WO2023240961A1 - 一种乙丙共聚催化剂组合物及其制备和应用 - Google Patents

一种乙丙共聚催化剂组合物及其制备和应用 Download PDF

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WO2023240961A1
WO2023240961A1 PCT/CN2022/138923 CN2022138923W WO2023240961A1 WO 2023240961 A1 WO2023240961 A1 WO 2023240961A1 CN 2022138923 W CN2022138923 W CN 2022138923W WO 2023240961 A1 WO2023240961 A1 WO 2023240961A1
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alkyl
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halogenated
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French (fr)
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李新乐
李华姝
辛世煊
周逸
胡泓梵
孙鑫
张雪芹
李阳
胡才仲
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中国石油天然气股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/28Metal alcoholates
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00Metallocenes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04Monomers containing three or four carbon atoms
    • C08F210/06Propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/02Carriers therefor
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the invention relates to an ethylene-propylene copolymerization catalyst composition and its preparation and application.
  • Metallocene complexes that introduce nitrogen, phosphorus, etc. into the cyclopentadienyl ring (Cp) or into the saturated or unsaturated ring adjacent to the Cp ring. Oxygen, sulfur, and other heteroatoms.
  • Metallocene complexes containing heteroatom rings either have special polymerization activity for olefins, or have special regio or stereoselectivity (C. De Rosa, F. Auriema, A. Di Capua, L. Resconi, S. Guidotti, I. Camurati, I.E. Nifant'ev, I.P. Laishevtsev, J. Am. Chem. Soc. 2004, 12, 17040).
  • US6756455 describes a class of nitrogen-containing ⁇ -ligand zirconocene complexes, particularly zirconocene complex catalysts coordinated by bridged indenoindole derivatives and bridged indenoindole derivatives.
  • This type of zirconocene complex catalyst has high activity, high molecular weight, and bimodal molecular weight distribution under appropriate conditions when used in ethylene homopolymerization.
  • US6683150 discloses numerous examples of Group IV transition metallocene complex catalysts using bridged indenoindole derivatives as ligands to catalyze the polymerization of propylene in a wide temperature range to produce high molecular weight polypropylene.
  • WO03089485 provides a catalytic system formed by a combination of a nitrogen-containing ⁇ -ligand Group IV transition metallocene complex and methylaluminoxane (MAO), using a very low aluminum/metal ratio and having high activity. When combined with appropriate carriers, high molecular weight linear low density polyethylene (mLLDPE) can be produced.
  • mLLDPE high molecular weight linear low density polyethylene
  • WO9924446 describes a class of cene complexes formed between nitrogen-containing heteroatom ⁇ -ligands and Group IV transition metals.
  • This type of metallocene complex is not only simple to synthesize and has high yield, but also is an excellent olefin polymerization catalyst after activation with methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), which can be polymerized to produce respectively.
  • MAO methylaluminoxane
  • MMAO modified methylaluminoxane
  • the resulting copolymer not only has a lower molecular weight, but the distribution of the two monomers in the copolymer is not random and tends to be segmented.
  • this type of zirconocene complex catalyst can greatly reduce the probability of 2,1- and 1,3-misinsertion when catalyzing propylene polymerization.
  • metallocene catalysts serve as homogeneous catalysts, and the polymer products produced have poor morphology, which can easily cause clogging of polymerization kettles and devices during polymerization and product transportation. They have poor adaptability to industrial devices, making industrial use difficult. Therefore, it needs to be supported on a solid catalyst for application.
  • Silica gel is a widely used carrier because of its high specific surface area, good fluidity, suitable bulk density, suitable average particle size and particle size distribution, and relatively suitable mechanical strength.
  • the activity is not particularly ideal, because during the loading process, the metal catalyst ligands can react with the hydroxyl groups on the carrier, causing the ligands to fall off, causing part of the catalyst to lose activity.
  • the catalyst may also interact with other parts of the support.
  • ethylene-propylene copolymerization requires larger-sized carrier pores to form a cross-linked rubber phase, and the pore size and pore volume distribution inside the silica gel carrier is not large enough, it often cannot meet the needs of ethylene-propylene copolymerization production with high rubber content.
  • One object of the present invention is to provide a catalyst composition suitable for producing ethylene-propylene copolymer. Another object of the present invention is to provide a method for preparing the above-mentioned olefin polymerization catalyst composition. Another object of the present invention is to provide the application of the above-mentioned olefin polymerization catalyst composition in ethylene-propylene copolymerization.
  • the embodiment of the present invention provides an olefin polymerization catalyst composition.
  • the catalyst composition includes a main catalyst, a cocatalyst and a magnesium compound carrier.
  • the magnesium compound carrier is selected from the group consisting of Mg(OR I )(OR II ), wherein, R I The same as or different from R II , it is a C 1 -C 8 hydrocarbon group, the cocatalyst is a Lewis acidic substance LA, and the main catalyst is a metallocene complex represented by the general formula (I):
  • M is a transition metal element in the third, fourth, fifth or sixth group of the periodic table of elements, including lanthanide and actinide elements;
  • R is a C 1 -C 20 linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, or an alkyl group containing heteroatoms of elements from groups 13 to 17 of the periodic table.
  • is a divalent free radical , including C 2 -C 40 alkylene, C 6 -C 30 arylene, C 7 -C 40 alkylene, C 7 -C 40 aryl alkylene; in -OR° In the O-structure, two oxygen atoms are at any position of the free radical;
  • n is an integer from 1 to 4; the sum of the charges of X is equal to the charge of M minus 2;
  • A is a ⁇ -ligand with a structure shown in chemical formula (II):
  • E is a divalent free radical of elements from Group 16 or Group 15 in the periodic table, including oxygen radicals, sulfur radicals, selenium radicals, NR′′ and PR′′, R′′ is C 1 -C 10 Linear alkyl, phenyl, monosubstituted or polysubstituted phenyl, benzyl, monosubstituted or polysubstituted benzyl, 1-naphthyl, 2-naphthyl, 2-anthracenyl, 1-phenanthrenyl, 2-phenanthrene base or 5-phenanthrene base;
  • L is a divalent free radical and has a structure represented by the following chemical formula (III), (IV), (V), (VI), (VII) or (VIII), where i is 2:
  • R 1 and R 12 are hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl or 2-thienyl;
  • R 2 , R 3 and R 13 are respectively hydrogen, fluorine or R, where R is a C 1 -C 20 linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group or contains an element Alkyl groups of heteroatoms of elements from Groups 13 to 17 of the periodic table, or C 3 -C 20 cycloalkyl groups, C 6 -C 30 aryl groups, C 7 -C 30 alkyl substituted aryl groups, or C 7 -C 30 aromatic substituted alkyl;
  • R 4 is H, methyl, trifluoromethyl, isopropyl, tert-butyl, phenyl, p-tert-butylphenyl, p-trimethylsilylphenyl, p-trifluoromethylphenyl, 3, 5-Dichloro-4-trimethylsilylphenyl or 2-naphthyl;
  • R 5 is hydrogen, fluorine or methyl
  • R 6 and R 7 are respectively hydrogen, fluorine or R, where R is a C 1 -C 20 linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, or a group containing elements in the periodic table of elements.
  • R 8 is methyl, ethyl, isopropyl, tert-butyl or phenyl;
  • R 9 and R 9' are phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3 -phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, furan, thiophene, quinoline or pyrimidine, wherein the substituent in the substituted phenyl group is cyano, nitro, F, methyl, ethyl, isopropyl, tert-butyl, methoxy, tert-butyl, trifluoromethoxy, Cl, trifluoromethyl, carbonyl or trimethylsilyl;
  • R 10 and R 10' are hydrogen, fluorine, chlorine, methyl, ethyl or phenyl;
  • R 11 and R 11' are hydrogen, fluorine, chlorine, ester, alkoxy, thiol, amine or phosphine.
  • the monovalent anion ⁇ -ligand of A has a chemical structure represented by the chemical formula (II)-Li + ;
  • the chemical formula (II) contains the basic structure of a cyclopentadiene ring,
  • the active hydrogen in the cyclopentadiene structure has electrophilic reactivity and can undergo an exchange reaction with a nucleophile to form a compound represented by chemical formula (II)-Li + .
  • the basic reaction is as shown in the following reaction formula:
  • the nucleophile in the reaction formula is an organolithium reagent LiR n , where R n is a C 1 -C 6 alkyl group or a C 6 -C 12 aryl group.
  • X is chlorine, bromine, C 1 -C 20 lower alkyl group or aryl group.
  • M is a transition metal element in the third, fourth, fifth or sixth group of the periodic table of elements, including lanthanide and actinide elements.
  • metal elements of the third and fourth groups or the lanthanide series are preferred, and zirconium, hafnium and titanium of the fourth group are most preferred.
  • X is the same or different from each other, and is hydrogen, halogen, alkyl R, alkoxy OR, mercapto SR, carboxyl OCOR, amine (NR 2 ), phosphine (PR 2 ), -OR°O- or OSO 2CF3 .
  • R is a C 1 -C 20 linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, and optionally contains elements from groups 13 to 17 of the periodic table.
  • C 1 -C 20 saturated alkyl and haloalkyl groups include: methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl , n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, Triethylsilyl, triphenylsilyl, etc., but are not limited thereto.
  • Examples of C 1 -C 20 unsaturated alkyl groups include vinyl, propenyl, allyl, etc., but are not limited thereto.
  • Examples of C 3 -C 20 cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantane, etc., but are not limited thereto.
  • C 6 -C 30 aryl groups include: phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-Phenyl, 4-Phenyl, 9-Phenyl, etc., but are not limited to these.
  • C 7 -C 30 alkyl substituted aryl groups include: 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylbenzene base, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl base, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-iso Propylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro -4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropyl
  • C 7 -C 30 aromatic substituted alkyl groups include: benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butyl Benzyl, etc., p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylbenzyl Base, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenylethyl, p-fluorophenylethyl, p-chlorophenylethyl, p-isopropylphenylethyl, p-tert-butylbenzene Ethyl, p-trimethylsilylphenylethyl, 2,6-difluor
  • is a divalent free radical, such as C 2 -C 40 alkylene, C 6 -C 30 arylene, C 7 -C 40 alkylene, C 7 -C 40 arylene alkyl.
  • the two oxygen atoms can be at any position of the free radical, but the preferred position of the two oxygen atoms is at the adjacent ( ⁇ , ⁇ -position) and interphase ( ⁇ , ⁇ -position) of the free radical. -bit) position combination.
  • X is preferably chlorine, bromine of halogen, and lower alkyl and aryl (such as methyl, phenyl, benzyl, etc., but not limited to this).
  • n is an integer from 1 to 4.
  • the total number of charges on X is equal to the number of charges on M minus 2.
  • R′ is the same or different, and is a C 1 -C 20 linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, and optionally contains the 13th to 13th elements in the periodic table of elements.
  • C 1 -C 20 saturated and haloalkyl groups include: methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n-butyl base, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethyl Silicon-based, triphenylsilyl-based, etc., but are not limited thereto.
  • Examples of C 1 -C 20 unsaturated alkyl groups include vinyl, propenyl, allyl, etc., but are not limited thereto.
  • Examples of C 3 -C 20 cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantyl, etc., but are not limited thereto.
  • C 6 -C 30 aryl groups include: phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-Phenyl, 4-Phenyl, 9-Phenyl, etc., but are not limited to these.
  • C 7 -C 30 alkyl substituted aryl groups include: 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, 2-fluoro-4-methylbenzene base, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl base, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-iso Propylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro -4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropyl
  • C 7 -C 30 aromatic substituted alkyl groups include: benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butyl Benzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylbenzyl , 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenylethyl, p-fluorophenylethyl, p-chlorophenylethyl, p-isopropylphenylethyl, p-tert-butylphenylethyl base, p-trimethylsilylphenylethyl, 2,6-difluorophen
  • R' is preferably methyl, ethyl, isopropyl, trimethylsilyl, phenyl or benzyl.
  • A is a ⁇ -ligand with a general structure shown in chemical formula (II);
  • E is a divalent free radical of an element in Group 16 or Group 15 of the periodic table, such as oxygen radical, sulfur radical, arsenic radical, NR′′, PR′′.
  • R′′ is a C 1 -C 20 linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, optionally containing elements from groups 13 to 17 of the periodic table of elements.
  • C 20 saturated and haloalkyl groups include: methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n-butyl, Isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilylmethyl, triethylsilyl Methyl, triphenylsilylmethyl, etc., but are not limited thereto.
  • C 1 -C 20 unsaturated alkyl groups include vinyl, propenyl, allyl, etc., but are not limited to these.
  • C 3 - Examples of C 20 cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantane, etc.
  • C 6 -C 30 aryl groups For example, phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, etc., but are not limited thereto.
  • C 7 -C 30 alkyl substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methyl Phenyl, 2-fluoro-4-methylphenyl, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methyl Phenyl, 2-chloro-4-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2 , 6-diethylphenyl, 2-isopropylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4 -Methylphenyl, 3,5-difluoro-4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-iso
  • C 7 -C 30 aromatic substituted alkyl groups include benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropyl benzyl, p-tert-butylbenzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3, 5-bistrimethylbenzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenylethyl, p-fluorophenylethyl, p-chlorophenylethyl, p-isopropylphenylethyl p-tert-butylphenylethyl, p-trimethylsilylphenylethyl, 2,6-difluorophenylethyl
  • R′′ in the above combination is preferably a C 4 -C 10 linear alkyl group, phenyl group, mono-substituted or multi-substituted phenyl group, benzyl group, mono-substituted or multi-substituted benzyl group, 1-naphthyl group, 2-naphthyl group , 2-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 5-phenanthrenyl. All R′′ below have the same meaning.
  • E is preferably elemental sulfur, oxygen, NR′′ and PR′′. where R′′ is as defined above.
  • R 1 is any one of the following, C 1 -C 40 saturated or unsaturated alkyl group, halogenated or non-halogenated alkyl group, alkyl group optionally containing heteroatoms of elements from groups 13 to 17 of the periodic table of elements. Or a C 3 -C 40 cycloalkyl group, a C 6 -C 40 aryl group, a C 7 -C 40 alkyl substituted aryl group, or a C 7 -C 40 aryl substituted alkyl group.
  • C 1 -C 40 saturated and haloalkyl groups include methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilylmethyl, trimethylsilyl Ethylsilylmethyl, triphenylsilylmethyl, etc., but are not limited thereto.
  • Examples of C 1 -C 20 unsaturated alkyl groups include vinyl, propenyl, allyl, etc., but are not limited thereto.
  • Examples of C 3 -C 40 cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantane, etc.
  • C 6 -C 40 aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-Phenyl, 4-Phenyl, 9-Phenyl, etc., but are not limited to these.
  • C 7 -C 40 alkyl substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, and 2-fluoro-4-methylbenzene base, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl base, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-iso Propylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro -4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropyl
  • C 7 -C 40 aromatic substituted alkyl groups include benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, and p-tert-butyl Benzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylbenzyl , 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenylethyl, p-fluorophenylethyl, p-chlorophenylethyl, p-isopropylphenylethyl, p-tert-butylphenylethyl base, p-trimethylsilylphenylethyl, 2,6-difluorophen
  • R 1 is preferably hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl. All R 1's below have the same meaning.
  • R 2 and R 3 are hydrogen, fluorine or R.
  • R is as defined above.
  • R 2 and R 3 are preferably hydrogen. All R 2 and R 3 below have the same meaning.
  • R 4 is any one of the following, C 1 -C 40 saturated or unsaturated alkyl group, halogenated or non-halogenated alkyl group, alkyl group optionally containing heteroatoms of elements from groups 13 to 17 of the periodic table of elements. Or a C 3 -C 40 cycloalkyl group, a C 6 -C 40 aryl group, a C 7 -C 40 alkyl substituted aryl group, or a C 7 -C 40 aryl substituted alkyl group.
  • C 1 -C 40 saturated and haloalkyl groups include methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethyl Silicone base, triphenylsilyl base, etc., but are not limited thereto.
  • Examples of C 1 -C 20 unsaturated alkyl groups include vinyl, propenyl, propyl, etc., but are not limited thereto.
  • Examples of C 3 -C 40 cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantane, etc.
  • C 6 -C 40 aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-Phenyl, 4-Phenyl, 9-Phenyl, etc., but are not limited to these.
  • C 7 -C 40 alkyl substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, and 2-fluoro-4-methylbenzene base, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl base, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-iso Propylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro -4-Methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-iso
  • C 7 -C 40 aromatic substituted alkyl groups include benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, and p-tert-butyl Benzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylsilyl Benzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenylethyl, p-fluorophenylethyl, p-chlorophenylethyl, p-isopropylphenylethyl, p-tert-butyl Phenethyl, p-trimethylsilylphenylethyl, 2,6-difluor
  • R 4 is preferably H, methyl, trifluoromethyl, isopropyl, tert-butyl, phenyl, p-tert-butylphenyl, p-trimethylsilylphenyl, p-trifluoromethylphenyl, 3 , 5-dichloro-4-trimethylsilylphenyl, 2-naphthyl. And all R 4 's below have the same meaning.
  • L is a divalent free radical and has any structure of the following general chemical formulas (III), (IV), (V), (VI), (VII), and (VIII);
  • i is an integer, i is not equal to zero, and i is preferably 2.
  • R 5 is the same or different, and is any one of the following, C 1 -C 40 saturated or unsaturated alkyl, halogenated or non-halogenated alkyl, optionally containing elements from groups 13 to 17 of the periodic table. Atom alkyl and C 3 -C 40 cycloalkyl, C 6 -C 40 aryl, C 7 -C 40 alkyl substituted aryl, C 7 -C 40 aryl substituted alkyl.
  • C 1 -C 40 saturated and haloalkyl groups include methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethyl Silicone base, triphenylsilyl base, etc., but are not limited thereto.
  • Examples of C 1 -C 20 unsaturated alkyl groups include vinyl, propenyl, allyl, etc., but are not limited thereto.
  • Examples of C 3 -C 40 cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantane, etc.
  • C 6 -C 40 aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-Phenyl, 4-Phenyl, 9-Phenyl, etc., but are not limited to these.
  • C 7 -C 40 alkyl substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, and 2-fluoro-4-methylbenzene base, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl base, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-iso Propylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro -4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropyl
  • C 7 -C 40 aromatic substituted alkyl groups include benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, and p-tert-butyl Benzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylsilyl Benzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenylethyl, p-fluorophenylethyl, p-chlorophenylethyl, p-isopropylphenylethyl, p-tert-butyl Phenethyl, p-trimethylsilylphenylethyl, 2,6-difluor
  • R 5 is preferably hydrogen, fluorine, or methyl. And all R 5's below have the same meaning.
  • R 6 and R 7 are equal to R 3 .
  • R3 is as defined above.
  • R 6 and R 7 are preferably hydrogen and fluorine elements. And all R 6 and R 7 below have the same meaning.
  • Z is a ⁇ -ligand.
  • Z has a chemical structure represented by the following general chemical formulas (IX), (X), (XI), (XII), (XIII), (XIV), (XV);
  • R 1 is as defined before.
  • R 1 is preferably methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, 2-furyl, 2-thienyl.
  • R 2 is hydrogen, fluorine, R.
  • R is as defined before.
  • R2 is preferably hydrogen.
  • R 8 is the same or different, and is any one of the following, C 1 -C 40 saturated or unsaturated alkyl, halogenated or non-halogenated alkyl, optionally containing elements from groups 13 to 17 of the periodic table. atomic alkyl group and C 3 -C 40 cycloalkyl group, C 6 -C 40 aryl group, C 7 -C 40 alkyl substituted aryl group, C 7 -C 40 aryl substituted alkyl group.
  • C 1 -C 40 saturated and haloalkyl groups include methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethyl Silicone base, triphenylsilyl base, etc., but are not limited thereto.
  • Examples of C 1 -C 20 unsaturated alkyl groups include vinyl, propenyl, allyl, etc., but are not limited thereto.
  • Examples of C 3 -C 40 cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantane, etc.
  • C 6 -C 40 aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrene base, 4-phenanthrene base, 9-phenanthrene base, etc., but are not limited to these.
  • C 7 -C 40 alkyl substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, and 2-fluoro-4-methylbenzene base, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl base, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-iso Propylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro -4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropyl
  • C 7 -C 40 aromatic substituted alkyl groups include benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, and p-tert-butyl Benzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylsilyl Benzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenylethyl, p-fluorophenylethyl, p-chlorophenylethyl, p-isopropylphenylethyl, p-tert-butyl Phenethyl, p-trimethylsilylphenylethyl, 2,6-difluor
  • R 8 is preferably methyl, ethyl, isopropyl, tert-butyl, or phenyl. And below all R 8 have the same meaning.
  • R 9 is the same or different, and is any one of the following, C 1 -C 40 saturated or unsaturated alkyl, halogenated or non-halogenated alkyl, optionally containing elements from groups 13 to 17 of the periodic table. atomic alkyl group and C 3 -C 40 cycloalkyl group, C 6 -C 40 aryl group, C 7 -C 40 alkyl substituted aryl group, C 7 -C 40 aryl substituted alkyl group.
  • C 1 -C 40 saturated and haloalkyl groups include methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethyl Silicone base, triphenylsilyl base, etc., but are not limited thereto.
  • Examples of C 1 -C 20 unsaturated alkyl groups include vinyl, propenyl, allyl, etc., but are not limited thereto.
  • Examples of C 3 -C 40 cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantane, etc.
  • C 6 -C 40 aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-Phenyl, 4-Phenyl, 9-Phenyl, etc., but are not limited to these.
  • C 7 -C 40 alkyl substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, and 2-fluoro-4-methylbenzene base, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl base, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-iso Propylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro -4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropyl
  • C 7 -C 40 aromatic substituted alkyl groups include benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, and p-tert-butyl Benzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylsilyl Benzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenylethyl, p-fluorophenylethyl, p-chlorophenylethyl, p-isopropylphenylethyl, p-tert-butyl Phenethyl, p-trimethylsilylphenylethyl, 2,6-difluor
  • R 9 is preferably a C 1 -C 20 linear or branched, saturated or unsaturated, partially or fully halogenated, linear or cyclic carbon radical. All R 9s below have the same meaning.
  • R 10 is the same or different, and is any one of the following, C 1 -C 40 saturated or unsaturated alkyl, halogenated or non-halogenated alkyl, optionally containing elements from groups 13 to 17 of the periodic table. atomic alkyl group and C 3 -C 40 cycloalkyl group, C 6 -C 40 aryl group, C 7 -C 40 alkyl substituted aryl group, C 7 -C 40 aryl substituted alkyl group.
  • C 1 -C 40 saturated and haloalkyl groups include methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethyl Silicone base, triphenylsilyl base, etc., but are not limited thereto.
  • Examples of C 1 -C 20 unsaturated alkyl groups include vinyl, propenyl, allyl, etc., but are not limited thereto.
  • Examples of C 3 -C 40 cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantane, etc.
  • C 6 -C 40 aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-Phenyl, 4-Phenyl, 9-Phenyl, etc., but are not limited to these.
  • C 7 -C 40 alkyl substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, and 2-fluoro-4-methylbenzene base, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl base, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-iso Propylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro -4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropyl
  • C 7 -C 40 aromatic substituted alkyl groups include benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, and p-tert-butyl Benzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylsilyl Benzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenylethyl, p-fluorophenylethyl, p-chlorophenylethyl, p-isopropylphenylethyl, p-tert-butyl Phenethyl, p-trimethylsilylphenylethyl, 2,6-difluor
  • R 10 is preferably hydrogen, fluorine, chlorine, methyl, ethyl or phenyl. And below all R 10 have the same meaning.
  • R 11 is the same or different, and is any one of the following; hydrogen, fluorine, chlorine, bromine, OR, SR, OCOR, NR 2 , PR 2 . where R is as defined above. Or R 11 is the same or different, and is any one of the following, C 1 -C 40 saturated or unsaturated alkyl group, halogenated or non-halogenated alkyl group, optionally containing elements from groups 13 to 17 of the periodic table of elements. Heteroatom alkyl group and C 3 -C 40 cycloalkyl group, C 6 -C 40 aryl group, C 7 -C 40 alkyl substituted aryl group, C 7 -C 40 aryl substituted alkyl group.
  • C 1 -C 40 saturated and haloalkyl groups include methyl, trifluoromethyl, ethyl, 1,1,1-trifluoroethyl, perfluoroethyl, n-propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-octadecyl, trimethylsilyl, triethyl Silicone base, triphenylsilyl base, etc., but are not limited thereto.
  • Examples of C 1 -C 20 unsaturated alkyl groups include vinyl, propenyl, allyl, etc., but are not limited thereto.
  • Examples of C 3 -C 40 cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, 1-adamantane, etc.
  • C 6 -C 40 aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-Phenyl, 4-Phenyl, 9-Phenyl, etc., but are not limited to these.
  • C 7 -C 40 alkyl substituted aryl groups include 2-methylphenyl, 2,6-dimethylphenyl, 2-fluoro-3-methylphenyl, and 2-fluoro-4-methylbenzene base, 2,6-difluoro-3-methylphenyl, 2,6-difluoro-4-methylphenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl base, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-iso Propylphenyl, 2,6-diisopropylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 3-fluoro-4-methylphenyl, 3,5-difluoro -4-methylphenyl, 3,5-difluoro-4-ethylphenyl, 3,5-difluoro-4-isopropyl
  • C 7 -C 40 aromatic substituted alkyl groups include benzyl, p-methylbenzyl, p-fluorobenzyl, p-chlorobenzyl, p-ethylbenzyl, p-isopropylbenzyl, and p-tert-butyl Benzyl, p-trifluoromethylbenzyl, p-trimethylsilylbenzyl, 3,5-difluorobenzyl, 3,4,5-trifluorobenzyl, 3,5-bistrimethylsilyl Benzyl, 3,5-bistrifluoromethylbenzyl, phenethyl, p-methylphenylethyl, p-fluorophenylethyl, p-chlorophenylethyl, p-isopropylphenylethyl, p-tert-butyl Phenethyl, p-trimethylsilylphenylethyl, 2,6-difluor
  • R 11 is preferably hydrogen, fluorine, chlorine, ester group, alkoxy group, thiol group, amine group or phosphine group. And all R 11 's below have the same meaning.
  • A is a monovalent anion ⁇ -ligand.
  • the precursor of A is a neutral, stable organic compound with a chemical structure as shown in general chemical formula (II);
  • R 1 , R 2 , R 3 , R 4 , L and E are as defined before.
  • the general chemical formula (II) contains the basic structure of a cyclopentadiene ring.
  • the active hydrogen in the cyclopentadiene structure has unique electrophilic reactivity and can undergo exchange reactions with nucleophiles such as Grignard reagents and organolithium reagents.
  • the basic reaction is as shown in the following reaction formula:
  • the nucleophile selects the organolithium reagent R n Li as a special case, but in practice, it is not limited to only using organolithium reagents.
  • R n is a C 1 -C 6 alkyl group, or a C 6 -C 12 aryl group.
  • the cocatalyst is Lewis acidic substance LA.
  • LA is polymethylaluminoxane or modified polymethylaluminoxane or organic boron reagent that has chain, cyclic and cage structure equilibrium states at the same time in the solution.
  • LA is a type of Lewis acidic substance with enlarged volume, delocalized electrons and poor coordination.
  • Representatives of this type of substance are polymethylaluminoxane (PMAO) which has chain, cyclic and cage structure equilibrium states at the same time in solution and polymethylaluminoxane (MMAO) modified on this basis.
  • PMAO polymethylaluminoxane
  • MMAO polymethylaluminoxane
  • the molar ratio of LA to metallocene complex LA M ⁇ 300.
  • the magnesium compound carrier Mg(OR I ) (OR II ) is dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium One of magnesium base, butoxyethoxymagnesium or their mixture.
  • the Mg:M molar ratio of the magnesium compound carrier and the metallocene complex (I) is 100 to 1000.
  • the embodiments of the present invention also relate to the synthesis method of the metallocene complex represented by the general formula (I):
  • T are the same or different from each other, and said T is a monodentate or bidentate neutral ligand;
  • LG is a leaving group, which may be the same or different from each other.
  • the LG is an organic free radical of hydrogen, an alkali metal element or a heavy element of Group 14.
  • the monodentate ligands include ether ROR, thioether RSR, tertiary amine NR 3 , tertiary phosphine PR 3 , cyclic ethers, cyclic thioethers, ketones, substituted cyclic ketones, substituted Pyridines, substituted pyrroles, substituted piperidines, esters, lactones, amides and lactams, where R is a C 1 -C 20 linear or branched alkyl, saturated or unsaturated alkyl, Halogenated or non-halogenated alkyl or alkyl containing heteroatoms of elements from Groups 13 to 17 of the periodic table, or C 3 -C 20 cycloalkyl, C 6 -C 30 aryl, C 7 - C 30 alkyl-substituted aryl group or C 7 -C 30 aryl-substituted alkyl group.
  • the bidentate ligands include ortho-diethers, ⁇ , ⁇ -diethers, ortho-diamines, ⁇ , ⁇ -diamines, ortho-disulfides, ⁇ , ⁇ -bis Thioethers, ortho-bisphosphines and ⁇ , ⁇ -bisphosphines.
  • x is 0 or the integer 1, 2 or 3.
  • the alkali metal elements include lithium, sodium and potassium;
  • the organic free radicals of the Group 14 heavy elements include SiR 3 , GeR 3 , SnR 3 , PdR 3 , ZnR, BaR, MgR and CaR, where, R Is a C 1 -C 20 linear or branched alkyl group, a saturated or unsaturated alkyl group, a halogenated or non-halogenated alkyl group, or an alkyl group containing heteroatoms of elements from groups 13 to 17 of the periodic table of elements, or C 3 -C 20 cycloalkyl, C 6 -C 30 aryl, C 7 -C 30 alkyl-substituted aryl or C 7 -C 30 aryl-substituted alkyl.
  • reaction medium during the synthesis process is saturated C 5 -C 15 alkane, cycloalkane or a mixture of two or more thereof.
  • the reaction medium during the synthesis process is hexane, heptane, octane, toluene or xylene.
  • the reaction temperature range is -100°C ⁇ +300°C.
  • reaction temperature range is -75°C ⁇ +250°C.
  • reaction temperature range is -50°C ⁇ +150°C.
  • the embodiment of the present invention relates to a method for preparing a magnesium compound carrier Mg(OR I )(OR II ): alcohol R I OH and alcohol R II OH and metal magnesium powder are heated and reacted in the presence of halogen until hydrogen is no longer produced, using Dilute and wash with an inert organic solvent to obtain Mg(OR I )(OR II ) solid.
  • the embodiment of the present invention relates to a preparation method of the catalyst composition: contacting a compound selected from the general formula (I) with a cocatalyst LA and a magnesium compound carrier Mg(OR I )(OR II ) in an inert organic solvent, thereby obtaining Catalyst composition.
  • the catalyst composition can be a dried solid powder, or can be dispersed or redispersed in an inert organic solvent to form a suspension.
  • the inert organic solvent is selected from: hexane, heptane, octane, decane or toluene.
  • Contact time is 1 minute to 8 hours.
  • the contact temperature is -75°C ⁇ 120°C.
  • Embodiments of the present invention also relate to the application of the catalyst composition in ethylene-propylene copolymerization.
  • the catalyst component of the present invention can be used in currently known olefin polymerization processes, including slurry and gas phase, and the polymerization conditions can be those commonly used in this field. Therefore, polymerization is generally carried out at 0 to 120°C, preferably 20 to 90°C.
  • the catalyst components may be pre-contacted with the alkyl aluminum compound before being introduced into the polymerization reactor. This pre-contacting step can be performed without polymerizable olefins.
  • the catalyst system of the metallocene main catalyst, the Lewis acid LA cocatalyst and the alkoxide magnesium carrier according to the present invention has high carrier particle strength and is not easily broken, effectively reduces the fine powder content of the polymer, and can greatly improve the problem of device clogging.
  • the magnesium alkoxide carrier has a large pore size and abundant holes inside, which is suitable for ethylene-propylene copolymerization production. It is conducive to generating a large amount of ethylene-propylene rubber in the holes and can greatly increase the ethylene-propylene rubber content in the copolymer. , improve copolymerization activity.
  • Comparative Example 5 does not use a carrier, the polymer has poor fluidity, agglomerates, and the packing density cannot be measured; the polymer data using a magnesium alkoxide carrier can be seen that the polymer morphology has improved. Low content of fine powder. It can be seen from Examples 1 to 4 that when using magnesium alkoxide carrier, compared with using ordinary silica gel carrier under the same conditions in Comparative Examples 1 to 4, the ethylene propylene copolymerization activity and ethylene propylene rubber content are greatly improved. The polymer molecular weight distribution is broad.
  • Determination of the actual ethylene-propylene rubber content Ru in polymer products The weight of the soluble part of xylene at room temperature as a percentage of the weight of the sample is the rubber content.
  • fine powder is defined as fine powder with a mesh size of less than 80 mesh (equivalent to a particle size less than 180um).
  • M is Zr.
  • the specific synthesis steps are described in Example 1 of CN105985368A.
  • the olefin polymerization catalyst component is carried by liquid propylene and continuously enters the first reactor through the reactor feed port.
  • the pressure is 2.0MPa
  • a certain amount of hydrogen is added to the reactor to control the molecular weight of homopolypropylene
  • the molar ratio of hydrogen to propylene is 2.5*10 -3 .
  • Residence time is 80 minutes.
  • the first gas phase reactor discharges the material, and the material enters the second gas phase reactor, where propylene and ethylene are copolymerized to obtain copolymerized polypropylene.
  • the gas phase reaction temperature is 75°C
  • the pressure is 2.1MPa
  • ethylene/propylene 1 (volume ratio)
  • a certain amount of hydrogen is added to the gas phase reactor feed
  • hydrogen / (ethylene + propylene) 0.001 (molar ratio)
  • low Pure nitrogen oxygen content 5000 ⁇ 6000ppm
  • Cat-1 to Cat4 are used as metallocene complexes.
  • Cat-1 to Cat4 are used as metallocene complexes.
  • Cat-1 to Cat4 are used as metallocene complexes.
  • Cat-1 ⁇ Cat-4 are used as metallocene complexes respectively.
  • the metallocene complexes Cat-1 to Cat-4 were respectively dissolved in toluene to prepare a solution with a concentration of 10 mM.
  • MAO methylaluminoxane
  • Cat-1 is used as the metallocene complex.
  • Comparative Example 5 does not use a carrier, the polymer has poor fluidity, agglomerates, and the packing density cannot be measured; the polymer data using a magnesium alkoxide carrier can be seen that the polymer morphology has improved. Low content of fine powder. It can be seen from Examples 1 to 4 that when using magnesium alkoxide carrier, compared with using ordinary silica gel carrier under the same conditions in Comparative Examples 1 to 4, the ethylene propylene copolymerization activity and ethylene propylene rubber content are greatly improved. The polymer molecular weight distribution is broad.

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Abstract

一种烯烃聚合催化剂组合物,包含主催化剂、助催化剂和镁化合物载体,所述镁化合物载体选自Mg(ORI)(ORII),其中,RI和RII相同或不同,是C1-C8的烃基;所述助催化剂为路易斯酸性物质LA;所述主催化剂为通式(I)所示的茂金属络合物:本发明还公开所述组合物的制备和应用。本发明所述组合物能大幅改善装置堵塞的问题;烷氧基镁载体孔容孔径较大,内部具有丰富的孔洞,适合用于乙丙共聚反应生产,有利于在孔洞中生成大量的乙丙橡胶,能大幅度提高共聚物中乙丙橡胶含量,提高共聚活性。

Description

一种乙丙共聚催化剂组合物及其制备和应用 技术领域
本发明涉及一种乙丙共聚催化剂组合物及其制备和应用。
背景技术
在茂金属络合物催化剂发展的过程中,除了经典的桥联取代环戊二烯(substituted-Cyclopentadienyl,Cp′)、桥联取代茚(substituted-Indenyl,Ind′)、桥联取代富烯(substituted fluorenyl,Flu′),及其Cp′/Ind′/Flu′之间互相组合,形成的数量庞大的茂金属络合物群之外(Metallocenes:Synthesis,Reactivity,Applications,A.Togni and R.L.Halterman Eds,Wiley,1998),近年来,尚有一定数量的茂金属络合物在环戊二烯基环(Cp)中,或与Cp环邻接的饱和或不饱和环中引入例如氮,磷,氧,硫,等杂原子。含杂原子环的茂金属络合物或具有特殊的对烯烃的聚合活性,或具有特殊的区域或立体选择性(C.De Rosa,F.Auriema,A.Di Capua,L.Resconi,S.Guidotti,I.Camurati,I.E.Nifant’ev,I.P.Laishevtsev,J.Am.Chem.Soc.2004,12,17040)。
US6756455描述了一类含氮π-配体锆茂络合物,特别是桥联的茚并砒硌衍生物和桥联的茚并吲哚衍生物配位的锆茂络合物催化剂。这类锆茂络合物催化剂用于乙烯均聚时具有高活性,高分子量,以及在适当条件下双峰分子量分布。US6683150揭示了桥联的茚并吲哚衍生物作为配位体的第四族过渡茂金属络合物催化剂,在较宽的温度范围内催化丙烯聚合,以生产高分子量聚丙烯的众多实例。WO03089485提供了一类含氮π-配位体第四族过渡茂金属络合物与甲基铝氧烷(MAO)组合形成的催化体系,使用非常低的铝/金属比,并具有高活性,与适当的载体配合时可生产高分子量线形低密度聚乙烯(mLLDPE)。WO9924446描述了一类含氮杂原子π-配位体与第四族过渡金属形成的茂络合物。这类茂金属络合物不但合成简单、产率高,而且经与甲基铝氧烷(MAO)或改性甲基铝氧烷(MMAO)活化后是优良的烯烃聚合催化剂,可分别聚合生产高分子量的聚乙烯和聚丙烯。
而利用同一催化体系对乙烯和丙烯进行共聚合时,得到的共聚物不但分子量较低,而且共聚物中两种单体的分布不是随机的,更趋向于崁段。同时与经典的C2-对称性锆茂络合物相比,这类锆茂络合物催化剂在催化丙烯聚合时可大大降低2,1-和1,3-误插入的几率。虽然含杂原子的π-配位茂金属络合物在乙烯以及α-烯烃均聚催化中表现非凡,但只有非常有限的关于乙烯与α-烯烃共聚催化的例子,且所得材料仍属塑料的一种(WO03-045964,WO03-0489485)。
在聚合生产应用中,茂金属催化剂作为均相催化剂,生产的聚合物产品形态差,在聚合和产品输送过程中易造成聚合釜及装置堵塞,对工业装置的适应性差,造成工业上使用困难。因此,需要将其负载在固体催化剂上应用。硅胶是被广泛采用的载体,因为其具有较高的比表面积、良好的流动性,适宜的堆密度,合适的平均粒径和粒径分布,以及较合适的机械强度。但其缺点是活性不是特别理想,因为在负载化过程中,金属催化剂配体能够与载体上的羟基反应,使配体脱落,导致部分催化剂失去活性。催化剂也可能与载体的其它部位发生作用。此外,由于乙丙共聚生成交联的橡胶相需要较大尺寸的载体孔洞,而硅胶载体内部的孔径孔容分布不够大,往往不能很好地满足高橡胶含量的乙丙共聚生产的需求。
发明内容
本发明的目的之一在于,提供一种适合于生产乙丙共聚物的催化剂组合物。本发明的另一目的在于提供上述烯烃聚合催化剂组合物的制备方法。本发明的再一目的在于提供上述烯烃聚合催化剂组合物的在乙丙共聚中的应用。
本发明实施例提供了一种烯烃聚合催化剂组合物,该催化剂组合物包含主催化剂、助催化剂和镁化合物载体,所述镁化合物载体选自Mg(OR I)(OR II),其中,R I和R II相同或不同,是C 1-C 8的烃基,所述助催化剂为路易斯酸性物质LA,所述主催化剂为通式(I)所示的茂金属络合物:
Figure PCTCN2022138923-appb-000001
其中,M是元素周期表中第三、第四、第五或第六族过渡金属元素,包括镧系和錒系元素;
X相互之间相同或不同,选自氢元素、卤素、烷基R、烷氧基OR、巯基SR、羧基OCOR、胺基NR 2、膦基PR 2、-OR°O-和OSO 2CF 3,R是C 1-C 20的直链或支化烷基、饱和或不饱和烷基、卤代或非卤代烷基或含有元素周期表中第十三到第十七族元素杂原子的烷基,或C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基;R°是二价自由基,包括C 2-C 40的亚烷基、C 6-C 30的亚芳基、C 7-C 40的烷代亚芳基、C 7-C 40的芳代亚烷基;在-OR°O-结构中,两个氧原子分别在自由基的任何位置;
n是从1到4的整数;X的电荷数之和等于M的电荷数减2;
Q是二价自由基,包括=CR′ 2、=SiR′ 2、=GeR′ 2、=NR′、=PR′、=BR′,其中,R′为甲基、乙基、异丙基、三甲基硅基、苯基或苄基;
A是π-配位体,具有如化学式(II)所示的结构:
Figure PCTCN2022138923-appb-000002
E是元素周期表中第十六族或第十五族元素的二价自由基,包括氧自由基、硫自由基、硒自由基、NR″和PR″,R″为C 1-C 10的直链烷基、苯基、单取代或多取代苯基、苄基、单取代或多取代苄基、1-萘基、2-萘基、2-蒽基、1-菲基、2-菲基或5-菲基;
L是二价自由基并具有下述化学式(III)、(IV)、(V)、(VI)、(VII)或(VIII)所示的结构,其中i为2:
Figure PCTCN2022138923-appb-000003
Z是一种π-配位体,Z=A,或Z具有下述化学式(IX)、(X)、(XI)、(XII)或(XIII)所 示的化学结构:
Figure PCTCN2022138923-appb-000004
其中,R 1、R 12为氢、甲基、乙基、异丙基、叔丁基、苯基、苄基、2-呋喃基或2-噻吩基;
R 2、R 3和R 13分别为氢、氟或R,其中,R是C 1-C 20的直链或支化烷基、饱和或不饱和烷基、卤代或非卤代烷基或含有元素周期表中第十三到第十七族元素杂原子的烷基,或C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基;
R 4为H、甲基、三氟甲基、异丙基、叔丁基、苯基、对叔丁基苯基、对三甲基硅基苯基、对三氟甲基苯基、3,5-二氯-4-三甲基硅基苯基或2-萘基;
R 5为氢、氟或甲基;
R 6和R 7分别为氢、氟或R,其中,R是C 1-C 20的直链或支化烷基、饱和或不饱和烷基、卤代或非卤代烷基或含有元素周期表中第十三到第十七族元素杂原子的烷基,或C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基;
R 8为甲基、乙基、异丙基、叔丁基或苯基;
R 9和R 9’为苯基、取代苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基、呋喃、噻吩、喹啉或嘧啶,其中取代苯基中的取代基为氰基、硝基、F、甲基、乙基、异丙基、叔丁基、甲氧基、叔丁基、三氟甲氧基、Cl、三氟甲基、羰基或三甲基硅基;
R 10和R 10’为氢、氟、氯、甲基、乙基或苯基;
R 11和R 11’为氢、氟、氯、酯基、烷氧基、硫醇基、胺基或膦基。
其中,化学结构式(I)中,A的一价阴离子π-配位体,具有化学式(II)-Li +所示的化学结构;化学式(II)中包含有环戊二烯环的基本结构,环戊二烯结构中的活泼氢具有亲电反应性,可与亲核试剂进行交换反应生成化学式(II)-Li +所示化合物,其基本反应如下列反应式所示:
Figure PCTCN2022138923-appb-000005
其中,反应式中亲核试剂为有机锂试剂LiR n,其中,R n是C 1-C 6的烷基或C 6-C 12的芳基。
其中,化学式(II)中符号﹡连接在化学键、原子或自由基上,表示﹡连接的此点与同类化学键、原子或自由基形成一个化学单键。
其中,X为氯、溴、C 1-C 20低碳烷基或芳基。
具体地,化学式(I)中:M是元素周期表中第三、第四、第五或第六族过渡金属元素,包括镧系和錒系元素。其中优选第三、第四族或镧系金属元素,最优选第四族的锆、鉿、钛。
X相互之间相同或不同,是氢元素、卤素、烷基R、烷氧基OR、巯基SR、羧基OCOR、胺基(NR 2),膦基(PR 2)、-OR°O-或OSO 2CF 3
其中,R是C 1-C 20的直链或支化烷基、饱和或不饱和烷基、卤代或非卤代烷基、选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基,或C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基、C 7-C 30的芳取代烷基。C 1-C 20饱和烷基及卤代烷基的例子如:甲基、三氟甲基、乙基、1,1,1-三氟乙基、全氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正十二烷基、正十八烷基、三甲基硅基、三乙基硅基、三苯基硅基等,但不局限于此。C 1-C 20不饱和烷基的例子如:乙烯基、丙烯基、烯丙基等、但不局限于此。C 3-C 20环烷基的例子如:环丙基、环丁基、环戊基、环己基、环辛基、1-金刚烷等,但不局限于此。C 6-C 30的芳基的例子如:苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等,但不局限于此。C 7-C 30烷取代芳基的例子如:2-甲基苯基、2,6-二甲基苯基、2-氟-3-甲基苯基、2-氟-4-甲基苯基、2,6-二氟-3-甲基苯基、2,6- 二氟-4-甲基苯基、2-氯-3-甲基苯基、2-氯-4-甲基苯基、2,6-二氯-3-甲基苯基、2,6-二氯-4-甲基苯基、2-乙基苯基、2,6-二乙基苯基、2-异丙基苯基、2,6-二异丙基苯基、3-甲基苯基、3,5-二甲基苯基、3-氟-4-甲基苯基、3,5-二氟-4-甲基苯基、3,5-二氟-4-乙基苯基、3,5-二氟-4-异丙基苯基、3,5-二氟-4-叔丁基苯基、3,5-二氟-4-三甲基硅基苯基、3-三氟甲基苯基、3,5-双三氟甲基苯基、4-甲基苯基、4-三氟甲基苯基、4-乙基苯基、4-异丙基苯基、4-叔丁基苯基、4-三甲基硅基苯基等,但不局限于此。C 7-C 30的芳取代烷基的例子如:苄基、对甲基苄基、对氟苄基、对氯苄基、对乙基苄基、对异丙基苄基、对叔丁基苄基等、对三氟甲基苄基、对三甲基硅基苄基、3,5-二氟苄基、3,4,5-三氟苄基、3,5-双三甲基苄基、3,5-双三氟甲基苄基、苯乙基、对甲基苯乙基、对氟苯乙基、对氯苯乙基、对异丙基苯乙基、对叔丁基苯乙基、对三甲基硅基苯乙基、2,6-二氟苯乙基、3,5—二氟苯乙基、3,4,5-三氟苯乙基、全氟代苯乙基、一位萘甲基、二位萘甲基等,但不局限于此。
R°是二价自由基,如C 2-C 40的亚烷基、C 6-C 30的亚芳基、C 7-C 40的烷代亚芳基、C 7-C 40的芳代亚烷基。在-OR°O-结构中,两个氧原子可分别在自由基的任何位置,但优选两个氧原子的位置为在自由基的相邻(α、β-位)和相间(α、γ-位)位置的组合。X在上述组合中优选为卤素的氯、溴,以及低碳烷基和芳基(如甲基、苯基、苄基等,但不局限于此)。
n是从1到4的整数。X的电荷数总数等于M的电荷数减2。
Q是二价自由基,如,=CR′ 2、=SiR′ 2、=GeR′ 2、=NR′、=PR′、=BR′。
其中:R′相同或不同,是C 1-C 20的直链或支化烷基、饱和或不饱和烷基、卤代或非卤代烷基、选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基,或C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基、C 7-C 30的芳取代烷基。C 1-C 20饱和及卤代烷基的例子如:甲基、三氟甲基、乙基、1,1,1-三氟乙基、全氟乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正十二烷基、正十八烷基、三甲基硅基、三乙基硅基、三苯基硅基等,但不局限于此。C 1-C 20不饱和烷基的例子如:乙烯基、丙烯基、烯丙基等,但不局限于此。C 3-C 20环烷基的例子如:环丙基、环丁基、环戊基、环己基、环辛基、1-金刚烷基等,但不局限于此。C 6-C 30的芳基的例子如:苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等,但不局限于此。C 7-C 30烷取代芳基的例子如:2-甲基苯基、2,6-二甲基苯基、2-氟-3-甲基苯基、2-氟-4-甲基苯基、2,6-二氟-3-甲基苯基、2,6-二氟-4-甲基苯基、2-氯-3-甲基苯基、2-氯-4-甲基苯基、2,6-二氯-3-甲基苯基、2,6- 二氯-4-甲基苯基、2-乙基苯基、2,6-二乙基苯基、2-异丙基苯基、2,6-二异丙基苯基、3-甲基苯基、3,5-二甲基苯基、3-氟-4-甲基苯基、3,5-二氟-4-甲基苯基、3,5-二氟-4-乙基苯基、3,5-二氟-4-异丙基苯基、3,5-二氟-4-叔丁基苯基、3,5-二氟-4-三甲基硅基苯基、3-三氟甲基苯基、3,5-双三氟甲基苯基、4-甲基苯基、4-三氟甲基苯基、4-乙基苯基、4-异丙基苯基、4-叔丁基苯基、4-三甲基硅基苯基等,但不局限于此。C 7-C 30的芳取代烷基的例子如:苄基、对甲基苄基、对氟苄基、对氯苄基、对乙基苄基、对异丙基苄基、对叔丁基苄基、对三氟甲基苄基、对三甲基硅基苄基、3,5-二氟苄基、3,4,5-三氟苄基、3,5-双三甲基苄基、3,5-双三氟甲基苄基、苯乙基、对甲基苯乙基、对氟苯乙基、对氯苯乙基、对异丙基苯乙基、对叔丁基苯乙基、对三甲基硅基苯乙基、2,6-二氟苯乙基、3,5—二氟苯乙基、3,4,5-三氟苯乙基、全氟代苯乙基、一位萘甲基、二位萘甲基等,但不局限于此。
在上述的组合中,R′优选为甲基、乙基、异丙基、三甲基硅基、苯基或苄基。A是π-配位体,具有如化学式(II)所示的一般结构;
Figure PCTCN2022138923-appb-000006
一般化学式(II)中,符号﹡无论连接在化学键、原子或自由基上,表示此点可与同类化学键、原子或自由基形成一个化学单键。且下文中所有符号﹡具有相同意义。
E是元素周期表中第十六族或第十五族元素的二价自由基,如氧自由基、硫自由基、砷自由基、NR″、PR″。
其中:R″是C 1-C 20的直链或支化烷基、饱和或不饱和烷基、卤代或非卤代烷基、选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基或C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基、C 7-C 30的芳取代烷基。C 1-C 20饱和及卤代烷基的例子如:甲基、三氟甲基、乙基、1,1,1-三氟乙基、全氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正十二烷基、正十八烷基、三甲基硅甲基、三乙基硅甲基、三苯基硅甲基等,但不局限于此。C 1-C 20不饱和烷基的例子如,乙烯基、丙烯基、烯丙基等,但不局限于此。C 3-C 20环烷基的例子如,环丙基、环丁基、环戊基、环己基、环辛基、1-金刚烷等,但不局限于此。C 6-C 30 的芳基的例子如,苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等,但不局限于此。C 7-C 30烷取代芳基的例子如,2-甲基苯基、2,6-二甲基苯基、2-氟-3-甲基苯基、2-氟-4-甲基苯基、2,6-二氟-3-甲基苯基、2,6-二氟-4-甲基苯基、2-氯-3-甲基苯基、2-氯-4-甲基苯基、2,6-二氯-3-甲基苯基、2,6-二氯-4-甲基苯基、2-乙基苯基、2,6-二乙基苯基、2-异丙基苯基、2,6-二异丙基苯基、3-甲基苯基、3,5-二甲基苯基、3-氟-4-甲基苯基、3,5-二氟-4-甲基苯基、3,5-二氟-4-乙基苯基、3,5-二氟-4-异丙基苯基、3,5-二氟-4-叔丁基苯基、3,5-二氟-4-三甲基硅基苯基、3-三氟甲基苯基、3,5-双三氟甲基苯基、4-甲基苯基、4-三氟甲基苯基、4-乙基苯基、4-异丙基苯基、4-叔丁基苯基、4-三甲基硅基苯基等,但不局限于此。C 7-C 30的芳取代烷基的例子如,苄基、对甲基苄基、对氟苄基、对氯苄基、对乙基苄基、对异丙基苄基、对叔丁基苄基、对三氟甲基苄基、对三甲基硅基苄基、3,5-二氟苄基、3,4,5-三氟苄基、3,5-双三甲基苄基、3,5-双三氟甲基苄基、苯乙基、对甲基苯乙基、对氟苯乙基、对氯苯乙基、对异丙基苯乙基、对叔丁基苯乙基、对三甲基硅基苯乙基、2,6-二氟苯乙基、3,5—二氟苯乙基、3,4,5-三氟苯乙基、全氟代苯乙基、一位萘甲基、二位萘甲基等,但不局限于此。
R″在上述组合中优选为C 4-C 10的直链烷基、苯基、单取代或多取代苯基、苄基、单取代或多取代苄基、1-萘基、2-萘基、2-蒽基、1-菲基、2-菲基、5-菲基。下文中所有R″具有相同意义。
E优选为元素硫、氧、NR″和P R″。其中R″如上述定义。
R 1是下述任意一种,C 1-C 40饱和或不饱和烷基、卤代或非卤代烷基、选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基或C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基。C 1-C 40饱和及卤代烷基的例子如,甲基、三氟甲基、乙基、1,1,1-三氟乙基、全氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正十二烷基、正十八烷基、三甲基硅甲基、三乙基硅甲基、三苯基硅甲基等,但不局限于此。C 1-C 20不饱和烷基的例子如,乙烯基、丙烯基、烯丙基等,但不局限于此。C 3-C 40环烷基的例子如,环丙基、环丁基、环戊基、环己基、环辛基、1-金刚烷等,但不局限于此。C 6-C 40的芳基的例子如,苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等,但不局限于此。C 7-C 40烷取代芳基的例子如,2-甲基苯基、2,6-二甲基苯基、2-氟-3-甲基苯基、2-氟-4-甲基苯基、2,6-二氟-3-甲基苯基、2,6-二氟-4-甲基苯基、2- 氯-3-甲基苯基、2-氯-4-甲基苯基、2,6-二氯-3-甲基苯基、2,6-二氯-4-甲基苯基、2-乙基苯基、2,6-二乙基苯基、2-异丙基苯基、2,6-二异丙基苯基、3-甲基苯基、3,5-二甲基苯基、3-氟-4-甲基苯基、3,5-二氟-4-甲基苯基、3,5-二氟-4-乙基苯基、3,5-二氟-4-异丙基苯基、3,5-二氟-4-叔丁基苯基、3,5-二氟-4-三甲基硅基苯基、3-三氟甲基苯基、3,5-双三氟甲基苯基、4-甲基苯基、4-三氟甲基苯基、4-乙基苯基、4-异丙基苯基、4-叔丁基苯基、4-三甲基硅基苯基等,但不局限于此。C 7-C 40的芳取代烷基的例子如,苄基、对甲基苄基、对氟苄基、对氯苄基、对乙基苄基、对异丙基苄基、对叔丁基苄基、对三氟甲基苄基、对三甲基硅基苄基、3,5-二氟苄基、3,4,5-三氟苄基、3,5-双三甲基苄基、3,5-双三氟甲基苄基、苯乙基、对甲基苯乙基、对氟苯乙基、对氯苯乙基、对异丙基苯乙基、对叔丁基苯乙基、对三甲基硅基苯乙基、2,6-二氟苯乙基、3,5—二氟苯乙基、3,4,5-三氟苯乙基、全氟代苯乙基、一位萘甲基、二位萘甲基等,但不局限于此。
R 1优选为氢、甲基、乙基、异丙基、叔丁基、苯基、苄基、2-呋喃基、2-噻吩基。下文中所有R 1具有相同意义。
R 2和R 3为氢、氟或R。R如上述定义。R 2和R 3优选为氢。下文中所有R 2和R 3具有相同意义。
R 4是下述任意一种,C 1-C 40饱和或不饱和烷基、卤代或非卤代烷基、选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基或C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基。C 1-C 40饱和及卤代烷基的例子如,甲基、三氟甲基、乙基、1,1,1-三氟乙基、全氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正十二烷基、正十八烷基、三甲基硅基、三乙基硅基、三苯基硅基等,但不局限于此。C 1-C 20不饱和烷基的例子如,乙烯基、丙烯基、丙基等,但不局限于此。C 3-C 40环烷基的例子如,环丙基、环丁基、环戊基、环己基、环辛基、1-金刚烷等,但不局限于此。C 6-C 40的芳基的例子如,苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等,但不局限于此。C 7-C 40烷取代芳基的例子如,2-甲基苯基、2,6-二甲基苯基、2-氟-3-甲基苯基、2-氟-4-甲基苯基、2,6-二氟-3-甲基苯基、2,6-二氟-4-甲基苯基、2-氯-3-甲基苯基、2-氯-4-甲基苯基、2,6-二氯-3-甲基苯基、2,6-二氯-4-甲基苯基、2-乙基苯基、2,6-二乙基苯基、2-异丙基苯基、2,6-二异丙基苯基、3-甲基苯基、3,5-二甲基苯基、3-氟-4-甲基苯基、3,5-二氟-4-甲基苯基、3,5-二氟-4-乙基苯基、3,5-二氟-4- 异丙基苯基、3,5-二氟-4-叔丁基苯基、3,5-二氟-4-三甲基硅基苯基、3-三氟甲基苯基、3,5-双三氟甲基苯基、4-甲基苯基、4-三氟甲基苯基、4-乙基苯基、4-异丙基苯基、4-叔丁基苯基、4-三甲基硅基苯基等,但不局限于此。C 7-C 40的芳取代烷基的例子如,苄基、对甲基苄基、对氟苄基、对氯苄基、对乙基苄基、对异丙基苄基、对叔丁基苄基、对三氟甲基苄基、对三甲基硅基苄基、3,5-二氟苄基、3,4,5-三氟苄基、3,5-双三甲基硅基苄基、3,5-双三氟甲基苄基、苯乙基、对甲基苯乙基、对氟苯乙基、对氯苯乙基、对异丙基苯乙基、对叔丁基苯乙基、对三甲基硅基苯乙基、2,6-二氟苯乙基、3,5—二氟苯乙基、3,4,5-三氟苯乙基、全氟代苯乙基、一位萘甲基、二位萘甲基等,但不局限于此。
R 4优选为H、甲基、三氟甲基、异丙基、叔丁基、苯基、对叔丁基苯基、对三甲基硅基苯基、对三氟甲基苯基、3,5-二氯-4-三甲基硅基苯基、2-萘基。且下文中所有R 4具有相同意义。
L是二价自由基并具有下述一般化学式(III)、(IV)、(V)、(VI)、(VII)、(VIII)的任意一种结构;
Figure PCTCN2022138923-appb-000007
符号﹡无论连接在化学键、原子、自由基上,表示此点可与同类化学键、原子、自由基形成一个化学单键。且下文中所有符号﹡具有相同意义。
一般化学式(III)和(IV)中,i是整数,i不等于零,i优选2。
R 5相同或不同,是下述任意一种,C 1-C 40饱和或不饱和烷基、卤代或非卤代烷基、选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基和C 3-C 40的环烷基、 C 6-C 40的芳基、C 7-C 40的烷取代芳基,C 7-C 40的芳取代烷基。C 1-C 40饱和及卤代烷基的例子如,甲基、三氟甲基、乙基、1,1,1-三氟乙基、全氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正十二烷基、正十八烷基、三甲基硅基、三乙基硅基、三苯基硅基等,但不局限于此。C 1-C 20不饱和烷基的例子如,乙烯基、丙烯基、烯丙基等,但不局限于此。C 3-C 40环烷基的例子如,环丙基、环丁基、环戊基、环己基、环辛基、1-金刚烷等,但不局限于此。C 6-C 40的芳基的例子如,苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等,但不局限于此。C 7-C 40烷取代芳基的例子如,2-甲基苯基、2,6-二甲基苯基、2-氟-3-甲基苯基、2-氟-4-甲基苯基、2,6-二氟-3-甲基苯基、2,6-二氟-4-甲基苯基、2-氯-3-甲基苯基、2-氯-4-甲基苯基、2,6-二氯-3-甲基苯基、2,6-二氯-4-甲基苯基、2-乙基苯基、2,6-二乙基苯基、2-异丙基苯基、2,6-二异丙基苯基、3-甲基苯基、3,5-二甲基苯基、3-氟-4-甲基苯基、3,5-二氟-4-甲基苯基、3,5-二氟-4-乙基苯基、3,5-二氟-4-异丙基苯基、3,5-二氟-4-叔丁基苯基、3,5-二氟-4-三甲基硅基苯基、3-三氟甲基苯基、3,5-双三氟甲基苯基、4-甲基苯基、4-三氟甲基苯基、4-乙基苯基、4-异丙基苯基、4-叔丁基苯基、4-三甲基硅基苯基等,但不局限于此。C 7-C 40的芳取代烷基的例子如,苄基、对甲基苄基、对氟苄基、对氯苄基、对乙基苄基、对异丙基苄基、对叔丁基苄基、对三氟甲基苄基、对三甲基硅基苄基、3,5-二氟苄基、3,4,5-三氟苄基、3,5-双三甲基硅基苄基、3,5-双三氟甲基苄基、苯乙基、对甲基苯乙基、对氟苯乙基、对氯苯乙基、对异丙基苯乙基、对叔丁基苯乙基、对三甲基硅基苯乙基、2,6-二氟苯乙基、3,5—二氟苯乙基、3,4,5-三氟苯乙基、全氟代苯乙基、一位萘甲基、二位萘甲基等,但不局限于此。
R 5优选为氢、氟、甲基。且下文中所有R 5具有相同意义。
一般化学式(V)、(VI)、(VII)、(VIII)中R 6和R 7等于R 3。R 3如上述定义。R 6和R 7优选为氢和氟元素。且下文中所有R 6和R 7具有相同意义。
一般化学式(I)中,Z是一种π-配位体。Z=A,A如前述定义。或Z具有下述一般化学式(IX)、(X)、(XI)、(XII)、(XIII)、(XIV)、(XV)所示的化学结构;
Figure PCTCN2022138923-appb-000008
符号﹡无论连接在化学键、原子、自由基上,表示此点可与同类化学键、原子、自由基形成一个化学单键。且下文中所有符号﹡具有相同意义。
上述一般化学式(IX)、(X)、(XI)、(XII)、(XIII)、中:
R 1如前定义。
R 1优选为甲基、乙基、异丙基、叔丁基、苯基、苄基、2-呋喃基、2-噻吩基。
R 2是氢、氟、R。R如前定义。R 2优选为氢。
R 8相同或不同,是下述任意一种,C 1-C 40饱和或不饱和烷基、卤代或非卤代烷基、选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基和C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基。C 1-C 40饱和及卤代烷基的例子如,甲基、三氟甲基、乙基、1,1,1-三氟乙基、全氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正十二烷基、正十八烷基、三甲基硅基、三乙基硅基、三苯基硅基等,但不局限于此。C 1-C 20不饱和烷基的例子如,乙烯基、丙烯基、烯丙基等,但不局限于此。C 3-C 40环烷基的例子如,环丙基、环丁基、环戊基、环己基、环辛基、1-金刚烷等,但不局限于此。C 6-C 40的芳基的例子如,苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基,9-菲基等,但不局限于此。C 7-C 40烷取代芳基的例子如,2-甲基苯基、2,6-二甲基苯基、2-氟-3-甲基苯基、2-氟-4-甲基苯基、2,6-二氟-3-甲基苯基、2,6-二氟-4-甲基苯基、2-氯-3-甲基苯基、2-氯-4-甲基苯基、2,6-二氯-3-甲基苯基、2,6-二氯-4-甲基苯基、2-乙基苯基、2,6-二乙基苯基、2-异丙基苯基、2,6-二异丙基苯基、3-甲基 苯基、3,5-二甲基苯基、3-氟-4-甲基苯基、3,5-二氟-4-甲基苯基、3,5-二氟-4-乙基苯基、3,5-二氟-4-异丙基苯基、3,5-二氟-4-叔丁基苯基、3,5-二氟-4-三甲基硅基苯基、3-三氟甲基苯基、3,5-双三氟甲基苯基、4-甲基苯基、4-三氟甲基苯基、4-乙基苯基、4-异丙基苯基、4-叔丁基苯基、4-三甲基硅基苯基等,但不局限于此。C 7-C 40的芳取代烷基的例子如,苄基、对甲基苄基、对氟苄基、对氯苄基、对乙基苄基、对异丙基苄基、对叔丁基苄基、对三氟甲基苄基、对三甲基硅基苄基、3,5-二氟苄基、3,4,5-三氟苄基、3,5-双三甲基硅基苄基、3,5-双三氟甲基苄基、苯乙基、对甲基苯乙基、对氟苯乙基、对氯苯乙基、对异丙基苯乙基、对叔丁基苯乙基、对三甲基硅基苯乙基、2,6-二氟苯乙基、3,5—二氟苯乙基、3,4,5-三氟苯乙基、全氟代苯乙基、一位萘甲基、二位萘甲基等,但不局限于此。
R 8优选为甲基、乙基、异丙基、叔丁基、苯基。且下文中所有R 8具有相同意义。
R 9相同或不同,是下述任意一种,C 1-C 40饱和或不饱和烷基、卤代或非卤代烷基、选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基和C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基。C 1-C 40饱和及卤代烷基的例子如,甲基、三氟甲基、乙基、1,1,1-三氟乙基、全氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正十二烷基、正十八烷基、三甲基硅基、三乙基硅基、三苯基硅基等,但不局限于此。C 1-C 20不饱和烷基的例子如,乙烯基、丙烯基、烯丙基等,但不局限于此。C 3-C 40环烷基的例子如,环丙基、环丁基、环戊基、环己基、环辛基、1-金刚烷等,但不局限于此。C 6-C 40的芳基的例子如,苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等,但不局限于此。C 7-C 40烷取代芳基的例子如,2-甲基苯基、2,6-二甲基苯基、2-氟-3-甲基苯基、2-氟-4-甲基苯基、2,6-二氟-3-甲基苯基、2,6-二氟-4-甲基苯基、2-氯-3-甲基苯基、2-氯-4-甲基苯基、2,6-二氯-3-甲基苯基、2,6-二氯-4-甲基苯基、2-乙基苯基、2,6-二乙基苯基、2-异丙基苯基、2,6-二异丙基苯基、3-甲基苯基、3,5-二甲基苯基、3-氟-4-甲基苯基、3,5-二氟-4-甲基苯基、3,5-二氟-4-乙基苯基、3,5-二氟-4-异丙基苯基、3,5-二氟-4-叔丁基苯基、3,5-二氟-4-三甲基硅基苯基、3-三氟甲基苯基、3,5-双三氟甲基苯基、4-甲基苯基、4-三氟甲基苯基、4-乙基苯基、4-异丙基苯基、4-叔丁基苯基、4-三甲基硅基苯基等,但不局限于此。C 7-C 40的芳取代烷基的例子如,苄基、对甲基苄基、对氟苄基、对氯苄基、对乙基苄基、对异丙基苄基、对叔丁基苄基、对三氟甲基苄基、对三甲基硅基苄基、3,5-二氟苄基、3,4, 5-三氟苄基、3,5-双三甲基硅基苄基、3,5-双三氟甲基苄基、苯乙基、对甲基苯乙基、对氟苯乙基、对氯苯乙基、对异丙基苯乙基、对叔丁基苯乙基、对三甲基硅基苯乙基、2,6-二氟苯乙基、3,5—二氟苯乙基、3,4,5-三氟苯乙基、全氟代苯乙基、一位萘甲基、二位萘甲基等,但不局限于此。
R 9优选为C 1-C 20的直链或支化的、饱和或不饱和的、部分或全部卤化的、线性的或环状的碳自由基。且下文中所有R 9具有相同意义。
R 10相同或不同,是下述任意一种,C 1-C 40饱和或不饱和烷基、卤代或非卤代烷基、选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基和C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基。C 1-C 40饱和及卤代烷基的例子如,甲基、三氟甲基、乙基、1,1,1-三氟乙基、全氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正十二烷基、正十八烷基、三甲基硅基、三乙基硅基、三苯基硅基等,但不局限于此。C 1-C 20不饱和烷基的例子如,乙烯基、丙烯基、烯丙基等,但不局限于此。C 3-C 40环烷基的例子如,环丙基、环丁基、环戊基、环己基、环辛基、1-金刚烷等,但不局限于此。C 6-C 40的芳基的例子如,苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等,但不局限于此。C 7-C 40烷取代芳基的例子如,2-甲基苯基、2,6-二甲基苯基、2-氟-3-甲基苯基、2-氟-4-甲基苯基、2,6-二氟-3-甲基苯基、2,6-二氟-4-甲基苯基、2-氯-3-甲基苯基、2-氯-4-甲基苯基、2,6-二氯-3-甲基苯基、2,6-二氯-4-甲基苯基、2-乙基苯基、2,6-二乙基苯基、2-异丙基苯基、2,6-二异丙基苯基、3-甲基苯基、3,5-二甲基苯基、3-氟-4-甲基苯基、3,5-二氟-4-甲基苯基、3,5-二氟-4-乙基苯基、3,5-二氟-4-异丙基苯基、3,5-二氟-4-叔丁基苯基、3,5-二氟-4-三甲基硅基苯基、3-三氟甲基苯基、3,5-双三氟甲基苯基、4-甲基苯基、4-三氟甲基苯基、4-乙基苯基、4-异丙基苯基、4-叔丁基苯基、4-三甲基硅基苯基等,但不局限于此。C 7-C 40的芳取代烷基的例子如,苄基、对甲基苄基、对氟苄基、对氯苄基、对乙基苄基、对异丙基苄基、对叔丁基苄基、对三氟甲基苄基、对三甲基硅基苄基、3,5-二氟苄基、3,4,5-三氟苄基、3,5-双三甲基硅基苄基、3,5-双三氟甲基苄基、苯乙基、对甲基苯乙基、对氟苯乙基、对氯苯乙基、对异丙基苯乙基、对叔丁基苯乙基、对三甲基硅基苯乙基、2,6-二氟苯乙基、3,5—二氟苯乙基、3,4,5-三氟苯乙基、全氟代苯乙基、一位萘甲基、二位萘甲基等,但不局限于此。
R 10优选为氢、氟、氯、甲基、乙基或苯基。且下文中所有R 10具有相同意义。
R 11相同或不同,是下述任意一种;氢、氟、氯、溴、OR、SR、OCOR、NR 2、PR 2。其中R如前述定义。或R 11相同或不同,是下述任意一种,C 1-C 40饱和或不饱和烷基、卤代或非卤代烷基、选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基和C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基。C 1-C 40饱和及卤代烷基的例子如,甲基、三氟甲基、乙基、1,1,1-三氟乙基、全氟代乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正庚基、正辛基、正十二烷基、正十八烷基、三甲基硅基、三乙基硅基、三苯基硅基等,但不局限于此。C 1-C 20不饱和烷基的例子如,乙烯基、丙烯基、烯丙基等,但不局限于此。C 3-C 40环烷基的例子如,环丙基、环丁基、环戊基、环己基、环辛基、1-金刚烷等,但不局限于此。C 6-C 40的芳基的例子如,苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等,但不局限于此。C 7-C 40烷取代芳基的例子如,2-甲基苯基、2,6-二甲基苯基、2-氟-3-甲基苯基、2-氟-4-甲基苯基、2,6-二氟-3-甲基苯基、2,6-二氟-4-甲基苯基、2-氯-3-甲基苯基、2-氯-4-甲基苯基、2,6-二氯-3-甲基苯基、2,6-二氯-4-甲基苯基、2-乙基苯基、2,6-二乙基苯基、2-异丙基苯基、2,6-二异丙基苯基、3-甲基苯基、3,5-二甲基苯基、3-氟-4-甲基苯基、3,5-二氟-4-甲基苯基、3,5-二氟-4-乙基苯基、3,5-二氟-4-异丙基苯基、3,5-二氟-4-叔丁基苯基、3,5-二氟-4-三甲基硅基苯基、3-三氟甲基苯基、3,5-双三氟甲基苯基、4-甲基苯基、4-三氟甲基苯基、4-乙基苯基、4-异丙基苯基、4-叔丁基苯基、4-三甲基硅基苯基等,但不局限于此。C 7-C 40的芳取代烷基的例子如,苄基、对甲基苄基、对氟苄基、对氯苄基、对乙基苄基、对异丙基苄基、对叔丁基苄基、对三氟甲基苄基、对三甲基硅基苄基、3,5-二氟苄基、3,4,5-三氟苄基、3,5-双三甲基硅基苄基、3,5-双三氟甲基苄基、苯乙基、对甲基苯乙基、对氟苯乙基、对氯苯乙基、对异丙基苯乙基、对叔丁基苯乙基、对三甲基硅基苯乙基、2,6-二氟苯乙基、3,5—二氟苯乙基、3,4,5-三氟苯乙基、全氟代苯乙基、一位萘甲基、二位萘甲基等,但不局限于此。
R 11优选为氢、氟、氯、酯基、烷氧基、硫醇基、胺基、膦基。且下文中所有R 11具有相同意义。
在一般化学结构式(I)中,A是一种一价阴离子π-配位体。且A的前驱体是一种中性的稳定有机化合物,具有如一般化学式(II)所示的化学结构;
在一般化学式(II)中,R 1、R 2、R 3、R 4、L和E,如前定义。而一般化学式(II)中包含有由环戊二烯环的基本结构。环戊二烯结构中的活泼氢具有独特的亲电反应性,可与 格氏试剂、有机锂试剂等亲核试剂进行交换反应。其基本反应如下列反应式所示:
Figure PCTCN2022138923-appb-000009
上列反应式中亲核试剂选择有机锂试剂R nLi作为特例,但实践中不局限于仅仅使用有机锂试剂。R n是C 1-C 6的烷基,或C 6-C 12的芳基。
助催化剂为路易斯酸性物质LA。
其中,LA为在溶液中同时具有链状、环状和笼状结构平衡态的聚甲基铝氧烷或改性的聚甲基铝氧烷或有机硼试剂。
LA是一类体积膨大,电子离域,配位性贫乏的路易斯酸性物质。这类物质的代表是在溶液中同时具有链状,环状和笼状结构平衡态的聚甲基铝氧烷(PMAO)以及在此基础上改性的聚甲基铝氧烷(MMAO)。
Figure PCTCN2022138923-appb-000010
本发明所述体积膨大,电子离域,和配位性贫乏的阴离子还有大量的例子可供选择,如;[B(C 6H 5) 4] -,[(CH 3)B(C 6F 5) 3] -,[B(C 6F 5) 4] -,[B(2,6-(CH 3) 2-C 6H 3) 4] -,[B(2,4,6-(CH 3) 3-C 6H 2) 4] -,[B(2,3,5,6-(CH 3) 4-C 6H) 4] -,[B(2,6-(CF 3) 2-C 6H 3) 4] -,[B(2,4,6-(CF 3) 3-C 6H 2) 4] -,[B(2,3,5,6-(CF 3) 4-C 6H) 4] -,[B(3,5-(CH 3) 2-C 6H 3) 4] -,[B(3,4,5-(CH 3) 3-C 6H 2) 4] -,[B(3,5-(CF 3) 2-C 6H 3) 4] -,[B(3,4,5-(CF 3) 3-C 6H 2) 4] -,[B(2,6-(CF 3) 2-C 6F 3) 4] -,[B(2,4,6-(CF 3) 3-C 6F 2) 4] -,[B(2,3,5,6-(CF 3) 4-C 6F) 4] -,[B(3,5-(CF 3) 2-C 6F 3) 4] -,[B(3,4,5-(CF 3) 3-C 6F 2) 4] -,[Al(C 6H 5) 4] -,[(CH 3)Al(C 6F 5) 3] -,[Al(C 6F 5) 4] -,[Al(2,6-(CH 3) 2-C 6H 3) 4] -,[Al(2,4,6-(CH 3) 3-C 6H 2) 4] -,[Al(2,3,5,6-(CH 3) 4-C 6H) 4] -,[Al(3,5-(CH 3) 2-C 6H 3) 4] -,[Al(3,4,5-(CH 3) 3-C 6H 2) 4] -,[Al(2,6-(CH 3) 2-C 6F 3) 4] -, [Al(2,4,6-(CH 3) 3-C 6F 2) 4] -,[Al(2,3,5,6-(CH 3) 4-C 6F) 4] -,[Al(3,5-(CH 3) 2-C 6F 3) 4] -,[Al(3,4,5-(CH 3) 3-C 6F 2) 4] -,[Al(2,6-(CF 3) 2-C 6H 3) 4] -,[Al(2,4,6-(CF 3) 3-C 6H 2) 4] -,[Al(2,3,5,6-(CF 3) 4-C 6H) 4] -,[Al(3,5-(CF 3) 2-C 6H 3) 4] -,[Al(3,4,5-(CF 3) 3-C 6H 2) 4] -,[Al(2,6-(CF 3) 2-C 6F 3) 4] -,[Al(2,4,6-(CF 3) 3-C 6F 2) 4] -,[Al(2,3,5,6-(CF 3) 4-C 6F) 4] -,[Al(3,5-(CF 3) 2-C 6F 3) 4] -,[Al(3,4,5-(CF 3) 3-C 6F 2) 4] -,{t-Bu-CH=C[B(C 6F 5) 2] 2(CH 3)} -,{Ph-CH=C[B(C 6F 5) 2] 2(CH 3)} -,{(C 6F 5)-CH=C[B(C 6F 5) 2] 2(CH 3)} -,{t-Bu-CH=C[Al(C 6F 5) 2] 2(CH 3)} -,{Ph-CH=C[Al(C 6F 5) 2] 2(CH 3)} -,{(C 6F 5)-CH=C[Al(C 6F 5) 2] 2(CH 3)} -,[1,1’-C 12F 8-2,2’=B(C 6F 5) 2] -,[1,1’-C 12F 8-2,2’=Al(C 6F 5) 2] -,[FB(1-C 6F 4-2-C 6F 5) 3] -,[(CH 3)B(1-C 6F 4-2-C 6F 5) 3] -,[(C 6F 5)B(1-C 6F 4-2-C 6F 5) 3] -,[(C 6F 5)Al(1-C 6F 4-2-C 6F 5) 3] -,[FAl(1-C 6F 4-2-C 6F 5) 3]-,[(CH 3)Al(1-C 6F 4-2-C 6F 5) 3]-,] -,[HB(1-C 6F 4-2-C 6F 5) 3] -,[HAl(1-C 6F 4-2-C 6F 5) 3] -,[(CH 3)B(2-C 10F 7) 3] -,[(CH 3)Al(2-C 10F 7) 3] -,[(CH 3)B(p-C 6F 4SiMe 3) 3] -,[B(p-C 6F 4SiMe 3) 4] -,[(CH 3)B(p-C 6F 4Si(n-Bu) 3) 3] -,[B(p-C 6F 4Si(n-Bu) 3) 4] -,[(CH 3)B(p-C 6F 4Si(i-Bu) 3) 3] -,[B(p-C 6F 4Si(i-Bu) 3) 4] -,[(CH 3)B(p-C 6F 4Si(t-Bu) 3) 3] -,[B(p-C 6F 4Si(t-Bu) 3) 4] -,[(C 6F 5) 3B-C 6F 4-B(C 6F 5) 2] -,[C 6F 4-1,2-(B(C 6F 5) 3) 2] -,[C 6F 4-1,2-(Al(C 6F 5) 3) 2] -,[(C 6F 4)-1,2-(B(C 6F 5) 2) 2-1’,2’-(C 6F 4)] -,[(C 6F 4)-1,2-(Al(C 6F 5) 2) 2-1’,2’-(C 6F 4)] -,[(C 6F 5) 3B-CN-B(C 6F 5) 3] -,[(C 6F 5) 3Al-CN-Al(C 6F 5) 3] -,[((C 6F 5) 3BNC) 4Ni] -,[((C 6F 5) 3AlNC) 4Ni] -,[(1,1’-C 12F 8) 2-2,2’-B] -,[(1,1’-C 12F 8) 2-2,2’-Al] -,[B(O-C 6F 5) 4] -,[Al(O-C 6F 5) 4] -,[(C 6F 5) 3Al-C 6F 4-Al(C 6F 5) 2] -,[(CH 3)Al(p-C 6F 4SiMe 3) 3] -,[Al(p-C 6F 4SiMe 3) 4] -,[(CH 3)Al(p-C 6F 4Si(n-Bu) 3) 3] -,[Al(p-C 6F 4Si(n-Bu) 3) 4] -,[(CH 3)Al(p-C 6F 4Si(i-Bu) 3) 3] -,[Al(p-C 6F 4Si(i-Bu) 3) 4] -,[(CH 3)Al(p-C 6F 4Si(t-Bu) 3) 3] -,[Al(p-C 6F 4Si(t-Bu) 3) 4] -,[C 5(C 6H 5) 5] -,[C 5(2,6-(CH 3) 2-C 6H 3) 5] -,[C 5(2,4,6-(CH 3) 3-C 6H 2) 5] -,[C 5(3,5-(CH 3) 2-C 6H 3) 5] -,[C 5(3,4,5-(CH 3) 3-C 6H 2) 5] -,[C 5(2,6-(CF 3) 2-C 6H 3) 5] -,[C 5(2,4,6-(CF 3) 3-C 6H 2) 5] -,[C 5(3,5-(CF 3) 2-C 6H 3) 5] -,[C 5(3,4,5-(CF 3) 3-C 6H 2) 5] -,[C 5(2,6-(CH 3) 2-C 6F 3) 5] -,[C 5(2,4,6-(CH 3) 3-C 6F 2) 5] -,[C 5(3,5-(CH 3) 2-C 6F 3) 5] -,[C 5(3,4,5-(CH 3) 3-C 6F 2) 5] -,[C 5(2,6-(CF 3) 2-C 6F 3) 5] -,[C 5(2,4,6-(CF 3) 3-C 6F 2) 5] -,[C 5(3,5-(CF 3) 2-C 6F 3) 5] -,[C 5(3,4,5-(CF 3) 3-C 6F 2) 5] -,[C 5(C 6F 5) 5] -,[Li(Ta(OC 6F 5) 4( 2-OC 6F 5) 2) 2] -,[Nb(OC 6F 5) 6] -,[PF 6] -,[AsF 6] -,[SbF 6] -,[BF 4] -,[ClO 4] -,炭硼烷阴离子如:[C 2B 9H 12] -,[CB 11H 12] -,但不限于此。
其中,LA与茂金属络合物的摩尔比LA:M≥300。
镁化合物载体Mg(OR I)(OR II)为二甲氧基镁、二乙氧基镁、二丙氧基镁、二丁氧基镁、乙氧基甲氧基镁、乙氧基丙氧基镁、丁氧基乙氧基镁中的一种或它们的混合物。
镁化合物载体与茂金属络合物(I)的Mg:M摩尔比为100~1000。
本发明实施例还涉及通式(I)所示的茂金属络合物的合成方法:
Figure PCTCN2022138923-appb-000011
其中,T互相间相同或不同,所述T是单齿或双齿的中性配位体;
LG是脱离基团,其互相之间相同或不同,所述LG为氢、碱金属元素或第十四族重元素的有机自由基。
其中,所述单齿配位体包括醚类ROR、硫醚类RSR、三级胺类NR 3、三级膦类PR 3、环醚、环硫醚类、酮类、取代环酮类、取代吡啶类、取代吡咯类、取代哌啶类、酯类、内酯类、酰胺类和内酰胺类,其中R是C 1-C 20的直链或支化烷基、饱和或不饱和烷基、卤代或非卤代烷基或含有元素周期表中第十三到第十七族元素杂原子的烷基,或C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基。
其中,所述双齿配位体包括邻位双醚类,α,ω-双醚类、邻位双胺类、α,ω-双胺类、邻位双硫醚类、α,ω-双硫醚类、邻位双膦类和α,ω-双膦类。其中,x是0或整数1、2或3。
其中,所述碱金属元素包括锂、钠和钾;所述第十四族重元素的有机自由基包括SiR 3、GeR 3、SnR 3、PdR 3、ZnR、BaR、MgR和CaR,其中,R是C 1-C 20的直链或支化烷基、饱和或不饱和烷基、卤代或非卤代烷基或含有元素周期表中第十三到第十七族元素杂原子的烷基,或C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基。
其中,合成过程中反应介质为饱和C 5-C 15烷烃、环烷烃或其中两种或两种以上的混合物。
其中,合成过程中反应介质为己烷、庚烷、辛烷、甲苯或二甲苯。其中,反应温度范围为-100℃~+300℃。
其中,反应温度范围为-75℃~+250℃。
其中,反应温度范围为-50℃~+150℃。
本发明实施例涉及镁化合物载体Mg(OR I)(OR II)的制备方法:将醇R IOH和醇R IIOH与金属镁粉在卤素的存在下加热反应至不再产生氢气为止,用惰性有机溶剂稀释洗涤,得到Mg(OR I)(OR II)固体。
本发明实施例涉及所述催化剂组合物的制备方法:使选自通式(I)的化合物与助催化剂LA和镁化合物载体Mg(OR I)(OR II)在惰性有机溶剂中接触,从而得到催化剂组合 物。
催化剂组合物可以是干燥后的固体粉末,也可以分散或再分散于惰性有机溶剂中形成悬浮液。
所述惰性有机溶剂选自:己烷、庚烷、辛烷、癸烷或甲苯。
接触时间为1分钟~8小时。
接触温度在-75℃~120℃。
本发明实施例还涉及所述的催化剂组合物在乙烯-丙烯共聚合中的应用。
本发明的催化剂组分可以用于目前已知的烯烃聚合工艺,包括淤浆、气相,聚合条件可以选用本领域常用的条件。因此,聚合一般在0~120℃,优选20~90℃。在任何使用的聚合方法中,在将催化剂组分引入到聚合反应器之前,催化剂组分可以与烷基铝化合物预接触。该预接触步骤可以在没有可聚合烯烃的情况下进行。
本发明所述茂金属主催化剂和路易斯酸性物质LA助催化剂与烷氧基镁载体的催化剂体系,载体颗粒强度较高不易破碎,有效降低了聚合物的细粉含量,能大幅改善装置堵塞的问题;烷氧基镁载体孔容孔径较大,内部具有丰富的孔洞,适合用于乙丙共聚反应生产,有利于在孔洞中生成大量的乙丙橡胶,能大幅度提高共聚物中乙丙橡胶含量,提高共聚活性。
由表2可以看出,比较实施例5没有使用载体,聚合物流动性差,有结块,无法测量堆积密度;使用烷氧基镁载体的聚合物数据可以看出,聚合物形态有所改善,细粉含量少。实施例1~4可以看出,在使用烷氧基镁载体,与比较实施例1~4中相同条件下使用普通硅胶载体相比,乙丙共聚活性和乙丙橡胶含量均有大幅度提高,聚合物分子量分布较宽。
具体实施方式
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述的实施例,下列实施例中未注明具体条件的工艺参数,通常按照常规条件。
在本发明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发明中具体公开。
下面通过实例详细说明本发明,但本发明并不限于此。
本发明相关技术采用的分析表征方法如下:
核磁:AV400,德国BRUKER。
聚合物产品中实际乙丙橡胶含量Ru的测定:二甲苯室温可溶解部分的重量占样品重量的百分比为橡胶含量。
细粉含量的测定:按照ASTME1187测定,80目筛网以下(相当于粒径小于180um)定义为细粉。
实施例1
(1)茂金属络合物Cat-1的合成:
Figure PCTCN2022138923-appb-000012
上面反应式中M为Zr,具体的合成步骤见CN105985368A的实施例1所述。
(2)烷氧基镁载体S mg1的制备:
在装有搅拌器的四口烧瓶中,安装回流冷凝器并在回流冷凝器上连接流量计,加入无水乙醇60ml,碘1克,使之溶解。加入5克金属镁,搅拌下升温至80℃,从回流开始每隔10分钟加入无水乙醇45ml,镁5克,共3次。在第三次加入完成后大约1~2小时液体黏度开始急剧上升,再加入甲苯220ml,继续反应直至反应终结不再产生氢气为止,整个反应时间大约6个小时左右。然后将剩余液体压滤干净,然后用600ml甲苯洗涤3次,得到载体S mg1。
(3)催化剂组合物CM-1的制备:
将茂金属络合物Cat-1溶解于甲苯,配制成浓度10mM的溶液。
将60mg乙氧基镁载体S mg1加入到装有20mL己烷的50mL烧瓶中,加入1mL上面配制的Cat-1甲苯溶液(10mM),室温搅拌30分钟,加入5000μmol的MAO(甲基铝氧烷)溶液,搅拌10分钟后,得到催化剂组合物CS-1。
(4)聚合:聚合反应在4kg/hr的卧式气相聚丙烯小试装置上进行,两个卧式釜串联。
烯烃聚合催化剂组分在液态丙烯携带下,由反应器进料口连续进入第一反应器中,在该反应器中完成丙烯均聚反应,加入MAO(Al/M=300),聚合温度70℃,压力2.0MPa,向反应器中加入一定量的氢气用于控制均聚聚丙烯的分子量,加入氢气与丙烯摩尔比为2.5*10 -3。停留时间80min。
第一气相反应器出料,物料进入第二气相反应器,丙烯和乙烯共聚得到共聚聚丙烯。气相反应温度75℃,压力2.1MPa,其中乙烯/丙烯=1(体积比),气相反应器进料中加入一定量的氢气,氢气/(乙烯+丙烯)=0.001(摩尔比),通入低纯氮(氧含量5000~6000ppm),停留时间50min。聚合性能见表2。
实施例2~33
(1)茂金属络合物Cat-2~Cat-33的合成:步骤同实施例1,原料替换为带有相应的取代基的配体原料,催化剂络合物的取代基见表1。
(2)烷氧基镁载体S mg1的制备:同实施例1。
(3)催化剂组合物CM-2~CM-33的制备:同实施例1,不同之处为将Cat-1分别替换为Cat-2~Cat-33。
(4)聚合:聚合条件同实施例1,聚合性能见表2。
实施例34~37
(1)茂金属络合物采用Cat-1~Cat4。
(2)烷氧基镁载体S mg2的制备:
在装有搅拌器的四口烧瓶中,安装回流冷凝器并在回流冷凝器上连接流量计,加入无水乙醇30ml、无水丙醇30mL,碘1克,使之溶解。加入5克金属镁,搅拌下升温至80℃,从回流开始每隔10分钟加入无水乙醇25ml、无水丙醇25mL,镁5克,共3次。在第三次加入完成后大约1~2小时液体黏度开始急剧上升,再加入甲苯220ml,继续反应直至反应终结不再产生氢气为止,整个反应时间大约6个小时左右。然后将剩余液体压滤干净,然后用600ml甲苯洗涤3次,得到载体乙氧基丙氧基S mg2。
(3)催化剂组合物CM-34~CM-37的制备:同实施例1,不同之处为用乙氧基丙氧基镁S mg2替换乙氧基镁S mg1。
(4)聚合:聚合条件同实施例1,聚合性能见表2。
实施例38~41
(1)茂金属络合物采用Cat-1~Cat4。
(2)烷氧基镁载体S mg3的制备:
在装有搅拌器的四口烧瓶中,安装回流冷凝器并在回流冷凝器上连接流量计,加入无水丁醇80ml碘1克,使之溶解。加入5克金属镁,搅拌下升温至80℃,从回流开始每隔10分钟加入无水丁醇70ml,镁5克,共3次。在第三次加入完成后大约1~2小时液体黏度开始急剧上升,再加入甲苯220ml,继续反应直至反应终结不再产生氢气为止,整个反应时间大约6个小时左右。然后将剩余液体压滤干净,然后用600ml甲苯洗涤3次,得到载体S mg2。
(3)催化剂组合物CM-34~CM-37的制备:同实施例1,不同之处为用丁氧基镁S mg2替换乙氧基镁S mg1。
(4)聚合:聚合条件同实施例1,聚合性能见表2。
实施例42~45
(1)茂金属络合物采用Cat-1~Cat4。
(2)烷氧基镁载体S mg4的制备:
在装有搅拌器的四口烧瓶中,安装回流冷凝器并在回流冷凝器上连接流量计,加入无水乙醇30ml、无水丁醇40mL,碘1克,使之溶解。加入5克金属镁,搅拌下升温至80℃,从回流开始每隔10分钟加入无水乙醇25ml、无水丁醇40mL,镁5克,共3次。在第三次加入完成后大约1~2小时液体黏度开始急剧上升,再加入甲苯220ml,继续反应直至反应终结不再产生氢气为止,整个反应时间大约6个小时左右。然后将剩余液体压滤干净,然后用600ml甲苯洗涤3次,得到载体S mg2。
(3)催化剂组合物CM-34~CM-37的制备:同实施例1,不同之处为用乙氧基丁氧基镁S mg2替换乙氧基镁S mg1。
(4)聚合:聚合条件同实施例1,聚合性能见表2。
比较实施例1~4
(1)茂金属络合物分别采用Cat-1~Cat-4。
(2)硅胶载体S 0的活化:
将Grace 955型号硅胶在450℃下抽真空3小时后,惰性气体保护下自然冷却至室温。
(3)催化剂组合物D1~D4的制备:
将茂金属络合物Cat-1~Cat-4分别溶解于甲苯,配制成浓度10mM的溶液。将50mg步骤(2)活化后的Grace-955硅胶载体加入到装有20mL己烷的50mL烧瓶中,加入5000μmol的MAO(甲基铝氧烷)溶液,搅拌五分钟后加入1mL上面配制的Cat-1~Cat-4 甲苯溶液(10mM),室温下搅拌30分钟,得到催化剂组合物D-1~D-4。
(4)聚合:聚合条件同实施例1,聚合性能见表2。
比较实施例5
(1)茂金属络合物采用Cat-1。
(2)催化剂组合物D5的制备:
将茂金属络合物Cat-1溶解于甲苯,配制成浓度10mM的溶液。取1mLCat-1的甲苯溶液加入5000μmol的MAO(甲基铝氧烷)溶液,室温下搅拌30分钟,得到催化剂组合物D5。
(3)聚合:聚合条件同实施例1,聚合性能见表2。
由表2可以看出,比较实施例5没有使用载体,聚合物流动性差,有结块,无法测量堆积密度;使用烷氧基镁载体的聚合物数据可以看出,聚合物形态有所改善,细粉含量少。实施例1~4可以看出,在使用烷氧基镁载体,与比较实施例1~4中相同条件下使用普通硅胶载体相比,乙丙共聚活性和乙丙橡胶含量均有大幅度提高,聚合物分子量分布较宽。
Figure PCTCN2022138923-appb-000013
Figure PCTCN2022138923-appb-000014
表2
Figure PCTCN2022138923-appb-000015
Figure PCTCN2022138923-appb-000016
上述仅为本发明较佳可行的实施例而已,非因此局限本发明保护范围,依照上述实施例所作各种变形或套用均在此技术方案保护范围之内。
尽管本发明的具体实施方式已经得到详细的描述,本领域技术人员将会理解。根据已经公开的所有教导,可以对那些细节进行各种修改和替换,这些改变均在本发明的保护范围之内。本发明的全部范围由所附权利要求及其任何等同物给出。

Claims (41)

  1. 一种烯烃聚合催化剂组合物,其中,所述催化剂组合物包含主催化剂、助催化剂和镁化合物载体,所述镁化合物载体选自Mg(OR I)(OR II),其中,R I和R II相同或不同,是C 1-C 8的烃基;所述助催化剂为路易斯酸性物质LA;所述主催化剂为通式(I)所示的茂金属络合物:
    Figure PCTCN2022138923-appb-100001
    其中,M是元素周期表中第三、第四、第五或第六族过渡金属元素,包括镧系和錒系元素;
    X相互之间相同或不同,选自氢元素、卤素、烷基R、烷氧基OR、巯基SR、羧基OCOR、胺基NR 2、膦基PR 2、-OR°O-和OSO 2CF 3,R是C 1-C 20的直链或支化烷基、C 1-C 20的饱和或不饱和烷基、C 1-C 20的卤代或非卤代烷基、C 1-C 20的含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基;R°是二价自由基,该二价自由基包括C 2-C 40的亚烷基、C 6-C 30的亚芳基、C 7-C 40的烷代亚芳基、C 7-C 40的芳代亚烷基;在-OR°O-结构中,两个氧原子分别在自由基的任何位置;
    n是从1到4的整数;X的电荷数之和等于M的电荷数减2;
    Q是二价自由基,该二价自由基选自=CR′ 2、=SiR′ 2、=GeR′ 2、=NR′、=PR′、=BR′,其中,R′为C 1-C 20的直链或支化烷基、C 1-C 20的饱和或不饱和烷基、C 1-C 20的卤代或非卤代烷基、C 1-C 20的选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基;
    A是π-配位体,具有如化学式(II)所示的结构:
    Figure PCTCN2022138923-appb-100002
    其中,E是元素周期表中第十六族或第十五族元素的二价自由基,该二价自由基包括氧自由基、硫自由基、硒自由基、NR″和PR″,R″为C 1-C 10的直链烷基、苯基、单取代苯基、多取代苯基、苄基、单取代苄基、多取代苄基、1-萘基、2-萘基、2-蒽基、1-菲基、2-菲基或5-菲基;
    L是二价自由基并具有下述化学式(III)、(IV)、(V)、(VI)、(VII)或(VIII)所示的结构,其中i为2:
    Figure PCTCN2022138923-appb-100003
    Z是一种π-配位体,Z=A,或Z具有下述化学式(IX)、(X)、(XI)、(XII)或(XIII)所示的化学结构:
    Figure PCTCN2022138923-appb-100004
    Figure PCTCN2022138923-appb-100005
    其中,R 1、R 12为氢、甲基、乙基、异丙基、叔丁基、苯基、苄基、2-呋喃基或2-噻吩基;
    R 2、R 3和R 13分别为氢、氟或R,其中,R是C 1-C 20的直链或支化烷基、C 1-C 20的饱和或不饱和烷基、C 1-C 20的卤代或非卤代烷基、C 1-C 20的含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基;
    R 4为H、甲基、三氟甲基、异丙基、叔丁基、苯基、对叔丁基苯基、对三甲基硅基苯基、对三氟甲基苯基、3,5-二氯-4-三甲基硅基苯基或2-萘基;
    R 5为氢、氟或甲基;
    R 6和R 7分别为氢、氟或R,其中,R是C 1-C 20的直链或支化烷基、C 1-C 20的饱和或不饱和烷基、C 1-C 20的卤代或非卤代烷基、C 1-C 20的含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基;
    R 8为甲基、乙基、异丙基、叔丁基或苯基;
    R 9和R 9’为苯基、取代苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基、呋喃、噻吩、喹啉或嘧啶,其中取代苯基中的取代基为氰基、硝基、F、甲基、乙基、异丙基、叔丁基、甲氧基、叔丁基、三氟甲氧基、Cl、三氟甲基、羰基或三甲基硅基;
    R 10和R 10’为氢、氟、氯、甲基、乙基或苯基;
    R 11和R 11’为氢、氟、氯、酯基、烷氧基、硫醇基、胺基或膦基。
  2. 权利要求1所述组合物,其中,R′为甲基、乙基、异丙基、三甲基硅基、苯基或苄基。
  3. 权利要求1所述组合物,其中,式(I)中,A的一价阴离子π-配位体,具有化学式(II)-Li +所示的化学结构;化学式(II)中包含有环戊二烯环的基本结构,环戊二烯结构中 的活泼氢具有亲电反应性,可与亲核试剂进行交换反应生成化学式(II)-Li +所示化合物,其基本反应如下列反应式所示:
    Figure PCTCN2022138923-appb-100006
    其中,反应式中亲核试剂为有机锂试剂LiR n,其中,R n是C 1-C 6的烷基或C 6-C 12的芳基。
  4. 权利要求1所述组合物,其中,X相互之间相同或不同,是氢元素、卤素、烷基R、烷氧基OR、巯基SR、羧基OCOR、胺基(NR 2),膦基(PR 2)、-OR°O-或OSO 2CF 3;其中,R是C 1-C 20的直链或支化烷基、C 1-C 20的饱和或不饱和烷基、C 1-C 20的卤代或非卤代烷基、C 1-C 20的选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基;
    R°是二价自由基;在-OR°O-结构中,两个氧原子可分别在自由基的任何位置。
  5. 权利要求4所述组合物,其中,X为氯、溴、C 1-C 20低碳烷基或芳基。
  6. 权利要求4所述组合物,其中,R°选自C 2-C 40的亚烷基、C 6-C 30的亚芳基、C 7-C 40的烷代亚芳基、C 7-C 40的芳代亚烷基。
  7. 权利要求4所述组合物,其中,在-OR°O-结构中,两个氧原子的位置为在自由基的相邻(α、β-位)和相间(α、γ-位)位置的组合。
  8. 权利要求1所述组合物,其中,A是π-配位体,具有如化学式(II)所示的一般结构;
    Figure PCTCN2022138923-appb-100007
    其中,E是元素周期表中第十六族或第十五族元素的二价自由基;
    R 1是下述任意一种:C 1-C 40的饱和或不饱和烷基、C 1-C 40的卤代或非卤代烷基、C 1-C 40的选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基;
    R 2和R 3为氢、氟或R;
    R 4是下述任意一种:C 1-C 40的饱和或不饱和烷基、C 1-C 40的卤代或非卤代烷基、C 1-C 40的选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基;
    L是二价自由基并具有下述一般化学式(III)、(IV)、(V)、(VI)、(VII)、(VIII)的任意一种结构;
    Figure PCTCN2022138923-appb-100008
    式(III)和(IV)中,i是整数,i不等于零;
    R 5相同或不同,是下述任意一种:C 1-C 40的饱和或不饱和烷基、C 1-C 40的卤代或非卤代烷基、C 1-C 40的选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基,C 7-C 40的芳取代烷基;
    式(V)、(VI)、(VII)、(VIII)中,R 6和R 7等于R 3
  9. 权利要求1所述组合物,其中,R′为甲基、乙基、异丙基、三甲基硅基、苯基或苄基。
  10. 权利要求8所述组合物,其中,E选自氧自由基、硫自由基、砷自由基、NR″、PR″;
    其中:R″选自C 1-C 20的直链或支化烷基、C 1-C 20的饱和或不饱和烷基、C 1-C 20的卤代或非卤代烷基、C 1-C 20的选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基、C 7-C 30的芳取代烷基。
  11. 权利要求10所述组合物,其中,E选自元素硫、氧、NR″、PR″。
  12. 权利要求10所述组合物,其中,R″选自C 4-C 10的直链烷基、苯基、单取代苯 基、多取代苯基、苄基、单取代苄基、多取代苄基、1-萘基、2-萘基、2-蒽基、1-菲基、2-菲基、5-菲基。
  13. 权利要求8所述组合物,其中,R 1选自氢、甲基、乙基、异丙基、叔丁基、苯基、苄基、2-呋喃基、2-噻吩基。
  14. 权利要求8所述组合物,其中,R 2和R 3为氢。
  15. 权利要求8所述组合物,其中,R 4选自H、甲基、三氟甲基、异丙基、叔丁基、苯基、对叔丁基苯基、对三甲基硅基苯基、对三氟甲基苯基、3,5-二氯-4-三甲基硅基苯基、2-萘基。
  16. 权利要求8所述组合物,其中,式(III)和(IV)中,i为2。
  17. 权利要求8所述组合物,其中,R 5选自氢、氟、甲基。
  18. 权利要求8所述组合物,其中,式(V)、(VI)、(VII)、(VIII)中,R 6和R 7选自氢和氟元素。
  19. 权利要求1所述组合物,其中,Z是一种π-配位体,Z=A,或Z具有下述一般化学式(IX)、(X)、(XI)、(XII)、(XIII)、(XIV)、(XV)所示的化学结构;
    Figure PCTCN2022138923-appb-100009
    式(IX)、(X)、(XI)、(XII)、(XIII)中:
    R 1选自甲基、乙基、异丙基、叔丁基、苯基、苄基、2-呋喃基、2-噻吩基;
    R 2选自氢、氟、R;
    R 8相同或不同,是下述任意一种:C 1-C 40的饱和或不饱和烷基、C 1-C 40的卤代或非 卤代烷基、C 1-C 40的选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基;
    R 9相同或不同,是下述任意一种:C 1-C 40的饱和或不饱和烷基、C 1-C 40的卤代或非卤代烷基、C 1-C 40的选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基;
    R 10相同或不同,是下述任意一种:C 1-C 40的饱和或不饱和烷基、C 1-C 40的卤代或非卤代烷基、C 1-C 40的选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基;
    R 11相同或不同,是下述任意一种:氢、氟、氯、溴、OR、SR、OCOR、NR 2、PR 2,或R 11相同或不同,是下述任意一种:C 1-C 40的饱和或不饱和烷基、C 1-C 40的卤代或非卤代烷基、C 1-C 40的选择性地含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 40的环烷基、C 6-C 40的芳基、C 7-C 40的烷取代芳基、C 7-C 40的芳取代烷基。
  20. 权利要求19所述组合物,其中,R 2是氢。
  21. 权利要求19所述组合物,其中,R 8选自甲基、乙基、异丙基、叔丁基、苯基。
  22. 权利要求19所述组合物,其中,R 9选自C 1-C 20的直链或支化的碳自由基、C 1-C 20的饱和或不饱和的碳自由基、C 1-C 20的部分或全部卤化的碳自由基、C 1-C 20的线性的或环状的碳自由基。
  23. 权利要求19所述组合物,其中,R 10选自氢、氟、氯、甲基、乙基或苯基。
  24. 权利要求19所述组合物,其中,R 11选自氢、氟、氯、酯基、烷氧基、硫醇基、胺基、膦基。
  25. 权利要求1所述组合物,其中,A是一种一价阴离子π-配位体,且A的前驱体是一种中性的稳定有机化合物,具有如式(II)所示的化学结构;
    式(II)中包含有由环戊二烯环的基本结构;环戊二烯结构中的活泼氢具有独特的亲电反应性,可与格氏试剂、有机锂试剂等亲核试剂进行交换反应,其基本反应如下列反应式所示:
    Figure PCTCN2022138923-appb-100010
    R n是C 1-C 6的烷基,或C 6-C 12的芳基。
  26. 权利要求1所述组合物,其中,LA为在溶液中同时具有链状、环状和笼状结构平衡态的聚甲基铝氧烷或改性的聚甲基铝氧烷或有机硼试剂。
  27. 权利要求1所述组合物,其中,LA与茂金属络合物的摩尔比LA:M≥300。
  28. 权利要求1所述组合物,其中,镁化合物载体Mg(OR I)(OR II)为二甲氧基镁、二乙氧基镁、二丙氧基镁、二丁氧基镁、乙氧基甲氧基镁、乙氧基丙氧基镁、丁氧基乙氧基镁中的一种或它们的混合物。
  29. 权利要求1所述组合物,其中,镁化合物载体与茂金属络合物(I)的Mg:M摩尔比为100~1000。
  30. 通式(I)所示的茂金属络合物的合成方法:
    Figure PCTCN2022138923-appb-100011
    其中,T互相间相同或不同,所述T是单齿或双齿的中性配位体;
    LG是脱离基团,其互相之间相同或不同,所述LG为氢、碱金属元素或第十四族重元素的有机自由基;
    所述单齿配位体包括醚类ROR、硫醚类RSR、三级胺类NR 3、三级膦类PR 3、环醚、环硫醚类、酮类、取代环酮类、取代吡啶类、取代吡咯类、取代哌啶类、酯类、内酯类、酰胺类和内酰胺类,其中R是C 1-C 20的直链或支化烷基、C 1-C 20的饱和或不饱和烷基、C 1-C 20的卤代或非卤代烷基、C 1-C 20的含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基;
    所述双齿配位体包括邻位双醚类、α,ω-双醚类、邻位双胺类、α,ω-双胺类、邻位双硫醚类、α,ω-双硫醚类、邻位双膦类和α,ω-双膦类;
    x是0或整数1、2或3;
    所述碱金属元素包括锂、钠和钾;
    所述第十四族重元素的有机自由基包括SiR 3、GeR 3、SnR 3、PdR 3、ZnR、BaR、MgR和CaR,其中,R是C 1-C 20的直链或支化烷基、C 1-C 20的饱和或不饱和烷基、C 1-C 20的卤代或非卤代烷基、C 1-C 20的含有元素周期表中第十三到第十七族元素杂原子的烷基、C 3-C 20的环烷基、C 6-C 30的芳基、C 7-C 30的烷取代芳基或C 7-C 30的芳取代烷基。
  31. 权利要求30所述方法,其中,合成过程中反应介质为饱和C 5-C 15烷烃、环烷烃或其中两种或两种以上的混合物。
  32. 权利要求31所述方法,其中,所述反应介质为己烷、庚烷、辛烷、甲苯或二甲苯。
  33. 权利要求30所述方法,其中,反应温度范围为-100℃~+300℃。
  34. 权利要求33所述方法,其中,反应温度范围为-75℃~+250℃。
  35. 权利要求34所述方法,其中,反应温度范围为-50℃~+150℃。
  36. 镁化合物载体Mg(OR I)(OR II)的制备方法,其中,将醇R IOH和醇R IIOH与金属镁粉在卤素的存在下加热反应至不再产生氢气为止,用惰性有机溶剂稀释洗涤,得到Mg(OR I)(OR II)固体。
  37. 权利要求1-29任一所述催化剂组合物的制备方法,其中,使选自通式(I)的化合物与助催化剂LA和镁化合物载体Mg(OR I)(OR II)在惰性有机溶剂中接触,从而得到催化剂组合物。
  38. 权利要求37所述方法,其中,所述惰性有机溶剂选自:己烷、庚烷、辛烷、癸烷或甲苯。
  39. 权利要求37所述方法,其中,接触时间为1分钟~8小时。
  40. 权利要求39所述方法,其中,接触温度在-75℃~120℃。
  41. 权利要求1-29任一所述的催化剂组合物在乙烯-丙烯共聚合中的应用。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11199612A (ja) * 1998-01-14 1999-07-27 Nippon Polyolefin Kk ポリオレフィンの製造方法
CN101160329A (zh) * 2005-04-18 2008-04-09 出光兴产株式会社 镁化合物、固体催化剂成分、乙烯系聚合催化剂以及乙烯系聚合物的制备方法
CN104592427A (zh) * 2015-01-28 2015-05-06 任丘市利和科技发展有限公司 一种烯烃聚合催化剂载体、其制备方法及应用
CN105985368A (zh) * 2015-02-06 2016-10-05 中国石油天然气股份有限公司 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11199612A (ja) * 1998-01-14 1999-07-27 Nippon Polyolefin Kk ポリオレフィンの製造方法
CN101160329A (zh) * 2005-04-18 2008-04-09 出光兴产株式会社 镁化合物、固体催化剂成分、乙烯系聚合催化剂以及乙烯系聚合物的制备方法
CN104592427A (zh) * 2015-01-28 2015-05-06 任丘市利和科技发展有限公司 一种烯烃聚合催化剂载体、其制备方法及应用
CN105985368A (zh) * 2015-02-06 2016-10-05 中国石油天然气股份有限公司 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用

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