF were added and stirred until evenly dispersed. The temperature was maintained at 0 °C. Then, the THF solution containing 2-allyl-2-methyl-1,3-propanediol was slowly added dropwise to the reactor. After the addition was complete, the reaction was carried out at room temperature for 2 hours. Then, the reaction temperature was lowered to 0 °C, and 9.7 g of benzene iodide was added. The reaction was carried out at 35 °C for 3 hours. After the reaction was complete, the reaction solution was washed with deionized water, and the reactants were extracted with diethyl ether. The mixture was then dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure to obtain 2-allyl-2-methyl-1,3-propanediol diphenyl ether, with a yield of 91%.

[0068] Preparation Example 3

[0069] This preparation example provides a 2-allyl-2-bromo-1,3-propanediol diisopropyl ether monomer, which is prepared by the following steps:

[0070] (1) Preparation of 2-allyl-2-bromo-1,3-propanediol (Reference: Total Synthesis of (±)-Acetomycin and Design of Esterase-Resistant Analogs, Uenishi J. et al., Chem. Pharm. Bull. 1999, Vol. 47, No. 4, pp. 517-523). It was prepared by reduction of 2-allyl-2-bromo-maleic acid diethyl ester (CAS: 78331-59-6) with LiAlH4: 8.0 g of 2-allyl-2-bromo-maleic acid diethyl ester and 150 ml of diethyl ether solvent were added to a 250 ml reactor, the temperature was lowered to -20 °C, 1.8 g of LiAlH4 was added, the mixture was stirred and dispersed evenly, and the reaction was carried out for 3 hours. After filtration and vacuum distillation, 2-allyl-2-bromo-1,3-propanediol was obtained with a yield of 89%.

[0071] (2) 3.5 g of 2-allyl-2-bromo-1,3-propanediol was dissolved in 80 ml of tetrahydrofuran solvent in a 250 ml reaction vessel. 5.8 g of NaH and 60 ml of THF were added to another 250 ml reaction vessel. The mixture was stirred and dispersed evenly, and the temperature was kept at 0 °C. Then, the above-mentioned THF solution containing 2-allyl-2-bromo-1,3-propanediol was slowly added dropwise to the reactor. After the addition was complete, the reaction was carried out at room temperature for 2 hours. Then, the reaction temperature was lowered to 0 °C, and 7.5 g of isopropane iodide was added. The reaction was carried out at 35 °C for 3 hours. After the reaction was complete, the reaction solution was washed with deionized water, and the reactants were extracted with diethyl ether. Then, the mixture was dried with anhydrous sodium sulfate, filtered, and distilled under reduced pressure to obtain 2-allyl-2-bromo-1,3-propanediol diisopropyl ether with a yield of 83%.

[0072] Preparation Example 4

[0073] This preparation example provides a 2-allyl-2-bromo-1,3-propanediol di(4-tert-butylphenyl) ether monomer, which is prepared by the following steps:

[0074] 3.5 g of 2-allyl-2-bromo-1,3-propanediol was dissolved in 100 ml of tetrahydrofuran solvent in a 250 ml reactor. In another 250 ml reactor, 5.6 g of NaH and 60 ml of THF were added and stirred until uniformly dispersed. The temperature was maintained at 0 °C. Then, the THF solution containing 2-allyl-2-bromo-1,3-propanediol was slowly added dropwise to the reactor. After the addition was complete, the reaction was carried out at room temperature for 2 hours. Then, the reaction temperature was lowered to 0 °C, and 16.5 g of 4-tert-butylphenyl iodide (CAS: 35779-04-5) was added. The reaction was carried out at 35 °C for 3 hours. After the reaction was complete, the reaction solution was washed with deionized water, and the reactants were extracted with diethyl ether, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure to obtain 2-allyl-2-bromo-1,3-propanediol di(4-tert-butylphenyl) ether, with a yield of 87%.

[0075] Preparation Example 5

[0076] This preparation example provides a 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diisopropyl ether monomer, which is prepared by the following steps:

[0077] (1) Preparation of 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol (Total Synthesis of (±)-Acetomycin and Design of Esterase-Resistant Analogs, Uenishi J. et al., Chem. Pharm. Bull. 1999, Vol. 47, No. 4, pp. 517-523) was prepared by reduction of 2-(1-chloroallyl)-2-isobutylmaleic acid (CAS: 100054-01-1) with LiAlH4: 8.0 g of 2-(1-chloroallyl)-2-isobutylmaleic acid and 150 ml of diethyl ether solvent were added to a 250 ml reactor, the temperature was lowered to -20 °C, and 2.0 g of... LiAlH4 was stirred and dispersed evenly, reacted for 3 hours, filtered, and distilled under reduced pressure to obtain 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol, with a yield of 87%.

[0078] (2) 4.0 g of 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol was dissolved in 80 ml of tetrahydrofuran solvent in a 250 ml reactor. 6.5 g of NaH and 60 ml of THF were added to another 250 ml reactor. The mixture was stirred and dispersed evenly, and the temperature was maintained at 0 °C. Then, the above-mentioned THF solution containing 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol was slowly added dropwise to the reactor. After the addition was complete, the reaction was carried out at room temperature for 2 hours. Then, the reaction temperature was lowered to 0 °C, and 8.2 g of 2-iodopropane was added. The reaction was carried out at 35 °C for 3 hours. After the reaction was complete, the reaction solution was washed with deionized water, and the reactants were extracted with diethyl ether. Then, the mixture was dried with anhydrous sodium sulfate, filtered, and distilled under reduced pressure to obtain 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diisopropyl ether with a yield of 83%.

[0079] Example 1

[0080] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0081] (1) Preparation of porous organic polymer carriers:

[0082] In a 250 mL glass reactor, 90 mL of ethanol, 10 mL of deionized water, and 15 mL of tetrahydrofuran were added. Then, 6.0 g of divinylbenzene (Aladdin reagent, 55%) and 2.0 g of 2-allyl-2-methyl-1,3-propanediol dimethyl ether were added. The mixture was stirred at room temperature for 5 min. Next, 2% (by monomer weight) of polyvinyl alcohol (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer. Then, 2.0% (0.15 g) of AIBN (by monomer weight) was added. The temperature was raised to 70 °C and reacted for 3 h. The temperature was then raised to 80 °C and reacted for 12 h, with a stirring speed of 350 rpm. After filtration, the mixture was washed three times with 100 mL of a 9:1 volume ratio of ethanol and water. After filtration and drying, 5.1 g of free-flowing porous organic polymer carrier POP-1 was obtained. The specific surface area of ​​the carrier was 187 m². 2 / g, pore volume 0.21ml / g;

[0083] (2) Preparation of ZN catalyst:

[0084] In a 250 ml glass reactor, 2 g of the carrier POP-1 prepared from the functional monomer 2-allyl-2-methyl-1,3-propanediol dimethyl ether was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. Then, 50 ml of toluene was added, and 50 ml of TiCl4 was added dropwise at room temperature. The mixture was heated to 60 °C and reacted for 2 hours. After filtration, the mixture was washed three times each with toluene and hexane. After drying, free-flowing catalyst particles were obtained, denoted as Cat-1. The catalyst Cat-1 had a Mg content of 3.0%, a titanium content of 3.8%, and an organic polymer carrier content of 75%.

[0085] Example 2

[0086] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0087] (1) Preparation of porous organic polymer carriers:

[0088] In a 250 ml glass reactor, 100 ml of ethanol, 10 ml of deionized water, and 15 ml of tetrahydrofuran were added. Then, 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 3.2 g of 2-allyl-2-methyl-1,3-propanediol diphenyl ether were added. The mixture was stirred at room temperature for 5 min. Then, 2% of the monomer mass of polyvinyl alcohol (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer. Then, 2.0% of the monomer mass of AIBN was added, and the temperature was raised to 70 °C and reacted for 3 h. The temperature was then raised to 80 °C and reacted for 12 h, with a stirring speed of 350 rpm. After filtration, the mixture was washed three times with 1000 ml of a 9:1 volume ratio of ethanol and water. After filtration and drying, 6.1 g of free-flowing porous organic polymer carrier POP-2 was obtained. The specific surface area of ​​the carrier was 475 m². 2 / g, pore volume 0.63ml / g;

[0089] (2) Preparation of ZN catalyst:

[0090] In a 250 ml glass reactor, 2 g of the POP-2 support prepared from the functional monomer of 2-allyl-2-methyl-1,3-propanediol diphenyl ether was added, along with 100 ml of toluene. The mixture was stirred, and then 8 ml of 3M methylmagnesium chloride Grignard reagent was added at 5 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. Then, 50 ml of toluene was added, and 35 ml of TiCl4 was added dropwise at room temperature. The temperature was raised to 80 °C, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added again. The mixture was reacted at 80 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-2. The catalyst Cat-2 had a Mg content of 2.7%, a titanium content of 2.5%, and an organic polymer support content of 81%.

[0091] Example 3

[0092] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0093] ZN catalyst preparation: In a 250 ml glass reactor, 2 g of the above-prepared support POP-2 was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M benzyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, and 40 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, then raised to 80 °C and carried out for 3 hours. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The reaction was carried out at 80 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-3. The catalyst Cat-3 had a Mg content of 3.2%, a titanium content of 2.4%, and an organic polymer support content of 78%.

[0094] Example 4

[0095] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0096] (1) Preparation of porous organic polymer carriers:

[0097] In a 250 ml glass reactor, 100 ml of ethanol, 20 ml of water, and 15 ml of ethyl acetate were added. Then, 6.0 g of divinylbenzene (Aladdin reagent, 80%) and 3.0 g of 2-allyl-2-bromo-1,3-propanediol diisopropyl ether were added. The mixture was stirred at room temperature for 5 min. Next, 2% of the monomer mass of F127, a block copolymer of ethylene oxide and propylene oxide, was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer. Then, 2.0% of the monomer mass of benzoyl peroxide (BPO) was added. The temperature was raised to 70 °C and reacted for 3 h. The temperature was then raised to 80 °C and reacted for 8 h, with a stirring speed of 550 rpm. After filtration, the mixture was washed three times with 100 ml of a 9:1 volume ratio of ethanol and water. After filtration and drying, 7.1 g of free-flowing porous organic polymer carrier POP-3 was obtained. The specific surface area of ​​the carrier was 283 m². 2 / g, pore volume 0.37ml / g;

[0098] (2) Preparation of ZN catalyst:

[0099] In a 250 ml glass reactor, 3 g of the carrier POP-3, prepared by polymerization of the functional monomer 2-allyl-2-bromo-1,3-propanediol diisopropyl ether, was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. 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 2 hours. The temperature was then raised to 80 °C, and the reaction was carried out for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-4. The catalyst Cat-4 had a Mg content of 4.2%, a titanium content of 4.0%, and an organic polymer carrier content of 72%.

[0100] Example 5

[0101] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0102] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of the support POP-3 prepared by polymerization of the functional monomer 2-allyl-2-bromo-1,3-propanediol diisopropyl ether was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature. The mixture was stirred for 3 hours, filtered, washed twice with toluene, and then 50 ml of toluene was added. The temperature was then raised to 50 °C, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.25 g of diisobutyl phthalate internal electron donor was added, and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-5. The catalyst Cat-5 had a Mg content of 2.8%, a titanium content of 3.7%, an internal electron donor content of 2.1%, and an organic polymer support content of 73%.

[0103] Example 6

[0104] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0105] (1) Preparation of porous organic polymer carriers:

[0106] In a 250 ml glass reactor, 90 ml of ethanol, 10 ml of water, and 30 ml of butyl acetate were added. Then, 6.0 g of divinylbenzene (Aladdin reagent, 55%) and 3.0 g of 2-allyl-2-bromo-1,3-propanediol di(4-tert-butylphenyl) ether were added. The mixture was stirred at room temperature for 5 min. Then, 5% of the monomer mass of F127, a block copolymer of ethylene oxide and propylene oxide, was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer. Then, 2.0% of the monomer mass of AIBN was added, and the temperature was raised to 70 °C and reacted for 3 h. The temperature was then raised to 80 °C and reacted for 8 h, with a stirring speed of 600 rpm. After filtration, the mixture was washed three times with 100 ml of a 9:1 volume ratio of ethanol and water. After filtration and drying, 5.8 g of free-flowing porous organic polymer carrier POP-4 was obtained. The specific surface area of ​​the carrier was 272 m². 2 / g, pore volume 0.51ml / g;

[0107] (2) Preparation of ZN catalyst: In a 250 ml glass reactor, 3 g of the support POP-4 prepared from the functional monomer of 2-allyl-2-bromo-1,3-propanediol di(4-tert-butylphenyl) ether was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M butylmagnesium bromide Grignard reagent was added at 35 °C. The mixture was stirred for 2 hours, filtered, washed twice with toluene, and then 50 ml of toluene was added. The temperature was then raised to 50 °C, and 30 ml of TiCl4 was added dropwise. The mixture was reacted for 2 hours, and then the temperature was raised to 80 °C. The mixture was reacted for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-6. The catalyst Cat-6 had a Mg content of 2.7%, a titanium content of 2.4%, and an organic polymer support content of 79%.

[0108] Example 7

[0109] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0110] (1) Preparation of porous organic polymer carriers:

[0111] In a 250 ml glass reactor, 110 ml of ethanol, 12 ml of water, and 20 ml of tetrahydrofuran were added. Then, 6.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.5 g of 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diisopropyl ether were added. The mixture was stirred at room temperature for 5 min. Then, 2% of the monomer mass of F127, a block copolymer of ethylene oxide and propylene oxide, was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer. Then, 2.0% of the monomer mass of AIBN was added, and the temperature was raised to 70 °C. The reaction was carried out for 3 h, then the temperature was raised to 80 °C, and the reaction was carried out for 8 h. The stirring speed was 550 rpm. After filtration, 100 ml of a 9:1 volume ratio of ethanol and water was added and the mixture was washed three times. After filtration and drying, 6.3 g of free-flowing porous organic polymer carrier POP-5 was obtained. The specific surface area of ​​the carrier was 538 m². 2 / g, pore volume 0.51ml / g;

[0112] (2) Preparation of ZN catalyst:

[0113] In a 250 ml glass reactor, 3 g of the POP-5 support prepared from the functional monomer 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diisopropyl ether was added, along with 100 ml of toluene. The mixture was stirred, and then 12 ml of 3M di-n-butylmagnesium was added at room temperature. The mixture was stirred for 3 hours, filtered, and washed twice with toluene. 50 ml of toluene was added, and the temperature was raised to 50 °C. 30 ml of TiCl4 was added dropwise, and the reaction was carried out for 2 hours. The temperature was then raised to 80 °C, filtered, and then 100 ml of TiCl4 was added. The reaction was carried out at 80 °C for 2 hours. After filtration, the mixture was washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-7. The catalyst Cat-7 had a Mg content of 3.2%, a titanium content of 3.5%, and an organic polymer support content of 74%.

[0114] Example 8

[0115] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0116] (1) Preparation of porous organic polymer carriers:

[0117] In a 250 ml glass reactor, 100 ml of ethanol, 15 ml of water, and 15 ml of tetrahydrofuran were added. Then, 6.0 g of divinylbenzene (Aladdin reagent, 80%), 2.5 g of 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diisopropyl ether, and 1.0 g of hydroxyethyl methacrylate were added. The mixture was stirred at room temperature for 5 min. Then, 2% of the monomer mass of F127, a block copolymer of polyethylene oxide and polypropylene oxide, was added. The mixture was stirred at 45 °C for 1 h to completely dissolve the stabilizer. 2.0% (3.0 g) of the monomer mass of AIBN 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 8 h, the stirring speed was 350 rpm. After filtration, 100 ml of a mixed solvent of ethanol and water (9:1 volume ratio) was added and the mixture was washed three times. After filtration and drying, 7.2 g of free-flowing porous organic polymer carrier POP-6 was obtained. The specific surface area of ​​the carrier is 308 m². 2 / g, pore volume 0.32ml / g;

[0118] (2) Preparation of ZN catalyst:

[0119] In a 250 ml glass reactor, add 3 g of the carrier POP-6 prepared from the functional monomers 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diisopropyl ether and the third monomer hydroxyethyl methacrylate, add 100 ml of toluene, stir, then add 15 ml of 3M methylmagnesium chloride Grignard reagent at 20°C, stir for 2 hours, filter, wash twice with toluene, add 50 ml of toluene, then heat to 50°C, add 30 ml of TiCl4 dropwise, react for 2 hours, then heat to 80°C, add 0.20 g of 9,9-dimethoxyfluorene internal electron donor, react for 3 hours, after the reaction is complete, filter, then add 100 ml of... TiCl4 was reacted at 80℃ for 1 hour, filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-8. The catalyst Cat-8 had a Mg content of 4.3%, a titanium content of 2.2%, an electron donor content of 2.3%, and an organic polymer support content of 71%.

[0120] Example 9

[0121] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0122] ZN catalyst preparation: In a 250 ml glass reactor, 3 g of the support POP-6 prepared from the functional monomers 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diisopropyl ether and the third monomer hydroxyethyl methacrylate was added. 100 ml of toluene was added, and the mixture was stirred. Then, 12 ml of 3M methylmagnesium chloride Grignard reagent was added at 20 °C, and the mixture was stirred for 2 hours. After filtration, the mixture was washed twice with toluene, and 50 ml of toluene was added. The temperature was then raised to 80 °C, and 50 ml of TiCl4 was added dropwise. The reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-9. The catalyst Cat-9 had a Mg content of 3.5%, a titanium content of 3.2%, and an organic polymer support content of 75%.

[0123] Comparative Example 1

[0124] This comparative example provides a ZN catalyst, which is prepared by the following steps:

[0125] Preparation of Zn-supported polypropylene catalyst on an inorganic support: In a 250 ml glass reactor, 3 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) was added, along with 100 ml of toluene. The mixture was stirred, and then 50 ml of TiCl4 was slowly added dropwise at 0 °C, controlling the dropping rate to maintain the temperature between 0 and 5 °C. After the addition was complete, the temperature was raised to 60 °C, and 0.30 g of DIBP internal electron donor was added. The reaction was carried out at 110 °C for 2 hours. After filtration, 100 ml of fresh TiCl4 was added, and the reaction was carried out at 110 °C for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-10, with a titanium content of 3.2% and an internal electron donor content of 8.9% (DIBP).

[0126] Comparative Example 2

[0127] This comparative example provides a ZN catalyst, which is prepared by the following steps:

[0128] Preparation of Zn-supported polypropylene catalyst on an inorganic support: In a 250 ml glass reactor, 3 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) was added, along with 100 ml of toluene. The mixture was stirred, and then 50 ml of TiCl4 was slowly added dropwise at 0 °C, controlling the dropping rate to maintain the temperature between 0 and 5 °C. After the addition was complete, the temperature was raised to 60 °C, and 0.40 g of 9,9-dimethoxyfluorene internal electron donor was added. The reaction was carried out at 110 °C for 2 hours. After filtration, 100 ml of fresh TiCl4 was added, and the reaction was carried out at 110 °C for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-11, with a titanium content of 3.2% and a 9,9-dimethoxyfluorene internal electron donor content of 6.2%.

[0129] Comparative Example 3

[0130] This comparative example provides an inorganic supported ZN catalyst, which is prepared by the following steps:

[0131] In a 250 ml glass reactor, 3 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) and 50 ml of toluene were added. The mixture was stirred, and 30 ml of TiCl4 was slowly added dropwise at 50 °C. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.25 g of diisobutyl phthalate (DIBP) internal electron donor was added, and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-12. The titanium content of catalyst Cat-12 was 3.8%, and the content of DIBP internal electron donor was 4.9%.

[0132] Comparative Example 4

[0133] This comparative example provides an inorganic supported ZN catalyst, which is prepared by the following steps:

[0134] In a 250 ml glass reactor, 3 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) was added, along with 50 ml of toluene. The temperature was raised to 50 °C, and then 30 ml of TiCl4 was slowly added dropwise. The reaction was allowed to proceed for 2 hours, followed by raising the temperature to 80 °C. 0.20 g of 9,9-dimethoxyfluorene internal electron donor was added, and the reaction was allowed to proceed for 3 hours. After the reaction was complete, the mixture was filtered, and then 100 ml of TiCl4 was added. The reaction was allowed to proceed for 1 hour at 80 °C. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-13. The catalyst Cat-13 contained 3.4% titanium and 3.7% 9,9-dimethoxyfluorene internal electron donor.

[0135] propylene polymerization

[0136] Test Example 1

[0137] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 86 mg of catalyst Cat-1 and 0.5 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.3 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 719 g of polypropylene product (PP-1) with a bulk density of 0.36 g / ml and a catalyst activity of 8360 gPP / gcat.h. The results are shown in Table 1.

[0138] Test Example 2

[0139] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 80 mg of catalyst Cat-1 and 0.5 ml of dicyclopentene dimethoxysilane (externally supplied) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 612 g of polypropylene product (PP-2) with a bulk density of 0.36 g / ml and a catalyst activity of 7650 gPP / gcat.h. The results are shown in Table 1.

[0140] Test Example 3

[0141] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 80 mg of catalyst Cat-2 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 760 g of polypropylene product (PP-3) with a bulk density of 0.36 g / ml and a catalyst activity of 9500 gPP / gcat.h. The results are shown in Table 1.

[0142] Test Example 4

[0143] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 80 mg of catalyst Cat-3 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 665 g of polypropylene product (PP-4) with a bulk density of 0.37 g / ml and a catalyst activity of 8313 gPP / gcat.h. The results are shown in Table 1.

[0144] Test Example 5

[0145] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 80 mg of catalyst Cat-4 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 932 g of polypropylene product (PP-5) with a bulk density of 0.37 g / ml and a catalyst activity of 11650 gPP / gcat.h. The results are shown in Table 1.

[0146] Test Example 6

[0147] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 80 mg of catalyst Cat-5 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1002 g of polypropylene product (PP-6) with a bulk density of 0.38 g / ml and a catalyst activity of 12525 gPP / gcat.h. The results are shown in Table 1.

[0148] Test Example 7

[0149] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 80 mg of catalyst Cat-6 and 0.5 ml of dicyclopentene dimethoxysilane (externally supplied) were added. 0.7 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1028 g of polypropylene product (PP-7) with a bulk density of 0.38 g / ml and a catalyst activity of 12850 gPP / gcat.h. The results are shown in Table 1.

[0150] Test Example 8

[0151] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 80 mg of catalyst Cat-7 and 0.5 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1136 g of polypropylene product (PP-8) with a bulk density of 0.40 g / ml and a catalyst activity of 14200 gPP / gcat.h. The results are shown in Table 1.

[0152] Test Example 9

[0153] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 885 mg of catalyst Cat-8 and 0.5 ml of dicyclopentene dimethoxysilane (externally supplied) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1179 g of polypropylene product (PP-9) with a bulk density of 0.38 g / ml and a catalyst activity of 13871 gPP / gcat.h. The results are shown in Table 1.

[0154] Test Case 10

[0155] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 82 mg of catalyst Cat-982 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 948 g of polypropylene product (PP-10) with a bulk density of 0.37 g / ml and a catalyst activity of 11560 gPP / gcat.h. The results are shown in Table 1.

[0156] Comparative Test Example 1

[0157] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 60 mg of catalyst Cat-10 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1119 g of polypropylene product (PP-11) with a bulk density of 0.37 g / ml and a catalyst activity of 18650 gPP / gcat.h. The results are shown in Table 1.

[0158] Comparative Test Example 2

[0159] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, then 160 mg of catalyst Cat-1 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1280 g of polypropylene product (PP-12) with a bulk density of 0.42 g / ml and a catalyst activity of 21333 gPP / gcat.h. The results are shown in Table 1.

[0160] Comparative Test Case 3

[0161] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm. Then, 60 mg of the comparative catalyst Cat-12 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 948 g of polypropylene product (PP-13) with a bulk density of 0.38 g / ml and a catalyst activity of 15800 gPP / gcat.h, as shown in Table 1.

[0162] Comparative Test Example 4

[0163] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm. Then, 360 mg of the comparative catalyst Cat-1 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1240 g of polypropylene product (PP-14) with a bulk density of 0.41 g / ml and a catalyst activity of 20667 gPP / gcat.h, as shown in Table 1.

[0164] Table 1. Propylene polymerization results

[0165]

[0166] Test Example 11: Copolymerization of Propylene and Ethylene

[0167] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum (TEA) (1.0 mol / L) were added. The mixture was stirred at 600 rpm. Then, 60 mg of the catalyst Cat-4 prepared above and 0.5 mL of cyclohexylmethyldimethoxysilane (externally supplied by C) were added, along with 0.3 g of hydrogen and 50 g of ethylene monomer. The mixture was heated to 70°C and polymerized at 600 rpm for 1 hour. The pressure was released, the mixture was cooled to room temperature, and dried to obtain 825 g of ethylene-propylene copolymer. The catalyst polymerization activity was 13750 gPP / gcat.h, the polymer weight-average molecular weight (Mw) was 417,000, and the molecular weight distribution coefficient was 5.3.

[0168] Test Example 12: Copolymerization of Propylene and Ethylene

[0169] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added. The mixture was stirred at 600 rpm. Then, 60 mg of catalyst Cat-5 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied by C) were added, along with 0.5 g of hydrogen and 50 g of ethylene monomer. The mixture was heated to 70°C and polymerized at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 889 g of ethylene-propylene copolymer. The catalyst activity was 14820 gPP / gcat.h, the polymer weight-average molecular weight (Mw) was 382,000, and the molecular weight distribution coefficient was 6.1.

[0170] Test Example 13: Copolymerization of Propylene and Ethylene

[0171] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum (TEA) (1.0 mol / L) were added. The mixture was stirred at 600 rpm. Then, 60 mg of the catalyst Cat-7 prepared above and 0.5 mL of cyclohexylmethyldimethoxysilane (externally supplied by C) were added, along with 0.5 g of hydrogen and 50 g of ethylene monomer. The mixture was heated to 70°C and polymerized at 600 rpm for 1 hour. The pressure was released, the mixture was cooled to room temperature, and dried to obtain 894 g of ethylene-propylene copolymer. The catalyst polymerization activity was 14900 gPP / gcat.h, the polymer weight-average molecular weight (Mw) was 295,000, and the molecular weight distribution coefficient was 5.8.

[0172] The polymerization results show that the solid component of the organic-supported POP-(ROR)2 / RMgX / TiCl4 polypropylene catalyst prepared by the functional monomer containing unsaturated 1,3-propanediol ether groups, which is capable of free radical polymerization, exhibits good catalytic activity. The homopolymerization activity of propylene can reach over 12000 gPP / gcat.h. Although this is lower than that of catalysts supported on traditional inorganic MgCl2 supports, its activity is significantly higher than that of existing organic polymer-supported polymerization catalysts, meeting the requirements of current industrial catalysts. By selecting the functional monomer containing unsaturated 1,3-propanediol ether groups capable of free radical polymerization, and relying on the 1,3-diether functional groups on the support, the microchemical environment of the metal active center can be controlled, giving the catalyst good stereotactic ability. Even without the addition of an internal electron donor, the prepared polypropylene has high isotacticity, reaching over 97%, and a narrow molecular weight distribution, with the molecular weight distribution coefficient controllable between 4 and 7.

[0173] Compared to Comparative Example 1 (which uses the same conventional internal electron donor such as DIBP), the polymer prepared by catalyst Cat-5 in Example 5 exhibits higher isotacticity than the catalysts in Comparative Examples 1 and 3. Compared to Comparative Examples 2 and 4 (which use the internal electron donor 9,9-dimethoxyfluorene with high stereoregularity and relatively narrow molecular weight distribution), the polypropylene prepared by catalyst Cat-8 in Example 8 exhibits higher stereoregularity and a narrower molecular weight distribution.

[0174] The POP-(ROR)2 / RMgX / TiCl4 polypropylene catalyst disclosed in this invention has a simple preparation method compared with existing catalysts. Its active center has high stereotacticity and a narrow molecular weight distribution, and it has good copolymerization performance, showing good prospects for industrialization.

Claims

1. A ZN catalyst, wherein the raw material composition, calculated as 100% by mass of the ZN catalyst, comprises 60-85 wt% organic polymer support, 1-5 wt% magnesium compound calculated as magnesium element, 1-5 wt% titanium compound calculated as titanium element, and 0-5 wt% internal electron donor; The organic polymer carrier is obtained by copolymerization of monomers including divinylbenzene and unsaturated 1,3-propanediol ether monomers; in, The unsaturated 1,3-propanediol ether monomers have the structure shown in Formula I: Formula I, In Formula I, R1, R2, and R3 are each independently selected from hydrogen, chlorine, fluorine, bromine, C1-C6 straight-chain alkyl, C1-C6 branched alkyl, cycloalkyl, and aryl groups; x is 0-3; R4 is selected from hydrogen, chlorine, fluorine, bromine, C1-C6 straight-chain alkyl, C1-C6 branched alkyl, cycloalkyl, and aryl groups. 10 Straight-chain alkyl, C1-C 10 Branched alkyl, cycloalkyl, aromatic, alkoxy groups; R5 and R6 are each independently selected from C1-C6. 10 Straight-chain hydrocarbon groups, C1-C 10 Branched hydrocarbon groups, cycloalkyl groups, and aromatic groups; Based on the organic polymer carrier mass being 100%, the mass fraction of the unsaturated 1,3-propanediol ether monomer is 20-60%. The specific surface area of ​​the organic polymer carrier is 100-600 m². 2 / g, pore volume > 0.2 ml / g.

2. The ZN catalyst according to claim 1, wherein, In Equation I, R1 and R4 are connected to form a ring.

3. The ZN catalyst according to claim 1, wherein, In Formula I, R1, R2, and R3 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, phenyl, chlorine, and bromine; R4 is selected from hydrogen, methyl, n-propyl, isopropyl, phenyl, fluorine, chlorine, bromine, 3-trifluoromethyl, isobutyl, benzoxy, 4-tert-butylphenyl, tert-butyl; R5 and R6 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-octyl, phenyl, benzyl, 4-tert-butylphenyl, 2-methylhexyl, 2-ethylpentyl, and 2-ethylhexyl. x is 0, 1, or 2.

4. The ZN catalyst according to claim 3, wherein, In Formula I, R1, R2, and R3 are each independently selected from hydrogen, methyl, bromine, and chlorine; R4 is selected from hydrogen, methyl, isopropyl, chlorine, bromine, and isobutyl; R5 and R6 are each independently selected from methyl, ethyl, isopropyl, isobutyl, phenyl, benzyl, and 4-tert-butylphenyl; and x is 1.

5. The ZN catalyst according to claim 1, wherein, The unsaturated 1,3-propanediol ether monomers are selected from 2-allyl-1,3-propanediol dimethyl ether, 2-allyl-1,3-propanediol diethyl ether, 2-allyl-1,3-propanediol di-n-propyl ether, 2-allyl-1,3-propanediol diisopropyl ether, 2-allyl-1,3-propanediol di-n-butyl ether, 2-allyl-1,3-propanediol diisobutyl ether, 2-allyl-1,3-propanediol diphenyl ether, 2-(1-methylallyl)-1,3-propanediol dimethyl ether, 2-(1-methylallyl)-1,3-propanediol diethyl ether, 2-(1-methylallyl)-1,3-propanediol di-n-propyl ether, 2-(1-methylallyl)-1,3-propanediol diiso ... Allyl)-1,3-propanediol di-n-butyl ether, 2-(1-methylallyl)-1,3-propanediol diisobutyl ether, 2-(1-methylallyl)-1,3-propanediol diphenyl ether, 2-allyl-2-propyl-1,3-propanediol dimethyl ether, 2-allyl-2-propyl-1,3-propanediol diethyl ether, 2-allyl-2-propyl-1,3-propanediol diisopropyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-butyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-butyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-butyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-pentyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-butyl ether Hexyl ether, 2-allyl-2-propyl-1,3-propanediol di-n-octyl ether, 2-allyl-2-propyl-1,3-propanediol di(2-methylpentyl) ether, 2-allyl-2-propyl-1,3-propanediol di(2-methylhexyl) ether, 2-allyl-2-propyl-1,3-propanediol di(2-ethylpentyl) ether, 2-allyl-2-propyl-1,3-propanediol di(2-ethylhexyl) ether, 2-allyl-2-propyl-1,3-propanediol diallyl ether, 2-allyl-2-propyl-1,3-propanediol di(2-methylallyl) ether, 2-allyl-2-propyl-1,3-propanediol di(4-pentenyl) ... (5-Hexenyl) ether, 2-Allyl-2-propyl-1,3-propanediol di(3-methyl-3-pentenyl) ether, 2-Allyl-2-propyl-1,3-propanediol di(2-ethyl-2-propenyl) ether, 2-Allyl-2-propyl-1,3-propanediol di(3-ethyl-3-butenyl) ether, 2-Allyl-2-propyl-1,3-propanediol di(6-heptenyl) ether, 2-Allyl-2-propyl-1,3-propanediol di(5-methyl-5-hexenyl) ether, 2-Allyl-2-propyl-1,3-propanediol di(7-octenyl) ether, 2-Allyl-2-propyl-1,3-propanediol di(4-methyl-4-pentenyl) ether, 2-Allyl-2-propyl-1,3-propanediol di(4-methyl-4-pentenyl) ether, 2-Allyl-2-propyl-1,3-Propanediol di(4-ethyl-4-pentenyl) ether, 2-allyl-2-propyl-1,3-propanediol di(5-ethyl-5-hexenyl) ether, 2-allyl-2-propyl-1,3-propanediol diphenyl ether, 2-allyl-2-methyl-1,3-propanediol dibenzyl ether, 2-allyl-2-methyl-1,3-propanediol dimethyl ether, 2-allyl-2-methyl-1,3-propanediol diethyl ether, 2-allyl-2-methyl-1,3-propanediol di-n-propyl ether, 2-allyl-2-methyl-1,3-propanediol diisopropyl ether, 2-allyl-2-methyl-1,3-propanediol di-n-butyl ether, 2-allyl-2-methyl-1,3-propanediol diiso ... 3-Propanediol di-n-pentyl ether, 2-allyl-2-methyl-1,3-propanediol di-n-hexyl ether, 2-allyl-2-methyl-1,3-propanediol di-n-octyl ether, 2-allyl-2-methyl-1,3-propanediol di(2-methylpentyl) ether, 2-allyl-2-methyl-1,3-propanediol di(2-methylhexyl) ether, 2-allyl-2-methyl-1,3-propanediol di(2-ethylpentyl) ether, 2-allyl-2-methyl-1,3-propanediol di(2-ethylhexyl) ether, 2-allyl-2-methyl-1,3-propanediol diphenyl ether, 2-allyl-2-isopropyl-1,3-propanediol dimethyl ether, 2-allyl-2-isopropyl-1,3-propanediol diethyl ether, 2-allyl-2- Isopropyl-1,3-propanediol di-n-propyl ether, 2-allyl-2-isopropyl-1,3-propanediol diisopropyl ether, 2-allyl-2-isopropyl-1,3-propanediol di-n-butyl ether, 2-allyl-2-isopropyl-1,3-propanediol diisobutyl ether, 2-allyl-2-isopropyl-1,3-propanediol di-n-pentyl ether, 2-allyl-2-isopropyl- 1,3-Propanediol dihexyl ether, 2-allyl-2-isopropyl-1,3-propanediol diphenyl ether, 2-allyl-2-isopropyl-1,3-propanediol dibenzyl ether, 2-(3-cyclopentenyl)-1,3-propanediol dimethyl ether, 2-(3-cyclopentenyl)-1,3-propanediol diethyl ether, 2-(3-cyclopentenyl)-1,3-propanediol diisopropyl ether Ethers, 2-(3-cyclopentenyl)-1,3-propanediol di-n-butyl ether, 2-(3-cyclopentenyl)-1,3-propanediol diisobutyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propanediol dimethyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propanediol diethyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propanediol diisopropyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propanediol di-n-butyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propanediol diphenyl ether, 2-allyl-2-phenyl-1,3-propanediol dimethyl ether, 2-allyl-2-phenyl-1,3-propanediol diethyl ...3-Propanediol diisopropyl ether, 2-allyl-2-phenyl-1,3-propanediol diphenyl ether, 2-allyl-2-phenyl-1,3-propanediol dibenzyl ether, 2-(1-chlorovinyl)-2-propyl-1,3-propanediol dimethyl ether, 2-allyl-2-propyl-1,3-propanediol dihydroxyethyl ether, 2-allyl-2-propyl-1,3-propanediol dihydroxypropyl ether, 2-allyl-2-chloro-1,3-propanediol diethyl ether, 2-allyl-2-chloro-1,3-propanediol diisopropyl ether, 2-allyl-2-chloro-1,3-propanediol diisobutyl ether, 2-allyl-2-chloro-1,3-propanediol di-n-butyl ether, 2-allyl-2-fluoro-1,3-propanediol diethyl ether, 2-allyl-2-fluoro- 1,3-Propanediol diisopropyl ether, 2-Allyl-2-fluoro-1,3-propanediol diisobutyl ether, 2-Allyl-2-fluoro-1,3-propanediol di-n-butyl ether, 2-Allyl-2-bromo-1,3-propanediol diisopropyl ether, 2-Allyl-2-bromo-1,3-propanediol di(4-tert-butylphenyl) ether, 2-Allyl-2-(3-trifluoromethyl)- 1,3-Propanediol diethyl ether, 2-allyl-2-(3-trifluoromethyl-propyl)-1,3-propanediol di-n-butyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-propanediol dimethyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diethyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diethyl ether 2-Propylene glycol diisopropyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol di-n-butyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diphenyl ether, 2-allyl-2-phenyl-1,3-propanediol diisobutyl ether, 2-allyl-2-phenyl-1,3-propanediol dipentyl ether, 2-allyl-2-benzoxy-1,3-propanediol dimethyl ether, 2-allyl-2-benzoxy-1,3-propanediol diethyl ether, 2-allyl-2-benzoxy-1,3-propanediol diisopropyl ether, 2-allyl-2-benzoxy-1,3-propanediol diisobutyl ether, 2-allyl-2-benzoxy-1,3-propanediol di-n-butyl ether, 2-allyl-2-phenyl ... One or more of the following: benzoyl-1,3-propanediol diphenyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,3-propanediol dimethyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,3-propanediol diethyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,3-propanediol di-n-butyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,3-propanediol diphenyl ether, 2-(1-chloroallyl)-2-tert-butyl-1,3-propanediol diphenyl ether, 2-(1-chloroallyl)-2-isobutyl-1,3-propanediol diisopropyl ether, and 2-allyl-2-methoxy-1,3-propanediol diisopropyl ether.

6. The ZN catalyst according to claim 1, wherein, The method for preparing the organic polymer carrier includes the following steps: The organic polymer carrier is prepared by copolymerization using monomers including the divinylbenzene, the unsaturated 1,3-propanediol ether monomers and additional monomers as raw materials. The mass ratio of the additional monomer to divinylbenzene is 0-1:1; the mass ratio of the unsaturated 1,3-propanediol ether monomer to divinylbenzene is 0.2-2:

1.

7. The ZN catalyst according to claim 6, wherein, The organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization. The dispersion polymerization method includes the following steps: adding divinylbenzene, unsaturated 1,3-propanediol ether monomers and additional monomers to a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, and reacting at 50-80°C for 5-12 hours to obtain the organic polymer carrier.

8. The ZN catalyst according to claim 6, wherein, The additional monomers include one or more of styrene, alkyl-substituted styrene, chloromethyl-substituted styrene, methacrylic acid, methacrylate, and hydroxyalkyl methacrylate.

9. The ZN catalyst according to claim 7, wherein, The dispersion solvent includes C1-C4 alcohols or a mixture of C1-C4 alcohols and water; in the mixed solvent, the mass ratio of alcohol to water is 5-15:

1.

10. The ZN catalyst according to claim 9, wherein, The C1-C4 alcohols include one or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol.

11. The ZN catalyst according to claim 9, wherein, The dispersing solvent further includes an additional solvent.

12. The ZN catalyst according to claim 11, wherein, The additional solvent includes one or more of ethyl acetate, methyl formate, butyl acetate, and tetrahydrofuran.

13. The ZN catalyst according to claim 7, wherein, The mass ratio of the total amount of monomer added to the dispersing solvent is 1:5-20.

14. The ZN catalyst according to claim 7, wherein, The stabilizer is polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer.

15. The ZN catalyst according to claim 7, wherein, The weight-average molecular weight of the stabilizer is 1,000-100,000.

16. The ZN catalyst according to claim 7, wherein, The mass ratio of the amount of stabilizer added to the total amount of monomer added is 0.5-5:

100.

17. The ZN catalyst according to claim 7, wherein, The initiator is azobisisobutyronitrile and / or benzoyl peroxide.

18. The ZN catalyst according to claim 7, wherein, The mass ratio of the amount of initiator added to the total amount of monomer added is 0.5-3:

100.

19. The ZN catalyst according to claim 6, wherein, The divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor.

20. The ZN catalyst according to claim 1, wherein, The organic polymer carrier contains 65-80 wt%, magnesium 2-5 wt%, and titanium 2-5 wt%.

21. The ZN catalyst according to claim 1, wherein, The magnesium compound is RMgX or R'MgR''; R, R', and R'' are each independently selected from C1-C8 alkyl, aryl, and alkoxy groups, and X is fluorine, chlorine, bromine, or iodine.

22. The ZN catalyst according to claim 21, wherein, R, R', and R'' are each independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl, and substituted phenyl.

23. The ZN catalyst according to claim 22, wherein, The magnesium compound is one or a combination of two or more of alkyl halide magnesium compounds, alkyl magnesium compounds, and alkoxy halide magnesium compounds.

24. The ZN catalyst according to claim 23, wherein, The magnesium compound includes one or more of the following: 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, dipropyl magnesium, dibutyl magnesium, and ethoxy magnesium chloride.

25. The ZN catalyst according to claim 1, wherein, The titanium compound is titanium tetrachloride.

26. The ZN catalyst according to claim 1, wherein, The internal electron donor is one or a combination of two or more of the following: diester compounds, diphenol ester compounds, diol ester compounds, succinate compounds, and diether compounds.

27. The ZN catalyst according to claim 26, wherein, The internal electron donor includes one or more of the following: diisobutyl phthalate, di-n-butyl phthalate, 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl methyl ester, and 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether.

28. A method for preparing the ZN catalyst according to any one of claims 1-27, comprising the following steps: Under anhydrous and oxygen-free conditions, the organic polymer support is added to an inert solvent, followed by the magnesium compound. After reacting at 0℃-50℃ for 15-120 minutes, the unreacted magnesium compound is filtered out. Then, an inert solvent and titanium tetrachloride are added, and the reaction is carried out at 0℃-80℃ for 15-180 minutes. Finally, the internal electron donor is added, and the reaction is carried out at 50℃-120℃ for 15-180 minutes. The mixture is then washed with an inert solvent to obtain the ZN catalyst.

29. A ZN catalyst system comprising a ZN catalyst, an external electron donor, and a co-catalyst; in, The ZN catalyst is the ZN catalyst according to any one of claims 1-27.

30. The ZN catalyst system according to claim 29, wherein, The external electron donor includes silane-based external electron donors.

31. The ZN catalyst system according to claim 30, wherein, The silane-based external electron donors include one or more combinations of cyclohexylmethyldimethoxysilane, dicyclopentenedimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, and tetraethoxysilane.

32. The ZN catalyst system according to claim 30, wherein, The molar ratio of silicon in the silane-based external electron donor to titanium in the ZN catalyst is 1-50.

33. The ZN catalyst system according to claim 29, wherein, The cocatalyst includes an alkylaluminum compound, wherein the alkylaluminum compound is Al(R''')3, and R''' is a C1-C6 alkyl group.

34. The ZN catalyst system according to claim 33, wherein, The R''' is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl.

35. The ZN catalyst system according to claim 29, wherein, The co-catalyst is triethylaluminum.

36. The ZN catalyst system according to claim 33, wherein, The molar ratio of aluminum in the alkylaluminum compound to titanium in the ZN catalyst is 10-500.

37. The use of the ZN catalyst according to any one of claims 1-27 or the ZN catalyst system according to claims 29-36 in olefin polymerization.

38. The application according to claim 37, wherein, The olefin polymerization is propylene homopolymerization, propylene-ethylene copolymerization, or α-olefin copolymerization.

39. The application according to claim 38, wherein, The α-olefin includes one or more combinations of butene, isobutene, pentene, hexene, octene, and 4-methyl-1-pentene.

40. The application according to claim 37, wherein, The olefin polymerization is gas-phase polymerization, bulk polymerization, or slurry polymerization.

41. The application according to claim 40, wherein, The reaction temperature for slurry polymerization is 30-80℃, and the reaction pressure is 0.1-2.0 MPa.

42. The application according to claim 40, wherein, The solvent for the slurry polymerization is C5-C. 10 Alkanes.

43. The application according to claim 40, wherein, The solvent used for slurry polymerization is hexane.

44. The application according to claim 40, wherein, The reaction pressure for the bulk polymerization is 2.8-4.0 MPa, and the reaction temperature is 68-72℃.

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