WO2002038619A1 - Method for producing a catalyst for homo- or co- polymerization of ethylene - Google Patents
Method for producing a catalyst for homo- or co- polymerization of ethylene Download PDFInfo
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- WO2002038619A1 WO2002038619A1 PCT/KR2001/001904 KR0101904W WO0238619A1 WO 2002038619 A1 WO2002038619 A1 WO 2002038619A1 KR 0101904 W KR0101904 W KR 0101904W WO 0238619 A1 WO0238619 A1 WO 0238619A1
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- hydroxy
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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
- C08F4/61—Pretreating the metal or compound covered by group C08F4/60 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/612—Pretreating with metals or metal-containing compounds
- C08F4/616—Pretreating with metals or metal-containing compounds with silicon 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 provides a method for producing a catalyst for homo-polymerization or co-polymerization of ethylene, or more particularly a method for producing a high-activity titanium solid complex catalyst supported on a carrier containing magnesium, wherein said catalyst is capable of producing polymers of high bulk density and narrow particle size distribution with low content of fine particles.
- Catalysts containing magnesium for polymerization or co-polymerization of ethylene are known to have very high catalytic activities and to accord polymers of high bulk density, which are suitable for liquid phase or gas phase polymerization.
- liquid phase polymerization of ethylene it denotes a polymerization process performed in a medium such as bulk ethylene, isopentane, or hexane, and as for the important characteristics of catalysts used in this process, there are as follows: high catalytic activity, bulk density of the resultant polymers, the content of low molecular weight molecules of the resultant polymers dissolved in a medium, the particle distribution of the resultant polymers, and the existence of fine particles within the resultant polymers.
- US Patent No. 5,459,116 has reported a method of production of a titanium solid catalyst by contact-reacting a magnesium solution containing an ester having at least one hydroxyl group as an electron donor with a titanium compound. By this method, it is possible to obtain a catalyst of high polymerization activity, which accords high bulk density to resultant polymers, but there is room for yet more improvements.
- Another objective of the present invention is to provide a simple process for producing a catalyst for homo-polymerization or co-polymerization of ethylene.
- the catalyst for homo-polymerization or co-polymerization of ethylene according to the present invention is produced by a simple yet efficient manufacturing process, which comprises (i) preparing a magnesium solution by contact-reacting a halogenated magnesium compound with alcohol, and adding mineral oil to adjust the viscosity of said magnesium solution; (ii) reacting said solution with an ester compound having at least one hydroxyl group and a silicon compound having at least one alkoxy group; and ( ⁇ i) producing a solid titanium catalyst by adding a mixture of a titanium compound and a silicon compound.
- Types of halogenated magnesium compounds used in the present invention are as follows: di-halogenated magnesiums such as magnesium chloride, magnesium iodide, magnesium fluoride, and magnesium bromide; alkymagnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide, and amylmagnesium halide; alkoxymagnesium halides such as methoxymagnesium halide, ethoxymagensium halide, isopropoxymagnesium halide, butoxymagnesium halide, octoxymagnesium halide; and aryloxymagnesium halides such as phenoxymagnesium halide and methyl-phenoxymagnesium halide.
- di-halogenated magnesiums such as magnesium chloride, magnesium io
- the following compounds can be used in the present invention: such compounds obtained by reacting magnesium compounds with polysilolxane compounds, silane compounds containing halogen, ester, or alcohol; and such compounds obtained by reacting magnesium metals with alcohol, phenol, or ether in the presence of halosilane, phosphorus pentachloride, or thionyl chloride.
- the preferable magnesium compounds are magnesium halides, especially magnesium chloride or alkylmagnesium chloride, preferably those having respectively an alkyl group of 1 ⁇ 10 carbons; alkoxymagnesium chlorides, preferably those having respectively 1 - 10 carbons; and aryloxymagnesium chlorides, preferably those having respectively 6 - 20 carbons.
- the magnesium solution used in the present invention can be produced as solution by using the aforementioned magnesium compounds in the presence a hydrocarbon solvent or in the absence thereof, in an alcohol solvent.
- hydrocarbon solvents used in the present invention include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene; alicyclic hydrocarbons such as cyclobenzene, methylcyclobenzene, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and cymene; and halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloroethylene, carbon tetrachloride, and chlorobenzene.
- aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene
- alicyclic hydrocarbons such as cyclobenzene, methylcyclobenzene,
- the average size of a target catalyst and its particle distribution can vary according to the types of alcohol, the total contents, the types of magnesium compounds, and the ratio of magnesium to alcohol, etc. Nevertheless, the total amount of alcohol required to obtain the magnesium solution is at least 0.5 mol per each mole of magnesium compounds, preferably about 1.0 - 20 mol, or more preferably about 2.0 - 10 mol.
- the reaction of a magnesium compound with alcohol is preferably carried out in the presence of a hydrocarbon medium.
- the reaction temperature while variable depending on the types and the amount of alcohol, is at least about - 25°C, preferably -10 - 200°C, or more preferably about 0 - 150°C. It is preferable to carry out the reaction for about 15 minutes - 5 hours, preferably for about 30 minutes - 4 hours.
- mineral oil white oil, p-irafinic hydrocarbon oil (e.g., Nujol), or silicone oil can be used.
- the viscosity of mineral oil used in the present invention is 5-85 centistoke at 40°C, or preferably 60-75 centistoke.
- the ester compounds respectively having at least one hydroxyl group include unsaturated aliphatic acid esters respectively having at least one hydroxyl group, such as 2-hydroxy ethylaciylate, 2-hydroxy ethylmethacrylate, 2- hydroxypropyl acrylate, 2-hydroxypropylmethacrylate, 4-hydroxy butylacrylate, pentae--ythritol tiiacrylate; aliphatic monoesters or polyesters respectively having at least one hydroxyl group, such as 2-hydroxy ethyl acetate, methyl 3-hydroxy butylate, ethyl 3-hydroxy butylate, methyl 2- hydroxy isobutylate, ethyl 2-hydroxy isobutylate, methyl-3-hydroxy-2-methyl propionate, 2,2- dimethyl-3-hydroxy propionate, ethyl-6-hydroxy hexanoate, t-butyl-2-hydroxy isobutylate, diethyl-3-hydroxy glutarate
- the following compounds can be used: dimethyldj-methoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenylmethoxysilane, diphenyldiethoxysilane, ethylt-rimethoxysilane, vinyl-rimethoxysilane, memyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethylsilicate, butylsilicate, methyltriaryloxysilane, etc.
- the amount of said compound is preferably 0.05 ⁇ 3mol per mole of magnesium, or more preferably 0.1 ⁇ 2mol.
- the temperature for the contact-reaction of the magnesium solution an ester compound having at least one hydroxyl group, and an alkoxy silicon compound
- the temperature of 0 - 100 ° C is appropriate, or more preferably 10 - 70 ° C.
- the magnesium compound solution obtained as such is reacted with a mixture of a liquid titanium compound represented by a general formula of Ti(OR) a 4 - a (here R is a hydrocarbon group, X a halogen atom, "a" a natural number from 0 to 4) and a compound represented by a general formula of R n SiC - n (here R is hydrogen, an alkyl group, an alkoxy, haloalkyl, or aryl group having 1—10 carbons, or halosilyl or a halosilylalkyl group having 1 ⁇ 8 carbons, and "n" a natural number from 0 to 3).
- R is an alkyl group having 1—10 carbon atoms.
- the types of titanium compounds which satisfy the general formula include 4-halogenated titanium such as TiC- , TiBr , and Til t ; 3-halogenated alkoxy-titanium such as Ti(OCH 3 )Cl 3 , Ti(OC 2 H 5 )Cl 3 , Ti(OC 2 H 5 )Br 3 , and Ti(O(i-C 4 H 9 ))Br 3 ; 2-halogenated alkoxy-titanium compounds such as Ti(OCH 3 ) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Cl 2 , Ti(O(i-G ⁇ H 9 )) 2 Cl 2 , and Ti(OC 2 H 5 ) 2 Br 2 ; and tetra-alkoxy titanium such as Ti(OCH 3 ) 4 , Ti(OC 2 H 5 ) 4 , and Ti(OG ⁇ H 9 ) 4 .
- a mixture of the above titanium compounds can also be used in the present invention.
- the preferable titanium compounds are those containing respectively
- n (here R is hydrogen, an alkyl group, an alkoxy, haloalkyl, or aryl group having 1-10 carbons, or halosilyl or a halosilylalkyl group having 1-8 carbons, and "n" a natural number from 0 to 3) include silicon tetrachloride; trichlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane; dichlorosilanes such as dimethyldichlorosilane, diethyldichlorosilane, di- phenyldichlorosilane, and methylphenyldichlorosilane; monochlorosilanes such as trimethylchlorosilane; and a mixture of these silicon compounds can also be used in the present invention, or more preferably silicon tet
- the amount of mixture of a titanium compound and a silicon compound used during re- crystallization of magnesium compound solution is appropriately 0.1 - 200 mol per mole of magnesium compounds, preferably 0.1 - 100 mol, or more preferably 0.2 - 80 mol.
- the molar ratio of the titanium compound to the silicon compound in mixture is appropriately 1 :0.05
- the reaction of the magnesium compound solution with the mixture of a titanium compound and a silicon compound should be carried out preferably at a sufficiently low temperature to result in formation of solid constituents. More preferably, the reaction should be carried out by contact- reaction at -70-70 °C, or most preferably at -50-50 °C. After the contact-reaction, the reacting temperature is slowly raised for sufficient reaction for the duration of 0.5 - 5 hours at 50 - 150°C.
- the catalyst produced according to the process of the present invention can be utilized for homo- or co-polymerization of ethylene.
- the catalyst is used in homo- polymerization of ethylene, and also in co-polymerization of ethylene and -olefin such as propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, or 1-hexene having three or more carbons.
- the polymerization reaction in the presence of a catalyst in the present invention is carried out by means of using (i) a solid complex titanium catalyst of the present invention, comprising magnesium, titanium, halogen, and an electron donor, and (ii) a catalyst system comprising compounds of organic metals of Groups II or HI of the Periodic Table.
- the solid complex titanium catalyst constituent can be used as a component in the polymerization reaction after pre-polymerization with ethylene or -olefin.
- the pre-polymerization can be carried out in the presence of a hydrocarbon solvent such as hexane, at a sufficiently low temperature, with ethylene or ⁇ -olefin under pressure, in the presence of the above catalyst constituent and such organic aluminium compound as triethyl--luminium.
- the pre-polymerization by maint--uning the shapes of catalysts by surrounding the catalyst particles with polymers, is helpful in producing good-quality post- polymerization shapes of polymers.
- the weight ratio of polymers to catalysts after pre- polymerization is ordinarily 0.1:1 - 20:1.
- the organometallic compound in the present invention can be represented by a general formula of MR n , wherein, M stands for a metal constituent of Group H or IDA. in the Periodic Table, such as magnesium, calcium, zinc, boron, aluminium, and gallium, R for an alkyl group with 1 - 20 carbons, such as a methyl, ethyl, butyl, hexyl, octyl, or decyl group, and n for the atomic valence of the metal constituent.
- M stands for a metal constituent of Group H or IDA. in the Periodic Table, such as magnesium, calcium, zinc, boron, aluminium, and gallium
- R for an alkyl group with 1 - 20 carbons, such as a methyl, ethyl, butyl, hexyl, octyl, or decyl group
- n for the atomic valence of the metal constituent.
- a trialkyl aluminium having an alkyl group of 1 - 6 carbons such as triethyl-durmnium and t-riisobutylaluminium, or the mixture thereof can be utilized.
- an organic aluminium compound having one or more halogen or hydride groups such as ethyl--iuminium dichloride, diethyl-duminium chloride, ethylaluminium -ye-sgr ⁇ chloride, or ⁇ -iisobuty uminium hydride can also be used.
- the polymerization reaction it is possible to carry out either the gas phase or bulk polymerization in the absence of an organic solvent, or the liquid slurry polymerization in the presence of an organic solvent. These polymerization methods, however, are carried out in the absence of oxygen, water, or other compounds that may act as catalytic poison.
- the concentration of the solid complex titanium catalyst (i) with respect to the polymerization reaction system, in case of liquid phase slurry polymerization, is approximately 0.001 ⁇ 5 mmol in terms of titanium atoms in catalyst per one liter of the solvent, or more preferably approximately 0.001 ⁇ 0.5 mmol.
- alkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, methylcyclohexane
- alkylaromatics such as toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene
- halogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene; and the mixtures thereof.
- the polymerization herein is carried out at a sufficiently high temperature, regardless of the polymerization process.
- the temperature of approximately 20 - 200 °C is appropriate, or more preferably approximately 20 - 95 °C.
- the appropriate pressure of monomers at the time of polymerization is the atmospheric to 100 atm, or more preferably 2 - 50 atm.
- melt index ASTM D 1238
- the value of the melt index generally becomes greater as the molecular weight decreases.
- the products obtained by the method of polymerization of the present invention are solid ethylene homo-polymers or the copolymers of ethylene and ⁇ -olefin, which have excellent bulk density and fluidity. Since the yields of polymer are sufficiently high, there is no need for the removal of catalyst residues.
- a solid complex titanium catalyst was produced by means of the following three steps: (i) Step : Production of magnesium solution
- the temperature of the reactor was lowered to room temperature, and an excessive amount of ethanol solution was added to the polymerized matters.
- the polymer thus produced was collected by separation and was dried in an oven at 50 °C for at least six hours, whereby polyethylene was obtained in the form of white powder.
- the polymerization activity (kg of polyethylene divided by gram of catalyst) was calculated as the weight (kg) ratio of the polymers as produced per the amount of catalysts so used (gram of catalyst).
- the results of polymerization are shown in Table 1, together with the bulk density (g ml) of the polymers, and the melt index (g 10 minutes).
- EXAMPLE 2 As in Step (i) of Example 1, 100ml of decane was used while producing magnesium solution under the same conditions. Then, 200ml of mineral oil was added thereto for adjusting the viscosity therein to produce catalysts as in Example 1. The titanium content of the catalyst thus produced was 5.2wt%. The polymerization was carried out as in Example 1, and the results thereof are shown in Table 1.
- Step (i) of Example 1 150ml of decane was used while producing magnesium solution under the same conditions. Then, 150ml of mineral oil was added thereto for adjusting the viscosity therein to produce catalysts as in Example 1. The titanium content of the catalyst thus produced was 4.8wt . The polymerization was carried out as in Example 1, and the results thereof are shown in Table 1.
- Step (i) of Example 1 200ml of decane with 100ml of mineral oil were used while producing magnesium solution under the same conditions, and thus the catalysts were produced as in Example 1.
- the titanium content of the catalyst thus produced was 5.1wt%.
- the polymerization was carried out as in Example 1, and the results thereof are shown in Table 1.
Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002541950A JP3950051B2 (en) | 2000-11-09 | 2001-11-09 | Method for producing ethylene polymerization or copolymerization catalyst |
US10/416,428 US6916759B2 (en) | 2000-11-09 | 2001-11-09 | Method for producing a catalyst for homo-or co-polymerization of ethylene |
EP01983847A EP1355952B1 (en) | 2000-11-09 | 2001-11-09 | Method for producing a catalyst for homo- or co- polymerization of ethylene |
AU2002215244A AU2002215244A1 (en) | 2000-11-09 | 2001-11-09 | Method for producing a catalyst for homo- or co- polymerization of ethylene |
DE60122581T DE60122581T2 (en) | 2000-11-09 | 2001-11-09 | PROCESS FOR PREPARING A CATALYST FOR THE HOMO OR COPOLYMERIZATION OF ETHYLENE |
Applications Claiming Priority (2)
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KR10-2000-0066411A KR100389475B1 (en) | 2000-11-09 | 2000-11-09 | Preparation method of catalyst for ethylene polymeration or copolymeration |
KR2000/0066411 | 2000-11-09 |
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WO2002038619A1 true WO2002038619A1 (en) | 2002-05-16 |
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PCT/KR2001/001904 WO2002038619A1 (en) | 2000-11-09 | 2001-11-09 | Method for producing a catalyst for homo- or co- polymerization of ethylene |
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US (2) | US6897274B2 (en) |
EP (1) | EP1355952B1 (en) |
JP (1) | JP3950051B2 (en) |
KR (1) | KR100389475B1 (en) |
CN (1) | CN1213075C (en) |
AT (1) | ATE337342T1 (en) |
AU (2) | AU2002212771A1 (en) |
DE (1) | DE60122581T2 (en) |
WO (1) | WO2002038619A1 (en) |
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KR100389475B1 (en) * | 2000-11-09 | 2003-06-27 | 삼성종합화학주식회사 | Preparation method of catalyst for ethylene polymeration or copolymeration |
US7153803B2 (en) | 2004-06-28 | 2006-12-26 | Engelhard Corporation | High activity and good hydrogen response Ziegler-Natta polyethylene catalyst |
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KR100389475B1 (en) * | 2000-11-09 | 2003-06-27 | 삼성종합화학주식회사 | Preparation method of catalyst for ethylene polymeration or copolymeration |
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US8536290B2 (en) | 2010-12-21 | 2013-09-17 | Dow Global Technologies Llc | Procatalyst composition with alkoxyalkyl 2-propenoate internal electron donor and polymer from same |
US20140046009A1 (en) * | 2010-12-21 | 2014-02-13 | Linfeng Chen | Procatalyst Composition with Alkoxyalkyl 2-Propenoate Internal Electron Donor and Polymer from Same |
US9315592B2 (en) | 2010-12-21 | 2016-04-19 | W. R. Grace & Co.-Conn. | Process for producing procatalyst composition with alkoxyalkyl ester internal electron donor and product |
US9382342B2 (en) | 2010-12-21 | 2016-07-05 | W. R. Grace & Co.-Conn. | Procatalyst composition with alkoxyalkyl 2-propenoate internal electron donor and polymer from same |
US9382343B2 (en) | 2010-12-21 | 2016-07-05 | W. R. Grace & Co.-Conn. | Procatalyst composition with alkoxypropyl ester internal electron donor and polymer from same |
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Also Published As
Publication number | Publication date |
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US6916759B2 (en) | 2005-07-12 |
KR100389475B1 (en) | 2003-06-27 |
ATE337342T1 (en) | 2006-09-15 |
EP1355952B1 (en) | 2006-08-23 |
KR20020036287A (en) | 2002-05-16 |
US6897274B2 (en) | 2005-05-24 |
AU2002212771A1 (en) | 2002-05-21 |
EP1355952A4 (en) | 2005-01-12 |
AU2002215244A1 (en) | 2002-05-21 |
US20040063571A1 (en) | 2004-04-01 |
CN1213075C (en) | 2005-08-03 |
US20040116278A1 (en) | 2004-06-17 |
JP3950051B2 (en) | 2007-07-25 |
CN1503810A (en) | 2004-06-09 |
JP2004513989A (en) | 2004-05-13 |
DE60122581D1 (en) | 2006-10-05 |
EP1355952A1 (en) | 2003-10-29 |
DE60122581T2 (en) | 2006-12-14 |
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