WO2009124722A1 - Procédé de fabrication d'un composant de catalyseur au titane, composant de catalyseur au titane, procédé de fabrication d'un catalyseur au titane et catalyseur au titane - Google Patents

Procédé de fabrication d'un composant de catalyseur au titane, composant de catalyseur au titane, procédé de fabrication d'un catalyseur au titane et catalyseur au titane Download PDF

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Publication number
WO2009124722A1
WO2009124722A1 PCT/EP2009/002566 EP2009002566W WO2009124722A1 WO 2009124722 A1 WO2009124722 A1 WO 2009124722A1 EP 2009002566 W EP2009002566 W EP 2009002566W WO 2009124722 A1 WO2009124722 A1 WO 2009124722A1
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Prior art keywords
compound
titanium
titanium catalyst
group
mol
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PCT/EP2009/002566
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English (en)
Inventor
Qi Guo
Yong Jiang
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Süd-Chemie AG
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Priority claimed from CNA2008100889138A external-priority patent/CN101245115A/zh
Priority claimed from CNA2008100943490A external-priority patent/CN101260166A/zh
Application filed by Süd-Chemie AG filed Critical Süd-Chemie AG
Priority to CN2009801146559A priority Critical patent/CN102272172A/zh
Priority to DE112009000794T priority patent/DE112009000794T5/de
Publication of WO2009124722A1 publication Critical patent/WO2009124722A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • the present invention relates to a method for preparing a titanium catalyst component, a titanium catalyst component, a method for preparing a titanium catalyst and a titanium catalyst .
  • the titanium catalyst on the basis of the titanium catalyst component according to the present invention is used for ethylene polymerization and copolymerization and can provide high catalytic activity to produce a polymer with a high bulk density, narrow particle size distribution and less fine particles.
  • Catalysts for producing polymers with high bulk density can be obtained using a magnesium-containing solution.
  • a magnesium compound is reacted with an electron-donating compound.
  • Electron-donating compounds include alcohols, amines, cyclic ethers or organic carboxylic acids.
  • the magnesium-containing solution is generally prepared in the presence of a hydrocarbon solvent.
  • Magnesium-carried catalysts can be prepared through the reaction of the magnesium-containing solution and a titanium halide compound (such as TiCl ⁇ i) .
  • a polymer with high bulk density can be produced by these catalysts, their catalytic activity is still insufficient. Moreover, a polymer produced with the above catalyst has a wide particle size distribution and a large quantity of fine particles, which can easily block the pipelines during the production process and impede a stable operation.
  • a slurry of a MgCl 2 • 6 C 2 H 5 OH adduct can be generated by the reaction between ground and crushed MgCl 2 and ethanol.
  • a titanium-containing catalyst loaded by MgCl 2 can be obtained through esterification of the MgCl 2 • 6 C 2 H 5 OH adduct with diethyl aluminum chloride and a Ti-loading reaction with TiCl 4 .
  • the preparation method of this catalyst is simple and the catalyst provides mild reaction conditions and a comparatively high activity for catalyzing ethylene polymerization
  • the MgCl 2 carrier cannot be dissolved in mineral oil and irregular flaky MgCl 2 particles exist in the slurry reaction system, which results in an irregular shape of the solid catalyst particles and inhomogeneous particle sizes. Therefore, the polymer also has an irregular shape and more fine particles, which easily generate static electricity and block the pipelines .
  • a higher content of oligomers is generated in the solvent by the catalyst during polymerization, which easily block the pipelines and impede a post-treatment.
  • US 4,311,414 proposes a catalyst preparation method, which includes drying Mg(OH) 2 in the air, wherein the obtained catalyst can produce a polymer with narrow particle size distribution and improved average particle size.
  • US 3,953,414 and US 4,111,835 also disclose a catalyst preparation method, which includes drying hydrous MgCl 2 in the air, wherein the obtained catalyst can produce a polymer with a specific shape and a very large average particle size.
  • auxiliary devices such as an air drier, are required for these methods.
  • the prepared catalyst provides lower catalytic activity and the obtained polymer contains very large particles, which makes the melting procedure of the polymer more difficult.
  • the catalyst is usually prepared by providing silica gel having a large particle size with active components (Ti and Mg) . Because the shape of the catalyst completely depends on the particle shape of the silica gel carrier, catalyst performance also depends on the particle size and the microporous structure of silica gel used to prepare the catalyst .
  • the average particle size of the silica gel used is generally 40 ⁇ m to 80 ⁇ m.
  • An LLDPE film-type resin made by this catalyst can provide excellent processing and mechanical properties.
  • ethylene polymerization activity of this catalyst is generally about 3500 g PE/g cat.
  • the activity will significantly lower due to a reduction of the residence time of the catalyst, in case it is used for the condensation technology of the gas-phase fluidized bed, which consequently increases the ash content of the obtained ethylene polymer, which affects its performance .
  • improving the catalytic activity of this kind of catalyst is one of the critical factors for enhancing the quality of an ethylene polymer produced by such a catalyst.
  • the form and particle size distribution of polymer particles are the major factors of affecting the stable operation of a gas-phase fluidized bed device.
  • excellent polymer particle morphology, particle size distribution and less content of fine powders is the target for this kind of catalyst.
  • fumed SiO 2 is used as the filler and mixed with a mixture obtained by reacting a titanium compound, a magnesium compound and an electron donor compound according to US 4,376,062 and CN 1,493,599 A.
  • the catalyst can be obtained by a spray drying method.
  • the particle size and morphology of the obtained catalyst can be easily controlled, while the catalyst efficiency is also improved to some extent.
  • the catalytic activity of the catalyst and the shape of the polymerization product are still unsatisfactory.
  • the purpose of the present invention is to overcome the above disadvantages of the current technical methods and provide a catalyst for ethylene polymerization and copolymerization, in particular for ethylene gas-phase polymerization using a fluidized bed in a condensation state or a super-condensation state, with high catalytic activity and good hydrogen response behavior for ethylene polymerization and copolymerization, which can produce a polymer with high bulk density, narrow particle size distribution and less fine particles.
  • the present invention provides in one aspect a method for preparing a titanium catalyst component, comprising the steps of:
  • the step of reacting a magnesium halide with a solvent in the method for preparing a titanium catalyst component according to the present invention is generally carried out at a reaction temperature of at least -25 0 C, preferably at a reaction temperature of -10 0 C to 200 0 C and more preferably at a reaction temperature of 0 0 C to 150 0 C.
  • the reaction time in this step is in general 15 min to 5 h, preferably 30 min to 4 h.
  • the magnesium halide is selected from the group consisting of magnesium dihalides, alkyl magnesium halides, alkoxy magnesium halides and aryloxy magnesium halides.
  • examples for the magnesium dihalides include MgCl 2 , MgBr 2 , MgF 2 and MgI 2 .
  • the alkyl magnesium halides include methyl magnesium halide, ethyl magnesium halide, propyl magnesium halide, butyl magnesium halide, isobutyl magnesium halide, hexyl magnesium halide and amyl magnesium halide .
  • the alkoxy magnesium halides include methoxy magnesium halide, ethoxy magnesium halide, isopropoxy magnesium halide, butoxy magnesium halide and octyl magnesium halide.
  • the aryloxy magnesium halides include phenoxy magnesium halide and methyl phenoxy magnesium halide. These magnesium halides can be used independently or two or more magnesium halides may be used in combination.
  • magnesium-containing metallic coordination compounds can be effectively used with magnesium-containing metallic coordination compounds.
  • the following compounds can be used as magnesium-containing metallic coordination compounds: compounds obtained through reaction between a magnesium compound and a polysiloxane, including silane compounds of halogen, ether or alcohol; compounds obtained through the reaction between metallic magnesium and alcohol, phenol or ether in the presence of a halogenated silane, PCl 5 or thionyl chloride .
  • Said magnesium compound can be a magnesium halide, in particular MgCl 2 , or an alkyl magnesium chloride containing 1 to 10 carbon atoms, an alkoxy magnesium chloride containing 1 to 10 carbon atoms and an aryloxy magnesium chloride containing 6 to 20 carbon atoms.
  • the organic boron compound is an organic boron compound without active hydrogen, in particular an organic boron compound having the general formula
  • R 1 and R 2 are independently a Ci-C 10 alkyl group, a Ci-Cio alkoxy group, a C 5 -C 10 aryl group or halogen,
  • R 3 is a Ci-Cio alkyl group, preferably a Ci to Ce alkyl group, an aryloxy group
  • Preferred boron compounds represented by the above general formula include at least one of methyldibutylborate, trimethylborate, triethylborate, tripropylborate, tributylborate, trioctylborate, phenyldiethylborate, triphenylborate, trimethylborane, triethylborane, methyl diethylborane, diethoxy methylborane, diethoxy ethylborane, dibutoxy ethylborane, dibutoxy butylborane, diphenoxy phenylborane, ethoxy diethylborane, ethoxy dibutylborane, phenoxy diphenylborane, chloro diethoxyborane, bromo diethoxyborane, chloro diphenoxyborane, dichloro ethoxyborane, dibromo ethoxyborane, dichloro butoxyborane
  • the organic boron compound is selected from at least one of methyldibutylborate, trimethylborate, triethylborate, tripropylborate, tributylborate, trioctylborate, phenyl diethylborate and triphenylborate .
  • the titanium compound has the general formula
  • R is an aliphatic Ci-Cio alkyl, preferably a Ci-C 4 alkyl group or a C 5 -Ci 0 aryl group, X is F, Cl, Br or I, a is 0, 1, 2 or 3, b is an integer of 1 to 4, and a + b is 3 or 4.
  • the titanium compound is selected from the group consisting of TiCl 3 , TiCl 4 , TiBr 4 , TiI 4 , Ti(OC 3 H 7 )Cl 3 and Ti(OC 4 Hg) 2 Cl 2 -
  • the homogeneous magnesium halide solution (magnesium-containing solution) is prepared by reacting said magnesium halide with a solvent including an alcohol.
  • the alcohol used to prepare the magnesium-containing solution includes those containing 1 to 20 carbon atoms and halogenated derivatives thereof, such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, 2-methyl pentanol, 2-ethyl hexanol, heptanol, 2-ethyl heptanol, octanol, decanol, dodecanol, octadecanol, benzenecarbinol, phenylethanol, isopropyl benzenecarbinol and cumic alcohol.
  • the alcohol is preferably selected from alcohols containing 1 to 12 carbon atoms .
  • the alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, 2-methyl pentanol, 2-ethyl hexanol, heptanol, 2-ethyl heptanol, octanol and decanol or a mixture of two or more thereof.
  • the solvent further includes a hydrocarbon solvent.
  • the hydrocarbon solvent is selected from the group consisting of aliphatic hydrocarbon H
  • solvents alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents and halogenated hydrocarbon solvents.
  • Examples for an aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, decane and kerosene.
  • Alicyclic hydrocarbon solvents include cyclobenzene, methyl cyclobenzene, cyclohexane and methyl cyclohexane.
  • Aromatic hydrocarbon solvents include benzene, toluene, xylene and ethylbenzene .
  • Halogenated hydrocarbon solvents include dichloropropane, dichloroethylene, trichloroethylene, CCI 4 and chlorobenzene .
  • the average particle size and the particle size distribution of the obtained catalyst depend on the type and amount of alcohol, the type of the magnesium halide and the ratio of magnesium halide/alcohol .
  • the shape and size of the precipitated component of the solid titanium catalyst component mainly depend on the reaction conditions .
  • the reaction with the titanium compound can be conducted once or several times .
  • the solid titanium catalyst component may be obtained through a reaction between said magnesium halide solution, the titanium compound and the organic boron compound at a low temperature.
  • the initial temperature thereof is set preferably to -70 0 C to 70 °C, more preferably to -50 °C to 50 0 C.
  • the temperature is slowly raised and maintained for 0.5 h to 5 h at 50 0 C to 150 0 C to provide a continuous and complete reaction.
  • the organic boron compound is added to the homogeneous solution before adding the titanium compound, or the organic boron compound is added to the homogeneous solution after adding the titanium compound.
  • an inorganic carrier is added together with the organic boron compound.
  • a spherical titanium catalyst component which can provide a spherical titanium catalyst with a high activity, which is in particular suitable for gas-phase polymerization of ethylene .
  • the inorganic carrier Before using the inorganic carrier in the method for preparing a titanium catalyst component according to the present invention, it is preferred to subject the inorganic carrier to a baking dehydration treatment or to an activating treatment by an alkylation.
  • the inorganic carrier is selected from the group consisting of SiO 2 , Al 2 O 3 and mixtures thereof.
  • the inorganic carrier has a spherical shape and a particle size of 0.1 ⁇ m to 150 ⁇ m.
  • the inorganic carrier is SiO 2 having a specific surface area of 80 m 2 /g to 300 m 2 /g.
  • the inorganic carrier is SiO 2 having a specific surface area of 80 m 2 /g to 300 m 2 /g, the loading amount of magnesium in the catalyst can be improved and therefore the loading amount of the catalytically active component for the catalyst can be improved. Furthermore, the use of this specific inorganic carrier prevents an irregular aggregation of MgCl 2 in the catalyst at a high Mg content and a resulting non-spherical shape of the corresponding catalyst particles.
  • 0.1 mol to 10.0 mol of the alcohol, 0.05 mol to 1.0 mol of the organic boron compound and 1.0 to 15.0 mol of the titanium compound are used based on 1 mol of the magnesium halide.
  • an inorganic carrier is used in the method for preparing a titanium catalyst component, 0.1 mol to 10.0 mol of the alcohol, 0.05 mol to 1.0 mol of the organic boron compound, 50 to 500 g of the inorganic carrier and 1.0 to 15.0 mol of the titanium compound are used based on 1 mol of the magnesium halide.
  • the present invention provides a titanium catalyst component, obtainable by the method for preparing a titanium catalyst component according to the present invention .
  • the present titanium catalyst component is used as a basis for a corresponding titanium catalyst, it can provide a titanium catalyst having high catalytic activity to produce a polymer with a high bulk density, narrow particle size distribution and less fine particles in case the titanium catalyst is used for ethylene polymerization and copolymerization.
  • the titanium catalyst component according to the present invention In order to be used for ethylene polymerization and copolymerization the titanium catalyst component according to the present invention must be activated, which means that it must be treated with sufficient activator compound to transform the Ti atoms in the titanium catalyst component to an active state, such that a titanium catalyst is obtained.
  • the present invention provides a method for preparing a titanium catalyst, comprising:
  • R is hydrogen or a Ci-C 2O alkyl group, preferably a Ci -Ce alkyl group
  • X is F, Cl, Br or I
  • the organic aluminum compound is selected from the group consisting of trialkyl aluminum compounds, dialkyl halogen aluminum compounds, and alkyldihalogen aluminum compounds, wherein each alkyl group contains 1 to 6 carbon atoms, like for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, isopentyl, hexyl and cyclohexyl.
  • the organic aluminum compound is selected from the group consisting of triethyl aluminum, triisobutyl aluminum, ethyl aluminum dichloride, diethyl aluminum chloride, ethyl aluminum sesquichloride and hydrogenated diisobutyl aluminum.
  • a pre-polymerization can be carried out with said titanium catalyst component and ethylene or an ⁇ -olefin.
  • This pre-polymerization can be conducted at a low temperature in the presence of a hydrocarbon solvent (such as hexane) , the above titanium catalyst component, said organic aluminum compound (such as triethyl aluminum) and ethylene or an ⁇ -olefin at an appropriate pressure.
  • a hydrocarbon solvent such as hexane
  • said organic aluminum compound such as triethyl aluminum
  • the present invention provides a titanium catalyst, obtainable by the method for preparing a titanium catalyst according to the present invention.
  • the molar ratio between the organic aluminum compound and the solid titanium catalyst component is in a range of 10 to 1000, preferably in a range of 20 to 200.
  • the present invention provides the use of a catalyst according to the present invention for ethylene polymerization and copolymerization .
  • the catalyst according to the present invention can be used for homopolymerization of ethylene or copolymerization of ethylene with other ⁇ -olefins, like for example propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-l-pentene .
  • a gas-phase method, a slurry method and a solution method may be used in the polymerization process.
  • the polymerization using a titanium catalyst according to the present invention should be conducted at a suitable temperature.
  • the polymerization temperature is 20 0 C to 200 0 C, preferably 60 0 C to 95 0 C.
  • the pressure of the monomer is preferably 1 atm to 100 atm, more preferably 2 atm to 50 atm.
  • the first embodiment of the present invention illustrated by examples 1 to 10 relates to the preparation of a titanium catalyst component using a magnesium halide, an organic boron compound and a titanium compound, and to a polymerization using the corresponding titanium catalyst obtained from said titanium catalyst component.
  • Example 2 After replacing the air in a 2 1 stainless reaction vessel by high-purity N 2 , the vessel is charged with 1 1 hexane and 1.0 ml triethyl aluminum (1 M), and a suitable amount of the above prepared titanium catalyst component is added to the vessel using a syringe. The contents of the vessel are heated to 75 0 C and H 2 is fed into the vessel such that the pressure in the vessel reaches 0.28 MPa. Then ethylene is fed into the vessel such that the total pressure in the vessel reaches 0.73 MPa (gauge pressure) and a polymerization is carried out for 2 h at 8O 0 C. The results of the polymerization are shown in Table 1.
  • Example 2 Example 2
  • Example 3 After replacing the air in a 2 1 stainless reaction vessel by high-purity N 2 , the vessel is charged with 1 1 hexane and 1.0 ml triethyl aluminum (1 M), and a suitable amount of the above prepared titanium catalyst component is added to the vessel using a syringe. The contents of the vessel are heated to 75 0 C and H 2 is fed into the vessel such that the pressure in the vessel reaches 0.28 MPa. Then ethylene is fed into the vessel such that the total pressure in the vessel reaches 0.73 MPa (gauge pressure) and a polymerization is carried out for 2 h at 80 0 C. The results of the polymerization are shown in Table 1.
  • Example 3 Example 3
  • Example 3 is carried out in the same manner as Example 1, except that the addition amount of tributylborate is 20 mitiol.
  • the results of the polymerization are shown in Table 1.
  • Example 4 is carried out in the same manner as Example 1, except that the addition amount of tributylborate is 10 mmol.
  • the results of the polymerization are shown in Table 1.
  • Example 5 is carried out in the same manner as Example 1, except that the addition amount of decane is 50 ml. The results of the polymerization are shown in Table 1.
  • the vessel After replacing the air in a 2 1 stainless reaction vessel by high-purity N 2 , the vessel is charged with 1 1 hexane and 1.0 ml triethyl aluminum (1 M), and a suitable amount of the above prepared titanium catalyst component is added to the vessel using a syringe. The contents of the vessel are heated to 75 0 C and H 2 is fed into the vessel such that the pressure in the vessel reaches 0.28 MPa. Then ethylene is fed into the vessel such that the total pressure in the vessel reaches 0.73 MPa (gauge pressure) and a polymerization is carried out for 2 h at 80 0 C. The results of the polymerization are shown in Table 1.
  • the obtained homogeneous solution is then cooled to room temperature.
  • the solution is dripped into 150 ml TiCl 4 (the temperature is maintained at 0 °C) during 1 h and the temperature of the mixture is maintained at 0 0 C for 1 h after dripping. After that the mixture is heated to 120 °C for 2 h and the temperature is maintained for 2 h.
  • the obtained solids are separated by heat filtration and the residue is washed with hexane and decane until no precipitated titanium compound is detected in the washing liquid. After drying, a solid titanium catalyst component is obtained.
  • the vessel After replacing the air in a 2 1 stainless reaction vessel by high-purity N 2 , the vessel is charged with 1 1 hexane and 1.0 ml triethyl aluminum (1 M), and a suitable amount of the above prepared titanium catalyst component is added to the vessel using a syringe. The contents of the vessel are heated to 75 0 C and H 2 is fed into the vessel such that the pressure in the vessel reaches 0.28 MPa. Then ethylene is fed into the vessel such that the total pressure in the vessel reaches 0.73 MPa (gauge pressure) and a polymerization is carried out for 2 h at 80 0 C. The results of the polymerization are shown in Table 1.
  • Example 8 is carried out in the same manner as Example 1, except that the added boron compound is isopropyldibutylborate .
  • the results of the polymerization are shown in Table 1.
  • Example 9 is carried out in the same manner as Example 1, except that the added boron compound is triethylborate .
  • the results of the polymerization are shown in Table 1.
  • the ethylene polymerization is carried out in the same manner as in example 1.
  • the results of the polymerization are shown in Table 1.
  • the titanium catalyst according to the present invention prepared from the titanium catalyst component according to the present invention can provide a polyethylene having a high bulk density, narrow particle size distribution and less fine particles.
  • the second embodiment of the present invention illustrated by examples 11 to 18 and a comparative example relates to the preparation of a titanium catalyst component using a magnesium halide, an organic boron compound, an inorganic carrier and a titanium compound, and to a polymerization using the corresponding titanium catalyst obtained from said titanium catalyst component.
  • a 2 1 reaction vessel is heated to 80 0 C and the air in the vessel is replaced by dry N 2 and H 2 is blown into the vessel.
  • the vessel is then charged with 1 1 hexane and 1.0 ml triethyl aluminum (1 M) , and a suitable amount of the above prepared titanium catalyst component using a syringe.
  • the contents of the vessel are heated to 75 0 C and H 2 is fed into the vessel such that the pressure in the vessel reaches 0.28 MPa.
  • ethylene is fed into the vessel such that the total pressure in the vessel reaches 1.03 MPa (gauge pressure) and a polymerization is carried out for 2 h at 80 0 C.
  • the results of the polymerization are shown in Table 2.
  • the ethylene polymerization is carried out in the same manner as in example 11.
  • the results of the polymerization are shown in Table 2.
  • Example 14 is carried out in the same manner as Example 11, except that the organic boron compound is replaced by 15 mmol phenyldiethylborate .
  • the ethylene polymerization is carried out in the same manner as in example 11.
  • the results of the polymerization are shown in Table 2.
  • Example 15 is carried out in the same manner as Example 11, except that the organic boron compound is replaced by 15 mmol tributylborate .
  • the ethylene polymerization is carried out in the same manner as in example 11.
  • the results of the polymerization are shown in Table 2.
  • a quantity of the obtained titanium catalyst component is weighed and 60 ml hexane are added to disperse the titanium catalyst component.
  • a precomplexing of the titanium catalyst component is carried out by adding AlEt 2 Cl such that the Ti:Al ratio (mol:mol) is 10 and reacting the mixture for 0.5 h.
  • a 2 1 reaction vessel is heated to 80 0 C and the air in the vessel is replaced by dry N 2 and H 2 is blown into the vessel.
  • the vessel is then charged with 1 1 hexane and 1.0 ml triethyl aluminum (1 M) , and 30 mg of the above prepared titanium catalyst subject to precomplexing.
  • the contents of the vessel are heated to 75 0 C and H 2 is fed into the vessel such that the pressure in the vessel reaches 0.28 MPa.
  • ethylene is fed into the vessel such that the total pressure in the vessel reaches 1.03 MPa (gauge pressure) and a polymerization is carried out for 2 h at 80 0 C.
  • the results of the polymerization are shown in Table 2.
  • Example 17 is carried out in the same manner as Example 16, except that the precomplexing is carried out at room temperature by adding AlEt 2 Cl such that the Ti:Al ratio (mol:mol) is 20.
  • the ethylene polymerization is carried out in the same manner as in example 16.
  • the results of the polymerization are shown in Table 2.
  • Example 18 is carried out in the same manner as Example 11, except that the amount of silica gel is 15 g.
  • the ethylene polymerization is carried out in the same manner as in example 11.
  • the results of the polymerization are shown in Table 2.
  • the contents of the flask are heated to 65 0 C under agitation, reacted for 2 h at 65 0 C and after that the reaction mixture is cooled to 30 0 C.
  • the solid titanium catalyst component obtained after spray drying had a content of Ti, Mg and THF of 2.41 %, 6.19 % and 33 %, respectively.
  • Mineral oil is added to the titanium catalyst component, such that a mineral oil solution with a solid content of 30 % is obtained.
  • AlEt 2 Cl is added to the mineral oil solution and reacted with the titanium catalyst component for 20 min, whereupon Al (CeHi 3 ) 3 is added.
  • AlEt 2 Cl and Al (CeHi 3 ) 3 are added such that the molar ratio of THF: AlEt 2 Cl : Al (C 6 Hi 3 ) 3 is 1:0.5:0.2.
  • a 2 1 reaction vessel is heated to 80 °C and the air in the vessel is replaced by dry N 2 and H 2 is blown into the vessel.
  • the vessel is then simultaneously charged with 1 1 hexane, 1.0 ml triethyl aluminum (IM), and 30 mg of the above prepared titanium catalyst .
  • the contents of the vessel are heated to 75 0 C and H 2 is fed into the vessel such that the pressure in the vessel reaches 0.28 MPa.
  • ethylene is fed into the vessel such that the total pressure in the vessel reaches 1.03 MPa (gauge pressure) and a polymerization is carried out for 2 h at 80 0 C.
  • the results of the polymerization are shown in Table 2.
  • the titanium catalyst according to the present invention prepared from the titanium catalyst component according to the present invention can provide a polyethylene having a high bulk density, a very narrow particle size distribution and a very low amount of fine particles, which is particularly suitable for ethylene gas-phase polymerization using a fluidized bed in a condensation state or a super-condensation state.

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Abstract

La présente invention porte sur un procédé de fabrication d'un composant de catalyseur au titane, comprenant les étapes consistant à : faire réagir un halogénure de magnésium dans un solvant comprenant un alcool pour obtenir une solution homogène, faire réagir au moins un composé organique du bore avec la solution homogène, faire réagir un composé du titane avec la solution homogène. L'invention porte également sur un composant de catalyseur au titane pouvant être obtenu par ledit procédé, sur un procédé de fabrication d'un catalyseur au titane et sur un catalyseur au titane pouvant être obtenu par ledit procédé.
PCT/EP2009/002566 2008-04-07 2009-04-07 Procédé de fabrication d'un composant de catalyseur au titane, composant de catalyseur au titane, procédé de fabrication d'un catalyseur au titane et catalyseur au titane WO2009124722A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2009801146559A CN102272172A (zh) 2008-04-07 2009-04-07 一种钛催化剂组分的制备方法及其钛催化剂组分，和一种钛催化剂的制备方法及其钛催化剂
DE112009000794T DE112009000794T5 (de) 2008-04-07 2009-04-07 Verfahren zur Herstellung einer Titankatalysatorkomponente, eine Titankatalysatorkomponente, ein Verfahren zur Herstellung eines Titankatalysators und ein Titankatalysator

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN200810088913.8 2008-04-07
CNA2008100889138A CN101245115A (zh) 2008-04-07 2008-04-07 一种乙烯均聚合与共聚合催化剂及其制备方法
CNA2008100943490A CN101260166A (zh) 2008-04-29 2008-04-29 一种乙烯均聚合与共聚合催化剂及其制备方法
CN200810094349.0 2008-04-29

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US11325928B2 (en) 2017-12-05 2022-05-10 Univation Technologies, Llc Modified spray-dried Ziegler-Natta (pro)catalyst systems
CN116023571A (zh) * 2021-10-25 2023-04-28 中国石油化工股份有限公司 一种人造草用聚乙烯和人造草专用料及其制备方法和应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104829758B (zh) * 2015-05-17 2017-03-08 北京化工大学 烯烃聚合催化剂及制备方法与应用
CN107446070A (zh) * 2017-08-29 2017-12-08 营口风光新材料股份有限公司 一种用于烯烃聚合催化剂的载体、制备方法及其应用
CN114539449A (zh) * 2020-11-24 2022-05-27 中国石油天然气股份有限公司 用于乙烯聚合的钛催化剂组分及其制备方法与应用
CN114573739B (zh) * 2020-12-02 2023-12-22 中国石油天然气股份有限公司 固体钛催化剂

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2044783A (en) * 1978-12-28 1980-10-22 Mitsubishi Petrochemical Co Polymerisation of olefines using supported catalysts
GB2101609A (en) * 1981-07-14 1983-01-19 Ici Plc Catalyst composition, production and use
US5141910A (en) * 1990-10-18 1992-08-25 Shell Oil Company Olefin polymerization catalyst
WO2003000747A1 (fr) * 2001-06-21 2003-01-03 Samsung General Chemicals Co., Ltd. Catalyseur pour la polymerisation et copolymerisation d'ethylene
US20040242409A1 (en) * 1999-05-27 2004-12-02 Samsung General Chemicals Co., Ltd. Method of producing a catalyst for ethylene homo-and co-polymerization
CN101260166A (zh) * 2008-04-29 2008-09-10 郭琦 一种乙烯均聚合与共聚合催化剂及其制备方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA920299A (en) 1968-08-01 1973-01-30 Mitsui Petrochemical Industries Process for the polymerization and/or copolymerization of olefins with use of ziegler-type catalytsts supported on carrier
NL160286C (fr) 1971-06-25
US3953414A (en) 1972-09-13 1976-04-27 Montecatini Edison S.P.A., Catalysts for the polymerization of olefins to spherically shaped polymers
IT1042667B (it) 1975-09-18 1980-01-30 Montedison Spa Catalizzatori per la polimerizzazione di olefine a polimeri in forma seroidale
US4302565A (en) 1978-03-31 1981-11-24 Union Carbide Corporation Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization
JPS56811A (en) 1979-06-18 1981-01-07 Mitsui Petrochem Ind Ltd Preparation of olefin polymer or copolymer
US4376062A (en) 1979-11-28 1983-03-08 Union Carbide Corporation Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization
US4311414A (en) 1980-02-29 1982-01-19 Halliburton Company Pile wiper seal
US4518706A (en) 1982-09-30 1985-05-21 E. I. Du Pont De Nemours And Company Hydrocarbon soluble catalyst supports and resultant polymerization catalysts
US4477639A (en) 1983-05-27 1984-10-16 Shell Oil Company Olefin polymerization catalyst component and composition and method of preparation
IT1241062B (it) 1990-01-10 1993-12-29 Himont Inc Componenti e catalizzatori per la polimerizzazione di olefine
CN1213082C (zh) 2002-10-31 2005-08-03 中国石油化工股份有限公司 用于乙烯聚合的催化剂
CN101245115A (zh) * 2008-04-07 2008-08-20 郭琦 一种乙烯均聚合与共聚合催化剂及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2044783A (en) * 1978-12-28 1980-10-22 Mitsubishi Petrochemical Co Polymerisation of olefines using supported catalysts
GB2101609A (en) * 1981-07-14 1983-01-19 Ici Plc Catalyst composition, production and use
US5141910A (en) * 1990-10-18 1992-08-25 Shell Oil Company Olefin polymerization catalyst
US20040242409A1 (en) * 1999-05-27 2004-12-02 Samsung General Chemicals Co., Ltd. Method of producing a catalyst for ethylene homo-and co-polymerization
WO2003000747A1 (fr) * 2001-06-21 2003-01-03 Samsung General Chemicals Co., Ltd. Catalyseur pour la polymerisation et copolymerisation d'ethylene
CN101260166A (zh) * 2008-04-29 2008-09-10 郭琦 一种乙烯均聚合与共聚合催化剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; GUO, QI ET AL GUO, QI ET AL: "Method for preparation of catalyst for homopolymerization and copolymerization of ethylene Method for preparation of catalyst for homopolymerization and copolymerization of ethylene", XP002539940, retrieved from STN Database accession no. 2008:1109766 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019112927A1 (fr) * 2017-12-05 2019-06-13 Univation Technologies, Llc Système de catalyseur ziegler-natta séché par pulvérisation activé
US11325928B2 (en) 2017-12-05 2022-05-10 Univation Technologies, Llc Modified spray-dried Ziegler-Natta (pro)catalyst systems
US11325927B2 (en) 2017-12-05 2022-05-10 Univation Technologies, Llc Activated spray-dried Ziegler-Natta catalyst system
CN116023571A (zh) * 2021-10-25 2023-04-28 中国石油化工股份有限公司 一种人造草用聚乙烯和人造草专用料及其制备方法和应用

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