• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    PURPOSE: Provided is a method for preparing a ziegler-natta catalyst which has high activity, high stereoregularity, and uniform particle size of polymerized polyolefin. CONSTITUTION: The method comprises the steps of (i) dissolving magnesium metal in mixture of alkyl halogen compound and ether compound, (ii) catalytically reacting solid components produced by adding 0.01-10 moles of mixture of organic silane and organic titanium per 1 mole of magnesium metal with mixture solution comprising 35-75 wt% of diether-based inner electron donor and titanium tetrachloride at 80-120 deg.C for 1-10 hours to obtain a solid compound, (iii) washing the solid compound with solvents, (iv) adding diether-based inner electron donor and titanium tetrachloride to effect repeatedly the catalytic reaction and washing steps.
    公开号:KR20020052690A
    申请号:KR1020000082119
    申请日:2000-12-26
    公开日:2002-07-04
    发明作者:김정호；홍수진
    申请人:조정래；주식회사 효성；
    IPC主号:
    专利说明:

    Method for Producing Ziegler-Natta Catalysts for Olefin Polymerization {Method of Producing Ziegler-Natta Catalyst for Poymerizing olefine}
    [1] The present invention relates to a method for preparing a Ziegler-Natta catalyst for olefin polymerization, and more particularly, to preparing a Ziegler-Natta catalyst having high activity and high stereoregularity starting from magnesium metal, titanium tetrachloride, diether, and the like. It is about a method.
    [2] The catalyst for olefin polymerization, generally called Ziegler-Natta type catalyst, refers to a catalyst system composed of a combination of a main catalyst composed mainly of a transition metal compound, a cocatalyst of an organometallic compound, and an electron donor. Many techniques are presented. Ziegler-Natta catalysts have been developed to improve the polymerization activity and stereoregularity until now, and the properties and particle distribution of polypropylene produced are determined according to the components and production methods. Therefore, in order to change the properties of polypropylene, changes in constituents and polymerization methods should be accompanied during the preparation of the catalyst.The catalyst activity and particle size of the polymer polymerized by the method of preparing each catalyst or the difference in the constituents are different. , Molecular weight and stereospecificity are different.
    [3] Many improvements have been made to existing catalysts based on titanium, magnesium and halogen compounds, and co-catalysts of organoaluminum compounds. However, they still lack activity and stereoregularity and lack uniformity in particle size and particle size distribution. There is a need to improve this.
    [4] U.S. Patent Nos. 4,210,738 and 4,339,560 disclose a method for preparing a Ziegler-Natta catalyst using magnesium metal as an initial supporting material. The problems such as lack of polymerization activity and stereoregularity of polymers and degradation of catalyst activity during the polymerization process are disclosed. In order to overcome this problem, the following methods have been proposed.
    [5] As for the stereoregularity problem, an example of improvement has been known by adding an electron donor in US Pat. No. 4,544,717. A high-stereoregular catalyst having an isotactic index of 94 to 95 or more is disclosed in US Pat. No. 4,226,741. Known. In addition, the technique of a solid Ziegler-Natta catalyst having the characteristics of high activity high stereoregularity is known from EP 045,977, and derivatives of certain carboxylic ester compounds, preferably phthalate derivatives, are solid catalyst compounds as internal electron donors. Coordinates with a titanium compound to produce a Ziegler-Natta catalyst. These main catalysts can increase the polymerization activity and stereoregularity by alpha-olefin polymerization using an aluminum alkyl compound and a silicon compound having at least one silicon-ether bond as an external electron donor.
    [6] However, these catalysts have different activity and stereoregularity, are not reproducible, and have difficulty in analyzing the catalyst due to the complicated manufacturing process and the catalyst component. In addition, in the case of the solid carrier made it is difficult to control the size of the particles arbitrarily, the size distribution was also often uneven.
    [7] On the other hand, in the polymerization experiment conducted as part of the catalyst evaluation, the catalyst of a compound made of magnesium dichloride as a carrier of these conventional methods has a significant difference in polymerization activity and stereoregularity depending on the type of external electron donor provided at the time of polymerization. Therefore, in order to control this, it is necessary to select an appropriate type of external electron donor and to input the correct amount of external electron donor.
    [8] The present invention is to solve the problems of the prior art as described above, and an object of the present invention is to provide a method for producing a Ziegler-Natta catalyst having high activity and high stereoregularity and uniform particle size of the polymerized polyolefin.
    [9] That is, according to the present invention, a solid component prepared by dissolving a magnesium metal in a mixture of an alkyl halogen compound and an ether compound, and adding 0.01 to 10 moles of a mixture of organosilane and organo titanium per mole of magnesium metal is added to the diester-based internal electron donor. A solid compound was obtained by contacting a mixed solution containing 35 to 75 wt% of titanium tetrachloride at 80 to 120 ° C. for 1 to 10 hours to obtain a solid compound, and then washing the solid compound with a solvent, followed by tetrachloride and an internal ether donor. The present invention relates to a method for preparing a Ziegler-Natta catalyst for olefin polymerization comprising adding titanium and repeating the contact reaction and washing process.
    [10] Hereinafter, the present invention will be described in more detail.
    [11] In the present invention, the conventional ether-based compound described above is used as the internal electron donor of the magnesium compound, and the magnesium-based carrier raw material is prepared by using magnesium metal rather than magnesium dichloride-based as follows.
    [12] The magnesium metal for Grignard reagent is added in a reactor of high purity nitrogen atmosphere, and the mixture which mixed the alkyl halogen compound in the ether compound, More preferably, the dialkyl ether is gradually added dropwise to obtain a uniform magnesium solution. Specifically, at a temperature of 30 ° C. to 90 ° C., a mixture of 0.5 mol to 10 mol of ether compound and 0.05 mol to 3 mol of alkyl halogen compound per mol of metal magnesium is slowly added over 3 to 5 hours, followed by stirring for 5 to 7 hours. To obtain a uniform magnesium solution.
    [13] The ether compound used at this time is specifically diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, 2,2-dicyclo hexyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl- 1,3-dimethoxypropane, 2-isopropyl-2,3,7-dimethyloxyl-1,3-diphenoxypropane, etc. are mentioned.
    [14] If the amount of the ether compound is small, the stirring is not smooth, if too large, the particle size of the carrier is not excellent, the precipitation is not easy to be noted. In addition, it is possible to freely adjust the particle size of the solid carrier by the amount of the alkyl halogen compound introduced at this time.
    [15] Next, the magnesium compound solution obtained as described above is added dropwise dropwise to a mixture of organic titanium, organic silane and a hydrocarbon solvent in a high purity nitrogen atmosphere to obtain a precipitate. The organic silane and organic titanium used at this time serve as precipitation aids and shape control agents, so that the composition of these mixtures and the reaction conditions with the mixtures greatly influence the shape control of the solid carrier. The reaction is continued for 4 to 6 hours at a reaction temperature of −10 ° C. to 30 ° C. to obtain a precipitate of uniform size.
    [16] The organic silane compound used at this time may specifically be tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylethoxysilane, triethylmethoxysilane, tributylethoxysilane, triethyl Butoxysilane, triethylethoxysilane, etc. are mentioned, As an organic titanium compound, tetramethoxy titanium, tetraethoxy titanium, tetrabutoxy titanium, tetraisobutoxy titanium, trimethyl butoxy titanium, triethyl butoxy Titanium, trimethylethoxytitanium, triethylmethoxytitanium and tributylethoxytitanium, and the like, and hydrocarbon solvents include pentane, nucleic acid, haptan, octane, decane, dodecane, cyclopentane, methylcyclopentane and cyclonucleic acid. And methylcyclonucleic acid, ethylcyclonucleic acid, cyclooctane, benzene, toluene, xylene, benzene chloride, and the like, and more preferably ethylcyclonucleic acid is used.
    [17] In general, the content of the mixture of the organic silane and the organic titanium is suitably 0.01 to 10 mol per mol of magnesium, preferably 0.05 to 5 mol, more preferably 0.1 to 3 mol. In the case of an organic silane which plays an important role as a dual shape modifier, about 0.03 to 0.1 mole per mole of magnesium is suitable, and when it is smaller than this, the effect as a shape modifier is weak, and when it is higher, excessive generation of Si-O bonds in the catalyst As a result, it is difficult to satisfy the catalyst configuration having the desired shape in the present invention.
    [18] Titanium tetrachloride and the internal electron donor were added to the mixed slurry of the solid component and the solvent produced above, and then contacted and reacted at a temperature of 80 ° C. to 120 ° C. for 1 to 10 hours, followed by filtering to collect only the solid components. It is cleaned with a hydrocarbon solvent such as toluene, to filter out excess titanium or other impurities on the solid surface. Specifically, it is preferable to add 5-20 mol of titanium tetrachloride and 0.1-10 mol of an electron donor with respect to 1 mol of magnesium compounds. The solid carrier obtained at this time had a particle shape close to a spherical shape and the particle size distribution was considerably clear. The obtained solid product can be used in a dry state or in a form stored in an inert solvent.
    [19] In this case, the titanium compound used may specifically include titanium tetrachloride, titanium tetrabromide, ethoxytitanium trichloride, butoxytitanium trichloride, ethoxytitanium tribromide, diethoxytitanium dichloride, dimethoxytitanium dichloride, ibutoxytitanium, Triethoxy titanium chloride, triphenoxytitanium chloride, triethoxytitanium bromide, tetrabutoxy titanium, tetraphenoxytitanium, tetraethoxytitanium or a mixture thereof.
    [20] Usually, a phthalate-based compound, a carboxylic acid ester compound, or a diether compound is used as the internal electron covalent carrier, but in the present invention, a diether compound is used. Specific examples of such diether compounds include 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, and 2,2-diisobutyl-1,3- Dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-enebutoxypropane, 2,2-diphenyl-1,3-dimethoxypropane , 2-methyl-2-isopropyl-1,3-dimethoxypropane, 1,3-diisobutoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane or mixtures thereof have.
    [21] The catalyst system using the Ziegler-Natta catalyst prepared as described above is used together with an organoaluminum compound as a cocatalyst and optionally an external electron donor as a cocatalyst when applied to the polymerization of olefins as a main catalyst.
    [22] As an organoaluminum compound which is a promoter component, the compound represented by following formula (1) is used.
    [23] R n AlY 3-n
    [24] Wherein R is a hydrocarbon having 1 to 20 carbon atoms, Y is halogen, and n is an integer satisfying 0 ≦ n ≦ 3.
    [25] As an external electron donor which is a cocatalyst component, the compound represented by following formula (2) is used specifically.
    [26]
    [27] In the above formula, R 1 and R 3 are each an alkoxy group or an arylalkyl group, and specifically methoxy group, ethoxy group, butoxy group, etc., R 2 is an alkyl group, an alkoxy group or an arylalkyl group, specifically methyl, ethyl, butyl group , A methoxy group, an ethoxy group, a butoxy group, and the like, and R 4 is an aromatic or cycloaliphatic group, specifically, a phenyl group, anthracenyl group, naphthalenyl group, cyclopentyl group, cyclohexyl group and cyclooctyl group And X is carbon, silicon, and the like.
    [28] Of these chemicals, silicone compounds are preferred. Specific examples include triethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. Diisopropyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, dicyclopentyldimeth Methoxysilane, dicyclopentyl diethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and the like, and preferably diphenyldimethoxysilane and cyclohexyl Methyl dimethoxysilane and dicyclopentyl diethoxysilane are used.
    [29] The content of the external electron donor should be 0.001-50 mol%, preferably 0.01-20 mol%, more preferably 0.02-10 mol% per mole of promoter. If the content is less than 0.001 mol%, the problem of improvement of stereoregularity does not occur, and if it exceeds 50 mol%, it no longer affects stereoregularity.
    [30] Applying such a catalyst system to the polymerization of polyolefin, it is possible to produce a polyolefin having a large particle size and uniformity. The term "polymerization" is used to include not only homopolymerization but also copolymerization. The polymerization reaction can be carried out in gas phase, liquid phase, or solution phase. When performing a polymerization reaction in a liquid phase, a hydrocarbon solvent may be used and olefin itself may be used as a solvent. Hydrocarbons used as solvents include aliphatic hydrocarbons such as butane, isobutane, pentane, nucleic acid, heptane, octane, nonane, decane, dodecane, nuxadecane and octadecane, cyclopentane, methylcyclopentane, cyclohexane and cyclooctane Alicyclic hydrocarbons, such as alicyclic hydrocarbons, such as benzene, toluene, and xylene, and petroleum components, such as gasoline, kerosene, and diesel, are mentioned. Polymerization temperature is -50-350 degreeC, Preferably it is the range of 0-310 degreeC. If the temperature is less than -50 ° C, the polymerization activity is not good, and at 350 ° C or higher, the stereoregularity is poor, which is not good. The polymerization pressure is usually at normal pressure to 250 kg / cm 2 , preferably at normal pressure to 200 kg / cm 2 , and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. In the case of 250 kg / cm 2 or more, it is not preferable from an industrial and economical point of view.
    [31] The heat stabilizer, light stabilizer, flame retardant, carbon black, pigment, antioxidant, etc., which are commonly added, may be added to the polypropylene prepared by the catalyst. Furthermore, it can be mixed with low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, polybutene, EP (ethylene / propylene) rubber, and the like.
    [32] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention should not be considered as being limited by the Examples.
    [33] Example 1
    [34] Ziegler-Natta catalyst manufacture
    [35] In a high-purity nitrogen atmosphere, 4.0 g of Grignard reagent magnesium metal was added to a double jacketed reactor with a stirrer, and a mixture of 15 g of butyl chloride dissolved in 60 ml of dialkyl ether was added dropwise at 50 ° C. over 4 hours. Stirring at 60 ° C. for 1 hour gave a uniform magnesium solution. After cooling the mixed solution to 5 ° C, a mixed solution of 70 ml of hexane, 18 g of tetrabutoxytitanium, and 1.7 g of tetrabutoxytylsilane was added dropwise over 3.5 hours to react to obtain a precipitate. The precipitate was washed three times with toluene and then 75 ml of toluene was poured into a mixed slurry. 25 ml of this mixed slurry was taken, the temperature was raised to 95 degreeC, and 9.3 ml of 2, 2- diisopropyl- 1, 3- dimethoxy propane were added. After stirring for 30 minutes, the mixture was filtered to collect only solid components, and then washed twice with 100 ml of toluene.
    [36] 15 ml of toluene, 1.3 ml of dibutyl ether, 19 ml of titanium tetrachloride, and 0.6 ml of 2,2-diisopropyl-1,3-dimethoxypropane were added to the solid component obtained as described above, followed by reaction at 100 ° C. for 3 hours. Washed twice with 100 ml of 60 ° C. purified nucleic acid. Subsequently, 15 ml of toluene, 1.3 ml of dibutyl ether, and 10 ml of titanium tetrachloride were added thereto, and the mixture was reacted at 100 ° C for 1 hour. The solid component was filtered and washed four times with 100 ml of purified nucleic acid to obtain a solid catalyst. At this time, the specific surface area of the catalyst was 450 m 2 / g and the composition of the catalyst was analyzed and the titanium content was 2.2% by weight.
    [37] Catalyst Performance Evaluation Experiment
    [38] The polymerization of propylene was carried out using a 1 L autoclave reactor. The reactor was decompressed to a vacuum of 3 torr or less and charged with nitrogen of high purity five times. After propylene was flowed into the reactor at a rate of 1.5 L / min for 5 minutes, 0.5 L was charged at a rate of 0.34 L / min under atmospheric pressure of propylene in the reactor. After putting 250 g of propylene into the reactor, while maintaining the temperature of the reactor at 25 ℃ 10 ml of hexane and 7.5 x 10 -4 mol of triethylaluminum, 7.5 x 10 -5 mol of normal propylmethyl dimethoxysilane, prepared above 3.0 × 10 −6 mol of the prepared catalyst was added sequentially, stirred at 450 rpm for 5 minutes, and the reactor temperature was raised to 70 ° C., stirred for 1 hour, and 5 ml of ethanol was added to terminate the polymerization. The reaction product was stirred for 24 hours in about 5% by weight of HCl-methanol, and then washed again with stirring for 24 hours in clean methanol, filtered through a filter paper, and vacuum dried at about 80 ° C for at least 24 hours to obtain a final polymerization product. The activity of the catalyst was determined in units of g-polymer / g-catalyst from the weight of the final product.
    [39] Example 2
    [40] The same procedure as in Example 1 was conducted except that 2,2-dienebutyl-1,3-dimethoxypropane was used instead of 2,2-diisopropyl-1,3-dimethoxypropane as the internal electron donor. Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.
    [41] Example 3
    [42] The procedure was the same as in Example 1 except that 2,2-diisobutyl-1,3-diethoxypropane was used instead of 2,2-diisopropyl-1,3-dimethoxypropane as an internal electron donor. . Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.
    [43] Example 4
    [44] The same procedure as in Example 1 was carried out except that 2,2-diphenyl-1,3-dimethoxypropane was used instead of 2,2-diisopropyl-1,3-dimethoxypropane as the internal electron donor. Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.
    [45] Example 5
    [46] It carried out similarly to Example 1 except using normal butylmethyl dimethoxysilane instead of normal propylmethyl dimethoxysilane as an organosilane compound. Table 1 shows the polymerization activity, the stereoregularity and the average particle diameter of the polymer.
    [47] Example 6
    [48] It carried out similarly to Example 1 except using normal hexylmethyl dimethoxysilane instead of normal propylmethyl dimethoxysilane as an organosilane compound. Table 1 shows the polymerization activity, the stereoregularity and the average particle diameter of the polymer.
    [49] Comparative Example 1
    [50] In a double jacketed catalytic reactor, 5 g of magnesium chloride, 25 ml of decane, and 24.5 ml of 2-ethylhexanol were added thereto, the temperature was raised to 130 ° C. while stirring, and stirring was continued until a clear solution was produced. 1.2 g of phthalic anhydride was added thereto, followed by stirring for 1 hour. After cooling the mixed solution to -20 ° C, 180 ml of titanium tetrachloride was added dropwise for 1 hour, and heated up to 32.5 ° C per hour. When the temperature reached 110 ° C, 2.0 ml of 2,2-diisopropyl-1,3-dimethoxypropane was added. After the addition, the reactor was kept at 110 ° C. for 2 hours. The solid component obtained after the reaction was obtained by filtration, and then 180 ml of titanium tetrachloride was added thereto and maintained at 110 ° C. for 2 hours. The solid catalyst was washed four times with 100 ml of purified heptane. Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.
    [51] Comparative Example 2
    [52] The same procedure was followed as in Comparative Example 1 except that diisobutyl phthalate was used instead of 2,2-diisopropyl-1,3-dimethoxypropane as the internal electron donor. Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.
    [53] Comparative Example 3
    [54] The same procedure as in Comparative Example 1 was conducted except that normal butylmethyl dimethoxysilane was used as the external electron donor. Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.
    [55] Internal electron donorSurface area (m 2 / g)Active (kg / g cat)Stereoregularity (II) a Particle size (㎛) Example 12,2-diisopropyl-1,3dimethoxypropane4503297960 Example 22,2-dienebutyl-1,3-dimethoxypropane3802594870 Example 32,2-diphenyl-1,3-dimethoxypropane3502896860 Example 4Diisobutyl-1,3-dimethoxypropane3802795790 Example 52,2-diisopropyl-1,3-dimethoxypropane4003096913 Example 62,2-diisopropyl-1,3-dimethoxypropane4602896920 Comparative Example 12,2-diisopropyl-1,3-dimethoxypropane2402693670 Comparative Example 2Diisobutyl phthalate2602892530 Comparative Example 32,2-diisopropyl-1,3-dimethoxypropane2602294690
    [56] * I.I.: Isotacticity Index: The stereoregularity of polypropylene was performed by the isotacticity index (I. I.), which is an amount insoluble in boiling heptane. The polymer was previously treated with a heat stabilizer to prevent degradation during analysis. A certain amount of the completely dried polymer was quantitatively placed in a timing filter and extracted with heptane in a Soxhlet type extraction apparatus. The extraction time was fixed at 5 hours, and the remaining polymer was collected after extraction, dried in vacuo at 80 ° C, quantitatively weighed, and the I.I. was calculated as the weight ratio of the polymer remaining without melting and the original polymer.
    [57] The Ziegler-Natta catalyst prepared according to the present invention exhibits high activity and high stereoregularity and can reduce the amount of expensive titanium, thereby reducing the catalyst cost and polymerizing the olefin using the catalyst results in large particle size. Uniform polyolefins can be prepared.
    权利要求:
    Claims (6)
    [1" claim-type="Currently amended] Magnesium metal was dissolved in a mixture of an alkyl halogen compound and an ether compound, and a solid component prepared by adding 0.01 to 10 moles of a mixture of organosilane and organo titanium per mole of magnesium metal was contained in a dietary internal electron donor and titanium tetrachloride. A solid compound was obtained by contact reaction with a mixed solution containing 75% by weight at 80 to 120 ° C. for 1 to 10 hours. The solid compound was washed with a solvent, and then a diether-based internal electron donor and titanium tetrachloride were added thereto. Method for preparing a Ziegler-Natta catalyst for olefin polymerization comprising the step of repeating the contact reaction and washing process.
    [2" claim-type="Currently amended] The method of claim 1, wherein the dissolving of the metal magnesium in a mixture of an alkylhalogen compound and an ether compound is performed in an amount of 0.5 mol to 10 mol of ether compound and 0.05 mol to 3 mol of alkyl relative to 1 mol of metal magnesium in a reactor into which the metallic magnesium is added. A method of producing a Ziegler-Natta catalyst for olefin polymerization, comprising stirring a mixture of halogen compounds at 30 ° C. to 90 ° C. over 3 to 5 hours while stirring for 5 to 7 hours.
    [3" claim-type="Currently amended] The method of claim 2, wherein the ether compound is diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, 2,2-dicyclo hexyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl Preparation of Ziegler-Natta catalyst for olefin polymerization characterized in that it is selected from the group consisting of -1,3-dimethoxypropane and 2-isopropyl-2,3,7-dimethyloxyl-1,3-diphenoxypropane. Way.
    [4" claim-type="Currently amended] The method of claim 1, wherein the organosilane is tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylethoxysilane, triethylmethoxysilane, tributylethoxysilane, triethyl 1 type selected from the group consisting of butoxysilane and triethylethoxysilane, and the organotitanium is tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium, tetraisobutoxytitanium, trimethylbutoxytitanium and triethyl A method for producing a Ziegler-Natta catalyst for olefin polymerization, characterized in that it is one selected from the group consisting of butoxytitanium, trimethylethoxytitanium, triethylmethoxytitanium and tributylethoxytitanium.
    [5" claim-type="Currently amended] The method for producing a Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein 5 to 20 mol of titanium tetrachloride and 0.1 to 10 mol of diether-based internal electron donors are added to 1 mol of the magnesium metal.
    [6" claim-type="Currently amended] The method of claim 1, wherein the titanium tetrachloride is titanium tetrachloride, titanium tetrabromide, ethoxytitanium trichloride, butoxytitanium trichloride, ethoxytitanium tribromide, diethoxytitanium dichloride, dimethoxytitanium dichloride, ibutoxytitanium , Triethoxy titanium chloride, triphenoxytitanium chloride, triethoxytitanium bromide, tetrabutoxy titanium, tetraphenoxytitanium, and tetraethoxytitanium, and the dietheric internal electron donor is Monoethoxyphthalate, dimethylphthalate, methylethylphthalate, diethyl 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2 -Diisobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-enbutoxypropane, 2,2-di Phenyl-1,3-dime Consisting of cipropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 1,3-diisobutoxypropane, and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane Method for producing a Ziegler-Natta catalyst for olefin polymerization, characterized in that selected from the group.
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    同族专利:
    公开号 | 公开日
    KR100574740B1|2006-04-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-12-26|Application filed by 조정래, 주식회사 효성
    2000-12-26|Priority to KR1020000082119A
    2002-07-04|Publication of KR20020052690A
    2006-04-27|Application granted
    2006-04-27|Publication of KR100574740B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR1020000082119A|KR100574740B1|2000-12-26|2000-12-26|Method of Producing Ziegler-Natta Catalyst for Poymerizing olefine|
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