WO2019223683A1 - 用于烯烃聚合的催化剂组分、其制备方法及包含其的催化剂 - Google Patents

用于烯烃聚合的催化剂组分、其制备方法及包含其的催化剂 Download PDF

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WO2019223683A1
WO2019223683A1 PCT/CN2019/087787 CN2019087787W WO2019223683A1 WO 2019223683 A1 WO2019223683 A1 WO 2019223683A1 CN 2019087787 W CN2019087787 W CN 2019087787W WO 2019223683 A1 WO2019223683 A1 WO 2019223683A1
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catalyst component
compound
alkyl
general formula
solid
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PCT/CN2019/087787
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English (en)
French (fr)
Inventor
张锐
谭忠
周奇龙
徐秀东
李凤奎
尹珊珊
于金华
宋维玮
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Priority claimed from CN201810489282.4A external-priority patent/CN110511301B/zh
Priority claimed from CN201810489207.8A external-priority patent/CN110511302B/zh
Priority claimed from CN201810489139.5A external-priority patent/CN110511303B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院 filed Critical 中国石油化工股份有限公司
Priority to BR112020023858-9A priority Critical patent/BR112020023858B1/pt
Priority to KR1020207036529A priority patent/KR20210013113A/ko
Priority to EP19807100.3A priority patent/EP3798241A4/en
Priority to US17/057,980 priority patent/US20210205787A1/en
Publication of WO2019223683A1 publication Critical patent/WO2019223683A1/zh

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    • 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
    • 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
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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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
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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
    • C08F4/651—Pretreating with non-metals or metal-free compounds
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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
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/02—Anti-static agent incorporated into the catalyst
    • 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
    • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
    • 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
    • C08F4/61—Pretreating the metal or compound covered by group C08F4/60 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/612—Pretreating with metals or metal-containing compounds
    • C08F4/614—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6143—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
    • 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

Definitions

  • the invention belongs to the technical field of catalysts, and particularly relates to a catalyst component for olefin polymerization, a preparation method thereof, and a catalyst containing the same.
  • a solid catalyst component containing magnesium, titanium, halogen, and an electron donor as basic components can be used for ⁇ -olefin polymerization, especially in those having 3 or more carbon atoms. Polymers that provide higher yields and higher stereoregularity in the polymerization of ⁇ -olefins.
  • One of the preparation methods includes the following steps: firstly preparing magnesium chloride into a homogeneous solution, and then carrying out solid precipitation, and supporting a titanium-containing active component.
  • a solid with uniform particle size and good morphology can be obtained only in the presence of a co-precipitating agent, wherein the co-precipitating agent is generally an organic acid anhydride, an organic acid, a ketone, an ether, an ester, etc. And it is sometimes considered an internal electron donor compound. See, for example, CN101864009, CN106317274, CN106317275, CN101906177, CN 102276765, CN 103012625, CN 103012626, CN103012627, CN 106608933.
  • the prepared solid catalyst component will contain a certain amount of the precipitation aid, and the precipitation aid can affect the solid catalyst component Performance.
  • the prior art has paid little attention to the influence of the type of the precipitation aid and its content in the solid catalyst component on the performance of the solid catalyst component.
  • CN1020448 discloses internal electron donor compounds of 1,3-diethers.
  • the catalyst component containing the 1,3-diether internal electron donor compound has high activity and good hydrogen modulation sensitivity when used for olefin polymerization, and the molecular weight distribution of the olefin polymer prepared is very narrow.
  • CN102311513 and CN102603931 disclose the use of diethyl 2-cyanosuccinate as an internal electron donor compound.
  • the obtained polyolefin catalyst is insensitive to hydrogen, has good stereospecificity, and the polypropylene obtained by using the catalyst has a wide molecular weight distribution.
  • a catalyst component for olefin polymerization comprising magnesium, titanium, halogen, an internal electron donor compound, and a precipitation aid, wherein the precipitation aid comprises at least one
  • the precipitation aid a represented by formula (I) and the precipitation aid a contains an isomer represented by the general formula (Ia) and / or the general formula (Ib):
  • R 1 and R 2 are each independently selected from substituted or unsubstituted C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 10 aryl, and C 7 -C 10
  • R 3 and R 4 are each independently selected from substituted or unsubstituted C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, and C 7 -C 20 aralkyl, and
  • the content of the precipitation aid a is less than 1.0% by weight based on the total weight of the catalyst components.
  • Another object of the present invention is to provide a method for preparing the above-mentioned catalyst component.
  • Another object of the present invention is to provide a catalyst for olefin polymerization, which comprises the following components:
  • Another object of the present invention is to provide a prepolymerization catalyst for olefin polymerization, which comprises the catalyst component or the prepolymer obtained by prepolymerizing the catalyst with an olefin.
  • Another object of the present invention is to provide an olefin polymerization method.
  • the method includes making the olefin Polymerizing in the presence of the catalyst or pre-polymerization catalyst of the present invention to form a polyolefin polymer; and recovering the obtained polyolefin polymer.
  • substituted refers to a group in question on one or more hydrogen atoms with a halogen atom, a hetero atom, C 1 -C 6 alkyl or C 1 -C 6 alkoxy Radicals, or carbon atoms in the main chain are replaced with heteroatoms.
  • halogen or "halogen atom” as used herein refers to at least one of fluorine, chlorine, bromine and iodine.
  • heteroatom refers to at least one selected from the group consisting of O, S, N, P, Si, and Ge.
  • polymerization as used herein includes homopolymerization and copolymerization.
  • polymer as used herein includes homopolymers, copolymers, and terpolymers.
  • solid catalyst component refers to a main catalyst component or a procatalyst, which together with a conventional cocatalyst such as an alkyl aluminum and an optional external electron donor constitute a catalyst for olefin polymerization ( It is also known in the art as a catalyst system).
  • the present invention provides a catalyst component for olefin polymerization, which comprises magnesium, titanium, halogen, a precipitation aid, and an internal electron donor compound, wherein the precipitation aid includes a general formula (I ), And the precipitating agent a contains an isomer represented by the general formula (Ia) and / or the general formula (Ib):
  • R 1 and R 2 are each independently selected from substituted or unsubstituted C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 10 aryl, and C 7 -C 10 Aralkyl, preferably R 1 and R 2 are each independently selected from substituted or unsubstituted C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 8 aryl, more Preferably R 1 and R 2 are each independently selected from substituted or unsubstituted C 1 -C 4 alkyl groups, even more preferably R 1 and R 2 are each independently selected from methyl, ethyl, n-propyl and isopropyl R 3 and R 4 are each independently selected from substituted or unsubstituted C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, and C 7 -C 20 Aralkyl, preferably
  • the precipitation aid a represented by the general formula (I) which can be used in the present invention is a glycol ester compound, which contains two chiral carbon atoms.
  • the compound represented by the general formula (I) includes The four isomers of R, R-configuration, S, S-configuration, R, S-configuration and S, R-configuration shown by Ia), (Ib), (Ic) and (Id).
  • examples of the precipitation aid a represented by the general formula (I) include, but are not limited to, 2,4-pentanediol dibenzoate, 2,4-pentanediol di-p-methyl Benzoate, 2,4-pentanediol di-p-ethylbenzoate, 2,4-pentanediol di-p-n-propylbenzoate, 2,4-pentanediol di-n-butyl Benzoate, 3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methylbenzoate, 3,5-heptanediol di-p-ethylbenzoate, 3,5-heptanediol di-n-propylbenzoate, 3,5-heptanediol di-n-butylbenzoate and mixtures thereof.
  • a precipitation aid is used in the preparation of the catalyst component, which contains the precipitation aid a represented by the general formula (I).
  • the raw material of the precipitating agent a generally contains (R, R)-and / or (S, S) in an amount of more than 80% by weight, preferably more than 90% by weight, more preferably more than 95% by weight, still more preferably more than 98% by weight based on its total weight. -isomer.
  • the (R, R)-and (S, S) -isomer content of the residual co-precipitating agent a in the final catalyst component depends on the composition of the raw material of the co-precipitating agent a used in the preparation of the catalyst component, and (R , S)-and (S, R) -isomer content can vary over a wide range. However, preferably, the (R, R)-and (S, S) -isomer content and (R, S)-and (S, R) -isomer of the residual co-precipitator a in the final catalyst component
  • the content ratio is not less than 1:10, preferably not less than 1: 5, more preferably not less than 1: 3, and still more preferably not less than 1: 2. This can be achieved by selecting the starting material for the precipitation aid a which has a high (R, R)-and (S, S) -isomer content.
  • the raw material of the co-precipitator a used in the preparation of the catalyst component is greater than 80% by weight, preferably greater than 90% by weight, more preferably greater than 95% by weight, based on its total weight, still More preferably, an amount greater than 98% by weight comprises at least one of the following isomer combinations:
  • the raw material of the coprecipitating agent a used in the preparation of the catalyst component is greater than 80% by weight, preferably greater than 90% by weight, more preferably greater than 95% by weight, still more preferably greater than 98% by weight, and contains the following isomers At least one of the following combinations: (R, R) -2,4-pentanediol dibenzoate and (S, S) -2,4-pentanediol dibenzoate, (R, R ) -2,4-pentanediol diparamethylbenzoate and (S, S) -2,4-pentanediol diparamethylbenzoate, (R, R) -2,4- Pentylene glycol di-p-ethyl benzoate and (S, S) -2,4-pentanediol di-p-ethyl benzoate, (R, R) -2,4-pentanediol di-p-ethyl be
  • the raw material of the co-precipitator a used in the preparation of the catalyst component is greater than 80% by weight, preferably greater than 90% by weight, more preferably greater than 95% by weight, still more preferably greater than 98% by weight, and contains At least one of a combination of conformers: (R, R) -2,4-pentanediol dibenzoate and (S, S) -2,4-pentanediol dibenzoate, (R, R) -2,4-pentanediol diparamethylbenzoate and (S, S) -2,4-pentanediol diparamethylbenzoate, (R, R) -2,4 -Pentanediol di-p-ethylbenzoate and (S, S) -2,4-pentanediol di-p-ethylbenzoate, (R, R) -3,5-heptanediol diphenyl
  • conformers
  • the content of the precipitation aid a in the catalyst component is less than 1.0 wt%, preferably less than 0.5 wt%, and more preferably less than 0.2 wt% based on the total weight of the catalyst component. , Still more preferably below 0.15% by weight.
  • the precipitation assisting agent optionally further includes a precipitation assisting agent b represented by the general formula (II):
  • R 7 is selected from C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl, X is halogen, and n is 1, 2, 3 or 4.
  • the precipitation aid b is selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, and tetra-n-titanate.
  • At least one of propyl ester and tetraisopropyl titanate is preferably tetraethyl titanate or tetra-n-butyl titanate.
  • the precipitation aid in the catalyst component of the present invention consists essentially of the above mentioned precipitation aid a and the precipitation aid b.
  • the precipitation aid in the catalyst component of the present invention consists essentially of the above-mentioned precipitation aid a.
  • the catalyst component of the present invention contains no other precipitation aids in addition to the above-mentioned precipitation aids a and b.
  • the internal electron donor in the catalyst component there is no particular limitation on the internal electron donor in the catalyst component, and any internal electron donor compound known in the art to impart desired properties to the catalyst component may be included in the catalyst component. .
  • the catalyst component of the present invention comprises, as an internal electron donor, at least one 2,2-dihydrocarbyl-1,3-propanediol dimethyl ether-based compound represented by the general formula (III):
  • R 5 and R 6 are each independently selected from substituted or unsubstituted C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 10 aryl, and C 7 -C 10 Alkyl aryl; preferably R 5 and R 6 are each independently selected from substituted or unsubstituted C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 8 aryl; Preferably, R 5 and R 6 are each independently selected from substituted or unsubstituted C 1 -C 6 alkyl; further preferably, R 5 and R 6 are each independently selected from methyl, ethyl, n-propyl, isopropyl , N-butyl, isobutyl, t-butyl, n-pentyl, iso-pentyl, t-pentyl, cyclopentyl, cyclohexyl, phenyl
  • Examples of suitable 2,2-dihydrocarbyl-1,3-propanediol dimethyl ether compounds represented by general formula (III) include, but are not limited to, 2,2-di-n-propyl-1,3-propanediol dimethyl Ether, 2,2-diisopropyl-1,3-propanediol dimethyl ether, 2,2-di-n-butyl-1,3-propanediol dimethyl ether, 2,2-diisobutyl-1,3 -Propylene glycol dimethyl ether, 2,2-di-n-pentyl-1,3-propanediol dimethyl ether, 2,2-diisopentyl-1,3-propanediol dimethyl ether, 2,2-di-n-hexyl- 1,3-propanediol dimethyl ether, 2,2-diisohexyl-1,3-diether, 2-n-propyl-2-isopropy
  • the catalyst component of the present invention comprises at least one compound selected from the group consisting of an internal electron donor: 2,2-diisopropyl-1,3-propanediol dimethyl ether, 2, 2-di-n-butyl-1,3-propanediol dimethyl ether, 2,2-diisobutyl-1,3-propanediol dimethyl ether, 2,2-di-n-pentyl-1,3-propanediol dimethyl ether Ether, 2,2-diisopentyl-1,3-propanediol dimethyl ether, 2-n-propyl-2-isopropyl-1,3-propanediol dimethyl ether, 2-n-propyl-2-iso Butyl-1,3-propanediol dimethyl ether, 2-n-propyl-2-isopentyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-
  • the catalyst component of the present invention comprises at least one compound selected from the group consisting of an internal electron donor: 2,2'-diisopropyl-1,3-propanediol dimethyl ether, 2 , 2'-diisobutyl-1,3-propanediol dimethyl ether, 2,2'-diisopentyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-isobutyl-1 , 3-propanediol dimethyl ether, 2-isopropyl-2-n-pentyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-isopentyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-isohexyl-1,3-propanediol dimethyl ether, 2-isobutyl-2-n-pentyl-1,3-propanediol diol di
  • the catalyst component of the present invention comprises at least one dicyano-2,3-dihydrocarbyl succinate-based compound represented by the general formula (III ′) as an internal electron donor :
  • R 5 and R 6 are each independently selected from substituted or unsubstituted C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 10 aryl, and C 7 -C 10 Aralkyl; preferably R 5 and R 6 are each independently selected from substituted or unsubstituted C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 8 aryl; more Preferably, R 5 and R 6 are each independently selected from substituted or unsubstituted C 1 -C 6 alkyl and phenyl; further preferably, R 5 and R 6 are each independently selected from methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, iso-pentyl, t-pentyl, cyclopentyl, cyclohexyl
  • Examples of suitable 2-cyano-2,3-dihydrocarbyl succinate diethyl compounds represented by general formula (III ′) include, but are not limited to: 2-cyano-2,3-di-n-propyl Diethyl succinate, diethyl 2-cyano-2,3-diisopropylsuccinate, diethyl 2-cyano-2,3-di-n-butylsuccinate, 2-cyano Diethyl-2,3-diisobutylsuccinate, 2-cyano-2,3-di-n-pentylsuccinate, 2-cyano-2,3-diisopentyl Diethyl succinate, Diethyl 2-cyano-2,3-dicyclopentylsuccinate, Diethyl 2-cyano-2,3-di-n-hexylsuccinate, 2-cyano -2,3-Diisohexyl succinate diethyl, 2-cyano-2-isopropyl-3-n-
  • the catalyst component of the present invention comprises at least one compound selected from the group consisting of an internal electron donor: 2-cyano-2,3-diisopropylsuccinate, Diethyl 2-cyano-2,3-di-n-butyl succinate, diethyl 2-cyano-2,3-diisobutyl succinate, 2-cyano-2,3-di Diethyl n-pentylsuccinate, 2-cyano-2,3-diisopentylsuccinate, 2-cyano-2-isopropyl-3-n-propylsuccinate di Ethyl ester, 2-cyano-2-isopropyl-3-n-butyl succinate, 2-cyano-2-isopropyl-3-isobutyl succinate, 2 -Cyano-2-isopropyl-3-n-pentylsuccinate diethyl, 2-cyano-2-isopropyl-3-isopentylsuccinate diethyl, 2-cyano-2
  • the catalyst component of the present invention comprises at least one compound selected from the group consisting of an internal electron donor: 2-cyano-2,3-diisopropylsuccinate, Diethyl 2-cyano-2,3-di-n-butyl succinate, diethyl 2-cyano-2,3-diisobutyl succinate, 2-cyano-2,3-di Diethyl n-pentylsuccinate, 2-cyano-2,3-diisopentylsuccinate, 2-cyano-2-isopropyl-3-n-butylsuccinate di Ethyl ester, 2-cyano-2-isopropyl-3-isobutyl succinate, 2-cyano-2-isopropyl-3-n-pentyl succinate, 2 -Cyano-2-isopropyl-3-isopentylsuccinate diethyl, 2-cyano-2-isopropyl-3-cyclopentylsuccinate diethyl, 2-cyano-2
  • the catalyst component of the present invention includes at least one phthalate compound represented by the general formula (III ′′) as an internal electron donor;
  • R 7 and R 8 are each independently selected from substituted or unsubstituted C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 10 aryl, and C 7 -C 10 Alkyl aryl; preferably R 7 and R 8 are each independently selected from substituted or unsubstituted C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 8 aryl; more Preferably, R 7 and R 8 are each independently selected from substituted or unsubstituted C 1 -C 6 alkyl; further preferably, R 7 and R 8 are each independently selected from methyl, ethyl, n-propyl, and isopropyl Groups, n-butyl, isobutyl, n-pentyl and isopentyl.
  • Suitable phthalate compounds represented by the general formula (III ′′) include, but are not limited to, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, Diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-pentyl phthalate and diisoamyl phthalate.
  • the phthalate compound represented by the general formula (III ′′) is selected from the group consisting of diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, and Di-n-butyl phthalate, di-isobutyl phthalate, and di-n-pentyl phthalate.
  • the phthalate compound represented by the general formula (III ′′) is selected from Diethyl phthalate, diisopropyl phthalate, di-n-butyl phthalate and diisobutyl phthalate.
  • the content of titanium is 1.0 wt% to 8.0 wt%, preferably 1.6 wt% to 6.0 wt%; and the content of magnesium is 10.0 wt % -70.0wt%, preferably 15.0wt% -40.0wt%; the content of the halogen is 20.0wt% -90.0wt%, preferably 30.0wt% -85.0wt%; the content of the internal electron donor compound is 2.0% to 30.0% by weight, preferably 3.0% to 20.0% by weight.
  • the catalyst component of the present invention includes a magnesium compound, a titanium compound, at least one internal electron donor compound, and a precipitating agent including at least one precipitating agent a represented by the general formula (I). reaction product.
  • Titanium compounds, magnesium compounds, and internal electron donor compounds that can be used to prepare Ziegler-Natta catalyst components by a dissolution-precipitation method are well known to those skilled in the art, and they can all be used to form conventional amounts in the art The catalyst component of the present invention. Some examples of the titanium compound and the magnesium compound are described later.
  • the amount of the precipitation aid a may be 0.005 to 0.3 mole, preferably 0.01 to 0.05, per mole of the magnesium compound; the precipitation aid a and the internal electron donor compound are used.
  • the molar ratio may be from 0.05: 1 to less than 0.8: 1, preferably from 0.1: 1 to 0.7: 1.
  • the co-precipitation agent used to prepare the catalyst component further includes the co-precipitation agent b as described above, and the amount of the co-precipitation agent b per mole of co-precipitation agent a It is 0.01-5 mol, preferably 0.5-3 mol.
  • the present invention provides a method for preparing an olefin polymerization catalyst component of the present invention.
  • any method known in the art that can be used to prepare a Ziegler-Natta catalyst by a dissolution-precipitation process can be used to prepare the catalyst components of the present invention, provided that the introduction of The precipitating agent including the precipitating agent a described above.
  • the present invention provides a method for preparing a catalyst component for olefin polymerization, which method includes the following steps:
  • the precipitation aid comprises at least one precipitation aid a as shown by the general formula (I);
  • R 1 and R 2 are each independently selected from substituted or unsubstituted C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 10 aryl, or C 7 -C 10
  • R 3 and R 4 are each independently selected from substituted or unsubstituted C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, or C 7 -C 20 aralkyl;
  • the precipitation aid a represented by the general formula (I) contains, for example, the general formula (Ia) and / or the general formula ( The isomer represented by Ib) based on the total weight of the precipitation aid a represented by the general formula (I);
  • a titanium-based active component is supported on the particulate magnesium-containing solid to form a solid catalyst component.
  • a first exemplary method that can be used to prepare the catalyst component for olefin polymerization of the present invention includes the following steps:
  • step (2) reacting the magnesium compound alcoholate solution obtained in step (1) with the first titanium compound in the presence of a precipitating agent to obtain a solid precipitate-containing mixture, wherein the precipitating agent comprises at least one (I) precipitation aid a;
  • R 1 and R 2 are each independently selected from substituted or unsubstituted C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 10 aryl, or C 7 -C 10
  • R 3 and R 4 are each independently selected from substituted or unsubstituted C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, or C 7 -C 20 aralkyl;
  • the precipitation aid a represented by the general formula (I) contains, for example, the general formula (Ia) and / or the general formula (I) in an amount of more than 80% by weight, preferably more than 90% by weight, more preferably more than 95% by weight, still more preferably more than 98% by weight.
  • the isomer represented by Ib) based on the total weight of the precipitation aid a represented by the general formula (I);
  • step (3) contacting the mixture obtained in step (2) with the first internal electron donor compound to obtain a suspension;
  • step (3) subjecting the suspension obtained in step (3) to solid-liquid separation to obtain a first solid intermediate product, and contacting the obtained first solid intermediate product with a second titanium compound and optionally a second internal electron donor compound To provide a mixture;
  • step (4) subjecting the mixture obtained in step (4) to solid-liquid separation to obtain a second solid intermediate product, and treating the second solid intermediate product with a third titanium compound to form a solid catalyst component;
  • the first, second, and third titanium compounds used in the first method may be the same or different, and the first and second internal electron donors may be the same or different.
  • the first method includes the following steps: (1) performing a first contact reaction between the magnesium compound and the alcohol compound in an inert hydrocarbon solvent to obtain a uniform solution of the magnesium compound alcoholate; 2) In the presence of a precipitating agent, subject the homogeneous solution obtained in step (1) to a second contact reaction with the first titanium compound to obtain a mixture containing a solid precipitate; (3) combine the mixture obtained in step (2) with the first A third contact reaction of an internal electron donor compound to obtain a suspension; (4) solid-liquid separation of the suspension obtained in step (3), and a solid intermediate product obtained with the second titanium compound and the second internal electron donor; The compound is subjected to a fourth contact reaction, and then subjected to solid-liquid separation to obtain a solid intermediate product; (5) The solid intermediate product obtained in step (4) is subjected to a fifth contact reaction with a third titanium compound, followed by solid-liquid separation to obtain the obtained The solid product was washed with an inert solvent and dried to obtain the final solid catalyst component.
  • the alcohol compound used in the first method may be a linear or branched fatty alcohol selected from C 1 to C 10, a alicyclic alcohol C 3 to C 12 , an aryl alcohol C 6 to C 20 , and C 7 -C 20 one or more of an aralkyl alcohol.
  • alcohol compounds include, but are not limited to, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, n-pentanol, isoamyl alcohol, n-hexanol, isohexanol, 2-ethyl alcohol Hexanol, benzyl alcohol, phenethyl alcohol, cyclopentanol, methylcyclopentanol, cyclohexanol and mixtures thereof, preferably 2-ethylhexanol.
  • the amount of the alcohol compound is 2-4 mol, preferably 2.5-3.5 mol, per mol of magnesium, and the titanium compound used in steps (2), (4), and (5)
  • the total amount is 1 to 40 moles, preferably 1.5 to 35 moles.
  • the process conditions used in the first method include: the temperature of the reaction / first contact reaction in step (1) is 30-150 ° C, preferably 60-140 ° C, and the reaction time is 0.5-10 hours, preferably 0.5- 6 hours; the temperature of the reaction / second contact reaction in step (2) is -40 ° C to 0 ° C, preferably -30 ° C to -20 ° C, and the reaction time is 3-5 hours, preferably 3.5-4.5 hours; step The temperature in the reaction / third contact reaction in (3) is 20-120 ° C, preferably 70-110 ° C, and the reaction time is 0.5-6 hours, preferably 1-4 hours; the reaction in step (4) / fourth The temperature of the contact reaction is 50-150 ° C, preferably 80-120 ° C, and the reaction time is 1-6 hours, preferably 2.5-4.5 hours; the temperature of the treatment / fifth contact reaction in step (5) is 50-150 ° C It is preferably 80-120 ° C and the time is 1-6 hours, preferably 2.5-4.5 hours.
  • a second exemplary method that can be used to prepare the catalyst component for olefin polymerization of the present invention includes the following steps:
  • step (2) reacting the magnesium compound solution obtained in step (1) with the first titanium compound and the first internal electron donor compound in the presence of a precipitation aid, to obtain a suspension containing a solid precipitate, wherein the precipitation aid Contains at least one precipitation aid a as shown by the general formula (I);
  • R 1 and R 2 are each independently selected from substituted or unsubstituted C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 10 aryl, or C 7 -C 10
  • R 3 and R 4 are each independently selected from substituted or unsubstituted C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, or C 7 -C 20 aralkyl;
  • the precipitation aid a represented by the general formula (I) contains, for example, the general formula (Ia) and / or the general formula ( The isomer represented by Ib) based on the total weight of the precipitation aid a represented by the general formula (I);
  • step (3) subjecting the suspension obtained in step (2) to solid-liquid separation to obtain a first solid intermediate product, and contacting the first solid intermediate product with a second titanium compound and optionally a second internal electron donor compound, To provide a mixture;
  • the first, second, and third titanium compounds used in the second method may be the same or different, and the first and second internal electron donors may be the same or different.
  • the second method includes the following steps: (1) performing a first contact reaction between the magnesium compound, the organic epoxy compound, and the organic phosphorus compound in an inert hydrocarbon solvent to obtain a uniform magnesium compound solution ; (2) performing a second contact reaction between the homogeneous solution obtained in step (1) and the first titanium compound and the first internal electron donor compound in the presence of a coprecipitating agent to obtain a suspension containing a solid precipitate; 3) The solid precipitate-containing suspension obtained in step (2) is subjected to solid-liquid separation, and the obtained solid intermediate product A undergoes a third contact reaction with the second titanium compound and the second internal electron donor compound, and is subjected to solid-liquid separation Then, a solid intermediate product B is obtained; (4) the solid intermediate product B obtained in step (3) is subjected to a fourth contact reaction with a third titanium compound, and the solid intermediate product C is obtained after solid-liquid separation; the solid intermediate product obtained Product C is further treated with a third titanium compound for 1-3 times, and solid-liquid separation is performed.
  • the organic epoxy compound used in the second method may be selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, butadiene double oxide, epichlorohydrin, and methyl formaldehyde. At least one of a glycidyl ether and a diglycidyl ether is preferably epichlorohydrin.
  • the organic phosphorus compound used in the second method may be at least one selected from the group consisting of ortho- or phosphorous-hydrocarbon-based or halogenated hydrocarbyl-esters, and is preferably selected from trimethyl orthophosphate and triethyl orthophosphate At least one of tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, or benzyl phosphite, and more preferably tributyl orthophosphate.
  • the amount of the organic epoxy compound is 0.2-10 mol, preferably 0.5-4.0 mol, and the amount of the organic phosphorus compound is 0.1-3.0 mol, preferably 0.3-1.5, mol per mol of magnesium;
  • the total amount of the titanium compound is 3 to 40 moles, preferably 5 to 35 moles.
  • the process conditions used in the second method include: the temperature of the reaction / first contact reaction in step (1) is 0-80 ° C, preferably 10-60 ° C, and the reaction time is 0.5-10 hours, preferably 0.5- 6 hours; the temperature of the reaction / second contact reaction in step (2) is -40 ° C to 0 ° C, preferably -30 ° C to -20 ° C, and the reaction time is 3-5 hours, preferably 3.5-4.5 hours; step The temperature of the reaction in the (3) / third contact reaction is 50-150 ° C, preferably 80-120 ° C, and the reaction time is 1-6 hours, preferably 2.5-4.5 hours; the treatment in step (5) / fourth The temperature of the contact reaction is 50-150 ° C, preferably 80-120 ° C, and the time is 1-6 hours, preferably 2.5-4.5 hours.
  • any internal electron donor compound known in the art that can impart the desired properties to the polyolefin catalyst component can be used in the method of the present invention as the internal electron donor or the first and / or second internal electron donor.
  • the method of the present invention utilizes at least one compound represented by Formula (III), Formula (III ′), or Formula (III ′′) described above as the first and / or second internal electron donor
  • the first and second internal electron donors may be the same or different.
  • the molar ratio of the first internal electron donor compound to the second internal electron donor compound may be (0.1-10): 1, preferably (0.2-5): 1, more Preferably, it is (0.2-1): 1.
  • IV a compound represented by the general formula (IV)
  • V a hydrate represented by the general formula (V)
  • VI an alcoholate represented by the general formula (VI).
  • R 8 and R 9 are each independently selected from halogen, C 1 -C 5 hydrocarbon group of, C 1 -C 5 hydrocarbon group of, C 1 -C 5 halogenated hydrocarbon group or a C 1 -C 5 haloalkyl Alkoxy; preferably R 8 and R 9 are each independently fluorine, chlorine, bromine or iodine, preferably chlorine or bromine,
  • q is 0.1-6.0, preferably 2.0-3.5;
  • R 0 is selected from a C 1 -C 18 hydrocarbon group, preferably a C 1 -C 5 alkyl group; p is 0.1-6.0, and preferably 2.0-3.5.
  • the magnesium compound is at least one selected from the group consisting of magnesium dichloride, magnesium dibromide, phenoxy magnesium chloride, isopropoxy magnesium chloride, and butoxy magnesium chloride.
  • the magnesium compound is anhydrous magnesium dichloride.
  • the inert hydrocarbon solvent may be any hydrocarbon solvent commonly used in the art that does not chemically interact with the magnesium compound, such as at least one of an alkane, a cycloalkane or an aromatic hydrocarbon, preferably decane, benzene, toluene or At least one of the xylenes is more preferably toluene.
  • the titanium compound useful in the method of the present invention includes at least one compound represented by the general formula (VII):
  • R 10 is a C 1 -C 20 hydrocarbon group, preferably a C 1 -C 5 alkyl group;
  • X is chlorine, bromine or iodine; and
  • m is 1, 2, 3, or 4.
  • the titanium compound is selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetraalkoxytitanium, alkoxytitanium trihalide, and dialkoxy. At least one of titanium dihalide and titanium trialkoxyhalide.
  • the titanium compound is titanium tetrachloride.
  • the present invention provides a catalyst for olefin polymerization comprising the following components:
  • the molar ratio of component 1) to component 2) is (5-5000): 1 in terms of titanium: aluminum, preferably (20-1000): 1, and more preferably (50-500): 1.
  • the component 2) alkylaluminum compound may be one or more of various alkylaluminum compounds that can be used as a co-catalyst of Ziegler-Natta type catalysts commonly used in the field of olefin polymerization.
  • the component 2) an aluminum alkyl compound includes at least one compound represented by the general formula (VIII);
  • R ′ is selected from H, C 1 -C 20 alkyl or C 6 -C 20 aryl, X ′ is halogen, and 1 ⁇ n ′ ⁇ 3.
  • the alkyl aluminum compound is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, monohydrogen At least one of diethylaluminum, dihydrodiisobutylaluminum, monochlorodiethylaluminum, monochlorodiisobutylaluminum, sesquiethylaluminum chloride, and dichloroethylaluminum.
  • the kind and amount of the external electron donor compound are not particularly limited.
  • the external electron donor compound may be one or more of various compounds commonly used in the field of olefin polymerization that can be used as Ziegler-Natta type catalysts. If used, the external electron donor compound is used in an amount commonly used in the art.
  • the molar ratio of the component 3) to the component 2) is 1: (0.1-500), preferably 1: (1-300), more preferably It is preferably 1: (3-100).
  • the external electron donor compound includes at least one compound represented by the general formula (IX):
  • R 1 ”and R 2 ” are each independently selected from H, halogen, C 1 -C 20 alkyl or haloalkyl, C 3 -C 20 cycloalkyl, and C 6 -C 20 aryl; 3 "selected from C 1 -C 20 alkyl or haloalkyl, C 3 -C 20 cycloalkyl, and C 6 -C 20 aryl; m" and n “are independently integers from 0-3, and m "+ n" ⁇ 4.
  • the external electron donor compound is selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxytriethylmethoxy Silane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, Diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane , Tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane,
  • the external electron donor compound is selected from the group consisting of dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxy At least one of silane, cyclohexylmethyldimethoxysilane, methyl tert-butyldimethoxysilane, and tetramethoxysilane.
  • the present invention provides a prepolymerization catalyst for olefin polymerization, which comprises a catalyst component according to the first aspect of the present invention or a catalyst according to the third aspect of the present invention to prepolymerize with an olefin.
  • the olefin used in the prepolymerization is ethylene or propylene.
  • the pre-polymerization temperature is -20 to 80 ° C, preferably 10-50 ° C.
  • the present invention provides an olefin polymerization method, wherein the olefin is in a catalyst component according to the first aspect of the present invention, a catalyst according to the third aspect of the present invention, or a fourth aspect of the present invention. Polymerization is performed under the action of the pre-polymerization catalyst.
  • the olefin polymerization method provided by the present invention can be used for homopolymerization of olefins, and can also be used for copolymerization of multiple olefins.
  • the olefin is selected from at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene.
  • the olefin may be at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene.
  • the olefin is propylene.
  • each component of the catalyst according to the present invention that is, the catalyst component provided by the present invention, the alkyl aluminum compound as a cocatalyst, and the optional external electron donor compound may be contacted with the olefin monomer before First contact, which is called “pre-contact” or “pre-complexation” in the industry; the three components can also be added to the polymerization reactor for polymerization reaction, that is, "pre-contact” is not implemented.
  • pre-contact the olefin polymerization method provided by the present invention, it is preferable to perform "pre-contact” of each component of the olefin polymerization catalyst.
  • the "pre-contact” time is 0.1-30 minutes, preferably 1-10 minutes; the "pre-contact” temperature is -20 ° C to 80 ° C, preferably 10-50 ° C.
  • the catalyst of the present invention is firstly pre-polymerized to a certain degree in the presence of a small amount of olefin monomer to obtain a pre-polymerized catalyst, and then the pre-polymerized catalyst is further contacted with the olefin monomer to perform an olefin polymer reaction.
  • This technology is called "pre-polymerization” in the industry, and it helps to improve the polymerization activity of the catalyst and increase the polymer bulk density.
  • a "pre-polymerization” process may or may not be used.
  • a "prepolymerization” process is used.
  • the polymerization conditions may be conventional conditions in the art.
  • the co-precipitating agent a used in the present invention that is, the specific optical configuration isomer (R, R-configuration and / or S, S-configuration isomer) content is greater than 80 %
  • the content of residual co-precipitating agent in the solid catalyst component prepared according to the method of the present invention is relatively low, so as not to interfere with the function of the internal electron donor component.
  • the precipitating agent a is a diol having a specific optical configuration isomer (R, R-configuration and / or S, S-configuration isomer) content of more than 80%
  • the ester can work well, so that the particle shape of the obtained catalyst component is better.
  • test method used in the present invention is as follows:
  • MI Polymer melt index
  • Isotacticity index of propylene polymer (II) determined by heptane extraction method: 2 g of dried polymer sample, placed in an extractor with boiling heptane for 6 hours, and dried the residue to The ratio of polymer weight (g) to 2 (g) obtained by constant weight is the isotacticity.
  • catalyst activity (mass of prepared polyolefin) / (mass of catalyst solid component) kg / g;
  • an ultra high performance liquid chromatograph is used to adjust the separation conditions of liquid chromatography so that the diol esters of R, R- configuration and S, S- configuration and the diol esters of R, S- configuration With different retention times, R, R- and S, S-configuration diol esters are distinguished from R, S-configuration diol esters.
  • the specific separation conditions are:
  • Chromatographic column ACQUITY UPLC, BEH, Shield RP18 (100mm ⁇ 2.1mm, 1.7 ⁇ m);
  • the detection wavelength of PDA is 229nm.
  • the retention times of the diol esters in the R, R- configuration and S, S- configuration are the same and relatively short, and the retention times of the diol esters in the R, S- configuration are relatively long.
  • the configuration of the diastereomers can also be determined based on the NMR signal peaks.
  • the synthesis method of the precipitating agent a glycol ester compound represented by the general formula (I) used in the examples is as follows.
  • the compound was obtained commercially and used in the form received.
  • the compound was obtained commercially and used in the form received.
  • the obtained solid intermediate product was added with 6300mL toluene and 700mL titanium tetrachloride, stirred at 80 ° C for 1 hour, then cooled to room temperature and pressure filtered. The solid intermediate product was further added with 6300mL toluene.
  • the catalyst component 1 obtained above was subjected to propylene polymerization.
  • the specific method is: in a 5L autoclave, after full replacement with gas-phase propylene, 5 mL of a triethylaluminum hexane solution (triethylaluminum concentration of 0.5 mmol / mL) and 1 mL of cyclohexylmethyl are added at room temperature.
  • a hexane solution of dimethoxysilane (CHMMS) (the concentration of CHMMS was 0.10 mmol / mL), 10 mL of anhydrous hexane, and 10 mg of solid catalyst component 1.
  • CHMMS dimethoxysilane
  • the preparation of the catalyst component is the same as in Example 1, except that the compound 1 is replaced with the compound 2 in step (1) to obtain a catalyst component 2.
  • the propylene polymerization method was the same as in Example 1, except that the catalyst component 1 was replaced with the catalyst component 2.
  • the polymerization results are shown in Table 1.
  • the catalyst component 3 obtained above was subjected to propylene polymerization.
  • the specific method is: in a 5L autoclave, after full replacement with gas phase propylene, 5 mL of triethylaluminum in hexane solution (triethylaluminum concentration of 0.5 mmol / mL) and 1 mL of cyclohexylmethyl are added at room temperature.
  • a hexane solution of dimethoxysilane (CHMMS) CHMMS concentration was 0.10 mmol / mL
  • 10 mL of anhydrous hexane and 10 mg of a solid catalyst component 3.
  • Polymerization was performed under two conditions. The polymerization results are shown in Table 1:
  • the preparation of the catalyst component is the same as in Example 3, except that the compound 1 is replaced with the compound 2 in step (1) to obtain a catalyst component 4.
  • the propylene polymerization method was the same as in Example 3, except that the catalyst component 3 was replaced with the catalyst component 4, and the polymerization results are shown in Table 1.
  • the preparation of the catalyst component is the same as in Example 1, except that the compound 1 is replaced with the compound 3 in step (1) to obtain a catalyst component C1.
  • the propylene polymerization method was the same as in Example 1, except that the catalyst component 1 was replaced with the catalyst component C1, and the polymerization results are shown in Table 1.
  • the preparation of the catalyst component is the same as in Example 1, except that the compound 1 is replaced with the compound 4 in step (1) to obtain a catalyst component C2.
  • the propylene polymerization method was the same as in Example 1, except that the catalyst component 1 was replaced with the catalyst component C2, and the polymerization results are shown in Table 1.
  • the preparation of the catalyst component is the same as in Example 3, except that the compound 1 is replaced with the compound 3 in step (1) to obtain a catalyst component C3.
  • the propylene polymerization method was the same as in Example 3, except that the catalyst component 3 was replaced with the catalyst component C3.
  • the polymerization results are shown in Table 1.
  • the preparation of the catalyst component is the same as in Example 3, except that the compound 1 is replaced with the compound 4 in step (1) to obtain a catalyst component C4.
  • the propylene polymerization method was the same as in Example 3, except that the catalyst component 3 was replaced with the catalyst component C4.
  • the polymerization results are shown in Table 1.
  • the catalyst component 5 obtained above was subjected to propylene polymerization.
  • the specific method is: in a 5L autoclave, after full replacement with gas-phase propylene, 5 mL of a triethylaluminum hexane solution (triethylaluminum concentration of 0.5 mmol / mL) and 1 mL of cyclohexylmethyl are added at room temperature.
  • a hexane solution of dimethoxysilane (CHMMS) (the concentration of CHMMS was 0.10 mmol / mL), 10 mL of anhydrous hexane, and 10 mg of a solid catalyst component 5.
  • CHMMS dimethoxysilane
  • Polymerization was performed under two conditions. The polymerization results are shown in Table 2:
  • the catalyst component was prepared as in Example 5, except that 35 g of 2-cyano 2,3-diisopropylsuccinic acid diethyl ester was replaced with 35 g of di-n-phthalate in step (2). Butyl ester (DNBP) to prepare catalyst component 6.
  • DNBP Butyl ester
  • the propylene polymerization method was the same as in Example 5, except that the catalyst component 5 was replaced with the catalyst component 6, and the polymerization results are shown in Table 2.
  • the preparation of the catalyst component is the same as in Example 5, except that the compound 1 is replaced with the compound 2 in step (1) to obtain a catalyst component 7.
  • the propylene polymerization method was the same as in Example 5, except that the catalyst component 5 was replaced with the catalyst component 7, and the polymerization results are shown in Table 2.
  • the preparation of the catalyst component was the same as in Example 5, except that in step (1), compound 1 was replaced with compound 2, and in step (2), 35 g of 2-cyano 2,3-diisopropylbutane Catalyst component 8 was prepared by replacing diethyl diacid with 35 g of di-n-butyl phthalate (DNBP).
  • DNBP di-n-butyl phthalate
  • the propylene polymerization method was the same as in Example 5, except that the catalyst component 5 was replaced with the catalyst component 8.
  • the polymerization results are shown in Table 2.
  • the catalyst component 9 obtained above was subjected to propylene polymerization.
  • the specific method is: in a 5L autoclave, after full replacement with gas-phase propylene, 5 mL of a triethylaluminum hexane solution (triethylaluminum concentration of 0.5 mmol / mL) and 1 mL of cyclohexylmethyl are added at room temperature.
  • a hexane solution of dimethoxysilane (CHMMS) (the concentration of CHMMS was 0.10 mmol / mL), 10 mL of anhydrous hexane, and 10 mg of a solid catalyst component 9.
  • CHMMS dimethoxysilane
  • the catalyst component was prepared as in Example 9 except that 36 g of 2-cyano 2,3-diisopropylsuccinic acid diethyl ester was replaced with 36 g of di-n-phthalate in step (2). Butyl ester (DNBP) to prepare catalyst component 10.
  • DNBP Butyl ester
  • the propylene polymerization method is the same as in Example 9, except that the catalyst component 9 is replaced with the catalyst component 10, and the polymerization results are shown in Table 2.
  • the preparation of the catalyst component is the same as in Example 9, except that the compound 1 is replaced with the compound 2 in step (1) to obtain a catalyst component 11.
  • the propylene polymerization method is the same as in Example 9 except that the catalyst component 9 is replaced with the catalyst component 11 and the polymerization results are shown in Table 2.
  • the preparation of the catalyst component was the same as in Example 9, except that the compound 1 was replaced with the compound 2 in step (1), and 36 g of 2-cyano 2,3-diisopropylbutane was used in step (2).
  • the diethyl diacid was replaced with 36 g of di-n-butyl phthalate (DNBP) to prepare a catalyst component 12.
  • DNBP di-n-butyl phthalate
  • the propylene polymerization method is the same as in Example 9, except that the catalyst component 9 is replaced with the catalyst component 12, and the polymerization results are shown in Table 2.
  • the preparation of the catalyst component is the same as in Example 5, except that the compound 1 is replaced with the compound 3 in step (1) to obtain a catalyst component C5.
  • the propylene polymerization method was the same as in Example 5, except that the catalyst component 5 was replaced with the catalyst component C5.
  • the polymerization results are shown in Table 2.
  • the preparation of the catalyst component is the same as in Example 6, except that the compound 1 is replaced with the compound 3 in step (1) to prepare a catalyst component C6.
  • the propylene polymerization method was the same as in Example 6, except that the catalyst component 6 was replaced with the catalyst component C6.
  • the polymerization results are shown in Table 2.
  • the preparation of the catalyst component is the same as in Example 7, except that the compound 1 is replaced with the compound 4 in step (1) to prepare a catalyst component C7.
  • the propylene polymerization method was the same as in Example 7, except that the catalyst component 7 was replaced with the catalyst component C7.
  • the polymerization results are shown in Table 2.
  • the preparation of the catalyst component is the same as in Example 8, except that the compound 1 is replaced with the compound 4 in step (1) to prepare a catalyst component C8.
  • the propylene polymerization method was the same as in Example 8, except that the catalyst component 8 was replaced with the catalyst component C8.
  • the polymerization results are shown in Table 2.
  • the preparation of the catalyst component is the same as in Example 9, except that the compound 1 is replaced with the compound 3 in step (1) to obtain a catalyst component C9.
  • the propylene polymerization method is the same as in Example 9, except that the catalyst component 9 is replaced with the catalyst component C9.
  • the polymerization results are shown in Table 2.
  • the preparation of the catalyst component is the same as in Example 10, except that the compound 1 is replaced with the compound 3 in step (1) to obtain a catalyst component C10.
  • the propylene polymerization method was the same as in Example 10, except that the catalyst component 10 was replaced with the catalyst component C10, and the polymerization results are shown in Table 2.
  • the preparation of the catalyst component is the same as in Example 11, except that the compound 1 is replaced with the compound 4 in step (1) to prepare a catalyst component C11.
  • the propylene polymerization method was the same as in Example 11, except that the catalyst component 11 was replaced with the catalyst component C11, and the polymerization results are shown in Table 2.
  • the preparation of the catalyst component is the same as in Example 12, except that the compound 1 is replaced with the compound 4 in step (1) to obtain a catalyst component C12.
  • the propylene polymerization method was the same as in Example 12, except that the catalyst component 12 was replaced with the catalyst component C12.
  • the polymerization results are shown in Table 2.
  • the catalyst component 13 obtained above was polymerized as described in Example 1. The polymerization results are shown in Table 3.
  • the polymerization was performed on a horizontal gas phase polypropylene pilot plant.
  • the polymerization reactor was two horizontal stirred reactors connected in series.
  • the polymerization method and steps were as follows:
  • Catalyst component 13, triethylaluminum, and isobutyldimethoxysilane were continuously added from the front of the first stirred tank to the horizontal stirred reaction tank under the carrying of propylene, and polymerized in the gas phase to form a homopolymer.
  • Propylene the heat of reaction is taken away by the sprayed propylene vaporization.
  • the resulting polymer was discharged from the end of the stirred tank.
  • the catalyst and polymer move in the reactor in a manner close to the flat flow.
  • the polymerization temperature is 66 ° C or a specified temperature, and the reaction pressure is 2.3 MPa.
  • the homopolypropylene is discharged from the first reactor, and the polymer is transferred to a second horizontal stirred reactor through a transfer device installed between the two reactors.
  • the polymer enters from the front end of the second stirred tank and is polymerized under the condition of ethylene to produce impact copolymerized polypropylene.
  • the reaction heat is taken away by the sprayed propylene vaporization.
  • the molar ratio of ethylene to propylene was maintained at 0.38-0.40.
  • the resulting polymer was discharged from the end of the stirred tank.
  • the catalyst and polymer move in the reactor in a manner close to the flat flow.
  • the polymerization temperature is 66 ° C or a specified temperature, and the reaction pressure is 2.2 MPa.
  • the polymer obtained by the reaction was degassed and deactivated with wet nitrogen to obtain a poly impact copolymer polypropylene.
  • the polymerization results are shown in Table 4.
  • the catalyst component was prepared in the same manner as in Example 13, except that the compound 1 was replaced with the compound 2 in step (1) to obtain a catalyst component 14.
  • the propylene polymerization method was the same as in Example 1, except that the catalyst component 1 was replaced with the catalyst component 14, and the polymerization results are shown in Table 3.
  • the method for preparing impact copolymerized polypropylene is the same as in Example 13, except that the catalyst component 13 is replaced with the catalyst component 14, and the polymerization results are shown in Table 4.
  • the preparation of the catalyst component was the same as in Example 13, except that the compound 1 was replaced with the compound 2 in step (1), and the di-n-butyl phthalate (DNBP) was replaced with Diisobutyl phthalate (DIBP) was prepared to obtain catalyst component 15.
  • DNBP di-n-butyl phthalate
  • DIBP Diisobutyl phthalate
  • the propylene polymerization method was the same as in Example 1, except that the catalyst component 1 was replaced with the catalyst component 15, and the polymerization results are shown in Table 3.
  • the impact copolymerization polypropylene is prepared in the same manner as in Example 13 except that the catalyst component 13 is replaced with the catalyst component 15 and the polymerization results are shown in Table 4.
  • the catalyst component 16 obtained above was subjected to propylene bonding as described in Example 1.
  • the polymerization results are shown in Table 3.
  • the catalyst component was prepared in the same manner as in Example 16 except that the compound 1 was replaced with the compound 2 in step (1) to prepare a catalyst component 17.
  • the propylene polymerization method was the same as in Example 1, except that the catalyst component 1 was replaced with the catalyst component 17, and the polymerization results are shown in Table 3.
  • the method for preparing impact copolymerized polypropylene is the same as that in Example 13, except that the catalyst component 13 is replaced with the catalyst component 17, and the polymerization results are shown in Table 4.
  • the catalyst component was prepared in the same manner as in Example 16 except that the compound 1 was replaced by the compound 2 in step (1), and the di-n-butyl phthalate (DNBP) was replaced by Diisobutyl phthalate (DIBP) was prepared to obtain catalyst component 18.
  • DNBP di-n-butyl phthalate
  • DIBP Diisobutyl phthalate
  • the propylene polymerization method was the same as in Example 1, except that the catalyst component 1 was replaced with the catalyst component 18, and the polymerization results are shown in Table 31.
  • the method for preparing impact copolymerized polypropylene is the same as in Example 13, except that the catalyst component 13 is replaced with the catalyst component 18, and the polymerization results are shown in Table 4.
  • the preparation of the catalyst component is the same as in Example 13, except that the compound 1 is replaced with the compound 3 in step (1) to obtain a catalyst component C13.
  • the propylene polymerization method was the same as that in Example 13, except that the catalyst component 13 was replaced with the catalyst component C13, and the polymerization results are shown in Table 3.
  • the impact copolymerization polypropylene is prepared in the same manner as in Example 13 except that the catalyst component 13 is replaced with the catalyst component C13.
  • the polymerization results are shown in Table 4.
  • the catalyst component was prepared in the same manner as in Example 14, except that the compound 2 was replaced with the compound 4 in step (1) to obtain a catalyst component C14.
  • the propylene polymerization method was the same as in Example 13, except that the catalyst component 13 was replaced with the catalyst component C14, and the polymerization results are shown in Table 3.
  • the method for preparing impact copolymerized polypropylene is the same as that in Example 13, except that the catalyst component 13 is replaced with the catalyst component C14, and the polymerization results are shown in Table 4.
  • the preparation of the catalyst component is the same as in Example 16, except that the compound 1 is replaced with the compound 3 in step (1) to obtain a catalyst component C15.
  • the propylene polymerization method was the same as in Example 1, except that the catalyst component 1 was replaced with the catalyst component C15, and the polymerization results are shown in Table 3.
  • the method for preparing impact copolymerized polypropylene is the same as in Example 13, except that the catalyst component 13 is replaced with the catalyst component C15, and the polymerization results are shown in Table 4.
  • the preparation of the catalyst component is the same as in Example 17, except that the compound 2 is replaced with the compound 4 in step (1) to obtain a catalyst component C16.
  • the propylene polymerization method was the same as in Example 1, except that the catalyst component 1 was replaced with the catalyst component C16, and the polymerization results are shown in Table 3.
  • the impact copolymerization polypropylene is prepared in the same manner as in Example 13 except that the catalyst component 13 is replaced by the catalyst component C16.
  • the polymerization results are shown in Table 4.
  • C2 Total ethylene content in copolymerized polypropylene
  • RCC2 is ethylene content in rubber phase
  • RC is rubber phase content in copolymer polypropylene.
  • transition phrase when the transition phrase "comprises” precedes a composition, element or element group, it should be understood that we also think of the same composition, element or element group, where the composition, element or element group is preceded by Transitional phrases “consisting essentially of”, “consisting of”, “selected from the group consisting of” or “yes” lead, and vice versa.

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Abstract

本发明涉及一种用于烯烃聚合的催化剂组分及包含其的催化剂。所述催化剂组分包含镁、钛、卤素、内给电子体化合物和助析出剂，其中所述助析出剂包括如通式(I)所示的助析出剂a；通式(I)所示的助析出剂a包含如通式(I-a)和/或通式(I-b)所示的异构体。

Description

用于烯烃聚合的催化剂组分、其制备方法及包含其的催化剂
相关申请的交叉引用
本申请要求2018年5月21日提交的中国专利申请号CN 201810489139.5、CN201810489207.8和CN201810489282.4的优先权和权益，它们的全部内容通过引用并入本文。
技术领域
本发明属于催化剂技术领域，具体涉及一种用于烯烃聚合的催化剂组分、其制备方法及包含其的催化剂。
背景技术
包含镁、钛、卤素和给电子体作为基本成分的固体催化剂组分，即本领域所公知的Ziegler-Natta催化剂，可用于α-烯烃聚合反应，特别是在具有3个或更多个碳原子的α-烯烃聚合中可以提供较高收率和较高立体规整性的聚合物。其制备方法之一包括以下步骤：先将氯化镁制备成均匀溶液，再进行固体析出，和负载含钛的活性组分。在这样的方法中，在析出固体步骤中，通常只有在助析出剂的存在下才能得到粒度均匀、形态良好的固体物，其中助析出剂一般是有机酸酐、有机酸、酮、醚、酯等，并且其有时也被视为内给电子体化合物。参见例如CN101864009、CN106317274、CN106317275、CN101906177，CN 102276765，CN 103012625，CN 103012626，CN103012627，CN 106608933。
可以预期，当在固体催化剂组分的制备中采用助析出剂时，所制备的固体催化剂组分将含有一定量的所述助析出剂，并且所述助析出剂能够影响所述固体催化剂组分的性能。但是，现有技术几乎没有关注助析出剂的种类以及其在固体催化剂组分中的含量对固体催化剂组分的性能的影响。
另外，文献中公开了能够赋予Ziegler-Natta催化剂希望的性能的各种内给电子体化合物。例如，CN1020448公开了1,3-二醚类内给电子体化合物。包含所述1,3-二醚类内给电子体化合物的催化剂组分用于烯烃聚合时具有高的活性和好的氢调敏感性，并且制备得到的烯烃聚合物分子量分布很窄。又例如，CN102311513和CN102603931公开了使用2-氰基丁二酸二乙酯作为内给电子体化合物。所得到的聚烯烃催化剂氢调不敏感，立体定向性较好，并且使用该催化剂制备得到的聚丙烯分子量分布很宽。
但是，现有技术没有教导过如何减少助析出剂对内给电子体化合物的作用的干扰。
本领域仍然需要显示各种希望的性能的改进的Ziegler-Natta催化剂及其制备方法。
发明概述
为了克服现有技术遇到的问题，本发明人进行了广泛深入的研究。结果，现已惊讶地发现，当在固体催化剂组分的制备中采用特定构型的异构体(即R,R-构型和/或S,S-构型异构体)含量大于80％的二醇酯作为助析出剂时，可以析出粒形较好的固体颗粒，且所得到的固体催化剂组分中残余助析出剂的含量极低，从而避免了助析出剂对内给电子体的干扰。在此基础上完成了本发明。
因此，本发明的一个目的是提供一种用于烯烃聚合的催化剂组分，其包含镁、钛、卤素、内给电子体化合物和助析出剂，其中所述助析出剂包含至少一种由通式(I)所示的助析出剂a，并且该助析出剂a包含由通式(I-a)和/或通式(I-b)所示的异构体：
Figure PCTCN2019087787-appb-000001
其中，R 1和R 2各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基和C 7-C 10的芳烷基；R 3和R 4各自独立地选自取代或未取代的C 1-C 20的烷基、C 3-C 20的环烷基、C 6-C 20的芳基和C 7-C 20的芳烷基，并且
其中基于催化剂组分的总重量计，所述助析出剂a的含量低于1.0wt％。
本发明的另一个目的是提供制备上述催化剂组分的方法。
本发明的又一个目的是提供一种用于烯烃聚合的催化剂，其包含下述组分：
1)本发明的催化剂组分；
2)烷基铝化合物；以及
任选地3)外给电子体化合物。
本发明的又一个目的是提供一种用于烯烃聚合的预聚合催化剂，其包括本发明的催化剂组分或催化剂与烯烃进行预聚合所得的预聚物。
本发明的又一个目的是提供一种烯烃聚合方法，所述烯烃的通式为CH 2＝CHR，其中R为氢、C 1-C 6的烷基或芳基，该方法包括使所述烯烃在本发明的催化剂或预聚合催化剂存在下聚合以形成聚烯烃聚合物；和回收所得到的聚烯烃聚合物。
优选实施方案的详细描述
定义
本文中使用的术语“取代”或“取代的”是指所讨论的基团上的一个或多个氢原子被卤原子、杂原子、C 1-C 6烷基或C 1-C 6烷氧基取代，或者主链上的碳原子被杂原子取代。
本文中使用的术语“卤素”或“卤原子”是指氟、氯、溴和碘中的至少一个。
本文中使用的术语“杂原子”是指选自O,S,N,P、Si和Ge中的至少一个。
本文中使用的术语“聚合”包括均聚和共聚。本文中使用的术语“聚合物”包括均聚物、共聚物和三元共聚物。
本文中使用的术语“(固体)催化剂组分”是指主催化剂组分或前催化剂，其与常规的助催化剂如烷基铝和任选的外给电子体一起构成用于烯烃聚合的催化剂(其在本领域中也被称为催化剂体系)。
在第一方面，本发明提供了一种用于烯烃聚合的催化剂组分，其包含镁、钛、卤素、助析出剂和内给电子体化合物，其中所述助析出剂包括如通式(I)所示的助析出剂a，并且该助析出剂a包含由通式(I-a)和/或通式(I-b)所示的异构体：
Figure PCTCN2019087787-appb-000002
其中，R 1和R 2各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基和C 7-C 10的芳烷基，优选R 1和R 2各自独立地选自取代或未取代的C 1-C 8的烷基、C 3-C 8的环烷基和C 6-C 8的芳基，更优选R 1和R 2各自独立地选自取代或未取代的C 1-C 4的烷基，甚至更优选R 1和R 2各自独立地选自甲基、乙基、正丙基和异丙基；R 3和R 4各自独立地选自取代或未取代的C 1-C 20的烷基、C 3-C 20的环烷基、C 6-C 20的芳基和C 7-C 20的芳烷基，优选R 3和R 4各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基和C 6-C 10的芳基，更优选R 3和R 4各自独立地选自取代或未取代的C 5-C 10的烷基、C 5-C 10环烷基、C 6-C 10芳基和C 7-C 10芳烷基，甚至更优选R 3和R 4各自独立地选自环戊基，环己基，苯基，对甲基苯基，对乙基苯基，对正丙基苯基，和对正丁基苯基。
可用于本发明的由通式(I)所示的助析出剂a为二醇酯类化合物，其含有两个手性碳原子。当R 1和R 2不相同和/或R 3和R 4不相同时，两个手性碳原子为不相同的手性碳原子，通式(I)所示的化合物包括分别由通式(I-a)、(I-b)、(I-c)和(I-d)所示的R,R-构型、S,S-构型、R,S-构型和S,R-构型四种异构体。当R 1和R 2相同且R 3和R 4相同时，两个手性碳原子是相同的手性碳原子，R,S-构型和S,R-构型成为完全相同的一种构型，并且因此由通式(I)所示的化合物具有分别由通式(I-a)、(I-b)和(I-c)所示的R,R-构型、S,S-构型和R,S-/S,R-构型三种异构体。
Figure PCTCN2019087787-appb-000003
在一些实施方案中，所述由通式(I)表示的助析出剂a的实例包括但不限于2,4-戊二醇二苯甲酸酯、2,4-戊二醇二对甲基苯甲酸酯、2,4-戊二醇二对乙基苯甲酸酯、2,4-戊二醇二对正丙基苯甲酸酯、2,4-戊二醇二对正丁基苯甲酸酯、3,5-庚二醇二苯甲酸酯、3,5-庚二醇二对甲基苯甲酸酯、3,5-庚二醇二对乙基苯甲酸酯、3,5-庚二醇二对正丙基苯甲酸酯、3,5-庚二醇二对正丁基苯甲酸酯和它们的混合物。
按照本发明，在催化剂组分的制备中使用助析出剂，其包含由所述通式(I)表示的助析出剂a。助析出剂a原料通常以基于其总重量计大于80wt％，优选大于90wt％，更优选大于95wt％，仍更优选大于98wt％的量包含(R,R)-和/或(S,S)-异构体。与(R,S)-和(S,R)-构型的异构体相比，所述(R,R)-和/或(S,S)-构型的异构体与催化剂组分的结合能力有较大差别，容易被洗脱，因此保留在最终催化剂组分中的助析出剂a将含有显著降低的比例的(R,R)-和(S,S)-异构体以及显著提高的比例的(R,S)-和(S,R)-异构体，与助析出剂a原料相比。取决于在催化剂组分的制备中使用的助析出剂a原料的组成，最终催化剂组分中残余助析出剂a的(R,R)-和(S,S)-异构体含量以及(R,S)-和(S,R)-异构体含量可以在宽范围内变化。但是，优选地，最终催化剂组分中残余助析出剂a的(R,R)-和(S,S)-异构体含量与(R,S)-和(S,R)-异构体含量之比不小于1:10，优选不小于1:5，更优选不小于1:3，仍更优选不小于1:2。这可以通过选择具有高的(R,R)-和(S,S)-异构体含量的助析出剂a原料来实现。
在一些具体的实施方案中，为了本发明的目的，在催化剂组分的制备中使用的助析出剂a原料以基于其总重量计大于80wt％，优选大于90wt％，更优选大于95wt％，仍更优选大于98wt％的量包含以下异构体组合中的至少一种：
(R,R)-2,4-戊二醇二苯甲酸酯和(S,S)-2,4-戊二醇二苯甲酸酯、(R,R)-2,4-戊二醇二对甲基苯甲酸酯和(S,S)-2,4-戊二醇二对甲基苯甲酸酯、(R,R)-2,4-戊二醇二对乙基苯甲酸酯和(S,S)-2,4-戊二醇二对乙基苯甲酸酯、(R,R)-2,4-戊二醇二对正丙基苯甲酸酯和(S,S)-2,4-戊二醇二对正丙基苯甲酸酯、(R,R)-2,4-戊二醇二对正丁基苯甲酸酯和(S,S)-2,4-戊二醇二对正丁基苯甲酸酯、(R,R)-3,5-庚二醇二苯甲酸酯和(S,S)-3,5-庚二醇二苯甲酸酯、(R,R)-3,5-庚二醇二对甲基苯甲酸酯和(S,S)-3,5-庚二醇二对甲基苯甲酸酯、(R,R)-3,5-庚二醇二对乙基苯甲酸酯和(S,S)-3,5-庚二醇二对乙基苯甲酸酯、(R,R)-3,5-庚二醇二对正丙基苯甲酸酯和(S,S)-3,5-庚二醇二对正丙基苯甲酸酯、(R,R)-3,5-庚二醇二对正丁基苯甲酸酯和(S,S)-3,5-庚二醇二对正丁基苯甲酸酯。
优选地，在催化剂组分的制备中使用的助析出剂a原料以基于其总重量计大于80wt％，优选大于90wt％，更优选大于95wt％，仍更优选大于98wt％的量包含以下异构体组合中的至少一种：(R,R)-2,4-戊二醇二苯甲酸酯和(S,S)-2,4-戊二醇二苯甲酸酯、(R,R)-2,4-戊二醇二对甲基苯甲酸酯和(S,S)-2,4-戊二醇二对甲基苯甲酸酯、(R,R)-2,4-戊二醇二对乙基苯甲酸酯和(S,S)-2,4-戊二醇二对乙基苯甲酸酯、(R,R)-2,4-戊二醇二对正丙基苯甲酸酯和(S,S)-2,4-戊二醇二对正丙基苯甲酸酯、(R,R)-3,5-庚二醇二苯甲酸酯和(S,S)-3,5-庚二醇二苯甲酸酯、(R,R)-3,5-庚二醇二对甲基苯甲酸酯和(S,S)-3,5-庚二醇 二对甲基苯甲酸酯、(R,R)-3,5-庚二醇二对乙基苯甲酸酯和(S,S)-3,5-庚二醇二对乙基苯甲酸酯、(R,R)-3,5-庚二醇二对正丙基苯甲酸酯和(S,S)-3,5-庚二醇二对正丙基苯甲酸酯。
最优选地，在催化剂组分的制备中使用的助析出剂a原料以基于其总重量计大于80wt％，优选大于90wt％，更优选大于95wt％，仍更优选大于98wt％的量包含以下异构体组合中的至少一种：(R,R)-2,4-戊二醇二苯甲酸酯和(S,S)-2,4-戊二醇二苯甲酸酯、(R,R)-2,4-戊二醇二对甲基苯甲酸酯和(S,S)-2,4-戊二醇二对甲基苯甲酸酯、(R,R)-2,4-戊二醇二对乙基苯甲酸酯和(S,S)-2,4-戊二醇二对乙基苯甲酸酯、(R,R)-3,5-庚二醇二苯甲酸酯和(S,S)-3,5-庚二醇二苯甲酸酯、(R,R)-3,5-庚二醇二对甲基苯甲酸酯和(S,S)-3,5-庚二醇二对甲基苯甲酸酯、(R,R)-3,5-庚二醇二对乙基苯甲酸酯和(S,S)-3,5-庚二醇二对乙基苯甲酸酯。
在本发明的一些实施方案中，基于催化剂组分的总重量计，催化剂组分中所述助析出剂a的含量低于1.0wt％，优选低于0.5wt％，更优选低于0.2wt％，仍更优选低于0.15wt％。
在本发明的一些实施方案中，所述助析出剂任选地还包括如通式(II)所示的助析出剂b：
Ti(OR 7) nX 4-n  (II)
其中，R 7选自C 1-C 10的烷基或C 3-C 10的环烷基，X为卤素，且n为1,2,3或4。
在本发明的一些优选的实施方案中，所述助析出剂b是选自钛酸四甲酯、钛酸四乙酯、钛酸四正丁酯、钛酸四异丁酯、钛酸四正丙酯和钛酸四异丙酯中的至少一种，优选为钛酸四乙酯或钛酸四正丁酯。
在一些实施方案中，本发明的催化剂组分中的助析出剂基本上由上述助析出剂a和助析出剂b组成。
在一些其它实施方案中，本发明的催化剂组分中的助析出剂基本上由上述助析出剂a组成。
在一些实施方案中，除上述助析出剂a和助析出剂b外，本发明的催化剂组分不含其它助析出剂。
根据本发明，对催化剂组分中的内给电子体没有特殊的限制，并且本领域中已知可赋予催化剂组分希望的性能的任何内给电子体化合物可以被包括在所述催化剂组分中。
在一些实施方案中，本发明的催化剂组分包含至少一种如通式(III)所示的2,2-二烃基-1,3-丙二醇二甲醚类化合物作为内给电子体：
Figure PCTCN2019087787-appb-000004
其中，R 5和R 6各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、 C 6-C 10的芳基和C 7-C 10的烷芳基；优选R 5和R 6各自独立地选自取代或未取代的C 1-C 8的烷基、C 3-C 8的环烷基和C 6-C 8的芳基；更优选R 5和R 6各自独立地选自取代或未取代的C 1-C 6的烷基；进一步优选R 5和R 6各自独立地选自甲基，乙基，正丙基，异丙基，正丁基，异丁基，特丁基，正戊基，异戊基，特戊基，环戊基，环己基，苯基。R 5和R 6任选地连接成环。相应的其它醚如二乙基醚、二丙基醚、甲乙醚等也已经被想到。
适宜的通式(III)所示的2,2-二烃基-1,3-丙二醇二甲醚类化合物的实例包括但不限于：2,2-二正丙基-1,3-丙二醇二甲醚、2,2-二异丙基-1,3-丙二醇二甲醚、2,2-二正丁基-1,3-丙二醇二甲醚、2,2-二异丁基-1,3-丙二醇二甲醚、2,2-二正戊基-1,3-丙二醇二甲醚、2,2-二异戊基-1,3-丙二醇二甲醚、2,2-二正己基-1,3-丙二醇二甲醚、2,2-二异己基-1,3-二醚、2-正丙基-2-异丙基-1,3-丙二醇二甲醚、2-正丙基-2-正丁基-1,3-丙二醇二甲醚、2-正丙基-2-异丁基-1,3-丙二醇二甲醚、2-正丙基-2-正戊基-1,3-丙二醇二甲醚、2-正丙基-2-异戊基-1,3-丙二醇二甲醚、2-正丙基-2-正己基-1,3-丙二醇二甲醚、2-正丙基-2-异己基-1,3-丙二醇二甲醚、2-异丙基-2-正丁基-1,3-丙二醇二甲醚、2-异丙基-2-异丁基-1,3-丙二醇二甲醚、2-异丙基-2-正戊基-1,3-丙二醇二甲醚、2-异丙基-2-异戊基-1,3-丙二醇二甲醚、2-异丙基-2-正己基-1,3-丙二醇二甲醚、2-异丙基-2-异己基-1,3-丙二醇二甲醚、2-正丁基-2-异丁基-1,3-丙二醇二甲醚、2-正丁基-2-正戊基-1,3-丙二醇二甲醚、2-正丁基-2-异戊基-1,3-丙二醇二甲醚、2-正丁基-2-正己基-1,3-丙二醇二甲醚、2-正丁基-2-异己基-1,3-丙二醇二甲醚、2-异丁基-2-正戊基-1,3-丙二醇二甲醚、2-异丁基-2-异戊基-1,3-丙二醇二甲醚、2-异丁基-2-正己基-1,3-丙二醇二甲醚、2-异丁基-2-异己基-1,3-丙二醇二甲醚、2-正戊基-2-异戊基-1,3-丙二醇二甲醚、2-正戊基-2-正己基-1,3-丙二醇二甲醚、2-正戊基-2-异己基-1,3-丙二醇二甲醚、2-异戊基-2-正己基-1,3-丙二醇二甲醚、2-异戊基-2-异己基-1,3-丙二醇二甲醚、2-正己基-2-异己基-1,3-丙二醇二甲醚。
在一些优选的实施方案中，本发明的催化剂组分包含至少一种选自下组的化合物作为内给电子体：2,2-二异丙基-1,3-丙二醇二甲醚、2,2-二正丁基-1,3-丙二醇二甲醚、2,2-二异丁基-1,3-丙二醇二甲醚、2,2-二正戊基-1,3-丙二醇二甲醚、2,2-二异戊基-1,3-丙二醇二甲醚、2-正丙基-2-异丙基-1,3-丙二醇二甲醚、2-正丙基-2-异丁基-1,3-丙二醇二甲醚、2-正丙基-2-异戊基-1,3-丙二醇二甲醚、2-异丙基-2-正丁基-1,3-丙二醇二甲醚、2-异丙基-2-异丁基-1,3-丙二醇二甲醚、2-异丙基-2-正戊基-1,3-丙二醇二甲醚、2-异丙基-2-异戊基-1,3-丙二醇二甲醚、2-异丙基-2-异己基-1,3-丙二醇二甲醚、2-正丁基-2-异丁基-1,3-丙二醇二甲醚、2-正丁基-2-异戊基-1,3-丙二醇二甲醚、2-正丁基-2-异己基-1,3-丙二醇二甲醚、2-异丁基-2-正戊基-1,3-丙二醇二甲醚、2-异丁基-2-异戊基-1,3-丙二醇二甲醚、2-异丁基-2-正己基-1,3-丙二醇二甲醚、2-异丁基-2-异己基-1,3-丙二醇二甲醚和2-正戊基-2-异戊基-1,3-丙二醇二甲醚。
在一些优选的实施方案中，本发明的催化剂组分包含至少一种选自下组的化合物作为内给电子体：2,2'-二异丙基-1,3-丙二醇二甲醚、2,2'-二异丁基-1,3-丙二醇二甲醚、 2,2'-二异戊基-1,3-丙二醇二甲醚、2-异丙基-2-异丁基-1,3-丙二醇二甲醚、2-异丙基-2-正戊基-1,3-丙二醇二甲醚、2-异丙基-2-异戊基-1,3-丙二醇二甲醚、2-异丙基-2-异己基-1,3-丙二醇二甲醚、2-异丁基-2-正戊基-1,3-丙二醇二甲醚、2-异丁基-2-异戊基-1,3-丙二醇二甲醚和2-正戊基-2-异戊基-1,3-丙二醇二甲醚。
在一些实施方案中，本发明的催化剂组分包含至少一种如通式(III′)所示的2-氰基-2,3-二烃基丁二酸二乙酯类化合物作为内给电子体：
Figure PCTCN2019087787-appb-000005
其中，R 5和R 6各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基和C 7-C 10的芳烷基；优选R 5和R 6各自独立地选自取代或未取代的C 1-C 8的烷基、C 3-C 8的环烷基和C 6-C 8的芳基；更优选R 5和R 6各自独立地选自取代或未取代的C 1-C 6的烷基和苯基；进一步优选R 5和R 6各自独立地选自甲基，乙基，正丙基，异丙基，正丁基，异丁基，特丁基，正戊基，异戊基，特戊基，环戊基，环己基，和苯基。相应的其它酯如二甲酯、二丙酯、甲乙酯等也已经被想到。
适宜的通式(III′)所示的2-氰基-2,3-二烃基丁二酸二乙酯类化合物的实例包括但不限于：2-氰基-2,3-二正丙基丁二酸二乙酯、2-氰基-2,3-二异丙基丁二酸二乙酯、2-氰基-2,3-二正丁基丁二酸二乙酯、2-氰基-2,3-二异丁基丁二酸二乙酯、2-氰基-2,3-二正戊基丁二酸二乙酯、2-氰基-2,3-二异戊基丁二酸二乙酯、2-氰基-2,3-二环戊基丁二酸二乙酯、2-氰基-2,3-二正己基丁二酸二乙酯、2-氰基-2,3-二异己基丁二酸二乙酯、2-氰基-2-异丙基-3-正丙基丁二酸二乙酯、2-氰基-2-异丙基-3-正丁基丁二酸二乙酯、2-氰基-2-异丙基-3-异丁基丁二酸二乙酯、2-氰基-2-异丙基-3-正戊基丁二酸二乙酯、2-氰基-2-异丙基-3-异戊基丁二酸二乙酯、2-氰基-2-异丙基-3-环戊基丁二酸二乙酯、2-氰基-2-正丁基-3-正丙基丁二酸二乙酯、2-氰基-2-正丁基-3-异丙基丁二酸二乙酯、2-氰基-2-正丁基-3-异丁基丁二酸二乙酯、2-氰基-2-正丁基-3-正戊基丁二酸二乙酯、2-氰基-2-正丁基-3-异戊基丁二酸二乙酯、2-氰基-2-正丁基-3-环戊基丁二酸二乙酯、2-氰基-2-异丁基-3-正丙基丁二酸二乙酯、2-氰基-2-异丁基-3-异丙基丁二酸二乙酯、2-氰基-2-异丁基-3-正丁基丁二酸二乙酯、2-氰基-2-异丁基-3-正戊基丁二酸二乙酯、2-氰基-2-异丁基-3-异戊基丁二酸二乙酯、2-氰基-2-异丁基-3-环戊基丁二酸二乙酯、2-氰基-2-正戊基-3-正丙基丁二酸二乙酯、2-氰基-2-正戊基-3-异丙基丁二酸二乙酯、2-氰基-2-正戊基-3-正丁基丁二酸二乙酯、2-氰基-2-正戊基-3-异丁基丁二酸二乙酯、2-氰基-2-正戊基-3-异戊基丁二酸二乙酯、2-氰基-2-正戊基-3-环戊基丁二酸二乙酯、2-氰基-2-异戊基-3-正丙基丁二酸二乙酯、2-氰基-2-异戊基-3-异丙基丁二酸二乙酯、2-氰基-2-异戊基-3-正丁基丁二酸二乙酯、2-氰基-2-异戊基-3-异丁基丁二酸二乙酯、2- 氰基-2-异戊基-3-正戊基丁二酸二乙酯、2-氰基-2-异戊基-3-环戊基丁二酸二乙酯、2-氰基-2-环戊基-3-正丙基丁二酸二乙酯、2-氰基-2-环戊基-3-异丙基丁二酸二乙酯、2-氰基-2-环戊基-3-正丁基丁二酸二乙酯、2-氰基-2-环戊基-3-异丁基丁二酸二乙酯、2-氰基-2-环戊基-3-正戊基丁二酸二乙酯和2-氰基-2-环戊基-3-异戊基丁二酸二乙酯。
在一些优选的实施方案中，本发明的催化剂组分包含至少一种选自下组的化合物作为内给电子体：2-氰基-2,3-二异丙基丁二酸二乙酯、2-氰基-2,3-二正丁基丁二酸二乙酯、2-氰基-2,3-二异丁基丁二酸二乙酯、2-氰基-2,3-二正戊基丁二酸二乙酯、2-氰基-2,3-二异戊基丁二酸二乙酯、2-氰基-2-异丙基-3-正丙基丁二酸二乙酯、2-氰基-2-异丙基-3-正丁基丁二酸二乙酯、2-氰基-2-异丙基-3-异丁基丁二酸二乙酯、2-氰基-2-异丙基-3-正戊基丁二酸二乙酯、2-氰基-2-异丙基-3-异戊基丁二酸二乙酯、2-氰基-2-异丙基-3-环戊基丁二酸二乙酯、2-氰基-2-正丁基-3-异丙基丁二酸二乙酯、2-氰基-2-正丁基-3-异丁基丁二酸二乙酯、2-氰基-2-正丁基-3-正戊基丁二酸二乙酯、2-氰基-2-异丁基-3-异丙基丁二酸二乙酯、2-氰基-2-异丁基-3-正丁基丁二酸二乙酯、2-氰基-2-异丁基-3-正戊基丁二酸二乙酯、2-氰基-2-正戊基-3-异丙基丁二酸二乙酯、2-氰基-2-正戊基-3-正丁基丁二酸二乙酯、2-氰基-2-正戊基-3-异丁基丁二酸二乙酯、2-氰基-2-异戊基-3-异丙基丁二酸二乙酯、2-氰基-2-异戊基-3-正丁基丁二酸二乙酯、2-氰基-2-异戊基-3-异丁基丁二酸二乙酯、2-氰基-2-环戊基-3-异丙基丁二酸二乙酯、2-氰基-2-环戊基-3-正丁基丁二酸二乙酯和2-氰基-2-环戊基-3-异丁基丁二酸二乙酯。
在一些优选的实施方案中，本发明的催化剂组分包含至少一种选自下组的化合物作为内给电子体：2-氰基-2,3-二异丙基丁二酸二乙酯、2-氰基-2,3-二正丁基丁二酸二乙酯、2-氰基-2,3-二异丁基丁二酸二乙酯、2-氰基-2,3-二正戊基丁二酸二乙酯、2-氰基-2,3-二异戊基丁二酸二乙酯、2-氰基-2-异丙基-3-正丁基丁二酸二乙酯、2-氰基-2-异丙基-3-异丁基丁二酸二乙酯、2-氰基-2-异丙基-3-正戊基丁二酸二乙酯、2-氰基-2-异丙基-3-异戊基丁二酸二乙酯、2-氰基-2-异丙基-3-环戊基丁二酸二乙酯、2-氰基-2-正丁基-3-异丙基丁二酸二乙酯、2-氰基-2-异丁基-3-异丙基丁二酸二乙酯、2-氰基-2-正戊基-3-异丙基丁二酸二乙酯、2-氰基-2-异戊基-3-异丙基丁二酸二乙酯和2-氰基-2-环戊基-3-异丙基丁二酸二乙酯。
在一些实施方案中，本发明的催化剂组分包含至少一种如通式(III″)所示的邻苯二甲酸酯类化合物作为内给电子体；
Figure PCTCN2019087787-appb-000006
其中，R 7和R 8各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基和C 7-C 10的烷芳基；优选R 7和R 8各自独立地选自取代或未取代的C 1-C 8的烷基、C 3-C 8的环烷基和C 6-C 8的芳基；更优选R 7和R 8各自独立地选自取代或未取 代的C 1-C 6的烷基；进一步优选，R 7和R 8各自独立地选自甲基，乙基，正丙基，异丙基，正丁基，异丁基，正戊基和异戊基。
适宜的通式(III″)所示的邻苯二甲酸酯类化合物的实例包括但不限于：邻苯二甲酸二甲酯，邻苯二甲酸二乙酯，邻苯二甲酸二正丙酯，邻苯二甲酸二异丙酯，邻苯二甲酸二正丁酯，邻苯二甲酸二异丁酯，邻苯二甲酸二正戊酯和邻苯二甲酸二异戊酯。
优选地，所述通式(III″)所示的邻苯二甲酸酯类化合物选自邻苯二甲酸二乙酯，邻苯二甲酸二正丙酯，邻苯二甲酸二异丙酯，邻苯二甲酸二正丁酯，邻苯二甲酸二异丁酯和邻苯二甲酸二正戊酯。最优选地，所述通式(III″)所示的邻苯二甲酸酯类化合物选自邻苯二甲酸二乙酯，邻苯二甲酸二异丙酯，邻苯二甲酸二正丁酯和邻苯二甲酸二异丁酯。
在本发明的催化剂组分中，基于催化剂组分的总重量计，所述钛的含量为1.0wt％-8.0wt％，优选为1.6wt％-6.0wt％；所述镁的含量为10.0wt％-70.0wt％，优选为15.0wt％-40.0wt％；所述卤素的含量为20.0wt％-90.0wt％，优选为30.0wt％-85.0wt％；所述内给电子体化合物的含量为2.0wt％-30.0wt％，优选为3.0wt％-20.0wt％。
在一些实施方案中，本发明的催化剂组分包括镁化合物、钛化合物、至少一种内给电子体化合物和至少包含至少一种通式(I)所示的助析出剂a的助析出剂的反应产物。可用于通过溶解-析出方法制备齐格勒-纳塔催化剂组分的钛化合物、镁化合物和内给电子体化合物是本领域技术人员熟知的，并且它们都可以以本领域的常规用量用于形成本发明的催化剂组分。所述钛化合物和所述镁化合物的一些实例被在后面描述。
在本发明的一些实施方案中，以每摩尔镁化合物计，所述助析出剂a的用量可以为0.005-0.3摩尔，优选0.01-0.05；所述助析出剂a与所述内给电子体化合物的摩尔比可以为0.05:1至小于0.8:1，优选为0.1：1-0.7:1。
在本发明的一些实施方案中，用于制备所述催化剂组分的助析出剂还包括如前所述的助析出剂b，以每摩尔助析出剂a计，所述助析出剂b的用量为0.01-5摩尔，优选0.5-3摩尔。
在第二方面，本发明提供了本发明的烯烃聚合催化剂组分的制备方法。原则上，本领域已知的、可用于通过溶解-析出过程制备齐格勒-纳塔催化剂的任何方法可用于制备本发明的催化剂组分，前提是在析出固体颗粒之前向反应体系中引入包括上面描述的助析出剂a在内的助析出剂。
因此，本发明提供了一种制备烯烃聚合用催化剂组分的方法，该方法包括以下步骤：
1)将镁化合物溶解在溶剂体系中以形成含镁化合物溶液；
2)在助析出剂存在下从所述含镁化合物溶液析出颗粒状含镁固体物，其中所述助析出剂包含至少一种如通式(I)所示的助析出剂a；
Figure PCTCN2019087787-appb-000007
其中，R 1和R 2各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基或C 7-C 10的芳烷基；R 3和R 4各自独立地选自取代或未取代的C 1-C 20的烷基、C 3-C 20的环烷基、C 6-C 20的芳基或C 7-C 20的芳烷基；
其中通式(I)所示的助析出剂a以大于80wt％，优选大于90wt％，更优选大于95wt％，仍更优选大于98wt％的量包含如通式(I-a)和/或通式(I-b)所示的异构体，基于通式(I)所示的助析出剂a的总重量计；
Figure PCTCN2019087787-appb-000008
3)在所述颗粒状含镁固体物上负载钛基活性组分，以形成固体催化剂组分。
可用于制备本发明的用于烯烃聚合的催化剂组分的第一示例性方法包括以下步骤：
(1)使镁化合物和醇化合物任选在惰性烃类溶剂存在下反应，得到均匀的镁化合物醇合物溶液；
(2)在助析出剂存在下，将步骤(1)所得的镁化合物醇合物溶液与第一钛化合物反应，得到含固体沉淀的混合物，其中所述助析出剂包含至少一种如通式(I)所示的助析出剂a；
Figure PCTCN2019087787-appb-000009
其中，R 1和R 2各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基或C 7-C 10的芳烷基；R 3和R 4各自独立地选自取代或未取代的C 1-C 20的烷基、C 3-C 20的环烷基、C 6-C 20的芳基或C 7-C 20的芳烷基；
其中通式(I)所示的助析出剂a以大于80wt％，优选大于90wt％，更优选大于95wt％，仍更优选大于98wt％的量包含如通式(I-a)和/或通式(I-b)所示的异构体，基于通式(I)所示的助析出剂a的总重量计；
Figure PCTCN2019087787-appb-000010
(3)使步骤(2)所得的混合物与第一内给电子体化合物接触，得到一种悬浮液；
(4)将步骤(3)得到的悬浮液进行固液分离以获得第一固体中间产物，并且使得到的第一固体中间产物与第二钛化合物和任选地第二内给电子体化合物接触，以提供一种混合物；
(5)将步骤(4)得到的混合物进行固液分离，得到第二固体中间产物，并且将该第二固体中间产物用第三钛化合物处理，以形成固体催化剂组分；和
(6)回收所述固体催化剂组分。
所述第一方法中使用的第一、第二和第三钛化合物可以相同或不同,并且第一和第二内给电子体可以相同或不同。
在一个具体的实施方案中，所述第一方法包括以下步骤：(1)将镁化合物和醇类化合物在惰性烃类溶剂中进行第一接触反应，得到均匀的镁化合物醇合物溶液；(2)在助析出剂的存在下，将步骤(1)所得的均匀溶液与第一钛化合物进行第二接触反应，得到含固体沉淀的混合物；(3)将步骤(2)所得的混合物与第一内给电子体化合物进行第三接触反应，得到悬浮液；(4)将步骤(3)得到的悬浮液进行固液分离，得到的固体中间产物与第二钛化合物和第二内给电子体化合物进行第四接触反应，再进行固液分离，得到固体中间产物；(5)将步骤(4)得到的固体中间产物与第三钛化合物进行第五接触反应，再进行固液分离，得到的固体产物使用惰性溶剂洗涤，干燥，得到最终的固体催化剂组分。
在所述第一方法中使用的醇类化合物可以是选自C 1-C 10的直链或支链脂肪醇、C 3-C 12脂环醇、C 6-C 20的芳基醇和C 7-C 20的芳烷基醇中的一种或多种。醇类化合物的实例包括但不限于乙醇、正丙醇、异丙醇、正丁醇、异丁醇、2-丁醇、正戊醇、异戊醇、正己醇、异己醇、2-乙基己醇、苯甲醇、苯乙醇、环戊醇、甲基环戊醇、环己醇和它们的混合物，优选2-乙基己醇。
在所述第一方法中，以每摩尔镁计，醇类化合物的用量为2-4摩尔，优选2.5-3.5摩尔，并且在步骤(2)、(4)和(5)中使用的钛化合物的总量为1-40摩尔，优选1.5-35摩尔。
所述第一方法中采用的工艺条件包括：步骤(1)中的反应/第一接触反应的温度为30-150℃，优选60-140℃，并且反应时间为0.5-10小时，优选0.5-6小时；步骤(2)中的反应/第二接触反应的温度为-40℃至0℃，优选-30℃至-20℃，并且反应时间为3-5小时，优选3.5-4.5小时；步骤(3)中的反应/第三接触反应的温度为20-120℃，优选 70-110℃，并且反应时间为0.5-6小时，优选1-4小时；步骤(4)中的反应/第四接触反应的温度为50-150℃，优选80-120℃，并且反应时间为1-6小时，优选2.5-4.5小时；步骤(5)中的处理/第五接触反应的温度为50-150℃，优选80-120℃，并且时间为1-6小时，优选2.5-4.5小时。
上述方法的更多细节可在CN 106317275中找到，该申请的全部公开内容通过引用结合在本文中。
可用于制备本发明的用于烯烃聚合的催化剂组分的第二示例性方法包括以下步骤：
(1)将镁化合物和有机环氧化合物、有机磷化合物任选在惰性烃类溶剂存在下接触，形成均匀的镁化合物溶液；
(2)在助析出剂存在下，使步骤(1)得到的镁化合物溶液与第一钛化合物和第一内给电子体化合物反应，得到含固体沉淀物的悬浮液，其中所述助析出剂包含至少一种如通式(I)所示的助析出剂a；
Figure PCTCN2019087787-appb-000011
其中，R 1和R 2各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基或C 7-C 10的芳烷基；R 3和R 4各自独立地选自取代或未取代的C 1-C 20的烷基、C 3-C 20的环烷基、C 6-C 20的芳基或C 7-C 20的芳烷基；
其中通式(I)所示的助析出剂a以大于80wt％，优选大于90wt％，更优选大于95wt％，仍更优选大于98wt％的量包含如通式(I-a)和/或通式(I-b)所示的异构体，基于通式(I)所示的助析出剂a的总重量计；
Figure PCTCN2019087787-appb-000012
(3)将步骤(2)得到的悬浮液进行固液分离，得到第一固体中间产物，并且使该第一固体中间产物与第二钛化合物和任选地第二内给电子体化合物接触，以提供一种混合物；
(4)将步骤(3)得到的混合物进行固液分离，以得到第二固体中间产物；
(5)将所述第二固体中间产物用第三钛化合物处理1-4次，以形成进行固体催化剂组分；和
(6)回收所述固体催化剂组分。
所述第二方法中使用的第一、第二和第三钛化合物可以相同或不同,并且第一和第二内给电子体可以相同或不同。
在一个具体的实施方案中，所述第二方法包括以下步骤：(1)将镁化合物和有机环氧化合物、有机磷化合物在惰性烃类溶剂中进行第一接触反应，得到均匀的镁化合物溶液；(2)在助析出剂的存在下，将步骤(1)得到的均匀溶液与第一钛化合物和第一内给电子体化合物进行第二接触反应，得到含固体沉淀物的悬浮液；(3)将步骤(2)得到的含固体沉淀物的悬浮液进行固液分离，得到的固体中间产物A与第二钛化合物和第二内给电子体化合物进行第三接触反应，经固液分离后，得到固体中间产物B；(4)将步骤(3)得到的固体中间产物B与第三钛化合物进行第四接触反应，经固液分离后，得到的固体中间产物C；得到的固体中间产物C再用第三钛化合物处理1-3次，进行固液分离，得到的固体产物使用惰性溶剂洗涤，干燥，得到最终的固体催化剂组分。
在所述第二方法中使用的有机环氧化合物可以是选自环氧乙烷、环氧丙烷、环氧丁烷、丁二烯氧化物、丁二烯双氧化物、环氧氯丙烷、甲基缩水甘油醚和二缩水甘油醚中的至少一种，优选环氧氯丙烷。
在所述第二方法中使用的有机磷化合物可以是选自正磷酸或亚磷酸的烃基酯或卤代烃基酯中的至少一种，优选是选自正磷酸三甲酯、正磷酸三乙酯、正磷酸三丁酯、正磷酸三苯酯、亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三丁酯或亚磷酸苯甲酯中的至少一种，更优选正磷酸三丁酯。
在所述第二方法中，以每摩尔镁计，有机环氧化合物的用量为0.2-10摩尔，优选0.5-4.0摩尔；有机磷化合物的用量为0.1-3.0摩尔，优选0.3-1.5，摩尔；钛化合物的总用量为3-40摩尔，优选5-35摩尔。
所述第二方法中采用的工艺条件包括：步骤(1)中的反应/第一接触反应的温度为0-80℃，优选10-60℃，并且反应时间为0.5-10小时，优选0.5-6小时；步骤(2)中的反应/第二接触反应的温度为-40℃至0℃，优选-30℃至-20℃，并且反应时间为3-5小时，优选3.5-4.5小时；步骤(3)中的反应/第三接触反应的温度为50-150℃，优选80-120℃，并且反应时间为1-6小时，优选2.5-4.5小时；步骤(5)中的处理/第四接触反应的温度为50-150℃，优选80-120℃，并且时间为1-6小时，优选2.5-4.5小时。
上述方法的更多细节可在CN 101864009中找到，该申请的全部公开内容通过引用结合在本文中。
本领域已知可赋予聚烯烃催化剂组分希望的性能的任何内给电子体化合物可被用于本发明的方法中作为内给电子体或者所述第一和/或第二内给电子体。在一些实施方案中，本发明的方法利用至少一种由前面描述的式(III)、式(III′)或式(III″)表示的化合物作为所述第一和/或第二内给电子体。所述第一和第二内给电子体可以相同或不同。
在上述第一和第二制备方法中，第一内给电子体化合物与第二内给电子体化合物 的摩尔比可以为(0.1-10):1，优选为(0.2-5):1，更优选为(0.2-1):1。
可用于上述第一和第二制备方法中的所述镁化合物的实例包括通式(IV)所示的化合物、通式(V)所示的水合物和通式(VI)所示的醇合物中的一种或多种：
MgR 8R 9(IV)
MgR 8R 9·qH 2O(V)
MgR 8R 9·pR 0OH(VI)
其中，R 8和R 9各自独立地选自卤素、C 1-C 5的烃基、C 1-C 5的烃氧基、C 1-C 5的卤代烃基或C 1-C 5的卤代烃氧基；优选R 8和R 9各自独立地为氟、氯、溴或碘，优选氯或溴，
其中在通式(V)中，q为0.1-6.0，优选为2.0-3.5；
其中在通式(VI)中，R 0选自C 1-C 18的烃基，优选为C 1-C 5的烷基；p为0.1-6.0，优选为2.0-3.5。
在本发明的一些优选的实施方案中，所述镁化合物是选自二氯化镁、二溴化镁、氯化苯氧基镁、氯化异丙氧基镁、氯化丁氧基镁中的至少一种。
在本发明的一些更优选的实施方案中，所述镁化合物为无水二氯化镁。
所述惰性烃类溶剂可以为本领域常用的、不与所述镁化合物发生化学作用的任何烃类溶剂，例如烷烃、环烷烃或芳香烃中的至少一种，优选癸烷、苯、甲苯或二甲苯中的至少一种，更优选为甲苯。
可用于本发明方法中的所述钛化合物包括至少一种通式(VII)所示的化合物：
TiX m(OR 10) 4-m   (VII)
其中，R 10为C 1-C 20的烃基，优选为C 1-C 5的烷基；X为氯、溴或碘；m为1、2、3或4。
在本发明的一些优选的实施方案中，所述钛化合物是选自四氯化钛、四溴化钛、四碘化钛、四烷氧基钛、烷氧基三卤化钛、二烷氧基二卤化钛、三烷氧基卤化钛中的至少一种。
在本发明的一些更优选的实施方案中，所述钛化合物为四氯化钛。
在第三方面，本发明提供了一种用于烯烃聚合的催化剂，其包含下述组分：
1)如本发明第一方面所述的催化剂组分；
2)烷基铝化合物；
以及任选地3)外给电子体化合物。
优选地，组分1)与组分2)的摩尔比以钛:铝计为(5-5000):1，优选为(20-1000):1，更优选为(50-500):1。
所述组分2)烷基铝化合物可以为烯烃聚合领域常用的各种能够用作齐格勒-纳塔型催化剂的助催化剂的烷基铝化合物中的一种或多种。
在本发明的一些优选的实施方案中，所述组分2)烷基铝化合物包括至少一种通式(VIII)所示的化合物；
AlR' n'X' 3-n'   (VIII)
其中，R'选自H、C 1-C 20的烷基或C 6-C 20的芳基，X'为卤素，1≤n'≤3。
在本发明的一些更优选的实施方案中，所述烷基铝化合物是选自三甲基铝、三乙基铝、三异丁基铝、三正己基铝、三正辛基铝、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、倍半乙基氯化铝和二氯乙基铝中的至少一种。
根据本发明，对所述外给电子体化合物的种类和其量没有特别的限定。所述外给电子体化合物可以为烯烃聚合领域常用的各种能够用作齐格勒-纳塔型催化剂的外给电子体化合物的化合物中的一种或多种。如果使用，所述外给电子体化合物被以本领域中通常采用的量使用。
在本发明的一些优选的实施方案中，所述组分3)与组分2)的摩尔比以硅:铝计为1:(0.1-500)，优选为1:(1-300)，更优选为1:(3-100)。
在本发明的一些优选的实施方案中，所述外给电子体化合物包括至少一种通式(IX)所示的化合物：
R 1" m"R 2" n"Si(OR 3") 4-m"-n"   (IX)
其中，R 1"和R 2"各自独立地选自H、卤素、C 1-C 20的烷基或卤代烷基、C 3-C 20的环烷基和C 6-C 20的芳基；R 3"选自C 1-C 20的烷基或卤代烷基、C 3-C 20的环烷基和C 6-C 20的芳基；m"和n"独立地为0-3的整数，且m"+n"＜4。
在本发明的一些更优选的实施方案中，所述外给电子体化合物是选自三甲基甲氧基硅烷、三甲基乙氧基硅烷、三甲基苯氧基三乙基甲氧基硅烷、三乙基乙氧基硅烷、二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、乙基异丙基二甲氧基硅烷、丙基异丙基二甲氧基硅烷、二异丙基二甲氧基硅烷、二异丁基二甲氧基硅烷、异丙基异丁基二甲氧基硅烷、二叔丁基二甲氧基硅烷、叔丁基甲基二甲氧基硅烷、叔丁基乙基二甲氧基硅烷、叔丁基丙基二甲氧基硅烷、叔丁基异丙基二甲氧基硅烷、叔丁基丁基二甲氧基硅烷、叔丁基异丁基二甲氧基硅烷、叔丁基(仲丁基)二甲氧基硅烷、叔丁基戊基二甲氧基硅烷、叔丁基壬基二甲氧基硅烷、叔丁基己基二甲氧基硅烷、叔丁基庚基二甲氧基硅烷、叔丁基辛基二甲氧基硅烷、叔丁基癸基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷、环己基甲基二甲氧基硅烷、环己基乙基二甲氧基硅烷、环己基丙基二甲氧基硅烷、环己基异丁基二甲氧基硅烷、二环己基二甲氧基硅烷、环己基叔丁基二甲氧基硅烷、环戊基甲基二甲氧基硅烷、环戊基乙基二甲氧基硅烷、环戊基丙基二甲氧基硅烷、环戊基叔丁基二甲氧基硅烷、二环戊基二甲氧基硅烷、环戊基环己基二甲氧基硅烷、双(2-甲基环戊基)二甲氧基硅烷、二苯基二甲氧基硅烷、二苯基二乙氧基硅烷、苯基三乙氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三甲氧基硅烷、乙基三乙氧基硅烷、丙基三甲氧基硅烷、异丙基三甲氧基硅烷、丁基三甲氧基硅烷、丁基三乙氧基硅烷、异丁基三甲氧基硅烷、叔丁基三甲氧基硅烷、仲丁基三甲氧基硅烷、戊基三甲氧基硅烷、异戊基三甲氧基硅烷、环戊基三甲氧基硅烷、环己基三甲氧基硅烷、二苯基二甲氧基硅烷、二苯基二乙氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、 正丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、四甲氧基硅烷、四乙氧基硅烷、四丁氧基硅烷、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至少一种。
在本发明的一些进一步优选的实施方案中，所述外给电子体化合物是选自二环戊基二甲氧基硅烷、二异丙基二甲氧基硅烷、二异丁基二甲氧基硅烷、环己基甲基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷和四甲氧基硅烷中的至少一种。
在第四方面，本发明提供了一种用于烯烃聚合的预聚合催化剂，其包括如本发明第一方面所述的催化剂组分或如本发明第三方面所述的催化剂与烯烃进行预聚合所得的预聚物；其中，所述预聚物的预聚倍数为5-1000g烯烃聚合物/g催化剂组分，优选为10-500g烯烃聚合物/g催化剂组分。优选地，预聚合所用烯烃为乙烯或丙烯。
在本发明的一些实施方案中，所述预聚合的温度为-20至80℃，优选为10-50℃。
在第五方面，本发明提供了一种烯烃聚合方法，其中所述烯烃在如本发明第一方面所述的催化剂组分、如本发明第三方面所述的催化剂或如本发明第四方面所述的预聚合催化剂的作用下进行聚合。所述烯烃的通式为CH 2＝CHR，其中R为氢、C 1-C 6的烷基或苯基。
本发明提供的烯烃聚合方法可以用于烯烃的均聚合，也可以用于将多种烯烃进行共聚合。所述烯烃选自乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯和4-甲基-1-戊烯中的至少一种。优选地，所述烯烃可以为乙烯、丙烯、1-丁烯、4-甲基-1-戊烯和1-己烯中的至少一种。优选所述烯烃为丙烯。
在制备聚烯烃时，本发明所述的催化剂的各组分，即本发明提供的催化剂组分、作为助催化剂的烷基铝化合物和任选的外给电子体化合物可以在接触烯烃单体之前先进行接触，这在业内被称为“预接触”或“预络合”；也可以将该三个组分分别加入到聚合反应器中进行聚合反应，即不实施“预接触”。在本发明提供的烯烃聚合方法中，优选进行烯烃聚合催化剂的各组分的“预接触”。“预接触”的时间为0.1-30min，优选为1-10分钟；“预接触”的温度为-20℃至80℃，优选为10-50℃。
在一些实施方案中，将本发明的催化剂先在少量烯烃单体的存在下进行一定程度的预聚合得到预聚合催化剂，再将预聚合催化剂进一步与烯烃单体接触进行反应得到烯烃聚合物。这一技术在业内称之为“预聚合”工艺，并且有助于催化剂聚合活性及聚合物堆积密度的提高等。在本发明提供的烯烃聚合方法中，可以采用“预聚合”工艺，也可以不采用“预聚合”工艺。优选地，采用“预聚合”工艺。
在本发明的烯烃聚合方法中，聚合条件可以为本领域常规条件。
不受任何特定理论束缚，据信本发明所采用的助析出剂a即特定光学构型的异构体(R,R-构型和/或S,S-构型异构体)含量大于80％的二醇酯能够被更容易地从固体催化剂组分中除去，与常规的相应二醇酯工业产品(R,R-构型和/或S,S-构型异构体含量通常在40％左右)相比。因此，按照本发明方法制备得到的固体催化剂组分中残余助析出剂的含量相当低，从而不会干扰内给电子体组分的功能。
而且，本发明人已经发现，所述助析出剂a即特定光学构型的异构体(R,R-构型和/或S,S-构型异构体)含量大于80％的二醇酯能够很好地发挥作用，从而使得得到的催化剂组分粒形较好。
具体实施方式
为使本发明更加容易理解，下面将结合实施例来详细说明本发明，这些实施例仅起说明性作用，并不限制本发明的范围。
本发明中使用的测试方法如下：
(1)助析出剂a二醇酯化合物的纯度和非对映异构体的比例采用美国Waters公司Acquity UPLC超高效液相色谱仪进行测定。
(2)助析出剂化合物构型采用Brukerdmx核磁共振仪(300MHz，溶剂CDCl 3，内标TMS，测定温度300K)进行确定。
(3)催化剂组分中的二醇酯化合物的含量：采用美国Waters公司Acquity UPLC超高效液相色谱仪进行测定。
(4)聚合物熔融指数(MI)：根据GB/T3682-2000测定。
(5)丙烯聚合物等规度指数(II)：采用庚烷抽提法测定：2g干燥的聚合物样品，放在抽提器中用沸腾庚烷抽提6小时后，将剩余物干燥至恒重所得的聚合物重量(g)与2(g)的比值即为等规度。
(6)活性(Ac)计算：催化剂活性＝(制备的聚烯烃质量)/(催化剂固体组分质量)kg/g；
(7)堆积密度(BD)测定：将制备所得的聚合物粉料于漏斗中从10cm高度自由落体到100mL容器中，称量容器中聚合物粉料重量为M g，则聚合物堆积密度为M/100g/cm 3。
(8)聚合物分子量分布MWD(MWD＝Mw/Mn)：采用PL-GPC220，以三氯苯为溶剂，在150℃下测定(标样：聚苯乙烯，流速：1.0mL/min，柱子：3 x Plgel 10um MlxED-B 300 x 7.5nm)。
本发明中，采用超高效液相色谱仪，通过调整液相色谱的分离条件，使R,R-构型和S,S-构型的二醇酯与R,S-构型的二醇酯具有不同的保留时间，从而将R,R-构型和S,S-构型的二醇酯同R,S-构型的二醇酯区分开来。具体的分离条件为：
(1)色谱柱：ACQUITY UPLC BEH Shield RP18(100mm×2.1mm，1.7μm)；
(2)柱温：35℃；
(3)流动相：75％甲醇，25％超纯水；
(4)流速0.3mL/min；
(5)PDA检测波长229nm。
在该条件下，R,R-构型和S,S-构型的二醇酯保留时间相同，且相对较短，R,S-构 型的二醇酯保留时间相对较长。同时，根据非对映异构体的核磁共振氢谱信号峰也可判断其构型。
制备实施例
实施例中采用的通式(I)所示的助析出剂a二醇酯化合物的合成方法如下。
化合物1：2,4-戊二醇二苯甲酸酯(R,R-构型+S,S-构型):R,S-构型＝99.1:0.16
(1)R,R-2,4-戊二醇和S,S-2,4-戊二醇的混合物的制备
将500g 2,4-戊二醇加入到1200mL无水乙醚中，搅拌均匀，降温至-50℃，保持1-1.5小时，快速过滤收集析出的固体，得到的固体继续使用乙醚在-20℃重结晶，反复三次，得到最终产物184.4g，纯度99.4％(GC)。
1H NMR(CDCl 3/TMS,300MHz)δ(ppm):1.202-1.258(m,6H,-CH(OH)CH 3),1.536-1.632(m,2H,-CH 2CH(OH)CH 3),4.048-4.211(m,2H,rac-CH(OH)CH 3)。
(2)2,4-戊二醇二苯甲酸酯的合成
将259.3g苯甲酰氯加入到500mL甲苯中得到苯甲酰氯溶液；将80g上面制备的R,R-2,4-戊二醇和S,S-2,4-戊二醇的混合物、152.3g无水吡啶和4.0g 4-二甲氨基吡啶加入到100mL甲苯中，待固体全部溶解后滴入到苯甲酰氯溶液中，保持温度在50℃以下。滴加完毕后升温至80℃反应4小时，继续升温至回流反应8小时。反应结束后将反应混合物冷却至室温，过滤，从滤液旋除部分甲苯，残余滤液使用等量的10％的碳酸钠溶液剧烈搅拌洗涤至pH＝12，分液，有机相使用饱和氯化铵溶液洗至pH＝6-7，分液后有机相使用无水硫酸镁干燥，过滤后旋干溶剂，减压蒸馏得到粗产物，该粗产物使用正己烷在-20℃重结晶得最终产物142.7g，纯度99.26％(LC)。其中，R,R-构型和S,S-构型异构体的含量为99.1％，非对映异构体比例(R,R-构型+S,S-构型):R,S-构型＝99.1:0.16。
1H NMR(CDCl 3/TMS,300MHz)δ(ppm):1.397-1.418(d,6H,-CH(OCO)CH 3),2.074-2.116(m,2H,-CH 2CH(OCO)CH 3),5.287-5.350(m,2H,-CH 2CH(OCO)CH 3),7.253-7.987(m,5H,-C 6H 5)。
化合物2：3,5-庚二醇二苯甲酸酯(R,R-构型+S,S-构型):R,S-构型＝96.3:1.0
(1)R,R-3,5-庚二醇和S,S-3,5-庚二醇的混合物的制备
用与合成化合物1中步骤(1)类似的方法，将2,4-戊二醇替换为3,5-庚二醇，制备得到R,R-3,5-庚二醇和S,S-3,5-庚二醇的混合物181.3g，纯度99.6％(GC)。
1H NMR(CDCl 3/TMS,300MHz)δ(ppm):0.923-0.972(m,6H,-CH(OH)CH 2CH 3),1.476-1.589(m,4H,-CH 2CH(OH)CH 2CH 3),1.607-1.627(m,2H,-CH 2CH(OH)CH 2CH 3),3.815-3.909(m,2H,rac-CH(OH)CH 3)。
(2)3,5-庚二醇二苯甲酸酯的合成
用与合成化合物1中步骤(2)类似的方法，将R,R-2,4-戊二醇和S,S-2,4-戊二醇的混合物替换为上面制备的R,R-3,5-庚二醇和S,S-3,5-庚二醇的混合物，合成3,5-庚二醇二苯甲酸酯142.7g，纯度97.3％(LC)。其中，R,R-构型和S,S-构型异构体的含量为96.3％，非对映异构体比例(R,R-构型+S,S-构型):R,S-构型＝96.3:1.0。
1H NMR(CDCl 3/TMS,300MHz)δ(ppm):0.933-0.983(d,6H,-CH(OCO)CH 2CH 3),1.737-1.785(m,4H,-CH 2CH(OCO)CH 2CH 3),2.062-2.103(m,2H,-CH 2CH(OCO)CH 2CH 3),5.194-5.275(m,2H,-CH 2CH(OCO)CH 2CH 3),7.243-7.981(m,5H,-C 6H 5)。
化合物3：2,4-戊二醇二苯甲酸酯(R,R-构型+S,S-构型):R,S-构型＝37:60
该化合物商购获得，以收到的形式使用。该化合物中R,R-构型和S,S-构型异构体的含量为37％，非对映异构体比例(R,R-构型+S,S-构型):R,S-构型＝37:60。
化合物4：3,5-庚二醇二苯甲酸酯(R,R-构型+S,S-构型):R,S-构型＝35:61
该化合物商购获得，以收到的形式使用。该化合物中R,R-构型和S,S-构型异构体的含量为35％，非对映异构体比例(R,R-构型+S,S-构型):R,S-构型＝35:61。
实施例1
一、催化剂组分的制备
(1)氯化镁醇合物溶液的配制：在经过高纯氮重复置换的反应釜中，依次加入1400mL异辛醇、1400mL甲苯和350g无水氯化镁。使内容物在搅拌转速1300rpm、温度为115℃的条件下反应3.5小时使固体全部溶解，形成均匀的氯化镁醇合物溶液。加入52.5mL钛酸四丁酯，在搅拌转速1300rpm、温度为110℃的条件下反应1.5小时，再加入1960mL甲苯，恒温半小时。然后加入140mL甲苯和45g化合物1，在搅拌转速1300rpm、温度为50℃的条件下反应0.5小时后冷却至室温，形成含有助析出剂的氯化镁醇合物溶液。
(2)催化剂组分的制备：将上述含有助析出剂的氯化镁醇合物溶液滴加到经氮气充分置换、装有4200mL四氯化钛及2800mL甲苯的反应器中，滴加时间3小时。滴加完毕后搅拌使内容物在-25℃下充分反应0.5小时，随后经6小时升温至110℃，加入35g 2-异丙基-2-异戊基-1,3-丙二醇二甲醚和100mL甲苯，保持110℃，恒温2小时后过滤去液体，得到的固体中间产物加入6300mL甲苯及700mL四氯化钛，80℃搅拌1小时后冷却至室温并压滤，固体中间产物再加入6300mL甲苯及700mL四氯化钛，升温至80℃，加入112g 2-异丙基-2-异戊基-1,3-丙二醇二甲醚和100mL甲苯，恒温1小时后过滤去液体，得到的固体中间产物加入5600mL甲苯及1400mL四氯化钛，升温至110℃，搅拌1小时，过滤去液体后得到的固体产物用6000mL己烷洗涤4次并干燥，得到烯烃聚合催化剂组分1。
二、丙烯聚合
将上述制得的催化剂组分1进行丙烯聚合。具体方法为：在一个5L高压釜中，经气相丙烯充分置换后，在室温下加入5mL三乙基铝的己烷溶液(三乙基铝的浓度为0.5mmol/mL)、lmL环己基甲基二甲氧基硅烷(CHMMS)的己烷溶液(CHMMS的浓度为0.10mmol/mL)、10mL无水己烷和10mg固体催化剂组分1。在两种条件下进行聚合反应，聚合结果见表1：
(1)4.5标准升氢气和2L的液体丙烯；70℃下聚合反应1小时，停搅拌，除去未聚合的丙烯单体，收集聚合物。
(2)1.0标准升氢气和2L的液体丙烯；70℃下聚合反应2小时，停搅拌，除去未聚合的丙烯单体，收集聚合物。
实施例2
催化剂组分的制备同实施例1，不同之处在于，在步骤(1)中将化合物1替换为化合物2，制备得到催化剂组分2。
丙烯聚合方法同实施例1，不同之处在于，将催化剂组分1替换为催化剂组分2，聚合结果见表1。
实施例3
一、催化剂组分的制备
(1)氯化镁溶液的配制：在经过高纯氮重复置换的反应釜中，常温下依次加入350g无水氯化镁、4667mL甲苯、576mL环氧氯丙烷、649mL磷酸三丁酯，搅拌转速1300rpm，升高温度至55℃，反应3.0小时使固体全部溶解，形成均匀的氯化镁溶液。
(2)催化剂组分的制备：将氯化镁溶液降温至-28℃，将4100mL四氯化钛、290mL甲苯、58g化合物1、36g 2-异丙基-2-异戊基-1,3-丙二醇二甲醚滴加到上述氯化镁溶液中。滴加完毕后搅拌使反应混合物在-28℃下充分反应1.0小时，随后经4.5小时升温至80℃，恒温1.5小时后压滤除去液体，加入8750mL甲苯洗涤，洗涤两次。加入51g2-异丙基-2-异戊基-1,3-丙二醇二甲醚和6560mL甲苯，保持80℃，恒温1小时后加入4375mL四氯化钛，升温至110℃搅拌1小时，压滤除去液体。加入4200mL甲苯及2800mL四氯化钛，搅拌1小时，压滤除去液体。加入4200mL甲苯及2800mL四氯化钛，搅拌1小时，压滤除去液体后得到的固体物用6000mL己烷洗涤5次并干燥，得到烯烃聚合催化剂组分3。
二、丙烯聚合
将上述制得的催化剂组分3进行丙烯聚合。具体方法为：在一个5L高压釜中，经气相丙烯充分置换后，在室温下加入5mL三乙基铝的己烷溶液(三乙基铝的浓度为0.5mmol/mL)、lmL环己基甲基二甲氧基硅烷(CHMMS)的己烷溶液(CHMMS的浓度为0.10mmol/mL)、10mL无水己烷和10mg固体催化剂组分3。在两种条件下进行 聚合反应，聚合结果见表1：
(1)4.5标准升氢气和2L的液体丙烯；70℃下聚合反应1小时，停搅拌，除去未聚合的丙烯单体，收集聚合物。
(2)1.0标准升氢气和2L的液体丙烯；70℃下聚合反应2小时，停搅拌，除去未聚合的丙烯单体，收集聚合物。
实施例4
催化剂组分的制备同实施例3，不同之处在于，在步骤(1)中将化合物1替换为化合物2，制备得到催化剂组分4。
丙烯聚合方法同实施例3，不同之处在于，将催化剂组分3替换为催化剂组分4，聚合结果见表1。
对比例1
催化剂组分的制备同实施例1，不同之处在于，在步骤(1)中将化合物1替换为化合物3，制备得到催化剂组分C1。
丙烯聚合方法同实施例1，不同之处在于，将催化剂组分1替换为催化剂组分C1，聚合结果见表1。
对比例2
催化剂组分的制备同实施例1，不同之处在于，在步骤(1)中将化合物1替换为化合物4，制备得到催化剂组分C2。
丙烯聚合方法同实施例1，不同之处在于，将催化剂组分1替换为催化剂组分C2，聚合结果见表1。
对比例3
催化剂组分的制备同实施例3，不同之处在于，在步骤(1)中将化合物1替换为化合物3，制备得到催化剂组分C3。
丙烯聚合方法同实施例3，不同之处在于，将催化剂组分3替换为催化剂组分C3，聚合结果见表1。
对比例4
催化剂组分的制备同实施例3，不同之处在于，在步骤(1)中将化合物1替换为化合物4，制备得到催化剂组分C4。
丙烯聚合方法同实施例3，不同之处在于，将催化剂组分3替换为催化剂组分C4，聚合结果见表1。
表1
Figure PCTCN2019087787-appb-000013
*A:B＝(R,R-构型+S,S-构型)：(R,S-构型)
从表1数据可以看出，当在制备催化剂组分中使用所述R,R-和S,S-构型的二醇酯类化合物作为助析出剂时，得到的催化剂组分中助析出剂二醇酯的含量极低，但仍保持了较高的活性和立体定向能力且制备的聚丙烯具有较窄的分子量分布。已观察到聚丙烯粉料颗粒形态良好，表明催化剂组分的颗粒形态较好。
实施例5
一、催化剂组分的制备
(1)氯化镁醇合物溶液的配制：在经过高纯氮重复置换的反应釜中，依次加入1400mL异辛醇、1400mL甲苯、350g无水氯化镁，使内容物在搅拌转速1300rpm、温度为115℃的条件下反应3.5小时使固体全部溶解形成均匀的氯化镁醇合物溶液。加入52.5mL钛酸四丁酯，在搅拌转速1300rpm、温度为110℃的条件下反应1.5小时，再加入1960mL甲苯，恒温半小时。然后加入140mL甲苯和45g化合物1，在搅拌转速1300rpm、温度为50℃的条件下反应0.5小时后冷却至室温，形成含有助析出剂的氯化镁醇合物溶液。
(2)催化剂组分的制备：将上述含有助析出剂的氯化镁醇合物溶液滴加到经氮气充分置换、装有4200mL四氯化钛及2800mL甲苯的反应器中，滴加时间3小时。滴加完毕后搅拌使反应混合物在-25℃下充分反应0.5小时，随后经6小时升温至110℃，加入35g 2-氰基2,3-二异丙基丁二酸二乙酯和100mL甲苯，保持110℃，恒温2小时后过滤去液体，向得到的固体中间产物中加入6300mL甲苯及700mL四氯化钛，80℃搅拌1小时后冷却至室温并压滤，固体中间产物再加入6300mL甲苯及700mL四氯化钛，升温至80℃，加入112g 2-氰基2,3-二异丙基丁二酸二乙酯和100mL甲苯，恒温1小时后过滤去液体，得到的固体中间产物加入5600mL甲苯及1400mL四氯化钛，升温至110℃，搅拌1小时，过滤去液体后将得到的固体产物用6000mL己烷洗涤4次并干燥，得到烯烃聚合催化剂组分5。
二、丙烯聚合
将上述制得的催化剂组分5进行丙烯聚合。具体方法为：在一个5L高压釜中，经气相丙烯充分置换后，在室温下加入5mL三乙基铝的己烷溶液(三乙基铝的浓度为0.5mmol/mL)、lmL环己基甲基二甲氧基硅烷(CHMMS)的己烷溶液(CHMMS的浓度为0.10mmol/mL)、10mL无水己烷和10mg固体催化剂组分5。在两种条件下进行聚合反应，聚合结果见表2：
(1)4.5标准升氢气和2L的液体丙烯；70℃下聚合反应1小时，停搅拌，除去未聚合的丙烯单体，收集聚合物。
(2)1.0标准升氢气和2L的液体丙烯；70℃下聚合反应2小时，停搅拌，除去未聚合的丙烯单体，收集聚合物。
实施例6
催化剂组分的制备同实施例5，不同之处在于，在步骤(2)中将35g 2-氰基2,3-二异丙基丁二酸二乙酯替换为35g邻苯二甲酸二正丁酯(DNBP)，制备得到催化剂组分6。
丙烯聚合方法同实施例5，不同之处在于，将催化剂组分5替换为催化剂组分6，聚合结果见表2。
实施例7
催化剂组分的制备同实施例5，不同之处在于，在步骤(1)中将化合物1替换为化合物2，制备得到催化剂组分7。
丙烯聚合方法同实施例5，不同之处在于，将催化剂组分5替换为催化剂组分7，聚合结果见表2。
实施例8
催化剂组分的制备同实施例5，不同之处在于，在步骤(1)中将化合物1替换为 化合物2，在步骤(2)中将35g 2-氰基2,3-二异丙基丁二酸二乙酯替换为35g邻苯二甲酸二正丁酯(DNBP)，制备得到催化剂组分8。
丙烯聚合方法同实施例5，不同之处在于，将催化剂组分5替换为催化剂组分8，聚合结果见表2。
实施例9
一、催化剂组分的制备
(1)氯化镁溶液的配制：在经过高纯氮重复置换的反应釜中，常温下依次加入350g无水氯化镁、4667mL甲苯、576mL环氧氯丙烷、649mL磷酸三丁酯，搅拌转速1300rpm，升高温度至55℃，反应3.0小时使固体全部溶解，形成均匀的氯化镁溶液。
(2)催化剂组分的制备：将氯化镁溶液降温至-28℃，然后将4100mL四氯化钛、290mL甲苯、58g化合物1、36g 2-氰基2,3-二异丙基丁二酸二乙酯滴加到上述氯化镁溶液中。滴加完毕后搅拌使反应混合物在-28℃下充分反应1.0小时，随后经4.5小时升温至80℃，恒温1.5小时后压滤除去液体。向固体物中加入8750mL甲苯洗涤，洗涤两次。加入51g 2-氰基2,3-二异丙基丁二酸二乙酯和6560mL甲苯，保持80℃恒温1小时后加入4375mL四氯化钛，升温至110℃搅拌1小时，压滤除去液体。加入4200mL甲苯及2800mL四氯化钛，搅拌1小时，压滤除去液体。加入4200mL甲苯及2800mL四氯化钛，搅拌1小时，压滤除去液体后得到的固体物用6000mL己烷洗涤5次并干燥，得到烯烃聚合催化剂组分9。
二、丙烯聚合
将上述制得的催化剂组分9进行丙烯聚合。具体方法为：在一个5L高压釜中，经气相丙烯充分置换后，在室温下加入5mL三乙基铝的己烷溶液(三乙基铝的浓度为0.5mmol/mL)、lmL环己基甲基二甲氧基硅烷(CHMMS)的己烷溶液(CHMMS的浓度为0.10mmol/mL)、10mL无水己烷和10mg固体催化剂组分9。在两种条件下进行聚合反应，聚合结果见表2：
(1)4.5标准升氢气和2L的液体丙烯；70℃下聚合反应1小时，停搅拌，除去未聚合的丙烯单体，收集聚合物。
(2)1.0标准升氢气和2L的液体丙烯；70℃下聚合反应2小时，停搅拌，除去未聚合的丙烯单体，收集聚合物。
实施例10
催化剂组分的制备同实施例9，不同之处在于，在步骤(2)中将36g 2-氰基2,3-二异丙基丁二酸二乙酯替换为36g邻苯二甲酸二正丁酯(DNBP)，制备得到催化剂组分10。
丙烯聚合方法同实施例9，不同之处在于，将催化剂组分9替换为催化剂组分10， 聚合结果见表2。
实施例11
催化剂组分的制备同实施例9，不同之处在于，在步骤(1)中将化合物1替换为化合物2，制备得到催化剂组分11。
丙烯聚合方法同实施例9，不同之处在于，将催化剂组分9替换为催化剂组分11，聚合结果见表2。
实施例12
催化剂组分的制备同实施例9，不同之处在于，在步骤(1)中将化合物1替换为化合物2，在步骤(2)中将36g 2-氰基2,3-二异丙基丁二酸二乙酯替换为36g邻苯二甲酸二正丁酯(DNBP)，制备得到催化剂组分12。
丙烯聚合方法同实施例9，不同之处在于，将催化剂组分9替换为催化剂组分12，聚合结果见表2。
对比例5
催化剂组分的制备同实施例5，不同之处在于，在步骤(1)中将化合物1替换为化合物3，制备得到催化剂组分C5。
丙烯聚合方法同实施例5，不同之处在于，将催化剂组分5替换为催化剂组分C5，聚合结果见表2。
对比例6
催化剂组分的制备同实施例6，不同之处在于，在步骤(1)中将化合物1替换为化合物3，制备得到催化剂组分C6。
丙烯聚合方法同实施例6，不同之处在于，将催化剂组分6替换为催化剂组分C6，聚合结果见表2。
对比例7
催化剂组分的制备同实施例7，不同之处在于，在步骤(1)中将化合物1替换为化合物4，制备得到催化剂组分C7。
丙烯聚合方法同实施例7，不同之处在于，将催化剂组分7替换为催化剂组分C7，聚合结果见表2。
对比例8
催化剂组分的制备同实施例8，不同之处在于，在步骤(1)中将化合物1替换为化合物4，制备得到催化剂组分C8。
丙烯聚合方法同实施例8，不同之处在于，将催化剂组分8替换为催化剂组分C8，聚合结果见表2。
对比例9
催化剂组分的制备同实施例9，不同之处在于，在步骤(1)中将化合物1替换为化合物3，制备得到催化剂组分C9。
丙烯聚合方法同实施例9，不同之处在于，将催化剂组分9替换为催化剂组分C9，聚合结果见表2。
对比例10
催化剂组分的制备同实施例10，不同之处在于，在步骤(1)中将化合物1替换为化合物3，制备得到催化剂组分C10。
丙烯聚合方法同实施例10，不同之处在于，将催化剂组分10替换为催化剂组分C10，聚合结果见表2。
对比例11
催化剂组分的制备同实施例11，不同之处在于，在步骤(1)中将化合物1替换为化合物4，制备得到催化剂组分C11。
丙烯聚合方法同实施例11，不同之处在于，将催化剂组分11替换为催化剂组分C11，聚合结果见表2。
对比例12
催化剂组分的制备同实施例12，不同之处在于，在步骤(1)中将化合物1替换为化合物4，制备得到催化剂组分C12。
丙烯聚合方法同实施例12，不同之处在于，将催化剂组分12替换为催化剂组分C12，聚合结果见表2。
表2
Figure PCTCN2019087787-appb-000014
*A:B＝(R,R-构型+S,S-构型)：(R,S-构型)
从表2数据可以看出，在催化剂组分制备中使用R,R-和S,S-构型的二醇酯类化合物作为助析出剂时，得到的催化剂组分中助析出剂二醇酯的含量极低，但催化剂组分仍具有较高的活性和立体定向能力且制备的聚丙烯具有很宽的分子量分布。已观察到聚丙烯粉料颗粒形态良好，表明催化剂组分的颗粒形态较好。
实施例13
一、催化剂组分的制备
(1)氯化镁醇合物溶液的配制：在经过高纯氮重复置换的反应釜中，依次加入1400mL异辛醇、1400mL甲苯、350g无水氯化镁，并且使内容物在搅拌转速1300rpm、温度为115℃的条件下反应3.5小时使固体全部溶解形成均匀的氯化镁醇合物溶液。加入52.5mL钛酸四丁酯，在搅拌转速1300rpm、温度为110℃的条件下反应1.5小时，再加入1960mL甲苯，恒温半小时。然后加入140mL甲苯和45g化合物1，在搅拌转速1300rpm、温度为50℃的条件下反应0.5小时后冷却至室温，形成含有助析出剂的氯化镁醇合物溶液。
(2)催化剂组分的制备：将上述含有助析出剂的氯化镁醇合物溶液滴加到经氮气充分置换、装有4200mL四氯化钛及2800mL甲苯的反应器中，滴加时间3小时，滴加完毕后搅拌使反应混合物在-25℃下充分反应0.5小时，随后经6小时升温至110℃，加入35g邻苯二甲酸二正丁酯和100mL甲苯，保持110℃，恒温2小时后过滤去液体，得到的固体中间产物加入6300mL甲苯及700mL四氯化钛，80℃搅拌1小时后冷却至室温并压滤，固体中间产物再加入6300mL甲苯及700mL四氯化钛，升温至80℃，加入112g邻苯二甲酸二正丁酯和100mL甲苯，恒温1小时后过滤去液体，得到的固体中间产物加入5600mL甲苯及1400mL四氯化钛，升温至110℃，搅拌1小时，过滤去液体后得到的固体产物用6000mL己烷洗涤4次并干燥，得到烯烃聚合催化剂组分13。
二、丙烯聚合
将上述制得的催化剂组分13如实施例1中所述进行丙烯聚合，聚合结果见表3。
三、抗冲共聚聚丙烯制备
聚合反应在一套卧式气相聚丙烯中试装置上进行，聚合反应器为两台串联的卧式搅拌反应釜，聚合方法及步骤如下：
催化剂组分13、三乙基铝、异丁基二甲氧基硅烷在丙烯的携带下从第一个搅拌釜前端连续地加入到卧式搅拌反应釜，在气相的条件下聚合生成均聚聚丙烯，反应热由喷淋的丙烯汽化带走。生成的聚合物由搅拌釜的末端排出。催化剂和聚合物以接近平推流的方式在反应器内运动，聚合温度为66℃或指定温度，反应压力2.3MPa。
均聚聚丙烯从第一个反应器排出，通过两个反应器间装有转移的设备，将聚合物转移到第二个卧式搅拌反应釜。聚合物从第二个搅拌釜前端进入，通入乙烯的条件下聚合生成抗冲共聚聚丙烯，反应热由喷淋的丙烯汽化带走。聚合过程中维持乙烯与丙 烯的摩尔比为0.38-0.40。生成的聚合物由搅拌釜的末端排出。催化剂和聚合物以接近平推流的方式在反应器内运动，聚合温度为66℃或指定温度，反应压力2.2MPa。反应得到的聚合物经脱气、湿氮气去活处理后，得到聚抗冲共聚聚丙烯，聚合结果见表4。
实施例14
催化剂组分的制备同实施例13，不同之处在于，在步骤(1)中将化合物1替换为化合物2，制备得到催化剂组分14。
丙烯聚合方法同实施例1，不同之处在于，将催化剂组分1替换为催化剂组分14，聚合结果见表3。
抗冲共聚聚丙烯制备方法同实施例13，不同之处在于，将催化剂组分13替换为催化剂组分14，聚合结果见表4。
实施例15
催化剂组分的制备同实施例13，不同之处在于，在步骤(1)中将化合物1替换为化合物2，在步骤(2)中将邻苯二甲酸二正丁酯(DNBP)替换为邻苯二甲酸二异丁酯(DIBP)，制备得到催化剂组分15。
丙烯聚合方法同实施例1，不同之处在于，将催化剂组分1替换为催化剂组分15，聚合结果见表3。
抗冲共聚聚丙烯制备方法同实施例13，不同之处在于，将催化剂组分13替换为催化剂组分15，聚合结果见表4。
实施例16
一、催化剂组分的制备
(1)氯化镁溶液的配制：在经过高纯氮重复置换的反应釜中，常温下依次加入350g无水氯化镁、4667mL甲苯、576mL环氧氯丙烷、649mL磷酸三丁酯，搅拌转速1300rpm，升高温度至55℃，反应3.0小时使固体全部溶解，形成均匀的氯化镁溶液。
(2)催化剂组分的制备：将氯化镁溶液降温至-28℃，然后将4100mL四氯化钛、290mL甲苯、58g化合物1、36g邻苯二甲酸二正丁酯滴加到上述氯化镁溶液中。滴加完毕后搅拌使反应混合物在-28℃下充分反应1.0小时，随后经4.5小时升温至80℃，恒温1.5小时后压滤除去液体，加入8750mL甲苯洗涤，洗涤两次。加入51g邻苯二甲酸二正丁酯和6560mL甲苯，保持80℃恒温1小时后加入4375mL四氯化钛，升温至110℃搅拌1小时，压滤除去液体。加入4200mL甲苯及2800mL四氯化钛，搅拌1小时，压滤除去液体。加入4200mL甲苯及2800mL四氯化钛，搅拌1小时，压滤除去液体后得到的固体物用6000mL己烷洗涤5次并干燥，得到烯烃聚合催化剂组分16。
二、丙烯聚合
将上述制得的催化剂组分16如实施例1所述进行丙烯结合，聚合结果见表3。
三、抗冲共聚聚丙烯制备
用上述制得的催化剂组分16如实施例13所述制备抗冲共聚聚丙烯，聚合结果见表4。
实施例17
催化剂组分的制备同实施例16，不同之处在于，在步骤(1)中将化合物1替换为化合物2，制备得到催化剂组分17。
丙烯聚合方法同实施例1，不同之处在于，将催化剂组分1替换为催化剂组分17，聚合结果见表3。
抗冲共聚聚丙烯制备方法同实施例13，不同之处在于，将催化剂组分13替换为催化剂组分17，聚合结果见表4。
实施例18
催化剂组分的制备同实施例16，不同之处在于，在步骤(1)中将化合物1替换为化合物2，在步骤(2)中将邻苯二甲酸二正丁酯(DNBP)替换为邻苯二甲酸二异丁酯(DIBP)，制备得到催化剂组分18。
丙烯聚合方法同实施例1，不同之处在于，将催化剂组分1替换为催化剂组分18，聚合结果见表31。
抗冲共聚聚丙烯制备方法同实施例13，不同之处在于，将催化剂组分13替换为催化剂组分18，聚合结果见表4。
对比例13
催化剂组分的制备同实施例13，不同之处在于，在步骤(1)中将化合物1替换为化合物3，制备得到催化剂组分C13。
丙烯聚合方法同实施例13，不同之处在于，将催化剂组分13替换为催化剂组分C13，聚合结果见表3。
抗冲共聚聚丙烯制备方法同实施例13，不同之处在于，将催化剂组分13替换为催化剂组分C13，聚合结果见表4。
对比例14
催化剂组分的制备同实施例14，不同之处在于，在步骤(1)中将化合物2替换为化合物4，制备得到催化剂组分C14。
丙烯聚合方法同实施例13，不同之处在于，将催化剂组分13替换为催化剂组分C14，聚合结果见表3。
抗冲共聚聚丙烯制备方法同实施例13，不同之处在于，将催化剂组分13替换为催化剂组分C14，聚合结果见表4。
对比例15
催化剂组分的制备同实施例16，不同之处在于，在步骤(1)中将化合物1替换为化合物3，制备得到催化剂组分C15。
丙烯聚合方法同实施例1，不同之处在于，将催化剂组分1替换为催化剂组分C15，聚合结果见表3。
抗冲共聚聚丙烯制备方法同实施例13，不同之处在于，将催化剂组分13替换为催化剂组分C15，聚合结果见表4。
对比例16
催化剂组分的制备同实施例17，不同之处在于，在步骤(1)中将化合物2替换为化合物4，制备得到催化剂组分C16。
丙烯聚合方法同实施例1，不同之处在于，将催化剂组分1替换为催化剂组分C16，聚合结果见表3。
抗冲共聚聚丙烯制备方法同实施例13，不同之处在于，将催化剂组分13替换为催化剂组分C16，聚合结果见表4。
表3
Figure PCTCN2019087787-appb-000015
*A:B＝(R,R-构型+S,S-构型)：(R,S-构型)
表4 a
Figure PCTCN2019087787-appb-000016
a.C2＝为共聚聚丙烯中总乙烯含量，RCC2为橡胶相中乙烯含量，RC为共聚聚丙烯中橡胶相含量。
从表3数据可以看出，在催化剂组分制备中使用R,R-和S,S-构型的二醇酯类化合物作为助析出剂时，得到的催化剂组分中助析出剂二醇酯的含量极低，同时催化剂组分显示高的聚合活性和高的立体定向性。已观察到聚丙烯粉料颗粒形态良好，表明催化剂组分的颗粒形态较好。
从表4数据可以看出，使用本发明的催化剂组分制备抗冲共聚聚丙烯时，在相同的乙烯/丙烯摩尔比条件下，制备的共聚聚丙烯中乙烯含量和橡胶相中的乙烯含量更高，表明本发明的催化剂具有更好的共聚能力。
尽管已经特别地描述了本发明的说明性实施方案，应该理解的是，各种其它修改对于本领域技术人员来说是显而易见的，并且可以由本领域技术人员容易地做出，而不背离本发明的精神和范围。因此，不打算将所附权利要求书的范围限制在本文所陈述的实施例和说明中，而是权利要求书应被理解为包括存在于本发明中的所有具有专利新颖性的特征，包括将被本发明所属领域技术人员作为其等同物看待的所有特征。在上面已经结合许多实施方案和具体实施例描述了本发明。考虑到以上的详细描述，许多变例对本领域技术人员来说是显而易见的。所有这样的各种变例都在所附权利要求书的整个意图的范围内。
在本公开中，当组合物、要素或者要素组前有过渡短语“包含”时，应理解我们还想到了相同的组合物、要素或者要素组，其中所述组合物、要素或者要素组前由过渡短语“基本上由…组成”、“由…组成”、“选自由…组成的组”或者“是”引导，反之亦然。

Claims (12)

  1. 一种用于烯烃聚合的催化剂组分，其包含镁、钛、卤素、内给电子体化合物和助析出剂，其中所述助析出剂包含至少一种如通式(I)所示的助析出剂a；
    Figure PCTCN2019087787-appb-100001
    其中，R 1和R 2各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基或C 7-C 10的芳烷基；R 3和R 4各自独立地选自取代或未取代的C 1-C 20的烷基、C 3-C 20的环烷基、C 6-C 20的芳基或C 7-C 20的芳烷基，并且其中基于催化剂组分的总重量，所述助析出剂a的含量低于1.0wt％；
    通式(I)所示的助析出剂a包含如通式(I-a)和/或通式(I-b)所示的异构体：
    Figure PCTCN2019087787-appb-100002
  2. 权利要求1所述的催化剂组分，其中在通式(I)中，R 1和R 2各自独立地选自取代或未取代的C 1-C 8的烷基、C 3-C 8的环烷基和C 6-C 8的芳基；优选R 1和R 2各自独立地选自取代或未取代的C 1-C 4的烷基；R 3和R 4各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基和C 6-C 10的芳基；优选R 3和R 4各自独立地选自取代或未取代的C 5-C 10的烷基、C 5-C 10环烷基、C 6-C 10芳基和C 7-C 10芳烷基。
  3. 权利要求1和权利要求2中任意一项所述的催化剂组分，其特征在于，基于催化剂组分的总重量，所述助析出剂a的含量低于0.5wt％，更优选低于0.2wt％。
  4. 权利要求1-3中任意一项所述的催化剂组分，其特征在于，所述助析出剂还包括如通式(II)所示的助析出剂b；
    Ti(OR 7) nX 4-n  (II)
    其中，每个R 7独立地选自C 1-C 10的烷基和C 3-C 10的环烷基，每个X为卤素，n为1、2、3或4。
  5. 权利要求1-4中任意一项所述的催化剂组分，其中所述内给电子体化合物包含选自下组中的至少一种：
    如通式(III)所示的2,2-二烃基-1,3-丙二醇二甲醚类化合物：
    Figure PCTCN2019087787-appb-100003
    其中，R 5和R 6各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基和C 7-C 10的烷芳基；优选R 5和R 6各自独立地选自取代或未取代的C 1-C 8的烷基、C 3-C 8的环烷基和C 6-C 8的芳基；更优选R 5和R 6各自独立地选自取代或未取代的C 1-C 6的烷基和苯基；R 5和R 6任选地连接成环；
    如通式(III′)所示的2-氰基-2,3-二烃基丁二酸二乙酯类化合物：
    Figure PCTCN2019087787-appb-100004
    其中，R 5和R 6各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基和C 7-C 10的芳烷基；优选R 5和R 6各自独立地选自取代或未取代的C 1-C 8的烷基、C 3-C 8的环烷基和C 6-C 8的芳基；更优选R 5和R 6各自独立地选自取代或未取代的C 1-C 6的烷基和苯基；和
    如通式(III″)所示的邻苯二甲酸酯类化合物:
    Figure PCTCN2019087787-appb-100005
    其中，R 7和R 8各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基和C 7-C 10的烷芳基；优选R 7和R 8各自独立地选自取代或未取代的C 1-C 8的烷基、C 3-C 8的环烷基和C 6-C 8的芳基；更优选R 7和R 8各自独立地选自取代或未取代的C 1-C 6的烷基。
  6. 权利要求1-5中任意一项所述的催化剂组分，其特征在于，基于催化剂组分的总重量计，所述钛的含量为1.0wt％-8.0wt％，优选为1.6wt％-6.0wt％；所述镁的含量为10.0wt％-70.0wt％，优选为15.0wt％-40.0wt％；所述卤素的含量为20.0wt％-90.0wt％，优选为30.0wt％-85.0wt％；所述内给电子体化合物的含量为2.0wt％-30.0wt％，优选为3.0wt％-20.0wt％。
  7. 权利要求1所述的催化剂组分，其特征在于，所述催化剂组分包括镁化合物、钛化合物、至少一种内给电子体化合物和包含至少一种通式(I)所示的助析出剂a的助析出剂的反应产物；
    其中，以每摩尔镁化合物计，所述助析出剂a的用量为0.005-0.3摩尔，优选0.01-0.05摩尔，并且所述助析出剂a以基于助析出剂a的总重量计大于80wt％，优选大于90wt％，更优选大于95wt％，仍更优选大于98wt％的量包含如通式(I-a)和/或通式(I-b)所示的异构体。
  8. 一种制备烯烃聚合用催化剂组分的方法，该方法包括以下步骤：
    1)将镁化合物溶解在溶剂体系中以形成含镁化合物溶液；
    2)在助析出剂存在下从所述含镁化合物溶液析出颗粒状含镁固体物，其中所述助析出剂包含至少一种如通式(I)所示的助析出剂a；
    Figure PCTCN2019087787-appb-100006
    其中，R 1和R 2各自独立地选自取代或未取代的C 1-C 10的烷基、C 3-C 10的环烷基、C 6-C 10的芳基和C 7-C 10的芳烷基；R 3和R 4各自独立地选自取代或未取代的C 1-C 20的烷基、C 3-C 20的环烷基、C 6-C 20的芳基和C 7-C 20的芳烷基；
    其中通式(I)所示的助析出剂a以大于80wt％，优选大于90wt％，更优选大于95wt％，仍更优选大于98wt％的量包含如通式(I-a)和/或通式(I-b)所示的异构体，基于通式(I)所示的助析出剂a的总重量计；
    Figure PCTCN2019087787-appb-100007
    3)在所述颗粒状含镁固体物上负载钛基活性组分，以形成固体催化剂组分。
  9. 权利要求8所述的方法，该方法包括以下步骤：
    (1)使镁化合物和醇化合物任选在惰性烃类溶剂存在下反应，得到均匀的镁化合物醇合物溶液；
    (2)在所述助析出剂存在下，将步骤(1)所得的镁化合物醇合物溶液与第一钛化合物反应，得到含固体沉淀的混合物；
    (3)使步骤(2)所得的混合物与第一内给电子体化合物接触，得到一种悬浮液；
    (4)将步骤(3)得到的悬浮液进行固液分离以获得第一固体中间产物，并且使得到的第一固体中间产物与第二钛化合物和任选地第二内给电子体化合物接触，以提供一种混合物；
    (5)将步骤(4)得到的混合物进行固液分离，得到第二固体中间产物，并且将该第二固体中间产物用第三钛化合物处理，以形成固体催化剂组分；和
    (6)回收所述固体催化剂组分，
    或者，该方法包括以下步骤：
    (1)将镁化合物和有机环氧化合物、有机磷化合物任选在惰性烃类溶剂存在下接触，形成均匀的镁化合物溶液；
    (2)在所述助析出剂存在下，将步骤(1)得到的镁化合物溶液与第一钛化合物 和第一内给电子体化合物接触，得到含固体沉淀物的悬浮液；
    (3)将步骤(2)得到的悬浮液进行固液分离，得到第一固体中间产物，并且使该第一固体中间产物与第二钛化合物和任选地第二内给电子体化合物接触，以提供一种混合物；
    (4)将步骤(3)得到的混合物进行固液分离，以得到第二固体中间产物；
    (5)将所述第二固体中间产物用第三钛化合物处理1-4次，以形成进行固体催化剂组分；和
    (6)回收所述固体催化剂组分。
  10. 一种用于烯烃聚合的催化剂，其包含下述组分：
    1)如权利要求1-7中任意一项所述的催化剂组分；
    2)烷基铝化合物；以及
    任选地3)外给电子体化合物；
    其中，组分1)与组分2)的摩尔比以钛:铝计为(5-5000):1，优选为(20-1000):1，更优选为(50-500):1。
  11. 一种用于烯烃聚合的预聚合催化剂，其包括如权利要求1-7中任意一项所述的催化剂组分或如权利要求10所述的催化剂与烯烃进行预聚合所得的预聚物；其中所述预聚物的预聚倍数为5-1000g烯烃聚合物/g催化剂组分，优选为10-500g烯烃聚合物/g催化剂组分；优选预聚合所用烯烃为乙烯或丙烯。
  12. 一种烯烃聚合方法，所述烯烃的通式为CH 2＝CHR，其中R为氢、C 1-C 6的烷基或芳基，该方法包括使所述烯烃在如权利要求1-7中任意一项所述的催化剂组分、如权利要求10所述的催化剂或如权利要求11所述的预聚合催化剂存在下聚合以形成聚烯烃聚合物；和回收所得到的聚烯烃聚合物。
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