KR100451085B1 - The Manufacturing Method Of Photo Catalyst For Olefine Polymerization - Google Patents

Abstract

The present invention relates to a method for preparing an olefin polymerization catalyst and a method for producing polypropylene using the catalyst, wherein the method for preparing a catalyst according to the present invention is a nonionic surfactant containing magnesium dichloride dissolved in a mixed solution of an organic alcohol and an aromatic hydrocarbon. And the mineral oil and the active ingredient are suspended in a mixed solution of titanium tetrachloride and prepared as a starting material by a conventional method. The method for preparing polypropylene of the present invention is the Ziegler-Natta prepared by the above method. An organoaluminum compound is used as a catalyst and a cocatalyst, and an organosilicon, an ether or an ester compound is used as an external electron donor. According to the present invention, it is possible to prepare a catalyst which maintains high activity and high stereoregularity and exhibits an excellent particle size of the polymer, and has an advantage of not excessively using titanium tetrachloride in the preparation step.

Description

Manufacturing Method Of Photo Catalyst For Olefine Polymerization

The present invention relates to a method for preparing a catalyst for olefin polymerization and a method for producing polypropylene using the catalyst. More specifically, magnesium dichloride dissolved in a mixed solution of an organic alcohol and an aromatic hydrocarbon may be used as a nonionic surfactant. Suspended with a mixed solution of mineral oil and titanium tetrachloride as an active ingredient, and based on the catalyst obtained as supporting material of internal electron donor and titanium tetrachloride as a starting material, a method for producing polypropylene having high activity, high stereoregularity and even particle size It is about.

The catalyst for olefin polymerization, commonly referred to as a Ziegler-Natta type catalyst, refers to a catalyst system composed of a combination of a main catalyst composed mainly of a transition metal compound, an organic metal compound cocatalyst, and an electron donor. There is also a great deal of technology.

This catalyst has been developed in the direction of improving polymerization activity and stereoregularity until now, and the properties and particle distribution of polypropylene produced are determined when its composition and production method are determined. Therefore, in order to change the properties of polypropylene, changes in constituents and polymerization methods should be accompanied during the preparation of catalysts. Size, molecular weight, stereospecificity, etc. will vary.

Many improvements have been made to the existing high activity and high stereoregular catalysts, which are composed mainly of titanium, magnesium, and halogen compounds, and the organoaluminum compound as a promoter. However, the problems of activity, stereoregularity, incomplete particle size and particle size distribution have been achieved. The lack of uniformity has led to further research.

The improvement in the problem of stereoregularity is known in the United States Patent 4,544,717 is the case that the improvement is made by the addition of the electron donor, the US Patent 4,226,741 for a high stereoregular catalyst having an isotactic index value of 94-95% or more Known in In addition, the technology of solid Ziegler-Natta catalysts having high activity and high stereoregularity characteristics is known from European Patent 045,977. Derivatives of certain carboxylic ester compounds, preferably phthalate derivatives, are used as internal electron donors to solid catalyst compounds. Coordination can be made 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.

In addition to derivatives of these carboxylic acid ester compounds, new coordination compounds have been researched and developed directly or indirectly as a catalyst for coordinating magnesium compounds. In the US Patent 4,971,937, an ether compound is used as an internal electron donor. An example of the preparation of a Ziegler-Natta catalyst is shown as starting material. These ether compounds have been used in the literature as hydrocarbon compound ligands having two or more ether functional groups and forming satisfactory ligands for magnesium and titanium compounds.

However, these catalysts show a lot of differences in activity and stereoregularity, respectively, and the reproducibility is not clear, and the catalyst preparation process and the catalyst components are complicated, which makes it difficult to analyze the catalyst. In addition, in the case of the solid carrier made, it showed a difficulty in controlling the size of the particles at will, and the distribution of the size was also uneven.

Japanese Laid-Open Patent Publication No. 58-83006 shows a method of preparing a catalyst by dissolving a magnesium compound using alcohol, aldehyde, amide, and carboxylic acid, and adding benzoic anhydride and dicarboxylic acid ester thereto. The catalyst prepared by this method has the problem of using a very large amount of titanium tetrachloride compounds, although the high activity and high polymer regularity of the polymer produced.

The present invention has been made to solve the above problems, and an object thereof is to provide a Ziegler-Natta-based catalyst composition for olefin polymerization having high activity and excellent stereoregularity without using excessive titanium tetrachloride compounds.

The Ziegler-Natta catalyst system is characterized in that it is formed of a [A] transition metal compound, an [A] organoaluminum compound as a cocatalyst, and an [C] electron donor as an optional subcatalyst. The catalyst component [A] is of the general formula MR ⁺ _x , wherein M is a metal, R is halogen or hydrocarbyloxy and x is the oxidation number of the metal. M is periodic table group IVB or VB or VIB group, preferably Is group IVB of the periodic table, more preferably titanium, R is chlorine, bromine, alkoxy or phenoxy, preferably chlorine or ethoxy and more preferably chlorine. In this case, the number of transition metal compounds is not limited.

The support is a chemically inert solid that does not cause a chemical reaction with the Ziegler-Natta catalyst. Cocatalyst component [B] is an organoaluminum compound represented by the general formula R _n AlY _3-n , wherein R is a hydrocarbon having 1 to 20 carbon atoms, Y is halogen, and 0 ≦ _n ≦ ₃ to be. The subcatalyst component [C] can be classified into an internal electron donor present in the catalyst as an electron donor and an external electron donor administered together with the promoter during polymerization.

The internal electron donor is added during the preparation of the catalyst, and phthalate-based compounds, carboxylic acid ester compounds or ether compounds are suitable. Specifically, the phthalate compounds may exemplify diisobutyl phthalate, dioctyl phthalate, dibutyl phthalate, dipropyl phthalate, diphenyl phthalate, or the like or a mixture thereof. Also ether compounds are 2,2-dimethyl 1,3-dimethoxypropane in the form of 1,3-diether, 2,2-diisopropyl-1,3-dimethoxypropane, 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 the like or these Can be exemplified. In addition, the ester compound can illustrate various benzoate compounds.

As an external electron donor, specifically, the compound which has a structure of following formula (III), especially a silicon compound is mainly used.

R ¹

|

R ⁴ ― X ― R ²

|

R ³

(Ⅲ)

(Wherein R ¹ , R ³ is an alkoxy group such as methoxy, ethoxy, butoxy or an arylalkyl group, R ² is an alkyl group such as methyl, ethyl, butyl or an alkoxy group such as methoxy, ethoxy, butoxy or an arylalkyl group) , R ⁴ is an aromatic group such as phenyl, anthracenyl, naphthalenyl or a cycloaliphatic group such as cyclopentyl, cyclohexyl, cyclooctyl, and X is carbon, silicon, etc.)

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 it is 0.001 mol% or less, the problem that the improvement of stereoregularity does not occur, and if it is 50 mol% or more, it no longer affects stereoregularity.

In preparing the catalyst, the nonionic surfactants used to precipitate the precursor components are polyhydric alcohols or polyalcohols, which is better when polyhydric alcohols are used, and this is best mixed with mineral oil.

In the present invention, a Ziegler-Natta-based catalyst having high activity, high stereoregularity and good particle size is prepared by using a phthalate compound as an internal electron donor in the catalyst precursor prepared from the mixed solution of the nonionic surfactant and the mineral oil. The manufacturing method is as follows.

Magnesium dichloride is used as a magnesium-based carrier material to dissolve in a mixed solution of an organic alcohol and an aromatic hydrocarbon solvent. In the next step, phthalic anhydride, which is a substance that helps precipitate with a titanium compound, is added. The melting temperature is preferably 0 to 110 ° C, particularly 50 to 70 ° C, and 0.1 to 10 moles of organic alcohol is added to 1 mole of magnesium dichloride. As the organic alcohol, aliphatic alcohols, alicyclic alcohols and aromatic alcohols having 5 to 20 carbon atoms are used, and 2-ethylnucleic acid is best. As the aromatic hydrocarbon solvent, benzene, toluene, xylene, benzene chloride, etc. may be used, and toluene is the best.

The temperature of the magnesium compound solution obtained as described above is lowered to 0 ° C., and stirring is continued while slowly dropwise adding a mixed solution of 30 ml of mineral oil, 3 ml of a nonionic surfactant propane diol, and 20 ml of titanium chloride to form a suspension. The time for dropwise addition of the titanium tetrachloride mixed solution is 1 to 3 hours to obtain a uniform size of precipitate.

The solid component obtained as described above was added to toluene, the temperature was raised to 80 ° C., and an internal electron donor was added. After 1 hour of holding, a mixed solution of titanium tetrachloride and toluene was added and maintained at a temperature of 80 to 110 ° C. for 1 to 3 hours. In addition, the solid component is filtered and washed with a hydrocarbon solvent such as nucleic acid, heptane, octane, benzene, toluene, etc. to filter out excess titanium or other impurities on the solid surface. More specifically, 5-20 mol of titanium tetrachloride is added to 1 mol of magnesium dichloride, followed by washing with a hydrocarbon solvent until no titanium is detected in the washing solvent, and then repeating the same process using dichloroethane. .

In the present invention, the term "polymerization" is used to include not only homopolymerization but also copolymerization, and the term "polymer" is used to mean not only homopolymer but also copolymer.

As used herein, the term "polypropylene" refers to a block or irregular copolymer of propylene homopolymers or other α-olefins having 2 to 18 carbon atoms. Examples of other α-olefins include ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene. The amount of α-olefin copolymerized with propylene is from 0 to 50 mol% per mol of propylene.

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, petroleum, such as gasoline, kerosene, and diesel, etc., and an external electron donor may not be added. Polymerization temperature is -50-350 degreeC normally, 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 atmospheric pressure to 250 kg / cm ² , preferably at atmospheric 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 more than 250 kg / cm ^{2 It} is not preferable in terms of industrial and economic.

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, polypropylene exhibiting properties and high stereoregularity according to the present invention can be mixed with low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, polybutene, EP (ethylene / propylene) rubber and the like.

Hereinafter, the present invention will be described by examples, but the present invention is not limited by these examples.

In the following examples, stereoregularity was measured by the following method.

Stereoregularity (I.I .: Isotacticity Index)

Stereoregularity of polypropylene was performed with the Isotacticity Index (I. I.), 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 after extraction, the remaining polymer was collected and dried in vacuo at 80 ° C., quantitatively weighed, and the weight ratio of the remaining polymer to the weight of the original polymer was calculated. It was.

(Example 1)

-Ziegler-Natta catalyst preparation

5 g of anhydrous magnesium chloride, 30 ml of toluene, and 24.5 ml of 2-ethylnucleic acid were added to a glass reactor with a stirrer, and the stirring was continued until a clear solution was produced while raising the temperature to 60 ° C. while stirring at 400 RPM. After the clear solution was formed, the temperature was lowered to 0 ° C., and a mixture of 30 ml of mineral oil, 3 ml of propane diol as a nonionic surfactant, and 20 ml of titanium chloride was slowly added dropwise to maintain a suspension. The solution was kept at room temperature for 1 hour, and then filtered to obtain a catalyst precursor.

The filtered catalyst precursor was placed in 30 ml of toluene, and the temperature was raised to 80 ° C., after which diisobutyl phthalate was added, and maintained at 80 ° C. for 1 hour. A mixed solution of 20 ml of titanium tetrachloride and 20 ml of toluene was added thereto and maintained at 90 ° C. for 2 hours. After filtering by a filter, the obtained catalyst was washed four times with 100 ml of purified heptane, and then washed four times with 100 ml of dichloroethane to obtain a solid catalyst.

The specific surface area of the catalyst was 330 m ² / g and the pore volume was 0.48 cc / g. The composition of the catalyst was analyzed and the titanium content was 2.0% by weight.

Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.

(Example 2)

Experiment was carried out under the same conditions as in Example 1. However, the nonionic surfactant was changed to ethylene glycol.

Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.

(Example 3)

Experiment was carried out under the same conditions as in Example 1. However, the nonionic surfactant was changed to 1,2-octanediol.

Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.

(Example 4)

Experiment was carried out under the same conditions as in Example 1. The internal electron donor was changed to ethyl benzoate.

Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.

(Comparative Example 1)

For comparison, instead of the catalyst prepared in the same manner as in Example, it was prepared in the following manner without the addition of a nonionic surfactant.

Magnesium dichloride was added to 5 g of anhydrous magnesium chloride, 30 ml of toluene and 24.5 ml of 2-ethylnucleic acid, and the stirring was continued at a rate of 400 RPM while raising the temperature to 60 ° C until a clear solution was produced. After the clear solution was formed, the temperature was lowered to 0 ° C., and the mixed solution of 20 ml of titanium tetrachloride was slowly added dropwise to continue stirring. The temperature of this solution is raised to 80 ° C., after which diisobutyl phthalate is added, it is maintained at 80 ° C. for 1 hour. To this, a mixture of 20 ml of titanium tetrachloride and 20 ml of toluene was added and maintained at 90 ° C. for 2 hours. The catalyst obtained after filtration was washed four times with 100 ml of purified heptane and then washed four times with 100 ml of dichloroethane to obtain a solid catalyst.

The specific surface area of the catalyst was 279 m ² / g and the pore volume was 0.38 cc / g. The composition of the catalyst was analyzed and the titanium content was 2.4% by weight.

Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.

(Comparative Example 2)

The experiment was carried out as in Comparative Example 1 and ethylbenzoate was used as the internal electron donor.

Polymerization activity, stereoregularity and average particle diameter of the polymer are shown in Table 1.

Catalytic Performance Evaluation

Propylene was polymerized using a 2 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 normal pressure of propylene in the reactor. After putting 450 g of propylene into the reactor, 7.5 × 10 ⁻⁴ mol of triethylaluminum, 7.5 × 10 ⁻⁵ mol of cyclohexyldimethoxymethylsilane or ethoxyethylbenzoate with the temperature set at 25 ° C., the catalyst prepared above 3.0 × 10 ⁻⁶ mol was added sequentially to maintain a stirring speed of 450 rpm for 5 minutes, and then the reactor temperature was raised to 70 ° C. to fix the total reaction time at 1 hour, and 5 ml of ethanol was added to terminate the polymerization. The reaction product was stirred for 24 hours in about 5 wt% HCl-methanol and again for 24 hours in clean methanol. Subsequently, the filter paper was filtered and dried in vacuo 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.

The polymerization results of the propylene polymerization catalyst prepared by the above method are shown in Table 1 below.

Surfactants Internal electron donor Active (per g-catalyst) Stereoregularity ^a Average particle size ^b (㎛) Example 1 Propanediol Diisobutyl phthalate 33,000 97 1,100 Example 2 Ethylene glycol Diisobutyl phthalate 30,000 94 900 Example 3 1,2-octanediol Diisobutyl phthalate 31,000 95 950 Example 4 Propanediol Ethylbenzoate 29,000 94 880 Comparative Example 1 - Diisobutyl phthalate 27,000 95 850 Comparative Example 2 - Ethylbenzoate 26,000 94 800

^a quantity left undissolved in boiling heptane

^b Average particle diameter of polymerized polypropylene

Polypropylene produced by the invention is reflected in the excellent particle size of the catalyst as it is, the particles are large, the size distribution is even, and the stereoregularity is also excellent, it is excellent in various injection moldings, sheets, plates, films, textile products.

Claims (2)

In the catalyst for preparing active, high-stereoregular polypropylene, magnesium dichloride is dissolved in a mixed solvent of organic alcohol and aromatic hydrocarbon, and then a suspension is formed by adding a mixed solution of mineral oil, nonionic surfactant and titanium tetrachloride. A method for producing a Ziegler-Natta catalyst for olefin polymerization, comprising preparing a precursor, adding an organophthalate compound to the precursor as an internal electron donor, and then carrying a halogen titanium compound. delete