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WO2007051410A1 - Catalyst component for ethylene polymerization, preparation thereof and catalyst containing the same - Google Patents

Catalyst component for ethylene polymerization, preparation thereof and catalyst containing the same Download PDF

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Publication number
WO2007051410A1
WO2007051410A1 PCT/CN2006/002923 CN2006002923W WO2007051410A1 WO 2007051410 A1 WO2007051410 A1 WO 2007051410A1 CN 2006002923 W CN2006002923 W CN 2006002923W WO 2007051410 A1 WO2007051410 A1 WO 2007051410A1
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WO
WIPO (PCT)
Prior art keywords
compound
catalyst component
catalyst
magnesium
alcohol
Prior art date
Application number
PCT/CN2006/002923
Other languages
English (en)
French (fr)
Inventor
Wei Chen
Zifang Guo
Junling Zhou
Hongtao Wang
Hongxu Yang
Ruixia Li
Ruiping Wang
Original Assignee
China Petroleum & Chemical Corporation
Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CNB2005101174285A external-priority patent/CN100513433C/zh
Priority claimed from CNB2005101174270A external-priority patent/CN100532406C/zh
Application filed by China Petroleum & Chemical Corporation, Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation filed Critical China Petroleum & Chemical Corporation
Priority to ES06805124.2T priority Critical patent/ES2575358T3/es
Priority to US12/084,258 priority patent/US20090318643A1/en
Priority to BRPI0619719-1A priority patent/BRPI0619719B1/pt
Priority to KR1020087011581A priority patent/KR101433174B1/ko
Priority to EP06805124.2A priority patent/EP1947123B1/en
Priority to SI200632060A priority patent/SI1947123T1/sl
Publication of WO2007051410A1 publication Critical patent/WO2007051410A1/zh
Priority to US14/611,626 priority patent/US20150239998A1/en

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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
    • 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
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/128—Mixtures of organometallic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • the present invention relates to a catalyst component for ethylene polymerization, a process for preparing the catalyst component, and a catalyst comprising the catalyst component.
  • the first one is to dissolve a magnesium compound such as magnesium chloride in a certain solvent to obtain a homogeneous solution, and then mix the solution with a titanium compound and optionally an electron donor to obtain magnesium, titanium and optionally by precipitation.
  • a solid object of an electron is obtained.
  • catalyst particles are obtained.
  • it is disclosed in Chinese Patent No. CN1099041A, CN1229092A and the like.
  • a disadvantage of this conventional method is that the particle size and particle size distribution of the catalyst particles are completely controlled by the precipitation process, which is a recrystallization process of the magnesium carrier component, and the stability control thereof is difficult.
  • a catalyst component using magnesium chloride as a carrier and titanium tetrachloride as an active component is disclosed, which is prepared as follows: First, MgCl 2 is dissolved in a solvent system to form a uniform transparent solution, and then The presence of the helper phthalic anhydride is reacted with TiCl 4 at a low temperature, and the solid catalyst component is precipitated by slowly increasing the temperature.
  • the obtained catalyst component is used for the polymerization of ethylene, although the particle morphology of the polymer is good, the hydrogen modulation sensitivity and catalytic activity of the catalyst are not satisfactory.
  • it is prepared and needs to be added in a large amount: chlorotitanium.
  • the second is to directly support the catalyst active component on an inert carrier such as silica gel or the like. Since the particle diameter of the silica gel is easily controlled and the particle morphology is good, the catalyst particles in which the particles are hooked can be obtained. However, since the loading amount of the active component on the carrier is limited, the catalyst obtained by this method has a low titanium content and a low polymerization activity.
  • an inert carrier such as silica gel or the like. Since the particle diameter of the silica gel is easily controlled and the particle morphology is good, the catalyst particles in which the particles are hooked can be obtained. However, since the loading amount of the active component on the carrier is limited, the catalyst obtained by this method has a low titanium content and a low polymerization activity.
  • a catalyst component comprising magnesium chloride and silica as a carrier and titanium tetrachloride as an active component is disclosed, which is prepared as follows:
  • the MgCI 2 is reacted with TiCl 4 in THF, and then mixed with the aluminum alkyl treated SiO 2 to remove the THF to obtain a catalyst component.
  • the titanium content in the catalyst component is low. Therefore, the polymerization activity is low. Therefore, although this catalyst system can be used in a gas phase fluidized bed polymerization process of ethylene, it is difficult to apply to a slurry polymerization process of ethylene because of its low catalytic activity.
  • It is an object of the present invention to provide a catalyst component for the polymerization of ethylene comprising a magnesium complex, at least one titanium compound, at least one alcohol compound, at least one silicon compound, and optionally one a reaction product of an organoaluminum compound; wherein the magnesium complex is a product obtained by dissolving 13 ⁇ 4 magnesium in a solvent system containing an organic epoxy compound and an organophosphorus compound;
  • the alcohol compound is a linear, branched alkyl or cycloalkyl alcohol having 1 to 10 carbon atoms, or an aromatic or aryl alcohol having 6 to 20 carbon atoms, and the alcohol is optionally Halogen atom substitution;
  • the organoaluminum compound has the formula AlR 4 n xV n , wherein R 4 is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X 1 is a halogen, and n is a number of 1 ⁇ n ⁇ 3.
  • Another object of the invention is to provide a process for the preparation of the catalyst component of the invention. It is still another object of the present invention to provide a catalyst for the polymerization of ethylene comprising the reaction product of the following components:
  • step (ii) recovering the polymer formed in step (i).
  • polymerization as used in the present invention includes homopolymerization and copolymerization.
  • polymer as used in the present invention, includes homopolymers, copolymers, and terpolymers.
  • catalyst component means a main catalyst component or a pre-catalyst which, together with a conventional cocatalyst such as an aluminum alkyl, constitutes a catalyst for the polymerization of acetamidine.
  • the present invention provides a catalyst component for ethylene polymerization comprising a magnesium complex, at least one titanium compound, at least one alcohol compound, at least one silicon compound, and optionally one A reaction product of organoaluminum.
  • the catalyst component of the invention has the advantages of high catalytic activity, good hydrogen modulation sensitivity and narrow particle size distribution of the polymer, and is very suitable for ethylene polymerization, especially slurry polymerization process and combined polymerization requiring high activity catalyst. In the process.
  • the magnesium composite is a product obtained by dissolving 1310 magnesium in a solvent system containing an organic epoxy compound and an organic phosphorus compound. Usually this product is a homogeneous, transparent solution.
  • the 3 ⁇ 4 magnesium is selected from two! a complex of water or an alcohol of magnesium, hydrated magnesium, or one or both of the 14 ⁇ 4 atoms of the magnesium dihalide is placed by a hydrocarbon group or a halooxy group. Changed derivatives. Specific compounds are, for example, magnesium dichloride, magnesium dibromide, magnesium phenoxide chloride, magnesium isopropoxide chloride, magnesium butoxide chloride, and the like, among which magnesium dichloride is preferred.
  • the magnesium halide compounds may be used singly or in combination.
  • the organic epoxy compound described in the solvent system is selected from aliphatic olefins, diolefins having a carbon number of 2 to 8 or! 3 ⁇ 4 generation of an aliphatic olefin or a diene oxide, a glycidyl ether and an internal ether.
  • aliphatic olefins diolefins having a carbon number of 2 to 8 or! 3 ⁇ 4 generation of an aliphatic olefin or a diene oxide, a glycidyl ether and an internal ether.
  • the organic epoxy compounds may be used singly or in combination with each other.
  • the organic monument compound described in the solvent system is a hydrocarbyl ester or a halogenated hydrocarbyl ester of orthophosphoric acid or phosphorous acid. Specifically, such as: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite or benzyl phosphite .
  • the organophosphorus compounds may be used singly or in combination with each other.
  • the amount of the organic epoxide is 0.2 to 10 mol, preferably 0.3 to 4 mol, per mol of the magnesium oxide; and the amount of the organophosphorus compound is 0.1 to 10 mol, preferably 0.2 to 4 mol.
  • an inert diluent may optionally be added to the solvent system.
  • the inert diluent includes an aromatic hydrocarbon compound or an alkane compound, and may be used as long as it contributes to the dissolution of the magnesium halide.
  • Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and derivatives thereof;
  • examples of the alkane compound include a linear chain of 3 to 20 carbons
  • An alkane, a branched alkane or a cycloalkane such as butane, pentane, hexane, cyclohexane, heptane or the like.
  • the above inert diluents may be used singly or in combination. If used, the amount of the inert diluent to be used is not particularly limited, but it is preferably from 0.2 to 10 L/mol of the magnesium oxide from the viewpoints of ease of handling and cost.
  • the alcohol compound includes a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aromatic or aryl alcohol having 6 to 20 carbon atoms, wherein the alcohol is optional. Substituted by a halogen atom.
  • alcohols include: fatty alcohols such as: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, glycerol, hexanol, 2-methylpentanol, 2 -ethylbutanol, positive Heptanol, 2-ethylhexanol, n-octanol, decyl alcohol, etc.; cycloalkanols, such as cyclohexanol, methylcyclohexanol; aromatic alcohols, such as benzyl alcohol, methyl benzyl alcohol, alpha-methyl benzene Methanol, ⁇ , ⁇ -dimethylbenzyl alcohol, isopropyl benzyl alcohol, phenylethyl alcohol, phenol, etc.; halogen-containing alcohols such as trichloromethanol, 2,2,2-trichloroethanol and trichlorohexanol.
  • a combination of said alcohols such as a combination of ethanol and 2-ethylhexanol
  • the various alcohols constituting the alcohol combination may be added simultaneously or separately.
  • the ratio of each alcohol in the alcohol composition is no particular limitation.
  • the molar ratio of ethanol to 2-ethylhexanol is preferably 1:4 to 4:1.
  • the organoaluminum compound has the general formula of AlR 4 n XV n , wherein R 4 is independently hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, particularly an alkyl group, an aralkyl group or an aryl group; X 1 is Halogen, especially chlorine and bromine; n is a number of 0 ⁇ n ⁇ 3.
  • organoaluminum compounds such as: trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, monohydrogen diethyl aluminum, dihydrogen diisobutyl aluminum, diethyl aluminum dichloride, monochloroethylene Alkyl aluminides such as isobutyl aluminum, sesquiethyl aluminum chloride, dichloroethyl aluminum, etc., of which aluminum alkyl is preferred! 3 ⁇ 4 compound, preferably diethylaluminum chloride is the best.
  • organoaluminum compounds may be used singly or in combination.
  • the organoaluminum compound is an optional component.
  • the organoaluminum compound is preferably used in an amount of from 0 to 5 moles relative to 1 mole of the magnesium halide.
  • Preferred are titanium tetrachloride, titanium tetrabromide, titanium tetrachloride, tetrabutoxy Titanium, tetraethoxytitanium, monochlorotriethoxytitanium, titanium trichloride, dichlorodiethoxytitanium, trichloromonoethoxytitanium.
  • the titanium compounds may be used singly or in combination with each other.
  • Examples of the silicon compound represented by the above formula include: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, ethyl Trimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, decyltrioxane Silane, mercaptotriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyl Trimethoxysilane, cyclohexyltrimethoxysilane, cyclo
  • tetraalkoxysilanes such as tetraethoxysilane and tetrabutoxysilane, and most preferred are tetraethoxysilane.
  • the silicon compounds may be used singly or in combination with each other.
  • a sufficient amount of a silicon compound should be contained in the finally obtained solid titanium catalyst component to improve the overall performance of the catalyst, and the silicon compound also functions as a co-precipitating agent for promoting precipitation of the catalyst component particles.
  • other silicon compounds capable of in situ formation of the alkoxy-containing organosilicon compound such as silicon tetrachloride, may also be employed in the preparation of the solid catalyst component.
  • the catalyst component for ethylene polymerization comprises the magnesium composite, at least one of the titanium compounds, at least one of the alcohol compounds, at least one of the silicon compounds, And optionally the reaction product of the organoaluminum compound, wherein the amount of each reactant is 0.1 to 10 moles, preferably 1 to 4 moles per mole of the halogen halide in the magnesium composite; 0.05 to the organosilicon compound ⁇ 1 mole; organoaluminum compound is 0 to 5 moles; titanium compound is 1 to 15 moles, preferably 2 to 10 moles.
  • the catalyst component of the present invention consists essentially of the above reaction product.
  • a catalyst component comprises: Ti: 4.0-7.5 wt%, Mg: 14-19 wt%, CI: 58-68 wt%, Si: 0.2-1.2 wt%, alkoxy group: 4.0-8.5 wt%, P : 0.1-1.0 wt%, and Al: 0 to 0.6 wt%.
  • the catalyst component of the present invention can be obtained in a supported form on an inorganic oxide support.
  • inorganic oxide supports include, but are not limited to, SiO 2 , A1 2 0 3 or mixtures thereof, and are commercially available.
  • the carrier is generally spherical in shape and has an average particle diameter of from 0.1 ⁇ m to 150 ⁇ m, preferably from ⁇ to 50 ⁇ , and most preferably from 5 ⁇ to 40 ⁇ . It is preferred to use a silica gel having a large specific surface area, preferably 80 m 2 /g to 300 m 2 /g, as a carrier.
  • a silica gel carrier is advantageous for increasing the loading of the magnesium compound in the catalyst component, thereby increasing the loading amount of the active component of the catalyst, preventing the occurrence of high magnesium content in the catalyst component!
  • the inert carrier is preferably subjected to a calcination dehydration treatment or an alkylation activation treatment prior to use. If used, the inorganic oxide support is used in an amount of from 40 to 400 grams, preferably from 80 to 250 grams, per mole of the magnesium halide in the magnesium composite.
  • the catalyst component of the present invention When the catalyst component of the present invention is obtained as a supported on an inorganic oxide support, it comprises: Ti: 1.5 - 4.5% by weight; Mg: 4 - 14% by weight; CI: 20 to 40% ( Wt); oxime: 1.5 ⁇ 4.5% (wt); P: 0.05 - 0.5% (wt); Al: 0 ⁇ 0.4% (wt); and inert carrier: 20 ⁇ 80% (wt). It will be understood that the catalyst component further comprises Si derived from the organosilicon compound.
  • the invention provides a method of preparing a catalyst component of the invention, the method comprising the steps of:
  • the dissolution temperature may be 40 to 110 ° C, preferably 50 ⁇
  • the time during which the step (1) is carried out is not particularly limited, but it is generally preferred to continue the maintenance for 20 minutes to 5 hours, preferably 30 minutes to 2 hours, after the solution becomes clear.
  • the magnesium compound is added to the reaction mixture before, during or after the formation of the homogenate solution in the solvent system containing the organic epoxy compound and the organophosphorus compound. If the alcohol compound is added before or during the formation of the homogenate solution, the resulting homogloc solution is the solution of the step (2) containing magnesium. If the alcohol compound is added after forming the homogeneous solution, the reaction mixture is preferably stirred at 0 ° C to 110 ° C, preferably at room temperature to 90 ° C for about 10 minutes to 5 hours, preferably 20 minutes to 2 hours. The solution containing 3 ⁇ 4 of magnesium is formed. For convenience, it is preferred to add an alcohol compound before or during the formation of the homogenate solution.
  • the organoaluminum compound is optionally added to the solution containing the magnesium salt obtained in the step (2) and the reaction is allowed to proceed for a certain period of time, preferably 10 minutes to 5 hours, more preferably 30 minutes. Up to 2 hours.
  • the reaction can be at zero. C ⁇ 80 ° C, preferably room temperature ⁇ 50 ° 0.
  • Step (3) is generally carried out at a lower temperature, preferably at a temperature in the range of -40 ° C to 20 ° C.
  • step (4) after the reaction mixture is slowly heated to a desired temperature, it may be maintained at this temperature for 30 minutes to 5 hours, preferably for 1 hour to 3 hours.
  • the recovery of step (5) includes, for example, filtration and washing with an inert diluent, and optionally including drying.
  • the recovery operation can be carried out in accordance with methods conventional in the art.
  • the above preparation methods are generally carried out entirely under an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere.
  • a combination of the alcohols such as a combination of ethanol and 2-ethylhexanol, is used.
  • the various alcohols constituting the alcohol combination may be added simultaneously or separately.
  • the reaction in the step (3) or (4) is carried out in the presence of the inorganic oxide carrier, thereby obtaining a catalyst component of the invention supported on an inorganic oxide support.
  • the present invention also provides a catalyst for ethylene polymerization
  • the catalyst comprises (1) a reaction product of the above-mentioned catalyst component of the present invention and (2) an organoaluminum cocatalyst of the formula AlR s n X 2 3 — n wherein R 5 may be hydrogen and the number of carbon atoms is a hydrocarbon group of 1 to 20, particularly an alkyl group, an aralkyl group, an aryl group; X 2 is a halogen, particularly chlorine and bromine; and 11 is a number of 0 ⁇ n ⁇ 3.
  • the catalyst of the present invention consists of the reaction product of the component (1) and the component (2).
  • organoaluminum cocatalyst examples include: trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, dihydrogendiethylaluminum, diisobutylaluminum hydride, monochlorodiethylidene Aluminium base, diisobutylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride or the like, among which a trialkyl aluminum compound is preferable, and triethyl aluminum or triisobutyl aluminum is preferable.
  • the organoaluminum cocatalysts may be used singly or in combination with each other.
  • the molar ratio of aluminum in the component (2) to titanium in the component (1) is 5 to 500, preferably 20 to 200.
  • the present invention provides an ethylene polymerization process, the method comprising:
  • the comonomer may be selected from the group consisting of a-olefins and diolefins having 3 to 20 carbon atoms.
  • a-olefins examples include propylene, butene-1, 4-methylpentanyl-1, hexene-1, octene-1, styrene, methylstyrene and the like.
  • diene examples include cyclopentadiene, vinyl norbornene, 5-ethylidene-2-norbornene and the like.
  • the polymerization process can be carried out in the liquid phase or in the gas phase.
  • the catalyst of the present invention is particularly suitable for slurry polymerization processes, or combined polymerization processes including slurry polymerization, such as slurry addition gas phase polymerization processes.
  • Examples of the medium used for liquid phase polymerization include: propane, isobutane, hexane, heptane, cyclohexane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc.
  • An inert solvent such as a hydrocarbon or an aromatic hydrocarbon.
  • hydrogen is used as a molecular weight regulator in the polymerization process of the present invention.
  • the catalyst of the present invention uses an organosilicon compound having no active hydrogen as a co-precipitating agent, particles of the catalyst component are easily precipitated at the time of preparation of the catalyst component, and it is not necessary to use a large amount of titanium tetrachloride to promote precipitation of the precipitate. It is also not necessary to use titanium tetrachloride to treat the precipitate multiple times, so the amount of titanium tetrachloride added is greatly reduced.
  • the addition of the organosilicon compound also contributes to an increase in the activity of the catalyst and an improvement in the particle morphology of the catalyst component, thereby further improving the particle morphology of the polymer.
  • the catalyst of the present invention When the catalyst of the present invention is used for the polymerization of ethylene, it exhibits a good hydrogen sensitivity. detailed description
  • catalyst component In a reactor sufficiently substituted with high-purity nitrogen, 4.0 g of magnesium dichloride, 50 ml of toluene, 4.0 ml of epichlorohydrin, 4.0 ml of tributyl phosphate, and 6.4 ml of ethanol were sequentially added. The temperature was raised to 70 ° C with stirring, and after the solid was completely dissolved to form a uniform solution, the mixture was maintained at 70 ° C for 1 hour. The temperature was lowered to 30 ° C, and 4.8 ml of a 2.2 M solution of diethylaluminum chlorobenzene was added dropwise, and the reaction was maintained at 30 ° C for 1 hour.
  • the system was cooled to -5 ° C, 40 ml of titanium tetrachloride was slowly added dropwise, and then 3 ml of tetraethoxysilane was added and reacted for 1 hour.
  • the temperature was slowly raised to 80 ° C and the reaction was carried out for 2 hours.
  • the stirring was stopped, the reaction mixture was allowed to stand, the suspension was quickly separated, the supernatant was removed, the residue was washed twice with toluene, washed four times with hexane, and dried under high-purity nitrogen to obtain a good fluidity and particle size distribution.
  • a narrow solid catalyst component The composition of the catalyst components is shown in Table 1.
  • the catalyst component was prepared in the same manner as in Example 1, except that the amount of ethanol was changed from 6.4 ml to 5.9 ml.
  • the preparation of the catalyst was the same as in Example 2 except that the amount of the monochloroaluminum solution was changed to 3.8 ml.
  • catalyst component In a reactor sufficiently substituted with high-purity nitrogen, 4.03 g of magnesium dichloride, 50 ml of toluene, 4.0 ml of epichlorohydrin, 4.0 ml of tributyl phosphate, and 6.4 ml of ethanol were sequentially added. The temperature was raised to 70 ° C with stirring, and after the solid was completely dissolved to form a uniform solution, the reaction was carried out at 70 ° C for 1 hour. The system was cooled to -5 ° C, and 40 ml of titanium tetrachloride was slowly added dropwise, followed by the addition of 3 ml of tetraethoxysilane for 1 hour.
  • the composition of the catalyst components is shown in Table 1.
  • the catalyst component was prepared in the same manner as in Example 4 except that the amount of tetraethoxysilane was changed to 2 ml.
  • the catalyst component was prepared in the same manner as in Example 4 except that the amount of tetraethoxysilane was changed to 5 ml.
  • the catalyst component was prepared in the same manner as in Example 4 except that the tetraethoxysilane was changed to silicon tetrachloride.
  • catalyst component In a reactor sufficiently substituted with high-purity nitrogen, 4.03 g of magnesium dichloride, 50 ml of toluene, 0.1 ml of epichlorohydrin, 6.0 ml of tributyl phosphate, and 3.4 ml of ethanol were sequentially added. The temperature was raised to 70 ° C with stirring, and after the solid was completely dissolved to form a uniform solution, the reaction was carried out for 1 hour under the conditions of 70 Torr. The system was cooled to -5 ° C, 60 ml of titanium tetrachloride was slowly added dropwise, and then 3 ml of tetraethoxysilane was added and reacted for 1 hour.
  • the composition of the catalyst components is shown in Table 1.
  • Example 10 The polymerization of women was the same as in Example 1. The polymerization results are shown in Table 2 .
  • Example 10
  • the catalyst component was prepared in the same manner as in Example 9, except that the amount of ethanol was changed to 3.9 ml.
  • the catalyst component was prepared in the same manner as in Example 9, except that the amount of ethanol was changed to 4.4 ml.
  • the catalyst component was prepared in the same manner as in Example 9, except that the amount of ethanol was changed to 5.0 ml.
  • the catalyst component was prepared in the same manner as in Example 4 except that tetraethoxysilane was changed to phthalic anhydride.
  • Example 4 (1) The procedure of Example 4 (1) was repeated except that tetraethoxysilane was not added. It was observed that the precipitation of the catalyst component was difficult, the precipitated particles were extremely fine, and it was difficult to settle, and the catalyst component could not be obtained. As can be seen from the polymerization data of Table 2, the catalyst of the present invention is more active under the same polymerization conditions. Moreover, since the organosilicon compound is introduced into the catalyst component of the present invention, the precipitation of the catalyst component is facilitated, and the particle size distribution of the obtained polymer is narrower than that of Comparative Example 1 (with phthalic anhydride as a precipitant). The resulting polymer has less coarse or too fine particles.
  • Example 1 6.1 16.0 60.0 0.2 6.7 0.49
  • Example 2 5.9 16.0 59.0 0.2 6.4 0.40
  • Example 3 6.2 15.0 59.0 0.3 6.5 0.51
  • Example 4 5.6 16.0 61.0 0.3 6.3 0.52
  • Example 5 5.8 17.0 59.0 0.2 6.1 0.48
  • Example 6 5.7 17.0 60.0 0.1 5.9 0.49
  • Example 7 6.0 16.0 60.0 0.4 6.4 0.51
  • Example 8 5.9 17.0 62.0 0.2 6.3 0.55
  • Example 9 5.6 16.0 60.0 0.4 6.3 0.49
  • Example 10 5.7 16.0 59.0 0.4 6.3 0.49
  • Example 11 6.0 16.0 60.0 0.3 6.4 0.50
  • Example 12 6.2 16.0 59.0 0.3 6.5 0.47
  • Example 13 5.7 16.0 60.0 0.3 6.3 0.49 Comparative Example 1 5.5 16.0 60.0 - - - It should be noted that in addition to the main components given in the above table, the catalyst component may also
  • catalyst component In a reactor sufficiently substituted with high-purity nitrogen, 4.0 g of magnesium dichloride, 80 ml of toluene, 4.0 ml of epichlorohydrin, 4.0 ml of tributyl phosphate, and 6.4 ml of ethanol were sequentially added. , warmed to 70 with stirring. C, after the solid is completely dissolved to form a uniform solution, 70. The reaction was carried out for 1 hour under C conditions. The temperature was lowered to 30 ° C, and 4.8 ml of a 2.2 M solution of diethylaluminum chloride in toluene was added dropwise, and the reaction was maintained at 30 ° C for 1 hour.
  • the system was cooled to -25 ° C, 40 ml of titanium tetrachloride was slowly added dropwise, and the reaction was stirred for 0.5 hour.
  • 5 g of the treated inert carrier (Davison Catalysts XP02485 silica gel, treatment conditions: calcination at 200 ° C for 2 hours, calcination at 600 ° C for 4 hours) was added, and the reaction was stirred for 0.5 hours.
  • 3 ml of tetraethoxysilane was added and reacted for 1 hour. The temperature was slowly raised to 85 ° C and the reaction was carried out for 2 hours.
  • a stainless steel reaction vessel having a volume of 2 L was sufficiently substituted with high-purity nitrogen gas, and 1 L of hexane, 1.0 M of a triethylaluminum hexane solution having a concentration of 1 M was added, and 10 mg of the solid catalyst component prepared above was added thereto, and the temperature was raised to 70 ° C.
  • Hydrogen was introduced to bring the pressure in the autoclave to 0.28 MPa (gauge pressure), and then ethylene was introduced to make the total pressure of the kettle reach 0.73 MPa (gauge pressure).
  • Polymerization was carried out at 80 ° C for 2 hours while replenishing ethylene to maintain a total pressure of 0.73 MPa (gauge pressure). The polymerization results are shown in Table 3.
  • the preparation of the catalyst component was the same as in Example 14, except that the amount of ethanol was changed from 6.4 ml to 3.2 ml.
  • the catalyst component was prepared in the same manner as in Example 15, except that diethylaluminum chloride was not added.
  • the catalyst component was prepared in the same manner as in Example 16, except that diethylaluminum chloride was not added.
  • catalyst component In a reactor sufficiently substituted with high-purity nitrogen, 4.03 g of a dichlorinated chain, 50 ml of toluene, 4.0 ml of epichlorohydrin, 4.0 ml of tributyl phosphate, and ethanol were sequentially added. 6.4 ml, the temperature was raised to 70 ° C under stirring, and after the solid was completely dissolved to form a uniform solution, the reaction was carried out at 70 ° C for 1 hour.
  • an inert carrier 5 g (XP0 2485 silica gel, calcined at 200 ° C for 2 h, calcined at 600 ° C for 4 h) was added, and the reaction was stirred for 0.5 hour.
  • 40 ml of titanium tetrachloride was slowly added dropwise, followed by the addition of 3 ml of tetraethoxysilane, and the reaction was carried out for 1 hour. Slowly warm to 85. C, the reaction was carried out for 2 hours.
  • the catalyst component was prepared in the same manner as in Example 17, except that the amount of tetraethoxysilane was changed to 4 ml.
  • the catalyst component was prepared in the same manner as in Example 17, except that the amount of tetraethoxysilane was changed to 5 ml.
  • Example 14 3.6 8.1 30.1 21.5 0.35 0.9 2.0 95.0 3.0 1
  • Example 15 3.5 8.0 30.0 23.1 0.36 1.0 1.2 96.3 2.5 1
  • Example 16 3.1 8.2 29.8 25.4 0.35 0.8 0.5 96.2 3.3 1
  • Implementation Example 17 3.3 8.1 30.0 24.1 0.35 0.8 0.8 97.1 2.1 1
  • Example 18 3.2 7.9 30.0 26.4 0.36 0.7 1.0 97.2 2.8 1
  • Example 19 3.3 8.0 30.0 25.5 0.35 0.9 0.5 96.7 2.8 1
  • Example 20 3.4 8.2 30.1 24.8 0.36 1.0 0.7 96.9 2.4 1
  • Example 21 3.4 8.1 30.4 24.9 0.36 0.9 0.3 97.0 2.7 1
  • Example 22 3.1 8.0 30.0 23.1 0.35 1.2 0.7 96.8 2.5 1
  • Example 23 8.3 30.0 22.0 0.37 1.2 0.1 97.5 2.4
  • catalyst component In a reactor sufficiently substituted with high-purity nitrogen, 4.0 g of magnesium dichloride, 50 ml of toluene, 4.0 ml of epichlorohydrin, 4.0 ml of tributyl phosphate, and 3.4 ml of ethanol were sequentially added. . The temperature was raised to 65 ° C with stirring, and after the solid was completely dissolved to form a uniform solution, 5.5 ml of 2-ethylhexanol was added dropwise, and the reaction mixture was at 65. Maintain 1 hour under C.
  • the system was cooled to -5 ° C, 60 ml of titanium tetrachloride was slowly added dropwise, and then 3 ml of tetraethoxysilane was added and reacted for 0.5 hour. Slowly raise the temperature to 85 ° C and react for 2 hours. Stirring was stopped, the reaction mixture was allowed to stand, and the suspension was quickly separated. The supernatant liquid was removed, and the residue was washed twice with toluene, washed four times with hexane, and dried with high-purity nitrogen gas to obtain a solid catalyst component having a good fluidity and a narrow particle size distribution.
  • a stainless steel reaction vessel having a volume of 2 L was sufficiently substituted with high-purity nitrogen gas, and 1 L of hexane, 1.0 ml of a 1 M triethylaluminum hexane solution, and a hexane suspension of the solid catalyst component prepared above (containing 0.3) were added. ⁇ ).
  • the temperature was raised to 70 ° C, hydrogen was introduced to bring the pressure in the autoclave to 0.28 MPa (gauge pressure), and ethylene was introduced to bring the total pressure in the autoclave to 0.73 MPa (gauge pressure).
  • the polymerization was carried out at 80 ° C for 2 hours while introducing ethylene to maintain a total pressure of 0.73 MPa (gauge pressure).
  • the polymerization results are shown in Table 4.
  • the catalyst component was prepared in the same manner as in Example 24 except that the amount of 2-ethylhexanol was changed from 5.5 ml to 7.7 ml.
  • the preparation of the catalyst component was the same as in Example 24 except that the amount of 2-ethylhexanol was changed to 3.3 mL.
  • Example 27 The catalyst component prepared in Example 24 was used.
  • a stainless steel reaction vessel having a volume of 2 L was sufficiently substituted with high-purity nitrogen gas, and 1 L of hexane, 1.0 ml of a triethylaluminum hexane solution having a concentration of 1 M, and a hexane suspension of the above solid catalyst component (containing 0.5 mg of titanium) were added. ).
  • the temperature was raised to 70 ° C, hydrogen was introduced to bring the pressure in the autoclave to 0.38 MPa (gauge pressure), and ethylene was introduced to bring the total pressure in the autoclave to 0.7:3 MPa (gauge pressure).
  • the polymerization was carried out at 80 ° C for 2 hours while introducing ethylene to maintain a total pressure of 0.73 MPa (gauge pressure). The polymerization results are shown in Table 4.
  • a stainless steel reaction vessel having a volume of 2 L was sufficiently substituted with high-purity nitrogen gas, and 1 L of hexane, 1.0 ml of a 1 M triethylaluminum hexane solution, and a hexane suspension of the above solid catalyst component (containing 0.8 g) were added. Titanium).
  • the temperature was raised to 70 ° C, hydrogen was introduced to bring the pressure in the autoclave to 0.48 MPa (gauge pressure), and ethylene was introduced to bring the total pressure in the autoclave to 0.7:3 MPa (gauge pressure).
  • the polymerization was carried out at 80 ° C for 2 hours while introducing ethylene to maintain a total pressure of 0.73 MPa (gauge pressure).
  • the polymerization results are shown in Table 4.
  • Example 30 The catalyst component prepared in Example 24 was used.
  • a stainless steel reaction vessel having a volume of 2 L was sufficiently substituted with high-purity nitrogen gas, and 1 L of hexane, 1.0 ml of a triethylaluminum hexanoate solution having a concentration of 1 M, and a hexane suspension of the above solid catalyst component (containing 1.8 mg of titanium) were added. ).
  • the temperature was raised to 70 ° C, hydrogen gas was introduced to bring the pressure in the autoclave to 0.68 MPa (gauge pressure), and ethylene was introduced to bring the total pressure in the autoclave to 0.73 MPa (gauge pressure).
  • the polymerization was carried out at 80 ° C for 2 hours while ethylene was fed to maintain a total pressure of 0.73 MPa (gauge pressure).
  • the catalyst component of the present invention has high activity, good hydrogen sensitivity, and a narrow particle size distribution and high polymer bulk density.

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Description

用干乙烯聚合的催化剂组分、 其制备
及包含该组分的催化剂 相关申请的交叉参考
本申请要求 2005年 10月 31 日提交的 CN200510117427.0和 2005年 10月 31 日提交的 CN200510117428.5的优先权， 通过引 用并且为了所有的目的将所述文件整体结合在本申请中。 技术领域
本发明涉及一种用于乙烯聚合的催化剂组分， 该催化剂组分 的制备方法和包含该催化剂组分的催化剂。 技术背景
众所周知， 含 Ti/Mg复合物的催化剂体系在聚乙烯的工业化 生产中占主导地位， 其研究重点主要在于催化剂的聚合活性、 催 化剂的颗粒形态和粒径分布、 催化剂的氢调敏感性和共聚性能等 等。 在乙烯的淤浆聚合工艺中， 除要求催化剂应具有较高的催化 活性外， 控制所生产的乙烯聚合物的粒径大小和粒径分布是十分 重要的。 在乙烯聚合， 特別是乙烯的淤浆法聚合过程中， 很容易 产生较细的聚合物粒子， 这种细粉易产生静电、造成"扬尘"现象， 有时易结块， 造成设备管道的堵塞。 而控制聚合物的粒径大小和 粒径分布最有效的方法是控制催化剂的粒径和粒径分布。
在现有技术中， 为了得到具有均勾颗粒直径和较好颗粒形态 的催化剂， 人们通常采用以下的两类方法来制备催化剂。
第一种是将氯化镁等镁化合物溶解在某些溶剂中得到均匀溶 液， 然后再将该溶液与钛化合物和任选地给电子体混合， 通过沉 淀的方法得到含镁、 钛和任选的给电子体的固体物。 将该固体物 进一步用液态钛化合物进行处理后得到催化剂颗粒。 例如中国专 利 CN1099041A、 CN1229092A等中所公开的。 这种传统方法的 缺点是催化剂颗粒的粒径和粒径分布完全是通过沉淀过程来控制 的， 这是镁载体成分的重结晶过程， 其稳定性的控制比较困难。
例如， 在专利 CN1229092中， 公开了以氯化镁为载体， 四氯 化钛为活性组分的催化剂组分， 其制备方法如下： 先将 MgCl2溶 解在溶剂体系中， 形成均勾透明溶液， 然后在助析出剂苯酐存在 和低温下与 TiCl4反应， 通过緩慢升温析出固体催化剂组分。 制 得的催化剂组分用于乙烯聚合时， 虽然聚合物的颗粒形态较好， 但催化剂的氢调敏感性和催化活性还不令人满意。 同时， 在制备 出， 并需要加入大量的:氯 钛。 因此不仅酸酐的存在对催化剂 产生不利的影响， 同时大量的四氯化钛的使用， 也会提高生产成 本和增大环境污染问题。 同时该种体系还容易发粘， 催化剂难以 制备。
第二种是将催化剂活性组分直接负载于惰性载体， 如硅胶等 之上。 由于硅胶的颗粒直径容易控制， 而且颗粒形态较好， 因此 可得到颗粒均勾的催化剂粒子。 但由于载体上活性组分的负载量 受到限制， 因此这种方法制得的催化剂中钛含量较低， 聚合活性 不高。 例如： 在专利 CN1268520中公开了以氯化镁、 二氧化硅为 载体， 四氯化钛为活性组分的催化剂组分， 其制备方法如下： 将
MgCI2在 THF中与 TiCl4反应，再与经烷基铝处理过的 Si02混合， 除去 THF后制得催化剂组分， 在用于乙烯聚合时， 由于催化剂组 分中的钛含量较低， 因此聚合活性较低。 因此， 这种催化剂体系 虽然可用于乙烯的气相流化床聚合工艺， 但由于较低的催化活性 很难适用于乙烯的淤浆聚合工艺中。
众所周知， 在乙烯的淤浆聚合工艺中， 除要求催化剂应具有 较高的催化活性和较好的颗粒分布外， 为了生产具有较好性能的 乙烯均聚物或共聚物， 还要求催化剂应具有较好的氢调敏感性， 即很容易地通过聚合过程中氢分压来调节最终聚合物的熔融指 数， 以得到不同商业牌号的聚乙烯树脂。 而上述的催化剂体系的 氢调敏感性还不令人满意。
因此， 非常需要提供一种适用于乙烯聚合， 特别是淤浆聚合 的催化剂， 其不仅应该催化活性高、 粒径均勾、 粒径分布窄， 并 且应具有较好的氢调敏感性。 发明概述
本发明的一个目的是提供一种用于乙烯聚合的催化剂組分， 其包含一种镁复合物， 至少一种钛化合物， 至少一种醇化合物、 至少一种硅化合物、 和任选地一种有机铝化合物的反应产物； 其中所述的镁复合物是将 1¾化镁溶解在含有机环氧化合物和 有机磷化合物的溶剂体系中所得到的产物；
所述的醇化合物是碳原子数为 1 - 10 的直链、 支链的烷基或 环烷基的醇、 或碳原子数为 6 - 20的芳醇或芳烷醇， 所述醇任选 被卤原子取代；
所述的钛化合物通式为 Ti(OR)aXb， 式中 R为 d Cw的脂族 烃基或芳族烃基， X为卤素， a是 0、 1或 2, b是 1至 4的整数， a+b=3或 4；
所述的硅化合物为如通式为 R^R^S OR3^所示的有机硅化 合物， 其中 R1 和 R2独立地为烃基或卤素， R3为烃基， 0≤x≤2, 0≤y≤2和 0≤z≤4， JL x + y + z=4;
所述的有机铝化合物的通式为 AlR4 nxVn, 式中 R4为氢或碳 原子数为 1 ~ 20的烃基， X1为卤素， n为 1 < n≤3的数。
本发明的另一个目的是提供制备本发明催化剂组分的方法。 本发明的又一个目的是提供一种用于乙烯聚合的催化剂， 其 包含以下组分的反应产物：
( 1 )上述的催化剂组分； 和
( 2 )通式为 AlR5 nX2 3-n的有机铝助催化剂， 式中 R5为氢或碳 原子数为 1 ~ 20的烃基， X2为卤素， 0<n≤3。
本发明的又一个目的是提供一种乙烯聚合方法， 该方法包括：
( i )使乙烯以及任选的共聚单体在聚合条件下与本发明的催 化剂接触， 以形成聚合物； 和
( ii ) 回收步骤 (i)中形成的聚合物。 优选实施方案的详细描述
本发明中使用的术语 "聚合 "包括均聚和共聚。 本发明中使用 的术语 "聚合物，，包括均聚物、 共聚物和三元共聚物。
本发明中使用的术语 "催化剂组分 "是指主催化剂组分或前催 化剂， 其与常规的助催化剂如烷基铝一起构成用于乙浠聚合的催 化剂。
在一个方面， 本发明提供了一种用于乙烯聚合的催化剂组分, 其包含一种镁复合物， 至少一种钛化合物， 至少一种醇化合物、 至少一种硅化合物、 和任选地一种有机铝的反应产物。 本发明的 催化剂组分具有较高的催化活性、 较好的氢调敏感性和聚合物粒 径分布窄等优点， 非常适用于乙烯聚合， 特别是淤浆聚合工艺和 需要高活性催化剂的组合聚合工艺中。
所述的镁复合物是将 1¾化镁溶解在含有机环氧化合物和有机 磷化合物的溶剂体系中所得到的产物。 通常这种产物是一均匀透 明的溶液。
所述的 ¾化镁选自二！ ¾化镁、 二 1¾化镁的水或醇的络合物、 二卤化镁分子式中其中一个或两个 1¾原子被烃基或卤烃氧基所置 换的衍生物。 具体的化合物如： 二氯化镁、 二溴化镁、 氯化苯氧 基镁、氯化异丙氧基镁、氯化丁氧基镁等，其中优选二氯化镁。 所 述鹵化镁化合物可以单独或混合使用。
溶剂体系中所述的有机环氧化合物选自碳原子数在 2 ~ 8的脂 肪族烯烃、 二烯烃或！ ¾代脂肪族烯烃或二烯烃的氧化物、 缩水甘 油醚和内醚。 例如但不局限于： 环氧乙烷、 环氧丙烷、 环氧丁烷、 丁二烯氧化物， 丁二烯双氧化物、 环氧氯丙烷、 甲基缩水甘油醚、 二缩水甘油醚。 所述有机环氧化合物可以单独或互相组合使用。
溶剂体系中所述的有机碑化合物为正磷酸或亚磷酸的烃基酯 或卤代烃基酯。 具体如： 正磷酸三甲酯、 正磷酸三乙酯、 正磷酸 三丁酯、 正磷酸三苯酯、 亚磷酸三甲酯、 亚磷酸三乙酯、 亚磷酸 三丁酯或亚磷酸苯甲酯。 所述有机磷化合物可以单独或互相组合 使用。
在形成所述镁复合物时， 以每摩尔 化镁计， 有机环氧化合 物用量为 0.2 ~ lOmol,优选 0.3 ~ 4 mol;有机磷化合物用量为 0.1 ~ lOmol, 优选 0.2 - 4mol。
为了使溶解更加充分， 在该溶剂体系中可任选地加入惰性稀 释剂， 通常这种惰性稀释剂包括芳烃类化合物或烷烃类化合物， 只要有助于卤化镁溶解的都可以使用。 芳烃类化合物的实例包括 苯、 甲苯、 二甲苯、 一氯代苯、 二氯代苯、 三氯代苯、 一氯甲苯 及其衍生物； 烷烃类化合物的实例包括 3 ~ 20个碳的直链烷烃、 支链烷烃或环烷烃， 如丁烷， 戊烷， 己烷， 环己烷， 庚烷等。 上 述的惰性稀释剂可单独使用， 也可组合使用。 如果使用， 对所述 惰性稀释剂的用量没有特别的限制， 但是从操作容易性和成本的 角度考虑， 其用量优选为 0.2-10L/mol所述 化镁。
所述的醇化合物包括碳原子数为 1 - 10 的直链、 支链或环烷 基的醇、 或碳原子数为 6 - 20的芳醇或芳烷醇， 其中所述醇任选 被鹵原子取代。 醇的例子包括： 脂肪醇， 如： 甲醇、 乙醇、 丙醇、 异丙醇、 丁醇、 异丁醇、 丙三醇、 己醇、 2-甲基戊醇、 2-乙基丁 醇、 正庚醇、 2-乙基己醇、 正辛醇、 癸醇等； 环烷醇， 如环己醇、 甲基环己醇； 芳香醇， 如苯甲醇、 甲基苯甲醇、 α-甲基苯甲醇、 α， α-二甲基苯甲醇、 异丙基苯甲醇、 苯乙醇、 苯酚等； 含卤素的醇， 如三氯甲醇、 2，2,2-三氯乙醇和三氯己醇等。其中优选乙醇、丁醇、 2-乙基己醇、 丙三醇。 所述醇化合物可以羊独或互相组合使用。
按照一个优选的实施方案， 使用所述醇的组合， 例如乙醇与 2-乙基己醇的组合。 构成所述醇组合的所述各种醇可以同时加入 或分开加入。 对醇组合物中各醇的比例没有特别的限制。 但是， 在乙醇与 2-乙基己醇组合的情况下， 乙醇与 2-乙基己醇的摩尔比 优选为 1:4至 4:1。
所迷的有机铝化合物的通式为 AlR4 nXVn， 式中 R4独立地为 氢或碳原子数为 1 ~ 20的烃基， 特别是烷基、 芳烷基或芳基； X1 为卤素， 特别是氯和溴； n为 0<n≤3的数。 具体化合物如： 三甲 基铝、 三乙基铝、 三异丁基铝、 三辛基铝、 一氢二乙基铝、 一氢 二异丁基铝、 一氯二乙基铝、 一氯二异丁基铝、 倍半乙基氯化铝、 二氯乙基铝等烷基铝 化物， 其中优选烷基铝的！ ¾化物， 优以一 氯二乙基铝为最好。这些有机铝化合物可以单独使用或组合使用。 本发明所述的催化剂组分中， 有机铝化合物是一个任选的組分。 加入一定量该組分后有利于提高催化剂组分的活性和氢调敏感 性， 但加入过量则会抑制催化剂组分的活性， 并会使体系发粘， 不利于催化剂組分的析出。因此，有机铝化合物的用量优选为 0 ~ 5摩尔， 相对于 1摩尔所述卤化镁。
所述的钛化合物通式为 Ti(OR)aXb， 式中 R为 Ci ~ C14的脂族 烃基或芳族烃基， X为卤素， a是 0、 1或 2, b是 1至 4的整数， a+b=3 或 4。 优选的是四氯化钛、 四溴化钛、 四換化钛、 四丁氧 基钛、 四乙氧基钛、 一氯三乙氧基钛、 三氯化钛、 二氯二乙氧基 钛、 三氯一乙氧基钛。 所述钛化合物可以单独或互相组合使用。
所述的硅化合物为无活性氢原子的有机硅化合物， 其通式为
Figure imgf000009_0001
其中 R1 和 R2独立地为烃基， 优选碳原子数为 1 - 10的烷基， 或 素， R3为烃基, 优选碳原子数为 1 - 10烷基， 其中 X， y, z为整数， 0<x<2, 0<y<2和 0<z<4, 且 x + y + z=4。
上述通式所表示的硅化合物的例子包括： 四甲氧基硅烷、 四 乙氧基硅烷、 四丙氧基硅烷、 四丁氧基硅烷、 四 （2-乙基己氧基） 硅烷、 乙基三甲氧基硅烷、 乙基三乙氧基硅烷、 甲基三甲氧基硅 烷、 甲基三乙氧基硅烷、 正丙基三乙氧基硅烷、 正丙基三甲氧基 硅烷、 癸基三曱氧基硅烷、 癸基三乙氧基硅烷、 环戊基三甲氧基 硅烷、 环戊基三乙氧基硅烷、 2-甲基环戊基三甲氧基硅烷、 2， 3- 二甲基环戊基三甲氧基硅烷、 环己基三甲氧基硅垸、 环己基三乙 氧基硅烷、 乙烯基三甲氧基硅烷、 乙烯基三乙氧基硅烷、 叔丁基 三乙氧基硅烷、 正丁基三甲氧基硅烷、 正丁基三乙氧基硅烷、 异 丁基三甲氧基硅烷、异丁基三乙氧基硅烷、环己基三乙氧基硅烷、 环己基三甲氧基硅烷、 苯基三甲氧基硅烷、 苯基三乙氧基硅烷、 一氯三 氧基硅垸、 一氯三乙氧基硅烷、 乙基三异丙氧基硅烷、 乙烯基三丁氧基硅烷、三甲基苯氧基硅烷、 甲基三烯丙氧基硅烷、 乙烯基三乙酸基硅烷、 二甲基二曱氧基硅烷、 二曱基二乙氧基硅 烷、 二异丙基二甲氧基硅烷、 二异丙基二乙氧基硅烷、 叔丁基甲 基二 ψ氧基硅烷、 叔丁基甲基二乙氧基硅烷、 叔戊基曱基二乙氧 基硅烷、 二环戊基二甲氧基硅烷、 二环戊基二乙氧基硅烷、 甲基 环戊基二乙氧基硅烷、 甲基环戊基二甲氧基硅烷、 二苯基二甲氧 基硅烷、 二苯基二乙氧基硅烷、 甲基苯基二乙氧基硅烷、 甲基苯 基二甲氧基硅烷、 默邻曱苯基二甲氡基硅烷、 双邻甲苯基二乙氧 基硅烷、 欢间甲苯基二甲氧基硅烷、 默间甲苯基二乙氧基硅烷、 对甲苯基二甲氧基硅烷、 默对甲苯基二乙氧基硅烷、 三甲基甲 氧基硅烷、 三甲基乙氧基硅烷、 三环戊基甲氧基硅烷、 三环戊基 乙氧基硅烷、 二环戊基甲基 ψ氧基硅烷和环戊基二甲基甲氧基硅 烷等。 其中较好的是四烷氧基硅烷、 例如四乙氧基硅垸和四丁氧 基硅烷， 最好的是四乙氧基硅烷。 所述硅化合物可以单独或互相 组合使用。
本发明中， 在最终得到的固体钛催化剂组分中应含有足够量 的硅化合物以提高催化剂的综合性能 , 同时硅化合物还起到促进 催化剂组分颗粒沉析成型的助析出剂的作用。 按照本发明的一个 实施方案， 在制备固体催化剂组分时也可以采用可以原位生成所 述含烷氧基的有机硅化合物的其它硅化合物， 例如四氯化硅。
如上面提到的， 本发明所述的用于乙烯聚合的催化剂组分包 含所述镁复合物， 至少一种所述钛化合物， 至少一种所述醇化合 物、 至少一种所述硅化合物、 和任选地所述有机铝化合物的反应 产物， 其中各反应物的用量以镁复合物中的每摩尔卤化镆计， 醇 化合物为 0.1 -10摩尔， 优选 1-4摩尔； 有机硅化合物为 0.05 ~ 1摩尔； 有机铝化合物为 0~5摩尔； 钛化合物为 1~ 15摩尔， 优 选 2~10摩尔。
在一个实施方案中， 本发明的催化剂组分基本上由上述反应 产物组成。这样的催化剂组分包含： Ti: 4.0-7.5 wt%, Mg: 14~ 19 wt%, CI: 58~68 wt%, Si: 0.2 ~ 1.2 wt%, 烷氧基： 4.0 - 8.5 wt%, P: 0.1-1.0 wt%, 和 Al: 0~0.6wt%。
在另一个实施方案中， 本发明的催化剂组分可以以负载在无 机氧化物载体上的形式被得到。
所述的无机氧化物载体的实例包括但不限于 Si02， A1203或其 混合物， 并且可以商购得到。 所述载体的形态一般呈球形， 其平 均粒径为 0·1μπι~ 150μιη，优选 Ιμιη ~ 50μιη，最优选 5μιη ~ 40μιη。 优选采用大比表面积， 优选 80m2/g ~ 300 m2/g的硅胶作为载体。 这样的硅胶载体有利于提高催化剂组分中镁化合物的负载量， 进 而提高催化剂活性组分的负载量， 防止高镁含量时催化剂组分中 出现! ¾化镁不规则聚集体， 导致催化剂組分颗粒形态不好的现象 出现。 惰性载体在使用之前， 最好进行焙烧脱水处理或烷基化活 化处理。 如果使用， 所述无机氧化物载体的用量为 40 ~ 400克， 优选 80 ~ 250克， 以镁复合物中的每摩尔卤化镁计。
当本发明的催化剂组分以负载在无机氧化物载体上的形式得 到时， 其包含： Ti: 1.5 - 4.5%(wt); Mg: 4 - 14%(wt); CI: 20 ~ 40%(wt); 垸氧基： 1.5 ~ 4.5%(wt); P: 0.05 - 0.5%(wt); Al: 0 ~ 0.4%(wt); 和惰性载体： 20 ~ 80%(wt)。 可以理解， 所述催化剂 组分还包含衍生自所述有机硅化合物的 Si。
在另一方面， 本发明提供了制备本发明催化剂组分的方法， 该方法包括如下步驟：
( 1 )将 )¾化镁溶解于含有机环氧化合物和有机磷化合物的溶 剂体系中， 任选但优选地在溶剂体系中加入惰性稀释剂， 形成均 匀溶液；
( 2 )在形成所述均勾溶液之前、过程中或之后加入醇化合物， 以最终形成一种含 1¾化镁的溶液；
( 3 )使步骤 (2)得到的溶液与钛化合物接触， 在该接触之前、 过程中或之后加入硅化合物， 得到一种混合物；
( 4 )将所述混合物緩慢升温至 60 °C ~ 110°C并维持一段时间， 在升温过程中有固体物逐渐析出； 和
( 5 ) 回收步骤（4 ) 中形成的固体物， 得到催化剂组分。
在上述步骤（1 ) 中， 溶解温度可以为 40 ~ 110°C， 优选 50 ~
90 °C。 步骤（ 1 )进行的时间没有特別的限制， 但是一般优选在溶 液变澄清后继续维持 20分钟至 5小时， 优选 30分钟至 2小时。 在将！ ¾化镁溶解于含有机环氧化合物和有机磷化合物的溶剂 体系中形成所述均勾溶液之前、 过程中或之后， 向反应混合物中 加入醇化合物。 如果醇化合物在形成所述均勾溶液之前或过程中 被加入，则形成的均勾溶液就是所述步骤（ 2 )的含! ¾化镁的溶液。 如果醇化合物在形成所述均匀溶液之后被加入， 则优选将反应混 合物在 0°C - 110°C， 优选室温 ~ 90 °C下搅拌约 10分钟至 5小时， 优选 20分钟至 2小时， 以形成所述含 ¾化镁的溶液。 为了方便， 优选在形成所述均勾溶液之前或过程中加入醇化合物。
在所述步骤 (3)之前， 任选向步骤 (2)得到的所述含 1¾化镁的溶 液中加入有机铝化合物并允许反应进行一定的时间，优选 10分钟 至 5小时， 更优选 30分钟至 2小时。 该反应可以在 0。C ~ 80°C , 优选室温~ 50°0进行。
步骤（3 ) —般在较低的温度下， 优选 -40°C ~ 20°C范围内的温 度下进行。
在步骤（4 )中， 在将反应混合物緩慢加热至需要的温度以后， 可以在该温度下维持 30分钟至 5小时， 优选 1小时至 3小时。
步驟 (5)的回收包括例如过滤和用惰性稀释剂洗涤， 并任选包 括干燥。 所述回收操作可以按照本领域常规的方法进行。
如本领域技术人员可以理解的， 上述制备方法一般全部在惰 性气氛下例如氮气氛下或氩气氛下进行。
按照一个实施方案， 使用所述醇的组合， 例如乙醇与 2-乙基 己醇的组合。 构成所述醇组合的所述各种醇可以同时加入或分开 加入。
按照另一个实施方案， 在步骤 (3)或 (4)的反应在所述无机氧化 物载体存在下进行， 从而得到负载在无机氧化物载体上的本发明 的催化剂组分。
在又一方面， 本发明还提供了一种用于乙烯聚合的催化剂， 该催化剂包含 （1 ) 上述的本发明的催化剂组分与 （2 ) 通式为 AlRs nX2 3_n的有机铝助催化剂的反应产物， 式中 R5可以为氢、 碳 原子数为 1 ~ 20的烃基， 特別是烷基、 芳烷基、 芳基； X2为卤素， 特别是氯和溴； 11为 0<n≤3的数。
在一个实施方案中， 本发明的催化剂由所述組分（1 ) 和所述 组分（2 ) 的反应产物组成。
所述有机铝助催化剂的例子包括： 三甲基铝、 三乙基铝、 三 异丁基铝、 三辛基铝、 一氢二乙基铝、 一氢二异丁基铝、 一氯二 乙基铝、 一氯二异丁基铝、 倍半乙基氯化铝、 二氯乙基铝等， 其 中优选三烷基铝化合物， 尤以三乙基铝、 三异丁基铝为好。 所述 有机铝助催化剂可以单独或互相组合使用。
在本发明的催化剂中， 組分（2 ) 中铝与组分（1 ) 中钛的摩 尔比为 5 ~ 500, 优选 20 ~ 200。
在又一方面， 本发明提供了一种乙烯聚合方法， 该方法包括：
( i )使乙烯以及任选的至少一种共聚单体在聚合条件下与本 发明的催化剂接触， 以形成聚合物； 和
( ii ) 回收步驟 (i)中形成的聚合物。
所述共聚单体可以选自 3 - 20个碳原子的 a-烯烃和二烯烃。 所述 α-烯烃的实例包括丙烯、 丁烯 -1、 4-甲基戊晞 -1、 己烯 -1、 辛 烯 -1、 苯乙浠、 甲基苯乙烯等。 所述二烯烃的实例包括环戊二烯、 乙烯基降冰片烯、 5-亚乙基 -2-降水片烯等。
所述聚合方法可以在液相或气相中进行。 本发明的催化剂尤 其适合于淤浆聚合工艺，或者包括淤浆聚合在内的組合聚合工艺， 例如淤浆相加气相聚合工艺。
液相聚合所采用的介质的实例包括： 丙烷、 异丁烷、 己烷、 庚烷、 环己烷、 石脑油、 抽余油、 加氢汽油、 煤油、 苯、 甲苯、 二甲苯等饱和脂肪烃或芳香烃等惰性溶剂。 为了调节最终聚合物的分子量， 在本发明的聚合方法中采用 氢气作分子量调节剂。
本发明的催化剂由于采用无活泼氢的有机硅化合物为助析出 剂， 因此在催化剂组分制备时很容易地析出催化剂组分的颗粒， 不需要使用大量的四氯化钛来促使沉淀的析出， 也不需要多次使 用四氯化钛来处理沉淀， 因此四氯化钛的加入量大大减少。 同时 有机硅化合物的加入还有助于提高催化剂的活性和催化剂组分的 颗粒形态的改善， 从而进一步改善聚合物的颗粒形态。 在本发明 的催化剂用于乙烯聚合时， 显示了较好的氢调敏感性。 具体实施方式
下面以实施例来说明本发明， 但并非限制发明范围。
实施例 1
(1)催化剂组分的制备： 在经过高纯氮气充分置换过的反应器 中， 依次加入 4.0g二氯化镁， 甲苯 50ml、 环氧氯丙烷 4.0ml、 磷 酸三丁酯 4.0 ml、 乙醇 6.4ml, 搅拌下升温至 70°C， 当固体完全 溶解形成均一的溶液后， 将所述混合物在 70°C下维持 1小时。 降 温至 30°C， 滴加 4.8ml浓度为 2.2M的一氯二乙基铝曱苯溶液， 并在 30°C维持反应 1小时。 将该体系冷却至 -5°C， 緩慢滴加 40ml 四氯化钛， 然后加入 3ml四乙氧基硅烷， 反应 1小时。 緩慢升温 至 80°C， 反应 2小时。 停止搅拌， 将反应混合物静置， 悬浮液很 快分层， 抽除上层清液， 残余物用甲苯洗涤两遍、 己烷洗涤四遍， 高纯氮气吹干， 得到流动性好、 粒径分布窄的固体催化剂组分。 催化剂组分的组成见表 1。
(2)乙烯聚合
在氮气氛下， 通过搅拌将约 0.58上述催化剂组分分散在 50ml 己烷中， 制成用于乙烯聚合的固体催化剂组分的己烷悬浮液。 容积为 2L的不锈钢反应釜， 经高纯氮气充分置换后， 加入己 烷 1L， 浓度 1M的三乙基铝己烷溶液 1.0ml, 加入上述制备的固 体催化剂组分的己烷悬浮液（含 0.3亳克钛） ， 升温至 70°C , 通 入氢气使釜内压力达到 0.28MPa (表压）， 再通入乙烯使釜内总压 达到 0.73MPa (表压） 。 在 80 °C条件下聚合 2小时， 同时补充乙 烯以维持 0.73MPa (表压） 的总压。 聚合结果见表 2。
实施例 2
(1) 催化剂组分的制备同实施例 1, 只是乙醇用量由 6.4ml改 为 5.9ml。
(2)乙烯聚 ^^同实施例 1。催化剂组分的组成及聚合结果见表 1 和表 2。
实施例 3
(1)催化剂的制备同实施例 2，只是一氯二乙基铝溶液的用量改 为 3.8ml。
(2)乙烯聚合同实施例 1。催化剂组分的组成及聚令结果见表 1 和表 2。
实施例 4
(1)催化剂组分的制备： 在经过高纯氮气充分置换过的反应器 中， 依次加入 4.03g二氯化镁， 甲苯 50ml、 环氧氯丙烷 4.0ml、 磷酸三丁酯 4.0 ml, 乙醇 6.4ml， 搅拌下升温至 70°C， 当固体完 全溶解形成均一的溶液后， 70°C条件下反应 1小时。 将该体系冷 却至 -5°C ,緩慢滴加 40ml四氯化钛，然后加入 3ml四乙氧基硅烷， 反应 1小时。 緩慢升温至 80°C， 反应 2小时。 停止搅拌， 将反应 混合物静置， 悬浮液很快分层， 抽除上层清液， 将残余物用甲苯 洗涤两遍、 己烷洗涤四遍， 高纯氮气吹干， 得到流动性好、 粒径 分布窄的固体催化剂组分。 催化剂组分的组成见表 1。
(2)乙烯聚合同实施例 1。 聚合结果见表 2。 实施例 5
(1) 催化剂组分的制备同实施例 4, 只是四乙氧基硅烷用量 改为 2ml。
(2) 乙烯聚合同实施例 1。 催化剂组分的组成及聚合结果见 表 1和表 2。
实施例 6
(1)催化剂组分的制备同实施例 4 ,只是四乙氧基硅烷用量改为 l ml o
(2)乙烯聚合同实施例 1。催化剂组分的组成及聚合结果见表 1 和表 2。
实施例 7
(1)催化剂组分的制备同实施例 4，只是四乙氧基硅烷用量改为 5ml。
(2)乙烯聚合同实施例 1，催化剂组分的组成及聚合结果见表 1 和表 2。
实施例 8
(1)催化剂組分的制备同实施例 4，只是四乙氧基硅烷改为四氯 化硅。
(2)乙烯聚合同实施例 1。催化剂组分的组成及聚合结果见表 1 和表 2。
实施例 9
(1)催化剂组分的制备： 在经过高纯氮气充分置换过的反应器 中， 依次加入 4.03g二氯化镁， 甲苯 50ml、 环氧氯丙烷 2·0ιη1、 磷酸三丁酯 6.0ml、 乙醇 3.4ml, 搅拌下升温至 70°C， 当固体完全 溶解形成均一的溶液后， 70Ό条件下反应 1小时。 将该体系冷却 至 -5°C , 緩慢滴加 60ml四氯化钛， 然后加入 3ml四乙氧基硅烷， 反应 1小时。 緩慢升温至 80°C , 反应 2小时。 停止搅拌， 将反应 混合物静置， 悬浮液很快分层， 抽除上层清液， 残余物用甲苯洗 涤两遍、 己烷洗涤四遍， 高纯氮气吹干， 得到流动性好、 粒径分 布窄的固体催化剂组分。 催化剂组分的組成见表 1。
(2)乙婦聚合同实施例 1。 聚合结果见表 2。 实施例 10
(1)催化剂组分的制备同实施例 9， 只是乙醇用量改为 3.9ml。
(2)乙烯聚合同实施例 1。催化剂组分的组成及聚合结果见表 1和 表 2。
实施例 11
(1)催化剂组分的制备同实施例 9, 只是乙醇用量改为 4.4ml。
(2)乙烯聚合同实施例 1。催化剂组分的组成及聚合结果见表 1和 表 2。
实施例 12
(1)催化剂组分的制备同实施例 9， 只是乙醇用量改为 5.0ml。
(2)乙烯聚合同实施例 1。催化剂组分的组成及聚合结果见表 1和 表 2。
实施例 13
(1)催化剂组分的制备： 在经过高纯氮气充分置换过的反应器 中， 依次加入 8.0Kg二氯化镁， 甲苯 100L、 环氧氯丙烷 4，0L、 磷 酸三丁酯 12L、 乙醇 6.9L, 搅拌下升温至 70°C , 当固体完全溶解 形成均一的溶液后， 70 V条件下反应 1小时。将该体系冷却至 -5 °C， 緩慢滴加 120L四氯化钛， 然后加入 6.0L四乙氧基硅烷， 反应 1 小时。 緩慢升温至 80°C， 反应 2小时。 停止搅拌， 将反应混合物 静置， 悬浮液很快分层， 抽除上层清液， 残余物用己烷洗涤四遍， 并真空干燥， 得到流动性好、 粒径分布窄的固体催化剂组分。 催 化剂组分的组成见表 1。
(2)乙浠聚合同实施例 1。 聚合结果见表 2。 对比例 1
(1)催化剂组分的制备同实施例 4,只是四乙氧基硅烷改为邻苯 二甲酸酐。
(2)乙烯聚合同实施例 4。催化剂组分的组成及聚合结果见表 1 和表 2。
对比例 2
(1)重复实施例 4(1)的程序， 只是不加四乙氧基硅烷。 观察到 催化剂组分的析出困难， 析出的粒子极细， 难于沉降， 未能得到 催化剂组分。 从表 2 的聚合数据可以看出， 在同样的聚合条件下， 本发明 的催化剂活性更高。 而且由于在本发明的催化剂组分中引入了所 述有机硅化合物， 使得催化剂组分的析出变得容易， 所得聚合物 的粒径分布要窄于对比例 1 (以苯酐作为析出剂） ， 在所得的聚 合物中过粗或过细的粒子均较少。
表 1催化剂组分的组成
编号 Ti Mg CI Si OEt P
(wt%) (wt%) (wt%) ( t%) (wt%) (wt%) 实施例 1 6.1 16.0 60.0 0.2 6.7 0.49 实施例 2 5.9 16.0 59.0 0.2 6.4 0.40 实施例 3 6.2 15.0 59.0 0.3 6.5 0.51 实施例 4 5.6 16.0 61.0 0.3 6.3 0.52 实施例 5 5.8 17.0 59.0 0.2 6.1 0.48 实施例 6 5.7 17.0 60.0 0.1 5.9 0.49 实施例 7 6.0 16.0 60.0 0.4 6.4 0.51 实施例 8 5.9 17.0 62.0 0.2 6.3 0.55 实施例 9 5.6 16.0 60.0 0.4 6.3 0.49 实施例 10 5.7 16.0 59.0 0.4 6.3 0.49 实施例 11 6.0 16.0 60.0 0.3 6.4 0.50 实施例 12 6.2 16.0 59.0 0.3 6.5 0.47 实施例 13 5.7 16.0 60.0 0.3 6.3 0.49 对比例 1 5.5 16.0 60.0 - - - 应该指出， 除上表中给出的主要组分以外， 所述催化剂組分 还可能含有溶剂 （挥发份） 和衍生自有机磷化合物、 有机环氧化 合物、 有机铝化合物等的物种。
表 2聚合结果
Figure imgf000020_0001
实施例 14
(1)催化剂组分的制备： 在经过高纯氮气充分置换过的反应器 中， 依次加入 4.0g二氯化镁， 甲苯 80ml、 环氧氯丙熄 4.0ml、 磷 酸三丁酯 4.0 ml、 乙醇 6.4ml, 搅拌下升温至 70。C， 当固体完全 溶解形成均一的溶液后， 70。C条件下反应 1小时。 降温至 30°C , 滴加 4.8ml浓度为 2.2M的一氯二乙基铝甲苯溶液， 并在 30°C维 持反应 1小时。 将该体系冷却至 -25°C， 緩慢滴加 40ml四氯化钛， 搅拌反应 0.5小时。加入 5g处理过的惰性载体（ Davison Catalysts XP02485硅胶，处理条件： 200°C煅烧 2小时， 600 °C煅烧 4小时）， 搅拌反应 0.5小时。 然后加入 3ml四乙氧基硅烷， 反应 1小时。 缓慢升温至 85°C， 反应 2小时。 停止搅拌， 将反应混合物静置， 悬浮液很快分层， 抽除上层清液， 残佘物用甲苯洗涤两遍、 己烷 洗涤四遍， 高纯氮气吹干， 得到流动性好、 粒径分布窄的固体催 化剂组分。
(2)乙烯聚合
容积为 2L的不锈钢反应釜， 经高纯氮气充分置换后， 加入己 烷 1L,浓度 1M的三乙基铝己烷溶液 1.0ml，加入上述制备的 10mg 固体催化剂组分，升温至 70°C，通入氢气使釜内压力达到 0.28MPa (表压），再通入乙烯使釜!^总压达到 0.73MPa (表压）。在 80°C 条件下聚合 2小时， 同时补充乙烯以维持 0.73MPa (表压） 的总 压， 聚合结果见表 3。
实施例 15
( 1 )催化剂组分的制备同实施例 14, 只是乙醇用量由 6.4ml 改为 5.9mL
(2)乙烯聚合同实施例 14。 聚合结果见表 3。
实施例 16
( 1 )催化剂组分的制备同实施例 14， 只是乙醇用量由 6.4ml 改为 3.2ml。
(2)乙烯聚合同实施例 14。 聚合结果见表 3。
实施例 17
(1)催化剂组分的制备同实施例 15， 只是不加一氯二乙基铝。
(2)乙烯聚合同实施例 14。 聚合结果见表 3。
实施例 18
(1)催化剂组分的制备同实施例 16, 只是不加一氯二乙基铝。
(2)乙烯聚合同实施例 14。 聚合结果见表 3。
实施例 19
(1)催化剂组分的制备： 在经过高纯氮气充分置换过的反应器 中， 依次加入 4.03g二氯化链， 甲苯 50ml、 环氧氯丙垸 4.0ml、 磷酸三丁酯 4.0ml、 乙醇 6.4ml, 搅拌下升温至 70°C , 当固体完全 溶解形成均一的溶液后， 70 °C条件下反应 1小时。 将该体系冷却 至 -25°C， 加入惰性载体 5g ( XP0 2485硅胶， 在 200°C煅烧 2h, 在 600°C煅烧 4h )，搅拌反应 0.5小时。緩慢滴加 40ml四氯化钛， 然后加入 3ml四乙氧基硅烷， 反应 1小时。 緩慢升温至 85。C， 反 应 2小时。 停止搅拌， 将反应混合物静置， 悬浮液很快分层， 抽 除上层清液， 残余物用甲苯洗涤两遍、 己烷洗涤四遍， 高纯氮气 吹干， 得到流动性好、 粒径分布窄的固体催化剂组分。
(2)乙婦聚合同实施例 14。 聚合结果见表 3。
实施例 20
( 1 )催化剂组分的制备同实施例 17， 只是四乙氧基硅烷用量 改为 4ml。
( 2 ) 乙烯聚合同实施例 14。 聚合结果见表 3。
实施例 21
(1)催化剂組分的制备同实施例 17, 只是四乙氧基硅烷用量改 为 5ml。
(2)乙烯聚合同实施例 14， 聚合结果见表 3。
实施例 22
(1)催化剂组分的制备同实施例 17, 只是四乙氧基硅烷改为四 氯化硅。
(2)乙烯聚合同实施例 14。 聚合结果见表 3。
实施例 23
(1)催化剂组分的制备同实施例 17， 只是用量 5.9ml的乙醇改 为 16.4ml的异辛醇。
(2)乙烯聚合同实施例 14。 聚合结果见表 3。 表 3
编号 Ti C1 活性 BD MI2.16 聚合物的粒径分布（目）
(wt%) (wt%) 104gPE/gcat g/cm"3 g/lOmin
<20 20-100 100-200 >200 实施例 14 3.6 8.1 30.1 21.5 0.35 0.9 2.0 95.0 3.0 1 实施例 15 3.5 8.0 30.0 23.1 0.36 1.0 1.2 96.3 2.5 1 实施例 16 3.1 8.2 29.8 25.4 0.35 0.8 0.5 96.2 3.3 1 实施例 17 3.3 8.1 30.0 24.1 0.35 0.8 0.8 97.1 2.1 1 实施例 18 3.2 7.9 30.0 26.4 0.36 0.7 1.0 97.2 2.8 1 实施例 19 3.3 8.0 30.0 25.5 0.35 0.9 0.5 96.7 2.8 1 实施例 20 3.4 8.2 30.1 24.8 0.36 1.0 0.7 96.9 2.4 1 实施例 21 3.4 8.1 30.4 24.9 0.36 0.9 0.3 97.0 2.7 1 实施例 22 3.1 8.0 30.0 23.1 0.35 1.2 0.7 96.8 2.5 1 实施例 23 3.5 8.3 30.0 22.0 0.37 1.2 0.1 97.5 2.4
(1)催化剂组分的制备： 在经过高纯氮气充分置换过的反应器 中， 依次加入 4.0g二氯化镁， 甲苯 50ml、 环氧氯丙梡 4.0ml、 磷 酸三丁酯 4.0 ml、 乙醇 3.4ml。 搅拌下升温至 65°C， 当固体完全 溶解形成均一的溶液后， 滴加 2-乙基己醇 5.5ml, 并将反应混合 物在 65。C下维持 1 小时。 将该体系冷却至 -5°C， 緩慢滴加 60ml 四氯化钛， 然后加入 3ml四乙氧基硅烷， 反应 0.5小时。 緩慢升 温至 85°C， 反应 2小时。 停止搅拌， 将反应混合物静置， 悬浮液 很快分层。 抽除上层清液， 残余物用甲苯洗涤两遍， 己烷洗涤四 遍， 高纯氮气吹干， 得到流动性好、 粒径分布窄的固体催化剂组 分。
(2)乙烯聚合
容积为 2L的不锈钢反应釜， 经高纯氮气充分置换后， 加入己 烷 1L， 浓度 1M的三乙基铝己烷溶液 1.0ml, 和上述制备的固体 催化剂组分的己烷悬浮液（含 0.3亳克钛） 。 升温至 70°C , 通入 氢气使釜内压力达到 0.28MPa (表压） ， 再通入乙烯使釜内总压 达到 0.73MPa (表压） 。 在 80°C条件下聚合 2小时， 同时通入乙 烯以维持 0.73MPa (表压） 的总压。 聚合结果见表 4。
实施例 25
(1)催化剂组分的制备同实施例 24, 只是 2-乙基己醇用量由 5.5ml改为 7.7ml。
(2)乙烯聚合同实施例 24， 聚合结果见表 4。
实施例 26
(1)催化剂組分的制备同实施例 24， 只是 2-乙基己醇用量改为 3.3mL
(2)乙烯聚合同实施例 24， 聚合结果见表 4。
实施例 27 (1)使用实施例 24制备的催化剂组分。
(2)乙烯聚合
容积为 2L的不锈钢反应釜， 经高纯氮气充分置换后， 加入己 垸 1L, 浓度 1M的三乙基铝己烷溶液 1.0ml， 和上述固体催化剂 组分的己烷悬浮液（含 0.5毫克钛） 。 升温至 70°C , 通入氢气使 釜内压力达到 0.38MPa (表压） ， 再通入乙烯使釜内总压达到 0.7:3MPa (表压） 。 在 80°C条件下聚合 2小时， 同时通入乙烯以 维持 0.73MPa (表压） 的总压。 聚合结果见表 4。
实施例 28
(1)使用实施例 24制备的催化剂组分。
(2)乙烯聚合
容积为 2L的不锈钢反应釜， 经高纯氮气充分置换后， 加入己 烷 1L， 浓度 1M的三乙基铝己烷溶液 1.0ml， 和上述固体催化剂 组分的己烷悬浮液（含 0.8亳克钛） 。 升温至 70°C， 通入氢气使 釜内压力达到 0.48MPa (表压） ， 再通入乙烯使釜内总压达到 0.7:3MPa (表压） 。 在 80°C条件下聚合 2小时， 同时通入乙烯以 维持 0.73MPa (表压） 的总压。 聚合结果见表 4。
实施例 29
(1)使用实施例 24制备的催化剂组分。
(2)乙烯聚合
容积为 2L的不锈钢反应釜， 经高纯氮气充分置换后， 加入己 烷 1L， 浓度 1M的三乙基铝己烷溶液 1.0ml, 和上述固体催化剂 组分的己垸悬浮液（含 1.3亳克钛） 。 升温至 70。C， 通入氢气使 釜内压力达到 0.58MPa (表压） ， 再通入乙烯使釜内总压达到 0.73MPa (表压） 。 在 80°C条件下聚合 2小时， 同时通入乙烯以 维持 0.73MPa (表压） 的总压。 聚合结果见表 4。
实施例 30 (1)使用实施例 24制备的催化剂组分。
(2)乙烯聚合
容积为 2L的不锈钢反应釜， 经高纯氮气充分置换后， 加入己 烷 1L， 浓度 1M的三乙基铝己梡溶液 1.0ml， 和上述固体催化剂 組分的己烷悬浮液（含 1.8毫克钛） 。 升温至 70°C , 通入氢气使 釜内压力达到 0.68MPa (表压） ， 再通入乙烯使釜内总压达到 0.73MPa (表压） 。 在 80 °C条件下聚合 2小时， 同时通入乙烯以 维持 0.73MPa (表压） 的总压。 聚合结果见表 4。 表 4
Figure imgf000026_0001
由表 4 所示结果可以看出， 在乙烯聚合中， 本发明的催化剂 组分具有较高的活性， 好的氢调敏感性能； 和窄的粒径分布和高 的聚合物堆积密度。

Claims

权 利 要 求
1. 用于乙烯聚合的催化剂组分， 包含一种镁复合物， 至少一 种钛化合物， 至少一种醇化合物、 至少一种硅化合物、 任选地和 一种有机铝化合物的反应产物；
其中所述的镁复合物是将！ ¾化镁溶解在含有机环氧化合物和 有机磷化合物的溶剂体系中所得到的产物；
所述的醇化合物是碳原子数为 1 - 10 的直链、 支链的烷基或 环烷基的醇、 或碳原子数为 6 - 20的芳醇或芳烷醇， 所述醇任选 被卤原子取代；
所述的钛化合物通式为 Ti(OR)aXb， 式中 R为 Ci ~ C14的脂族 烃基或芳族烃基， X为卤素， a是 0、 1或 2, b是 1至 4的整数， a+b=3或 4；
所述的硅化合物为如通式为
Figure imgf000027_0001
所示的有机硅化 合物，其中 R1 和 R2分别为烃基或卤素， R3为烃基，0≤x≤2，0≤y≤2 和 0<z<4, JL X + y + z=4;
所述的有机铝化合物的通式为 AlR4 nxVn， 式中 R4为氢或碳 原子数为 1 ~ 20的烃基， X1为卤素， n为 1 < n≤3的数。
2. 根据权利要求 1 所述的催化剂組分， 其中， 通式
Figure imgf000027_0002
中， R1 和 R2独立地为碳原子数为 1 - 10的烷基或 卤素， R3为碳原子数为 1 - 10烷基。
3. 根据杈利要求 1所述的催化剂組分， 其中所述的硅化合物 选自四甲氧基硅烷、 四乙氧基硅烷、 四丙氧基硅烷、 四丁氧基硅 烷和四 （2-乙基己氧基）硅烷。
4. 根据权利要求 1 - 3之一所述的催化剂組分， 其中各反应物 的用量以镁复合物中的每摩尔卤化镁计， 醇化合物为 0.1 - 10摩 尔， 有机硅化合物为 0.05 ~ 1摩尔， 有机铝化合物为 0 ~ 5摩尔， 钛化合物为 1~15摩尔。
5. 根据权利要求 1-3之一所述的催化剂组分， 其中， 所述的 溶剂体系含有 0.3 - 4 mol有机环氧化合物和 0.2 ~ 4mol有机磷化 合物， 相对于每摩尔 !¾化镁。
6. 权利要求 5所述的催化剂組分， 其中， 所述的溶剂体系还 含有选自芳烃类化合物或烷烃类化合物中的至少一种惰性稀释 剂， 其用量为 0.2-10L/mol所述 !¾化镁。
7. 根据权利要求 1-6之一所述的催化剂组分， 其中， 所述醇 化合物以两种或更多种所述醇的组合的形式使用。
8. 权利要求 7所述的催化剂组分， 其中， 所述醇混合物为乙 醇与 2-乙基己醇的组合。
9. 根据权利要求 1 -8之一所述的催化剂组分， 其含有 Ti: 4.0-7.5 wt%, Mg: 14~ 19wt%, CI: 58~68wt%, Si: 0.2 ~ 1.2 wt%, 烷氧基： 4.0-8.5 wt%, P: 0.1- 1.0 wt%, Al: 0~ 0.6 wt%。
10. 根据权利要求 1一 8之一所述的催化剂组分， 其呈负载在 无机氧化物载体上的形式。
11. 权利要求 10所述的催化剂组分， 其中所述无机氧化物载 体选自二氧化硅、 氧化铝以及它们的组合。
12. 权利要求 10或 11所述的催化剂组分， 其中所述无机氧化 物载体的用量为 40-400克， 以镁复合物中的每摩尔！ ¾化镁计。
13. 一种制备用于乙烯聚合的催化剂组分的方法， 该方法包括 如下步驟：
( 1 )将1¾化镁溶解于含有机环氧化合物和有机磷化合物的溶 剂体系中， 任选但优选地在溶剂体系中加入惰性稀释剂， 形成均 匀溶液；
( 2 )在形成所述均勾溶液之前、过程中或之后加入醇化合物， 以最终形成一种含 !¾化镁的溶液；
( 3 )使步骤 (2)得到的溶液与钛化合物接触， 在该接触之前、 过程中或之后加入硅化合物， 得到一种混合物；
( 4 )将所述混合物緩慢升温至 60。C - 110。C并维持一段时间， 在升温过程中有固体物逐渐析出； 和
( 5 ) 回收步驟（4 ) 中形成的固体物， 得到催化剂组分； 其中： 所述的醇化合物是碳原子数为 1 - 10 的直链、 支链的 烷基或环烷基的醇、 或碳原子数为 6 - 20的芳醇或芳烷醇， 所述 醇任选被! ¾原子取代；
所述的钛化合物通式为 Ti(OR)aXb， 式中 R为 d Cw的脂族 烃基或芳族烃基， X为卤素， a是 0、 1或 2， b是 1至 4的整数， a+b=3或 4; 和
所述的硅化合物为如通式为 R^R^S OR^所示的有机硅化 合物，其中 R1 和 R2分别为烃基或卤素， R3为烃基， 0≤x≤2， 0<y<2 和 0≤z≤4 , 且 x + y + z=4。
14.权利要求 13的方法， 其中在所述步驟 (3)之前， 向步骤 (2)得到 的所述含 1¾化镁的溶液中加入有机铝化合物并允许反应进行一定 的时间， 所述的有机铝化合物的通式为 AlR4 nxVn， 式中 R4为氢 或碳原子数为 1 ~ 20的烃基， X1为卤素， n为 1 < n≤3的数。
15. 权利要求 13或 14的方法， 其中所述醇化合物以两种或更 多种所述醇的组合的形式使用。
16. 权利要求 15所述的方法， 其中所述醇混合物为乙醇与 2- 乙基己醇的组合。
17. 权利要求 13-16之一所述的方法，其中步骤 (3)或 (4)的反应 在无机氧化物载体存在下进行。
18. 权利要求 17所述的方法， 其中所述无机氧化物载体选自 二氧化硅、 氧化铝以及它们的组合。
19. 一种用于乙烯聚合的催化剂， 其包含以下组分的反应产 物：
(1) 权利要求 1-12之一所述的催化剂组分； 和
(2) 通式为 AlRs nX2 3_n的有机铝助催化剂， 式中 Rs为氢或 碳原子数为 1~20的烃基， X2为鹵素， 并且 n为满足 0<11≤3的 值。
20. 根据权利要求 19所述的催化剂， 其中组份（ 2 ) 中铝与组 分（1) 中钛的摩尔比为 20 ~ 200。
21. 一种乙烯聚合方法， 该方法包括：
(i)使乙烯以及任选的共聚单体在聚合条件下与权利要求 19或 20所述的催化剂接触， 以形成聚合物； 和
(ii) 回收步骤 (i)中形成的聚合物。
PCT/CN2006/002923 2005-10-31 2006-10-31 Catalyst component for ethylene polymerization, preparation thereof and catalyst containing the same WO2007051410A1 (en)

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