WO2022048630A1 - 用于烯烃聚合的催化剂的载体及其应用和用于烯烃聚合的催化剂及其应用以及烯烃聚合方法 - Google Patents

用于烯烃聚合的催化剂的载体及其应用和用于烯烃聚合的催化剂及其应用以及烯烃聚合方法 Download PDF

Info

Publication number
WO2022048630A1
WO2022048630A1 PCT/CN2021/116417 CN2021116417W WO2022048630A1 WO 2022048630 A1 WO2022048630 A1 WO 2022048630A1 CN 2021116417 W CN2021116417 W CN 2021116417W WO 2022048630 A1 WO2022048630 A1 WO 2022048630A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
formula
carrier
olefin polymerization
alkyl group
Prior art date
Application number
PCT/CN2021/116417
Other languages
English (en)
French (fr)
Inventor
凌永泰
周俊领
夏先知
刘月祥
李威莅
刘涛
任春红
赵瑾
高富堂
陈龙
谭扬
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院 filed Critical 中国石油化工股份有限公司
Priority to EP21863692.6A priority Critical patent/EP4209516A4/en
Priority to US18/044,188 priority patent/US20230406965A1/en
Priority to KR1020237011167A priority patent/KR20230065285A/ko
Priority to JP2023514982A priority patent/JP2023540543A/ja
Priority to BR112023004120A priority patent/BR112023004120A2/pt
Publication of WO2022048630A1 publication Critical patent/WO2022048630A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/68—Preparation of metal alcoholates
    • C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/08—Ethanol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/28—Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/34—Halogenated alcohols
    • C07C31/36—Halogenated alcohols the halogen not being fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/005—Friedel-Crafts catalysts in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size

Definitions

  • the invention relates to the field of olefin polymerization catalysts, in particular to a catalyst spherical carrier for olefin polymerization, a method for preparing a catalyst spherical carrier for olefin polymerization, a spherical carrier prepared by the method, and the spherical carrier in Use in the preparation of a catalyst for olefin polymerization, a catalyst containing the spherical support, and use of the catalyst in catalyzing olefin polymerization.
  • Ziegler-Natta catalyst prepared from magnesium chloride alcoholate especially the catalyst prepared from spherical magnesium chloride alcoholate, when used for olefin polymerization, the catalyst performance is usually significantly better than that of other supported catalysts . Therefore, most of the catalysts currently used for olefin polymerization are prepared by supporting titanium halide on magnesium chloride alcoholate.
  • magnesium chloride alcoholates are prepared by quenching and solidifying high temperature alcoholate melts at low temperature.
  • Such a technology not only consumes a large amount of energy, the preparation process is complicated, and multiple reactors are required for joint preparation, but also the particle size distribution of the prepared alcoholate is wider.
  • CN102040683A discloses a method for preparing a carrier by reacting a magnesium halide alcoholate with an ethylene oxide compound.
  • a method for preparing a carrier by reacting a magnesium halide alcoholate with an ethylene oxide compound.
  • using this method to prepare a catalyst carrier often requires adding a surfactant, and the preparation process is unstable, the carrier is prone to sticking, and the carrier molding effect is not good.
  • the purpose of the present invention is to overcome the defects in the prior art that the olefin polymerization catalyst carrier has poor particle morphology, cannot prepare a small particle size carrier, and the catalyst prepared from the carrier is used for olefin polymerization. .
  • the inventors of the present invention have unexpectedly found that, in the process of preparing the catalyst carrier, an alcohol compound and a halohydrin compound are added to form a fluidized mixture, and a catalyst carrier with a novel composition and good particle shape can be obtained by spray drying,
  • the catalyst carrier basically does not have irregular particles; a carrier with a small particle size can be prepared, the range of the particle size that can be prepared for the carrier is widened, and the carrier can be directly synthesized without using a surfactant and an inert solvent during the preparation process. , the preparation process is stable; further, when the catalyst prepared by the carrier is used for olefin polymerization, the sensitivity of hydrogen adjustment is high. Based on the above findings, the inventors have completed the present invention.
  • An object of the present invention is to provide a catalyst spherical carrier for olefin polymerization, the carrier comprising at least one magnesium-containing compound having a structure represented by formula (1);
  • R 1 is a C 1-10 alkyl group
  • R 2 and R 3 are each independently selected from H, C 1-10 alkyl and C 1-10 alkyl substituted with 1-10 halogen atoms;
  • R 4 is selected from C 1-10 alkyl substituted by at least one halogen atom and C 6-20 aryl substituted by at least one halogen atom;
  • R 5 is C 1-5 alkyl
  • X is selected from fluorine, chlorine, bromine and iodine
  • n is 0.1-1.9
  • m+n 2; 0 ⁇ q ⁇ 0.2; 0 ⁇ a ⁇ 0.1.
  • Another object of the present invention is to provide a method for preparing a catalyst spherical carrier for olefin polymerization, the method comprising:
  • component B contains an oxirane compound having a structure represented by formula (2);
  • component C contains a halohydrin with a general formula of R 4 OH and a second alcohol with a general formula of R 5 OH compound;
  • R 1 is a C 1-10 alkyl group
  • R 2 and R 3 are each independently selected from H, a C 1-10 alkyl group, and a C 1-10 alkyl group substituted with 1-10 halogen atoms;
  • R 4 is selected from C 1-10 alkyl substituted by at least one halogen atom and C 6-20 aryl substituted by at least one halogen atom;
  • R 5 is a C 1-5 alkyl group
  • X is selected from fluorine, chlorine, bromine and iodine
  • Y is selected from fluorine, chlorine, bromine, iodine, C 1-6 alkyl, C 1-6 alkoxy, C 6-14 aryl and C 6-14 aryloxy groups;
  • the amount of the component A, the component B and the component C is such that the obtained spherical carrier contains the magnesium-containing compound having the structure shown in formula (1):
  • n 0.1-1.9
  • m+n 2; 0 ⁇ q ⁇ 0.2; 0 ⁇ a ⁇ 0.1;
  • step (3) relative to 1 mol of the magnesium halide, the amount of the halohydrin is 0.05-6.5 mol, and the amount of the second alcohol compound is 5-100 mol.
  • Another object of the present invention is to provide a spherical carrier prepared by the aforementioned method.
  • Another object of the present invention is to provide the application of the spherical carrier in the preparation of a catalyst for olefin polymerization.
  • Still another object of the present invention is to provide a catalyst containing the aforementioned spherical carrier.
  • Yet another object of the present invention is to provide the use of the aforementioned catalyst in catalyzing olefin polymerization.
  • the present invention has at least the following advantages:
  • the particle shape of the spherical carrier of the catalyst for olefin polymerization provided by the present invention is good, and there are basically no irregular particles; the method provided by the present invention does not need to add surfactants or solvents, the preparation process is stable, and it can be prepared
  • the carrier with very small particle size greatly broadens the particle size range of the carrier that can be prepared;
  • the catalyst prepared by the spherical carrier When the catalyst prepared by the spherical carrier is used for olefin polymerization, such as propylene polymerization, it has good polymerization activity and high hydrogen modulation sensitivity, and has great industrial application prospects.
  • FIG. 1 is an electron micrograph of the spherical support from Example 1.
  • FIG. 1 is an electron micrograph of the spherical support from Example 1.
  • alkyl refers to an paraffinic hydrocarbon group, which may be straight-chain, branched, or cyclic, that can be derived from an alkane by removing one or more hydrogens from a chemical formula.
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, Isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl Base et al.
  • aryl refers to an aromatic hydrocarbon group that can be derived from an aromatic hydrocarbon by removing one or more hydrogens from a chemical formula.
  • aryl groups include, but are not limited to, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, naphthyl, benzyl, phenethyl, and the like.
  • halogen refers to fluorine, chlorine, bromine or iodine.
  • C 1-10 alkyl group substituted with 1-10 halogen atoms refers to a group formed by replacing 1-10 hydrogen atoms in the C 1-10 alkyl group with halogen atoms, which can be Multiple hydrogen atoms on the same carbon atom are replaced by halogen atoms, or hydrogen atoms on different carbon atoms are replaced; when multiple halogen atoms are substituted, the halogen atoms may be the same or different.
  • Examples include, but are not limited to -CF3 , -CH2CF3 , -CH2CF2H , -CF2CF3 , -CF2CH2CF2H , -CH2CF2CF2H , -CH2CH 2 CH 2 Cl, -CH 2 CH 2 CH 2 Br, etc.
  • C 1-10 alkyl substituted with at least one (or at least two) halogen atoms and “C 6-20 alkyl substituted with at least one (or at least two) halogen atoms” are used herein.
  • Aryl refers to a group formed by substituting at least one (or at least two) hydrogen atoms in a C 1-10 alkyl group and a C 6-20 aryl group with a halogen atom, respectively.
  • the hydrogen atom may be a hydrogen atom on one carbon or a hydrogen atom on a different carbon, and the halogen atoms may be the same or different.
  • C 1-10 alkyl substituted with at least one halogen atom examples include, but are not limited to, CF 3 , -CH 2 CF 3 , -CH 2 CF 2 H, -CF 2 CF 3 , -CF 2 CH 2 CF 2 H , -CH 2 CF 2 CF 2 H, -CH 2 CH 2 CH 2 Cl, -CH 2 CH 2 CH 2 Br, etc.
  • C 6-20 aryl groups substituted by at least one halogen atom include, but are not limited to, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-bromophenyl, 2,3- , 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dibromophenyl, 4-trifluoromethylphenyl.
  • the present invention provides a catalyst spherical carrier for olefin polymerization, the carrier comprising at least one magnesium-containing compound having the structure represented by formula (1);
  • R 1 is C 1-10 linear, branched or cyclic alkyl
  • R 2 and R 3 are each independently selected from H, C 1-10 linear or branched alkyl and C 1-10 linear or branched alkyl substituted with 1-10 halogen atoms ;
  • R 4 is selected from C 1-10 linear, branched or cyclic alkyl substituted by at least one halogen atom and C 6-20 aryl substituted by at least one halogen atom;
  • R 5 is C 1-5 alkyl
  • X is selected from fluorine, chlorine, bromine and iodine
  • n is 0.1-1.9
  • m+n 2; 0 ⁇ q ⁇ 0.2; 0 ⁇ a ⁇ 0.1.
  • the carrier of the present invention consists essentially of the at least one magnesium-containing compound having the structure represented by formula (1).
  • the carrier of the present invention consists of the at least one magnesium-containing compound having the structure represented by formula (1).
  • R 1 is a C 1-8 linear, branched or cyclic alkyl group; more preferably, R 1 is a C 1-6 linear, branched or cyclic alkyl group .
  • R 2 and R 3 are each independently selected from H, C 1-5 straight or branched chain alkyl and C 1-5 straight or branched chain substituted with 1-10 halogen atoms the alkyl group.
  • R 4 is selected from C 1-10 linear, branched or cyclic alkyl substituted by at least two halogen atoms and C 6-20 aryl substituted by at least two halogen atoms, and
  • the halogen atom is preferably at least one selected from a chlorine atom, a bromine atom and an iodine atom.
  • R 5 is a C 1-2 alkyl group.
  • X is selected from chlorine and bromine.
  • m is 0.3-1.7, more preferably m is 0.6-1.4, still more preferably m is 0.8-1.2.
  • n is 0.3-1.7, more preferably n is 0.6-1.4, still more preferably n is 0.8-1.2.
  • the spherical carrier has an average particle diameter of 2-100 microns and a particle size distribution of less than 2. More preferably, the spherical carrier has an average particle diameter of 2-19 microns and a particle size distribution of 0.6-1.6.
  • the spherical carrier has an average particle diameter of 2-10 microns and a particle size distribution of 0.6 -1.
  • the average particle diameter refers to D50.
  • the size of the particle size distribution is defined as (D90-D10)/D50.
  • the average particle diameter and particle size distribution of the catalyst carrier are measured using a laser particle size analyzer such as a Master Sizer 2000 laser particle size analyzer (manufactured by Malvern Instruments Ltd).
  • a laser particle size analyzer such as a Master Sizer 2000 laser particle size analyzer (manufactured by Malvern Instruments Ltd).
  • hexane can be used as an inert dispersion medium in the test.
  • the present invention provides a method for preparing a catalyst spherical carrier for olefin polymerization, the method comprising:
  • component B contains an oxirane compound having a structure represented by formula (2);
  • component C contains a halohydrin with a general formula of R 4 OH and a second alcohol with a general formula of R 5 OH compound;
  • R 1 is a C 1-10 linear, branched or cyclic alkyl group
  • R 2 and R 3 are each independently selected from H, C 1-10 straight or branched chain alkyl, and C 1-10 straight chain or C 1-10 substituted with 1-10 halogen atoms. branched alkyl;
  • R 4 is selected from C 1-10 linear, branched or cyclic alkyl groups substituted with at least one halogen atom and C 6-20 aryl groups substituted with at least one halogen atom ;
  • R 5 is a C 1-5 alkyl group
  • X is selected from fluorine, chlorine, bromine and iodine
  • Y is selected from fluorine, chlorine, bromine, iodine, C 1-6 linear or branched alkyl, C 1-6 linear or branched alkoxy, C 6-14 aryl and C 6-14 aryloxy;
  • the component A, the component B and the component C are used in amounts such that the obtained spherical carrier contains the magnesium-containing compound having the structure represented by the formula (1), substantially composed of the
  • the magnesium-containing compound of the structure is composed of or consists of a magnesium-containing compound having the structure represented by the formula (1):
  • step (3) relative to 1 mol of the magnesium halide, the amount of the halohydrin is 0.05-6.5 mol, and the amount of the second alcohol compound is 5-100 mol.
  • R 1 , R 2 , R 3 , R 4 and R 5 groups are the same as those defined in the first aspect of the present invention.
  • X is selected from chlorine and bromine
  • Y is selected from chlorine, bromine, C 1-5 linear or branched alkyl, C 1-5 alkyl Linear or branched alkoxy, C 6-10 aryl and C 6-10 aryloxy.
  • the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride, more preferably magnesium chloride.
  • R 1 is a C 1-8 linear, branched or cyclic alkyl group.
  • the first alcohol compound is selected from ethanol, propanol, isopropanol, n-butanol, isobutanol, amyl alcohol, isoamyl alcohol, n-hexanol, n-octanol and 2-ethylhexanol at least one of.
  • R 2 and R 3 are each independently selected from H, C 1-5 straight-chain or branched-chain alkyl, and C 1-10 A C 1-5 straight-chain or branched-chain alkyl group substituted with a halogen atom.
  • the ethylene oxide compound is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, epibromohydrin and epibromobutane at least one of.
  • the halohydrin may be a monohalohydrin or a polyhalohydrin, preferably a chlorohydrin, a bromohydrin or an iodohydrin, such as 2,2,2-trichloroethanol , 2,2-dichloroethanol, 2-chloroethanol, 3-chloro-1-propanol, 6-chloro-1-hexanol, 3-bromo-1-propanol, 5-chloro-1-pentanol, 4-chloro-1-butanol, 2-chlorocyclohexanol, 1,2-dichloroethanol, 1,3-dichloropropanol, 1,4-dichlorobutanol or 2-iodoethanol, etc.
  • a chlorohydrin preferably a bromohydrin or an iodohydrin
  • an iodohydrin such as 2,2,2-trichloroethanol , 2,2-dichloroethanol, 2-chloroethanol, 3-chloro-1-
  • R 4 is selected from C 1-10 linear, branched or cyclic alkyl substituted with at least two halogen atoms and a A C 6-20 aryl group substituted with at least two halogen atoms, and the halogen atom is selected from at least one of a chlorine atom, a bromine atom and an iodine atom.
  • the halohydrin is selected from 2,2,2-trichloroethanol, 2,2-dichloroethanol, 1,2-dichloroethanol, 1,3-dichloropropanol, 1,4-dichloroethanol At least one of chlorobutanol.
  • the second alcohol compound is at least one of C 1-5 alcohol compounds, such as ethanol, methanol, n-propanol, isopropanol, n-butanol or isobutanol.
  • R 5 is a C 1-2 alkyl group, that is, the second alcohol compound is methanol and/or ethanol.
  • the amount of the first alcohol compound is 1-30 mol
  • the amount of the ethylene oxide compound is 1-10 mol
  • the amount of the halogenated alcohol is 1-10 mol.
  • the amount of the compound is 0.05-6.5mol
  • the amount of the second alcohol compound is 5-100mol.
  • the amount of the first alcohol compound is 6-22 mol
  • the amount of the ethylene oxide compound is 2-6 mol
  • the amount of the halogenated alcohol is 1- 5mol
  • the amount of the second alcohol compound is 8-80mol, more preferably 31-50mol.
  • the trace amount of water carried in the above-mentioned reactants will also participate in the reaction of forming the spherical carrier. Therefore, the prepared spherical carrier may contain trace amounts of water from the reaction raw materials and the reaction medium. Water should not be construed as a limitation of the present invention by those skilled in the art.
  • the first contact is performed under stirring conditions, and the conditions for the first contact include: the temperature is 40-130°C, preferably 50-130°C, more preferably 80-120°C , the time is 0.3-24h, preferably 0.5-10h, more preferably 0.5-5h.
  • the conditions of the first contact include: a temperature of 80-100° C. and a time of 0.5-3 h.
  • the present invention does not specifically limit the specific operation method for applying the shearing force, which can be performed by a method known to those skilled in the art.
  • it is carried out with low-speed shearing or high-speed shearing.
  • the stirring rate of the low-speed shearing is 400-800 rpm.
  • the high-speed shearing method is well known to those skilled in the art, for example, the high stirring speed disclosed in CN1330086A is used.
  • the operation of applying shearing force can also be performed with reference to the method disclosed in the following patent application, as disclosed in CN1580136A, the solution containing the liquid magnesium halide compound is rotated and dispersed in a supergravity bed (the speed of rotation is 100-3000rpm);
  • CN1463990A discloses that the solution containing liquid magnesium halide adduct is output in an emulsifier at a speed of 1500-8000 rpm;
  • US6020279A discloses applying shear force to the solution containing liquid magnesium halide adduct by spraying.
  • the conditions for the second contact include: a temperature of 30-130° C., preferably 50-120° C., and a time of 10-180 min, preferably 20-60 min;
  • the conditions of the second contact include: a temperature of 80-100° C. and a time of 20-50 min.
  • step (3) it further comprises: washing the second product with an inert solvent and then performing the third contact with each component in component C, preferably , the inert solvent is selected from at least one of pentane, hexane, heptane, petroleum ether and gasoline.
  • the inert solvent is selected from at least one of pentane, hexane, heptane, petroleum ether and gasoline.
  • the present invention does not specifically limit the specific conditions of the third contact in step (3), as long as the component C and the second product can be fully contacted to form a fluid, but in order to obtain better
  • the performance of the catalyst carrier preferably, in step (3), the conditions of the third contact include: under stirring conditions, the temperature is 0-120 ° C, and the time is 0.5-6 h.
  • the present invention has no particular limitation on the specific manner of the third contact in step (3).
  • Both the halohydrin and the second alcohol compound can be mixed and contacted with the second component simultaneously, or The halohydrin and the second alcohol compound can be sequentially contacted with the second component in any order.
  • the conditions of the spray drying can adopt existing conditions capable of forming a catalyst carrier for olefin polymerization.
  • the spray drying is carried out in a sprayer with an atomizing nozzle, the atomizing nozzle contains a material conduit and a nozzle tip, through which the third product is led to the Evaporation and solidification are carried out in the nozzle head and sprayed through the nozzle head into the tower body containing the inert medium of the sprayer.
  • the temperature of the third product in the material conduit is between 0°C and 80°C, and the temperature of the third product in the nozzle head is 80-180°C; more preferably the first The temperature of the tertiary product in the nozzle tip was 120-180°C.
  • the conditions of the spray drying include: the temperature is 60-200°C, more preferably 90-150°C.
  • the temperature of the spray drying refers to the temperature of the inert medium in the sprayer.
  • the inert medium may include a protective gas medium and/or an inert liquid medium
  • the type of the protective gas medium is not particularly limited, for example, it may be nitrogen or an inert gas medium such as helium, or is other suitable gas such as carbon dioxide, etc.
  • the inert liquid medium is a variety of liquid media commonly used in the field that do not chemically interact with reactants and reaction products, preferably the inert liquid medium is silicone oil and/or inert liquid hydrocarbon solvents ; More preferably, the inert liquid medium is selected from at least one of kerosene, paraffin oil, petrolatum oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil species, more preferably white oil.
  • the dosage of the inert liquid medium in the sprayer can be selected according to the dosage of magnesium halide whose general formula is MgXY, preferably 0.8-10L/mol magnesium halide, more preferably 2-8L/mol magnesium halide .
  • the method described in the second aspect of the present invention also includes post-processing means such as solid-liquid separation, washing, drying, etc. conventional in the art, which are not particularly limited in the present invention.
  • the solid-liquid separation can adopt various existing methods that can realize the separation of solid phase and liquid phase, such as suction filtration, pressure filtration or centrifugal separation, etc.
  • the solid-liquid separation method is pressure filtration method.
  • the present invention does not specifically limit the conditions of the pressure filtration, and it is subject to the separation of the solid phase and the liquid phase as fully as possible.
  • the washing can be performed by a method known to those skilled in the art to wash the obtained solid phase product, for example, an inert hydrocarbon solvent (such as pentane, hexane, heptane, petroleum ether and gasoline) can be used to wash the obtained solid phase product. wash.
  • an inert hydrocarbon solvent such as pentane, hexane, heptane, petroleum ether and gasoline
  • the specific conditions of the drying are not particularly limited in the present invention.
  • the drying temperature can be 20-70° C.
  • the drying time can be 0.5-10 h
  • the drying can be carried out under normal pressure or reduced pressure. .
  • the inventors found that by using specific types and amounts of alcohol compounds and halohydrin compounds to coordinate with components such as magnesium halide and ethylene oxide compounds, and matching the spray drying method, it is possible to obtain particles with a novel composition and good quality.
  • the catalyst carrier has a shape, and the catalyst carrier basically has no irregular particles; and the preparation process does not need to add a surfactant, and the process is stable.
  • the method provided by the present invention can prepare a carrier with a very small particle size, which greatly expands the size range of the carrier that can be prepared; and when the catalyst prepared from the carrier is used for olefin polymerization, the hydrogen modulation sensitivity is high .
  • the present invention provides a spherical carrier prepared by the method described in the aforementioned second aspect.
  • the catalyst spherical carrier prepared by the method of the present invention has a good particle shape and basically does not appear irregular particles.
  • the present invention provides the use of the spherical carrier described in the first aspect or the third aspect in the preparation of a catalyst for olefin polymerization.
  • the present invention provides a catalyst comprising the spherical carrier described in the first aspect or the third aspect.
  • the composition of the catalyst is not particularly limited, and may be the composition of the catalyst for olefin polymerization existing in the art, but in order to obtain a catalyst suitable for olefin polymerization, especially propylene polymerization, preferably , the catalyst contains the carrier, a titanium halide compound and an electron donor compound.
  • the titanium halide is selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetra-n-butoxide titanium, tetraethoxide titanium, monochlorotri-n-butoxide titanium, dichlorodi-n-butoxide At least one of butoxytitanium, trichloromono-n-butoxytitanium, monochlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium and titanium trichloride.
  • the electron donor compound is selected from at least one of phthalates such as diisobutyl phthalate, carboxylic acid glycols, phosphates, ethers such as 1,3-diether.
  • phthalates such as diisobutyl phthalate
  • carboxylic acid glycols such as phosphates
  • ethers such as 1,3-diether.
  • the content of each component in the catalyst is not particularly limited in the present invention, and those skilled in the art can make reasonable adjustment and design according to actual needs.
  • an olefin polymerization catalyst is prepared by treating the spherical support with a titanium halide compound, optionally in an inert liquid medium, optionally introducing an internal electron donor into the support before, during, or after the treatment body compound.
  • a titanium halide compound optionally in an inert liquid medium
  • an internal electron donor optionally introduced into the support before, during, or after the treatment body compound.
  • the present invention provides the application of the catalyst described in the fifth aspect in catalyzing olefin polymerization.
  • the specific operation method of the application is not particularly limited in the present invention, and those skilled in the art can use the conventional method for olefin polymerization in the art to operate, and the present invention will not be described in detail here.
  • the present invention enumerates a specific operation process hereinafter, which should not be construed as a limitation of the present invention by those skilled in the art.
  • the present invention provides an olefin polymerization process comprising contacting at least one C2-C10 olefin monomer and optional comonomer with the catalyst under polymerizable conditions to form an olefin polymerization material, and recovery of the olefin polymer.
  • the catalyst prepared from the spherical carrier provided by the present invention is used for olefin polymerization, especially propylene polymerization, and has good polymerization activity, basically no occurrence of irregular materials, and significantly higher sensitivity to hydrogen modulation than the prior art, and is extremely industrial. application prospects.
  • the raw materials used are all commercially available products, and are used in the form as received.
  • 1,3-Dichloropropanol was purchased from Bailingwei Company;
  • Diisobutyl phthalate was purchased from Bailingwei Company;
  • Titanium tetrachloride was purchased from Bailingwei Company;
  • Triethylaluminum was purchased from Bailingwei Company;
  • Methylcyclohexyldimethoxysilane was purchased from Bailingwei Company.
  • the average particle diameter and particle size distribution of the catalyst carrier The Masters Sizer 2000 particle size analyzer manufactured by Malvern Instruments was used for measurement, and hexane was used as the dispersion medium;
  • the structure and composition of the catalyst carrier The AVANCE 300 nuclear magnetic resonance spectrometer from Bruker, Switzerland was used to test the carrier, and the PY-2020iD cracker from Fronteerlab and the TraceGC Ultra chromatograph from Thermo Fisher were used. It is obtained by testing the carrier with DSQ II mass spectrometer;
  • Catalyst activity Evaluate by the ratio of the weight of the product obtained after polymerization to the weight of the catalyst dosage;
  • Melt flow rate index of polyolefin powder measured according to ISO1133, 230° C., under a load of 2.16 kg.
  • the third product was sprayed into the circulating nitrogen at 100° C. in the sprayer tower for spray drying, and the third product was in the material conduit.
  • the temperature was 15°C and the temperature in the nozzle head was 120°C, obtaining spherical carriers Z1.
  • the average particle diameter (D50) of the catalyst spherical carrier Z1 was 4 microns, and the particle size distribution ((D90-D10)/D50) was 0.9.
  • Figure 1 shows a photomicrograph of the spherical carrier Z1. It can be seen from FIG. 1 that the particle shape of the catalyst spherical carrier Z1 is relatively regular, the surface is smooth, and basically spherical, the particle size distribution is relatively concentrated, and there are basically no irregular particles.
  • the third product was sprayed into the circulating nitrogen at 100° C. in the sprayer tower for spray drying, and the third product was in the material conduit.
  • the temperature was 15°C, and the temperature in the nozzle tip was 120°C, resulting in a catalyst spherical carrier Z2.
  • the average particle diameter (D50) of the catalyst spherical carrier Z2 is 4 microns, and the particle size distribution ((D90-D10)/D50) is 0.8.
  • the particle shape of the spherical carrier Z2 for olefin polymerization is relatively regular, the surface is smooth, and basically spherical, the particle size distribution is relatively concentrated, and there are basically no irregular particles.
  • the third product was sprayed into the circulating nitrogen at 100°C in the sprayer tower using a sprayer B-290 containing a nozzle head and a material conduit, and the temperature of the third product in the material conduit was 15 °C, the temperature in the nozzle head was 120 °C, resulting in a spherical carrier Z3.
  • the catalyst spherical carrier Z3 has an average particle diameter (D50) of 5 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
  • the particle shape of the catalyst spherical carrier Z3 is relatively regular, the surface is smooth, and basically spherical, the particle size distribution is relatively concentrated, and there are basically no irregular particles.
  • the third product was sprayed into the circulating nitrogen at 100° C. in the sprayer tower for spray drying, and the third product was in the material conduit.
  • the temperature was 20°C and the temperature in the nozzle tip was 120°C, resulting in catalyst spherical carrier Z4.
  • the average particle diameter (D50) of the catalyst spherical carrier Z4 is 5 microns, and the particle size distribution ((D90-D10)/D50) is 1.0.
  • the particle shape of the spherical carrier Z4 for olefin polymerization is relatively regular, the surface is smooth, and basically spherical, the particle size distribution is relatively concentrated, and there are basically no irregular particles.
  • the fluid mixture obtained in the step (1) is easy to precipitate, which is easy to cause the spray drying to be unable to proceed normally, and is easy to cause the blockage of the nozzle.
  • the average particle diameter (D50) of the catalyst carrier for olefin polymerization DZ1 was 15 microns, and the particle size distribution ((D90-D10)/D50) was 1.3.
  • the fluid mixture is sprayed into circulating nitrogen gas at 100°C using a sprayer containing a nozzle head and a material conduit, and the temperature of the third product in the material conduit is 15°C, and the temperature of the third product in the material conduit is 15°C.
  • the temperature in the head was 120°C, and the catalyst carrier DZ2 for olefin polymerization was obtained.
  • the average particle diameter (D50) of the catalyst carrier for olefin polymerization DZ2 was 3 microns, and the particle size distribution ((D90-D10)/D50) was 0.8.
  • the catalyst spherical carrier was prepared in the same manner as in Example 1, except that in step (3), the second alcohol compound was not used, only halohydrin (1,3-dichloropropanol) and The second product is fully mixed and stirred for the third contact, and the amount of the halohydrin used is the same as that in Example 1, to obtain a catalyst carrier DZ3.
  • the carrier was agglomerated, and subsequent operations could not be performed.
  • Test Example 1 The spherical carrier of the catalyst for olefin polymerization provided by the present invention was used to prepare a catalyst for olefin polymerization, and the prepared catalyst for olefin polymerization was used to prepare olefin.
  • the activity of the catalyst prepared in this test example is 36.1KgPP/g ⁇ Cat;
  • the bulk density of the obtained polypropylene powder was 0.41 g/cm 3 , and the melt flow rate index was 11.9 g/10 min.
  • the polypropylene powder had a good particle shape and basically did not have special-shaped materials, as shown in Table 1 for details.
  • Polypropylene was prepared in a manner similar to Test Example 1-1, except that in step (2), the volume of hydrogen used was different, and the rest were the same as in Test Example 1-1.
  • the activity of the catalyst prepared in this test example is 36.0KgPP/g ⁇ Cat;
  • the bulk density of the obtained polypropylene powder was 0.41 g/cm 3 , and the melt flow rate index was 45.8 g/10min.
  • the polypropylene powder had a good particle shape and basically did not have special-shaped materials, as shown in Table 1 for details.
  • the polypropylene was prepared in the same manner as in Test Example 1-1, except that in step (1), the type of catalyst carrier used was different, and the rest were the same as in Test Example 1-1.
  • the activity of the catalyst prepared in this test example is 37.6KgPP/g ⁇ Cat;
  • the bulk density of the obtained polypropylene powder was 0.41 g/cm 3 , and the melt flow rate index was 11.0 g/10 min.
  • the polypropylene powder had a good particle shape and basically did not have special-shaped materials, as shown in Table 1 for details.
  • the polypropylene was prepared in the same manner as in Test Example 2-1, except that in step (2), the volume of hydrogen used was different, and the rest were the same as in Test Example 2-1.
  • the activity of the catalyst prepared in this test example is 37.2KgPP/g ⁇ Cat;
  • the bulk density of the obtained polypropylene powder was 0.41 g/cm 3 , and the melt flow rate index was 41.2 g/10min.
  • the polypropylene powder had a good particle shape and basically did not have special-shaped materials, as shown in Table 1 for details.
  • the polypropylene was prepared in the same manner as in Test Example 1-1, except that in step (1), the type of catalyst carrier used was different, and the rest were the same as in Test Example 1-1.
  • the activity of the catalyst prepared in this test example is 38.5KgPP/g ⁇ Cat;
  • the bulk density of the obtained polypropylene powder was 0.41 g/cm 3 , and the melt flow rate index was 10.0 g/10 min.
  • the polypropylene powder had a good particle shape and basically did not have special-shaped materials, as shown in Table 1 for details.
  • Polypropylene was prepared in a similar manner to Test Example 3-1, except that in step (2), the volume of hydrogen used was different, and the rest were the same as in Test Example 3-1.
  • the activity of the catalyst prepared in this test example is 38.2KgPP/g ⁇ Cat;
  • the bulk density of the obtained polypropylene powder was 0.41 g/cm 3 , and the melt flow rate index was 39.0 g/10min.
  • the polypropylene powder had a good particle shape and basically did not have special-shaped materials, as shown in Table 1 for details.
  • the polypropylene was prepared in the same manner as in Test Example 1-1, except that in step (1), the type of catalyst carrier used was different, and the rest were the same as in Test Example 1-1.
  • the activity of the catalyst prepared in this test example is 34.8KgPP/g ⁇ Cat;
  • the bulk density of the obtained polypropylene powder was 0.37 g/cm 3 , and the melt flow rate index was 9.1 g/10 min, as shown in Table 1 for details.
  • the polypropylene was prepared in a manner similar to that of Test Example 1-1, except that in step (1), the type of catalyst carrier used was different, and the rest were the same as Test Example 1-1.
  • the activity of the catalyst prepared in this test example is 39.0KgPP/g ⁇ Cat;
  • the bulk density of the obtained polypropylene powder was 0.41 g/cm 3 , and the melt flow rate index was 9.5 g/10 min, as shown in Table 1 for details.
  • Polypropylene was prepared in a manner similar to that of Comparative Test Example 2-1, except that in step (2), the volume of hydrogen used was different, and the rest were the same as Comparative Test Example 2-1.
  • the activity of the catalyst prepared in this test example is 37.9KgPP/g ⁇ Cat;
  • the bulk density of the obtained polypropylene powder was 0.41 g/cm 3 , and the melt flow rate index was 37.5 g/10 min, as shown in Table 1 for details.
  • the particle shape of the olefin polymerization catalyst carrier prepared by the method of the present invention is good, and there are basically no irregular particles.
  • the method provided by the present invention can prepare a catalyst carrier with a smaller particle size, which greatly expands the particle size range of the carrier that can be prepared.
  • the catalyst prepared with the obtained carrier is used for the polymerization of olefin (especially propylene)
  • the catalyst has good activity, good shape of polypropylene powder particles, basically no anisotropic material, and high sensitivity to hydrogen modulation.
  • Comparative Example 2 can obtain a catalyst carrier with a smaller particle size
  • the catalyst prepared from the catalyst carrier prepared therefrom is used for the polymerization of olefins (especially propylene) During the reaction, the polymer melt index is smaller, and the corresponding hydrogen modulation sensitivity is lower.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种用于烯烃聚合的催化剂球形载体及其制备方法与应用和一种催化剂及其应用，该载体包含至少一种具有式（1）所示结构的含镁化合物。本发明的烯烃聚合催化剂球形载体的颗粒形态较好、基本不会出现异形粒子；本发明提供的方法能够制备粒径很小的载体，极大地扩展了载体的可制备粒径范围；以所得的载体制备的催化剂用于烯烃聚合时，聚合活性好、基本无异性料的出现，氢调敏感性好。

Description

用于烯烃聚合的催化剂的载体及其应用和用于烯烃聚合的催化剂及其应用以及烯烃聚合方法 技术领域
本发明涉及烯烃聚合催化剂领域，具体涉及一种用于烯烃聚合的催化剂球形载体、一种制备用于烯烃聚合的催化剂球形载体的方法、由所述方法制备得到的球形载体、所述球形载体在制备用于烯烃聚合的催化剂中的应用、一种含有所述球形载体的催化剂和所述催化剂在催化烯烃聚合反应中的应用。
背景技术
由氯化镁醇合物制备的齐格勒-纳塔(Ziegler-Natta)催化剂，特别是由球形氯化镁醇合物制备的催化剂，用于烯烃聚合时，催化剂性能通常明显优于其它载体所负载的催化剂。因此，目前用于烯烃聚合的催化剂大多是通过将卤化钛负载于氯化镁醇合物上制备得到的。
但是，由上述氯化镁醇合物制备的催化剂用于烯烃聚合时，在聚合过程中很容易发生聚合物粒子的破碎现象，从而造成聚合物细粉较多。
为了克服这一缺点，人们尝试将给电子体化合物提前引入到氯化镁醇合物载体的制备中，如CN1397568A和CN1563112A教导将内给电子体邻苯二甲酸酯类化合物引入到氯化镁醇合物载体的合成中，从而得到“氯化镁-醇-邻苯二甲酸酯”球形载体，然后将该载体与四氯化钛反应以形成催化剂。但所述的复合物球形载体在制备过程中容易发粘，难于形成粒径大小适宜的球形颗粒。
此外，上述氯化镁醇合物大多是采用低温骤冷固化高温的醇合物熔体制得。这样的技术不仅对能源的消耗较大、制备工艺复杂、须多个反应器联合制备，而且所制得的醇合物的粒径分布较宽。
为了解决该问题，CN102040683A公开了一种通过卤化镁醇合物与环氧乙烷类化合物反应来制备载体的方法。然而，采用该方法制备催化剂载体往往需要加入表面活性剂，且存在制备过程不稳定，容易发生载体粘连，载体成型效果不好的缺点。
因此，仍需要开发一种新的制备烯烃聚合催化剂载体的方法。
发明内容
本发明的目的是为了克服现有技术中烯烃聚合催化剂载体存在的颗粒形态较差、无法制备得到小粒径载体且由载体制得的催化剂用于烯烃聚合反应时氢调敏感性较低的缺陷。
本发明人意外地发现，在制备催化剂载体的过程中加入醇类化合物及卤代醇化合物，形成流体化混合物，通过喷雾干燥方式，能够得到一种具有新型组成且具有良好颗粒形态的催化剂载体，所述催化剂载体基本不存在异形粒子；能够制备得到粒径很小的载体，扩宽了载体的可制备粒径范围，并且制备过程不需要使用表面活性剂而且无需使用惰性溶剂即可直接合成载体，制备过程稳定；进一步地所述载体制备得到的催化剂用于烯烃聚合时，氢调敏感性高。基于上述发现，发明人完成了本发明。
本发明的一个目的是提供一种用于烯烃聚合的催化剂球形载体，该载体包含至少一种具有式(1)所示结构的含镁化合物；
Figure PCTCN2021116417-appb-000001
其中，
R 1是C 1-10的烷基；
R 2和R 3各自独立地选自H、C 1-10的烷基和由1-10个卤素原子取代的C 1-10的烷基；
R 4选自由至少一个卤素原子取代的C 1-10的烷基和由至少一个卤素原子取代的C 6-20的芳基；
R 5是C 1-5的烷基；
X选自氟、氯、溴和碘；
m为0.1-1.9，n为0.1-1.9，且m+n＝2；0<q<0.2；0<a<0.1。
本发明的另一个目的是提供一种制备用于烯烃聚合的催化剂球形载体的方法，该方法包括：
(1)将组分A的材料进行第一接触和然后对所得到的混合物施加剪切力，得到第一产物，所述组分A含有通式为MgXY的卤化镁和通式为R 1OH的第一醇类化合物；
(2)将所述第一产物与组分B进行第二接触，得到第二产物，所述组分B含有具有式(2)所示结构的环氧乙烷类化合物；
(3)将所述第二产物与组分C进行第三接触，得到第三产物，所述组分C含有通式为R 4OH的卤代醇和通式为R 5OH的第二醇类化合物；
(4)将所述第三产物进行喷雾干燥；
Figure PCTCN2021116417-appb-000002
其中，在式R 1OH中，R 1是C 1-10的烷基；
在式(2)中，R 2和R 3各自独立地选自H、C 1-10的烷基和由1-10个卤素原子取代的C 1-10的烷基；
在式R 4OH中，R 4选自由至少一个卤素原子取代的C 1-10的烷基和由至少一个卤素原子取代的C 6-20的芳基；
在式R 5OH中，R 5是C 1-5的烷基；
在式MgXY中，X选自氟、氯、溴和碘；Y选自氟、氯、溴、碘、C 1-6的烷基、C 1-6的烷氧基、C 6-14的芳基和C 6-14的芳氧基；
所述组分A、所述组分B和所述组分C的用量使得得到的球形载体包含具有式(1)所示的结构的含镁化合物：
Figure PCTCN2021116417-appb-000003
其中，m为0.1-1.9，n为0.1-1.9，且m+n＝2；0<q<0.2；0<a<0.1；
其中，在步骤(3)中，相对于1mol所述卤化镁，所述卤代醇的用量为0.05-6.5mol，所述第二醇类化合物的用量为5-100mol。
本发明的另一个目的是提供由前述方法制备得到的球形载体。
本发明的另一个目的是提供所述球形载体在制备用于烯烃聚合的催化剂中的应用。
本发明的又一个目的是提供一种含有前述球形载体的催化剂。
本发明的又一个目的是提供前述催化剂在催化烯烃聚合反应中的应用。
与现有技术相比，本发明至少具有如下优点：
(1)本发明提供的用于烯烃聚合的催化剂球形载体的颗粒形态较好、基本不会出现异形粒子；本发明提供的方法无需加入表面活性剂、无需溶剂，制备过程稳定，并且能够制备得到粒径很小的载体，极大地扩宽了载体的可制备粒径范围；
(2)以所述球形载体制备得到的催化剂用于烯烃聚合，如丙烯聚合时，聚合活性好、氢调敏感性较高，极具工业应用前景。
本发明的其它特征和优点将通过随后的具体实施方式部分予以详细描述。
附图简要说明
图1是得自实施例1的球形载体的电子显微照片。
优选实施方案的描述
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本文中使用的术语“烷基”是指可以通过从化学式中去掉一个或更多个氢而衍生自烷烃的烷属烃基，其可以是直链的、支链的或者环状的。烷基的实例包括但不限于甲基、乙基、正丙基、异丙基、环丙基、正丁基、仲丁基、异丁基、叔丁基、环丁基、正戊基、异戊基、新戊基、环戊基、正己基、异己基、环己基、1-乙基丙基，2-甲基丁基，3-甲基丁基，2,2-二甲基丙基等。
本文中使用的术语“芳基”是指可以通过从化学式中去掉一个或更多个氢而衍生自芳烃的芳香属烃基。芳基的实例包括但不限于苯基、邻甲苯基、间甲苯基、对甲苯基、邻乙苯基、间乙苯基、对乙苯基、萘基、苄基、苯乙基等。
本文中使用的术语“卤素”是指氟、氯、溴或碘”。
本文中使用的术语“由1-10个卤素原子取代的C 1-10的烷基”指C 1-10的烷基中的1-10个氢原子被卤素原子取代而形成的基团，可以是同一个碳原子上的多个氢原子被卤素原子取代，也可以是不同碳原子上的氢原子被取代；当多个卤素原子取代时，所述卤素原子可以相同，也可以不同。实例包括但不限于-CF 3、-CH 2CF 3、-CH 2CF 2H、-CF 2CF 3、-CF 2CH 2CF 2H、-CH 2CF 2CF 2H、-CH 2CH 2CH 2Cl、-CH 2CH 2CH 2Br等。
类似地，本文中使用的术语“由至少一个(或至少两个)卤素原子取代的C 1-10的烷基”和“由至少一个(或至少两个)卤素原子取代的C 6-20的芳基”分别是指C 1-10的烷基和C 6-20的芳基中的至少一个(或至少两个)氢原子被卤素原子取代而形成的基团。当超过一个氢原子被卤素原子取代时，所述氢原子可以是一个碳上的氢原子也可以是不同碳上的氢原子，并且所述卤素原子可以相同，也可以不同。由至少一个卤素原子取代的C 1-10的烷基的实例包括但不限于CF 3、-CH 2CF 3、-CH 2CF 2H、-CF 2CF 3、-CF 2CH 2CF 2H、-CH 2CF 2CF 2H、-CH 2CH 2CH 2Cl、-CH 2CH 2CH 2Br等。由至少一个卤素原子取代的C 6-20的芳基的实例包括但不限于2-、3-或4-氯代苯基，2-、3-或4-溴代苯基，2,3-、2,4-、2,5-、2,6-、3,4-或3,5-二氯苯基，2,3-、2,4-、2,5-、2,6-、3,4-或3,5-二溴苯基，4-三氟甲基苯基。
如前所述，在第一方面，本发明提供了一种用于烯烃聚合的催化剂球形载体，该载体包含至少一种具有式(1)所示结构的含镁化合物；
Figure PCTCN2021116417-appb-000004
其中，
R 1是C 1-10的直链的、支链的或者环状的烷基；
R 2和R 3各自独立地选自H、C 1-10的直链的或支链的烷基和由1-10个卤素原子取代的C 1-10的直链的或支链的烷基；
R 4选自由至少一个卤素原子取代的C 1-10的直链的、支链的或者环状的烷基和由至少一个卤素原子取代的C 6-20的芳基；
R 5是C 1-5的烷基；
X选自氟、氯、溴和碘；
m为0.1-1.9，n为0.1-1.9，且m+n＝2；0<q<0.2；0<a<0.1。
在一些实施方案中，本发明的载体基本上由所述至少一种具有式(1)所示结构的含镁化合物组成。
在一些实施方案中，本发明的载体由所述至少一种具有式(1)所示结构的含镁化合物组成。
优选地，R 1是C 1-8的直链的、支链的或者环状的烷基；更优选地，R 1是C 1-6的直链的、支链的或者环状的烷基。
优选地，R 2和R 3各自独立地选自H、C 1-5的直链的或支链的烷基和由1-10个卤素原子取代的C 1-5的直链的或支链的烷基。
优选地，R 4选自由至少两个卤素原子取代的C 1-10的直链的、支链的或者环状的烷基和由至少两个卤素原子取代的C 6-20的芳基，且所述卤素原子优选选自氯原子、溴原子和碘原子中的至少一种。
优选地，R 5是C 1-2的烷基。
优选地，X选自氯和溴。
优选地，m为0.3-1.7，更优选m为0.6-1.4，仍更优选m为0.8-1.2。
优选地，n为0.3-1.7，更优选n为0.6-1.4，仍更优选n为0.8-1.2。
优选地，0.001<q<0.15。
优选地，0.001<a<0.08。
优选地，所述球形载体的平均颗粒直径为2-100微米，粒径分布小于2，更优选地，所述球形载体的平均颗粒直径为2-19微米，粒径分布为0.6-1.6。
为了使得采用所述球形载体制备的催化剂用于烯烃聚合时能够得到具有更高堆积密度的烯烃聚合物，进一步优选地，所述球形载体的平均颗粒直径为2-10微米，粒径分布为0.6-1。
本发明中，所述平均颗粒直径指的是D50。
本发明中，所述粒径分布的大小被定义为(D90-D10)/D50。
本发明中，所述催化剂载体的平均颗粒直径和粒径分布是采用激光粒度仪如Master Sizer 2000激光粒度仪(由Malvern Instruments Ltd生产制造)测得的。在测试中可以采用例如己烷作为惰性分散介质。
如前所述，在第二方面，本发明提供了一种制备用于烯烃聚合的催化剂球形载体的方法，该方法包括：
(1)将组分A的材料进行第一接触和然后对所得到的混合物施加剪切力，得到第一产物，所述组分A含有通式为MgXY的卤化镁和通式为R 1OH的第一醇类化合物；
(2)将所述第一产物与组分B进行第二接触，得到第二产物，所述组分B含有具有式(2)所示结构的环氧乙烷类化合物；
(3)将所述第二产物与组分C进行第三接触，得到第三产物，所述组分C含有通式为R 4OH的卤代醇和通式为R 5OH的第二醇类化合物；
(4)将所述第三产物进行喷雾干燥；
Figure PCTCN2021116417-appb-000005
其中，在式R 1OH中，R 1是C 1-10的直链的、支链的或者环状的烷基；
在式(2)中，R 2和R 3各自独立地选自H、C 1-10的直链或支链的烷基和由1-10个卤素原子取代的C 1-10的直链或支链的烷基；
在式R 4OH中，R 4选自由至少一个卤素原子取代的C 1-10的直链的、支链的或者环状的烷基和由至少一个卤素原子取代的C 6-20的芳基；
在式R 5OH中，R 5是C 1-5的烷基；
在式MgXY中，X选自氟、氯、溴和碘；Y选自氟、氯、溴、碘、C 1-6的直链的或支链的烷基、C 1-6的直链的或支链的烷氧基、C 6-14的芳基和C 6-14的芳氧基；
所述组分A、所述组分B和所述组分C的用量使得得到的球形载体包含具有式(1) 所示的结构的含镁化合物、基本上由具有式(1)所示的结构的含镁化合物组成或者由具有式(1)所示的结构的含镁化合物组成：
Figure PCTCN2021116417-appb-000006
在式(1)中，R 1-R 5和X定义如上，m为0.1-1.9，n为0.1-1.9，且m+n＝2；0<q<0.2；0<a<0.1；
其中，在步骤(3)中，相对于1mol所述卤化镁，所述卤代醇的用量为0.05-6.5mol，所述第二醇类化合物的用量为5-100mol。
在本发明的第二方面中，所述R 1、R 2、R 3、R 4和R 5基团的定义和优先选项与本发明第一方面的定义对应相同。
根据本发明一种优选的具体实施方式，在式MgXY中，X选自氯和溴，Y选自氯、溴、C 1-5的直链的或支链的烷基、C 1-5的直链的或支链的烷氧基、C 6-10的芳基和C 6-10的芳氧基。
更优选地，所述卤化镁选自氯化镁、溴化镁、氯化苯氧基镁、氯化异丙氧基镁和氯化正丁氧基镁中的至少一种，更进一步优选为氯化镁。
根据本发明另一种优选的具体实施方式，在式R 1OH中，R 1是C 1-8的直链的、支链的或环状的烷基。
更优选地，所述第一醇类化合物选自乙醇、丙醇、异丙醇、正丁醇、异丁醇、戊醇、异戊醇、正己醇、正辛醇和2-乙基己醇中的至少一种。
根据本发明又一种优选的具体实施方式，在式(2)中，R 2和R 3各自独立地选自H、C 1-5的直链的或支链的烷基和由1-10个卤素原子取代的C 1-5的直链的或支链的烷基。
更优选地，所述环氧乙烷类化合物选自环氧乙烷、环氧丙烷、环氧丁烷、环氧氯丙烷、环氧氯丁烷、环氧溴丙烷和环氧溴丁烷中的至少一种。
根据本发明的一些实施方案，所述卤代醇可以为单卤代醇或多卤代醇，优选为氯代醇、溴代醇或碘代醇，例如为2,2,2-三氯乙醇、2,2-二氯乙醇、2-氯乙醇、3-氯-1-丙醇、6-氯-1-己醇、3-溴-1-丙醇、5-氯-1-戊醇、4-氯-1-丁醇、2-氯环己醇、1,2-二氯乙醇、1,3-二氯丙醇、1,4-二氯丁醇或2-碘乙醇等。
根据本发明的一种优选的具体实施方式，在式R 4OH中，R 4选自由至少两个卤素原子取代的C 1-10的直链的、支链的或者环状的烷基和由至少两个卤素原子取代的C 6-20的芳基，且所述卤素原子选自氯原子、溴原子和碘原子中的至少一种。
优选地，所述卤代醇选自2,2,2-三氯乙醇、2,2-二氯乙醇、1,2-二氯乙醇、1,3-二氯丙醇、1,4-二氯丁醇中的至少一种。
根据本发明，所述第二醇类化合物是C 1-5的醇类化合物中的至少一种，例如为乙醇、甲醇、正丙醇、异丙醇、正丁醇或异丁醇。根据本发明一种优选的具体实施方式，在式R 5OH中，R 5是C 1-2的烷基，也即所述第二醇类化合物为甲醇和/或乙醇。
发明人发现，当所述卤代醇化合物和所述醇类化合物的用量过大时，所得催化剂载体发粘结块，无法进行后续操作。
在本发明公开的方法中，相对于1mol所述卤化镁，所述第一醇类化合物的用量为1-30mol，所述环氧乙烷类化合物的用量为1-10mol，所述卤代醇的用量为0.05-6.5mol，所述第二醇类化合物的用量为5-100mol。
优选地，相对于1mol所述卤化镁，所述第一醇类化合物的用量为6-22mol，所述环氧乙烷类化合物的用量为2-6mol，所述卤代醇的用量为1-5mol，所述第二醇类化合物的用量为8-80mol，更优选为31-50mol。
需要说明的是，上述各反应物中携带的微量水也会参与形成所述球形载体的反应中，因此，制备得到的所述球形载体中可能会含有来自于反应原料和反应介质所带的微量水，本领域技术人员不应理解为对本发明的限制。
优选地，在步骤(1)中，所述第一接触在搅拌的条件下进行，所述第一接触的条件包括：温度为40-130℃，优选50-130℃，更优选80-120℃，时间为0.3-24h，优选0.5-10h，更优选0.5-5h。
更优选地，在步骤(1)中，所述第一接触的条件包括：温度为80-100℃，时间为0.5-3h。
在步骤(1)中，本发明对所述施加剪切力的具体操作方法没有特别限制，可以采用本领域技术人员公知的方法进行。例如采用低速剪切或高速剪切进行。优选地，采用低速剪切时，所述低速剪切的搅拌速率为400-800rpm。所述高速剪切的方法为本领域技术人员所公知，例如采用CN1330086A公开的高搅拌速度进行。此外，还可以参照以下专利申请公开的方法进行所述施加剪切力操作，如CN1580136A公开的将含有液态卤化镁化合物的溶液在超重力床中进行旋转分散(旋转的速度为100-3000rpm)；再如CN1463990A公开的将含有液态卤化镁加合物的溶液在乳化机中以1500-8000rpm的速度输出；又如US6020279A公开的通过喷雾法对含有液态卤化镁加合物的溶液施加剪切力。
优选地，在步骤(2)中，所述第二接触的条件包括：温度为30-130℃，优选50-120℃，时间为10-180min，优选20-60min；
更优选地，在步骤(2)中，所述第二接触的条件包括：温度为80-100℃，时间为20-50min。
根据本发明一种优选的具体实施方式，在步骤(3)中还包括，将所述第二产物使用惰性溶剂洗涤后再与组分C中的各组分进行所述第三接触，优选地，所述惰性溶剂选自戊烷、己烷、庚烷、石油醚和汽油中的至少一种。
本发明对步骤(3)中的所述第三接触的具体条件没有特别限制，只要能够使得所述组分C与所述第二产物能够充分接触形成流体即可，但是为了能够获得具有更好性能的催化剂载体，优选地，在步骤(3)中，所述第三接触的条件包括：在搅拌的条件下进行，温度为0-120℃，时间为0.5-6h。
本发明对步骤(3)中的所述第三接触的具体方式没有特别限制，可以将所述卤代醇和所述第二醇类化合物两者混合同步与所述第二组分进行接触，也可以将所述卤代醇和所述第二醇类化合物以任何顺序相继与所述第二组分进行接触。
本发明中，所述喷雾干燥的条件可以采用现有的能够形成用于烯烃聚合的催化剂载体的条件。根据本发明一种优选的具体实施方式，所述喷雾干燥在具有雾化喷嘴的喷雾机中实施，所述雾化喷嘴含有物料导管和喷嘴头，所述第三产物通过所述物料导管引至所述喷嘴头中，并且通过所述喷嘴头喷射至喷雾机的含有惰性介质的塔体内进行蒸发和固化。优选地，所述第三产物在所述物料导管中的温度为0℃至80℃之间，并且所述第三产物在所述喷嘴头中的温度为80-180℃；更加优选所述第三产物在所述喷嘴头中的温度为120-180℃。
在本发明中，在步骤(4)中，优选地，所述喷雾干燥的条件包括：温度为60-200℃，更优选为90-150℃。本发明中，所述喷雾干燥的温度指的是所述喷雾机中的惰性介质的温度。
在本发明中，所述惰性介质可以包括保护气体介质和/或惰性液体介质，对所述保护气体介质的种类没有特别的限定，例如可以为氮气也可以为惰性气体介质如氦气，也可以是其它适宜气体如二氧化碳等；所述惰性液体介质为本领域常用的各种不与反应物和反应产物发生化学作用的液体介质，优选所述惰性液体介质为硅油和/或惰性液体烃类溶剂；更优选地，所述惰性液体介质选自煤油、石蜡油、凡士林油、白油、甲基硅油、乙基硅油、甲基乙基硅油、苯基硅油和甲基苯基硅油中的至少一种，更进一步优选为白油。
在本发明中，所述喷雾机中的惰性液体介质的用量可以根据通式为MgXY的卤化镁的用量来选择，优选为0.8-10L/摩尔卤化镁，更优选为2-8L/摩尔卤化镁。
在本发明第二方面所述的方法中，还包括本领域常规的如固液分离、洗涤、干燥等 后处理手段，本发明对此没有特别限制。所述固液分离可以采用现有的各种能够实现固相与液相分离的方法，例如抽滤、压滤或离心分离等，优选情况下，所述固液分离的方法为压滤法。本发明对压滤的条件没有特别地限定，以尽可能充分地实现固相与液相的分离为准。所述洗涤可以采用本领域技术人员公知的方法将得到的固相产物进行洗涤，例如可以采用惰性烃类溶剂(如戊烷、己烷、庚烷、石油醚和汽油)对得到的固相产物进行洗涤。本发明对于所述干燥的具体条件没有特别限定，例如所述干燥的温度可以为20-70℃，所述干燥的时间可以为0.5-10h，所述干燥可以在常压或减压条件下进行。
发明人发现，通过使用特定种类和用量的醇类化合物和卤代醇化合物与卤化镁和环氧乙烷类化合物等组分进行配合，同时匹配喷雾干燥方式，能够得到具有新型组成且具有良好颗粒形态的催化剂载体，所述催化剂载体基本不存在异形粒子；并且制备过程不需要加入表面活性剂，过程稳定。
特别地，本发明提供的方法能够制备得到粒径很小的载体，极大地扩展了载体的可制备粒径范围；并且所述载体制备得到的催化剂用于烯烃聚合时，氢调敏感性较高。
如前所述，在第三方面，本发明提供了由前述第二方面中所述的方法制备得到的球形载体。
发明人发现，采用本发明的方法制备得到的催化剂球形载体的颗粒形态较好、基本不会出现异形粒子。
如前所述，在第四方面，本发明提供了前述第一方面或第三方面所述的球形载体在制备用于烯烃聚合的催化剂中的应用。
如前所述，在第五方面，本发明提供了一种含有前述第一方面或第三方面所述的球形载体的催化剂。
由球形载体制备用于烯烃聚合的催化剂的方法以及由此得到的催化剂是本领域技术人员已知的。本发明中，对所述催化剂的组成没有特别限制，可以为本领域现有的用于烯烃聚合的催化剂的组成，但是为了能够得到适于用于烯烃聚合，特别是丙烯聚合的催化剂，优选地，所述催化剂中含有所述载体、卤化钛化合物和给电子体化合物。优选地，所述卤化钛选自四氯化钛、四溴化钛、四碘化钛、四正丁氧基钛、四乙氧基钛、一氯三正丁氧基钛、二氯二正丁氧基钛、三氯一正丁氧基钛、一氯三乙氧基钛、二氯二乙氧基钛、三氯一乙氧基钛和三氯化钛中的至少一种。优选地，所述给电子体化合物选自邻苯二甲酸酯如邻苯二甲酸二异丁酯、羧酸二醇酯、磷酸酯、醚如1,3-二醚中的至少一种。同时，本发明对所述催化剂中的各组分的含量没有特别限制，本领域技术人员可以根据实际需要进行合理的调节设计。
本发明对所述催化剂的制备方法没有特别限制，可以采用本领域现有的制备烯烃聚合催化剂的方法。在一个实施方案中，通过用卤化钛化合物任选在惰性液体介质中处理所述球形载体来制备烯烃聚合催化剂，任选地在该处理之前、过程中或之后向所述载体中引入内给电子体化合物。本发明在后文中的实施例中列举了一种具体的操作过程，本领域技术人员不应理解为对本发明的限制。
如前所述，在第六方面，本发明提供了前述第五方面所述的催化剂在催化烯烃聚合反应中的应用。
本发明对所述应用的具体操作方法没有特别限制，本领域技术人员可以采用本领域常规的进行烯烃聚合反应的方法进行操作，本发明在此不做详述。本发明在后文中列举了一种具体的操作过程，本领域技术人员不应理解为对本发明的限制。
因此，在一个实施方案中，本发明提供了烯烃聚合方法，该方法包括使至少一种C2-C10烯烃单体和任选的共聚单体与所述催化剂在可聚合条件下接触以形成烯烃聚合物，和回收所述烯烃聚合物。
发明人发现，由本发明提供的球形载体制备得到的催化剂用于烯烃聚合，特别是丙烯聚合时，聚合活性好、基本无异形料的出现、氢调敏感性明显较现有技术高，极具工业应用前景。
以下将通过实例对本发明进行详细描述。
以下实例中，在没有特别说明的情况下，所用原料均为市售品，以收到的形式使用。
1,3-二氯丙醇购自百灵威公司；
环氧氯丙烷购自百灵威公司；
邻苯二甲酸二异丁酯购自百灵威公司；
四氯化钛购自百灵威公司；
三乙基铝购自百灵威公司；
甲基环己基二甲氧基硅烷购自百灵威公司。
以下实例中，涉及到的性能是通过如下方式测试得到的：
1、催化剂载体的平均颗粒直径和粒径分布：采用Malvern Instruments公司生产制造的Masters Sizer 2000粒度仪进行测定，采用已烷作为分散介质；
2、催化剂载体的形貌：通过美国FEI公司生产的XL-30型场发射电子显微镜观察；
3、催化剂载体的结构及组成：采用瑞士Bruker公司的AVANCE 300核磁共振谱仪，对载体进行1H-NMR测试，以及采用Fronteerlab公司的PY-2020iD型裂解器、Thermo Fisher公司的TraceGC Ultra型色谱仪和DSQⅡ型质谱仪对载体进行测试得到；
4、催化剂活性：通过聚合后所得产物的重量与催化剂用量重量的比值进行评测；
5、聚烯烃粉料的堆密度：采用GB/T 1636-2008规定的方法进行测定；
6、聚烯烃粉料的熔体流动速率指数：按照ISO1133，230℃，2.16kg载荷下测量。
以下实例中，没有特别说明的情况下，在催化剂载体的制备过程中，施加剪切力均是通过在600rpm的搅拌下进行的。
实施例1
(1)在0.6L的反应釜中，加入0.08mol氯化镁、1.7mol乙醇(第一醇类化合物)，在搅拌下升温至90℃，恒温反应1h进行第一接触，然后进行对所得到的混合物施加剪切力，得到第一产物；
(2)将所述第一产物与0.48mol的环氧氯丙烷进行第二接触，得到第二产物，所述第二接触的条件包括：温度为90℃，时间为30min；
(3)将所述第二产物压滤后，所得固体与2.5mol乙醇(第二醇类化合物)和0.35mol的1,3-二氯丙醇(卤代醇)充分混合搅拌进行第三接触形成流体，得到第三产物；
(4)使用含有喷嘴头和物料导管的喷雾机B-290将所述第三产物喷入喷雾机塔内100℃的循环氮气中进行喷雾干燥，所述第三产物在所述物料导管中的温度为15℃，在所述喷嘴头中的温度为120℃，获得球形载体Z1。
经测试，所得催化剂球形载体Z1的结构及组成为：
Figure PCTCN2021116417-appb-000007
经测试，所述催化剂球形载体Z1的平均颗粒直径(D50)为4微米，粒径分布((D90-D10)/D50)为0.9。
附图1显示了所述球形载体Z1的显微照片。从图1可以看大，所述催化剂球形载体Z1的颗粒形态比较规整，表面光滑，基本上都是球形的，颗粒尺寸分布比较集中，且基本上没有异形粒子存在。
在制备所述催化剂球形载体Z1的过程中，所述喷雾机的喷嘴头处没有发生堵塞现象，共得到11.8g载体Z1。
实施例2
(1)在0.6L的反应釜中，加入0.08mol氯化镁、1.4mol乙醇(第一醇类化合物)， 在搅拌下升温至90℃，恒温反应1.5h进行第一接触，然后通过对所得到的混合物施加剪切力，得到第一产物；
(2)将所述第一产物与0.35mol环氧氯丙烷进行第二接触，得到第二产物，所述第二接触的条件包括：温度为90℃，时间为30min；
(3)将所述第二产物压滤后，所得固体与2.5mol乙醇(第二醇类化合物)和0.25mol的1,3-二氯丙醇(卤代醇)充分混合搅拌进行第三接触形成流体，得到第三产物；
(4)使用含有喷嘴头和物料导管的喷雾机B-290将所述第三产物喷入喷雾机塔内100℃的循环氮气中进行喷雾干燥，所述第三产物在所述物料导管中的温度为15℃，在所述喷嘴头中的温度为120℃，得到催化剂球形载体Z2。
经测试，所得催化剂球形载体Z2的结构及组成为：
Figure PCTCN2021116417-appb-000008
经测试，所述催化剂球形载体Z2的平均颗粒直径(D50)为4微米，粒径分布((D90-D10)/D50)为0.8。
经观测，烯烃聚合用球形载体Z2的颗粒形态比较规整，表面光滑，基本上都是球形的，颗粒尺寸分布比较集中，且基本上没有异形粒子存在。
在制备所述催化剂球形载体Z2的过程中，所述喷雾机的喷嘴头处没有发生堵塞现象，共得到11.9g的所述催化剂球形载体Z2。
实施例3
(1)在0.6L的反应釜中，加入0.08mol氯化镁、1.4mol乙醇(第一醇类化合物)，在搅拌下升温至90℃，恒温反应1.5h进行第一接触，然后对所得到的混合物施加剪切力，得到第一产物；
(2)将所述第一产物与0.35mol环氧氯丙烷，进行第二接触，得到第二产物，所述第二接触的条件包括：温度为90℃，时间为30min；
(3)将所述第二产物压滤后所得固体与2.5mol乙醇(第二醇类化合物)和0.1mol的1,3-二氯丙醇(卤代醇)合并，搅拌进行第三接触至形成流体，得到第三产物；
(4)使用含有喷嘴头和物料导管的喷雾机B-290将所述第三产物喷入喷雾机塔内100℃的循环氮气中，所述第三产物在所述物料导管中的温度为15℃，在所述喷嘴头中的温度为120℃，得到球形载体Z3。
经测试，所得催化剂球形载体Z3的结构及组成为：
Figure PCTCN2021116417-appb-000009
经测试，所述催化剂球形载体Z3的平均颗粒直径(D50)为5微米，粒径分布((D90-D10)/D50)为0.8。
经观测，所述催化剂球形载体Z3的颗粒形态比较规整，表面光滑，基本上都是球形的，颗粒尺寸分布比较集中，且基本上没有异形粒子存在。
在制备所述催化剂球形载体Z3的过程中，所述喷雾机的喷嘴头处没有发生堵塞现象，共得到12.0g的所述催化剂球形载体Z3。
实施例4
(1)在0.6L的反应釜中，加入0.08mol氯化镁、1.4mol乙醇(第一醇类化合物)，在搅拌下升温至90℃，恒温反应1.5h进行第一接触，然后通过对所得到的混合物施加剪切力，得到第一产物；
(2)将所述第一产物与0.35mol环氧氯丙烷进行第二接触，得到第二产物，所述第二接触的条件包括：温度为90℃，时间为30min；
(3)将所述第二产物压滤后，所得固体与2.5mol乙醇(第二醇类化合物)和0.25mol的1,3-二氯丙醇(卤代醇)混合搅拌，使用超声波探头超声，共6次，每次30min，形成流体，得到第三产物；
(4)使用含有喷嘴头和物料导管的喷雾机B-290将所述第三产物喷入喷雾机塔内100℃的循环氮气中进行喷雾干燥，所述第三产物在所述物料导管中的温度为20℃，在所述喷嘴头中的温度为120℃，得到催化剂球形载体Z4。
经测试，所得催化剂球形载体Z4的结构及组成为：
Figure PCTCN2021116417-appb-000010
经测试，所述催化剂球形载体Z4的平均颗粒直径(D50)为5微米，粒径分布((D90-D10)/D50)为1.0。
经观测，烯烃聚合用球形载体Z4的颗粒形态比较规整，表面光滑，基本上都是球形的，颗粒尺寸分布比较集中，且基本上没有异形粒子存在。
在制备所述催化剂球形载体Z4的过程中，所述喷雾机的喷嘴头处没有发生堵塞现象，共 得到12.4g的所述催化剂球形载体Z4。
对比例1
(1)在0.6L的反应釜中，加入0.08mol氯化镁、1.4mol乙醇，在搅拌下升温至90℃，恒温反应1.5h，然后加入0.35mol环氧氯丙烷，在90℃下反应30min，得到流态混合物质；
(2)使用含有喷嘴头和物料导管的喷雾机将所述流态混合物质喷入100℃的循环氮气中，以及所述流态混合物质在所述物料导管中的温度为90℃，在所述喷嘴头中的温度为120℃，得到烯烃聚合用催化剂载体DZ1。
在喷雾过程中，步骤(1)所得到的流态混合物质极易沉淀，易导致喷雾干燥不能正常进行，而且易造成喷头堵塞。
所述烯烃聚合用催化剂载体DZ1的平均颗粒直径(D50)为15微米，粒径分布((D90-D10)/D50)为1.3。
对比例2
(1)在0.6L的反应釜中，加入0.08mol氯化镁、1.7mol乙醇，在搅拌下升温至90℃，恒温反应1h后，加入0.48mol环氧氯丙烷在90℃下反应30min，得到第一产物；
(2)将所述第一产物压滤后，向固体残余物中加入2.5mol乙醇进行搅拌至形成流态混合物；
(3)使用含有喷嘴头和物料导管的喷雾机将所述流态混合物喷入100℃的循环氮气中，以及所述第三产物在所述物料导管中的温度为15℃，在所述喷嘴头中的温度为120℃，得到烯烃聚合用催化剂载体DZ2。
所述烯烃聚合用催化剂载体DZ2的平均颗粒直径(D50)为3微米，粒径分布((D90-D10)/D50)为0.8。
对比例3
采用与实施例1相似的方式制备所述催化剂球形载体，不同的是：在步骤(3)中，不使用第二醇类化合物，仅使用卤代醇(1,3-二氯丙醇)与所述第二产物充分混合搅拌进行第三接触，且使用的卤代醇的用量与实施例1相同，得到催化剂载体DZ3。
在制备催化剂载体DZ3的过程中，载体发粘结块，无法进行后续操作。
测试例采用本发明上述提供的烯烃聚合用催化剂球形载体制备烯烃聚合用催化剂，并且使用制备得到的烯烃聚合用催化剂制备烯烃。
测试例1-1
(1)制备烯烃聚合用催化剂
在300mL的反应瓶中，加入100mL的四氯化钛，冷却至零下20℃，将8克的由实施例1得到的催化剂球形载体Z1加入其中，并在零下20℃下搅拌30min。然后开始缓慢升温至110℃，在升温过程中加入1.5mL的邻苯二甲酸二异丁酯，在110℃下维持30min后，滤去液体。然后用四氯化钛洗涤2次，最后用已烷洗3次，干燥，得到烯烃聚合用催化剂C1。
(2)丙烯聚合反应
在一个5L的不锈钢高压反应釜中，在氮气保护气氛下，加入1mmol的三乙基铝的己烷溶液(三乙基铝的浓度为0.5mmol/mL)、0.05mmol的甲基环己基二甲氧基硅烷、10mL的无水己烷、10mg的步骤(1)得到的烯烃聚合用催化剂C1、1.5L(标准体积)的氢气和2.5L的液体丙烯单体，升温至70℃，在该温度下反应1h，然后降温、放压、出料、干燥，得到聚丙烯粉料。
本测试例制备得到的催化剂活性为36.1KgPP/g·Cat；
所得聚丙烯粉料的堆密度为0.41g/cm 3，熔体流动速率指数为11.9g/10min，该聚丙烯粉料颗粒形态好，基本不存在异形料，具体可见表1。
测试例1-2
采用与测试例1-1相似的方式制备聚丙烯，不同的是：在步骤(2)中，使用的氢气的体积不同，其余均与测试例1-1中相同。
具体的：1.5L(标准体积)的氢气替换为6.5L(标准体积)的氢气，得到聚丙烯粉料。
本测试例制备得到的催化剂活性为36.0KgPP/g·Cat；
所得聚丙烯粉料的堆密度为0.41g/cm 3，熔体流动速率指数为45.8g/10min，该聚丙烯粉料颗粒形态好，基本不存在异形料，具体可见表1。
测试例2-1
采用与测试例1-1相似的方式制备聚丙烯，不同的是：在步骤(1)中，使用的催化剂载体的种类不同，其余均与测试例1-1中相同。
具体的：用相同重量的实施例2制备得到的所述催化剂球形载体Z2代替所述催化剂球形载体Z1，得到烯烃聚合催化剂C2；然后采用烯烃聚合催化剂C2按照测试例1-1的步 骤(2)制备得到聚丙烯粉料。
本测试例制备得到的催化剂活性为37.6KgPP/g·Cat；
所得聚丙烯粉料的堆密度为0.41g/cm 3，熔体流动速率指数为11.0g/10min，该聚丙烯粉料颗粒形态好，基本不存在异形料，具体可见表1。
测试例2-2
采用与测试例2-1相似的方式制备聚丙烯，不同的是：在步骤(2)中，使用的氢气的体积不同，其余均与测试例2-1中相同。
具体的：1.5L(标准体积)的氢气替换为6.5L(标准体积)的氢气，得到聚丙烯粉料。
本测试例制备得到的催化剂活性为37.2KgPP/g·Cat；
所得聚丙烯粉料的堆密度为0.41g/cm 3，熔体流动速率指数为41.2g/10min，该聚丙烯粉料颗粒形态好，基本不存在异形料，具体可见表1。
测试例3-1
采用与测试例1-1相似的方式制备聚丙烯，不同的是：在步骤(1)中，使用的催化剂载体的种类不同，其余均与测试例1-1中相同。
具体的：用相同重量的实施例3制备得到的所述催化剂球形载体Z3代替所述催化剂球形载体Z1，得到烯烃聚合催化剂C3；然后采用烯烃聚合催化剂C3按照测试例1-1的步骤(2)制备得到聚丙烯粉料。
本测试例制备得到的催化剂活性为38.5KgPP/g·Cat；
所得聚丙烯粉料的堆密度为0.41g/cm 3，熔体流动速率指数为10.0g/10min，该聚丙烯粉料颗粒形态好，基本不存在异形料，具体可见表1。
测试例3-2
采用与测试例3-1相似的方式制备聚丙烯，不同的是：在步骤(2)中，使用的氢气的体积不同，其余均与测试例3-1中相同。
具体的：1.5L(标准体积)的氢气替换为6.5L(标准体积)的氢气，得到聚丙烯粉料。
本测试例制备得到的催化剂活性为38.2KgPP/g·Cat；
所得聚丙烯粉料的堆密度为0.41g/cm 3，熔体流动速率指数为39.0g/10min，该聚丙 烯粉料颗粒形态好，基本不存在异形料，具体可见表1。
对比测试例1
采用与测试例1-1相似的方式制备聚丙烯，不同的是：在步骤(1)中，使用的催化剂载体的种类不同，其余均与测试例1-1中相同。
具体的：用相同重量的对比例1制备得到的所述催化剂球形载体DZ1代替所述催化剂球形载体Z1，得到烯烃聚合催化剂DC1，然后采用烯烃聚合催化剂DC1按照测试例1-1的步骤(2)制备得到聚丙烯粉料。
本测试例制备得到的催化剂活性为34.8KgPP/g·Cat；
所得聚丙烯粉料的堆密度为0.37g/cm 3，熔体流动速率指数为9.1g/10min，具体可见表1。
对比测试例2-1
采用与测试例1-1相似的方式制备聚丙烯，不同的是：在步骤(1)中，使用的催化剂载体的种类不同，其余均与测试例1-1相同。
具体的：用相同重量的对比例2制备得到的所述催化剂球形载体DZ2代替所述催化剂球形载体Z1，得到烯烃聚合催化剂DC2，然后采用烯烃聚合催化剂DC2按照测试例1-1的步骤(2)制备得到聚丙烯粉料。
本测试例制备得到的催化剂活性为39.0KgPP/g·Cat；
所得聚丙烯粉料的堆密度为0.41g/cm 3，熔体流动速率指数为9.5g/10min，具体可见表1。
对比测试例2-2
采用与对比测试例2-1相似的方式制备聚丙烯，不同的是：在步骤(2)中，使用的氢气的体积不同，其余均与对比测试例2-1相同。
具体的：1.5L(标准体积)的氢气替换为6.5L(标准体积)的氢气，得到聚丙烯粉料。
本测试例制备得到的催化剂活性为37.9KgPP/g·Cat；
所得聚丙烯粉料的堆密度为0.41g/cm 3，熔体流动速率指数为37.5g/10min，具体可见表1。
表1
Figure PCTCN2021116417-appb-000011
从以上结果能够看出，采用本发明的方法制备得到的烯烃聚合催化剂载体的颗粒形态较好、基本不会出现异形粒子。并且，本发明提供的方法能够制备得到粒径较小的催化剂载体，极大地扩展了载体的可制备粒径范围。同时，以所得的载体制备的催化剂用于烯烃(特别是丙烯)聚合时，催化剂活性好、聚丙烯粉料颗粒形态良好、基本无异性料的出现，氢调敏感性高。
特别地，通过对比例2和实施例1比较能够看出，虽然对比例2能够得到粒径较小的催化剂载体，但是由其制得的催化剂载体制备的催化剂用于烯烃(特别是丙烯)聚合反应时，聚合物熔融指数较小，相应氢调敏感性较低。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (9)

  1. 一种用于烯烃聚合的催化剂球形载体，该载体包含具有式(1)所示结构的含镁化合物；
    Figure PCTCN2021116417-appb-100001
    其中，
    R 1是C 1-10的烷基；
    R 2和R 3各自独立地选自H、C 1-10的烷基和由1-10个卤素原子取代的C 1-10的烷基；
    R 4选自由至少一个卤素原子取代的C 1-10的烷基和由至少一个卤素原子取代的C 6-20的芳基；
    R 5是C 1-5的烷基；
    X选自氟、氯、溴和碘；
    m为0.1-1.9，n为0.1-1.9，且m+n＝2；0<q<0.2；0<a<0.1。
  2. 根据权利要求1所述的球形载体，其具有以下特征至少之一
    -R 1是C 1-8的烷基；优选地，R 1是C 1-6的烷基；
    -R 2和R 3各自独立地选自H、C 1-5的烷基和由1-10个卤素原子取代的C 1-5的烷基；
    -R 4选自由至少两个卤素原子取代的C 1-10的烷基和由至少两个卤素原子取代的C 6-20的芳基；
    -R 5是C 1-2的烷基；
    -X选自氯和溴。
  3. 根据权利要求1或2所述的球形载体，其中，所述球形载体的平均颗粒直径为2-100微米，粒径分布小于2；
    优选地，所述球形载体的平均颗粒直径为2-19微米，粒径分布为0.6-1.6。
  4. 一种制备用于烯烃聚合的催化剂球形载体的方法，该方法包括：
    (1)将组分A进行第一接触和然后对所得到的混合物施加剪切力，得到第一产物，所述组分A含有通式为MgXY的卤化镁和通式为R 1OH的第一醇类化合物；
    (2)将所述第一产物与组分B进行第二接触，得到第二产物，所述组分B含有具有式(2)所示结构的环氧乙烷类化合物；
    (3)将所述第二产物与组分C进行第三接触，得到第三产物，所述组分C含有通式为R 4OH的卤代醇和通式为R 5OH的第二醇类化合物；
    (4)将所述第三产物进行喷雾干燥；
    Figure PCTCN2021116417-appb-100002
    其中，在式R 1OH中，R 1是C 1-10的烷基；
    在式(2)中，R 2和R 3各自独立地选自H、C 1-10的烷基和由1-10个卤素原子取代的C 1-10的烷基；
    在式R 4OH中，R 4选自由至少一个卤素原子取代的C 1-10的烷基和由至少一个卤素原子取代的C 6-20的芳基；
    在式R 5OH中，R 5是C 1-5的烷基；
    在式MgXY中，X选自氟、氯、溴和碘；Y选自氟、氯、溴、碘、C 1-6的烷基、C 1-6的烷氧基、C 6-14的芳基和C 6-14的芳氧基；
    所述组分A、所述组分B和所述组分C的用量使得得到的球形载体包含具有式(1)所示的结构的含镁化合物：
    Figure PCTCN2021116417-appb-100003
    在式(1)中，R 1-R 5和X定义如上，m为0.1-1.9，n为0.1-1.9，且m+n＝2；0<q<0.2；0<a<0.1；
    其中，在步骤(3)中，相对于1mol所述卤化镁，所述卤代醇的用量为0.05-6.5mol，所述第二醇类化合物的用量为5-100mol。
  5. 根据权利要求4所述的方法，其具有以下特征至少之一：
    -在式MgXY中，X选自氯和溴，Y选自氯、溴、C 1-5的烷基、C 1-5的烷氧基、C 6-10的芳 基和C 6-10的芳氧基；
    或者所述卤化镁选自氯化镁、溴化镁、氯化苯氧基镁、氯化异丙氧基镁和氯化正丁氧基镁中的至少一种；
    -在式R 1OH中，R 1是C 1-8的烷基；
    或者所述第一醇类化合物选自乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正戊醇、异戊醇、正己醇、正辛醇和2-乙基己醇中的至少一种；
    -在式(2)中，R 2和R 3各自独立地选自H、C 1-5的烷基和由1-10个卤素原子取代的C 1-5的烷基；
    或者所述环氧乙烷类化合物选自环氧乙烷、环氧丙烷、环氧丁烷、环氧氯丙烷、环氧氯丁烷、环氧溴丙烷和环氧溴丁烷中的至少一种；
    -在式R 4OH中，R 4选自由至少两个卤素原子取代的C 1-10的烷基和由至少两个卤素原子取代的C 6-20的芳基；
    或者所述卤代醇选自2,2,2-三氯乙醇、2,2-二氯乙醇、1,2-二氯乙醇、1,3-二氯丙醇、1,4-二氯丁醇中的至少一种；
    -在式R 5OH中，R 5是C 1-2的烷基；
    -相对于1mol所述卤化镁，所述第一醇类化合物的用量为6-22mol，所述环氧乙烷类化合物的用量为2-6mol，所述卤代醇的用量为1-5mol，所述第二醇类化合物的用量为8-80mol；
    -在步骤(1)中，所述第一接触在搅拌的条件下进行，所述第一接触的条件包括：温度为80-120℃，时间为0.5-5h；
    或者在步骤(1)中，所述第一接触的条件包括：温度为80-100℃，时间为0.5-3h；
    -在步骤(2)中，所述第二接触的条件包括：温度为50-120℃，时间为20-60min；
    或者在步骤(2)中，所述第二接触的条件包括：温度为80-100℃，时间为20-50min。
    -在步骤(3)中，所述第三接触的条件包括：在搅拌的条件下进行，温度为0-120℃，时间为0.5-6h；
    -在步骤(4)中，所述喷雾干燥的条件包括：温度为60-200℃，优选为90-150℃。
  6. 由权利要求4-5中任意一项所述的方法制备得到的球形载体。
  7. 权利要求1-3和6中任意一项所述的球形载体在制备用于烯烃聚合的催化剂中的 应用。
  8. 一种含有权利要求1-3和6中任意一项所述的球形载体的催化剂。
  9. 权利要求8所述的催化剂在催化烯烃聚合反应中的应用。
PCT/CN2021/116417 2020-09-05 2021-09-03 用于烯烃聚合的催化剂的载体及其应用和用于烯烃聚合的催化剂及其应用以及烯烃聚合方法 WO2022048630A1 (zh)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP21863692.6A EP4209516A4 (en) 2020-09-05 2021-09-03 SUPPORT FOR OLEFIN POLYMERIZATION CATALYST AND APPLICATION THEREOF, CATALYST FOR OLEFIN POLYMERIZATION AND APPLICATION THEREOF, AND OLEFIN POLYMERIZATION PROCESS
US18/044,188 US20230406965A1 (en) 2020-09-05 2021-09-03 Carrier for olefin polymerization catalyst and application thereof, catalyst for olefin polymerization and application thereof, and olefin polymerization method
KR1020237011167A KR20230065285A (ko) 2020-09-05 2021-09-03 올레핀 중합 촉매용 담체 및 이의 응용, 올레핀 중합용 촉매 및 이의 응용, 및 올레핀 중합 방법
JP2023514982A JP2023540543A (ja) 2020-09-05 2021-09-03 オレフィン重合触媒用担体およびその適用、オレフィン重合用触媒およびその適用、ならびにオレフィン重合方法
BR112023004120A BR112023004120A2 (pt) 2020-09-05 2021-09-03 Transportador esférico de catalisadores para polimerização de olefinas, método para preparar um transportador esférico de catalisadores para polimerização de olefinas, transportador esférico, uso do transportador esférico e catalisador e uso do catalisador

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010924610.6A CN114149523B (zh) 2020-09-05 2020-09-05 一种用于烯烃聚合的催化剂球形载体及其制备方法与应用和一种催化剂及其应用
CN202010924610.6 2020-09-05

Publications (1)

Publication Number Publication Date
WO2022048630A1 true WO2022048630A1 (zh) 2022-03-10

Family

ID=80460529

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/116417 WO2022048630A1 (zh) 2020-09-05 2021-09-03 用于烯烃聚合的催化剂的载体及其应用和用于烯烃聚合的催化剂及其应用以及烯烃聚合方法

Country Status (7)

Country Link
US (1) US20230406965A1 (zh)
EP (1) EP4209516A4 (zh)
JP (1) JP2023540543A (zh)
KR (1) KR20230065285A (zh)
CN (1) CN114149523B (zh)
BR (1) BR112023004120A2 (zh)
WO (1) WO2022048630A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073632A (zh) * 2022-05-19 2022-09-20 万华化学集团股份有限公司 一种聚烯烃产品的生产工艺

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6020279A (en) 1994-09-06 2000-02-01 Chisso Corporation Process for producing a solid catalyst component for olefin polymerization and a process for producing an olefin polymer
CN1330086A (zh) 2000-06-15 2002-01-09 中国石油化工股份有限公司 用于烯烃聚合或共聚合的球形催化剂组分及其催化剂
CN1397568A (zh) 2002-08-15 2003-02-19 浙江大学 球形催化剂载体MgCl2－醇－有机络合剂复合物的制备方法
CN1463990A (zh) 2002-06-10 2003-12-31 营口市向阳催化剂有限责任公司 一种烯烃聚合球型催化剂组分及载体的制备方法
US20040229748A1 (en) * 2003-02-24 2004-11-18 China Petroleum & Chemical Corporation Composite carrier of catalysts for propylene polymerization, a catalyst component and a catalyst comprising the same
CN1563112A (zh) 2004-03-25 2005-01-12 浙江大学 球形MgCl2－醇－有机络合剂载体负载的烯烃聚合催化剂及制备方法
CN1580136A (zh) 2003-08-08 2005-02-16 中国石油化工股份有限公司 一种卤化镁/醇加合物及其制备方法和应用
CN102040683A (zh) 2009-10-16 2011-05-04 中国石油化工股份有限公司 用于烯烃聚合催化剂的球形载体及其制备方法
CN105440176A (zh) * 2014-08-15 2016-03-30 中国石油化工股份有限公司 一种烯烃聚合催化剂载体及其制备方法和应用
CN109206541A (zh) * 2017-07-01 2019-01-15 中国石油化工股份有限公司 一种烯烃聚合用催化剂载体及其制备方法和应用

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2502107B2 (ja) * 1986-12-26 1996-05-29 東燃株式会社 オレフイン重合用触媒担体の製造方法
US4960743A (en) * 1987-11-30 1990-10-02 Toa Nenryo Kogyo K.K. Method for production of catalyst carrier for polymerization of olefin
IT1230134B (it) * 1989-04-28 1991-10-14 Himont Inc Componenti e catalizzatori per la polimerizzazione di olefine.
JPH0649119A (ja) * 1992-07-30 1994-02-22 Tonen Corp オレフィン重合用触媒成分の製造方法
CN100532406C (zh) * 2005-10-31 2009-08-26 中国石油化工股份有限公司 用于乙烯聚合的催化剂组分及其催化剂
CN102040685B (zh) * 2009-10-16 2013-09-25 中国石油化工股份有限公司 一种用于乙烯聚合的催化剂组分及催化剂
CN102286120A (zh) * 2010-06-18 2011-12-21 中国石油化工股份有限公司 一种用于乙烯聚合的催化剂组分及催化剂
CN102432716B (zh) * 2010-09-29 2013-08-14 中国石油化工股份有限公司 一种用于乙烯聚合的催化剂组分、制备方法及应用
CN103788248B (zh) * 2012-10-29 2016-03-30 中国石油化工股份有限公司 用于烯烃聚合的催化剂组分及其应用和用于烯烃聚合的催化剂及其应用以及烯烃聚合方法
CN106478850B (zh) * 2015-09-01 2019-06-28 中国石油化工股份有限公司 用于乙烯聚合的催化剂组分的制备方法及乙烯聚合催化剂
CN106543299B (zh) * 2015-09-23 2018-11-30 中国石油化工股份有限公司 烯烃聚合用催化剂及其制备方法和应用以及烯烃聚合的方法
CN109206546B (zh) * 2017-07-01 2021-05-11 中国石油化工股份有限公司 一种烯烃聚合用催化剂载体及其制备方法和应用
CN109694423B (zh) * 2017-10-24 2021-07-30 中国石油化工股份有限公司 用于乙烯聚合的催化剂组分及其制备方法和用于乙烯聚合的催化剂
CN111072797B (zh) * 2018-10-19 2021-07-02 中国石油化工股份有限公司 烯烃聚合催化剂球形载体及其制备方法和催化剂组分与催化剂及应用
CN111100218B (zh) * 2018-10-25 2022-05-10 中国石油天然气股份有限公司 一种球形烷氧基镁颗粒及其制备方法
CN111138574B (zh) * 2018-11-05 2022-03-29 中国石油天然气股份有限公司 负载型齐格勒-纳塔催化剂、其制备方法及在烯烃聚合上的应用

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6020279A (en) 1994-09-06 2000-02-01 Chisso Corporation Process for producing a solid catalyst component for olefin polymerization and a process for producing an olefin polymer
CN1330086A (zh) 2000-06-15 2002-01-09 中国石油化工股份有限公司 用于烯烃聚合或共聚合的球形催化剂组分及其催化剂
CN1463990A (zh) 2002-06-10 2003-12-31 营口市向阳催化剂有限责任公司 一种烯烃聚合球型催化剂组分及载体的制备方法
CN1397568A (zh) 2002-08-15 2003-02-19 浙江大学 球形催化剂载体MgCl2－醇－有机络合剂复合物的制备方法
US20040229748A1 (en) * 2003-02-24 2004-11-18 China Petroleum & Chemical Corporation Composite carrier of catalysts for propylene polymerization, a catalyst component and a catalyst comprising the same
CN1580136A (zh) 2003-08-08 2005-02-16 中国石油化工股份有限公司 一种卤化镁/醇加合物及其制备方法和应用
CN1563112A (zh) 2004-03-25 2005-01-12 浙江大学 球形MgCl2－醇－有机络合剂载体负载的烯烃聚合催化剂及制备方法
CN102040683A (zh) 2009-10-16 2011-05-04 中国石油化工股份有限公司 用于烯烃聚合催化剂的球形载体及其制备方法
CN105440176A (zh) * 2014-08-15 2016-03-30 中国石油化工股份有限公司 一种烯烃聚合催化剂载体及其制备方法和应用
CN109206541A (zh) * 2017-07-01 2019-01-15 中国石油化工股份有限公司 一种烯烃聚合用催化剂载体及其制备方法和应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEN LIYI, HANISCH CHRISTIAN, RIEGER BERNHARD: "Controllable Formation of MgCl 2 -based Spherical Catalyst Support Precursors via Composites of Liquid Inorganics and Polymers", ZEITSCHRIFT FUR NATURFORSCHUNG - SECTION B JOURNAL OF CHEMICAL SCIENCES, WALTER DE GRUYTER GMBH, DE, vol. 64, 1 January 2009 (2009-01-01), DE , pages 509 - 516, XP055909900, ISSN: 0932-0776 *
LING, YONGTAI: "Effect of Reaction Byproducts on HQ Support", PETROCHEMICAL INDUSTRY TECHNOLOGY, 1 January 2018 (2018-01-01), XP055909909, [retrieved on 20220406] *
See also references of EP4209516A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073632A (zh) * 2022-05-19 2022-09-20 万华化学集团股份有限公司 一种聚烯烃产品的生产工艺
CN115073632B (zh) * 2022-05-19 2023-12-19 万华化学集团股份有限公司 一种聚烯烃产品的生产工艺

Also Published As

Publication number Publication date
US20230406965A1 (en) 2023-12-21
KR20230065285A (ko) 2023-05-11
EP4209516A1 (en) 2023-07-12
JP2023540543A (ja) 2023-09-25
BR112023004120A2 (pt) 2023-04-04
CN114149523A (zh) 2022-03-08
EP4209516A4 (en) 2024-10-02
CN114149523B (zh) 2022-11-18

Similar Documents

Publication Publication Date Title
CN111072797B (zh) 烯烃聚合催化剂球形载体及其制备方法和催化剂组分与催化剂及应用
CN111072812B (zh) 用于烯烃聚合的催化剂组分和催化剂及其应用与烯烃聚合方法
WO2022048630A1 (zh) 用于烯烃聚合的催化剂的载体及其应用和用于烯烃聚合的催化剂及其应用以及烯烃聚合方法
CN111072804B (zh) 烯烃聚合催化剂组分及其应用和烯烃聚合催化剂及烯烃聚合方法
CN111072803B (zh) 烯烃聚合催化剂载体及其制备方法和应用
CN111072811B (zh) 烯烃聚合催化剂球形载体及其制备方法和催化剂组分与催化剂及其应用
CN109400763B (zh) 烯烃聚合催化剂载体及其制备方法和应用
CN109206541B (zh) 一种烯烃聚合用催化剂载体及其制备方法和应用
JP7479361B2 (ja) オレフィン重合用触媒成分、触媒及びその応用
CN111072808B (zh) 催化剂组分和催化剂及其应用与烯烃聚合方法
CN105985462A (zh) 粘土改性硅胶复合载体及其制备方法
CN112694550A (zh) 烯烃聚合催化剂载体及其制备方法与催化剂组分和应用
CN109206546B (zh) 一种烯烃聚合用催化剂载体及其制备方法和应用
CN114478864B (zh) 用于烯烃聚合的催化剂球形载体及其制备方法与应用
CN111072813B (zh) 用于烯烃聚合的催化剂组分和催化剂及其应用与烯烃聚合方法
CN116023543B (zh) 烯烃聚合用催化剂组分、烯烃聚合用催化剂及其应用
CN114478860B (zh) 用于烯烃聚合的催化剂载体及其制备方法与应用和烯烃聚合催化剂及其应用
CN114149518B (zh) 用于烯烃聚合的催化剂载体及其制备方法与应用和催化剂及其应用
CN109206544B (zh) 一种烯烃聚合用催化剂载体及其制备方法和应用
CN111072809B (zh) 用于烯烃聚合的催化剂组分和催化剂及其应用与烯烃聚合方法
CN111072805A (zh) 用于烯烃聚合的催化剂组分和催化剂及其应用与烯烃聚合方法
CN114478862A (zh) 烯烃聚合催化剂载体及其制备方法和应用
CN114149524A (zh) 用于烯烃聚合的催化剂载体及其制备方法与应用和催化剂及其应用
CN117467046A (zh) 用于烯烃聚合的催化剂组分与用于烯烃聚合的催化剂及其应用
CN117467037A (zh) 烯烃聚合用催化剂载体及其制备方法与应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21863692

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2023514982

Country of ref document: JP

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112023004120

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 20237011167

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 112023004120

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20230306

WWE Wipo information: entry into national phase

Ref document number: 202317025402

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021863692

Country of ref document: EP

Effective date: 20230405

WWE Wipo information: entry into national phase

Ref document number: 523442836

Country of ref document: SA

WWE Wipo information: entry into national phase

Ref document number: 523442836

Country of ref document: SA