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

Abstract

The invention provides an organic polymer carrier, a Z-N catalyst and a preparation method and application thereof. The organic polymer carrier is obtained by copolymerizing monomers including divinyl benzene and unsaturated 1, 3-propylene glycol ether monomers; wherein the unsaturated 1, 3-propylene glycol ether monomer has a structure as shown in a formula I: # imgabs0 #, and the catalyst has the characteristics of good olefin insertion, stereotactic ability, catalyst activity, narrow molecular weight distribution and the like.

Description

Technical Field

[0001] The invention belongs to the field of catalysts, and in particular relates to a ZN catalyst supported by an organic carrier and a preparation method thereof. Background Art

[0003] At present, industrial polypropylene catalysts are mainly ZN-type catalysts and metallocene catalysts, which mainly produce high-isotactic polypropylene; in addition, metallocene catalysts, post-metallocene catalysts and other catalysts are used to produce a small amount of syndiotactic polypropylene, atactic polypropylene and propylene-based elastomers. For industrial polypropylene production equipment, if slurry polymerization, bulk polymerization or gas phase polymerization processes are used, the catalyst needs to be loaded to control the morphology of the generated polymer and avoid problems such as reactor agglomeration or blockage.

[0004] Existing industrial catalysts mainly use inorganic carriers to load ZN catalysts and metallocene catalysts. Inorganic carriers are mainly silica, magnesium chloride, ethoxymagnesium, molecular sieves, etc., for catalyst loading. For ZN catalysts, commonly used carriers are ethoxymagnesium, anhydrous magnesium chloride, etc., which are all MgCl2-loaded ZN catalysts after reacting with TiCl4; during the catalyst preparation process, electron donors or Lewis bases are usually added to regulate the microchemical environment of the catalyst metal active center, thereby regulating the performance of the catalyst. For example, MgCl2-loaded polypropylene catalysts usually include the following components: MgCl2 / TiCl4 / internal electron donor (ID) / silane external electron donor (ED); common internal electron donors include phthalate internal electron donors (such as diisobutyl phthalate (DIBP), di-n-butyl phthalate (DNBP)), phenolic ester internal electron donors, succinate internal electron donors, diether internal electron donors, etc. The internal electron donor or Lewis base added to the catalyst system provides a unique electronic and steric environment for the MgCl2 / TiCl4 surface, which has a significant impact on the activity, stereoregularity, hydrogen sensitivity, molecular weight and distribution of the catalyst. In addition, the MgCl2 surface grain size, Ti active center content and distribution can also be regulated. In the past three decades, most of the research in the development of high-performance polypropylene catalysts has focused on the design and screening of new internal electron donors. "Progress in MgCl2 supported Ziegler-Natta catalyzed polyolefin products and applications" (Volume 28, 2021, 45) in Journal of Polymer Research reviewed the internal electron donors used in polyolefin catalysts, including succinates (US20140200316), 1,3-diesters, diethers (US7022640), bicycloalkane diacids, bicycloalkene diacids (US20140005345), silicon-containing compounds (US8088872B2) and other internal electron donors. Using different internal electron donors, its polypropylene catalysts show different polymerization activities, stereoregularity, hydrogen sensitivity and product molecular weight distribution. Among them, the ZN polypropylene catalyst (CN105408371A) with 1,3-diether as the internal electron donor has a higher isotacticity and a narrower molecular weight distribution.

[0005] Generally, polypropylene catalysts supported by inorganic carriers have high polymerization activity, better control of polymer morphology, and high bulk density, but inorganic carriers usually introduce additional impurities (except for Mg and Ti active centers), which limits their application in the development of high-clean polypropylene products. Organic polymer carriers are different from reported inorganic carriers. POP carriers themselves do not introduce impurities, thereby affecting polymer properties. In addition, organic carriers have controllable pore structures, high specific surface areas, stable thermal properties, and are easy to functionalize. Through the design and functionalization of carriers, high-performance or characteristic polyolefin catalysts can be prepared. There are public reports on porous organic carrier-supported ZN catalysts, and organic carriers containing functional groups such as carboxylic acid, hydroxyl, cyano, and amino groups are usually used to prepare ZN catalysts. However, organic carrier-based olefin catalysts are mainly polyethylene catalysts, and there are few reports on their use in propylene polymerization. For example, "Sulfonatedporous organic polymer supported ZN polypropylene catalysts with highstereoregularity and broad molecular weight distribution" (Vol. 343, 2022, 112151) in Microporous and Mesoporous Materials reports a POP carrier-loaded ZN catalyst prepared using styrenesulfonic acid functional monomers. The product catalyzed by this catalyst has a wide molecular weight distribution with a distribution value of more than 11. When additional diphenol ester is added as an internal electron donor, the isotacticity reaches more than 98%. Summary of the invention

[0006] In order to solve the above problems, the present invention aims to provide an organic polymer carrier, a ZN catalyst and a preparation method and application thereof. The catalyst has good olefin insertion, stereospecific ability, catalyst activity and narrow molecular weight distribution.

[0007] In order to achieve the above object, the present invention provides an organic polymer carrier, which is obtained by copolymerizing 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:

[0008]

[0009] In Formula I, R1, R2, and R3 are each independently selected from hydrogen, chlorine, fluorine, bromine, hydroxyl, C1-C6 straight-chain alkyl and its derivatives, C1-C6 branched-chain alkyl and its derivatives, cycloalkyl and its derivatives, aromatic and its derivatives; x is 0-3, and when x is 0, the double-bonded carbon atom connected to R3 directly bonds with the carbon atom connected to R4; R4 is selected from hydrogen, chlorine, fluorine, bromine, hydroxyl, C1-C 10 Straight-chain alkyl and its derivatives, C1-C 10 branched alkyl and its derivatives, cycloalkyl and its derivatives, aromatic and its derivatives, alkoxy; R5, R6 are each independently selected from C1-C 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 connected to each other to form a ring.

[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, 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, benzyloxy, 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.

[0011] 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.

[0012] According to a specific embodiment of the present invention, preferably, the unsaturated 1,3-propylene glycol ether monomer is selected from 2-allyl-1,3-propylene glycol dimethyl ether, 2-allyl-1,3-propylene glycol diethyl ether, 2-allyl-1,3-propylene glycol di-n-propyl ether, 2-allyl-1,3-propylene glycol diisopropyl ether, 2-allyl-1,3-propylene glycol di-n-butyl ether, 2-allyl-1,3-propylene glycol diisobutyl ether, 2-allyl-1,3-propylene glycol diphenyl ether, 2-(1-methylallyl)-1,3-propylene glycol dimethyl ether, 2-(1-methylallyl)-1,3-propylene glycol diethyl ether, 2-(1-methylallyl)-1,3-propylene glycol di-n-propyl ether, 2-(1-methylallyl)-1,3-propylene glycol diisobutyl ether, 2-(1-methylallyl)-1,3-propylene glycol diisopropyl ether, 2-(1-methylallyl)-1,3-propylene glycol diisobutyl ether, 2-(1-methylallyl)-1,3-propylene glycol diphenyl ether, 2-allyl-2-propyl-1,3-propylene glycol dimethyl ether, 2-allyl-2-propyl-1,3-propylene glycol diethyl ether, 2-allyl-2-propyl-1,3-propylene glycol diisopropyl ether, 2-allyl-2-propyl-1,3-propylene glycol di-n-propyl ether, 2-allyl-2-propyl-1,3-propylene glycol di-n-butyl ether, 2-allyl-2-propyl-1,3-propylene glycol diisobutyl ether, 2-allyl-2-propyl-1,3-propylene glycol di-n-pentyl ether, 2-allyl-2-propyl-1 ,3-propylene glycol di-n-hexyl ether, 2-allyl-2-propyl-1,3-propylene glycol di-n-octyl ether, 2-allyl-2-propyl-1,3-propylene glycol di(2-methylpentyl) ether, 2-allyl-2-propyl-1,3-propylene glycol di(2-methylhexyl) ether, 2-allyl-2-propyl-1,3-propylene glycol di(2-ethylpentyl) ether, 2-allyl-2-propyl-1,3-propylene glycol di(2-ethylhexyl) ether, 2-allyl-2-propyl-1,3-propylene glycol diallyl ether, 2-allyl-2-propyl-1,3-propylene glycol di(2-methylallyl) ether, 2-allyl-2-propyl-1,3-propylene glycol di(4-pentenyl) ether, 2-allyl-2-propyl-1,3-propylene glycol di(2-methylhexyl) ether 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-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 diisobutyl ether, 2-allyl-2-methyl-1,3-propanediol diisobutyl ether, 2-allyl-2-methyl-1,3-propanediol diisobutyl ether, 2-allyl-2-methyl-1, 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-propylene glycol di-n-propyl ether, 2-allyl-2-isopropyl-1,3-propylene glycol di-n-butyl ether, 2-allyl-2-isopropyl-1,3-propylene glycol di-n-butyl ether, 2-allyl-2-isopropyl-1,3-propylene glycol di-n-butyl ether, 2-allyl-2-isopropyl-1,3-propylene glycol di-n-pentyl ether, 2-allyl-2-isopropyl- 1,3-Propanediol di-n-hexyl 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, 2-(3-cyclopentenyl)-1,3-propylene glycol di-n-butyl ether, 2-(3-cyclopentenyl)-1,3-propylene glycol diisobutyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propylene glycol dimethyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propylene glycol diethyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propylene glycol diisopropyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propylene glycol di-n-butyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propylene glycol diphenyl ether, 2-allyl-2-phenyl-1,3-propylene glycol dimethyl ether, 2-allyl-2-phenyl-1,3-propylene glycol diethyl ether, 2-allyl-2-phenyl-1,3-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-butyl ether, 2-allyl-2-chloro-1,3-propanediol 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-1,3-propanediol dimethyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diethyl 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 ether, 2-allyl-2-phenyl-1, 3-Propanediol dipentyl ether, 2-allyl-2-benzyloxy-1,3-propanediol dimethyl ether, 2-allyl-2-benzyloxy-1,3-propanediol diethyl ether, 2-allyl-2-benzyloxy-1,3-propanediol diisopropyl ether, 2-allyl-2-benzyloxy-1,3-propanediol diisobutyl ether, 2-allyl-2-benzyloxy-1,3-propanediol di-n-butyl ether, 2-allyl-2-benzyloxy-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-propylene glycol di-n-butyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,3-propylene glycol diphenyl ether, 2-(1-chloroallyl)-2-tert-butyl-1,3-propylene glycol diphenyl ether, 2-(1-chloroallyl)-2-isobutyl-1,3-propylene glycol diisopropyl ether, 2-allyl-2-methoxy-1,3-propylene glycol diisopropyl ether, or a combination of two or more thereof.

[0013] According to a specific embodiment of the present invention, preferably, based on the mass of the organic polymer carrier being 100%, the mass fraction of the unsaturated 1,3-propylene glycol ether monomer is 20-60%; the content of the functional monomer in the carrier is determined by the added amount of divinylbenzene and the unsaturated 1,3-propylene glycol ether functional monomer.

[0014] The present invention also provides a method for preparing the above-mentioned organic polymer carrier, which comprises the following steps: using monomers including the divinylbenzene, the unsaturated 1,3-propylene glycol ether monomer and the additional monomer as raw materials, and obtaining the organic polymer carrier through copolymerization; the mass ratio of the additional monomer to divinylbenzene is 0-1:1; the mass ratio of the unsaturated 1,3-propylene glycol ether monomer to divinylbenzene is 0.2-2:1.

[0015] 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.

[0016] 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-propylene glycol ether monomers, and additional monomers to a dispersion solvent, and 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, which is recorded 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 narrow dispersion and good fluidity.

[0017] According to a specific embodiment of the present invention, preferably, in the above preparation method, the additional monomer includes one or a combination of two or more of styrene, alkyl-substituted styrene, chloromethyl-substituted styrene, methacrylic acid, methacrylate, and hydroxyalkyl methacrylate, such as hydroxyethyl methacrylate.

[0018] According to a specific embodiment of the present invention, preferably, in the above preparation method, the dispersing solvent includes C1-C4 alcohol or a mixed solvent of C1-C4 alcohol and water; in the mixed solvent, the mass ratio of alcohol to water is 5-15:1.

[0019] According to a specific embodiment of the present invention, preferably, in the above preparation method, the C1-C4 alcohol includes one or a combination of two or more of methanol, ethanol, propanol, isopropanol, 1-butanol and isobutanol.

[0020] According to a specific embodiment of the present invention, preferably, in the above-mentioned preparation method, the dispersing solvent further includes an additional solvent, and more preferably, the additional solvent includes one or a combination of two or more of ethyl acetate, methyl formate, butyl acetate, and tetrahydrofuran, which can further adjust the solubility parameter of the solvent system, thereby controlling the pore structure and morphology of the prepared carrier.

[0021] 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 dispersion solvent is 1:5-20, so that the system is evenly dispersed.

[0022] According to a specific embodiment of the present invention, preferably, in the above preparation method, the stabilizer is polyvinyl alcohol and / or polypropylene oxide-polyethylene oxide copolymer.

[0023] 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.

[0024] According to a specific embodiment of the present invention, preferably, in the above preparation method, the mass ratio of the amount of the stabilizer added to the total amount of the monomers added is 0.5-5:100.

[0025] According to a specific embodiment of the present invention, preferably, in the above preparation method, the initiator is azobisisobutyronitrile (AIBN) and / or dibenzoyl peroxide (BPO).

[0026] According to a specific embodiment of the present invention, preferably, in the above preparation method, the mass ratio of the amount of the initiator added to the total amount of the monomers added is 0.5-3:100.

[0027] According to a specific embodiment of the present invention, preferably, in the above preparation method, the divinylbenzene is pretreated divinylbenzene, and the pretreatment is to remove the polymerization inhibitor.

[0028] The present invention also provides a ZN catalyst, which, based on the mass of the ZN catalyst being 100%, comprises 60-85wt% of the organic polymer carrier, 1-5wt% of a magnesium compound calculated as magnesium element, 1-5wt% of a titanium compound calculated as titanium element and 0-5wt% of an internal electron donor.

[0029] According to a specific embodiment of the present invention, preferably, the content of the organic polymer carrier is 65-80wt%, the content of magnesium is 2-5wt%, and the content of titanium is 2-5wt%.

[0030] According to a specific embodiment of the present invention, preferably, the magnesium compound is RMgX or R'MgR", wherein R, R', R" are each independently selected from C1-C8 alkyl and derivatives thereof, aryl and derivatives thereof, alkoxy and derivatives thereof, and X is fluorine, chlorine, bromine or iodine.

[0031] According to a specific embodiment of the present invention, preferably, the R, R', and R" are each independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl, and substituted phenyl.

[0032] According to a specific embodiment of the present invention, preferably, the magnesium compound is one or a combination of two or more of an alkyl magnesium halide compound, an alkyl magnesium compound, and an alkoxy magnesium halide compound, and more preferably an alkyl magnesium chloride compound.

[0033] According to a specific embodiment of the present invention, preferably, the magnesium compound includes one or a combination of two or more of methylmagnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, tert-butylmagnesium chloride, benzylmagnesium chloride, ethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, n-butylmagnesium bromide, benzylmagnesium bromide, methylmagnesium iodide, tert-butylmagnesium iodide, benzylmagnesium iodide, n-butylmagnesium iodide, methylmagnesium fluoride, tert-butylmagnesium fluoride, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, and ethoxymagnesium chloride; after the magnesium compound is contacted with the organic polymer carrier, a porous organic carrier treated with a magnesium compound is prepared, which is recorded as POP-(ROR)2...MgX.

[0034] According to a specific embodiment of the present invention, preferably, the titanium compound is titanium tetrachloride; the porous organic support treated with the above magnesium-containing compound (POP-(ROR)2...MgX) is further reacted with titanium tetrachloride to obtain the ZN catalyst, recorded as POP-(ROR)2...MgX / TiCl4.

[0035] The ZN catalyst of the present invention can selectively add an additional internal electron donor (ID), and the obtained ZN catalyst is recorded 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 a diester compound, a diphenol ester compound, a glycol ester compound, a succinate ester compound, and a diether compound.

[0036] According to a specific embodiment of the present invention, preferably, the internal electron donor includes one or a combination of two or more of diisobutyl phthalate (DIBP), di-n-butyl phthalate (DNBP), 9,9-dimethoxyfluorene, 2,3-diisobutyl diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzyl ester (IAIPPDB), and 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether (IAIPDMP).

[0037] The present invention also provides a method for preparing the above ZN catalyst, which comprises the following steps:

[0038] Under anhydrous and oxygen-free conditions, the organic polymer carrier is added to an inert solvent, the magnesium compound is added, and the reaction is carried out at 0°C-50°C for 15-120 minutes. The unreacted magnesium compound is filtered, and an inert solvent and titanium tetrachloride are added. The reaction is carried out at 0°C-80°C for 15-180 minutes. The internal electron donor is added, and the reaction is carried out at 50°C-120°C for 15-180 minutes. Finally, the ZN catalyst is washed with an inert solvent to obtain the ZN catalyst.

[0039] In the ZN catalyst of the present invention, the content of functional monomers (unsaturated 1,3-propylene glycol ether monomers) of the organic polymer carrier is generally 0.5 mmol / g carrier to 5 mmol / g carrier, preferably 1 mmol / g carrier to 4 mmol / g carrier; the content of functional monomers is usually regulated by the ratio of the functional monomers to the divinylbenzene (DVB) monomer addition during the carrier preparation process; the ratio of the amount of magnesium compound reagent added (in terms of the molar number of magnesium Mg) to the carrier is 1 mmol / g carrier to 30 mmol / g carrier, preferably 3 mmol / g carrier to 20 mmol / g carrier; an excess Ti metal compound, such as TiCl4, is usually added to load the catalyst, and the amount of Ti metal compound added (in terms of the molar number of titanium Ti) is generally 5 mmol / g carrier to 200 mmol / g carrier, preferably 50 mmol / g carrier to 150 mmol / g carrier; the ratio of the additional internal electron donor to the carrier is 0 to 0.3 g internal electron donor / g carrier.

[0040] The present invention also provides a ZN catalyst system, which comprises the ZN catalyst, an external electron donor and a co-catalyst.

[0041] According to a specific embodiment of the present invention, preferably, the external electron donor includes a silane external electron donor.

[0042] According to a specific embodiment of the present invention, preferably, the silane external electron donor includes one or a combination of two or more of cyclohexylmethyldimethoxysilane (C external donor), dicyclopentenedimethoxysilane (D external donor), diisopropyldimethoxysilane (P external donor), diisobutyldimethoxysilane (B external donor), and tetraethoxysilane (TEOS).

[0043] 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.

[0044] 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, where R'' is a C1-C6 alkyl group; in addition, the alkyl aluminum compound can also be used as an impurity remover for the polymerization reaction system.

[0045] According to a specific embodiment of the present invention, preferably, the R'' is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.

[0046] According to a specific embodiment of the present invention, preferably, the co-catalyst is triethylaluminum.

[0047] According to a specific embodiment of the present invention, preferably, the molar ratio of aluminum in the alkyl aluminum compound to titanium in the ZN catalyst is 10-500.

[0048] The present invention also provides application of the ZN catalyst or the ZN catalyst system in olefin polymerization.

[0049] According to a specific embodiment of the present invention, preferably, the olefin polymerization is ethylene or propylene homopolymerization, propylene and ethylene copolymerization or α-olefin copolymerization.

[0050] According to a specific embodiment of the present invention, preferably, the α-olefin includes one or a combination of two or more of butene, isobutylene, pentene, hexene, octene, and 4-methyl-1-pentene.

[0051] According to a specific embodiment of the present invention, preferably, the olefin polymerization is gas phase polymerization, bulk polymerization or slurry polymerization.

[0052] According to a specific embodiment of the present invention, preferably, the reaction temperature of the slurry polymerization is 30-80°C, and the reaction pressure is 0.1-2.0Mpa.

[0053] According to a specific embodiment of the present invention, preferably, the solvent for the slurry polymerization is C5-C 10 An alkane, more preferably hexane.

[0054] 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 usually used in the polymerization process to adjust the molecular weight of the polymer or the melt index of the polymer.

[0055] The functional monomer selected for preparing the organic polymer carrier of the present invention is an unsaturated 1,3-propylene glycol ether monomer that can be used for free radical polymerization. By selecting a solvent system with a suitable solubility parameter, a POP carrier with good specific surface area, pore volume, bulk density, fluidity, etc. is prepared by dispersion polymerization. Due to the addition of the 1,3-propylene glycol ether functional group in the carrier POP-(ROR)2, the microchemical environment of the Ti and Mg active centers is regulated, so that the prepared catalyst has good olefin insertion, stereospecific ability, catalyst activity, narrow molecular weight distribution and other characteristics, and the catalyst has good olefin copolymerization performance. In the catalyst preparation process, it is not necessary to add an additional internal electron donor (additional internal electron donors can also be added). When propylene is polymerized, a silane external electron donor and a triethylaluminum co-catalyst are added, and the catalyst has good polymerization activity, and the polymer isotacticity is high, which can reach more than 98%. In addition, the product has a narrower molecular weight distribution, and the molecular weight distribution is between 4 and 7.

[0056] The ZN olefin polymerization catalyst system of organic polymer load of the present invention needs to add extra external electron donor in polymerization, and both should be matched appropriately to give play to the excellent performance of high catalytic activity and high directional ability. Usually, the cocatalyst AlEt3 can be complexed with the internal electron donor, causing the Ti atom and the internal electron donor to lose stability, and will reoccupy the random active position complexed by the internal electron donor, causing the decline of the catalyst directional ability. Adding the external electron donor, it can be preferentially combined with AlEt3, avoiding the internal electron donor from falling off, making the internal electron donor compound by AlEt3 The amount of removal is reduced, ensuring the stability of the stereoactive center. Thereby in the polymerization process, it is necessary to supplement the extra external electron donor, so that the polymerization prepared has higher isotacticity. DETAILED DESCRIPTION

[0057] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0058] In the present invention, divinylbenzene (DVB) can be a commercially available monomer with a DVB content of 55% or 80%. The monomer needs to be pretreated before use to remove the polymerization inhibitor. There are many methods for removing the polymerization inhibitor in the prior art. For example, divinylbenzene and styrene can be washed with NaOH solution and distilled water. Additional monomers such as hydroxyethyl methacrylate can be used after removing the polymerization inhibitor using a neutral alumina column.

[0059] There are many methods for preparing the unsaturated 1,3-propylene glycol ether in the present invention. The unsaturated 1,3-propylene glycol ether can be prepared by reacting unsaturated propylene glycol with the corresponding chloroalkane according to the prior art (reference document 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).

[0060] The specific surface area of ​​the organic polymer carrier prepared by the present invention is tested by Nova 2000e using the BET nitrogen adsorption method, and the specific surface area of ​​the carrier prepared by the present invention is controlled to be greater than 100m 2 / g, usually controlled at 100-600m 2 / g, and the pore volume is greater than 0.2ml / g.

[0061] The molecular weight and distribution of the polymer prepared by olefin polymerization in the present invention are obtained by gel permeation chromatography (GPC) of Polymer Char Company; the isotacticity of the polymer is obtained by n-heptane extraction test (refer to standard GBT 2412-2008). The internal electron donor content can be determined by extraction and gas chromatography.

[0062] Preparation of unsaturated 1,3-propylene glycol ether functional monomers

[0063] Preparation Example 1

[0064] This preparation example provides 2-allyl-2-methyl-1,3-propylene glycol dimethyl ether monomer, which is prepared by the following steps:

[0065] All reactions were carried out under the protection of dry nitrogen. 3.4 g of 2-allyl-2-methyl-1,3-propanediol (CAS: 25462-37-7) was added to a 250 ml reactor and dissolved in 80 ml of tetrahydrofuran solvent. 5.2 g of NaH and 60 ml of THF were added to another 250 ml reactor, and the mixture was stirred and dispersed evenly. The temperature was kept 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 completed, the mixture was reacted at room temperature (25° C., the same below) for 2 hours. Then, the reaction temperature was lowered to 0° C., 7.5 g of iodomethane was added, and the mixture was reacted at 35° C. for 3 hours. After the reaction was completed, the reaction solution was washed with deionized water, the reactant was extracted with ether, and then dried with anhydrous sodium sulfate, filtered, and distilled under reduced pressure to obtain 2-allyl-2-methyl-1,3-propanediol dimethyl ether with a yield of 85%.

[0066] Preparation Example 2

[0067] This preparation example provides a 2-allyl-2-methyl-1,3-propylene glycol diphenyl ether monomer, which is prepared by the following steps:

[0068] In a 250 ml reactor, 3.8 g of 2-allyl-2-methyl-1,3-propanediol was added and dissolved in 80 ml of tetrahydrofuran solvent. In another 250 ml reactor, 5.2 g of NaH and 60 ml of THF were added, and the mixture was stirred and dispersed evenly. 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 completed, the mixture was reacted at room temperature for 2 hours. Then, the reaction temperature was lowered to 0° C., 9.7 g of iodinated benzene was added, and the mixture was reacted at 35° C. for 3 hours. After the reaction was completed, the reaction solution was washed with deionized water, the reactant was extracted with ether, and then dried with 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%.

[0069] Preparation Example 3

[0070] This preparation example provides 2-allyl-2-bromo-1,3-propanediol diisopropyl ether monomer, which is prepared by the following steps:

[0071] (1) Preparation of 2-allyl-2-bromo-1,3-propanediol (reference document Total Synthesis of (±)-Acetomycin and Design of Esterase-Resistant Analogs, published by Uenishi J. et al. in Chem. Pharm. Bull. 1999, Vol. 47, No. 4, pp. 517-523), 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 ether solvent were added to a 250 ml reactor, cooled to -20°C, 1.8 g of LiAlH4 was added, stirred and dispersed evenly, reacted for 3 hours, filtered, and distilled under reduced pressure to obtain 2-allyl-2-bromo-1,3-propanediol with a yield of 89%;

[0072] (2) Add 3.5 g of 2-allyl-2-bromo-1,3-propanediol and dissolve it in 80 ml of tetrahydrofuran solvent in a 250 ml reactor. Add 5.8 g of NaH and 60 ml of THF to another 250 ml reactor, stir and disperse evenly, keep the temperature at 0°C, then slowly drop the THF solution containing 2-allyl-2-bromo-1,3-propanediol into the reactor. After the dropwise addition is completed, react at room temperature for 2 hours, then lower the reaction temperature to 0°C, add 7.5 g of isopropyl iodide, and react at 35°C for 3 hours. After the reaction is completed, wash the reaction solution with deionized water, extract the reactant with ether, then dry it with anhydrous sodium sulfate, filter it, and distill it under reduced pressure to obtain 2-allyl-2-bromo-1,3-propanediol diisopropyl ether with a yield of 83%.

[0073] Preparation Example 4

[0074] This preparation example provides 2-allyl-2-bromo-1,3-propanediol di(4-tert-butylphenyl) ether monomer, which is prepared by the following steps:

[0075] 3.5 g of 2-allyl-2-bromo-1,3-propanediol was added to a 250 ml reactor and dissolved in 100 ml of tetrahydrofuran solvent. 5.6 g of NaH and 60 ml of THF were added to another 250 ml reactor, and the mixture was stirred and dispersed evenly. 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 completed, the mixture was reacted at room temperature for 2 hours. Then, the reaction temperature was lowered to 0° C., 16.5 g of 4-tert-butylphenyl iodide (CAS: 35779-04-5) was added, and the mixture was reacted at 35° C. for 3 hours. After the reaction was completed, the reaction solution was washed with deionized water, the reactant was extracted with ether, and then dried with 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%.

[0076] Preparation Example 5

[0077] This preparation example provides 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diisopropyl ether monomer, which is prepared by the following steps:

[0078] (1) Preparation of 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol Reference (Total Synthesis of (±)-Acetomycin and Design of Esterase-Resistant Analogs, published by Uenishi J. et al. in Chem. Pharm. Bull. 1999, Vol. 47, No. 4, pp. 517-523) 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 ether solvent were added to a 250 ml reactor, cooled 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%;

[0079] (2) Add 4.0 g of 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol and dissolve it in 80 ml of tetrahydrofuran solvent in a 250 ml reactor. Add 6.5 g of NaH and 60 ml of THF to another 250 ml reactor, stir and disperse evenly, keep the temperature at 0°C, then slowly drop the THF solution containing 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol into the reactor. After the dropwise addition is completed, react at room temperature for 2 hours, then lower the reaction temperature to 0°C, add 8.2 g of 2-iodopropane, and react at 35°C for 3 hours. After the reaction is completed, wash the reaction solution with deionized water, extract the reactant with ether, and then dry it with anhydrous sodium sulfate, filter it, and distill it under reduced pressure to obtain 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diisopropyl ether with a yield of 83%.

[0080] Example 1

[0081] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0082] (1) Preparation of porous organic polymer carrier:

[0083] In a 250mL glass reactor, add 90ml ethanol, 10ml deionized water and 15ml tetrahydrofuran, then add 6.0g divinylbenzene (Aladdin reagent, 55%) and 2.0g 2-allyl-2-methyl-1,3-propylene glycol dimethyl ether, stir at room temperature for 5min, then add 2% monomer mass of polyvinyl alcohol PVA (PVA, degree of polymerization 1750), stir at 45°C for 1h to completely dissolve the stabilizer, add 2.0% (0.15g) monomer mass of AIBN, heat to 70°C, react for 3 hours, then raise the temperature to 80°C, react for 12 hours, stir at 350 rpm, filter, add 100ml of ethanol and water (9:1 volume ratio) mixed solvent, wash 3 times, filter and dry to obtain 5.1g of free-flowing porous organic polymer carrier POP-1. The specific surface area of ​​the carrier is 187m 2 / g, pore volume 0.21ml / g;

[0084] (2) Preparation of ZN catalyst:

[0085] In a 250ml glass reactor, add 2g of the carrier POP-1 prepared from the above-mentioned 2-allyl-2-methyl-1,3-propylene glycol dimethyl ether functional monomer, add 100ml of toluene, stir, then add 10ml of 3M methylmagnesium chloride Grignard reagent at room temperature, stir for 2 hours, filter, wash twice with toluene, then add 50ml of toluene, add 50ml of TiCl4 dropwise at room temperature, heat to 60°C and react for 2 hours, filter, wash with toluene and hexane 3 times each, and obtain free-flowing catalyst particles after drying, recorded as Cat-1. The Mg content of catalyst Cat-1 is 3.0%, the titanium content is 3.8%, and the organic polymer carrier content is 75%.

[0086] Example 2

[0087] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0088] (1) Preparation of porous organic polymer carrier:

[0089] In a 250ml glass reactor, add 100ml ethanol, 10ml deionized water and 15ml tetrahydrofuran, then add 5.0g divinylbenzene (Aladdin reagent, 80%) and 3.2g 2-allyl-2-methyl-1,3-propylene glycol diphenyl ether, stir at room temperature for 5min, then add 2% monomer weight of polyvinyl alcohol PVA (PVA, degree of polymerization 1750), stir at 45°C for 1h to completely dissolve the stabilizer, add 2.0% monomer weight of AIBN, heat to 70°C, react for 3 hours, then raise the temperature to 80°C, react for 12 hours, stir at 350 rpm, filter, add 1000ml of ethanol and water (9:1 volume ratio) mixed solvent, wash 3 times, filter and dry to obtain 6.1g of free-flowing porous organic polymer carrier POP-2. The carrier has a specific surface area of ​​475m 2 / g, pore volume 0.63ml / g;

[0090] (2) Preparation of ZN catalyst:

[0091] In a 250ml glass reactor, add 2g of the carrier POP-2 prepared from the above-mentioned 2-allyl-2-methyl-1,3-propylene glycol diphenyl ether functional monomer, add 100ml of toluene, stir, then add 8ml of 3M methylmagnesium chloride Grignard reagent at 5°C, stir for 2 hours, filter, wash twice with toluene, then add 50ml of toluene, add 35ml of TiCl4 dropwise at room temperature, heat to 80°C, react for 1 hour, filter after the reaction, then add 50ml of toluene and 30ml of TiCl4 and react at 80°C for 2 hours, filter after the reaction, wash 3 times with toluene and hexane respectively, and obtain free-flowing catalyst particles after drying, which are recorded as Cat-2. The Mg content of the catalyst Cat-2 is 2.7%, the titanium content is 2.5%, and the organic polymer carrier content is 81%.

[0092] Example 3

[0093] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0094] Preparation of ZN catalyst: In a 250ml glass reactor, add 2g of the carrier POP-2 prepared above, add 100ml of toluene, stir, then add 10ml of 3M benzylmagnesium chloride Grignard reagent at 35°C, stir for 2 hours, filter, wash twice with toluene, then heat to 50°C, add 40ml TiCl4 dropwise, react for 2 hours, then heat to 80°C, react for 3 hours, after the reaction is completed, filter, then add 50ml toluene and 30ml TiCl4 and react at 80°C for 2 hours, filter after the reaction is completed, wash 3 times with toluene and hexane respectively, and obtain free-flowing catalyst particles after drying, recorded as Cat-3. The Mg content of catalyst Cat-3 is 3.2%, the titanium content is 2.4%, and the organic polymer carrier content is 78%.

[0095] Example 4

[0096] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0097] (1) Preparation of porous organic polymer carrier:

[0098] In a 250ml glass reactor, add 100ml ethanol, 20ml water and 15ml ethyl acetate, then add 6.0g divinylbenzene (Aladdin reagent, 80%) and 3.0g 2-allyl-2-bromo-1,3-propylene glycol diisopropyl ether, stir at room temperature for 5min, then add 2% monomer mass of block copolymer F127 of polyethylene oxide and polypropylene oxide, stir at 45℃ for 1h to completely dissolve the stabilizer, add 2.0% monomer mass of dibenzoyl peroxide BPO, heat to 70℃, react for 3 hours, then raise the temperature to 80℃, react for 8 hours, stir at 550 rpm, filter, add 100ml mixed solvent of ethanol and water (9:1 volume ratio) and wash 3 times, filter and dry to obtain 7.1g free-flowing porous organic polymer carrier POP-3. The specific surface area of ​​the carrier is 283m 2 / g, pore volume 0.37ml / g;

[0099] (2) Preparation of ZN catalyst:

[0100] In a 250ml glass reactor, add 3g of the carrier POP-3 prepared by polymerization of the functional monomer of 2-allyl-2-bromo-1,3-propylene glycol diisopropyl ether, add 100ml of toluene, stir, then add 15ml of 3M methylmagnesium chloride Grignard reagent at 35°C, stir for 2 hours, filter, wash twice with toluene, add 50ml of toluene, then heat to 50°C, add 50mlTiCl4 dropwise, react for 2 hours, then heat to 80°C, react for 2 hours, filter after the reaction, wash with toluene and hexane 3 times each, and obtain free-flowing catalyst particles after drying, recorded as Cat-4. The Mg content of catalyst Cat-4 is 4.2%, the titanium content is 4.0%, and the organic polymer carrier content is 72%.

[0101] Example 5

[0102] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0103] Preparation of ZN catalyst: In a 250ml glass reactor, add 3g of the carrier POP-3 prepared by polymerization of 2-allyl-2-bromo-1,3-propylene glycol diisopropyl ether functional monomer, add 100ml of toluene, stir, then add 10ml of 3M methylmagnesium chloride Grignard reagent at room temperature, stir for 3 hours, filter, wash twice with toluene, add 50ml of toluene, then heat to 50°C, add 30ml TiCl4 dropwise, react for 2 hours, then heat to 80°C, add 0.25g of diisobutyl phthalate internal electron donor, react for 3 hours, after the reaction is completed, filter, wash 3 times with toluene and hexane respectively, and obtain free-flowing catalyst particles after drying, recorded as Cat-5. The Mg content of catalyst Cat-5 is 2.8%, the titanium content is 3.7%, the internal electron donor content is 2.1%, and the organic polymer carrier content is 73%.

[0104] Example 6

[0105] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0106] (1) Preparation of porous organic polymer carrier:

[0107] In a 250ml glass reactor, add 90ml ethanol, 10ml water and 30ml butyl acetate, then add 6.0g divinylbenzene (Aladdin reagent, 55%) and 3.0g 2-allyl-2-bromo-1,3-propylene glycol di(4-tert-butylphenyl) ether, stir at room temperature for 5min, then add 5% monomer mass of block copolymer F127 of polyethylene oxide and polypropylene oxide, stir at 45℃ for 1h to completely dissolve the stabilizer, add 2.0% monomer mass of AIBN, heat to 70℃, react for 3 hours, then raise the temperature to 80℃, react for 8 hours, stir at 600 rpm, filter, add 100ml mixed solvent of ethanol and water (9:1 volume ratio) and wash 3 times, filter and dry to obtain 5.8g free-flowing porous organic polymer carrier POP-4. The specific surface area of ​​the carrier is 272m 2 / g, pore volume 0.51ml / g;

[0108] (2) Preparation of ZN catalyst: In a 250 ml glass reactor, add 3 g of the carrier POP-4 prepared from the functional monomer of 2-allyl-2-bromo-1,3-propanediol di(4-tert-butylphenyl)ether, add 100 ml of toluene, stir, then add 10 ml of 3M butylmagnesium bromide Grignard reagent at 35°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, react for 3 hours. After the reaction is completed, filter, wash with toluene and hexane 3 times each, and dry to obtain free-flowing catalyst particles, denoted as Cat-6. The Mg content of catalyst Cat-6 is 2.7%, the titanium content is 2.4%, and the organic polymer carrier content is 79%.

[0109] Example 7

[0110] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0111] (1) Preparation of porous organic polymer carrier:

[0112] In a 250ml glass reactor, add 110ml ethanol, 12ml water and 20ml tetrahydrofuran, then add 6.0g divinylbenzene (Aladdin reagent, 80%) and 2.5g 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propylene glycol diisopropyl ether, stir at room temperature for 5min, then add 2% monomer mass of polyethylene oxide and polypropylene oxide block copolymer F127, stir at 45℃ for 1h to completely dissolve the stabilizer, add 2.0% monomer mass of AIBN, heat to 70℃, react for 3 hours, then raise the temperature to 80℃, react for 8 hours, stir at 550 rpm, filter, add 100ml of ethanol and water (9:1 volume ratio) mixed solvent to wash 3 times, filter and dry to obtain 6.3g of free-flowing porous organic polymer carrier POP-5. The carrier has a specific surface area of ​​538m 2 / g, pore volume 0.51ml / g;

[0113] (2) Preparation of ZN catalyst:

[0114] In a 250ml glass reactor, add 3g of the carrier POP-5 prepared from the functional monomer of 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propylene glycol diisopropyl ether, add 100ml of toluene, stir, then add 12ml3M di-n-butyl magnesium at room temperature, stir for 3 hours, filter, wash twice with toluene, add 50ml of toluene, then heat to 50°C, add 30mlTiCl4 dropwise, react for 2 hours, then heat to 80°C, filter, then add 100ml TiCl4 and react at 80°C for 2 hours. After filtering, wash with toluene and hexane 3 times each, and obtain free-flowing catalyst particles after drying, recorded as Cat-7. The Mg content of catalyst Cat-7 is 3.2%, the titanium content is 3.5%, and the organic polymer carrier content is 74%.

[0115] Example 8

[0116] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0117] (1) Preparation of porous organic polymer carrier:

[0118] In a 250 ml glass reactor, 100 ml of ethanol, 15 ml of water and 15 ml of tetrahydrofuran were added, followed by 6.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.5 g of 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propylene glycol diisopropyl ether and 1.0 g of hydroxyethyl methacrylate. The mixture was stirred at room temperature for 5 min, and then 2% of the monomer mass of the block copolymer of polyethylene oxide and polypropylene oxide F127 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, the temperature was raised to 70 ° C, and the reaction was carried out for 3 hours. The temperature was then raised to 80 ° C. After the reaction for 8 hours, the stirring speed was 350 rpm. After filtration, 100 ml of a mixed solvent of ethanol and water (9:1 volume ratio) was added to wash 3 times. After filtration and drying, 7.2 g of a free-flowing porous organic polymer carrier POP-6 was obtained. The specific surface area of ​​the carrier is 308m 2 / g, pore volume 0.32ml / g;

[0119] (2) Preparation of ZN catalyst:

[0120] In a 250 ml glass reactor, add 3 g of the carrier POP-6 prepared from the functional monomer of 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propylene glycol 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, filter after the reaction, then add 100 ml TiCl4 was reacted at 80°C for 1 hour, filtered, washed 3 times with toluene and 3 times with hexane, and dried to obtain free-flowing catalyst particles, which were designated 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 carrier content of 71%.

[0121] Example 9

[0122] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0123] Preparation of ZN catalyst: In a 250ml glass reactor, add 3g of the carrier POP-6 prepared from the functional monomer of 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propylene glycol diisopropyl ether and the third monomer hydroxyethyl methacrylate, add 100ml of toluene, stir, then add 12ml of 3M methylmagnesium chloride Grignard reagent at 20°C, stir for 2 hours, filter, wash twice with toluene, add 50ml of toluene, then heat to 80°C, add 50ml of TiCl4 dropwise, react for 3 hours, filter after the reaction, wash 3 times with toluene and hexane respectively, and obtain free-flowing catalyst particles after drying, recorded as Cat-9. The Mg content of catalyst Cat-9 is 3.5%, the titanium content is 3.2%, and the organic polymer carrier content is 75%.

[0124] Comparative Example 1

[0125] This comparative example provides a ZN catalyst, which is prepared by the following steps:

[0126] Preparation of inorganic carrier-supported ZN polypropylene catalyst: In a 250ml glass reactor, add 3g of spherical ethoxymagnesium carrier (Japan Soda Co., Ltd.), add 100ml of toluene, stir, then slowly add 50ml of TiCl4 at 0°C, control the dropping speed, and control the temperature at 0-5°C. After the addition is complete, heat to 60°C, add 0.30g of DIBP internal electron donor, react at 110°C for 2 hours, filter, then add 100ml of fresh TiCl4, react at 110°C for 2 hours, filter, and then wash with toluene and hexane 3 times each. After drying, free-flowing catalyst particles are obtained, recorded as Cat-10, with a titanium content of 3.2% and an electron donor content of 8.9% in DIBP.

[0127] Comparative Example 2

[0128] This comparative example provides a ZN catalyst, which is prepared by the following steps:

[0129] Preparation of inorganic carrier-supported ZN polypropylene catalyst: In a 250ml glass reactor, add 3g of spherical ethoxymagnesium carrier (Japan Soda Co., Ltd.), add 100ml of toluene, stir, then slowly add 50ml of TiCl4 at 0℃, control the dropping speed, and control the temperature at 0-5℃. After the addition is completed, heat to 60℃, add 0.40g of 9,9-dimethoxyfluorene internal electron donor, react at 110℃ for 2 hours, filter, and then add 100ml of fresh TiCl4, react at 110℃ for 2 hours. After the reaction is completed, filter, wash with toluene and hexane 3 times each, and obtain free-flowing catalyst particles after drying, recorded as Cat-11, with a titanium content of 3.2% and a 9,9-dimethoxyfluorene internal electron donor content of 6.2%.

[0130] Comparative Example 3

[0131] This comparative example provides an inorganic carrier-supported ZN catalyst, which is prepared by the following steps:

[0132] In a 250ml glass reactor, add 3g of spherical ethoxymagnesium carrier (Japan Soda Co., Ltd.), add 50ml of toluene, stir, slowly add 30ml of TiCl4 at 50°C, react for 2 hours, heat to 80°C, add 0.25g of diisobutyl phthalate internal electron donor, react for 3 hours. After the reaction is completed, filter, wash with toluene and hexane 3 times each, and obtain free-flowing catalyst particles after drying, recorded as Cat-12. The titanium content of catalyst Cat-12 is 3.8%, and the content of DIBP internal electron donor is 4.9%.

[0133] Comparative Example 4

[0134] This comparative example provides an inorganic carrier-supported ZN catalyst, which is prepared by the following steps:

[0135] In a 250ml glass reactor, 3g of spherical ethoxymagnesium carrier (Japan Soda Co., Ltd.) was added, 50ml of toluene was added, the temperature was raised to 50°C, and then 30ml of TiCl4 was slowly added dropwise, the reaction was carried out for 2 hours, and then the temperature was raised to 80°C, 0.20g of 9,9-dimethoxyfluorene internal electron donor was added, and the reaction was carried out for 3 hours. After the reaction was completed, it was filtered, and 100ml of TiCl4 was added and reacted at 80°C for 1 hour. After the reaction was completed, it was filtered, and the mixture was washed 3 times with toluene and hexane respectively. After drying, free-flowing catalyst particles were obtained, which were recorded as Cat-13. The titanium content of catalyst Cat-13 was 3.4%, and the content of 9,9-dimethoxyfluorene internal electron donor was 3.7%.

[0136] Propylene polymerization

[0137] Test Example 1

[0138] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 6mg of catalyst Cat-18 and 0.5ml of cyclohexylmethyldimethoxysilane (C external supply) were added, and 0.3g of hydrogen was added. The temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature and dried to obtain 719g of polypropylene product (PP-1) with a bulk density of 0.36g / ml and a catalyst activity of 8360gPP / gcat.h. The results are shown in Table 1.

[0139] Test Example 2

[0140] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 80mg of the catalyst Cat-1 and 0.5ml of dicyclopentene dimethoxysilane (D externally supplied) were added. 0.5g of hydrogen was added, the temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature and dried to obtain 612g of a polypropylene product (PP-2) with a bulk density of 0.36g / ml and a catalyst activity of 7650gPP / gcat.h. The results are shown in Table 1.

[0141] Test Example 3

[0142] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 80mg of the catalyst Cat-2 and 0.3ml of cyclohexylmethyldimethoxysilane (C externally supplied) were added. 0.5g of hydrogen was added, the temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 760g of a polypropylene product (PP-3) was obtained, with a bulk density of 0.36g / ml and a catalyst activity of 9500gPP / gcat.h. The results are shown in Table 1.

[0143] Test Example 4

[0144] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 80mg of the catalyst Cat-3 and 0.3ml of cyclohexylmethyldimethoxysilane (C external supply) were added. 0.5g of hydrogen was added, the temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 665g of a polypropylene product (PP-4) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 8313gPP / gcat.h. The results are shown in Table 1.

[0145] Test Example 5

[0146] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 80mg of the catalyst Cat-4 and 0.3ml of cyclohexylmethyldimethoxysilane (C externally supplied) were added. 0.5g of hydrogen was added, the temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 932g of a polypropylene product (PP-5) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 11650gPP / gcat.h. The results are shown in Table 1.

[0147] Test Example 6

[0148] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 80mg of the catalyst Cat-5 and 0.3ml of cyclohexylmethyldimethoxysilane (C externally supplied) were added. 0.5g of hydrogen was added, the temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 1002g of a polypropylene product (PP-6) was obtained, with a bulk density of 0.38g / ml and a catalyst activity of 12525gPP / gcat.h. The results are shown in Table 1.

[0149] Test Example 7

[0150] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 80mg of the catalyst Cat-6 and 0.5ml of dicyclopentene dimethoxysilane (D externally supplied) were added. 0.7g of hydrogen was added, and the temperature was raised to 70°C. Polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 1028g of a polypropylene product (PP-7) was obtained, with a bulk density of 0.38g / ml and a catalyst activity of 12850gPP / gcat.h. The results are shown in Table 1.

[0151] Test Example 8

[0152] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 80mg of the catalyst Cat-7 and 0.5ml of cyclohexylmethyldimethoxysilane (C external supply) were added. 0.5g of hydrogen was added, the temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 1136g of a polypropylene product (PP-8) was obtained, with a bulk density of 0.40g / ml and a catalyst activity of 14200gPP / gcat.h. The results are shown in Table 1.

[0153] Test Example 9

[0154] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 85mg of the catalyst Cat-8 and 0.5ml of dicyclopentene dimethoxysilane (D externally supplied) were added, and 0.5g of hydrogen was added. The temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 1179g of a polypropylene product (PP-9) was obtained, with a bulk density of 0.38g / ml and a catalyst activity of 13871gPP / gcat.h. The results are shown in Table 1.

[0155] Test Example 10

[0156] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 82mg of the catalyst Cat-9 and 0.3ml of cyclohexylmethyldimethoxysilane (C external supply) were added, and 0.5g of hydrogen was added. The temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature and dried to obtain 948g of a polypropylene product (PP-10) with a bulk density of 0.37g / ml and a catalyst activity of 11560gPP / gcat.h. The results are shown in Table 1.

[0157] Comparative test example 1

[0158] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 60mg of the catalyst Cat-10 and 0.3ml of cyclohexylmethyldimethoxysilane (C external supply) were added. 0.5g of hydrogen was added, the temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 1119g of a polypropylene product (PP-11) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 18650gPP / gcat.h. The results are shown in Table 1.

[0159] Comparative test example 2

[0160] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 160mg of the catalyst Cat-1 and 0.3ml of cyclohexylmethyldimethoxysilane (C external supply) were added. 0.5g of hydrogen was added, the temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 1280g of a polypropylene product (PP-12) was obtained, with a bulk density of 0.42g / ml and a catalyst activity of 21333gPP / gcat.h. The results are shown in Table 1.

[0161] Comparative test example 3

[0162] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 260mg of comparative catalyst Cat-1 and 0.3ml of cyclohexylmethyldimethoxysilane (C external supply) were added, and 0.5g of hydrogen was added. The temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature and dried to obtain 948g of a polypropylene product (PP-13) with a bulk density of 0.38g / ml and a catalyst activity of 15800gPP / gcat.h, as shown in Table 1.

[0163] Comparative test example 4

[0164] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 360mg of comparative catalyst Cat-1 and 0.3ml of cyclohexylmethyldimethoxysilane (C external supply) were added, and 0.5g of hydrogen was added. The temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 1240g of polypropylene product (PP-14) was obtained, with a bulk density of 0.41g / ml and a catalyst activity of 20667gPP / gcat.h, as shown in Table 1.

[0165] Table 1 Propylene polymerization results

[0166]

[0167] Test Example 11 Copolymerization of propylene and ethylene

[0168] In a 10L dried propylene polymerization reactor, 2.0kg liquid propylene, 10ml triethylaluminum TEA (1.0 mol / L) were added, the stirring speed was 600 rpm, then 60mg of the above-prepared catalyst Cat-4 and 0.5ml cyclohexylmethyldimethoxysilane (C external supply) were added, 0.3g hydrogen and 50g ethylene monomer were added, the temperature was raised to 70°C, the polymerization was carried out under stirring at 600 rpm for 1 hour, the pressure was released, the mixture was cooled to room temperature, and 825g of ethylene-propylene copolymer product was obtained after drying. The catalyst polymerization activity was 13750gPP / gcat.h, the weight average molecular weight Mw of the polymer was 417,000, and the molecular weight distribution coefficient was 5.3.

[0169] Test Example 12 Copolymerization of propylene and ethylene

[0170] In a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 60mg of the catalyst Cat-5 and 0.3ml of cyclohexylmethyldimethoxysilane (C external supply) were added. 0.5g of hydrogen and 50g of ethylene monomer were added, and the temperature was raised to 70°C. Polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 889g of ethylene-propylene copolymer product was obtained, with a catalyst activity of 14820gPP / gcat.h, a polymer weight-average molecular weight Mw of 382,000, and a molecular weight distribution coefficient of 6.1.

[0171] Test Example 13 Copolymerization of propylene and ethylene

[0172] In a 10L dried propylene polymerization reactor, 2.0kg liquid propylene, 10ml triethylaluminum TEA (1.0 mol / L) were added, the stirring speed was 600 rpm, then 60mg of the above-prepared catalyst Cat-7 and 0.5ml cyclohexylmethyldimethoxysilane (C external supply) were added, 0.5g hydrogen and 50g ethylene monomer were added, the temperature was raised to 70°C, the polymerization was carried out under stirring at 600 rpm for 1 hour, the pressure was released, the mixture was cooled to room temperature, and 894g of ethylene-propylene copolymer product was obtained after drying. The catalyst polymerization activity was 14900gPP / gcat.h, the weight average molecular weight Mw of the polymer was 295,000, and the molecular weight distribution coefficient was 5.8.

[0173] From the above polymerization results, it can be seen that the organic carrier type POP-(ROR)2 / RMgX / TiCl4 polypropylene catalyst solid component prepared by using free radical polymerizable functional monomers containing unsaturated 1,3-propylene glycol ether groups in the present invention has good catalytic activity, and the propylene homopolymerization activity can reach more than 12000gPP / gcat.h. Although it is lower than the catalyst supported by the traditional inorganic MgCl2 carrier, its activity is greatly improved compared with the polymerization activity of the existing organic polymer carrier, which can meet the level of the existing industrial catalyst. Through the screened free radical polymerizable functional monomers containing unsaturated 1,3-propylene glycol ether groups, relying on the functional groups of 1,3-diether on the carrier, the microchemical environment of the metal active center is regulated, so that the catalyst has good stereospecific ability, even if no additional internal electron donor is added, the prepared polypropylene has a high isotacticity, which can reach more than 97%, the polymer molecular weight distribution is narrow, and the molecular weight distribution coefficient can be controlled between 4-7.

[0174] Compared with Comparative Example 1 (adding the same conventional internal electron donor such as DIBP), the polymer prepared by the catalyst Cat-5 prepared in Example 5 has higher isotacticity than the catalysts in Comparative Examples 1 and 3; compared with Comparative Examples 2 and 4 (using 9,9-dimethoxyfluorene internal electron donor with high stereoregularity and relatively narrow molecular weight distribution), the catalyst Cat-8 prepared in Example 8 has higher stereoregularity and narrower molecular weight distribution.

[0175] Compared with existing catalysts, the POP-(ROR)2 / RMgX / TiCl4 polypropylene catalyst disclosed in the present invention has a simple preparation method, its active center has high stereospecific ability, narrow molecular weight distribution, good copolymerization performance, and good industrial prospects.

Claims

1. An organic polymer carrier obtained by copolymerizing monomers including divinylbenzene and unsaturated 1,3-propylene glycol ether monomers; in, The unsaturated 1,3-propylene glycol ether monomer has a structure shown in Formula I: In Formula I, R1, R2, and R3 are each independently selected from hydrogen, chlorine, fluorine, bromine, hydroxyl, C1-C6 straight-chain alkyl and its derivatives, C1-C6 branched-chain alkyl and its derivatives, cycloalkyl and its derivatives, aromatic group and its derivatives; x is 0-3; R4 is selected from hydrogen, chlorine, fluorine, bromine, hydroxyl, C1-C 10 Straight-chain alkyl and its derivatives, C1-C 10 branched alkyl and its derivatives, cycloalkyl and its derivatives, aromatic and its derivatives, alkoxy; R5, R6 are each independently selected from C1-C 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 connected to each other to form a ring.

2. The organic polymer carrier 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, bromine, and hydroxyl; R4 is selected from hydrogen, methyl, n-propyl, isopropyl, phenyl, fluorine, chlorine, bromine, 3-trifluoromethyl, isobutyl, hydroxy, benzyloxy, 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, 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; Preferably, 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.

3. The organic polymer carrier according to claim 1, wherein The unsaturated 1,3-propylene glycol ether monomer is selected from 2-allyl-1,3-propylene glycol dimethyl ether, 2-allyl-1,3-propylene glycol diethyl ether, 2-allyl-1,3-propylene glycol di-n-propyl ether, 2-allyl-1,3-propylene glycol diisopropyl ether, 2-allyl-1,3-propylene glycol di-n-butyl ether, 2-allyl-1,3-propylene glycol diisobutyl ether, 2-allyl-1,3-propylene glycol diphenyl ether, 2-(1-methylallyl)-1,3-propylene glycol dimethyl ether, 2-(1-methylallyl)-1,3-propylene glycol diethyl ether, 2-(1-methylallyl)-1,3-propylene glycol di-n-propyl ether, 2-(1-methylallyl)-1,3-propanediol diisopropyl ether, 2-(1-methylallyl)-1,3-propanediol diisopropyl ether, 2-(1-methylallyl)-1,3-propylene glycol di-n-butyl ether, 2-(1-methylallyl)-1,3-propylene glycol diisobutyl ether, 2-(1-methylallyl)-1,3-propylene glycol diphenyl ether, 2-allyl-2-propyl-1,3-propylene glycol dimethyl ether, 2-allyl-2-propyl-1,3-propylene glycol diethyl ether, 2-allyl-2-propyl-1,3-propylene glycol diisopropyl ether, 2-allyl-2-propyl-1,3-propylene glycol di-n-propyl ether, 2-allyl-2-propyl-1,3-propylene glycol di-n-butyl ether, 2-allyl-2-propyl-1,3-propylene glycol diisobutyl ether, 2-allyl-2-propyl-1,3-propylene glycol di-n-pentyl ether, 2-allyl-2-propyl-1,3-propylene glycol di-n-butyl ether 2-allyl-2-propyl-1,3-propanediol dioctyl 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) ether, 2-allyl-2-propyl-1,3-propanediol di 2-allyl-2-propyl-1,3-propanediol di(5-methyl-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-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 diisobutyl ether, 2-allyl-2-methyl-1,3-propanediol diisobutyl ether, 2-allyl-2-methyl-1,3-propanediol diisobutyl ether, 2-allyl-2-methyl-1, 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-propylene glycol di-n-propyl ether, 2-allyl-2-isopropyl-1,3-propylene glycol di-n-butyl ether, 2-allyl-2-isopropyl-1,3-propylene glycol di-n-butyl ether, 2-allyl-2-isopropyl-1,3-propylene glycol di-n-butyl ether, 2-allyl-2-isopropyl-1,3-propylene glycol di-n-pentyl ether, 2-allyl-2-isopropyl- 1,3-Propanediol di-n-hexyl 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, 2-(3-cyclopentenyl)-1,3-propylene glycol di-n-butyl ether, 2-(3-cyclopentenyl)-1,3-propylene glycol diisobutyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propylene glycol dimethyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propylene glycol diethyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propylene glycol diisopropyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propylene glycol di-n-butyl ether, 2-(1-chloroallyl)-2-propyl-1,3-propylene glycol diphenyl ether, 2-allyl-2-phenyl-1,3-propylene glycol dimethyl ether, 2-allyl-2-phenyl-1,3-propylene glycol diethyl ether, 2-allyl-2-phenyl-1,3-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-butyl ether, 2-allyl-2-chloro-1,3-propanediol 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-1,3-propanediol dimethyl ether, 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol 2-(3-chloro-2-butenyl)-2-isobutyl-1,3-propanediol diethyl 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 ether, 2-allyl-2-phenyl-1, 3-Propanediol dipentyl ether, 2-allyl-2-benzyloxy-1,3-propanediol dimethyl ether, 2-allyl-2-benzyloxy-1,3-propanediol diethyl ether, 2-allyl-2-benzyloxy-1,3-propanediol diisopropyl ether, 2-allyl-2-benzyloxy-1,3-propanediol diisobutyl ether, 2-allyl-2-benzyloxy-1,3-propanediol di-n-butyl ether, 2-allyl-2-benzyloxy-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-propylene glycol di-n-butyl ether, 2-(1-chloroallyl)-2-(4-tert-butylphenyl)-1,3-propylene glycol diphenyl ether, 2-(1-chloroallyl)-2-tert-butyl-1,3-propylene glycol diphenyl ether, 2-(1-chloroallyl)-2-isobutyl-1,3-propylene glycol diisopropyl ether, 2-allyl-2-methoxy-1,3-propylene glycol diisopropyl ether, or a combination of two or more thereof.

4. The organic polymer carrier according to claim 1, wherein Calculated based on 100% of the mass of the organic polymer carrier, the mass fraction of the unsaturated 1,3-propylene glycol ether monomer is 20-60%.

5. The method for preparing the organic polymer carrier according to any one of claims 1 to 4, comprising the following steps: The organic polymer carrier is prepared by copolymerizing monomers including the divinylbenzene, the unsaturated 1,3-propylene glycol ether monomer and the additional monomer as raw materials; The mass ratio of the additional monomer to divinylbenzene is 0-1:1; the mass ratio of the unsaturated 1,3-propylene glycol ether monomer to divinylbenzene is 0.2-2:1; Preferably, the organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization; the dispersion polymerization method comprises the following steps: adding divinylbenzene, unsaturated 1,3-propylene glycol ether monomer, additional monomer into a dispersion solvent, and 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.

6. The preparation method according to claim 5, wherein: The additional monomers include one or a combination of two or more of styrene, alkyl-substituted styrene, chloromethyl-substituted styrene, methacrylic acid, methacrylate, and hydroxyalkyl methacrylate.

7. The preparation method according to claim 5, wherein: 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 the alcohol to water is 5-15:1; Preferably, the C1-C4 alcohol includes one or a combination of two or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol; Preferably, the dispersion solvent further comprises an additional solvent; Preferably, the additional solvent includes one or a combination of two or more of ethyl acetate, methyl formate, butyl acetate, and tetrahydrofuran.

8. The preparation method according to claim 5, wherein The mass ratio of the total amount of monomer added to the dispersing solvent is 1:5-20.

9. The preparation method according to claim 5, wherein: The stabilizer is polyvinyl alcohol and / or polypropylene oxide-polyethylene oxide copolymer; Preferably, the weight average molecular weight of the stabilizer is 1000-100000; Preferably, the mass ratio of the amount of the stabilizer added to the total amount of the monomers added is 0.5-5:

100.

10. The preparation method according to claim 5, wherein: The initiator is azobisisobutyronitrile and / or dibenzoyl peroxide; Preferably, the mass ratio of the amount of the initiator added to the total amount of the monomers added is 0.5-3:

100.

11. The preparation method according to claim 5, wherein: The divinylbenzene is pretreated divinylbenzene, and the pretreatment is to remove the polymerization inhibitor.

12. A ZN catalyst, wherein the raw material composition comprises 60-85wt% of an organic polymer carrier, 1-5wt% of a magnesium compound calculated as magnesium element, 1-5wt% of a titanium compound calculated as titanium element, and 0-5wt% of an internal electron donor, based on the mass of the ZN catalyst being 100%. The organic polymer carrier is the organic polymer carrier according to any one of claims 1 to 4; Preferably, the content of the organic polymer carrier is 65-80wt%, the content of magnesium is 2-5wt%, and the content of titanium is 2-5wt%.

13. The ZN catalyst according to claim 12, wherein The magnesium compound is RMgX or R'MgR", wherein R, R', and R" are 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; Preferably, the R, R' and R" are each independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl and substituted phenyl.

14. The ZN catalyst according to claim 13, wherein The magnesium compound is one or a combination of two or more of an alkyl halogenated magnesium compound, an alkyl magnesium compound, and an alkoxy magnesium halide compound; Preferably, the magnesium compound includes one or a combination of two or more of methylmagnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, tert-butylmagnesium chloride, benzylmagnesium chloride, ethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, n-butylmagnesium bromide, benzylmagnesium bromide, methylmagnesium iodide, tert-butylmagnesium iodide, benzylmagnesium iodide, n-butylmagnesium iodide, methylmagnesium fluoride, tert-butylmagnesium fluoride, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, and ethoxymagnesium chloride.

15. The ZN catalyst according to claim 12, wherein The titanium compound is titanium tetrachloride.

16. The ZN catalyst according to claim 12, wherein The internal electron donor is one or a combination of two or more of diester compounds, diphenol ester compounds, glycol ester compounds, succinate ester compounds, and diether compounds.

17. The ZN catalyst according to claim 16, wherein The internal electron donor includes one or a combination of two or more of 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 dibenzyl ester, and 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether.

18. A method for preparing the ZN catalyst according to any one of claims 12 to 17, comprising the following steps: Under anhydrous and oxygen-free conditions, the organic polymer carrier is added to an inert solvent, the magnesium compound is added, and the reaction is carried out at 0°C-50°C for 15-120 minutes. The unreacted magnesium compound is filtered, and an inert solvent and titanium tetrachloride are added. The reaction is carried out at 0°C-80°C for 15-180 minutes. The internal electron donor is added, and the reaction is carried out at 50°C-120°C for 15-180 minutes. Finally, the ZN catalyst is washed with an inert solvent to obtain the ZN catalyst.

19. 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 12 to 17.

20. The ZN catalyst system according to claim 19, wherein The external electron donor includes a silane external electron donor; Preferably, the silane-based external electron donor includes one or a combination of two or more of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane and tetraethoxysilane.

21. The ZN catalyst system according to claim 20, wherein The molar ratio of silicon in the silane-based external electron donor to titanium in the ZN catalyst is 1-50.

22. The ZN catalyst system according to claim 19, wherein 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; Preferably, the R'' is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl; Preferably, the co-catalyst is triethylaluminum.

23. The ZN catalyst system according to claim 22, wherein: The molar ratio of aluminum in the alkyl aluminum compound to titanium in the ZN catalyst is 10-500.

24. Use of the ZN catalyst according to any one of claims 12 to 17 or the ZN catalyst system according to claims 19 to 23 in olefin polymerization.

25. The use according to claim 24, wherein: The olefin polymerization is propylene homopolymerization, propylene and ethylene copolymerization or α-olefin copolymerization; Preferably, the α-olefin includes one or a combination of two or more of butene, isobutylene, pentene, hexene, octene, and 4-methyl-1-pentene.

26. The use according to claim 24, wherein: The olefin polymerization is gas phase polymerization, bulk polymerization or slurry polymerization; Preferably, the reaction temperature of the slurry polymerization is 30-80°C and the reaction pressure is 0.1-2.0Mpa; Preferably, the solvent for the slurry polymerization is C5-C 10 An alkane, more preferably hexane; Preferably, the reaction pressure of the bulk polymerization is 2.8-4.0 MPa, and the reaction temperature is 68-72°C.

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