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

Abstract

The invention provides an organic polymer carrier, a Z-N catalyst as well as a preparation method and application of the Z-N catalyst. The organic polymer carrier is obtained by copolymerizing monomers including divinyl benzene and unsaturated organic phosphonate monomers; wherein the unsaturated organic phosphonate monomer has a structure as shown in a formula I: # imgabs0 #, the catalyst has good stereotactic ability and polymerization catalytic activity, and can be used for polymerization of ethylene and propylene and copolymerization of propylene and other alpha-olefins, an obtained polymer product is high in isotacticity, and molecular weight distribution can be adjusted in a wide range.

Description

Technical Field

[0001] The invention belongs to the field of catalysts, and specifically relates to an organic polymer carrier, a ZN catalyst, and a preparation method and application thereof. Background Art

[0002] Since the discovery of ZN catalysts in the 1950s, with the innovation of polyolefin production technology and catalysts, the production and demand of polyolefins have continued to grow. In 2021, the global polyethylene production exceeded 110 million tons and the global polypropylene production exceeded 76 million tons. At present, commercial polypropylene catalysts are mainly ZN-type catalysts with high stereoregularity, which are used to produce isotactic polypropylene (iPP) or ethylene-propylene impact copolymer polypropylene containing a rubber phase dispersed in an iPP matrix. The isotacticity of the homopolymer part of polypropylene is usually greater than 96%; in addition, metallocene catalysts, post-metallocene catalysts and other catalysts are used to produce a small amount of isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene and propylene-based elastomers. For industrial polypropylene production equipment, such as slurry polymerization, bulk or gas phase polymerization processes, the catalyst needs to be loaded to control the morphology of the generated polymer and avoid problems such as reactor agglomeration or blockage.

[0003] 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; in 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, such as 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 reviews 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. The above internal electron donors show good polymerization activity and high chain regularity during propylene polymerization.

[0004] In addition, the catalyst can also be prepared by a dissolution-precipitation process to prepare a polypropylene catalyst. For example, in CN1258684A, tributyl phosphate and epichlorohydrin solvents are used to dissolve anhydrous MgCl2, and then phthalic anhydride is added. When TiCl4 is slowly added, a solid catalyst is precipitated, and finally an internal electron donor such as diisobutyl phthalate is added, and a polypropylene catalyst is obtained after secondary titanium loading.

[0005] In food and pharmaceutical packaging materials, polypropylene is usually required to have high isotacticity or low organic solvent precipitation content to meet the requirements of materials in these fields. Inorganic carrier-supported polypropylene catalysts usually 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. The POP carrier itself will not introduce impurities, thereby affecting the performance of the polymer; in addition, organic carriers have controllable pore structure, high specific surface area, stable thermal properties, and are easy to functionalize; high-performance or characteristic polyolefin catalysts can be prepared through the design and functionalization of the carrier. 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 support-based olefin catalysts are mainly polyethylene catalysts, and there are few reports on their use in propylene polymerization. For example, “Sulfonated porous organic polymer supported ZN polypropylene catalysts with high stereoregularity and broad molecular weight distribution” (Vol. 343, 2022, 112151) in Microporous and Mesoporous Materials reports a POP support-loaded ZN catalyst prepared using styrene sulfonic acid functional monomers. When an additional diphenol ester is added as an internal electron donor, the catalyst has a wider molecular weight distribution and a higher isotacticity, reaching more than 98%. However, the isotacticity and activity of the polypropylene obtained by this catalyst system without the addition of an additional internal electron donor are low, and have not yet reached commercial levels. Summary of the invention

[0006] In order to solve the above problems, the purpose of the present invention is to provide an organic polymer carrier, a ZN catalyst and a preparation method and application thereof. The catalyst has good stereospecific ability and polymerization catalytic activity, can be used for the polymerization of ethylene and propylene, and the copolymerization of propylene and other α-olefins. The obtained polymer product has high isotacticity and the molecular weight distribution can be adjusted within a wide range.

[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 organic phosphonate monomers;

[0008] Wherein, the unsaturated organic phosphonate monomer has a structure shown in Formula I:

[0009]

[0010] In Formula I, R1 and R2 are each independently selected from hydrogen, C1-C 10 Straight-chain alkyl and its derivatives, C1-C 10 R3, R4 and R5 are each independently selected from hydrogen, halogen, C1-C8 straight or branched chain hydrocarbon groups and derivatives thereof, cycloalkyl groups and derivatives thereof, aromatic groups and derivatives thereof; wherein halogen is preferably F, Cl or Br; R6 is selected from a single bond, C1-C8 straight or branched chain alkylene groups and derivatives thereof, cycloalkylene groups and derivatives thereof, aromatic groups and derivatives thereof; a single bond means that there is no substituent at this position, and the carbon atom on the olefin group is directly bonded to the P atom.

[0011] According to a specific embodiment of the present invention, preferably, in Formula I, R1 and R2 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, isopentyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, phenyl, benzyl; R3, R4 and R5 are each independently selected from hydrogen, methyl, ethyl, propyl, chlorine, phenyl; R6 is selected from a single bond, methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,4-phenylene.

[0012] According to a specific embodiment of the present invention, preferably, the unsaturated organic phosphonate monomer is selected from dimethyl vinylphosphonate, diethyl vinylphosphonate, di-n-propyl vinylphosphonate, diisopropyl vinylphosphonate, di-n-butyl vinylphosphonate, diisobutyl vinylphosphonate, diisopentyl vinylphosphonate, di-n-hexyl vinylphosphonate, di-n-heptyl vinylphosphonate, diisoheptyl vinylphosphonate, di-n-octyl vinylphosphonate, diisooctyl vinylphosphonate, diphenyl vinylphosphonate, dibenzyl vinylphosphonate, vinylphosphonic acid, dimethyl allylphosphonate, dimethyl 2-methylallylphosphonate, diethyl allylphosphonate, diethyl 2-methylallylphosphonate, di-n-propyl allylphosphonate. , diisopropyl allylphosphonate, di-n-butyl allylphosphonate, diisobutyl allylphosphonate, diisopentyl allylphosphonate, di-n-hexyl allylphosphonate, di-n-heptyl allylphosphonate, diisoheptyl allylphosphonate, di-n-octyl allylphosphonate, diisooctyl allylphosphonate, diphenyl allylphosphonate, dibenzyl allylphosphonate, allylphosphonic acid, dimethyl 1-butenylphosphonate, diethyl 1-butenylphosphonate, diisopropyl 1-butenylphosphonate, di-n-propyl 1-butenylphosphonate, di-n-butyl 1-butenylphosphonate, di-n-pentyl 1-butenylphosphonate, di-n-hexyl 1-butenylphosphonate, di-n-heptyl 1-butenylphosphonate, di-n-octyl 1-butenylphosphonate, 1-chloro-1-butenylphosphonate, diethyl 2-butenylphosphonate, dimethyl 2-butenylphosphonate, diethyl 2-butenylphosphonate, di-n-propyl 2-butenylphosphonate, diisopropyl 2-butenylphosphonate, di-n-butyl 2-butenylphosphonate, diisobutyl 2-butenylphosphonate, (3-phenylallyl)phosphonic acid, dimethyl (3-phenylallyl)phosphonate, diethyl (3-phenylallyl)phosphonate, di-n-propyl (3-phenylallyl)phosphonate, diisopropyl (3-phenylallyl)phosphonate, di-n-butyl (3-phenylallyl)phosphonate, diisobutyl (3-phenylallyl)phosphonate, dimethyl 4-vinylphenylphosphonate, diethyl 4-vinylphenylphosphonate, di-n-propyl 4-vinylphenylphosphonate, 4-vinyl The invention comprises one or a combination of two or more of diisopropyl phenylphosphonate, di-n-butyl 4-vinylphenylphosphonate, di-n-pentyl 4-vinylphenylphosphonate, di-isopentyl 4-vinylphenylphosphonate, di-n-hexyl 4-vinylphenylphosphonate, di-n-heptyl 4-vinylphenylphosphonate, di-isoheptyl 4-vinylphenylphosphonate, di-n-octyl 4-vinylphenylphosphonate, di-isooctyl 4-vinylphenylphosphonate, diethyl 4-vinylbenzylphosphonate, dimethyl 1-pentenylphosphonate, diethyl 1-pentenylphosphonate, di-n-propyl 1-pentenylphosphonate, diisopropyl 1-pentenylphosphonate, di-n-butyl 1-pentenylphosphonate and diisobutyl 1-pentenylphosphonate; the above compounds are preferably in trans configuration.

[0013] According to a specific embodiment of the present invention, preferably, the mass fraction of the unsaturated organic phosphonate monomer is 20-70% based on the mass of the organic polymer carrier being 100%; the content of the functional monomer in the carrier is determined by the added amount of divinylbenzene and the unsaturated organic phosphonate 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 and the unsaturated organic phosphonate monomers as raw materials, copolymerizing to obtain the organic polymer carrier; the mass ratio of the unsaturated organic phosphonate monomer to divinylbenzene is 0.2-2:1.

[0015] According to a specific embodiment of the present invention, preferably, 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 and unsaturated organic phosphonate 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-PO3; 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 dispersing solvent includes a fatty acid ester solvent and / or tetrahydrofuran.

[0018] According to a specific embodiment of the present invention, preferably, the fatty acid ester solvent includes one or a combination of two or more of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-butyl acetate, n-pentyl acetate, ethyl formate, n-propyl formate and n-butyl formate.

[0019] 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.

[0020] 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.

[0021] According to a specific embodiment of the present invention, preferably, the weight average molecular weight of the stabilizer is 1,000-100,000.

[0022] According to a specific embodiment of the present invention, preferably, the mass ratio of the amount of the stabilizer added to the total amount of the monomers added is 0.5-5:100.

[0023] 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).

[0024] According to a specific embodiment of the present invention, preferably, the mass ratio of the amount of the initiator added to the total amount of the monomers added is 0.5-3:100.

[0025] 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.

[0026] The present invention also provides a ZN catalyst, which, based on 100% mass of the ZN catalyst, comprises 55-80wt% of the organic polymer carrier, 1-6wt% of a magnesium compound calculated as magnesium element, 1-6wt% of a titanium compound calculated as titanium element and 0-8wt% of an internal electron donor.

[0027] According to a specific embodiment of the present invention, preferably, the content of the organic polymer carrier is 60-75wt%, the content of magnesium is 2-5wt%, the content of titanium is 2-5wt%, and the content of the internal electron donor is 2-6wt%.

[0028] According to a specific embodiment of the present invention, preferably, the magnesium compound is RMgX or R' (2-n) MgX n , n is 0, 1 or 2; the R and R' are each independently selected from C1-C8 alkyl and its derivatives, aryl and its derivatives, alkoxy and its derivatives, and the X is fluorine, chlorine, bromine or iodine.

[0029] According to a specific embodiment of the present invention, preferably, the R and R' are each independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl, and substituted phenyl.

[0030] 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.

[0031] 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 anhydrous magnesium 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-PO3...MgX.

[0032] According to a specific embodiment of the present invention, preferably, the titanium compound is titanium tetrachloride; the porous organic support (POP-PO3...MgX) treated with the above magnesium-containing compound is further reacted with titanium tetrachloride to obtain the ZN catalyst, which is recorded as POP-PO3...MgX / TiCl4.

[0033] The ZN catalyst of the present invention can selectively add an additional internal electron donor (ID) to further improve the stereospecific ability of the catalyst. The obtained ZN catalyst is recorded as POP-PO3...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 diol ester compound, a succinate ester compound, and a diether compound.

[0034] 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).

[0035] The present invention also provides a method for preparing the above ZN catalyst, which comprises the following steps:

[0036] 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 then an inert solvent and titanium tetrachloride are added. After reacting at 0°C-120°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, and the reaction is filtered. Inert solvent and titanium tetrachloride are added to the filtrate, and the reaction is carried out at 50°C-120°C for 30-180 minutes. After the reaction is completed, the reaction is filtered, and finally the inert solvent is used for washing to obtain the ZN catalyst.

[0037] In the ZN catalyst of the present invention, the content of functional monomers (unsaturated organic phosphonate 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 monomer to the amount of divinylbenzene (DVB) monomer added during the carrier preparation process; 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 of 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 amount ratio of internal electron donor to carrier is 0 to 0.3 g internal electron donor / g carrier.

[0038] The present invention also provides a ZN catalyst system, which comprises the ZN catalyst, an external electron donor and a co-catalyst.

[0039] According to a specific embodiment of the present invention, preferably, the external electron donor includes a silane external electron donor.

[0040] 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).

[0041] 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 5-100.

[0042] 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.

[0043] According to a specific embodiment of the present invention, preferably, the R" is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.

[0044] According to a specific embodiment of the present invention, preferably, the co-catalyst is triethylaluminum.

[0045] 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.

[0046] The present invention also provides application of the ZN catalyst or the ZN catalyst system in olefin polymerization.

[0047] According to a specific embodiment of the present invention, preferably, the olefin polymerization is propylene homopolymerization, propylene and ethylene copolymerization or α-olefin copolymerization.

[0048] According to a specific embodiment of the present invention, preferably, the α-olefin is butene and / or isobutylene.

[0049] According to a specific embodiment of the present invention, preferably, the isotacticity of the polypropylene obtained by propylene polymerization reaches more than 99%, and the molecular weight distribution coefficient is 6-12; the TREF high temperature elution temperature reaches 124°C.

[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°C, and the reaction pressure is 0.1-2.0Mpa.

[0052] 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.

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

[0054] The porous organic polymer carrier-supported ZN olefin catalyst provided by the present invention is obtained by copolymerizing divinylbenzene with an unsaturated organic phosphonate functional monomer to obtain a porous structured POP carrier (denoted as POP-PO3) containing an organic phosphate group. The organic phosphonate functional groups in the carrier interact with Mg and Ti at the active center, and an additional internal electron donor can be selectively added to prepare a porous organic polymer (POP) type ZN polyolefin catalyst (denoted as POP-PO3...MgX / TiCl4 / ID). The functional monomer selected for the organic polymer carrier of the present invention is an unsaturated organic phosphonate functional monomer, which not only has an important influence on the prepared carrier, but also, due to the introduction of organic phosphonate functional groups on the carrier, the microchemical environment of Ti and Mg at the active center is modified, and combined with the additional internal electron donor, the prepared catalyst has good stereospecific ability and polymerization catalytic activity. When the catalyst is used for propylene polymerization, a silane external electron donor and a co-catalyst such as triethylaluminum can be added at the same time. The obtained polypropylene has a high isotacticity, which can reach more than 99%. The TREF high temperature elution temperature can reach 124°C, which is higher than the conventional isotactic polypropylene (iPP) elution temperature (121-123°C). In addition, the polymer molecular weight distribution can be adjusted in a wide range, and the molecular weight distribution coefficient can be controlled between 6 and 12. In addition, the catalyst has good copolymerization ability and can be used for ethylene and propylene polymerization, as well as propylene and other α-olefin copolymerization.

[0055] The organic polymer-loaded ZN olefin polymerization catalyst system of the present invention requires the addition of an external electron donor and a co-catalyst during polymerization, and the two must be properly matched to exert the excellent performance of high catalytic activity and high directional ability; usually, the co-catalyst AlEt3 can complex with the internal electron donor, causing the Ti atom and the internal electron donor to lose stability and re-occupy the random active position complexed by the internal electron donor, causing the catalyst's directional ability to decrease; the addition of the external electron donor can preferentially combine with AlEt3, avoiding the internal electron donor from falling off, reducing the amount of the internal electron donor compound removed by AlEt3, and ensuring the stability of the stereoactive center; therefore, an additional external electron donor needs to be added during the polymerization process, so that the prepared polymer has a higher isotacticity. DETAILED DESCRIPTION

[0056] 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.

[0057] 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, and the inhibitor is removed before use. The method for removing the inhibitor can be carried out according to the prior art, such as washing divinylbenzene with a NaOH solution and distilled water, and then drying with anhydrous magnesium sulfate before use. Unsaturated organic phosphonate functional monomers can be directly purchased or synthesized using literature methods. For example, unsaturated double bond chlorides can be reacted with phosphorous acid diesters or triesters to obtain corresponding unsaturated organic phosphonic acid diester compounds (reference document 1: Synthesis and solid-state NMR studies of p-vinylbenzylphosphonic acid paper published by Richard Frantz et al. in Chemistry-A European Journal, 2003, Vol. 9, No. 3, pp. 770-775).

[0058] 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.

[0059] In the present invention, the specific surface area of ​​the prepared organic polymer carrier 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, 100-600m 2 / g, and the pore volume is greater than 0.2ml / g.

[0060] Example 1

[0061] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0062] (1) Preparation of porous organic polymer carrier:

[0063] In a 250ml glass reactor, add 130ml butyl acetate, then add 5.0g divinylbenzene (Aladdin reagent, 80%) and 3.0g diethyl vinylphosphonate (CAS: 682-30-4, Aladdin reagent, ≥98%), 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, then add 2.0% monomer weight of AIBN, heat to 70°C, react for 3 hours, rotate at 450 rpm, then heat to 80°C, react for 12 hours, filter, wash with ethyl acetate 3 times, filter, dry to obtain 5.8g free-flowing porous organic polymer carrier POP-1. The carrier has a specific surface area of ​​452m 2 / g, pore volume 0.57ml / g;

[0064] (2) Preparation of ZN catalyst:

[0065] In a 250ml glass reactor, 2g of the carrier POP-1 prepared by using the functional monomer of diethyl vinylphosphonate was added, 100ml of toluene was added, stirred, then 8ml of 3M methylmagnesium chloride Grignard reagent was added at 5°C, stirred for 2 hours, filtered, washed twice with toluene, then heated to 50°C, 50ml of toluene was added, 30ml of TiCl was added dropwise, reacted for 2 hours, then heated to 80°C, 0.2g of di-n-butyl phthalate was added, reacted for 1 hour, after completion of the reaction, filtered, 50ml of toluene and 30ml of TiCl were added, reacted at 100°C for 2 hours, filtered after completion of the reaction, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, denoted as Cat-1. The catalyst Cat-1 has a Mg content of 3.5%, a titanium content of 3.2%, an internal electron donor content of 3.8%, and an organic polymer carrier content of 71%.

[0066] Example 2

[0067] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0068] Preparation of ZN catalyst: In a 250ml glass reactor, 2g of the carrier POP-1 prepared by using the functional monomer of diethyl vinylphosphonate was added, 100ml of toluene was added, stirred, and then 10ml of 3M methylmagnesium chloride Grignard reagent was added at room temperature (25°C, the same below), stirred for 1 hour, filtered, washed twice with toluene, then heated to 50°C, added 50ml of toluene, 40ml of TiCl4 was added dropwise, reacted for 2 hours, then heated to 80°C, 0.2g of diisobutyl phthalate was added, reacted for 1 hour, after completion of the reaction, filtered, 50ml of toluene and 30ml of TiCl4 were added, reacted at 100°C for 2 hours, filtered after completion of the reaction, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-2. The Mg content of catalyst Cat-2 was 4.8%, the titanium content was 3.8%, the internal electron donor content was 4.2%, and the organic polymer carrier content was 65%.

[0069] Example 3

[0070] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0071] (1) Preparation of porous organic polymer carrier:

[0072] In a 250ml glass reactor, add 130ml butyl acetate, then add 5.0g divinylbenzene (Aladdin reagent, 80%) and 3.0g diethyl allylphosphonate (CAS: 1067-87-4), stir at room temperature for 5min, then add 2% monomer mass of block copolymer of polyethylene oxide and polypropylene oxide F127, stir at 45℃ for 1h, then add 2.0% monomer mass of AIBN, heat to 70℃, react for 3 hours, speed is 350 rpm, then heat to 80℃, react for 8 hours, filter, wash with ethyl acetate 3 times, filter and dry to obtain 6.3g free-flowing porous organic polymer carrier POP-2. The carrier specific surface area is 431m 2 / g, pore volume 0.53ml / g;

[0073] (2) Preparation of ZN catalyst:

[0074] In a 250ml glass reactor, 2g of the carrier POP-2 prepared by the functional monomer of diethyl allylphosphonate was added, 100ml of toluene was added, stirred, then 10ml of 3M methylmagnesium chloride Grignard reagent was added at 5°C, stirred for 2 hours, filtered, washed twice with toluene, then heated to 50°C, 50ml of toluene was added, 40ml of TiCl was added dropwise, reacted for 2 hours, then heated to 80°C, 0.2g of diisobutyl phthalate was added, reacted for 1 hour, after completion of the reaction, filtered, 50ml of toluene and 30ml of TiCl were added, reacted at 100°C for 2 hours, filtered after completion of the reaction, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, denoted as Cat-3. The catalyst Cat-3 had a Mg content of 4.5%, a titanium content of 4.0%, an internal electron donor content of 3.4%, and an organic polymer carrier content of 64%.

[0075] Example 4

[0076] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0077] Preparation of ZN catalyst: In a 250ml glass reactor, add 2g of the carrier POP-2 prepared using the functional monomer of diethyl allylphosphonate, 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 heat to 50°C, add 50ml of toluene, add 40ml of TiCl4 dropwise, react for 2 hours, then heat to 80°C, add 0.2g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate (CAS: 1232839-86-9), react for 1 hour, filter after the reaction, add 50ml of toluene and 30ml of TiCl4 was reacted at 100°C for 2 hours. After the reaction was completed, it was filtered, washed with toluene and hexane 3 times each, and dried to obtain free-flowing catalyst particles, which were recorded as Cat-4. The Mg content of catalyst Cat-4 was 4.2%, the titanium content was 4.0%, the internal electron donor content was 2.5%, and the organic polymer carrier content was 66%.

[0078] Example 5

[0079] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0080] (1) Preparation of porous organic polymer carrier:

[0081] In a 250ml glass reactor, add 130ml ethyl acetate, then add 5.0g divinylbenzene (Aladdin reagent, 80%) and 2.0g 2-butenylphosphonic acid diethyl ester (CAS: 682-34-8, mainly trans), stir at room temperature for 5min, then add 3% monomer mass of polyethylene oxide and polypropylene oxide block copolymer F127, stir at 45℃ for 1h, then add 2.0% monomer mass of AIBN, heat to 70℃, react for 3 hours, speed is 450 rpm, then heat to 80℃, react for 8 hours, filter, wash with ethyl acetate 3 times, filter and dry to obtain 4.5g free-flowing porous organic polymer carrier POP-3. The carrier specific surface area is 242m 2 / g, pore volume 0.26ml / g;

[0082] (2) Preparation of ZN catalyst:

[0083] In a 250ml glass reactor, 2g of the carrier POP-3 prepared by using the functional monomer of diethyl 2-butenylphosphonate was added, 100ml of toluene was added, stirred, and then 8ml of 3M benzylmagnesium bromide was added at room temperature, stirred for 2 hours, filtered, washed twice with toluene, then heated to 50°C, added 60ml of toluene, 30ml of TiCl4 was added dropwise, reacted for 2 hours, then heated to 80°C, 0.2g of diisobutyl phthalate was added, reacted for 1 hour, after completion of the reaction, filtered, 50ml of toluene and 30ml of TiCl4 were added, reacted at 100°C for 2 hours, filtered after completion of the reaction, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-5. The catalyst Cat-5 has a Mg content of 3.5%, a titanium content of 3.2%, an internal electron donor content of 4.8%, and an organic polymer carrier content of 67%.

[0084] Example 6

[0085] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0086] Preparation of ZN catalyst: In a 250ml glass reactor, add 2g of the carrier POP-3 prepared using the above-mentioned 2-butenylphosphonic acid diethyl ester functional monomer, add 100ml of toluene, stir, then add 8ml of 3M butylmagnesium chloride at room temperature, stir for 2 hours, filter, wash twice with toluene, then heat to 50°C, add 60ml of toluene, add 40ml of TiCl4 dropwise, react for 2 hours, then heat to 80°C, add 0.15g of 9,9-dimethoxyfluorene internal electron donor, react for 1 hour, filter after the reaction, add 50ml of toluene and 30ml of TiCl4, react at 100°C for 2 hours, filter after the reaction, wash 3 times with toluene and hexane respectively, and obtain free-flowing catalyst particles after drying, recorded as Cat-6. The Mg content of catalyst Cat-6 is 4.0%, the titanium content is 3.5%, the internal electron donor content is 2.9%, and the organic polymer carrier content is 66%.

[0087] Example 7

[0088] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0089] (1) Preparation of porous organic polymer carrier:

[0090] In a 250ml glass reactor, add 130ml ethyl acetate, then add 5.0g divinylbenzene (Aladdin reagent, 55%) and 3.0g allylphosphonic acid (CAS: 6833-67-6), stir at room temperature for 5min, then add 5% monomer mass of block copolymer of polyethylene oxide and polypropylene oxide F127, stir at 45°C for 1h, then add 2.0% monomer mass of AIBN, heat to 70°C, react for 3 hours, rotate at 450 rpm, then heat to 80°C, react for 8 hours, filter, wash with ethyl acetate 3 times, filter and dry to obtain 4.5g free-flowing porous organic polymer carrier POP-4. The carrier has a specific surface area of ​​198m 2 / g, pore volume 0.34ml / g;

[0091] (2) Preparation of ZN catalyst:

[0092] In a 250ml glass reactor, 2g of the carrier POP-4 prepared by adopting the allylphosphonic acid functional monomer is added, 100ml of toluene is added, stirred, then 10ml of 3M methylmagnesium chloride is added at room temperature, stirred for 1 hour, filtered, washed twice with toluene, then heated to 50°C, 60ml of toluene is added, 30ml of TiCl is added dropwise, reacted for 2 hours, then heated to 80°C, 0.20g of diisobutyl phthalate internal electron donor is added, reacted for 1 hour, after completion of the reaction, filtered, 50ml of toluene and 30ml of TiCl are added again, reacted at 100°C for 2 hours, filtered after completion of the reaction, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-7, the Mg content of catalyst Cat-7 is 3.8%, the titanium content is 3.2%, the internal electron donor content is 4.7%, and the organic polymer carrier content is 65%.

[0093] Example 8

[0094] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0095] (1) Preparation of porous organic polymer carrier:

[0096] In a 250ml glass reactor, add 130ml butyl acetate, then add 5.0g divinylbenzene (Aladdin reagent, 80%) and 2.4g allylphosphonic acid (CAS: 6833-67-6), stir at room temperature for 5min, then add 5% monomer mass of block copolymer of polyethylene oxide and polypropylene oxide F127, stir at 45℃ for 1h, then add 2.0% monomer mass of dibenzoyl peroxide BPO, heat to 70℃, react for 3 hours, speed is 450 rpm, then heat to 80℃, react for 8 hours, filter, wash with ethyl acetate 3 times, filter and dry to obtain 4.5g free-flowing porous organic polymer carrier POP-5. The carrier specific surface area is 337m 2 / g, pore volume 0.45ml / g;

[0097] (2) Preparation of ZN catalyst:

[0098] In a 250ml glass reactor, 2g of the carrier POP-5 prepared by adopting the allylphosphonic acid functional monomer is added, 100ml of toluene is added, stirred, then 15ml of 3M methylmagnesium chloride is added at room temperature, stirred for 2 hours, filtered, washed twice with toluene, then heated to 50°C, 60ml of toluene is added, 40ml of TiCl is added dropwise, reacted for 2 hours, then heated to 80°C, 0.30g of diisobutyl phthalate internal electron donor is added, reacted for 1 hour, after completion of the reaction, filtered, 50ml of toluene and 40ml of TiCl are added again, reacted at 100°C for 2 hours, filtered after completion of the reaction, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-8, the Mg content of catalyst Cat-8 is 6.8%, the titanium content is 5.2%, the internal electron donor content is 7.2%, and the organic polymer carrier content is 58%.

[0099] Example 9

[0100] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0101] (1) Preparation of porous organic polymer carrier:

[0102] In a 250ml glass reactor, add 130ml butyl acetate, then add 5.0g divinylbenzene (Aladdin reagent, 80%) and 2.5g 4-vinylbenzylphosphonic acid diethyl ester (CAS: 726-61-4, refer to document 1, obtained by reacting p-chloromethylstyrene with diethyl phosphite, yield of about 93%), stir at room temperature for 5min, then add 3% monomer mass of block copolymer F127 of polyethylene oxide and polypropylene oxide, stir at 45°C for 1h, then add 2.0% monomer mass of AIBN, heat to 70°C, react for 3 hours, rotate at 450 rpm, then heat to 80°C, react for 8 hours, filter, wash 3 times with ethyl acetate, filter and dry to obtain 4.5g free-flowing porous organic polymer carrier POP-6. The specific surface area of ​​the carrier is 352m 2 / g, pore volume 0.49ml / g;

[0103] (2) Preparation of ZN catalyst:

[0104] In a 250ml glass reactor, 2g of the carrier POP-6 prepared by using the functional monomer of diethyl 4-vinylbenzylphosphonate was added, 100ml of toluene was added, stirred, and then 8ml of 3M methylmagnesium chloride Grignard reagent was added at 0°C, stirred for 2 hours, filtered, washed twice with toluene, and then 50ml of toluene was added, 30ml of TiCl4 was added dropwise at room temperature, reacted for 1 hour, heated to 80°C, 0.20g of diisobutyl phthalate internal electron donor was added, reacted for 1 hour, after the reaction was completed, filtered, 50ml of toluene and 30ml of TiCl4 were added, reacted at 80°C for 2 hours, filtered after the reaction was completed, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-9. The catalyst Cat-9 has a Mg content of 2.8%, a titanium content of 2.5%, an internal electron donor content of 3.2%, and an organic polymer carrier content of 73%.

[0105] Example 10

[0106] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0107] Preparation of ZN catalyst: In a 250 ml glass reactor, add 2 g of the carrier POP-6 prepared using the above-mentioned 4-vinylbenzylphosphonic acid diethyl functional monomer, add 100 ml of toluene, stir, then add 8 ml of 3M methyl magnesium chloride Grignard reagent at 5°C, stir for 2 hours, filter, wash twice with toluene, then add 50 ml of toluene, add 35 ml of TiCl4 dropwise at room temperature, react for 1 hour, heat to 80°C, add 0.25 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate internal electron donor, react for 1 hour, filter after the reaction, add 50 ml of toluene and 30 ml of TiCl4, 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, recorded as Cat-10. The Mg content of the catalyst Cat-10 is 3.0%, the titanium content is 3.2%, the internal electron donor content is 2.5%, and the organic polymer carrier content is 68%.

[0108] Embodiment 11

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

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

[0111] In a 250ml glass reactor, add 130ml butyl acetate, then add 5.0g divinylbenzene (Aladdin reagent, 80%) and 2.4g (3-phenylallyl) diethyl phosphonate (CAS: 58922-31-9, refer to document 1, obtained by reaction of β-phenylpropylene chloride and diethyl phosphite, yield 93%), stir at room temperature for 5min, then add 3% monomer mass of block copolymer F127 of polyethylene oxide and polypropylene oxide, stir at 45°C for 1h, then add 2.0% monomer mass of BPO, heat to 70°C, react for 3 hours, rotate at 450 rpm, then heat to 80°C, react for 8 hours, filter, wash 3 times with ethyl acetate, filter and dry to obtain 4.5g free-flowing porous organic polymer carrier POP-7. The carrier has a specific surface area of ​​387m 2 / g, pore volume 0.52ml / g;

[0112] (2) Preparation of ZN catalyst:

[0113] In a 250 ml glass reactor, 2 g of the carrier POP-7 prepared using the (3-phenylallyl) diethyl phosphonate functional monomer was added, 100 ml of toluene was added, stirred, and then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at 5° C., stirred for 2 hours, filtered, washed twice with toluene, and then 50 ml of toluene was added. 35 ml of TiCl4 was added dropwise at room temperature, reacted for 1 hour, heated to 80° C., and then 0.25 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate internal electron donor was added, reacted for 1 hour, filtered after the reaction, and then 50 ml of toluene and 30 ml of TiCl4 were added to react at 80° C. for 2 hours. After the reaction was completed, filtered, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-11. The catalyst Cat-11 has a Mg content of 3.4%, a titanium content of 2.8%, an internal electron donor content of 2.3%, and an organic polymer carrier content of 67%.

[0114] Example 12

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

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

[0117] In a 250ml glass reactor, add 130ml butyl acetate, then add 5.0g divinylbenzene (Aladdin reagent, 80%) and 2.0g (3-phenylallyl) dimethyl phosphonate (refer to document 1, obtained by reacting β-phenylpropylene chloride with dimethyl phosphite, yield 92%), stir at room temperature for 5min, then add 5% monomer mass of block copolymer F127 of polyethylene oxide and polypropylene oxide, stir at 45°C for 1h, then add 2.0% monomer mass of AIBN, heat to 70°C, react for 3 hours, rotate at 450 rpm, then heat to 80°C, react for 8 hours, filter, wash 3 times with ethyl acetate, filter and dry to obtain 4.5g free-flowing porous organic polymer carrier POP-8. The specific surface area of ​​the carrier is 288m 2 / g, pore volume 0.37ml / g;

[0118] (2) Preparation of ZN catalyst:

[0119] In a 250ml glass reactor, 2g of the carrier POP-8 prepared by the above-mentioned (3-phenylallyl) dimethyl phosphonate functional monomer was added, 100ml of toluene was added, stirred, and then 8ml of 3M methylmagnesium chloride Grignard reagent was added at 5°C, stirred for 2 hours, filtered, washed twice with toluene, then 50ml of toluene was added, 35ml of TiCl was added dropwise at room temperature, reacted for 1 hour, warmed to 80°C, then 0.20g of diisobutyl phthalate internal electron donor was added, reacted for 1 hour, after completion of the reaction, filtered, 50ml of toluene and 30ml of TiCl were added, reacted at 80°C for 2 hours, filtered after completion of the reaction, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-12, the catalyst Cat-12 having a Mg content of 2.7%, a titanium content of 2.8%, an internal electron donor content of 3.8%, and an organic polymer carrier content of 72%.

[0120] Embodiment 13

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

[0122] (1) Preparation of porous organic polymer carrier:

[0123] In a 250ml glass reactor, add 130ml of n-propyl formate, then add 5.0g of divinylbenzene (Aladdin reagent, 55%) and 2.5g of (3-phenylallyl)phosphonic acid (reference 1, obtained by reacting β-phenylallyl chloride with phosphoric acid, yield 90%), stir at room temperature for 5min, then add 5% monomer mass of block copolymer F127 of polyethylene oxide and polypropylene oxide, stir at 45°C for 1h, then add 2.0% monomer mass of AIBN, heat to 70°C, react for 3 hours, rotate at 450 rpm, then heat to 80°C, react for 8 hours, filter, wash 3 times with ethyl acetate, filter and dry to obtain 4.5g of free-flowing porous organic polymer carrier POP-9. The carrier has a specific surface area of ​​182m 2 / g, pore volume 0.27ml / g;

[0124] (2) Preparation of ZN catalyst:

[0125] In a 250ml glass reactor, 2g of the carrier POP-9 prepared by the (3-phenylallyl)phosphonic acid functional monomer was added, 100ml of toluene was added, stirred, and then 8ml of 3M methylmagnesium chloride Grignard reagent was added at 5°C, stirred for 2 hours, filtered, washed twice with toluene, then 50ml of toluene was added, 35ml of TiCl was added dropwise at room temperature, reacted for 1 hour, heated to 80°C, then 0.20g of diisobutyl phthalate internal electron donor was added, reacted for 1 hour, after completion of the reaction, filtered, 50ml of toluene and 30ml of TiCl were added, reacted at 80°C for 2 hours, filtered after completion of the reaction, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, denoted as Cat-13. The catalyst Cat-13 has a Mg content of 3.0%, a titanium content of 3.0%, an internal electron donor content of 4.1%, and an organic polymer carrier content of 71%.

[0126] Embodiment 14

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

[0128] In a 250ml glass reactor, 2g of the carrier POP-9 prepared by using the (3-phenylallyl)phosphonic acid functional monomer was added, 100ml of toluene was added, stirred, and then 8ml of 3M methylmagnesium chloride Grignard reagent was added at 35°C, stirred for 2 hours, filtered, washed twice with toluene, and then 50ml of toluene was added, 35ml of TiCl4 was added dropwise at room temperature, reacted for 1 hour, heated to 80°C, reacted for 1 hour, filtered after the reaction was completed, and then 50ml of toluene and 30ml of TiCl4 were added to react at 100°C for 2 hours. After the reaction was completed, filtered, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-14. The Mg content of the catalyst Cat-14 was 3.8%, the titanium content was 3.8%, and the organic polymer carrier content was 79%.

[0129] Comparative Example 1

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

[0131] Preparation of inorganic carrier-supported ZN polypropylene catalyst: In a 250ml glass reactor, add 3g of spherical ethoxy magnesium carrier (Japan Soda Co., Ltd.), add 100ml of toluene, stir, and 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, add 100ml of fresh TiCl4, react at 110°C for 2 hours, filter after completion of the reaction, use toluene and hexane to wash 3 times each, and obtain free-flowing catalyst particles after drying, recorded as Cat-15. The titanium content of catalyst Cat-15 is 3.2%, and the content of DIBP internal electron donor is 8.9%.

[0132] Comparative Example 2

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

[0134] 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, and 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 completed, heat to 60°C, add 0.40g of 9,9-dimethoxyfluorene internal electron donor, react at 110°C for 2 hours, filter, add 100ml of fresh TiCl4, react at 110°C for 2 hours, filter after completion of the reaction, use toluene and hexane to wash 3 times each, and obtain free-flowing catalyst particles after drying, recorded as Cat-16. The titanium content of catalyst Cat-16 is 3.2%, and the content of 9,9-dimethoxyfluorene internal electron donor is 6.2%.

[0135] Comparative Example 3

[0136] This comparative example provides an inorganic carrier-supported ZN catalyst, which is prepared by the following steps:

[0137] In a 250ml glass reactor, add 2g of spherical ethoxymagnesium carrier (Japan Soda Co., Ltd.), add 50ml of toluene, stir, slowly add 30ml of TiCl4 at room temperature, react for 1 hour, heat to 80°C, add 0.20g of diisobutyl phthalate internal electron donor, react for 1 hour, filter after the reaction, add 50ml of toluene and 30ml of TiCl4 at 80°C to 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-17. The titanium content of catalyst Cat-17 is 3.5%, and the content of DIBP internal electron donor is 6.2%.

[0138] Comparative Example 4

[0139] This comparative example provides an inorganic carrier-supported ZN catalyst, which is prepared by the following steps:

[0140] In a 250ml glass reactor, add 2g of spherical ethoxymagnesium carrier (Japan Soda Co., Ltd.), add 60ml of toluene, slowly add 40ml of TiCl4 at 50°C, react for 2 hours, then raise the temperature to 80°C, add 0.15g of 9,9-dimethoxyfluorene internal electron donor, react for 1 hour, filter after the reaction, add 50ml of toluene and 30ml of TiCl4 at 100°C 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-18. The titanium content of catalyst Cat-18 is 3.8%, and the content of 9,9-dimethoxyfluorene internal electron donor is 4.6%.

[0141] Propylene polymerization performance test

[0142] Test Example 1

[0143] 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 Cat-1 catalyst 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. After drying, 1005g of polypropylene product (PP-1) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 12563gPP / gcat.h, as shown in Table 1.

[0144] Test Example 2

[0145] 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 Cat-1 catalyst and 0.5ml of dicyclopentyldimethoxysilane (D externally supplied) 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 864g of a polypropylene product (PP-2) with a bulk density of 0.37g / ml and a catalyst activity of 10800gPP / gcat.h, as shown in Table 1.

[0146] Test Example 3

[0147] 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 Cat-2 catalyst 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, 1024g of a polypropylene product (PP-3) was obtained, with a bulk density of 0.39g / ml and a catalyst activity of 12800gPP / gcat.h, as shown in Table 1.

[0148] Test Example 4

[0149] 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 Cat-3 catalyst 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. After drying, 1086g of polypropylene product (PP-4) was obtained, with a bulk density of 0.38g / ml and a catalyst activity of 13575gPP / gcat.h, as shown in Table 1.

[0150] Test Example 5

[0151] 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 Cat-4 catalyst 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, 1160g of polypropylene product (PP-5) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 14500gPP / gcat.h, as shown in Table 1.

[0152] Test Example 6

[0153] 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 Cat-4 catalyst and 0.3ml of dicyclopentyldimethoxysilane (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, 1002g of polypropylene product (PP-6) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 12525gPP / gcat.h, as shown in Table 1.

[0154] Test Example 7

[0155] 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 Cat-5 catalyst and 0.3ml 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. After drying, 850g of polypropylene product (PP-7) was obtained, with a bulk density of 0.38g / ml and a catalyst activity of 10625gPP / gcat.h, as shown in Table 1.

[0156] Test Example 8

[0157] 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 Cat-6 catalyst and 0.5ml of dicyclopentyldimethoxysilane (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 and dried to obtain 900g of a polypropylene product (PP-8) with a bulk density of 0.38g / ml and a catalyst activity of 11250gPP / gcat.h, as shown in Table 1.

[0158] Test Example 9

[0159] 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 Cat-7 catalyst and 0.5ml 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, 1050g of polypropylene product (PP-9) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 13125gPP / gcat.h, as shown in Table 1.

[0160] Test Example 10

[0161] 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 Cat-8 catalyst 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. After drying, 1142g of polypropylene product (PP-10) was obtained, with a bulk density of 0.38g / ml and a catalyst activity of 14275gPP / gcat.h, as shown in Table 1.

[0162] Test Example 11

[0163] 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-9 and 0.3ml 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. After drying, 840g of a polypropylene product (PP-11) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 10500gPP / gcat.h, as shown in Table 1.

[0164] Test Example 12

[0165] 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-10 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, 944g of a polypropylene product (PP-12) was obtained, with a bulk density of 0.38g / ml and a catalyst activity of 11800gPP / gcat.h, as shown in Table 1.

[0166] Test Example 13

[0167] 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-11 and 0.3ml of cyclohexylmethyldimethoxysilane (external C) 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, 788g of a polypropylene product (PP-13) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 9850gPP / gcat.h, as shown in Table 1.

[0168] Test Case 14

[0169] 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-12 and 0.3ml of cyclohexylmethyldimethoxysilane (C 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, 748g of a polypropylene product (PP-14) was obtained, with a bulk density of 0.36g / ml and a catalyst activity of 9350gPP / gcat.h, as shown in Table 1.

[0170] Test Example 15

[0171] 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-13 and 0.3ml of cyclohexylmethyldimethoxysilane (external C) 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, 985g of a polypropylene product (PP-15) was obtained, with a bulk density of 0.38g / ml and a catalyst activity of 12313gPP / gcat.h, as shown in Table 1.

[0172] Test Case 16

[0173] 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-13 and 0.5ml of dicyclopentyldimethoxysilane (D externally supplied) 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. After drying, 952g of a polypropylene product (PP-16) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 11900gPP / gcat.h, as shown in Table 1.

[0174] Test Case 17

[0175] 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, 80mg of the catalyst Cat-14 and 0.5ml of dicyclopentyldimethoxysilane (D externally supplied) 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 628g of a polypropylene product (PP-17) with a bulk density of 0.36g / ml. Without the additional addition of an internal electron donor, no obvious agglomeration of the polymer was observed, the polymer isotacticity was 96.5%, and the catalyst activity was 7850gPP / gcat.h, as shown in Table 1.

[0176] Comparative test example 1

[0177] 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 comparative catalyst Cat-15 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, 1119g of polypropylene product (PP-18) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 18650gPP / gcat.h, as shown in Table 1.

[0178] Comparative test example 2

[0179] 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 comparative catalyst Cat-16 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, 1280g of polypropylene product (PP-19) was obtained, with a bulk density of 0.42g / ml and a catalyst activity of 21333gPP / gcat.h, as shown in Table 1.

[0180] Comparative test example 3

[0181] 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 comparative catalyst Cat-17 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, 1030g of polypropylene product (PP-20) was obtained, with a bulk density of 0.38g / ml and a catalyst activity of 17167gPP / gcat.h, as shown in Table 1.

[0182] Comparative test example 4

[0183] 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 comparative catalyst Cat-18 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, 1145g of polypropylene product (PP-21) was obtained, with a bulk density of 0.41g / ml and a catalyst activity of 19083gPP / gcat.h, as shown in Table 1.

[0184] Table 1 Propylene polymerization results

[0185]

[0186] Test Example 18 Propylene and Ethylene Copolymerization Test

[0187] 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 Cat-1 catalyst 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 858g of ethylene-propylene copolymer product was obtained after drying. The catalyst polymerization activity was 14300gPP / gcat.h, the polymer weight average molecular weight Mw was 712,000 g / mol, and the molecular weight distribution coefficient was 8.92.

[0188] Test Example 19 Propylene and Ethylene Copolymerization Test

[0189] 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 Cat-4 catalyst, 0.5ml cyclohexylmethyldimethoxysilane (C external), 0.50ml TiCl4, 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 924g of ethylene-propylene copolymer product was obtained after drying. The catalyst polymerization activity was 15400gPP / gcat.h, the weight average molecular weight Mw of the polymer was 735,000 g / mol, and the molecular weight distribution coefficient was 10.9.

[0190] Test Example 20 Propylene and Butene Copolymerization Test

[0191] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10L dried propylene polymerization reactor, and the stirring speed was 600 rpm. Then 60 mg of the above-prepared Cat-4 catalyst and 0.5 ml of cyclohexylmethyldimethoxysilane (external C) were added, 0.5 g of hydrogen and 50 g of 1-butene monomer were added, the temperature was raised to 70°C, and 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 564 g of propylene butene copolymer product was obtained after drying. The catalyst polymerization activity was 9400 gPP / gcat.h.

[0192] From the above polymerization results, it can be seen that the ZN polyolefin catalyst supported by the organic polymer carrier in the present invention is obtained by copolymerizing divinylbenzene with a functional monomer containing an unsaturated double-bond organic phosphonate group to obtain a POP carrier with a porous structure containing an organic phosphate group. Relying on the organic phosphate functional group on the POP carrier, the microchemical environment of the metal active center is regulated, and the organic carrier-supported POP-PO3...MgX / TiCl4 / ID polypropylene catalyst solid component is designed and prepared, which has good catalytic activity, and the propylene homopolymerization activity can reach more than 14000gPP / gcat.h. Although it is lower than the catalyst supported by the traditional inorganic MgCl2 carrier, its activity is greatly improved compared with the existing organic polymer carrier polymerization activity, which can meet the level of existing industrial catalysts. Even without the additional addition of an internal electron donor, the POP-PO3...MgX / TiCl4 polypropylene catalyst has good stereoregularity. The catalyst Cat-14 prepared in Example 14 catalyzes propylene polymerization to obtain a polypropylene with an isotacticity of 96.5%, which is comparable to that of Cat-17 in Comparative Example 3. During the polymerization, no obvious agglomeration of the polymer due to low isotacticity was observed. In addition, compared with the inorganic carrier-supported polypropylene catalyst using the same internal electron donor (such as catalyst Cat-2 in Example 2 and catalyst Cat-15 in Comparative Example 1, catalyst Cat-9 in Example 9 and Cat-17 in Comparative Example 3, using the same internal electron donor diisobutyl phthalate; catalyst Cat-6 in Example 6 and catalyst Cat-16 in Comparative Example 2 and catalyst Cat-18 in Comparative Example 4, using the same 9,9-dimethoxyfluorene (the internal electron donor has high stereoregularity) as the internal electron donor), the catalyst of the present invention has better stereospecific ability, and the prepared polypropylene has a higher isotacticity, which can reach more than 98%, and the TREF high temperature elution temperature is higher, which can reach 124°C, which is higher than the conventional isotactic polypropylene (iPP) elution temperature (121-123°C). In addition, the polymer molecular weight distribution can be adjusted within a wider range, and the molecular weight distribution can be controlled between 6 and 12. Compared with existing catalysts, the POP-PO3...MgX / TiCl4 / ID catalyst disclosed in the present invention has a simple preparation method and good industrialization prospects. It adopts an organic carrier to avoid the introduction of unnecessary inorganic impurities, making the catalyst system advantageous in the development of low-precipitation and high-crystalline polyolefin products.

Claims

1. An organic polymer carrier obtained by copolymerizing monomers including divinylbenzene and unsaturated organic phosphonate monomers; in, The unsaturated organic phosphonate monomer has a structure shown in Formula I: In Formula I, R1 and R2 are each independently selected from hydrogen, C1-C 10 Straight-chain alkyl and its derivatives, C1-C 10 R3, R4 and R5 are each independently selected from hydrogen, halogen, C1-C8 straight or branched hydrocarbon groups and derivatives thereof, cycloalkyl groups and derivatives thereof, aromatic groups and derivatives thereof; wherein halogen is preferably F, Cl or Br; R6 is selected from a single bond, C1-C8 straight or branched hydrocarbon groups and derivatives thereof, cycloalkyl groups and derivatives thereof, aromatic groups and derivatives thereof.

2. The organic polymer carrier according to claim 1, wherein In formula I, R1 and R2 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, isopentyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, phenyl, benzyl; R3, R4 and R5 are each independently selected from hydrogen, methyl, ethyl, propyl, chloro, phenyl; R6 is selected from a single bond, methylene, ethylene, 1,3-propylene, 1,4-butylene, and 1,4-phenylene.

3. The organic polymer carrier according to claim 1, wherein The unsaturated organic phosphonate monomer is selected from the group consisting of dimethyl vinylphosphonate, diethyl vinylphosphonate, di-n-propyl vinylphosphonate, diisopropyl vinylphosphonate, di-n-butyl vinylphosphonate, diisobutyl vinylphosphonate, diisopentyl vinylphosphonate, di-n-hexyl vinylphosphonate, di-n-heptyl vinylphosphonate, diisoheptyl vinylphosphonate, di-n-octyl vinylphosphonate, diisooctyl vinylphosphonate, diphenyl vinylphosphonate, dibenzyl vinylphosphonate, vinylphosphonic acid, dimethyl allylphosphonate, dimethyl 2-methylallylphosphonate, diethyl allylphosphonate, diethyl 2-methylallylphosphonate, di-n-propyl allylphosphonate, diisopropyl allyl ...propyl vinylphosphonate, di-n-octyl vinylphosphonate, diisooctyl vinylphosphonate, diphenyl vinylphosphonate, dibenzyl vinylphosphonate, vinylphosphonic acid, Ester, di-n-butyl allylphosphonate, di-isobutyl allylphosphonate, di-isopentyl allylphosphonate, di-n-hexyl allylphosphonate, di-n-heptyl allylphosphonate, di-isoheptyl allylphosphonate, di-n-octyl allylphosphonate, di-isooctyl allylphosphonate, diphenyl allylphosphonate, dibenzyl allylphosphonate, allylphosphonic acid, dimethyl 1-butenylphosphonate, diethyl 1-butenylphosphonate, di-isopropyl 1-butenylphosphonate, di-n-propyl 1-butenylphosphonate, di-n-butyl 1-butenylphosphonate, di-n-pentyl 1-butenylphosphonate, di-n-hexyl 1-butenylphosphonate, di-n-heptyl 1-butenylphosphonate, di-n-octyl 1-butenylphosphonate, 1-chloro-1-butene 2-Butenylphosphonic acid, diethyl 2-butenylphosphonic acid, diethyl 2-butenylphosphonic acid, di-n-propyl 2-butenylphosphonic acid, diisopropyl 2-butenylphosphonic acid, di-n-butyl 2-butenylphosphonic acid, diisobutyl 2-butenylphosphonic acid, (3-phenylallyl)phosphonic acid, dimethyl (3-phenylallyl)phosphonic acid, diethyl (3-phenylallyl)phosphonic acid, di-n-propyl (3-phenylallyl)phosphonic acid, diisopropyl (3-phenylallyl)phosphonic acid, di-n-butyl (3-phenylallyl)phosphonic acid, diisobutyl (3-phenylallyl)phosphonic acid, dimethyl 4-vinylphenylphosphonic acid, diethyl 4-vinylphenylphosphonic acid, di-n-propyl 4-vinylphenylphosphonic acid , diisopropyl 4-vinylphenylphosphonate, di-n-butyl 4-vinylphenylphosphonate, di-n-pentyl 4-vinylphenylphosphonate, diisopentyl 4-vinylphenylphosphonate, di-n-hexyl 4-vinylphenylphosphonate, di-n-heptyl 4-vinylphenylphosphonate, diisoheptyl 4-vinylphenylphosphonate, di-n-octyl 4-vinylphenylphosphonate, diisooctyl 4-vinylphenylphosphonate, diethyl 4-vinylbenzylphosphonate, dimethyl 1-pentenylphosphonate, diethyl 1-pentenylphosphonate, di-n-propyl 1-pentenylphosphonate, diisopropyl 1-pentenylphosphonate, di-n-butyl 1-pentenylphosphonate, and diisobutyl 1-pentenylphosphonate, or a combination of two or more thereof.

4. The organic polymer carrier according to claim 1, wherein Calculated based on the mass of the organic polymer carrier being 100%, the mass fraction of the unsaturated organic phosphonate monomer is 20-70%.

5. The method for preparing the organic polymer carrier according to any one of claims 1 to 4, comprising the following steps: Using monomers including the divinylbenzene and the unsaturated organic phosphonate monomers as raw materials, copolymerizing to obtain the organic polymer carrier; The mass ratio of the unsaturated organic phosphonate 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 and unsaturated organic phosphonate 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.

6. The preparation method according to claim 5, wherein: The dispersing solvent includes fatty acid ester solvent and / or tetrahydrofuran.

7. The preparation method according to claim 6, wherein: The fatty acid ester solvent includes one or a combination of two or more of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-butyl acetate, n-pentyl acetate, ethyl formate, n-propyl formate, and n-butyl formate.

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 55-80wt% of an organic polymer carrier, 1-6wt% of a magnesium compound calculated as magnesium element, 1-6wt% of a titanium compound calculated as titanium element, and 0-8wt% 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 60-75wt%, the content of magnesium is 2-5wt%, the content of titanium is 2-5wt%, and the content of the internal electron donor is 2-6wt%.

13. The ZN catalyst according to claim 12, wherein The magnesium compound is RMgX or R' (2-n) MgX n , n is 0, 1 or 2; R and R' are each independently selected from C1-C8 alkyl and its derivatives, aryl and its derivatives, alkoxy and its derivatives, and X is fluorine, chlorine, bromine or iodine; Preferably, the 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 anhydrous magnesium 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 a 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 then an inert solvent and titanium tetrachloride are added. After reacting at 0°C-120°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, and the reaction is filtered. Inert solvent and titanium tetrachloride are added to the filtrate, and the reaction is carried out at 50°C-120°C for 30-180 minutes. After the reaction is completed, the reaction is filtered, and finally the inert solvent is used for washing 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 5-100.

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 is butene and / or isobutylene.

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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