WO2016086837A1 - Composé d'ester d'acide disulfonique, utilisation de celui-ci, composant catalyseur de polymérisation d'oléfines et catalyseur de polymérisation d'oléfines - Google Patents

Composé d'ester d'acide disulfonique, utilisation de celui-ci, composant catalyseur de polymérisation d'oléfines et catalyseur de polymérisation d'oléfines Download PDF

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WO2016086837A1
WO2016086837A1 PCT/CN2015/096119 CN2015096119W WO2016086837A1 WO 2016086837 A1 WO2016086837 A1 WO 2016086837A1 CN 2015096119 W CN2015096119 W CN 2015096119W WO 2016086837 A1 WO2016086837 A1 WO 2016086837A1
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group
hydrogen
methyl
butyl
halogen atom
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PCT/CN2015/096119
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Chinese (zh)
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尹宝作
义建军
孙天旭
崔伟松
袁苑
张明革
李红明
崔亮
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中国石油天然气股份有限公司
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Priority claimed from CN201410736716.8A external-priority patent/CN104402776B/zh
Priority claimed from CN201410738688.3A external-priority patent/CN104496865A/zh
Priority claimed from CN201410742935.7A external-priority patent/CN105712909B/zh
Priority claimed from CN201410740490.9A external-priority patent/CN104403027B/zh
Priority claimed from CN201410738164.4A external-priority patent/CN105712908A/zh
Priority claimed from CN201410736720.4A external-priority patent/CN104402777B/zh
Application filed by 中国石油天然气股份有限公司 filed Critical 中国石油天然气股份有限公司
Publication of WO2016086837A1 publication Critical patent/WO2016086837A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/73—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—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
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/651—Pretreating with non-metals or metal-free compounds

Definitions

  • the present invention relates to a disulfonate compound and use thereof, and an olefin polymerization catalyst component prepared by using the disulfonate compound, and an olefin polymerization catalyst comprising the catalyst component and
  • the application of the catalyst belongs to the technical field of olefin polymerization catalysts.
  • Ziegler-Natta catalysts for the polymerization of olefins generally comprise a main catalyst and a cocatalyst.
  • the main catalyst is mostly a solid titanium catalyst prepared by reacting a titanium compound, a magnesium compound and an internal electron donor as a basic raw material.
  • Olefin polymers having higher yields and higher stereoregularity can be prepared by using such a main catalyst.
  • magnesium compounds act as carriers (for example, MgCl 2 , etc.) mainly as a skeleton; the morphology of the carrier directly determines the morphology of the particles of the main catalyst and the olefin polymer; titanium compounds (such as TiCl 4 , etc.) mainly To form the active center; while the internal electron donor mainly plays the role of improving catalytic activity and stereotactic ability, and affects the hydrogen modulating sensitivity of the main catalyst and other aspects of performance, and with the development of internal electron donor compounds This has led to the continuous upgrading of olefin polymerization catalysts.
  • various internal electron donor compounds have been disclosed, mainly including polycarboxylic acids, monocarboxylic acid esters or polycarboxylic acid esters, acid anhydrides, ketones, monoethers or polyethers, alcohols, amines, and the like, and derivatives thereof.
  • aromatic carboxylic acid ester internal electron donors such as ethyl benzoate, di-n-butyl phthalate, diisobutyl phthalate, etc. (see CN85100997A, US4784983, EP0045977, etc.)
  • an aliphatic dicarboxylic acid ester internal electron donor commonly including malonate compounds, succinate compounds, glutarate compounds, etc.
  • diether internal electron donors generally 1,3-diether compounds containing two ether groups, such as 2-isopropyl-2-isopentyl- 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane and 9,9-bis(methoxymethyl)anthracene (see EP0361493, EP0361494, EP0728724) , EP0728769, US4971937, US2004014597, US2003027715, CN1042547A, CN1143651A, CN1141285A and WO03076480, etc.; ethyl cyanate internal electron donor (see CN1242780A, etc.); male
  • EP 0 361 494, CN 1 141 285 A discloses ZN catalysts containing diether internal electron donors which have outstanding characteristics such as high activity, hydrogen sensitivity and high stereotactic ability.
  • the catalyst is a MgCl 2 /SiO 2 spherical composite support prepared by spray drying, and is prepared by using a diether compound as an internal electron donor.
  • the catalyst exhibits high catalytic propylene polymerization activity, sensitive hydrogen modulation property and high stereospecific ability, the obtained propylene homopolymer has a narrow molecular weight distribution, which brings inconvenience to the post-processing process; The bulk density of propylene polymers is low and is not convenient for practical industrial production.
  • the aromatic carboxylic acid ester compound disclosed above, a 1,3-diether compound containing two ether groups, and an aliphatic dicarboxylic acid ester compound are used as internal electron donors.
  • Catalysts for olefin polymerization have certain drawbacks in practical applications.
  • a catalyst prepared by using an aromatic carboxylic acid ester to an electron donor has a low activity, and the molecular weight distribution of the obtained polymer is also narrow; a catalyst prepared by using a 1,3-diether donor electron donor has a high activity and a catalyst.
  • Hydrogen sensitivity is also good, but the molecular weight distribution of the obtained olefin polymer is narrow, which is not conducive to the development of different grades of olefin polymer; while the catalyst prepared by using the recently disclosed aliphatic dicarboxylic acid ester to electrons can be used.
  • the molecular weight distribution of the obtained propylene polymer is significantly broadened, but the activity of the catalyst is still low, and the isotacticity of the obtained olefin polymer is low when no external electron donor is used.
  • Catalysts prepared using different internal electron donor compounds have different characteristics, some have higher activity, some have better hydrogen regulation properties, and some catalysts have polyolefins with wider molecular weight distribution.
  • two or more (including two) internal electron donors have been attempted to prepare a catalyst, and the related contents are disclosed in WO9957160, WO0230998, WO03002617, JP2001139621, JP2002249507, CN1242780A, CN1268957A, and CN1524886A.
  • WO9957160, WO0230998, WO03002617, JP2001139621, JP2002249507, CN1242780A, CN1268957A, and CN1524886A In the literature.
  • CN 1524886 A discloses a composite support for olefin polymerization, in particular propylene polymerization or copolymerization catalysts, and a catalyst component and catalyst using the composite support.
  • the catalyst component ie, the main catalyst
  • the catalyst component is prepared by first contacting the magnesium halide with one or more of a fatty alcohol, an aromatic alcohol, an organic epoxy compound, an organophosphorus compound, and the like as an internal electron donor.
  • the solution is mixed with silica gel having an average particle diameter of less than 30 ⁇ m, and spray-dried to obtain spherical composite carrier particles; then the carrier is loaded with a titanium compound and a conventional internal electron donor such as an aliphatic group.
  • the polypropylene resin prepared by using the catalyst component has a high isotacticity, but the catalyst activity is not satisfactory.
  • an object of the present invention is to provide a disulfonic acid ester compound and use thereof.
  • the disulfonic acid ester compound can be used as an internal electron donor for the preparation of an olefin polymerization catalyst component, and can have an excellent overall performance of the obtained hydrocarbon polymerization catalyst component.
  • Another object of the present invention is to provide an olefin polymerization catalyst component prepared by using the disulfonic acid ester compound.
  • the present invention first provides a disulfonate compound having the following formula I,
  • n is an integer and n ⁇ 0;
  • R 1 and R 2 are the same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20;
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, and a C3-C20 cycloalkane. a group consisting of a C6-C20 aryl group, a C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are not all hydrogen and/or a halogen atom.
  • the alkyl group, ring in the group selected from the group consisting of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Any one or more of the carbon atoms and/or hydrogen atoms in the alkyl group, the aryl group, the arylalkyl group, the alkaryl group, the alkene group and the fused ring aryl group are substituted by a halogen atom. More preferably, any one or several hydrogen atoms on any one or several of the aryl, alkaryl and aralkyl groups selected from the group of R 1 and R 2 are replaced by a halogen atom .
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 contain at least one hetero atom selected from nitrogen, oxygen, sulfur, A group of silicon, phosphorus, and halogen atoms.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 (and a carbon attached to these substituents) form a ring (ring form)
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 (and a carbon attached to these substituents) form a ring (ring form)
  • R 3 - R 8 may be any of R 3 - R 8 into a ring, can be a three-membered ring, four-membered ring, five-membered ring, six-membered ring, fused ring, etc.), forming a cycloalkyl-substituted diol a sulfonate or aryl substituted diphenol sulfonate, and a sulfonate in which one oxygen in the ester group is attached to the aryl group (phenol) and the other oxygen is linked to the alkyl group (alcohol).
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 may be double-bonded.
  • R 1 and R 2 are respectively selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Composition of tert-butyl, n-pentyl, cyclopentyl, cyclohexyl, phenyl, alkylphenyl, halophenyl, haloalkylphenyl, fluorenyl, benzyl, phenylethyl and fused ring aryl Group.
  • R 1 and R 2 are each selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylbenzene a group consisting of a halo, a halophenyl group, and a haloalkylphenyl group.
  • aryl group and the fused ring aryl group are a group substituted or unsubstituted by a halogen atom.
  • At least one of R 3 and R 4 is selected from the group consisting of hydrogen, a halogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • R 5 and R 6 is selected from the group consisting of hydrogen , halogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl substituted phenyl) And a group consisting of halophenyl groups.
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are groups which are substituted or unsubstituted by a halogen atom. More preferably, R 3 and R 4 are not all phenyl groups, and R 5 and R 6 are not all phenyl groups.
  • R 3 and R 4 are each selected from the group consisting of hydrogen, a halogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a benzene group.
  • R 5 and R 6 are each selected from hydrogen, a halogen atom, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl-substituted phenyl) and halogenated A group consisting of phenyl groups.
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are groups which are substituted or unsubstituted by a halogen atom.
  • R 3 and R 4 are not all phenyl groups, and R 5 and R 6 are not all phenyl groups.
  • one of R 3 and R 4 is hydrogen and the other is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkyl a group consisting of a phenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halophenyl group;
  • one of R 5 and R 6 is hydrogen and the other is selected from the group consisting of methyl, ethyl, and n-propyl a group consisting of isopropyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl-substituted phenyl) and halophenyl;
  • R 7 and R 8 is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary.
  • R 7 and R 8 are each selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkane A group consisting of a phenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halophenyl group.
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are groups which are substituted or unsubstituted by a halogen atom.
  • R 7 and R 8 are not all phenyl groups.
  • R 7 and R 8 are a group containing a benzene ring. More preferably, the benzene ring-containing group is a phenyl group, a phenyl group substituted by a C1-C20 alkyl group and/or a halogen atom. Particularly preferably, R 7 and R 8 are each selected from the group consisting of a phenyl group, a phenyl group substituted by a C1-C20 alkyl group and/or a halogen atom.
  • n 0, 1, 2, 3, 4 or 5.
  • the disulfonate compound has the following general formula IV:
  • n 1
  • at least one of R 3 , R 4 , R 5 and R 6 is hydrogen.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a halogen atom, but R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are not all hydrogen and/or a halogen atom; and at least one of the groups of the groups R 3 and R 4 , R 5 and R 6 is hydrogen, but R 3 , R 4 , R 5 and R 6 are not all hydrogen.
  • n 1, and three of R 3 , R 4 , R 5 and R 6 are hydrogen, the other is a halogen-substituted or unsubstituted methyl group. , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or phenyl.
  • the other two groups The group is not all halogen. More preferably, when R 3 and R 4 , R 5 and R 6 are the same group other than hydrogen, and only one of R 7 and R 8 is hydrogen, then another of R 7 and R 8 A group other than hydrogen is different from a group other than hydrogen in R 3 , R 4 , R 5 and R 6 .
  • R 5 and R 6 is selected from linear and branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkene and C6-C20 thick a group consisting of a cyclic aryl group (more preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, phenyl and substituted or unsubstituted) a group consisting of an alkylphenyl group (preferably a C1-C20 alkyl-substituted phenyl group), and when they are the same, R 7 and R 8 are not all hydrogen, and one of R
  • a group consisting of a C2-C20 olefin group and a C6-C20 fused ring aryl group (more preferably selected from a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group substituted or unsubstituted by a halogen atom)
  • Base isobutyl, tert-butyl, phenyl and alkylphenyl (preferably C1-C20 alkyl substituted phenyl) The group formed).
  • alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkaryl group, the alkene group and the fused ring aryl group are a group in which a halogen atom is substituted or unsubstituted.
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are not Hydrogen and/or halogen atoms.
  • R 3 and R 4 are hydrogen or a halogen atom
  • at least one of R 5 and R 6 is hydrogen or a halogen atom
  • R 7 , R 8 , R 9 and R 10 are not all hydrogen. More preferably, only one of R 3 and R 4 is hydrogen or a halogen atom, and only one of R 5 and R 6 is hydrogen or a halogen atom, and R 7 , R 8 , R 9 and R 10 are not all hydrogen.
  • R 1 and R 2 are each selected from the group consisting of a phenyl group, a phenyl group substituted by a C1-C20 alkyl group and/or a halogen atom.
  • R 3 and R 4 is hydrogen and the other is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkane a group consisting of a phenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halophenyl group;
  • one of R 5 and R 6 is hydrogen and the other is selected from the group consisting of methyl, ethyl, and a group consisting of propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl-substituted phenyl) and halophenyl
  • R 7 , R 8 , R 9 and R 10 are respectively selected from hydrogen
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are groups which are substituted or unsubstituted by a halogen atom.
  • R 3 and R 4 is hydrogen
  • the other is methyl
  • one of R 5 and R 6 is hydrogen
  • One is a methyl group
  • R 7 and R 8 are all hydrogen or hydrogen and methyl respectively
  • at least one of R 1 and R 2 is a halogen atom and/or an alkyl group (preferably a C1-C20 alkyl group). Substituted phenyl.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are not hydrogen, and R 3 , Several groups of R 4 , R 5 , R 6 , R 7 and R 8 respectively bonded to different carbon atoms form a fused ring; more preferably, and at least one of R 1 and R 2 is selected from a halogen atom Or a group consisting of an unsubstituted aryl group and an alkaryl group; particularly preferably, both of R 1 and R 2 are selected from the group consisting of an aryl group and an alkylaryl group substituted or unsubstituted with a halogen atom.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are not ring-formed, and at least R 1 and R 2 are There is a group consisting of an aryl group and an alkylaryl group which are substituted or unsubstituted by a halogen atom; more preferably, R 1 and R 2 are each selected from an aryl group and an alkylaryl group which are substituted or unsubstituted by a halogen atom. Group.
  • R 1 and R 2 are each selected from the group consisting of a phenyl group, a phenyl group substituted by a C1-C20 alkyl group and/or a halogen atom.
  • R 3 and R 4 is hydrogen and the other is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkyl a group consisting of a phenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halophenyl group;
  • one of R 5 and R 6 is hydrogen and the other is selected from the group consisting of methyl, ethyl, and n-propyl a group consisting of isopropyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl-substituted phenyl) and halophenyl;
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are groups which are substituted or unsubstituted by a halogen atom.
  • the disulfonate compound of formula I comprises a compound of formula V:
  • X is carbon or nitrogen
  • Y is carbon or nitrogen
  • R 1 and R 2 are the same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20;
  • R 3 ', R 4 ', R 5 ' and R 6 ' are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, A group consisting of an aryl group of C6-C20, an aralkyl group of C7-C20, an alkaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20.
  • the disulfonate compound of formula I comprises a compound of formula VI:
  • a and B are each selected from the group consisting of carbon, nitrogen, oxygen and sulfur;
  • R 1 and R 2 are the same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20;
  • R 3 ", R 4 ", R 5 “ and R 6 " are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, A group consisting of an aryl group of C6-C20, an aralkyl group of C7-C20, an alkaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20.
  • the disulfonate compound of formula I comprises a compound of formula VII:
  • R 1 and R 2 are the same or different and are respectively selected from a linear and branched alkyl group derived from C1 to C10, a cycloalkyl group of C3-C20, an aryl group of C6-C20, an aralkyl group of C7-C20, a group consisting of alkyl alkaryl groups of C7-C20;
  • R 3 , R 4 , R 5 and R 6 are the same or different and are respectively selected from hydrogen, C1-C10 linear and branched alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C7-.
  • the disulfonate compound of formula I comprises a compound of formula VIII:
  • R 1 and R 2 are the same or different and are respectively selected from a linear or branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group. a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, a fused ring aryl group of C6-C20, optionally hydrogen in the phenyl ring of the aryl group, the alkylaryl group or the aralkyl group The ground is replaced or unsubstituted by a halogen atom;
  • R 11 - R 16 are each hydrogen or methyl.
  • the disulfonate compound of formula I comprises a compound of formula IX:
  • R 1 and R 2 are the same or different and are respectively selected from a linear or branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group. a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, a fused ring aryl group of C6-C20, optionally hydrogen in the phenyl ring of the aryl group, the alkylaryl group or the aralkyl group The ground is replaced or unsubstituted by a halogen atom;
  • R 3 , R 4 , R 5 and R 6 are the same or different and are respectively selected from hydrogen, a halogen atom, a linear or branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, and a C6-C20 aromatic group. a group consisting of a C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;
  • R 11 '-R 18 ' is hydrogen or methyl, respectively.
  • the disulfonate compound of formula I comprises a compound of formula X:
  • R 1 and R 2 are the same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group. a group consisting of a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;
  • R 3 , R 4 , R 5 , R 6 , R 11 ′′ and R 12 ′′ are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, and a C3-C20 group. a group consisting of a cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;
  • R 3 , R 4 , R 5 , R 6 , R 11 ′′ and R 12 ′′ are not all hydrogen and/or a halogen atom.
  • the disulfonate compound of formula I comprises a compound of formula XI:
  • R 1 and R 2 are the same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group. a group consisting of a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;
  • R 3 , R 4 , R 5 and R 6 are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 group.
  • R 3 , R 4 , R 5 and R 6 contain at least one hetero atom selected from the group consisting of nitrogen, oxygen, sulfur, silicon, phosphorus and a halogen atom, and in R 3 , R 4 , R 5 and R 6 Several are looped or not looped together;
  • R 1 ", R 2 ", R 3 “ and R 4 " are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6 group. a group of -C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkene and C6-C20 fused ring aryl, and R 1 ", R 2 Several of “, R 3 “ and R 4 " form or not form a fused ring structure.
  • disulfonate compound represented by Formula I of the present invention includes, but is not limited to, the following:
  • the above-mentioned disulfonic acid ester compound provided by the present invention can be obtained by the following method: a diol compound, a diphenol compound or a monophenol monool compound (that is, one hydroxyl group to be esterified is linked to an aryl group, and the other hydroxyl group is The alkyl-linked compound) is esterified with a sulfonic acid or a sulfonyl chloride to give the disulfonate compound.
  • the disulfonate compounds of the present invention can be prepared by a variety of methods.
  • the method for preparing the above-mentioned disulfonic acid ester compound comprises the steps of: a hydrocarbyl sulfonic acid (RSO 3 H, wherein R is R 1 or R 2 in the above formula I) or a hydrocarbyl sulfonate
  • An acid chloride (RSO 3 Cl, wherein R is R 1 or R 2 in the above formula I) is esterified with a diol compound, a diphenol compound or a monophenol monool compound having the formula XII to give the Disulfonate compound,
  • n is an integer and n ⁇ 0;
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, and a C3-C20 cycloalkane. a group consisting of a C6-C20 aryl group, a C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are not all hydrogen and/or halogen.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as described above and will not be described herein.
  • the diol compound, the diphenol compound or the monophenol monool compound having the formula XII can be produced according to the preparation method in the prior art, as in the case of CN1041752A, pages 5-6, CN1141285A.
  • a method for producing the disclosed diol compound and a method for synthesizing 9,9-(bishydroxymethyl)anthracene (Acta Chemica Scandina-vica 21, pp. 718-720). The entire contents of the above-mentioned three documents are hereby incorporated by reference herein.
  • the diol compound, the diphenol compound or the monophenol monool compound has the following formula XIV:
  • the diol compound, the diphenol compound or the monophenol monool compound has the following formula XV:
  • the present invention also provides the use of the above disulfonic acid ester compound in the preparation of an olefin polymerization catalyst component.
  • the disulfonate compound of the present invention is applied to the preparation of the olefin polymerization catalyst component to obtain a catalyst component excellent in overall performance.
  • the use of the catalyst component as a main catalyst for catalyzing the polymerization of olefins has high catalytic activity and sensitivity to hydrogen modulation, and a polymer having high stereospecificity and a broad molecular weight distribution can also be obtained.
  • the above olefin polymerization catalyst component can be produced by a method in the prior art, such as the following methods.
  • One of the methods is: grinding the anhydrous magnesium dichloride and the disulfonic acid ester compound of the present invention under the activation condition of magnesium dichloride; and grinding the mixture at 80-135 ° C with excess TiCl 4
  • the reaction is carried out once or several times for each reaction time of 0.5 to 4 hours; then the solid mixture after the reaction is washed with a hydrocarbon solvent (washing is required after each reaction) until it is free of chloride ions, and an olefin polymerization catalyst component is obtained.
  • Another method is: grinding magnesium dichloride, a titanium compound and a disulfonate compound of the present invention in an anhydrous state to obtain a ground mixture; and then using, for example, 1,2-dichloroethane, chlorobenzene,
  • the halogenated hydrocarbon such as dichloromethane is reacted with the milled mixture at a temperature of from 40 ° C to the boiling point of the halogenated hydrocarbon for 1-4 hours; then the solid mixture after the reaction is washed with an inert hydrocarbon solvent such as hexane.
  • An olefin polymerization catalyst component is obtained.
  • Still another method is: pre-activation of magnesium dichloride by a known method, and then reacting with pre-activated magnesium dichloride at 80-135 ° C using an excess of TiCl 4 solution containing the disulfonate compound of the present invention or Several times, the solid mixture after the reaction is washed with an inert hydrocarbon solvent such as hexane to remove unreacted TiCl 4 to obtain an olefin polymerization catalyst component.
  • an inert hydrocarbon solvent such as hexane
  • Still another method is to prepare an olefin polymerization catalyst by reacting a magnesium alkoxide or a chloroalcoholate with an excess TiCl 4 solution containing the disulfonic acid ester compound of the present invention at 80 to 135 °C.
  • the reaction is carried out for 0.5 to 2 hours to prepare an olefin polymerization catalyst.
  • the adduct of the formula MgCl 2 ⁇ pTOH can be suitably formed into a spherical shape by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon solvent which is not miscible with the adduct, so that the emulsion rapidly quenches. Thereby, the adduct is cured in the form of spherical particles.
  • examples of spherical MgCl 2 ⁇ pTOH adducts prepared in accordance with this method can be found in USP 4,399,054 and USP 4,469,648.
  • the MgCl 2 ⁇ pTOH adduct obtained by this method can be directly reacted with the titanium compound, or it can be subjected to a thermally controlled dealcoholization (at 80-130 ° C) to obtain a new adduct, wherein The number of moles of alcohol is generally less than 4, preferably from 2 to 3.5.
  • the reaction with the titanium compound can be carried out by suspending the MgCl 2 ⁇ pTOH adduct (dealcoholated or unde-alcoholized) in cold TiCl 4 (generally below 0 ° C). Wherein TiCl 4 is used as the titanium compound, and other titanium compounds may be used instead of TiCl 4 , and the reaction with TiCl 4 may be carried out once or several times.
  • the disulfonic acid ester compound of the present invention may be added to TiCl 4 to carry out the reaction, and one or several reactions may be carried out. After the reaction, the solid mixture is washed to obtain an olefin polymerization catalyst
  • Still another method is: using a solution of an aromatic hydrocarbon (for example, toluene, xylene, etc.) of TiCl 4 containing the disulfonate compound of the present invention at 80 to 130 ° C with, for example, a dialkoxymagnesium or a diaryloxy group.
  • a magnesium alkoxide compound such as magnesium is reacted for a reaction time of 0.5 to 4 hours, and may be reacted once or several times, after which the solid mixture after the reaction is washed to obtain an olefin polymerization catalyst component.
  • the present invention provides an olefin polymerization catalyst component prepared by using the above-described disulfonic acid ester compound, which comprises the reaction product of the following raw materials:
  • Raw material (1) composite carrier which forms a solution by contacting a magnesium halide with one or several compounds capable of dissolving magnesium halide, and then mixing the solution with silica having an average particle diameter of less than 10 ⁇ m, and preparing by spray drying ;
  • electron donor b at least one selected from the group consisting of aliphatic mono- and dicarboxylic acid ester compounds, aromatic mono- and dicarboxylic acid ester compounds, and diether compounds represented by formula XVI
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and are respectively selected from hydrogen, C1-C10 linear and branched alkyl, C3-C10 cycloalkyl, C6 a group consisting of an aryl group of C10, an aralkyl group of C7-C10, an alkylaryl group of C7-C10; R 7 and R 8 are the same or different and are respectively selected from linear and branched alkane from C1 to C10; a group consisting of a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, and a C7-C20 alkaryl group;
  • Raw material (4) titanium halide at least one compound selected from the group consisting of titanium compounds represented by the general formula Ti(OQ) 4-m Z m , wherein Q is selected from the group consisting of C1-C14 aliphatic hydrocarbon groups Group, several Qs may be the same or different, Z is selected from the group consisting of F, Cl and Br, several Z may be the same or different, and m is an integer from 1 to 4;
  • the total amount of the electron donor a and the electron donor b is 0.01 to 1 mole per mole of the magnesium halide in the composite carrier, and the molar ratio of the electron donor a to the electron donor b is 0.1 to 10, the titanium compound It is 1-100 moles.
  • the electron donor b is selected from the group consisting of a benzoate compound, a phthalate compound, a malonate compound, a succinate compound, and a pentane compound.
  • the malonate compound is represented by the formula XVII:
  • R 1 ' and R 2 ' are the same or different and are each selected from the group consisting of methyl and ethyl;
  • R 3 ' and R 4 ' are the same or different and are each selected from a C1-C20 hydrocarbon group and a hydrocarbon oxygen group.
  • the glutarate compound is represented by the formula XVIII:
  • R 1" and R 2" are the same or different and are each selected from the group consisting of hydrocarbyl groups;
  • R 3" - R 8" are the same or different and are each selected from the group consisting of hydrogen, C1-C20 hydrocarbyl groups.
  • R 3" - R 8" is preferably a hydrocarbon group which is substituted by a halogen atom and which has two substituents on the same carbon atom bonded to form a ring.
  • the succinate compound is represented by the formula XVX:
  • R 1"' and R 2"' are the same or different and are each selected from the group consisting of a C1-C20 hydrocarbon group (which may contain a hetero atom);
  • R 3"' -R 6"' are the same or different, respectively a group consisting of hydrogen, C1-C20 hydrocarbon groups (which may contain heteroatoms); preferably, R 3"' -R 6"' is not all hydrogen, and R 3"' -R 6"' is not
  • the group of hydrogen is selected from the group consisting of a C1-C20 hydrocarbon group which may contain a hetero atom.
  • the magnesium halide used in the composite carrier has a general formula of Mg(OJ) 2-v G v , wherein J is selected from a linear chain of C 1 - C 14 , a group consisting of branched and cyclic alkyl groups, several J may be the same or different, G is selected from the group consisting of F, Cl and Br, several G may be the same or different, v is 0, 1 or 2.
  • the magnesium halide includes, but is not limited to, magnesium dichloride, magnesium dibromide, magnesium phenoxide chloride, magnesium isopropoxide chloride, magnesium butoxide chloride, magnesium diethoxylate, and the like.
  • the magnesium halide may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.
  • the compound for dissolving the magnesium halide is selected from the group consisting of halogenated fatty alcohols, halogenated aromatic alcohols, aliphatic ethers, cyclic ethers, aliphatic ketones, fatty acid alkyl esters, aromatic acids. a group consisting of alkyl esters.
  • halogenated C1-C8 saturated fatty alcohols are halogenated C1-C8 saturated fatty alcohols; lower alkyl esters of C1-C4 saturated aliphatic carboxylic acids; C7-C8 aromatic mono- and polycarboxylic acid lower alkyl esters; C2-C8, Preferred are C4-C5 fatty ethers; C4-C5 aliphatic ethers; C4-C5 cycloaliphatic ethers; preferably C4 monoethers or diethers; and C3-C6, preferably C4-C5 Aliphatic ketone.
  • “Lower alkyl” as used herein refers to a C1-C6 alkyl group.
  • the compound for dissolving the magnesium halide comprises at least one group selected from the group consisting of halogenated C1-C8 fatty alcohols, C7-C10 aromatic alcohols.
  • the compound is at least one of a halogenated C1-C8 fatty alcohol and a C7-C10 aromatic alcohol, or a halogenated C1-C8 fatty alcohol and/or a C7-C10 aromatic alcohol and a C1-C6 Fatty ether, C3-C5 cyclic ether, fat or A mixture of C1-C6 alkyl esters of aromatic carboxylic acids.
  • examples of the compound for dissolving the magnesium halide include, but are not limited to, methanol, ethanol, isopropanol, n-butanol, isobutanol, isoamyl alcohol, n-octanol, and isooctyl Alcohol, ethylene glycol, propylene glycol, chlorohydrin, trichloroethanol, diethyl ether, dibutyl ether, methyl formate, ethyl acetate, butyl acetate, hexyl ether, tetrahydrofuran (THF), acetone, methyl isobutyl ketone, benzene Ethyl formate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, etc., preferably ethanol, isopropanol, n-butanol, trichloroethanol,
  • the compound for dissolving the magnesium halide further includes a system containing an organic epoxy compound selected from the group consisting of C2-C8 fat, and/or an organic phosphorus compound.
  • the organophosphorus compound is selected from the group consisting of C1-C10 hydrocarbyl esters of orthophosphoric acid and phosphorous acid and halohydrocarbyl esters.
  • C1-C10 hydrocarbyl esters of orthophosphoric acid and phosphorous acid and halohydrocarbyl esters For example: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl methyl phosphite .
  • the compound for dissolving the magnesium halide may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.
  • the preparation of such a solution can be carried out in the presence of an inert solvent which does not form an adduct with the magnesium halide.
  • the inert solvent is selected from the group consisting of C5-C12 alkane, C1-C6 halogenated hydrocarbon and C6-C12 aromatic hydrocarbon, such as hexane, heptane, dichloromethane, toluene, xylene, B. Benzene, etc.
  • the inert solvent may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.
  • the silica is generally selected from silica having an average particle diameter of less than 10 ⁇ m, also referred to as fumed silica, to facilitate spray molding to obtain a composite carrier of smaller particles.
  • the specific surface area of such silica is generally 200 ⁇ 50 m 2 /g.
  • the silica has an average particle size of less than 1 ⁇ m.
  • the solution is mixed with silica to obtain a slurry suitable for spraying.
  • silica is added in an amount of from 10 to 200 g per liter of the solution.
  • the spray drying may be carried out by the following steps: a slurry obtained by mixing a solution with silica and a dry dry gas are spray-dried by a spray dryer to obtain a spherical composite carrier solid. Particles.
  • the composite carrier has an average diameter of 5 to 60 ⁇ m, more preferably 10 to 40 ⁇ m, particularly preferably 12 to 30 ⁇ m, which is capable of making the composite carrier more suitable.
  • the titanium halide may be selected from titanium tetrahalide, particularly titanium tetrachloride, trichlorobutoxy and trichlorophenoxy titanium; tetraalkoxy titanium, particularly It is titanium tetrabutoxide, titanium tetraethoxide, and the like.
  • the titanium halide may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.
  • the total amount of the electron donor a and the electron donor b is 0.05 to 0.5 mole per mole of the magnesium halide in the composite carrier; the electron donor a and the electron donor b
  • the molar ratio is 0.2-5.
  • the olefin polymerization catalyst component of the present invention can be produced by various published production methods.
  • the electron donor a and the electron donor b may be treated before or after the reaction of the composite carrier with the titanium compound.
  • the electron donor a and the electron donor b can be used together in a variety of ways, can be added under the same or different steps or conditions, preferably in the same steps and conditions.
  • the olefin polymerization catalyst component of the present invention can be produced by the following method:
  • the magnesium halide solution can be prepared according to some of the disclosed methods, such as the magnesium halide dissolution system disclosed in US Pat. No. 4,478,983 and US Pat.
  • the magnesium halide solution is prepared as follows:
  • an alcohol or a mixture of two or more alcohols may be added, or an ether or an ester may be further added, and then anhydrous magnesium halide is added, and the magnesium halide is dissolved by heating; wherein the alcohol and the magnesium halide are The molar ratio is (3-50): 1, and the molar ratio of the ether or ester to the magnesium halide is (0-20):1.
  • the above magnesium halide may also be dissolved in an inert solvent in an amount of 0-20 mL/g based on the mass of the magnesium halide;
  • the amount of silica gel is 0.1-2 g per gram of magnesium halide, and the silica gel used is fumed silica having an average particle diameter of less than 10 ⁇ m; then stirring at 10-100 ° C 0.5-3h, the slurry is prepared; then the slurry is spray-dried together with the inert dry gas by a spray dryer to obtain a spherical Mg(OJ) 2-v G v /SiO 2 composite carrier having an average particle size of 5-60 ⁇ m; The inlet air temperature during spray drying is controlled at 80-300 ° C, and the outlet gas temperature is controlled at 50-200 ° C; in general, the composition of the composite carrier is:
  • SiO 2 10% - 60% by weight
  • the above composite carrier is suspended in a mixture of a titanium halide and an inert solvent (preferably hexane) (the amount of titanium halide is 5-10 mL/g by mass of the composite carrier, and the volume ratio of the inert solvent to the titanium halide is 0-2)
  • a titanium halide preferably hexane
  • an inert solvent preferably hexane
  • the amount of titanium halide is 5-10 mL/g by mass of the composite carrier, and the volume ratio of the inert solvent to the titanium halide is 0-2
  • an excess of titanium halide the amount of titanium halide is 12-16 mL / g based on the mass of the composite carrier
  • the temperature is slowly raised to 100-120 ° C, and the electron donor a and the electron donor b are simultaneously added during the temperature increase, and the total amount of the electron donor a and the electron donor b is calculated per mole of the magnesium halide in the composite carrier.
  • the molar ratio of electron donor a to electron donor b is 0.1-10; after 1-2 hours of reaction, it can be filtered; then a certain amount of titanium halide can be added, maintained at 120 ° C for 1-2 h, and then filtered (final The step of adding a titanium halide may be omitted; washing the solid product with an inert solvent such as hexane or the like, and then drying the solid product under vacuum at 30 to 50 ° C to obtain an olefin polymerization catalyst of the present invention.
  • the olefin polymerization catalyst component of the invention is used in combination with a composite carrier and two internal electron donor compounds, thereby ensuring high activity, high stereospecificity and high hydrogen modulating sensitivity of the obtained catalyst, and at the same time, can be prepared by using the catalyst.
  • the polymer has a high bulk density and a broad molecular weight distribution, which is advantageous for industrial production and post-polymer processing.
  • the present invention also provides an olefin polymerization catalyst comprising the following components:
  • Component (1) the above olefin polymerization catalyst component
  • Component (2) an alkyl aluminum compound.
  • the olefin polymerization catalyst component of the present invention may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.
  • the alkyl aluminum compound is preferably triethyl aluminum and/or triisobutyl aluminum.
  • the alkyl aluminum compounds may be used singly or in combination of several kinds, and when used in combination, may be mixed in any ratio.
  • the catalyst further comprises an organosilicon compound of the formula (3) of the formula T 1 u Si(OT 2 ) 4-u as an external electron donor component, wherein T 1 Selected from the group consisting of hydrogen, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group and a halogenated alkyl group, several T 1 's may be the same or different; T 2 is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a halogenated alkyl group.
  • T 2 may be the same or different; T 1 and T 2 are the same or different; u is an integer of 0-3.
  • the organosilicon compound may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.
  • the ratio between the component (1) and the component (2) is 1: (5-1000), preferably 1: (20-500) in terms of a molar ratio of titanium: aluminum. .
  • the ratio between the component (1) and the component (3) is 1: (5-500) in terms of a molar ratio of titanium: silicon.
  • the ratio between the component (2) and the component (3) is from 0.1 to 500, more preferably from 1 to 300, particularly preferably from 3 to 100, in terms of a molar ratio of aluminum: silicon. .
  • the present invention also provides the use of the above olefin polymerization catalyst in the polymerization of olefins.
  • the polymerization of the olefin can be carried out according to known methods, such as in the liquid phase of a liquid monomer or a solution of a monomer in an inert solvent, or in a gas phase, or by a combined polymerization process in a gas phase. Take action.
  • the polymerization temperature is usually from 0 to 150 ° C, preferably from 60 to 100 ° C.
  • the polymerization pressure is normal pressure or higher.
  • the present invention provides a dibasic acid ester compound having a specific structure which is used as an internal electron donor for the preparation of an olefin polymerization catalyst component (i.e., a main catalyst), and a catalyst component excellent in overall performance can be obtained.
  • a catalyst component i.e., a main catalyst
  • a catalyst component excellent in overall performance can be obtained.
  • the catalyst component is used for the polymerization of propylene, a satisfactory polymerization yield can be obtained; and the obtained polymer has high stereospecificity, and even when an external electron donor is not used, a higher isotacticity can be obtained.
  • the polymer at the same time, the catalyst component is also very sensitive to hydrogen modulation; and the molecular weight distribution of the obtained polymer is wide, which is favorable for the development of different grades of polymers.
  • the catalyst component can give less gel content when used for copolymerization of olefins, particularly ethylene-propylene copolymerization, and thus has better copoly
  • the present invention utilizes the above-mentioned disulfonic acid ester compound having a special structure in combination with a conventional internal electron donor compound, and is combined with a composite carrier to prepare an olefin polymerization catalyst having high activity, high stereospecificity and high hydrogen sensitivity sensitivity.
  • the catalyst is compounded with a catalyst such as an alkyl aluminum compound to make the prepared polymer have a higher bulk density and a broader molecular weight distribution, which is advantageous for industrial production and post-polymer processing; and the activity of the catalyst It has a certain balance with the stereoregularity of the polymer (especially polypropylene resin), that is, the high activity catalyst can be obtained, and the higher stereoregularity of the polymer can be ensured.
  • the industrial application of catalysts is very important.
  • melt index use The MI-4 melt indexer was used for the measurement, and the test method was in accordance with GB/T3682-2000.
  • Measurement of nuclear magnetic resonance Measurement was carried out by using a Bruker-400 nuclear magnetic resonance apparatus 1 H-NMR (400 MHz, solvent CDCl 3 , TMS as an internal standard, and a measurement temperature of 300 K).
  • the isotacticity of the polymer is determined by heptane extraction (boiling heptane extraction for 6 hours): 2 g of the dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The ratio of the weight (g) of the polymer obtained by drying the remaining polymer sample to constant weight is 2, which is isotactic.
  • This example provides 1,2-butanediol ditosylate which is prepared by the following method:
  • 1,2-butanediol (2.50 g), pyridine (8.80 g) and tetrahydrofuran (70 mL) were added to the reactor, and after mixing uniformly, p-toluenesulfonyl chloride (10.60 g) was added in four portions, and at 0. After reacting at ° C for 4 hours, the reaction was continued to room temperature for 6 hours, and then water was added to the reaction system until the inorganic phase was transparent; the organic phase was separated, and the inorganic phase was extracted with diethyl ether, and the extracted diethyl ether solution was combined with the organic phase. The organic phase combined with the extracted diethyl ether solution was washed and dried over anhydrous sodium sulfate.
  • This example provides 2,3-butanediol xylene sulfonate, which is prepared in substantially the same manner as the preparation method in Example 1, except that the raw material 1,2-butanediol in Example 1 is used. It was replaced with 2,3-butanediol in the same amount as in Example 1, to give the product 4.69 g.
  • the results of nuclear magnetic resonance measurement of the product were: ⁇ 1.4-1.6 (6H), 2.3-2.6 (6H), 5.3-5.5 (2H), 7.2-8.0 (8H), and it was confirmed that the preparation of this example obtained 2, 3 - Butanediol ditosylate.
  • This example provides catechol di-p-toluenesulfonate, which is prepared by the following method:
  • This example provides dimethyl 2,5-dicarboxylate-3,4-dihydroxydi-p-toluenesulfonate, which is prepared by the following method:
  • Examples 5-8 each provide an olefin polymerization catalyst component which is prepared according to the preparation method as described below:
  • Example 5-8 After the filtrate was drained, 60 mL of toluene and 40 mL of TiCl 4 were added, and the mixture was reacted at 100 ° C for 2 hours to remove the filtrate; 60 mL of toluene was added, and the mixture was washed three times in a boiling state. Further, 60 mL of hexane was added, washed three times in a boiling state, and then 60 mL of hexane was added, and after washing twice at normal temperature, the olefin polymerization catalyst component of Example 5-8 was obtained.
  • This example provides 2,4-pentanediol di-p-toluenesulfonate, which is prepared by the following method:
  • 2,4-pentanediol (2.92 g), pyridine (8.80 g) and tetrahydrofuran (70 mL) were added to the reactor, and after mixing uniformly, p-toluenesulfonyl chloride (10.60 g) was added in four portions under stirring.
  • This example provides 2,4-pentanediol diphenyl sulfonate, which is prepared by the following method:
  • 2,4-pentanediol (2.92 g), pyridine (8.80 g) and tetrahydrofuran (70 mL) were added to the reactor, and after mixing uniformly, benzenesulfonyl chloride (10.60 g) was added in four portions under stirring, and After reacting at 0 ° C for 4 hours, the reaction was continued to room temperature for 6 hours, and then water was added to the reaction system until the inorganic phase was transparent; the organic phase was separated, and the inorganic phase was extracted with diethyl ether, and then the extracted diethyl ether solution was combined with the organic phase.
  • This example provides 2,4-pentanediol di-p-chlorobenzenesulfonate, which is prepared by the following method:
  • This example provides 2,6-dimethyl-3,5-heptanediol diphenyl sulfonate, which is prepared by the following method:
  • This example provides 2,6-dimethyl-3,5-heptanediol di-p-toluenesulfonate, which is prepared by the following method:
  • This example provides 2,6-dimethyl-3,5-heptanediol di-p-chlorobenzenesulfonate, which is prepared by the following method:
  • This example provides 3-methyl-2,4-pentanediol di-p-chlorobenzenesulfonate, which is prepared by the following method:
  • This example provides 3-methyl-2,4-pentanediol di-p-toluenesulfonate, which is prepared by the following method:
  • This example provides 2-ethyl-1,3-hexanediol xylene sulfonate which is prepared by the following method:
  • This example provides 2,2,4-trimethyl-1,3-pentanediol diphenyl sulfonate, which is prepared by the following method:
  • This example provides 6-heptene-2,4-heptanediol diphenyl sulfonate, which is prepared by the following method:
  • 6-heptene-2,4-heptanediol was added to the reactor in 0.02 mol, pyridine 0.06 mol, and then 0.05 mol of benzenesulfonyl chloride was slowly added dropwise. After the end of the reaction, the reaction was carried out for 8 hours; after the reaction was completed, the reaction mixture was filtered, and the solid fraction was washed three times with anhydrous diethyl ether; then the organic phase was washed with brine, and then dried over anhydrous magnesium sulfate. After chromatography separation, the product was obtained.
  • This example provides 1,8-dinaphthol di-p-toluenesulfonate, which is prepared by the following method:
  • This example provides 9,9-bis(p-toluenesulfonylmethyl)fluorene, which is prepared in substantially the same manner as in the preparation method of Example 10, except that the raw material 2 in Example 10 is used.
  • the 4-pentanediol was replaced with 9,9-bishydroxyindole in the same molar amount as in Example 10.
  • the results of nuclear magnetic resonance measurement of the product were: ⁇ 2.3-2.6 (6H), 7.2-7.8 (16H), and it was confirmed that 9,9-bis(p-toluenesulfonylmethyl)anthracene was obtained in the present example.
  • This example provides cis-1,2-bis(p-toluenesulfonylmethyl)cyclohexane, which is prepared in substantially the same manner as the preparation method in Example 9, except that the same will be given in Example 9.
  • the raw material 1,3-butanediol was replaced with cis-1,2-cyclohexanediol in the same molar amount as in Example 9.
  • the results of nuclear magnetic resonance measurement of the product were: ⁇ 1.2-1.5 (10H), 2.3-2.6 (6H), 3.5-3.7 (4H), 7.2-7.8 (8H), and it was confirmed that the preparation of this example gave 1,1- Bis(p-toluenesulfonylmethyl)cyclohexane.
  • Examples 26-29 respectively provide an olefin polymerization catalyst component which is prepared according to the preparation method as follows:
  • This example provides 2,3-diethyl-1,4-butanediol di-p-toluenesulfonate, which is prepared by the following method:
  • This example provides 2,5-dimethyl-2,5-hexanediol di-p-toluenesulfonate, which is prepared in substantially the same manner as in the preparation method of Example 30, except that Example 30 will be used.
  • the raw material 2,3-diethyl-1,4-butanediol was replaced with 2,5-dimethyl-2,5-hexanediol in the same molar amount as in Example 1, to give the product 7.92. g.
  • the results of nuclear magnetic resonance measurement of the product were: ⁇ 1.5-1.7 (12H), 2.1-2.3 (4H), 2.3-2.6 (6H), 7.2-7.9 (8H), and it was confirmed that the preparation of this example gave 2,5. - Dimethyl-2,5-hexanediol di-p-toluenesulfonate.
  • This example provides 3,6-dimethyl-3,6-dioctanol di-p-toluenesulfonate, which is prepared in substantially the same manner as in the preparation method of Example 30, except that Example 30 will be used.
  • the raw material 2,3-diethyl-1,4-butanediol was replaced by 3,6-dimethyl-3,6-dioctanol in the same molar amount as in Example 1, to obtain the product 8.34. g.
  • This example provides cis-2-butene-1,4-diol di-p-toluenesulfonate, which is prepared in substantially the same manner as the preparation method in Example 1, except that the raw material in Example 30 is used.
  • Replace 2,3-diethyl-1,4-butanediol with cis 2-butene-1,4-diol was added in the same amount as in Example 1 to give the product 9.78 g.
  • the results of nuclear magnetic resonance measurement of the product were: ⁇ 2.3-2.6 (6H), 3.8-4.2 (4H), 5.3-5.8 (2H), 7.2-7.9 (8H), and it was confirmed that cis-2 was prepared in this example.
  • - Butene-1,4-diol di-p-toluenesulfonate
  • Examples 34-37 respectively provide an olefin polymerization catalyst component which is prepared according to the preparation method as follows:
  • the temperature was raised to 100 ° C for 2 hours, after draining the filtrate, add 60 mL of toluene, 40 mL of TiCl 4 , react at 100 ° C for 2 hours, drain the filtrate; add 60 mL of toluene, wash three times in boiling state, then add 60 mL of hexane, The mixture was washed three times in a boiling state, and then 60 mL of hexane was added thereto, and after washing twice at normal temperature, the olefin polymerization catalyst component of Examples 34 to 37 was obtained.
  • This example provides 1,5-diphenyl-1,5-pentanediol di-p-toluenesulfonate, which is prepared by the following method:
  • the present embodiment provides 1,4-hexanediol di-p-toluenesulfonyl ester, which is prepared in the same manner as in the preparation method of Example 1, except that the raw material 1,5-diphenyl in Example 1 is used.
  • the benzyl-1,5-pentanediol was replaced with 1,4-hexanediol in the same molar amount as in Example 1, and the step of reducing the ketone to an alcohol was omitted to obtain a product.
  • the results of nuclear magnetic resonance measurement of the product are: ⁇ 1.1-1.2 (8H), 1.8-1.9 (2H), 2.3-2.6 (6H), 4.2-4.3 (4H), 7.2-7.8 (8H), and the present embodiment can be determined.
  • 1,4-hexanediol di-p-toluenesulfonyl ester was obtained.
  • This example provides 1,5-hexanediol di-p-toluenesulfonate, which is prepared in the same manner as the preparation method in Example 1, except that the raw material 1,5-diphenyl in Example 1 is used.
  • the benzyl-1,5-pentanediol was replaced with 1,5-hexanediol in the same amount as in Example 1, and the step of reducing the ketone to the alcohol was omitted to obtain a product.
  • the present embodiment provides 2,2'-biphenyldiethanol di-p-toluenesulfonate, which is prepared in the same manner as in the first embodiment, except that the raw material in the first embodiment is 1,5- Diphenyl-1,5-pentanediol was replaced with 2,2'-biphenyldimethanol in the same molar amount as in Example 1, and the step of reducing the ketone to the alcohol was omitted to obtain the product.
  • Examples 42-45 provide an olefin polymerization catalyst component, respectively, which is prepared according to the preparation method described below:
  • the temperature was raised to 100 ° C for 2 hours, after draining the filtrate, add 60 mL of toluene, 40 mL of TiCl 4 , react at 100 ° C for 2 hours, drain the filtrate; add 60 mL of toluene, wash three times in boiling state, then add 60 mL of hexane, The mixture was washed three times in a boiling state, then 60 mL of hexane was added, and after washing twice at normal temperature, the olefin polymerization catalyst component of Examples 42 to 45 was obtained.
  • This comparative example provides an olefin polymerization catalyst component which is prepared in substantially the same manner as in the preparation methods of Examples 5-8, 26-29, 34-37 and 42-45, except that the disulfide is disulfide.
  • the acid ester compound (internal electron donor) is replaced by ethylene glycol di-p-toluenesulfonate.
  • This comparative example provides an olefin polymerization catalyst component, which is prepared in the same manner as in Examples 5-8, 26-29, 34-37.
  • the preparation method is basically the same as in 42-45 except that the disulfonate compound (internal electron donor) is replaced with ethyl benzoate.
  • This comparative example provides an olefin polymerization catalyst component which is prepared in substantially the same manner as in the preparation methods of Examples 5-8, 26-29, 34-37 and 42-45, except that the disulfide is disulfide.
  • the acid ester compound (internal electron donor) is replaced with di-n-butyl phthalate.
  • the solid catalyst components of the above Examples 5-8, 26-29, 34-37 and 42-45 and Comparative Examples 1-3 were used to catalyze the polymerization of propylene.
  • the propylene polymerization was carried out by disposing a 5 L stainless steel autoclave having a volume of 5 rpm with a gas propylene, and then adding AlEt 3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 thereto. Further, 8-10 mg (preferably 10 mg) of the solid catalyst component prepared in the above Examples 5-8, 26-29, 34-37 and 42-45 and Comparative Examples 1-3 and 1.2 L of hydrogen were added, respectively.
  • CHMMS methylcyclohexyldimethoxysilane
  • the solid catalyst component prepared in Examples 5-8, 26-29, 34-37, 42-45 or Comparative Example 1-3, AlEt 3 and CHMMS constitute an olefin polymerization catalyst, which collectively catalyzes the polymerization of propylene.
  • the catalyst activity is calculated by the amount of the obtained polypropylene / the amount of the solid catalyst component added, and the obtained polypropylene powder is subjected to isotacticity, melt index and molecular weight distribution test, and the test method is as described above. The results are shown in Table 1.
  • the catalytic activity of the olefin polymerization catalyst component prepared in Examples 5-8, 26-29, 34-37 and 42-45 is higher, and the stereospecific orientation of the polymer prepared by using the catalyst component is obtained. Higher properties and wider molecular weight distribution are beneficial for processing applications.
  • This example provides an olefin polymerization catalyst component which is prepared by the following method:
  • the present embodiment provides an olefin polymerization catalyst component, which is prepared in substantially the same manner as the preparation method in Example 46, except that the addition of 1,8-dinaphthol di-p-toluenesulfonate is simultaneously Dibutyl phthalate was added in an amount of 1.24 g.
  • the present embodiment provides an olefin polymerization catalyst component, a preparation method thereof and a preparation method in the embodiment 46 Basically the same, the only difference is that 1,8-dinaphthol di-p-toluenesulfonate is replaced with 9,9-bis(p-toluenesulfonylmethyl)phosphonium, which is used in an amount of 3.20 g. 9,9-bis(methoxymethyl)anthracene was added in an amount of 1.16 g.
  • the present comparative example provides an olefin polymerization catalyst component which is prepared in substantially the same manner as in the preparation method of Example 46 except that 1,8-dinaphthol dip-toluenesulfonate is replaced with 1, 3-butanediol ditosylate, which was used in an amount of 2.74 g.
  • This comparative example provides an olefin polymerization catalyst component which is prepared in substantially the same manner as in the preparation method of Example 46 except that 1,8-dinaphthol di-p-toluenesulfonate is replaced with o-benzene.
  • Dibutyl diformate was used in an amount of 2.29 g.
  • the present comparative example provides an olefin polymerization catalyst component which is prepared in substantially the same manner as in the preparation method of Example 46 except that 1,8-dinaphthol dip-toluenesulfonate is replaced with 9 , 9-bis(methoxymethyl)anthracene, used in an amount of 1.75 g.
  • the solid catalyst component prepared in the above Examples 46-48 and Comparative Examples 4-6 was used to catalyze the polymerization of propylene.
  • the propylene polymerization was carried out by disposing a 5 L stainless steel autoclave having a volume of 5 rpm with a gas propylene, and then adding AlEt 3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 thereto.
  • CHMMS methylcyclohexyldimethoxysilane

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Abstract

L'invention concerne un composé d'ester d'acide disulfonique de formule générale I, un composant catalyseur de polymérisation d'oléfines préparé à l'aide du composé d'ester d'acide disulfonique, d'un support composite d'halogénure de magnésium et de dioxyde de silicium, d'un composé donneur d'électrons interne classique et d'un composé d'halogénure de titane en tant que matières premières de la réaction, de manière à utiliser deux composés donneurs d'électrons internes afin de garantir ainsi à la fois l'activité d'un catalyseur et la tacticité d'un polymère ainsi préparé. L'invention concerne également un catalyseur de polymérisation d'oléfines comprenant le composant et l'utilisation de celui-ci.
PCT/CN2015/096119 2014-12-05 2015-12-01 Composé d'ester d'acide disulfonique, utilisation de celui-ci, composant catalyseur de polymérisation d'oléfines et catalyseur de polymérisation d'oléfines WO2016086837A1 (fr)

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CN201410738688.3A CN104496865A (zh) 2014-12-05 2014-12-05 一种二元醇磺酸酯化合物及其制备方法与应用
CN201410736716.8 2014-12-05
CN201410742935.7A CN105712909B (zh) 2014-12-05 2014-12-05 用于制备烯烃聚合催化剂的二元磺酸酯化合物
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CN201410740490.9A CN104403027B (zh) 2014-12-05 2014-12-05 一种烯烃聚合催化剂及含其的组合催化剂和其应用
CN201410738164.4A CN105712908A (zh) 2014-12-05 2014-12-05 用于制备烯烃聚合催化剂的1,3二元磺酸酯化合物
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