Organic polymer carrier and z-n catalyst, and preparation methods therefor and uses thereof

Abstract

Provided in the present invention are an organic polymer carrier and a Z-N catalyst, and preparation methods therefor and the uses thereof. The organic polymer carrier is obtained by copolymerizing monomers comprising divinylbenzene and an unsaturated catechol ester monomer, wherein the unsaturated catechol ester monomer has a structure as represented by formula (I). The catalyst has good stereospecificity; and when the catalyst is used for propylene homopolymerization, the obtained polypropylene has the characteristics of high stereoregularity and a relatively wide molecular weight distribution.

Description

An organic polymer carrier, ZN catalyst and its preparation method and application Technical Field

[0001] The present invention belongs to the field of catalysts, and specifically relates to an organic polymer carrier, a ZN catalyst, a preparation method and application thereof, and especially relates to a catalyst system for polypropylene with high stereoregularity and wide molecular weight distribution. Background Art

[0002] Since the discovery of ZN catalyst in the 1950s, with the innovation of polyolefin production technology and catalysts, the production and demand of polyolefins have continued to grow. In 2020, global polyolefin consumption exceeded approximately 200 million tons / year, and polypropylene was also the fastest-growing synthetic resin. It is expected that in the next five years, the production and consumption of polypropylene will continue to grow, and global demand will exceed 80 million tons / year.

[0003] Currently, industrial polypropylene catalysts are primarily ZN-type catalysts and metallocene catalysts, primarily used to produce highly isotactic polypropylene. In addition, metallocene and post-metallocene catalysts are used to produce smaller amounts of syndiotactic polypropylene, atactic polypropylene, and propylene-based elastomers. Industrial polypropylene production equipment, such as those using slurry, bulk, or gas-phase polymerization processes, requires catalyst loading to control the morphology of the resulting polymer and avoid problems such as reactor agglomeration and blockage.

[0004] Existing industrial catalysts primarily support ZN catalysts and metallocene catalysts on inorganic supports. These supports primarily include silica, magnesium chloride, magnesium ethoxide, and molecular sieves. For ZN catalysts, commonly used supports include magnesium ethoxide and anhydrous magnesium chloride. After reaction with TiCl₄, these ZN catalysts are MgCl₂-supported. During catalyst preparation, electron donors or Lewis bases are often added to modulate the microchemical environment of the catalyst's metal active centers, thereby adjusting catalyst performance. For example, MgCl₂-supported polypropylene catalysts typically consist of the following components: MgCl₂ / TiCl₄ / internal electron donor (ID) / silane external electron donor (ED). Common internal electron donors include phthalate esters (e.g., diisobutyl phthalate (DIBP), di-n-butyl phthalate (DNBP)), phenolic esters, succinates, and diethers. Internal electron donors or Lewis bases added to the catalyst system provide a unique electronic and steric environment on the MgCl2 / TiCl4 surface, significantly influencing the catalyst's activity, stereoregularity, hydrogen sensitivity, product molecular weight, and distribution. Furthermore, they can regulate the MgCl2 surface crystallite size and the content and distribution of Ti active centers. Over the past three decades, the majority of research in the development of high-performance polypropylene catalysts has focused on the design and screening of novel internal electron donors. "Progress in MgCl2supported Ziegler-Natta catalyzed polyolefin products and applications" (Volume 28, 2021, 45) in the Journal of Polymer Research reviewed the internal electron donors used in polyolefin catalysts, including succinates (US20140200316), 1,3-diesters, diethers (US7022640), bicycloalkane diacids, bicycloalkene diacids (US20140005345), silicon-containing compounds (US8088872B2) and other internal electron donors. The above internal electron donors showed good polymerization activity and high chain regularity during propylene polymerization.

[0005] In food and pharmaceutical packaging materials, polypropylene is usually required to have high isotacticity or low organic solvent precipitation content to meet the requirements of the materials in these fields. Polypropylene catalysts supported by inorganic carriers usually have high polymerization activity, better control of polymer morphology, and high bulk density, but inorganic carriers usually introduce additional impurities (in addition to Mg and Ti active centers), which limits their application in the development of high-cleanliness polypropylene products. Organic polymer carriers are different from reported inorganic carriers. POP carriers themselves do not introduce impurities, thereby affecting polymer properties. In addition, organic carriers have controllable pore structure, high specific surface area, stable thermal properties, and are easy to functionalize. Through the design and functionalization of the carrier, high-performance or special polyolefin catalysts can be prepared. There are public reports on ZN catalysts supported by porous organic carriers. Organic carriers containing functional groups such as carboxylic acid groups, hydroxyl groups, cyano groups, and amino groups are usually used to prepare ZN catalysts. However, organic support-based olefin catalysts are mainly polyethylene catalysts, and there are few reports on their use in propylene polymerization. For example, “Sulfonated porous organic polymer supported ZN polypropylene catalysts with high stereoregularity and broad molecular weight distribution” (Volume 343, 2022, 112151) in Microporous and Mesoporous Materials reports a POP-supported ZN catalyst prepared using styrenesulfonic acid functional monomers. When an additional diphenol ester is added as an internal electron donor, the catalyst has a wide molecular weight distribution and a high isotacticity, reaching more than 98%. However, the isotacticity and activity of the polypropylene obtained by this catalyst system without the addition of an additional internal electron donor are low, and have not yet reached commercial levels.

[0006] Summary of the Invention

[0007] In order to solve the above problems, the purpose of the present invention is to provide an organic polymer carrier, a ZN catalyst and its preparation method and application. The catalyst has good stereospecific ability. When used for propylene homopolymerization, the resulting polypropylene has high stereoregularity and a wide molecular weight distribution.

[0008] In order to achieve the above object, the present invention provides an organic polymer carrier, which is obtained by copolymerizing monomers including divinylbenzene and unsaturated catechol ester monomers; wherein the unsaturated catechol ester monomer has a structure shown in Formula I:

[0009] In formula I, R1, R2, R3, and R6 are each independently selected from hydrogen, chlorine, fluorine, bromine, hydroxyl, C1-C6 straight-chain alkyl groups and their derivatives, C1-C6 branched-chain alkyl groups and their derivatives, cycloalkyl groups and their derivatives, and aromatic groups and their derivatives; x is 0-3, and when x is 0, the carbon atom connected to R3 is directly connected to the benzene ring; R4 and R5 are each independently selected from hydrogen, C1-C8 straight-chain hydrocarbon groups and their derivatives, C1-C8 branched-chain hydrocarbon groups and their derivatives, cycloalkyl groups and their derivatives, and aromatic groups and their derivatives.

[0010] According to a specific embodiment of the present invention, preferably, in Formula I, R1, R2, R3, and R6 are each independently selected from hydrogen, chlorine, methyl, isobutyl, chlorine, fluorine, bromine, and hydroxyl; R4 and R5 are each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, n-heptyl, 2-methylhexyl, 2-ethylpentyl, phenyl, vinyl, and isopropenyl; and x is 0 or 1.

[0011] According to a specific embodiment of the present invention, preferably, the unsaturated catechol ester monomer is selected from 4-allyl catechol dicarboxylate, 4-allyl catechol diacetate, 4-allyl catechol dipropionate, 4-allyl catechol di-n-butyrate, 4-allyl catechol diisobutyrate, 4-allyl catechol di-n-valerate, 4-allyl catechol di-n-hexanoate, 4-allyl catechol di-n-octanoate, 4-allyl catechol diisooctanoate, 4-allyl catechol di(2-methylheptanoate), 4-allyl catechol di(2-ethylhexanoate), 4-allyl catechol dibenzoate, 4-vinyl catechol diacetate, 4-vinyl catechol dipropionate, 4-Vinylcatechol di-n-butyrate, 4-Vinylcatechol diisobutyrate, 4-Vinylcatechol di-n-valerate, 4-Vinylcatechol di-n-hexanoate, 4-Vinylcatechol di-n-octanoate, 4-Vinylcatechol diisooctanoate, 4-Vinylcatechol di(2-methylheptanoate), 4-Vinylcatechol di(2-ethylhexanoate), 4-Vinylcatechol dibenzoate, 4-allyl-6-methylcatechol dicarboxylate, 4-allyl-6-methylcatechol diacetate, 4-allyl-6-methylcatechol dipropionate, 4-allyl-6-methylcatechol di-n-butyrate, 4-allyl-6-methylcatechol diisobutyrate, 4-allyl- 6-Methylcatechol di-n-valerate, 4-allyl-6-methylcatechol di-n-hexanoate, 4-allyl-6-methylcatechol di-n-octanoate, 4-allyl-6-methylcatechol di-isooctanoate, 4-allyl-6-methylcatechol di(2-methylheptanoate), 4-allyl-6-methylcatechol di(2-ethylhexanoate), 4-allyl-6-methylcatechol dibenzoate, 4-allyl-6-isobutylcatechol dicarboxylate, 4-allyl-6-isobutylcatechol diacetate, 4-allyl-6-isobutylcatechol dipropionate, 4-allyl-6-isobutylcatechol di-n-butyrate, 4-allyl-6-isobutylcatechol diisobutyrate, 4-allyl-6-isobutylcatechol di-n-butyrate, 4-allyl-6-isobutylcatechol di-isobutyrate, 4-allyl-6-methylcatechol di-n-pentanoate, 4-allyl-6-methylcatechol di-n-octanoate, 4-allyl-6-methylcatechol di-isooctanoate, 4-allyl-6-methylcatechol di-n-pent ... -allyl-6-isobutylcatechol di-n-valerate, 4-allyl-6-isobutylcatechol di-n-hexanoate, 4-allyl-6-isobutylcatechol di-n-octanoate, 4-allyl-6-isobutylcatechol di-isooctanoate, 4-allyl-6-isobutylcatechol di(2-methylheptanoate), 4-allyl-6-isobutylcatechol di(2-ethylhexanoate), 4-allyl-6-isobutylcatechol dibenzoate, 4-allyl-6-chlorocatechol diformate, 4-allyl-6-chlorocatechol diacetate, 4-allyl-6-chlorocatechol dipropionate, 4-allyl-6-chlorocatechol di-n-butyrate, 4-allyl-6-chlorocatechol diisobutyrate,4-allyl-6-chlorocatechol di-n-valerate, 4-allyl-6-chlorocatechol di-n-hexanoate, 4-allyl-6-chlorocatechol di-n-octanoate, 4-allyl-6-chlorocatechol di-isooctanoate, 4-allyl-6-chlorocatechol di(2-methylheptanoate), 4-allyl-6-chlorocatechol di(2-ethylhexanoate), 4-allyl-6-chlorocatechol dibenzoate, 4-allyl-6-fluorocatechol dicarboxylate, 4-allyl-6-fluorocatechol diacetate, 4-allyl-6-fluorocatechol dipropionate, 4-allyl-6-fluorocatechol di-n-butyrate, 4-allyl-6-fluorocatechol diisobutyrate, 4-allyl-6-fluorocatechol di 4-allyl-6-fluorocatechol di-n-hexanoate, 4-allyl-6-fluorocatechol di-n-octanoate, 4-allyl-6-fluorocatechol di-isooctanoate, 4-allyl-6-fluorocatechol di(2-methylheptanoate), 4-allyl-6-fluorocatechol di(2-ethylhexanoate), 4-allyl-6-fluorocatechol dibenzoate, 4-allyl-6-bromocatechol diformate, 4-allyl-6-bromocatechol diacetate, 4-allyl-6-bromocatechol dipropionate, 4-allyl-6-bromocatechol di-n-butyrate, 4-allyl-6-bromocatechol diisobutyrate, 4-allyl-6-bromocatechol di-n-valerate, 4-allyl-6-bromocatechol Catechol di-n-hexanoate, 4-allyl-6-bromocatechol di-n-octanoate, 4-allyl-6-bromocatechol di-isooctanoate, 4-allyl-6-bromocatechol di(2-methylheptanoate), 4-allyl-6-bromocatechol di(2-ethylhexanoate), 4-allyl-6-bromocatechol dibenzoate, 4-(1-chloroallyl)catechol dicarboxylate, 4-(1-chloroallyl)catechol diacetate, 4-(1-chloroallyl)catechol dipropionate, 4-(1-chloroallyl)catechol di-n-butyrate, 4-(1-chloroallyl)catechol di-isobutyrate, 4-(1-chloroallyl)catechol di-n-valerate, 4-(1-chloroallyl)catechol di-n-hexanoate Acid esters, 4-(1-chloroallyl)catechol di-n-octanoate, 4-(1-chloroallyl)catechol diisooctanoate, 4-(1-chloroallyl)catechol di(2-methylheptanoate), 4-(1-chloroallyl)catechol di(2-ethylhexanoate), 4-(1-chloroallyl)catechol dibenzoate, 4-allyl-6-hydroxycatechol dicarboxylate, 4-allyl-6-hydroxycatechol diacetate, 4-allyl-6-hydroxycatechol dipropionate, 4-allyl-6-hydroxycatechol di-n-butyrate, 4-allyl-6-hydroxycatechol diisobutyrate, 4-allyl-6-hydroxycatechol di-n-valerate, 4-allyl-6-hydroxycatechol di-n-hexanoate,4-allyl-6-hydroxycatechol dioctanoate, 4-allyl-6-hydroxycatechol diisooctanoate, 4-allyl-6-hydroxycatechol di(2-methylheptanoate), 4-allyl-6-hydroxycatechol di(2-ethylhexanoate), 4-allyl-6-hydroxycatechol dibenzoate, 4-allyl catechol diacrylate, 4-allyl catechol dimethacrylate, or a combination of two or more thereof.

[0012] According to a specific embodiment of the present invention, preferably, the mass fraction of the unsaturated catechol ester monomer is 20-70% based on the mass of the organic polymer carrier being 100%; the content of the functional monomer in the carrier is determined by the added amount of divinylbenzene and the unsaturated catechol ester functional monomer.

[0013] The present invention also provides a method for preparing the above-mentioned organic polymer carrier, which comprises the following steps: using monomers including divinylbenzene, the unsaturated catechol ester monomer and an additional monomer as raw materials, and copolymerizing to obtain the organic polymer carrier; the mass ratio of the additional monomer to divinylbenzene is 0-1:1; the mass ratio of the unsaturated catechol ester monomer to divinylbenzene is 0.2-2:1.

[0014] 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.

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

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

[0017] According to a specific embodiment of the present invention, preferably, in the above preparation method, the dispersing solvent includes C1-C4 alcohol, water, and an additional solvent, and the additional solvent includes tetrahydrofuran and / or fatty acid ester; the mass ratio of the C1-C4 alcohol to water is 5-15:1; the mass ratio of the additional solvent to the C1-C4 alcohol is 0-2:1; during the preparation of the carrier, the solubility parameter of the solvent system is adjusted by the solvent, thereby controlling the pore structure and morphology of the prepared carrier.

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

[0019] According to a specific embodiment of the present invention, preferably, in the above preparation method, the fatty acid ester includes ethyl acetate and / or butyl acetate.

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

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

[0022] According to a specific embodiment of the present invention, preferably, in the above preparation method, the weight average molecular weight of the stabilizer is 1,000-100,000.

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

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

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

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

[0027] The present invention also provides a ZN catalyst, which, based on 100% by mass of the ZN catalyst, comprises 60-85wt% of the organic polymer carrier, 1-5wt% of a magnesium compound calculated as magnesium element, 1-5wt% of a titanium compound calculated as titanium element, and 0-5wt% of an internal electron donor.

[0028] According to a specific embodiment of the present invention, preferably, the content of the organic polymer carrier is 65-80 wt%, the content of magnesium is 2-4 wt%, and the content of titanium is 2-4 wt%.

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

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

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

[0032] According to a specific embodiment of the present invention, preferably, the magnesium compound includes one or a combination of two or more of methylmagnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, tert-butylmagnesium chloride, benzylmagnesium chloride, ethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, n-butylmagnesium bromide, benzylmagnesium bromide, methylmagnesium iodide, tert-butylmagnesium iodide, benzylmagnesium iodide, n-butylmagnesium iodide, methylmagnesium fluoride, tert-butylmagnesium fluoride, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, and ethoxymagnesium chloride; after the magnesium compound is contacted with the organic polymer support, a porous organic support treated with a magnesium compound is prepared, which is recorded as POP-Ph-(OCO)2...MgX.

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

[0034] The ZN catalyst of the present invention can selectively add an additional internal electron donor (ID), and the resulting ZN catalyst is recorded as POP-Ph-(OCO)2...MgX / TiCl4 / ID; according to a specific embodiment of the present invention, preferably, the internal electron donor is one or a combination of two or more of a diester compound, a diphenol ester compound, a glycol ester compound, a succinate ester compound, and a diether compound.

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

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

[0037] Under anhydrous and oxygen-free conditions, the organic polymer carrier is added to an inert solvent, the magnesium compound is added, and the mixture is reacted at 0°C-50°C for 15-120 minutes. The unreacted magnesium compound is filtered, and an inert solvent and titanium tetrachloride are added. The mixture is reacted at 0°C-120°C for 15-180 minutes. The internal electron donor (optional) is added, and the mixture is reacted at 50°C-120°C for 15-180 minutes. Finally, the mixture is washed with an inert solvent to obtain the ZN catalyst.

[0038] In the ZN catalyst of the present invention, the content of the functional monomer (the unsaturated catechol ester functional monomer) in the organic polymer support is generally 0.5 to 5 mmol / g support, preferably 1 to 4 mmol / g support; the functional monomer content is generally controlled by the ratio of the functional monomer to the divinylbenzene (DVB) monomer added during the support preparation process; the ratio of the magnesium compound reagent added (measured in moles of magnesium Mg) to the support is 1 to 30 mmol / g support, preferably 3 to 20 mmol / g support; an excess of a Ti metal compound, such as TiCl4, is generally added to support the catalyst, and the Ti metal compound added (measured in moles of titanium Ti) is generally 5 to 200 mmol / g support, preferably 50 to 150 mmol / g support; and the ratio of the internal electron donor to the support is 0 to 0.3 g internal electron donor / g support.

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

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

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

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

[0043] According to a specific embodiment of the present invention, preferably, the co-catalyst includes an alkyl aluminum compound, and the alkyl aluminum compound is Al(R'')3, where R'' is a C1-C6 alkyl group; in addition, the added alkyl aluminum compound can also serve as an impurity remover for the polymerization reaction system.

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

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

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

[0047] The present invention also provides use of the ZN catalyst or the ZN catalyst system in olefin polymerization.

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

[0049] According to a specific embodiment of the present invention, preferably, the α-olefin is butene and / or isobutylene.

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

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

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

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

[0054] The porous organic polymer carrier-supported ZN olefin catalyst of the present invention starts from the carrier level, and the functional monomer of the catechol ester containing unsaturated double bonds is polymerized with monomers such as divinylbenzene through the unsaturated double bonds to obtain a porous organic polymer (POP) carrier (denoted as POP-Ph-(OCO)2). The catechol ester functional groups in the carrier interact with the active centers Mg and Ti, thereby preparing a porous organic polymer (POP) type ZN catalyst (denoted as POP-Ph-(OCO)2 / RMgX / TiCl4). An internal electron donor can be optionally added. Among them, the selected functional monomer not only has a significant influence on the prepared carrier, directly affecting the specific surface area, pore volume, bulk density, fluidity, etc. of the prepared carrier, but also because the catechol ester functional groups are introduced into the carrier, the chelate structure group can play the role of the internal electron donor in the ZN catalyst, and the active centers Ti and M are Mg-Mn ... The g microchemical environment is modified, and the prepared catalyst has good stereospecificity and catalytic activity, and the product catalyzed by the catalyst has a wide molecular weight distribution. During the catalyst preparation process, even without the addition of an internal electron donor (additional internal electron donors can also be added), the obtained catalyst still has stereospecificity, and the polypropylene isotacticity can reach over 98%. In addition, the POP-supported polypropylene catalyst prepared using this functional monomer has the characteristics of a wide molecular weight distribution, with a molecular weight distribution coefficient between 8 and 20. When used in propylene polymerization, the addition of a silane external electron donor and triethylaluminum co-catalyst can achieve a high isotacticity of the obtained polymer, which can reach over 98%. The TREF high-temperature elution peak temperature (high isotactic polypropylene fraction) is higher than that of other commercial high isotactic polypropylene catalysts, and its high-temperature elution peak can reach 124°C. In addition, the product has a wide molecular weight distribution, with a molecular weight distribution coefficient between 8 and 20.

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

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

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

[0058] The catechol ester functional monomer containing an unsaturated double bond in the present invention can be prepared by esterification reaction of catechol containing an unsaturated double bond with a corresponding acid using existing technology.

[0059] The molecular weight and distribution of the polymer prepared by olefin polymerization in the present invention are obtained by gel permeation chromatography (GPC) of Polymer Char. The isotacticity of the polymer is obtained by n-heptane extraction test (referring to standard GBT 2412-2008). The internal electron donor content can be determined by extraction and gas chromatography.

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

[0061] Preparation of unsaturated catechol ester functional monomers

[0062] Preparation Example 1

[0063] This preparation example provides 4-allyl catechol diacetate monomer, which is prepared by the following steps:

[0064] 4-allylcatechol diacetate compound can be prepared by esterifying 4-allylcatechol (CAS: 1126-61-0, 97%) with acetic anhydride at 20-50° C. and normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain 4-allylcatechol diacetate (reference: Alejandro Madrid Villegas et al., New Catechol Derivatives of Safrole and Their Antiproliferative Activity towards Breast Cancer Cells, Molecules 2011, Vol. 16, No. 6, P4632-4641). Specifically, 6.0 g of 4-allylcatechol, 10 g of acetic anhydride, 300 ml of dried dichloromethane solvent, and 0.02 g of 4-allylcatechol diacetate are added to a 500 ml reactor. 4-Dimethylaminopyridine (DMAP) was reacted at room temperature for 3 hours, and then 10 g of anhydrous K2CO3 was added and esterified under normal pressure to obtain a crude product. After filtration, neutralization, water washing, and reduced pressure distillation, 4-allylcatechol diacetate was obtained with a yield of 92%.

[0065] Preparation Example 2

[0066] This preparation example provides 4-allyl catechol dibenzoate monomer, which is prepared by the following steps:

[0067] 4-allyl catechol dibenzoate compound can be prepared by esterifying 4-allyl catechol (CAS: 1126-61-0, 97%, also known as 4-allyl-1,2-benzenediol) with benzoic acid at 20-50° C. and normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain 4-allyl catechol dibenzoate. Specifically, 6.0 g of 4-allyl catechol, 12 g of benzoic acid, 300 ml of dried CH2Cl2 solvent, and 0.02 g of DMAP are added to a 500 ml reactor, reacted at room temperature for 3 hours, and then 10 g of anhydrous K2CO3 is added. The crude product is esterified under normal pressure to obtain a crude product, which is then filtered, neutralized, washed with water, and distilled under reduced pressure to obtain 4-allyl catechol dibenzoate with a yield of 91%.

[0068] Preparation Example 3

[0069] This preparation example provides 4-allyl-6-bromocatechol diisobutyrate monomer, which can be prepared by esterification of 4-allyl-6-bromocatechol with isobutyric acid in the following steps:

[0070] (1) The preparation method of 4-allyl-6-bromocatechol can refer to the literature (Hypervalent iodine-mediated oxygenative phenol dearomatization reactions, Laurent Pouysegu et al., Tetrahedron, 2010, Vol. 66, No. 31, pp. 5908-5917). 6-Bromo-4-allyl-2-methoxyphenol (CAS: 5746-37-2) was used to obtain a catechol compound by demethylation reaction with a yield of about 67%. 4.86 g of 4-allyl-6-bromocatechol was added to a 500 ml glass reaction bottle. 6-bromo-4-allyl-2-methoxyphenol was prepared by adding 1.1 mol equivalent of 2-iodoacylbenzoic acid (CAS: 61717-82-6) in tetrahydrofuran, and reacting at room temperature (25°C, the same below) for 3 hours. Then, a freshly prepared excess of sodium dithionite (CAS: 7775-14-6) aqueous solution was added, and the reaction was continued for 1 hour. The mixture was filtered and distilled under reduced pressure to obtain 4-allyl 6-bromocatechol with a yield of 67%.

[0071] (2) In a 500 ml reactor, 6.0 g of 4-allyl-6-bromocatechol, 12 g of isobutyric acid, 300 ml of dried CH2Cl2 solvent, and 0.02 g of DMAP were added and reacted at room temperature for 3 hours. Then, 10 g of anhydrous K2CO3 was added and esterified at normal pressure to obtain a crude product. The crude product was filtered, neutralized, washed with water, and distilled under reduced pressure to obtain 4-allyl-6-bromocatechol diisobutyrate with a yield of 89%.

[0072] Preparation Example 4

[0073] This preparation example provides 4-allyl-6-bromo-catechol diacetate monomer, which is prepared by the following steps:

[0074] In a 500 ml reactor, 6.0 g of 4-allyl-6-bromocatechol, 12 g of acetic acid, 300 ml of dried CH2Cl2 solvent, and 0.02 g of DMAP were added and reacted at room temperature for 3 hours. 10 g of anhydrous K2CO3 was then added and esterified at normal pressure to obtain a crude product. The product was filtered, neutralized, washed with water, and distilled under reduced pressure to obtain 4-allyl-6-bromocatechol diethyl ester in a yield of 91%.

[0075] Preparation Example 5

[0076] This preparation example provides 4-allyl-6-bromocatechol dibenzoate monomer, which is prepared by the following steps:

[0077] In a 500 ml reactor, 5.8 g of 4-allyl-6-bromocatechol, 11.8 g of benzoic acid, 300 ml of dried CH2Cl2 solvent, and 0.02 g of DMAP were added and reacted at room temperature for 3 hours. Then, 10 g of anhydrous K2CO3 was added and esterified at normal pressure to obtain a crude product. The product was filtered, neutralized, washed with water, and distilled under reduced pressure to obtain 4-allyl-6-bromocatechol dibenzoate in a yield of 92%.

[0078] Example 1

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

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

[0081] In a 250ml glass reactor, 100ml of ethanol, 12ml of deionized water, and 20ml of butyl acetate were added, followed by 5.0g of divinylbenzene (Aladdin reagent, 55%) and 2.5g of 4-allylcatechol diacetate. The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% monomer weight of polyvinyl alcohol (PVA, degree of polymerization 1750) and stirring at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% monomer weight of AIBN was added, the temperature was raised to 70°C, and the reaction was continued for 3 hours. The temperature was then raised to 80°C and the reaction was continued for 12 hours at a stirring speed of 350 rpm. After filtration, 1000ml of a mixed solvent of ethanol and water (9:1 volume ratio) was added, washed three times, filtered, and dried to obtain 4.9g of a free-flowing porous organic polymer carrier POP-1. The carrier has a specific surface area of ​​285m 2 / g, pore volume 0.42ml / g;

[0082] (2) Preparation of ZN catalyst:

[0083] In a 250 ml glass reactor, 2 g of the carrier POP-1 prepared using the functional monomer 4-allyl catechol diacetate was added, followed by 100 ml of toluene and stirring. Then, 10 ml of 3 M methylmagnesium chloride Grignard reagent was added at room temperature and stirred for 2 hours. After filtering, the mixture was washed twice with toluene. Then, 50 ml of toluene was added, and 50 ml of TiCl4 was added dropwise at room temperature. The temperature was raised to 60° C. and the reaction was carried out for 2 hours. After filtering, the mixture was washed three times with toluene and three times with hexane. After drying, free-flowing catalyst particles were obtained, designated Cat-1. Catalyst Cat-1 had a Mg content of 2.8%, a titanium content of 4.1%, and an organic polymer support content of 81%.

[0084] Example 2

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

[0086] (1) Preparation of porous organic polymer carrier:

[0087] In a 250ml glass reactor, 100ml of ethanol, 10ml of deionized water, and 15ml of tetrahydrofuran were added, followed by 5.0g of divinylbenzene (Aladdin reagent, 80%) and 3.0g of 4-allyl catechol dibenzoate (98.5%). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% monomer weight of polyvinyl alcohol (PVA, degree of polymerization 1750) and stirring at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% monomer weight of AIBN was added, the reaction was heated to 70°C, and the reaction was continued for 3 hours. The temperature was then raised to 80°C and the reaction was continued for 12 hours at a stirring speed of 350 rpm. After filtration, 1000ml of a mixed solvent of ethanol and water (9:1 volume ratio) was added, washed three times, filtered, and dried to obtain 5.8g of a free-flowing porous organic polymer carrier POP-2. The carrier has a specific surface area of ​​485m 2 / g, pore volume 0.47ml / g;

[0088] (2) Preparation of ZN catalyst:

[0089] In a 250ml glass reactor, 2g of the carrier POP-2 prepared using the above-mentioned 4-allyl catechol dibenzoate functional monomer was added, 100ml of toluene was added and stirred, then 8ml of 3M methylmagnesium chloride Grignard reagent was added at 5°C, stirred for 2 hours, filtered, washed twice with toluene, then 50ml of toluene was added, 35ml of TiCl4 was added dropwise at room temperature, reacted for 1 hour, heated to 80°C, reacted for 1 hour, filtered, 50ml of toluene and 30ml of TiCl4 were added, reacted at 80°C for 2 hours, filtered after completion of the reaction, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, recorded as Cat-2. Catalyst Cat-2 has a Mg content of 2.5%, a titanium content of 2.7%, and an organic polymer support content of 82%.

[0090] Example 3

[0091] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0092] Preparation of ZN catalyst: In a 250ml glass reactor, 2g of the carrier POP-2 prepared using the above-mentioned 4-allyl catechol dibenzoate functional monomer was added, 100ml of toluene was added and stirred, and then 10ml of 3M benzylmagnesium chloride Grignard reagent was added at 35°C, stirred for 2 hours, filtered, washed twice with toluene, 50ml of toluene was added, and then the temperature was raised to 50°C, 40ml of TiCl4 was slowly added dropwise, and the reaction was carried out for 2 hours, and then the temperature was raised to 80°C and the reaction was carried out for 3 hours. After the reaction was completed, it was filtered, and 50ml of toluene and 30ml of TiCl4 were added. The reaction was carried out at 80°C for 2 hours. After the reaction was completed, it was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, which were recorded as Cat-3. The Mg content of catalyst Cat-3 was 3.2%, the titanium content was 3.0%, and the organic polymer support content was 78%.

[0093] Example 4

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

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

[0096] In a 250ml glass reactor, 100ml of ethanol, 20ml of water, and 15ml of ethyl acetate were added, followed by 6.0g of divinylbenzene (Aladdin reagent, 80%) and 3.0g of 4-allyl-6-bromocatechol diisobutyrate. The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% by weight of a block copolymer of polyethylene oxide and polypropylene oxide, F127. The mixture was stirred at 45°C for 1 hour to completely dissolve the stabilizer, followed by the addition of 2.0% by weight of dibenzoyl peroxide (BPO). The reaction was heated to 70°C for 3 hours, then to 80°C for 8 hours at a stirring speed of 550 rpm. After filtration, the mixture was washed three times with 100ml of a mixed solvent of ethanol and water (9:1 by volume). After filtration and drying, 7.1g of a free-flowing porous organic polymer support, POP-3, was obtained. The support had a specific surface area of ​​328m2. 2 / g, pore volume 0.45ml / g;

[0097] (2) Preparation of ZN catalyst:

[0098] In a 250 ml glass reactor, 3 g of the carrier POP-3 prepared by polymerization of the functional monomer 4-allyl-6-bromocatechol diisobutyrate was added, followed by 100 ml of toluene and stirring. Then, 10 ml of 3 M methylmagnesium chloride Grignard reagent was added at 35° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene. 50 ml of toluene was added, the temperature was raised to 50° C., 30 ml of TiCl4 was added dropwise, and the reaction was carried out for 2 hours. The temperature was then raised to 80° C. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated as Cat-4. Catalyst Cat-4 had a Mg content of 2.5%, a titanium content of 2.2%, and an organic polymer support content of 83%.

[0099] Example 5

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

[0101] Preparation of ZN catalyst: In a 250ml glass reactor, 3g of the carrier POP-3 prepared by polymerization of the functional monomer 4-allyl-6-bromocatechol diisobutyrate was added, 100ml of toluene was added and stirred, then 10ml of 3M methylmagnesium chloride Grignard reagent was added at room temperature, stirred for 3 hours, filtered, washed twice with toluene, 50ml of toluene was added, then the temperature was raised to 50°C, 30ml of TiCl4 was added dropwise, and the reaction was carried out for 2 hours. Then the temperature was raised to 80°C, 0.25g of diisobutyl phthalate internal electron donor was added, and the reaction was carried out for 3 hours. After completion of the reaction, the catalyst was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, which were designated as Cat-5. Catalyst Cat-5 had a Mg content of 3.0%, a titanium content of 2.1%, an internal electron donor content of 3.1%, and an organic polymer support content of 76%.

[0102] Example 6

[0103] This embodiment provides a ZN catalyst, which is prepared by the following steps:

[0104] (1) Preparation of porous organic polymer carrier:

[0105] In a 250ml glass reactor, 90ml of ethanol, 10ml of water, and 30ml of butyl acetate were added, followed by 6.0g of divinylbenzene (Aladdin reagent, 55%) and 4.0g of 4-allyl-6-bromocatechol diacetate. The mixture was stirred at room temperature for 5 minutes, followed by the addition of 5% by weight of a block copolymer of polyethylene oxide and polypropylene oxide, F127. The mixture was stirred at 45°C for 1 hour to completely dissolve the stabilizer. AIBN (2.0% by weight of the monomer) was then added, and the reaction was heated to 70°C for 3 hours, then to 80°C for 8 hours at 600 rpm. After filtration, the mixture was washed three times with 100ml of a mixed solvent of ethanol and water (9:1 by volume). After filtration and drying, 6.3g of a free-flowing porous organic polymer support, POP-4, was obtained. The support had a specific surface area of ​​249m2. 2 / g, pore volume 0.49ml / g;

[0106] (2) Preparation of ZN catalyst:

[0107] In a 250 ml glass reactor, 3 g of the carrier POP-4 prepared from the functional monomer 4-allyl-6-bromocatechol diacetate was added, and 100 ml of toluene was added and stirred. Then, 10 ml of 3 M butylmagnesium bromide Grignard reagent was added at 35° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene. 60 ml of toluene was added, and the temperature was raised to 50° C., 30 ml of TiCl4 was added dropwise, and the reaction was carried out for 2 hours. Then, the temperature was raised to 80° C. and the reaction was carried out for 3 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, which were designated as Cat-6. Catalyst Cat-6 had a Mg content of 2.5%, a titanium content of 2.5%, and an organic polymer support content of 78%.

[0108] Example 7

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

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

[0111] In a 250ml glass reactor, 110ml of ethanol, 12ml of water, and 20ml of tetrahydrofuran were added, followed by 6.0g of divinylbenzene (Aladdin reagent, 80%) and 3.0g of 4-allyl-6-bromocatechol dibenzoate. The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% of the monomer weight of a block copolymer of polyethylene oxide and polypropylene oxide, F127. The mixture was stirred at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% of the monomer weight of AIBN was added, the reaction was heated to 70°C, and the reaction was continued for 3 hours. The temperature was then raised to 80°C and the reaction was continued for 8 hours at a stirring speed of 550 rpm. After filtration, the mixture was washed three times with 100ml of a mixed solvent of ethanol and water (9:1 volume ratio). After filtration and drying, 6.5g of a free-flowing porous organic polymer carrier, POP-5, was obtained. The carrier had a specific surface area of ​​527m 2 / g, pore volume 0.41ml / g;

[0112] (2) Preparation of ZN catalyst:

[0113] In a 250 ml glass reactor, 3 g of the carrier POP-5 prepared from the functional monomer 4-allyl-6-bromocatechol dibenzoate was added, followed by 100 ml of toluene and stirring. Then, 12 ml of 3 M di-n-butyl magnesium was added at room temperature and stirred for 3 hours. After filtering, the mixture was washed twice with toluene. 50 ml of toluene was added, the temperature was raised to 50° C., 30 ml of TiCl4 was slowly added dropwise, and the mixture was reacted for 2 hours. The temperature was then raised to 80° C. and filtered. 100 ml of TiCl4 was added and the mixture was reacted at 80° C. for 2 hours. After filtering, the mixture was washed three times with toluene and three times with hexane. After drying, free-flowing catalyst particles were obtained, designated Cat-7. Catalyst Cat-7 had a Mg content of 3.2%, a titanium content of 3.7%, and an organic polymer support content of 74%.

[0114] Example 8

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

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

[0117] In a 250ml glass reactor, 100ml of ethanol, 10ml of water, and 15ml of tetrahydrofuran were added, followed by 6.0g of divinylbenzene (Aladdin reagent, 80%), 2.5g of 4-allyl-6-bromocatechol dibenzoate, and 1.0g of hydroxyethyl methacrylate. The mixture was stirred at room temperature for 5 minutes. Then, 2% by weight of a block copolymer of polyethylene oxide and polypropylene oxide, F127, was added. The mixture was stirred at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% (3.0g) of the monomer weight of AIBN was added. The reaction was heated to 70°C for 3 hours, then raised to 80°C for 8 hours at a stirring speed of 350 rpm. After filtration, the mixture was washed three times with 100ml of a mixed solvent of ethanol and water (9:1 by volume). After filtration and drying, 7.2g of a free-flowing porous organic polymer support, POP-6, was obtained. The support had a specific surface area of ​​352m 2 / g, pore volume 0.33ml / g;

[0118] (2) Preparation of ZN catalyst:

[0119] In a 250 ml glass reactor, 3 g of the carrier POP-6 prepared from the above-mentioned 4-allyl-6-bromocatechol dibenzoate functional monomer and the third monomer hydroxyethyl methacrylate was added, 100 ml of toluene was added and stirred, then 15 ml of 3M methylmagnesium chloride Grignard reagent was added at 20° C. and stirred for 2 hours. After filtering, the mixture was washed twice with toluene. 50 ml of toluene was added, and the temperature was raised to 50° C., 30 ml of TiCl4 was slowly added dropwise, and the reaction was carried out for 2 hours. The temperature was then raised to 80° C., 0.20 g of 9,9-dimethoxyfluorene internal electron donor was added, and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was filtered, and then 100 ml of TiCl4 was added and the reaction was carried out at 80° C. for 1 hour. After filtering, the mixture was washed three times with toluene and hexane respectively. After drying, free-flowing catalyst particles were obtained, which were recorded as Cat-8. The Mg content of catalyst Cat-8 was 4.5%, the titanium content was 2.1%, the internal electron donor content was 1.9%, and the organic polymer support content was 73%.

[0120] Example 9

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

[0122] Preparation of ZN catalyst: In a 250ml glass reactor, 3g of the carrier POP-6 prepared from the functional monomer 4-allyl-6-bromocatechol dibenzoate and the third monomer hydroxyethyl methacrylate was added, and 100ml of toluene was added and stirred. Then, 12ml of 3M methylmagnesium chloride Grignard reagent was added at 20°C and stirred for 2 hours. After filtering, the mixture was washed twice with toluene. The temperature was then raised to 80°C, 50ml of toluene was added, and 50ml of TiCl4 was slowly added dropwise. The reaction was allowed to react for 3 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-9. Catalyst Cat-9 has a Mg content of 3.7%, a titanium content of 3.0%, and an organic polymer support content of 75%.

[0123] Comparative Example 1

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

[0125] Preparation of inorganic carrier-supported ZN polypropylene catalyst: In a 250ml glass reactor, 3g of spherical ethoxymagnesium support (Japan Soda Co., Ltd.) was added, 100ml of toluene was added and stirred, and then 50ml of TiCl4 was slowly added dropwise at 0°C. The addition rate was controlled to control the temperature at 0-5°C. After the addition was complete, the temperature was raised to 60°C, 0.30g of DIBP internal electron donor was added, and the mixture was reacted at 110°C for 2 hours. After filtering, 100ml of fresh TiCl4 was added, and the mixture was reacted at 110°C for 2 hours. After the reaction was complete, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, which were designated as Cat-10. The titanium content of catalyst Cat-10 was 3.2% and the DIBP internal electron donor content was 8.9%.

[0126] Comparative Example 2

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

[0128] Preparation of ZN polypropylene catalyst supported on an inorganic carrier: In a 250 ml glass reactor, 3 g of a spherical ethoxymagnesium carrier (Soda Co., Ltd., Japan) and 100 ml of toluene were added and stirred. Then, 50 ml of TiCl4 was slowly added dropwise at 0°C. The addition rate was controlled to keep the temperature between 0 and 5°C. After the addition was complete, the temperature was raised to 60°C, 0.40 g of 9,9-dimethoxyfluorene internal electron donor was added, and the mixture was reacted at 110°C for 2 hours. After filtering, 100 ml of fresh TiCl4 was added and the mixture was reacted at 110°C for 2 hours. After the reaction was completed, the mixture was filtered and washed 3 times with toluene and hexane respectively. After drying, free-flowing catalyst particles were obtained, which were designated as Cat-11. The titanium content of catalyst Cat-11 was 3.2%, and the 9,9-dimethoxyfluorene internal electron donor content was 6.2%.

[0129] Comparative Example 3

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

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

[0132] Comparative Example 4

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

[0134] In a 250ml glass reactor, 3g of spherical ethoxymagnesium support (Soda Co., Ltd., Japan) was added, 50ml of toluene was added, the temperature was raised to 50°C, and then 30ml of TiCl4 was slowly added dropwise and reacted for 2 hours. Then the temperature was raised to 80°C, 0.20g of 9,9-dimethoxyfluorene internal electron donor was added, and the reaction was carried out for 3 hours. After the reaction was completed, it was filtered, and 100ml of TiCl4 was added and reacted at 80°C for 1 hour. After the reaction was completed, it was filtered, washed with toluene and hexane 3 times each, and dried to obtain free-flowing catalyst particles, which were recorded as Cat-13. The titanium content of catalyst Cat-13 was 3.4%, and the 9,9-dimethoxyfluorene internal electron donor content was 3.7%.

[0135] Propylene polymerization

[0136] Test Example 1

[0137] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 82 mg of catalyst Cat-1 and 0.5 ml of cyclohexylmethyldimethoxysilane (C supplied externally) were added. 0.3 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 703 g of a polypropylene product (PP-1) with a bulk density of 0.36 g / ml and a catalyst activity of 8580 gPP / gcat.h, as shown in Table 1.

[0138] Test Example 2

[0139] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 80 mg of catalyst Cat-1 and 0.5 ml of dicyclopentenyldimethoxysilane (D supplied externally) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 635 g of a polypropylene product (PP-2) with a bulk density of 0.36 g / ml and a catalyst activity of 7938 gPP / gcat.h, as shown in Table 1.

[0140] Test Example 3

[0141] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 80 mg of the catalyst Cat-2 and 0.3 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 840 g of a polypropylene product (PP-3) with a bulk density of 0.38 g / ml and a catalyst activity of 10,500 gPP / gcat.h, as shown in Table 1.

[0142] Test Example 4

[0143] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 80 mg of the catalyst Cat-3 and 0.3 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1048 g of a polypropylene product (PP-4) with a bulk density of 0.40 g / ml and a catalyst activity of 13100 gPP / gcat.h, as shown in Table 1.

[0144] Test Example 5

[0145] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 80 mg of Cat-4 catalyst and 0.3 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 896 g of a polypropylene product (PP-5) with a bulk density of 0.37 g / ml and a catalyst activity of 11,200 gPP / gcat.h, as shown in Table 1.

[0146] Test Example 6

[0147] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 80 mg of Cat-5 catalyst and 0.3 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 842 g of a polypropylene product (PP-6) with a bulk density of 0.38 g / ml and a catalyst activity of 10525 gPP / gcat.h, as shown in Table 1.

[0148] Test Example 7

[0149] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 80 mg of the Cat-6 catalyst and 0.5 ml of dicyclopentenyldimethoxysilane (D supplied externally) were added. 0.7 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 900 g of a polypropylene product (PP-7) with a bulk density of 0.38 g / ml and a catalyst activity of 11250 gPP / gcat.h, as shown in Table 1.

[0150] Test Example 8

[0151] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 80 mg of the Cat-7 catalyst and 0.5 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1098 g of a polypropylene product (PP-8) with a bulk density of 0.40 g / ml and a catalyst activity of 13725 gPP / gcat.h, as shown in Table 1.

[0152] Test Example 9

[0153] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 82 mg of the Cat-8 catalyst and 0.5 ml of dicyclopentenyldimethoxysilane (D supplied externally) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1023 g of a polypropylene product (PP-9) with a bulk density of 0.39 g / ml and a catalyst activity of 12476 gPP / gcat.h, as shown in Table 1.

[0154] Test Example 10

[0155] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 80 mg of Cat-9 catalyst and 0.3 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1000 g of a polypropylene product (PP-10) with a bulk density of 0.40 g / ml and a catalyst activity of 12500 gPP / gcat.h, as shown in Table 1.

[0156] Comparative test example 1

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

[0158] Comparative test example 2

[0159] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 60 mg of the Cat-11 catalyst and 0.3 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1280 g of a polypropylene product (PP-12) with a bulk density of 0.42 g / ml and a catalyst activity of 21333 gPP / gcat.h, as shown in Table 1.

[0160] Comparative test example 3

[0161] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 60 mg of comparative catalyst Cat-12 and 0.3 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 948 g of a polypropylene product (PP-13) with a bulk density of 0.38 g / ml and a catalyst activity of 15,800 gPP / gcat.h, as shown in Table 1.

[0162] Comparative test example 4

[0163] To a 10 L dried propylene polymerization reactor, 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) were added with stirring at 600 rpm. Then, 60 mg of comparative catalyst Cat-13 and 0.3 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen was added, and the temperature was raised to 70° C. The polymerization was carried out under stirring at 600 rpm for 1 hour. After completion of the reaction, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 1240 g of a polypropylene product (PP-14) with a bulk density of 0.41 g / ml and a catalyst activity of 20667 gPP / gcat.h, as shown in Table 1.

[0164] Table 1 Propylene polymerization results

[0165] Test Example 11 Copolymerization of propylene and ethylene

[0166] A 10-liter dried propylene polymerization reactor was charged with 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) at a stirring rate of 600 rpm. Then, 60 mg of the above-prepared catalyst, Cat-1, and 0.5 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.3 g of hydrogen and 50 g of ethylene monomer were also added. The reactor was heated to 70°C and polymerized at 600 rpm for 1 hour. The reactor was then depressurized, cooled to room temperature, and dried to yield 758 g of ethylene-propylene copolymer. The catalyst polymerization activity was 12,633 g PP / gcat.h, the polymer weight-average molecular weight (Mw) was 687,000 g / mol, and the molecular weight distribution coefficient was 11.2.

[0167] Test Example 12 Copolymerization of propylene and ethylene

[0168] In a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added with stirring at 600 rpm. Then, 60mg of the catalyst Cat-3 and 0.3ml of cyclohexylmethyldimethoxysilane (C externally supplied) were added. 0.5g of hydrogen and 50g of ethylene monomer were added. The temperature was raised to 70°C and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, the mixture was cooled to room temperature, and dried to obtain 936g of ethylene-propylene copolymer product with a catalyst activity of 15600gPP / gcat.h, a polymer weight-average molecular weight Mw of 632,000 g / mol, and a molecular weight distribution coefficient of 9.1.

[0169] Test Example 13 Copolymerization of propylene and ethylene

[0170] A 10-liter dried propylene polymerization reactor was charged with 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L). The reactor was stirred at 600 rpm. Then, 60 mg of the Cat-7 catalyst prepared above and 0.5 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen and 50 g of ethylene monomer were added. The reactor was heated to 70°C and polymerized at 600 rpm for 1 hour. The reactor was then depressurized, cooled to room temperature, and dried to yield 948 g of ethylene-propylene copolymer. The catalyst polymerization activity was 15,800 gPP / gcat.h, the polymer weight-average molecular weight (Mw) was 715,000 g / mol, and the molecular weight distribution coefficient was 9.4.

[0171] Test Example 14 Copolymerization of propylene and butene

[0172] A 10-liter dried propylene polymerization reactor was charged with 2.0 kg of liquid propylene and 10 ml of triethylaluminum (TEA) (1.0 mol / L) and stirred at 600 rpm. Then, 60 mg of the Cat-7 catalyst prepared above and 0.5 ml of cyclohexylmethyldimethoxysilane (external C) were added. 0.5 g of hydrogen and 50 g of 1-butene monomer were also added. The reactor was heated to 70°C and stirred at 600 rpm for 1 hour. The reactor was then depressurized, cooled to room temperature, and dried to yield 624 g of a butene-propylene copolymer. The catalyst polymerization activity was 10,400 gPP / gcat.h.

[0173] The above polymerization results show that the organic carrier-supported POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst solid component (an internal electron donor can be optionally added), prepared using free-radical polymerizable catechol ester functional monomers containing unsaturated double bonds, has good catalytic activity, with a propylene homopolymerization activity of over 13,000 gPP / gcat.h. Although this is lower than that of catalysts supported on conventional inorganic MgCl2 carriers, its activity is significantly improved over the polymerization activity of existing organic polymer carriers and meets the level of existing industrial catalysts. By screening out free-radically polymerizable catechol ester functional monomers containing unsaturated double bonds and relying on the functional groups of the catechol ester on the carrier to regulate the microchemical environment of the metal active center, an integrated design and preparation of an organic carrier-supported POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst solid component was achieved. This gives the catalyst good stereospecificity. Even without the addition of an internal electron donor, the prepared polypropylene has a high isotacticity of over 98%, and the TREF high-temperature elution temperature can reach 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 over a wide range, with the molecular weight distribution coefficient controllable between 8 and 20.

[0174] Compared with Comparative Example 1 (adding the same conventional internal electron donor such as DIBP), the polymer prepared by the catalyst Cat-5 prepared in Example 5 of the present invention has a significantly higher isotacticity than the catalysts in Comparative Examples 1 and 3; compared with Comparative Examples 2 and 4 (using the internal electron donor 9,9-dimethoxyfluorene internal electron donor with high stereoregularity and relatively narrow molecular weight distribution), the catalyst Cat-8 prepared in Example 8 has a higher stereoregularity, a TREF high temperature elution temperature of about 124.0°C, and a wider molecular weight distribution. The molecular weight distribution of the polymer prepared by the catalyst Cat-8 is 10.6.

[0175] Compared with existing catalysts, the POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst disclosed in the present invention has a simple preparation method, its active center has high stereospecific ability and wide molecular weight distribution characteristics, and has good industrial prospects. In particular, this catalyst system has advantages in developing low-precipitation polypropylene and high-rigidity-toughness balanced polypropylene products.

Claims

1. An organic polymer carrier obtained by copolymerizing monomers including divinylbenzene and unsaturated catechol ester monomers; in, The unsaturated catechol ester monomer has a structure shown in Formula I: In formula I, R1, R2, R3, and R6 are each independently selected from hydrogen, chlorine, fluorine, bromine, hydroxyl, C1-C6 straight-chain alkyl and derivatives thereof, C1-C6 branched-chain alkyl and derivatives thereof, cycloalkyl and derivatives thereof, aromatic group and derivatives thereof; x is 0-3; R4 and R5 are each independently selected from hydrogen, C1-C8 straight-chain hydrocarbon group and derivatives thereof, C1-C8 branched-chain hydrocarbon group and derivatives thereof, cycloalkyl and derivatives thereof, aromatic group and derivatives thereof.

2. The organic polymer carrier according to claim 1, wherein In formula I, R1, R2, R3, and R6 are each independently selected from hydrogen, chlorine, methyl, isobutyl, chlorine, fluorine, bromine, and hydroxyl; R4 and R5 are each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, n-heptyl, 2-methylhexyl, 2-ethylpentyl, phenyl, vinyl, and isopropenyl; x is 0 or 1.

3. The organic polymer carrier according to claim 1, wherein The unsaturated catechol ester monomer is selected from 4-allyl catechol diformate, 4-allyl catechol diacetate, 4-allyl catechol dipropionate, 4-allyl catechol di-n-butyrate, 4-allyl catechol diisobutyrate, 4-allyl catechol di-n-valerate, 4-allyl catechol di-n-hexanoate, 4-allyl catechol di-n-octanoate, 4-allyl catechol di-isooctanoate, 4-allyl catechol di(2-methylheptanoate), 4-allyl catechol di(2-ethylhexanoate), 4-allyl catechol dibenzoate, 4-vinyl catechol diacetate, 4-vinylcatechol dipropionate, 4-vinylcatechol di-n-butyrate, 4-vinylcatechol diisobutyrate, 4-vinylcatechol di-n-valerate, 4-vinylcatechol di-n-hexanoate, 4-vinylcatechol di-n-octanoate, 4-vinylcatechol diisooctanoate, 4-vinylcatechol di(2-methylheptanoate), 4-vinylcatechol di(2-ethylhexanoate), 4-vinylcatechol dibenzoate, 4-allyl-6-methylcatechol diformate, 4-allyl-6-methylcatechol diacetate, 4-allyl-6-methylcatechol dipropionate, 4-allyl-6-methylcatechol di-n-butyrate, 4-allyl-6-methylcatechol di-isobutyrate, 4-allyl-6-methylcatechol di-n-valerate, 4-allyl-6-methylcatechol di-n-hexanoate, 4-allyl-6-methylcatechol di-n-octanoate, 4-allyl-6-methylcatechol di-isooctanoate, 4-allyl-6-methylcatechol di(2-methyl) 4-allyl-6-methylcatechol di(2-ethylhexanoate), 4-allyl-6-methylcatechol dibenzoate, 4-allyl-6-isobutylcatechol dicarboxylate, 4-allyl-6-isobutylcatechol diacetate, 4-allyl-6-isobutylcatechol dipropionate, 4-allyl-6-isobutylcatechol di-n-butyrate, 4-allyl-6-isobutylcatechol di-n-butyrate Butyl catechol diisobutyrate, 4-allyl-6-isobutylcatechol di-n-valerate, 4-allyl-6-isobutylcatechol di-n-hexanoate, 4-allyl-6-isobutylcatechol di-n-octanoate, 4-allyl-6-isobutylcatechol di-isooctanoate, 4-allyl-6-isobutylcatechol di-(2-methylheptanoate), 4-allyl-6-isobutylcatechol di-(2 4-allyl-6-chlorocatechol dipropionate, 4-allyl-6-chlorocatechol di-n-butyrate, 4-allyl-6-chlorocatechol diisobutyrate, 4-allyl-6-chlorocatechol di-n-valerate,4-allyl-6-chlorocatechol di-n-hexanoate, 4-allyl-6-chlorocatechol di-n-octanoate, 4-allyl-6-chlorocatechol di-isooctanoate, 4-allyl-6-chlorocatechol di(2-methylheptanoate), 4-allyl-6-chlorocatechol di(2-ethylhexanoate), 4-allyl-6-chlorocatechol dibenzoate, 4-allyl-6-fluorocatechol dicarboxylate, 4-allyl-6-fluorocatechol diacetate, 4-allyl-6-fluorocatechol dipropionate, 4-allyl-6-fluorocatechol di-n-butyrate, 4-allyl-6-chlorocatechol di-n-octanoate, 4-allyl-6-chlorocatechol di-isooctanoate, 4-allyl-6-chlorocatechol di-(2-methylheptanoate), 4-allyl-6-chlorocatechol di-(2-ethylhexanoate), 4-allyl-6-chlorocatechol dibenzoate, 4-allyl-6-fluorocatechol dicarboxylate, 4-allyl-6-fluorocatechol diacetate, 4-allyl-6-fluorocatechol dipropionate, 4-allyl-6-fluorocatechol di-n-butyrate, 4-allyl-6-chlorocatechol di-isooctanoate ... Propyl-6-fluorocatechol diisobutyrate, 4-allyl-6-fluorocatechol di-n-valerate, 4-allyl-6-fluorocatechol di-n-hexanoate, 4-allyl-6-fluorocatechol di-n-octanoate, 4-allyl-6-fluorocatechol di-isooctanoate, 4-allyl-6-fluorocatechol di(2-methylheptanoate), 4-allyl-6-fluorocatechol di(2-ethylhexanoate), 4-allyl-6-fluorocatechol dibenzoate, 4-allyl-6-bromocatechol dicarboxylate, 4-allyl-6-bromocatechol diacetate, 4-allyl 4-allyl-6-bromocatechol dipropionate, 4-allyl-6-bromocatechol di-n-butyrate, 4-allyl-6-bromocatechol di-isobutyrate, 4-allyl-6-bromocatechol di-n-valerate, 4-allyl-6-bromocatechol di-n-hexanoate, 4-allyl-6-bromocatechol di-n-octanoate, 4-allyl-6-bromocatechol di-isooctanoate, 4-allyl-6-bromocatechol di(2-methylheptanoate), 4-allyl-6-bromocatechol di(2-ethylhexanoate), 4-allyl-6-bromocatechol dibenzoate, 4-(1-chloro 4-(1-chloroallyl)catechol dicarboxylate, 4-(1-chloroallyl)catechol diacetate, 4-(1-chloroallyl)catechol dipropionate, 4-(1-chloroallyl)catechol di-n-butyrate, 4-(1-chloroallyl)catechol diisobutyrate, 4-(1-chloroallyl)catechol di-n-valerate, 4-(1-chloroallyl)catechol di-n-hexanoate, 4-(1-chloroallyl)catechol di-n-octanoate, 4-(1-chloroallyl)catechol di-isooctanoate, 4-(1-chloroallyl)catechol di(2-methylheptanoate), 4-(1-chloroallyl)catechol di-n-butylate, 4-(1-chloroallyl)catechol di-isobutylate, 4-(1-chloroallyl)catechol di-n-pentanoate, 4-(1-chloroallyl)catechol di-n-hexanoate, 4-(1-chloroallyl)catechol di-n-octanoate, 4-(1-chloroallyl)catechol di-isooctanoate, 4-(1-chloroallyl)catechol di(2-methylheptanoate), 4-(1-chloroallyl)catechol di-n-butylate 4-allyl-6-hydroxycatechol di(2-ethylhexanoate), 4-(1-chloroallyl)catechol dibenzoate, 4-allyl-6-hydroxycatechol dicarboxylate, 4-allyl-6-hydroxycatechol diacetate, 4-allyl-6-hydroxycatechol dipropionate, 4-allyl-6-hydroxycatechol di-n-butyrate, 4-allyl-6-hydroxycatechol diisobutyrate, 4-allyl-6-hydroxycatechol di-n-valerate, 4-allyl-6-hydroxycatechol di-n-hexanoate, 4-allyl-6-hydroxycatechol di-n-octanoate,4-allyl-6-hydroxycatechol diisooctanoate, 4-allyl-6-hydroxycatechol di(2-methylheptanoate), 4-allyl-6-hydroxycatechol di(2-ethylhexanoate), 4-allyl-6-hydroxycatechol dibenzoate, 4-allyl catechol diacrylate, 4-allyl catechol dimethacrylate, or a combination of two or more thereof.

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

5. The method for preparing the organic polymer carrier according to any one of claims 1 to 4, comprising the following steps: The organic polymer carrier is prepared by copolymerizing monomers including the divinylbenzene, the unsaturated catechol ester monomer and the additional monomer as raw materials; The mass ratio of the additional monomer to divinylbenzene is 0-1:1; the mass ratio of the unsaturated catechol ester monomer to divinylbenzene is 0.2-2:

1.

6. The preparation method 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 comprises the following steps: adding divinylbenzene, unsaturated catechol ester monomers and additional monomers into 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.

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

8. The preparation method according to claim 6, wherein: The dispersing solvent includes C1-C4 alcohol, water, and an additional solvent, and the additional solvent includes tetrahydrofuran and / or fatty acid ester; The mass ratio of the C1-C4 alcohol to water is 5-15:1; the mass ratio of the additional solvent to the C1-C4 alcohol is 0-2:

1.

9. The preparation method according to claim 8, wherein: The C1-C4 alcohol includes one or a combination of two or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol.

10. The preparation method according to claim 8, wherein: The fatty acid esters include ethyl acetate and / or butyl acetate.

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

12. The preparation method according to claim 6, wherein: The stabilizer is polyvinyl alcohol and / or polypropylene oxide-polyethylene oxide copolymer.

13. The preparation method according to claim 6, wherein: The weight average molecular weight of the stabilizer is 1,000-100,000.

14. The preparation method according to claim 6, wherein: The mass ratio of the amount of the stabilizer added to the total amount of the monomers added is 0.5-5:

100.

15. The preparation method according to claim 6, wherein: The initiator is azobisisobutyronitrile and / or dibenzoyl peroxide.

16. The preparation method according to claim 6, wherein: The mass ratio of the added amount of the initiator to the total amount of the added monomers is 0.5-3:

100.

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

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

19. The ZN catalyst according to claim 18, wherein The content of the organic polymer carrier is 65-80wt%, the content of magnesium is 2-4wt%, and the content of titanium is 2-4wt%.

20. The ZN catalyst according to claim 18, wherein The magnesium compound is RMgX or R'MgR"; R, R', R" are independently selected from C1-C8 alkyl and its derivatives, aryl and its derivatives, alkoxy and its derivatives, and X is fluorine, chlorine, bromine or iodine.

21. The ZN catalyst according to claim 20, wherein The R, R' and R" are each independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl and substituted phenyl.

22. The ZN catalyst according to claim 20, wherein The magnesium compound is one or a combination of two or more of an alkyl halogenated magnesium compound, an alkyl magnesium compound, and an alkoxy magnesium halide compound.

23. The ZN catalyst according to claim 22, wherein The magnesium compound includes one or a combination of two or more of methylmagnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, tert-butylmagnesium chloride, benzylmagnesium chloride, ethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, n-butylmagnesium bromide, benzylmagnesium bromide, methylmagnesium iodide, tert-butylmagnesium iodide, benzylmagnesium iodide, n-butylmagnesium iodide, methylmagnesium fluoride, tert-butylmagnesium fluoride, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, and ethoxymagnesium chloride.

24. The ZN catalyst according to claim 18, wherein The titanium compound is titanium tetrachloride.

25. The ZN catalyst according to claim 18, wherein The internal electron donor is one or a combination of two or more of diester compounds, diphenol ester compounds, glycol ester compounds, succinate ester compounds, and diether compounds.

26. The ZN catalyst according to claim 25, wherein The internal electron donor includes one or a combination of two or more of diisobutyl phthalate, di-n-butyl phthalate, 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzyl ester, and 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether.

27. A method for preparing a ZN catalyst according to any one of claims 18 to 26, comprising the following steps: Under anhydrous and oxygen-free conditions, the organic polymer carrier is added to an inert solvent, the magnesium compound is added, and the reaction is carried out at 0°C-50°C for 15-120 minutes. The unreacted magnesium compound is filtered, and an inert solvent and titanium tetrachloride are added. The reaction is carried out at 0°C-120°C for 15-180 minutes. The internal electron donor is added, and the reaction is carried out at 50°C-120°C for 15-180 minutes. Finally, the ZN catalyst is washed with an inert solvent to obtain the ZN catalyst.

28. 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 18 to 26.

29. The ZN catalyst system according to claim 28, wherein The external electron donor includes a silane external electron donor.

30. The ZN catalyst system according to claim 29, wherein The silane-based external electron donor includes one or a combination of two or more of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane and tetraethoxysilane.

31. The ZN catalyst system of claim 29, wherein: The molar ratio of silicon in the silane-based external electron donor to titanium in the ZN catalyst is 1-50.

32. The ZN catalyst system of claim 28, wherein: The co-catalyst comprises an alkyl aluminum compound, wherein the alkyl aluminum compound is Al(R'')3, and R''' is a C1-C6 alkyl group.

33. The ZN catalyst system according to claim 32, wherein The R'' is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.

34. The ZN catalyst system according to claim 33, wherein The co-catalyst is triethylaluminum.

35. The ZN catalyst system of claim 32, wherein: The molar ratio of aluminum in the alkyl aluminum compound to titanium in the ZN catalyst is 10-500.

36. Use of the ZN catalyst according to any one of claims 18 to 26 or the ZN catalyst system according to claims 28 to 35 in olefin polymerization.

37. The use according to claim 36, wherein: The olefin polymerization is propylene homopolymerization, propylene and ethylene copolymerization or α-olefin copolymerization.

38. The use according to claim 37, wherein: The α-olefin is butene and / or isobutylene.

39. The use according to claim 36, wherein: The olefin polymerization is gas phase polymerization, bulk polymerization or slurry polymerization.

40. The use according to claim 39, wherein: The reaction temperature of the slurry polymerization is 30-80°C, and the reaction pressure is 0.1-2.0 MPa.

41. The use according to claim 39, wherein: The solvent for the slurry polymerization is C5-C 10 of alkanes.

42. The use according to claim 41, wherein: The solvent for the slurry polymerization is hexane.

43. The use according to claim 39, wherein: The reaction pressure of the bulk polymerization is 2.8-4.0Mpa, and the reaction temperature is 68-72°C.

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