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

Abstract

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

Description

Technical Field

[0001] This invention belongs to the field of catalysts, specifically relating to an organic polymer support, a ZN catalyst, its preparation method, and its application. Background Technology

[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, global polyethylene production exceeded 110 million tons, and global polypropylene production exceeded 76 million tons. Currently, commercially available polypropylene catalysts are mainly Zn-type catalysts with high stereoregularity, 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 polypropylene is usually greater than 96%. In addition, metallocene catalysts and post-metallocene catalysts are used to produce small amounts of isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, and propylene-based elastomers. For industrial polypropylene production plants, such as those using slurry polymerization, bulk polymerization, or gas-phase polymerization processes, catalyst loading is required to control the morphology of the generated polymer and avoid problems such as reactor agglomeration or blockage.

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

[0004] In addition, polypropylene catalysts can also be prepared through a dissolution-precipitation process. For example, in CN1258684A, anhydrous MgCl2 is dissolved in tributyl phosphate and epichlorohydrin solvent, then phthalic anhydride is added. When TiCl4 is slowly added, a solid catalyst is precipitated. Finally, internal electron donors such as diisobutyl phthalate are added, and after secondary titanium loading, a polypropylene catalyst is obtained.

[0005] In food and pharmaceutical packaging materials, polypropylene typically requires high isotacticity or low organic solvent precipitation to meet the requirements of these fields. Inorganic supported polypropylene catalysts generally exhibit high polymerization activity, well-controlled polymer morphology, and high bulk density. However, inorganic supports often introduce additional impurities (besides Mg and Ti active centers), limiting their application in the development of high-purity polypropylene products. Organic polymer supports differ from reported inorganic supports; POP supports themselves do not introduce impurities that affect polymer performance. Furthermore, organic supports offer controllable pore structure, high specific surface area, stable thermal properties, and ease of functionalization. High-performance or specialty polyolefin catalysts can be prepared through support design and functionalization. Porous organic supports supporting Zn catalysts have been publicly reported, typically using organic supports containing functional groups such as carboxylic acid, hydroxyl, cyano, and amino groups for Zn catalyst preparation. However, since organic supported olefin catalysts are mainly polyethylene catalysts, there are few reports on their use in propylene polymerization. For example, the paper "Sulfonated porous organic polymer supported ZN polypropylene catalysts with high stereoregularity and broad molecular weight distribution" in Microporous and Mesoporous Materials (Vol. 343, 2022, 112151) reported a POP-supported ZN catalyst prepared using a styrene sulfonic acid functional monomer. When an additional bisphenol ester is added as an internal electron donor, the catalyst has a broad molecular weight distribution and a high isotacticity, reaching over 98%. However, the polypropylene isotacticity and activity obtained by this catalyst system without the addition of an additional internal electron donor are both low, and it has not yet reached the commercial level. Summary of the Invention

[0006] To address the aforementioned problems, the present invention aims to provide an organic polymer support, a Zn catalyst, and its preparation method and application. This catalyst possesses excellent stereotacticity and polymerization catalytic activity, and can be used for the polymerization of ethylene and propylene, as well as the copolymerization of propylene with other α-olefins. The resulting polymer products exhibit high isotacticity and their molecular weight distribution can be adjusted over a wide range.

[0007] To achieve the above objectives, the present invention provides an organic polymer carrier obtained by copolymerization of monomers including divinylbenzene and unsaturated organophosphonate monomers;

[0008] The unsaturated organophosphonate monomers have the 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 groups and their derivatives, C1-C 10 Branched alkyl groups and their derivatives, cycloalkyl groups and their derivatives, aromatic groups and their derivatives; R3, R4 and R5 are each independently selected from hydrogen, halogens, C1-C8 straight-chain or branched hydrocarbon groups and their derivatives, cycloalkyl groups and their derivatives, aromatic groups and their derivatives; wherein, the halogen is preferably F, Cl or Br; R6 is selected from single bonds, C1-C8 straight-chain or branched alkylene groups and their derivatives, cycloalkylene groups and their derivatives, arylene groups and their derivatives, where 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, and benzyl; R3, R4, and R5 are each independently selected from hydrogen, methyl, ethyl, propyl, chloro, and phenyl; and R6 is selected from single bond, methylene, ethylene, 1,3-propylene, 1,4-butylene, and 1,4-phenylene.

[0012] According to a specific embodiment of the present invention, preferably, the unsaturated organophosphonate 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-methylallylylphosphonate, diethyl allylphosphonate, diethyl 2-methylallylphosphonate, and di-n-propyl allylphosphonate. Allylphosphonate diisopropyl ester, allylphosphonate di-n-butyl ester, allylphosphonate diisobutyl ester, allylphosphonate diisopentyl ester, allylphosphonate di-n-hexyl ester, allylphosphonate di-n-heptyl ester, allylphosphonate diisoheptyl ester, allylphosphonate di-n-octyl ester, allylphosphonate diisooctyl ester, allylphosphonate diphenyl ester, allylphosphonate dibenzyl ester, allylphosphonic acid, 1-butenylphosphonate dimethyl ester, 1-butenylphosphonate diethyl ester, 1-butenylphosphonate diisopropyl ester, 1-butenylphosphonate di-n-propyl ester, 1-butenylphosphonate di-n-butyl ester, 1-butenylphosphonate di-n-pentyl ester, 1-butenylphosphonate di-n-hexyl ester, 1-butenylphosphonate di-n-heptyl ester, 1-butenylphosphonate di-n-octyl ester, 1-chloro-1-butenylphosphonate di-n-octyl ester 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 One or more of the following compounds: diisopropyl phenylphosphonate, di-n-butyl 4-vinylphenylphosphonate, di-n-pentyl 4-vinylphenylphosphonate, diisopentyl 4-vinylphenylphosphonate, di-n-hexyl 4-vinylphenylphosphonate, di-n-heptyl 4-vinylphenylphosphonate, di-isoheptyl 4-vinylphenylphosphonate, di-n-octyl 4-vinylphenylphosphonate, di-isooctyl 4-vinylbenzylphosphonate, diethyl 4-vinylphosphonate, dimethyl 1-pentenylphosphonate, diethyl 1-pentenylphosphonate, di-n-propyl 1-pentenylphosphonate, diisopropyl 1-pentenylphosphonate, di-n-butyl 1-pentenylphosphonate, and diisobutyl 1-pentenylphosphonate; the trans configuration is preferred.

[0013] According to a specific embodiment of the present invention, preferably, the mass fraction of the unsaturated organophosphonate monomer is 20-70% when the mass of the organic polymer carrier is 100%; the content of functional monomers in the carrier is determined by the amount of divinylbenzene and unsaturated organophosphonate functional monomers added.

[0014] The present invention also provides a method for preparing the above-mentioned organic polymer carrier, which includes the following steps: using monomers including the divinylbenzene and the unsaturated organophosphonate monomer as raw materials, the organic polymer carrier is obtained by copolymerization; the mass ratio of the unsaturated organophosphonate monomer to the 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 organophosphonate monomers to a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, and reacting at 50-80°C for 5-12 hours to obtain the organic polymer carrier, denoted as POP-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 a narrow dispersion and good flowability.

[0017] According to a specific embodiment of the present invention, preferably, in the above preparation method, the dispersing solvent includes fatty acid ester solvents and / or tetrahydrofuran.

[0018] According to a specific embodiment of the present invention, preferably, the fatty acid ester solvent includes one 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 mass of the dispersing solvent is 1:5-20, so that the system is uniformly 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-ethylene oxide copolymer.

[0021] According to a specific embodiment of the present invention, preferably, the weight-average molecular weight of the stabilizer is 1000-100000.

[0022] According to a specific embodiment of the present invention, preferably, the mass ratio of the amount of stabilizer added to the total amount of monomer 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 benzoyl peroxide (BPO).

[0024] According to a specific embodiment of the present invention, preferably, the mass ratio of the amount of initiator added to the total amount of monomer 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 a pretreated divinylbenzene, and the pretreatment is to remove the polymerization inhibitor.

[0026] The present invention also provides a ZN catalyst, wherein the raw material composition, calculated as 100% by mass of the ZN catalyst, includes 55-80 wt% of the organic polymer support, 1-6 wt% of magnesium compound calculated as magnesium element, 1-6 wt% of titanium compound calculated as titanium element, and 0-8 wt% of internal electron donor.

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

[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; R and R' are each independently selected from C1-C8 alkyl groups and their derivatives, aryl groups and their derivatives, alkoxy groups and their derivatives, and X is fluorine, chlorine, bromine or iodine.

[0029] According to a specific embodiment of the present invention, preferably, R and R' are each independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl, or 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 alkyl magnesium halide compounds, alkyl magnesium compounds, and alkoxy magnesium halide compounds, more preferably an alkyl chloride magnesium compound.

[0031] According to a specific embodiment of the present invention, preferably, the magnesium compound includes one or more of the following: methyl magnesium chloride, n-butyl magnesium chloride, isobutyl magnesium chloride, tert-butyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-butyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, tert-butyl magnesium iodide, benzyl magnesium iodide, n-butyl magnesium iodide, methyl magnesium fluoride, tert-butyl magnesium fluoride, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, and anhydrous magnesium chloride; after the magnesium compound is contacted with the organic polymer carrier, a porous organic carrier treated with magnesium compound is prepared, denoted as POP-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-mentioned magnesium compound is further reacted with titanium tetrachloride to obtain the ZN catalyst, denoted as POP-PO3...MgX / TiCl4.

[0033] The ZN catalyst of the present invention may selectively incorporate additional internal electron donors (ID) to further enhance the stereotactic ability of the catalyst, and the resulting ZN catalyst is denoted 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 diester compounds, diphenol ester compounds, diol ester compounds, succinate compounds, and diether compounds.

[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 the following: diisobutyl phthalate (DIBP), di-n-butyl phthalate (DNBP), 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl methyl ester (IAIPPDB), and 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether (IAIPDMP).

[0035] This invention also provides a method for preparing the above-mentioned ZN catalyst, which includes the following steps:

[0036] Under anhydrous and oxygen-free conditions, the organic polymer support is added to an inert solvent, followed by the magnesium compound. After reacting at 0℃-50℃ for 15-120 minutes, the unreacted magnesium compound is filtered out. Then, an inert solvent and titanium tetrachloride are added, and the reaction is carried out at 0℃-120℃ for 15-180 minutes. Next, the internal electron donor is added, and the reaction is carried out at 50℃-120℃ for 15-180 minutes. After filtration, an inert solvent and titanium tetrachloride are added to the filtrate, and the reaction is carried out at 50℃-120℃ for 30-180 minutes. After the reaction is complete, the mixture is filtered out, and finally washed with an inert solvent to obtain the ZN catalyst.

[0037] In the ZN catalyst of the present invention, the content of the functional monomer (unsaturated organophosphonate monomer) of the organic polymer support is generally 0.5 mmol / g support to 5 mmol / g support, preferably 1 mmol / g support to 4 mmol / g support; the content of the functional monomer is usually controlled during the support preparation process by the ratio of the functional monomer to the added amount of divinylbenzene (DVB) monomer; the ratio of the amount of magnesium compound reagent added (in moles of magnesium Mg) to the amount of support is 1 mmol / g support to 30 mmol / g support, preferably 3 mmol / g support to 20 mmol / g support; an excess of Ti metal compound, such as TiCl4, is usually added for catalyst loading, and the amount of Ti metal compound added (in moles of titanium Ti) is generally 5 mmol / g support to 200 mmol / g support, preferably 50 mmol / g support to 150 mmol / g support; the ratio of the internal electron donor to the support is 0 to 0.3 g internal electron donor / g support.

[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-based external electron donor.

[0040] According to a specific embodiment of the present invention, preferably, the silane-based external electron donor includes one or more combinations of cyclohexylmethyldimethoxysilane (C external donor), dicyclopentenedimethoxysilane (D external donor), diisopropyldimethoxysilane (P external donor), diisobutyldimethoxysilane (B external donor), and tetraethoxysilane (TEOS).

[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, and R” is a C1-C6 alkyl group; in addition, the alkyl aluminum compound can also be used as a purifying agent for the polymerization reaction system.

[0043] According to a specific embodiment of the present invention, preferably, 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 alkylaluminum compound to titanium in the ZN catalyst is 10-500.

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

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

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

[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℃ and the reaction pressure is 0.1-2.0 MPa.

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

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

[0054] The ZN-type olefin catalyst supported on a porous organic polymer support provided by this invention is obtained by copolymerizing divinylbenzene with unsaturated organophosphonate functional monomers to obtain a porous POP support containing organophosphonate groups (denoted as POP-PO3). The organophosphonate functional groups in the support interact with the Mg and Ti active centers, and additional internal electron donors can be selectively added, thereby preparing a porous organic polymer (POP) type ZN polyolefin catalyst (denoted as POP-PO3...MgX / TiCl4 / ID). The functional monomers selected for the organic polymer support in this invention are unsaturated organophosphonate functional monomers, which not only have an important influence on the prepared support, but also, due to the introduction of organophosphonate functional groups on the support, modify the microchemical environment of the Ti and Mg active centers, combined with the addition of additional internal electron donors, the prepared catalyst has good stereotacticity and polymerization catalytic activity. When used for propylene polymerization, this catalyst can be used with silane-based external electron donors and co-catalysts such as triethylaluminum. The resulting polypropylene exhibits high isotacticity, exceeding 99%, and a TREF high-temperature elution temperature of 124°C, higher than the elution temperature of conventional isotactic polypropylene (iPP) (121-123°C). Furthermore, the polymer molecular weight distribution can be adjusted over a wide range, with the molecular weight distribution coefficient controllable between 6 and 12. In addition, the catalyst possesses excellent copolymerization ability and can be used for ethylene and propylene polymerization, as well as the copolymerization of propylene with other α-olefins.

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

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

[0057] In this invention, divinylbenzene (DVB) can be a commercially available monomer with a DVB content of 55% or 80%. This monomer requires pretreatment before use to remove polymerization inhibitors. The method for removing polymerization inhibitors can follow existing techniques; for example, divinylbenzene can be washed with NaOH solution and distilled water, and then dried with anhydrous magnesium sulfate before use. Unsaturated organophosphonic acid ester functional monomers can be purchased directly or synthesized using methods described in the literature. For example, the corresponding unsaturated organophosphonic acid diester compounds can be obtained by reacting unsaturated double-bond chlorides with phosphite diesters or triesters (see reference 1: Richard Frantz et al., *Synthesis and solid-state NMR studies of p-vinylbenzylphosphonic acid*, Chemistry-A European Journal, 2003, Vol. 9, No. 3, pp. 770-775).

[0058] The molecular weight and distribution of the polymers prepared by olefin polymerization in this invention were obtained by gel permeation chromatography (GPC) using PolymerCharts; the isotacticity of the polymers was obtained by n-heptane extraction testing (referencing standard GB / T 2412-2008). The content of internal electron donors could be determined by extraction and gas chromatography.

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

[0063] In a 250 ml glass reactor, 130 ml of butyl acetate was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 3.0 g of diethyl vinylphosphonate (CAS: 682-30-4, Aladdin reagent, ≥98%). The mixture was stirred at room temperature for 5 min, then 2% of monomeric polyvinyl alcohol (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h, then 2.0% of monomeric AIBN was added. The temperature was raised to 70 °C, and the reaction was carried out for 3 h at a rotation speed of 450 rpm. The temperature was then raised to 80 °C, and the reaction was carried out for 12 h. After filtration, the mixture was washed three times with ethyl acetate, filtered, and dried to obtain 5.8 g of free-flowing porous organic polymer carrier POP-1. The specific surface area of ​​the carrier was 452 m². 2 / g, pore volume 0.57ml / g;

[0064] (2) Preparation of ZN catalyst:

[0065] In a 250 ml glass reactor, 2 g of the carrier POP-1 prepared using diethyl vinylphosphonate functional monomer was added, along with 100 ml of toluene. The mixture was stirred, and then 8 ml of 3M methylmagnesium chloride Grignard reagent was added at 5 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, 50 ml of toluene was added, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.2 g of di-n-butyl phthalate was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The reaction was carried out at 100 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-1. The catalyst Cat-1 had 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] ZN catalyst preparation: In a 250 ml glass reactor, 2 g of the support POP-1 prepared using diethyl vinylphosphonate functional monomer was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M methylmagnesium chloride Grignard reagent was added at room temperature (25°C). The mixture was stirred for 1 hour, filtered, and washed twice with toluene. The temperature was then raised to 50°C, 50 ml of toluene was added, and 40 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, then the temperature was raised to 80°C, and 0.2 g of diisobutyl phthalate was added. The reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The mixture was reacted at 100°C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-2. The catalyst Cat-2 had a Mg content of 4.8%, a titanium content of 3.8%, an internal electron donor content of 4.2%, and an organic polymer support content of 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 carriers:

[0072] In a 250 ml glass reactor, 130 ml of butyl acetate was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 3.0 g of diethyl allylphosphonate (CAS: 1067-87-4). The mixture was stirred at room temperature for 5 min, then 2% of the monomer mass of F127, a block copolymer of ethylene oxide and propylene oxide, was added. The mixture was stirred at 45 °C for 1 h, then 2.0% of the monomer mass of AIBN was added. The temperature was raised to 70 °C, and the reaction was carried out for 3 h at a rotation speed of 350 rpm. The temperature was then raised to 80 °C, and the reaction was carried out for 8 h. After filtration, the mixture was washed three times with ethyl acetate, filtered, and dried to obtain 6.3 g of free-flowing porous organic polymer carrier POP-2. The specific surface area of ​​the carrier was 431 m². 2 / g, pore volume 0.53ml / g;

[0073] (2) Preparation of ZN catalyst:

[0074] In a 250 ml glass reactor, 2 g of the carrier POP-2 prepared using the functional monomer of allyl phosphonate diethyl ester was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at 5 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, 50 ml of toluene was added, and 40 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.2 g of diisobutyl phthalate was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The reaction was carried out at 100 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-3. The catalyst Cat-3 had a Mg content of 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] ZN catalyst preparation: In a 250 ml glass reactor, add 2 g of the POP-2 support prepared using the allyl phosphonate diethyl ester 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 heat to 50 °C, add 50 ml of toluene, add 40 ml of TiCl4 dropwise, react for 2 hours, then heat to 80 °C, add 0.2 g of 3-methyl-5-tert-butyl-1,2-benzenediphenol benzoate (CAS: 1232839-86-9), react for 1 hour, after the reaction is complete, filter, then add 50 ml of toluene and 30 ml of... TiCl4 was reacted at 100℃ for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-4. The catalyst Cat-4 had a Mg content of 4.2%, a titanium content of 4.0%, an internal electron donor content of 2.5%, and an organic polymer support content of 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 carriers:

[0081] In a 250 ml glass reactor, 130 ml of ethyl acetate was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.0 g of diethyl 2-butenylphosphonate (CAS: 682-34-8, mainly trans-form). The mixture was stirred at room temperature for 5 min, then 3% of the monomer mass of F127, a block copolymer of polyethylene oxide and polypropylene oxide, was added. The mixture was stirred at 45 °C for 1 h, then 2.0% of the monomer mass of AIBN was added. The temperature was raised to 70 °C, and the reaction was carried out for 3 h at a rotation speed of 450 rpm. The temperature was then raised to 80 °C, and the reaction was carried out for 8 h. After filtration, the mixture was washed three times with ethyl acetate, filtered, and dried to obtain 4.5 g of free-flowing porous organic polymer carrier POP-3. The specific surface area of ​​the carrier was 242 m². 2 / g, pore volume 0.26ml / g;

[0082] (2) Preparation of ZN catalyst:

[0083] In a 250 ml glass reactor, 2 g of the carrier POP-3 prepared using the functional monomer of 2-butenylphosphonic acid diethyl ester was added, along with 100 ml of toluene. The mixture was stirred, and then 8 ml of 3M benzyl magnesium bromide was added at room temperature. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, 60 ml of toluene was added, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.2 g of diisobutyl phthalate was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The mixture was reacted at 100 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-5. The catalyst Cat-5 had 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] ZN catalyst preparation: In a 250 ml glass reactor, 2 g of the support POP-3 prepared using the functional monomer of 2-butenylphosphonic acid diethyl ester was added, along with 100 ml of toluene. The mixture was stirred, and then 8 ml of 3M butyl magnesium chloride was added at room temperature. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, 60 ml of toluene was added, and 40 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.15 g of 9,9-dimethoxyfluorene internal electron donor was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The mixture was reacted at 100 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-6. The catalyst Cat-6 had a Mg content of 4.0%, a titanium content of 3.5%, an internal electron donor content of 2.9%, and an organic polymer support content of 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 carriers:

[0090] In a 250 ml glass reactor, 130 ml of ethyl acetate was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 55%) and 3.0 g of allylphosphonic acid (CAS: 6833-67-6). The mixture was stirred at room temperature for 5 min, then 5% of the monomer mass of F127, a block copolymer of polyethylene oxide and polypropylene oxide, was added. The mixture was stirred at 45 °C for 1 h, then 2.0% of the monomer mass of AIBN was added. The temperature was raised to 70 °C, and the reaction was carried out for 3 h at a rotation speed of 450 rpm. The temperature was then raised to 80 °C, and the reaction was carried out for 8 h. After filtration, the mixture was washed three times with ethyl acetate, filtered, and dried to obtain 4.5 g of free-flowing porous organic polymer carrier POP-4. The specific surface area of ​​the carrier was 198 m². 2 / g, pore volume 0.34ml / g;

[0091] (2) Preparation of ZN catalyst:

[0092] In a 250 ml glass reactor, 2 g of the POP-4 support prepared using allylphosphonic acid functional monomers was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M methyl magnesium chloride was added at room temperature. The mixture was stirred for 1 hour, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, 60 ml of toluene was added, and 30 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.20 g of diisobutyl phthalate (DIP) internal electron donor was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The reaction was carried out at 100 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-7. The catalyst Cat-7 had a Mg content of 3.8%, a titanium content of 3.2%, an internal electron donor content of 4.7%, and an organic polymer support content of 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 carriers:

[0096] In a 250 ml glass reactor, 130 ml of butyl acetate was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.4 g of allylphosphonic acid (CAS: 6833-67-6). The mixture was stirred at room temperature for 5 min, then 5% of the monomer mass of F127, a block copolymer of ethylene oxide and propylene oxide, was added. The mixture was stirred at 45 °C for 1 h, then 2.0% of the monomer mass of benzoyl peroxide (BPO) was added. The temperature was raised to 70 °C, and the reaction was carried out for 3 h at a rotation speed of 450 rpm. The temperature was then raised to 80 °C, and the reaction was carried out for 8 h. After filtration, the mixture was washed three times with ethyl acetate, filtered, and dried to obtain 4.5 g of free-flowing porous organic polymer carrier POP-5. The specific surface area of ​​the carrier was 337 m². 2 / g, pore volume 0.45ml / g;

[0097] (2) Preparation of ZN catalyst:

[0098] In a 250 ml glass reactor, 2 g of the POP-5 support prepared using allylphosphonic acid functional monomers was added, along with 100 ml of toluene. The mixture was stirred, and then 15 ml of 3M methyl magnesium chloride was added at room temperature. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. The temperature was then raised to 50 °C, 60 ml of toluene was added, and 40 ml of TiCl4 was added dropwise. The reaction was carried out for 2 hours, and then the temperature was raised to 80 °C. 0.30 g of diisobutyl phthalate (DIP) internal electron donor was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 40 ml of TiCl4 were added. The reaction was carried out at 100 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-8. The catalyst Cat-8 had a Mg content of 6.8%, a titanium content of 5.2%, an internal electron donor content of 7.2%, and an organic polymer support content of 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 carriers:

[0102] In a 250 ml glass reactor, 130 ml of butyl acetate was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.5 g of diethyl 4-vinylbenzylphosphonate (CAS: 726-61-4, see reference 1, obtained by the reaction of p-chloromethylstyrene with diethyl phosphite, yield approximately 93%). The mixture was stirred at room temperature for 5 min, then 3% of the monomer mass of F127, a block copolymer of polyethylene oxide and polypropylene oxide, was added. The mixture was stirred at 45 °C for 1 h, then 2.0% of the monomer mass of AIBN was added. The temperature was raised to 70 °C, and the reaction was carried out for 3 h at a rotation speed of 450 rpm. The temperature was then raised to 80 °C, and the reaction was carried out for 8 h. After filtration, the mixture was washed three times with ethyl acetate, filtered, and dried to obtain 4.5 g of free-flowing porous organic polymer carrier POP-6. The specific surface area of ​​the carrier was 352 m². 2 / g, pore volume 0.49ml / g;

[0103] (2) Preparation of ZN catalyst:

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

[0105] Example 10

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

[0107] ZN catalyst preparation: In a 250 ml glass reactor, 2 g of the support POP-6 prepared using the functional monomer of 4-vinylbenzylphosphonic acid diethyl ester was added, along with 100 ml of toluene. The mixture was stirred, and then 8 ml of 3M methylmagnesium chloride Grignard reagent was added at 5 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. Then, 50 ml of toluene was added, and 35 ml of TiCl4 was added dropwise at room temperature. The reaction was carried out for 1 hour, and the temperature was raised to 80 °C. 0.25 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate internal electron donor was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The reaction was carried out at 80 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-10. The catalyst Cat-10 had a Mg content of 3.0%, a titanium content of 3.2%, an internal electron donor content of 2.5%, and an organic polymer support content of 68%.

[0108] Example 11

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

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

[0111] In a 250 ml glass reactor, 130 ml of butyl acetate was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.4 g of diethyl (3-phenylallyl) phosphonate (CAS: 58922-31-9, see reference 1, obtained by reacting β-phenylpropenyl chloride with diethyl phosphite, yield 93%). The mixture was stirred at room temperature for 5 min, then 3% of the monomer mass of F127, a block copolymer of polyethylene oxide and polypropylene oxide, was added. The mixture was stirred at 45 °C for 1 h, then 2.0% of the monomer mass of BPO was added. The temperature was raised to 70 °C, and the reaction was carried out for 3 h at a rotation speed of 450 rpm. The temperature was then raised to 80 °C, and the reaction was carried out for 8 h. After filtration, the mixture was washed three times with ethyl acetate, filtered, and dried to obtain 4.5 g of free-flowing porous organic polymer carrier POP-7. The specific surface area of ​​the carrier was 387 m². 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 functional monomer of (3-phenylallyl)phosphonate diethyl ester was added, along with 100 ml of toluene. The mixture was stirred, and then 10 ml of 3M methylmagnesium chloride Grignard reagent was added at 5 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. Then, 50 ml of toluene was added, and 35 ml of TiCl4 was added dropwise at room temperature. The reaction was carried out for 1 hour, and the temperature was raised to 80 °C. Then, 0.25 g of 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate internal electron donor was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The reaction was carried out at 80 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-11. The catalyst Cat-11 had 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 carriers:

[0117] In a 250 ml glass reactor, 130 ml of butyl acetate was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.0 g of dimethyl (3-phenylallyl)phosphonate (obtained from reference 1 by reacting β-phenylpropenyl chloride with dimethyl phosphite, yield 92%). The mixture was stirred at room temperature for 5 min, then 5% of the monomer mass of F127, a block copolymer of ethylene oxide and propylene oxide, was added. The mixture was stirred at 45 °C for 1 h, followed by 2.0% of the monomer mass of AIBN. The temperature was raised to 70 °C, and the reaction was carried out for 3 h at a rotation speed of 450 rpm. The temperature was then raised to 80 °C, and the reaction was carried out for 8 h. After filtration, the mixture was washed three times with ethyl acetate, filtered, and dried to obtain 4.5 g of free-flowing porous organic polymer carrier POP-8. The carrier had a specific surface area of ​​288 m². 2 / g, pore volume 0.37ml / g;

[0118] (2) Preparation of ZN catalyst:

[0119] In a 250 ml glass reactor, 2 g of the carrier POP-8 prepared using the functional monomer of (3-phenylallyl)phosphonate dimethyl ester was added, along with 100 ml of toluene. The mixture was stirred, and then 8 ml of 3M methyl magnesium chloride Grignard reagent was added at 5 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. Then, 50 ml of toluene was added, and 35 ml of TiCl4 was added dropwise at room temperature. The reaction was carried out for 1 hour, and the temperature was raised to 80 °C. Then, 0.20 g of diisobutyl phthalate internal electron donor was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The reaction was carried out at 80 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-12. The catalyst Cat-12 had 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] Example 13

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

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

[0123] In a 250 ml glass reactor, 130 ml of n-propyl formate was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 55%) and 2.5 g of (3-phenylallyl)phosphonic acid (from reference 1, obtained by the reaction of β-phenylpropenyl chloride with phosphoric acid, yield 90%). The mixture was stirred at room temperature for 5 min, then 5% of the monomer mass of F127, a block copolymer of polyethylene oxide and polypropylene oxide, was added. The mixture was stirred at 45 °C for 1 h, then 2.0% of the monomer mass of AIBN was added. The temperature was raised to 70 °C and the reaction was carried out for 3 h at a rotation speed of 450 rpm. The temperature was then raised to 80 °C and the reaction was carried out for 8 h. After filtration, the mixture was washed three times with ethyl acetate, filtered, and dried to obtain 4.5 g of free-flowing porous organic polymer carrier POP-9. The specific surface area of ​​the carrier was 182 m². 2 / g, pore volume 0.27ml / g;

[0124] (2) Preparation of ZN catalyst:

[0125] In a 250 ml glass reactor, 2 g of the POP-9 support prepared using the (3-phenylallyl)phosphonic acid functional monomer was added, along with 100 ml of toluene. The mixture was stirred, and then 8 ml of 3M methylmagnesium chloride Grignard reagent was added at 5 °C. The mixture was stirred for 2 hours, filtered, and washed twice with toluene. Then, 50 ml of toluene was added, and 35 ml of TiCl4 was added dropwise at room temperature. The reaction was carried out for 1 hour, and the temperature was raised to 80 °C. Then, 0.20 g of diisobutyl phthalate (DIP) internal electron donor was added, and the reaction was carried out for 1 hour. After the reaction was completed, the mixture was filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The reaction was carried out at 80 °C for 2 hours. After the reaction was completed, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, denoted as Cat-13. The catalyst Cat-13 had a Mg content of 3.0%, a titanium content of 3.0%, an internal electron donor content of 4.1%, and an organic polymer support content of 71%.

[0126] Example 14

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

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

[0129] Comparative Example 1

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

[0131] Preparation of Zn-supported polypropylene catalyst on an inorganic support: In a 250 ml glass reactor, 3 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) was added, along with 100 ml of toluene. The mixture was stirred, and then 50 ml of TiCl4 was slowly added dropwise at 0 °C, controlling the dropping rate to maintain the temperature between 0 and 5 °C. After the addition was complete, the temperature was raised to 60 °C, and 0.30 g of DIBP internal electron donor was added. The reaction was carried out at 110 °C for 2 hours. After filtration, 100 ml of fresh TiCl4 was added, and the reaction was carried out at 110 °C for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-15. The titanium content of catalyst Cat-15 was 3.2%, and the content of DIBP internal electron donor was 8.9%.

[0132] Comparative Example 2

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

[0134] Preparation of Zn-supported polypropylene catalyst on an inorganic support: In a 250 ml glass reactor, 3 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) was added, along with 100 ml of toluene. The mixture was stirred, and then 50 ml of TiCl4 was slowly added dropwise at 0 °C, controlling the dropping rate to maintain the temperature between 0 and 5 °C. After the addition was complete, the temperature was raised to 60 °C, and 0.40 g of 9,9-dimethoxyfluorene internal electron donor was added. The reaction was carried out at 110 °C for 2 hours. After filtration, 100 ml of fresh TiCl4 was added, and the reaction was carried out at 110 °C for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-16. The titanium content of catalyst Cat-16 was 3.2%, and the content of 9,9-dimethoxyfluorene internal electron donor was 6.2%.

[0135] Comparative Example 3

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

[0137] In a 250 ml glass reactor, 2 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) and 50 ml of toluene were added. The mixture was stirred, and 30 ml of TiCl4 was slowly added dropwise at room temperature. The reaction was allowed to proceed for 1 hour. The temperature was then raised to 80 °C, and 0.20 g of diisobutyl phthalate (DIBP) internal electron donor was added. The reaction was allowed to proceed for 1 hour. After the reaction was complete, the mixture was filtered. Then, 50 ml of toluene and 30 ml of TiCl4 were added, and the reaction was allowed to proceed at 80 °C for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-17. The titanium content of catalyst Cat-17 was 3.5%, and the content of the internal electron donor in DIBP was 6.2%.

[0138] Comparative Example 4

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

[0140] In a 250 ml glass reactor, 2 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) was added, along with 60 ml of toluene. 40 ml of TiCl4 was slowly added dropwise at 50 °C, and the reaction was allowed to proceed for 2 hours. The temperature was then raised to 80 °C, and 0.15 g of 9,9-dimethoxyfluorene internal electron donor was added. The reaction was allowed to proceed for 1 hour. After the reaction was complete, the mixture was filtered. Then, 50 ml of toluene and 30 ml of TiCl4 were added, and the reaction was allowed to proceed at 100 °C for 2 hours. After the reaction was complete, the mixture was filtered again, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-18. The catalyst Cat-18 contained 3.8% titanium and 4.6% 9,9-dimethoxyfluorene internal electron donor.

[0141] Propylene polymerization performance test

[0142] Test Example 1

[0143] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of Cat-1 catalyst and 0.5 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.3 g of hydrogen was added, and the temperature was raised to 70°C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1005 g of polypropylene product (PP-1) with a bulk density of 0.37 g / ml and a catalyst activity of 12563 gPP / gcat.h, as shown in Table 1.

[0144] Test Example 2

[0145] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of Cat-1 catalyst and 0.5 mL of dicyclopentyldimethoxysilane (externally supplied by D) were added. 0.3 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 864 g of polypropylene product (PP-2) with a bulk density of 0.37 g / mL and a catalyst activity of 10800 gPP / gcat.h, as shown in Table 1.

[0146] Test Example 3

[0147] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of Cat-2 catalyst and 0.3 mL of cyclohexylmethyldimethoxysilane (externally supplied C) were added, along with 0.5 g of hydrogen. The temperature was raised to 70°C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1024 g of polypropylene product (PP-3) with a bulk density of 0.39 g / mL and a catalyst activity of 12800 gPP / gcat.h, as shown in Table 1.

[0148] Test Example 4

[0149] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum TEA (1.0 mol / L) were added. The mixture was stirred at 600 rpm, followed by 80 mg of Cat-3 catalyst and 0.5 mL of cyclohexylmethyldimethoxysilane (externally supplied C). 0.3 g of hydrogen was added, and the mixture was heated to 70°C and polymerized at 600 rpm for 1 hour. After the reaction was complete, the reaction was terminated, cooled to room temperature, and dried to obtain 1086 g of polypropylene product (PP-4) with a bulk density of 0.38 g / mL and a catalyst activity of 13575 gPP / gcat.h, as shown in Table 1.

[0150] Test Example 5

[0151] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of Cat-4 catalyst and 0.3 mL of cyclohexylmethyldimethoxysilane (externally supplied C) were added, along with 0.5 g of hydrogen. The temperature was raised to 70°C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1160 g of polypropylene product (PP-5) with a bulk density of 0.37 g / mL and a catalyst activity of 14500 gPP / gcat.h, as shown in Table 1.

[0152] Test Example 6

[0153] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of Cat-4 catalyst and 0.3 mL of dicyclopentyldimethoxysilane (externally supplied) were added, along with 0.5 g of hydrogen. The temperature was raised to 70°C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1002 g of polypropylene product (PP-6) with a bulk density of 0.37 g / mL and a catalyst activity of 12525 gPP / gcat.h, as shown in Table 1.

[0154] Test Example 7

[0155] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum TEA (1.0 mol / L) were added. The mixture was stirred at 600 rpm, followed by 80 mg of Cat-5 catalyst and 0.3 mL of cyclohexylmethyldimethoxysilane (externally supplied C). 0.3 g of hydrogen was added, and the mixture was heated to 70°C and polymerized at 600 rpm for 1 hour. After the reaction was complete, the reaction was terminated, cooled to room temperature, and dried to obtain 850 g of polypropylene product (PP-7) with a bulk density of 0.38 g / mL and a catalyst activity of 10625 gPP / gcat.h, as shown in Table 1.

[0156] Test Example 8

[0157] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of Cat-6 catalyst and 0.5 ml of dicyclopentyldimethoxysilane (externally supplied) were added, along with 0.5 g of hydrogen. The temperature was raised to 70°C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 900 g of polypropylene product (PP-8) with a bulk density of 0.38 g / ml and a catalyst activity of 11250 gPP / gcat.h, as shown in Table 1.

[0158] Test Example 9

[0159] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of Cat-7 catalyst and 0.5 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70°C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1050 g of polypropylene product (PP-9) with a bulk density of 0.37 g / ml and a catalyst activity of 13125 gPP / gcat.h, as shown in Table 1.

[0160] Test Case 10

[0161] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm, followed by 80 mg of Cat-8 catalyst and 0.5 ml of cyclohexylmethyldimethoxysilane (externally supplied C). 0.3 g of hydrogen was added, and the mixture was heated to 70 °C and polymerized at 600 rpm for 1 hour. After the reaction was complete, the reaction was terminated, cooled to room temperature, and dried to obtain 1142 g of polypropylene product (PP-10) with a bulk density of 0.38 g / ml and a catalyst activity of 14275 gPP / gcat.h, as shown in Table 1.

[0162] Test Example 11

[0163] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum TEA (1.0 mol / L) were added. The mixture was stirred at 600 rpm. Then, 80 mg of catalyst Cat-9 and 0.3 mL of cyclohexylmethyldimethoxysilane (externally supplied C) were added, along with 0.3 g of hydrogen. The temperature was raised to 70°C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 840 g of polypropylene product (PP-11) with a bulk density of 0.37 g / mL and a catalyst activity of 10500 gPP / gcat.h, as shown in Table 1.

[0164] Test Example 12

[0165] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of catalyst Cat-10 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70°C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 944 g of polypropylene product (PP-12) with a bulk density of 0.38 g / ml and a catalyst activity of 11800 gPP / gcat.h, as shown in Table 1.

[0166] Test Example 13

[0167] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of catalyst Cat-11 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70°C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 788 g of polypropylene product (PP-13) with a bulk density of 0.37 g / ml and a catalyst activity of 9850 gPP / gcat.h, as shown in Table 1.

[0168] Test Example 14

[0169] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum TEA (1.0 mol / L) were added. The mixture was stirred at 600 rpm. Then, 80 mg of catalyst Cat-12 and 0.3 mL of cyclohexylmethyldimethoxysilane (externally supplied C) were added, along with 0.5 g of hydrogen. The temperature was raised to 70°C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 748 g of polypropylene product (PP-14) with a bulk density of 0.36 g / mL and a catalyst activity of 9350 gPP / gcat.h, as shown in Table 1.

[0170] Test Example 15

[0171] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of catalyst Cat-13 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70°C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 985 g of polypropylene product (PP-15) with a bulk density of 0.38 g / ml and a catalyst activity of 12313 gPP / gcat.h, as shown in Table 1.

[0172] Test Example 16

[0173] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of catalyst Cat-13 and 0.5 mL of dicyclopentyldimethoxysilane (externally supplied) were added, along with 0.3 g of hydrogen. The temperature was raised to 70°C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 952 g of polypropylene product (PP-16) with a bulk density of 0.37 g / mL and a catalyst activity of 11900 gPP / gcat.h, as shown in Table 1.

[0174] Test Example 17

[0175] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm. Then, 80 mg of catalyst Cat-14 and 0.5 mL of dicyclopentyldimethoxysilane (external donor) were added, along with 0.3 g of hydrogen. The temperature was raised to 70°C, and polymerization was carried out at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 628 g of polypropylene product (PP-17) with a bulk density of 0.36 g / mL. No obvious polymer agglomeration was observed without the addition of an internal electron donor. The polymer isotacticity was 96.5%, and the catalyst activity was 7850 gPP / gcat.h, as shown in Table 1.

[0176] Comparative Test Example 1

[0177] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm. Then, 60 mg of the comparative catalyst Cat-15 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1119 g of polypropylene product (PP-18) with a bulk density of 0.37 g / ml and a catalyst activity of 18650 gPP / gcat.h, as shown in Table 1.

[0178] Comparative Test Example 2

[0179] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm. Then, 60 mg of the comparative catalyst Cat-16 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1280 g of polypropylene product (PP-19) with a bulk density of 0.42 g / ml and a catalyst activity of 21333 gPP / gcat.h, as shown in Table 1.

[0180] Comparative Test Case 3

[0181] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm. Then, 60 mg of the comparative catalyst Cat-17 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1030 g of polypropylene product (PP-20) with a bulk density of 0.38 g / ml and a catalyst activity of 17167 gPP / gcat.h, as shown in Table 1.

[0182] Comparative Test Example 4

[0183] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10 L dried propylene polymerization reactor. The mixture was stirred at 600 rpm. Then, 60 mg of the comparative catalyst Cat-18 and 0.3 ml of cyclohexylmethyldimethoxysilane (externally supplied C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70 °C. Polymerization was carried out for 1 hour under stirring at 600 rpm. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 1145 g of polypropylene product (PP-21) with a bulk density of 0.41 g / ml and a catalyst activity of 19083 gPP / gcat.h, as shown in Table 1.

[0184] Table 1. Propylene polymerization results

[0185]

[0186] Test Example 18: Copolymerization Test of Propylene and Ethylene

[0187] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum (TEA) (1.0 mol / L) were added. The mixture was stirred at 600 rpm. Then, 60 mg of the Cat-1 catalyst prepared above and 0.5 mL of cyclohexylmethyldimethoxysilane (externally supplied by C) were added, along with 0.3 g of hydrogen and 50 g of ethylene monomer. The mixture was heated to 70°C and polymerized at 600 rpm for 1 hour. After depressurization, the mixture was cooled to room temperature and dried to obtain 858 g of ethylene-propylene copolymer product. The catalyst polymerization activity was 14300 gPP / 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: Copolymerization Test of Propylene and Ethylene

[0189] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum (TEA) (1.0 mol / L) were added. The mixture was stirred at 600 rpm. Then, 60 mg of the prepared Cat-4 catalyst and 0.5 mL of cyclohexylmethyldimethoxysilane (externally supplied by C) were added, along with 0.50 mL of TiCl4, hydrogen gas, and 50 g of ethylene monomer. The mixture was heated to 70°C and polymerized at 600 rpm for 1 hour. After depressurization, the mixture was cooled to room temperature and dried to obtain 924 g of ethylene-propylene copolymer product. The catalyst polymerization activity was 15400 gPP / gcat.h, the polymer weight-average molecular weight (Mw) was 735,000 g / mol, and the molecular weight distribution coefficient was 10.9.

[0190] Test Example 20: Copolymerization Test of Propylene and Butene

[0191] In a 10L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 mL of triethylaluminum (TEA) (1.0 mol / L) were added. The mixture was stirred at 600 rpm. Then, 60 mg of the Cat-4 catalyst prepared above and 0.5 mL of cyclohexylmethyldimethoxysilane (externally supplied by C) were added, along with 0.5 g of hydrogen and 50 g of 1-butene monomer. The mixture was heated to 70°C and polymerized at 600 rpm for 1 hour. The pressure was released, and the mixture was cooled to room temperature and dried to obtain 564 g of propylene-butene copolymer product. The catalyst polymerization activity was 9400 gPP / gcat.h.

[0192] As can be seen from the above polymerization results, the ZN polyolefin catalyst supported on the organic polymer support in this invention is obtained by copolymerizing divinylbenzene with functional monomers containing unsaturated double-bonded organophosphonate groups to obtain a porous POP support containing organophosphate groups. Relying on the organophosphate functional groups on the POP support, the microchemical environment of the metal active center is regulated, and the solid component of the POP-PO3...MgX / TiCl4 / ID polypropylene catalyst supported on the organic support is designed and prepared. It has good catalytic activity, and the homopolymerization activity of propylene can reach more than 14000gPP / gcat.h. Although it is lower than that of the catalyst supported on the traditional inorganic MgCl2 support, its activity is significantly improved compared with the polymerization activity of existing organic polymer supports, which can meet the level of existing industrial catalysts. Even without the addition of an internal electron donor, the POP-PO3...MgX / TiCl4 polypropylene catalyst exhibits good stereoregularity. The isotacticity of the polypropylene obtained by the propylene polymerization catalyzed by the catalyst Cat-14 prepared in Example 14 is 96.5%, which is comparable to that of Cat-17 in Comparative Example 3. No obvious polymer agglomeration due to low isotacticity was observed during polymerization. Furthermore, compared with inorganic carrier-supported polypropylene catalysts 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 catalyst 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 (which has high stereoregularity) as the internal electron donor), the catalyst of the present invention has better stereoregularity, and the prepared polypropylene has a higher isotacticity, which can reach more than 98%. The TREF high-temperature elution temperature is higher, reaching 124°C, which is higher than the elution temperature of conventional isotactic polypropylene (iPP) (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. The POP-PO3...MgX / TiCl4 / ID catalyst disclosed in this invention has a simple preparation method and good industrialization prospects compared with existing catalysts. It uses an organic support to avoid introducing excess inorganic impurities, which gives the catalyst system an advantage in developing low-precipitation, high-crystallization polyolefin products.

Claims

1. A ZN catalyst, wherein the raw material composition comprises 55-80 wt% organic polymer support, 1-6 wt% magnesium compound (calculated as magnesium element), 1-6 wt% titanium compound (calculated as titanium element), and 0-8 wt% internal electron donor, based on 100% of the ZN catalyst by mass. The organic polymer carrier is obtained by copolymerization of monomers including divinylbenzene and unsaturated organophosphonate monomers; in, The unsaturated organophosphonate monomer has the structure shown in Formula I: Formula I In Equation I, R1 and R2 are each independently selected from C1-C 10 Straight-chain alkyl, C1-C 10 Branched alkyl, cycloalkyl, and aromatic groups; R3, R4, and R5 are each independently selected from hydrogen, halogen, C1-C8 straight-chain or branched hydrocarbon groups, cycloalkyl groups, and aromatic groups; R6 is selected from single bonds, C1-C8 straight-chain or branched hydrocarbon groups, cycloalkylene groups, and aromaticene groups. Based on the organic polymer carrier having a mass of 100%, the mass fraction of the unsaturated organophosphonate monomer is 20-70%. The specific surface area of ​​the organic polymer carrier is 100-600 m². 2 / g, pore volume > 0.2 ml / g.

2. The ZN catalyst according to claim 1, wherein, In Formula I, the halogen is F, Cl, or Br.

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

4. The ZN catalyst according to claim 1, wherein, The unsaturated organophosphonate monomers are 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, dimethyl allylphosphonate, dimethyl 2-methylallylphosphonate, diethyl allylphosphonate, diethyl 2-methylallylphosphonate, di-n-propyl allylphosphonate, and diisopropyl allylphosphonate. Esters, allylphosphonate di-n-butyl ester, allylphosphonate diisobutyl ester, allylphosphonate diisopentyl ester, allylphosphonate di-n-hexyl ester, allylphosphonate di-n-heptyl ester, allylphosphonate diisoheptyl ester, allylphosphonate di-n-octyl ester, allylphosphonate diisooctyl ester, allylphosphonate diphenyl ester, allylphosphonate dibenzyl ester, 1-butenylphosphonate dimethyl ester, 1-butenylphosphonate diethyl ester, 1-butenylphosphonate diisopropyl ester, 1-butenylphosphonate di-n-propyl ester, 1-butenylphosphonate di-n-butyl ester, 1-butenylphosphonate di-n-pentyl ester, 1-butenylphosphonate di-n-hexyl ester, 1-butenylphosphonate di-n-heptyl ester, 1-butenylphosphonate di-n-octyl ester, 1-chloro-1-butene 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, 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, di-4-vinylphenylphosphonate One or more of the following: diisopropyl phenylphosphonate, di-n-butyl 4-vinylphenylphosphonate, di-n-pentyl 4-vinylphenylphosphonate, diisopentyl 4-vinylphenylphosphonate, di-n-hexyl 4-vinylphenylphosphonate, di-n-heptyl 4-vinylphenylphosphonate, di-n-isoheptyl 4-vinylphenylphosphonate, di-n-octyl 4-vinylphenylphosphonate, di-isooctyl 4-vinylbenzylphosphonate, diethyl 1-pentenylphosphonate, diethyl 1-pentenylphosphonate, di-n-propyl 1-pentenylphosphonate, diisopropyl 1-pentenylphosphonate, di-n-butyl 1-pentenylphosphonate, and diisobutyl 1-pentenylphosphonate.

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

1.

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

7. The ZN catalyst according to claim 6, wherein, The dispersion solvent includes fatty acid ester solvents and / or tetrahydrofuran.

8. The ZN catalyst according to claim 7, wherein, The fatty acid ester solvents include one or more of the following: 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.

9. The ZN catalyst according to claim 6, wherein, The mass ratio of the total amount of monomer added to the dispersing solvent is 1:5-20.

10. The ZN catalyst according to claim 6, wherein, The stabilizer is polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer.

11. The ZN catalyst according to claim 6, wherein, The weight-average molecular weight of the stabilizer is 1,000-100,000.

12. The ZN catalyst according to claim 6, wherein, The mass ratio of the amount of stabilizer added to the total amount of monomer added is 0.5-5:

100.

13. The ZN catalyst according to claim 6, wherein, The initiator is azobisisobutyronitrile and / or benzoyl peroxide.

14. The ZN catalyst according to claim 6, wherein, The mass ratio of the amount of initiator added to the total amount of monomer added is 0.5-3:

100.

15. The ZN catalyst according to claim 5, wherein, The divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor.

16. The ZN catalyst according to claim 1, wherein, The organic polymer carrier has a content of 60-75 wt%, magnesium content of 2-5 wt%, titanium content of 2-5 wt%, and internal electron donor content of 2-6 wt%.

17. The ZN catalyst according to claim 1, 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, aryl or alkoxy groups, and X is fluorine, chlorine, bromine or iodine.

18. The ZN catalyst according to claim 17, wherein, R and R' are each independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl, and substituted phenyl.

19. The ZN catalyst according to claim 17, wherein, The magnesium compound is one or a combination of two or more of alkyl halide magnesium compounds, alkyl magnesium compounds, and alkoxy halide magnesium compounds.

20. The ZN catalyst according to claim 19, wherein, The magnesium compound includes one or more of the following: methyl magnesium chloride, n-butyl magnesium chloride, isobutyl magnesium chloride, tert-butyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-butyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, tert-butyl magnesium iodide, benzyl magnesium iodide, n-butyl magnesium iodide, methyl magnesium fluoride, tert-butyl magnesium fluoride, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, and anhydrous magnesium chloride.

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

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

23. The ZN catalyst according to claim 22, wherein, The internal electron donor includes one or more of the following: diisobutyl phthalate, di-n-butyl phthalate, 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl methyl ester, and 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether.

24. A method for preparing the ZN catalyst according to any one of claims 1-23, comprising the following steps: Under anhydrous and oxygen-free conditions, the organic polymer support is added to an inert solvent, followed by the magnesium compound. After reacting at 0℃-50℃ for 15-120 minutes, the unreacted magnesium compound is filtered out. Then, an inert solvent and titanium tetrachloride are added, and the reaction is carried out at 0℃-120℃ for 15-180 minutes. Next, the internal electron donor is added, and the reaction is carried out at 50℃-120℃ for 15-180 minutes. After filtration, an inert solvent and titanium tetrachloride are added to the filtrate, and the reaction is carried out at 50℃-120℃ for 30-180 minutes. After the reaction is complete, the mixture is filtered out, and finally washed with an inert solvent to obtain the ZN catalyst.

25. A ZN catalyst system comprising a ZN catalyst, an external electron donor, and a co-catalyst; in, The ZN catalyst is the ZN catalyst according to any one of claims 1-23.

26. The ZN catalyst system according to claim 25, wherein, The external electron donor includes silane-based external electron donors.

27. The ZN catalyst system according to claim 26, wherein, The silane-based external electron donors include one or more combinations of cyclohexylmethyldimethoxysilane, dicyclopentenedimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, and tetraethoxysilane.

28. The ZN catalyst system according to claim 26, wherein, The molar ratio of silicon in the silane-based external electron donor to titanium in the ZN catalyst is 5-100.

29. The ZN catalyst system according to claim 25, wherein, The cocatalyst includes an alkylaluminum compound, wherein the alkylaluminum compound is Al(R'')3, and R'' is a C1-C6 alkyl group.

30. The ZN catalyst system according to claim 29, wherein, The R'' is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl.

31. The ZN catalyst system according to claim 25, wherein, The co-catalyst is triethylaluminum.

32. The ZN catalyst system according to claim 29, wherein, The molar ratio of aluminum in the alkylaluminum compound to titanium in the ZN catalyst is 10-500.

33. The application of the ZN catalyst according to any one of claims 1-23 or the ZN catalyst system according to claims 25-32 in olefin polymerization.

34. The application according to claim 33, wherein, The olefin polymerization is propylene homopolymerization, propylene-ethylene copolymerization, or α-olefin copolymerization.

35. The application according to claim 34, wherein, The α-olefin is butene and / or isobutene.

36. The application according to claim 33, wherein, The olefin polymerization is gas-phase polymerization, bulk polymerization, or slurry polymerization.

37. The application according to claim 36, wherein, The reaction temperature for slurry polymerization is 30-80℃, and the reaction pressure is 0.1-2.0 MPa.

38. The application according to claim 36, wherein, The solvent for the slurry polymerization is C5-C. 10 Alkanes.

39. The application according to claim 36, wherein, The solvent used for slurry polymerization is hexane.

40. The application according to claim 36, wherein, The reaction pressure for the bulk polymerization is 2.8-4.0 MPa, and the reaction temperature is 68-72℃.

Images