KR100361225B1 - Process for preparing a catalyst for ethylene homo- and co-polymerization - Google Patents

Abstract

The present invention relates to a method for preparing a catalyst for ethylene polymerization and copolymerization, and more specifically, to prepare a magnesium solution by contacting a magnesium halide compound with an alcohol, and reacting a silicon compound having a phosphorus compound with an alkoxy group, A method for producing a solid complex titanium catalyst for ethylene polymerization and copolymerization, in which a mixture of a titanium compound and a silicon compound is reacted. The catalyst prepared by the present invention is highly active, and the (co) polymer prepared using the catalyst of the present invention has the advantage of high apparent density and narrow molecular weight distribution.

Description

Process for preparing a catalyst for ethylene homo- and co-polymerization

The present invention relates to a method for producing a catalyst for ethylene polymerization or copolymerization, and more particularly, a solid titanium supported on a support containing magnesium capable of producing a polymer having high activity, high apparent density, and narrow molecular weight distribution. It relates to a method for producing a catalyst.

Catalysts for ethylene polymerization and copolymerization containing magnesium have a very high catalytic activity and are known to produce polymers of apparent density, and are also known to be suitable for liquid and gas phase polymerization. Ethylene liquid phase polymerization refers to a polymerization process which takes place in a medium such as bulk ethylene, isopentane, or hexane, and important properties of the catalyst used therein are high activity, apparent density of the prepared polymer, and the like. In addition, the molecular weight distribution is an important variable for determining the physical properties of the ethylene polymer, and in particular, the ethylene polymer having a narrow molecular weight distribution may be an important characteristic for improving physical properties according to the application.

Many catalysts and catalyst-making processes for olefin polymerization, including magnesium and based on titanium, have been reported. In particular, many methods using a magnesium solution are known to obtain the catalyst for olefin polymerization having a high apparent density. There is a method of obtaining a magnesium solution by reacting a magnesium compound with an electron donor such as alcohol, amine, cyclic ether, organic carboxylic acid, etc. in the presence of a hydrocarbon solvent, the use of alcohols being mentioned in US Pat. Nos. 4,330,649 and 5,106,807. In addition, a method of preparing a magnesium supported catalyst by reacting the liquid magnesium solution with a halogen-containing compound such as titanium tetrachloride is well known. In addition, attempts have been made to control polymerization activity and molecular weight distribution by adding compounds of esters. Such catalysts provide a high apparent density of the polymer, but there is much room for improvement in terms of catalyst activity and molecular weight distribution of the polymer. 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, dialkyl phthalates, phthaloyl chlorides, and titanium chloride compounds, It has been reported how to prepare a catalyst for olefin polymerization in which the apparent density of the prepared polymer is improved.

U.S. Patent No. 5,459,116 reports a method of preparing a supported titanium solid catalyst by contact reaction of a magnesium solution comprising a ester having at least one hydroxy group as an electron donor with a titanium compound. However, although a catalyst having a high polymerization activity and an excellent apparent density of the prepared polymer can be obtained using this method, there is room for improvement in terms of molecular weight distribution.

As described above, while the manufacturing process is simple, high polymerization activity, catalyst particles are controlled to give a high polymer apparent density, and the development of a new catalyst for ethylene polymerization and copolymerization having a narrow molecular weight distribution of the polymer is required. Therefore, the present invention provides a method for producing a catalyst having excellent catalytic activity and having a high apparent density from a low-cost compound through a simple manufacturing process, and particularly for a catalyst having a narrow molecular weight distribution of the produced polymer. . In addition, specific catalyst preparation steps or processes to be disclosed in the present invention are not known in the existing patents or literature.

It is therefore an object of the present invention to provide new catalyst solid components for ethylene polymerization and copolymerization with high catalytic activity and apparent density of polymerized polymers and narrow molecular weight distributions of polymers. Specifically, it is an object of the present invention to provide a catalyst solid component for ethylene polymerization and copolymerization in which the form of the catalyst particles is controlled, the polymerization activity is high, and the molecular weight distribution of the polymer is narrow.

It is a further object of the present invention to provide a process for preparing a catalyst solid component for ethylene polymerization and copolymerization via the simple and specific methods and processes of the invention.

Other objects and benefits of the present invention will become more apparent with reference to the following description and claims of the present invention.

The method for preparing a solid titanium catalyst for ethylene polymerization and copolymerization capable of producing a polymer having excellent catalytic activity and apparent density of the polymer and having a narrow molecular weight distribution of the polymer is provided by (i) a magnesium halide compound and an alcohol. A magnesium solution is prepared by contact reaction, and (ii) a silicon compound having a phosphorus compound and an alkoxy group is reacted thereto, and (i) a mixture of a titanium compound and a silicon compound is added to prepare a solid titanium catalyst. Manufacturing process.

Types of magnesium halide compounds used in the present invention include dihalogenated magnesiums 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 and amylmagnesium halide and the like; Alkoxymagnesium halides such as methoxymagnesium halide, ethoxymagnesium halide, isopropoxymagnesium halide, butoxymagnesium halide and octoxymagnesium halide; Examples are aryloxymagnesium halides such as phenoxyshimam halides and methylphenoxymagnesium halides. Two or more of the magnesium compounds may be used in a mixture, and the magnesium compound is effective even when used in the form of a complex with another metal.

The compounds listed above may be represented by simple chemical formulas, but in some cases, they may not be represented by simple formulas depending on the method of preparing magnesium compounds. In this case it can generally be regarded as a mixture of the magnesium compounds listed above. 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 an alcohol, phenol, or ether in the presence of halo silane, phosphorus pentachloride, or thionyl chloride can also be used in the present invention. Preferred magnesium compounds are magnesium halides, in particular magnesium chloride, alkyl magnesium chlorides, preferably having alkyl groups of 1 to 10 carbon atoms, alkoxy magnesium chlorides, preferably having alkoxy groups of 1 to 10 carbon atoms, and aryloxy magnesium chloride It is preferable to have a C6-C20 aryloxy group preferably. The magnesium solution used in the present invention can be prepared as the solution of the above-described magnesium compound using an alcohol solvent in the presence or absence of a hydrocarbon solvent.

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

Alcohol is used in the presence of the aforementioned hydrocarbons when converting the magnesium compound into a magnesium solution. Types of alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenyl ethyl alcohol, isopropyl benzyl alcohol, cumyl alcohol Alcohol containing 20 carbon atoms is mentioned, A preferable alcohol is an alcohol containing 1-12 carbon atoms. The average size and particle distribution of the desired catalyst vary depending on the type of alcohol, the total amount, the type of magnesium compound, the ratio of magnesium to alcohol, etc., but the total amount of alcohol to obtain a magnesium solution is at least 0.5 mole per mole of magnesium compound, preferably Is about 1.0 to 20 moles, more preferably about 2.0 to 10 moles.

The reaction of the magnesium compound with the alcohol in the preparation of the magnesium solution is preferably carried out in a hydrocarbon medium, the reaction temperature varies depending on the type and amount of alcohol, but at least about -25 ℃, preferably -10 to 200 ℃, more preferably In the following, it is preferably carried out at about 0 to 150 ° C. for about 15 minutes to 5 hours, preferably about 30 minutes to 4 hours.

Phosphorus compound which is an electron donor used in the present invention is represented by the following general formula.

PX _a R ¹ _b (OR ² ) _c or POX _d R ³ _e (OR ⁴ ) _f ,

X is a halogen atom, and R ¹ , R ² , R ³ and R ⁴ are hydrocarbons having 1 to 20 carbon atoms, and are alkyl, alkenyl, aryl, and the like, and may be the same or different. And a + b + c = 3, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 0 ≦ c ≦ 3, d + e + f = 3, 0 ≦ d ≦ 3, 0 ≦ e ≦ 3, 0 ≤f≤3.

Specific examples thereof include phosphorus trichloride, phosphorus tribromide, diethylchlorophosphite, diphenylchlorophosphite, diethylbromophosphite, diphenylbromophosphite, dimethylchlorophosphite, phenylchlorophosphite, trimethylphosphite, Triethyl phosphite, tri-normal butyl phosphite, trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, triethyl phosphate, tri-normal butyl phosphate, triphenyl phosphate, etc. Compounds may also be used. The amount of these used is preferably 0.01 to 0.25 mol per mol of the magnesium compound, more preferably 0.01 to 0.2 mol per mol.

Another electron donor used in the present invention, a silicon compound having an alkoxy group is a general formula of R _n Si (OR) _4-n (where R is a hydrocarbon having 1 to 12 carbon atoms, n is a natural number of 1 to 3) Preference is given to compounds having Specifically, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenylmethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, phenyl Trimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethylsilicate And compounds such as butyl silicate and methyltriaryloxysilane can be used. The amount thereof is preferably 0.05 to 3 mol, more preferably 0.1 to 2 mol per mol of the magnesium compound.

0-100 degreeC is suitable and the contact reaction temperature of a liquid magnesium compound solution, a phosphorus compound, and an alkoxy silicone compound is 10-70 degreeC still more preferable.

A magnesium compound solution reacted with a phosphorus compound and a silicon compound having an alkoxy group is _a titanium compound of the general formula Ti (OR) _a X _{4-a in} the liquid state (R is a hydrocarbon group, X is a halogen atom, and a is 0-4). Natural number) and the silicon compound R _n SiCl _n-4 (R is hydrogen or alkyl having 1 to 10 carbon atoms, alkoxy, haloalkyl, aryl group or halosilyl and halosilylalkyl group having 1 to 8 carbon atoms, and n is 0 to 0). Reacted with a mixture of natural water 3) to recrystallize the catalyst particles.

Examples of the titanium compound satisfying the general formula Ti (OR) _a X _4-a include titanium tetrahalide such as TiCl ₄ , TiBr ₄ , and TiI ₄ , Ti (OCH ₃ ) Cl ₃ , and Ti (OC ₂ H ₅ ) Trihalogenated alkoxytitanium such as Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ and Ti (O (iC ₄ H ₉ )) Br ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , halogenated alkoxytitanium such as Ti (O (iC ₄ H ₉ ) ₂ ) Cl ₂ and Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ and Ti Tetraalkoxy titanium like (OC ₄ H ₉ ) ₄ is exemplified. Mixtures of the above titanium compounds may also be used in the present invention. Preferred titanium compounds are halogen-containing titanium compounds, and more preferred titanium compounds are titanium tetrachloride.

Examples of the silicone compound satisfying the general formula R _n SiCl _n-4 include trichlorosilane such as silicon tetrachloride, methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, Examples include dichlorosilanes such as diphenyldichlorosilane, methylphenyldichlorosilane, and the like, and monochlorosilanes such as trimethylchlorosilane, and mixtures of the aforementioned silicone compounds can also be used in the present invention. Preferred silicone compounds are silicon tetrachloride.

The amount of the mixture of the titanium compound and the silicon compound to be used for recrystallization of the magnesium compound solution is suitably 0.1 to 200 moles per mole of magnesium halide compound, preferably 0.1 to 100 moles, and more preferably 0.2 to 80 moles. The mixing ratio of the titanium compound and the silicon compound is preferably 0.05 to 0.95 in molar ratio, and more preferably 0.1 to 0.8. The shape and size of the solid catalyst component recrystallized by the reaction conditions when reacting the magnesium compound solution with the mixture of the titanium compound and the silicon compound greatly change. Therefore, the reaction of the magnesium compound solution with the mixture of the titanium compound and the silicon compound is preferably performed at a sufficiently low temperature to produce a solid component. Preferably, the contact reaction is preferably carried out at -70 to 70 占 폚, more preferably at -50 to 50 占 폚. After the contact reaction, the reaction temperature is gradually raised to fully react for 0.5 to 5 hours at 50 to 150 ° C.

The solid catalyst particles obtained above can be further reacted with the titanium compound. Titanium compounds are titanium halides and halogenated alkoxy titanium having 1 to 20 carbon atoms in the alkoxy functional group. In some cases, mixtures thereof may also be used. Of these, titanium halides and alkoxy halide titanium having 1 to 8 carbon atoms of the alkoxy functional group are preferable, and titanium tetrahalide is more preferable.

Solid titanium catalysts prepared by the process presented herein are advantageously used for the polymerization and copolymerization of ethylene. In particular, this catalyst is used for homopolymerization of ethylene and copolymerization of ethylene with 3 or more carbon atoms of olefins such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene.

The polymerization reaction in the presence of the catalyst of the present invention comprises (a) a solid titanium catalyst according to the invention consisting of magnesium, titanium, halogen, and electron donor, and (b) a catalyst system composed of Group II and III organometallic compounds of the periodic table. Is performed using.

The solid complex titanium catalyst (a) of the present invention can be prepolymerized with ethylene or α-olefin before being used for the polymerization reaction. Prepolymerization can be carried out in the presence of a hydrocarbon solvent such as hexane and at the sufficiently low temperature and ethylene or α-olefin pressure conditions in the presence of the above catalyst component and an organoaluminum compound such as triethylaluminum. 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 / catalyst after prepolymerization is usually from 0.1: 1 to 20: 1.

The organometallic compound (b) used in the polymerization reaction using the catalyst of the present invention may be represented by the general formula of MR _n , where M is a periodic table group II such as magnesium, calcium, zinc, boron, aluminum, gallium or A group IIIA metal component, R represents an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, butyl, hexyl, octyl and decyl, and n represents the valence of the metal component. More preferred organometallic compounds are trialkylaluminums having 1 to 6 carbon atoms, such as triethylaluminum and triisobutylaluminum, and mixtures thereof. In some cases, an organoaluminum compound having one or more halogen or hydride groups such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diisobutylaluminum hydride may be used.

The polymerization reaction is possible 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 processes are carried out in the absence of oxygen, water and other compounds that can act as catalyst poisons.

In the case of liquid phase slurry polymerization, the preferred concentration of the solid titanium catalyst (a) in the polymerization reaction system is about 0.001 to 5 mmol, preferably about 0.001 to 0.5 mmol, of titanium atoms of the catalyst with respect to 1 liter of solvent. Solvents include alkanes or cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethyl Alkylaromatics such as benzene, halogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, and mixtures thereof are advantageous.

In the case of gas phase polymerization, the amount of solid titanium catalyst is about 0.001 to 5 mmol, preferably about 0.001 to 1.0 mmol, more preferably about 0.01 to 0.5 mmol, of titanium atoms of the catalyst per 1 liter of the polymerization zone. good.

The preferred concentration of the organometallic compound (b) is about 1 to 2000 moles per mole of titanium atoms in the catalyst (a), calculated from aluminum atoms, more preferably about 5 to 500 moles.

In order to obtain a high polymerization rate, the polymerization reaction is carried out at a sufficiently high temperature regardless of the polymerization process. Generally about 20-200 degreeC is suitable, More preferably, it is 20-95 degreeC. As for the pressure of the monomer at the time of superposition | polymerization, atmospheric pressure-100 atmospheres are suitable, More preferably, the pressure of 2-50 atmospheres is suitable.

Molecular weight in the present invention is represented by the melt index (ASTM D 1238) commonly known in the art. In general, the melt index is higher when the molecular weight is lower. And the molecular weight distribution of the polymer was obtained by measuring by GPC (Gel Permeation Chromatography), the measuring method of the method is commonly used in the art.

The product obtained by the polymerization method using the catalyst of the present invention is a solid ethylene homopolymer or a copolymer of ethylene and an α-olefin, and the yield of the polymer is also high enough that the removal of the catalyst residue is not necessary, and has an excellent apparent density and fluidity. have.

Example

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the present invention is not limited to these examples.

Example 1

Catalyst manufacturing

Solid titanium catalyst component was prepared through the following three steps.

(Iii) step: preparation of magnesium solution

9.5 g of MgCl ₂ and 500 ml of toluene were added to a 1.0 liter reactor equipped with a mechanical stirrer, which was replaced with a nitrogen atmosphere, stirred at 500 rpm, and 72 ml of 2-ethylhexanol was added thereto. The reaction was carried out for hours. The homogeneous solution obtained after reaction was cooled to room temperature (25 degreeC).

(Ii) step: catalytic reaction of magnesium solution with phosphorus compound and alkoxy silane compound

To the magnesium solution cooled to 25 ° C., 8.1 ml of tributyl phosphate and 15.0 ml of silicon tetraethoxide were added and reacted for 1 hour.

(Iii) step: treatment of a mixture of titanium and silicon compounds

90 ml of titanium tetrachloride and 90 ml of silicon tetrachloride were added dropwise to the solution at room temperature (25 ° C.) for 2 hours. When the dropping was completed, the temperature of the reactor was raised to 80 ° C. over 1 hour and maintained for 1 hour. After stopping the stirring, the solution of the upper layer was separated, and then 300ml of toluene and 100ml 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 400 ml of hexane was washed until unreacted free titanium tetrachloride was removed. The titanium content of the prepared solid catalyst was 4.3%.

polymerization

The high-pressure reactor with a capacity of 2 liters was dried in an oven and assembled in a hot state, and then nitrogen and vacuum were operated three times in alternation to make the reactor into a nitrogen atmosphere. After 1000 ml of n-hexane was injected into the reactor, 2 mmol of triethylaluminum and 0.03 mmol of a solid catalyst were injected on a titanium atom, and 1000 ml of hydrogen was injected. The temperature of the reactor was raised to 80 ° C. while stirring at 700 rpm, and the ethylene pressure was adjusted to 80 psi, followed by polymerization 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. The resulting polymer was collected separately and dried in a vacuum oven at 50 ° C. for at least 6 hours to obtain a white powder of polyethylene.

Polymerization activity (kg polyethylene / millimoles Ti) was calculated as the weight (kg) ratio of polymer produced per catalyst amount used (millimoles Ti). The polymerization results are shown in Table 1 together with the apparent density (g / ml), melt index (g / 10 min) and molecular weight distribution (Mw / Mn) of the polymer.

Example 2

In the step (ii) of preparing the catalyst of Example 1, 5.4 ml of tributyl phosphate and 15.0 ml of silicon tetraethoxide were used to prepare a catalyst. The titanium content of the prepared catalyst was 4.7%. The polymerization was carried out as in Example 1, and the results are shown in Table 1.

Example 3

In step (ii) of the catalyst preparation process of Example 1, a catalyst was prepared using 5.1 ml of triethylphosphate and 15.0 ml of silicon tetraethoxide, and the titanium content of the prepared catalyst was 4.9%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 4

In step (ii) of the catalyst preparation process of Example 1, 7.2 mL of triethylphosphate and 15.0 mL of silicon tetraethoxide were prepared, and the titanium content of the prepared catalyst was 5.2%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 5

In step (ii) of the catalyst preparation process of Example 1, a catalyst was prepared using 8.1 ml of tributyl phosphite and 15.0 ml of silicon tetraethoxide, and the titanium content of the prepared catalyst was 4.5%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 6

In the step (iii) of the catalyst preparation process of Example 1, the catalyst was prepared by adjusting the dropping time of 40 ml of titanium tetrachloride and 40 ml of silicon tetrachloride to 1 hour, and the titanium content of the prepared catalyst was 3.9%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 7

In the step (iii) of the catalyst preparation process of Example 1, the catalyst was prepared by adjusting the dropping time of the mixed solution of 20 ml of titanium tetrachloride and 20 ml of silicon tetrachloride to 30 minutes, and the titanium content of the prepared catalyst was 4.1%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 8

In step (iii) of the catalyst preparation process of Example 1, 400 ml of decane was used as a solvent for preparing a magnesium solution, and 300 ml of decane was used instead of toluene in (iii), and the titanium content of the prepared catalyst was used. Was 4.3%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 9

In step (iii) of the catalyst preparation process of Example 6, 400 ml of decane was used as a solvent for preparing a magnesium solution, and 300 ml of decane was used instead of toluene in (iii), and the titanium content of the prepared catalyst was used. Was 4.5%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 10

In the step (iii) of the catalyst preparation process of Example 1, a catalyst was prepared using 135.0 ml of titanium tetrachloride and 45.0 ml of silicon tetrachloride, and the titanium content of the prepared catalyst was 5.1%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 11

In the step (iii) of the catalyst preparation process of Example 1, a catalyst was prepared using 45.0 ml of titanium tetrachloride and 135.0 ml of silicon tetrachloride, and the titanium content of the prepared catalyst was 4.1%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 12

In step (ii) of the catalyst preparation process of Example 1, 2.6 mL of phosphorus trichloride and 15.0 mL of silicon tetraethoxide were prepared, and the titanium content of the prepared catalyst was 4.2%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 13

In step (ii) of the catalyst preparation process of Example 1, 4.3 mL of diethylchlorophosphite and 15.0 mL of silicon tetraethoxide were prepared, and the titanium content of the prepared catalyst was 4.9%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Example 14

In step (ii) of the catalyst preparation process of Example 1, a catalyst was prepared using 2.6 mL of phosphorus trichloride and 7.5 mL of silicon tetraethoxide, and the titanium content of the prepared catalyst was 5.3%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Comparative example

Comparative Example 1

In step (ii) of the catalyst preparation process of Example 1, 15.0 mL of silicon tetraethoxide was used, and the catalyst was prepared without using tributyl phosphate, and the titanium content of the prepared catalyst was 4.1%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Comparative Example 2

In step (ii) of the catalyst preparation step of Example 3, 5.1 ml of triethylphosphate was used and the catalyst was prepared without using silicon tetraethoxide, and the titanium content of the prepared catalyst was 4.6%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Comparative Example 3

In step (ii) of the catalyst preparation process of Example 1, a catalyst was prepared without using tributylphosphate and silicon tetraethoxide, the titanium content of the prepared catalyst was 4.8%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Comparative Example 4

In the step (iii) of the catalyst preparation process of Example 1, a catalyst was prepared using 90 ml of titanium tetrachloride, and the titanium content of the prepared catalyst was 4.6%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Comparative Example 5

In the process of preparing the catalyst of Example 8, in step (ii), 15.0 ml of silicon tetraethoxide was used, and the catalyst was prepared without using tributyl phosphate, and the titanium content of the prepared catalyst was 3.9%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Comparative Example 6

In step (ii) of the catalyst preparation process of Example 8, 5.4 ml of tributylphosphate was used and the catalyst was prepared without using silicon tetraethoxide, and the titanium content of the prepared catalyst was 4.1%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

Comparative Example 7

In step (ii) of the catalyst preparation process of Example 8, tributylphosphate and silicon tetraethoxide were not used, and in (iii), 90 ml of titanium tetrachloride was used to prepare a catalyst, and the titanium content of the prepared catalyst was used. Was 4.8%. The polymerization reaction was carried out under the conditions of Example 1 and the results are shown in Table 1.

As described above, the method for producing the catalyst for ethylene polymerization or copolymerization of the present invention is simple, and has excellent catalytic activity, producing a polymer having a high apparent density, and has the effect of narrowing the molecular weight distribution of the polymer.

Claims (9)

(Iii) a magnesium solution is prepared by bringing a magnesium halide compound into contact with an alcohol, (Ii) reacting a phosphorus compound with a silicon compound having an alkoxy group (Iii) A method for producing a solid titanium catalyst for ethylene polymerization and copolymerization, comprising adding a mixture of a titanium compound and a silicon compound. The compound of claim 1, wherein the phosphorus compound is selected from PX _a R ¹ _b (OR ² ) _c or POX _d R ³ _e (OR ⁴ ) _f (where X is a halogen atom and R ¹ , R ² , R ³ , R ⁴ Are hydrocarbons having 1 to 20 carbon atoms, alkyl, alkenyl, aryl, each of which may be the same or different, and a + b + c = 3, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 0 ≦ c ≦ 3, d + e + f = 3, 0 ≦ d ≦ 3, 0 ≦ e ≦ 3, and 0 ≦ f ≦ 3). The silicon compound having an alkoxy group is an ethylene characterized by a compound represented by the general formula of R _n Si (OR) _4-n (wherein R is a hydrocarbon having 1 to 12 carbons and n is a natural number of 1 to 3). Method for producing a solid titanium catalyst for polymerization and copolymerization. The phosphorus compound according to claim 2, wherein the phosphorus compound is phosphorus trichloride, phosphorus tribromide, diethylchlorophosphite, diphenylchlorophosphite, diethylbromophosphite, diphenylbromophosphite, dimethylchlorophosphite, phenylchlorophosphite, Ethylene polymerization and trimethyl phosphite, triethyl phosphite, trinormal butyl phosphite, trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, triethyl phosphate, trinormal butyl phosphate or triphenyl phosphate Method for producing a solid titanium catalyst for copolymerization. The silicone compound according to claim 2, wherein the silicone compound having an alkoxy group is selected from the group consisting of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenylmethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane and vinyltrimethoxysilane. , Methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane, A vinyl tributoxysilane, ethyl silicate, butyl silicate or methyltriaryloxysilane, the process for producing a solid titanium catalyst for ethylene polymerization and copolymerization. The method of claim 1, wherein the titanium compound and the silicon compound are each represented by the general formula Ti (OR) _a X _4-a (R is a hydrocarbon group, X is a halogen atom, and a is a natural number of 0 to 4) and R _n SiCl _{n− 4} (R is hydrogen or an alkyl, alkoxy, haloalkyl, aryl group having 1 to 10 carbon atoms, or a halosilyl or halosilylalkyl group having 1 to 8 carbon atoms, n is a natural number of 0 to 3) Method for producing a solid titanium catalyst for ethylene polymerization and copolymerization, characterized in that the compound. The titanium compound according to claim 5, wherein the titanium compound is TiCl ₄ , TiBr ₄ , titanium tetrahalide such as TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ And trihalogenated alkoxytitanium such as 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 Dihalogenated alkoxytitanium such as) Cl ₂ and Ti (OC ₂ H ₅ ) ₂ Br ₂ , tetraalkoxytitanium such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ and Ti (OC ₄ H ₉ ) ₄ The silicone compound is silicon tetrachloride and trichlorosilane such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, dichlorosilane such as methylphenyldichlorosilane, A method for producing a solid titanium catalyst for ethylene polymerization and copolymerization, characterized in that it is a monochlorosilane such as trimethylchlorosilane. The method for producing a solid titanium catalyst for ethylene polymerization and copolymerization according to claim 5, wherein the titanium compound is titanium tetrachloride and the silicon compound is silicon tetrachloride. The amount of the phosphorus compound is 0.01 to 0.25 mol or less per mol of the magnesium compound, the amount of the silicon compound having an alkoxy group is 0.05 to 3 mol per mol of the magnesium compound to prepare a solid titanium catalyst for ethylene polymerization and copolymerization. Way. The solid titanium for ethylene polymerization and copolymerization according to claim 1, wherein the amount of the mixture of the titanium compound and the silicon compound is 0.1 to 200 moles per mole of the magnesium compound, and the mixing ratio of the titanium compound and the silicon compound is 0.05 to 0.95 in a molar ratio. Method for preparing a catalyst.