WO2020078353A1 - 用于烯烃聚合催化剂的载体及其制备方法和应用 - Google Patents

用于烯烃聚合催化剂的载体及其制备方法和应用 Download PDF

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WO2020078353A1
WO2020078353A1 PCT/CN2019/111253 CN2019111253W WO2020078353A1 WO 2020078353 A1 WO2020078353 A1 WO 2020078353A1 CN 2019111253 W CN2019111253 W CN 2019111253W WO 2020078353 A1 WO2020078353 A1 WO 2020078353A1
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substituted
unsubstituted
alkyl
sulfur
aryl
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English (en)
French (fr)
Inventor
凌永泰
夏先知
刘月祥
李威莅
赵瑾
高富堂
任春红
谭扬
刘涛
陈龙
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority to KR1020217015117A priority Critical patent/KR102877758B1/ko
Priority to JP2021520558A priority patent/JP7546557B2/ja
Priority to SG11202103780YA priority patent/SG11202103780YA/en
Priority to EP19873179.6A priority patent/EP3868794A4/en
Priority to US17/286,765 priority patent/US12319773B2/en
Publication of WO2020078353A1 publication Critical patent/WO2020078353A1/zh
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    • 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
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    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F4/02—Carriers therefor
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08F4/00—Polymerisation catalysts
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    • 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
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    • 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
    • C08F4/6491—Catalysts containing a specific non-metal or metal-free compound organic hydrocarbon
    • C08F4/6492—Catalysts containing a specific non-metal or metal-free compound organic hydrocarbon containing aliphatic unsaturation
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    • 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
    • C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
    • 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
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • 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
    • 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
    • C08F2410/07—Catalyst support treated by an anion, e.g. Cl-, F-, SO42-

Definitions

  • the invention belongs to the field of olefin polymerization, and more specifically, relates to a carrier for an olefin polymerization catalyst and a preparation method thereof, and also relates to a catalyst component, a catalyst and an olefin polymerization method for olefin polymerization.
  • Polypropylene catalysts include Ziegler-Natta catalysts, metallocene catalysts and non-metallocene catalysts. Among them, Ziegler-Natta catalysts have been the most important catalytic system in the production of propylene polymerization. The Ziegler-Natta catalyst started in the 1950s and has been one of the main catalysts for industrial production through multiple upgrades. Moreover, its research has always been one of the hot spots of polypropylene catalysts.
  • the spherical morphology of the catalyst in the polymerization production process and polymer subsequent processing process It has huge advantages, and it is especially conducive to the production of polymer alloys. Therefore, among the polypropylene catalysts currently used in industry, the proportion of spherical catalysts is very large.
  • Spherical carrier and internal electron donor are two important components of spherical polypropylene catalyst.
  • the spherical carrier mainly comes from the magnesium chloride alcoholate carrier.
  • Magnesium chloride and alcohol are reacted at high temperature to form magnesium chloride alcoholate, and then melted and dispersed in an inert component to form an emulsion through high shear action, and the emulsion is transferred to a low temperature medium and alcoholized
  • the material is cured to form a carrier.
  • a melting process at a high temperature and a solidification process at a low temperature are required, so more energy is consumed.
  • CN102040683A discloses a method for preparing a carrier by reacting a magnesium halide alcoholate with an ethylene oxide compound, and specifically discloses that after the magnesium halide alcoholate is melted and dispersed, an ethylene oxide compound is added Or, the magnesium halide alcoholate is melt-dispersed and directly added to the reactor containing ethylene oxide compounds.
  • the preparation of the catalyst carrier by this method has the disadvantages that the preparation process is unstable, the carrier adhesion is likely to occur, and the carrier molding effect is not good, and the particle size distribution is wide.
  • the inventor of the present invention has unexpectedly found that adding sulfur in the preparation process of the olefin polymerization catalyst carrier can obtain a carrier with a new composition, the carrier particles have a good morphology, a smooth surface, substantially no irregular particles, and the particle size Can achieve less than 20 microns, narrow particle size distribution.
  • the catalyst prepared from the carrier has higher activity and better hydrogen adjustment sensitivity. When the catalyst is used for olefin polymerization, it can increase the polymer bulk density.
  • the first aspect of the present invention provides a carrier for an olefin polymerization catalyst, the carrier including a magnesium-containing compound and sulfur.
  • the sulfur may be present in the carrier in a simple substance, a complex state or a combined state.
  • the present invention provides a method for preparing a carrier for an olefin polymerization catalyst, which includes (1) preparing a mixture containing elemental sulfur and / or sulfur-containing compounds of the general formula MgX 1 Y Magnesium halide, compound of the general formula R 1 OH, optional inert liquid medium and optional surfactant, preferably by combining elemental sulfur and / or sulfur-containing compounds, magnesium halide of the general formula MgX 1 Y, general formula A compound that is R 1 OH, an optional inert liquid medium, and an optional surfactant are mixed and heated to obtain the mixture;
  • X 1 is halogen, preferably chlorine or bromine;
  • Y is selected from halogen, substituted or unsubstituted C1-C10 linear alkyl, substituted or unsubstituted C3-C10 branched alkyl, substituted Or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C7-C20 aralkyl and substituted or unsubstituted C7-C20 alkaryl;
  • R 1 is selected from substituted or unsubstituted C1-C10 linear alkyl, substituted or unsubstituted C3-C10 branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted Or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl and substituted or unsubstituted C7-C20 alkaryl; preferably, R 1 is selected from substituted or unsubstituted C1-C8 straight Alkyl alkyl, substituted or unsubstituted C3-C8 branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7-C15 aralkyl Group and substituted or unsubstituted C7-C
  • R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C3-C10 branched-chain alkyl, substituted or unsubstituted C3- C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl and substituted or unsubstituted C7-C20 alkaryl; preferably, R 5 and R 6 are each independent Earthly selected from hydrogen, substituted or unsubstituted C1-C8 linear alkyl, substituted or unsubstituted C3-C8 branched chain alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6- C10 aryl, substituted or unsubstituted C7-C10 aralkyl and substitute
  • the present invention also provides a catalyst component for olefin polymerization, the catalyst component comprising the carrier according to the first aspect of the invention and / or according to the second aspect of the invention Carrier prepared by the method of preparation, titanium, and optional electron donor and / or including the carrier prepared by the carrier described in the first aspect of the invention and / or the carrier prepared by the preparation method described in the second aspect of the invention and titanium The reaction product of the compound and optional electron donor.
  • the invention also provides a carrier according to the first aspect of the invention and / or a carrier prepared according to the preparation method according to the second aspect of the invention and / or a third aspect of the invention The application of said catalyst component in preparing catalyst for olefin polymerization.
  • the present invention provides a catalyst for olefin polymerization, the catalyst comprising: (1) the catalyst component of the third aspect of the present invention; (2) an aluminum alkyl compound; and (3 ) Optional external electron donor compound.
  • the present invention provides an olefin polymerization method, comprising: contacting one or more olefins with the above-mentioned catalyst of the present invention under olefin polymerization conditions.
  • FIG. 1 is an optical microscope photograph of a spherical carrier of an olefin polymerization catalyst prepared in Preparation Example 1.
  • FIG. 1 is an optical microscope photograph of a spherical carrier of an olefin polymerization catalyst prepared in Preparation Example 1.
  • FIG. 2 is an optical microscope photograph of the spherical carrier of the olefin polymerization catalyst prepared in Preparation Example 6.
  • FIG. 2 is an optical microscope photograph of the spherical carrier of the olefin polymerization catalyst prepared in Preparation Example 6.
  • FIG. 3 is an optical microscope photograph of the spherical carrier of the olefin polymerization catalyst prepared in Preparation Example 7.
  • FIG. 3 is an optical microscope photograph of the spherical carrier of the olefin polymerization catalyst prepared in Preparation Example 7.
  • FIG. 4 is an optical microscope photograph of the spherical carrier of the olefin polymerization catalyst prepared in Preparation Example 8.
  • FIG. 4 is an optical microscope photograph of the spherical carrier of the olefin polymerization catalyst prepared in Preparation Example 8.
  • FIG. 5 is an optical microscope photograph of the olefin polymerization catalyst carrier prepared in Comparative Preparation Example 1.
  • the first aspect of the present invention provides a carrier for an olefin polymerization catalyst, the carrier including a magnesium-containing compound and sulfur.
  • the sulfur may be present in the carrier in a simple substance, a complex state or a combined state.
  • the magnesium-containing compound has a group selected from halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, and substituted or unsubstituted aryloxy One or more groups in the group.
  • the molar ratio of magnesium to sulfur in the magnesium-containing compound is 1: q, where 0 ⁇ q ⁇ 0.5, preferably 0.0001 ⁇ q ⁇ 0.3, and more preferably 0.001 ⁇ q ⁇ 0.1.
  • the magnesium-containing compound has a linear alkyl group selected from halogen, substituted or unsubstituted C1-C10, a substituted or unsubstituted C3-C10 branched alkyl group, a substituted or unsubstituted C3 -C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C7-C20 aryl One or more groups of alkyl and substituted or unsubstituted C7-C20 alkaryl.
  • the magnesium-containing compound is selected from magnesium compounds represented by formula (I):
  • R 1 is selected from substituted or unsubstituted C1-C10 linear alkyl, substituted or unsubstituted C3-C10 branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or Unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl and substituted or unsubstituted C7-C20 alkaryl; preferably, R 1 is selected from substituted or unsubstituted C1-C8 straight chain Alkyl, substituted or unsubstituted C3-C8 branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7-C15 aralkyl And substituted or unsubstituted C7-C15 alkaryl; more
  • R 2 and R 3 are the same or different, and are each independently selected from hydrogen, substituted or unsubstituted C1-C10 straight chain alkyl, substituted or unsubstituted C3-C10 branched chain alkyl, substituted or unsubstituted C3- C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, and substituted or unsubstituted C7-C20 alkaryl; preferably, R 2 and R 3 are each independent Earthly selected from hydrogen, substituted or unsubstituted C1-C10 linear alkyl, substituted or unsubstituted C3-C8 branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6- C10 aryl, substituted or unsubstituted C7-C10 aralkyl
  • X is halogen, preferably chlorine or bromine
  • n 0.1-1.9
  • m + n 2.
  • the carrier is spherical or quasi-spherical.
  • the average particle size of the carrier of the olefin polymerization catalyst of the present invention can be controlled in a wide range, for example, it can be 10-100 microns.
  • the average particle diameter (D50) of the spherical carrier of the olefin polymerization catalyst can be controlled to be less than or equal to 30 microns, preferably to be less than or equal to 20 microns.
  • the olefin is polymerized
  • the catalyst prepared by the catalyst spherical carrier can obtain olefin polymer with higher bulk density.
  • the average particle diameter and particle size distribution of the spherical carrier of the olefin polymerization catalyst can be measured using a Master Sizer 2000 laser particle size analyzer (manufactured by Malvern Instruments).
  • the average particle diameter of the carrier is less than or equal to 30 microns, preferably less than or equal to 20 microns.
  • the particle size distribution (D90-D10) / D50) is less than 1.2, preferably the particle size distribution is less than or equal to 0.8.
  • the synthetic raw materials of the carrier include elemental sulfur and / or sulfur-containing compounds, magnesium halide with the general formula MgX 1 Y, compounds with the general formula R 4 OH, and ethylene oxide compounds.
  • X 1 is halogen, preferably chlorine or bromine;
  • Y is selected from halogen, substituted or unsubstituted C1-C10 linear alkyl, substituted or unsubstituted C3 -C10 branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C20 Aryloxy, substituted or unsubstituted C7-C20 aralkyl and substituted or unsubstituted C7-C20 alkaryl.
  • R 1 is selected from substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C3-C10 branched-chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl and substituted or unsubstituted C7-C20 alkaryl; preferably, R 1 is selected from substituted Or unsubstituted C1-C8 linear alkyl, substituted or unsubstituted C3-C8 branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C15 aryl, substituted or Unsubstituted C7-C15 aralkyl and substituted or
  • the structure of the ethylene oxide compound is as shown in formula (II):
  • R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C3-C10 branched-chain alkyl, substituted or unsubstituted C3- C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl and substituted or unsubstituted C7-C20 alkaryl; preferably, R 5 and R 6 are each independent Earthly selected from hydrogen, substituted or unsubstituted C1-C8 linear alkyl, substituted or unsubstituted C3-C8 branched chain alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6- C10 aryl, substituted or unsubstituted C7-C10 aralkyl and substitute
  • X 1 is chlorine or bromine
  • Y is chlorine, bromine, C 1 -C 5 alkoxy or C 6 -C 10 aryloxy.
  • the magnesium halide of the general formula MgX 1 Y is selected from at least one of magnesium chloride, magnesium bromide, phenoxy magnesium chloride, isopropoxy magnesium chloride, and n-butoxy magnesium chloride.
  • R 1 is C 1 -C 8 alkyl.
  • the compound of the general formula R 1 OH is selected from ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, n-hexanol, 2-ethylhexanol and n-octyl At least one alcohol.
  • R 5 and R 6 are each independently hydrogen, C 1 -C 3 alkyl or C 1 -C 3 Of halogenated alkyl.
  • the ethylene oxide compound is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, bromopropylene oxide and bromobutylene oxide At least one.
  • the carrier of the olefin polymerization catalyst may contain water, and the contained water comes from trace water carried by the synthesis raw materials and the reaction medium.
  • the present invention provides a method for preparing a carrier for an olefin polymerization catalyst.
  • the method includes the following steps:
  • step (2) The mixture obtained in step (1) is reacted with an ethylene oxide compound.
  • X 1 is halogen, preferably chlorine or bromine;
  • Y is selected from halogen, substituted or unsubstituted C1-C10 linear alkyl, substituted or unsubstituted C3-C10 branched alkyl, substituted Or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C7-C20 aralkyl and substituted or unsubstituted C7-C20 alkaryl.
  • R 1 is selected from substituted or unsubstituted C1-C10 linear alkyl, substituted or unsubstituted C3-C10 branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted Or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl and substituted or unsubstituted C7-C20 alkaryl; preferably, R 1 is selected from substituted or unsubstituted C1-C8 straight Alkyl alkyl, substituted or unsubstituted C3-C8 branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7-C15 aralkyl Group and substituted or unsubstituted C7-C
  • R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C3-C10 branched-chain alkyl, substituted or unsubstituted C3- C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl and substituted or unsubstituted C7-C20 alkaryl; preferably, R 5 and R 6 are each independent Earthly selected from hydrogen, substituted or unsubstituted C1-C8 linear alkyl, substituted or unsubstituted C3-C8 branched chain alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6- C10 aryl, substituted or unsubstituted C7-C10 aralkyl and substitute
  • X 1 is chlorine or bromine
  • Y is chlorine, bromine, C 1 -C 5 alkoxy or C 6 -C 10 aryloxy.
  • the magnesium halide of the general formula MgX 1 Y is selected from at least one of magnesium chloride, magnesium bromide, phenoxy magnesium chloride, isopropoxy magnesium chloride, and n-butoxy magnesium chloride.
  • R 1 is C 1 -C 8 alkyl.
  • the compound of the general formula R 1 OH is selected from ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, n-hexanol, 2-ethylhexanol and n-octyl At least one alcohol.
  • R 5 and R 6 are each independently hydrogen, C 1 -C 3 alkyl or C 1 -C 3 Of halogenated alkyl.
  • the ethylene oxide compound is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, bromopropylene oxide and bromobutylene oxide At least one.
  • the amount of elemental sulfur and / or sulfur-containing compound is 0.0001-0.5 mol, and the amount of compound of general formula R 1 OH is 4 -30mol, the amount of ethylene oxide compounds is 1-10mol.
  • the amount of the compound with the general formula R 1 OH is 6-20 mol, and the amount of the ethylene oxide compound is 2-6 mol.
  • the heating temperature is 80-120 ° C and the time is 0.5-5 hours; preferably, the heating temperature is 80-100 ° C and the time is 0.5- 3 hours.
  • the conditions of the contact reaction include: a temperature of 40-120 ° C. and a time of 15-60 minutes; preferably, the conditions of the contact reaction include: a temperature of 60 -100 °C, time is 20-50 minutes.
  • the inert liquid medium is a silicone oil solvent and / or a hydrocarbon solvent; preferably, the inert liquid medium is selected from kerosene, paraffin oil, petrolatum oil, white oil, methyl silicone oil, ethyl alcohol At least one of base silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methyl phenyl silicone oil.
  • the amount of the inert liquid medium is 0.8-10 L.
  • the surfactant is selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polystyrene sulfonate, and naphthalenesulfonate formaldehyde Condensate, condensed alkyl phenyl ether sulfate, condensed alkyl phenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer modified polyethyleneimine, 1-dodec-4-ethylene pyridine bromide Polymers, polyvinylbenzyltrimethylamine salt, polyethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether and polyalkyl methacrylate At least one of the esters.
  • the amount of the surfactant is 1-20 g.
  • the elemental sulfur is selected from at least one of ⁇ -sulfur, ⁇ -sulfur, ⁇ -sulfur, and polymeric sulfur.
  • the sulfur-containing compound has a thiol group (-SH), a thioether group (-S-), a thiocarbonyl group One or more groups in.
  • exemplary sulfur-containing compounds include 2-mercaptoethanol, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, and the like.
  • the method may further include solid-liquid separation of the product obtained from the contact reaction, and washing and drying the separated solid-phase product.
  • the solid-liquid separation may be a variety of existing methods that can achieve solid-phase and liquid-phase separation, such as suction filtration, pressure filtration, or centrifugal separation.
  • the solid-liquid separation method is a pressure filtration method.
  • the conditions of the pressure filtration are not particularly limited, as long as the separation of the solid phase and the liquid phase is as full as possible.
  • the obtained solid phase product can be washed by a method known to those skilled in the art.
  • an inert hydrocarbon solvent for example: pentane, hexane, heptane, petroleum ether, and gasoline
  • an inert hydrocarbon solvent for example: pentane, hexane, heptane, petroleum ether, and gasoline
  • the drying conditions are not particularly limited.
  • the drying temperature may be 20-70 ° C
  • the drying time may be 0.5-10 hours.
  • the drying can be performed under normal pressure or reduced pressure.
  • sulfur is added in the preparation process of the olefin polymerization catalyst carrier, and a spherical carrier with a new composition can be obtained.
  • Sulfur can reduce the collision probability between the unformed particles and reduce the adhesion between the carrier particles, so that the resulting carrier particles have a small particle size, a narrow distribution and good morphology, and the catalyst prepared by the carrier has a narrow particle size distribution and a relatively high activity Good, good hydrogen adjustment sensitivity, it can increase polymer bulk density when used in olefin polymerization.
  • the present invention also provides a catalyst component for olefin polymerization, the catalyst component comprising the carrier according to the first aspect of the invention and / or according to the second aspect of the invention Carrier prepared by the method of preparation, titanium, and optional internal electron donor and / or including the carrier prepared by the method described in the first aspect of the invention and / or the carrier prepared according to the preparation method described in the second aspect of the invention and The reaction product of a titanium compound and optionally an internal electron donor.
  • the catalyst component is spherical or quasi-spherical, and its average particle diameter is less than or equal to 30 microns, preferably less than or equal to 20 microns.
  • the catalyst component is spherical or quasi-spherical, and its particle size distribution is less than 1.2, preferably the particle size distribution is less than or equal to 0.8.
  • the titanium compound may be a titanium compound commonly used in the art.
  • the titanium compound is a compound represented by formula XI and / or formula XII:
  • X is halogen
  • R 27 and R 28 are each independently a C 1 -C 20 alkyl group
  • p is an integer of 1-4
  • q is an integer of 1-3.
  • the titanium compound is titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxy titanium chloride, dibutoxy titanium dichloride, butoxy titanium trichloride, One or more of triethoxy titanium chloride, diethoxy titanium dichloride, ethoxy titanium trichloride, and titanium trichloride.
  • the titanium compound is titanium tetrachloride.
  • the preparation method of the catalyst component for olefin polymerization of the present invention may include the steps of: reacting a magnesium compound with a titanium compound, and within one or more time periods before, during, and after the magnesium compound reacts with the titanium compound Join the internal electron body.
  • the invention also provides a carrier according to the first aspect of the invention and / or a carrier prepared according to the preparation method according to the second aspect of the invention and / or a third aspect of the invention The application of said catalyst component in preparing catalyst for olefin polymerization.
  • the present invention provides a catalyst for olefin polymerization, the catalyst comprising: (1) the catalyst component of the fourth aspect of the present invention; (2) an aluminum alkyl compound; and (3 ) Optional external electron donor compound.
  • the aluminum alkyl compound may be various aluminum aluminum compounds commonly used in the field of olefin polymerization that can be used as a cocatalyst of the olefin polymerization catalyst.
  • the aluminum alkyl compound is a compound represented by formula XIII,
  • R ′ is C 1 -C 8 alkyl or haloalkyl
  • X ′ is halogen, preferably one or more of chlorine, bromine and iodine, more preferably chlorine
  • n ′ is 1-3 Integer.
  • the aluminum alkyl compound is triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-isobutyl aluminum , Monohydrodiethylaluminum, monohydrodiisobutylaluminum, monochlorodiethylaluminum, monochlorodiisobutylaluminum, dichloroethylaluminum, Al (nC 6 H 13 ) 3 and Al (nC 8 One or more of H 17 ) 3 .
  • the alkyl aluminum compound is triethyl aluminum and / or triisobutyl aluminum.
  • the amount of the aluminum alkyl compound may be a conventional amount in the art.
  • the molar ratio of aluminum in the aluminum alkyl compound to titanium in the catalyst component is (1-2000): 1.
  • the molar ratio of aluminum in the aluminum alkyl compound to titanium in the catalyst component is (10-500): 1.
  • the type and content of the external electron donor in the olefin polymerization catalyst are not particularly limited.
  • the molar ratio of aluminum in the aluminum alkyl compound to the external electron donor compound is (2-200): 1, more preferably (2.5-100): 1.
  • the use of the external electron donor compound in combination with the internal electron donor compound a and the internal electron donor compound b can further increase the isotactic index of the olefin polymer obtained by the method of the present invention.
  • the external electron donor compound may be a variety of external electron donor compounds commonly used in the art that can achieve the above objectives, for example: carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, ketone, ether, alcohol, lactone, organic phosphorus One or more of compounds and organosilicon compounds.
  • the external electron donor compound is an organosilicon compound represented by formula XIV,
  • R 29 , R 30 and R 31 are each independently a C 1 -C 18 hydrocarbon group, optionally containing a heteroatom, the heteroatom is one of F, Cl, Br, N and I or Multiple; m 'and p' are each independently an integer of 0-2, q 'is an integer of 1-3, and the sum of m', p 'and q' is 4.
  • R 29 and R 30 are each independently a C 3 -C 10 linear or branched alkyl group, a C 3 -C 10 linear or branched alkene group, a C 3 -C 10 substitution or not Substituted alkylene groups, C 3 -C 10 substituted or unsubstituted cycloalkyl groups and C 6 -C 10 substituted or unsubstituted aryl groups, optionally containing heteroatoms, the heteroatoms being F, Cl , Br, N, and I; R 31 is a C 1 -C 10 linear or branched alkyl group, more preferably a methyl group.
  • specific examples of the external electron donor compound may include, but are not limited to: cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, Diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl tert-butyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, tert-hexyltrimethoxy Silane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl) -2-ethyl One or more of piperidinyl dimethoxysilane and (1,1,1-, trifluoro-2-propyl) -methyld
  • the external electron donor compound is cyclohexylmethyldimethoxysilane and / or dicyclopentyldimethoxysilane.
  • the aluminum alkyl and the optional external electron donor compound may be separately reacted with the catalyst component for olefin polymerization, or the aluminum alkyl may also be used It is mixed with an optional external electron donor in advance and then mixed with and reacted with the catalyst component for olefin polymerization.
  • the catalyst component for olefin polymerization, the aluminum alkyl, and the optional external electron donor can be separately added to the polymerization reactor, and It can be added to the polymerization reactor after mixing, or it can be added to the polymerization reactor after the prepolymerization of olefin by a prepolymerization method well known in the industry.
  • the present invention provides an olefin polymerization method, comprising: contacting one or more olefins with the above-mentioned catalyst of the present invention under olefin polymerization conditions.
  • R is hydrogen or C 1 -C straight or branched alkyl of 6.
  • the olefin polymerization method of the present invention may be homopolymerization of a single olefin or copolymerization of multiple olefins.
  • the olefin polymerization conditions may be conventional conditions in the art.
  • the olefin polymerization conditions may include: a temperature of 0-150 ° C, a time of 0.1-8 hours, and a pressure of 0.01-10 MPa.
  • the olefin polymerization conditions include: a temperature of 50-100 ° C., a time of 0.5-3 hours, and a pressure of 0.5-5 MPa.
  • the amount of the olefin polymerization catalyst may be various conventional amounts of olefin catalysts in the prior art.
  • the elemental sulfur may be any subtype of elemental sulfur, including but not limited to: at least one of ⁇ -sulfur, ⁇ -sulfur, ⁇ -sulfur, and polymeric sulfur.
  • the elemental sulfur may be anhydrous elemental sulfur or elemental sulfur containing bound water. The above elemental sulfur can be obtained through commercial purchase.
  • halogen is selected from fluorine, chlorine, bromine and iodine.
  • the C1-C10 alkyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, Tert-amyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl or isooctyl.
  • the C1-C10 alkoxy group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.
  • the C 6 -C 10 aryl group may be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, or naphthyl.
  • the C 6 -C 10 aryloxy group may be, for example, phenoxy or naphthoxy.
  • the C 3 -C 8 cycloalkyl group may be, for example, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, or cyclohexylmethyl.
  • substituted means that the described group may be substituted with one or more common substituents, which may be alkyl, alkoxy, halogen, amino, hydroxyl, etc., for example C1-C6 alkyl, C1-C6 alkoxy, halogen, amino, hydroxyl, etc.
  • the average particle diameter and particle size distribution of the spherical carrier of the olefin polymerization catalyst and the catalyst component are measured using a Masters Sizer 2000 particle size analyzer (manufactured by Malvern Instruments).
  • the bulk density of polyolefin powder is determined by the method specified in GB / T1636-2008.
  • This preparation example is used to explain the olefin polymerization catalyst spherical carrier provided by the present invention and the preparation method thereof.
  • the olefin polymerization catalyst spherical carrier Z1 has an average particle diameter (D50) of 15 microns and a particle size distribution ((D90-D10) / D50) of 0.6. As shown in Figure 1, the morphology of the spherical carrier Z1 of the olefin polymerization catalyst was observed with an optical microscope. The morphology of the spherical carrier Z1 was relatively regular, the surface was smooth, basically all were spherical, the particle size distribution was relatively concentrated, and there were basically no irregular particles.
  • the composition of Z1 includes structural formula The magnesium-containing compound and sulfur, wherein the molar ratio of magnesium to sulfur in the magnesium-containing compound is 1: 0.2.
  • This preparation example is used to explain the olefin polymerization catalyst spherical carrier provided by the present invention and the preparation method thereof.
  • the olefin polymerization catalyst spherical carrier Z2 has an average particle diameter (D50) of 18 microns and a particle size distribution ((D90-D10) / D50) of 0.7.
  • the morphology of the spherical carrier Z2 of the olefin polymerization catalyst was observed with an optical microscope. The particle morphology was relatively regular, the surface was smooth, basically all were spherical, the particle size distribution was concentrated, and there were basically no irregular particles.
  • the composition of Z2 includes the structural formula The magnesium-containing compound and sulfur, wherein the molar ratio of magnesium to sulfur in the magnesium-containing compound is 1: 0.01.
  • This preparation example is used to explain the olefin polymerization catalyst spherical carrier provided by the present invention and the preparation method thereof.
  • the spherical particle carrier Z3 of the olefin polymerization catalyst has an average particle diameter (D50) of 20 microns and a particle size distribution ((D90-D10) / D50) of 0.8.
  • the morphology of the spherical carrier Z3 of the olefin polymerization catalyst was observed with an optical microscope. The particle morphology was relatively regular, the surface was smooth, basically all were spherical, the particle size distribution was concentrated, and there were basically no irregular particles.
  • the composition of Z3 includes structural formula as The magnesium-containing compound and sulfur, wherein the molar ratio of magnesium to sulfur in the magnesium-containing compound is 1: 0.007.
  • This preparation example is used to explain the olefin polymerization catalyst spherical carrier provided by the present invention and the preparation method thereof.
  • the average particle diameter (D50) of the spherical carrier Z4 of the olefin polymerization catalyst is 25 microns, and the particle size distribution ((D90-D10) / D50) is 0.9.
  • the morphology of the spherical carrier Z4 of olefin polymerization catalyst was observed with an optical microscope. The particle morphology was relatively regular, the surface was smooth, basically all were spherical, the particle size distribution was relatively concentrated, and there were basically no irregular particles.
  • the composition of Z4 includes structural formula The magnesium-containing compound and sulfur, wherein the molar ratio of magnesium to sulfur in the magnesium-containing compound is 1: 0.01.
  • This preparation example is used to explain the olefin polymerization catalyst spherical carrier provided by the present invention and the preparation method thereof.
  • the average particle diameter (D50) of the spherical carrier Z5 of the olefin polymerization catalyst is 26 microns, and the particle size distribution ((D90-D10) / D50) is 0.9.
  • the morphology of the spherical carrier Z5 of the olefin polymerization catalyst was observed with an optical microscope. The particle morphology was relatively regular, the surface was smooth, basically all were spherical, the particle size distribution was relatively concentrated, and there were basically no irregular particles.
  • the composition of Z5 includes structural formula as The magnesium-containing compound and sulfur, wherein the molar ratio of magnesium to sulfur in the magnesium-containing compound is 1: 0.01.
  • This preparation example is used to explain the olefin polymerization catalyst spherical carrier provided by the present invention and the preparation method thereof.
  • the average particle diameter (D50) of the olefin polymerization catalyst spherical carrier Z6 is 35.2 microns.
  • D50 average particle diameter
  • the particle morphology is relatively regular, the surface is smooth, basically all are spherical, the particle size distribution is relatively concentrated, and there are basically no irregular particles, as shown in Figure 2.
  • This preparation example is used to explain the olefin polymerization catalyst spherical carrier provided by the present invention and the preparation method thereof.
  • the average particle diameter (D50) of the olefin polymerization catalyst spherical carrier Z7 is 45.1 microns.
  • the morphology of the spherical carrier Z7 of olefin polymerization catalyst was observed with an optical microscope. The particle morphology was relatively regular, the surface was smooth, basically all were spherical, the particle size distribution was relatively concentrated, and there were basically no irregular particles, as shown in Figure 3.
  • This preparation example is used to explain the olefin polymerization catalyst spherical carrier provided by the present invention and the preparation method thereof.
  • the average particle diameter (D50) of the olefin polymerization catalyst spherical carrier Z8 is 50.1 microns.
  • the morphology of the spherical carrier Z8 of the olefin polymerization catalyst was observed with an optical microscope. The particle morphology was relatively regular, the surface was smooth, basically all were spherical, the particle size distribution was relatively concentrated, and there were basically no irregular particles, as shown in Figure 4.
  • This comparative preparation example is used to illustrate the reference olefin polymerization catalyst carrier and its preparation method.
  • the average particle diameter (D50) of the catalyst carrier DZ1 for olefin polymerization is 60 microns, and the particle size distribution ((D90-D10) / D50) is 1.3.
  • the particle morphology observed with an optical microscope is shown in Figure 4. It can be seen from FIG. 4 that the catalyst carrier DZ1 for olefin polymerization has irregular shaped particles and the surface is relatively rough.
  • the average particle diameter (D50) of the catalyst carrier DZ2 for olefin polymerization is 80 microns, and the particle size distribution ((D90-D10) / D50) is 1.5. Using optical microscope to observe the particle morphology, there are special-shaped particles in DZ2, and the surface is relatively rough.
  • the average particle diameter (D50) of the catalyst carrier DZ3 for olefin polymerization is 88 microns, and the particle size distribution ((D90-D10) / D50) is 1.7. Observe the particle morphology using an optical microscope. DZ3 has irregular particles and the surface is relatively rough.
  • This example is used to illustrate the preparation of the olefin polymerization catalyst provided by the present invention.
  • the average particle diameter (D50) of olefin polymerization catalyst C1 is 14 microns, the particle size distribution is 0.6, the activity is 38.9 kgPP / g ⁇ cat, the melt flow rate index of polypropylene powder P1 is 12.0 g / 10 min, and the bulk density is 0.46g / cm 3 , in addition, the polypropylene powder particles have a good morphology, and there is basically no shaped material.
  • This example is used to illustrate the preparation of the olefin polymerization catalyst provided by the present invention.
  • the preparation of the olefin polymerization catalyst and the propylene polymerization reaction were carried out according to the method of Example 1, except that the olefin polymerization catalyst spherical carrier Z1 was replaced with the olefin polymerization catalyst spherical carrier Z2 obtained in Preparation Example 2, to obtain an olefin polymerization catalyst C2 And polypropylene powder P2.
  • the average particle diameter (D50) of the olefin polymerization catalyst C2 is 17 microns, the particle size distribution is 0.6, the activity is 37.8 kgPP / g ⁇ cat, the melt flow rate index of the polypropylene powder P2 is 11.0 g / 10 min, and the bulk density is 0.46g / cm 3 , in addition, the polypropylene powder particles have a good morphology, and there is basically no shaped material.
  • This example is used to illustrate the preparation of the olefin polymerization catalyst provided by the present invention.
  • the preparation of the olefin polymerization catalyst and the propylene polymerization reaction were carried out according to the method of Example 1, except that the olefin polymerization catalyst spherical carrier Z1 was replaced with the olefin polymerization catalyst spherical carrier Z3 obtained in Preparation Example 3 to obtain an olefin polymerization catalyst C3 And polypropylene powder P3.
  • the average particle diameter (D50) of olefin polymerization catalyst C3 is 19 microns, the particle size distribution is 0.7, the activity is 37.0 kgPP / g ⁇ cat, the melt flow rate index of polypropylene powder P3 is 12.0 g / 10 min, and the bulk density is 0.46g / cm 3 , in addition, the polypropylene powder particles have a good morphology, and there is basically no shaped material.
  • This example is used to illustrate the preparation of the olefin polymerization catalyst provided by the present invention.
  • the activity of the olefin polymerization catalyst C1 is 40.0 kgPP / g ⁇ cat
  • the melt flow rate index of the polypropylene powder P4 is 45.0 g / 10min
  • the bulk density is 0.46 g / cm 3.
  • the polypropylene powder has good particle morphology , There is basically no shaped material.
  • the preparation of the olefin polymerization catalyst and the propylene polymerization reaction were carried out according to the method of Example 1, except that the olefin polymerization catalyst spherical carrier Z1 was replaced with the olefin polymerization catalyst spherical carrier Z4 obtained in Preparation Example 4, to obtain an olefin polymerization catalyst C5 And polypropylene powder P5.
  • the average particle diameter (D50) of olefin polymerization catalyst C5 is 23 microns, the particle size distribution is 0.8, the activity is 37.6 kgPP / g ⁇ cat, the melt flow rate index of polypropylene powder P5 is 11.1 g / 10 min, and the bulk density is 0.46g / cm 3 , in addition, the polypropylene powder particles have a good morphology, and there is basically no shaped material.
  • the activity of olefin polymerization catalyst C5 is 39.7kgPP / g ⁇ cat
  • the melt flow rate index of polypropylene powder P6 is 45.2g / 10min
  • the bulk density is 0.46g / cm 3.
  • the polypropylene powder has good particle morphology , There is basically no shaped material.
  • the preparation of the olefin polymerization catalyst and the propylene polymerization reaction were carried out according to the method of Example 1, except that the olefin polymerization catalyst spherical carrier Z1 was replaced with the olefin polymerization catalyst spherical carrier Z5 obtained in Preparation Example 5, to obtain an olefin polymerization catalyst C7 And polypropylene powder P7.
  • the average particle diameter (D50) of olefin polymerization catalyst C7 is 25 microns, the particle size distribution is 0.8, the activity is 37.1 kgPP / g ⁇ cat, the melt flow rate index of polypropylene powder P7 is 11.2g / 10min, and the bulk density is 0.46g / cm 3 , in addition, the polypropylene powder particles have a good morphology, and there is basically no shaped material.
  • the activity of olefin polymerization catalyst C7 is 39.8kgPP / g ⁇ cat
  • the melt flow rate index of polypropylene powder P8 is 45.7g / 10min
  • the bulk density is 0.46g / cm 3.
  • the polypropylene powder has good particle morphology , There is basically no shaped material.
  • This comparative example is used to illustrate the preparation of a reference olefin polymerization catalyst.
  • the preparation of the olefin polymerization catalyst and the propylene polymerization reaction were carried out according to the method of Example 1, except that the olefin polymerization catalyst spherical carrier Z1 was replaced with the olefin polymerization catalyst carrier DZ1 obtained in Comparative Preparation Example 1, to obtain an olefin polymerization catalyst DC1 And polypropylene powder DP1.
  • the average particle diameter of olefin polymerization catalyst DC1 is 58 microns, the particle size distribution is 1.2, the activity is 32.0 kgPP / g ⁇ cat, the melt flow rate index of polypropylene powder DP1 is 7.0 g / 10 min, and the bulk density is 0.39 g / cm 3 , in addition, the polypropylene powder particles have irregular shapes, and the fluidity is not good.
  • the activity of olefin polymerization catalyst DC1 is 33.1 kgPP / g ⁇ cat
  • the melt flow rate index of polypropylene powder DP2 is 37.0 g / 10 min
  • the bulk density is 0.39 g / cm 3.
  • the polypropylene powder particles are present Shaped materials, poor fluidity.
  • This comparative example is used to illustrate the preparation of a reference olefin polymerization catalyst.
  • the preparation of the olefin polymerization catalyst and the propylene polymerization reaction were carried out according to the method of Example 1, except that the spherical carrier Z1 of the olefin polymerization catalyst was replaced with the olefin polymerization catalyst carrier DZ2 obtained in Comparative Preparation Example 2, to obtain an olefin polymerization catalyst DC3 And polypropylene powder DP3.
  • the average particle diameter of the olefin polymerization catalyst DC3 is 66 microns, the particle size distribution is 1.4, the activity is 32.3kgPP / g ⁇ cat, the melt flow rate index of polypropylene powder DP3 is 7.4g / 10min, and the bulk density is 0.39g / cm 3 , in addition, the polypropylene powder particles have irregular shapes, and the fluidity is not good.
  • the activity of olefin polymerization catalyst DC3 is 33.6kgPP / g ⁇ cat
  • the melt flow rate index of polypropylene powder DP4 is 37.7g / 10min
  • the bulk density is 0.39g / cm 3.
  • the polypropylene powder particles are present Shaped materials, poor fluidity.
  • This comparative example is used to illustrate the preparation of a reference olefin polymerization catalyst.
  • the preparation of the olefin polymerization catalyst and the propylene polymerization reaction were carried out according to the method of Example 1, except that the olefin polymerization catalyst spherical carrier Z1 was replaced with the olefin polymerization catalyst carrier DZ3 obtained in Comparative Preparation Example 3 to obtain an olefin polymerization catalyst DC5 And polypropylene powder DP5.
  • the average particle diameter of olefin polymerization catalyst DC5 is 83 microns, the particle size distribution is 1.6, the activity is 32.8kgPP / g ⁇ cat, the melt flow rate index of polypropylene powder DP5 is 7.8g / 10min, and the bulk density is 0.38g cm 3 , in addition, the polypropylene powder particles have irregular shapes, and the fluidity is not good.
  • the activity of olefin polymerization catalyst DC5 is 34.0kgPP / g ⁇ cat
  • the melt flow rate index of polypropylene powder DP6 is 37.5g / 10min
  • the bulk density is 0.37g / cm 3.
  • the polypropylene powder particles are present Shaped materials, poor fluidity.
  • the spherical carrier of the olefin polymerization catalyst with a novel composition of the present invention has a narrow particle size distribution, good particle morphology, smooth surface, and substantially no irregular particles, and the catalyst prepared by the carrier has a narrow particle size distribution and activity Better, and more sensitive to hydrogen regulation.
  • the catalyst when used in the polymerization of olefins (especially propylene), it can also increase the bulk density of the polymerization product, and there is basically no occurrence of foreign materials in the polymerization product.
  • the spherical carrier of the olefin polymerization catalyst of the present invention has great industrial application prospects.

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Abstract

涉及一种用于烯烃聚合催化剂的载体及其制备方法和应用。该用于烯烃聚合催化剂的载体包括含镁化合物和硫，所述硫为单质硫、络合态硫和化合态硫中的至少一种。该载体颗粒形态良好、表面光滑、基本不存在异形粒子，粒径分布较窄。由该载体制备的催化剂的活性较高，氢调敏感性较好，该催化剂用于烯烃聚合时可提高聚合物堆密度。

Description

用于烯烃聚合催化剂的载体及其制备方法和应用
相关申请的交叉引用
本申请要求享有2018年10月19日提交的申请号为201811224586.4、发明名称为“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”的中国专利申请的优先权，其全部内容通过引用结合在本文中。
技术领域
本发明属于烯烃聚合领域，更具体地，涉及一种用于烯烃聚合催化剂的载体及其制备方法，还涉及一种用于烯烃聚合的催化剂组分、催化剂以及烯烃聚合方法。
背景技术
近年来，聚丙烯产业取得迅猛发展，在通用塑料甚至是特种塑料中所占的比例一直在上升，这主要是由于催化剂技术的进步、丙烯聚合工艺的发展及其所带来的丙烯聚合物性能的进一步拓展。聚丙烯催化剂包括Ziegler-Natta催化剂、茂金属催化剂及非茂金属催化剂，其中，Ziegler-Natta催化剂一直是丙烯聚合生产中最主要的催化体系。Ziegler-Natta催化剂始于20世纪50年代，通过多次的更新换代，仍然是工业生产的主要催化剂之一，而且对它的研究一直是聚丙烯催化剂的热点之一。
由于球形聚丙烯催化剂的形貌特点以及存在从催化剂到聚合物的“复制”现象(即只有球形催化剂才可以得到球形聚合物)，球形形貌的催化剂在聚合生产过程及聚合物后续处理加工过程中具有巨大的优势，而且特别有利于高分子合金的生产。因此，目前工业上应用的聚丙烯催化剂中，球形催化剂所占比例非常大。球形载体和内给电子体是球形聚丙烯催化剂的两个重要组成部分。球形载体主要来自于氯化镁醇合物载体，将氯化镁与醇在高温下反应形成氯化镁醇合物，再熔融分散在惰性组分中后经高剪切作用形成乳液，将乳液移入低温介质后醇合物固化成型得到载体。在载体的生产过程中需要高温下的熔融及低温下的固化过程，因此需要耗费较多的能源。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，具体公开了将卤化镁醇合物熔融分散后，加入环氧乙烷类化合物；或者是将卤化镁醇合物熔融分散后直接加入到含环氧乙烷类化合物的反应器中。然而，采用该方法制备催化剂载体存在制备过程不稳定，容易发生载体粘连，且载 体成型效果不好，粒径分布宽的缺点。
因此，开发一种能够克服现有技术上述缺陷的新的烯烃聚合用催化剂载体具有重要意义。
发明内容
本发明的发明人意外地发现，在烯烃聚合催化剂载体的制备过程中加入硫，能够得到一种具有新型组成的载体，该载体颗粒形态良好、表面光滑、基本不存在异形粒子，并且其粒径可实现小于20微米、粒径分布较窄。由该载体制备的催化剂的活性较高，氢调敏感性较好，该催化剂用于烯烃聚合时可提高聚合物堆密度。
基于此，本发明的第一方面提供一种烯烃聚合催化剂的载体，该载体包括含镁化合物和硫。所述硫可以以单质、络合态或者化合态存在于载体中。
在第二个方面，本发明提供了一种用于烯烃聚合催化剂的载体的制备方法，包括(1)制备混合物，所述混合物包含单质硫和/或含硫化合物、通式为MgX 1Y的卤化镁、通式为R 1OH的化合物、可选的惰性液体介质以及可选的表面活性剂，优选通过将单质硫和/或含硫化合物、通式为MgX 1Y的卤化镁、通式为R 1OH的化合物、可选的惰性液体介质、可选的表面活性剂混合并加热得到所述混合物；
(2)将步骤(1)得到的混合物与环氧乙烷类化合物接触反应；
通式MgX 1Y中，X 1为卤素，优选为氯或溴；Y选自卤素、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C1-C10烷氧基、取代或未取代的C6-C20芳氧基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；
通式R 1OH中，R 1选自取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 1选自取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C15芳基、取代或未取代的C7-C15芳烷基和取代或未取代的C7-C15烷芳基；更优选地，R 1选自取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；
所述环氧乙烷类化合物的结构如式(Ⅱ)所示：
Figure PCTCN2019111253-appb-000001
式(Ⅱ)中，R 5和R 6各自独立地为氢、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 5和R 6各自独立地选自氢、取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；更优选地，R 5和R 6各自独立地选自氢、取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C8芳基、取代或未取代的C7-C9芳烷基和取代或未取代的C7-C9烷芳基。
在第三个方面，本发明还提供了一种用于烯烃聚合的催化剂组分，所述催化剂组分包括本发明第一个方面所述的载体和/或根据本发明第二个方面所述的制备方法制备的载体、钛、以及任选的给电子体和/或包括由本发明第一个方面所述的载体和/或根据本发明第二个方面所述的制备方法制备的载体与钛化合物以及任选的给电子体的反应产物。
在第四个方面，本发明还提供了一种本发明第一个方面所述的载体和/或根据本发明第二个方面所述的制备方法制备的载体和/或本发明第三个方面所述的催化剂组分在制备用于烯烃聚合的催化剂中的应用。
在第五个方面，本发明提供了一种用于烯烃聚合的催化剂，该催化剂含有：(1)本发明第三个方面所述的催化剂组分；(2)烷基铝化合物；以及(3)任选的外给电子体化合物。
在第六个方面，本发明提供了一种烯烃聚合方法，包括：在烯烃聚合条件下，将一种或多种烯烃与本发明上述的催化剂接触。
附图说明
通过结合附图对本发明示例性实施方式进行更详细的描述。
图1为制备例1制备的烯烃聚合催化剂球形载体的光学显微镜照片。
图2为制备例6制备的烯烃聚合催化剂球形载体的光学显微镜照片。
图3为制备例7制备的烯烃聚合催化剂球形载体的光学显微镜照片。
图4为制备例8制备的烯烃聚合催化剂球形载体的光学显微镜照片。
图5为对比制备例1制备的烯烃聚合催化剂载体的光学显微镜照片。
具体实施方式
本发明的第一方面提供一种烯烃聚合催化剂的载体，该载体包括含镁化合物和硫。所述硫可以以单质、络合态或者化合态存在于载体中。
根据本发明的一些实施方式，所述含镁化合物具有选自卤素、取代或未取代的烷基、取代或未取代的芳基、取代或未取代的烷氧基和取代或未取代的芳氧基中一种或多种基团。
根据本发明的一些实施方式，所述含镁化合物中的镁与硫的摩尔比为1：q，其中，0<q≤0.5，优选0.0001<q≤0.3，更优选0.001<q≤0.1。
根据本发明的一些实施方式，所述含镁化合物具有选自卤素、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C1-C10烷氧基、取代或未取代的C6-C20芳氧基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基的一种或多种基团。
根据本发明的一些实施方式，所述含镁化合物为选自如式(I)所示的镁化合物：
Figure PCTCN2019111253-appb-000002
式(I)中，R 1选自取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 1选自取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C15芳基、取代或未取代的C7-C15芳烷基和取代或未取代的C7-C15烷芳基；更优选地，R 1选自取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；
R 2和R 3相同或不相同，各自独立地选自氢、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 2和R 3各自独立地选自氢、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C8支链烷基、取代或 未取代的C3-C8环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；更优选地，R 2和R 3各自独立地选自氢、取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C8芳基、取代或未取代的C7-C9芳烷基和取代或未取代的C7-C9烷芳基；
X为卤素，优选为氯或溴；
m为0.1-1.9，n为0.1-1.9，m+n＝2。
根据本发明的一些实施方式，所述载体为球形或类球形。本发明的烯烃聚合催化剂的载体的平均颗粒可在较宽的范围内控制，例如可以为10-100微米。根据本发明的一种优选实施方式，所述烯烃聚合催化剂球形载体的平均颗粒直径(D50)可控制到小于等于30微米，优选控制到小于等于20微米在该优选实施方式中，由该烯烃聚合催化剂球形载体制备的催化剂能够得到具有更高堆积密度的烯烃聚合物。在本发明中，所述烯烃聚合催化剂球形载体的平均颗粒直径和粒径分布可以采用Master Sizer 2000激光粒度仪(由Malvern Instruments Ltd生产制造)测得。根据本发明的一些实施方式，所述载体的平均颗粒直径小于等于30微米，优选小于等于20微米。根据本发明的一些实施方式，粒径分布(D90-D10)/D50)小于1.2，优选粒径分布小于等于0.8。
根据本发明的一些实施方式，所述载体的合成原料包括单质硫和/或含硫化合物、通式为MgX 1Y的卤化镁、通式为R 4OH的化合物以及环氧乙烷类化合物。
根据本发明的一些实施方式，通式MgX 1Y中，X 1为卤素，优选为氯或溴；Y选自卤素、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C1-C10烷氧基、取代或未取代的C6-C20芳氧基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基。
根据本发明的一些实施方式，通式R 1OH中，R 1选自取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 1选自取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C15芳基、取代或未取代的C7-C15芳烷基和取代或未取代的C7-C15烷芳基；更优选地，R 1选自取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基。
根据本发明的一些实施方式，所述环氧乙烷类化合物的结构如式(Ⅱ)所示：
Figure PCTCN2019111253-appb-000003
式(Ⅱ)中，R 5和R 6各自独立地为氢、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 5和R 6各自独立地选自氢、取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；更优选地，R 5和R 6各自独立地选自氢、取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C8芳基、取代或未取代的C7-C9芳烷基和取代或未取代的C7-C9烷芳基。
根据本发明的一些实施方式，通式MgX 1Y中，X 1为氯或溴，Y为氯、溴、C 1-C 5烷氧基或C 6-C 10芳氧基。优选地，通式为MgX 1Y的卤化镁选自氯化镁、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。
根据本发明的一些实施方式，通式R 1OH中，R 1为C 1-C 8烷基。优选地，通式为R 1OH的化合物选自乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正戊醇、异戊醇、正己醇、2-乙基己醇和正辛醇中的至少一种。
根据本发明的一些实施方式，结构如式(Ⅱ)所示的环氧乙烷类化合物中，R 5和R 6各自独立地为氢、C 1-C 3的烷基或C 1-C 3的卤代烷基。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，所述烯烃聚合催化剂的载体中可能含有水，含有的水来自于合成原料和反应介质所带的微量水。
在第二个方面，本发明提供了一种用于烯烃聚合催化剂的载体的制备方法，所述制备方法包括以下步骤：
(1)制备混合物，所述混合物包含单质硫和/或含硫化合物、通式为MgX 1Y的卤化镁、通式为R 1OH的化合物、可选的惰性液体介质以及可选的表面活性剂，优选通过将单质硫和/或含硫化合物、通式为MgX 1Y的卤化镁、通式为R 1OH的化合物、可选的惰性液体介质、可选的表面活性剂一起或者分步混合并加热得到所述混合物；
(2)将步骤(1)得到的混合物与环氧乙烷类化合物接触反应。
通式MgX 1Y中，X 1为卤素，优选为氯或溴；Y选自卤素、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C1-C10烷氧基、取代或未取代的C6-C20芳氧基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基。
通式R 1OH中，R 1选自取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 1选自取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C15芳基、取代或未取代的C7-C15芳烷基和取代或未取代的C7-C15烷芳基；更优选地，R 1选自取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基。
所述环氧乙烷类化合物的结构如式(Ⅱ)所示：
Figure PCTCN2019111253-appb-000004
式(Ⅱ)中，R 5和R 6各自独立地为氢、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 5和R 6各自独立地选自氢、取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；更优选地，R 5和R 6各自独立地选自氢、取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C8芳基、取代或未取代的C7-C9芳烷基和取代或未取代的C7-C9烷芳基。
根据本发明的一些实施方式，通式MgX 1Y中，X 1为氯或溴，Y为氯、溴、C 1-C 5烷氧基或C 6-C 10芳氧基。优选地，通式为MgX 1Y的卤化镁选自氯化镁、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。
根据本发明的一些实施方式，通式R 1OH中，R 1为C 1-C 8烷基。优选地，通式为R 1OH的化合物选自乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正戊醇、异戊醇、正己醇、2-乙基 己醇和正辛醇中的至少一种。
根据本发明的一些实施方式，结构如式(Ⅱ)所示的环氧乙烷类化合物中，R 5和R 6各自独立地为氢、C 1-C 3的烷基或C 1-C 3的卤代烷基。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式，以1mol通式为MgX 1Y的卤化镁为基准，单质硫和/或含硫化合物的用量为0.0001-0.5mol，通式为R 1OH的化合物的用量为4-30mol，环氧乙烷类化合物的用量为1-10mol。
优选地，以1mol通式为MgX 1Y的卤化镁为基准，通式为R 1OH的化合物的用量为6-20mol，环氧乙烷类化合物的用量为2-6mol。
根据本发明的一些实施方式，步骤(1)中，所述加热的温度为80-120℃，时间为0.5-5小时；优选地，所述加热的温度为80-100℃，时间为0.5-3小时。
根据本发明的一些实施方式，步骤(2)中，所述接触反应的条件包括：温度为40-120℃，时间为15-60分钟；优选地，所述接触反应的条件包括：温度为60-100℃，时间为20-50分钟。
根据本发明的一些实施方式，所述惰性液体介质为硅油类溶剂和/或烃类溶剂；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。
根据本发明的一些实施方式，以1mol通式为MgX 1Y的卤化镁为基准，所述惰性液体介质的用量为0.8-10L。
根据本发明的一些实施方式，所述表面活性剂选自聚乙烯吡咯烷酮、聚乙二醇、聚乙烯醇、聚丙烯酸、聚丙烯酸盐、聚丙烯酰胺、聚苯乙烯磺酸盐、萘磺酸甲醛缩合物、缩合烷基苯基醚硫酸酯、缩合烷基苯酚聚氧乙烯醚磷酸酯、氧基烷基丙烯酸酯共聚物改性聚乙撑亚胺、1-十二-4-乙烯吡啶溴化物的聚合物、聚乙烯基苄基三甲胺盐、聚环氧乙烷环氧丙烷嵌段共聚物、聚乙烯吡咯烷酮醋酸乙烯酯共聚物、烷基苯基聚氧乙烯醚和聚甲基丙烯酸烷基酯中的至少一种。
根据本发明的一些实施方式，以1mol通式为MgX 1Y的卤化镁为基准，所述表面活性剂的用量为1-20g。
根据本发明的一些实施方式，所述单质硫选自α-硫、β-硫、γ-硫和聚合型硫中的至少一种。
根据本发明的一些实施方式，所述含硫化合物具有选自巯基(-SH)、硫醚基(-S-)、 硫羰基
Figure PCTCN2019111253-appb-000005
中的一种或多种基团。示例性的所述含硫化合物包括2-巯基乙醇、一硫化四甲基秋兰姆、二硫化四甲基秋兰姆等。
根据本发明，该方法还可以包括将接触反应得到的产物进行固液分离，将分离得到的固相产物洗涤并进行干燥。所述固液分离可以是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，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(例如：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0.5-10小时。根据本发明，所述干燥可以在常压或减压条件下进行。
采用本发明的技术方案，在烯烃聚合催化剂载体的制备过程中加入硫，能够得到一种具有新型组成的球形载体。硫能够降低未成型粒子间的碰撞机率、减少载体粒子间的粘连，使得到的载体颗粒粒径小、分布较窄且形态良好，并且，利用该载体所制备的催化剂粒径分布窄、活性较好、氢调敏感性较好，用于烯烃聚合时可提高聚合物堆密度。
在第三个方面，本发明还提供了一种用于烯烃聚合的催化剂组分，所述催化剂组分包括本发明第一个方面所述的载体和/或根据本发明第二个方面所述的制备方法制备的载体、钛、以及任选的内给电子体和/或包括由本发明第一个方面所述的载体和/或根据本发明第二个方面所述的制备方法制备的载体与钛化合物以及任选的内给电子体的反应产物。
根据本发明的一些实施方式，所述催化剂组分为球形或类球形，其平均颗粒直径小于等于30微米，优选小于等于20微米。
根据本发明的一些实施方式，所述催化剂组分为球形或类球形，其粒径分布小于1.2，优选粒径分布小于等于0.8。
本发明中，所述钛化合物可以为本领域常用的钛化合物。优选地，所述钛化合物为式Ⅺ和/或式Ⅻ所示的化合物：
TiX p(OR 27) 4-p     式XI，
TiX q(OR 28) 3-q      式XII，
式XI和式XII中，X为卤素，R 27、R 28各自独立地为C 1-C 20的烷基，p为1-4的整数，q为1-3的整数。
进一步优选情况下，所述钛化合物为四氯化钛、四溴化钛、四碘化钛、三丁氧基氯化钛、 二丁氧基二氯化钛、丁氧基三氯化钛、三乙氧基氯化钛、二乙氧基二氯化钛、乙氧基三氯化钛和三氯化钛中的一种或多种。最优选情况下，所述钛化合物为四氯化钛。
本发明的用于烯烃聚合的催化剂组分的制备方法可包括如下步骤：将镁化合物与钛化合物反应，并在所述镁化合物与钛化合物反应之前、期间和之后的一个或多个时间段内加入内给电子体。
在第四个方面，本发明还提供了一种本发明第一个方面所述的载体和/或根据本发明第二个方面所述的制备方法制备的载体和/或本发明第三个方面所述的催化剂组分在制备用于烯烃聚合的催化剂中的应用。
在第五个方面，本发明提供了一种用于烯烃聚合的催化剂，该催化剂含有：(1)本发明第四个方面所述的催化剂组分；(2)烷基铝化合物；以及(3)任选的外给电子体化合物。
根据本发明，在上述用于烯烃聚合的催化剂中，所述烷基铝化合物可以为烯烃聚合领域常用的各种能够用作烯烃聚合催化剂的助催化剂的烷基铝化合物。优选情况下，所述烷基铝化合物为式XIII所示的化合物，
AlR’ n'X’ 3-n'      式XIII，
式XIII中，R’为C 1-C 8的烷基或卤代烷基，X’为卤素，优选为氯、溴和碘中的一种或多种，更优选为氯，n'为1-3的整数。
进一步优选情况下，所述烷基铝化合物为三乙基铝、三丙基铝、三正丁基铝、三异丁基铝、三正己基铝、三正辛基铝、三异丁基铝、一氢二乙基铝、一氢二异丁基铝、一氯二乙基铝、一氯二异丁基铝、二氯乙基铝、Al(n-C 6H 13) 3和Al(n-C 8H 17) 3中的一种或多种。
最优选地，所述烷基铝化合物为三乙基铝和/或三异丁基铝。
根据本发明，所述烷基铝化合物的用量可以为本领域的常规用量。优选情况，所述烷基铝化合物中的铝与所述催化剂组分中的钛的摩尔比为(1-2000)：1。进一步优选情况下，所述烷基铝化合物中的铝与所述催化剂组分中的钛的摩尔比为(10-500)：1。
本发明对烯烃聚合催化剂中的外给电子体的种类和含量没有特别的限定。优选的情况下，所述烷基铝化合物中的铝和所述外给电子体化合物的摩尔比为(2-200)：1，更优选为(2.5-100)：1。
根据本发明，所述外给电子体化合物与所述内给电子体化合物a和所述内给电子体化合物b结合使用可以进一步提高根据本发明的方法得到的烯烃聚合物的等规指数。所述外给电子体化合物可以为本领域常用的各种能够实现上述目的的外给电子体化合物，例如：羧酸、 羧酸酸酐、羧酸酯、酮、醚、醇、内酯、有机磷化合物和有机硅化合物中的一种或多种。优选地，所述外给电子体化合物为式XIV所示的有机硅化合物，
(R 29) m’(R 30) p’Si(OR 31) q’   式XIV，
式XIV中，R 29、R 30和R 31各自独立地为C 1-C 18的烃基，任选地含有杂原子，所述杂原子为F、Cl、Br、N和I中的一种或多种；m’和p’各自独立地为0-2的整数，q’为1-3的整数，且m’、p’和q’的和为4。
优选情况下，R 29和R 30各自独立地为C 3-C 10的直链或支链烷基，C 3-C 10的直链或支链烯烃基、C 3-C 10的取代或未取代的亚烷基、C 3-C 10的取代或未取代的环烷基和C 6-C 10的取代或未取代的芳基，任选地含有杂原子，所述杂原子为F、Cl、Br、N和I中的一种或多种；R 31为C 1-C 10的直链或支链烷基，更优选为甲基。
根据本发明，所述外给电子体化合物的具体实例可以包括但不限于：环己基甲基二甲氧基硅烷、二异丙基二甲氧基硅烷、二正丁基二甲氧基硅烷、二异丁基二甲氧基硅烷、二苯基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷、环己基三甲氧基硅烷、叔丁基三甲氧基硅烷、叔己基三甲氧基硅烷、二环戊基二甲氧基硅烷、2-乙基哌啶基-2-叔丁基二甲氧基硅烷、(1,1,1-三氟-2-丙基)-2-乙基哌啶基二甲氧基硅烷和(1,1,1-,三氟-2-丙基)-甲基二甲氧基硅烷中的一种或多种。这些外给电子体可单一使用也可复合多种使用。
进一步优选情况下，所述外给电子体化合物为环己基甲基二甲氧基硅烷和/或二环戊基二甲氧基硅烷。
根据本发明，在用于烯烃聚合的催化剂的制备过程中，烷基铝和任选的外给电子体化合物可以分别与用于烯烃聚合的催化剂组分混合后反应，或者也可以将烷基铝和任选的外给电子体事先混合后再与用于烯烃聚合的催化剂组分混合并反应。
根据本发明，在将用于烯烃聚合的催化剂用于烯烃聚合时，所述用于烯烃聚合的催化剂组分、烷基铝、以及任选的外给电子体可分别加入聚合反应器中，也可混合后加入聚合反应器中，也可采用本行业公知的预聚合方法将烯烃预聚后加入到聚合反应器中。
在第六个方面，本发明提供了一种烯烃聚合方法，包括：在烯烃聚合条件下，将一种或多种烯烃与本发明上述的催化剂接触。
在一些实施方式中，所述烯烃为至少一种由式CH2＝CHR表示的烯烃，其中R为氢或C 1-C 6的直链或支链烷基。所述由式CH 2＝CHR表示的烯烃的具体实例可以包括：乙烯、丙烯、1-正丁烯、1-正戊烯、1-正己烯、1-正辛烯、4-甲基-1-戊烯。优选情况下，所述由式CH 2＝CHR表示的烯烃为乙烯、丙烯、1-正丁烯、1-正己烯、4-甲基-1-戊烯。更优选地，所述由式CH 2＝CHR 表示的烯烃为丙烯。
本发明的烯烃聚合方法可以为单一烯烃的均聚合，也可以为多种烯烃的共聚合。
根据本发明的烯烃聚合方法，所述烯烃聚合条件可以为本领域的常规条件。一般地，所述烯烃聚合条件可以包括：温度为0-150℃，时间为0.1-8小时，压力为0.01-10MPa。优选地，所述烯烃聚合条件包括：温度为50-100℃，时间为0.5-3小时，压力为0.5-5MPa。所述烯烃聚合催化剂的用量可以为现有技术烯烃催化剂的各种常规用量。
本申请中，所述单质硫可以为任何单质硫的亚型，包括但不限于：α-硫、β-硫、γ-硫和聚合型硫中的至少一种。所述单质硫可以为无水单质硫或含有结合水的单质硫。上述单质硫均可通过商购获得。
本申请中，术语卤素选自氟、氯、溴和碘。
本申请中，C1-C10烷基例如可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基、己基、异己基、庚基、异庚基、辛基或异辛基。
本申请中，C1-C10烷氧基例如可以为甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基或异丁氧基。
本申请中，C 6-C 10的芳基例如可以为苯基、邻甲苯基、间甲苯基、对甲苯基、邻乙苯基、间乙苯基、对乙苯基或萘基。
本申请中，所述C 6-C 10的芳氧基例如可以为苯氧基或萘氧基。
本申请中，C 3-C 8的环烷基例如可以为环戊基、环戊基甲基、环戊基乙基、环己基或环己基甲基。
在本发明中，术语“取代的”是指所描述的基团可以被一个或多个常见取代基取代，所述常见取代基可以是烷基、烷氧基、卤素、氨基、羟基等，例如C1-C6烷基、C1-C6烷氧基、卤素、氨基、羟基等。
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
以下将通过实施例对本发明进行详细描述。
在实施例和对比例中：
1、烯烃聚合催化剂球形载体、催化剂组分的平均颗粒直径和粒径分布采用Masters Sizer 2000粒度仪(由Malvern Instruments Ltd生产制造)进行测定。
2、烯烃聚合催化剂球形载体的表观形貌通过商购自Nikon公司的型号为Eclipse E200的光学显微镜进行观察。
3、熔体流动速率(MFR)：按照ISO1133，230℃，2.16kg载荷下测量。
4、聚烯烃粉料的堆密度采用GB/T 1636-2008规定的方法进行测定。
制备例1
该制备例用于说明本发明提供的烯烃聚合催化剂球形载体及其制备方法。
在0.6L的反应釜中，加入8.0g(0.08mol)氯化镁、56mL(0.96mol)乙醇、1g(0.03mol)α-硫，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至90℃，恒温反应2小时后加入38mL(0.48mol)环氧氯丙烷，继续90℃恒温反应半个小时后压滤，将压滤产物用已烷洗涤5次，最后将产物真空干燥，得到烯烃聚合用催化剂球形载体Z1。
所述烯烃聚合催化剂球形载体Z1的平均颗粒直径(D50)为15微米，粒径分布((D90-D10)/D50)为0.6。如图1所示，采用光学显微镜观察烯烃聚合催化剂球形载体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。
根据气质联用、元素分析及核磁表征，Z1的组成包括结构式为
Figure PCTCN2019111253-appb-000006
的含镁化合物和硫，其中含镁化合物中的镁与硫的摩尔比为1：0.2。
其中，核磁共振氢谱(1-HNMR)：
Figure PCTCN2019111253-appb-000007
制备例2
该制备例用于说明本发明提供的烯烃聚合催化剂球形载体及其制备方法。
在0.6L的反应釜中，加入300mL白油、8.0g(0.08mol)氯化镁、28mL(0.48mol)乙醇、 0.3g(0.009mol)β-硫，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至100℃，恒温反应1小时后加入12.5mL(0.16mol)环氧氯丙烷，继续100℃恒温反应20分钟后压滤，将压滤产物用已烷洗涤5次，最后将产物真空干燥，得到烯烃聚合催化剂球形载体Z2。
所述烯烃聚合催化剂球形载体Z2的平均颗粒直径(D50)为18微米，粒径分布((D90-D10)/D50)为0.7。采用光学显微镜观察烯烃聚合催化剂球形载体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。
根据气质联用、元素分析及核磁表征，Z2的组成包括结构式为
Figure PCTCN2019111253-appb-000008
的含镁化合物和硫，其中含镁化合物中的镁与硫的摩尔比为1：0.01。
制备例3
该制备例用于说明本发明提供的烯烃聚合催化剂球形载体及其制备方法。
在0.6L的反应釜中，加入300mL白油、8.0g(0.08mol)氯化镁、28mL(0.48mol)乙醇、0.2g(0.006mol)α-硫，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至100℃，恒温反应1小时后加入12.5mL(0.16mol)环氧氯丙烷，继续100℃恒温反应20分钟后压滤，将压滤产物用已烷洗涤5次，最后将产物真空干燥，得到烯烃聚合催化剂球形载体Z3。
所述烯烃聚合催化剂球形载体Z3的平均颗粒直径(D50)为20微米，粒径分布((D90-D10)/D50)为0.8。采用光学显微镜观察烯烃聚合催化剂球形载体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。
根据气质联用、元素分析及核磁表征，Z3的组成包括结构式为
Figure PCTCN2019111253-appb-000009
的含镁化合物和硫，其中含镁化合物中的镁与硫的摩尔比为1：0.007。
制备例4
该制备例用于说明本发明提供的烯烃聚合催化剂球形载体及其制备方法。
在0.6L的反应釜中，加入8.0g(0.08mol)氯化镁、59mL(0.48mol)环己甲醇、0.3g(0.009mol)β-硫，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至60℃，恒温反应1小时 后加入12.5mL(0.16mol)环氧氯丙烷，继续60℃恒温反应20分钟后压滤，将压滤产物用已烷洗涤5次，最后将产物真空干燥，得到烯烃聚合催化剂球形载体Z4。
所述烯烃聚合催化剂球形载体Z4的平均颗粒直径(D50)为25微米，粒径分布((D90-D10)/D50)为0.9。采用光学显微镜观察烯烃聚合催化剂球形载体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。
根据气质联用、元素分析及核磁表征，Z4的组成包括结构式为
Figure PCTCN2019111253-appb-000010
的含镁化合物和硫，其中含镁化合物中的镁与硫的摩尔比为1：0.01。
制备例5
该制备例用于说明本发明提供的烯烃聚合催化剂球形载体及其制备方法。
在0.6L的反应釜中，加入8.0g(0.08mol)氯化镁、28mL(0.48mol)乙醇、0.3g(0.009mol)α-硫，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至70℃，恒温反应1小时后加入11.2mL(0.16mol)环氧丙烷，继续70℃恒温反应20分钟后压滤，将压滤产物用已烷洗涤5次，最后将产物真空干燥，得到烯烃聚合催化剂球形载体Z5。
所述烯烃聚合催化剂球形载体Z5的平均颗粒直径(D50)为26微米，粒径分布((D90-D10)/D50)为0.9。采用光学显微镜观察烯烃聚合催化剂球形载体Z5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。
根据气质联用、元素分析及核磁表征，Z5的组成包括结构式为
Figure PCTCN2019111253-appb-000011
的含镁化合物和硫，其中含镁化合物中的镁与硫的摩尔比为1：0.01。
制备例6
该制备例用于说明本发明提供的烯烃聚合催化剂球形载体及其制备方法。
在0.6L的反应釜中，加入8.0g(0.08mol)氯化镁、28mL(0.48mol)乙醇、2mL 2-巯基乙醇，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至70℃，恒温反应1小时后加入11.2mL(0.16mol)环氧丙烷，继续70℃恒温反应20分钟后压滤，将压滤产物用已烷 洗涤5次，最后将产物真空干燥，得到烯烃聚合催化剂球形载体Z6。
所述烯烃聚合催化剂球形载体Z6的平均颗粒直径(D50)为35.2微米。采用光学显微镜观察烯烃聚合催化剂球形载体Z6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，如图2所示。
制备例7
该制备例用于说明本发明提供的烯烃聚合催化剂球形载体及其制备方法。
在0.6L的反应釜中，加入8.0g(0.08mol)氯化镁、28mL(0.48mol)乙醇、2mL二硫化四甲基秋兰姆，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至70℃，恒温反应1小时后加入11.2mL(0.16mol)环氧丙烷，继续70℃恒温反应20分钟后压滤，将压滤产物用已烷洗涤5次，最后将产物真空干燥，得到烯烃聚合催化剂球形载体Z7。
所述烯烃聚合催化剂球形载体Z7的平均颗粒直径(D50)为45.1微米。采用光学显微镜观察烯烃聚合催化剂球形载体Z7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，如图3所示。
制备例8
该制备例用于说明本发明提供的烯烃聚合催化剂球形载体及其制备方法。
在0.6L的反应釜中，加入8.0g(0.08mol)氯化镁、28mL(0.48mol)乙醇、5mL一硫化四甲基秋兰姆，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至70℃，恒温反应1小时后加入11.2mL(0.16mol)环氧丙烷，继续70℃恒温反应20分钟后压滤，将压滤产物用已烷洗涤5次，最后将产物真空干燥，得到烯烃聚合催化剂球形载体Z7。
所述烯烃聚合催化剂球形载体Z8的平均颗粒直径(D50)为50.1微米。采用光学显微镜观察烯烃聚合催化剂球形载体Z8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，如图4所示。
对比制备例1
该对比制备例用于说明参比烯烃聚合催化剂载体及其制备方法。
在0.6L的反应釜中，加入0.08mol氯化镁、0.96mol乙醇，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至90℃，恒温反应2小时后加入38mL(0.48mol)环氧氯丙烷，继续90℃恒温反应半个小时后压滤，将压滤产物用已烷洗涤5次，最后将产物真空干燥，得到烯烃聚合用催化剂载体DZ1。
所述烯烃聚合用催化剂载体DZ1的平均颗粒直径(D50)为60微米，粒径分布((D90-D10)/D50)为1.3。采用光学显微镜观察的粒子形貌如图4所示。从图4中可以看出，烯烃聚合用催化剂载体DZ1中存在异形粒子，且表面较为粗糙。
对比制备例2
在0.6L的反应釜中，加入8.0g(0.08mol)氯化镁、59mL(0.48mol)环己甲醇，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至60℃，恒温反应1小时后加入12.5mL(0.16mol)环氧氯丙烷，继续60℃恒温反应20分钟后压滤，将压滤产物用已烷洗涤5次，最后将产物真空干燥，得到烯烃聚合催化剂球形载体DZ2。
所述烯烃聚合用催化剂载体DZ2的平均颗粒直径(D50)为80微米，粒径分布((D90-D10)/D50)为1.5。采用光学显微镜观察粒子形貌，DZ2中存在异形粒子，且表面较为粗糙。
对比制备例3
在0.6L的反应釜中，加入8.0g(0.08mol)氯化镁、28mL(0.48mol)乙醇，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至70℃，恒温反应1小时后加入11.2mL(0.16mol)环氧丙烷，继续70℃恒温反应20分钟后压滤，将压滤产物用已烷洗涤5次，最后将产物真空干燥，得到烯烃聚合催化剂球形载体DZ3。
所述烯烃聚合用催化剂载体DZ3的平均颗粒直径(D50)为88微米，粒径分布((D90-D10)/D50)为1.7。采用光学显微镜观察粒子形貌，DZ3中存在异形粒子，且表面较为粗糙。
实施例1
该实施例用于说明本发明提供的烯烃聚合催化剂的制备。
(1)烯烃聚合催化剂的制备
在300mL的玻璃反应瓶中，加入100mL的四氯化钛，冷却至-20℃，将40克的由制备例1得到的所述烯烃聚合催化剂球形载体Z1加入其中，并在-20℃下搅拌30min。之后，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，加入四氯化钛洗涤2次，最后用已烷洗3次，干燥后得到烯烃聚合催化剂C1。
(2)丙烯聚合反应
在一个5L的不锈钢高压反应釜中，采用氮气气流进行吹扫，然后在氮气气流中引入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的无水己烷和10mg的由步骤(1)得到的烯烃聚合催化剂C1、1.5L(标准体积)的氢气和2.5L的液体丙烯。升温至70℃，并在该温度下反应1小时，降温，放压，出料干燥得到聚丙烯粉料P1。
烯烃聚合催化剂C1的平均颗粒直径(D50)为14微米，粒径分布为0.6，活性为 38.9kgPP/g·cat，聚丙烯粉料P1的熔体流动速率指数为12.0g/10min，堆密度为0.46g/cm 3，此外，该聚丙烯粉料颗粒形态良好，基本不存在异形料。
实施例2
该实施例用于说明本发明提供的烯烃聚合催化剂的制备。
按照实施例1的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，所述烯烃聚合催化剂球形载体Z1用制备例2得到的所述烯烃聚合催化剂球形载体Z2替代，得到烯烃聚合催化剂C2和聚丙烯粉料P2。
烯烃聚合催化剂C2的平均颗粒直径(D50)为17微米，粒径分布为0.6，活性为37.8kgPP/g·cat，聚丙烯粉料P2的熔体流动速率指数为11.0g/10min，堆密度为0.46g/cm 3，此外，该聚丙烯粉料颗粒形态良好，基本不存在异形料。
实施例3
该实施例用于说明本发明提供的烯烃聚合催化剂的制备。
按照实施例1的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，所述烯烃聚合催化剂球形载体Z1用制备例3得到的所述烯烃聚合催化剂球形载体Z3替代，得到烯烃聚合催化剂C3和聚丙烯粉料P3。
烯烃聚合催化剂C3的平均颗粒直径(D50)为19微米，粒径分布为0.7，活性为37.0kgPP/g·cat，聚丙烯粉料P3的熔体流动速率指数为12.0g/10min，堆密度为0.46g/cm 3，此外，该聚丙烯粉料颗粒形态良好，基本不存在异形料。
实施例4
该实施例用于说明本发明提供的烯烃聚合催化剂的制备。
按照实施例1的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，加入6.5L而不是1.5L(标准体积)的氢气，得到聚丙烯粉料P4。
烯烃聚合催化剂C1的活性为40.0kgPP/g·cat，聚丙烯粉料P4的熔体流动速率指数为45.0g/10min，堆密度为0.46g/cm 3，此外，该聚丙烯粉料颗粒形态良好，基本不存在异形料。
实施例5
按照实施例1的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，所述烯烃聚合催化剂球形载体Z1用制备例4得到的所述烯烃聚合催化剂球形载体Z4替代，得到烯烃 聚合催化剂C5和聚丙烯粉料P5。
烯烃聚合催化剂C5的平均颗粒直径(D50)为23微米，粒径分布为0.8，活性为37.6kgPP/g·cat，聚丙烯粉料P5的熔体流动速率指数为11.1g/10min，堆密度为0.46g/cm 3，此外，该聚丙烯粉料颗粒形态良好，基本不存在异形料。
实施例6
按照实施例5的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，加入6.5L而不是1.5L(标准体积)的氢气，得到聚丙烯粉料P6。
烯烃聚合催化剂C5的活性为39.7kgPP/g·cat，聚丙烯粉料P6的熔体流动速率指数为45.2g/10min，堆密度为0.46g/cm 3，此外，该聚丙烯粉料颗粒形态良好，基本不存在异形料。
实施例7
按照实施例1的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，所述烯烃聚合催化剂球形载体Z1用制备例5得到的所述烯烃聚合催化剂球形载体Z5替代，得到烯烃聚合催化剂C7和聚丙烯粉料P7。
烯烃聚合催化剂C7的平均颗粒直径(D50)为25微米，粒径分布为0.8，活性为37.1kgPP/g·cat，聚丙烯粉料P7的熔体流动速率指数为11.2g/10min，堆密度为0.46g/cm 3，此外，该聚丙烯粉料颗粒形态良好，基本不存在异形料。
实施例8
按照实施例7的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，加入6.5L而不是1.5L(标准体积)的氢气，得到聚丙烯粉料P8。
烯烃聚合催化剂C7的活性为39.8kgPP/g·cat，聚丙烯粉料P8的熔体流动速率指数为45.7g/10min，堆密度为0.46g/cm 3，此外，该聚丙烯粉料颗粒形态良好，基本不存在异形料。
对比例1
该对比例用于说明参比烯烃聚合催化剂的制备。
按照实施例1的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，所述烯烃聚合催化剂球形载体Z1用对比制备例1得到的所述烯烃聚合催化剂载体DZ1替代，得到烯烃聚合催化剂DC1和聚丙烯粉料DP1。
烯烃聚合催化剂DC1的平均颗粒直径为58微米，粒径分布为1.2，活性为32.0kgPP/g·cat， 聚丙烯粉料DP1的熔体流动速率指数为7.0g/10min，堆密度为0.39g/cm 3，此外，该聚丙烯粉料颗粒中存在异形料，流动性不好。
对比例2
按照对比例1的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，加入6.5L而不是1.5L(标准体积)的氢气，得到聚丙烯粉料DP2。
烯烃聚合催化剂DC1的活性为33.1kgPP/g·cat，聚丙烯粉料DP2的熔体流动速率指数为37.0g/10min，堆密度为0.39g/cm 3，此外，该聚丙烯粉料颗粒中存在异形料，流动性不好。
对比例3
该对比例用于说明参比烯烃聚合催化剂的制备。
按照实施例1的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，所述烯烃聚合催化剂球形载体Z1用对比制备例2得到的所述烯烃聚合催化剂载体DZ2替代，得到烯烃聚合催化剂DC3和聚丙烯粉料DP3。
烯烃聚合催化剂DC3的平均颗粒直径为66微米，粒径分布为1.4，活性为32.3kgPP/g·cat，聚丙烯粉料DP3的熔体流动速率指数为7.4g/10min，堆密度为0.39g/cm 3，此外，该聚丙烯粉料颗粒中存在异形料，流动性不好。
对比例4
按照对比例3的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，加入6.5L而不是1.5L(标准体积)的氢气，得到聚丙烯粉料DP4。
烯烃聚合催化剂DC3的活性为33.6kgPP/g·cat，聚丙烯粉料DP4的熔体流动速率指数为37.7g/10min，堆密度为0.39g/cm 3，此外，该聚丙烯粉料颗粒中存在异形料，流动性不好。
对比例5
该对比例用于说明参比烯烃聚合催化剂的制备。
按照实施例1的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，所述烯烃聚合催化剂球形载体Z1用对比制备例3得到的所述烯烃聚合催化剂载体DZ3替代，得到烯烃聚合催化剂DC5和聚丙烯粉料DP5。
烯烃聚合催化剂DC5的平均颗粒直径为83微米，粒径分布为1.6，活性为32.8kgPP/g·cat，聚丙烯粉料DP5的熔体流动速率指数为7.8g/10min，堆密度为0.38g/cm 3，此外，该聚丙烯粉 料颗粒中存在异形料，流动性不好。
对比例6
按照对比例5的方法进行烯烃聚合催化剂的制备和丙烯聚合反应，不同的是，加入6.5L而不是1.5L(标准体积)的氢气，得到聚丙烯粉料DP6。
烯烃聚合催化剂DC5的活性为34.0kgPP/g·cat，聚丙烯粉料DP6的熔体流动速率指数为37.5g/10min，堆密度为0.37g/cm 3，此外，该聚丙烯粉料颗粒中存在异形料，流动性不好。
从以上结果可以看出，本发明的具有新型组成的烯烃聚合催化剂球形载体的粒径分布窄、颗粒形态良好、表面光滑、基本无异形粒子，而且以该载体制备的催化剂粒径分布窄、活性更好、氢调敏感性更好，该催化剂用于烯烃(特别是丙烯)聚合时，还能够提高聚合产物的堆密度，且聚合产物中基本无异性料的出现。本发明的烯烃聚合催化剂球形载体极具工业应用前景。
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。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，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，这些简单变型均属于本发明的保护范围。

Claims (22)

  1. 一种用于烯烃聚合催化剂的载体，包括含镁化合物和硫，所述硫为单质硫、络合态硫和化合态硫中的至少一种。
  2. 根据权利要求1所述的载体，其中，所述含镁化合物中镁与硫的摩尔比为1：q，其中，0<q≤0.5，优选0.0001<q≤0.3，更优选0.001<q≤0.1。
  3. 根据权利要求1或2所述的载体，其中，所述含镁化合物具有选自卤素、取代或未取代的烷基、取代或未取代的芳基、取代或未取代的烷氧基和取代或未取代的芳氧基中一种或多种基团；优选地，所述含镁化合物具有选自卤素、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C1-C10烷氧基、取代或未取代的C6-C20芳氧基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基的一种或多种基团。
  4. 根据权利要求1-3中任一项所述的载体，其中，所述含镁化合物为选自如式(I)所示的镁化合物：
    Figure PCTCN2019111253-appb-100001
    式(I)中，R 1选自取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 1选自取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C15芳基、取代或未取代的C7-C15芳烷基和取代或未取代的C7-C15烷芳基；更优选地，R 1选自取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；
    R 2和R 3相同或不相同，各自独立地选自氢、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 2和R 3各自独立地选自氢、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取 代或未取代的C7-C10烷芳基；更优选地，R 2和R 3各自独立地选自氢、取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C8芳基、取代或未取代的C7-C9芳烷基和取代或未取代的C7-C9烷芳基；
    X为卤素，优选为氯或溴；
    m为0.1-1.9，n为0.1-1.9，m+n＝2。
  5. 根据权利要求1-4中任一项所述的载体，其中，所述载体为球形或类球形，其平均颗粒直径小于等于30微米，优选小于等于20微米。
  6. 根据权利要求1-5中任一项所述的载体，其中，所述载体为球形或类球形，其粒径分布小于1.2，优选粒径分布小于等于0.8。
  7. 根据权利要求1-6中任一项所述的载体，其中，所述载体的合成原料包括单质硫和/或含硫化合物、通式为MgX 1Y的卤化镁、通式为R 4OH的化合物以及环氧乙烷类化合物；
    优选所述含硫化合物具有选自巯基(-SH)、硫醚基(-S-)、硫羰基
    Figure PCTCN2019111253-appb-100002
    中的一种或多种基团，更优选所述含硫化合物选自2-巯基乙醇、一硫化四甲基秋兰姆、二硫化四甲基秋兰姆；
    通式MgX 1Y中，X 1为卤素，优选为氯或溴；Y选自卤素、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C1-C10烷氧基、取代或未取代的C6-C20芳氧基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；
    通式R 1OH中，R 1选自取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 1选自取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C15芳基、取代或未取代的C7-C15芳烷基和取代或未取代的C7-C15烷芳基；更优选地，R 1选自取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；
    所述环氧乙烷类化合物的结构如式(Ⅱ)所示：
    Figure PCTCN2019111253-appb-100003
    Figure PCTCN2019111253-appb-100004
    式(Ⅱ)中，R 5和R 6各自独立地为氢、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 5和R 6各自独立地选自氢、取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；更优选地，R 5和R 6各自独立地选自氢、取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C8芳基、取代或未取代的C7-C9芳烷基和取代或未取代的C7-C9烷芳基。
  8. 一种用于烯烃聚合催化剂的载体的制备方法，包括以下步骤：
    (1)制备混合物，所述混合物包含单质硫和/或含硫化合物、通式为MgX 1Y的卤化镁、通式为R 1OH的化合物、可选的惰性液体介质以及可选的表面活性剂；
    (2)将步骤(1)得到的混合物与环氧乙烷类化合物接触反应；通式MgX 1Y中，X 1为卤素，优选为氯或溴；Y选自卤素、取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C1-C10烷氧基、取代或未取代的C6-C20芳氧基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；
    通式R 1OH中，R 1选自取代或未取代的C1-C10直链烷基、取代或未取代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 1选自取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C15芳基、取代或未取代的C7-C15芳烷基和取代或未取代的C7-C15烷芳基；更优选地，R 1选自取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；
    所述环氧乙烷类化合物的结构如式(Ⅱ)所示：
    Figure PCTCN2019111253-appb-100005
    式(Ⅱ)中，R 5和R 6各自独立地为氢、取代或未取代的C1-C10直链烷基、取代或未取 代的C3-C10支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6-C20芳基、取代或未取代的C7-C20芳烷基和取代或未取代的C7-C20烷芳基；优选地，R 5和R 6各自独立地选自氢、取代或未取代的C1-C8直链烷基、取代或未取代的C3-C8支链烷基、取代或未取代的C3-C8环烷基、取代或未取代的C6-C10芳基、取代或未取代的C7-C10芳烷基和取代或未取代的C7-C10烷芳基；更优选地，R 5和R 6各自独立地选自氢、取代或未取代的C1-C6直链烷基、取代或未取代的C3-C6支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C8芳基、取代或未取代的C7-C9芳烷基和取代或未取代的C7-C9烷芳基。
  9. 根据权利要求8所述的制备方法，其中，以1mol通式为MgX 1Y的卤化镁为基准，单质硫和/或含硫化合物的用量为0.0001-0.5mol，通式为R 1OH的化合物的用量为4-30mol，环氧乙烷类化合物的用量为1-10mol；
    优选地，以1mol通式为MgX 1Y的卤化镁为基准，通式为R 1OH的化合物的用量为6-20mol，环氧乙烷类化合物的用量为2-6mol。
  10. 根据权利要求8或9所述的制备方法，其中，步骤(1)中，通过将单质硫和/或含硫化合物、通式为MgX 1Y的卤化镁、通式为R 1OH的化合物、可选的惰性液体介质以及可选的表面活性剂一起或者分步混合并加热获得所述混合物，优选地，所述加热的温度为80-120℃，时间为0.5-5小时；更优选地，所述加热的温度为80-100℃，时间为0.5-3小时。
  11. 根据权利要求8-10中任一项所述的制备方法，其中，步骤(2)中，所述接触反应的条件包括：温度为40-120℃，时间为15-60分钟；优选地，所述接触反应的条件包括：温度为60-100℃，时间为20-50分钟。
  12. 根据权利要求8-11中任一项所述的制备方法，其中，所述惰性液体介质为硅油类溶剂和/或烃类溶剂；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；和/或
    以1mol通式为MgX 1Y的卤化镁为基准，所述惰性液体介质的用量为0.8-10L。
  13. 根据权利要求8-12中任一项所述的制备方法，其中，所述表面活性剂选自聚乙烯吡咯烷酮、聚乙二醇、聚乙烯醇、聚丙烯酸、聚丙烯酸盐、聚丙烯酰胺、聚苯乙烯磺酸盐、萘磺酸甲醛缩合物、缩合烷基苯基醚硫酸酯、缩合烷基苯酚聚氧乙烯醚磷酸酯、氧基烷基丙烯酸酯共聚物改性聚乙撑亚胺、1-十二-4-乙烯吡啶溴化物的聚合物、聚乙烯基苄基三甲胺盐、聚环氧乙烷环氧丙烷嵌段共聚物、聚乙烯吡咯烷酮醋酸乙烯酯共聚物、烷基苯基聚氧乙烯醚和聚甲基丙烯酸烷基酯中的至少一种；和/或
    以1mol通式为MgX 1Y的卤化镁为基准，所述表面活性剂的用量为1-20g。
  14. 根据权利要求8-13中任一项所述的制备方法，其中，所述单质硫选自α-硫、β-硫、 γ-硫和聚合型硫中的至少一种；所述含硫化合物具有选自巯基(-SH)、硫醚基(-S-)、硫羰基
    Figure PCTCN2019111253-appb-100006
    中的一种或多种基团，优选所述含硫化合物选自2-巯基乙醇、一硫化四甲基秋兰姆、二硫化四甲基秋兰姆。
  15. 根据权利要求8-14中任一项所述的制备方法，其中，通式MgX 1Y中，X 1为氯或溴，Y为氯、溴、C 1-C 5烷氧基或C 6-C 10芳氧基；优选地，通式为MgX 1Y的卤化镁选自氯化镁、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；和/或
    通式R 1OH中，R 1为C 1-C 8烷基；优选地，通式为R 1OH的化合物选自乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正戊醇、异戊醇、正己醇、2-乙基己醇和正辛醇中的至少一种；和/或
    结构如式(Ⅱ)所示的环氧乙烷类化合物中，R 5和R 6各自独立地为氢、C 1-C 3的烷基或C 1-C 3的卤代烷基；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。
  16. 一种用于烯烃聚合的催化剂组分，包括根据权利要求1-7中任一项所述的载体和/或根据权利要求8-15中任一项所述的制备方法制备的载体、钛、以及任选的给电子体。
  17. 一种用于烯烃聚合的催化剂组分，包括由根据权利要求1-7中任一项所述的载体或根据权利要求8-15中任一项所述的制备方法制备的载体与钛化合物以及任选的给电子体的反应产物。
  18. 根据权利要求16或17所述的催化剂组分，其中，所述催化剂组分为球形或类球形，其平均颗粒直径小于等于30微米，优选小于等于20微米。
  19. 根据权利要求16-18中任一项所述的催化剂组分，其中，所述催化剂组分为球形或类球形，其粒径分布小于1.2，优选粒径分布小于等于0.8。
  20. 根据权利要求1-7中任一项所述的载体和/或根据权利要求8-15中任一项所述的制备方法制备的载体和/或权利要求16-19中任一项所述的催化剂组分在制备用于烯烃聚合的催化剂中的应用。
  21. 一种用于烯烃聚合的催化剂，该催化剂含有：
    (1)权利要求16-19中任一项所述的催化剂组分；
    (2)烷基铝化合物；以及
    (3)任选的外给电子体化合物。
  22. 一种烯烃聚合方法，包括：在烯烃聚合条件下，将一种或多种烯烃与权利要求21所述的催化剂接触，优选地，所述烯烃为CH2＝CHR表示的烯烃，R选自氢和C1-C6直链或 支链烷基。
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