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

Abstract

The invention provides an organic polymer carrier, a Z-N catalyst as well as a preparation method and application of the Z-N catalyst. The organic polymer carrier is obtained by copolymerizing monomers including divinyl benzene and unsaturated catechol ester monomers; wherein the unsaturated catechol ester monomer has a structure as shown in a formula I: # imgabs0 #, the catalyst has good stereotactic ability, and when the catalyst is used for propylene homopolymerization, the obtained polypropylene has high stereoregularity and wider molecular weight distribution characteristic.

Description

Technical Field

[0001] The 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 particularly 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 will exceed about 200 million tons / year, and polypropylene is also the fastest-growing synthetic resin among them. It is expected that in the next five years, the production and consumption of polypropylene will continue to grow, and the global demand will exceed 80 million tons / year.

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

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

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

[0006] In order to solve the above problems, the purpose of the present invention is to provide an organic polymer carrier, a ZN catalyst and a preparation method and application thereof. The catalyst has good stereospecific ability and when used for propylene homopolymerization, the resulting polypropylene has high stereoregularity and wide molecular weight distribution characteristics.

[0007] In order to achieve the above object, the present invention provides an organic polymer carrier, which is obtained by copolymerizing monomers including divinylbenzene and unsaturated catechol ester monomers; wherein the unsaturated catechol ester monomer has a structure shown in Formula I:

[0008]

[0009] 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, 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 group and derivatives thereof, C1-C8 branched-chain hydrocarbon group and derivatives thereof, cycloalkyl and derivatives thereof, aromatic group and derivatives thereof.

[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 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 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 di-isobutyrate, 4-vinylcatechol di-n-valerate, 4-vinylcatechol di-n-hexanoate, 4-vinylcatechol di-n-octanoate, 4-vinylcatechol di-isooctanoate, 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 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 diformate, 4-allyl-6-isobutylcatechol diacetate, 4-allyl-6-isobutylcatechol dipropionate, 4-allyl-6-isobutylcatechol di-n-butyrate, 4-allyl-6-isobutylcatechol di-isobutyrate, 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-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 diformate, 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 di-isobutyrate, 4-allyl-6-bromocatechol di-n-valerate, 4-allyl-6-bromo 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 diformate, 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-hexyl esters, 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-(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 di-isobutyrate, 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 the divinylbenzene, the unsaturated catechol ester monomer and the additional monomer as raw materials, and obtaining the organic polymer carrier through copolymerization; the mass ratio of the additional monomer to divinylbenzene is 0-1:1; the mass ratio of the unsaturated 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, additional monomers, and then adding stabilizers and initiators to a dispersion solvent, 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; in the process of preparing the carrier, the solubility parameter of the solvent system is adjusted by the solvent, so as to control 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 dispersion 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 1000-100000.

[0023] According to a specific embodiment of the present invention, preferably, in the above preparation method, the mass ratio of the amount of 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 the mass of the ZN catalyst being 100%, comprises 60-85wt% of the organic polymer carrier, 1-5wt% of a magnesium compound calculated as magnesium element, 1-5wt% of a titanium compound calculated as titanium element and 0-5wt% of an internal electron donor.

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

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

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

[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, and 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 carrier, a porous organic carrier 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 above magnesium-containing compound (POP-Ph-(OCO)2...MgX) is further reacted 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 obtained 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 diol 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-propanedimethyl ether (IAIPDMP).

[0036] The present invention also provides a method for preparing the above 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 reaction is carried out at 0°C-50°C for 15-120 minutes. The unreacted magnesium compound is filtered, and then an inert solvent and titanium tetrachloride are added. After reacting at 0°C-120°C for 15-180 minutes, the internal electron donor (optional) 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.

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

[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), dicyclopentenedimethoxysilane (D external donor), diisopropyldimethoxysilane (P external donor), diisobutyldimethoxysilane (B external donor), and tetraethoxysilane (TEOS).

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

[0043] According to a specific embodiment of the present invention, preferably, the co-catalyst comprises an alkyl aluminum compound, wherein the alkyl aluminum compound is Al(R'')3, where R'' is a C1-C6 alkyl group; in addition, the added alkyl aluminum compound can also be used 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 application 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 0.1-2.0Mpa.

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

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

[0054] The porous organic polymer carrier-supported ZN olefin catalyst of the present invention starts from the carrier level, and the functional monomer of catechol ester containing unsaturated double bonds is polymerized with monomers such as divinylbenzene through its unsaturated double bonds to obtain a porous organic polymer (POP) carrier (denoted as POP-Ph-(OCO)2), and the catechol ester functional group in the carrier interacts 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), and an internal electron donor can be added selectively; wherein the selected functional monomer not only has an important influence on the prepared carrier, but also directly affects the specific surface area, pore volume, bulk density, fluidity, etc. of the prepared carrier, and because the catechol ester functional group is introduced on the carrier, the chelate structure group can play the role of the internal electron donor in the ZN catalyst, and has an effect on the active centers Ti and M. g microchemical environment is modified, and the prepared catalyst has good stereospecific ability and catalyst activity, and the product catalyzed by the catalyst has a wide molecular weight distribution; in the catalyst preparation process, even if no additional internal electron donor is added (additional internal electron donor can also be added), the obtained catalyst still has stereospecific ability, and the polypropylene isotacticity can reach more than 98%. In addition, the POP carrier-type polypropylene catalyst prepared by using the functional monomer has the characteristics of wide molecular weight distribution, and the molecular weight distribution coefficient is between 8-20; when used for propylene polymerization, silane external electron donors and triethylaluminum co-catalysts are added, and the obtained polymer has a high isotacticity, which can reach more than 98%, and 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, and the molecular weight distribution coefficient is between 8-20.

[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 atom and the internal electron donor to lose stability and re-occupy the random active position complexed by the internal electron donor, causing the catalyst's directional ability to decrease; the addition of the external electron donor can preferentially combine with AlEt3, avoiding the internal electron donor from falling off, reducing the amount of the internal electron donor compound removed by AlEt3, and ensuring the stability of the stereoactive center; therefore, it is necessary to supplement an additional external electron donor during the polymerization process, so that the prepared polymer has a higher isotacticity. DETAILED DESCRIPTION

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

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

[0058] The catechol ester functional monomer containing unsaturated double bonds in the present invention can be prepared by esterification reaction of catechol containing unsaturated double bonds with 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 Company; the isotacticity of the polymer is obtained by the result of n-heptane extraction test (refer to standard GBT 2412-2008); and the content of the internal electron donor can be determined by extraction and gas chromatography.

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

[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-allyl catechol diacetate compound can be prepared by esterifying 4-allyl catechol (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-allyl catechol 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-allyl catechol, 10 g of acetic anhydride, 300 ml of dried dichloromethane solvent and 0.02 g of acetic anhydride are added into 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 at normal pressure to obtain a crude product, which was filtered, neutralized, washed with water, and distilled under reduced pressure to obtain 4-allylcatechol diacetate 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%, alias: 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, 6.0g of 4-allyl catechol, 12g of benzoic acid, 300ml of dried CH2Cl2 solvent and 0.02g of DMAP are added into a 500ml reactor, reacted at room temperature for 3 hours, and then 10g of anhydrous K2CO3 is added, esterified under normal pressure to obtain a crude product, 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 reaction 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), using 6-bromo-4-allyl-2-methoxyphenol (CAS: 5746-37-2) to obtain a catechol compound with a yield of about 67%: 4.86 g of 4-allyl-2-methoxyphenol was added to a 500 ml glass reaction bottle. 6-bromo-4-allyl-2-methoxyphenol, then add 1.1 mol equivalent of 2-iodoacylbenzoic acid (CAS: 61717-82-6) tetrahydrofuran solution, react at room temperature (25°C, the same below) for 3 hours, then add a freshly prepared excess sodium dithionite (CAS: 7775-14-6) aqueous solution, react for 1 hour, filter, and distill 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] 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 into a 500 ml reactor, and the mixture was 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 diethyl ester with 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] 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 into a 500 ml reactor, and the mixture was 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 dibenzoate with 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, add 100ml ethanol, 12ml deionized water and 20ml butyl acetate, then add 5.0g divinylbenzene (Aladdin reagent, 55%) and 2.5g 4-allyl catechol diacetate, stir at room temperature for 5min, then add 2% monomer weight of polyvinyl alcohol PVA (PVA, degree of polymerization 1750), stir at 45°C for 1h to completely dissolve the stabilizer, add 2.0% monomer weight of AIBN, heat to 70°C, react for 3 hours, then raise the temperature to 80°C, react for 12 hours, stir at 350 rpm, filter, add 1000ml of ethanol and water (9:1 volume ratio) mixed solvent, wash 3 times, filter and dry to obtain 4.9g of 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, add 2 g of the carrier POP-1 prepared using the above-mentioned 4-allyl catechol diacetate functional monomer, add 100 ml of toluene, stir, then add 10 ml of 3M methyl magnesium chloride Grignard reagent at room temperature, stir for 2 hours, filter, wash twice with toluene, then add 50 ml of toluene, add 50 ml of TiCl4 dropwise at room temperature, heat to 60°C, react for 2 hours, filter, wash with toluene and hexane 3 times each, and obtain free-flowing catalyst particles after drying, which are recorded as Cat-1. The Mg content of the catalyst Cat-1 is 2.8%, the titanium content is 4.1%, and the organic polymer carrier content is 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, add 100ml ethanol, 10ml deionized water and 15ml tetrahydrofuran, then add 5.0g divinylbenzene (Aladdin reagent, 80%) and 3.0g 4-allyl catechol dibenzoate (98.5%), stir at room temperature for 5min, then add 2% monomer weight of polyvinyl alcohol PVA (PVA, degree of polymerization 1750), stir at 45℃ for 1h to completely dissolve the stabilizer, add 2.0% monomer weight of AIBN, heat to 70℃, react for 3 hours, then raise the temperature to 80℃, react for 12 hours, stir at 350 rpm, filter, add 1000ml mixed solvent of ethanol and water (9:1 volume ratio) and wash 3 times, filter and dry to obtain 5.8g free-flowing porous organic polymer carrier POP-2. The carrier specific surface area is 485m 2 / g, pore volume 0.47ml / g;

[0088] (2) Preparation of ZN catalyst:

[0089] In a 250ml glass reactor, add 2g of the carrier POP-2 prepared by using the above-mentioned 4-allyl catechol dibenzoate functional monomer, add 100ml of toluene, stir, then add 8ml of 3M methylmagnesium chloride Grignard reagent at 5°C, stir for 2 hours, filter, wash twice with toluene, then add 50ml of toluene, add 35ml of TiCl4 dropwise at room temperature, react for 1 hour, heat to 80°C, react for 1 hour, filter, then add 50ml of toluene and 30ml of TiCl4, react at 80°C for 2 hours, filter after the reaction, wash 3 times with toluene and hexane respectively, and obtain free-flowing catalyst particles after drying, which are recorded as Cat-2. The Mg content of catalyst Cat-2 is 2.5%, the titanium content is 2.7%, and the organic polymer carrier content is 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, add 2g of the carrier POP-2 prepared by using the functional monomer of 4-allyl catechol dibenzoate, add 100ml of toluene, stir, then add 10ml of 3M benzylmagnesium chloride Grignard reagent at 35°C, stir for 2 hours, filter, wash twice with toluene, add 50ml of toluene, then heat to 50°C, slowly add 40ml TiCl4 dropwise, react for 2 hours, then heat to 80°C, react for 3 hours, filter after the reaction, add 50ml of toluene and 30ml TiCl4, react at 80°C for 2 hours, filter after the reaction, wash 3 times with toluene and hexane respectively, and obtain free-flowing catalyst particles after drying, which are recorded as Cat-3. The Mg content of catalyst Cat-3 is 3.2%, the titanium content is 3.0%, and the organic polymer carrier content is 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, add 100ml ethanol, 20ml water and 15ml ethyl acetate, then add 6.0g divinylbenzene (Aladdin reagent, 80%) and 3.0g 4-allyl-6-bromocatechol diisobutyrate, stir at room temperature for 5min, then add 2% monomer mass of block copolymer of polyethylene oxide and polypropylene oxide F127, stir at 45℃ for 1h to completely dissolve the stabilizer, add 2.0% monomer mass of dibenzoyl peroxide BPO, heat to 70℃, react for 3 hours, then raise the temperature to 80℃, react for 8 hours, stir at 550 rpm, filter, add 100ml mixed solvent of ethanol and water (9:1 volume ratio) to wash 3 times, filter and dry to obtain 7.1g free-flowing porous organic polymer carrier POP-3. The carrier specific surface area is 328m 2 / g, pore volume 0.45ml / g;

[0097] (2) Preparation of ZN catalyst:

[0098] In a 250ml glass reactor, add 3g of the carrier POP-3 prepared by polymerization of the functional monomer 4-allyl-6-bromocatechol diisobutyrate, add 100ml of toluene, stir, then add 10ml of 3M methylmagnesium chloride Grignard reagent at 35°C, stir for 2 hours, filter, wash twice with toluene, add 50ml of toluene, then heat to 50°C, add 30mlTiCl4 dropwise, react for 2 hours, then heat to 80°C, filter after the reaction, wash 3 times with toluene and hexane respectively, and obtain free-flowing catalyst particles after drying, recorded as Cat-4. The Mg content of catalyst Cat-4 is 2.5%, the titanium content is 2.2%, and the organic polymer carrier content is 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 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, 100 ml of toluene was added, stirred, and then 10 ml of 3M methylmagnesium chloride Grignard reagent was added at room temperature, stirred for 3 hours, filtered, washed twice with toluene, 50 ml of toluene was added, and then the temperature was raised to 50° C., 30 ml of TiCl4 was added dropwise, reacted for 2 hours, and then the temperature was raised to 80° C., 0.25 g of diisobutyl phthalate internal electron donor was added, and reacted for 3 hours. After the reaction was completed, it was filtered, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-5. The Mg content of the catalyst Cat-5 was 3.0%, the titanium content was 2.1%, the internal electron donor content was 3.1%, and the organic polymer carrier content was 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, add 90ml ethanol, 10ml water and 30ml butyl acetate, then add 6.0g divinylbenzene (Aladdin reagent, 55%) and 4.0g 4-allyl-6-bromocatechol diacetate, stir at room temperature for 5min, then add 5% monomer mass of block copolymer of polyethylene oxide and polypropylene oxide F127, stir at 45℃ for 1h to completely dissolve the stabilizer, add 2.0% monomer mass of AIBN, heat to 70℃, react for 3 hours, then raise the temperature to 80℃, react for 8 hours, stir at 600 rpm, filter, add 100ml mixed solvent of ethanol and water (9:1 volume ratio) and wash 3 times, filter and dry to obtain 6.3g free-flowing porous organic polymer carrier POP-4. The specific surface area of ​​the carrier is 249m 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 of 4-allyl-6-bromocatechol diacetate was added, 100 ml of toluene was added, stirred, and then 10 ml of 3M butylmagnesium bromide Grignard reagent was added at 35° C., stirred for 2 hours, filtered, washed twice with toluene, 60 ml of toluene was added, and then the temperature was raised to 50° C., 30 ml of TiCl4 was added dropwise, reacted for 2 hours, and then the temperature was raised to 80° C. and reacted for 3 hours. After the reaction was completed, it was filtered, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-6. The Mg content of the catalyst Cat-6 was 2.5%, the titanium content was 2.5%, and the organic polymer carrier content was 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, add 110ml ethanol, 12ml water and 20ml tetrahydrofuran, then add 6.0g divinylbenzene (Aladdin reagent, 80%) and 3.0g 4-allyl-6-bromocatechol dibenzoate, stir at room temperature for 5min, then add 2% monomer mass of block copolymer F127 of polyethylene oxide and polypropylene oxide, stir at 45℃ for 1h to completely dissolve the stabilizer, add 2.0% monomer mass of AIBN, heat to 70℃, react for 3 hours, then raise the temperature to 80℃, react for 8 hours, stir at 550 rpm, filter, add 100ml mixed solvent of ethanol and water (9:1 volume ratio) and wash 3 times, filter and dry to obtain 6.5g free-flowing porous organic polymer carrier POP-5. The specific surface area of ​​the carrier is 527m 2 / g, pore volume 0.41ml / g;

[0112] (2) Preparation of ZN catalyst:

[0113] In a 250ml glass reactor, 3g of the carrier POP-5 prepared from the functional monomer of 4-allyl-6-bromocatechol dibenzoate was added, 100ml of toluene was added, stirred, then 12ml of 3M di-n-butyl magnesium 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 slowly added dropwise, reacted for 2 hours, then the temperature was raised to 80°C, filtered, 100ml of TiCl4 was added and reacted at 80°C for 2 hours, filtered, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-7. The Mg content of the catalyst Cat-7 is 3.2%, the titanium content is 3.7%, and the organic polymer carrier content is 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, add 100ml ethanol, 10ml water and 15ml tetrahydrofuran, then add 6.0g divinylbenzene (Aladdin reagent, 80%) and 2.5g 4-allyl-6-bromocatechol dibenzoate and 1.0g hydroxyethyl methacrylate, stir at room temperature for 5min, then add 2% monomer mass of block copolymer F127 of polyethylene oxide and polypropylene oxide, stir at 45℃ for 1h to completely dissolve the stabilizer, add 2.0% (3.0g) monomer mass of AIBN, heat to 70℃, react for 3 hours, then heat to 80℃, react for 8 hours, stir at 350 rpm, filter, add 100ml mixed solvent of ethanol and water (9:1 volume ratio) and wash 3 times, filter and dry to obtain 7.2g free-flowing porous organic polymer carrier POP-6. The carrier specific surface area is 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 functional monomer of 4-allyl-6-bromocatechol dibenzoate and the third monomer hydroxyethyl methacrylate was added, 100 ml of toluene was added, stirred, and then 15 ml of 3M methylmagnesium chloride Grignard reagent was added at 20° C., stirred for 2 hours, filtered, washed twice with toluene, 50 ml of toluene was added, and then the temperature was raised to 50° C., 30 ml of TiCl4 was slowly added dropwise, reacted for 2 hours, and then the temperature was raised to 80° C., 0.20 g of 9,9-dimethoxyfluorene internal electron donor was added, and reacted for 3 hours. After the reaction was completed, filtered, and then 100 ml of TiCl4 was added to react at 80° C. for 1 hour. After filtering, toluene and hexane were used to wash 3 times each, and free-flowing catalyst particles were obtained after drying, which were recorded as Cat-8. The Mg content of the catalyst Cat-8 was 4.5%, the titanium content was 2.1%, the internal electron donor content was 1.9%, and the organic polymer carrier 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 250 ml glass reactor, add 3 g of the carrier POP-6 prepared from the functional monomer of 4-allyl-6-bromocatechol dibenzoate and the third monomer hydroxyethyl methacrylate, add 100 ml of toluene, stir, then add 12 ml of 3M methylmagnesium chloride Grignard reagent at 20°C, stir for 2 hours, filter, wash twice with toluene, then heat to 80°C, add 50 ml of toluene, slowly add 50 ml of TiCl4 dropwise, react for 3 hours, filter after completion of the reaction, wash 3 times with toluene and hexane respectively, and obtain free-flowing catalyst particles after drying, recorded as Cat-9. The Mg content of the catalyst Cat-9 is 3.7%, the titanium content is 3.0%, and the organic polymer carrier content is 75%.

[0123] Comparative Example 1

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

[0125] Preparation of ZN polypropylene catalyst supported by inorganic carrier: In a 250ml glass reactor, 3g of spherical ethoxy magnesium carrier (Japan Soda Co., Ltd.) was added, 100ml of toluene was added, stirred, and then 50ml of TiCl4 was slowly added dropwise at 0°C, the dropping speed was controlled, and the temperature was controlled at 0-5°C. After the addition was completed, the temperature was raised to 60°C, 0.30g of DIBP internal electron donor was added, and the reaction was carried out at 110°C for 2 hours. After filtering, 100ml of fresh TiCl4 was added, and the reaction was carried out at 110°C for 2 hours. After the reaction was completed, it was filtered, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, recorded as Cat-10. The titanium content of catalyst Cat-10 is 3.2%, and the content of electron donor in DIBP is 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, stirred, and then 50 ml of TiCl4 was slowly added dropwise at 0°C. The dropping speed was controlled to control the temperature at 0-5°C. After the addition was completed, the temperature was raised to 60°C, 0.40 g of 9,9-dimethoxyfluorene internal electron donor was added, and the reaction was carried out at 110°C for 2 hours. After filtering, 100 ml of fresh TiCl4 was added and the reaction was carried out at 110°C for 2 hours. After the reaction was completed, the catalyst was filtered, washed 3 times with toluene and hexane respectively, and dried to obtain free-flowing catalyst particles, which were recorded as Cat-11. The titanium content of the catalyst Cat-11 was 3.2%, and the content of the 9,9-dimethoxyfluorene internal electron donor 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 250ml glass reactor, add 3g of spherical ethoxymagnesium carrier (Japan Soda Co., Ltd.), add 50ml of toluene, stir, slowly add 30ml of TiCl4 at 50°C, react for 2 hours, heat to 80°C, add 0.25g of diisobutyl phthalate internal electron donor, react for 3 hours. After the reaction is completed, filter, wash with toluene and hexane 3 times each, and obtain free-flowing catalyst particles after drying, recorded as Cat-12. The titanium content of catalyst Cat-12 is 3.8%, and the content of DIBP internal electron donor is 4.9%.

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

[0135] Propylene polymerization

[0136] Test Example 1

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

[0138] Test Example 2

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

[0140] Test Example 3

[0141] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 80mg of the catalyst Cat-2 and 0.3ml of cyclohexylmethyldimethoxysilane (C external supply) were added, and 0.5g of hydrogen was added. The temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 840g of a polypropylene product (PP-3) was obtained, with a bulk density of 0.38g / ml and a catalyst activity of 10500gPP / gcat.h, as shown in Table 1.

[0142] Test Example 4

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

[0144] Test Example 5

[0145] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 80mg of the catalyst Cat-4 and 0.3ml of cyclohexylmethyldimethoxysilane (C external supply) were added, and 0.5g of hydrogen was added. The temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour. After the reaction was completed, the reaction was terminated, and the mixture was cooled to room temperature. After drying, 896g of a polypropylene product (PP-5) was obtained, with a bulk density of 0.37g / ml and a catalyst activity of 11200gPP / gcat.h, as shown in Table 1.

[0146] Test Example 6

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

[0148] Test Example 7

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

[0150] Test Example 8

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

[0152] Test Example 9

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

[0154] Test Example 10

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

[0156] Comparative test example 1

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

[0158] Comparative test example 2

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

[0160] Comparative test example 3

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

[0162] Comparative test example 4

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

[0164] Table 1 Propylene polymerization results

[0165]

[0166] Test Example 11 Copolymerization of propylene and ethylene

[0167] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10L dried propylene polymerization reactor, and the stirring speed was 600 rpm. Then 60 mg of the above-prepared 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 added, the temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour, the pressure was released, the mixture was cooled to room temperature, and 758 g of ethylene-propylene copolymer product was obtained after drying. The catalyst polymerization activity was 12633 gPP / gcat.h, the weight average molecular weight Mw of the polymer was 687,000 g / mol, and the molecular weight distribution coefficient was 11.2.

[0168] Test Example 12 Copolymerization of propylene and ethylene

[0169] Into a 10L dried propylene polymerization reactor, 2.0kg of liquid propylene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, 60mg of the catalyst Cat-3 and 0.3ml of cyclohexylmethyldimethoxysilane (C external supply) 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, 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.

[0170] Test Example 13 Copolymerization of propylene and ethylene

[0171] In a 10L dried propylene polymerization reactor, add 2.0kg liquid propylene, 10ml triethylaluminum TEA (1.0 mol / L), stir at 600 rpm, then add 60mg of the above-prepared catalyst Cat-7, and 0.5ml cyclohexylmethyldimethoxysilane (C external), add 0.5g hydrogen and 50g ethylene monomer, heat to 70°C, stir at 600 rpm for 1 hour, release the pressure, cool to room temperature, and dry to obtain 948g of ethylene propylene copolymer product. The catalyst polymerization activity is 15800gPP / gcat.h, the polymer weight average molecular weight Mw is 715,000 g / mol, and the molecular weight distribution coefficient is 9.4.

[0172] Test Example 14 Copolymerization of propylene and butene

[0173] 2.0 kg of liquid propylene and 10 ml of triethylaluminum TEA (1.0 mol / L) were added to a 10L dried propylene polymerization reactor, and the stirring speed was 600 rpm. Then 60 mg of the above-prepared Cat-7 catalyst and 0.5 ml of cyclohexylmethyldimethoxysilane (external C) were added, 0.5 g of hydrogen and 50 g of 1-butene monomer were added, the temperature was raised to 70°C, and the polymerization was carried out under stirring at 600 rpm for 1 hour, the pressure was released, the mixture was cooled to room temperature, and 624 g of butene-propylene copolymer product was obtained after drying. The catalyst polymerization activity was 10400 gPP / gcat.h.

[0174] From the above polymerization results, it can be seen that the organic carrier-supported POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst solid component (internal electron donor can be selectively added) prepared by using free radical polymerizable catechol ester functional monomers containing unsaturated double bonds in the present invention has good catalytic activity, and the propylene homopolymerization activity can reach more than 13000gPP / gcat.h. Although it is lower than the catalyst supported by the traditional inorganic MgCl2 carrier, its activity is greatly improved compared with the existing organic polymer carrier polymerization activity, which can meet the level of existing industrial catalysts. By screening out free radical polymerizable catechol ester functional monomers containing unsaturated double bonds, relying on the functional groups of catechol ester on the carrier, the microchemical environment of the metal active center is regulated, and an organic carrier-loaded POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst solid component is integratedly designed and prepared, so that the catalyst has good stereospecific ability. Even without the addition of internal electron donors, the prepared polypropylene has a high isotacticity, which can reach more than 98%. The TREF high-temperature elution temperature can reach 124°C, which is higher than the conventional isotactic polypropylene (iPP) elution temperature (121-123°C). In addition, the polymer molecular weight distribution can be adjusted in a wide range, and the molecular weight distribution coefficient can be controlled between 8-20.

[0175] Compared with Comparative Example 1 (adding the same conventional internal electron donor such as DIBP), the isotacticity of the polymer prepared by the catalyst Cat-5 prepared in Example 5 of the present invention is significantly higher than that of the catalysts in Comparative Examples 1 and 3; compared with Comparative Examples 2 and 4 (using 9,9-dimethoxyfluorene internal electron donor with high stereoregularity and relatively narrow molecular weight distribution), the catalyst Cat-8 prepared in Example 8 has a higher stereoregularity of the prepared polypropylene, and its TREF high temperature elution temperature is about 124.0°C higher, and has a wider molecular weight distribution. The molecular weight distribution of the polymerization prepared by the catalyst Cat-8 is 10.6.

[0176] Compared with existing catalysts, the POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst disclosed in the present invention has a simple preparation method, and its active center has high stereospecific ability and wide molecular weight distribution characteristics, and has good industrial prospects. In particular, the 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 either 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-vinyl catechol dipropionate, 4-vinyl catechol di-n-butyrate, 4-ethyl 4-Allyl-6-methylcatechol diisobutyrate, 4-vinyl-6-methylcatechol di-n-valerate, 4-vinyl-6-methylcatechol di-n-hexanoate, 4-vinyl-6-methylcatechol di-n-octanoate, 4-vinyl-6-methylcatechol di-isooctanoate, 4-vinyl-6-methylcatechol di(2-methylheptanoate), 4-vinyl-6-methylcatechol di(2-ethylhexanoate), 4-vinyl-6-methylcatechol 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 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 di-isobutyrate, 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-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 di-isobutyrate, 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 diformate, 4-allyl-6-fluorocatechol diacetate, 4-allyl-6-fluorocatechol dipropionate, 4-allyl-6-fluorocatechol di-n-butyrate, 4-allyl-6-fluorocatechol di-isobutyrate, 4-allyl-6-fluorocatechol di-n-valerate, 4-allyl-6-fluorocatechol di 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 di-isobutyrate, 4-allyl-6-bromocatechol di-n-valerate, 4-allyl-6-bromocatechol di-n-hexanoate, 4-allyl-6-bromocatechol di-n-butylate, 4-allyl-6-bromocatechol di-isobutylate, 4-allyl-6-bromocatechol di-n-pentanoate, 4-allyl-6-bromocatechol di-n-hexanoate, 4-allyl-6-bromocatechol di-n-butylate 4-allyl-6-bromocatechol dioctanoate, 4-allyl-6-bromocatechol diisooctanoate, 4-allyl-6-bromocatechol di(2-methylheptanoate), 4-allyl-6-bromocatechol di(2-ethylhexanoate), 4-allyl-6-bromocatechol dibenzoate, 4-(1-chloroallyl)catechol diformate, 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 esters, 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 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; Preferably, the organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization; the dispersion polymerization method comprises the following steps: adding divinylbenzene, unsaturated catechol ester monomers, additional monomers into a dispersion solvent, and then adding a stabilizer and an initiator, stirring and dispersing, and reacting at 50-80°C for 5-12 hours to obtain the organic polymer carrier.

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

7. The preparation method according to claim 5, wherein: The dispersing solvent includes 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; Preferably, the C1-C4 alcohol includes one or a combination of two or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol; Preferably, the fatty acid ester comprises ethyl acetate and / or butyl acetate.

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

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

100.

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

100.

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

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

13. The ZN catalyst according to claim 12, wherein The magnesium compound is RMgX or R'MgR", wherein R, R', and R" are independently selected from C1-C8 alkyl groups and their derivatives, aryl groups and their derivatives, alkoxy groups and their derivatives, and X is fluorine, chlorine, bromine or iodine; Preferably, the R, R' and R" are each independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl and substituted phenyl.

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

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

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

17. The ZN catalyst according to claim 16, wherein The internal electron donor includes one or a combination of two or more of diisobutyl phthalate, di-n-butyl phthalate, 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzyl ester, and 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether.

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

19. A ZN catalyst system, comprising a ZN catalyst, an external electron donor and a co-catalyst; in, The ZN catalyst is the ZN catalyst according to any one of claims 12 to 17.

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

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

22. The ZN catalyst system according to claim 19, wherein The co-catalyst comprises an alkyl aluminum compound, wherein the alkyl aluminum compound is Al(R'')3, and R'' is a C1-C6 alkyl group; Preferably, the R'' is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl; Preferably, the co-catalyst is triethylaluminum.

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

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

25. The use according to claim 24, wherein: The olefin polymerization is propylene homopolymerization, propylene and ethylene copolymerization or α-olefin copolymerization; Preferably, the α-olefin is butene and / or isobutylene.

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

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