WO2023072179A1 - 烯烃聚合催化剂组分、催化剂体系及预聚合催化剂组合物和烯烃聚合方法 - Google Patents

烯烃聚合催化剂组分、催化剂体系及预聚合催化剂组合物和烯烃聚合方法 Download PDF

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WO2023072179A1
WO2023072179A1 PCT/CN2022/127883 CN2022127883W WO2023072179A1 WO 2023072179 A1 WO2023072179 A1 WO 2023072179A1 CN 2022127883 W CN2022127883 W CN 2022127883W WO 2023072179 A1 WO2023072179 A1 WO 2023072179A1
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substituted
unsubstituted
compound
olefin polymerization
chain alkyl
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French (fr)
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张纪贵
周俊领
于杨典辰
高富堂
齐琳
王宇
李威莅
任春红
刘涛
张天一
李然
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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 to EP22886054.0A priority Critical patent/EP4424720A1/en
Priority to KR1020247017941A priority patent/KR20240091180A/ko
Publication of WO2023072179A1 publication Critical patent/WO2023072179A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention claims the priority of the Chinese patent application entitled “Olefin Polymerization Catalyst Component, Catalyst System and Application, and Olefin Polymerization Method” filed on October 28, 2021, with application number CN202111264973.2, and the entire content of the application Incorporated herein by reference.
  • the invention belongs to the technical field of olefin polymerization catalysts, and in particular relates to an olefin polymerization catalyst component, a catalyst system, a prepolymerization catalyst composition and an olefin polymerization method.
  • the prepared catalysts have different characteristics, such as some catalysts have higher polymerization activity, some catalysts have better hydrogenation sensitivity, and some catalysts prepare polyolefin resins with wider Molecular weight distribution (as disclosed in CN1436766A and CN1552740A diol ester compounds and their catalysts), but in the industrial production of polyolefins, it is very important that the catalyst used for polymerization has very good overall performance.
  • people usually adopt the method of adding various internal electron-donating compounds in the catalyst preparation process to improve the overall performance of the catalyst.
  • the catalyst prepared by compounding succinate and phthalate not only maintains the characteristics of succinate single internal electron donor catalyst for the wide molecular weight distribution of the polymer obtained by propylene polymerization, but also The stereospecificity of the catalyst is further improved;
  • the catalyst component and catalyst disclosed in CN1743346A are catalysts prepared by compounding 1,3-dibasic alcohol esters with dibutyl phthalate and ethyl benzoate The polymer obtained by propylene polymerization has higher isotacticity and wider molecular weight distribution.
  • CN102796213B selects the catalyst prepared by compounding hydroxybenzoyl compound and phthalate compound or diether compound, which shows high polymerization activity, good hydrogen adjustment sensitivity and high orientation when used for propylene homopolymerization ability.
  • this type of catalyst is used for olefin copolymerization, the olefin copolymerization ability of the catalyst is relatively insufficient.
  • alkoxysilane compounds are generally used as external electron donors to improve the hydrogen tuning sensitivity of catalyst systems.
  • CN103509137A found that when alkoxysilane compounds are used in the preparation of olefin polymerization catalyst components by the precipitation method, the preparation time of the catalyst components can be effectively shortened, and at the same time, the particle shape of the catalyst and the content of fine polymer powder can be improved.
  • CN1373777A found that when alkoxysilane is used in the preparation of ethylene polymerization catalyst, it can improve the polymerization activity and hydrogen adjustment sensitivity of the catalyst.
  • the catalyst component and its catalyst system catalyze olefins to obtain polymer particles with good morphology.
  • a kind of olefin polymerization catalyst component is provided, and this catalyst component contains magnesium, titanium, halogen and internal electron donor; Described internal electron donor comprises: compound B and compound C; Wherein,
  • the compound B is selected from one or more of ester compounds and ether compounds other than hydroxybenzoyl compounds shown in formula (I);
  • R 1 is selected from hydrogen, substituted or unsubstituted C 1 -C 20 straight chain alkyl, substituted or unsubstituted C 3 -C 20 branched chain alkyl, substituted or unsubstituted C 3 -C 20 cycloalkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 7 -C 20 aralkyl, each of R 2 , R 3 , R 4 and R 5 independently selected from hydrogen, halogen, nitro, substituted or unsubstituted C 1 -C 20 straight chain alkyl, substituted or unsubstituted C 3 -C 20 branched chain alkyl, substituted or unsubstituted C 3 -C 20 cycloalkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 7 -C 20 aralkyl; or among R 2
  • the compound C is selected from alkoxysilanes represented by the formula R n Si(OR 6 ) 4-n ; in the formula R n Si(OR 6 ) 4-n , R and R 6 are each independently selected from hydrogen, substituted Or unsubstituted C 1 -C 20 straight chain alkyl, substituted or unsubstituted C 3 -C 20 branched chain alkyl, substituted or unsubstituted C 3 -C 20 cycloalkyl, substituted or unsubstituted C 6 -C 20 aryl group, substituted or unsubstituted C 7 -C 20 aralkyl group, n is an integer of 0-3.
  • an olefin polymerization catalyst component contains magnesium, titanium, halogen and an internal electron donor; the internal electron donor includes compound A, compound B and compound C; in,
  • the compound A is selected from the hydroxybenzoyl compounds shown in formula (I); the compound B is selected from one or more of the ester compounds and ether compounds except the compound A; the compound C Alkoxysilanes selected from the formula R n Si(OR 6 ) 4-n ;
  • R 1 is selected from hydrogen, substituted or unsubstituted C 1 -C 20 straight chain alkyl, substituted or unsubstituted C 3 -C 20 branched chain alkyl, substituted or unsubstituted C 3 -C 20 cycloalkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 7 -C 20 aralkyl; each of R 2 , R 3 , R 4 and R 5 independently selected from hydrogen, halogen, nitro, substituted or unsubstituted C 1 -C 20 straight chain alkyl, substituted or unsubstituted C 3 -C 20 branched chain alkyl, substituted or unsubstituted C 3 -C 20 cycloalkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 7 -C 20 aralkyl; or among R 2
  • R and R 6 are each independently selected from hydrogen, substituted or unsubstituted C 1 -C 20 linear alkyl, substituted or unsubstituted C 3 -C 20 branched alkyl, substituted or unsubstituted C 3 -C 20 cycloalkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 7 -C 20 aralkyl, n is an integer of 0-3.
  • R 1 is selected from hydrogen, substituted or unsubstituted C 1 -C 6 straight chain alkyl, substituted or unsubstituted C 3 -C 6 branched chain alkyl , substituted or unsubstituted C 3 -C 6 cycloalkyl, substituted or unsubstituted C 6 -C 10 aryl, substituted or unsubstituted C 7 -C 10 aralkyl;
  • R 2 , R 3 , R 4 and R 5 are each independently selected from hydrogen, substituted or unsubstituted C 1 -C 8 straight chain alkyl, substituted or unsubstituted C 3 -C 8 branched chain alkyl, substituted or unsubstituted C 3 -C 6 cycloalkyl, substituted or unsubstituted C 6 -C 10 aryl, substituted or unsubstituted C 7 -C 10 aralkyl.
  • R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, Benzyl or phenethyl;
  • R 2 , R 3 , R 4 and R 5 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl , n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl or tolyl.
  • compound A is selected from 4-hydroxybenzoic acid compounds, 4-hydroxybenzoic acid ester compounds, 2-hydroxybenzoyl compounds, One or more of benzoic acid compounds and 2-hydroxybenzoate compounds; more preferably one or more of 2-hydroxybenzoic acid compounds and 2-hydroxybenzoate compounds.
  • compound A may include, but are not limited to: methyl 2-hydroxybenzoate, ethyl 2-hydroxybenzoate, n-propyl 2-hydroxybenzoate, isopropyl 2-hydroxybenzoate, 2-hydroxybenzoate -n-butyl hydroxybenzoate, isobutyl 2-hydroxybenzoate, n-pentyl 2-hydroxybenzoate, n-hexyl 2-hydroxybenzoate, methyl 2-hydroxy-3-methylbenzoate, 2-hydroxy -4-methylbenzoate, 2-hydroxy-5-methylbenzoate, 2-hydroxy-3-ethylbenzoate, 2-hydroxy-4-ethylbenzoate, 2 -Hydroxy-5-ethylbenzoic acid methyl ester, 2-hydroxy-3-methylbenzoic acid ethyl ester, 2-hydroxy-4-methylbenzoic acid ethyl ester, 2-hydroxy-5-methylbenzoic acid ethyl ester , Ethyl 2-Hydr
  • the ester compound in the compound B is selected from monobasic aliphatic carboxylate, polybasic aliphatic carboxylate, monobasic aromatic carboxylate, polybasic aromatic carboxylate and glycol ester compounds One or more; preferably polybasic aromatic carboxylic acid ester; more preferably polybasic aromatic carboxylic acid alkyl ester; further preferably dibasic aromatic carboxylic acid alkyl ester.
  • the dibasic aromatic carboxylic acid alkyl ester is an alkyl phthalate, preferably a C 1 -C 10 linear alkyl ester of phthalic acid, a C 3 - one or more of branched chain alkyl esters of C 10 and cycloalkyl esters of C 3 -C 10 of phthalic acid.
  • the term "monohydric aliphatic carboxylic acid ester” refers to a compound formed by an esterification reaction of a monohydric aliphatic carboxylic acid and a monohydric alcohol.
  • polyhydric aliphatic carboxylic acid ester refers to a compound formed by an esterification reaction of a polyhydric aliphatic carboxylic acid and a monohydric alcohol.
  • monoaromatic carboxylic acid ester refers to a compound formed by an esterification reaction of a monoaromatic carboxylic acid and a monohydric alcohol.
  • polyaromatic carboxylic acid ester refers to a compound formed by esterification reaction of polyvalent aromatic carboxylic acid and monohydric alcohol.
  • examples of the monobasic aliphatic carboxylate, polybasic aliphatic carboxylate, monobasic aromatic carboxylate and polybasic aromatic carboxylate may be: benzoate, phthalate, Malonates, succinates, glutarates, pivalates and carbonates; preferably alkyl benzoates, alkyl phthalates, alkyl malonates, alkyl succinates , alkyl glutarates, alkyl pivalates and alkyl carbonates.
  • examples of the monobasic aliphatic carboxylate, polybasic aliphatic carboxylate, monobasic aromatic carboxylate and polybasic aromatic carboxylate may include, but are not limited to: ethyl benzoate, ortho Diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-phthalate Octyl ester, diethyl malonate, dibutyl malonate, diisobutyl malonate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-diisopropyl succinate Isobutyl ester, 2,3-diisopropyl di-n-butyl succinate, 2,3-diisopropyl dimethyl succinate, 2,2-dimethyl diisobutyl succinate, 2-ethyl Diisobutyl 2-methylsuccinate, diethyl benzoate,
  • diol ester compound refers to a compound formed by an esterification reaction between a diol and a monocarboxylic acid or a polycarboxylic acid.
  • the glycol ester compound may be a compound represented by formula (II).
  • R I , R II , R III , R IV , R V and R VI are each independently selected from hydrogen, substituted or unsubstituted C 1 -C 10 aliphatic hydrocarbon groups, substituted or unsubstituted C 6 -C 10 aryl, substituted or unsubstituted C 7 -C 10 aralkyl; or, two or more of R I , R II , R III , R IV , R V and R VI The groups are bonded to each other to form a ring; R VII and R VIII are each independently selected from substituted or unsubstituted C 1 -C 10 straight chain alkyl, substituted or unsubstituted C 3 -C 10 branched chain alkane group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted or unsubstituted C 6 -C 20 aryl group, substituted or unsubstituted C 7 -C 20 aryl
  • R I , R II , R III , R IV , R V and R VI are each independently selected from hydrogen, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted Or unsubstituted C 1 -C 6 branched chain alkyl, substituted or unsubstituted C 2 -C 6 straight chain alkenyl, substituted or unsubstituted C 3 -C 6 branched chain alkenyl, substituted or unsubstituted Substituted C 3 -C 6 cycloalkyl, substituted or unsubstituted C 6 -C 10 aryl, substituted or unsubstituted C 7 -C 10 aralkyl; or, R I , R II , R Two or more groups in III , R IV , R V and R VI are bonded to each other to form a ring; R VII and R VIII are each independently selected from substituted or unsubstituted C
  • R I , R II , R V and R VI are hydrogen, and R I , R II , R V and R VI are not simultaneously hydrogen.
  • glycol ester compound may include, but are not limited to:
  • 1,3-propanediol dibenzoate 2-methyl-1,3-propanediol dibenzoate, 2-ethyl-1,3-propanediol dibenzoate, 2,2-dimethyl -1,3-propanediol dibenzoate, (R)-1-phenyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol dibenzoate , 1,3-diphenyl-1,3-propanediol di-n-propionate, 1,3-diphenyl-2-methyl-1,3-propanediol di-n-propionate, 1,3-diphenyl 2-methyl-1,3-propanediol diacetate, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol dibenzoate, 1,3-diphenyl Dimethyl-2,2-dimethyl-1,3-propaned
  • the above-mentioned glycol ester compound is disclosed in CN1213080C, CN1169845C, WO03/068828 and WO 03/068723, and its relevant content is hereby incorporated into the present invention as a reference.
  • the ether compound in the compound B is a diether compound; the diether compound is preferably selected from 1,3-diether compounds represented by formula (III).
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 -C 20 linear alkyl, substituted or Unsubstituted C 3 -C 20 branched chain alkyl, substituted or unsubstituted C 3 -C 20 cycloalkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 7 -Aralkyl of C 20 ; or, two or more groups among R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are bonded to each other to form a ring; R 7 and R 8 each independently selected from substituted or unsubstituted C 1 -C 20 straight chain alkyl, substituted or unsubstituted C 3 -C 20 branched chain alkyl, substituted or unsubstituted C 3 -C 20 cyclo
  • R 1 , R 2 , R 5 and R 6 are hydrogen;
  • R 7 and R 8 are each independently one of substituted or unsubstituted C 1 -C 4 straight chain alkyl, substituted or unsubstituted C 3 -C 4 branched chain alkyl, more preferably methyl ;
  • R3 is any one of methyl, ethyl, n-propyl and isopropyl
  • R4 is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, isopentyl Any one of base, 2-ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl and benzyl
  • R3 is hydrogen
  • R4 is ethyl, n-butyl, sec-butyl Any one of base, tert-butyl, 2-ethylhexyl, cyclohexylethyl, diphenylmethyl, p-chlorophenyl, 1-naphthyl and 1-decalinyl
  • R3 and R4 is the same and is any one of ethyl, n-propyl, isopropyl,
  • R and R 6 are each independently selected from hydrogen, substituted or unsubstituted C 1 -C 6 linear alkane substituted or unsubstituted C 3 -C 6 branched chain alkyl, substituted or unsubstituted C 3 -C 6 cycloalkyl, substituted or unsubstituted C 6 -C 10 aryl, substituted or unsubstituted Substituted C 7 -C 10 aralkyl, n is an integer from 0 to 2; more preferably, R and R 6 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl , isobutyl, tert-butyl, n-pentyl, isopentyl, phenyl, 2-hydroxyethyl or 3-hydroxypropyl, n is 0
  • examples of the alkoxysilane R n Si(OR 6 ) 4-n may include, but are not limited to: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane Silane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-n-pentoxysilane, tetraisopentoxysilane, diethoxydimethoxysilane, tetrakis(2-hydroxyethoxy)silane And one or more of tetrakis(3-hydroxypropoxy)silane, diphenyldimethoxysilane, diphenyldiethoxysilane, propyltrimethoxysilane, propyltriethoxysilane kind.
  • the catalyst components according to the invention comprise, in addition to the abovementioned two or three types of electron donor compounds, titanium, magnesium and halogens.
  • the catalyst component is a reaction product of supporting a titanium-containing compound and compound B, compound C on a magnesium halide, or a reaction product of supporting a titanium-containing compound and compound A, compound B, or compound C, said
  • the halide of magnesium is preferably magnesium dihalide in an activated state, more preferably activated magnesium dichloride.
  • Such magnesium dichloride is well known in the art as a support for Ziegler-Natta catalysts.
  • such magnesium dichloride in an activated state is characterized in that in the X-ray diffraction pattern the most intense diffraction peaks appearing in the diffraction pattern of inactive magnesium dichloride are reduced in intensity and broadened into a halo.
  • the preparation method of the activated magnesium dihalide is well known in the art. Generally, it can be obtained by grinding the inactive magnesium dihalide through a grinder; it can also be obtained by mixing alkylmagnesium halide, alkylmagnesium, alkoxymagnesium or inactive magnesium dihalide with a halide (such as Aluminum halides, halosilanes or halides of titanium) are prepared; it can also be prepared by reacting inactive magnesium dihalides with one or more of esters, alcohols and ether electron donor compounds to form magnesium halide adducts
  • the magnesium halide adduct optionally contains a small amount of water, and then undergoes chemical reaction or heat treatment under negative pressure to remove the coordinated electron donor to obtain activated magnesium dihalide.
  • the activated magnesium dihalide can be prepared in advance, or can be obtained simultaneously during the preparation of the olefin polymerization catalyst component.
  • the titanium-containing compound is selected from one or more of titanium compounds represented by titanium trihalide and the general formula Ti(OR′′) 4-m X′′ m , where R′′ is substituted or unsubstituted Any one of C 1 -C 10 straight-chain alkyl and substituted or unsubstituted C 3 -C 10 branched-chain alkyl, X" is halogen, and m is an integer of 0-4.
  • the titanium-containing compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, monochlorotributoxytitanium, dichlorodibutoxy trichlorobutoxytitanium, monochlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium or titanium trichloride. More preferably, the titanium-containing compound is titanium tetrachloride.
  • the preparation of the olefin polymerization catalyst component of the present invention can be carried out according to various known methods.
  • the preparation method of the solid catalyst component described in CN1006071B can be used, first dissolving the inactive magnesium halide in the solvent system to form a solution, and then adding the titanium-containing compound and the compound B and compound C of the present invention or the compound A of the present invention , compound B and compound C, in the presence of a precipitating agent, by raising the temperature, re-precipitate the olefin polymerization catalyst component containing the active center.
  • Activated magnesium halide is simultaneously generated in the above reaction.
  • the relevant content described in CN1006071B is hereby incorporated into the present invention as a reference.
  • the magnesium halide adduct is prepared first, preferably the magnesium halide adduct is represented by the general formula MgX 1 X 2 ⁇ m(R′′'OH) ⁇ nE ⁇ qH 2 O, and the adduct Compound particles are spherical, where m is 1.0-5.0, n is 0-1.0, q is 0-0.8; X 1 and X 2 are each independently any one of chlorine and bromine; R"' is substituted or unsubstituted Any one of substituted C 1 -C 4 straight chain alkyl and substituted or unsubstituted C 3 -C 4 branched chain alkyl; E is an electron donor compound, which can be ether or ester.
  • m is 1.5 to 3.5, and n is 0 to 0.5.
  • the magnesium halide adduct particle is reacted with titanium-containing compound, compound B, compound C or the magnesium halide adduct particle is reacted with titanium-containing compound, compound A, compound B and compound C to finally obtain activated magnesium halide Catalyst components for olefin polymerization.
  • the preparation of this olefin polymerization catalyst component can be carried out with reference to the methods disclosed in CN1036011C, CN1151183C, CN101565475A, CN101486776B and CN102796213B, and the relevant contents disclosed are hereby fully incorporated into the present invention as a reference.
  • compound A, compound B and compound C can be added before, during or after the reaction of the magnesium halide or magnesium halide adduct with the titanium-containing compound; preferably added in the reaction with the titanium-containing compound .
  • Compound A, Compound B and Compound C can also be selected to be added simultaneously or step by step, and each of Compound A, Compound B and Compound C can also be added in multiple times, and the addition of Compound A, Compound B and Compound C
  • the order can be in any order.
  • the molar ratio of compound B, compound C and the halide of titanium-containing compound and magnesium can be calculated per mole of magnesium. 0.01 ⁇ 0.5:0.005 ⁇ 0.4:5 ⁇ 100:1; preferably, the molar ratio of compound B, compound C and titanium-containing compound to magnesium halide is 0.05 ⁇ 0.35:0.01 ⁇ 0.25:15 ⁇ 90:1; more Preferably, the molar ratio of the compound B, the compound C and the titanium-containing compound to the magnesium halide is 0.05-0.25:0.015-0.15:25-80:1.
  • the halogenation of compound A, compound B, compound C and the titanium-containing compound with magnesium is calculated per mole of magnesium.
  • the molar ratio of compounds can be 0.005 ⁇ 0.4:0.01 ⁇ 0.5:0.005 ⁇ 0.4:5 ⁇ 100:1; preferably, the molar ratio of compound A, compound B, compound C and titanium-containing compound to magnesium halide is 0.01 ⁇ 0.25:0.05 ⁇ 0.35:0.01 ⁇ 0.25:15 ⁇ 90:1; more preferably, the molar ratio of compound A, compound B, compound C and titanium-containing compound to magnesium halide is 0.02 ⁇ 0.18:0.05 ⁇ 0.25:0.015 ⁇ 0.15:25 ⁇ 80:1.
  • a catalyst system for the polymerization of olefins comprising the following components or the reaction product of the following components:
  • At least one external electron donor compound is optionally, at least one organic compound.
  • the olefin polymerization catalyst system of the present invention using the catalyst component according to the present invention not only maintains higher polymerization activity, good Hydrogen tuning sensitivity and high orientation ability, and unexpectedly show excellent olefin copolymerization ability.
  • the alkylaluminum compound may be various alkylaluminum compounds commonly used in the art.
  • the alkylaluminum compound can be one or more of the compounds shown in the alkylaluminum sesquichloride and the general formula AlR I R II R III , where R I , R II and R III in the general formula are independently ground can be any one of chlorine, substituted or unsubstituted C 1 -C 8 straight chain alkyl and substituted or unsubstituted C 3 -C 8 branched chain alkyl, and R I , R II and R At least one of III is any one of a substituted or unsubstituted C 1 -C 8 linear alkyl group and a substituted or unsubstituted C 3 -C 8 branched chain alkyl group.
  • the alkylaluminum compound is triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, monochlorodiethylaluminum, monochlorodiisobutyl Aluminum dichloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride, monoethylaluminum dichloride, 1-isobutylaluminum dichloride, 1-n-butylaluminum dichloride, 1-n-hexylaluminum dichloride and Al 2 One or more of Et 3 Cl 3 .
  • the molar ratio of the alkylaluminum compound calculated as aluminum element to the catalyst component calculated as titanium element can be 1-2000:1, preferably 20-2000:1. 700:1.
  • the external electron donor compound may be various electron donor compounds commonly used in the art.
  • the external electron donor compound may be one or more of carboxylic acid, acid anhydride, ester, ketone, ether, alcohol, organophosphorus and organosilicon compound; preferably organosilicon compound.
  • R a and R b are selected from substituted or unsubstituted C 3 -C 10 branches with or without heteroatoms
  • R c is selected from substituted or One of unsubstituted C 1 -C 10 straight chain alkyl and substituted or unsubstituted C 3 -C 10 branched chain alkyl, preferably methyl, x is 1, y is 1, z is 2 ; or, R b is a substituted or unsubstituted C 3 -C 10 branched alkyl group or a substituted or unsubstituted C 3 -C 10 cycloalkyl group, and R c is methyl, x is 0,
  • examples of the organosilicon compound may be, but not limited to: cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, n-butylcyclohexyldimethoxysilane, diisobutyldimethoxysilane, Methoxysilane, diphenyldimethoxysilane, methyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethylsilane Oxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methoxysilane Dimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane,
  • the amount of the external electron donor compound is 0.005-0.5 moles, preferably 0.01-0.4 Moore.
  • the alkylaluminum compound and optional external electron donor compound may be reacted in contact with the catalyst component alone or as a mixture of the two components.
  • the olefin polymerization catalyst system according to the invention described above is suitable as a catalyst system for olefin polymerization.
  • a prepolymerized catalyst composition for olefin polymerization comprising:
  • the term "prepolymerized catalyst composition” refers to a catalyst composition which has undergone a polymerization step and contains an olefin polymer having a lower degree of prepolymerization than the catalyst components.
  • the prepolymerization ratio is 0.1-1000 g olefin polymer/g catalyst component.
  • the prepolymerization ratio is 0.2-500 g olefin polymer/g catalyst component, more preferably 0.5-100 g olefin polymer/g catalyst component.
  • the same olefin as that used for the polymerization can be used for prepolymerization, preferably propylene or a mixture of propylene and one or more non-propylene ⁇ -olefins with a molar content of up to 20%.
  • the prepolymerization step can be carried out in-line as part of a continuous polymerization process, or independently in a batch operation.
  • the prepolymerization reaction conditions of the present invention can adopt known conditions, and the prepolymerization temperature can be 0-50°C, preferably 10-30°C.
  • a kind of olefin polymerization method comprises under olefin polymerization conditions, one or more olefins and at least a touch.
  • the olefin polymerization method according to the present invention can produce a polymer having a high ethylene content and a high rubber content with a perfect particle shape by using the olefin polymerization catalyst system or the prepolymerized catalyst composition according to the present invention.
  • the olefin polymerization method of the present invention is not particularly limited to the olefin polymerization conditions and the olefin used.
  • the olefin may also contain a small amount of diene if necessary.
  • the polymerization of the olefin can be homopolymerization or copolymerization.
  • the polymerization of the olefin can be carried out according to methods known in the art, for example, the polymerization can be bulk polymerization, gas phase polymerization, slurry polymerization or combined liquid phase bulk-gas phase polymerization.
  • the olefin polymerization temperature can be conventional conditions in this field, for example, the polymerization temperature can be 0°C to 150°C, preferably 60°C to 90°C; the polymerization reaction pressure can be normal pressure or pressure pressure.
  • the present invention includes the following beneficial effects:
  • ester compounds or diether compounds and alkoxysilane compounds as internal electron donors, compared with using ester compounds or diether compounds alone, it shows significantly improved olefin copolymerization ability , while maintaining a high orientation ability; compared with the single use of alkoxysilane compounds, it also shows high orientation ability and olefin copolymerization ability.
  • the prepared catalyst maintains a high At the same time as the orientation ability, the hydrogen adjustment sensitivity of the catalyst and the olefin copolymerization ability are further improved.
  • the polymer particles obtained by using the catalyst system and the prepolymerization catalyst composition of the invention to catalyze olefins have good particle shape and high sphericity of the polymer particles.
  • test methods involved are as follows:
  • Polymer isotactic index (II) Measured by n-heptane extraction method (n-heptane boiling extraction for 6 hours), about 2 grams of dry polymer samples are placed in a Soxhlet extractor with boiling normal Heptane was extracted for 6 hours, and then the residue was dried to constant weight, and the ratio of the obtained residue weight (g) to 2 was the isotactic index.
  • Xylene soluble content (X.S): Put the copolymer in a vacuum drying oven at 75°C and bake for 30 minutes, then quickly put it in a desiccator to cool to room temperature; take about 2g of the copolymer, weigh it, and put it in 500ml In the Erlenmeyer flask, add 200ml of xylene and heat to dissolve, cool the dissolved sample at room temperature for 12-14min, then put it in a constant temperature water bath at 25°C for cooling and crystallization for 60min, filter the crystallization, heat and bake the soluble matter , Weigh and calculate the content.
  • Ethylene content carried out by Magna-IR760 infrared spectrometer of Nicolet Company, hot pressing film forming method, 170°C, 20MPa.
  • SPHT Polymer screening and average sphericity
  • the liquid was filtered off.
  • Add 80mL of titanium tetrachloride raise the temperature to 120°C, maintain at 120°C for 30min, then filter off the liquid; repeat the above operation once.
  • the obtained solid was washed 5 times with 60° C. hexane (the amount of hexane was 80 mL/time); and the obtained solid was vacuum-dried to obtain a spherical catalyst component.
  • the content of titanium in the catalyst component was 2.4% by weight.
  • the liquid-phase bulk polymerization of propylene was carried out in a 5L stainless steel autoclave. Under the protection of nitrogen, 5 mL of triethylaluminum in hexane (0.5 mmol/mL) and 1 mL of cyclohexylmethyldimethoxysilane in hexane (0.1 mmol/mL) were successively added to the reactor. and 9 mg of the above spherical catalyst component. The autoclave was closed and 6.5 L of hydrogen (standard volume) and 2.3 L of liquid propylene were added. Raise the temperature to 70°C and react for 1 hour. Then, the temperature is lowered, the pressure is released, the material is discharged, and dried to obtain polypropylene. The polymerization results are shown in Table 1, and the polymer screening results are shown in Table 7.
  • the spherical catalyst component was prepared by the same method as in Example 1 (1), except that the amount of tetraethoxysilane was changed to 1.25 mL.
  • the content of titanium in the catalyst component was 2.5% by weight.
  • Example 2 The same method as in Example 1 (3) was used to carry out olefin copolymerization, except that the catalyst component was the catalyst component prepared in the above step (1) of this example.
  • the aggregation results are shown in Table 2.
  • the spherical catalyst component was prepared by the same method as in Example 1(1), except that tetraethoxysilane was not used.
  • the content of titanium in the catalyst component was 2.3% by weight.
  • Example 2 The same method as in Example 1 (3) was used for olefin copolymerization, except that the catalyst component was the catalyst component prepared in the above-mentioned step (1) of this comparative example.
  • the aggregation results are shown in Table 2.
  • the spherical catalyst component was prepared by the same method as in Example 1 (1), except that diisobutyl phthalate was not used.
  • the content of titanium in the catalyst component was 3.5% by weight.
  • Example 2 The same method as in Example 1 (3) was used for olefin copolymerization, except that the catalyst component was the catalyst component prepared in the above-mentioned step (1) of this comparative example.
  • the aggregation results are shown in Table 2.
  • the temperature was slowly raised to 110° C., and 0.4 mL of ethyl 2-hydroxybenzoate, 1.5 mL of diisobutyl phthalate and 0.2 mL of tetraethoxysilicon were added during the temperature rise.
  • the liquid was filtered off.
  • Add 80mL of titanium tetrachloride raise the temperature to 120°C, maintain at 120°C for 30min, then filter off the liquid; repeat the above operation once.
  • the obtained solid was washed 5 times with 60° C. hexane (the amount of hexane was 80 mL/time); and the obtained solid was vacuum-dried to obtain a spherical catalyst component.
  • the content of titanium in the catalyst component was 2.2% by weight.
  • the liquid-phase bulk polymerization of propylene was carried out in a 5L stainless steel autoclave. Under the protection of nitrogen, 5 mL of triethylaluminum in hexane (0.5 mmol/mL) and 1 mL of cyclohexylmethyldimethoxysilane in hexane (0.1 mmol/mL) were successively added to the reactor. and 9 mg of the above spherical catalyst component. The autoclave was closed and 6.5 L of hydrogen (standard volume) and 2.3 L of liquid propylene were added. Raise the temperature to 70°C and react for 1 hour. Then, the temperature is lowered, the pressure is released, the material is discharged, and dried to obtain polypropylene. The aggregation results are shown in Table 3.
  • the spherical catalyst component was prepared by the same method as in Example 3 (1), except that the amount of tetraethoxysilane was 0.4 mL.
  • the content of titanium in the catalyst component was 2.4% by weight.
  • Example 3 (3) The same method as in Example 3 (3) was used to carry out olefin copolymerization, except that the catalyst component was the catalyst component prepared in the above step (1) of this example.
  • the aggregation results are shown in Table 4.
  • the spherical catalyst component was prepared by the same method as in Example 3 (1), except that the amount of tetraethoxysilane was 1.0 mL.
  • the content of titanium in the catalyst component was 2.2% by weight.
  • Example 3 (3) The same method as in Example 3 (3) was used to carry out olefin copolymerization, except that the catalyst component was the catalyst component prepared in the above step (1) of this example.
  • the aggregation results are shown in Table 4.
  • the spherical catalyst component was prepared by the same method as in Example 4(1), except that tetraethoxysilane was not used.
  • the content of titanium in the catalyst component was 2.3% by weight.
  • Example 4 (3) The same method as in Example 4 (3) was used to carry out olefin copolymerization, except that the catalyst component was the catalyst component prepared in the above-mentioned step (1) of this comparative example.
  • the aggregation results are shown in Table 4.
  • the spherical catalyst component was prepared by the same method as in Example 4(1), except that diisobutyl phthalate was not used.
  • the content of titanium in the catalyst component was 7.3% by weight.
  • Example 4 (3) The same method as in Example 4 (3) was used to carry out olefin copolymerization, except that the catalyst component was the catalyst component prepared in the above-mentioned step (1) of this comparative example.
  • the aggregation results are shown in Table 4.
  • the spherical catalyst component is prepared in the same manner as in Example 4 (1), except that 0.4 mL of ethyl 2-hydroxybenzoate is changed into 0.4 mL of (2-hydroxyethyl) methacrylate, and o-phthalic acid is not used. Diisobutyl dicarboxylate. The content of titanium in the catalyst component was 4.3% by weight.
  • Example 4 (3) The same method as in Example 4 (3) was used to carry out olefin copolymerization, except that the catalyst component was the catalyst component prepared in the above-mentioned step (1) of this comparative example.
  • the aggregation results are shown in Table 4.
  • Adopt the method identical with embodiment 3 (1) to prepare spherical catalyst component difference is that 1.5mL diisobutyl phthalate is changed into 1.2mL 2-isopropyl-2-isoamyl-1, 3-Dimethoxypropane.
  • the content of titanium in the catalyst component was 2.5% by weight.
  • catalyst component is the catalyst component prepared by the above-mentioned step (1) of this embodiment.
  • the aggregation results are shown in Table 6.
  • the spherical catalyst component was prepared by the same method as in Example 6 (1), except that the amount of tetraethoxysilane was changed to 0.4 mL.
  • the content of titanium in the catalyst component was 2.5% by weight.
  • Example 6 The same method as in Example 6 (3) was used to carry out olefin copolymerization, except that the catalyst component was the catalyst component prepared in the above step (1) of this example.
  • the aggregation results are shown in Table 6.
  • a spherical catalyst component was prepared in the same manner as in Example 6(1), except that tetraethoxysilane was not used.
  • the content of titanium in the catalyst component was 2.6% by weight.
  • Example 6 The same method as in Example 6 (3) was used to carry out olefin copolymerization, except that the catalyst component was the catalyst component prepared in the above-mentioned step (1) of this comparative example.
  • the aggregation results are shown in Table 6.
  • Table 1 and Table 2 respectively list the polymerization results of the catalyst components, catalyst systems and prepolymerized catalyst compositions obtained in Examples 1-2 and Comparative Examples 1-2 when they are used for olefin polymerization.
  • the catalyst system of the present invention prepared by the catalyst component of the present invention comprising electron donor compounds B and C and the prepolymerized catalyst composition of the present invention are in the same hydrogen fraction When used for homopolymerization of olefins under low pressure conditions, it still has high polymerization activity, good hydrogen adjustment sensitivity and high orientation ability.
  • Comparative Example 2 shows that when only the electron donor compound C is contained in the catalyst component, the catalyst system and the prepolymerized catalyst composition have too low orientation ability and have no practical application value in the olefin industrial application.
  • the data in Table 2 shows that when the catalyst system of the present invention prepared by the catalyst component of the present invention containing electron donors B and C and the prepolymerized catalyst composition of the present invention catalyze the copolymerization of ethylene and propylene, the ethylene content in the resin is significantly increased, This shows that the catalyst component of the present invention and the catalyst system and prepolymerized catalyst composition prepared from the catalyst component of the present invention have significantly improved olefin copolymerization ability.
  • Table 3 and Table 4 respectively list the polymerization results of the catalyst components, catalyst systems and prepolymerized catalyst compositions obtained in Examples 3-5 and Comparative Examples 3-5 when they are used for olefin polymerization. Similar to the results shown in Table 1, it can be seen from Table 3 that compared to the existing similar catalyst technology, the catalyst system of the present invention prepared by the catalyst component of the present invention containing electron donor compounds A, B and C and the catalyst system of the present invention When the prepolymerized catalyst composition is used for olefin homopolymerization under the same hydrogen partial pressure condition, it still has high polymerization activity, good hydrogen adjustment sensitivity and high orientation ability.
  • the hydrogen adjustment sensitivity of the catalyst system and the prepolymerized catalyst composition prepared by the catalyst component containing electron donor compounds A, B and C in the present invention is compared with that of the catalyst that does not contain electron donor compound A in the catalyst component
  • the system and prepolymerized catalyst composition are somewhat improved.
  • the catalyst system of the present invention prepared from the catalyst component of the present invention containing electron donor compounds A, B and C at the same time is comparable to the prepared catalyst of the present invention.
  • the polymerization catalyst composition catalyzes the copolymerization of ethylene and propylene
  • the ethylene content in the resin is significantly increased, which shows that the catalyst component containing electron donor compounds A, B and C of the present invention and the catalyst system and preparation prepared by the catalyst component
  • the polymerization catalyst composition also has significantly improved olefin copolymerization ability, and the olefin copolymerization ability is stronger compared with the catalyst system of the present invention and the prepolymerization catalyst composition of the present invention that do not contain the electron donor compound A.
  • a point mentioned in the value is that Comparative Examples 4 and 5 show that when the catalyst components contain electron donor compounds A and C at the same time, the orientation ability of the further prepared catalyst system and prepolymerized catalyst composition is too low. There is no practical application value in the application.
  • Table 5 and Table 6 list the polymerization results when the catalyst components, catalyst system and prepolymerized catalyst composition obtained in Examples 6-7 and Comparative Example 6 are used for olefin polymerization.
  • Tables 5 and 6 it can also be clearly seen that when the present invention uses alkoxysilane compounds, 2-hydroxybenzoyl compounds, and 1,3-diether compounds as internal electron donors, the obtained The catalyst system of the present invention comprising the catalyst component of the present invention and the prepolymerized catalyst composition of the present invention also exhibit excellent overall performance, that is, compared with the existing similar catalyst technology, the catalyst system of the present invention comprising the catalyst component of the present invention and The prepolymerized catalyst composition of the present invention exhibits obviously improved olefin copolymerization ability while maintaining high polymerization activity, good hydrogen adjustment sensitivity and high orientation ability.
  • the present invention uses alkoxysilane compounds compounded with 2-hydroxybenzoyl compounds and 1,3-diether compounds as catalyst components, catalyst systems and prepolymerized catalyst compositions as internal electron donors.
  • the obtained polymer particles When used in olefin polymerization, the obtained polymer particles have good shape, high sphericity and little fine powder.

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Abstract

本发明提供了一种烯烃聚合催化剂组分、催化剂体系及预聚合催化剂组合物和烯烃聚合方法，属于烯烃聚合催化剂领域。该催化剂组分含有镁、钛、卤素和内给电子体，内给电子体包括化合物A、化合物B和化合物C，化合物A选自如式(Ⅰ)所示的羟基苯甲酰类化合物，化合物B选自除化合物A以外的酯类化合物或醚类化合物，化合物C选自如式R nSi(OR 6) 4-n所示的烷氧基硅烷，其中，化合物A的含量可以为零。由包含有催化剂组分和助催化剂组分或两者反应产物的催化剂体系或进一步预聚合制备的预聚合催化剂组合物用于烯烃共聚合时，显示出优异的烯烃共聚合能力，且保持有良好的聚合活性、定向能力和氢调敏感性，所得聚合物粒子的形态好、球形度高、细粉少。

Description

烯烃聚合催化剂组分、催化剂体系及预聚合催化剂组合物和烯烃聚合方法
相关申请的交叉引用
本发明要求享有2021年10月28日提交的名称为“烯烃聚合催化剂组分、催化剂体系及应用和烯烃聚合方法”，申请号为CN202111264973.2的中国专利申请的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本发明属于烯烃聚合催化剂技术领域，具体涉及一种烯烃聚合催化剂组分、催化剂体系及预聚合催化剂组合物和烯烃聚合方法。
背景技术
将钛化合物及给电子体化合物负载于活性卤化镁上来制备Ziegler-Natta催化剂在现有技术中是众所周知的。特别地，在用于烯烃(特别是丙烯)聚合时，为了改善催化剂的聚合活性、立构定向性、氢调敏感性及烯烃共聚合能力等，给电子体化合物是催化剂组分中必不可少的成分之一。
随着给电子体化合物的发展，聚烯烃催化剂不断地更新换代。迄今为止，已有许多专利公开了大量的适用于制备Ziegler-Natta催化剂的给电子体化合物，主要包括：邻苯二甲酸酯类化合物(EP0045977)、1,3-二醚类化合物(EP0361493、EP0728724)、1,3-二酮类化合物(CN1105671A)、特殊取代的丙二酸酯类化合物(CN1236732A、CN1236733A、CN1236734A、CN1292800A)、琥珀酸酯类化合物(WO0063261、US6825309B2、US7005487B2)、β-取代戊二酸酯类化合物(WO0055215)、氰基酯类化合物(CN1242780A)、二胺类化合物(CN1087918A)、顺丁烯二酸二酯类化合物(WO03022894)以及特殊的多元酯类化合物(CN1436766A、CN1436796A)等。
采用不同的内给电子体化合物会使所制备的催化剂具有不同的特性，如有些催化剂具有较高的聚合活性，有些催化剂具有较好的氢调敏感性，有些催化剂制备的聚烯烃树脂具有较宽的分子量分布(如CN1436766A和CN1552740A所公开的二元醇酯类化合物及其催化剂)，但在聚烯烃的工业生产中，非常需要聚合所使用的催化剂具有十分优良的综合性能。在现有技术中，人们通常采用在催 化剂制备过程中加入多种内给电子化合物的方法来改善催化剂的综合性能。如US6825309B2所公开的技术中，将琥珀酸酯和邻苯二甲酸酯复配制备的催化剂不仅保持了琥珀酸酯单内给电子体催化剂用于丙烯聚合所得聚合物宽分子量分布的特点，而且进一步提高了催化剂的立构定向性；CN1743346A所公开的催化剂组分和催化剂，采用将1,3-二元醇酯与邻苯二甲酸二丁酯、苯甲酸乙酯复配的方法制备的催化剂用于丙烯聚合得到的聚合物具有较高的等规度和较宽的分子量分布。
随着社会发展的需要，具有良好烯烃共聚性能的催化剂成为本领域内十分重要的一个研究方向。CN102796213B选用羟基苯甲酰类化合物与邻苯二甲酸酯类化合物或二醚类化合物复配制备的催化剂，用于丙烯均聚合时表现出高的聚合活性、良好的氢调敏感性和高的定向能力。但实际应用显示，该类催化剂在用于烯烃共聚合反应时，催化剂的烯烃共聚能力相对不足。在本领域内，烷氧基硅烷类化合物通常被用做外给电子体，用于改善催化剂体系的氢调敏感性。CN103509137A发现，烷氧基硅烷化合物在用于沉淀析出法制备烯烃聚合催化剂组分时，可有效缩短催化剂组分的制备时间，同时对催化剂的颗粒形态和聚合物细粉含量具有改善的作用。CN1373777A发现，烷氧基硅烷在用于乙烯聚合催化剂制备时，可以提高催化剂的聚合活性和氢调敏感性。
发明内容
本发明的目的在于提供一种用于烯烃聚合的催化剂组分，该催化剂组分与烷基铝及任选的外给电子体化合物一起用于烯烃(特别是乙烯和丙烯)共聚合时，显示出优异的烯烃共聚合能力，同时还保持有良好的聚合活性、定向能力和氢调敏感性。另外，该催化剂组分及其催化剂体系催化烯烃所得聚合物粒子的形态很好。
根据本发明的一个方面，提供了一种烯烃聚合催化剂组分，该催化剂组分含有镁、钛、卤素和内给电子体；所述内给电子体包括：化合物B和化合物C；其中，
所述化合物B选自除式(Ⅰ)所示的羟基苯甲酰类化合物以外的酯类化合物和醚类化合物中的一种或多种；
Figure PCTCN2022127883-appb-000001
式(Ⅰ)中，R 1选自氢、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基，R 2、R 3、R 4和R 5各自独立地选自氢、卤素、硝基、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基；或者R 2、R 3、R 4和R 5中的两个或两个以上基团相互键合成环；
所述化合物C选自如式R nSi(OR 6) 4-n所示的烷氧基硅烷；式R nSi(OR 6) 4-n中，R和R 6各自独立地选自氢、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基，n为0～3的整数。
根据本发明的另一个方面，提供了一种烯烃聚合催化剂组分，该催化剂组分含有镁、钛、卤素和内给电子体；所述内给电子体包括化合物A、化合物B和化合物C；其中，
所述化合物A选自如式(Ⅰ)所示的羟基苯甲酰类化合物；所述化合物B选自除化合物A以外的酯类化合物和醚类化合物中的一种或多种；所述化合物C选自如式R nSi(OR 6) 4-n所示的烷氧基硅烷；
Figure PCTCN2022127883-appb-000002
式(Ⅰ)中，R 1选自氢、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20 的芳基、取代或未取代的C 7-C 20的芳烷基；R 2、R 3、R 4和R 5各自独立地选自氢、卤素、硝基、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基；或者R 2、R 3、R 4和R 5中的两个或两个以上基团相互键合，以形成环；
式R nSi(OR 6) 4-n中，R和R 6各自独立地选自氢、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基，n为0～3的整数。
根据本发明，优选地，式(Ⅰ)中，R 1选自氢、取代或未取代的C 1-C 6的直链烷基、取代或未取代的C 3-C 6的支链烷基、取代或未取代的C 3-C 6的环烷基、取代或未取代的C 6-C 10的芳基、取代或未取代的C 7-C 10的芳烷基；R 2、R 3、R 4和R 5各自独立地选自氢、取代或未取代的C 1-C 8的直链烷基、取代或未取代的C 3-C 8的支链烷基、取代或未取代的C 3-C 6的环烷基、取代或未取代的C 6-C 10的芳基、取代或未取代的C 7-C 10的芳烷基。
根据本发明，优选地，式(Ⅰ)中，R 1选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、正己基、苄基或苯乙基；R 2、R 3、R 4和R 5各自独立地选自氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、环戊基、正己基、正庚基或甲苯基。
根据本发明，优选地，在化合物A为式(Ⅰ)所示的羟基苯甲酰类化合物时，化合物A选自4-羟基苯甲酸类化合物、4-羟基苯甲酸酯类化合物、2-羟基苯甲酸类化合物和2-羟基苯甲酸酯类化合物中的一种或多种；更优选为2-羟基苯甲酸类化合物和2-羟基苯甲酸酯类化合物中的一种或多种。
根据本发明，化合物A的具体实例可以包括但不限于：2-羟基苯甲酸甲酯、2-羟基苯甲酸乙酯、2-羟基苯甲酸正丙酯、2-羟基苯甲酸异丙酯、2-羟基苯甲酸正丁酯、2-羟基苯甲酸异丁酯、2-羟基苯甲酸正戊酯、2-羟基苯甲酸正己酯、2-羟基-3-甲基苯甲酸甲酯、2-羟基-4-甲基苯甲酸甲酯、2-羟基-5-甲基苯甲酸甲酯、2-羟基-3-乙基苯甲酸甲酯、2-羟基-4-乙基苯甲酸甲酯、2-羟基-5-乙基苯甲酸甲酯、2-羟基-3-甲基苯甲酸乙酯、2-羟基-4-甲基苯甲酸乙酯、2-羟基-5-甲基苯甲酸乙酯、2-羟基-3-乙基苯甲酸乙酯、2-羟基-4-乙基苯甲酸乙酯、2-羟基-5-乙基苯甲酸乙酯、2-羟基-3-甲基苯甲酸正丙酯、2-羟基-4-甲基苯甲酸正丙酯、2-羟基-5-甲基苯甲酸 正丙酯、2-羟基-3-乙基苯甲酸正丙酯、2-羟基-4-乙基苯甲酸正丙酯、2-羟基-5-乙基苯甲酸正丙酯、2-羟基-3-甲基苯甲酸异丙酯、2-羟基-4-甲基苯甲酸异丙酯、2-羟基-5-甲基苯甲酸异丙酯、2-羟基-3-乙基苯甲酸异丙酯、2-羟基-4-乙基苯甲酸异丙酯、2-羟基-5-乙基苯甲酸异丙酯、2-羟基-3-甲基苯甲酸异丁酯、2-羟基-4-甲基苯甲酸异丁酯、2-羟基-5-甲基苯甲酸异丁酯、2-羟基-3-乙基苯甲酸异丁酯、2-羟基-4-乙基苯甲酸异丁酯、2-羟基-5-乙基苯甲酸异丁酯、2-羟基-3-正丙基苯甲酸乙酯、2-羟基-4-正丙基苯甲酸乙酯、2-羟基-5-正丙基苯甲酸乙酯、2-羟基-4-异丙基苯甲酸乙酯、2-羟基-4-异丁基苯甲酸乙酯、2-羟基-4-叔丁基苯甲酸乙酯、2-羟基-4-正戊基苯甲酸乙酯、2-羟基-4-异戊基苯甲酸乙酯和2-羟基-4-环戊基苯甲酸乙酯。
根据本发明，所述化合物B中的酯类化合物选自一元脂肪族羧酸酯、多元脂肪族羧酸酯、一元芳香族羧酸酯、多元芳香族羧酸酯和二元醇酯化合物中的一种或多种；优选为多元芳香族羧酸酯；更优选为多元芳香族羧酸烷基酯；进一步优选为二元芳香族羧酸烷基酯。
根据本发明，所述二元芳香族羧酸烷基酯为邻苯二甲酸烷基酯，优选为邻苯二甲酸的C 1-C 10的直链烷基酯、邻苯二甲酸的C 3-C 10的支链烷基酯和邻苯二甲酸的C 3-C 10的环烷基酯中的一种或多种。
本发明中，术语“一元脂肪族羧酸酯”是指由一元脂肪族羧酸与一元醇通过酯化反应形成的化合物。术语“多元脂肪族羧酸酯”是指由多元脂肪族羧酸与一元醇通过酯化反应形成的化合物。术语“一元芳香族羧酸酯”是指由一元芳香族羧酸与一元醇通过酯化反应形成的化合物。术语“多元芳香族羧酸酯”是指由多元芳香族羧酸与一元醇通过酯化反应形成的化合物。
本发明中，所述一元脂肪族羧酸酯、多元脂肪族羧酸酯、一元芳香族羧酸酯和多元芳香族羧酸酯的实例可以为：苯甲酸酯、邻苯二甲酸酯、丙二酸酯、琥珀酸酯、戊二酸酯、新戊酸酯和碳酸酯；优选为苯甲酸烷基酯、邻苯二甲酸烷基酯、丙二酸烷基酯、琥珀酸烷基酯、戊二酸烷基酯、新戊酸烷基酯和碳酸烷基酯。
具体地，本发明中，所述一元脂肪族羧酸酯、多元脂肪族羧酸酯、一元芳香族羧酸酯和多元芳香族羧酸酯的实例可以包括但不限于：苯甲酸乙酯、邻苯二甲酸酯二乙酯、邻苯二甲酸酯二异丁酯、邻苯二甲酸酯二正丁酯、邻苯二甲酸酯二异辛酯、邻苯二甲酸酯二正辛酯、丙二酸二乙酯、丙二酸二丁酯、丙二酸二异丁酯、2,3-二异丙基琥珀酸二乙酯、2,3-二异丙基琥珀酸二异丁酯、2,3-二异丙基 琥珀酸二正丁酯、2,3-二异丙基琥珀酸二甲酯、2,2-二甲基琥珀酸二异丁酯、2-乙基-2-甲基琥珀酸二异丁酯、2-乙基-2-甲基琥珀酸二乙酯、戊二酸二乙酯、戊二酸二正丁酯、戊二酸二异丁酯、碳酸二甲酯、碳酸二乙酯、碳酸二异丁酯、己二酸二乙酯、己二酸二正丁酯、癸二酸二乙酯、癸二酸二正丁酯、顺丁烯二酸二乙酯、顺丁烯二酸二正丁酯、萘二羧酸二乙酯、萘二羧酸二正丁酯、偏苯三酸三乙酯、偏苯三酸三正丁酯、联苯三酸三乙酯、联苯三酸三正丁酯、均苯四酸四乙酯和均苯四酸四正丁酯。
本发明中，术语“二元醇酯化合物”是指二元醇与一元羧酸或多元羧酸通过酯化反应形成的化合物。例如，所述二元醇酯化合物可以为式(Ⅱ)所示的化合物。
Figure PCTCN2022127883-appb-000003
式(Ⅱ)中，R I、R II、R III、R IV、R V和R VI各自独立地选自氢、取代或未取代的C 1-C 10的脂肪烃基、取代或未取代的C 6-C 10的芳基、取代或未取代的C 7-C 10的芳烷基；或者，R I、R II、R III、R IV、R V和R VI中的两个或两个以上基团相互键合，以生成环；R VII和R VIII各自独立地选自取代或未取代的C 1-C 10的直链烷基、取代或未取代的C 3-C 10的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳基脂肪烃基。。
优选地，式(Ⅱ)中，R I、R II、R III、R IV、R V和R VI各自独立地选自氢、取代或未取代的C 1-C 6的直链烷基、取代或未取代的C 1-C 6的支链烷基、取代或未取代的C 2-C 6的直链烯基、取代或未取代的C 3-C 6的支链烯基、取代或未取代的C 3-C 6的环烷基、取代或未取代的C 6-C 10的芳基、取代或未取代的C 7-C 10的芳烷基；或者，R I、R II、R III、R IV、R V和R VI中的两个或两个以上基团相互键合，以形成环；R VII和R VIII各自独立地选自取代或未取代的C 1-C 6的直链烷基、取代或未取代的C 3-C 6的支链烷基、取代或未取代的C 3-C 6的环烷基、取代或未取代的C 6-C 10的芳基、取代或未取代的C 7-C 10的芳烷基、取代或未取代的C 7-C 10的芳烯基。
更优选地，式(Ⅱ)中，R I、R II、R V和R VI中的至少一个为氢，且R I、R II、R V和R VI不同时为氢。
进一步优选地，式(Ⅱ)中，R I和R II中至少有一个为氢，且在R I和R II中仅有一个为氢时，R I和R II中的另一个基团为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、苯基和卤代苯基中的一种；R V和R VI中至少有一个为氢，且在R V和R VI中仅有一个为氢时，R V和R VI中的另一个基团为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、苯基和卤代苯基中的一种；R III和R IV各自独立地为氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、烯丙基、正戊基、异戊基和正己基中的一种；或者，R III和R IV相互键合，以形成取代或未取代的芴基；R VII和R VIII各自独立地为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、新戊基、环戊基、环己基、苯基、卤代苯基、甲苯基、卤代甲基苯基、苄基、苯乙基和苯乙烯基中的一种。
具体地，所述二元醇酯化合物的实例可以包括但不限于：
1,3-丙二醇二苯甲酸酯、2-甲基-1,3-丙二醇二苯甲酸酯、2-乙基-1,3-丙二醇二苯甲酸酯、2,2-二甲基-1,3-丙二醇二苯甲酸酯、(R)-1-苯基-1,3-丙二醇二苯甲酸酯、1,3-二苯基-1,3-丙二醇二苯甲酸酯、1,3-二苯基-1,3-丙二醇二正丙酸酯、1,3-二苯基-2-甲基-1,3-丙二醇二正丙酸酯、1,3-二苯基-2-甲基-1,3-丙二醇二乙酸酯、1,3-二苯基-2,2-二甲基-1,3-丙二醇二苯甲酸酯、1,3-二苯基-2,2-二甲基-1,3-丙二醇二正丙酸酯、1,3-二叔丁基-2-乙基-1,3-丙二醇二苯甲酸酯、1,3-二苯基-1,3-丙二醇二乙酸酯、1,3-二异丙基-1,3-丙二醇二(4-正丁基苯甲酸)酯、1-苯基-2-氨基-1,3-丙二醇二苯甲酸酯、1-苯基-2-甲基-1,3-丁二醇二苯甲酸酯、1-苯基-2-甲基-1,3-丁二醇二新戊酸酯、3-正丁基-2,4-戊二醇二苯甲酸酯、3,3-二甲基-2,4-戊二醇二苯甲酸酯、(2S,4S)-(+)-2,4-戊二醇二苯甲酸酯、(2R,4R)-(+)-2,4-戊二醇二苯甲酸酯、2,4-戊二醇二(对氯苯甲酸)酯、2,4-戊二醇二(间氯苯甲酸)酯、2,4-戊二醇二(对溴苯甲酸)酯、2,4-戊二醇二(邻溴苯甲酸)酯、2,4-戊二醇二(对甲基苯甲酸)酯、2,4-戊二醇二(对叔丁基苯甲酸)酯、2,4-戊二醇二(对正丁基苯甲酸)酯、2-甲基-1,3-戊二醇二(对氯苯甲酸)酯、2-甲基-1,3-戊二醇二(对甲基苯甲酸)酯、2-正丁基-1,3-戊二醇二(对甲基苯甲酸)酯、2-甲基-1,3-戊二醇二(对叔丁基苯甲酸)酯、2-甲基-1,3-戊二醇二新戊酸酯、2-甲基-3-肉桂酰氧基-1-正戊醇苯甲酸酯、2,2-二甲基-1,3-戊二醇二苯甲酸酯、2,2-二甲基-3-肉桂酰氧基-1-正戊醇苯甲酸酯、2-乙基-1,3-戊二醇二苯甲酸酯、2-正丁基-1,3-戊二醇二苯甲酸酯、2-烯丙基-1,3-戊二醇二苯甲酸酯、2-甲基-1,3-戊二醇二苯甲酸酯、2-乙基-1,3-戊二醇二苯甲酸酯、2-正丙基-1,3-戊二醇二苯甲酸酯、2-正丁基-1,3-戊二醇二苯甲酸酯、2,2-二正丙基-1,3-戊 二醇二苯甲酸酯、1,3-戊二醇二(对氯苯甲酸)酯、1,3-戊二醇二(间氯苯甲酸)酯、1,3-戊二醇二(对溴苯甲酸)酯、1,3-戊二醇二(邻溴苯甲酸)酯、1,3-戊二醇二(对甲基苯甲酸)酯、1,3-戊二醇二(对叔丁基苯甲酸)酯、1,3-戊二醇二(对丁基苯甲酸)酯、3-肉桂酰氧基-1-正戊醇苯甲酸酯、1,3-戊二醇二肉桂酸酯、1,3-戊二醇二正丙酸酯、2-乙基-1,3-戊二醇二苯甲酸酯、2-正丁基-1,3-戊二醇二苯甲酸酯、2-烯丙基-1,3-戊二醇二苯甲酸酯、2,2,4-三甲基-1,3-戊二醇二异丙基甲酸酯、1-三氟甲基-3-甲基-2,4-戊二醇二苯甲酸酯、2,4-戊二醇二对氟代甲基苯甲酸酯、2,4-戊二醇二(2-呋喃甲酸)酯、2-甲基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3-甲基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、4-甲基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、5-甲基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、6-甲基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3-乙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、4-乙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、5-乙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、6-乙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3-正丙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、4-正丙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、5-正丙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、6-正丙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3-正丁基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、4-正丁基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、5-正丁基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、6-正丁基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3,5-二甲基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3,5-二乙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3,5-二正丙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3,5-二正丁基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3,3-二甲基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3,3-二乙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3,3-二正丙基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3,3-二正丁基-6-(1-正庚烯)基-2,4-庚二醇二苯甲酸酯、3-乙基-3,5-庚二醇二苯甲酸酯、4-乙基-3,5-庚二醇二苯甲酸酯、5-乙基-3,5-庚二醇二苯甲酸酯、3-正丙基-3,5-庚二醇二苯甲酸酯、4-正丙基-3,5-庚二醇二苯甲酸酯、3-正丁基-3,5-庚二醇二苯甲酸酯、2,3-二甲基-3,5-庚二醇二苯甲酸酯、2,4-二甲基-3,5-庚二醇二苯甲酸酯、2,5-二甲基-3,5-庚二醇二苯甲酸酯、2,6-二甲基-3,5-庚二醇二苯甲酸酯、3,5-二甲基-3,5-庚二醇二苯甲酸酯、4,4-二甲基-3,5-庚二醇二苯甲酸酯、4,5-二甲基-3,5-庚二醇二苯甲酸酯、4,6-二甲基-3,5-庚二醇二苯甲酸酯、6,6-二甲基-3,5-庚二醇二苯甲酸酯、2-甲基-3-乙基-3,5-庚二醇二苯甲酸酯、2-甲基-4-乙基-3,5-庚二醇二苯甲酸酯、2-甲基-5-乙基-3,5-庚二醇二苯甲酸酯、3-甲基-3-乙基-3,5-庚二醇二 苯甲酸酯、3-甲基-4-乙基-3,5-庚二醇二苯甲酸酯、3-甲基-5-乙基-3,5-庚二醇二苯甲酸酯、4-甲基-3-乙基-3,5-庚二醇二苯甲酸酯、4-甲基-4-乙基-3,5-庚二醇二苯甲酸酯、9,9-双(苯甲酰氧基甲基)芴、9,9-双((间甲氧基苯甲酰氧基)甲基)芴、9,9-双((间氯苯甲酰氧基)甲基)芴、9,9-双((对氯苯甲酰氧基)甲基)芴、9,9-双(肉桂酰氧基甲基)芴、9-(苯甲酰氧基甲基)-9-(丙酰氧基基甲基)芴、9,9-双(丙酰氧基甲基)芴、9,9-双(丙烯酰氧基甲基)芴和9,9-双(新戊酰氧基甲基)芴。
本发明中上述的二元醇酯化合物公开于CN1213080C、CN1169845C、WO03/068828和WO 03/068723中，其相关内容在此引入本发明作为参考。
根据本发明，所述化合物B中的醚类化合物为二醚类化合物；所述二醚类化合物优选自如式(Ⅲ)所示的1,3-二醚类化合物。
Figure PCTCN2022127883-appb-000004
式(Ⅲ)中，R 1、R 2、R 3、R 4、R 5和R 6各自独立地选自氢、卤素、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基；或者，R 1、R 2、R 3、R 4、R 5和R 6中的两个或两个以上基团相互键合，以形成环；R 7和R 8各自独立地选自取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基。
优选地，式(Ⅲ)中，R 1、R 2、R 5和R 6为氢；
R 7和R 8各自独立地为取代或未取代的C 1-C 4的直链烷基、取代或未取代的C 3-C 4的支链烷基中的一种，更优选为甲基；
R 3为甲基、乙基、正丙基和异丙基中的任意一种，R 4为乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、异戊基、2-乙基己基、环戊基、环己基、甲基环己基、苯基和苄基中的任意一种；或者，R 3为氢，R 4为乙基、正丁基、仲丁基、叔丁基、2-乙基己基、环己基乙基、二苯基甲基、对氯苯基、1-萘基和1-十氢萘基中的任意一种；或者，R 3和R 4相同，且为乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、新戊基、苯基、苄基、环己基和环戊基中的任意一种；或者，R 3和R 4相互键合，以形成环戊二烯基、芴基或茚基。
本发明中上述的1,3-二醚类化合物公开于CN1015062B和CN1121368C中，其公开的相关内容全部引入本发明作为参考。
根据本发明，优选地，所述烷氧基硅烷R nSi(OR 6) 4-n中，R和R 6各自独立地选自氢、取代或未取代的C 1-C 6的直链烷基、取代或未取代的C 3-C 6的支链烷基、取代或未取代的C 3-C 6的环烷基、取代或未取代的C 6-C 10的芳基、取代或未取代的C 7-C 10的芳烷基，n为0～2的整数；更优选地，R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、叔丁基、正戊基、异戊基、苯基、2-羟乙基或3-羟丙基，n为0或1。
具体地，所述烷氧基硅烷R nSi(OR 6) 4-n的实例可以包括但不限于：四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、四异丙氧基硅烷、四正丁氧基硅烷、四异丁氧基硅烷、四正戊氧基硅烷、四异戊氧基硅烷、二乙氧基二甲氧基硅烷、四(2-羟基乙氧基)硅烷和四(3-羟基丙氧基)硅烷、二苯基二甲氧基硅烷、二苯基二乙氧基硅烷、丙基三甲氧基硅烷、丙基三乙氧基硅烷中的一种或多种。
根据本发明的催化剂组分除了上述两类或三类给电子体化合物外，还包含钛、镁和卤素。优选地，该催化剂组分是在一种镁的卤化物上负载含钛化合物和化合物B、化合物C的反应产物，或负载含钛化合物和化合物A、化合物B、化合物C的反应产物，所述镁的卤化物优选具有活化状态的二卤化镁，更优选活化二氯化镁。这种二氯化镁作为Ziegler-Natta催化剂的载体，在本领域中是众所周知的。通常，这种具有活化状态的二氯化镁的特征在于，在X射线衍射图谱中，出现在非活性二氯化镁的衍射图谱中的最强烈的衍射峰的强度减小且扩大成一个晕。
根据本发明，所述活化二卤化镁的制备方法在本领域内是公知的。一般地，可以通过研磨机对非活性二卤化镁进行研磨而获得；也可以通过将烷基卤化镁、烷基镁、烷氧基镁或非活性二卤化镁在溶剂体系中与卤化物(如卤化铝、卤硅烷或钛的卤化物)反应而制得；还可以通过将非活性二卤化镁与酯、醇和醚类给电子体化合物中的一种或多种反应，以形成卤化镁加合物，所述卤化镁加合物选择性地含有微量水，然后再通过化学反应或在负压下加热处理，使配位的给电子体脱除而得到活化二卤化镁。根据所述活化二卤化镁制备方法的不同，相比于烯烃聚合催化剂组分的制备，所述活化二卤化镁可以预先制备，也可以在烯烃聚合催化剂组分的制备过程中同时获得。
根据本发明，所述含钛化合物选自三卤化钛和通式Ti(OR″) 4-mX″ m所示钛化 合物中的一种或多种，式中R″为取代或未取代的C 1-C 10的直链烷基和取代或未取代的C 3-C 10的支链烷基中的任意一种，X″为卤素，m为0～4的整数。优选地，所述含钛化合物选自四氯化钛、四溴化钛、四碘化钛、四丁氧基钛、四乙氧基钛、一氯三丁氧基钛、二氯二丁氧基钛、三氯一丁氧基钛、一氯三乙氧基钛、二氯二乙氧基钛、三氯一乙氧基钛或三氯化钛。更优选地，所述含钛化合物为四氯化钛。
本发明烯烃聚合催化剂组分的制备可以按照各种公知的方法来进行。例如，可以使用CN1006071B所阐述的固体催化剂组分的制备方法，首先将非活性卤化镁溶解于溶剂体系中形成溶液，然后加入含钛化合物和本发明的化合物B和化合物C或本发明的化合物A、化合物B和化合物C，在助析出剂存在下，通过升温，重新析出含活性中心的烯烃聚合催化剂组分。活化卤化镁在上述反应中同时生成。CN1006071B所述相关内容在此引入本发明作为参考。
也可按照另一种方法，首先制备卤化镁加合物，优选该卤化镁加合物如通式MgX 1X 2·m(R″′OH)·nE·qH 2O所示，且该加合物颗粒呈球形，其中m为1.0～5.0，n为0～1.0，q为0～0.8；X 1和X 2各自独立地为氯和溴中的任意一种；R″′为取代或未取代的C 1-C 4的直链烷基和取代或未取代的C 3-C 4的支链烷基中的任意一种；E为给电子体化合物，可为醚或酯。优选m为1.5～3.5，n为0～0.5。然后将该卤化镁加合物颗粒与含钛化合物、化合物B、化合物C反应或者将卤化镁加合物颗粒与含钛化合物、化合物A、化合物B和化合物C反应，最终得到含活化卤化镁的烯烃聚合用催化剂组分。有关这种烯烃聚合催化剂组分的制备可以参照CN1036011C、CN1151183C、CN101565475A、CN101486776B及CN102796213B中公开的方法进行，其公开的相关内容在此全部引入本发明作为参考。
在任何的制备方法中，化合物A、化合物B和化合物C可以选择在卤化镁或卤化镁加合物与含钛化合物反应前、反应中或反应后加入；优选在与含钛化合物的反应中加入。根据本发明，化合物A、化合物B和化合物C也可以选择同时加入或分步加入，并且化合物A、化合物B和化合物C各自也可分多次加入，且化合物A、化合物B和化合物C的加入顺序可以不分先后。
在本发明的催化剂组分的制备过程中，当内给电子体包括化合物B和化合物C时，以每摩尔镁计，化合物B、化合物C及含钛化合物与镁的卤化物的摩尔比可以为0.01～0.5:0.005～0.4:5～100:1；优选地，化合物B、化合物C及含钛化合物与镁的卤化物的摩尔比为0.05～0.35:0.01～0.25:15～90:1；更优选地，化合物B、化合物C及含钛化合物与镁的卤化物的摩尔比为0.05～0.25: 0.015～0.15:25～80:1。
在本发明的催化剂组分的制备过程中，当内给电子体包括化合物A、化合物B和化合物C时，以每摩尔镁计，化合物A、化合物B、化合物C及含钛化合物与镁的卤化物的摩尔比可以为0.005～0.4:0.01～0.5:0.005～0.4:5～100:1；优选地，化合物A、化合物B、化合物C及含钛化合物与镁的卤化物的摩尔比为0.01～0.25:0.05～0.35:0.01～0.25:15～90:1；更优选地，化合物A、化合物B、化合物C及含钛化合物与镁的卤化物的摩尔比为0.02～0.18:0.05～0.25:0.015～0.15:25～80:1。
根据本发明的又一个方面，提供了一种用于烯烃聚合的催化剂体系，该催化剂体系包含下述组分或下述组分的反应产物：
a、上述的烯烃聚合催化剂组分；
b、烷基铝化合物；
c、任选地，至少一种外给电子体化合物。
与现有技术的用于烯烃聚合的催化剂体系相比，使用了根据本发明的催化剂组分的本发明烯烃聚合催化剂体系，在用于烯烃聚合反应时不仅保持着较高的聚合活性、良好的氢调敏感性和高的定向能力，而且令人意外地显示出优异的烯烃共聚合能力。
根据本发明的烯烃聚合催化剂体系，所述烷基铝化合物可以为本领域常用的各种烷基铝化合物。例如所述烷基铝化合物可以为烷基铝倍半氯化物和通式AlR IR IIR III所示化合物中的一种或多种，通式中的R I、R II和R III各自独立地可以为氯、取代或未取代的C 1-C 8的直链烷基和取代或未取代的C 3-C 8的支链烷基中的任意一种，且R I、R II和R III中的至少一个为取代或未取代的C 1-C 8的直链烷基和取代或未取代的C 3-C 8的支链烷基中的任意一种。优选地，所述烷基铝化合物为三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝、一氯二乙基铝、一氯二异丁基铝、一氯二正丁基铝、一氯二正己基铝、二氯一乙基铝、二氯一异丁基铝、二氯一正丁基铝、二氯一正己基铝和Al 2Et 3Cl 3中的一种或多种。
一般地，根据本发明的用于烯烃聚合的催化剂体系，所述以铝元素计的烷基铝化合物和以钛元素计的催化剂组分的摩尔比可以为1～2000:1，优选为20～700:1。
根据本发明的烯烃聚合催化剂体系，所述外给电子体化合物可以为本领域常用的各种给电子体化合物。例如所述外给电子体化合物可以为羧酸、酸酐、酯、 酮、醚、醇、有机磷和有机硅化合物中的一种或多种；优选为有机硅化合物。
根据本发明的烯烃聚合催化剂体系，所述外给电子体更优选为如通式R a xR b ySi(OR c) z所示的有机硅化合物，该通式中，R a、R b和R c各自独立地为含或不含杂原子的取代或未取代的C 1-C 18的烃基；x和y各自独立地为0～2的整数，z为1～3的整数，且x+y+z＝4。进一步优选地，通式R a xR b ySi(OR c) z中，R a和R b中的至少一个选自取代或未取代的C 3-C 10的含或不含杂原子的支链烷基、取代或未取代的C 3-C 10的含或不含杂原子的环烷基、取代或未取代的C 6-C 10的芳基中的一种，R c选自取代或未取代的C 1-C 10的直链烷基和取代或未取代的C 3-C 10的支链烷基中的一种，优选为甲基，x为1，y为1，z为2；或者，R b为取代或未取代的C 3-C 10的支链烷基或取代或未取代的C 3-C 10的环烷基，且R c为甲基，x为0，y为1，z为3。
具体地，所述有机硅化合物的实例可以为但不限于：环己基甲基二甲氧基硅烷、二异丙基二甲氧基硅烷、正丁基环己基二甲氧基硅烷、二异丁基二甲氧基硅烷、二苯基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷、二环戊基二甲氧基硅烷、2-乙基哌啶基-2-叔丁基二甲氧基硅烷、(1,1,1-三氟-2-丙基)-2-乙基哌啶基二甲氧基硅烷、(1,1,1-三氟-2-丙基)-甲基二甲氧基硅烷、环己基三甲氧基硅烷、叔丁基三甲氧基硅烷和叔己基三甲氧基硅烷。
一般地，根据本发明的用于烯烃聚合的催化剂体系，相对于1摩尔的以铝元素计的烷基铝化合物，所述外给电子体化合物的用量为0.005～0.5摩尔，优选为0.01～0.4摩尔。
在本发明中，所述烷基铝化合物和任选的外给电子体化合物可以单独或作为两种组分的混合物与催化剂组分接触反应。
上述根据本发明的烯烃聚合催化剂体系适于作为烯烃聚合的催化剂体系。
根据本发明的又一个方面，提供了一种用于烯烃聚合的预聚合催化剂组合物，所述预聚合催化剂组合物包括：
a、经过烯烃预聚合反应步骤的上述的烯烃聚合催化剂体系；
b、所述烯烃预聚合反应步骤得到的预聚物。
根据本发明，术语“预聚合催化剂组合物”指经过聚合步骤的含有相比于催化剂组分来说预聚倍数较低的烯烃聚合物的催化剂组合物。一般地，预聚倍数为0.1～1000g烯烃聚合物/g催化剂组分。优选地，预聚倍数为0.2～500g烯烃聚合物/g催化剂组分，进一步优选为0.5～100g烯烃聚合物/g催化剂组分。本发明中， 可以采用与聚合所用烯烃相同的烯烃来进行预聚合，优选为丙烯或丙烯与摩尔含量最高为20％的一种或多种非丙烯α-烯烃的混合物。
根据本发明的预聚合催化剂组合物，所述预聚合反应步骤可以作为连续聚合工艺中的一部分在线进行，或在间歇操作中独立地进行。
本发明预聚合反应条件可以采用公知的条件，预聚合温度可为0～50℃，优选为10～30℃。
根据本发明的又一个方面，提供了一种烯烃聚合方法，该方法包括在烯烃聚合条件下，将一种或多种烯烃与本发明提供的烯烃聚合催化剂体系和预聚合催化剂组合物中的至少一种接触。
根据本发明的烯烃聚合方法通过使用根据本发明的烯烃聚合催化剂体系或预聚合催化剂组合物，能够制备具有高乙烯含量和高的橡胶含量且其颗粒形态完美的聚合物。本发明的烯烃聚合方法对于烯烃聚合条件和所使用的烯烃没有特别限定。
一般地，根据本发明的烯烃聚合方法，所述烯烃可以为通式CH 2＝CHR′所示的烯烃，其中，R′可以为氢、取代或未取代的C 1-C 12的直链烷基、取代或未取代的C 3-C 12的支链烷基、取代或未取代的C 6-C 12的芳基中的一种。根据本发明的烯烃聚合方法，必要时，所述烯烃还可以含有少量的二烯烃。根据本发明的烯烃聚合方法，所述烯烃优选为丙烯，或者丙烯和CH 2＝CHR′所示烯烃的混合物，其中，R′为氢、取代或未取代的C 1-C 6的直链烷基、取代或未取代的C 3-C 6的支链烷基中的一种。
根据本发明的烯烃聚合方法，所述烯烃的聚合既可以是均聚，也可以是共聚。所述烯烃的聚合可以按照本领域所公知的方法进行，例如，所述聚合可以为本体聚合、气相聚合、淤浆聚合或液相本体-气相组合聚合。根据本发明的烯烃聚合方法，所述烯烃聚合温度可以为本领域的常规条件，例如，聚合温度可以为0℃～150℃，优选为60℃～90℃；聚合反应压力可以为常压或加压。
与现有技术相比，本发明包括以下有益效果：
当本发明采用酯类化合物或二醚类化合物与烷氧基硅烷类化合物复配做内给电子体，与单独使用酯类化合物或二醚类化合物相比，显示出明显改善的烯烃共聚合能力，同时保持有高的定向能力；与单独使用烷氧基硅烷类化合物相比，同时显示出高的定向能力和烯烃共聚合能力。
当本发明采用烷氧基硅烷类化合物和羟基苯甲酰类化合物、酯类化合物复 配或和羟基苯甲酰类化合物、二醚类化合物复配作为内给电子，制备的催化剂在保持高的定向能力的同时，进一步改善了催化剂氢调敏感性和烯烃共聚合能力。
采用本发明的催化剂体系及预聚合催化剂组合物催化烯烃所得的聚合物粒子具有良好的颗粒形态，聚合物粒子的球形度高。
具体实施方式
通过以下实施例进一步说明本发明，并不用来限制本发明的范围。
以下实施例中，涉及的测试方法如下：
1、聚合物熔融指数(M.I)：根据ASTM D1238-99测定。
2、聚合物等规指数(II)：采用正庚烷抽提法测定(正庚烷沸腾抽提6小时)，即将2克干燥的聚合物样品，置于索氏抽提器中用沸腾正庚烷抽提6小时，然后，将剩余物干燥至恒重，所得的剩余物重量(g)与2的比值即为等规指数。
3、二甲苯可溶物含量(X.S)：将共聚物置于真空干燥箱中75℃下烘烤30min后，迅速放入干燥器冷却至室温；取2g左右共聚物称量计重，放入500ml锥形瓶中，加入200ml二甲苯加热溶解，将溶解好的试样在室温下冷却12～14min后放入恒温水浴中25℃下冷却结晶60min，过滤结晶物后将可溶物加热、烘烤、称重并计算含量。
4、乙烯含量：采用Nicolet公司Magna-IR760型红外光谱仪进行，热压成膜法，170℃，20MPa。
5、采用分光光度法测定催化剂组分中钛的含量。
6、聚合物筛分及平均球形度(SPHT)测试：采用Retsch Technology公司的Camsizer仪器测试，SPHT值越接近1，代表颗粒越接近于球形。
实施例1
(1)烯烃聚合催化剂组分的制备
在经过高纯氮气充分置换的带搅拌的300mL玻璃反应瓶中，加入90mL的四氯化钛和18mL的无水己烷，冷却至-20℃，加入8.0g球形氯化镁加合物MgCl 2·2.7CH 3CH 2OH·0.02E(E为邻甲氧基苯甲酸乙酯)(制备方法参见CN101486722A)，并维持-20℃搅拌30min。然后，缓慢升温至110℃，并在升温过程中加入1.5mL邻苯二甲酸二异丁酯和0.4mL四乙氧基硅。在110℃恒温反应30min后，滤除液体。加入80mL四氯化钛，升温至120℃，在120℃维持30min 后滤除液体；重复上述操作一次。最后用60℃的己烷对得到的固体洗涤5次(己烷用量为80mL/次)；并真空干燥所得固体物，从而得到球形催化剂组分。该催化剂组分中钛的含量为2.4wt％。
(2)烯烃均聚合
丙烯液相本体聚合在5L的不锈钢高压反应釜中进行。在氮气保护下向反应釜中依次加入5mL三乙基铝的己烷溶液(浓度为0.5mmol/mL)、1mL环己基甲基二甲氧基硅烷的己烷溶液(浓度为0.1mmol/mL)和9mg上述球形催化剂组分。关闭高压釜，加入6.5L氢气(标准体积)和2.3L的液体丙烯。升温至70℃，反应1小时。然后，降温，卸压，出料，并进行干燥，从而得到聚丙烯。聚合结果见表1，聚合物筛分结果见表7。
(3)烯烃共聚合
在400mL不锈钢高压反应釜中进行。反应釜经气相丙烯充分置换后，加入100g丙烯和800mL的氢气(通过气体质量流量计控制)，升温至20℃，将事先预络合的三乙基铝、环己基甲基二甲氧基硅烷和催化剂混合物(铝:丙烯＝0.13g/kg，铝:硅＝16mol/mol，催化剂1mg)经机械臂自动注射加入，开动搅拌并计时。预聚10min后快速升温至69℃进行本体聚合，100分钟后，排空釜内剩余丙烯，快速加入事先按比例配置的乙烯/丙烯混合气(乙烯:丙烯＝2:3mol/mol)，快速升温至80℃，气相聚合期间丙烯/乙烯的比例通过气相色谱进行实时调控。反应30min后，通入终止气，停止加热，停止搅拌，泄压，出料，并将聚合物干燥，从而得到聚丙烯。聚合结果见表2。
实施例2
(1)烯烃聚合催化剂组分的制备
采用与实施例1(1)相同的方法制备球形催化剂组分，不同的是，将四乙氧基硅的用量改为1.25mL。该催化剂组分中钛的含量为2.5wt％。
(2)烯烃均聚合
采用与实施例1(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本实施例上述步骤(1)制备的催化剂组分。聚合结果见表1。
(3)烯烃共聚合
采用与实施例1(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为本实施例上述步骤(1)制备的催化剂组分。聚合结果见表2。
对比例1
(1)烯烃聚合催化剂组分的制备
采用与实施例1(1)相同的方法制备球形催化剂组分，不同的是，不使用四乙氧基硅。该催化剂组分中钛的含量为2.3wt％。
(2)烯烃均聚合
采用与实施例1(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表1，聚合物筛分结果见表7。
(3)烯烃共聚合
采用与实施例1(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表2。
对比例2
(1)烯烃聚合催化剂组分的制备
采用与实施例1(1)相同的方法制备球形催化剂组分，不同的是，不使用邻苯二甲酸二异丁酯。该催化剂组分中钛的含量为3.5wt％。
(2)烯烃均聚合
采用与实施例1(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表1，聚合物筛分结果见表7。
(3)烯烃共聚合
采用与实施例1(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表2。
实施例3
(1)烯烃聚合催化剂组分的制备
在经过高纯氮气充分置换的带搅拌的300mL玻璃反应瓶中，加入90mL的四氯化钛和18mL的无水己烷，冷却至-20℃，加入8.0g球形氯化镁加合物MgCl 2·2.7CH 3CH 2OH·0.02E(E为邻甲氧基苯甲酸乙酯)(制备方法参见CN101486722A)，并维持-20℃搅拌30min。然后，缓慢升温至110℃，并在升温 过程中加入0.4mL 2-羟基苯甲酸乙酯、1.5mL邻苯二甲酸二异丁酯和0.2mL四乙氧基硅。在110℃恒温反应30min后，滤除液体。加入80mL四氯化钛，升温至120℃，在120℃维持30min后滤除液体；重复上述操作一次。最后用60℃的己烷对得到的固体洗涤5次(己烷用量为80mL/次)；并真空干燥所得固体物，从而得到球形催化剂组分。该催化剂组分中钛的含量为2.2wt％。
(2)烯烃均聚合
丙烯液相本体聚合在5L的不锈钢高压反应釜中进行。在氮气保护下向反应釜中依次加入5mL三乙基铝的己烷溶液(浓度为0.5mmol/mL)、1mL环己基甲基二甲氧基硅烷的己烷溶液(浓度为0.1mmol/mL)和9mg上述球形催化剂组分。关闭高压釜，加入6.5L氢气(标准体积)和2.3L的液体丙烯。升温至70℃，反应1小时。然后，降温，卸压，出料，并进行干燥，从而得到聚丙烯。聚合结果见表3。
(3)烯烃共聚合
在400mL不锈钢高压反应釜中进行。反应釜经气相丙烯充分置换后，加入100g丙烯和800mL的氢气(通过气体质量流量计控制)，升温至20℃，将事先预络合的三乙基铝、环己基甲基二甲氧基硅烷和催化剂混合物(铝:丙烯＝0.13g/kg，铝:硅＝16mol/mol，催化剂1mg)经机械臂自动注射加入，开动搅拌并计时。预聚10min后快速升温至69℃进行本体聚合，100分钟后，排空釜内剩余丙烯，快速加入事先按比例配置的乙烯/丙烯混合气(乙烯:丙烯＝2:3mol/mol)，快速升温至80℃，气相聚合期间丙烯/乙烯的比例通过气相色谱进行实时调控。反应30min后，通入终止气，停止加热，停止搅拌，泄压，出料，并将聚合物干燥，从而得到聚丙烯。聚合结果见表4。
实施例4
(1)烯烃聚合催化剂组分的制备
采用与实施例3(1)相同的方法制备球形催化剂组分，不同的是，四乙氧基硅的用量为0.4mL。该催化剂组分中钛的含量为2.4wt％。
(2)烯烃均聚合
采用与实施例3(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本实施例上述步骤(1)制备的催化剂组分。聚合结果见表3，聚合物筛分结果见表7。
(3)烯烃共聚合
采用与实施例3(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为本实施例上述步骤(1)制备的催化剂组分。聚合结果见表4。
实施例5
(1)烯烃聚合催化剂组分的制备
采用与实施例3(1)相同的方法制备球形催化剂组分，不同的是，四乙氧基硅烷的用量为1.0mL。该催化剂组分中钛的含量为2.2wt％。
(2)烯烃均聚合
采用与实施例3(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本实施例上述步骤(1)制备的催化剂组分。聚合结果见表3。
(3)烯烃共聚合
采用与实施例3(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为本实施例上述步骤(1)制备的催化剂组分。聚合结果见表4。
对比例3
(1)烯烃聚合催化剂组分的制备
采用与实施例4(1)相同的方法制备球形催化剂组分，不同的是，不使用四乙氧基硅。该催化剂组分中钛的含量为2.3wt％。
(2)烯烃均聚合
采用与实施例4(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表3，聚合物筛分结果见表7。
(3)烯烃共聚合
采用与实施例4(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表4。
对比例4
(1)烯烃聚合催化剂组分的制备
采用与实施例4(1)相同的方法制备球形催化剂组分，不同的是，不使用邻苯二甲酸二异丁酯。该催化剂组分中钛的含量为7.3wt％。
(2)烯烃均聚合
采用与实施例4(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表3，聚合物筛分结果见表7。
(3)烯烃共聚合
采用与实施例4(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表4。
对比例5
(1)烯烃聚合催化剂组分的制备
采用与实施例4(1)相同的方法制备球形催化剂组分，不同的是，将0.4mL2-羟基苯甲酸乙酯改为0.4mL甲基丙烯酸(2-羟基乙)酯，且不使用邻苯二甲酸二异丁酯。该催化剂组分中钛的含量为4.3wt％。
(2)烯烃均聚合
采用与实施例4(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表3，聚合物筛分结果见表7。
(3)烯烃共聚合
采用与实施例4(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表4。
实施例6
(1)烯烃聚合催化剂组分的制备
采用与实施例3(1)相同的方法制备球形催化剂组分，不同的是，将1.5mL邻苯二甲酸二异丁酯改为1.2mL 2-异丙基-2-异戊基-1,3-二甲氧基丙烷。该催化剂组分中钛的含量为2.5wt％。
(2)烯烃均聚合
采用与实施例3(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本实施例上述步骤(1)制备的催化剂组分。聚合结果见表5。
(3)烯烃共聚合
采用与实施例3(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为 本实施例上述步骤(1)制备的催化剂组分。聚合结果见表6。
实施例7
(1)烯烃聚合催化剂组分的制备
采用与实施例6(1)相同的方法制备球形催化剂组分，不同的是，将四乙氧基硅的用量改为0.4mL。该催化剂组分中钛的含量为2.5wt％。
(2)烯烃均聚合
采用与实施例6(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本实施例上述步骤(1)制备的催化剂组分。聚合结果见表5，聚合物筛分结果见表7。
(3)烯烃共聚合
采用与实施例6(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为本实施例上述步骤(1)制备的催化剂组分。聚合结果见表6。
对比例6
(1)烯烃聚合催化剂组分的制备
采用与实施例6(1)相同的方法制备球形催化剂组分，不同的是，不使用四乙氧基硅。该催化剂组分中钛的含量为2.6wt％。
(2)烯烃均聚合
采用与实施例6(2)相同的方法进行丙烯聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表5。
(3)烯烃共聚合
采用与实施例6(3)相同的方法进行烯烃共聚合，不同的是催化剂组分为本对比例上述步骤(1)制备的催化剂组分。聚合结果见表6。
表1
Figure PCTCN2022127883-appb-000005
表2
Figure PCTCN2022127883-appb-000006
表1和表2分别列出了由实施例1-2和对比例1-2所得催化剂组分及催化剂体系和预聚合催化剂组合物用于烯烃聚合时的聚合结果。从表1可以看出，相比于现有同类催化剂技术，包含有给电子体化合物B和C的本发明催化剂组分制备的本发明催化剂体系和本发明预聚合催化剂组合物在相同的氢分压条件下用于烯烃均聚合时，仍具有高的聚合活性、良好的氢调敏感性和高的定向能力。对比例2显示，催化剂组分中仅含有给电子体化合物C时，催化剂体系和预聚合催化剂组合物的定向能力太低，在烯烃工业应用中不具有实际应用价值。表2的数据显示，由同时含有给电子体B和C的本发明催化剂组分制备的本发明催化剂体系与本发明预聚合催化剂组合物催化乙烯和丙烯共聚合时，树脂中乙烯含量明显提高，这说明本发明的催化剂组分及由本发明催化剂组分制备的催化剂体系和预聚合催化剂组合物具有明显改善的烯烃共聚合能力。
表3
Figure PCTCN2022127883-appb-000007
表4
Figure PCTCN2022127883-appb-000008
Figure PCTCN2022127883-appb-000009
表3和表4分别列出了由实施例3-5和对比例3-5所得催化剂组分及催化剂体系和预聚合催化剂组合物用于烯烃聚合时的聚合结果。与表1展示的结果类似，从表3可以看出，相比于现有同类催化剂技术，同时含有给电子体化合物A、B和C的本发明催化剂组分制备的本发明催化剂体系和本发明预聚合催化剂组合物在相同的氢分压条件下用于烯烃均聚合时，仍具有高的聚合活性、良好的氢调敏感性和高的定向能力。其中，本发明同时含有给电子体化合物A、B和C的催化剂组分制备的催化剂体系和预聚合催化剂组合物的氢调敏感性相比于催化剂组分中不含有给电子体化合物A的催化剂体系和预聚合催化剂组合物有一定的改善。有意义的是，从表4同样可以看出，相比于现有同类催化剂技术，由同时含有给电子体化合物A、B和C的本发明催化剂组分制备的本发明催化剂体系与本发明预聚合催化剂组合物催化乙烯和丙烯共聚合时，树脂中乙烯含量明显提高，这说明本发明的含有给电子体化合物A、B和C的催化剂组分及由该催化剂组分制备的催化剂体系和预聚合催化剂组合物也具有明显改善的烯烃共聚合能力，且相比于不含有给电子体化合物A的本发明催化剂体系和本发明预聚合催化剂组合物，烯烃共聚合能力更强。值的提及的一点是，对比例4和5显示，催化剂组分中同时含有给电子体化合物A和C时，进一步制备的催化剂体系和预聚合催化剂组合物的定向能力太低，在烯烃工业应用中不具有实际应用价值。
另外，从表7可见，仅含有给电子体化合物C或同时含有给电子体化合物A和C的对比例2、4和5所述催化剂体系和预聚合催化剂组合物在用于丙烯聚合时，聚合破碎严重，细粉量很多，且有时伴有严重的结块现象；而包含本发明催化剂组分的本发明催化剂体系和本发明预聚合催化剂组合物聚合丙烯所得聚合物粒子的形态很好，球形度高，细粉量很少。
表5
实施例 聚合活性 等规指数 聚合物熔指
  (KgPP/gCat) (wt％) (g/10min)
实施例6(2) 56.0 97.3 77.4
实施例7(2) 58.0 97.2 75.8
对比例6(2) 56.3 97.6 75.0
表6
Figure PCTCN2022127883-appb-000010
表5和表6列出了由实施例6-7和对比例6所得催化剂组分及催化剂体系和预聚合催化剂组合物用于烯烃聚合时的聚合结果。结合表5和6同样可以清晰地看出，当本发明以烷氧基硅烷化合物与2-羟基苯甲酰类化合物、1,3-二醚类化合物复配作为内给电子体使用时，所得包含本发明催化剂组分的本发明催化剂体系和本发明预聚合催化剂组合物同样表现出优异的综合性能，即，与现有同类催化剂技术相比，包含本发明催化剂组分的本发明催化剂体系和本发明预聚合催化剂组合物在保持有高的聚合活性、良好的氢调敏感性和高的定向能力的同时，显示出明显改善的烯烃共聚合能力。同样地，本发明以烷氧基硅烷化合物与2-羟基苯甲酰类化合物、1,3-二醚类化合物复配作为内给电子体的催化剂组分及催化剂体系和预聚合催化剂组合物在用于烯烃聚合时，所得聚合物粒子的形态很好，球形度高，且细粉量很少。
表7
Figure PCTCN2022127883-appb-000011
Figure PCTCN2022127883-appb-000012
应当注意的是，在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。

Claims (15)

  1. 一种烯烃聚合催化剂组分，其特征在于，所述烯烃聚合催化剂组分包括：镁、钛、卤素和内给电子体；所述内给电子体包括：化合物B和化合物C；其中，
    所述化合物B选自除式(Ⅰ)所示的羟基苯甲酰类化合物以外的酯类化合物和醚类化合物中的一种或多种；
    Figure PCTCN2022127883-appb-100001
    式(Ⅰ)中，R 1选自氢、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基，R 2、R 3、R 4和R 5各自独立地选自氢、卤素、硝基、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基；或者R 2、R 3、R 4和R 5中的两个或两个以上基团相互键合成环；
    所述化合物C选自如式R nSi(OR 6) 4-n所示的烷氧基硅烷；式R nSi(OR 6) 4-n中，R和R 6各自独立地选自氢、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基，n为0～3的整数。
  2. 一种烯烃聚合催化剂组分，其特征在于，所述烯烃聚合催化剂组分包括：镁、钛、卤素和内给电子体；所述内给电子体包括：化合物A、化合物B和化合物C；其中，
    所述化合物A选自如式(Ⅰ)所示的羟基苯甲酰类化合物；
    Figure PCTCN2022127883-appb-100002
    Figure PCTCN2022127883-appb-100003
    式(Ⅰ)中，R 1选自氢、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基，R 2、R 3、R 4和R 5各自独立地选自氢、卤素、硝基、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基；或者R 2、R 3、R 4和R 5中的两个或两个以上基团相互键合成环；
    所述化合物B选自除化合物A以外的酯类化合物和醚类化合物中的一种或多种；
    所述化合物C选自如式R nSi(OR 6) 4-n所示的烷氧基硅烷；式R nSi(OR 6) 4-n中，R和R 6各自独立地选自氢、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基，n为0～3的整数。
  3. 根据权利要求1或2所述的烯烃聚合催化剂组分，其特征在于，式(Ⅰ)中，R 1选自氢、取代或未取代的C 1-C 6的直链烷基、取代或未取代的C 3-C 6的支链烷基、取代或未取代的C 3-C 6的环烷基、取代或未取代的C 6-C 10的芳基、取代或未取代的C 7-C 10的芳烷基，R 2、R 3、R 4和R 5各自独立地选自氢、取代或未取代的C 1-C 8的直链烷基、取代或未取代的C 3-C 8的支链烷基、取代或未取代的C 3-C 6的环烷基、取代或未取代的C 6-C 10的芳基、取代或未取代的C 7-C 10的芳烷基；
    优选地，式(Ⅰ)中，R 1选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、正己基、苄基或苯乙基，R 2、R 3、R 4和R 5各自独立地选自氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、环戊基、正己基、正庚基或甲苯基。
  4. 根据权利要求1-3中任一项所述的烯烃聚合催化剂组分，其特征在于，式(Ⅰ)所示的羟基苯甲酰类化合物选自4-羟基苯甲酸类化合物、4-羟基苯甲酸酯类化合物、2-羟基苯甲酸类化合物和2-羟基苯甲酸酯类化合物中的一种或多种。
  5. 根据权利要求1-4中任一项所述的烯烃聚合催化剂组分，其特征在于，所述化合物B中的酯类化合物选自一元脂肪族羧酸酯、多元脂肪族羧酸酯、一元芳香族羧酸酯、多元芳香族羧酸酯和如式(Ⅱ)所示的二元醇酯化合物中的一种或多种；
    Figure PCTCN2022127883-appb-100004
    式(II)中，R I、R II、R III、R IV、R V和R VI各自独立地选自氢、取代或未取代的C 1-C 10的脂肪烃基、取代或未取代的C 6-C 10的芳基、取代或未取代的C 7-C 10的芳烷基；或者，R I、R II、R III、R IV、R V和R VI中的两个或两个以上基团相互键合成环；R VII和R VIII各自独立地选自取代或未取代的C 1-C 10的直链烷基、取代或未取代的C 3-C 10的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳基脂肪烃基。
  6. 根据权利要求1-5中任一项所述的烯烃聚合催化剂组分，其特征在于，所述化合物B中的酯类化合物为二元芳香族羧酸烷基酯。
  7. 根据权利要求1-6中任一项所述的烯烃聚合催化剂组分，其特征在于，所述化合物B中的醚类化合物为二醚类化合物。
  8. 根据权利要求7所述的烯烃聚合催化剂组分，其特征在于，所述二醚类化合物选自如式(Ⅲ)所示的1,3-二醚类化合物；
    Figure PCTCN2022127883-appb-100005
    式(Ⅲ)中，R 1、R 2、R 3、R 4、R 5和R 6各自独立地选自氢、卤素、取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基；或者，R 1、R 2、R 3、R 4、R 5和R 6中的两个或两个以上基团相互键合成环；R 7和R 8各自独立地选自取代或未取代的C 1-C 20的直链烷基、取代或未取代的C 3-C 20的支链烷基、取代或未取代的C 3-C 20的环烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的C 7-C 20的芳烷基。
  9. 根据权利要求8所述的烯烃聚合催化剂组分，其特征在于，，式(Ⅲ)中，R 1、R 2、R 5和R 6为氢；
    R 7和R 8各自独立地为取代或未取代的C 1-C 4的直链烷基、取代或未取代的C 3-C 4的支链烷基中的一种，更优选为甲基；
    R 3为甲基、乙基、正丙基和异丙基中的任意一种，R 4为乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、异戊基、2-乙基己基、环戊基、环己基、甲基环己基、苯基和苄基中的任意一种；或者，R 3为氢，R 4为乙基、正丁基、仲丁基、叔丁基、2-乙基己基、环己基乙基、二苯基甲基、对氯苯基、1-萘基和1-十氢萘基中的任意一种；或者，R 3和R 4相同，且为乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、新戊基、苯基、苄基、环己基和环戊基中的任意一种；或者，R 3和R 4相互键合，以形成环戊二烯基、芴基或茚基。
  10. 根据权利要求1-9中任一项所述的烯烃聚合催化剂组分，其特征在于，式R nSi(OR 6) 4-n中，R和R 6各自独立地选自氢、取代或未取代的C 1-C 6的直链烷基、取代或未取代的C 3-C 6的支链烷基、取代或未取代的C 3-C 6的环烷基、取代或未取代的C 6-C 10的芳基、取代或未取代的C 7-C 10的芳烷基，n为0～2的整数；优选地，R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、叔丁基、正戊基、异戊基、苯基、2-羟乙基或3-羟丙基，n为0或1。
  11. 一种烯烃聚合催化剂体系，其特征在于，所述烯烃聚合催化剂体系包括如下组分或如下组分的反应产物：
    a、权利要求1-10中任一项所述的烯烃聚合催化剂组分；
    b、烷基铝化合物；
    c、任选地，至少一种外给电子体化合物。
  12. 一种用于烯烃聚合的预聚合催化剂组合物，其特征在于，所述预聚合催化剂组合物包括：
    a、经过烯烃预聚合反应步骤的权利要求11所述的烯烃聚合催化剂体系；
    b、所述烯烃预聚合反应步骤得到的预聚物，预聚倍数为0.1～1000g烯烃聚合物/g催化剂组分。
  13. 一种烯烃聚合方法，其特征在于，所述烯烃聚合方法包括：在烯烃聚合条件下，将一种或多种烯烃与权利要求11所述的烯烃聚合催化剂体系和权利要求12所述的预聚合催化剂组合物中的至少一种接触。
  14. 根据权利要求13所述的烯烃聚合方法，其特征在于，所述一种或多种烯烃选自如CH 2＝CHR′所示烯烃，其中R′选自氢、取代或未取代的C 1-C 12的直链烷基、取代或未取代的C 3-C 12的支链烷基、取代或未取代的C 6-C 12的芳基。
  15. 根据权利要求14所述的烯烃聚合方法，其特征在于，所述烯烃为丙烯，或者丙烯和CH 2＝CHR′所示烯烃的混合物，其中，R′选自氢、取代或未取代的 C 1-C 6的直链烷基、取代或未取代的C 3-C 6的支链烷基。
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CN105541877A (zh) * 2014-10-28 2016-05-04 中国石油化工股份有限公司 卤化镁加合物及应用和用于烯烃聚合的催化剂组分和催化剂体系及应用和烯烃聚合方法

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