KR100723369B1 - Olefin polymerization and copolymerization method - Google Patents

Abstract

The present invention relates to a process for olefin polymerization and copolymerization, wherein (A) in the presence of (a) a solid complex titanium catalyst, (b) an aluminum alkyl and (c) an electron donor prepared by a production process comprising the following steps: Prepolymerization catalysts obtained by prepolymerization of olefins; (i) dissolving the magnesium halide compound in an oxygen solvent which is a mixed solvent of a cyclic ether and at least one alcohol compound to obtain a magnesium compound solution, (ii) the magnesium compound solution at -10 to 30 ° C with a titanium halide compound After the first reaction, the temperature is increased or aged to obtain particles, and then secondaryly reacted with a titanium halide compound to prepare a carrier, (iii) the carrier is reacted with a titanium halide compound and an electron donor to form a titanium supported catalyst. Preparing, (iv) washing the prepared catalyst with a hydrocarbon solvent at a temperature of 40-200 ° C., (v) reacting the washed catalyst with an aluminum compound or boron compound having two or more alkoxy groups; (B) a periodic table of Group II or Group III organometallic compounds; And (C) polymerizing or copolymerizing the olefin in the presence of an external electron donor. The olefin polymerization and copolymerization method of the present invention can provide an olefin polymer having a high stereoregularity and a wide molecular weight distribution, and has an effect of increasing the polymerization activity and increasing the productivity of the polymerization process.

Olefin polymerization, prepolymerization, cyclic ether, oxygen solvent, metal halide compound, solid complex titanium catalyst

Description

Olefin polymerization and copolymerization method {OLEFIN POLYMERIZATION AND COPOLYMERIZATION METHOD}

The present invention relates to an olefin polymerization and copolymerization method, and more particularly, to an olefin polymerization and copolymerization method using a prepolymerization catalyst obtained by prepolymerizing an olefin at low temperature and low pressure with a solid complex titanium catalyst.

Although many olefin polymerization catalysts and polymerization methods using the same have been reported so far, efforts to improve productivity or product quality by improving physical properties of a polymer obtained using the catalyst invented in order to give the catalyst a greater commercial meaning. There is a continuing need to improve the activity and stereoregularity of the catalyst itself.

A number of olefin polymerization catalysts and catalysts containing magnesium have been reported, and in particular, many methods for preparing a catalyst using a solution of a magnesium compound to control the particle shape and size of the catalyst and the like are known.

There is a method of obtaining a magnesium solution by reacting a magnesium compound with an electron donor such as alcohol, amine, ether, ester, carboxylic acid, etc. in the presence of a hydrocarbon solvent. In the case of using alcohol, US Pat. Nos. 4,330,649, 5,106,807, and Japan Reference is made to published patent publication no. 58-83006. In addition, U.S. Patent Nos. 4,315,874, 4,399,054, and 4,071,674 report a method for preparing magnesium solutions.

Tetrahydrofuran, a cyclic ether, is variously used as a magnesium chloride compound (for example, US Pat. No. 4,482,687), as an additive for a promoter (US Pat. No. 4,158,642), and as a solvent (US Pat. No. 4,477,639). Has been.

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, the catalytic activity is complemented, but there are irregularities in the shape of the catalyst such as the shape, size, and size distribution of the catalyst, and there are disadvantages in that stereoregularity must be complemented.

As described above, the improvement aspect for improving the commercial value of the catalyst for alpha olefin polymerization is to produce a catalyst having high polymerization activity and stereoregularity and to improve the quality of the product, and to control the shape and size of the catalyst to improve productivity. Efforts have been made to increase the production cost and to improve the production yield and activity of the catalyst in the production of the catalyst, and efforts are being made to reduce the production cost.

The present invention has been made to overcome the above problems, an object of the present invention is to provide a method for olefin polymerization and copolymerization showing high stereoregularity and broad molecular weight distribution, having a high catalytic activity.

The olefin polymerization and copolymerization method of the present invention,

(A) a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of (a) a solid complex titanium catalyst, (b) aluminum alkyl and (c) an electron donor prepared by a production process comprising the following steps;

(i) dissolving the magnesium halide compound in an oxygen solvent which is a mixed solvent of a cyclic ether and at least one alcohol compound to obtain a magnesium compound solution,

(ii) preparing a carrier by first reacting the magnesium compound solution with the titanium halide compound at -10 to 30 ° C., then raising or aging the temperature to obtain particles, and then secondly reacting with the titanium halide compound to prepare a carrier,

(iii) reacting the carrier with a titanium halide compound and an electron donor to prepare a titanium supported catalyst,

(iv) washing the prepared catalyst with a hydrocarbon solvent at a temperature of 40-200 ° C.,

(v) reacting the washed catalyst with an aluminum compound or boron compound having two or more alkoxy groups;

(B) a periodic table of Group II or Group III organometallic compounds; And

(C) characterized in that the olefin is polymerized or copolymerized in the presence of an external electron donor.

In the method for preparing the solid complex titanium catalyst (a), examples of the magnesium halide compound used in step (i) include magnesium halides, alkylmagnesium halides, alkoxy magnesium halides, and aryloxymagnesium halides. The magnesium halide compound may be used as a mixture of two or more kinds, and is effective even when used in the form of a complex with another metal.

The cyclic ether used in the step (i) is preferably a cyclic ether having 3 to 6 carbon atoms and a derivative thereof, more preferably tetrahydrofuran, 2-methyl tetrahydrofuran, and most preferably Preferably tetrahydrofuran.

The alcohol compound used in step (i) is preferably a monovalent or polyhydric alcohol having 1 to 20 carbon atoms, and more preferably an alcohol containing 2 to 12 carbon atoms.

The amount of the oxygen-containing solvent in step (i) is 1 to 15 mol, preferably about 2 to 10 mol, per mol of magnesium atom of the halide compound of magnesium. When the amount of use is less than 1 mole, dissolution of the magnesium halide compound is difficult, and when it exceeds 15 moles, the amount of the magnesium halide compound to be added to obtain the catalyst particles is too large, and the particle is also difficult to control.

Since the use ratio of the cyclic ether and the alcohol, which are the oxygen-containing solvent used in the step (i), depends on the particle characteristics and the size of the catalyst prepared according to the use ratio, it can be used by appropriately adjusting, preferably the cyclic 0.5 to 3.5 moles of alcohol per mole of ether.

The dissolution temperature in step (i) depends on the type and amount of cyclic ether and alcohol, but is preferably 20 to 200 ° C, more preferably about 50 to 150 ° C.

In step (i), a hydrocarbon solvent may additionally be used as a diluent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and trichloro Examples are halogenated hydrocarbons such as ethylene, carbon tetrachloride and chlorobenzene.

In the method for preparing a solid complex titanium catalyst (a), the step (ii) is added to the magnesium halide compound represented by the following general formula (I) in the magnesium compound solution obtained in step (i) at -10 ~ 30 ℃ In order not to occur, the molar ratio of the oxygen solvent: titanium halide compound is 1: 3.0 to 10, and the particle is precipitated by raising or aging the temperature, and then the titanium halide compound is added as a secondary reaction to use as a carrier. To obtain solid particles.

Ti (OR) _a X _(4-a) ‥‥‥ (I)

[Where R represents an alkyl group of 1 to 10 carbon atoms, X is a halogen group element, and a is an integer of 0 to 3 in order to match the valence of the general formula.]

When the titanium halide compound is first introduced into the magnesium compound solution in the step (ii), it is necessary to adjust the conditions such as the input temperature, the molar ratio of the oxygenated solvent and the titanium halide compound to prevent precipitation during the first charge. It is important to control the shape of the catalyst, and the production rate of the catalyst can be increased by adding a titanium halide compound and reacting it after the production of carrier particles.

In the method of preparing a solid complex titanium catalyst (a), step (iii) is a step of reacting the carrier obtained in step (ii) with a titanium halide compound and an electron donor to support titanium. Although it may be completed, it is preferable to proceed with two or three or more reactions.

Preferably, in step (iii), the carrier obtained in step (ii) is reacted with the titanium halide compound or with an appropriate electron donor, and the slurry remaining after separating the liquid mixture is subjected to the titanium compound and the electron donor. After reacting with and once again, the solid component is separated and dried to obtain a catalyst.

Examples of the kind of the electron donor used in the step (iii) include a compound containing oxygen, nitrogen, and phosphorus. Specific examples of such compounds include organic acids, organic acid esters, alcohols, ethers, aldehydes, ketones, amines, amine oxides, amides, phosphate esters, and the like, preferably ethyl benzoate, ethyl bromobenzoate and butyl benzoate. Benzene acid alkyl esters such as isobutyl benzoate, hexyl benzoate, cyclohexyl benzoate and derivatives thereof and dialkyl aryl having 2 to 10 carbon atoms such as diisobutyl phthalate, diethyl phthalate, ethyl butyl phthalate and dibutyl phthalate Phthalates and their derivatives.

In the method of preparing a solid complex titanium catalyst (a), step (iv) is a step of washing the catalyst prepared in step (iii) with a hydrocarbon solvent at a high temperature, through which the high-stereoregular catalyst is completed. .

Examples of hydrocarbon solvents used in step (iv) include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, benzene, toluene, xylene and ethylbenzene; And aromatic hydrocarbons such as trichloroethylene, carbon tetrachloride and chlorobenzene.

In order to further enhance the stereoregularity of the solid complex titanium catalyst, the temperature at the time of washing in step (iv) is preferably 40 to 200 ° C, more preferably about 50 to 150 ° C.

In the method of preparing a solid complex titanium catalyst (a), step (v) is a process of surface treating the catalyst washed in the step (iv) with an aluminum compound or a boron compound having two or more alkoxy groups, wherein the two The aluminum compound or boron compound having the alkoxy group described above is preferably selected from aluminum triisopropoxide, aluminum trialkoxide such as aluminum triethoxide, trialkyl borate such as triethyl borate and tributyl borate, and the like.

As the aluminum compound or boron compound having two or more alkoxy groups, it is preferable to use 2 to 2,000 moles per mole of the magnesium halide compound used in step (i). If the content is less than 2 moles, it is difficult to obtain the polymerization activity of the present invention, and if the content exceeds 2,000 moles, there is a problem in that adverse effects such as a decrease in polymerization activity.

The surface treatment reaction of step (v) is a catalytic reaction of the catalyst washed at -70 ~ 50 ℃ and aluminum compound or boron compound, the reaction may be carried out using a solvent, or without using a solvent.

The solid complex titanium catalyst prepared through the above steps (i) to (v) is used in the prepolymerization process for preparing the prepolymerization catalyst used in the present invention.

The prepolymerization process is a process of prepolymerizing an olefin in the presence of (a) solid complex titanium catalyst, (b) aluminum alkyl and (c) electron donor prepared as described above.

It is preferable that the reaction temperature at the time of the said prepolymerization is -50-50 degreeC. When the reaction temperature is less than -50 ° C, the polymerization reaction proceeds slowly, and when the reaction temperature exceeds 50 ° C, the polymerization reaction proceeds quickly and there is a problem in controlling the polymer shape.

The olefin monomer is reacted at the reaction temperature as described above to polymerize the high molecular weight polymer on the surface of the solid complex titanium catalyst. As a result, the high molecular weight polymer polymerized on the surface of the solid complex titanium catalyst is about 1 to 100 g per g of the solid complex titanium catalyst.

As the olefin monomer used in the prepolymerization process, one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene and 1-octene is preferably used.

When the prepolymerization is carried out in the liquid phase, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may serve as the reaction medium.

In the case of liquid phase prepolymerization, the concentration of the (a) solid complex titanium catalyst in the prepolymerization reaction system is about 0.01 to about 500 mmol, preferably about 1 to about 50 mmol, calculated as titanium atoms per 1 L of solvent. If the concentration is less than 0.01 mmol, it is difficult to effectively proceed with the polymerization reaction, and if it exceeds 500 mmol, there is a problem in that the catalyst is overactivated during the polymerization reaction.

The (b) aluminum alkyl in the prepolymerization reaction system is preferably selected from trialkylaluminum and trialkenylaluminum, and examples of the trialkylaluminum include triethylaluminum or tributylaluminum, and the trialkenylaluminum As an example, triisoprenyl aluminum is mentioned.

The amount of the aluminum alkyl (b) used is about 1 to 100 moles, preferably about 2 to 50 moles per mole of titanium atoms in the (a) solid complex titanium catalyst. If the amount is less than 1 mole, it is difficult to effectively proceed with the polymerization reaction, and if the amount exceeds 100 moles, the polymerization reaction is initially overactivated.

It is preferable that the said (c) electron donor in a prepolymerization reaction system is an alkoxysilane compound which is an organosilicon compound which has an alkoxy group. Examples of the alkoxysilane compound include aromatic silanes such as diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane, phenylmethyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, di Isopropyldimethoxysilane, di-t-butyldimethoxysilane, t-butyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, 2-norbornanetrier Aliphatic silanes such as methoxysilane, 2-norbornanemethyldimethoxysilane, vinyltriethoxysilane and mixtures thereof, more preferably branched alkyldialkoxysilanes such as diisobutyldimethoxysilane or As a cycloalkyldialkoxysilane, such as dicyclopentyldimethoxysilane, one or more of the alkoxysilanes can be selected and used.

The amount of the (c) electron donor used is 0.001 to 3 moles, preferably 0.1 to 1.0 mole per mole of titanium atoms in the (a) solid complex titanium catalyst. If the amount is less than 0.001 mole it is difficult to obtain the effect of using the electron donor, if it exceeds 3 moles there is a problem that the adverse effect of excessive use occurs.

The prepolymerization catalyst prepared as above is advantageously used for the polymerization of olefins such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, vinylcycloalkane or cycloalkene. In particular, the prepolymerization catalyst is capable of polymerizing α-olefins having three or more carbon atoms, copolymerizing them with each other, copolymerizing them with less than 20 mol% of ethylene, and polyunsaturated compounds such as conjugated or nonconjugated dienes. Advantageously applied to their copolymerization.

Polymerization method of the olefin according to the present invention is (A) prepolymerization catalyst encapsulated with a high molecular weight polymer prepared by the above manufacturing process, (B) Group II or III organometallic compound of the periodic table and (C) external electron donor It is a process of polymerizing or copolymerizing an olefin in presence of.

Examples of the organometallic compound (B) used as a promoter in the polymerization process include trialkylaluminum such as triethylaluminum and tributylaluminum, trialkenylaluminum such as triisoprenylaluminum, partially alkoxylated alkyl Aluminum, e.g., dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide, alkylaluminum sesquialkoxy, ethyl such as ethylaluminum sesquiethoxide and butylaluminum sesquiethoxide, ethyl Alkyl aluminum dihalides such as aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide, partially halogenated aluminum, dialkyl aluminum hydride such as diethyl aluminum hydride or dibutyl aluminum hydride, ethyl aluminum ethoxy chloride Butyl Aluminum Butoxycle Partially alkoxylated and halogenated alkylaluminums such as lauride and ethylaluminum ethoxybromide and the like.

As the (C) external electron donor used in the polymerization process, an external electron donor material commonly used for olefin polymerization may be used. These external electron donors are mainly used to optimize the activity and stereoregularity of the catalyst in the polymerization of olefins.

Examples of external electron donors usable in the present invention include organic acids, organic acid anhydrides, organic acid esters, alcohols, ethers, aldehydes, ketones, silanes, amines, amine oxides, amides, diols, oxygen such as phosphate esters, silicon, nitrogen, sulfur, And organic compounds containing heteroatoms such as phosphorus and mixtures thereof. Preferred external electron donors are alkoxy silane compounds which are organosilicon compounds having an alkoxy group, and their kinds include aromatic silanes such as diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane and phenylmethyldimethoxysilane, Isobutyltrimethoxysilane, diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, t-butyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxy Aliphatic silanes such as silane, dicyclohexyldimethoxysilane, 2-norbornaneethethoxysilane, 2-norbornanemethyldimethoxysilane, vinyltriethoxysilane and mixtures thereof, in particular the More preferred are branched alkyl dialkoxysilanes such as isobutyldimethoxysilane and cycloalkyl dialkoxysilanes such as dicyclopentyldimethoxysilane. It may be mixed with poison, or two or more species.

When the polymerization method of the present invention is carried out in a liquid phase, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may serve as the reaction medium. In the case of liquid phase polymerization, the preferred concentration of the (A) prepolymerization catalyst in the polymerization reaction system is about 0.001 to about 5 mmol, preferably about 0.001 to about 0.5 mmol, calculated as titanium atoms for 1 L of solvent. In the case of gas phase polymerization, the amount of the (A) prepolymerization catalyst is about 0.001 to about 5 mmol, preferably about 0.001 to about 1.0 mmol, more preferably 0.01 to about 0.5 mmol, based on 1 L of the polymerization zone in terms of titanium atoms. (B) The ratio of organometallic atoms in the organometallic compound is (A) about 1 to 2,000 moles, preferably about 5 to 500 moles per mole of titanium atoms in the prepolymerization catalyst, and (C) of the external electron donor The ratio is about 0.001 to 10 moles, preferably about 0.01 to 2 moles, more preferably 0.05 to 1 mole per mole of organometallic atoms in the organometallic compound (B), calculated as heteroatoms in the external electron donor.

The polymerization or copolymerization of olefins in the presence of the catalyst system of the present invention proceeds in the same way as in the polymerization of olefins using conventional Ziegler-type catalysts.

When the reaction conditions are explained in more detail, the polymerization reaction of the olefin proceeds substantially in the absence of oxygen and water, and the reaction temperature is preferably about 20 to 200 캜, more preferably about 50 to 180 캜, and the reaction pressure. May be carried out under a pressure of about 1 to 100 atmospheres, preferably about 2 to 50 atmospheres.

The polymerization reaction can be carried out batchwise, semibatch or continuously, or it is also possible to carry out the polymerization in two or more stages having different reaction conditions.

The present invention may be understood in more detail by the following examples, which are intended to illustrate the present invention and are not intended to limit the protection scope of the present invention.

[ Example ]

Example  One

Prepolymerization  Preparation of Catalyst (A)

Step 1: Prepare Magnesium Compound Solution

15 kg of MgCl ₂ , 225 kg of toluene, 17 kg of tetrahydrofuran, and 31 kg of butanol were added to a 500L reactor equipped with a mechanical stirrer substituted with a nitrogen atmosphere, and heated at 110 ° C. while stirring at 70 rpm to obtain a uniform solution.

Step 2: prepare the carrier

The temperature of the solution obtained in step 1 was cooled to 17 ° C, 32 kg of TiCl ₄ was added, and the temperature of the reactor was raised to 60 ° C over 1 hour, and when the reactor reached 60 ° C, 13 kg of TiCl _{4 was added} thereto. 40 minutes was added and reacted for 30 minutes. After the reaction, the mixture was allowed to stand for 30 minutes to settle the carrier and to remove the upper solution. 90 kg of toluene was added to the remaining slurry in the reactor, and the process of stirring, standing, and removing the supernatant was repeated three times.

Step 3: preparing a solid complex titanium catalyst

80 kg of toluene and 90 kg of TiCl ₄ were added to the carrier prepared in step 2 at a stirring speed of 60 rpm, and then the temperature of the reactor was raised to 110 ° C. for 1 hour, aged for 1 hour, and left for 15 minutes to settle the precipitate. The supernatant was then separated. To this was added 87 kg of toluene, 52 kg of TiCl ₄ and 4.2 kg of diisobutyl phthalate. The temperature of the reactor is raised to 120 ° C., and the reaction is maintained for 1 hour. After the reaction, the mixture was allowed to stand for 30 minutes to separate the supernatant, and 80 kg of toluene and 76 kg of TiCl ₄ were injected again, followed by reaction at 100 ° C. for 30 minutes. After the reaction was allowed to stand for 30 minutes, the supernatant was separated, and 65 Kg of hexane was added thereto, followed by stirring while maintaining the temperature of the reactor at 60 ° C. for 30 minutes. The stirring was stopped and the supernatant was separated after standing for 30 minutes. Hexane was added to the remaining catalyst slurry layer and washed six times in the same manner to prepare a final solid complex titanium catalyst. Ti content of the prepared catalyst was 2.8%.

Step 4: surface treatment of solid complex titanium catalyst

15 g of the solid complex titanium catalyst prepared in step 3 was added to 500 ml of hexane and 50 ml of aluminum triethoxide, followed by reaction at room temperature for 1 hour. The surface treated catalyst was stored after drying in a nitrogen atmosphere. The titanium atom content of the surface treated catalyst was 2.5% by weight.

Step 5: prepolymerization

     The high pressure reactor with a capacity of 0.5 L was washed with propylene, and then, 4 g of the catalyst obtained in step 4, 300 ml of hexane, 10 mmol of triethylaluminum, and 0.5 mmol of cyclohexylmethyldimethoxysilane were added to the reactor maintained at 15 ° C., followed by 30 After stirring for 3 minutes, prepolymerization was carried out at 15 ° C. for 3 hours while flowing at 80 mL / min with propylene. In the prepolymerization catalyst thus obtained, the amount of the high molecular weight polymer polymerized around the catalyst was 6.8 g per 1 g of catalyst.

polymerization

Propylene polymerization was performed to evaluate the performance of the prepared prepolymerization catalyst. The prepolymerization catalyst prepared above was placed in a high pressure bomb containing 10 mg of the solid complex titanium catalyst and mounted in a 2L high pressure polymerization reactor, and the polymerization reactor was purged with nitrogen for about 1 hour so that the atmosphere of the reactor was dried nitrogen. To this, triethylaluminum (Al / Ti molar ratio = 450) and dicyclopentyldimethoxysilane (Si / Al molar ratio = 0.1) were added as an external electron donor, and the reactor was sealed. After injecting 1000 ml of hydrogen, 1,200 ml of liquid propylene was added using a syringe pump, the temperature of the reactor was raised to 70 ° C. over 20 minutes, and a prepolymerization catalyst was added to the reactor for polymerization for 1 hour. After 1 hour of reaction, the unreacted propylene was vented to air, and the temperature of the reactor was lowered to room temperature. The resulting polymer was dried in a vacuum oven at 50 ° C. and then weighed, and analyzed by xylene solubles and GPC (molecular weight distribution = Mw / Mn). The results are shown in Table 1 below. The xylene lysate measuring method is one of methods for evaluating the isotactic index of a polymer, and a predetermined amount of a polymer sample is placed in a xylene solution, completely dissolved at a high temperature of 110 ° C. or higher, and then cooled to room temperature to dissolve the melt. After cooling, the precipitate is separated by a filter and the content is measured.

Example  2

In the fourth step of the prepolymerization catalyst manufacturing process of Example 1, except that the prepolymerization catalyst was prepared using 50 ml of aluminum triisopropoxide was carried out under the same conditions as in Example 1, the analysis results are shown in Table 1 Shown in

Example  3

In the four steps of the prepolymerization catalyst of Example 1, except that the prepolymerization catalyst was prepared using 50 ml of triethyl borate was carried out under the same conditions as in Example 1, the analysis results are shown in Table 1 .

Example  4

In the fourth step of the prepolymerization catalyst of Example 1, except that the prepolymerization catalyst was prepared using 50 ml of tributyl borate was carried out under the same conditions as in Example 1, the analysis results are shown in Table 1 .

Example  5

In the fourth step of the prepolymerization catalyst of Example 1, except that the prepolymerization catalyst was prepared using 100 ml of tributyl borate was carried out under the same conditions as in Example 1, the analysis results are shown in Table 1 .

Example  6

In the fourth step of the prepolymerization catalyst production process of Example 1, except that the prepolymerization catalyst was prepared using 150 ml of tributyl borate was carried out under the same conditions as in Example 1, the analysis results are shown in Table 1 .

Comparative example  One

The same process as in Example 1 was carried out except that four steps of the prepolymerization catalyst manufacturing process of Example 1 were omitted and the prepolymerization catalyst was prepared, and the analysis results are shown in Table 1.

Comparative example  2

In the fourth step of the prepolymerization catalyst of Example 1, except that the prepolymerization catalyst was prepared using 50 ml of triethylborane was carried out under the same conditions as in Example 1, the analysis results are shown in Table 1 .

Comparative example  3

In the fourth step of the prepolymerization catalyst of Example 1, the prepolymerization catalyst was prepared using 50 ml of trioctyl aluminum (1M in hexane) under the same conditions as in Example 1, and the analysis results were performed. Table 1 shows.

Polymerization Activity (kgPP / gCat) Xylene Melt (%) GPC (Molecular Weight Distribution = Mw / Mn) Example 1 38 1.7 5.8 Example 2 36 1.8 5.9 Example 3 35 1.8 5.7 Example 4 34 1.6 5.9 Example 5 36 1.7 6.0 Example 6 34 1.8 6.1 Comparative Example 1 22 2.4 4.6 Comparative Example 2 18 2.2 5.0 Comparative Example 3 15 2.5 5.2

As shown in Table 1, the embodiments according to the olefin polymerization and copolymerization method of the present invention, compared to the comparative examples, the amount of xylene solubles of the produced polymer is reduced, and the high stereoregularity and broad molecular weight distribution It can be seen that the polymerization activity is higher.

According to the present invention, the produced polymer exhibits high stereoregularity and broad molecular weight distribution, and also provides an olefin polymerization and copolymerization method with high polymerization activity, thereby increasing the productivity of the polymerization process.

Claims (11)

An olefin polymerization or copolymerization method characterized by polymerizing or copolymerizing an olefin in the presence of the following (A), (B) and (C): (A) a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of (a) a solid complex titanium catalyst, (b) aluminum alkyl and (c) an electron donor prepared by a production process comprising the following steps; (i) dissolving the magnesium halide compound in an oxygen solvent which is a mixed solvent of a cyclic ether and at least one alcohol compound to obtain a magnesium compound solution, (ii) preparing a carrier by first reacting the magnesium compound solution with the titanium halide compound at -10 to 30 ° C., then raising or aging the temperature to obtain particles, and then secondly reacting with the titanium halide compound to prepare a carrier, (iii) reacting the carrier with a titanium halide compound and an electron donor to prepare a titanium supported catalyst, (iv) washing the prepared catalyst with a hydrocarbon solvent at a temperature of 40-200 ° C., (v) reacting the washed catalyst with an aluminum compound or boron compound having two or more alkoxy groups; (B) a periodic table of Group II or Group III organometallic compounds; And (C) External electron donor. The compound of claim 1, wherein the aluminum compound having at least two alkoxy groups in step (v) is aluminum triisopropoxide or aluminum triethoxide, and the boron compound having two or more alkoxy groups is triethylborate or tributyl It is a borate, The olefin polymerization or copolymerization method characterized by the above-mentioned. The method for olefin polymerization or copolymerization according to claim 1 or 2, wherein the aluminum compound or boron compound is used in an amount of 2 to 2,000 moles per mole of the magnesium halide compound. The olefin polymerization or copolymerization method according to claim 1, wherein the reaction temperature at the time of prepolymerization is -50 to 50 ° C. The method of claim 1, wherein the olefin is one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene and 1-octene. The method for olefin polymerization or copolymerization according to claim 1, wherein the concentration of the (a) solid complex titanium catalyst is 0.01 to 500 mmol in terms of titanium atoms relative to 1 L of the solvent in the prepolymerization reaction system. The method of olefin polymerization or copolymerization according to claim 1, wherein the aluminum alkyl (b) is selected from trialkylaluminum and trialkenylaluminum. The method for olefin polymerization or copolymerization according to claim 1, wherein the amount of the aluminum alkyl (b) is 1 to 100 moles per mole of titanium atoms in the (a) solid complex titanium catalyst. The method of olefin polymerization or copolymerization according to claim 1, wherein the (c) electron donor is an alkoxysilane compound. The method of claim 9, wherein the alkoxysilane compound is diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane, phenylmethyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, di Isopropyldimethoxysilane, di-t-butyldimethoxysilane, t-butyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, 2-norbornanetrier An olefin polymerization or copolymerization method, characterized in that at least one member is selected from the group consisting of oxysilane, 2-norbornanemethyldimethoxysilane and vinyltriethoxysilane. The method for olefin polymerization or copolymerization according to claim 1, wherein the amount of the (c) electron donor is used in an amount of 0.001 to 3 mol per mole of titanium atoms in the (a) solid complex titanium catalyst.