WO2011081404A2 - 폴리올레핀 중합용 촉매 및 이의 제조방법 - Google Patents
폴리올레핀 중합용 촉매 및 이의 제조방법 Download PDFInfo
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- WO2011081404A2 WO2011081404A2 PCT/KR2010/009418 KR2010009418W WO2011081404A2 WO 2011081404 A2 WO2011081404 A2 WO 2011081404A2 KR 2010009418 W KR2010009418 W KR 2010009418W WO 2011081404 A2 WO2011081404 A2 WO 2011081404A2
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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
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
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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
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Definitions
- the present invention relates to a method for producing a catalyst used to polymerize polyolefin, and more particularly to a method for producing a Ziegler-Natta type catalyst for polyolefin polymerization.
- Conventional polyolefin polymerization catalysts can be classified into Ziegler-Natta catalysts, chromium catalysts and metallocene catalysts according to the type of the central metal used. These catalysts are selectively used depending on the production process and the application product because the catalyst activity, the molecular weight distribution characteristics of the polymer and the reaction characteristics to the comonomers are different from each other.
- Ziegler-Natta type catalysts are the most used among the catalysts, and most of them are used in a magnesium chloride supported type.
- These magnesium chloride-supported Ziegler-Natta catalysts generally consist of solid catalyst components composed of magnesium, titanium, halogens, and electron-donating organic compounds, and are applied to various commercial processes such as slurry polymerization, bulk polymerization, and gas phase polymerization. In addition to the basic properties such as high activity and stereoregularity, appropriate particle morphology and size, uniform particle size distribution, and high apparent density of the polymer to be produced should be satisfied.
- the catalyst prepared by using a dialkoxy magnesium obtained by reacting magnesium with alcohol which is one of the methods using a chemical reaction, has a high activity and stereoregularity.
- the apparent density is rather low, resulting in inferior process stability and productivity.
- US Pat. No. 4,816,433 discloses a process for making a solid catalyst for olefin polymerization by using a dialkoxymagnesium single carrier and reacting titanium tetrachloride and an internal electron donor.
- this technique has a disadvantage that the apparent density of the polymerization product is less than 0.45g / ml lower productivity due to a lower production weight per unit volume of the reactor in a commercial process.
- US Pat. No. 5,028,671 discloses a process for producing a solid catalyst for producing spherical olefins obtained by reacting a spherical magnesium halide carrier containing alcohol prepared by spray drying with titanium tetrachloride and an internal electron donor.
- this technique also has a disadvantage in that it is not suitable as an environmentally friendly material of the future because of relatively high residual catalyst residues in the polymerization product of less than 30kg-PP / g-cat during the synthesis of polypropylene.
- the present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing a catalyst for polyolefin polymerization which can exhibit high activity and a catalyst for polyolefin polymerization produced thereby.
- Another object of the present invention is to provide a method for producing a polyolefin having a high apparent density by using the catalyst for polyolefin polymerization.
- the present invention comprises the steps of: a) dissolving the magnesium halide in the first alcohol and the first hydrocarbon to prepare a magnesium halide precursor solution; b) preparing a dialkoxy magnesium carrier by reacting a metal compound with a halogen compound and a second alcohol; And c) reacting the magnesium halide precursor solution and the dialkoxy magnesium carrier with titanium tetrachloride and an internal electron donor in the presence of a second hydrocarbon.
- the present invention uses the dialkoxy magnesium particles obtained by reacting a mixed precursor solution of a first alcohol and a first hydrocarbon in which magnesium halide is dissolved with a metal magnesium and a second alcohol in the presence of a halogen compound as a reaction initiator.
- a two-component carrier comprising a precursor solution and the dialkoxy magnesium particles is prepared, and titanium tetrachloride and an internal electron donor are reacted therein to prepare a catalyst for polyolefin polymerization.
- the magnesium halide precursor solution and the dialkoxy magnesium carrier are first reacted with titanium tetrachloride in the presence of a second hydrocarbon to obtain a solid product; And secondly reacting the solid product with titanium tetrachloride and an internal electron donor in the presence of a second hydrocarbon.
- the solid product is a two-component carrier, obtained by recrystallization (precipitating) magnesium halide on the surface of the dialkoxy magnesium carrier, and is a carrier in which two components of dialkoxy magnesium-magnesium halides are bonded.
- the present invention can be provided by the production method described above, it can provide a catalyst for polyolefin polymerization, characterized in that it comprises magnesium, titanium, internal electron donor and halogen atoms.
- the present invention can provide a method for producing a polyolefin using the catalyst for polyolefin polymerization prepared by the above-described production method.
- the magnesium halide precursor solution according to the present invention can be obtained by injecting a first alcohol and a predetermined amount of first hydrocarbon into a magnesium halide and then stirring it at a high temperature to homogeneously dissolve it.
- the magnesium halide that can be used is not particularly limited, but may be selected from the group consisting of magnesium chloride, magnesium fluoride, magnesium bromide, magnesium iodide, phenoxy magnesium chloride, isoproxy magnesium chloride, butoxy magnesium chloride as a compound having no reducing properties.
- Such a catalyst using magnesium chloride is easy to prepare a polymer (polyolefin) having a high apparent density.
- the 1st alcohol which can be used is not specifically limited, Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, neopentanol, cyclopentanol, n-hexane
- Aliphatic alcohols such as ol, n-heptanol, n-octanol, decanol, dodecanol, 2-methylpentanol, 2-ethylbutanol and 2-ethylhexanol
- Aliphatic alcohols represented by the formula R 1 OH such as cyclohexanol and methylcyclohexanol, wherein R 1 is an aliphatic hydrocarbon having 1 to 12 carbon atoms (specifically, an alkyl group);
- the mixing ratio is not particularly limited when two or more types of first alcohols are mixed and used, so that the first alcohols used in total are 1 to 6 moles, specifically 2 to 4 moles, based on 1 mole of magnesium halide. It is desirable to.
- the first hydrocarbon that can be used is not particularly limited.
- non-limiting examples of the aliphatic hydrocarbon having 6 to 20 carbon atoms include hexane, heptane, octane, decane, dodecane, tetradecane, mineral oil, cyclic hexane, cyclic octane, methyl cyclic pentane and methyl cyclic hexane.
- Etc. can be mentioned.
- first hydrocarbons selected from aliphatic hydrocarbons are preferably used alone or in combination, and the mixing ratio is not particularly limited when two or more kinds of first hydrocarbons are selected and mixed from aliphatic hydrocarbons.
- carbon number of the said aliphatic hydrocarbon is 6-20, Especially, it is good that it is 8-15. This is because when the carbon number of the aliphatic hydrocarbon is smaller than the above range, the boiling point of the first hydrocarbon solvent is low, and thus the reaction temperature is limited. .
- the amount of magnesium halide, first alcohol, and first hydrocarbon is used in an amount of 1 to 10 parts by weight of the first alcohol and 1 to 20 parts by weight of the first hydrocarbon based on 1 part by weight of the magnesium halide. It is desirable to. If the first alcohol is less than the above range, the magnesium halide is not dissolved well. If the first alcohol is more than the above range, recrystallization may not occur well during the synthesis of the catalyst. In addition, when the first hydrocarbon is less than the above range, the magnesium halide dissolved in the first alcohol is not dispersed well, so that during the synthesis of the catalyst, a two-component carrier is not formed and a magnesium halide alone carrier is formed. This is because the volume of the solution may increase, which may affect the concentration of all reactants in the synthesis of the catalyst.
- the reaction temperature (dissolution temperature) in which the magnesium halide and the first alcohol react in the presence of the first hydrocarbon is preferably 70 to 150 ° C. Specifically, the reaction temperature is 100 ° C or higher, and the upper limit of the reaction temperature is used with the first hydrocarbon used. It is preferable not to be higher than the boiling point of the first alcohol. In addition, it is preferable to install a stirrer in the reactor for the dispersion of the precursor solution to be prepared to ensure sufficient agitation.
- the dialkoxy magnesium carrier according to the present invention may be obtained in the form of particles by reacting a metal magnesium with a second alcohol in the presence of a halogen compound as a reaction initiator.
- the metal magnesium is preferably in the form of particles, the size of which is preferably 10 to 1000 ⁇ m, specifically 30 to 500 ⁇ m in powder form.
- halogen compound As the halogen compound as the reaction initiator, a halogen molecule, an alkyl halide compound, an acyl halide compound, or a metal halide compound may be used.
- Non-limiting examples include magnesium chloride, magnesium dichloride, magnesium fluoride, magnesium bromide, magnesium iodide, and phenoxy magnesium Chloride, isoproxy magnesium chloride or butoxy magnesium chloride.
- the halogen compound may be used in an amount of 0.01 to 10 parts by weight, specifically 0.1 to 5 parts by weight, based on 1 part by weight of the metal magnesium. If the halogen compound is less than the above range, the reaction rate is slow, and if it exceeds the above range, the particle size of the product may be too large or a large amount of fine particles may be produced.
- the second alcohol that can be used is not particularly limited, but methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, neopentanol, cyclopentanol, n-hexane
- Aliphatic alcohols represented by the formula R 3 OH such as allol and cyclohexanol, wherein R 3 is an aliphatic hydrocarbon having 1 to 6 carbon atoms (specifically, an alkyl group);
- R 4 OH is an aromatic hydrocarbon having 6 carbon atoms
- a mixing ratio is not specifically limited.
- Such second alcohol is preferably used 5 to 50 parts by weight, specifically 7 to 20 parts by weight based on 1 part by weight of the metal magnesium.
- the viscosity of the slurry that is, a mixture of the liquid second alcohol and the solid dialkoxymagnesium and unreacted metal magnesium
- the apparent density of the resulting carrier may be drastically reduced or the surface of the carrier particles may be roughened.
- the apparent density of the carrier is lowered, the apparent density of the catalyst is lowered, and thus, the apparent density of the finally produced polymer (polyolefin) may also be lowered. If the surface of the carrier particles is roughened, the polymerization reaction may occur. It can act as a factor that hinders process stability.
- the reaction temperature is preferably 25 ⁇ 110 °C, specifically 45 ⁇ 90 °C, if the reaction temperature is less than 25 °C reaction is too slow and exceeds 110 °C This is because the reaction may be so rapid that the fine particles may increase.
- the catalyst for polyolefin polymerization of the present invention can be prepared by reacting the prepared magnesium halide precursor solution and the dialkoxy magnesium carrier in the form of particles (spherical) with titanium tetrachloride and an internal electron donor in the presence of a second hydrocarbon.
- magnesium halide precursor solution prepared as described above and the dialkoxy magnesium carrier in the form of particles (spherical) are first reacted with titanium tetrachloride in the presence of a second hydrocarbon to prepare a solid product (two-component carrier), and then again a second hydrocarbon. It is also possible to prepare by secondary reaction with titanium tetrachloride and the internal electron donor in the presence.
- the second hydrocarbon that can be used is not particularly limited.
- One or two or more hydrocarbons selected from the group consisting of aliphatic hydrocarbons having 6 to 12 carbon atoms and aromatic hydrocarbons having 6 to 12 carbon atoms may be used alone or in combination.
- one or two or more selected from saturated aliphatic hydrocarbons having 7 to 10 carbon atoms or aromatic hydrocarbons having 6 to 12 carbon atoms are selected and used alone or in combination.
- non-limiting examples of aliphatic hydrocarbons having 6 to 12 carbon atoms include hexane, heptane, octane, decane, dodecane, tetradecane or mineral oil, and non-limiting examples of aromatic hydrocarbons having 6 to 12 carbon atoms.
- aromatic hydrocarbons having 6 to 12 carbon atoms include Benzene, toluene, xylene, ethylbenzene, cumene, and the like.
- the material that can be used as the internal electron donor is not particularly limited, but is preferably selected from the group consisting of phthalate compounds, carboxylic acid ester compounds, and diether compounds.
- Non-limiting examples of the phthalate-based compound include monoethoxy phthalate, diketyl phthalate, methyl ethyl phthalate, diethyl phthalate, dinormal propyl phthalate, diisopropyl phthalate, dinormal butyl phthalate, diisobutyl phthalate, dinormal Octylphthalate, dipentylphthalate, or mixtures thereof, and the like.
- Non-limiting examples of the carboxylic acid ester compound include methyl acetate, ethyl acetate, phenyl acetate, ethyl propane, ethyl butyrate, diethyl malonate, or Mixtures thereof
- non-limiting examples of the diether compounds include 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3 in the form of 1,3-diether -Dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-ene part Oxypropane, again Mixtures thereof and the like.
- a magnesium halide precursor solution and a titanium tetrachloride compound are added to a suspension solution in which a dialkoxy magnesium carrier is suspended in a second hydrocarbon solvent, and the first reaction is performed.
- the reaction temperature is -50 to 50 ° C, Specifically, it is good that it is the range of -30-20 degreeC.
- the particle shape of the catalyst which is the final product, may be destroyed to generate a large amount of fine particles. In the case of using a catalyst having a high content of fine particles, process stability may be lowered in commercial production.
- the quantity of the magnesium halide contained in the magnesium halide precursor solution is 0.01-10 weight part with respect to 1 weight part of dialkoxy magnesium carriers, specifically, 0.05-0.5 weight part. If the amount of magnesium halide is less than the above range, the magnesium halide component of the bicomponent carrier may be reduced, thereby reducing the apparent density improvement effect of the polymer (polyolefin). It is because it is not preferable because it is formed.
- the amount of titanium tetrachloride used in the first reaction is preferably 0.1 to 10 parts by weight, specifically 3 to 8 parts by weight based on 1 part by weight of the dialkoxy magnesium carrier.
- magnesium halide precursor solution and titanium tetrachloride is preferably added slowly over 30 minutes to 5 hours, and after the addition is completed, the temperature is gradually raised to 60 to 100 ° C to complete the two-component carrier formation reaction. have.
- the slurry mixture containing the carrier is washed one or more times with the second hydrocarbon, and then titanium tetrachloride is added thereto, and the mixture is heated to 90 to 130 ° C. for secondary reaction.
- the amount of titanium tetrachloride used is preferably 0.1 to 10 parts by weight, more preferably 2 to 7 parts by weight based on 1 part by weight of the dialkoxy magnesium carrier used initially.
- the internal electron donor is introduced during the temperature increase process of the secondary reaction, and the input temperature and the number of times of injection are not particularly limited, and the total amount of the internal electron donor used is 0.1 parts by weight based on 1 part by weight of the dialkoxy magnesium carrier used. It is preferable that it is-1 weight part.
- the stereoregularity may be degraded when the polyolefin is prepared using the polymerization activity of the prepared catalyst or the prepared catalyst.
- the mixture of the slurry state completed until the secondary reaction may be further added to the process of washing by heating at least once with the second hydrocarbon and then adding titanium tetrachloride to a temperature of 90 to 130 ° C.
- the amount of titanium tetrachloride used is preferably 0.1 to 10 parts by weight, more preferably 2 to 7 parts by weight, more preferably 2 to 7 parts by weight based on 1 part by weight of dialkoxymagnesium used initially, followed by washing with a second hydrocarbon and vacuum.
- the drying process it is possible to obtain the resulting polyolefin polymerization catalyst according to the present invention. In this way, it is possible to increase the activity of the catalyst by tertiary reaction with titanium tetrachloride.
- the catalyst for polyolefin polymerization according to the present invention prepared by the method as described above includes magnesium, titanium, an internal electron donor and a halogen atom, and the content of each component is not particularly limited because it can be adjusted according to the content of the raw material. However, preferably 20 to 40 parts by weight of magnesium, 1 to 10 parts by weight of titanium, 5 to 20 parts by weight of the internal electron donor and 40 to 70 parts by weight of halogen atoms are preferable.
- the present invention can produce a polyolefin using the catalyst for polyolefin polymerization prepared as described above. That is, a polyolefin can be prepared by preparing a catalyst in the same manner as described above and polymerizing (reacting) the olefin and the promoter in the presence of the catalyst thus prepared. Specifically, an alkylaluminum compound and an external electron donor are added to the polymerization reactor as a cocatalyst, a catalyst prepared as described above is added thereto, and hydrogen is supplied. Then, a polyolefin may be formed by adding an olefin monomer to the polymerization reaction for a predetermined time.
- non-limiting examples of the material usable as the alkylaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, or ethylaluminum sesquichloride.
- Non-limiting examples of materials that can be used as the electron donor include silane compounds such as cyclic hexylmethyldimethoxysilane, dicyclic pentyldimethoxysilane, diisopropyldimethoxysilane and vinyltriethoxysilane, or mixtures of the above silane compounds. Can be mentioned.
- the catalyst of the present invention used in the polyolefin polymerization process can be used in the gas phase, bulk or slurry phase, when polymerization is carried out in the bulk or slurry phase, a separate solvent or olefin itself can be used as a medium, and used for polymerization
- the olefins to be used may be used alone or in combination of two or more thereof.
- the solvent and olefin which can be used are not particularly limited, but butane, pentane, hexane, heptane, cyclopentane, cyclohexane and the like can be used, and as the olefin, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and the like can be used.
- the polyolefin polymerization temperature is 0 to 200 ° C, preferably 30 to 150 ° C
- the polymerization pressure is 1 to 100 atm, preferably 2 to 40 atm.
- a 350 ml sized reactor equipped with a stirrer, an oil circulation heater, and a cooling reflux was sufficiently ventilated with nitrogen, and then 9.52 g of anhydrous magnesium chloride, 57.85 mL of 2-ethylhexanol, and 50 mL of normal decane were added and stirred at 300 rpm at 135 ° C. And melted.
- anhydrous magnesium chloride was completely melted into a homogeneous solution, it was aged for 1 hour and then cooled to room temperature to obtain a magnesium halide precursor solution.
- the mixture was washed eight times with 1 L of normal hexane at 50 ° C.
- the washed resultant was dried in vacuo to obtain 160 g of a white powdery diethoxy magnesium carrier having good flowability.
- the obtained diethoxy magnesium spherical carrier had an average particle diameter of 45 ⁇ m and an apparent density of 0.33 g / ml.
- Example 2 the final solid product of Example 1 was washed four times with 1,000 ml of toluene, and then, 1,000 ml of fresh toluene and 154.7 ml of titanium tetrachloride were added thereto, and further reacted at 110 ° C for 2 hours. After the reaction, the solid product was allowed to settle and washed five times with 1,000 ml of toluene, followed by five times with 1,000 ml of normal hexane. The washed product was dried in vacuo to give a catalyst with a titanium content of 3.0%.
- a catalyst was obtained in the same manner as in Example 1 except that the magnesium halide precursor solution was added to 55.75 ml for 1 hour in Example 1, and the titanium content was 3.3%.
- a catalyst was obtained in the same manner as in Example 1, except that Example 1 was not added with the magnesium halide precursor solution, and the titanium content was 2.8%.
- a 2-liter high-pressure stainless steel reactor was sufficiently ventilated with nitrogen, and 2 mmol of triethylaluminum and 0.15 mmol of cyclohexylmethyldimethoxysilane were added thereto, and prepared according to Examples 1 to 3 and Comparative Examples 1 to 2. 5 mg of the prepared catalyst was added. Subsequently, 1000 ml of hydrogen and 500 g of liquid propylene were sequentially added thereto, followed by prepolymerization at 25 ° C. for 5 minutes, followed by polymerization at 250 ° C. at 70 ° C. for 1 hour.
- Example 1 Example 2
- Example 3 Comparative Example 1 Comparative Example 2
- Catalytic activity (kg-PP / g-cat, hr) 36.7 45.8 42.2 35.9 22.6
- Apparent density (g / mL) 0.48 0.49 0.46 0.42 0.42
- Stereoregularity (XIS) 98.0 98.1 98.7 98.5 97.2
- Examples 1 to 3 according to the present invention in the apparent density all have a higher value (expressing 0.45 g / mL or more) than Comparative Examples 1 to 2, and exhibits high overall activity even in catalytic activity I could confirm that.
- a magnesium halide precursor solution obtained by dissolving a magnesium halide in a first alcohol and a first hydrocarbon, and a dialkoxy magnesium carrier obtained by reacting a metal compound with a halogen compound and a second alcohol are used as the first hydrocarbon.
- the present invention can provide a polyolefin having a high apparent density as the polyolefin is prepared using the catalyst for polyolefin polymerization described above.
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Abstract
Description
실시예1 | 실시예2 | 실시예3 | 비교예1 | 비교예2 | |
촉매활성(kg-PP/g-cat,hr) | 36.7 | 45.8 | 42.2 | 35.9 | 22.6 |
겉보기 밀도(g/mL) | 0.48 | 0.49 | 0.46 | 0.42 | 0.42 |
입체규칙성(XIS) | 98.0 | 98.1 | 98.7 | 98.5 | 97.2 |
Claims (9)
- a) 마그네슘 할라이드를 제1알코올과 제1탄화수소에 용해시켜 마그네슘 할라이드 전구체 용액를 준비하는 단계;b) 금속 마그네슘에 할로겐 화합물과 제2알코올을 반응시켜 디알콕시마그네슘 담체를 준비하는 단계; 및c) 상기 마그네슘 할라이드 전구체 용액과 상기 디알콕시마그네슘 담체를 제2탄화수소의 존재 하에 사염화티타늄 및 내부전자공여체와 반응시키는 단계를 포함하는 폴리올레핀 중합용 촉매의 제조방법.
- 제1항에 있어서,상기 c) 단계의 마그네슘 할라이드 전구체 용액에 포함된 마그네슘 할라이드는 상기 디알콕시마그네슘 담체 1중량부에 대하여 0.01 ~ 5중량부 범위로 포함되는 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 제1항에 있어서,상기 a) 단계는, 상기 마그네슘 할라이드 1중량부에 대하여 1 ~ 10중량부의 제1알코올과 1 ~ 20중량부의 제1탄화수소를 사용하는 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 제1항에 있어서,상기 a) 단계에서 사용되는 제1알코올은, R1OH(이때, 상기 R1은 탄소수 1 ~ 12의 지방족 탄화수소이다)로 표시되는 지방족 알코올 및 R2OH(이때, 상기 R2는 탄소수 6 ~ 12의 방향족 탄화수소이다)로 표시되는 방향족 알코올로 이루어진 군에서 선택되는 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 제1항에 있어서,상기 a) 단계에서 사용되는 상기 제1탄화수소는, 탄소수 6 ~ 20인 지방족 탄화수소인 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 제1항에 있어서,상기 b) 단계는 상기 금속 마그네슘 1중량부에 대하여 상기 할로겐 화합물 0.01 ~ 10중량부와 상기 제2알코올 5 ~ 50중량부를 사용하는 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 제1항에 있어서,상기 b) 단계에서 사용되는 제2알코올은, R3OH(이때, R3은 탄소수 1 ~ 6의 지방족 탄화수소이다)로 표시되는 지방족 알코올 및 R4OH(이때, R4는 탄소수 6의 방향족 탄화수소이다)로 표시되는 방향족 알코올로 이루어진 군에서 선택되는 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 제1항에 있어서,상기 c) 단계에서 사용되는 제2탄화수소는, 탄소수 6 ~ 12인 지방족 탄화수소 및 탄소수 6 ~ 12인 방향족 탄화수소로 이루어진 군에서 선택되는 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 제1항 내지 제8항 중 어느 한 항에 따른 제조방법에 의해 제조된 폴리올레핀 중합용 촉매를 사용하는 것을 특징으로 하는 폴리올레핀의 제조방법.
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JP2012547013A JP2013515831A (ja) | 2009-12-28 | 2010-12-28 | ポリオレフィン重合用触媒及びその製造方法 |
US13/519,530 US20120296056A1 (en) | 2009-12-28 | 2010-12-28 | Catalyst for polymerization of polyolefin and preparation method thereof |
EP10841236.2A EP2520591B8 (en) | 2009-12-28 | 2010-12-28 | Catalyst for polyolefin polymerisation and a production method for the same |
CN201080059670.0A CN102741299B (zh) | 2009-12-28 | 2010-12-28 | 聚烯烃聚合用催化剂及其制备方法 |
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KR1020090132229A KR101126946B1 (ko) | 2009-12-28 | 2009-12-28 | 폴리올레핀 중합용 촉매 및 이의 제조방법 |
KR10-2009-0132229 | 2009-12-28 |
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US (1) | US20120296056A1 (ko) |
EP (1) | EP2520591B8 (ko) |
JP (1) | JP2013515831A (ko) |
KR (1) | KR101126946B1 (ko) |
CN (1) | CN102741299B (ko) |
WO (1) | WO2011081404A2 (ko) |
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KR101309457B1 (ko) * | 2011-07-15 | 2013-09-23 | 삼성토탈 주식회사 | 올레핀 중합 촉매용 구형 담체의 제조방법 및 이를 이용한 고체 촉매 및 프로필렌 중합체의 제조방법 |
EP2917246A4 (en) | 2012-11-08 | 2016-07-27 | Basf Corp | METHOD FOR PRODUCING A POLYMERIZATION CATALYST WITH REGULATED CATALYST PROPERTIES AND USE THEREOF IN OLEFIN POLYMERIZATIONS |
KR101373775B1 (ko) | 2012-11-23 | 2014-03-13 | 롯데케미칼 주식회사 | 폴리올레핀 합성용 촉매의 제조방법 및 이를 이용한 폴리올레핀의 제조방법 |
KR101526480B1 (ko) * | 2013-11-29 | 2015-06-05 | 롯데케미칼 주식회사 | 폴리올레핀 합성용 고체 촉매 조성물, 고체 촉매의 제조방법, 및 이를 이용한 폴리올레핀의 제조방법 |
KR102122133B1 (ko) | 2018-11-13 | 2020-06-11 | 한화토탈 주식회사 | Voc 저감을 위한 프로필렌 중합용 고체촉매 및 이를 이용한 폴리프로필렌 제조방법 |
CN112707449B (zh) * | 2019-10-24 | 2023-02-28 | 中国石油化工股份有限公司 | 一种处理含钛废液的方法 |
CN116041576A (zh) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | 烯烃聚合催化剂前体和烯烃聚合催化剂载体及其制备方法和应用 |
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US4816433A (en) | 1986-01-06 | 1989-03-28 | Toho Titanium Co., Ltd. | Solid catalyst component for the polymerization of olefins and an olefin polymerization catalyst |
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US5108972A (en) * | 1989-10-16 | 1992-04-28 | Akzo Nv | Process of making halide/alkoxy-containing magnesium complex |
US6693058B1 (en) * | 1997-01-28 | 2004-02-17 | Fina Technology, Inc. | Ziegler-natta catalyst for narrow to broad MWD of polyoefins, method of making, method of using, and polyolefins made therewith |
EP0926165B1 (en) * | 1997-12-23 | 2002-02-27 | Borealis Technology Oy | Catalyst component comprising magnesium, titanium, a halogen and a electron donor, its preparation and use |
EP1114070B1 (en) * | 1999-06-04 | 2003-12-10 | LG Chemical Ltd. | Process for preparing polyolefin polymerization catalysts |
JP2001114812A (ja) * | 1999-10-15 | 2001-04-24 | Toho Titanium Co Ltd | オレフィン類重合用固体触媒成分及び触媒 |
WO2003099749A1 (fr) * | 2002-05-24 | 2003-12-04 | Idemitsu Kosan Co., Ltd | Compose de magnesium, catalyseur solide destine a la polymerisation des olefines, catalyseur destine a la polymerisation des olefines et procede de production d'une polyolefine |
JP4170667B2 (ja) * | 2002-05-24 | 2008-10-22 | 出光興産株式会社 | マグネシウム化合物、オレフィン重合用固体触媒成分、オレフィン重合用触媒及びポリオレフィンの製造方法 |
KR100466511B1 (ko) * | 2003-10-23 | 2005-01-15 | (주) 디엔에프솔루션 | 폴리올레핀 제조용 고활성 실리카 담지 중합촉매의제조방법 및 그 제조방법에 의해 제조된 신규한 중합촉매 |
KR20100007076A (ko) * | 2008-07-11 | 2010-01-22 | 삼성토탈 주식회사 | 올레핀 중합 촉매용 구형 담체의 크기를 조절하는 방법 |
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- 2010-12-28 CN CN201080059670.0A patent/CN102741299B/zh active Active
- 2010-12-28 WO PCT/KR2010/009418 patent/WO2011081404A2/ko active Application Filing
- 2010-12-28 US US13/519,530 patent/US20120296056A1/en not_active Abandoned
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US4816433A (en) | 1986-01-06 | 1989-03-28 | Toho Titanium Co., Ltd. | Solid catalyst component for the polymerization of olefins and an olefin polymerization catalyst |
US5028671A (en) | 1987-03-13 | 1991-07-02 | Mitsui Petrochemical Industries, Ltd. | Process for polymerization of olefins and polymerization catalyst |
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See also references of EP2520591A4 |
Also Published As
Publication number | Publication date |
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WO2011081404A3 (ko) | 2011-12-01 |
KR101126946B1 (ko) | 2012-03-20 |
JP2013515831A (ja) | 2013-05-09 |
KR20110075706A (ko) | 2011-07-06 |
EP2520591B1 (en) | 2015-04-01 |
US20120296056A1 (en) | 2012-11-22 |
CN102741299A (zh) | 2012-10-17 |
EP2520591A2 (en) | 2012-11-07 |
EP2520591A4 (en) | 2013-10-09 |
EP2520591B8 (en) | 2015-06-10 |
CN102741299B (zh) | 2014-07-09 |
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