WO2023124895A1 - Olefin polymerization catalyst, catalyst composition, preparation method therefor and use thereof - Google Patents

Olefin polymerization catalyst, catalyst composition, preparation method therefor and use thereof Download PDF

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WO2023124895A1
WO2023124895A1 PCT/CN2022/137837 CN2022137837W WO2023124895A1 WO 2023124895 A1 WO2023124895 A1 WO 2023124895A1 CN 2022137837 W CN2022137837 W CN 2022137837W WO 2023124895 A1 WO2023124895 A1 WO 2023124895A1
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bis
preparation
amino
trifluoromethanesulfonyl
compound
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Chinese (zh)
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李红明
张明革
义建军
窦彤彤
孟子逸
李荣波
洪柳婷
高玉李
朱百春
雷珺宇
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中国石油天然气股份有限公司
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    • 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
    • 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
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • 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
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • 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
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium 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
    • 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
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/656—Pretreating with metals or metal-containing compounds with silicon or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to the field of olefin polymerization catalysts, in particular to an olefin polymerization catalyst, a catalyst composition and a preparation method and application thereof.
  • Patent CN101891849B dissolves a magnesium halide compound in an organic solvent to form a uniform solution system, and then adds a transition metal halide dropwise to slowly precipitate a solid catalyst.
  • a large amount of hydrogen chloride gas is released, resulting in poor particle shape and uneven particle size distribution of the final solid catalyst, and it is easy to cause the catalyst to stick to the wall.
  • Patent CN102358761B reports a method for preparing an olefin polymerization catalyst.
  • a carrier by dropping a silicon halide compound into a homogeneous organic solvent of magnesium halide, and then adds a transition metal halide dropwise into an organic solvent dispersed with a carrier to obtain a solid polymer.
  • Olefin catalyst components The fine powder content in the product polymer obtained by catalyst catalysis obtained by the method is relatively high, which is unfavorable for industrial production.
  • catalysts are also required to be It has good sensitivity to hydrogen adjustment, that is, it is easy to adjust the melt index of the final polymer through the partial pressure of hydrogen in the polymerization process, so as to obtain polyolefin resins with different properties.
  • the hydrogen modulation sensitivity of the catalyst systems described above is still not satisfactory.
  • the object of the present invention is to provide an olefin polymerization catalyst, a catalyst composition and a preparation method and application thereof.
  • the first aspect of the present invention provides a kind of preparation method of olefin polymerization catalyst, comprises the steps:
  • the sulfonamide silane compound is selected from at least one of the compounds represented by the general formula (I),
  • R 1 and R 2 are the same or different, and R 1 and R 2 are each independently selected from hydrogen atom, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl , substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroatom-containing ring;
  • R 3 , R 4 , R 5 are each independently selected from C 1 -C 8 Straight chain or branched chain alkyl, C 1 -C 8 straight chain or branched chain alkoxy.
  • R and R are each independently selected from fluorine atom, bromine atom, methyl , ethyl, benzenesulfonylmethyl, difluoromethyl , dibromomethyl, trifluoromethyl or tribromomethyl.
  • At least one of R 3 , R 4 , and R 5 is selected from C 1 -C 8 linear or branched alkoxy groups.
  • R 3 , R 4 , and R 5 are each independently selected from methyl, ethyl, n-propyl, isopropyl, methoxy, ethyl Oxygen or 3-propoxyl.
  • At least one of R 3 , R 4 , and R 5 is selected from methoxy, ethoxy or 3-propoxy.
  • R 3 , R 4 , and R 5 are not methyl at the same time.
  • the sulfonamide silane compound is selected from [bis(trifluoromethanesulfonyl)amino]trimethoxysilane, [bis(trifluoromethanesulfonyl) Amino]triethoxysilane, [bis(trifluoromethanesulfonyl)amino]tris(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]methyldimethoxysilane, [bis(trifluoromethanesulfonyl)amino]methyldimethoxysilane, (Trifluoromethanesulfonyl)amino]methyldiethoxysilane, [bis(trifluoromethanesulfonyl)amino]methylbis(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amin
  • the present invention provides several structural formulas of preferred sulfonamide silane compounds (compounds A-E), as follows.
  • the sulfonamide silane compound can be prepared by the following method: make the compound represented by general formula (II) and alkyllithium in tetrahydrofuran or toluene under the condition of -80°C to 30°C in a protective gas atmosphere React for 1-48h, the reaction system is not separated, add R 3 R 4 R 5 SiCl to it and continue to react at -80°C to 30°C for 1-48h, and the silane compound is obtained after the reaction; wherein, the general formula The compound shown in (II): the molar ratio of alkyl lithium: R 3 R 4 R 5 SiCl is 1:(1-5):(1-5).
  • the first reaction temperature is 100°C-150°C
  • the first reaction time is 2-6h.
  • the second reaction temperature is 30°C-60°C, and the second reaction time is 1-5h.
  • the third reaction temperature is -25°C to 0°C
  • the second reaction time is 0.5-8h.
  • the temperature of the third reaction liquid is raised to 80°C-130°C and maintained for 1-4h, and the temperature increase rate of the third reaction liquid is 10°C/h- 60°C/h.
  • the molar ratio of the silane compound to the magnesium compound is 0.01-10, more preferably 0.05-2.
  • the molar ratio of the titanium compound to the magnesium compound is 1-100, more preferably 20-50.
  • the molar ratio of the alcohol to the magnesium compound is 1-10, more preferably 2-6.
  • the magnesium compound is selected from the group consisting of magnesium dihalide, magnesium dihalide hydrate, magnesium dihalide alcoholate, hydrocarbyl magnesium halide and hydrocarbyl magnesium halide One or more of them, preferably magnesium dichloride.
  • the titanium compound is selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, and monochlorotriethoxytitanium , one or more of dichlorodiethoxytitanium and trichloroethoxytitanium.
  • the alcohol is selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, 2-methylpentanol
  • the above preparation method further includes filtering, washing and drying the solid.
  • an inert diluent is used for washing the solid, and the inert diluent is selected from one of hexane, heptane, octane, nonane and decane or Various, preferably hexane and decane.
  • the molar ratio of the inert diluent to the magnesium compound is 1-150, preferably 5-30.
  • the second aspect of the present invention provides an olefin polymerization catalyst obtained by the above preparation method.
  • the third aspect of the present invention provides a catalyst composition, which includes the above-mentioned olefin polymerization catalyst and an organoaluminum compound, and the molar ratio of aluminum element to titanium element in the catalyst composition is 10-1000, preferably 50-500.
  • the general formula of the organoaluminum compound is AlR' n X 3-n , wherein R' is an alkyl group, X is a halogen, and n is 1, 2 or 3.
  • the organoaluminum compound is selected from the group consisting of triethylaluminum, triisobutylaluminum, monochlorodiethylaluminum, dichloroethylaluminum and sesqui
  • ethylaluminum chloride preferably triethylaluminum and triisobutylaluminum.
  • the fourth aspect of the present invention provides an application of the above-mentioned olefin polymerization catalyst or the above-mentioned catalyst composition in olefin polymer.
  • the olefin polymerization is homopolymerization of ethylene or propylene.
  • the olefin polymerization is the copolymerization of ethylene or propylene and an ⁇ -olefin, and the ⁇ -olefin is selected from the group consisting of propylene, butene, pentene, hexene, octane ene, 4-methyl-1-pentene, more preferably propylene.
  • the polymerization method adopts a slurry method, a gas phase method or a solution method.
  • the olefin polymerization catalyst of the invention is suitable for homopolymerization of ethylene or propylene, and copolymerization of ethylene and propylene or other ⁇ -olefins. Compared with the existing catalysts, the olefin polymerization catalyst of the invention has the advantages of uniform particle size distribution, narrow particle size distribution, low polymer fine powder content and good hydrogen adjustment sensitivity.
  • the evaluation and analysis methods adopted include:
  • Catalyst polymerization evaluation Polyethylene was obtained by ethylene slurry polymerization according to the method in the examples. The ratio of the polyethylene mass to the catalyst mass was the catalyst polymerization activity, and the activity unit was kgPE/(gcat.h).
  • the preparation method of the compound A-E that sulfonamide silane compound adopts is as follows:
  • the preparation method of compound A Take a 200ml Schlenk bottle, add 4g of bistrifluoromethanesulfonimide and 40ml of tetrahydrofuran (THF), cool down to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, After reacting for 2 hours, 7 g of dimethylmethoxychlorosilane was added dropwise, allowed to rise to room temperature and reacted for 24 hours, the solvent was removed in vacuo, 60 ml of n-hexane was added for filtration, then the n-hexane was removed in vacuo, and compound A was obtained by distillation under reduced pressure.
  • THF tetrahydrofuran
  • the preparation method of compound B Take a 200ml Schlenk bottle, add 4g of bistrifluoromethanesulfonimide and 40ml of THF, cool down to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, and react for 2h Afterwards, 7 g of methyldimethoxychlorosilane was added dropwise, and allowed to rise to room temperature to react for 24 hours. The solvent was removed in vacuo, and 60 ml of n-hexane was added to filter, then the hexane was removed in vacuo, and the compound B was obtained by distillation under reduced pressure.
  • n-butyllithium 1.6M n-hexane solution
  • the preparation method of compound C Take a 200ml Schlenk bottle, add 4g of bistrifluoromethanesulfonimide and 40ml of THF, cool down to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, and react for 2h , dropwise added 7g of trimethoxychlorosilane, naturally rose to room temperature and reacted for 24 hours, removed the solvent in vacuo, added 60ml of n-hexane for filtration, then removed the n-hexane in vacuo, and distilled under reduced pressure to obtain compound C.
  • n-butyllithium 1.6M n-hexane solution
  • the preparation method of compound D Take a 200ml Schlenk bottle, add 8g of bistrifluoromethanesulfonimide and 80ml of THF, cool down to 0°C, slowly add 60ml of n-butyllithium (1.6M n-hexane solution) dropwise, and react for 2h , dropwise added 14 g of monomethyltrichlorosilane, naturally rose to room temperature and reacted for 24 hours, removed the solvent in vacuo, added 100 ml of n-hexane to filter, then removed the n-hexane in vacuo, and distilled under reduced pressure to obtain the intermediate [bis(trifluoromethanesulfonyl ) amino] methyl dichlorosilane; get a 500ml schlenk bottle, add the above-synthesized intermediate [two (trifluoromethanesulfonyl) amino] methyl dichlorosilane 5g and 100mL toluene, then add drop
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • the temperature of the mixture was kept at -20°C for 1 hour, and then the temperature of the system was raised to 110°C over 3 hours, and this temperature was maintained for 2 hours.
  • the generated solid is separated by hot filtration, and then the solid catalyst is fully washed with hexane until no precipitated titanium compound is detected in the cleaning solution.
  • Uniform, spherical solid catalyst finished product that is, olefin polymerization catalyst.
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • the temperature of the mixture was kept at -20°C for 1 hour, and then the temperature of the system was raised to 110°C over 3 hours, and this temperature was maintained for 2 hours.
  • the generated solid is separated by hot filtration, and then the solid catalyst is fully washed with hexane until no precipitated titanium compound is detected in the cleaning solution.
  • Uniform, spherical solid catalyst finished product that is, olefin polymerization catalyst.
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • the temperature of the mixture was kept at -20°C for 1 hour, and then the temperature of the system was raised to 110°C over 3 hours, and this temperature was maintained for 2 hours.
  • the generated solid is separated by hot filtration, and then the solid catalyst is fully washed with hexane until no precipitated titanium compound is detected in the cleaning solution.
  • Uniform, spherical solid catalyst finished product that is, olefin polymerization catalyst.
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • the preparation method of the olefin polymerization catalyst was the same as in Example 1, except that compound A was replaced by [bis(trifluoromethanesulfonyl)amino]methyldimethoxysilane (compound B).
  • the ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • the preparation method of the olefin polymerization catalyst was the same as in Example 1, except that [bis(trifluoromethanesulfonyl)amino]trimethoxysilane (compound C) was used instead of compound A.
  • the ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • the preparation method of the olefin polymerization catalyst was the same as in Example 1, except that compound A was replaced by [bis(trifluoromethanesulfonyl)amino]methyldiethoxysilane (compound D).
  • the ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • the preparation method of the olefin polymerization catalyst was the same as in Example 1, except that [bis(trifluoromethanesulfonyl)amino]triethoxysilane (compound E) replaced compound A.
  • the ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • the preparation method of the olefin polymerization catalyst was the same as in Example 1, except that the amount of [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane (compound A) added was 3.7 ml.
  • the ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • the preparation method of the olefin polymerization catalyst is the same as that of Example 1, the only difference being that the addition of [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane (compound A) is 1.5ml.
  • the ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
  • This comparative example provides a kind of preparation method of catalyst, specifically as follows:
  • the preparation method of the catalyst is the same as that of Example 1, and the catalyst component is prepared by the same method as that of Example 1, except that no sulfonamide silane compound is added.
  • the catalyst was difficult to separate out, and the solid was difficult to settle, failing to form a catalyst.
  • This comparative example provides a kind of preparation method and application of catalyst, specifically as follows:
  • the preparation method of the catalyst is the same as in Example 1, except that compound A is replaced by tetraethoxysilane.
  • the ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
  • This comparative example provides a kind of preparation method and application of catalyst, specifically as follows:

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Abstract

The present invention provides an olefin polymerization catalyst, a catalyst composition, a preparation method therefor and the use thereof. The preparation method for the olefin polymerization catalyst comprises the following steps: (1) dissolving a magnesium compound in an alcohol to perform a first reaction to obtain a first reaction solution; (2) adding a sulfonamide silane compound into the first reaction solution to perform a second reaction to obtain a second reaction solution; (3) adding the second reaction solution into a titanium compound to perform a third reaction to obtain a third reaction solution; and (4) heating the third reaction solution, keeping the temperature, and generating a solid so as to obtain the olefin polymerization catalyst. The olefin polymerization catalyst of the present invention has the advantages of uniform and narrow particle size distribution, low polymer fine powder content and good hydrogen response.

Description

烯烃聚合催化剂、催化剂组合物及其制备方法与应用Olefin polymerization catalyst, catalyst composition, preparation method and application thereof 技术领域technical field
本发明涉及烯烃聚合催化剂领域，具体涉及一种烯烃聚合催化剂、催化剂组合物及其制备方法与应用。The invention relates to the field of olefin polymerization catalysts, in particular to an olefin polymerization catalyst, a catalyst composition and a preparation method and application thereof.
背景技术Background technique
近年来茂金属与非茂金属等单活性中心催化剂成为聚烯烃催化剂研究与开发的热点，单中心催化剂的工业化应用也逐渐增加，但Ziegler-Natta催化剂在聚烯烃的工业化生产中仍旧占据主导地位。Ziegler-Natta催化剂产品层出不穷，催化剂稳定性与聚合活性也不断提高。但是，目前所用的催化剂在聚合过程中很容易产生较细的聚合物粒子，这种细粉的存在往往会导致聚合物的低堆积密度，造成设备或管道的堵塞，影响装置的长周期运行。In recent years, single-site catalysts such as metallocenes and non-metallocenes have become hot spots in the research and development of polyolefin catalysts, and the industrial application of single-site catalysts has gradually increased, but Ziegler-Natta catalysts still occupy a dominant position in the industrial production of polyolefins. Ziegler-Natta catalyst products emerge in endlessly, and catalyst stability and polymerization activity are also continuously improved. However, the catalysts currently used are prone to produce finer polymer particles during the polymerization process. The existence of such fine powders often leads to low bulk density of the polymer, causing blockage of equipment or pipelines, and affecting the long-term operation of the device.
专利CN101891849B将卤化镁化合物溶解于有机溶剂中，形成均一的溶液体系，然后滴加过渡金属卤化物缓慢析出固体催化剂。但由于向卤化镁均相溶液中直接滴加过渡金属卤化物过程反应剧烈，氯化氢气体大量释放，使得最终所得固体催化剂颗粒形态较差、粒径分布不均匀，且容易造成催化剂粘壁现象。专利CN102358761B报道了一种烯烃聚合催化剂制备方法，其先通过向卤化镁的均相有机溶剂中滴加卤化硅化合物得到载体，再向分散有载体的有机溶剂中滴加过渡金属卤化物得到固体聚烯烃催化剂组分。该方法所得催化剂催化所得产物聚合物中细粉含量较高，不利于工业生产。Patent CN101891849B dissolves a magnesium halide compound in an organic solvent to form a uniform solution system, and then adds a transition metal halide dropwise to slowly precipitate a solid catalyst. However, due to the violent reaction during the direct dropwise addition of transition metal halides to the homogeneous magnesium halide solution, a large amount of hydrogen chloride gas is released, resulting in poor particle shape and uneven particle size distribution of the final solid catalyst, and it is easy to cause the catalyst to stick to the wall. Patent CN102358761B reports a method for preparing an olefin polymerization catalyst. It first obtains a carrier by dropping a silicon halide compound into a homogeneous organic solvent of magnesium halide, and then adds a transition metal halide dropwise into an organic solvent dispersed with a carrier to obtain a solid polymer. Olefin catalyst components. The fine powder content in the product polymer obtained by catalyst catalysis obtained by the method is relatively high, which is unfavorable for industrial production.
另外，在工业装置生产聚烯烃的过程中，除要求催化剂应具有较高的催化活性和较好的颗粒分布外，为了生产具有较好性能的聚烯烃均聚物或共聚物，还要求催化剂应具有较好的氢调敏感性，即很容易地通过聚合过程中氢分压来调节最终聚合物的熔融指数，以得到不同性能的聚烯烃树脂。而上述的催化剂体系的氢调敏感性还不能令人满意。In addition, in the process of producing polyolefins in industrial plants, in addition to requiring catalysts to have higher catalytic activity and better particle distribution, in order to produce polyolefin homopolymers or copolymers with better performance, catalysts are also required to be It has good sensitivity to hydrogen adjustment, that is, it is easy to adjust the melt index of the final polymer through the partial pressure of hydrogen in the polymerization process, so as to obtain polyolefin resins with different properties. However, the hydrogen modulation sensitivity of the catalyst systems described above is still not satisfactory.
发明内容Contents of the invention
为解决上述技术问题，发明人意外地发现，在烯烃聚合催化剂制备时，加入一种新型硅烷类化合物，催化体系具有良好的氢调敏感性和聚合活性。基于上述发现，本发明的目的在于提供一种烯烃聚合催化剂、催化剂组合物及其制备方法与应用。In order to solve the above technical problems, the inventors unexpectedly found that when a new type of silane compound is added to the preparation of the olefin polymerization catalyst, the catalytic system has good hydrogenation sensitivity and polymerization activity. Based on the above findings, the object of the present invention is to provide an olefin polymerization catalyst, a catalyst composition and a preparation method and application thereof.
为达到上述目的，本发明第一方面提供一种烯烃聚合催化剂的制备方法，包括如下步骤：In order to achieve the above object, the first aspect of the present invention provides a kind of preparation method of olefin polymerization catalyst, comprises the steps:
(1)将镁化合物溶解于醇中进行第一反应，得到第一反应液；(1) dissolving the magnesium compound in alcohol to carry out the first reaction to obtain the first reaction solution;
(2)向所述第一反应液中加入磺酰胺硅烷类化合物进行第二反应，得到第二反应 液；(2) adding a sulfonamide silane compound to the first reaction solution to carry out a second reaction to obtain a second reaction solution;
(3)将所述第二反应液加入至钛化合物中进行第三反应，得到第三反应液；(3) adding the second reaction solution to the titanium compound to perform a third reaction to obtain a third reaction solution;
(4)将所述第三反应液升温并保持该温度，生成固体，从而得到所述烯烃聚合催化剂；(4) raising the temperature of the third reaction solution and maintaining the temperature to generate a solid, thereby obtaining the olefin polymerization catalyst;
所述磺酰胺硅烷类化合物选自通式(I)所示化合物中至少一种，The sulfonamide silane compound is selected from at least one of the compounds represented by the general formula (I),
Figure PCTCN2022137837-appb-000001
Figure PCTCN2022137837-appb-000001
其中，R 1、R 2相同或不同，R 1和R 2各自独立地选自氢原子、卤素、取代或未取代的烷基、取代或未取代的环烷基、取代或未取代的芳基、取代或未取代的芳烷基、取代或未取代的烷基芳基、取代或未取代的含杂原子的环；R 3、R 4、R 5各自独立地选自C 1-C 8的直链或支链烷基、C 1-C 8的直链或支链烷氧基。 Wherein, R 1 and R 2 are the same or different, and R 1 and R 2 are each independently selected from hydrogen atom, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl , substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroatom-containing ring; R 3 , R 4 , R 5 are each independently selected from C 1 -C 8 Straight chain or branched chain alkyl, C 1 -C 8 straight chain or branched chain alkoxy.
根据本发明的具体实施方案，优选地，通式(I)中，R 1和R 2各自独立地选自氟原子、溴原子、甲基、乙基、苯磺酰基甲基、二氟甲基、二溴甲基、三氟甲基或三溴甲基。 According to a specific embodiment of the present invention, preferably, in general formula (I), R and R are each independently selected from fluorine atom, bromine atom, methyl , ethyl, benzenesulfonylmethyl, difluoromethyl , dibromomethyl, trifluoromethyl or tribromomethyl.
根据本发明的具体实施方案，优选地，通式(I)中，R 3、R 4、R 5中至少一个选自C 1-C 8的直链或支链烷氧基。 According to a specific embodiment of the present invention, preferably, in the general formula (I), at least one of R 3 , R 4 , and R 5 is selected from C 1 -C 8 linear or branched alkoxy groups.
根据本发明的具体实施方案，优选地，通式(I)中，R 3、R 4、R 5各自独立地选自甲基、乙基、正丙基、异丙基、甲氧基、乙氧基或3-丙氧基。 According to a specific embodiment of the present invention, preferably, in general formula (I), R 3 , R 4 , and R 5 are each independently selected from methyl, ethyl, n-propyl, isopropyl, methoxy, ethyl Oxygen or 3-propoxyl.
根据本发明的具体实施方案，优选地，通式(I)中，R 3、R 4、R 5中至少一个选自甲氧基、乙氧基或3-丙氧基。 According to a specific embodiment of the present invention, preferably, in the general formula (I), at least one of R 3 , R 4 , and R 5 is selected from methoxy, ethoxy or 3-propoxy.
根据本发明的具体实施方案，优选地，通式(I)中，R 3、R 4、R 5不同时为甲基。 According to a specific embodiment of the present invention, preferably, in the general formula (I), R 3 , R 4 , and R 5 are not methyl at the same time.
根据本发明的具体实施方案，优选地，上述制备方法中，所述磺酰胺硅烷类化合物选自[双(三氟甲磺酰基)氨基]三甲氧基硅烷、[双(三氟甲磺酰基)氨基]三乙氧基硅烷、[双(三氟甲磺酰基)氨基]三(3-丙氧基)硅烷、[双(三氟甲磺酰基)氨基]甲基二甲氧基硅烷、[双(三氟甲磺酰基)氨基]甲基二乙氧基硅烷、[双(三氟甲磺酰基)氨基]甲基二(3-丙氧基)硅烷、[双(三氟甲磺酰基)氨基]二甲基甲氧基硅烷、[双(三氟甲磺酰基)氨基]二甲基乙氧基硅烷、[双(三氟甲磺酰基)氨基]二甲基(3-丙氧基)硅烷、[双(三氟甲磺酰基)氨基]乙基二甲氧基硅烷、[双(三氟甲磺酰基)氨基]乙基二乙氧基硅烷、[双(三氟甲磺酰基)氨基]乙基二 (3-丙氧基)硅烷、[双(三氟甲磺酰基)氨基]二乙基甲氧基硅烷、[双(三氟甲磺酰基)氨基]二乙基乙氧基硅烷、[双(三氟甲磺酰基)氨基]二乙基(3-丙氧基)硅烷、[双(三溴甲磺酰基)氨基](3-丙基)二甲氧基硅烷、[双(三溴甲磺酰基)氨基](3-丙基)二乙氧基硅烷、[双(三溴甲磺酰基)氨基](3-丙基)二(3-丙氧基)硅烷、[双(三溴甲磺酰基)氨基]二(3-丙基)甲氧基硅烷、[双(三溴甲磺酰基)氨基]二(3-丙基)乙氧基硅烷、[双(三溴甲磺酰基)氨基]二(3-丙基)(3-丙氧基)硅烷中的一种或多种。According to a specific embodiment of the present invention, preferably, in the above preparation method, the sulfonamide silane compound is selected from [bis(trifluoromethanesulfonyl)amino]trimethoxysilane, [bis(trifluoromethanesulfonyl) Amino]triethoxysilane, [bis(trifluoromethanesulfonyl)amino]tris(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]methyldimethoxysilane, [bis(trifluoromethanesulfonyl)amino]methyldimethoxysilane, (Trifluoromethanesulfonyl)amino]methyldiethoxysilane, [bis(trifluoromethanesulfonyl)amino]methylbis(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino ]Dimethylmethoxysilane, [bis(trifluoromethanesulfonyl)amino]dimethylethoxysilane, [bis(trifluoromethanesulfonyl)amino]dimethyl(3-propoxy)silane , [bis(trifluoromethanesulfonyl)amino]ethyldimethoxysilane, [bis(trifluoromethanesulfonyl)amino]ethyldiethoxysilane, [bis(trifluoromethanesulfonyl)amino] Ethylbis(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]diethylmethoxysilane, [bis(trifluoromethanesulfonyl)amino]diethylethoxysilane, [Bis(trifluoromethanesulfonyl)amino]diethyl(3-propoxy)silane, [bis(tribromomethanesulfonyl)amino](3-propyl)dimethoxysilane, [bis(tri Bromomethanesulfonyl)amino](3-propyl)diethoxysilane, [bis(tribromomethanesulfonyl)amino](3-propyl)bis(3-propoxy)silane, [bis(tribromomethanesulfonyl)amino](3-propyl)bis(3-propoxy)silane, Bromomethanesulfonyl)amino]bis(3-propyl)methoxysilane, [bis(tribromomethanesulfonyl)amino]bis(3-propyl)ethoxysilane, [bis(tribromomethanesulfonyl) ) Amino] one or more of two (3-propyl) (3-propoxy) silanes.
根据本发明的具体实施方案，本发明提供几种优选磺酰胺硅烷类化合物(化合物A-E)的结构式，具体如下。According to specific embodiments of the present invention, the present invention provides several structural formulas of preferred sulfonamide silane compounds (compounds A-E), as follows.
Figure PCTCN2022137837-appb-000002
Figure PCTCN2022137837-appb-000002
Figure PCTCN2022137837-appb-000003
Figure PCTCN2022137837-appb-000003
在本发明中，所述磺酰胺硅烷类化合物可以采用如下方法制备得到：使通式(II)所示化合物和烷基锂在保护气氛围、-80℃至30℃条件下于四氢呋喃或甲苯中反应1-48h，反应体系不经分离，向其中加入R 3R 4R 5SiCl继续在-80℃至30℃条件下反应1-48h，反应结束后得到所述硅烷类化合物；其中，通式(II)所示化合物：烷基锂：R 3R 4R 5SiCl的摩尔比为1:(1-5):(1-5)。 In the present invention, the sulfonamide silane compound can be prepared by the following method: make the compound represented by general formula (II) and alkyllithium in tetrahydrofuran or toluene under the condition of -80°C to 30°C in a protective gas atmosphere React for 1-48h, the reaction system is not separated, add R 3 R 4 R 5 SiCl to it and continue to react at -80°C to 30°C for 1-48h, and the silane compound is obtained after the reaction; wherein, the general formula The compound shown in (II): the molar ratio of alkyl lithium: R 3 R 4 R 5 SiCl is 1:(1-5):(1-5).
Figure PCTCN2022137837-appb-000004
Figure PCTCN2022137837-appb-000004
根据本发明的具体实施方案，优选地，上述制备方法中，所述第一反应温度为100℃-150℃，第一反应时间为2-6h。According to a specific embodiment of the present invention, preferably, in the above preparation method, the first reaction temperature is 100°C-150°C, and the first reaction time is 2-6h.
根据本发明的具体实施方案，优选地，上述制备方法中，所述第二反应温度为30℃-60℃，第二反应时间为1-5h。According to a specific embodiment of the present invention, preferably, in the above preparation method, the second reaction temperature is 30°C-60°C, and the second reaction time is 1-5h.
根据本发明的具体实施方案，优选地，上述制备方法中，所述第三反应温度为-25℃至0℃，第二反应时间为0.5-8h。According to a specific embodiment of the present invention, preferably, in the above preparation method, the third reaction temperature is -25°C to 0°C, and the second reaction time is 0.5-8h.
根据本发明的具体实施方案，优选地，上述制备方法中，所述第三反应液升温至 80℃-130℃并保持1-4h，所述第三反应液的升温速率为10℃/h-60℃/h。According to a specific embodiment of the present invention, preferably, in the above preparation method, the temperature of the third reaction liquid is raised to 80°C-130°C and maintained for 1-4h, and the temperature increase rate of the third reaction liquid is 10°C/h- 60°C/h.
根据本发明的具体实施方案，优选地，上述制备方法中，所述硅烷类化合物与镁化合物的摩尔比为0.01-10，更优选为0.05-2。According to a specific embodiment of the present invention, preferably, in the above preparation method, the molar ratio of the silane compound to the magnesium compound is 0.01-10, more preferably 0.05-2.
根据本发明的具体实施方案，优选地，上述制备方法中，所述钛化合物与镁化合物的摩尔比为1-100，更优选为20-50。According to a specific embodiment of the present invention, preferably, in the above preparation method, the molar ratio of the titanium compound to the magnesium compound is 1-100, more preferably 20-50.
根据本发明的具体实施方案，优选地，上述制备方法中，所述醇与镁化合物的摩尔比为1-10，更优选为2-6。According to a specific embodiment of the present invention, preferably, in the above preparation method, the molar ratio of the alcohol to the magnesium compound is 1-10, more preferably 2-6.
根据本发明的具体实施方案，优选地，上述制备方法中，所述镁化合物选自二卤化镁、二卤化镁的水合物、二卤化镁的醇合物、烃基卤化镁和烃氧基卤化镁中的一种或多种，优选为二氯化镁。According to a specific embodiment of the present invention, preferably, in the above preparation method, the magnesium compound is selected from the group consisting of magnesium dihalide, magnesium dihalide hydrate, magnesium dihalide alcoholate, hydrocarbyl magnesium halide and hydrocarbyl magnesium halide One or more of them, preferably magnesium dichloride.
根据本发明的具体实施方案，优选地，上述制备方法中，所述钛化合物选自四氯化钛、四溴化钛、四碘化钛、四丁氧基钛、一氯三乙氧基钛、二氯二乙氧基钛和三氯一乙氧基钛中一种或多种。According to a specific embodiment of the present invention, preferably, in the above preparation method, the titanium compound is selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, and monochlorotriethoxytitanium , one or more of dichlorodiethoxytitanium and trichloroethoxytitanium.
根据本发明的具体实施方案，优选地，上述制备方法中，所述醇选自甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、戊醇、己醇、2-甲基戊醇、2-乙基丁醇、庚醇、2-乙基己醇、辛醇、癸醇、十二烷醇、十四烷醇和十八烷醇中的一种或多种，更优选为2-乙基己醇、2-甲基戊醇和2-乙基丁醇中的一种或多种。According to a specific embodiment of the present invention, preferably, in the above preparation method, the alcohol is selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, 2-methylpentanol One or more of alcohol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, myristyl alcohol and stearyl alcohol, more preferably 2 - one or more of ethylhexanol, 2-methylpentanol and 2-ethylbutanol.
根据本发明的具体实施方案，优选地，上述制备方法还包括对所述固体进行过滤、洗涤和干燥。According to a specific embodiment of the present invention, preferably, the above preparation method further includes filtering, washing and drying the solid.
根据本发明的具体实施方案，优选地，上述制备方法中，洗涤所述固体采用惰性稀释剂，所述惰性稀释剂选自己烷、庚烷、辛烷、壬烷和癸烷中的一种或多种，优选己烷和癸烷。According to a specific embodiment of the present invention, preferably, in the above preparation method, an inert diluent is used for washing the solid, and the inert diluent is selected from one of hexane, heptane, octane, nonane and decane or Various, preferably hexane and decane.
根据本发明的具体实施方案，优选地，上述制备方法中，所述惰性稀释剂与镁化合物的摩尔比为1-150，优选为5-30。According to a specific embodiment of the present invention, preferably, in the above preparation method, the molar ratio of the inert diluent to the magnesium compound is 1-150, preferably 5-30.
本发明第二方面提供一种上述制备方法得到的烯烃聚合催化剂。The second aspect of the present invention provides an olefin polymerization catalyst obtained by the above preparation method.
本发明第三方面提供一种催化剂组合物，其包括上述烯烃聚合催化剂和有机铝化合物，所述催化剂组合物中铝元素与钛元素的摩尔比为10-1000，优选为50-500。The third aspect of the present invention provides a catalyst composition, which includes the above-mentioned olefin polymerization catalyst and an organoaluminum compound, and the molar ratio of aluminum element to titanium element in the catalyst composition is 10-1000, preferably 50-500.
根据本发明的具体实施方案，优选地，上述催化剂组合物中，所述有机铝化合物的通式为AlR’ nX 3-n，其中，R’为烷基、X为卤素，n为1、2或3。 According to a specific embodiment of the present invention, preferably, in the above catalyst composition, the general formula of the organoaluminum compound is AlR' n X 3-n , wherein R' is an alkyl group, X is a halogen, and n is 1, 2 or 3.
根据本发明的具体实施方案，优选地，上述催化剂组合物中，所述有机铝化合物选自三乙基铝、三异丁基铝、一氯二乙基铝、二氯乙基铝和倍半乙基氯化铝中的一种或多 种，优选三乙基铝和三异丁基铝。According to a specific embodiment of the present invention, preferably, in the above catalyst composition, the organoaluminum compound is selected from the group consisting of triethylaluminum, triisobutylaluminum, monochlorodiethylaluminum, dichloroethylaluminum and sesqui One or more of ethylaluminum chloride, preferably triethylaluminum and triisobutylaluminum.
本发明第四方面提供一种上述烯烃聚合催化剂或上述催化剂组合物在烯烃聚合物中的应用。The fourth aspect of the present invention provides an application of the above-mentioned olefin polymerization catalyst or the above-mentioned catalyst composition in olefin polymer.
根据本发明的具体实施方案，优选地，上述应用中，所述烯烃聚合为乙烯或丙烯的均聚合。According to a specific embodiment of the present invention, preferably, in the above application, the olefin polymerization is homopolymerization of ethylene or propylene.
根据本发明的具体实施方案，优选地，上述应用中，所述烯烃聚合为乙烯或丙烯与α-烯烃的共聚合，所述α-烯烃选自丙烯、丁烯、戊烯、己烯、辛烯、4-甲基1-戊烯，更优选为丙烯。According to a specific embodiment of the present invention, preferably, in the above application, the olefin polymerization is the copolymerization of ethylene or propylene and an α-olefin, and the α-olefin is selected from the group consisting of propylene, butene, pentene, hexene, octane ene, 4-methyl-1-pentene, more preferably propylene.
根据本发明的具体实施方案，优选地，上述应用中，聚合方式采用淤浆法、气相法或溶液法。According to a specific embodiment of the present invention, preferably, in the above application, the polymerization method adopts a slurry method, a gas phase method or a solution method.
本发明的烯烃聚合催化剂及其制备方法与应用，具有如下有益效果：The olefin polymerization catalyst of the present invention and its preparation method and application have the following beneficial effects:
本发明的烯烃聚合催化剂适用于乙烯或丙烯的均聚合，以及乙烯与丙烯或其它α-烯烃的共聚合反应。与现有的催化剂相比，本发明的烯烃聚合催化剂的优点是颗粒大小分布均匀，粒径分布窄，聚合物细粉含量低，同时还具有良好的氢调敏感性。The olefin polymerization catalyst of the invention is suitable for homopolymerization of ethylene or propylene, and copolymerization of ethylene and propylene or other α-olefins. Compared with the existing catalysts, the olefin polymerization catalyst of the invention has the advantages of uniform particle size distribution, narrow particle size distribution, low polymer fine powder content and good hydrogen adjustment sensitivity.
具体实施方式Detailed ways
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.
在本发明的具体实施方案中，采用的评价分析方法包括：In a specific embodiment of the present invention, the evaluation and analysis methods adopted include:
1、根据国家标准GB/T 3682-2018，测定聚合产物的熔融指数，5kg砝码；1. According to the national standard GB/T 3682-2018, measure the melt index of the polymerization product, 5kg weight;
2、根据国家标准GB/T 1636-2008，测定聚合产物的堆密度；2. According to the national standard GB/T 1636-2008, measure the bulk density of the polymerization product;
3、根据国家标准GB/T 21843-2008，测定聚合产物的粒径分布；3. According to the national standard GB/T 21843-2008, measure the particle size distribution of the polymerization product;
4、催化剂聚合评价：按照实施例中方式进行乙烯淤浆聚合得到聚乙烯，聚乙烯质量与催化剂质量之比即为催化剂聚合活性，活性单位为kgPE/(gcat.h)。4. Catalyst polymerization evaluation: Polyethylene was obtained by ethylene slurry polymerization according to the method in the examples. The ratio of the polyethylene mass to the catalyst mass was the catalyst polymerization activity, and the activity unit was kgPE/(gcat.h).
在本发明的具体实施方式中，磺酰胺硅烷类化合物采用的化合物A-E的制备方法如下：In the specific embodiment of the present invention, the preparation method of the compound A-E that sulfonamide silane compound adopts is as follows:
化合物A的制备方法：取200ml Schlenk瓶，加入双三氟甲基磺酰亚胺4g和四氢呋喃(THF)40ml，降温至0℃，缓慢滴加正丁基锂(1.6M正己烷溶液)30ml，反应2h后，滴加二甲基甲氧基氯硅烷7g，自然升至室温反应24小时，真空除去溶剂，加入60ml正己烷过滤，然后真空除去正己烷，减压蒸馏，得到化合物A。The preparation method of compound A: Take a 200ml Schlenk bottle, add 4g of bistrifluoromethanesulfonimide and 40ml of tetrahydrofuran (THF), cool down to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, After reacting for 2 hours, 7 g of dimethylmethoxychlorosilane was added dropwise, allowed to rise to room temperature and reacted for 24 hours, the solvent was removed in vacuo, 60 ml of n-hexane was added for filtration, then the n-hexane was removed in vacuo, and compound A was obtained by distillation under reduced pressure.
化合物B的制备方法：取200ml Schlenk瓶，加入双三氟甲基磺酰亚胺4g和THF 40 ml，降温至0℃，缓慢滴加正丁基锂(1.6M正己烷溶液)30ml，反应2h后，滴加甲基二甲氧基氯硅烷7g，自然升至室温反应24小时，真空除去溶剂，加入60ml正己烷过滤，然后真空除去正己烷，减压蒸馏，得到化合物B。The preparation method of compound B: Take a 200ml Schlenk bottle, add 4g of bistrifluoromethanesulfonimide and 40ml of THF, cool down to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, and react for 2h Afterwards, 7 g of methyldimethoxychlorosilane was added dropwise, and allowed to rise to room temperature to react for 24 hours. The solvent was removed in vacuo, and 60 ml of n-hexane was added to filter, then the hexane was removed in vacuo, and the compound B was obtained by distillation under reduced pressure.
化合物C的制备方法：取200ml Schlenk瓶，加入双三氟甲基磺酰亚胺4g和THF 40ml，降温至0℃，缓慢滴加正丁基锂(1.6M正己烷溶液)30ml，反应2h后，滴加三甲氧基氯硅烷7g，自然升至室温反应24小时，真空除去溶剂，加入60ml正己烷过滤，然后真空除去正己烷，减压蒸馏，得到化合物C。The preparation method of compound C: Take a 200ml Schlenk bottle, add 4g of bistrifluoromethanesulfonimide and 40ml of THF, cool down to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, and react for 2h , dropwise added 7g of trimethoxychlorosilane, naturally rose to room temperature and reacted for 24 hours, removed the solvent in vacuo, added 60ml of n-hexane for filtration, then removed the n-hexane in vacuo, and distilled under reduced pressure to obtain compound C.
化合物D的制备方法：取200ml Schlenk瓶，加入双三氟甲基磺酰亚胺8g和THF 80ml，降温至0℃，缓慢滴加正丁基锂(1.6M正己烷溶液)60ml，反应2h后，滴加一甲基三氯硅烷14g，自然升至室温反应24小时，真空除去溶剂，加入100ml正己烷过滤，然后真空除去正己烷，减压蒸馏，得到中间体[双(三氟甲磺酰基)氨基]甲基二氯硅烷；取500ml schlenk瓶，加入上面合成的中间体[双(三氟甲磺酰基)氨基]甲基二氯硅烷5g和100mL甲苯，然后滴加无水乙醇7.5g和三乙胺15g的甲苯溶液，反应12h，真空下除去溶剂，加正己烷过滤，然后真空除去正己烷，减压蒸馏，得到化合物D。The preparation method of compound D: Take a 200ml Schlenk bottle, add 8g of bistrifluoromethanesulfonimide and 80ml of THF, cool down to 0°C, slowly add 60ml of n-butyllithium (1.6M n-hexane solution) dropwise, and react for 2h , dropwise added 14 g of monomethyltrichlorosilane, naturally rose to room temperature and reacted for 24 hours, removed the solvent in vacuo, added 100 ml of n-hexane to filter, then removed the n-hexane in vacuo, and distilled under reduced pressure to obtain the intermediate [bis(trifluoromethanesulfonyl ) amino] methyl dichlorosilane; get a 500ml schlenk bottle, add the above-synthesized intermediate [two (trifluoromethanesulfonyl) amino] methyl dichlorosilane 5g and 100mL toluene, then add dropwise dehydrated alcohol 7.5g and A toluene solution of 15 g of triethylamine was reacted for 12 hours, the solvent was removed under vacuum, and n-hexane was added to filter, then the n-hexane was removed under vacuum, and compound D was obtained by distillation under reduced pressure.
化合物E的制备方法：取200ml Schlenk瓶，加入双三氟甲基磺酰亚胺4g和THF 40ml，降温至0℃，缓慢滴加正丁基锂(1.6M正己烷溶液)30ml，反应2h后，滴加三乙氧基氯硅烷7g，自然升至室温反应24小时，真空除去溶剂，加入60ml正己烷过滤，然后真空除去正己烷，减压蒸馏，得到化合物E。The preparation method of compound E: Take a 200ml Schlenk bottle, add 4g of bistrifluoromethanesulfonimide and 40ml of THF, cool down to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, and react for 2h , dropwise added 7g of triethoxychlorosilane, naturally rose to room temperature and reacted for 24 hours, removed the solvent in vacuo, added 60ml of n-hexane for filtration, then removed the n-hexane in vacuo, and distilled under reduced pressure to obtain compound E.
下面结合具体实施例详细描述本发明。The present invention will be described in detail below in conjunction with specific embodiments.
实施例1Example 1
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
(1)烯烃聚合催化剂的制备：(1) Preparation of olefin polymerization catalyst:
在经过氮气充分置换过的反应器中，加入5g二氯化镁，50ml正癸烷，23ml异辛醇，搅拌升温至130℃，恒温反应3h，固体完全溶解形成均一透明的溶液。降温至50℃，加入[双(三氟甲磺酰基)氨基]二甲基甲氧基硅烷(化合物A)2.8ml，反应2h，得到均一溶液。将上述得到的均一溶液冷却至室温，然后在1小时内将其滴加到温度保持为-20℃的200mL四氯化钛中。滴完后使混合物温度在-20℃下保持1小时，然后在3小时内将体系升温至110℃，并将此温度保持2小时。当2小时反应结束后，对生成的固体进行热过滤分离，然后用己烷对固体催化剂进行充分洗涤，直至在清洗液中检测不出析出的钛化合物，干燥后得到流动性好、粒径分布均匀、呈类球形的固体催化剂成品，即烯烃聚 合催化剂。Add 5g of magnesium dichloride, 50ml of n-decane, and 23ml of isooctyl alcohol into the reactor that has been fully replaced with nitrogen, stir and raise the temperature to 130°C, react at constant temperature for 3 hours, and the solids are completely dissolved to form a uniform and transparent solution. Cool down to 50°C, add 2.8ml of [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane (Compound A), and react for 2h to obtain a homogeneous solution. The homogeneous solution obtained above was cooled to room temperature, and then added dropwise to 200 mL of titanium tetrachloride maintained at -20° C. within 1 hour. After the dropwise completion, the temperature of the mixture was kept at -20°C for 1 hour, and then the temperature of the system was raised to 110°C over 3 hours, and this temperature was maintained for 2 hours. When the 2-hour reaction is over, the generated solid is separated by hot filtration, and then the solid catalyst is fully washed with hexane until no precipitated titanium compound is detected in the cleaning solution. Uniform, spherical solid catalyst finished product, that is, olefin polymerization catalyst.
(2)乙烯聚合：(2) Ethylene polymerization:
将2L聚合釜充氢气和抽真空交替进行三次，加入1.0L己烷、5mmol三乙基铝和本实施例制备的烯烃聚合催化剂，反应釜升温至70℃，通入氢气使釜内压力达到0.28MPa，然后再通入乙烯使釜内总压达到0.73MPa，在80℃下聚合反应2小时。聚合结果见表1。Fill the 2L polymerization kettle with hydrogen and vacuumize it alternately three times, add 1.0L of hexane, 5mmol of triethylaluminum and the olefin polymerization catalyst prepared in this example, raise the temperature of the reaction kettle to 70°C, and feed hydrogen to make the pressure inside the kettle reach 0.28 MPa, and then feed ethylene to make the total pressure in the kettle reach 0.73 MPa, and conduct polymerization reaction at 80°C for 2 hours. The aggregation results are shown in Table 1.
实施例2Example 2
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
(1)烯烃聚合催化剂的制备：(1) Preparation of olefin polymerization catalyst:
在经过氮气充分置换过的反应器中，加入5g二氯化镁，40ml正癸烷，23ml异辛醇，搅拌升温至130℃，恒温反应3h，固体完全溶解形成均一透明的溶液。降温至50℃，加入[双(三氟甲磺酰基)氨基]二甲基甲氧基硅烷(化合物A)2.8ml，反应2h，得到均一溶液。将上述得到的均一溶液冷却至室温，然后在1小时内将其滴加到温度保持为-20℃的100mL四氯化钛中。滴完后使混合物温度在-20℃下保持1小时，然后在3小时内将体系升温至110℃，并将此温度保持2小时。当2小时反应结束后，对生成的固体进行热过滤分离，然后用己烷对固体催化剂进行充分洗涤，直至在清洗液中检测不出析出的钛化合物，干燥后得到流动性好、粒径分布均匀、呈类球形的固体催化剂成品，即烯烃聚合催化剂。Add 5g of magnesium dichloride, 40ml of n-decane, and 23ml of isooctyl alcohol into the reactor fully replaced by nitrogen, stir and raise the temperature to 130°C, react at constant temperature for 3 hours, and the solids are completely dissolved to form a uniform and transparent solution. Cool down to 50°C, add 2.8ml of [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane (Compound A), and react for 2h to obtain a homogeneous solution. The homogeneous solution obtained above was cooled to room temperature, and then added dropwise to 100 mL of titanium tetrachloride maintained at -20°C within 1 hour. After the dropwise completion, the temperature of the mixture was kept at -20°C for 1 hour, and then the temperature of the system was raised to 110°C over 3 hours, and this temperature was maintained for 2 hours. When the 2-hour reaction is over, the generated solid is separated by hot filtration, and then the solid catalyst is fully washed with hexane until no precipitated titanium compound is detected in the cleaning solution. Uniform, spherical solid catalyst finished product, that is, olefin polymerization catalyst.
(2)乙烯聚合：(2) Ethylene polymerization:
将2L聚合釜充氢气和抽真空交替进行三次，加入1.0L己烷、5mmol三乙基铝和本实施例制备的烯烃聚合催化剂，反应釜升温至70℃，通入氢气使釜内压力达到0.28MPa，然后再通入乙烯使釜内总压达到0.73MPa，在80℃下聚合反应2小时。聚合结果见表1。Fill the 2L polymerization kettle with hydrogen and vacuumize it alternately three times, add 1.0L of hexane, 5mmol of triethylaluminum and the olefin polymerization catalyst prepared in this example, raise the temperature of the reaction kettle to 70°C, and feed hydrogen to make the pressure inside the kettle reach 0.28 MPa, and then feed ethylene to make the total pressure in the kettle reach 0.73 MPa, and conduct polymerization reaction at 80°C for 2 hours. The aggregation results are shown in Table 1.
实施例3Example 3
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
(1)烯烃聚合催化剂的制备：(1) Preparation of olefin polymerization catalyst:
在经过氮气充分置换过的反应器中，加入5g二氯化镁，50ml正癸烷，23ml异辛醇，搅拌升温至130℃，恒温反应3h，固体完全溶解形成均一透明的溶液。降温至50℃，加入[双(三氟甲磺酰基)氨基]二甲基甲氧基硅烷(化合物A)1.4ml，反应2h，得到均一溶液。将上述得到的均一溶液冷却至室温，然后在1小时内将其滴加到温度保持为-20℃的200mL四氯化钛中。滴完后使混合物温度在-20℃下保持1小时，然后在3小时内将体系升温至110℃，并将此温度保持2小时。当2小时反应结束后，对生成的固体进行热过滤分离，然后用己烷对固体催化剂进行充分洗涤，直至在清洗液中检测不出析出的钛 化合物，干燥后得到流动性好、粒径分布均匀、呈类球形的固体催化剂成品，即烯烃聚合催化剂。Add 5g of magnesium dichloride, 50ml of n-decane, and 23ml of isooctyl alcohol into the reactor that has been fully replaced with nitrogen, stir and raise the temperature to 130°C, react at constant temperature for 3 hours, and the solids are completely dissolved to form a uniform and transparent solution. Cool down to 50°C, add [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane (compound A) 1.4ml, and react for 2h to obtain a homogeneous solution. The homogeneous solution obtained above was cooled to room temperature, and then added dropwise to 200 mL of titanium tetrachloride maintained at -20° C. within 1 hour. After the dropwise completion, the temperature of the mixture was kept at -20°C for 1 hour, and then the temperature of the system was raised to 110°C over 3 hours, and this temperature was maintained for 2 hours. When the 2-hour reaction is over, the generated solid is separated by hot filtration, and then the solid catalyst is fully washed with hexane until no precipitated titanium compound is detected in the cleaning solution. Uniform, spherical solid catalyst finished product, that is, olefin polymerization catalyst.
(2)乙烯聚合：(2) Ethylene polymerization:
将2L聚合釜充氢气和抽真空交替进行三次，加入1.0L己烷、5mmol三乙基铝和本实施例制备的烯烃聚合催化剂，反应釜升温至70℃，通入氢气使釜内压力达到0.28MPa，然后再通入乙烯使釜内总压达到0.73MPa，在80℃下聚合反应2小时。聚合结果见表1。Fill the 2L polymerization kettle with hydrogen and vacuumize it alternately three times, add 1.0L of hexane, 5mmol of triethylaluminum and the olefin polymerization catalyst prepared in this example, raise the temperature of the reaction kettle to 70°C, and feed hydrogen to make the pressure inside the kettle reach 0.28 MPa, and then feed ethylene to make the total pressure in the kettle reach 0.73 MPa, and conduct polymerization reaction at 80°C for 2 hours. The aggregation results are shown in Table 1.
实施例4Example 4
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
烯烃聚合催化剂的制备方法与实施例1相同，不同之处仅在于，以[双(三氟甲磺酰基)氨基]甲基二甲氧基硅烷(化合物B)代替化合物A。The preparation method of the olefin polymerization catalyst was the same as in Example 1, except that compound A was replaced by [bis(trifluoromethanesulfonyl)amino]methyldimethoxysilane (compound B).
乙烯聚合方法同实施例1，聚合结果见表1。The ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
实施例5Example 5
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
烯烃聚合催化剂的制备方法与实施例1相同，不同之处仅在于，以[双(三氟甲磺酰基)氨基]三甲氧基硅烷(化合物C)代替化合物A。The preparation method of the olefin polymerization catalyst was the same as in Example 1, except that [bis(trifluoromethanesulfonyl)amino]trimethoxysilane (compound C) was used instead of compound A.
乙烯聚合方法同实施例1，聚合结果见表1。The ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
实施例6Example 6
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
烯烃聚合催化剂的制备方法与实施例1相同，不同之处仅在于，以[双(三氟甲磺酰基)氨基]甲基二乙氧基硅烷(化合物D)代替化合物A。The preparation method of the olefin polymerization catalyst was the same as in Example 1, except that compound A was replaced by [bis(trifluoromethanesulfonyl)amino]methyldiethoxysilane (compound D).
乙烯聚合方法同实施例1，聚合结果见表1。The ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
实施例7Example 7
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
烯烃聚合催化剂的制备方法与实施例1相同，不同之处仅在于，[双(三氟甲磺酰基)氨基]三乙氧基硅烷(化合物E)代替化合物A。The preparation method of the olefin polymerization catalyst was the same as in Example 1, except that [bis(trifluoromethanesulfonyl)amino]triethoxysilane (compound E) replaced compound A.
乙烯聚合方法同实施例1，聚合结果见表1。The ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
实施例8Example 8
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
烯烃聚合催化剂的制备方法与实施例1相同，不同之处仅在于，[双(三氟甲磺酰基)氨基]二甲基甲氧基硅烷(化合物A)的加入量为3.7ml。The preparation method of the olefin polymerization catalyst was the same as in Example 1, except that the amount of [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane (compound A) added was 3.7 ml.
乙烯聚合方法同实施例1，聚合结果见表1。The ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
实施例9Example 9
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
烯烃聚合催化剂的制备方法与实施例1相同，不同之处仅在于，不同之处仅在于，[双(三氟甲磺酰基)氨基]二甲基甲氧基硅烷(化合物A)的加入量为1.5ml。The preparation method of the olefin polymerization catalyst is the same as that of Example 1, the only difference being that the addition of [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane (compound A) is 1.5ml.
乙烯聚合方法同实施例1，聚合结果见表1。The ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
实施例10Example 10
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
(1)烯烃聚合催化剂的制备：同实施例1。(1) Preparation of olefin polymerization catalyst: same as Example 1.
(2)乙烯聚合：(2) Ethylene polymerization:
将2L聚合釜充氢气和抽真空交替进行三次，加入1.0L己烷、5mmol三乙基铝和上述固体催化剂组分，反应釜升温至70℃，通入氢气使釜内压力达到0.73MPa，然后再通入乙烯使釜内总压达到1.0MPa，在80℃下聚合反应2小时。聚合结果见表1。Fill the 2L polymerizer with hydrogen and vacuumize it three times alternately, add 1.0L of hexane, 5mmol of triethylaluminum and the above-mentioned solid catalyst component, heat up the reactor to 70°C, feed hydrogen to make the pressure inside the reactor reach 0.73MPa, and then Then, ethylene was introduced to make the total pressure in the kettle reach 1.0 MPa, and the polymerization reaction was carried out at 80° C. for 2 hours. The aggregation results are shown in Table 1.
实施例11Example 11
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
(1)烯烃聚合催化剂的制备：同实施例2。(1) Preparation of olefin polymerization catalyst: same as Example 2.
(2)乙烯聚合：(2) Ethylene polymerization:
将2L聚合釜充氢气和抽真空交替进行三次，加入1.0L己烷、5mmol三乙基铝和上述固体催化剂组分，反应釜升温至70℃，通入氢气使釜内压力达到0.73MPa，然后再通入乙烯使釜内总压达到1.0MPa，在80℃下聚合反应2小时。聚合结果见表1。Fill the 2L polymerizer with hydrogen and vacuumize it three times alternately, add 1.0L of hexane, 5mmol of triethylaluminum and the above-mentioned solid catalyst component, heat up the reactor to 70°C, feed hydrogen to make the pressure inside the reactor reach 0.73MPa, and then Then, ethylene was introduced to make the total pressure in the kettle reach 1.0 MPa, and the polymerization reaction was carried out at 80° C. for 2 hours. The aggregation results are shown in Table 1.
实施例12Example 12
本实施例提供一种烯烃聚合催化剂的制备方法和应用，具体如下：This embodiment provides a preparation method and application of an olefin polymerization catalyst, specifically as follows:
(1)烯烃聚合催化剂的制备：同实施例1。(1) Preparation of olefin polymerization catalyst: same as Example 1.
(2)乙烯共聚合：(2) Ethylene copolymerization:
将2L聚合釜充氢气和抽真空交替进行三次，加入1.0L己烷、5mmol三乙基铝和上述固体催化剂组分，加入1-己烯10ml，反应釜升温至70℃，通入氢气使釜内压力达到0.28MPa，然后再通入乙烯使釜内总压达到0.73MPa，在80℃下聚合反应2小时。聚合结果见表1。Fill the 2L polymerizer with hydrogen and vacuumize it three times alternately, add 1.0L of hexane, 5mmol of triethylaluminum and the above-mentioned solid catalyst component, add 10ml of 1-hexene, raise the temperature of the reactor to 70°C, and feed hydrogen to make the reactor The internal pressure reached 0.28MPa, and then ethylene was introduced to make the total pressure in the kettle reach 0.73MPa, and the polymerization reaction was carried out at 80°C for 2 hours. The aggregation results are shown in Table 1.
对比例1Comparative example 1
本对比例提供一种催化剂的制备方法，具体如下：This comparative example provides a kind of preparation method of catalyst, specifically as follows:
催化剂的制备方法与实施例1相同，用与实施例1相同方法制得催化剂组分，不同之处仅在于，不添加磺酰胺硅烷类化合物。催化剂析出困难，固体很难沉降，未能形成 催化剂。The preparation method of the catalyst is the same as that of Example 1, and the catalyst component is prepared by the same method as that of Example 1, except that no sulfonamide silane compound is added. The catalyst was difficult to separate out, and the solid was difficult to settle, failing to form a catalyst.
对比例2Comparative example 2
本对比例提供一种催化剂的制备方法和应用，具体如下：This comparative example provides a kind of preparation method and application of catalyst, specifically as follows:
催化剂的制备方法与实施例1相同，不同之处仅在于，以四乙氧基硅烷代替化合物A。The preparation method of the catalyst is the same as in Example 1, except that compound A is replaced by tetraethoxysilane.
乙烯聚合方法同实施例1，聚合结果见表1。The ethylene polymerization method is the same as in Example 1, and the polymerization results are shown in Table 1.
对比例3Comparative example 3
本对比例提供一种催化剂的制备方法和应用，具体如下：This comparative example provides a kind of preparation method and application of catalyst, specifically as follows:
(1)催化剂的制备：同对比例2。(1) Preparation of catalyst: same as Comparative Example 2.
(2)乙烯聚合：(2) Ethylene polymerization:
将2L聚合釜充氢气和抽真空交替进行三次，加入1.0L己烷、5mmol三乙基铝和上述固体催化剂组分，反应釜升温至70℃，通入氢气使釜内压力达到0.73MPa，然后再通入乙烯使釜内总压达到1.0MPa，在80℃下聚合反应2小时。聚合结果见表1。Fill the 2L polymerizer with hydrogen and vacuumize it three times alternately, add 1.0L of hexane, 5mmol of triethylaluminum and the above-mentioned solid catalyst component, heat up the reactor to 70°C, feed hydrogen to make the pressure inside the reactor reach 0.73MPa, and then Then, ethylene was introduced to make the total pressure in the kettle reach 1.0 MPa, and the polymerization reaction was carried out at 80° C. for 2 hours. The aggregation results are shown in Table 1.
表1实施例和对比例的聚合结果The polymerization result of table 1 embodiment and comparative example
Figure PCTCN2022137837-appb-000005
Figure PCTCN2022137837-appb-000005
从表1的聚合数据可以看出，磺酰胺硅烷类化合物的加入，提高了聚合物的堆密度，聚合物粒径分布更加均匀，＞200目的细粉含量更低，并且得到的聚合物的熔融指数更高，尤其是在高氢聚合条件下(氢气压力＝0.73MPa)所得聚合物的熔融指数大幅提高，由此说明本发明磺酰胺硅烷类化合物的加入明显提高了催化剂的氢调敏感性。From the polymerization data in Table 1, it can be seen that the addition of sulfonamide silane compounds increases the bulk density of the polymer, the particle size distribution of the polymer is more uniform, the content of fine powder > 200 mesh is lower, and the melting of the obtained polymer The index is higher, especially under high hydrogen polymerization conditions (hydrogen pressure = 0.73MPa), the melt index of the obtained polymer is greatly increased, which shows that the addition of the sulfonamide silane compound of the present invention obviously improves the hydrogen adjustment sensitivity of the catalyst.

Claims (23)

  1. 一种烯烃聚合催化剂的制备方法，其特征在于，包括如下步骤：A kind of preparation method of olefin polymerization catalyst is characterized in that, comprises the steps:
    (1)将镁化合物溶解于醇中进行第一反应，得到第一反应液；(1) dissolving the magnesium compound in alcohol to carry out the first reaction to obtain the first reaction solution;
    (2)向所述第一反应液中加入磺酰胺硅烷类化合物进行第二反应，得到第二反应液；(2) adding a sulfonamide silane compound to the first reaction liquid to carry out a second reaction to obtain a second reaction liquid;
    (3)将所述第二反应液加入至钛化合物中进行第三反应，得到第三反应液；(3) adding the second reaction solution to the titanium compound to perform a third reaction to obtain a third reaction solution;
    (4)将所述第三反应液升温并保持该温度，生成固体，从而得到所述烯烃聚合催化剂；(4) raising the temperature of the third reaction solution and maintaining the temperature to generate a solid, thereby obtaining the olefin polymerization catalyst;
    所述磺酰胺硅烷类化合物选自通式(I)所示化合物中至少一种，The sulfonamide silane compound is selected from at least one of the compounds represented by the general formula (I),
    Figure PCTCN2022137837-appb-100001
    Figure PCTCN2022137837-appb-100001
    其中，R 1、R 2相同或不同，R 1和R 2各自独立地选自氢原子、卤素、取代或未取代的烷基、取代或未取代的环烷基、取代或未取代的芳基、取代或未取代的芳烷基、取代或未取代的烷基芳基、取代或未取代的含杂原子的环；R 3、R 4、R 5各自独立地选自C 1-C 8的直链或支链烷基、C 1-C 8的直链或支链烷氧基。 Wherein, R 1 and R 2 are the same or different, and R 1 and R 2 are each independently selected from hydrogen atom, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl , substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroatom-containing ring; R 3 , R 4 , R 5 are each independently selected from C 1 -C 8 Straight chain or branched chain alkyl, C 1 -C 8 straight chain or branched chain alkoxy.
  2. 根据权利要求1所述的制备方法，其特征在于，R 1和R 2各自独立地选自氟原子、溴原子、甲基、乙基、苯磺酰基甲基、二氟甲基、二溴甲基、三氟甲基或三溴甲基。 The preparation method according to claim 1 , wherein R and R are each independently selected from fluorine atom, bromine atom, methyl, ethyl, benzenesulfonylmethyl, difluoromethyl, dibromomethyl group, trifluoromethyl or tribromomethyl.
  3. 根据权利要求1所述的制备方法，其特征在于，R 3、R 4、R 5中至少一个选自C 1-C 8的直链或支链烷氧基。 The preparation method according to claim 1, characterized in that at least one of R 3 , R 4 , and R 5 is selected from C 1 -C 8 linear or branched alkoxy groups.
  4. 根据权利要求1所述的制备方法，其特征在于，R 3、R 4、R 5各自独立地选自甲基、乙基、正丙基、异丙基、甲氧基、乙氧基或3-丙氧基，并且R 3、R 4、R 5中至少一个选自甲氧基、乙氧基或3-丙氧基。 The preparation method according to claim 1, wherein R 3 , R 4 , and R 5 are each independently selected from methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy or 3 - propoxy, and at least one of R 3 , R 4 , R 5 is selected from methoxy, ethoxy or 3-propoxy.
  5. 根据权利要求1-4任一项所述的制备方法，其特征在于，R 3、R 4、R 5不同时为甲基。 The preparation method according to any one of claims 1-4, characterized in that R 3 , R 4 , and R 5 are not methyl at the same time.
  6. 根据权利要求1-5任一项所述的制备方法，其特征在于，所述磺酰胺硅烷类化合物选自[双(三氟甲磺酰基)氨基]三甲氧基硅烷、[双(三氟甲磺酰基)氨基]三乙氧基硅烷、[双(三氟甲磺酰基)氨基]三(3-丙氧基)硅烷、[双(三氟甲磺酰基)氨基]甲基二甲氧基硅烷、 [双(三氟甲磺酰基)氨基]甲基二乙氧基硅烷、[双(三氟甲磺酰基)氨基]甲基二(3-丙氧基)硅烷、[双(三氟甲磺酰基)氨基]二甲基甲氧基硅烷、[双(三氟甲磺酰基)氨基]二甲基乙氧基硅烷、[双(三氟甲磺酰基)氨基]二甲基(3-丙氧基)硅烷、[双(三氟甲磺酰基)氨基]乙基二甲氧基硅烷、[双(三氟甲磺酰基)氨基]乙基二乙氧基硅烷、[双(三氟甲磺酰基)氨基]乙基二(3-丙氧基)硅烷、[双(三氟甲磺酰基)氨基]二乙基甲氧基硅烷、[双(三氟甲磺酰基)氨基]二乙基乙氧基硅烷、[双(三氟甲磺酰基)氨基]二乙基(3-丙氧基)硅烷、[双(三溴甲磺酰基)氨基](3-丙基)二甲氧基硅烷、[双(三溴甲磺酰基)氨基](3-丙基)二乙氧基硅烷、[双(三溴甲磺酰基)氨基](3-丙基)二(3-丙氧基)硅烷、[双(三溴甲磺酰基)氨基]二(3-丙基)甲氧基硅烷、[双(三溴甲磺酰基)氨基]二(3-丙基)乙氧基硅烷、[双(三溴甲磺酰基)氨基]二(3-丙基)(3-丙氧基)硅烷中的一种或多种。According to the preparation method described in any one of claims 1-5, it is characterized in that, the sulfonamide silane compound is selected from [bis(trifluoromethanesulfonyl)amino]trimethoxysilane, [bis(trifluoromethanesulfonyl) Sulfonyl)amino]triethoxysilane, [bis(trifluoromethanesulfonyl)amino]tris(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]methyldimethoxysilane , [bis(trifluoromethanesulfonyl)amino]methyldiethoxysilane, [bis(trifluoromethanesulfonyl)amino]methylbis(3-propoxy)silane, [bis(trifluoromethanesulfonyl) Acyl)amino]dimethylmethoxysilane, [bis(trifluoromethanesulfonyl)amino]dimethylethoxysilane, [bis(trifluoromethanesulfonyl)amino]dimethyl(3-propoxy base) silane, [bis(trifluoromethanesulfonyl)amino]ethyldimethoxysilane, [bis(trifluoromethanesulfonyl)amino]ethyldiethoxysilane, [bis(trifluoromethanesulfonyl)amino]ethyldiethoxysilane, [bis(trifluoromethanesulfonyl) )amino]ethylbis(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]diethylmethoxysilane, [bis(trifluoromethanesulfonyl)amino]diethylethoxy base silane, [bis(trifluoromethanesulfonyl)amino]diethyl(3-propoxy)silane, [bis(tribromomethanesulfonyl)amino](3-propyl)dimethoxysilane, [ Bis(tribromomethanesulfonyl)amino](3-propyl)diethoxysilane, [bis(tribromomethanesulfonyl)amino](3-propyl)bis(3-propoxy)silane, [ Bis(tribromomethanesulfonyl)amino]bis(3-propyl)methoxysilane, [bis(tribromomethanesulfonyl)amino]bis(3-propyl)ethoxysilane, [bis(tribromomethanesulfonyl)ethoxysilane, One or more of methylsulfonyl)amino]bis(3-propyl)(3-propoxy)silane.
  7. 根据权利要求1所述的制备方法，其特征在于，所述第一反应温度为100℃-150℃，第一反应时间为2-6h。The preparation method according to claim 1, characterized in that, the first reaction temperature is 100°C-150°C, and the first reaction time is 2-6h.
  8. 根据权利要求1所述的制备方法，其特征在于，所述第二反应温度为30℃-60℃，第二反应时间为1-5h。The preparation method according to claim 1, characterized in that, the second reaction temperature is 30°C-60°C, and the second reaction time is 1-5h.
  9. 根据权利要求1所述的制备方法，其特征在于，所述第三反应温度为-25℃至0℃，第二反应时间为0.5-8h。The preparation method according to claim 1, characterized in that, the third reaction temperature is -25°C to 0°C, and the second reaction time is 0.5-8h.
  10. 根据权利要求1所述的制备方法，其特征在于，所述第三反应液升温至80℃-130℃并保持1-4h，所述第三反应液的升温速率为10℃/h-60℃/h。The preparation method according to claim 1, characterized in that, the temperature of the third reaction solution is raised to 80°C-130°C and maintained for 1-4h, and the heating rate of the third reaction solution is 10°C/h-60°C /h.
  11. 根据权利要求1所述的制备方法，其特征在于，所述硅烷类化合物与镁化合物的摩尔比为0.01-10，优选为0.05-2。The preparation method according to claim 1, characterized in that the molar ratio of the silane compound to the magnesium compound is 0.01-10, preferably 0.05-2.
  12. 根据权利要求1所述的制备方法，其特征在于，所述钛化合物与镁化合物的摩尔比为1-100，更优选为20-50。The preparation method according to claim 1, characterized in that the molar ratio of the titanium compound to the magnesium compound is 1-100, more preferably 20-50.
  13. 根据权利要求1所述的制备方法，其特征在于，所述醇与镁化合物的摩尔比为1-10，更优选为2-6。The preparation method according to claim 1, characterized in that the molar ratio of the alcohol to the magnesium compound is 1-10, more preferably 2-6.
  14. 根据权利要求1所述的制备方法，其特征在于，所述镁化合物选自二卤化镁、二卤化镁的水合物、二卤化镁的醇合物、烃基卤化镁和烃氧基卤化镁中的一种或多种，优选为二氯化镁。The preparation method according to claim 1, wherein the magnesium compound is selected from the group consisting of magnesium dihalide, magnesium dihalide hydrate, magnesium dihalide alcoholate, hydrocarbyl magnesium halide and hydrocarbyl magnesium halide One or more, preferably magnesium dichloride.
  15. 根据权利要求1所述的制备方法，其特征在于，所述钛化合物选自四氯化钛、四溴化钛、四碘化钛、四丁氧基钛、一氯三乙氧基钛、二氯二乙氧基钛和三氯一乙氧基钛中一种或多种；The preparation method according to claim 1, wherein the titanium compound is selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, monochlorotriethoxytitanium, di One or more of chlorodiethoxy titanium and trichloro monoethoxy titanium;
    优选地，所述醇选自甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、戊醇、己醇、2- 甲基戊醇、2-乙基丁醇、庚醇、2-乙基己醇、辛醇、癸醇、十二烷醇、十四烷醇和十八烷醇中的一种或多种，优选为2-乙基己醇、2-甲基戊醇和2-乙基丁醇中的一种或多种。Preferably, the alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2 -One or more of ethylhexanol, octanol, decanol, dodecanol, myristyl alcohol and stearyl alcohol, preferably 2-ethylhexanol, 2-methylpentanol and 2- One or more of ethyl butanol.
  16. 根据权利要求1所述的制备方法，其特征在于，所述制备方法还包括对所述固体进行过滤、洗涤和干燥；The preparation method according to claim 1, wherein the preparation method further comprises filtering, washing and drying the solid;
    洗涤所述固体采用惰性稀释剂，所述惰性稀释剂选自己烷、庚烷、辛烷、壬烷和癸烷中的一种或多种，更优选己烷和癸烷；Washing described solid adopts inert diluent, and described inert diluent is selected from one or more in hexane, heptane, octane, nonane and decane, more preferably hexane and decane;
    所述惰性稀释剂与镁化合物的摩尔比为1-150，更优选为5-30。The molar ratio of the inert diluent to the magnesium compound is 1-150, more preferably 5-30.
  17. 一种权利要求1-16任一项所述的制备方法得到的烯烃聚合催化剂。An olefin polymerization catalyst obtained by the preparation method described in any one of claims 1-16.
  18. 一种催化剂组合物，其特征在于，包括权利要求17所述的烯烃聚合催化剂和有机铝化合物，所述催化剂组合物中铝元素与钛元素的摩尔比为10-1000，优选为50-500。A catalyst composition, characterized in that it comprises the olefin polymerization catalyst according to claim 17 and an organoaluminum compound, and the molar ratio of aluminum element to titanium element in the catalyst composition is 10-1000, preferably 50-500.
  19. 根据权利要求18所述的催化剂组合物，其特征在于，所述有机铝化合物的通式为AlR’ nX 3-n，其中，R’为烷基、X为卤素，n为1、2或3。 The catalyst composition according to claim 18, wherein the general formula of the organoaluminum compound is AlR' n X 3-n , wherein R' is an alkyl group, X is a halogen, and n is 1, 2 or 3.
  20. 根据权利要求19所述的催化剂组合物，其特征在于，所述有机铝化合物选自三乙基铝、三异丁基铝、一氯二乙基铝、二氯乙基铝和倍半乙基氯化铝中的一种或多种，更优选三乙基铝和三异丁基铝。The catalyst composition according to claim 19, wherein the organoaluminum compound is selected from the group consisting of triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, ethylaluminum dichloride and sesquiethylaluminum One or more of aluminum chloride, more preferably triethylaluminum and triisobutylaluminum.
  21. 权利要求17所述的烯烃聚合催化剂或权利要求18-20任一项所述的催化剂组合物在烯烃聚合物中的应用。The application of the olefin polymerization catalyst described in claim 17 or the catalyst composition described in any one of claims 18-20 in olefin polymers.
  22. 根据权利要求21所述的应用，其特征在于，所述烯烃聚合为乙烯或丙烯的均聚合。The use according to claim 21, characterized in that the olefin polymerization is homopolymerization of ethylene or propylene.
  23. 根据权利要求21所述的应用，其特征在于，所述烯烃聚合为乙烯或丙烯与α-烯烃的共聚合，所述α-烯烃选自丙烯、丁烯、戊烯、己烯、辛烯、4-甲基1-戊烯。The application according to claim 21, characterized in that, the olefin polymerization is the copolymerization of ethylene or propylene and α-olefin, and the α-olefin is selected from propylene, butene, pentene, hexene, octene, 4-Methyl-1-pentene.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101323650A (en) * 2007-06-13 2008-12-17 中国石油天然气股份有限公司 Olefin polymerizing catalyst, preparation and use thereof
CN101628950A (en) * 2009-08-07 2010-01-20 中国石油天然气股份有限公司 Polypropylene catalyst containing sulfonyl compounds, preparation method and application thereof
CN101735346A (en) * 2008-11-07 2010-06-16 中国石油天然气股份有限公司 Propylene homopolymerized or copolymerized catalyst and preparation method and application thereof
CN101735354A (en) * 2009-12-23 2010-06-16 中国石油天然气股份有限公司 Method for preparing beta-crystal form polypropylene resin by in-situ polymerization
CN104356259A (en) * 2014-10-10 2015-02-18 中国石油天然气股份有限公司 Olefin polymerization catalyst and combined catalyst containing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101323650A (en) * 2007-06-13 2008-12-17 中国石油天然气股份有限公司 Olefin polymerizing catalyst, preparation and use thereof
CN101735346A (en) * 2008-11-07 2010-06-16 中国石油天然气股份有限公司 Propylene homopolymerized or copolymerized catalyst and preparation method and application thereof
CN101628950A (en) * 2009-08-07 2010-01-20 中国石油天然气股份有限公司 Polypropylene catalyst containing sulfonyl compounds, preparation method and application thereof
CN101735354A (en) * 2009-12-23 2010-06-16 中国石油天然气股份有限公司 Method for preparing beta-crystal form polypropylene resin by in-situ polymerization
CN104356259A (en) * 2014-10-10 2015-02-18 中国石油天然气股份有限公司 Olefin polymerization catalyst and combined catalyst containing same

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