KR20090087632A - A catalyst and a preparation method for ethylene polymer or copolymer using the same - Google Patents

Abstract

A solid titanium complex catalyst is provided to ensure high polymerization activity, to control the shape and size of catalyst particles and to prepare an ethylene polymer or copolymer with high apparent density. A solid titanium complex catalyst for ethylene polymerization or copolymerization is manufactured by the steps of: dissolving a magnesium halide compound in a solvent mixture of cyclic ether and at least one kind of alcohol; injecting a silane compound having an alkoxy group in the resultant and performing the reaction; reacting the resultant and a titanium compound represented by chemical formula: Ti(OR)aX(4-a) to prepare a carrier; and reacting a compound having a titanium compound and a phthalic group with the carrier.

Description

A catalyst for ethylene polymerization or copolymerization, and a method for producing an ethylene polymer or copolymer using the same {A CATALYST AND A PREPARATION METHOD FOR ETHYLENE POLYMER OR COPOLYMER USING THE SAME}

The present invention relates to a catalyst for ethylene polymerization or copolymerization and a method for preparing an ethylene polymer or copolymer using the same, and more particularly, to a solid complex titanium catalyst having a high catalytic activity, and having a controlled particle form, and having a high apparent density using the same. The present invention relates to a method for producing an ethylene (co) polymer having a uniform particle distribution and a spherical particle shape.

Catalysts for ethylene polymerization and copolymerization containing magnesium are known to provide very high catalytic activity and apparent density and are also suitable for liquid and gas phase polymerization. Polyethylene liquid polymerization refers to a polymerization process performed in a medium such as bulk ethylene, isopentane or hexane, and when the catalyst used in the process is applied to the process, high activity, catalyst shape, size, size distribution, apparent The properties of the catalyst, such as density, low molecular weight content, soluble in the medium, are important considerations.

Many catalysts for the polymerization of olefins and catalysts containing titanium and based on titanium have been reported. In particular, many methods using magnesium solution are known to obtain the above-mentioned apparently high density olefin polymerization catalyst. There is a method of obtaining a magnesium solution by reacting a magnesium compound with an electron donor such as an alcohol, an amine, a cyclic ether, or an organic carboxylic acid in the presence of a hydrocarbon solvent. In the case of using alcohol, US Pat. Nos. 3,642,746, 4,336,360, 4,330,649 and 5,106,807. Although a method of preparing a magnesium-supported catalyst by reacting the liquid magnesium solution with a halogen compound such as titanium tetrachloride is well known, such a catalyst provides a high apparent density but has to be improved in terms of the active or hydrogen reactivity of the catalyst. There is this. Tetrahydrofuran, a cyclic ether, is used in US Pat. Nos. 4,477,639 and 4,518,706 as solvents of magnesium compounds.

U.S. Patent Nos. 4,847,227, 4,816,433, 4,829,037, 4,970,186, and 5,130,284 have excellent polymerization activity by reacting electron donors such as magnesium alkoxides, dialkylphthalates, phthaloyl chlorides, and titanium chloride compounds. It is reported that an olefin polymerization catalyst having an improved apparent density is prepared.

U.S. Patent Nos. 4,347,158, 4,422,957, 4,425,257, 4,618,661 and 4,680,381 propose a method of preparing a catalyst after pulverizing a Lewis acid compound such as aluminum chloride to magnesium chloride as a support.

However, in the above patents, although catalytic activity is complemented, there is a problem in that the shape of the catalyst such as the shape, size, size distribution of the catalyst is irregular, and stereoregularity must be complemented.

U.S. Patent No. 5,459,116 reports a method of preparing a supported titanium solid catalyst by bringing a magnesium solution including a ester having at least one hydroxy group as an electron donor into contact with a titanium compound. However, the catalyst having excellent polymerization activity and apparent density can be obtained using the above method, but there is room for improvement in terms of particle shape.

As described above, while the manufacturing process is simple, it is required to develop a new catalyst for ethylene polymerization and copolymerization which can give high polymer apparent density by controlling high polymerization activity, shape and size of catalyst particles, and the like.

An object of the present invention, in order to solve the above problems, a solid complex titanium catalyst having a high catalytic activity, the particle shape is adjustable, and the particle size and particle distribution is controlled and polymerized, thereby ethylene polymer having a high apparent density or It is to provide a method for producing a copolymer.

The solid complex titanium catalyst for ethylene polymerization or copolymerization according to the present invention is characterized by being prepared through the following steps:

(1) dissolving a magnesium halide compound in a mixed solvent of a cyclic ether and at least one alcohol;

(2) injecting a silicon compound having an alkoxy group into the reactant obtained in step (1) and reacting it;

(3) preparing a carrier by reacting the reactant obtained in step (2) with a titanium compound represented by the following general formula (I); And

Ti (OR) _a X _(4-a) ‥‥‥ (I)

(Here, R is an alkyl group having 1 to 10 carbon atoms and X is a halogen atom. In addition, a is an integer of 0 to 3 to match the valence of the general formula.)

(4) reacting a compound having a titanium compound and a phthalic group with the carrier obtained in step (3).

Examples of the magnesium halide compound of step (1) in the method for producing a solid complex titanium catalyst for polyethylene polymerization or copolymerization of the present invention include magnesium halides such as magnesium chloride, magnesium iodide, magnesium fluoride and magnesium bromide; Alkylmagnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide, amylmagnesium halide and the like; Alkoxymagnesium halides such as methoxymagnesium halide, ethoxymagnesium halide, isopropoxymagnesium halide, butoxymagnesium halide and octoxymagnesium halide; And aryloxymagnesium halides such as phenoxyshimam halide and methylphenoxymagnesium halide, and one or two or more of the magnesium halide compounds may be used alone or in combination. can be used as a complex form of the other metal, of preferably a magnesium halide, a C ₁ ~ C ₁₀ alkyl magnesium with an alkyl halide, an alkoxy magnesium halide having an alkoxy group of C ₁ ~ C _10, and C ₆ ~ C ₂₀ Aryloxy magnesium halides having an aryloxy group.

The magnesium halide compounds listed above may be represented by a simple chemical formula, but in some cases, they may not be represented by a simple formula depending on the preparation method of the magnesium compound. have. For example, a compound obtained by reacting a magnesium compound with a polysiloxane compound, a halogen-containing silane compound, an ester, an alcohol, or the like; Compounds obtained by reacting magnesium metal with alcohol, phenol, or ether in the presence of halo silane or thionyl chloride can be used.

In order to dissolve the magnesium halide compound used in the present invention, a mixed solvent of a cyclic ether and at least one alcohol is used in the presence or absence of a hydrocarbon solvent.

The cyclic ether is a cyclic ether having 3 to 6 carbon atoms and a derivative thereof, and for example, tetrahydrofuran, 2-methyltetrahydrofuran and the like can be used, and the most preferred cyclic ether Is tetrahydrofuran.

The hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene, cycloaliphatic hydrocarbons such as cyclobenzene, methylcyclobenzene, cyclohexane and methylcyclohexane, benzene, toluene, xylene, ethylbenzene, cumene And aromatic hydrocarbons such as cymene, dichloropropane, dichloroethylene, trichloroethylene, halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.

The alcohol is a monovalent or polyhydric alcohol having 1 to 20 carbon atoms, preferably an alcohol having 2 to 12 carbon atoms, and the alcohol may be used alone or in combination of two or more thereof.

When the magnesium halide compound is dissolved in a mixed solvent of cyclic ether and alcohol, the molar ratio of the mixed solvent of cyclic ether and alcohol to the magnesium halide compound is 3: 1 to 10: 1, preferably 4: 1 to 8: 1. When the molar ratio is less than 3: 1, dissolution of magnesium compound is not preferable, and when the molar ratio is more than 10: 1, the amount of titanium compound added to obtain catalyst particles in a subsequent step is too large and difficult to control particles. Although not preferable, the dissolution temperature at the time of dissolution depends on the type and amount of cyclic ether and alcohol, but it is preferable to dissolve at a temperature of 200 ° C. or lower, about 50 ° C. to 150 ° C. at room temperature, and it does not dissolve if it is outside the above range. It is not preferable because it is difficult to raise the temperature.

Step (2) in the method for preparing a solid complex titanium catalyst for ethylene polymerization or copolymerization of the present invention is a step of injecting a silicon compound having an alkoxy group into the reactant obtained in step (1) and reacting the same.

The silicon compound having the alkoxy group used as the electron donor in the step (2) can be represented by the following general formula,

R _n Si (OR) _4-n

(Where R is a hydrocarbon having 1 to 12 carbon atoms and n is a natural number of 1 to 3).

Specific examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenylmethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane and phenyl Trimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethylsilicate , Butyl silicate and methyltriaryloxysilane, and the like, and can be used alone or in combination of two or more thereof.

The silicon compound having an alkoxy group used in step (2) is preferably 0.005 to 3 mol, more preferably 0.05 to 2 mol, more preferably 100 ° C. or less, more preferably 10 to 70 ° C. per mol of the magnesium halide compound. Inject and react.

Step (3) of the method for preparing a solid complex titanium catalyst for ethylene polymerization or copolymerization of the present invention is a step of reacting a titanium compound with the reactant obtained in step (2).

The titanium compound may be represented by the following general formula.

Ti (OR) _a X _(4-a) ‥‥‥ (I)

(Wherein R is an alkyl group having 1 to 10 carbon atoms, X is a halogen atom and a is an integer of 0 to 3).

Examples of the compound of the general formula (I) include TiCl ₄ and TiBr _4. Titanium tetrahalides such as TiI ₄ and the like; Trihalogenated alkoxytitanium such as Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ and Ti (O (iC ₄ H ₉ )) Br ₃ ; Dihalogenated alkoxytitanium such as Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (O (iC ₄ H ₉ )) ₂ Cl ₂ and Ti (OC ₂ H ₅ ) ₂ Br ₂ ; Tetraalkoxytitanium such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₄ H ₉ ) _4, and the like, and the like, and one or two or more selected from these may be used alone or in combination. Can be used. Preferred titanium compounds are halogen-containing titanium compounds, and more preferred titanium compounds are titanium tetrachloride.

The amount of the titanium compound is preferably 0.1 to 500 mol, more preferably 0.1 to 300 mol, most preferably 0.2 to 200 mol per mol of the magnesium halide compound. When reacting the reactant of the step (2) with the titanium compound, the shape and size of the solid component recrystallized in accordance with the reaction conditions changes a lot. Therefore, the reaction between the reactant of step (2) and the titanium compound is preferably performed at an appropriate temperature to produce a solid component. Therefore, the temperature at which the titanium compound is brought into contact with the reactant of step (2) is preferably 10 to 80 ° C, more preferably 20 to 60 ° C, and after the contacting reaction, the reaction temperature is gradually raised to 50 to 150 ° C. It is preferable to sufficiently react for 0.5 to 5 hours, but it is not preferable because the desired particle formation and particle size distribution cannot be obtained outside the above range.

Step (4) of the method for producing a solid complex titanium catalyst for ethylene polymerization or copolymerization of the present invention is a step of reacting the carrier obtained in step (3) with a compound having a titanium compound and a phthalic group.

Step (4) may be completed by one reaction, or may be completed by two or three or more reactions. Therefore, the step (4) is preferably determined in consideration of the performance of the catalyst, the material input, and the economics of the reaction. In addition, after the carrier obtained in step (3) is reacted with a compound having a titanium compound and a phthalic group, the liquid mixture is separated, washed with hexane, and dried to obtain a catalyst.

The compound having a phthalic group used in the step (4) is a generic term for an organic compound having two ester groups, it can be represented by the following general formula,

C ₆ H ₄ -1- [CO ₂ -R] -a- [CO ₂ -R '] ₂

Here, R and R 'are hydrocarbons having 1 to 20 carbon atoms, and are alkyl, isoalkyl, tertiaryalkyl, alkenyl, aryl, and the like, and R and R' are the same as or different from each other. It is a natural number of 2 ~ 4.)

Specific examples thereof include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, diallyl phthalate, dicyclohexyl phthalate, benzyl butyl phthalate, diphenyl phthalate, dimethyl isophthalate, Diphenyl isophthalate, dimethyl terephthalate, dioctyl terephthalate and the like, and other compounds that satisfy the above formula other than the above examples may also be used. These can be used individually or in mixture of 2 or more types.

The type of the titanium compound used in the step (4) is not particularly limited, but the titanium compound mentioned in the step (3) may be preferably used.

It is preferable that the usage-amount of the compound which has the said phthalic group is 0.01-0.5 mol per mol of magnesium halide compounds, It is more preferable that it is 0.05-0.2 mol, The usage-amount of the said titanium compound of the said (4) step is 1-100 per mol of magnesium compounds It is preferable that it is a mole.

The catalyst prepared by the method presented in the present invention is used for the polymerization and copolymerization of ethylene to produce polyethylene, and the catalyst is preferably used for homopolymerization of ethylene and copolymerization of ethylene and an olefin monomer, and specific examples of the olefin monomer. And α-olefins having 3 or more carbon atoms such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, and the like.

The method for producing the ethylene polymer or copolymer of the present invention is carried out by polymerizing ethylene or copolymerizing ethylene and α-olefin in the presence of the above-mentioned solid complex titanium catalyst as a cocatalyst of the Group II or Group III organometallic compound.

The above-mentioned solid complex titanium catalyst component may be prepolymerized with ethylene or α-olefin before being used in the polymerization reaction. The prepolymerization can be carried out at a sufficiently low temperature and ethylene or α-olefin pressure conditions in the presence of a hydrocarbon solvent (eg hexane), the catalyst component and the organoaluminum compound (eg triethylaluminum). have. Prepolymerization helps to improve the shape of the polymer after polymerization by surrounding the catalyst particles with a polymer to maintain the catalyst shape. The weight ratio of polymer to catalyst after prepolymerization is usually from 0.1: 1 to 60: 1.

The periodic table group II or group III organometallic compound used as a promoter for the polymerization reaction may be represented by the general formula MR _n . Here, M is a periodic table group II or IIIA metal component such as magnesium, calcium, zinc, boron, aluminum, gallium, R is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, butyl, hexyl, octyl, decyl, etc. N is the valence of the metal component.

Among the compounds satisfying the above general formula, trialkylaluminum having an alkyl group having 1 to 6 carbon atoms such as triethylaluminum, triisobutylaluminum and the like and a mixture thereof are more preferable. In some cases, organoaluminum compounds containing at least one halogen or hydride group such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diisobutylaluminum hydride and the like may also be used.

The polymerization reaction can be carried out by gas phase or bulk polymerization in the absence of an organic solvent or by liquid phase slurry polymerization in the presence of an organic solvent. These polymerization methods are carried out in the absence of oxygen, water and other compounds that can act as catalyst poisons.

In the case of gas phase polymerization, the amount of the solid complex titanium catalyst is about 0.001 to 5 mmol, preferably about 0.001 to 1.0 mmol, more preferably about 0.001 based on the molar ratio of titanium atoms in the catalyst to 1 liter of the polymerization zone. ˜0.5 mmol.

In the case of liquid slurry polymerization, as an organic solvent, alkanes or cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n Alkylaromatics such as -propylbenzene, diethylbenzene and the like, and halogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, and the like, and the like can be used alone or in combination of two or more thereof. Do.

In the case of the liquid phase polymerization, the concentration of the solid complex titanium catalyst on the polymerization reaction system is about 0.001 to 5 mmol, preferably about 0.001 to 0.5 mmol, based on the molar ratio of titanium atoms in the catalyst to 1 liter of solvent.

The preferred amount of the organometallic compound used as the promoter is about 1 to 2000 moles per mole of titanium atoms in the catalyst, calculated as organometallic atoms (for example, aluminum atoms), more preferably about 5 to 500 It's a mole.

The temperature of the polymerization reaction is carried out at a sufficiently high temperature irrespective of the polymerization process to obtain a high polymerization rate, generally about 20 ~ 200 ℃, more preferably 20 ~ 95 ℃. The pressure of the monomer is preferably atmospheric pressure to 100 atmospheres, more preferably 2 to 50 atmospheres.

According to the present invention, a highly active catalyst can be prepared, and a polymer obtained by polymerizing ethylene with the catalyst according to the present invention can obtain polyethylene having a spherical shape, uniform particle distribution and high apparent density.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these embodiments are for illustrative purposes only.  The invention is not limited to these examples.

Example

Example  One

Solid complex  Titanium Catalyst Component

The solid complex titanium catalyst component was prepared through the following four steps.

(1) Step: Magnesium Halide  Compound solution preparation

230 g of magnesium chloride (MgCl ₂ ), 2800 mL of toluene, 240 mL of tetrahydrofuran, and 710 mL of butanol were added to a 10L reactor equipped with a mechanical stirrer replaced with a nitrogen atmosphere. Got it.

(2) step: magnesium Halide  Compound solution and alkoxy Of silane compounds  Contact reaction

To the magnesium chloride compound solution cooled to 70 ° C., silicon tetraethoxide was added as silicon tetraethoxide / MgCl ₂ compound solution = 0.15 (molar ratio) and reacted for 1 hour.

(3) step: titanium compound reaction ( carrier  Produce)

The temperature of the solution obtained in step 2 was cooled to 35 ° C., 415 mL of TiCl ₄ was added over 80 minutes, and the temperature of the reactor was raised to 60 ° C. over 1 hour, and aged for 1 hour. After the reaction, the carrier was allowed to stand for 30 minutes to settle the carrier and remove the upper solution. The remaining slurry in the reactor was added 3,000 mL of hexane, and washed three times by stirring, standing, and removing the supernatant.

(4) step; Catalyst manufacturing

The carrier prepared in step 3 was injected into a reactor adjusted to 5 ° C. at 1600 mL of toluene, 1400 mL of TiCl ₄ was added at a stirring speed of 250 rpm, and the temperature of the reactor was raised to 25 ° C. over 1 hour. 65 mL of diethylphthalate was slowly injected at 25 ° C., the temperature of the reactor was raised to 70 ° C. for 1 hour, aged for 2 hours, and allowed to stand for 30 minutes to settle the precipitate, and then the supernatant was separated. The prepared catalyst slurry was washed 7 times with 1600 mL of purified hexane. Titanium (Ti) content of the prepared solid catalyst was 2.9% by weight, the average particle size was 7.1μm.

In addition, the particle size distribution of the catalyst was measured using a laser particle analyzer (Mastersizer X, Malvern Instruments), the result is the average size of D (v, 0.5), the distribution is (D (v, 0.9) -D ( v, 0.1)) / D (v, 0.5). Here, D (v, 0.5) represents the average particle size represented by 50% of the sample, and D (v, 0.9) and D (v, 0.1) represent the average particle size represented by the 90% and 10% of the sample, respectively. Display. The smaller the value of the distribution chart, the narrower the distribution. The composition of the catalyst was analyzed by ICP.

The measurement results are shown in Table 1 together.

polymerization

The 2-liter high pressure reactor was dried in an oven, assembled in a hot state, and then operated nitrogen and vacuum three times in alternation to bring the reactor into a nitrogen atmosphere. After 1000 ml of n-hexane was injected into the reactor, 2 mmol of triisobutylaluminum and 1000 ml of hydrogen were injected. While stirring the stirrer to 700rpm and the temperature of the reactor was raised to 80 ℃ and ethylene pressure to 120psig, 0.02mmol based on the titanium atom of the solid catalyst prepared above was injected, and the polymerization was carried out for one hour. After the polymerization was completed, the temperature of the reactor was lowered to room temperature, and an excess ethanol solution was added to the polymerization contents to terminate the reaction. The resulting polymer was collected by filtration and collected in a vacuum oven at 50 ° C. for at least 6 hours to obtain a white powder of polyethylene.

Polymerization activity (kg polyethylene / g catalyst) was calculated as the weight (kg) ratio of the resulting polymer per gram of catalyst used. The polymerization results are shown in Table 1 together with the apparent density (g / ml) of the polymer.

Example  2

In step (4) of Example 1, except that the diethyl phthalate was adjusted to 32 mL, a catalyst was prepared under the same conditions as in Example 1, and polymerization was performed using the obtained catalyst, and the results are shown in Table 1 below. It was.

Example  3

In step (4) of Example 1, except that the diethyl phthalate was adjusted to 12 mL, a catalyst was prepared under the same conditions as in Example 1, and polymerization was performed using the obtained catalyst, and the results are shown in Table 1 below. It was.

Example  4

In step (4) of Example 1, a catalyst was prepared under the same conditions as in Example 1 except that diisobutyl phthalate was adjusted to 35 mL instead of diethyl phthalate, and polymerization was performed using the obtained catalyst. The results are shown in Table 1.

Example  5

In step (4) of Example 1, a catalyst was prepared under the same conditions as in Example 1 except that di-n-butylbutylphthalate was adjusted to 35 mL instead of diethyl phthalate, and polymerization was performed using the obtained catalyst. It carried out, and the results are shown in Table 1.

Comparative Example 1

In step (2) of Example 1, a catalyst was prepared under the same conditions as in Example 1 by reacting for 1 hour without using silicon tetraethoxide, and polymerization was performed using the obtained catalyst. Table 1 Shown in

Comparative example  2

In step (4) of Example 1, a catalyst was prepared under the same conditions as in Example 1 without using diethylphthalate, and polymerization was performed using the obtained catalyst. The results are shown in Table 1 below.

Comparative example  3

Preparation of the catalyst

(Stage 1

In a 1.0L reactor equipped with a mechanical stirrer replaced with a nitrogen atmosphere, 95 g of magnesium hachloride and 4000 ml of toluene were added and stirred at 300 rpm. Then, 620 ml of 2-ethylhexanol was added thereto, and the temperature was raised to 120 ° C., followed by 3 hours. Reacted for a while. The homogeneous solution obtained after the reaction was cooled to 70 deg.

(2) step

100.0 ml of silicon tetraethoxide was added to the magnesium compound solution cooled to 70 ° C. and reacted for 1 hour.

(3) step

The solution was adjusted to room temperature (25 ° C.) and 600 ml of titanium tetrachloride were added dropwise for 1 hour. When the dropwise addition was completed, 32 ml of diethylphthalate was added, and the temperature of the reactor was raised to 70 ° C. over 1 hour and maintained for 1 hour. After the stirring was stopped, the solution of the upper layer was separated, and 3000 ml of toluene and 1000 ml of titanium tetrachloride were continuously injected into the remaining solid layer, and the temperature was raised to 100 ° C. and maintained for 2 hours. After the reaction, the reactor was cooled to room temperature and washed by injecting 4000 ml of hexane until unreacted free titanium tetrachloride was removed. The titanium content of the prepared solid catalyst was 3.5%.

polymerization

The polymerization was carried out in the same manner as in Example 1 using the catalyst obtained above, and the measurement results are shown in Table 1.

Comparative example  4

In step (2) of Comparative Example 3, the reaction was performed for 1 hour without using silicon tetraethoxide to prepare a catalyst under the same conditions as in Comparative Example 3, and polymerization was performed using the obtained catalyst. Table 1 Shown in

Table 1

Catalyst size (㎛) Catalyst size distribution ^{1 )} Polymerization Activity (kgPE / g Catalyst) Apparent density (g / ml) Example 1 7.1 0.85 19.2 0.40 Example 2 6.6 0.77 20.9 0.39 Example 3 6.3 0.84 23.9 0.38 Example 4 6.7 0.75 22.2 0.38 Example 5 6.2 0.79 25.6 0.39 Comparative Example 1 6.9 1.5 17.4 0.29 Comparative Example 2 6.4 0.85 18.2 0.32 Comparative Example 3 8.9 1.4 14.8 0.32 Comparative Example 4 7.4 3.1 16.2 0.27

1) Catalyst size distribution = (D (v, 0.9) -D (v, 0.1)) / D (v, 0.5)

As shown in Table 1, it can be seen that the Examples have a smaller catalyst size distribution, higher polymerization activity, and higher apparent density of the polymer than the Comparative Example.

Claims (12)

Solid complex titanium catalyst for ethylene polymerization or copolymerization, characterized in that it is prepared by the following steps: (1) dissolving a magnesium halide compound in a mixed solvent of a cyclic ether and at least one alcohol; (2) injecting a silane compound having an alkoxy group into the reactant obtained in step (1) and reacting it; (3) preparing a carrier by reacting the reactant obtained in step (2) with a titanium compound represented by the following general formula (I); And Ti (OR) _a X _(4-a) ‥‥‥ (I) (Here, R is an alkyl group having 1 to 10 carbon atoms and X is a halogen atom. In addition, a is an integer of 0 to 3 to match the valence of the general formula.) (4) reacting a compound having a titanium compound and a phthalic group with the carrier obtained in step (3). The method of claim 1, wherein the magnesium halide compound is magnesium chloride, magnesium iodide, magnesium fluoride, and magnesium bromide; Methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide, amyl magnesium halide; Methoxymagnesium halides, ethoxymagnesium halides, isopropoxymagnesium halides, butoxymagnesium halides, and octoxymagnesium halides; A solid complex titanium catalyst for ethylene polymerization or copolymerization, characterized in that it is one or two or more selected from phenoxy magnesium halides and methylphenoxy magnesium halides. The solid catalyst titanium catalyst for ethylene polymerization or copolymerization according to claim 1, wherein the cyclic ether is at least one selected from tetrahydrofuran and 2-methyltetrahydrofuran. The solid complex titanium for ethylene polymerization or copolymerization according to claim 1, wherein the alcohol is a monohydric or polyhydric alcohol having 1 to 20 carbon atoms, and the alcohol is used alone or in combination. catalyst. The solid catalyst titanium catalyst for ethylene polymerization or copolymerization according to claim 1, wherein the molar ratio of the mixed solvent of the cyclic ether and the alcohol: the magnesium halide compound is 3: 1 to 10: 1. The solid catalyst titanium catalyst for ethylene polymerization or copolymerization according to claim 1, wherein the silane compound having the alkoxy group in step (2) is represented by the following general formula: R _n Si (OR) _4-n (Where R is a hydrocarbon having 1 to 12 carbon atoms and n is a natural number of 1 to 3). The silane compound having an alkoxy group according to claim 6, wherein the silane compound has a dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenylmethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, vinyltrimethoxy Silane, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane 1 or 2 or more types of vinyl tributoxysilane, ethyl silicate, butyl silicate, and methyl triaryloxysilane, The solid complex titanium catalyst for ethylene polymerization or copolymerization characterized by the above-mentioned. The method of claim 7, wherein the titanium compound is TiCl ₄ , TiBr ₄ , TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O (iC ₄ H ₉ )) Br ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (O (iC ₄ H ₉ )) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ and Ti (OC ₄ H ₉ ) ₄ One or two or more selected from solid complex titanium for ethylene polymerization or copolymerization catalyst. The solid catalyst titanium catalyst for ethylene polymerization or copolymerization according to claim 8, wherein the titanium compound is TiCl ₄ . The solid catalyst titanium catalyst for ethylene polymerization or copolymerization according to claim 1, wherein the compound having a phthalic group in step (4) is represented by the following general formula: C ₆ H ₄ -1- [CO ₂ -R] -a- [CO ₂ -R '] ₂ (Herein, R and R 'are hydrocarbons having 1 to 20 carbon atoms, R and R' are the same as or different from each other, and a is a natural number of 2 to 4). The compound having a phthalic group is dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, diallyl phthalate, dicyclohexyl phthalate, benzyl butyl phthalate, Solid catalyst titanium catalyst for ethylene polymerization or copolymerization, characterized in that at least one selected from diphenyl phthalate, dimethyl isophthalate, diphenyl isophthalate, dimethyl terephthalate and dioctyl terephthalate. 12. Polymerization of ethylene or copolymerization of ethylene and α-olefin using a periodic table Group II or Group III organometallic compound as the solid complex titanium catalyst according to any one of claims 1 to 11. Method for producing an ethylene polymer or copolymer