Organic polymer support, ZN catalyst and its manufacturing method and use

Abstract

The present invention provides an organic polymer support obtained by copolymerizing a monomer containing divinylbenzene and an unsaturated catechol ester monomer, wherein the unsaturated catechol ester monomer has a structure represented by Formula I, a ZN catalyst, and a method for producing and using the same. The catalyst has good stereo-orientation ability, and when used in the homopolymerization of propylene, the resulting polypropylene has high stereoregularity and a wide molecular weight distribution. JPEG2025540830000005.jpg50104

Description

[Technical Field]

[0001] The present invention relates to the field of catalysts, specifically to organic polymer supports, ZN catalysts and their preparation and use, and more particularly to a catalyst system for polypropylene with high stereoregularity and broad molecular weight distribution. [Background technology]

[0002] Since the discovery of Zinc nitrate catalysts in the 1950s, innovations in polyolefin production technology and catalysts have led to a continuous increase in both polyolefin production and demand. In 2020, global polyolefin consumption exceeded approximately 200 million tons per year, with polypropylene being the synthetic resin with the fastest growth. It is expected that polypropylene production and consumption will continue to grow over the next five years, with global demand exceeding 80 million tons per year.

[0003] Currently, industrialized polypropylene catalysts are mainly ZN catalysts and metallocene catalysts, which are mainly used to produce high-isotactic polypropylene. Metallocene catalysts, post-metallocene catalysts, and other catalysts are also used to produce small quantities of syndiotactic polypropylene, random polypropylene, and propylene-based elastomers. When industrialized polypropylene production equipment uses slurry polymerization, bulk polymerization, or gas-phase polymerization processes, it is necessary to support the catalyst to control the morphology of the produced polymer and avoid problems such as agglomeration or clogging in the reactor.

[0004] In conventional industrial catalysts, ZN catalysts and metallocene catalysts are mainly supported by inorganic supports. Inorganic supports are mainly silica, magnesium chloride, ethoxy magnesium, molecular sieves, etc. For ZN catalysts, commonly used supports include ethoxy magnesium and anhydrous magnesium chloride, which become MgCl2-supported ZN catalysts after reacting with TiCl4. During the catalyst preparation process, electron donors or Lewis bases are usually added to adjust and control the microchemical environment of the catalytic metal active center, thereby adjusting and controlling the catalytic performance. For example, MgCl-supported polypropylene catalysts typically contain MgCl / TiCl / internal electron donor (ID) / silane-based external electron donor (ED). Typical internal electron donors include phthalate ester-based internal electron donors (e.g., diisobutyl phthalate (DIBP) and di-n-butyl phthalate (DNBP)), phenol ester-based internal electron donors, succinate ester-based internal electron donors, and diether-based internal electron donors. The internal electron donor or Lewis base added to the catalyst system significantly influences the catalyst's activity, stereoregularity, hydrogen coordination sensitivity, product molecular weight, and distribution by providing a unique electronic and steric hindrance environment on the MgCl / TiCl surface. It can also control the crystal particle size on the MgCl surface and the content and distribution of Ti active centers. Over the past 30 years, the development of high-performance polypropylene catalysts has focused primarily on the design and screening of novel internal electron donors.The Journal of Polymer Research, Vol. 28, 2021, p. 45, entitled "Progress in MgCl2-supported Ziegler-Natta catalyzed polyolefin products and applications," provides a review of internal electron donors used in polyolefin catalysts, including succinic acid esters (US20140200316), 1,3-diesters, diethers (US7022640), bicycloalkanedioic acid esters, bicycloalkenedioic acid esters (US20140005345), and silicon-containing compounds (US8088872 B2). The authors note that these internal electron donors exhibit good polymerization activity and high chain regularity during propylene polymerization.

[0005] In packaging materials for food, pharmaceuticals, and other applications, polypropylene is typically required to have high isotacticity or low organic solvent precipitate content to meet the material requirements in these fields. Polypropylene catalysts supported on inorganic supports typically have high polymerization activity, well-controlled polymer morphology, and high bulk density. However, inorganic supports typically contain excess impurities (except for Mg and Ti active centers), limiting their use in the development of high-purity polypropylene products. Unlike reported inorganic supports, organic polymer supports do not introduce impurities from the POP support itself that affect polymer performance. Furthermore, organic supports have controllable pore structure, high specific surface area, thermal stability, and ease of functionalization. Through support design and functionalization, high-performance or unique polyolefin catalysts can be produced. Zinc nitrate catalysts supported on porous organic supports have been reported, and Zinc nitrate catalysts are typically produced using organic supports containing functional groups such as carboxylic acid groups, hydroxyl groups, cyano groups, and amino groups. However, organic support-based olefin catalysts are mainly polyethylene catalysts, and few have been reported for use in propylene polymerization. For example, in Microporous and Mesoporous Materials, "Sulfonated porous organic polymer supported ZN polypropylene catalysts with high stereoregularity and broad molecular weight distribution" (Vol. 343, 2022, 112151) reports a POP support-supported ZN catalyst produced using a p-styrenesulfonic acid functional monomer. When an additional diphenol ester is added to the catalyst as an internal electron donor, the catalyst has a broad molecular weight distribution and high isotacticity, with an isotacticity of 98% or more. However, the polypropylene obtained with this catalyst system without the addition of an additional internal electron donor has low isotacticity and activity, and is not at a commercial level. Summary of the Invention [Problem to be solved by the invention]

[0006] In order to solve the above problems, the present invention aims to provide an organic polymer support and a ZN catalyst which have good stereoregularity and a wide molecular weight distribution when used in the homopolymerization of propylene, and a method for producing the same and a use thereof. [Means for solving the problem]

[0007] In order to achieve the above object, the present invention provides an organic polymer support obtained by copolymerizing a monomer containing divinylbenzene and an unsaturated catechol ester monomer, wherein the unsaturated catechol ester monomer has a structure represented by Formula I:

[0008] [ka]

[0009] (In Formula I, R1, R2, R3, and R6 are each independently selected from hydrogen, chlorine, fluorine, bromine, a hydroxyl group, a C1-C6 linear alkyl group and a derivative thereof, a C1-C6 branched alkyl group and a derivative thereof, a cycloalkyl group and a derivative thereof, and an aryl group and a derivative thereof. x is 0-3, and when x is 0, the carbon atom connected to R3 is directly connected to a benzene ring. R4 and R5 are each independently selected from hydrogen, a C1-C8 linear hydrocarbon group and a derivative thereof, a C1-C8 branched hydrocarbon group and a derivative thereof, a cycloalkyl group and a derivative thereof, and an aryl group and a derivative 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, a methyl group, an isobutyl group, chlorine, fluorine, bromine, and a hydroxyl group; R4 and R5 are each independently selected from hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, an n-heptyl group, a 2-methylhexyl group, a 2-ethylpentyl group, a phenyl group, a vinyl group, and an isopropenyl group; and x is 0 or 1.

[0011] According to a specific embodiment of the present invention, the unsaturated catechol ester monomer is preferably 4-allylcatechol dicarboxylate, 4-allylcatechol diacetate, 4-allylcatechol dipropionate, 4-allylcatechol di-n-butyrate, 4-allylcatechol diisobutyrate, 4-allylcatechol di-n-pentanoate, 4-allylcatechol di-n-hexanoate, 4-allylcatechol di-n-octanoate, 4-allylcatechol diisooctanoate, 4-allylcatechol bis(2-methylheptanoate), ester), 4-allylcatechol bis(2-ethylhexanoate), 4-allylcatechol dibenzoate, 4-vinylcatechol diacetate, 4-vinylcatechol dipropionate, 4-vinylcatechol di-n-butyrate, 4-vinylcatechol diisobutyrate, 4-vinylcatechol di-n-pentanoate, 4-vinylcatechol di-n-hexanoate, 4-vinylcatechol di-n-octanoate, 4-vinylcatechol diisooctanoate, 4-vinylcatechol bis(2-methylheptanoate), 4-vinylcatechol Rubis(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-pentanoate, 4-allyl-6-methylcatechol di-n-hexanoate, 4-allyl-6-methylcatechol di-n-octanoate, 4-allyl Allyl-6-methylcatechol diisooctanoate, 4-allyl-6-methylcatechol bis(2-methylheptanoate), 4-allyl-6-methylcatechol bis(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-butylate, 4-allyl-6-isobutylcatechol diisobutyrate,4-Allyl-6-isobutylcatechol di-n-pentanoate, 4-allyl-6-isobutylcatechol di-n-hexanoate, 4-allyl-6-isobutylcatechol di-n-octanoate, 4-allyl-6-isobutylcatechol diisooctanoate, 4-allyl-6-isobutylcatechol bis(2-methylheptanoate), 4-allyl-6-isobutylcatechol bis(2-ethylhexanoate), 4-allyl-6-isobutylcatechol dibenzoate, 4-allyl-6-chlorocatechol dicarboxylate, 4-allyl 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-pentanoate, 4-allyl-6-chlorocatechol di-n-hexanoate, 4-allyl-6-chlorocatechol di-n-octanoate, 4-allyl-6-chlorocatechol diisooctanoate, 4-allyl-6-chlorocatechol bis(2-methylheptanoate), 4-allyl -6-chlorocatechol bis(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-n-pentanoate, 4-allyl-6-fluorocatechol di-n-hexanoate, 4-allyl 4-allyl-6-fluorocatechol di-n-octanoate, 4-allyl-6-fluorocatechol diisooctanoate, 4-allyl-6-fluorocatechol bis(2-methylheptanoate), 4-allyl-6-fluorocatechol bis(2-ethylhexanoate), 4-allyl-6-fluorocatechol dibenzoate, 4-allyl-6-bromocatechol dicarboxylate, 4-allyl-6-bromocatechol diacetate, 4-allyl-6-bromocatechol dipropionate, 4-allyl-6-bromocatechol di-n-butylate,4-Allyl-6-bromocatechol diisobutyrate, 4-allyl-6-bromocatechol di-n-pentanoate, 4-allyl-6-bromocatechol di-n-hexanoate, 4-allyl-6-bromocatechol di-n-octanoate, 4-allyl-6-bromocatechol diisooctanoate, 4-allyl-6-bromocatechol bis(2-methylheptanoate), 4-allyl-6-bromocatechol bis(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 diisobutyrate, 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 diisooctanoate, 4-(1-chloroallyl)catechol Rubis(2-methylheptanoate), 4-(1-chloroallyl)catechol bis(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-pentanoate, 4- The compound may be one or a combination of two or more selected from allyl-6-hydroxycatechol di-n-hexanoate, 4-allyl-6-hydroxycatechol di-n-octanoate, 4-allyl-6-hydroxycatechol diisooctanoate, 4-allyl-6-hydroxycatechol bis(2-methylheptanoate), 4-allyl-6-hydroxycatechol bis(2-ethylhexanoate), 4-allyl-6-hydroxycatechol dibenzoate, 4-allylcatechol diacrylate, and 4-allylcatechol dimethacrylate.

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

[0013] The present invention further provides a method for producing the organic polymer carrier, comprising copolymerizing monomers including the divinylbenzene, the unsaturated catechol ester monomer, and an additional monomer as raw materials to obtain the organic polymer carrier, wherein the mass ratio of the additional monomer to divinylbenzene is 0-1:1, and 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, the organic polymer carrier is preferably prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization.

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

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

[0017] According to a specific embodiment of the present invention, preferably, in the above preparation method, the dispersion solvent comprises a C1-C4 alcohol, water, and an additional solvent, the additional solvent comprises tetrahydrofuran and / or a fatty acid ester, the mass ratio of the C1-C4 alcohol to water is 5-15:1, and 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, in the above-mentioned preparation method, the C1-C4 alcohol preferably 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 production method, the fatty acid ester comprises 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 added monomers to the dispersion solvent is 1:5-20, so as to make the system uniformly dispersed.

[0021] According to a specific embodiment of the present invention, preferably, in the above-mentioned production 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-mentioned production 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-mentioned production 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 production 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-mentioned 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-mentioned production method, the divinylbenzene is pretreated divinylbenzene, and the pretreatment is for removing a polymerization inhibitor.

[0027] The present invention further provides a ZN catalyst, the raw material composition of which, relative to 100 mass% of the ZN catalyst, includes 60-85 wt% of the organic polymer support, 1-5 wt% of a magnesium compound in terms of magnesium element, 1-5 wt% of a titanium compound in terms of titanium element, and 0-5 wt% 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 element is 2-4 wt%, and the content of titanium element is 2-4 wt%.

[0029] According to a specific embodiment of the present invention, the magnesium compound is preferably RMgX or R'MgR'', wherein R, R', and R'' are each independently selected from a C1-C8 alkyl group and its derivatives, an aryl group and its derivatives, and an alkoxy group and its derivatives, 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 a methyl group, an ethyl group, a propyl group, a butyl group, an alkoxy group, a phenyl group, and a substituted phenyl group.

[0031] According to a specific embodiment of the present invention, the magnesium compound is preferably 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 a chloroalkyl magnesium compound.

[0032] According to a specific embodiment of the present invention, the magnesium compound preferably comprises one or a combination of two or more of methyl magnesium chloride, n-butyl magnesium chloride, isobutyl magnesium chloride, tert-butyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-butyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, tert-butyl magnesium iodide, benzyl magnesium iodide, n-butyl magnesium iodide, methyl magnesium fluoride, tert-butyl magnesium fluoride, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, and ethoxy magnesium chloride. After contacting the magnesium compound with the organic polymer support, a magnesium-containing compound-treated porous organic support (represented as POP-Ph-(OCO)2...MgX) is prepared.

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

[0034] The ZN catalyst of the present invention may optionally contain an additional internal electron donor (ID) to obtain a ZN catalyst (represented as POP-Ph-(OCO)2...MgX / TiCl4 / ID). According to a specific embodiment of the present invention, the internal electron donor is preferably 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, the internal electron donor preferably comprises one or a combination of two or more of diisobutyl phthalate (DIBP), di-n-butyl phthalate (DNBP), 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-phenylenedibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate (IAIPPDB), and 2-isopropyl-2-isopentyl-1,3-propanediol dimethyl ether (IAIPDMP).

[0036] The present invention further provides a method for preparing the above-mentioned ZN catalyst, which comprises the steps of: adding the organic polymer support to an inert solvent under anhydrous and oxygen-free conditions; adding the magnesium compound; reacting at 0°C-50°C for 15-120 minutes; filtering off unreacted magnesium compound; adding an inert solvent and titanium tetrachloride; reacting at 0°C-120°C for 15-180 minutes; adding the internal electron donor (optional); reacting at 50°C-120°C for 15-180 minutes; and finally washing with an inert solvent to obtain the ZN catalyst.

[0037] 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 mmol / g to 5 mmol / g, preferably 1 mmol / g to 4 mmol / g. The content of the functional monomer is usually adjusted by adjusting the ratio of the amount of functional monomer to the amount of divinylbenzene (DVB) monomer added during the support production process. The ratio of the amount of magnesium compound reagent added (in terms of moles of magnesium Mg) to the amount of support used is 1 mmol / g to 30 mmol / g, preferably 3 mmol / g to 20 mmol / g. Typically, an excess Ti metal compound, such as TiCl4, is added to support the catalyst, and the amount of Ti metal compound added (in terms of moles of titanium Ti) is generally 5 mmol / g to 200 mmol / g, preferably 50 mmol / g to 150 mmol / g. The ratio of the amount of internal electron donor to the amount of carrier used is 0-0.3 g of internal electron donor / 1 g of carrier.

[0038] The present invention further provides a ZN catalyst system comprising the ZN catalyst, an external electron donor, and a cocatalyst in a composition.

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

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

[0041] According to a specific embodiment of the present invention, preferably, the molar ratio of silicon in the silane-based external electron donor to titanium in the ZN catalyst is 1-50.

[0042] According to a specific embodiment of the present invention, the co-catalyst preferably comprises an alkyl aluminum compound, and the alkyl aluminum compound is Al(R'''), where R''' is a C1-C6 alkyl group. The added alkyl aluminum compound may also be used as an impurity remover for the polymerization reaction system.

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

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

[0045] According to a specific embodiment of the present invention, preferably, the molar ratio of aluminum in the alkylaluminum compound to titanium in the ZN catalyst is 10-500.

[0046] The present invention further provides the use of the ZN catalyst or the ZN catalyst system in the polymerization of olefins.

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

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

[0049] According to a specific embodiment of the present invention, the olefin polymerization is preferably gas phase polymerization, bulk polymerization or slurry polymerization.

[0050] According to a specific embodiment of the present invention, the reaction temperature of the slurry polymerization is preferably 30-80°C, and the reaction pressure is preferably 0.1-2.0Mpa.

[0051] According to a specific embodiment of the present invention, the solvent for the slurry polymerization is preferably C5-C 10 The alkane is preferably hexane.

[0052] According to a specific embodiment of the present invention, the bulk polymerization is preferably carried out under a reaction pressure of 2.8-4.0 MPa and a reaction temperature of 68°C-72°C, and hydrogen gas is usually used during the polymerization process to adjust the molecular weight or melt index of the polymer.

[0053] The ZN-type olefin catalyst supported on a porous organic polymer support of the present invention is prepared by polymerizing a catechol ester functional monomer having an unsaturated double bond with a monomer such as divinylbenzene via the unsaturated double bond on the support surface to obtain a porous organic polymer (POP) support (represented as POP-Ph-(OCO)2), and the catechol ester functional group in the support interacts with the active centers Mg and Ti to produce a porous organic polymer (POP)-type ZN catalyst (represented as POP-Ph-(OCO)2 / RMgX / TiCl4). An internal electron donor may be added as desired. The functional monomer selected here has a significant impact on the carrier produced, directly affecting the specific surface area, pore volume, bulk density, and fluidity of the carrier. Furthermore, the introduction of catechol ester functional groups into the carrier allows the chelate group to function as an internal electron donor in the ZN catalyst, modifying the microchemical environment of the active centers Ti and Mg. This allows the catalyst produced to have good stereo-orientation and catalytic activity, and the product catalyzed by this catalyst to have a broad molecular weight distribution. Even without the addition of an internal electron donor during the catalyst production process (although additional internal electron donors may be added), the resulting catalyst still has stereo-orientation, and the polypropylene isotacticity can reach 98% or more. Furthermore, the POP-supported polypropylene catalyst produced using this functional monomer is characterized by a broad molecular weight distribution, with a molecular weight distribution coefficient of 8-20. When used in propylene polymerization, the polymer obtained by adding a silane-based external electron donor and triethylaluminum cocatalyst has a high isotacticity of over 98%. The TREF high temperature elution peak temperature (high isotactic polypropylene fraction) is higher than that of other commercial high isotactic polypropylene catalysts, reaching 124°C. The product also has a broad molecular weight distribution with a molecular weight distribution factor of 8-20.

[0054] The organic polymer-supported ZN olefin polymerization catalyst system of the present invention requires the addition of an external electron donor during polymerization. Only by properly combining the two can it achieve excellent performance, such as high catalytic activity and high orientation ability. Typically, the cocatalyst AlEt3 can complex with the internal electron donor, destabilizing the relationship between the Ti atom and the internal electron donor, thereby reoccupying the random active sites complexed by the internal electron donor and reducing the orientation ability of the catalyst. When an external electron donor is added, it can preferentially bond with AlEt3, preventing the internal electron donor from detaching, reducing the amount of internal electron donor removed by AlEt3, and ensuring the stability of the stereoactive center. Therefore, an external electron donor must be added during the polymerization process to ensure high isotacticity in the resulting polymer. DETAILED DESCRIPTION OF THE INVENTION

[0055] In order to make the technical features, objectives and beneficial effects of the present invention more clearly understood, the technical invention of the present invention will be described in detail below, but not to limit the scope of the present invention.

[0056] In the present invention, divinylbenzene (DVB) may be a commercially available monomer with a DVB content of 55% or 80%, and these monomers must 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, and additional monomers such as hydroxyethyl methacrylate can be used after removing the polymerization inhibitor using a neutral alumina column.

[0057] The catechol ester functional monomer having an unsaturated double bond in the present invention may be produced by an esterification reaction between a catechol having an unsaturated double bond and a corresponding acid according to conventional techniques.

[0058] In the present invention, the molecular weight and distribution of the polymer produced by olefin polymerization can be determined by gel permeation chromatography (GPC) from Polymer Char, the isotacticity of the polymer can be determined by the results of n-heptane extraction test (GBT 2412-2008 is used as the reference standard), and the content of internal electron donors can be measured by extraction and gas chromatography.

[0059] In the present invention, the specific surface area of ​​the produced organic polymer support is measured by the BET nitrogen adsorption method using Nova2000e. 2 / g or more, 100-600m 2 / g and a pore volume of more than 0.2 ml / g.

[0060] <Production of unsaturated catechol ester functional monomers>

[0061] <Production Example 1>

[0062] This preparation example provides a 4-allylcatechol diacetate monomer prepared by the following procedure.

[0063] The 4-allylcatechol diacetate compound can be obtained by esterifying 4-allylcatechol (CAS: 1126-61-0, 97%) with acetic anhydride at 20-50°C under atmospheric pressure to produce a crude product, which is then distilled under reduced pressure to obtain 4-allylcatechol diacetate (Reference: Alejandro Madrid Villegas et al., New Catechol Derivatives of Sabrole and Their Antiproliferative Activity towards Breast Cancer Cells, Molecular es 2011, Vol. 16, No. 6, pp. 4632-4641). Specifically, 6.0g of 4-allylcatechol, 10g of acetic anhydride, 300ml of dried dichloromethane solvent and 0.02g of 4-dimethylaminopyridine (DMAP) were added to a 500ml reaction vessel, and the mixture was allowed to react at room temperature for 3 hours. Then, 10g of anhydrous K2CO3 was added and the mixture was esterified under normal pressure to obtain a crude product. After filtration, neutralization, washing with water and distillation under reduced pressure, 4-allylcatechol diacetate was obtained, with a yield of 92%.

[0064] <Production Example 2>

[0065] This preparation provides a 4-allylcatechol dibenzoate monomer prepared by the following procedure.

[0066] 4-Allylcatechol dibenzoate compound can be obtained by esterifying 4-allylcatechol (CAS: 1126-61-0, 97%, also known as 4-allyl-1,2-benzenediol) and benzoic acid at 20-50°C under atmospheric pressure to produce a crude product, which is then distilled under reduced pressure to obtain 4-allylcatechol dibenzoate. Specifically, 6.0g of 4-allylcatechol, 12g of benzoic acid, 300ml of dry CHCl solvent, and 0.02g of DMAP were added to a 500ml reaction vessel and reacted at room temperature for 3 hours. After this, 10g of anhydrous KCO was added and the crude product was esterified under atmospheric pressure. After filtering, neutralizing, washing with water, and distilling under reduced pressure, 4-allylcatechol dibenzoate was obtained in a yield of 91%.

[0067] <Production Example 3>

[0068] This production example provides a 4-allyl-6-bromocatechol diisobutyrate monomer produced by the esterification reaction of 4-allyl-6-bromocatechol with isobutyric acid according to the following procedure.

[0069] (1) The method for producing 4-allyl-6-bromocatechol may refer to the literature (Hypervalent iodine-mediated oxygenative phenol dearomalization reactions, Laurent Pouysegu et al., Tetrahedron, 2010, Vol. 66, No. 31, pp. 5908-5917), in which 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 6-bromo-4-allyl-2-methoxyphenol was added to a 500 ml glass reaction flask, followed by the addition of 1.1 mol equivalent of a tetrahydrofuran solution of 2-iodoxybenzoic acid (CAS: 61717-82-6). The mixture was allowed to react at room temperature (25°C, hereinafter the same) for 3 hours, after which an excess of freshly prepared aqueous sodium dithionite (CAS: 7775-14-6) was added and the mixture was allowed to react for 1 hour. The mixture was then filtered and distilled under reduced pressure to obtain 4-allyl-6-bromocatechol in a yield of 67%.

[0070] (2) Into a 500ml reactor, add 6.0g of 4-allyl-6-bromocatechol, 12g of isobutyric acid, 300ml of dry CHCl solvent and 0.02g of DMAP, react at room temperature for 3 hours, then add 10g of anhydrous KCO and esterify under normal pressure to obtain a crude product, which is filtered, neutralized, washed with water and distilled under reduced pressure to obtain 4-allyl-6-bromocatechol diisobutyrate, with a yield of 89%.

[0071] <Production Example 4>

[0072] This preparation example provides a 4-allyl-6-bromocatechol diacetate monomer prepared by the following procedure.

[0073] Into a 500ml reactor, add 6.0g of 4-allyl-6-bromocatechol, 12g of acetic acid, 300ml of dry CHCl solvent and 0.02g of DMAP, react at room temperature for 3 hours, then add 10g of anhydrous KCO under normal pressure to esterify the crude product, which is filtered, neutralized, washed with water and distilled under reduced pressure to obtain 4-allyl-6-bromocatechol diacetate, with a yield of 91%.

[0074] <Production Example 5>

[0075] This preparation provides 4-allyl-6-bromocatechol dibenzoate monomer prepared by the following procedure.

[0076] Into a 500ml reactor, add 5.8g of 4-allyl-6-bromocatechol, 11.8g of benzoic acid, 300ml of dry CHCl solvent and 0.02g of DMAP, react at room temperature for 3 hours, then add 10g of anhydrous KCO under normal pressure to obtain crude product, which is filtered, neutralized, washed with water and distilled under reduced pressure to obtain 4-allyl-6-bromocatechol dibenzoate, with a yield of 92%.

[0077] Example 1

[0078] This example provides a ZN catalyst prepared by the following procedure.

[0079] (1) Preparation of porous organic polymer supports

[0080] A 250 ml glass reactor was charged with 100 ml of ethanol, 12 ml of deionized water, and 20 ml of butyl acetate, followed by the addition of 5.0 g of divinylbenzene (Aladdin reagent, 55%) and 2.5 g of 4-allylcatechol diacetate. After stirring at room temperature for 5 minutes, 2% monomer weight of polyvinyl alcohol (PVA, degree of polymerization 1750) was added and stirred at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% monomer weight of AIBN was added, the mixture was heated to 70°C, reacted for 3 hours, then heated to 80°C, reacted for 12 hours, and the stirring speed was increased to 350 rpm. After filtration, the mixture was washed three times with 1000 ml of a mixed solvent of ethanol and water (volume ratio 9:1), filtered, and dried to obtain 4.9 g of a free-flowing porous organic polymer support POP-1. The support had a specific surface area of ​​285 m. 2 / g and the pore volume was 0.42 ml / g.

[0081] (2) Production of ZN catalyst

[0082] 2 g of the support POP-1, prepared using the 4-allylcatechol diacetate functional monomer, was added to a 250 ml glass reactor, 100 ml of toluene was added, and after stirring, 10 ml of 3 M methylmagnesium chloride Grignard reagent was added at room temperature. The mixture was stirred for 2 hours, filtered, washed twice with toluene, added 50 ml of toluene, and 50 ml of TiCl4 was added dropwise at room temperature. The mixture was heated to 60 °C and reacted for 2 hours. After filtering, the mixture was washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-1. Catalyst Cat-1 had a magnesium content of 2.8%, a titanium content of 4.1%, and an organic polymer support content of 81%.

[0083] Example 2

[0084] This example provides a ZN catalyst prepared by the following procedure.

[0085] (1) Preparation of porous organic polymer supports

[0086] A 250 ml glass reactor was charged with 100 ml of ethanol, 10 ml of deionized water, and 15 ml of tetrahydrofuran. Then, 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 3.0 g of 4-allylcatechol dibenzoate (98.5%) were added. After stirring at room temperature for 5 minutes, 2% polyvinyl alcohol (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% AIBN was added. The mixture was heated to 70°C and reacted for 3 hours, then to 80°C and reacted for 12 hours. The stirring speed was increased to 350 rpm. After filtration, the mixture was washed three times with 1000 ml of a mixed solvent of ethanol and water (volume ratio 9:1). After filtration and drying, 5.8 g of a free-flowing porous organic polymer support, POP-2, was obtained. The support had a specific surface area of ​​485 m. 2 / g and the pore volume was 0.47 ml / g.

[0087] (2) Production of ZN catalyst

[0088] 2 g of the support POP-2 prepared using the above 4-allylcatechol dibenzoate functional monomer was added to a 250 ml glass reactor, 100 ml of toluene was added, and after stirring, 8 ml of 3 M methylmagnesium chloride Grignard reagent was added at 5 ° C., and the mixture was stirred for 2 hours. After filtering, the mixture was washed twice with toluene, and then 50 ml of toluene was added. 35 ml of TiCl4 was added dropwise at room temperature and reacted for 1 hour. The mixture was heated to 80 ° C., reacted for 1 hour, filtered, and then 50 ml of toluene and 30 ml of TiCl4 were added. The mixture was reacted at 80 ° C. for 2 hours. After the reaction was completed, the mixture was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-2. Catalyst Cat-2 had a magnesium content of 2.5%, a titanium content of 2.7%, and an organic polymer support content of 82%.

[0089] Example 3

[0090] This example provides a ZN catalyst prepared by the following procedure.

[0091] Preparation of ZN catalyst: 2 g of the support POP-2 prepared using the above 4-allylcatechol dibenzoate functional monomer was added to a 250 ml glass reactor, 100 ml of toluene was added, and after stirring, 10 ml of 3 M benzyl magnesium chloride Grignard reagent was added at 35 °C, and the mixture was stirred for 2 hours. After filtration, the mixture was washed twice with toluene, 50 ml of toluene was added, and the mixture was heated to 50 °C. 40 ml of TiCl4 was slowly added dropwise, and the mixture was allowed to react for 2 hours. The mixture was then heated to 80 °C and allowed to react for 3 hours. After the reaction was complete, the mixture was filtered, and another 50 ml of toluene and 30 ml of TiCl4 were added, and the mixture was allowed to react for 2 hours at 80 °C. After the reaction was complete, the mixture was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-3. Catalyst Cat-3 had a magnesium content of 3.2%, a titanium content of 3.0%, and an organic polymer support content of 78%.

[0092] Example 4

[0093] This example provides a ZN catalyst prepared by the following procedure.

[0094] (1) Preparation of porous organic polymer supports

[0095] A 250 ml glass reactor was charged with 100 ml of ethanol, 20 ml of water, and 15 ml of ethyl acetate, followed by the addition of 6.0 g of divinylbenzene (Aladdin reagent, 80%) and 3.0 g of 4-allyl-6-bromocatechol diisobutyrate. After stirring at room temperature for 5 minutes, 2% by weight of a polyethylene oxide and polypropylene oxide block copolymer F127 was added. The mixture was stirred at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% by weight of dibenzoyl peroxide BPO was added, the mixture was heated to 70°C, reacted for 3 hours, then heated to 80°C, reacted for 8 hours, and the stirring speed was increased to 550 rpm. After filtration, the mixture was washed three times with 100 ml of a mixed solvent of ethanol and water (volume ratio 9:1), filtered, and dried to obtain 7.1 g of a free-flowing porous organic polymer support POP-3. The support had a specific surface area of ​​328 m. 2 / g and the pore volume was 0.45 ml / g.

[0096] (2) Production of ZN catalyst

[0097] A 250ml glass reactor was charged with 3g of the support POP-3, prepared by polymerizing the 4-allyl-6-bromocatechol diisobutyrate functional monomer. 100ml of toluene was added and stirred. 10ml of 3M methylmagnesium chloride Grignard reagent was added at 35°C, stirred for 2 hours, filtered, washed twice with toluene, added 50ml of toluene, heated to 50°C, 30ml of TiCl4 was added dropwise, reacted for 2 hours, and then heated to 80°C. After the reaction was complete, the catalyst was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-4. Catalyst Cat-4 had a magnesium content of 2.5%, a titanium content of 2.2%, and an organic polymer support content of 83%.

[0098] Example 5

[0099] This example provides a ZN catalyst prepared by the following procedure.

[0100] Preparation of ZN catalyst: 3 g of the support POP-3, prepared by polymerizing the 4-allyl-6-bromocatechol diisobutyrate functional monomer, was added to a 250 ml glass reactor. 100 ml of toluene was added and stirred. After stirring, 10 ml of 3M methylmagnesium chloride Grignard reagent was added at room temperature. The mixture was stirred for 3 hours, filtered, washed twice with toluene, heated to 50 °C, and 30 ml of TiCl4 was added dropwise. The mixture was then heated to 80 °C and 0.25 g of diisobutyl phthalate internal electron donor was added. The mixture was allowed to react for 3 hours. After the reaction was complete, the mixture was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-5. Catalyst Cat-5 had a magnesium 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%.

[0101] Example 6

[0102] This example provides a ZN catalyst prepared by the following procedure.

[0103] (1) Preparation of porous organic polymer supports

[0104] A 250 ml glass reactor was charged with 90 ml of ethanol, 10 ml of water, and 30 ml of butyl acetate, followed by the addition of 6.0 g of divinylbenzene (Aladdin reagent, 55%) and 4.0 g of 4-allyl-6-bromocatechol diacetate. After stirring at room temperature for 5 minutes, 5% by monomer mass of a polyethylene oxide and polypropylene oxide block copolymer F127 was added and stirred at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% by monomer mass of AIBN was added, the mixture was heated to 70°C and reacted for 3 hours, then heated to 80°C and reacted for 8 hours. The stirring speed was increased to 600 rpm, and the mixture was filtered. After washing three times with 100 ml of a mixed solvent of ethanol and water (volume ratio 9:1), filtered, and dried, 6.3 g of a free-flowing porous organic polymer support POP-4 was obtained. The support had a specific surface area of ​​249 m. 2 / g and the pore volume was 0.49 ml / g.

[0105] (2) Production of ZN catalyst

[0106] 3 g of the support POP-4, prepared from the 4-allyl-6-bromocatechol diacetate functional monomer, was added to a 250 ml glass reactor, 100 ml of toluene was added, and the mixture was stirred. 10 ml of 3M butylmagnesium bromide Grignard reagent was added at 35°C, and the mixture was stirred for 2 hours. It was then filtered and washed twice with toluene. 60 ml of toluene was added, the mixture was heated to 50°C, 30 ml of TiCl4 was added dropwise, and the mixture was allowed to react for 2 hours. The mixture was then heated to 80°C and allowed to react for 3 hours. After the reaction was complete, the mixture was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-6. Catalyst Cat-6 had a magnesium content of 2.5%, a titanium content of 2.5%, and an organic polymer support content of 78%.

[0107] Example 7

[0108] This example provides a ZN catalyst prepared by the following procedure.

[0109] (1) Preparation of porous organic polymer supports

[0110] A 250 ml glass reactor was charged with 110 ml of ethanol, 12 ml of water, and 20 ml of tetrahydrofuran, followed by the addition of 6.0 g of divinylbenzene (Aladdin reagent, 80%) and 3.0 g of 4-allyl-6-bromocatechol dibenzoate. After stirring at room temperature for 5 minutes, 2% by weight of a polyethylene oxide / polypropylene oxide block copolymer F127 was added and stirred at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% by weight of AIBN was added, the mixture was heated to 70°C and reacted for 3 hours, then heated to 80°C and reacted for 8 hours. The stirring speed was increased to 550 rpm, and the mixture was filtered. After washing three times with 100 ml of a mixed solvent of ethanol and water (volume ratio 9:1), filtered, and dried, 6.5 g of a free-flowing porous organic polymer support POP-5 was obtained. The support had a specific surface area of ​​527 m. 2 / g and the pore volume was 0.41 ml / g.

[0111] (2) Production of ZN catalyst

[0112] 3 g of the support POP-5, made from the 4-allyl-6-bromocatechol dibenzoate functional monomer, was added to a 250 ml glass reactor, 100 ml of toluene was added, and after stirring, 12 ml of 3M di-n-butylmagnesium was added at room temperature, stirred for 3 hours, filtered, washed twice with toluene, added 50 ml of toluene, heated to 50 °C, 30 ml of TiCl4 was added dropwise, reacted for 2 hours, heated to 80 °C, filtered, added 100 ml of TiCl4, reacted at 80 °C for 2 hours, filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-7. Catalyst Cat-7 had a magnesium content of 3.2%, a titanium content of 3.7%, and an organic polymer support content of 74%.

[0113] Example 8

[0114] This example provides a ZN catalyst prepared by the following procedure.

[0115] (1) Preparation of porous organic polymer supports

[0116] A 250 ml glass reactor was charged with 100 ml of ethanol, 10 ml of water, and 15 ml of tetrahydrofuran, followed by the addition of 6.0 g of divinylbenzene (Aladdin reagent, 80%), 2.5 g of 4-allyl-6-bromocatechol dibenzoate, and 1.0 g of hydroxyethyl methacrylate. After stirring at room temperature for 5 minutes, 2% by weight of a polyethylene oxide and polypropylene oxide block copolymer F127 was added and stirred at 45°C for 1 hour to completely dissolve the stabilizer. 2.0% by weight (3.0 g) of AIBN was added, the mixture was heated to 70°C, reacted for 3 hours, then heated to 80°C, reacted for 8 hours, and the stirring speed was increased to 350 rpm. After filtration, the mixture was washed three times with 100 ml of a mixed solvent of ethanol and water (volume ratio 9:1), filtered, and dried to obtain 7.2 g of a free-flowing porous organic polymer support POP-6. The carrier has a specific surface area of ​​352 m 2 / g and the pore volume was 0.33 ml / g.

[0117] (2) Production of ZN catalyst

[0118] Into a 250ml glass reactor, 3g of the carrier POP-6 made from the above 4-allyl-6-bromocatechol dibenzoate functional monomer and the third monomer hydroxyethyl methacrylate was added, 100ml of toluene was added, and after stirring, 15ml of 3M methyl magnesium chloride Grignard reagent was added at 20°C, and stirred for 2 hours, filtered, washed twice with toluene, added 50ml of toluene, heated to 50°C, 30ml of TiCl4 was slowly added dropwise, reacted for 2 hours, heated to 80°C, 0.20g of 9,9-dimethoxyfluorene internal electron donor was added, reacted for 3 hours, filtered after the reaction was completed, then 100ml of TiCl4 was added, reacted at 80°C for 1 hour, filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-8. The catalyst Cat-8 had a Mg content of 4.5%, a titanium content of 2.1%, an internal electron donor content of 1.9%, and an organic polymer support content of 73%.

[0119] Example 9

[0120] This example provides a ZN catalyst prepared by the following procedure.

[0121] Preparation of ZN catalyst: 3 g of the support POP-6, made from the 4-allyl-6-bromocatechol dibenzoate functional monomer and the third monomer hydroxyethyl methacrylate, was added to a 250 ml glass reactor, 100 ml of toluene was added, and after stirring, 12 ml of 3M methylmagnesium chloride Grignard reagent was added at 20 ° C., and the mixture was stirred for 2 hours. After filtration and washing twice with toluene, the mixture was heated to 80 ° C., 50 ml of toluene was added, and 50 ml of TiCl4 was slowly added dropwise. The mixture was allowed to react for 3 hours. After the reaction was complete, the mixture was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-9. Catalyst Cat-9 had a magnesium content of 3.7%, a titanium content of 3.0%, and an organic polymer support content of 75%.

[0122] Comparative Example 1

[0123] This comparative example provides a ZN catalyst prepared by the following procedure.

[0124] Preparation of inorganic-supported Zinc-Nitride polypropylene catalyst: 3 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) was added to a 250 ml glass reactor, followed by 100 ml of toluene. After stirring, 50 ml of TiCl4 was added dropwise at 0°C, controlling the rate of addition. The temperature was maintained at 0-5°C. After addition, the mixture was heated to 60°C, and 0.30 g of DIBP internal electron donor was added. The mixture was then reacted at 110°C for 2 hours. After filtration, 100 ml of fresh TiCl4 was added and the mixture was reacted at 110°C for 2 hours. After reaction, the mixture was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-10. Catalyst Cat-10 had a titanium content of 3.2% and a DIBP internal electron donor content of 8.9%.

[0125] Comparative Example 2

[0126] This comparative example provides a ZN catalyst prepared by the following procedure.

[0127] Preparation of inorganic-supported zinc-nitride polypropylene catalyst: 3 g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.) was added to a 250 ml glass reactor, followed by 100 ml of toluene. After stirring, 50 ml of TiCl4 was added dropwise at 0°C, controlling the rate of addition. The temperature was maintained at 0-5°C. After addition, the mixture was heated to 60°C, and 0.40 g of 9,9-dimethoxyfluorene internal electron donor was added. The mixture was then reacted at 110°C for 2 hours. After filtration, 100 ml of fresh TiCl4 was added and the mixture was reacted at 110°C for 2 hours. After reaction, the mixture was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-11. Catalyst Cat-11 had a titanium content of 3.2% and a 9,9-dimethoxyfluorene internal electron donor content of 6.2%.

[0128] Comparative Example 3

[0129] This comparative example provides an inorganic carrier-supported ZN catalyst prepared by the following procedure.

[0130] A 250ml glass reactor was charged with 3g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.), 50ml of toluene, and stirred. 30ml of TiCl4 was slowly added dropwise at 50°C, and the mixture was allowed to react for 2 hours. The temperature was then raised to 80°C, and 0.25g of diisobutyl phthalate internal electron donor was added. The mixture was allowed to react for 3 hours. After the reaction was complete, the catalyst was filtered, washed three times with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-12. Catalyst Cat-12 had a titanium content of 3.8% and a DIBP internal electron donor content of 4.9%.

[0131] Comparative Example 4

[0132] This comparative example provides an inorganic carrier-supported ZN catalyst prepared by the following procedure.

[0133] A 250ml glass reactor was charged with 3g of spherical ethoxymagnesium support (Nippon Soda Co., Ltd.), 50ml of toluene, and the mixture was heated to 50°C. 30ml of TiCl4 was added dropwise and allowed to react for 2 hours. The mixture was then heated to 80°C, 0.20g of 9,9-dimethoxyfluorene internal electron donor was added, and the mixture was allowed to react for 3 hours. After the reaction was complete, the mixture was filtered, and another 100ml of TiCl4 was added. The mixture was allowed to react at 80°C for 1 hour. 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, designated Cat-13. Catalyst Cat-13 had a titanium content of 3.4% and a 9,9-dimethoxyfluorene internal electron donor content of 3.7%.

[0134] <Propylene polymerization>

[0135] <Test Example 1>

[0136] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. 82mg of catalyst Cat-1 and 0.5mL of cyclohexylmethyldimethoxysilane (C-type external donor) were then added, followed by 0.3g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 703g of polypropylene product (PP-1). As shown in Table 1, the bulk density was 0.36g / mL and the catalytic activity was 8580gPP / gcat.h.

[0137] <Test Example 2>

[0138] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. 80mg of catalyst Cat-1 and 0.5mL of dicyclopentenyldimethoxysilane (D-type external donor) were then added, followed by 0.5g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 635g of polypropylene product (PP-2). As shown in Table 1, the bulk density was 0.36g / mL and the catalytic activity was 7938gPP / gcat.h.

[0139] <Test Example 3>

[0140] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. 80mg of Cat-2 catalyst and 0.3mL of cyclohexylmethyldimethoxysilane (C-type external donor) were then added, followed by 0.5g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 840g of polypropylene product (PP-3). As shown in Table 1, the bulk density was 0.38g / mL and the catalytic activity was 10500gPP / gcat.h.

[0141] Test Example 4

[0142] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. Then, 80mg of Cat-3 catalyst and 0.3mL of cyclohexylmethyldimethoxysilane (C-type external donor) were added, followed by 0.5g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 1048g of polypropylene product (PP-4). As shown in Table 1, the bulk density was 0.40g / mL and the catalytic activity was 13100gPP / gcat.h.

[0143] Test Example 5

[0144] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. Then, 80mg of Cat-4 catalyst and 0.3mL of cyclohexylmethyldimethoxysilane (C-type external donor) were added, followed by 0.5g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 896g of polypropylene product (PP-5). As shown in Table 1, the bulk density was 0.37g / mL and the catalytic activity was 11200gPP / gcat.h.

[0145] Test Example 6

[0146] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. Then, 80mg of Cat-5 catalyst and 0.3mL of cyclohexylmethyldimethoxysilane (C-type external donor) were added, followed by 0.5g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 842g of polypropylene product (PP-6). As shown in Table 1, the bulk density was 0.38g / mL and the catalytic activity was 10525gPP / gcat.h.

[0147] Test Example 7

[0148] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. 80mg of Cat-6 catalyst and 0.5mL of dicyclopentenyldimethoxysilane (D-type external donor) were then added, followed by 0.7g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 900g of polypropylene product (PP-7). As shown in Table 1, the bulk density was 0.38g / mL and the catalytic activity was 11250gPP / gcat.h.

[0149] Test Example 8

[0150] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. 80mg of Cat-7 catalyst and 0.5mL of cyclohexylmethyldimethoxysilane (C-type external donor) were then added, followed by 0.5g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 1098g of polypropylene product (PP-8). As shown in Table 1, the bulk density was 0.40g / mL and the catalytic activity was 13725gPP / gcat.h.

[0151] Test Example 9

[0152] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. 82mg of Cat-8 catalyst and 0.5mL of dicyclopentenyldimethoxysilane (D-type external donor) were then added, followed by 0.5g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 1023g of polypropylene product (PP-9). As shown in Table 1, the bulk density was 0.39g / mL and the catalytic activity was 12476gPP / gcat.h.

[0153] <Test Example 10>

[0154] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. Then, 80mg of Cat-9 catalyst and 0.3mL of cyclohexylmethyldimethoxysilane (C-type external donor) were added, followed by 0.5g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 1000g of polypropylene product (PP-10). As shown in Table 1, the bulk density was 0.40g / mL and the catalytic activity was 12500gPP / gcat.h.

[0155] <Comparative test example 1>

[0156] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), stirring at 600rpm. 60mg of Cat-10 catalyst and 0.3mL of cyclohexylmethyldimethoxysilane (C-type external donor) were then added, followed by 0.5g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 1119g of polypropylene product (PP-11). As shown in Table 1, the bulk density was 0.37g / mL and the catalytic activity was 18650gPP / gcat.h.

[0157] <Comparative Test Example 2>

[0158] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), and the stirring speed was set to 600rpm. 60mg of Cat-11 catalyst and 0.3mL of cyclohexylmethyldimethoxysilane (C-type external donor) were then added, followed by 0.5g of hydrogen gas. The mixture was heated to 70°C and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 1280g of polypropylene product (PP-12). As shown in Table 1, the bulk density was 0.42g / mL and the catalytic activity was 21333gPP / gcat.h.

[0159] <Comparative Test Example 3>

[0160] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), and the stirring speed was set to 600rpm. 60mg of comparative catalyst Cat-12 and 0.3mL of cyclohexylmethyldimethoxysilane (C-type external donor) were then added, followed by 0.5g of hydrogen gas. The mixture was heated to 70℃ and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 948g of polypropylene product (PP-13). As shown in Table 1, the bulk density was 0.38g / mL and the catalytic activity was 15800gPP / gcat.h.

[0161] <Comparative Test Example 4>

[0162] A 10L dry propylene polymerization reactor was charged with 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L), and the stirring speed was set to 600rpm. 60mg of comparative catalyst Cat-13 and 0.3mL of cyclohexylmethyldimethoxysilane (C-type external donor) were then added, followed by 0.5g of hydrogen gas. The mixture was heated to 70℃ and stirred at 600rpm for 1 hour. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 1240g of polypropylene product (PP-14). As shown in Table 1, the bulk density was 0.41g / mL and the catalytic activity was 20667gPP / gcat.h.

[0163] [Table 1]

[0164] Test Example 11: Copolymerization of propylene and ethylene

[0165] Into a 10L dry propylene polymerization reactor, 2.0kg liquid propylene and 10mL triethylaluminum TEA (1.0mol / L) were added, and the stirring speed was set to 600rpm. Then, 60mg of the above-prepared catalyst Cat-1 and 0.5mL cyclohexylmethyldimethoxysilane (C-type external donor) were added, 0.3g hydrogen gas and 50g ethylene monomer were added, and the temperature was raised to 70℃, and the polymerization was carried out for 1 hour while stirring at 600rpm. The pressure was released, and the mixture was cooled to room temperature and dried to obtain 758g of ethylene-propylene copolymer. The catalyst polymerization activity was 12633g PP / g cat.h, the polymer weight average molecular weight Mw was 687,000g / mol, and the molecular weight distribution coefficient was 11.2.

[0166] Test Example 12: Copolymerization of propylene and ethylene

[0167] A 10L dry propylene polymerization reactor was charged with 2.0kg liquid propylene and 10mL triethylaluminum TEA (1.0mol / L), stirring at 600rpm. 60mg catalyst Cat-3 and 0.3mL cyclohexylmethyldimethoxysilane (C-type external donor) were then added. 0.5g hydrogen gas and 50g ethylene monomer were added, and the temperature was raised to 70℃. Polymerization was carried out for 1 hour with stirring at 600rpm. After the reaction was completed, the reaction was stopped, cooled to room temperature, and dried to obtain 936g of ethylene-propylene copolymer. The catalytic activity was 15600g PP / g cat.h, the polymer weight average molecular weight Mw was 632,000g / mol, and the molecular weight distribution coefficient was 9.1.

[0168] Test Example 13: Copolymerization of propylene and ethylene

[0169] Into a 10L dry propylene polymerization reactor, 2.0kg liquid propylene and 10mL triethylaluminum TEA (1.0mol / L) were added, and the stirring speed was set to 600rpm. Then, 60mg of the above-prepared catalyst Cat-7 and 0.5mL cyclohexylmethyldimethoxysilane (C-type external donor) were added, followed by 0.5g hydrogen gas and 50g ethylene monomer. The temperature was raised to 70℃, and the polymerization was carried out for 1 hour while stirring at 600rpm. The pressure was released, and the mixture was cooled to room temperature and dried to obtain 948g of ethylene-propylene copolymer. The catalyst polymerization activity was 15800gPP / gcat.h, the polymer weight average molecular weight Mw was 715,000g / mol, and the molecular weight distribution coefficient was 9.4.

[0170] Test Example 14: Copolymerization of propylene and butene

[0171] In a 10L dry propylene polymerization reactor, 2.0kg of liquid propylene and 10mL of triethylaluminum TEA (1.0mol / L) were added, and the stirring speed was set to 600rpm. Then, 60mg of the above-prepared Cat-7 catalyst and 0.5mL of cyclohexylmethyldimethoxysilane (C-type external donor) were added, followed by 0.5g of hydrogen gas and 50g of 1-butene monomer. The temperature was raised to 70℃, and the polymerization was carried out for 1 hour while stirring at 600rpm. The pressure was released, and the mixture was cooled to room temperature and dried to obtain 624g of butene-propylene copolymer. The catalyst polymerization activity was 10400gPP / gcat.h.

[0172] As can be seen from the above polymerization results, the POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst solid component (optionally containing an internal electron donor) supported on an organic carrier prepared in the present invention using a catechol ester-based functional monomer having a radically polymerizable unsaturated double bond has good catalytic activity, with a propylene homopolymerization activity of 13,000 gPP / gcat.h or more. Although this is lower than that of catalysts supported on conventional inorganic MgCl2 carriers, it is a significant improvement in polymerization activity compared to conventional organic polymer carrier systems and meets the level of existing industrial catalysts. By using a selected catechol ester functional monomer with a radically polymerizable unsaturated double bond, the microchemical environment of the metal active center can be controlled through the functional groups of the catechol ester on the support, and by integrated design, a solid component of POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst supported on an organic support is produced. This catalyst has good stereo-orientation ability, and without the addition of an internal electron donor, the produced polypropylene has a high isotacticity of over 98% and a TREF high-temperature elution temperature of 124°C, which is higher than the elution temperature of ordinary isotactic polypropylene (iPP) (121-123°C). Furthermore, the molecular weight distribution of the polymer can be adjusted over a relatively wide range, with the molecular weight distribution coefficient being controlled between 8 and 20.

[0173] Compared with Comparative Example 1 (which uses the same conventional internal electron donor, such as DIBP), the polymer produced using catalyst Cat-5 produced 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 (which use 9,9-dimethoxyfluorene internal electron donor, an internal electron donor with high stereoregularity and a relatively narrow molecular weight distribution), the polypropylene produced using catalyst Cat-8 in Example 8 has a higher stereoregularity, a higher TREF high temperature elution temperature of about 124.0 ° C., and a broader molecular weight distribution, with the molecular weight distribution of the polymer produced using catalyst Cat-8 being 10.6.

[0174] The POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst disclosed in the present invention is easier to prepare than conventional catalysts, and its active center has the characteristics of high stereo-orientation ability and a wide molecular weight distribution, making it promising for industrial application. In particular, this catalyst system has advantages in the development of polypropylene products with low precipitation and a good balance of stiffness and toughness.

Claims

1. An organic polymer support obtained by copolymerizing a monomer containing divinylbenzene and an unsaturated catechol ester monomer, The unsaturated catechol ester monomer has a structure represented by Formula I: 【Chemistry 1】 (In formula I, R １ , R ２ , R ３ , R ６ are each independently hydrogen, chlorine, fluorine, bromine, a hydroxyl group, C １ -C ６ linear alkyl groups and derivatives thereof, １ -C ６ x is selected from the group consisting of branched alkyl groups and derivatives thereof, cycloalkyl groups and derivatives thereof, and aryl groups and derivatives thereof. R ４ , R ５ are each independently hydrogen, C １ -C ８ Straight chain hydrocarbon groups and derivatives thereof, １ -C ８ and a branched hydrocarbon group and a derivative thereof, a cycloalkyl group and a derivative thereof, and an aryl group and a derivative thereof.

2. In formula I, R １ , R ２ , R ３ , R ６ are each independently selected from hydrogen, chlorine, a methyl group, an isobutyl group, chlorine, fluorine, bromine, and a hydroxyl group; R ４ , R ５ are each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, n-heptyl, 2-methylhexyl, 2-ethylpentyl, phenyl, vinyl, and isopropenyl; 2. The organic polymer support of claim 1, wherein x is 0 or 1.

3. The unsaturated catechol ester monomers include 4-allylcatechol dicarboxylate, 4-allylcatechol diacetate, 4-allylcatechol dipropionate, 4-allylcatechol di-n-butyrate, 4-allylcatechol diisobutyrate, 4-allylcatechol di-n-pentanoate, 4-allylcatechol di-n-hexanoate, 4-allylcatechol di-n-octanoate, 4-allylcatechol diisooctanoate, 4-allylcatechol bis(2-methylheptanoate), 4-allylcatechol bis(2-ethylhexanoate), catechol dibenzoate, 4-vinylcatechol diacetate, 4-vinylcatechol dipropionate, 4-vinylcatechol di-n-butyrate, 4-vinylcatechol diisobutyrate, 4-vinylcatechol di-n-pentanoate, 4-vinylcatechol di-n-hexanoate, 4-vinylcatechol di-n-octanoate, 4-vinylcatechol diisooctanoate, 4-vinylcatechol bis(2-methylheptanoate), 4-vinylcatechol bis(2-ethylhexanoate), 4-vinylcatechol Allyl 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-pentanoate, 4-allyl-6-methylcatechol di-n-hexanoate, 4-allyl-6-methylcatechol di-n-octanoate, 4-allyl-6-methylcatechol diisooctanoate, 4-allyl 4-allyl-6-methylcatechol bis(2-methylheptanoate), 4-allyl-6-methylcatechol bis(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-butylate, 4-allyl-6-isobutylcatechol diisobutyrate, 4-allyl-6-isobutylcatechol di-n-pentanoate,4-Allyl-6-isobutylcatechol di-n-hexanoate, 4-allyl-6-isobutylcatechol di-n-octanoate, 4-allyl-6-isobutylcatechol diisooctanoate, 4-allyl-6-isobutylcatechol bis(2-methylheptanoate), 4-allyl-6-isobutylcatechol bis(2-ethylhexanoate), 4-allyl-6-isobutylcatechol dibenzoate, 4-allyl-6-chlorocatechol dicarboxylate, 4-allyl-6-chlorocatechol diacetate, 4-allyl-6-chloro ... 4-allyl-6-chlorocatechol dipropionate, 4-allyl-6-chlorocatechol di-n-butyrate, 4-allyl-6-chlorocatechol diisobutyrate, 4-allyl-6-chlorocatechol di-n-pentanoate, 4-allyl-6-chlorocatechol di-n-hexanoate, 4-allyl-6-chlorocatechol di-n-octanoate, 4-allyl-6-chlorocatechol diisooctanoate, 4-allyl-6-chlorocatechol bis(2-methylheptanoate), 4-allyl-6-chlorocatechol bis(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-n-pentanoate, 4-allyl-6-fluorocatechol di-n-hexanoate, 4-allyl-6-fluorocatechol di-n-octanoate, 4- Allyl-6-fluorocatechol diisooctanoate, 4-allyl-6-fluorocatechol bis(2-methylheptanoate), 4-allyl-6-fluorocatechol bis(2-ethylhexanoate), 4-allyl-6-fluorocatechol dibenzoate, 4-allyl-6-bromocatechol dicarboxylate, 4-allyl-6-bromocatechol diacetate, 4-allyl-6-bromocatechol dipropionate, 4-allyl-6-bromocatechol di-n-butylate, 4-allyl-6-bromocatechol diisobutyrate,4-Allyl-6-bromocatechol di-n-pentanoate, 4-allyl-6-bromocatechol di-n-hexanoate, 4-allyl-6-bromocatechol di-n-octanoate, 4-allyl-6-bromocatechol diisooctanoate, 4-allyl-6-bromocatechol bis(2-methylheptanoate), 4-allyl-6-bromocatechol bis(2-ethylhexanoate), 4-allyl-6-bromocatechol dibenzoate, 4-(1-chloroallyl)catechol dicarboxylate, 4-(1-chloroallyl)catechol diisooctanoate, ...methylheptanoate), 4-allyl-6-bromocatechol bis(2-ethylhexanoate), 4-allyl-6-bromocatechol dibenzoate, 4-(1-chloroallyl)catechol dicarboxylate, 4-(1-chloroallyl)catechol diisooctanoate, 4-allyl-6-bromocatechol diisooctanoate, 4-allyl-6-bromocatechol bis(2-methylheptanoate), 4-allyl-6-bromocatechol bis(2-ethylhexanoate), 4-allyl-6-bromocatechol diisooctanoate, 4-allyl-6-bromocatechol diisooctanoate, 4-allyl-6-bromocatechol bis(2-ethylhexanoate), 4-allyl-6-bromocatechol diisooctanoate, 4-allyl-6-bromocatechol diisooctanoate, 4-ally 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-pentanoate, 4-(1-chloroallyl)catechol di-n-hexanoate, 4-(1-chloroallyl)catechol di-n-octanoate, 4-(1-chloroallyl)catechol diisooctanoate, 4-(1-chloroallyl)catechol bis(2-methylheptanoate), 4-( 1-chloroallyl)catechol bis(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-pentanoate, 4-allyl-6-hydroxycatechol di-n 4-allyl-6-hydroxycatechol bis(2-methylhexanoate), 4-allyl-6-hydroxycatechol bis(2-ethylhexanoate), 4-allyl-6-hydroxycatechol dibenzoate, 4-allylcatechol diacrylate, and 4-allylcatechol dimethacrylate.

4. 2. The organic polymer carrier according to claim 1, wherein the unsaturated catechol ester monomer is present in an amount of 20 to 70% by mass relative to 100% by mass of the organic polymer carrier.

5. A method for producing the organic polymer support according to any one of claims 1 to 4, comprising: a step of copolymerizing the divinylbenzene, the unsaturated catechol ester monomer, and the additional monomer as raw materials to obtain the organic polymer carrier; The mass ratio of the additional monomer to divinylbenzene is 0-1:1, and the mass ratio of the unsaturated catechol ester monomer to divinylbenzene is 0.2-2:

1.

6. The organic polymer support is produced by dispersion polymerization, precipitation polymerization, suspension polymerization, or emulsion polymerization; 6. The method of claim 5, wherein the dispersion polymerization method comprises adding divinylbenzene, an unsaturated catechol ester monomer, and an additional monomer to a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, and then reacting at 50-80°C for 5-12 hours to obtain the organic polymer carrier.

7. The method of claim 5, wherein the additional monomer comprises one or a combination of two or more of styrene, alkyl-substituted styrene, chloromethyl-substituted styrene, methacrylic acid, methacrylate, and hydroxyalkyl methacrylate.

8. The dispersion solvent is C １ -C ４ the alcohol, water, and an additional solvent, wherein the additional solvent comprises tetrahydrofuran and / or a fatty acid ester; Said C １ -C ４ The weight ratio of alcohol to water is 5-15:1, and the additional solvent and C １ -C ４ The method of claim 6, wherein the mass ratio of the alcohol to the hydroxybenzoate is 0-2:

1.

9. Said C １ -C ４ The method according to claim 8, wherein the alcohol comprises one or a combination of two or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol.

10. The method according to claim 8 , wherein the fatty acid ester comprises ethyl acetate and / or butyl acetate.

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

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

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

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

100.

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

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

100.

17. 6. The method of claim 5, wherein the divinylbenzene is pretreated divinylbenzene, and the pretreatment is for removing a polymerization inhibitor.

18. A Z-N catalyst, The raw material composition includes, relative to 100 mass% of the Z-N catalyst, 60-85 wt% of an organic polymer support, 1-5 wt% of a magnesium compound as magnesium element, 1-5 wt% of a titanium compound as titanium element, and 0-5 wt% of an internal electron donor; A Z-N catalyst, wherein the organic polymer support is the organic polymer support according to any one of claims 1 to 4.

19. 19. The Z-N catalyst according to claim 18, wherein the content of said organic polymer support is 65-80 wt%, the content of magnesium element is 2-4 wt%, and the content of titanium element is 2-4 wt%.

20. The magnesium compound is RMgX or R'MgR'', and R, R', and R'' are each independently C １ -C ８ 19. The Z-N catalyst of claim 18, wherein X is selected from the group consisting of alkyl groups and derivatives thereof, aryl groups and derivatives thereof, and alkoxy groups and derivatives thereof, and wherein X is fluorine, chlorine, bromine, or iodine.

21. 21. The Z-N catalyst of claim 20, wherein R, R', and R'' are each independently selected from a methyl group, an ethyl group, a propyl group, a butyl group, an alkoxy group, a phenyl group, and a substituted phenyl group.

22. 21. The Z-N catalyst of claim 20, wherein 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.

23. 23. The Z-N catalyst of claim 22, wherein the magnesium compound comprises one or a combination of two or more of methyl magnesium chloride, n-butyl magnesium chloride, isobutyl magnesium chloride, tert-butyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-butyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, tert-butyl magnesium iodide, benzyl magnesium iodide, n-butyl magnesium iodide, methyl magnesium fluoride, tert-butyl magnesium fluoride, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, and ethoxy magnesium chloride.

24. 19. The Z-N catalyst of claim 18, wherein the titanium compound is titanium tetrachloride.

25. The Z-N catalyst according to claim 18, wherein 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.

26. 26. The Z-N catalyst of claim 25, wherein the internal electron donor comprises one or a combination of two or more of diisobutyl phthalate, di-n-butyl phthalate, 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropyl succinate, 3-methyl-5-tert-butyl-1,2-phenylenedibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dimethyl ether.

27. A method for producing a Z-N catalyst according to any one of claims 18 to 26, comprising: The method includes the steps of: adding the organic polymer support to an inert solvent under anhydrous and oxygen-free conditions; adding the magnesium compound; reacting at 0°C-50°C for 15-120 minutes; filtering off the unreacted magnesium compound; adding an inert solvent and titanium tetrachloride; reacting at 0°C-120°C for 15-180 minutes; adding the internal electron donor; reacting at 50°C-120°C for 15-180 minutes; and finally washing with an inert solvent to obtain the Z-N catalyst.

28. A Z-N catalyst system comprising a Z-N catalyst, an external electron donor, and a co-catalyst, A Z-N catalyst system, wherein the Z-N catalyst is the Z-N catalyst of any one of claims 18 to 26.

29. 30. The Z-N catalyst system of claim 28, wherein the external electron donor comprises a silane-based external electron donor.

30. 30. The Z-N catalyst system of claim 29, wherein the silane-based external electron donor comprises one or a combination of two or more of cyclohexylmethyldimethoxysilane, dicyclopentenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, and tetraethoxysilane.

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

32. The co-catalyst comprises an alkyl aluminum compound, and the alkyl aluminum compound is Al(R'") ３ and R''' is C １ -C ６ 29. The Z-N catalyst system of claim 28, wherein the alkyl group is:

33. 33. The Z-N catalyst system of claim 32, wherein R''' is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl groups.

34. 34. The Z-N catalyst system of claim 33, wherein the co-catalyst is triethylaluminum.

35. 33. The Z-N catalyst system of claim 32, wherein the molar ratio of aluminum in said alkylaluminum compound to titanium in said Z-N catalyst is 10-500.

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

37. 37. The use according to claim 36, wherein the olefin polymerization is the homopolymerization of propylene, the copolymerization of propylene with ethylene, or the copolymerization of propylene with an α-olefin.

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

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

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

41. The solvent for the slurry polymerization is C ５ -C １０ 40. The use according to claim 39, wherein the alkane is

42. 42. The use of claim 41, wherein the slurry polymerization solvent is hexane.

43. The use according to claim 39, wherein the bulk polymerization is carried out at a reaction pressure of 2.8-4.0 MPa and a reaction temperature of 68°C-72°C.

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