WO2024255875A1 - 用于烯烃聚合的催化剂组分及其制备方法和用途 - Google Patents

用于烯烃聚合的催化剂组分及其制备方法和用途 Download PDF

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WO2024255875A1
WO2024255875A1 PCT/CN2024/099347 CN2024099347W WO2024255875A1 WO 2024255875 A1 WO2024255875 A1 WO 2024255875A1 CN 2024099347 W CN2024099347 W CN 2024099347W WO 2024255875 A1 WO2024255875 A1 WO 2024255875A1
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Prior art keywords
dimethoxypropane
catalyst component
group
furan
magnesium
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English (en)
French (fr)
Inventor
赵瑾
周俊领
谭扬
陈龙
夏先知
杨睿
任春红
马长友
高富堂
李威莅
凌永泰
刘月祥
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Sinopec Beijing Research Institute Of Chemical Industry Co Ltd
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute Of Chemical Industry Co Ltd
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority claimed from CN202310721613.3A external-priority patent/CN119143903B/zh
Priority claimed from CN202310722783.3A external-priority patent/CN119143904B/zh
Application filed by Sinopec Beijing Research Institute Of Chemical Industry Co Ltd, Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute Of Chemical Industry Co Ltd
Priority to KR1020257039787A priority Critical patent/KR20260003195A/ko
Priority to EP24822822.3A priority patent/EP4711388A1/en
Priority to JP2025550588A priority patent/JP2026509210A/ja
Publication of WO2024255875A1 publication Critical patent/WO2024255875A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof

Definitions

  • the invention belongs to the field of olefin polymerization catalysts, and in particular relates to a catalyst component for olefin polymerization and a preparation method and application thereof.
  • the third-generation Z-N catalysts have developed from monobasic acid ester compounds, such as ethyl benzoate and ethyl p-ethoxybenzoate, to dibasic acid ester compounds, such as di(iso)butyl phthalate of the fourth-generation Z-N catalyst.
  • Phthalate compounds plasticizers
  • plasticizers are currently the most commonly used internal electron donors in polypropylene catalysts. According to research, they can cause serious damage to the growth and development and reproductive system of animals, and may also have similar effects on humans.
  • countries and regions such as the United States and the European Union have successively listed such compounds as toxic chemicals, and their use (especially in infant toys, etc.) is strictly restricted. Therefore, it is imperative to develop high-performance catalysts that do not contain phthalate compounds.
  • High fluidity polypropylene is one of the main development directions of polypropylene in the future due to its good processing properties.
  • the upper limit of the amount of hydrogen that can be added is limited by the pressure resistance of the polymerization reactor.
  • the partial pressure of the olefin gas to be polymerized has to be reduced, in which case the productivity will be reduced.
  • the polymers obtained by the olefin polymerization catalyst in the prior art when used for olefin polymerization have the problem of insufficient processing properties of low fluidity polymers and the problem of many precipitates of high fluidity polymers.
  • the purpose of the present invention is to provide an olefin polymerization catalyst, which, when used for olefin polymerization, can narrow the molecular weight distribution of the prepared polymer as the melt index increases, so that the polymer with a low melt index has good processing performance and the polymer with a high melt index has lower precipitates, thereby taking into account both good processing performance and environmental protection.
  • the catalyst component of the present invention does not contain phthalate compounds (plasticizers).
  • the first aspect of the present invention provides a catalyst component for olefin polymerization, the catalyst component comprising magnesium, titanium, halogen and an electron donor; wherein the electron donor comprises a furan compound and a diether compound; the furan compound is selected from at least one of the furan compounds represented by formula (I),
  • R1 and R3 are each independently selected from hydrogen, a C1 - C20 straight chain or branched alkyl group, a C3 - C20 cycloalkyl group, a C6 - C20 aryl group, a C7 - C20 aralkyl group or a C7 - C20 alkaryl group;
  • R2 and R4 are each independently selected from a C1 - C10 straight chain or branched alkyl group, a C3 - C10 cycloalkyl group, a C6 - C10 aryl group, a C7 - C10 aralkyl group or a C7 - C10 alkaryl group.
  • the second aspect of the present invention provides a method for preparing a catalyst component for olefin polymerization, the method comprising: mixing a magnesium source, a titanium source and an electron donor, wherein the electron donor comprises a furan compound and a diether compound; the furan compound is selected from at least one of the furan compounds represented by formula (I),
  • R1 and R3 are each independently selected from hydrogen, C1 - C20 straight-chain alkyl, C3 - C20 branched-chain alkyl, C3 - C20 cycloalkyl, C6 - C20 aryl, C7 - C20 aralkyl or C7 - C20 alkaryl;
  • R2 and R4 are each independently selected from C1 - C10 straight-chain alkyl, C3 - C10 branched-chain alkyl, C3 - C10 cycloalkyl, C6 - C10 aryl, C7 - C10 The aralkyl group or the C 7 -C 10 alkylaryl group.
  • the third aspect of the present invention provides a catalyst system for olefin polymerization, the catalyst system comprising:
  • the fourth aspect of the present invention provides use of the catalyst component described in the first aspect and/or the catalyst component prepared by the method described in the second aspect and/or the catalyst system described in the third aspect in olefin polymerization.
  • the fifth aspect of the present invention provides an olefin polymerization method, which comprises: conducting an olefin polymerization reaction in the presence of the catalyst component described in the first aspect and/or the catalyst component prepared by the method described in the second aspect and/or the catalyst system described in the third aspect.
  • the present invention achieves the following beneficial effects:
  • the present invention uses a furan compound and a diether compound as the catalyst component of the electron donor, and the polymer prepared under low hydrogen polymerization conditions has a wide molecular weight distribution, which can effectively improve the processing performance of the polymer; and with the increase of hydrogen, the molecular weight distribution of the polymer prepared under high hydrogen polymerization conditions becomes narrower, which can reduce the content of small molecules in the high melt index polymer, which is conducive to reducing the content of precipitates, and the high melt index product itself has good processing performance.
  • the catalyst component has a good balance between hydrogen sensitivity and stereospecificity when used for olefin polymerization.
  • the catalyst component of the present invention which uses a magnesium-containing solid component containing sulfur as a carrier and a furan compound and a diether compound as an electron donor, has a narrow particle size distribution.
  • the catalyst component not only has a good balance between hydrogen sensitivity and stereospecificity, but also the molecular weight distribution of the prepared polymer can be narrowed with the increase of the melt index, and the polymer has a lower fine powder content.
  • the electron donor generally refers to an internal electron donor in the art.
  • Other electron donors are generally referred to as external electron donors in the art.
  • the first aspect of the present invention provides a catalyst component for olefin polymerization, the catalyst component comprising magnesium, titanium, halogen and an electron donor; wherein the electron donor comprises a furan compound and a diether compound; the furan compound is selected from at least one of the furan compounds represented by formula (I),
  • R1 and R3 are each independently selected from hydrogen, a C1 - C20 straight-chain alkyl group, a C3 - C20 branched-chain alkyl group, a C3 - C20 cycloalkyl group, a C6 - C20 aryl group, a C7 - C20 aralkyl group or a C7 - C20 alkaryl group;
  • R2 and R4 are each independently selected from a C1 - C10 straight-chain alkyl group, a C3 - C10 branched-chain alkyl group, a C3 - C10 cycloalkyl group, a C6 - C10 aryl group, a C7 - C10 aralkyl group or a C7 - C10 alkaryl group.
  • R1 and R3 can be independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; preferably, in formula (I), R1 and R3 are independently selected from hydrogen, C1 - C6 straight-chain alkyl, C3 - C6 branched-chain alkyl.
  • R2 and R4 can each independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; preferably, in formula (I), R2 and R4 can each independently be selected from C1 - C6 straight-chain alkyl, C3 - C6 branched-chain alkyl; more preferably selected from C1 - C3 straight-chain alkyl.
  • the inventors of the present invention unexpectedly discovered that when the diether compound and the furan compound represented by the formula (I) of the present application are compounded and used as electron donors, a synergistic effect can be exerted, and when used for olefin polymerization, the molecular weight distribution of the prepared polymer can be narrowed as the melt index increases, thereby achieving good processing performance and environmental protection.
  • the catalyst component has a good balance between hydrogen sensitivity and stereospecificity.
  • the content of the furan compound relative to each mole of the diether compound is 0.01-2 moles; for example, in the catalyst component, the content of the furan compound relative to each mole of the diether compound can be 0.01 mole, 0.05 mole, 0.06 mole, 0.07 mole, 0.08 mole, 0.09 mole, 0.1 mole, 0.15 mole, 0.2 mole, 0.25 mole, 0.3 mole, 0.35 mole, 0.4 mole, 0.45 mole, 0.5 mole, 0.6 mole, 0.7 mole, 0.8 mole, 0.9 mole, 1 mole, 1.1 mole, 1.2 mole, 1.5 mole, 2 moles, and the range formed by any two of the above points.
  • the catalyst component In the catalyst component the content of the furan compound is 0.03-1.2 moles per mole of the diether compound, and more preferably 0.05-0.4 moles.
  • the molar ratio of the diether compound to the furan compound in the catalyst component is within the above further preferred range, the synergistic effect of the two electron donors is more obvious, the hydrogen modulation sensitivity and stereospecificity can be further improved, and the molecular weight distribution of the polymer under high hydrogen conditions is narrower.
  • the total content of the furan compound and the diether compound in the electron donor is 70 wt %-100 wt %, more preferably 80 wt %-100 wt %, further preferably 90-100 wt %.
  • the furan compound is selected from at least one of the furan compounds represented by formula (I-1),
  • R1, R2, R3, and R4 are as described in formula (I) and are not described in detail here.
  • the furan compound is selected from at least one of (3R,3aR,6S,6aR)-3-methoxy-6-propoxyhexahydrofuro[3,2-b]furan, (3R,3aR,6S,6aR)-3-methoxy-6-ethoxyhexahydrofuro[3,2-b]furan, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuro[3,2-b]furan, (3R,3aR,6S,6aR)-3,6-diethoxyhexahydrofuro[3,2-b]furan and (3R,3aR,6S,6aR)-3,6-dipropoxyhexahydrofuro[3,2-b]furan. More preferably, the furan compound is (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofurano[3,2-b]furan.
  • the diether compound may be any diether compound that can be used as an electron donor in a catalyst for olefin polymerization.
  • the diether compound is selected from at least one of the diether compounds represented by formula (II):
  • R I , R II , R III , R IV , R V and R VI are the same or different, and are each independently selected from hydrogen, a halogen atom, a C 1 -C 20 straight-chain alkyl group, a C 3 -C 20 branched-chain alkyl group, a C 3 -C 20 cycloalkyl group, a C 6 -C 20 aryl group, a C 7 -C 20 aralkyl group or a C 7 -C 20 alkaryl group; the groups of R I -R VI may be optionally bonded to form a ring; R VII and R VIII are the same or different, and are each independently selected from a C 1 -C 20 straight-chain alkyl group, a C 3 -C 20 branched-chain alkyl group, a C 3 -C 20 cycloalkyl group, a C 6 -C 20 aryl group, a C 7 -C 20 alkaryl group or
  • R I , R II , R III , R IV , R V and R VI are each independently selected from hydrogen, a C 1 -C 20 straight-chain alkyl group, or a C 3 -C 20 branched-chain alkyl group; or, R III and R IV are bonded to form a fluorene ring. More preferably, in formula (II), R I , R II , R III , R IV , R V and R VI are each independently selected from hydrogen, a C 1 -C 7 straight-chain alkyl group, or a C 3 -C 7 branched-chain alkyl group.
  • the diether compound when R III and R IV are bonded to form a fluorene ring, the diether compound has a structure of formula (II-1),
  • R I , R II , R V , R VI , R VII and R VIII are as shown in formula (II).
  • R VII and R VIII are each independently selected from C 1 -C 5 straight chain alkyl and C 3 -C 5 branched chain alkyl.
  • the diether compound is selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxy 2,2-dicyclopentyl-1,3-dimethoxypropane,
  • the content of magnesium element can be 2-18 parts by weight, preferably 3-16 parts by weight, per part by weight of titanium element.
  • the content of the electron donor can be 2-17 parts by weight, preferably 3-15 parts by weight, per part by weight of titanium element.
  • the catalyst component may further contain halogen, and the halogen in the catalyst component may be at least one of fluorine, chlorine, bromine, and iodine.
  • the source of the halogen in the catalyst component may be the halogen contained in the source of magnesium and/or the source of titanium.
  • the source of the magnesium element can be any magnesium-containing compound that can prepare a polyolefin catalyst component; preferably, the source of the magnesium element is selected from at least one of magnesium halides (such as magnesium chloride and/or magnesium bromide), magnesium alcoholates (such as diethoxymagnesium), magnesium halogenated alcoholates (such as ethoxymagnesium chloride), magnesium halide alcohol adducts, magnesium halide adducts (such as magnesium halide adducts disclosed in patent applications CN1091748, CN101050245, CN101486722, CN102796132B, CN102796129B and CN102796128B, and the relevant contents disclosed in these patent applications are all introduced into the present invention as a reference) and magnesium-containing solid components.
  • magnesium halides such as magnesium chloride and/or magnesium bromide
  • magnesium alcoholates such as diethoxymagnesium
  • magnesium halogenated alcoholates such as ethoxymagnesium chloride
  • the magnesium halide alcohol adduct may be, for example, at least one of the structures shown in formula (IV); MgX 2 ⁇ m'R 7 OH Formula (IV)
  • X is halogen, preferably chlorine or bromine; m' is 1-5; R7 is a C1 - C6 straight chain or branched chain alkyl group, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl.
  • the magnesium-containing solid component may be, for example, at least one of the structures shown in formula (III);
  • R1 is a C1 - C6 straight chain or branched alkyl group
  • R2 and R3 are the same or different and are independently hydrogen or a C1 - C5 straight chain or branched alkyl group, wherein the hydrogen on the alkyl group may be optionally replaced by a halogen atom
  • X is a halogen, preferably chlorine or bromine
  • m is 0.1-1.9
  • n is 0.1-1.9
  • m+n 2, 0 ⁇ q ⁇ 0.5.
  • the average particle diameter of the magnesium-containing solid component is 12-30 microns, and the particle size distribution is less than 1.2, more preferably 0.2-0.8.
  • the average particle diameter and particle size distribution of the olefin polymerization catalyst support (containing magnesium solid component) can be measured using a Master Sizer 2000 laser particle size analyzer (manufactured by Malvern Instruments Ltd).
  • the magnesium-containing solid component synthesis raw material contains a sulfur source, a magnesium halide of the general formula MgX2Y , a compound of the general formula R4OH , and an oxirane compound; in the general formula MgX2Y , X2 is a halogen, and Y is a halogen or a C1 - C6 alkyl group, a C1 - C5 alkoxy group, a C6 - C10 aryl group, or a C6 - C10 aryloxy group; in the general formula R4OH , R4 is a C1 - C8 alkyl group or a C3 - C8 cycloalkyl group; the structure of the oxirane compound is shown in formula (V):
  • R 5 and R 6 are each independently hydrogen, C 1 -C 5 alkyl or C 1 -C 5 halogenated alkyl.
  • the sulfur source is anhydrous sulfur or sulfur containing crystal water, sulfur or sulfur bromide, sulfur chloride or sulfur iodide, preferably sulfur and/or sulfur chloride; more preferably ⁇ -sulfur and/or ⁇ -sulfur.
  • X2 is preferably chlorine or bromine
  • Y is preferably chlorine, bromine, a C1 - C5 alkyl group, a C1 - C5 alkoxy group, a C6 - C10 aryl group or a C6 - C10 aryloxy group
  • the C1 - C5 alkyl group may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a tert-pentyl group or a neopentyl group
  • the C1 - C5 alkoxy group may be, for example, a methoxy group, an ethoxy group, a prop
  • the magnesium halide of the general formula MgX2Y may be a single magnesium halide or a mixture of multiple magnesium halides. Specific examples of the magnesium halide of the general formula MgX2Y may be, but are not limited to, one or more of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride. From the perspective of raw material availability, magnesium chloride is preferred.
  • R 4 is preferably a C 1 -C 8 alkyl group; the C 1 -C 8 alkyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl or isooctyl.
  • the C 1 -C 8 alkyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl
  • Specific examples of the compound of the general formula R 4 OH may be, but are not limited to, one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, amyl alcohol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.
  • R 5 and R 6 are preferably independently hydrogen, C 1 -C 3 alkyl or C 1 -C 3 halogenated alkyl.
  • Specific examples of the oxirane compound may be, but are not limited to, one or more of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, epibromohydrin and epibromobutylene oxide.
  • the water contained in the magnesium-containing solid component comes from trace water carried by the synthetic raw materials and the reaction medium.
  • the method for preparing the magnesium-containing solid component of the present invention comprises the following steps:
  • step (b) emulsifying the liquid mixture obtained in step (a), and contacting the emulsified product with an oxirane compound for reaction.
  • magnesium halide with the general formula MgX 2 Y compound with the general formula R 4 OH, sulfur source, and ethylene oxide compound have been described above and will not be described in detail here.
  • the amount of sulfur source used is 0.0001-0.1 mol
  • the amount of compound of the general formula R 4 OH used is 4-30 mol
  • the structure of ethylene oxide shown in formula (V) is The amount of the alkane compound is 1-10 mol; preferably, based on 1 mol of magnesium halide of the general formula MgX 2 Y, the amount of the compound of the general formula R 4 OH is 6-20 mol, and the amount of the oxirane compound of the structure shown in formula (V) is 2-6 mol.
  • a trace amount of water in the above-mentioned reactants can also participate in the reaction of forming the magnesium-containing solid component.
  • a surfactant can be added to the liquid mixture described in step (a), and the surfactant is selected from the group consisting of polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG), polyacrylic acid, polyacrylate, polystyrene sulfonate, naphthalenesulfonic acid formaldehyde condensate, condensed alkyl phenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer modified polyethyleneimine, 1-dode-4-vinyl pyridinium bromide polymer, polyvinyl benzyl trimethylamine salt, polyvinyl alcohol, polyacrylamide, polyethylene oxide propylene oxide block copolymer, polyvinyl pyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether and polymethacrylate alkyl ester compounds, or
  • step (a) there is no particular limitation on the conditions for heating the mixture of the sulfur source, the magnesium halide of the general formula MgX 2 Y, the compound of the general formula R 4 OH, and the inert liquid medium, as long as the heating conditions can melt the magnesium halide of the general formula MgX 2 Y and fully react with the sulfur source.
  • the heating conditions include: the temperature can be 80-120°C, and the time can be 0.5-5 hours; preferably, the temperature is 80-100°C, and the time is 0.5-3 hours.
  • the amount of the inert liquid medium can be selected according to the amount of the magnesium halide of the general formula MgX2Y .
  • the amount of the inert liquid medium can be 0.8-10L, preferably 2-8L.
  • the inert liquid medium can be various liquid media commonly used in the art that do not chemically interact with the reactants and reaction products.
  • the inert liquid medium can be silicone oil and/or an inert liquid hydrocarbon solvent.
  • the inert liquid medium can be one or more of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil and methylphenyl silicone oil.
  • the inert liquid medium of the present invention is particularly preferably white oil.
  • the liquid mixture obtained in step (a) can be emulsified by various methods known to those skilled in the art.
  • the liquid mixture can be subjected to low-speed shearing or high-speed shearing to emulsify it.
  • the stirring rate of the low-speed shearing is generally 400-800 rpm.
  • the high-speed shearing method is well known to those skilled in the art, such as the high-speed stirring method disclosed in CN1151183C (i.e., stirring the solution containing the liquid magnesium halide adduct at a speed of 2000-5000 rpm).
  • the liquid mixture can also be emulsified by referring to the methods disclosed in the following patents: CN1267508C discloses a solution containing the liquid magnesium halide adduct being rotated and dispersed in a supergravity bed (the rotation speed can be 100-3000 rpm); CN1463990A discloses a solution containing the liquid magnesium halide adduct being rotated and dispersed in a supergravity bed (the rotation speed can be 100-3000 rpm); The solution of the magnesium halide adduct is output in an emulsifier at a speed of 1500-8000 rpm; US6020279 discloses emulsifying a solution containing a liquid magnesium halide adduct by a spraying method.
  • the conditions for the contact reaction of the emulsified product with the ethylene oxide compound can be various existing conditions that can form an olefin polymerization catalyst carrier.
  • the contact reaction conditions include a temperature of 50-120°C and a time of 20-60 minutes; preferably, the temperature is 60-100°C and the time is 20-50 minutes.
  • the method may further include performing solid-liquid separation on the product obtained by the contact reaction, washing the solid phase product and drying it.
  • the solid-liquid separation may be any existing method capable of achieving solid-liquid separation, such as suction filtration, filter pressing or centrifugal separation.
  • the solid-liquid separation method is filter pressing.
  • the present invention does not particularly limit the conditions for filter pressing, and is subject to achieving the separation of the solid phase and the liquid phase as fully as possible.
  • the washing may be performed by a method known to those skilled in the art to wash the obtained solid phase product, for example, an inert hydrocarbon solvent (for example, pentane, hexane, heptane, petroleum ether and gasoline) may be used to wash the obtained solid phase product.
  • an inert hydrocarbon solvent for example, pentane, hexane, heptane, petroleum ether and gasoline
  • the present invention does not particularly limit the conditions for the drying, for example, the drying temperature may be 20-70°C, and the drying time may be 0.5-10 hours. According to the present invention, the drying may be performed under normal pressure or reduced pressure.
  • the magnesium-containing solid component particles obtained in the above process of preparing the magnesium-containing solid component are washed with an inert hydrocarbon solvent (such as hexane, heptane, octane, decane, toluene, etc.), dried, and used in the subsequent step to prepare the catalyst component for olefin polymerization.
  • an inert hydrocarbon solvent such as hexane, heptane, octane, decane, toluene, etc.
  • the source of the titanium element can be any titanium-containing compound capable of preparing a polyolefin catalyst component; preferably, the source of the titanium element is selected from titanium compounds of the general formula Ti(OR′) 3-a Z a and/or Ti(OR′) 4-b Z b , wherein R′ is a C 1 -C 20 alkyl group, preferably a C 1 -C 14 aliphatic hydrocarbon group, preferably a C 1 -C 8 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.; Z is F, Cl, Br or I, a is an integer of 1-3, b is an integer of 0-4, preferably an integer of 1-4.
  • the source of the titanium element is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxytitanium chloride, dibutoxytitanium dichloride, butoxytitanium trichloride, triethoxytitanium chloride, diethoxytitanium dichloride, ethoxytitanium trichloride and titanium trichloride.
  • the present invention also provides a catalyst component for olefin polymerization, the catalyst component comprising a reaction product of the following components: a magnesium source, a titanium source and an electron donor, the electron donor comprising a furan compound and a diether compound.
  • the present invention also provides a catalyst component for olefin polymerization, the catalyst component comprising a reaction product of the following components:
  • a magnesium-containing solid component (1) A magnesium-containing solid component
  • the electron donor contains a furan compound and a diether compound; and the magnesium-containing solid component is at least one of the structures shown in formula (III).
  • the second aspect of the present invention provides a method for preparing a catalyst component for olefin polymerization, the method comprising: mixing a magnesium source, a titanium source and an electron donor, wherein the electron donor comprises a furan compound and a diether compound; the furan compound is selected from at least one of the furan compounds represented by formula (I),
  • R1 and R3 are each independently selected from hydrogen, a C1 - C20 straight-chain alkyl group, a C3 - C20 branched-chain alkyl group, a C3 - C20 cycloalkyl group, a C6 - C20 aryl group, a C7 - C20 aralkyl group or a C7 - C20 alkaryl group;
  • R2 and R4 are each independently selected from a C1 - C10 straight-chain alkyl group, a C3 - C10 branched-chain alkyl group, a C3 - C10 cycloalkyl group, a C6 - C10 aryl group, a C7 - C10 aralkyl group or a C7 - C10 alkaryl group.
  • the catalyst component for olefin polymerization of the present invention can be prepared by conventional methods.
  • the mixing method includes: contacting a magnesium source with a titanium source, and adding an electron donor in one or more time periods before, during and after the contact reaction between the magnesium source and the titanium source.
  • the components of the electron donor can be added separately or simultaneously.
  • the electron donor includes a furan compound and a diether compound.
  • the reaction of the magnesium source and the titanium source can be carried out in the same manner as in the prior art.
  • the titanium source can be cooled to below 0°C (preferably -5 to -30°C), and then the magnesium source is added, and stirred and mixed at this temperature for 10-60 minutes, and then the temperature is raised to the reaction temperature (i.e., about 60-130°C), and maintained at the reaction temperature for 0.5-10 hours, preferably 0.5-5 hours.
  • the time period before the reaction of the magnesium source and the titanium source refers to the time period after the magnesium source is added to the reactor and before the temperature is raised to the reaction temperature.
  • a method for preparing a catalyst component for olefin polymerization comprises: adding a titanium source (e.g., titanium halide) to a reaction vessel, cooling to -30°C to 0°C, adding a magnesium source to the reaction vessel, and stirring and mixing at this temperature for 10-60 minutes; then heating to 0-130°C (preferably 80°C-130°C), adding an electron donor during the heating process, and then maintaining the temperature at 0-130°C (preferably 80°C-130°C) for 10-900 minutes. After 20-240 minutes (preferably), the liquid is filtered off. Then, a titanium source (such as titanium halide) is added for washing, and then washed with a non-polar solvent (such as hexane), and the catalyst component is obtained after drying.
  • a titanium source e.g., titanium halide
  • the types of furan compounds and diether compounds used in the method for preparing the catalyst component for olefin polymerization are as described in the first aspect and will not be described in detail here.
  • the types of magnesium source and titanium source used in the method for preparing the catalyst component for olefin polymerization are the same as those described for the source of magnesium element and the source of titanium element in the first aspect, and will not be described in detail here.
  • the amount of the furan compound in the method for preparing a catalyst component for olefin polymerization, can be 0.1-3 moles per mole of the diether compound, for example, the amount of the furan compound can be 0.1 mole, 0.2 mole, 0.3 mole, 0.4 mole, 0.5 mole, 0.6 mole, 0.7 mole, 0.8 mole, 0.9 mole, 1 mole, 1.1 mole, 1.2 mole, 1.3 mole, 1.4 mole, 1.5 mole, 1.6 mole, 1.7 mole, 1.8 mole, 1.9 mole, 2 mole, 2.1 mole, 2.5 mole, 3 mole, and the range of any two of the above points.
  • the amount of the furan compound is 0.1-2 moles per mole of the diether compound, and more preferably 0.15-1.8 moles.
  • the molar ratio of the diether compound to the furan compound in the catalyst component is within the above preferred range, the synergistic effect of the two electron donors is more obvious, which can further improve the hydrogen modulation sensitivity and stereospecificity, and further obtain a polymer with a higher melt index and a narrower molecular weight distribution.
  • the amount of the furan compound can also be 0.1-1.5 mol, or 0.15-1.5 mol, or 0.15-1.2 mol, or 0.15-1 mol, or 0.2-1 mol per mol of the diether compound.
  • the molar ratio of the magnesium source calculated as magnesium element to the titanium source calculated as titanium element can be 1:5, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:200, 1:220, and the range composed of any two of the above points.
  • the molar ratio of the magnesium source calculated as magnesium element to the titanium source calculated as titanium element is 1:5-220, more preferably 1:15-180, and further preferably 1:18-150.
  • the molar ratio of the amount of the magnesium source to the electron donor calculated as magnesium element can be 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1:1, 1:1.2, and the range composed of any two of the above points.
  • the molar ratio of the amount of the magnesium source to the electron donor calculated as magnesium element is 1:0.05-1.2, more preferably 1:0.1-1, and further preferably 1:0.15-0.9.
  • the amount of The molar ratio of the magnesium source, the titanium source calculated as titanium element and the electron donor is 1:15-180:0.1-1, more preferably 1:18-150:0.15-0.9.
  • the present invention also provides a method for preparing a catalyst component for olefin polymerization, the method comprising: contacting and reacting a magnesium-containing solid component with a titanium compound, and adding an electron donor containing a furan compound and a diether compound.
  • the amount of the titanium compound can be 5-220 moles per mole of magnesium, preferably 10-200 moles; the amount of the electron donor can be 0.05-1.2 moles per mole of magnesium, preferably 0.07-1.0 moles, and more preferably 0.1-0.8 moles.
  • the third aspect of the present invention provides a catalyst system for olefin polymerization, the catalyst system comprising:
  • the amount of the alkyl aluminum can be the conventional amount in the art.
  • the molar ratio of the alkyl aluminum calculated as aluminum element to the catalyst component calculated as titanium element is 1-2000:1, more preferably 20-500:1, and further preferably 30-300:1.
  • the amount of the other electron donor can be a conventional amount in the art.
  • the molar ratio of the other electron donor to the alkyl aluminum compound calculated as aluminum element is 1:1-300, more preferably 1:2-100.
  • the alkyl aluminum can be various alkyl aluminums conventionally used in the art.
  • the general formula of the alkyl aluminum can be AlR′′ n1X′3 -n1 , wherein R′′ is a C1 - C8 alkyl group, the hydrogen on the alkyl group is optionally substituted by a halogen atom, X′ is a halogen, and n1 is an integer of 0 ⁇ n1 ⁇ 3.
  • C1 - C8 alkyl group can include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, n-heptyl, and n-octyl, and the halogen can be fluorine, chlorine, bromine, or iodine.
  • the alkylaluminum is selected from one or more of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride, monoethylaluminum dichloride, monoisobutylaluminum dichloride, mono-n-butylaluminum dichloride and mono-n-hexylaluminum dichloride.
  • the other electron donor can be various external electron donors commonly used in the art.
  • the other electron donor can be selected from at least one of carboxylic acids, carboxylic anhydrides, carboxylates, ketones, ethers, alcohols, lactones, organophosphorus compounds and organosilicon compounds.
  • the other electron donor is selected from silicon compounds containing at least one Si-OR 19 bond and having the general formula (R 17 ) x (R 18 ) y Si(OR 19 ) z , wherein R 17 , R 18 and R 19 are each independently a C 1 -C 18 hydrocarbon group, x and y are each independently an integer of 0-2, z is an integer of 1-3, and the sum of x, y and z is 4.
  • R 17 and R 18 are preferably C 3 -C 10 alkyl or C 3 -C 10 cycloalkyl, optionally containing heteroatoms;
  • R 19 is preferably C 1 -C 10 alkyl, optionally containing heteroatoms.
  • the other electron donor is selected from at least one of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane and (1,1,1-, trifluoro-2-propyl)-methyldimethoxysilane.
  • the alkyl aluminum and the optional other electron donors can be mixed with the catalyst components for olefin polymerization separately and then reacted, or the alkyl aluminum compound and the optional other electron donors can be mixed first and then mixed with the catalyst components for olefin polymerization and reacted.
  • the fourth aspect of the present invention provides use of the catalyst component described in the first aspect and/or the catalyst component prepared by the method described in the second aspect and/or the catalyst system described in the third aspect in olefin polymerization.
  • the catalyst component, alkyl aluminum, and other optional electron donors can be added to the polymerization reactor separately, or mixed and added to the polymerization reactor, or the olefin can be prepolymerized by a prepolymerization method known in the industry and then added to the polymerization reactor.
  • the catalyst is preferably prepolymerized with propylene and/or other ⁇ -olefin monomers before the polymerization reaction.
  • the prepolymerization reaction temperature can be 5-40°C, preferably 10-30°C.
  • the specific type of olefin, the polymerization method and conditions of olefin can be conventionally selected according to the prior art.
  • the fifth aspect of the present invention provides an olefin polymerization method, which comprises: conducting an olefin polymerization reaction in the presence of the catalyst component described in the first aspect and/or the catalyst component prepared by the method described in the second aspect and/or the catalyst system described in the third aspect.
  • the polymerization reaction of olefins can be carried out according to existing methods, specifically, under the protection of inert gas, in liquid monomers or inert solvents containing polymerizable monomers, or in gas phase, or by a combined polymerization process in gas and liquid phase.
  • the temperature of the polymerization reaction can generally be 0-150°C, preferably 60-90°C.
  • the pressure of the polymerization reaction can be normal pressure or higher, for example, 0.01-10MPa, preferably 0.01-5MPa, more preferably 0.1-4Mpa, and the pressure of the present invention refers to the gauge pressure.
  • the polymer molecular weight regulator is added to the reaction system to adjust the molecular weight and melt index of the polymer.
  • the types and amounts of the inert gas and solvent are well known to those skilled in the art and will not be described in detail here.
  • the catalyst component and the olefin can also be subjected to a prepolymerization reaction; the temperature of the prepolymerization reaction is 5-40°C, preferably 10-30°C.
  • the titanium content in the catalyst component of the present invention can be measured by colorimetry. Specifically, 0.2-0.5 g of the sample is dissolved in 50 mL of 2N H 2 SO 4 , the upper floating matter is filtered, and the clear liquid is taken for colorimetry; 2N H 2 SO 4 solution is used as a blank, the thickness of the cuvette is 1 cm, and the absorbance E1 is measured at a wavelength of 410 ⁇ m, and then 1 drop of 30 wt % H 2 O 2 is dripped, shaken, and the absorbance E2 is measured.
  • the titanium content Ti (%) is calculated according to the following formula:
  • G is the sample mass (g); VE is the amount of EDTA consumed (mL); NE is the equivalent number of EDTA solution; 24.31 is the atomic weight of magnesium.
  • the catalyst component is weighed, dissolved in methanol, and then filtered through a membrane to test the content of furan compounds in the catalyst component.
  • the content of furan compounds in the catalyst component of the present invention is tested using Agilent's 7890A-5975C gas chromatograph-mass spectrometer.
  • Chromatographic conditions HP-5 MS UI gas chromatograph column (30m ⁇ 0.25mm ⁇ 0.25 ⁇ m), programmed temperature, 35°C for 3min, 10°C/min to 250°C, and maintained for 3min.
  • Carrier gas He flow rate 1.0mL/min, split injection, split ratio 50:1, injection port temperature 250°C, transfer
  • the transmission line temperature was 250°C.
  • Mass spectrometry conditions quadrupole mass spectrometer, EI ionization source, electron energy 70 eV, source temperature 200°C, full scan acquisition mode, mass range m/z 20-400.
  • the catalyst component is weighed and then acidified with dilute hydrochloric acid, extracted with cyclohexane, and then the content of the diether compound in the catalyst component is tested.
  • the content of the diether compound in the catalyst component of the present invention is tested using Agilent's 7890 gas chromatograph. Chromatographic column: HP-INNO WAX (60m ⁇ 0.530mm ⁇ 1 ⁇ m), internal standard method, internal standard: amyl ester.
  • the molecular weight distribution (Mw/Mn) of the polymer in the present invention was tested by using a PL-GPC220 gel permeation chromatograph produced by Polymer Laboratories of the United Kingdom, with trichlorobenzene as solvent, a test temperature of 150°C, polystyrene as standard, a flow rate of 1.0 mL/min, and a 3 ⁇ Plgel 10 mMlXED-B 300 ⁇ 7.5 nm column.
  • the polymer melt index in the present invention is measured according to GB3682-2000 at 230°C and a load of 2.16 kg.
  • the isotactic index of the polymer in the present invention is measured by the heptane extraction method.
  • the average particle diameter and particle size distribution of the catalyst components and their carriers in the present invention are measured using a Masters Sizer 2000 particle size analyzer (manufactured by Malvern Instruments Ltd);
  • the fine powder content of the polymer in the present invention is tested by MICROTRAC MRB camsizer P4.
  • the data in the table are the polymer content below 100 mesh (mesh/inch) after sieving with a standard sieve, that is, the polymer content that can pass through a sieve aperture of 150 ⁇ m.
  • Example A is used to illustrate the preparation method of the catalyst component using the alcohol adduct of magnesium halide as a carrier and the furan compound and diether compound as an electron donor and the process of preparing the polymer.
  • the bulk polymerization of propylene in liquid phase was carried out in a 5L stainless steel autoclave. Under nitrogen protection, 2mL of triethylaluminum hexane solution (concentration of 0.5mmol/mL), 0.4mL of cyclohexylmethyldimethoxysilane (CHMMS) hexane solution (concentration of 0.1mmol/mL) and 9mg of the above-mentioned catalyst component Cat-1A for olefin polymerization were added to the autoclave in sequence. The autoclave was closed, and hydrogen (the amount of hydrogen is shown in Table 1) and 2.3L of liquid propylene were added. The temperature was raised to 70°C, and after reacting for 1 hour, the temperature was lowered, the pressure was released, and the material was discharged. The obtained propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1A, except that 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was not added during the heating process, and the amounts of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofurano[3,2-b]furan and 9,9-bis(methoxymethyl)fluorene added were 5 mmol and 7.5 mmol, respectively, to obtain a catalyst component Cat-2A for olefin polymerization.
  • the catalyst component Cat-2A was tested to have a magnesium content of 5.22 parts by weight and an electron donor content of 5.63 parts by weight per part by weight of titanium.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1A, except that the amounts of (3R, 3aR, 6S, 6aR)-3,6-dimethoxyhexahydrofuran [3,2-b] furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane added during the heating process were 7 mmol and 6 mmol, respectively, to obtain a catalyst component Cat-3A for olefin polymerization.
  • the catalyst component Cat-3A was tested to have a magnesium content of 5.20 parts by weight and an electron donor content of 4.71 parts by weight per part by weight of titanium.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1A, except that the amounts of (3R, 3aR, 6S, 6aR)-3, 6-dimethoxyhexahydrofuran [3, 2-b] furan and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane added during the heating process were 2 mmol and 8 mmol, respectively, to obtain a catalyst component Cat-4A for olefin polymerization.
  • the catalyst component Cat-4A was tested to have a magnesium content of 5.74 parts by weight and an electron donor content of 5.48 parts by weight per part by weight of titanium.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1A, except that the amounts of (3R, 3aR, 6S, 6aR)-3, 6-dimethoxyhexahydrofuran [3, 2-b] furan and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane added during the heating process were 8.7 mmol and 3.2 mmol, respectively, to obtain a catalyst component Cat-5A for olefin polymerization.
  • the catalyst component Cat-5A was tested to have a magnesium content of 4.67 parts by weight and an electron donor content of 3.62 parts by weight per part by weight of titanium.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1A, except that during the preparation of the catalyst component, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan was not added, and only 11 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added to obtain the catalyst component DCat-1A for olefin polymerization.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1A, except that during the preparation of the catalyst component, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was not added, and only 11 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan was added to obtain the catalyst component DCat-2A for olefin polymerization.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1A, except that during the preparation of the catalyst component, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was replaced with an equimolar amount of 4-ethyl-3,5-heptanediol dibenzoate to obtain a catalyst component DCat-3A for olefin polymerization.
  • nFuran diether represents the molar ratio of furan compounds to diether compounds.
  • the catalyst when the electron donor contains a certain proportion of furan compounds and diether compounds, the catalyst has high hydrogen modulation sensitivity and stereospecificity, and its balance is good, and the molecular weight distribution of the prepared low melt index polymer is wider than that of the high melt index polymer, and the catalyst component of the present invention It does not contain phthalates (plasticizers).
  • Example B The following preparation examples and Example B are used to illustrate the preparation method of the catalyst component using a magnesium-containing solid component as a carrier and a furan compound and a diether compound as an electron donor and the process of preparing a polymer.
  • This preparation example is used to illustrate the olefin polymerization catalyst carrier and the preparation method thereof provided by the present invention.
  • the average particle diameter (D50) of the olefin polymerization catalyst carrier Z1 is 15 microns, and the particle size distribution ((D90-D10)/D50) is 0.6.
  • the particle morphology of the olefin polymerization catalyst carrier Z1 is relatively regular, the surface is smooth, and it is basically spherical.
  • the particle size distribution is relatively concentrated, and there are basically no irregular particles.
  • This preparation example is used to illustrate the olefin polymerization catalyst carrier and the preparation method thereof provided by the present invention.
  • the average particle diameter (D50) of the olefin polymerization catalyst carrier Z2 is 18 microns, and the particle size distribution ((D90-D10)/D50) is 0.7.
  • the particle morphology of the olefin polymerization catalyst carrier Z2 is relatively regular, the surface is smooth, and it is basically spherical.
  • the particle size distribution is relatively concentrated, and there is basically no abnormal shape. Particles exist.
  • the molar ratio of furan compounds to diether compounds in the catalyst component is shown in Table 2.
  • the content of magnesium element is 5.06 parts by weight
  • the content of electron donor is 5.87 parts by weight per part by weight of titanium element.
  • the bulk polymerization of propylene in liquid phase was carried out in a 5L stainless steel autoclave. Under nitrogen protection, 5mL of triethylaluminum hexane solution (concentration of 0.5mmol/mL), 1mL of cyclohexylmethyldimethoxysilane (CHMMS) hexane solution (concentration of 0.1mmol/mL) and 7.5mg of the above-mentioned solid catalyst Cat-1B were added to the reactor in sequence. The autoclave was closed, and hydrogen (the amount of hydrogen is shown in Table 2) and 2.3L of liquid propylene were added. The temperature was raised to 70°C, and after reacting for 1 hour, the temperature was lowered, the pressure was released, and the material was discharged. The obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 3.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1B, except that the solid component added was Z2, and 3.2 mmol of (3R, 3aR, 6S, 6aR)-3,6-dimethoxyhexahydrofuran [3,2-b] furan and 7.0 mmol of 9,9-bis (methoxymethyl) fluorene were added during the heating process to obtain a solid catalyst component Cat-2B.
  • the content of magnesium in the catalyst component Cat-2B was 4.85 parts by weight per part by weight of titanium element, and the content of magnesium in the catalyst component Cat-2B was 4.85 parts by weight.
  • the content of the daughter body is 5.53 parts by weight.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1B, except that the solid component added was Z2, and 4.7 mmol of (3R, 3aR, 6S, 6aR)-3,6-dimethoxyhexahydrofuran [3,2-b] furan and 6.5 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added during the heating process to obtain a solid catalyst component Cat-3B.
  • the content of magnesium element in the catalyst component Cat-3B was 4.63 parts by weight, and the content of electron donor was 4.45 parts by weight, calculated per part by weight of titanium element.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1B, except that 5.8 mmol and 6.3 mmol of (3R, 3aR, 6S, 6aR)-3,6-dimethoxyhexahydrofurano[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added during the heating process to obtain a catalyst component Cat-4B for olefin polymerization.
  • the catalyst component Cat-4B was tested to have a magnesium content of 4.78 parts by weight and an electron donor content of 4.64 parts by weight per part by weight of titanium.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1B, except that 7.5 mmol and 4.2 mmol of (3R, 3aR, 6S, 6aR)-3,6-dimethoxyhexahydrofurano[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added during the heating process to obtain a catalyst component Cat-5B for olefin polymerization.
  • the catalyst component was tested to have a magnesium content of 4.64 parts by weight and an electron donor content of 4.22 parts by weight per part by weight of titanium.
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1B, except that during the preparation of the catalyst component, 8 g of a magnesium halide carrier (prepared according to the method disclosed in Example 1 of CN1267508C) was added instead of the solid component Z1, and the (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofurano[3,2-b]furan was replaced by the same molar amount of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane to obtain a catalyst component DCat-1B for olefin polymerization.
  • a magnesium halide carrier prepared according to the method disclosed in Example 1 of CN1267508C
  • the catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1B, except that during the preparation of the catalyst component, 8 g of a magnesium halide carrier (prepared according to the method disclosed in Example 1 of CN1267508C) was added instead of the solid component Z1, and the 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was replaced by the same molar amount of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan to obtain a catalyst component DCat-2B for olefin polymerization.
  • a magnesium halide carrier prepared according to the method disclosed in Example 1 of CN1267508C
  • Span represents the width of particle size distribution
  • Span (D90-D10)/D50
  • Furan diether represents the molar ratio of furan compounds to diether compounds.
  • the particle size distribution of the catalyst component of the present invention is narrow, and when the catalyst component of the present invention is used, the catalyst has high hydrogen regulation sensitivity and stereospecificity as well as high polymerization activity, the content of the obtained polypropylene fine powder is low, and the molecular weight distribution of the prepared low melt index polymer is wider than that of the high melt index polymer, and the catalyst component of the present invention does not contain phthalate compounds (plasticizers).

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Abstract

本发明涉及烯烃聚合催化剂，公开了一种用于烯烃聚合的催化剂组分及其制备方法和应用。本发明的催化剂组分包括镁元素、钛元素、卤素和给电子体；其中，给电子体包括呋喃类化合物和二醚类化合物。该催化剂组分在用于烯烃聚合时所制备的低熔融指数聚合物的分子量分布要宽于高熔融指数聚合物的分子量分布。

Description

用于烯烃聚合的催化剂组分及其制备方法和用途
相关申请的交叉引用
本申请要求2023年06月16日提交的中国专利申请202310721613.3和202310722783.3的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明属于烯烃聚合催化剂领域，具体涉及一种用于烯烃聚合的催化剂组分及其制备方法和用途。
背景技术
众所周知，Z-N催化剂自其问世以来，经不断发展己成为工业化烯烃聚合反应用催化剂的主体。
作为推动Z-N催化剂发展的内给电子体，由第三代Z-N催化剂的一元酸酯类化合物，如苯甲酸乙酯和对乙氧基苯甲酸乙酯等，发展到二元酸酯类化合物，如第四代Z-N催化剂的邻苯二甲酸二(异)丁酯。邻苯二甲酸酯类化合物(塑化剂)是目前最常用的聚丙烯催化剂内给电子体，而据研究发现，其对动物的生长发育和生殖系统会造成严重损害，同时，对人类也可能产生类似的影响。美国、欧盟等国家和地区先后将此类化合物列为毒性化学物质，其用途(尤其在婴幼儿玩具等方面)受到严格限制。因此，开发不含邻苯二甲酸酯类化合物的高性能催化剂是势在必行的。
高流动性聚丙烯由于其良好的加工性能，是未来聚丙烯的主要发展方向之一。为了得到高熔体流动速率的烯烃聚合物，一般需要在聚合时添加大量的氢，从而使得聚合物低分子化。但是，可添加氢量的上限会受到聚合反应器耐压的限制。为了添加更多的氢而不得不降低聚合的烯烃气体的分压，在这种情况下生产率会降低。同时现有技术中的烯烃聚合催化剂在用于烯烃聚合时得到的聚合物存在：低流动性聚合物的加工性能不足的问题，以及高流动性聚合物的析出物多的问题。
发明内容
本发明的目的是为了提供一种烯烃聚合催化剂，该烯烃聚合催化剂在用于烯烃聚合时，制备得到的聚合物的分子量分布可随着熔融指数的增加而变窄，使低熔融指数的聚合物具有良好的加工性能，高熔融指数的聚合物具有较低的析出物，从而可以兼顾良好的加工性能和环保性。而且本发明的催化剂组分不含有邻苯二甲酸酯类化合物(塑化剂)。
本发明第一方面提供了一种用于烯烃聚合的催化剂组分，该催化剂组分包括镁元素、钛元素、卤素和给电子体；其中，给电子体包括呋喃类化合物和二醚类化合物；所述呋喃类化合物选自式(Ⅰ)所示呋喃类化合物中的至少一种，
式(Ⅰ)中，R1和R3各自独立地选自氢、C1-C20的直链或支链烷基、C3-C20的环烷基、C6-C20的芳基、C7-C20的芳烷基或C7-C20的烷芳基；R2和R4各自独立地选自C1-C10的直链或支链烷基、C3-C10的环烷基、C6-C10的芳基、C7-C10的芳烷基或C7-C10烷芳基。
本发明第二方面提供了一种制备用于烯烃聚合的催化剂组分的方法，该方法包括：将镁源、钛源和给电子体混合，其中，所述给电子体包括呋喃类化合物和二醚类化合物；所述呋喃类化合物选自式(Ⅰ)所示呋喃类化合物中的至少一种，
式(Ⅰ)中，R1和R3各自独立地选自氢、C1-C20的直链烷基、C3-C20的支链烷基、C3-C20的环烷基、C6-C20的芳基、C7-C20的芳烷基或C7-C20的烷芳基；R2和R4各自独立地选自C1-C10的直链烷基、C3-C10的支链烷基、C3-C10的环烷基、C6-C10的芳基、C7-C10 的芳烷基或C7-C10烷芳基。
本发明第三方面提供了一种用于烯烃聚合的催化剂体系，该催化剂体系包括：
(1)第一方面所述的催化剂组分和/或第二方面所述的方法制备得到的催化剂组分；
(2)至少一种烷基铝；以及
(3)任选的其他给电子体。
本发明第四方面提供了第一方面所述的催化剂组分和/或第二方面所述的方法制备得到的催化剂组分和/或第三方面所述的催化剂体系在烯烃聚合中的用途。
本发明第五方面提供了一种烯烃聚合方法，该烯烃聚合方法包括：在第一方面所述的催化剂组分和/或第二方面所述的方法制备得到的催化剂组分和/或第三方面所述的催化剂体系存在下进行烯烃聚合反应。
通过上述技术方案，本发明取得了以下有益效果：
(1)本发明采用式(Ⅰ)所示呋喃类化合物和二醚类化合物复配作为给电子体的催化剂组分，在低氢聚合条件下制备的聚合物具有较宽的分子量分布，可以有效提高聚合物的加工性能；而随着氢气的增加，在高氢聚合条件下其所制备的聚合物分子量分布变窄，这样可减少高熔融指数聚合物中小分子部分的含量，有利于减少析出物含量，同时高熔融指数的产品本身具有较好的加工性能。且催化剂组分在用于烯烃聚合时具有良好的氢调敏感性和立构定向性的平衡性。
(2)优选地，本发明采用含有硫元素的含镁固体组分作为载体，并以呋喃类化合物和二醚类化合物复配作为给电子体的催化剂组分的粒径分布较窄，该催化剂组分在用于烯烃聚合时不仅具有良好的氢调敏感性和立构定向性的平衡性，并且所制备聚合物的分子量分布可随着熔融指数的增加而变窄，而且聚合物具有较低的细粉含量。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明中，在没有特别说明的情况下，给电子体通常是指本领域中的内给电子体， 其他给电子体通常是指本领域中的外给电子体。
本发明第一方面提供了一种用于烯烃聚合的催化剂组分，该催化剂组分包括镁元素、钛元素、卤素和给电子体；其中，给电子体包括呋喃类化合物和二醚类化合物；所述呋喃类化合物选自式(Ⅰ)所示呋喃类化合物中的至少一种，
式(Ⅰ)中，R1和R3各自独立地选自氢、C1-C20的直链烷基、C3-C20的支链烷基、C3-C20的环烷基、C6-C20的芳基、C7-C20的芳烷基或C7-C20的烷芳基；R2和R4各自独立地选自C1-C10的直链烷基、C3-C10的支链烷基、C3-C10的环烷基、C6-C10的芳基、C7-C10的芳烷基或C7-C10烷芳基。
根据本发明，式(Ⅰ)中，R1和R3各自独立地可以为氢、甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基；优选地，式(Ⅰ)中，R1和R3各自独立地选自氢、C1-C6的直链烷基、C3-C6的支链烷基。
根据本发明，式(Ⅰ)中，R2和R4各自独立地可以为甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基；优选地，式(Ⅰ)中，R2和R4各自独立地选自C1-C6的直链烷基、C3-C6的支链烷基；更优选选自C1-C3的直链烷基。
本发明的发明人意外地发现当将二醚类化合物与本申请的式(Ⅰ)所示的呋喃类化合物复配使用作为给电子体时能够发挥协同作用，用于烯烃聚合时所制备聚合物的分子量分布可随着熔融指数的增加而变窄，从而可以兼顾良好的加工性能和环保性。并且催化剂组分具有良好的氢调敏感性和立构定向性的平衡性。
根据本发明，优选地，所述催化剂组分中，相对于每摩尔的二醚类化合物，呋喃类化合物的含量为0.01-2摩尔；例如，所述催化剂组分中，相对于每摩尔的二醚类化合物，呋喃类化合物的含量可以为0.01摩尔、0.05摩尔、0.06摩尔、0.07摩尔、0.08摩尔、0.09摩尔、0.1摩尔、0.15摩尔、0.2摩尔、0.25摩尔、0.3摩尔、0.35摩尔、0.4摩尔、0.45摩尔、0.5摩尔、0.6摩尔、0.7摩尔、0.8摩尔、0.9摩尔、1摩尔、1.1摩尔、1.2摩尔、1.5摩尔、2摩尔，以及上述任意两点组成的范围。更优选地，所述催化剂组 分中，相对于每摩尔的二醚类化合物，呋喃类化合物的含量为0.03-1.2摩尔，进一步优选为0.05-0.4摩尔。当催化剂组分中二醚类化合物与呋喃类化合物的摩尔比在上述进一步优选的范围内时，这两种给电子体的协同作用更加明显，能够进一步提高氢调敏感性和立构定向性，且高氢条件下聚合物的分子量分布更窄。
根据本发明，优选地，以给电子体的总重量为基准，所述呋喃类化合物和二醚类化合物在给电子体中的总含量为70重量％-100重量％，更优选为80重量％-100重量％，进一步优选为90-100重量％。
根据本发明，优选地，所述呋喃类化合物选自式(Ⅰ-1)所示呋喃类化合物中的至少一种，
式(Ⅰ-1)中，R1、R2、R3、R4如式(Ⅰ)中所述，在此不再赘述。
根据本发明，优选地，所述呋喃类化合物选自(3R,3aR,6S,6aR)-3-甲氧基-6-丙氧基六氢呋喃并[3,2-b]呋喃、(3R,3aR,6S,6aR)-3-甲氧基-6-乙氧基六氢呋喃并[3,2-b]呋喃、(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃、(3R,3aR,6S,6aR)-3,6-二乙氧基六氢呋喃并[3,2-b]呋喃、(3R,3aR,6S,6aR)-3,6-二丙氧基六氢呋喃并[3,2-b]呋喃中的至少一种。更优选地，所述呋喃类化合物为(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃。
根据本发明，所述二醚类化合物可以为各种能够用于烯烃聚合的催化剂中给电子体的二醚类化合物，优选地，所述二醚类化合物选自式(Ⅱ)所示二醚类化合物中的至少一种，
式(Ⅱ)中，RⅠ、RⅡ、RⅢ、RⅣ、RⅤ和RⅥ相同或不同，各自独立地选自氢、卤原子、C1-C20的直链烷基、C3-C20的支链烷基、C3-C20的环烷基、C6-C20的芳基、C7-C20的芳烷基或C7-C20的烷芳基，RⅠ-RⅥ的基团间可任选地键接成环；RⅦ和RⅧ相同或不同，各自独立地选自C1-C20的直链烷基、C3-C20的支链烷基、C3-C20的环烷基、C6-C20的芳基、C7-C20的烷芳基或C7-C20的芳烷基。
根据本发明，优选地，式(Ⅱ)中，RⅠ、RⅡ、RⅢ、RⅣ、RⅤ和RⅥ各自独立地选自氢、C1-C20的直链烷基、C3-C20的支链烷基；或者，RⅢ、RⅣ键接形成芴环。更优选地，式(Ⅱ)中，RⅠ、RⅡ、RⅢ、RⅣ、RⅤ和RⅥ各自独立地选自氢、C1-C7的直链烷基、C3-C7的支链烷基。
根据本发明，优选地，式(Ⅱ)中，RⅢ、RⅣ键接形成芴环时，所述二醚类化合物具有式(Ⅱ-1)的结构，
其中，式(Ⅱ-1)中，RⅠ、RⅡ、RⅤ、RⅥ、RⅦ和RⅧ如式(Ⅱ)中所示。
根据本发明，优选地，式(Ⅱ)中，RⅦ和RⅧ各自独立地选自C1-C5的直链烷基、C3-C5的支链烷基。
根据本发明，优选地，所述二醚类化合物选自2-(2-乙基己基)-1,3-二甲氧基丙烷、2-异丙基-1,3-二甲氧基丙烷、2-丁基-1,3-二甲氧基丙烷、2-仲丁基-1,3-二甲氧基丙烷、2-环己基-1,3-二甲氧基丙烷、2-苯基-1,3-二甲氧基丙烷、2-(2-苯基乙基)-1,3-二甲氧基丙烷、2-(2-环己基乙基)-1,3-二甲氧基丙烷、2-(对-氯苯基)-1,3-二甲氧基丙烷、2-(二苯基甲基)-1,3-二甲氧基丙烷、2,2-二环己基-1,3-二甲氧基丙烷、2,2-二环戊基-1,3-二甲氧基丙烷、2,2-二乙基-1,3-二甲氧基丙烷、2,2-二丙基-1,3-二甲氧基丙烷、2,2-二异丙基-1,3-二甲氧基丙烷、2,2-二丁基-1,3-二甲氧基丙烷、2-甲基-2-丙基-1,3-二甲氧基丙烷、2-甲基-2-苄基-1,3-二甲氧基丙烷、2-甲基-2-乙基-1,3-二甲氧基丙烷、2-甲基-2-异丙基-1,3-二甲氧基丙烷、2-甲基-2-苯基-1,3-二甲氧基丙烷、2-甲基-2-环己基-1,3-二甲氧基丙烷、 2,2-双(2-环己基乙基)-1,3-二甲氧基丙烷、2-甲基-2-异丁基-1,3-二甲氧基丙烷、2-甲基-2-(2-乙基己基)-1,3-二甲氧基丙烷、2,2-二异丁基-1,3-二甲氧基丙烷、2,2-二苯基-1,3-二甲氧基丙烷、2,2-二苄基-1,3-二甲氧基丙烷、2,2-双(环己基甲基)-1,3-二甲氧基丙烷、2-异丁基-2-异丙基-1,3-二甲氧基丙烷、2-(1-甲基丁基)-2-异丙基-1,3-二甲氧基丙烷、2-异丙基-2-异戊基-1,3-二甲氧基丙烷、2-苯基-2-异丙基-1,3-二甲氧基丙烷、2-苯基-2-仲-丁基-1,3-二甲氧基丙烷、2-苄基-2-异丙基-1,3-二甲氧基丙烷、2-环戊基-2-异丙基-1,3-二甲氧基丙烷、2-环戊基-2-仲-丁基-1,3-二甲氧基丙烷、2-环己基-2-异丙基-1,3-二甲氧基丙烷、2-环己基-2-仲-丁基-1,3-二甲氧基丙烷、2-异丙基-2-仲-丁基-1,3-二甲氧基丙烷、2-环己基-2-环己基甲基-1,3-二甲氧基丙烷和9,9-双(甲氧基甲基)芴中的至少一种。更优选地，所述二醚类化合物为2-异丙基-2-异戊基-1,3-二甲氧基丙烷和/或9,9-双(甲氧基甲基)芴。
本发明催化剂组分中，以每重量份的钛元素计，镁元素的含量可以为2-18重量份，优选为3-16重量份。
本发明催化剂组分中，以每重量份的钛元素计，给电子体的含量可以为2-17重量份，优选为3-15重量份。
根据本发明，所述催化剂组分中还可以含有卤素，所述催化剂组分中的卤素可以为氟元素、氯元素、溴元素、碘元素中的至少一种。所述催化剂组分中的卤素的来源可以为镁元素的来源和/或钛元素的来源中含有的卤素。
根据本发明，所述镁元素的来源可以为任何能够制备聚烯烃催化剂组分的含镁化合物；优选地，所述镁元素的来源选自卤化镁(例如氯化镁和/或溴化镁)、镁的醇化物(例如二乙氧基镁)、镁的卤代醇化物(例如氯化乙氧基镁)、卤化镁醇加合物、卤化镁加合物(例如专利申请CN1091748、CN101050245、CN101486722、CN102796132B、CN102796129B及CN102796128B等公开的卤化镁加合物，并将这些专利申请公开的相关内容全部引入本发明中作为参考)和含镁固体组分中的至少一种。
本发明中，卤化镁醇加合物例如可以为式(Ⅳ)所示结构中的至少一种；
MgX2·m’R7OH      式(Ⅳ)
式(Ⅳ)中X为卤素，优选为氯或溴；m’为1-5；R7为C1-C6的直链或支链烷基，例如可以为甲基、乙基、丙基、丁基、戊基、己基。
本发明中，含镁固体组分例如可以为式(Ⅲ)所示结构中的至少一种；
式(Ⅲ)中，R1为C1-C6的直链或支链烷基；R2和R3相同或不相同，独立地为氢或C1-C5直链或支链烷基，其中烷基上的氢可任选地被卤原子取代；X为卤素，优选为氯或溴；m为0.1-1.9，n为0.1-1.9，m+n＝2，0<q≤0.5。
根据本发明，优选地，所述含镁固体组分的平均颗粒直径为12-30微米，粒径分布小于1.2，更优选为0.2-0.8。在本发明中，烯烃聚合催化剂载体(含镁固体组分)的平均颗粒直径和粒径分布可以采用Master Sizer 2000激光粒度仪(由Malvern Instruments Ltd生产制造)测得。
所述含镁固体组分合成原料含有硫源、通式为MgX2Y的卤化镁、通式为R4OH的化合物、环氧乙烷类化合物；在通式MgX2Y中，X2为卤素，Y为卤素或C1-C6的烷基、C1-C5的烷氧基、C6-C10的芳基或C6-C10的芳氧基；在通式R4OH中，R4为C1-C8的烷基或C3-C8的环烷基；所述环氧乙烷类化合物的结构如式(Ⅴ)所示：
式(Ⅴ)中，R5和R6各自独立地为氢、C1-C5的烷基或C1-C5的卤代烷基。
根据本发明，硫源为无水硫或含有结晶水的硫，为硫或溴化硫、氯化硫或碘化硫，优选为硫和/或氯化硫；更优选为α-硫和/或β-硫。
根据本发明，在通式MgX2Y中，X2优选为氯或溴，Y优选为氯、溴、C1-C5的烷基、C1-C5的烷氧基、C6-C10的芳基或C6-C10的芳氧基；所述C1-C5的烷基例如可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、叔戊基或新戊基，所述C1-C5的烷氧基例如可以为甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基或异丁氧基，所述C6-C10的芳基例如可以为苯基、邻甲苯基、间甲苯基、对甲苯基、邻乙苯基、间乙苯基、对乙苯基或萘基，所述C6-C10的芳氧基例如可以为苯氧基或萘氧基。
通式为MgX2Y的卤化镁可以为一种卤化镁，或者是多种卤化镁的混合物。通式为MgX2Y的卤化镁的具体实例可以为但不限于：氯化镁、溴化镁、氯化苯氧基镁、氯化异丙氧基镁和氯化正丁氧基镁中的一种或多种。从原料易得性的角度出发，优选为氯化镁。
根据本发明，在通式R4OH中，R4优选为C1-C8的烷基；所述C1-C8的烷基例如可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基、己基、异己基、庚基、异庚基、辛基或异辛基。通式为R4OH的化合物的具体实例可以为但不限于：乙醇、丙醇、异丙醇、正丁醇、异丁醇、戊醇、异戊醇、正己醇、正辛醇和2-乙基己醇中的一种或多种。
根据本发明，在结构如式(Ⅴ)所示的环氧乙烷类化合物中，R5和R6优选各自独立地为氢、C1-C3的烷基或C1-C3的卤代烷基。所述环氧乙烷类化合物的具体实例可以为但不限于：环氧乙烷、环氧丙烷、环氧丁烷、环氧氯丙烷、环氧氯丁烷、环氧溴丙烷和环氧溴丁烷中的一种或多种。
根据本发明，所述含镁固体组分中含有的水来自于合成原料和反应介质所带的微量水。
本发明所述含镁固体组分的制备方法，包括以下步骤：
(a)将硫源、通式为MgX2Y的卤化镁、通式为R4OH的化合物、可选的惰性液体介质，混合并加热，得到液态混合物；
(b)将步骤(a)得到的液态混合物乳化，并将乳化产物与环氧乙烷类化合物接触反应。
在通式MgX2Y中，X2为卤素，Y为卤素或C1-C6的烷基；在通式R4OH中，R4为C1-C8的烷基或C3-C8的环烷基；所述环氧乙烷类化合物的结构如式(Ⅴ)所示：
其中，通式为MgX2Y的卤化镁、通式为R4OH的化合物、硫源、环氧乙烷类化合物的种类已在上文中描述，在此将不再赘述。
根据本发明，其中，以1mol通式为MgX2Y的卤化镁为基准，硫源的用量为0.0001-0.1mol，通式为R4OH的化合物的用量为4-30mol，结构如式(Ⅴ)所示的环氧乙 烷类化合物的用量为1-10mol；优选地，以1mol通式为MgX2Y的卤化镁为基准，通式为R4OH的化合物的用量为6-20mol，结构如式(Ⅴ)所示的环氧乙烷类化合物的用量为2-6mol。
根据本发明，上述各反应物中的微量水也可以参与形成含镁固体组分的反应。
根据本发明，可以在步骤(a)所述的液态混合物中添加使用表面活性剂，所述表面活性剂选自聚乙烯吡咯烷酮(PVP)、聚乙二醇(PEG)、聚丙烯酸、聚丙烯酸盐、聚苯乙烯磺酸盐、萘磺酸甲醛缩合物、缩合烷基苯基醚硫酸酯、缩合烷基苯酚聚氧乙烯醚磷酸酯、氧基烷基丙烯酸酯共聚物改性聚乙撑亚胺、1-十二-4-乙烯吡啶溴化物的聚合物、聚乙烯基苄基三甲胺盐、聚乙烯醇、聚丙烯酰胺、聚环氧乙烷环氧丙烷嵌段共聚物、聚乙烯吡咯烷酮醋酸乙烯酯共聚物、烷基苯基聚氧乙烯醚和聚甲基丙烯酸烷基酯类化合物中的一种或组合使用，优选为聚乙烯吡咯烷酮、聚乙烯吡咯烷酮醋酸乙烯酯共聚物和聚乙二醇中的一种或组合使用。
根据本发明，步骤(a)中，对于将硫源、通式为MgX2Y的卤化镁、通式为R4OH的化合物、可选地与惰性液体介质的混合物加热的条件没有特别限定，只要所述加热的条件能够使得通式为MgX2Y的卤化镁熔融并与硫源充分反应即可。一般地，所述加热的条件包括：温度可以为80-120℃，时间可以为0.5-5小时；优选地，所述温度为80-100℃，时间为0.5-3小时。
根据本发明，所述惰性液体介质的用量可以根据通式为MgX2Y的卤化镁的用量来选择。一般地，以1mol通式为MgX2Y的卤化镁为基准，所述惰性液体介质的用量可以为0.8-10L，优选为2-8L。所述惰性液体介质可以为本领域常用的各种不与反应物和反应产物发生化学相互作用的液体介质。例如：所述惰性液体介质可以为硅油和/或惰性液体烃类溶剂。具体地，所述惰性液体介质可以为煤油、石蜡油、凡士林油、白油、甲基硅油、乙基硅油、甲基乙基硅油、苯基硅油和甲基苯基硅油中的一种或多种。本发明所述惰性液体介质特别优选为白油。
根据本发明，可以采用本领域技术人员公知的各种方法将步骤(a)得到的液态混合物乳化。例如，可以将所述液态混合物进行低速剪切或高速剪切，从而将其乳化。所述低速剪切的搅拌速率通常为400-800转/分钟。所述高速剪切的方法为本领域技术人员所公知，如CN1151183C公开的高速搅拌法(即，将含有液态卤化镁加合物的溶液以2000-5000转/分钟的速度进行搅拌)。此外，还可以参照以下专利公开的方法将所述液态混合物乳化：CN1267508C公开的将含有液态卤化镁加合物的溶液在超重力床中进行旋转分散(旋转的速度可以为100-3000转/分钟)；CN1463990A公开的将含有液态卤 化镁加合物的溶液在乳化机中以1500-8000转/分钟的速度输出；US6020279公开的通过喷雾法将含有液态卤化镁加合物的溶液乳化。
根据本发明，步骤(b)中，将乳化产物与环氧乙烷类化合物接触反应的条件可以为现有的各种能够形成烯烃聚合催化剂载体的条件，例如，所述接触反应的条件包括温度可以为50-120℃，时间可以为20-60分钟；优选地，所述温度为60-100℃，时间为20-50分钟。
根据本发明，步骤(b)中，该方法还可以包括将接触反应得到的产物中进行固液分离，将固相产物洗涤并进行干燥。所述固液分离可以是现有的各种能够实现固相与液相分离的方法，例如抽滤、压滤或离心分离，优选情况下，所述固液分离的方法为压滤法。本发明对压滤的条件没有特别地限定，以尽可能充分地实现固相与液相的分离为准。所述洗涤可以采用本领域技术人员公知的方法将得到的固相产物进行洗涤，例如可以采用惰性烃类溶剂(例如：戊烷、己烷、庚烷、石油醚和汽油)对得到的固相产物进行洗涤。本发明对于所述干燥的条件没有特别限定，例如：所述干燥的温度可以为20-70℃，所述干燥的时间可以为0.5-10小时。根据本发明，所述干燥可以在常压或减压条件下进行。
优选地，上述制备含镁固体组分的过程中得到的含镁固体组分颗粒经惰性烃类溶剂(如己烷、庚烷、辛烷、癸烷、甲苯等)洗涤、干燥后，用于后续步骤中以制备所述用于烯烃聚合的催化剂组分。
根据本发明，所述钛元素的来源可以为任何能够制备聚烯烃催化剂组分的含钛化合物；优选地，所述钛元素的来源选自通式为Ti(OR′)3-aZa和/或Ti(OR′)4-bZb的钛化合物，其中，R′为C1-C20的烷基，优选为C1-C14的脂肪烃基，优选为C1-C8的烷基，如甲基、乙基、丙基、丁基、戊基、己基、庚基等；Z为F、Cl、Br或I，a为1-3的整数，b为0-4的整数，优选为1-4的整数。更优选地，所述钛元素的来源选自四氯化钛、四溴化钛、四碘化钛、三丁氧基氯化钛、二丁氧基二氯化钛、丁氧基三氯化钛、三乙氧基氯化钛、二乙氧基二氯化钛、乙氧基三氯化钛和三氯化钛中的一种或多种。
根据本发明的一种具体实施方式，本发明还提供了一种用于烯烃聚合的催化剂组分，所述催化剂组分包含以下组分的反应产物：镁源、钛源和给电子体，所述给电子体包含呋喃类化合物和二醚类化合物。
根据本发明的一种具体实施方式，本发明还提供了一种用于烯烃聚合的催化剂组分，该催化剂组分含有以下组分的反应产物：
(1)含镁固体组分；
(2)至少一种含钛化合物(钛源)；以及
(3)给电子体；
其中，所述给电子体含有呋喃类化合物和二醚类化合物；含镁固体组分为式(Ⅲ)所示结构中的至少一种。
本发明第二方面提供了一种制备用于烯烃聚合的催化剂组分的方法，该方法包括：将镁源、钛源和给电子体混合，其中，所述给电子体包括呋喃类化合物和二醚类化合物；所述呋喃类化合物选自式(Ⅰ)所示呋喃类化合物中的至少一种，
式(Ⅰ)中，R1和R3各自独立地选自氢、C1-C20的直链烷基、C3-C20的支链烷基、C3-C20的环烷基、C6-C20的芳基、C7-C20的芳烷基或C7-C20的烷芳基；R2和R4各自独立地选自C1-C10的直链烷基、C3-C10的支链烷基、C3-C10的环烷基、C6-C10的芳基、C7-C10的芳烷基或C7-C10烷芳基。
本发明用于烯烃聚合的催化剂组分可以采用常规的方法制得，例如，所述混合的方式包括：将镁源与钛源进行接触反应，并在所述镁源与钛源进行接触反应之前、期间和之后的一个或多个时间段内加入给电子体，给电子体的各组分可分别加入，也可以同时加入，所述给电子体包含呋喃类化合物和二醚类化合物。具体地，所述镁源与钛源的反应可以按照与现有技术相同的方式进行，例如，可以将钛源冷却至0℃以下(优选为-5至-30℃)，然后加入镁源，并在该温度下搅拌混合10-60分钟，之后升温至反应温度(即约60-130℃)，并在该反应温度下维持0.5-10小时优选0.5-5小时。所述镁源与钛源的反应之前的时间段是指在所述镁源加入反应器中之后且在升温至反应温度之前的时间段。
根据本发明一种特别优选的实施方式，制备用于烯烃聚合的催化剂组分的方法包括：在反应容器中加入钛源(例如卤化钛)，冷却至-30℃至0℃，再向反应容器中加入镁源，并在该温度下搅拌混合10-60分钟；然后将升温至0-130℃(优选80℃-130℃)，并在升温过程中加入给电子体，然后在0-130℃(优选80℃-130℃)在保持10-900min (优选20-240min)后滤去液体。然后，加入钛源(例如卤化钛)洗涤，然后用非极性溶剂(例如已烷)洗，干燥后得到催化剂组分。
本发明中，制备用于烯烃聚合的催化剂组分的方法中采用的呋喃类化合物、二醚类化合物的种类如第一方面所述，在此不再赘述。
本发明中，制备用于烯烃聚合的催化剂组分的方法中采用的镁源和钛源的种类如第一方面的镁元素的来源和钛元素的来源所述，在此不再赘述。
根据本发明，制备用于烯烃聚合的催化剂组分的方法中，相对于每摩尔的二醚类化合物，呋喃类化合物的用量可以为0.1-3摩尔，例如，相对于每摩尔的二醚类化合物，呋喃类化合物的用量可以为0.1摩尔、0.2摩尔、0.3摩尔、0.4摩尔、0.5摩尔、0.6摩尔、0.7摩尔、0.8摩尔、0.9摩尔、1摩尔、1.1摩尔、1.2摩尔、1.3摩尔、1.4摩尔、1.5摩尔、1.6摩尔、1.7摩尔、1.8摩尔、1.9摩尔、2摩尔、2.1摩尔、2.5摩尔、3摩尔，以及上述任意两点组成的范围。优选地，相对于每摩尔的二醚类化合物，呋喃类化合物的用量为0.1-2摩尔，更优选为0.15-1.8摩尔。当催化剂组分中二醚类化合物与呋喃类化合物的摩尔用量比在上述优选的范围内时，这两种给电子体的协同作用更加明显，能够进一步提高氢调敏感性和立构定向性，进一步获得熔融指数更高且分子量分布更窄的聚合物。相对于每摩尔的二醚类化合物，呋喃类化合物的用量还可以为0.1-1.5摩尔，或者0.15-1.5摩尔，或者0.15-1.2摩尔，或者0.15-1摩尔，或者0.2-1摩尔。
本发明中，制备用于烯烃聚合的催化剂组分的方法中，以镁元素计的镁源与以钛元素计的钛源用量摩尔比可以为1:5、1:15、1:20、1:25、1:30、1:35、1:40、1:45、1:50、1:60、1:70、1:80、1:90、1:100、1:110、1:120、1:130、1:140、1:150、1:160、1:170、1:180、1:200、1:220，以及上述任意两点组成的范围。优选地，制备用于烯烃聚合的催化剂组分的方法中，以镁元素计的镁源与以钛元素计的钛源的用量摩尔比为1:5-220，更优选为1:15-180，进一步优选为1:18-150。
本发明中，制备用于烯烃聚合的催化剂组分的方法中，以镁元素计的镁源与给电子体的用量摩尔比可以为1:0.05、1:0.1、1:0.15、1:0.2、1:0.25、1:0.3、1:0.35、1:0.4、1:0.45、1:0.5、1:0.55、1:0.6、1:0.65、1:0.7、1:0.75、1:0.8、1:0.85、1:0.9、1:0.95、1:1、1:1.2，以及上述任意两点组成的范围。优选地，制备用于烯烃聚合的催化剂组分的方法中，以镁元素计的镁源与给电子体的用量摩尔比为1:0.05-1.2，更优选为1:0.1-1，进一步优选为1:0.15-0.9。
根据本发明，优选地，制备用于烯烃聚合的催化剂组分的方法中，以镁元素计的 镁源、以钛元素计的钛源和给电子体的用量摩尔比为1:15-180:0.1-1，更优选为1:18-150:0.15-0.9。
根据本发明的一种具体实施方式，本发明还提供了一种用于烯烃聚合的催化剂组分的制备方法，该方法包括：将含镁固体组分与钛化合物接触反应，加入含有呋喃类化合物和二醚类化合物的给电子体。在本发明催化剂组分的制备过程中，以每摩尔镁计，所述钛化合物的用量可以为5-220摩尔，优选为10-200摩尔；以每摩尔镁计，所述给电子体的用量可以为0.05-1.2摩尔，优选为0.07-1.0摩尔，进一步优选为0.1-0.8摩尔。
本发明第三方面提供了一种用于烯烃聚合的催化剂体系，该催化剂体系包括：
(1)第一方面所述的催化剂组分和/或第二方面所述的方法制备得到的催化剂组分；
(2)至少一种烷基铝；以及
(3)任选的其他给电子体。
根据本发明，所述烷基铝的用量可以为本领域的常规用量。优选地，以铝元素计所述烷基铝与以钛元素计所述催化剂组分的摩尔比为1-2000:1，更优选为20-500:1，进一步优选为30-300:1。
根据本发明，所述其他给电子体的用量可以为本领域的常规用量。优选地，所述其他给电子体和以铝元素计所述烷基铝化合物的摩尔比为1:1-300，更优选为1:2-100。
根据本发明，所述烷基铝可以为本领域常规使用的各种烷基铝，例如，所述烷基铝的通式可以为AlR″n1X′3-n1，其中R″为C1-C8的烷基，烷基上的氢任选地被卤原子取代，X′为卤素，n1为0<n1≤3的整数。所述C1-C8的烷基的具体实例可以包括但不限于：甲基、乙基、丙基、正丁基、异丁基、戊基、己基、正庚基、正辛基，所述卤素可以为氟、氯、溴、碘。
根据本发明，优选地，所述烷基铝选自三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、一氯二乙基铝、一氯二异丁基铝、一氯二正丁基铝、一氯二正己基铝、二氯一乙基铝、二氯一异丁基铝、二氯一正丁基铝和二氯一正己基铝中的一种或多种。
根据本发明，所述其他给电子体可以为本领域常用的各种外给电子体，例如，所述其他给电子体可以选自羧酸、羧酸酐、羧酸酯、酮、醚、醇、内酯、有机磷化合物和有机硅化合物中的至少一种。
优选情况下，所述其他给电子体选自含有至少一个Si-OR19键、且通式为(R17)x(R18)ySi(OR19)z的硅化合物，其中，R17、R18和R19各自独立地为C1-C18的烃基， 任选地含有杂原子；x和y各自独立为0-2的整数，z为1-3的整数，且x、y、z的和为4。R17、R18优选为C3-C10的烷基、C3-C10的环烷基，任选地含有杂原子；R19优选为C1-C10的烷基，任选地含有杂原子。更优选地，所述其他给电子体选自环己基甲基二甲氧基硅烷、二异丙基二甲氧基硅烷、二正丁基二甲氧基硅烷、二异丁基二甲氧基硅烷、二苯基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷、二环戊基二甲氧基硅烷、2-乙基哌啶基-2-叔丁基二甲氧基硅烷、(1,1,1-三氟-2-丙基)-2-乙基哌啶基二甲氧基硅烷和(1,1,1-,三氟-2-丙基)-甲基二甲氧基硅烷中的至少一种。
根据本发明，在用于烯烃聚合的催化剂体系的制备过程中，烷基铝和任选的其他给电子体可以分别与用于烯烃聚合的催化剂组分混合后反应，或者也可以将烷基铝化合物和任选的其他给电子体先混合后再与用于烯烃聚合的催化剂组分混合并反应。
本发明第四方面提供了第一方面所述的催化剂组分和/或第二方面所述的方法制备得到的催化剂组分和/或第三方面所述的催化剂体系在烯烃聚合中的用途。
本发明的催化剂体系在用于烯烃聚合反应时，催化剂组分、烷基铝、以及任选的其他给电子体可分别加入聚合反应器中，也可混合后加入聚合反应器中，也可采用本行业公知的预聚合方法将烯烃预聚后加入到聚合反应器中。根据本发明的一种优选方式，在催化剂组分、烷基铝、以及任选的其他给电子体预接触反应后，聚合反应前，优选将催化剂与丙烯和/或其它ɑ-烯烃单体进行预聚合反应。预聚合反应温度可以为5-40℃，优选10-30℃。
本发明中，烯烃的具体种类、烯烃的聚合反应方法和条件均可以根据现有技术进行常规选择。
本发明第五方面提供了一种烯烃聚合方法，该烯烃聚合方法包括：在第一方面所述的催化剂组分和/或第二方面所述的方法制备得到的催化剂组分和/或第三方面所述的催化剂体系存在下进行烯烃聚合反应。
根据本发明，优选地，所述烯烃选自式CH2＝CHR″′所示化合物中的至少一种，其中R″′为氢、C1-C6的烷基、C6-C12的芳基。
根据本发明，所述烯烃的聚合反应可以按照现有的方法进行，具体地，在惰性气体的保护下，在液相单体或含聚合单体的惰性溶剂中，或在气相中，或通过在气液相中的组合聚合工艺进行聚合反应。所述聚合反应的温度一般可以为0-150℃，优选为60-90℃。所述聚合反应的压力可以为常压或更高，例如可以为0.01-10MPa，优选为0.01-5MPa，更优选为0.1-4Mpa，本发明的压力均指表压。在聚合过程中，氢气可用作 聚合物分子量调节剂加入到反应体系中以调节聚合物的分子量和熔融指数。此外，在烯烃的聚合反应过程中，所述惰性气体、溶剂的种类和用量为本领域技术人员公知，在此将不再赘述。根据本发明，在进行聚合反应前，还可以将催化剂组分与烯烃进行预聚合反应；所述预聚合反应的温度为5-40℃，优选10-30℃。
本发明中未加以限定的参数均属于本领域的常规技术手段。
以下将通过实施例对本发明进行详细描述。
实施例与对比例中采用的原料，如果没有特别限定，那么均是现有技术公开的，例如可直接购买获得或者根据现有技术公开的制备方法制得。
本发明的催化剂组分中钛含量可以根据比色法测得。具体地，取样品0.2-0.5g用50mL 2N H2SO4溶解，将上层漂浮物过滤，取清液，待比色；用2N H2SO4溶液做空白，比色皿厚度为1cm，在410μm波长下，测其吸光度E1，然后滴入1滴30重量％H2O2，摇匀，测其吸光度E2，根据以下公式计算钛含量Ti(％)：
Ti％＝[(E2-E1)×100)/(K·L·W·100)]×100％
式中：W—样品重(g)；L—比色皿厚度(cm)；K—比消光系数(K＝15.52)；E1—空白吸光度；E2—样品吸光度。
本发明的催化剂组分中镁含量可以根据EDTA滴定法测得。具体地，取样品0.2-0.5g于250mL锥形瓶中，加入20-30mL 2N H2SO4溶液溶解，加20mL三乙醇胺(1+2)标准溶液，用20重量％NaOH溶液调pH＝10，摇动，加10mL pH＝10的缓冲溶液，再加6滴浓度为30％的H2O2及30-50mL蒸馏水，加入少量铬黑T指示剂，摇匀，用0.02NEDTA溶液滴定到由紫红色变为蓝色(紫光消失)为终点，根据以下公式计算镁含量Mg(％)：
Mg(％)＝[(VE·NE×24.31)/(G·1000)]×100％
式中：G—样品质量(g)；VE—消耗EDTA的量(mL)；NE—EDTA溶液当量数；24.31—镁的原子量。
本发明中将催化剂组分称重后，溶解于甲醇，然后经过膜过滤后测试催化剂组分中呋喃化合物的含量。本发明的催化剂组分中呋喃化合物的含量采用Agilent公司7890A-5975C气相色谱-质谱联用仪测试。色谱条件：HP-5 MS UI气相色谱柱(30m×0.25mm×0.25μm)，程序升温，35℃保持3min，10℃/min速率升至250℃，保持3min。载气He，流速1.0mL/min，分流进样，分流比50：1，进样口温度250℃，传 输线温度250℃。质谱条件：四级杆质谱仪，EI电离源，电子能量70eV，源温200℃，全扫描采集模式，质量范围m/z 20-400。
本发明中将催化剂组分称重后用稀盐酸酸解，再用环己烷萃取，然后测试催化剂组分中的二醚类化合物的含量。本发明的催化剂组分中二醚类化合物的含量采用安捷伦公司的7890气相色谱仪测试。色谱柱：HP-INNO WAX(60m×0.530mm×1μm)，内标法，内标物：戊酯。
本发明中聚合物的分子量分布(Mw/Mn)：采用英国PolymerLaboratories公司生产的PL-GPC220型凝胶渗透色谱仪测试，三氯苯为溶剂，测试温度150℃，聚苯乙烯为标样，流量1.0mL/min，3×Plgel 10mMlXED-B 300×7.5nm柱。
本发明中聚合物熔融指数：根据GB3682-2000，在230℃、2.16kg载荷下测定。
本发明中聚合物等规指数：采用庚烷抽提法测定。
本发明中催化剂组分及其载体的平均颗粒直径和粒径分布采用Masters Sizer 2000粒度仪(由Malvern Instruments Ltd生产制造)进行测定；
本发明中聚合物的细粉含量采用MICROTRAC MRB camsizer P4测试，表中数据为采用标准筛筛分后低于100目(mesh/inch)的聚合物含量，即可通过150μm筛网孔径的聚合物含量。
以下实施例A用于说明以卤化镁的醇加合物为载体，以呋喃类化合物和二醚类化合物为给电子体的催化剂组分的制备方法及制备聚合物的过程。
实施例1A
(1)制备催化剂组分
在300mL的玻璃反应瓶中，加入90mL的四氯化钛并冷却至-20℃，将以镁元素计的38mmol的二氯化镁的醇加合物(结构式为MgCl2·2.6C2H5OH)载体加入其中，并在该温度下搅拌40min，然后升温至112℃，并在升温过程中加入2.6mmol的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和8mmol的2-异丙基-2-异戊基-1,3-二甲氧基丙烷，在110℃下维持30min后滤去液体，用四氯化钛洗涤，然后用已烷洗涤，真空干燥后得到用于烯烃聚合的催化剂组分Cat-1A。催化剂组分中呋喃类化合物与二醚类化合物的摩尔比如表1所示。经测试催化剂组分Cat-1A中，以每重量份的钛元素计，镁元素的含量为5.65重量份，给电子体的含量为5.55重量份。
(2)丙烯液相本体聚合
丙烯液相本体聚合是在5L的不锈钢高压反应釜中进行。在氮气保护下向反应釜中依次加入2mL三乙基铝的己烷溶液(浓度为0.5mmol/mL)、0.4mL环己基甲基二甲氧基硅烷(CHMMS)的己烷溶液(浓度为0.1mmol/mL)和9mg上述用于烯烃聚合的催化剂组分Cat-1A。关闭高压釜，加入氢气(氢气的用量如表1所示)和2.3L的液体丙烯。升温至70℃，反应1小时后，降温，卸压，出料，将所得丙烯均聚物干燥后称重并分析，结果如表1所示。
实施例2A
按照实施例1A的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在升温过程中不加入2-异丙基-2-异戊基-1,3-二甲氧基丙烷，加入的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和9,9-双(甲氧基甲基)芴的量分别为5mmol和7.5mmol，得到用于烯烃聚合的催化剂组分Cat-2A。经测试催化剂组分Cat-2A中，以每重量份的钛元素计，镁元素的含量为5.22重量份，给电子体的含量为5.63重量份。
实施例3A
按照实施例1A的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在升温过程中加入的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和2-异丙基-2-异戊基-1,3-二甲氧基丙烷的量分别为7mmol和6mmol，得到用于烯烃聚合的催化剂组分Cat-3A。经测试催化剂组分Cat-3A中，以每重量份的钛元素计，镁元素的含量为5.20重量份，给电子体的含量为4.71重量份。
实施例4A
按照实施例1A的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在升温过程中加入的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和2-异丙基-2-异戊基-1,3-二甲氧基丙烷的量分别为2mmol和8mmol，得到用于烯烃聚合的催化剂组分Cat-4A。经测试催化剂组分Cat-4A中，以每重量份的钛元素计，镁元素的含量为5.74重量份，给电子体的含量为5.48重量份。
实施例5A
按照实施例1A的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在升温过程中加入的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和2-异丙基-2-异戊基-1,3-二甲氧基丙烷的量分别为8.7mmol和3.2mmol，得到用于烯烃聚合的催化剂组分Cat-5A。经测试催化剂组分Cat-5A中，以每重量份的钛元素计，镁元素的含量为4.67重量份，给电子体的含量为3.62重量份。
实施例6A
(1)制备催化剂组分
在300mL的玻璃反应瓶中，加入80mL的四氯化钛并冷却至-15℃，将以镁元素计的38mmol的二氯化镁的醇加合物(结构式为MgCl2·2.6C2H5OH)载体加入其中，并在该温度下搅拌30min，然后升温至115℃，并在升温过程中加入3mmol的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和8.2mmol的2-异丙基-2-异戊基-1,3-二甲氧基丙烷，在115℃下维持45min后滤去液体，用四氯化钛洗涤，然后用已烷洗涤，真空干燥后得到用于烯烃聚合的催化剂组分Cat-6A。经测试催化剂组分Cat-6A中，以每重量份的钛元素计，镁元素的含量为6.19重量份，给电子体的含量为6.63重量份。
(2)丙烯液相本体聚合与实施例1A相同。
对比例1A
按照实施例1A的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在催化剂组分的制备过程中，不加入(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃，只加入11mmol的2-异丙基-2-异戊基-1,3-二甲氧基丙烷，得到用于烯烃聚合的催化剂组分DCat-1A。
对比例2A
按照实施例1A的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在催化剂组分的制备过程中，不加入2-异丙基-2-异戊基-1,3-二甲氧基丙烷，只加入11mmol的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃，得到用于烯烃聚合的催化剂组分DCat-2A。
对比例3A
按照实施例1A的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在催化剂组分的制备过程中，将2-异丙基-2-异戊基-1,3-二甲氧基丙烷替换为等摩尔的4-乙基-3,5-庚二醇二苯甲酸酯，得到用于烯烃聚合的催化剂组分DCat-3A。
表1
注：n呋喃：二醚表示呋喃类化合物与二醚类化合物的摩尔比。
由表1可以看出，当所述给电子体含有一定比例的呋喃类化合物和二醚类化合物时，催化剂具有高的氢调敏感性和立构定向性，且其平衡性好，并且所制备的低熔融指数聚合物的分子量分布要宽于高熔融指数聚合物的分子量分布，且本发明的催化剂组分 中不含邻苯二甲酸酯类化合物(塑化剂)。
以下制备例和实施例B用于说明以含镁固体组分为载体，以呋喃类化合物和二醚类化合物为给电子体的催化剂组分的制备方法及制备聚合物的过程。
制备例1含镁固体组分(催化剂载体)
该制备例用于说明本发明提供的烯烃聚合催化剂载体及其制备方法。
在0.6L的反应釜中，加入0.08mol氯化镁、0.96mol乙醇、1gα-硫，0.5g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至90℃。恒温反应2小时后，加入环氧氯丙烷0.48mol，反应半个小时后压滤，将压滤产物用己烷洗涤5次，真空干燥，得到烯烃聚合用催化剂载体Z1。
所述烯烃聚合催化剂载体Z1的平均颗粒直径(D50)为15微米，粒径分布((D90-D10)/D50)为0.6。采用光学显微镜观察烯烃聚合催化剂载体Z1的颗粒形态比较规整，表面光滑，基本上都是球形的，颗粒尺寸分布比较集中，且基本上没有异形粒子存在。
根据气质联用、元素分析及核磁表征，Z1的结构式为：
制备例2含镁固体组分(催化剂载体)
该制备例用于说明本发明提供的烯烃聚合催化剂载体及其制备方法。
在0.6L的反应釜中，加入300mL白油、0.08mol氯化镁、0.48mol乙醇、0.3g β-硫，1g PVP(聚乙烯吡咯烷酮)作为表面活性剂，在搅拌下升温至100℃。恒温反应1小时后加入0.16mol环氧氯丙烷，继续100℃恒温反应20分钟后压滤，将压滤产物用己烷洗涤5次，最后将产物真空干燥，得到烯烃聚合催化剂载体Z2。
所述烯烃聚合催化剂载体Z2的平均颗粒直径(D50)为18微米，粒径分布((D90-D10)/D50)为0.7。采用光学显微镜观察烯烃聚合催化剂载体Z2的颗粒形态比较规整，表面光滑，基本上都是球形的，颗粒尺寸分布比较集中，且基本上没有异形 粒子存在。
根据气质联用、元素分析及核磁表征，Z2的结构式为：
实施例1B
(1)制备催化剂组分
在300mL的玻璃反应瓶中，加入80mL的四氯化钛，冷却至-20℃，加入8g上述固体组分Z1，并在该温度下搅拌40min，升温至115℃。在升温过程中加入2.3mmol的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和8.9mmol的2-异丙基-2-异戊基-1,3-二甲氧基丙烷，在110℃下维持1h后滤去液体，用四氯化钛洗涤，然后用己烷洗涤，真空干燥后得到固体催化剂组分Cat-1B。催化剂组分中呋喃类化合物与二醚类化合物的摩尔比如表2所示。经测试催化剂组分Cat-1B中，以每重量份的钛元素计，镁元素的含量为5.06重量份，给电子体的含量为5.87重量份。
(2)丙烯液相本体聚合
丙烯液相本体聚合是在5L的不锈钢高压反应釜中进行。在氮气保护下向反应釜中依次加入5mL三乙基铝的己烷溶液(浓度为0.5mmol/mL)、1mL环己基甲基二甲氧基硅烷(CHMMS)的己烷溶液(浓度为0.1mmol/mL)和7.5mg上述固体催化剂Cat-1B。关闭高压釜，加入氢气(氢气的用量如表2所示)和2.3L的液体丙烯。升温至70℃，反应1小时后，降温，卸压，出料，将所得丙烯均聚物干燥后称重并分析，结果如表3所示。
实施例2B
按照实施例1B的方法制备催化剂组分和进行丙烯液相本体聚合，不同的是加入的固体组分为Z2，在升温过程中加入3.2mmol的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和7.0mmol的9,9-双(甲氧基甲基)芴，得到固体催化剂组分Cat-2B。经测试催化剂组分Cat-2B中，以每重量份的钛元素计，镁元素的含量为4.85重量份，给电 子体的含量为5.53重量份。
实施例3B
按照实施例1B的方法制备催化剂组分和进行丙烯液相本体聚合，不同的是加入的固体组分为Z2，在升温过程中加入4.7mmol的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和6.5mmol的2-异丙基-2-异戊基-1,3-二甲氧基丙烷，得到固体催化剂组分Cat-3B。经测试催化剂组分Cat-3B中，以每重量份的钛元素计，镁元素的含量为4.63重量份，给电子体的含量为4.45重量份。
实施例4B
按照实施例1B的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在升温过程中加入的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和2-异丙基-2-异戊基-1,3-二甲氧基丙烷分别为5.8mmol和6.3mmol，得到用于烯烃聚合的催化剂组分Cat-4B。经测试催化剂组分Cat-4B中，以每重量份的钛元素计，镁元素的含量为4.78重量份，给电子体的含量为4.64重量份。
实施例5B
按照实施例1B的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在升温过程中加入的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃和2-异丙基-2-异戊基-1,3-二甲氧基丙烷分别为7.5mmol和4.2mmol，得到用于烯烃聚合的催化剂组分Cat-5B。经测试催化剂组分中，以每重量份的钛元素计，镁元素的含量为4.64重量份，给电子体的含量为4.22重量份。
对比例1B
按照实施例1B的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在催化剂组分的制备过程中，加入8g的卤化镁载体(按CN1267508C实施例1公开的方法制备)代替固体组分Z1加入其中，所述(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃用相同摩尔量的2-异丙基-2-异戊基-1,3-二甲氧基丙烷替代，得到用于烯烃聚合的催化剂组分DCat-1B。
对比例2B
按照实施例1B的方法制备催化剂组分和实施丙烯液相本体聚合，不同的是，在催化剂组分的制备过程中，加入8g的卤化镁载体(按CN1267508C实施例1公开的方法制备)代替固体组分Z1加入其中，所述2-异丙基-2-异戊基-1,3-二甲氧基丙烷用相同摩尔量的(3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃替代，得到用于烯烃聚合的催化剂组分DCat-2B。
表2
注：Span表示粒度分布的宽度，Span＝(D90-D10)/D50；n呋喃：二醚表示呋喃类化合物与二醚类化合物的摩尔比。
表3

从表2-3实施例与对比例的结果可以看出，本发明催化剂组分的粒径分布窄，且当采用本发明中的催化剂组分时，催化剂同时具有高的氢调敏感性和立构定向性以及高的聚合活性，制得的聚丙烯细粉含量低，并且所制备的低熔融指数聚合物的分子量分布要宽于高熔融指数聚合物的分子量分布，并且本发明的催化剂组分中不含邻苯二甲酸酯类化合物(塑化剂)。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (16)

  1. 一种用于烯烃聚合的催化剂组分，其特征在于，该催化剂组分包括镁元素、钛元素、卤素和给电子体；其中，给电子体包括呋喃类化合物和二醚类化合物；所述呋喃类化合物选自式(Ⅰ)所示呋喃类化合物中的至少一种，
    式(Ⅰ)中，R1和R3各自独立地选自氢、C1-C20的直链烷基、C3-C20的支链烷基、C3-C20的环烷基、C6-C20的芳基、C7-C20的芳烷基或C7-C20的烷芳基；R2和R4各自独立地选自C1-C10的直链烷基、C3-C10的支链烷基、C3-C10的环烷基、C6-C10的芳基、C7-C10的芳烷基或C7-C10烷芳基。
  2. 根据权利要求1所述的催化剂组分，其中，相对于每摩尔的二醚类化合物，呋喃类化合物的含量为0.01-2摩尔，优选为0.03-1.2摩尔；
    和/或，R2和R4各自独立地选自C1-C3的直链烷基。
  3. 根据权利要求1或2所述的催化剂组分，其中，所述呋喃类化合物选自式(Ⅰ-1)所示呋喃类化合物中的至少一种，
    其中，式(Ⅰ-1)中，R1、R2、R3、R4如权利要求1或2中所述；
    优选地，所述呋喃类化合物选自(3R,3aR,6S,6aR)-3-甲氧基-6-丙氧基六氢呋喃并[3,2-b]呋喃、(3R,3aR,6S,6aR)-3-甲氧基-6-乙氧基六氢呋喃并[3,2-b]呋喃、 (3R,3aR,6S,6aR)-3,6-二甲氧基六氢呋喃并[3,2-b]呋喃、(3R,3aR,6S,6aR)-3,6-二乙氧基六氢呋喃并[3,2-b]呋喃、(3R,3aR,6S,6aR)-3,6-二丙氧基六氢呋喃并[3,2-b]呋喃中的至少一种。
  4. 根据权利要求1-3中任意一项所述的催化剂组分，其中，所述二醚类化合物选自式(Ⅱ)所示二醚类化合物中的至少一种，
    式(Ⅱ)中，RⅠ、RⅡ、RⅢ、RⅣ、RⅤ和RⅥ相同或不同，各自独立地选自氢、卤原子、C1-C20的直链烷基、C3-C20的支链烷基、C3-C20的环烷基、C6-C20的芳基、C7-C20的芳烷基或C7-C20的烷芳基，RⅠ-RⅥ的基团间可任选地键接成环；RⅦ和RⅧ相同或不同，各自独立地选自C1-C20的直链烷基、C3-C20的支链烷基、C3-C20的环烷基、C6-C20的芳基、C7-C20的烷芳基或C7-C20的芳烷基。
  5. 根据权利要求4所述的催化剂组分，其中，RⅠ、RⅡ、RⅢ、RⅣ、RⅤ和RⅥ各自独立地选自氢、C1-C20的直链烷基、C3-C20的支链烷基；
    和/或，RⅢ、RⅣ键接形成芴环；
    和/或，RⅦ和RⅧ各自独立地选自C1-C5的直链烷基、C3-C5的支链烷基。
  6. 根据权利要求1-5中任意一项所述的催化剂组分，其中，所述二醚类化合物选自2-(2-乙基己基)-1,3-二甲氧基丙烷、2-异丙基-1,3-二甲氧基丙烷、2-丁基-1,3-二甲氧基丙烷、2-仲丁基-1,3-二甲氧基丙烷、2-环己基-1,3-二甲氧基丙烷、2-苯基-1,3-二甲氧基丙烷、2-(2-苯基乙基)-1,3-二甲氧基丙烷、2-(2-环己基乙基)-1,3-二甲氧基丙烷、2-(对-氯苯基)-1,3-二甲氧基丙烷、2-(二苯基甲基)-1,3-二甲氧基丙烷、2,2-二环己基-1,3-二甲氧基丙烷、2,2-二环戊基-1,3-二甲氧基丙烷、2,2-二乙基-1,3-二甲氧基丙烷、2,2-二丙基-1,3-二甲氧基丙烷、2,2-二异丙基-1,3-二甲氧基丙烷、2,2-二丁基-1,3-二甲氧基丙烷、2-甲基-2-丙基-1,3-二甲氧基丙烷、2-甲基-2-苄基-1,3-二甲氧基丙烷、2-甲基-2-乙基-1,3- 二甲氧基丙烷、2-甲基-2-异丙基-1,3-二甲氧基丙烷、2-甲基-2-苯基-1,3-二甲氧基丙烷、2-甲基-2-环己基-1,3-二甲氧基丙烷、2,2-双(2-环己基乙基)-1,3-二甲氧基丙烷、2-甲基-2-异丁基-1,3-二甲氧基丙烷、2-甲基-2-(2-乙基己基)-1,3-二甲氧基丙烷、2,2-二异丁基-1,3-二甲氧基丙烷、2,2-二苯基-1,3-二甲氧基丙烷、2,2-二苄基-1,3-二甲氧基丙烷、2,2-双(环己基甲基)-1,3-二甲氧基丙烷、2-异丁基-2-异丙基-1,3-二甲氧基丙烷、2-(1-甲基丁基)-2-异丙基-1,3-二甲氧基丙烷、2-异丙基-2-异戊基-1,3-二甲氧基丙烷、2-苯基-2-异丙基-1,3-二甲氧基丙烷、2-苯基-2-仲-丁基-1,3-二甲氧基丙烷、2-苄基-2-异丙基-1,3-二甲氧基丙烷、2-环戊基-2-异丙基-1,3-二甲氧基丙烷、2-环戊基-2-仲-丁基-1,3-二甲氧基丙烷、2-环己基-2-异丙基-1,3-二甲氧基丙烷、2-环己基-2-仲-丁基-1,3-二甲氧基丙烷、2-异丙基-2-仲-丁基-1,3-二甲氧基丙烷、2-环己基-2-环己基甲基-1,3-二甲氧基丙烷和9,9-双(甲氧基甲基)芴中的至少一种。
  7. 根据权利要求1-6中任意一项所述的催化剂组分，其中，以每重量份的钛元素计，镁元素的含量为2-18重量份，优选为3-16重量份；给电子体的含量为2-17重量份，优选为3-15重量份；
    和/或，所述镁元素的来源选自卤化镁、镁的醇化物、镁的卤代醇化物、卤化镁醇加合物、卤化镁加合物和含镁固体组分中的至少一种。
  8. 根据权利要求1-7中任意一项所述的催化剂组分，其中，所述钛元素的来源选自通式为Ti(OR′)3-aZa和/或Ti(OR′)4-bZb的钛化合物，其中，R′为C1-C20的烷基，Z为F、Cl、Br或I，a为1-3的整数，b为1-4的整数；
    优选地，所述钛元素的来源选自四氯化钛、四溴化钛、四碘化钛、三丁氧基氯化钛、二丁氧基二氯化钛、丁氧基三氯化钛、三乙氧基氯化钛、二乙氧基二氯化钛、乙氧基三氯化钛和三氯化钛中的一种或多种。
  9. 一种制备用于烯烃聚合的催化剂组分的方法，其特征在于，该方法包括：将镁源、钛源和给电子体混合，其中，所述给电子体包括呋喃类化合物和二醚类化合物；所述呋喃类化合物选自式(Ⅰ)所示呋喃类化合物中的至少一种，
    式(Ⅰ)中，R1和R3各自独立地选自氢、C1-C20的直链烷基、C3-C20的支链烷基、C3-C20的环烷基、C6-C20的芳基、C7-C20的芳烷基或C7-C20的烷芳基；R2和R4各自独立地选自C1-C10的直链烷基、C3-C10的支链烷基、C3-C10的环烷基、C6-C10的芳基、C7-C10的芳烷基或C7-C10烷芳基。
  10. 根据权利要求9所述的方法，其中，相对于每摩尔的二醚类化合物，呋喃类化合物的用量为0.1-3摩尔；更优选为0.1-2摩尔，进一步优选为0.15-1.8摩尔。
  11. 一种用于烯烃聚合的催化剂体系，其特征在于，该催化剂体系包括：
    (1)权利要求1-8中任意一项所述的催化剂组分和/或权利要求9或10所述的方法制备得到的催化剂组分；
    (2)至少一种烷基铝；以及
    (3)任选的其他给电子体。
  12. 根据权利要求11所述的催化剂体系，其中，以铝元素计所述烷基铝与以钛元素计所述催化剂组分的摩尔比为1-2000:1，优选为20-500:1，更优选为30-300:1；
    和/或，所述其他给电子体和以铝元素计所述烷基铝化合物的摩尔比为1:1-300，优选为1:2-100。
  13. 根据权利要求11或12所述的催化剂体系，其中，所述烷基铝的通式为AlR″n1X1 3-n1，其中R″为C1-C8的烷基，烷基上的氢任选地被卤原子取代，X1为卤素，n1为0<n1≤3的整数；
    优选地，所述烷基铝选自三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、一氯二乙基铝、一氯二异丁基铝、一氯二正丁基铝、一氯二正己基铝、二氯一乙基铝、二氯一异丁基铝、二氯一正丁基铝和二氯一正己基铝中的一种或多种。
  14. 根据权利要求11-13中任意一项所述的催化剂体系，其中，所述其他给电子体选自羧酸、羧酸酐、羧酸酯、酮、醚、醇、内酯、有机磷化合物和有机硅化合物中的至少一种；
    优选地，所述其他给电子体选自环己基甲基二甲氧基硅烷、二异丙基二甲氧基硅烷、二正丁基二甲氧基硅烷、二异丁基二甲氧基硅烷、二苯基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷、二环戊基二甲氧基硅烷、2-乙基哌啶基-2-叔丁基二甲氧基硅烷、(1,1,1-三氟-2-丙基)-2-乙基哌啶基二甲氧基硅烷和(1,1,1-,三氟-2-丙基)-甲基二甲氧基硅烷中的至少一种。
  15. 权利要求1-8中任意一项所述的催化剂组分和/或权利要求9或10所述的方法制备得到的催化剂组分和/或权利要求11-14中任意一项所述的催化剂体系在烯烃聚合中的用途。
  16. 一种烯烃聚合方法，其特征在于，该烯烃聚合方法包括：在权利要求1-8中任意一项所述的催化剂组分和/或权利要求9或10所述的方法制备得到的催化剂组分和/或权利要求11-14中任意一项所述的催化剂体系存在下进行烯烃聚合反应；
    优选地，所述烯烃选自式CH2＝CHR″′所示化合物中的至少一种，其中R″′为氢、C1-C6的烷基、C6-C12的芳基；
    优选地，所述聚合反应的条件包括：温度为0-150℃，优选为60-90℃；压力为0.01-10MPa，优选为0.01-5MPa。
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