KR100874029B1 - Method for producing a polyolefin polymer production catalyst having a narrow molecular weight distribution and the catalyst obtained thereby - Google Patents

Abstract

A method for producing a titanium-containing catalyst for polyolefin polymerization having magnesium, titanium and halogen as essential components, comprising: a) iii) a magnesium compound; Ii) alcohols having 6 or more carbon atoms; And iii) stirring the hydrocarbon solvent to produce a homogeneous solution; b) preparing a mixture by adding an alcohol having 5 or less carbon atoms to the homogeneous solution obtained in step a); c) contacting the mixture obtained in step b) with a halogenated titanium compound; And d) contacting the catalyst component obtained in the step c) with a silane compound. A method of producing a titanium-containing catalyst for polyolefin polymerization is provided.

Catalyst preparation method according to the present invention is easy to control the particle size of the catalyst is possible to prepare a polymer powder having a variety of average particle size distribution, it is also not preferable in the polyolefin polymer powder by using a catalyst prepared according to the method of the present invention It is possible to obtain a polyolefin polymer having a low amount of fine particles, a uniform particle size of the polymer powder, and a narrow molecular weight distribution.

Description

Method for preparing catalyst for polymerizing polyolefin having narrow range molecular weight distribution and the catalyst prepared using the same

The present invention relates to a method for preparing a catalyst for producing a polyolefin polymer and a catalyst prepared by the above method, and more particularly, to a polymer having a very uniform polymer particle size distribution, easy to control the average particle size, and a narrow molecular weight distribution in a polyolefin polymerization. The present invention relates to a method for producing a titanium-containing catalyst and a catalyst produced by the above method.

In the above, particle size means the diameter of the polyolefin polymer powder obtained by polymerization. In the process of making the powder into pellets again, if the powder particle size is too large, there is a problem in that the powder is not melted well in the process of melting the powder to make the pellet, if the particle size is too small, the powder is scattered and is not suitable for processing As such, the polyolefin polymer needs to be adjusted to a suitable size particle size.

The average particle size (average particle diameter of powder particles) and particle size distribution of polyolefin polymers prepared in powder form using a Ziegler type catalyst are generally influenced by the particle size and particle size distribution of the catalyst used. Because of these replication phenomena, techniques for controlling the particle size and distribution of Ziegler type catalysts are the key to producing polyolefin polymer powders of the desired average particle size. For this reason, many techniques for controlling the particle size of catalysts have been published. These often include treating the carrier in various ways. As one of such techniques, many techniques have been shown in the literature to dissolve a carrier in a soluble solvent and then recrystallize it. (U.S. Patent Nos. 4,330,649, 5,106,807, 5,459,116, 4,315,874, 4,399,054, 4,071,674, 4,439,540, JP 63-54004)

Magnesium chloride, one of the most commonly used carriers, is a soluble solvent commonly used in recrystallization methods because of high solubility in alcohol, aldehydes, amines, and the like. Among them, alcohols having 6 or more carbon atoms, among them, octanol is present as a homogeneous solution in which magnesium is completely dissolved at a high temperature of 100 ° C. or higher when used with hydrocarbon solvents such as decane, kerosene, hexane, etc., and magnesium compounds do not reprecipitate even at room temperature. . This type of homogeneous solution can produce a catalyst of a solid component through various treatment methods. Most easily, the homogeneous solution is brought into contact with a tetravalent halogen-containing titanium compound such as titanium tetrachloride to obtain a solid titanium compound. This method eliminates the recrystallization process by lowering the temperature of the solution or adding a non-solvent, and forms a solid catalyst by directly reacting the homogeneous solution of the liquid magnesium compound with the halogen-containing titanium compound. It has the advantage of being easy to use, excellent in activity, very high specific gravity of polymer and very uniform particle size distribution. The particle size of the catalyst prepared in this way is greatly influenced by the reaction temperature of the homogeneous solution and the titanium chloride compound and the magnesium concentration of the homogeneous solution. The average particle size of the catalyst formed when the reaction temperature of the homogeneous solution and the titanium chloride compound is at a high temperature such as room temperature (25 ° C) is higher than that of the catalyst formed when the reaction temperature of the homogeneous solution and the titanium chloride compound is relatively low, such as -20 ° C. Smaller than the average particle size, the average particle size of the prepared polymer powder is reduced as well as the content of undesirable microparticles is increased. In addition, when the magnesium content of the homogeneous solution is high, the particle size of the prepared catalyst decreases, thereby increasing the content of the fine particles in the prepared polymer powder.

 Korean Patent No. 0371405 discloses a technique for producing a solid component catalyst by contacting a halogen-containing titanium mixture with one or more alcohols added to a homogeneous solution of a magnesium compound. By controlling the magnesium concentration of the mixture to which alcohol is added and the temperature at the time of first contact with the halogen-containing titanium, it is possible to easily control the catalyst particle size and obtain a catalyst having a very high activity. In addition, the polyolefin polymer obtained using this catalyst contains less fine particles and has a higher specific gravity.

On the other hand, molecular weight distribution is a particularly important property for polyolefin polymers. The molecular weight distribution affects the rheological behavior of the melt and hence the processability and final mechanical properties. In the polyolefin polymer having a wide molecular weight distribution, the high molecular weight portion may improve physical properties and the low molecular weight portion may serve to improve processability. In general, two reactors are successively used to secure a polymer having a wide molecular weight distribution. In the first reactor, a low molecular weight polymer is produced, and a high molecular weight polymer is formed in the second reactor. However, in general, when the molecular weight distribution of the polymer produced by the catalyst is widened, unnecessarily low molecular weight polymer of the final product increases, which may cause problems in the production process or productivity, and adversely affect the processability and physical properties of the final product. There are side effects.

Accordingly, it is an object of the present invention to provide a method for producing a titanium-containing catalyst capable of producing a polyolefin polymer having a very uniform particle size distribution of polymer powder, easy control of the average particle size, and a narrow molecular weight distribution.

Another object of the present invention is to provide a catalyst prepared by the above method.

In order to achieve the above object, the present invention provides a method for producing a titanium-containing catalyst for polyolefin polymerization containing magnesium, titanium, halogen and silane compounds,

a) magnesium compound; Alcohols having 6 or more carbon atoms; And stirring the hydrocarbon solvent to prepare a homogeneous solution;

b) preparing a mixture by adding an alcohol having 5 or less carbon atoms to the homogeneous solution obtained in step a);

c) contacting the mixture obtained in step b) with a halogenated titanium compound to prepare a mixture comprising a titanium containing catalyst; And

d) a method of producing a titanium-containing catalyst for polyolefin polymerization, comprising contacting a mixture comprising a titanium-containing catalyst obtained in step c) with a silane compound.

According to one embodiment of the present invention, the amount of the silane compound added in step d) may be 0.1 to 100 moles per mole of titanium-containing catalyst produced from step c).

According to another embodiment of the present invention, the silane compound of step d) may be one or more mixtures selected from the group consisting of compounds represented by the following Chemical Formula 1:

Si (OR ') _m R ” _(4-m)

Wherein R 'is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or amino group having 1 to 14 carbon atoms, R' is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 14 carbon atoms, phenyl or halide, m Is an integer having a range of 0 ≦ m ≦ 4.

In order to achieve the above another object, the present invention also provides a titanium-containing catalyst for polyolefin polymerization produced by the above production method.

According to the catalyst production method according to the invention it is easy to control the particle size of the catalyst. Therefore, using the catalyst obtained thereby, it is possible to produce a polymer powder having a variety of average particle size distribution. The polyolefin polymer powder also has a low amount of undesirable microparticles, a uniform particle size, and a narrow molecular weight distribution.

Hereinafter, the present invention will be described in more detail.

Method for producing a titanium-containing catalyst for polyolefin polymerization comprising magnesium, titanium, halogen and silane compounds according to the present invention,

a) magnesium compound; Alcohols having 6 or more carbon atoms; And stirring the hydrocarbon solvent to prepare a homogeneous solution;

b) preparing a mixture by adding an alcohol having 5 or less carbon atoms to the homogeneous solution obtained in step a);

c) contacting the mixture obtained in step b) with a halogenated titanium compound to prepare a mixture comprising a titanium containing catalyst; And

d) contacting the mixture comprising the titanium containing catalyst obtained in step c) with a silane compound.

The present invention is an improvement of Korean Patent No. 0371405, which claims a method for preparing a titanium-containing catalyst for polyolefin polymerization, comprising steps a), b) and c), wherein step d), ie, contacting a silane compound It characterized in that it further comprises the step of. According to the present invention, the particle size of the catalyst prepared by the Republic of Korea Patent No. 0371405 is uniform, and the average particle size of the catalyst can be easily adjusted, so that a polymer powder having a uniform particle size can be produced, and polyolefin having various average particle sizes. While maintaining the characteristics that the polymer powder can be produced, the silane compound is brought into contact with the catalyst prepared by Korean Patent No. 0371405, thereby preparing a catalyst capable of producing a polymer having a narrower molecular weight distribution.

In the catalyst according to the present invention, the particle size of the final polyolefin polymer powder is controlled in the same manner as in Korean Patent No. 0371405, in which the concentration of the magnesium compound in the homogeneous solution obtained in step a), and the alcohol used in steps a) and b). It can achieve as a kind, reaction temperature, etc., By using a catalyst by this, the polyolefin polymer powder which has a desired average particle size and particle size distribution can be manufactured.

On the other hand, in the conventional production of a titanium-containing catalyst for polyolefin polymerization, the silane compound is already included in the carrier generation step to act as a nucleating agent for particle generation, or used as an electron donor in the post-treatment step, the silane compound in the present invention is a carrier By being used in the step of reforming the catalyst after production, the process operation is very simple by acting as a modifier and by contacting after carrier production.

The catalyst of the present invention uses a magnesium compound and an alcohol having at least 6 carbon atoms as a hydrocarbon solvent to form a homogeneous solution of the magnesium compound, and then adds one or more alcohols having 1 to 5 carbon atoms to the liquid tetravalent liquid. A solid component formed by contacting with a halogenated titanium compound and then contacting with a silane compound again includes magnesium, titanium and halogen as essential components.

 Magnesium compounds used in the present invention are non-reducible, such as magnesium halides such as magnesium chloride, magnesium bromide, magnesium fluoride, magnesium iodide and the like; Magnesium alkoxy halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isoproxy magnesium chloride, magnesium butoxy chloride, ocoxy magnesium chloride and the like; Allyloxy halide magnesium such as phenoxy magnesium chloride and the like; Alkoxy magnesium, such as ethoxy magnesium, isoproxy magnesium, butoxy magnesium, etc., These magnesium compounds can be used in mixture of 2 or more. Of these, halogen-containing magnesium is useful, and magnesium chloride is particularly preferable.

 Alcohols having 6 or more carbon atoms used in the present invention include n-hexanol, n-heptanol, n-octanol, decanol, dodecanol, 2-methylpentanol, 2-ethylbutanol, 2-ethylhexanol, and the like. Like aliphatic alcohols; Arylcyclic alcohols such as cyclohexanol, methylcyclohexanol and the like; Aromatic alcohols such as benzyl alcohol, methyl benzyl alcohol, isopropyl benzyl alcohol, α-methyl benzyl alcohol, and the like, and may be used by mixing two or more kinds thereof. Preferably, aliphatic alcohols are useful, especially 2-ethylhexyl alcohol. desirable.

Homogeneous solutions of magnesium compounds can be obtained by contacting the above-mentioned magnesium compounds with alcohols having 6 or more carbon atoms with a hydrocarbon solvent, and the hydrocarbon solvents usable here are pentane, hexane, heptane, octane, decane, dodecane, tetradecane, kerosene. Aliphatic hydrocarbons such as sen; Alicyclic hydrocarbons such as cyclic pentane, cyclic hexane, cyclic octane, methyl cyclic pentane, methyl cyclic hexane and the like; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; Halogenated hydrocarbons such as dichloroethane, dichloropentane, trichloroethane, carbon tetrachloride, chlorobenzene and the like, and preferably aliphatic hydrocarbons are used, and hexane, heptane and decan are particularly preferred. Alcohols of 5 or less carbon atoms may be used instead, but only about 15 times the molar ratio of magnesium compounds is completely dissolved. If less than this, alcohol precipitates of magnesium compounds may be formed at room temperature.

The homogeneous solution of the magnesium compound can be formed by simply mixing and stirring a magnesium compound, an alcohol having 6 or more carbon atoms, and a hydrocarbon solvent, but applying heat greatly helps dissolving the magnesium compound. Dissolution temperature is preferably 100 to 150 ℃. At this time, the alcohol to be used is 0.5 to 10 mol per mol of the magnesium compound, preferably 1.5 to 5 mol is useful. The dissolution of the magnesium compound depends on the magnesium compound used, the type and molar ratio of alcohol and hydrocarbon, but in general, the higher the molar ratio of alcohol, the higher the dissolution temperature, the easier dissolution, and when the magnesium compound is not completely dissolved, more alcohol may be added or Higher temperatures will help dissolve the magnesium compound.

In step a), the amount of the C6 or more alcohol to 1 mol of the magnesium compound is preferably 0.5 to 10 mol, and the amount of the hydrocarbon solvent is preferably 15 to 200 mol. When less than 0.5 mole of alcohol having 6 or more carbon atoms per mole of the magnesium compound is added, there is a problem that magnesium is not dissolved, and when it exceeds 10 moles, there is a problem that heat removal is difficult when adding a titanium compound. In addition, when less than 15 moles of hydrocarbon solvent per 1 mole of magnesium compound, there is a problem that does not dissolve when dissolving magnesium, there is a problem that the reactivity becomes low when excessively added in excess of more than 200 moles Can be.

Next, one or more alcohols having 5 or less carbon atoms are added to the homogeneous solution of the magnesium compound to form a mixture. At this time, the molar ratio of the alcohol having 5 or less carbon atoms to 1 mol of the magnesium compound is 0.5 to 6 mol, preferably 0.5 to 3 mol. When less than 0.5 mol of alcohol having 5 or less carbon atoms is added to 1 mol of the magnesium compound, there is a problem in that the particle size distribution of the catalyst is widened, and when it exceeds 6 mol, there is a problem in that the particle size distribution of the catalyst is widened. Examples of the alcohol having 5 or less carbon atoms include methanol, ethanol, isopropanol, n-butanol, tert-butanol, n-pentanol, and the like. If the molar ratio of methanol and ethanol is high, precipitation of a magnesium compound may be formed. Among the above examples, the alcohol having 5 or less carbon atoms is preferably ethanol, and more preferably, ethanol and methanol are used together.

Next, a tetravalent halogenated titanium compound represented by the formula (2) is brought into contact with the compound to form a catalyst.

Ti (OR) _n X _4-n

In the above formula, R is a hydrocarbon group, n is an integer having a range of 0 ≦ n <4, and X is halogen.

Specific examples of such a halogenated titanium compound include titanium tetrahalide such as TiCl ₄ , TiBr ₄ , TiI ₄ ; Alkoxy titanium trihalides such as Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br _3, and the like; Alkoxy titanium dihalides such as Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br _2, and the like; Alkoxy tritide halides such as Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br, and the like. Among them, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferred. More preferred.

When the mixture formed by adding alcohol having 5 or less carbon atoms to the homogeneous solution of the magnesium compound is contacted with the halogenated titanium compound, the average particle size of the catalyst is higher than the catalyst which is contacted with the halogenated titanium compound without adding alcohol having 5 or less carbon atoms to the homogeneous solution of the magnesium compound. Increases significantly. That is, the addition of alcohols having 5 or less carbon atoms before the reaction of the homogeneous solution with the halogenated titanium compound has the effect of increasing the average particle size of the final catalyst, especially when mixed with ethanol and methanol, the average particle size of the catalyst further increases , Fine particles of less than 100 μm are also significantly reduced.

 The reaction temperature of the homogeneous solution or mixture of the magnesium compound and the titanium halide compound is -50 to 100 ° C, preferably -20 to 80 ° C, particularly 10 to 50 ° C. This is the reaction temperature of the first homogeneous solution or mixture with the titanium compound.The reaction proceeds in the form of stirring the homogeneous solution or mixture in the reactor and adding a certain amount of titanium compound little by little for a certain time. Post-treatment can be done by adding or adding other types of titanium compounds.

 The magnesium concentration of the homogeneous solution or mixture, together with the reaction temperature with the halogenated titanium compound, affects the average particle size of the catalyst and the magnesium concentration is from 5 to 100 g / l, preferably from 10 to 50 g / l. The concentration of the catalyst can be controlled by the amount of hydrocarbon solvent when the magnesium compound is dissolved in the soluble solvent, and the average particle size of the catalyst tends to decrease as the concentration of the magnesium compound in the homogeneous solution or mixture is increased.

 The catalyst of the present invention is formed by contacting a silane compound represented by the following formula (1) with a solid complex titanium-containing catalyst formed as described above.

<Formula 1>

Si (OR ') _m R ” _(4-m)

Wherein R 'is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or amino group having 1 to 14 carbon atoms, R' is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 14 carbon atoms, phenyl or halide, m Is an integer having a range of 0 ≦ m ≦ 4.

Preferably, the silane compound is allyltrialkoxysilane, allyltrialkylsilane, alkyltrialkoxysilane, cycloalkylalkyldialkoxysilane, dialkyldialkoxysilane, phenyltrialkylsilane, phenyltrialkoxysilane, alkylaminotrie At least one mixture selected from the group consisting of oxysilane and aminotrialkoxysilane.

Specific examples of the silane compound represented by Formula 1 include cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane, methyltriethoxysilane, methyltrichlorosilane, phenyltrimethylsilane, phenyltriethoxysilane and dicyclopentyl Dimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, diisopropyldimethoxysilane, dibutyl butyldimethoxysilane, dicyclohexyldimethoxysilane, isobutylisopropyldimethoxysilane , Isobutyl secondary butyl dimethoxysilane, isobutyl cyclopentyldimethoxysilane, isopropyl secondary butyldimethoxysilane, isopropylcyclopentyldimethoxysilane, diisopropyldicyclopentylsilane, dimethyldiisopropeneoxysilane, di Phenyldimethoxysilane, Diphenyldiethoxysilane, Dodecyltriethoxysilane, Isobutyltriethoxysilane, Isobutylt Silane, the silane, vinyl tri on ethylamino tree and the like can be given silane or methyl cyclopentyl dimethoxysilane.

Preferably, the silane compound is preferably used from 0.1 to 100 moles per mole of titanium components in the titanium-containing catalyst produced from step c). When the amount of the silane compound used is less than 0.1 mole per mole of the titanium component in the titanium-containing catalyst produced from step c), MFRR does not decrease, and when it exceeds 100 moles, there is a problem that the catalytic activity falls.

(d) The reaction temperature of the contacting step of the silane compound is preferably 0 to 100 ° C., and is sufficiently stirred for 0.1 to 1 hour.

The contact with the silane compound of step d) serves to narrow the molecular weight distribution of the polymer. That is, in the case of contacting the silane compound with the catalyst prepared by Korean Patent No. 0371405 again, the contact of the silane compound is eventually uniform by inactivating the place where the molecular weight of the polymer may be too small or too large at the polymer production site on the carrier. The polymer produced by producing a polymer of molecular weight has a narrow molecular weight distribution.

MFRR (melt flow rate ratio) is a value indicating the distribution of the molecular weight of the polymer. A high value of MFRR means a wide distribution of the polymer molecular weight, and a low value means that the distribution of the polymer molecular weight is narrow. Therefore, MFRR values were measured and compared in order to confirm the effect of narrowing the polymer molecular weight distribution by contacting with a silane compound in Examples described later.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the examples are only for illustrating the present invention and are not limited thereto.

Example

What is shown in this embodiment is that by comparing the catalyst prepared by the catalyst preparation method of the present invention with the catalyst according to the invention of Korean Patent No. 0371405, the particle size distribution which is a property of the catalyst according to the invention of Korean Patent No. 0371405 is uniform. In addition to maintaining the properties capable of producing a polymer (see Table 2), it was also confirmed that the addition of the contacting step of the silane compound of step d) has an effect of narrowing the molecular weight distribution of the polymer (see Table 1).

Comparative Example 1

[Production of Solid Titanium-Containing Catalyst Component]

Preparation of the catalyst for polyolefin polymerization was prepared according to the method shown in Example 1 of Korean Patent No. 0371405. The contents of the patents relating to the preparation of the catalyst for polyolefin polymerization used in this embodiment are cited in this embodiment as a whole, even if there is no special mention.

The solid dried catalyst thus obtained contained 3.0 wt% titanium, 56.4 wt% chlorine, and 17.2 wt% magnesium.

[polymerization]

1 L of purified hexane was added to a 5 L stainless autoclave sufficiently substituted with nitrogen, the temperature was adjusted to 80 ° C., 4 mmol of triethylaluminum was added, and then the solid catalyst component prepared by the above-mentioned method. 0.05 mmol was added based on the titanium atom. Hydrogen was added so that the pressure in the reactor was 60 psi, the pressure in the reactor was maintained at 128 psi and ethylene was added for 1 hour to polymerize. After the polymerization, the polymer in the form of a slurry was filtered to give 411 g of a polymer in powder form. The polymer had a melt index of 0.85 (2.16 kg / 10 min), an apparent density of 0.24 and an average particle size of 156 μm.

Example 1

[Production of Solid Titanium-Containing Catalyst Component]

100 mL of the catalyst (31.4 mM) used in Comparative Example 1 was placed in a 250 mL flask and 6.2 mL of cyclohexylmethyldimethoxysilane was added at room temperature for 10 minutes. Stir at room temperature for 2 hours. The catalyst thus well dried was 1.5 wt% titanium, 26.0 wt% chlorine, and 7.7 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in the polymerization example of Comparative Example 1, and the polymerization results are shown in Table 1.

Example 2

[Production of Solid Titanium-Containing Catalyst Component]

Prepared in the same manner as in the catalyst component preparation method of Example 1, except that 0.62 mL of cyclohexylmethyldimethoxysilane was used in Example 1. The catalyst thus well dried was 2.9 wt% titanium, 50.7 wt% chlorine, and 14.5 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in the polymerization example of Comparative Example 1, and the polymerization results are shown in Table 1.

Example 3

[Production of Solid Titanium-Containing Catalyst Component]

100 mL of the catalyst (31.4 mM) used in Comparative Example 1 was placed in a 250 mL flask, and 7.5 mL of diethylaminotriethoxysilane was added at room temperature for 10 minutes. Stir at room temperature for 2 hours. The catalyst thus well dried was 1.5 wt% titanium, 21.8 wt% chlorine, and 6.7 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in the polymerization example of Comparative Example 1, and the polymerization results are shown in Table 1.

Example 4

[Production of Solid Titanium-Containing Catalyst Component]

100 mL of catalyst (31.4 mM) used in Comparative Example was placed in a 250 mL flask, and 6.2 mL of diisopropyldimethoxysilane was added at room temperature for 10 minutes. Stir at room temperature for 2 hours. The well dried catalyst thus obtained had a content of 1.4 wt% titanium, 28.1 wt% chlorine, and 8.3 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in the polymerization example of Comparative Example 1, and the polymerization results are shown in Table 1.

Example 5

[Production of Solid Titanium-Containing Catalyst Component]

100 mL of the catalyst (31.4 mM) used in Comparative Example 1 was placed in a 250 mL flask, and 7.6 mL of phenyltriethoxysilane was added at room temperature for 10 minutes. Stir at room temperature for 2 hours. The well dried catalyst thus obtained had a content of 1.2 wt% titanium, 23.7 wt% chlorine and 6.7 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in the polymerization example of Comparative Example 1, and the polymerization results are shown in Table 1.

Example 6

[Production of Solid Titanium-Containing Catalyst Component]

100 mL of the catalyst (31.4 mM) used in Comparative Example 1 was placed in a 250 mL flask, and 6.3 mL of methyltriethoxysilane was added at room temperature for 10 minutes. Stir at room temperature for 2 hours. The catalyst thus well dried was 1.5 wt% titanium, 26.9 wt% chlorine, and 8.0 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in the polymerization example of Comparative Example 1, and the polymerization results are shown in Table 1.

Example 7

[Production of Solid Titanium-Containing Catalyst Component]

100 mL of the catalyst (31.4 mM) used in Comparative Example 1 was placed in a 250 mL flask, and 5.4 mL of phenyltrimethylsilane was added at room temperature for 10 minutes. Stir at room temperature for 2 hours. The well dried catalyst thus obtained had a content of 1.7 wt% titanium, 29.4 wt% chlorine and 8.9 wt% magnesium.

[polymerization]

The polymerization was carried out in the same manner as in the polymerization example of Comparative Example 1, and the polymerization results are shown in Table 1.

division Amount Melt Index (MFR, 2.16kg) MFRR Apparent Density (BD) Average particle size g g / 10min 21.6Kg / 2.16Kg g / cm 3 Μm Comparative Example 1 411 0.85 33.8 0.33 156 Example 1 55 0.29 31.9 0.12 79 Example 2 33 0.26 31.1 - 66 Example 3 64 0.89 27.0 0.20 66 Example 4 32 0.20 31.9 - 65 Example 5 12 0.54 30.8 - 50 Example 6 13 0.36 30.6 - 56

Table 1 shows the particle size, distribution, etc. of the catalysts according to Examples 1 to 9, further comprising contacting the catalyst according to the invention of Korean Patent No. 0371405 (Comparative Example 1) with the step silane compound d) of the present invention. have. In the above, the values of MFRR values of Examples 1 to 9 are significantly smaller than those of Comparative Example 1. Since the MFRR value shows the resulting polymer molecular weight distribution, it was confirmed that the effect of narrowing the molecular weight distribution of the polymer can be obtained by further including the step of contacting the silane compound of step d) according to the present invention.

Comparative Example 1 Example 7 Average particle size (㎛) 156 152 Polymer powder particle size (%) Particles less than 63 μm 2.0 2.7 > 841 μm 0 0 841 μm to 500 μm 0 0 500 μm to 250 μm 4.3 3.9 250 μm to 160 μm 41.9 39.2 160 μm to 63 μm 51.7 54.2 63 μm to 37 μm 0.9 1.2 <37 μm 1.2 1.5

Table 2 compares the particle size distribution of the polymer powder of Comparative Example 1, which is a catalyst according to the invention of Korean Patent No. 0371405, and Example 7, of the present invention. Both results show a nearly similar distribution. Therefore, even if the present invention further comprises the step of contacting the silane compound of step d), the effect of the catalyst (Comparative Example 1) according to the invention of Korea Patent No. 0371405 having a uniform particle size distribution is maintained as it is, according to the present invention. It can be seen that the polymer powder produced by the catalyst also has a uniform particle size distribution.

According to the catalyst production method according to the invention it is easy to control the particle size of the catalyst. Therefore, using the catalyst obtained thereby, it is possible to produce a polymer powder having a variety of average particle size distribution. The polyolefin polymer powder also has a low amount of undesirable microparticles, a uniform particle size, and a narrow molecular weight distribution.

Claims (15)

A method for producing a titanium-containing catalyst for polyolefin polymerization comprising magnesium, titanium, halogen and silane compound, a) magnesium compound; Alcohols having 6 to 10 carbon atoms; And stirring the hydrocarbon solvent to prepare a homogeneous solution; b) preparing a mixture by adding an alcohol having 5 or less carbon atoms to the homogeneous solution obtained in step a); c) contacting the mixture obtained in step b) with a halogenated titanium compound to prepare a mixture comprising a titanium containing catalyst; And d) contacting the mixture comprising the titanium containing catalyst obtained in step c) with a silane compound, The magnesium compound is a method for producing a titanium-containing catalyst for polyolefin polymerization, characterized in that at least one selected from the group consisting of magnesium halide, C _1-8 alkoxyhalogenated magnesium, C _1-5 allyloxyhalogenated magnesium and C _1-4 alkoxymagnesium. . [Claim 2] The polyolefin polymerization method of claim 1, wherein the amount of the alcohol having 6 to 10 carbon atoms is 0.5 to 10 mol, and the amount of the hydrocarbon solvent is 15 to 200 mol to 1 mol of the magnesium compound in step a). Process for producing titanium containing catalyst. The method for producing a titanium-containing catalyst for polyolefin polymerization according to claim 1, wherein the magnesium concentration of the homogeneous solution obtained in step a) is 5 to 100 g / l. The method according to claim 1, wherein the amount of the alcohol having 5 or less carbon atoms in step b) is 0.5 to 6 mol per mol of the magnesium compound. The method for preparing a titanium-containing catalyst for polyolefin polymerization according to claim 1, wherein the contact temperature between the mixture and the halogenated titanium compound in step c) is -50 to 100 ° C. The method for producing a titanium-containing catalyst for polyolefin polymerization according to claim 1, wherein the amount of the silane compound added in step d) is 0.1 to 100 moles per mole of titanium component in the titanium-containing catalyst produced from step c). delete The method of claim 1, wherein the alcohol having 6 to 10 carbon atoms in step a) is at least one selected from the group consisting of aliphatic alcohols, arylcyclic alcohols and aromatic alcohols. The method of claim 1, wherein the hydrocarbon solvent is selected from the group consisting of aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons in step a). [Claim 2] The polyolefin polymerization of claim 1, wherein the alcohol having 5 or less carbon atoms in step b) is at least one selected from the group consisting of methanol, ethanol, isopropanol, N-butanol, tert-butanol and n-pentanol. Method for producing a titanium containing catalyst. The method according to claim 1, wherein the titanium halide compound in step c) is at least one compound selected from the group consisting of compounds represented by the formula (2). <Formula 2> Ti (OR) _n X _4-n Wherein R is an alkane having 1 or 2 carbon atoms, n is an integer having a range of 0 ≦ n <4, and X is halogen. 12. The titanium-containing catalyst for polyolefin polymerization according to claim 11, wherein the halogenated titanium compound represented by the formula (2) is selected from the group consisting of titanium tetrahalide, alkoxy titanium trihalide, alkoxy titanium dihalide and alkoxy trititanium halide. Manufacturing method. The method for preparing a titanium-containing catalyst for polyolefin polymerization according to claim 1, wherein the silane compound in step d) is at least one compound selected from the group consisting of compounds represented by Formula 1 below: <Formula 1> Si (OR ') _m R ” _(4-m) In the above formula, R 'is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or amino group having 1 to 14 carbon atoms, R' 'is an aliphatic, alicyclic or aromatic hydrocarbon group or halogen atom having 1 to 14 carbon atoms, m is It is an integer having a range of 0 ≦ m ≦ 4. The silane compound represented by the formula (1) is an allyltrialkoxysilane, allyltrialkylsilane, alkyltrialkoxysilane, cycloalkylalkyldialkoxysilane, dialkyl dialkoxysilane, phenyltrialkylsilane, or phenyltri. Method for producing a titanium-containing catalyst for polyolefin polymerization, characterized in that at least one compound selected from the group consisting of alkoxysilane, alkylaminotriethoxysilane and aminotrialkoxysilane. Solid titanium-containing catalyst for polyolefin polymerization prepared by the production method according to claim 1.