KR0119268B1 - Catalyst for Alpha-olefin Polymerization - Google Patents

Abstract

The present invention relates to a catalyst capable of producing a high-stereoregular polymer or copolymer in a high yield when applied to α-olefin polymerization or copolymerization having 3 or more carbon atoms. The olefin polymer can be polymerized.

Description

α-olefin polymerization catalyst

The present invention relates, in particular, to catalysts capable of producing high-stereoregular polymers or copolymers in high yields when applied to α-olefin polymerization or copolymerization of 3 or more carbon atoms.

In more detail, the present invention is monoethylene glycol (hereinafter referred to as MEG), diethylene in a polycarboxylic acid ester compound as an electron donor in order to improve the activity of α-olefin polymerization and obtain a high stereoregular polymer Diethylene glycol (hereinafter referred to as DEG), Triethylene glycol (hereinafter referred to as TEG), Polyethylene glycol (hereinafter referred to as PEG, Monopropylene glycol (hereinafter referred to as MPG) and dipropylene A derivative of glycol (hereinafter referred to as DPG) relates to a catalyst prepared by adding mono or diesters each or a mixture thereof.

To prepare a high-stereoregular polymer or copolymer using a solid complex titanium catalyst containing at least magnesium, titanium and halogen treated with an electron donor, as a catalyst for α-olefin polymerization or copolymer containing at least 3 carbon atoms. A number of preceding methods have been known (e.g., Japanese Patent Laid-Open Nos. 73-16986, 73-16987, and Federal Republic of Germany Patent Nos. 2,153,520, 2,230,672, 2,230,728, 2,230,752, and 2,553,104). number).

These preceding methods suggest a process for mixing and catalyst formation of certain catalyst components. As is well known, the properties of catalysts containing this kind of solid complex titanium components vary greatly depending on the mixing of the catalyst components, the bonding of the catalyst forming process and the difference in bonding of these conditions. Thus, when produced under any given binding conditions, it is extremely impossible to predict whether similar results can be obtained. Sometimes catalysts with extremely poor properties are produced.

Solid complex titanium components containing at least magnesium, titanium and halogens are no exception. In the polymerization or copolymerization of an α-olefin containing at least three carbon atoms in the presence of hydrogen using a catalyst composed of a titanium component and an organometallic compound of Groups I to IV metals of the periodic table, the metal aluminium, When a catalyst composed of titanium trichloride obtained by reducing titanium tetrachloride with hydrogen or an organoaluminum compound is used in combination with an electron donor known to inhibit amorphous polymer formation, the effect changes unexpectedly depending on the donor used. The reason for this is that the electron donor is not simply added, but it is accepted that the microstructure of the solid complex catalyst is fundamentally changed by electronically and steric bonding with magnesium and titanium compounds.

The present inventors have a higher yield of high solids rules using solid complex titanium components containing at least magnesium, titanium and halogens, organometallic compounds of Groups I to III metals of the periodic table and the special ester electron donors described above. We have developed a catalyst that can produce a polymer and advantageously overcome the challenges of amorphous polymer production. Accordingly, an object of the present invention is to provide a catalyst capable of polymerizing a high-stereoregular olefin polymer in high yield by using an appropriate electron donor.

The catalyst for α-olefin polymerization prepared by the present invention is composed of a solid complex titanium containing magnesium, titanium, a halogen and an electron donor, an organometallic compound of a group I to group III metal of the periodic table and an organic acid anhydride component, In the presence of an electron donor without active hydrogen, a magnesium compound having no reducing ability in the liquid state may be prepared by a direct contact reaction with the liquid titanium compound, that is, by directly contacting each other in the body state. Alternatively, a solid catalyst may be produced from a magnesium compound in the absence of an electron donor having no active hydrogen, and then contacted with the electron donor to obtain a solid catalyst.

The component of the solid complex titanium is a solid complex whose halogen titanium molar ratio is at least about 4 and which does not substantially liberate the titanium compound by hexane washing at room temperature. The chemical structure of this solid complex is unknown, but it is assumed that magnesium and titanium atoms are firmly bonded by halogen. In the example of the solid complex titanium component, the molar ratio of halogen titanium is about 4 or more, preferably about 5 or more, more preferably about 8 or more, and the molar ratio of magnesium / titanium is about 3 or more, preferably about 5 to about The molar ratio of the electron donor / titanium is about 0.2 to 6, preferably about 0.4 to 3, more preferably about 0.8 to 2. Furthermore, the specific surface area of the solid is at least 10 m 2 / g, preferably at least about 50 m 2 / g, more preferably at least 100 m 2 / g. It is also desirable that the X-ray spectra of the solid complex exhibit amorphous properties regardless of the starting magnesium, or are more amorphous than the commercial grade of conventional magnesium halides.

Solid complex titanium can be prepared in several ways. Most commonly known are various methods of contacting a magnesium compound with a titanium compound containing at least one halogen and, if necessary, treating the product with an electron donor, which can be used in the present invention. Some of these methods are described in JP 2,230,672, 2,504,036, 2,553,104 and 2,605,922 and JP 76-28189, 76-136625 and 77-87486. have. In addition, a method of producing a solid titanium compound containing an electron donor by reacting a liquid magnesium with an electron donor and a titanium compound in a liquid state has been disclosed in Japanese Unexamined Patent Publication No. 79-40293.

Suitable magnesium compounds used for the production of solid complex titanium compounds contact at least one of the components selected from the group consisting of alcohols, organic carboxylic acids, aldehydes, amines and mixtures thereof in the presence of solvents such as hexane, heptane, decane and the like. It is obtained by making it react. Examples of magnesium compounds having no reducing properties include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, and methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, and octoxymagnesium Alkoxymagnesium halides such as chlorides, aryloxymagnesium halides such as phenoxyshimamagnesium chloride and methylphenoxyshima chloride, alkoxymagnesiums such as magnesium ethoxypropoxy, butoxymagnesium and octoxymagnesium, and phenoxymagnesium And magnesium salts of aryloxy magnesium such as dimethylphenoxy magnesium and carboxylic acids such as lauryl magnesium and magnesium stearate. The magnesium compound may be used in the form of a complex with another metal or with a mixture with other metals. Two or more magnesium compounds may be used in the mixture. Preferred magnesium compounds are hydrogen-containing magnesium compounds, among others magnesium chloride, alkoxymagnesium chloride, preferably those having C ₁ to C ₁₀ alkoxy and aryloxymagnesium chloride, C ₆ to C ₂₀ aryloxy.

Usually, the above-listed compounds may be represented by simple chemical formulas, but sometimes they cannot be expressed by simple formulas depending on the preparation method of the magnesium compound. These are generally regarded as mixtures of the aforementioned compounds. For example, a method of reacting magnesium metal with an alcohol or a phenol in the presence of halosilane, phosphorus pentachloride, or thionyl chloride and pyrolysis of a Grignaed reagent or hydroxyl group, carbonyl ester bond, ether bond, or the like Compounds obtained by a decomposition method using the same are regarded as a mixture of various compounds according to the reagent or the reactivity thereof, and these compounds may also be used in the present invention. In the present invention, a solution of a magnesium compound in a liquid magnesium compound or a hydrocarbon solvent having no reducing property is mainly used. They can be prepared by reacting with at least one electron donor selected from the group consisting of alcohols, organic carboxylic acids, aldehydes, amines and mixtures thereof in the presence or absence of a hydrocarbon solvent capable of dissolving the aforementioned magnesium compound.

Hydrocarbon solvents used for these purposes include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane, benzene, Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene and cymene and halogenated hydrocarbons such as dichloroethane, dichloropropane, dichloroethylene, trichloroethylene, carbon tetrachloride and chlorobenzene.

Solutions of magnesium compounds in such hydrocarbon solvents are simply present by mixing and heating both or in the presence of a soluble electron donor in a magnesium compound selected from the group consisting of alcohols, aldehydes, amines, carboxylic acids and mixtures thereof or mixtures thereof and other electrons. It can be prepared by mixing in the presence of a donor and heating any mixture. However, this recipe depends on the type of magnesium and solvent. When alcohol is used as the electron donor to dissolve the hydrogen-containing magnesium compound in the hydrocarbon solvent, although the amount varies depending on the amount and type of the magnesium compound and the hydrocarbon solvent, the alcohol is preferably at least 0.5 mole per mole of the magnesium compound. It is preferred to use about 1.0 to 20 moles, more preferably about 2.0 to about 10 moles.

When aliphatic hydrocarbons or cycloaliphatic hydrocarbons are used as hydrocarbon solvents, the alcohols are used in the amounts described above, but if they use alcohols having at least six carbon atoms, at least 0.5 mole per mole of magnesium containing halogen, preferably When at least 1.0 mole is used, the halogen-containing magnesium compound can be dissolved and a catalyst component having high activity can be obtained using a small amount of alcohol. In this case, if only an alcohol having 5 or less carbon atoms is used, the total amount of alcohol should be at least about 15 moles per mole of halogen-containing magnesium compound, and the resulting catalyst component also has lower catalytic activity than when alcohol is used in the above-described method. Meanwhile, when used as an aromatic hydrocarbon solvent, the hydrogen-containing magnesium compound may be dissolved by using the alcohol in an amount of about 20 moles, preferably about 1.5 to 12 moles, regardless of the type of alcohol.

The contact reaction of the halogen containing magnesium compound with the alcohol is preferably carried out in a hydrocarbon medium. The contact reaction is about 15 minutes to 5 hours at room temperature or high temperature, for example, about 65 ° C, preferably 30 to 200 ° C, more preferably about 60 to 150 ° C, depending on the type of magnesium compound and alcohol. , Preferably for about 30 minutes to 3 hours. The electron donor used to form the magnesium compound in the liquid state includes 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol having a minimum of 6 carbon atoms, preferably 6 to 20 carbon atoms. Aliphatic alcohols such as 2-ethylhexanol, decanol, dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol and stearyl alcohol, alicyclic alcohols such as cyclohexanol and methylcyclohexanol and benzyl alcohol, And aromatic alcohols such as methyl benzyl alcohol, isopropylene benzyl alcohol, α-methylbenzyl alcohol and α, α-dimethylbenzyl alcohol. Alcohols having 5 or less carbon atoms include methanol, ethanol, protanol, butanol, ethylene glycol, and methylcarbitol.

When preparing the magnesium compound in the solid state, the contact reaction temperature is about -70 ° C to about 200 ° C. In general, it is desirable to avoid high temperatures during mixing to obtain the form of granular or spherical particles. However, if the contact temperature is too low, precipitation of the solid product does not occur, so the reaction is preferably carried out at a temperature of about 20 ° C. to 150 ° C.

Examples of electron donors generally include oxygen-containing electron donors such as water, alcohols, phenols, ketones, aldehydes, carboxylic acids, esters, ethers and acid amides, ammonia, amines, nitriles and isocyanates; And nitrogen-containing electron donors, and specific examples thereof include methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol and isopropylbenzyl alcohol. Alcohols containing 18 carbon atoms, ketones containing 6 to 15 carbon atoms which may contain lower alkyl groups such as phenol, cresol, xylene, ethylphenol, propylphenol, cumipenyl and naphthol, acetaldehyde, 2 to 15 carbon atoms, such as propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphtholaldehyde Aldehydes containing, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valeric acid, methyl chloroacetate, ethyl dichloroacetate and methyl methacrylate Ethyl crotonate, ethyl cyclohexanecarboxylic acid, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl aniseate, ethyl aniseate, ethyl ethoxy benzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, cyclohexyl acetate, ethyl propionate, methyl butyrate, methylbarate, methylchloroacetate, ethyldichloroacetate, methyl methacrylate, ethylcycloate , Phenylbenzoate, methyltoluate, ethyltoluate, propylbenzoate, butylbenzoate, cyclohexylbenzoate, amyltoluate, ethyl Organic acid esters containing 2 to 18 carbon atoms, such as carbonate and ethylene carboxylate, acid halides containing 2 to 15 carbon atoms, such as acetyl chloride, benzyl chloride, toluic acid chloride, and anhydrous chloride acid, methyl Acid amides such as ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisol and diphenyl ether, methylamine, ethylamine, diethylamine, tributylamine, piperidine, Compounds such as aluminum, silicon, tin, etc. containing amines such as tribenzylamine, aniline, pyridine, pinolin and tetramethylethyleneamine, nitriles such as acetonitrile, benzonitrile and tolunitrile and the aforementioned functional groups in the molecule There is. In the present invention, however, certain electron donors have been reacted to improve the stereoregularity of the -olefin polymer and to produce the polymer in high yield. More specifically, the esters of MEG, DEG, TEG, PEG, MPG and DPG are more specifically examples of benzoate, such as acetate, propionate, n- and iso-butylate, benzoate, toluate, etc. Glycol monobenzoate, monoethylene glycol dibenzoate, diethylene glycol monobenzoate, diethylene glycol dibenzoate, triethylene glycol monobenzoate, triethylene glycol dibenzoate, monopropylene glycol monobenzoate, dipropylene Glycol monobenzoate, dipropylene glycol dibenzoate, tripropylene glycol monobenzoate and the like. These electron donors can be used as mixtures of two or more, especially aromatic esters are preferred and such donors are not always necessary as starting materials, and can also be used during the preparation of solid titanium catalyst components, as adducts of other compounds or It may also be used in the form of a complex. The amount of electron donor can be changed as appropriate. For example, from about 0.01 to 10 moles, preferably from about 0.01 to 5 moles, more preferably from 0.05 to about 1 mole per mole of magnesium compound.

The liquid titanium compound which will react directly with the magnesium compound is preferably a tetravalent titanium compound having the general formula Ti (OR) mX ₄ -m.

In the general formula, R is a hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, X is a halogen atom, and m is an integer of 0 ≦ m ≦ 4.

Examples of such titanium compounds are titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ , Ti (OCH ₃ ) C ₁₃ , Ti (OC ₂ H ₅ ) C1 ₃ , Ti (OC ₄ H ₉ ) C ₁₃ , Ti ( OC ₂ H ₅₎ Br ₃ and _{Ti (O (iC 2 H 5} ) three halogenated alkoxy titanium such as _{Br3, Ti (OCH 3) 2} C1 2, Ti (OC 2 H 5) 2 C1 2, Ti (OC 4 H ₉ ) Dihalogenated alkoxytitanium such as ₂ C1 ₂ and Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ C1, Ti (OC ₂ H ₅ ) ₃ C1, Ti (OC ₄ H ₉ ) ₃ C1 And tetraalkoxytitanium mixtures such as monohalogenated alkoxytitanium such as Ti (OC ₂ H ₅ ) ₃ Br, Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₄ H ₉ ) ₄ . Preference is given to double halogen-containing titanium compounds, in particular titanium tetrahalide, in particular titanium tetrachloride.

The magnesium compound in the liquid state is recrystallized into a spherical solid component using silicon tetrahalide, silicon alkyl halide, tin tetrahalide, tin alkyl halide, tin hydrohalide and titanium tetrahalide. The polymer obtained through slurry polymerization using the catalyst thus obtained is in the form of granular or spherical particles having a good particle size distribution and has a high bulk density and good fluidity.

The amount of the silicon compound, tin compound or titanium compound used to recrystallize the liquid magnesium compound into a spherical solid may be appropriately added. The amount of silicon compound, tin compound or titanium compound per mole of magnesium compound is preferably 0.1 to 20 moles. Preferably it is 0.1-10 mol, More preferably, it is 0.2-2 mol. When the liquid magnesium compound is reacted with a silicon compound, a tin compound or a titanium compound, the shape and size of the magnesium carrier vary depending on the reaction conditions. When the two mixtures are contacted, they are mixed at a sufficiently low temperature so that they do not change into solid products by their contact reaction, and the reaction products are heated to gradually produce a solid product. By this method, a spherical carrier capable of easily obtaining a spherical solid titanium catalyst forms a carrier.

The titanium compound is used in an amount of at least 1 mole, typically 3 to about 200 moles, especially about 5 to 100 moles, per mole of magnesium compound having no reducing ability. When contacting the solid magnesium carrier with the liquid titanium compound, it is advisable to slowly increase the reaction temperature after mixing at low temperature. For example, the two compounds are brought into contact with each other at -70 ° C to about 50 ° C so as not to react rapidly, and the reaction temperature is slowly raised to 50 to 150 ° C, the reaction is carried out for a sufficient time, and then the product The hydrocarbon used in the reaction is washed until no free titanium is detected. This catalyst preparation method can produce a solid titanium catalyst of excellent performance.

The catalyst produced by the process of the invention is advantageously used for the polymerization of olefins such as ethylene, propylene, 1-butene or 4-methyl-1-pentene. In particular, this catalyst is suitable for the polymerization of α-olefins having three or more carbon atoms, copolymerization of these mutually, their copolymerization with less than 10 mol% of ethylene, and those having polyunsaturated compounds such as conjugated or nonconjugated dienes. It is advantageously applied to the copolymerization.

The polymerization reaction can be carried out in a liquid phase or a gas phase. When proceeding 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 polymerization, the preferred concentration of solid complex titanium compound in the polymerization reaction system is from about 0.001 to about 5 mmol, preferably from about 0.001 to about 0.5 mmol, calculated as titanium atoms per liter of solvent. In the case of gas phase polymerization, the amount of the solid complex titanium compound is calculated to be 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, per liter of the polymerization zone when calculated as titanium atoms. It is good.

The polymerization reaction of olefins in the presence of the catalyst of the present invention proceeds in the same manner as in the polymerization of olefins using a conventional Ziegler-type catalyst. In particular, the reaction is carried out substantially in the absence of oxygen and water. The polymerization of the olefins may preferably be carried out at a temperature of about 20 to 200 ° C, more preferably at a temperature of about 50 to 180 ° C and a pressure of atmospheric pressure to 100 atm, preferably at a pressure of about 2 to 50 atm. This polymerization can be carried out batchwise, semibatch or continuously, and it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

The present invention is explained in more detail by the following examples and comparative examples.

Example 1

Preparation of catalyst: 5 g (0.053 mole) of MgCl ₂ and 50 ml of n-decane were put together in a 1 liter reactor, and Daup 2-ethyl-1-hexanol (2-ethyl-1-) was stirred under nitrogen atmosphere for 1 hour at room temperature. Slowly add 25 ml (0.16 mol) of hexanol. The solution is heated to 120 ° C. for 2 hours, and then 2 ml of diisobutyl phthalate is added to react for 1 hour to obtain a homogeneous solution. After the temperature was lowered to room temperature and 30 ml of TiCl ₄ was added dropwise, the reaction temperature was slowly raised to 90 ° C. and reacted for 2 hours to form a solid carrier, followed by 2.0 g (0.007 mol) of monoethylene glycol dibenzoate as a secondary electron donor. ) Is added and reacted at 90 ° C. for 1 hour. The solid was collected by filtration and washed sufficiently with purified hexane until no free titanium tetrachloride was detected in the wash. After purifying heptane was added to the carrier, 40 ml of TiCl ₄ was added dropwise thereto over 1 hour, and the reaction mixture was heated at 100 ° C. for 2 hours, and then the free titanium component of the prepared solid catalyst was detected with purified hexane. After washing, the solid is dried and stored under nitrogen atmosphere. The prepared solid complex contained 5.0 weight% of titanium atoms.

Polymerization

After washing a 1-liter high-pressure reactor with propylene, the catalyst was placed in a glass bottle containing 30 mg (titanium component of 0.04 mmol in terms of titanium atoms) and settled in the reactor three times under nitrogen / vacuum. Make a vacuum. 5 mmol of triethylaluminum and 0.5 mmol of cyclohexylmethyldimethoxysilane are injected into the reactor together with 500 ml of n-hexane. After hexane is injected, 300 ml of hydrogen is added, and the temperature is increased to 70 ° C. Propylene gas was injected into the polymerization reactor (1 liter Parr Reactor, model # 4521) through an oxygen scavenger and a molecular sieve trap and through a Mass Flow Controller (MFC). The reaction was started by breaking the vial mounted in the reactor with a stirrer when the propylene was in the gas-liquid equilibrium at a total pressure of 6 kg / cm 2. The reaction was carried out for 1 hour, and after the reaction was completed, the contents of the high pressure product was cooled to room temperature, and about 10 ml of ethanol was injected to remove the catalyst active site. The resulting polymer was collected by filtration and dried in a vacuum oven at 50 ° C. for about 6 hours to obtain 70.0 g of polypropylene as a white powder. This polymer had a boiling n-heptane extraction residue of 96.3%, an apparent density of 0.33 g / ml and a melt index of 2.9.

Example 2

The catalyst was prepared in the same manner as in Example 1, but 1.6 ml (0.007 mol) of diethylene glycol dibenzoate was used instead of monoethylene glycol dibenzoate as the secondary electron donor. The polymerization reaction was repeated under the conditions of Example 1 and the results are shown in Table 1.

Example 3

The catalyst was prepared in the same manner as in Example 1, but instead of monoethylene glycol dibenzoate as a secondary electron donor, 2.14 g (0.007 mol) of triethylene glycol dibenzoate was used. The polymerization reaction was repeated under the conditions of Example 1 and the results are shown in Table 1.

Example 4

The catalyst was prepared in the same manner as in Example 1, but 2.0 ml (0.007 mol) of dipropylene glycol dibenzoate was used instead of monoethylene glycol dibenzoate as a secondary electron donor. The polymerization reaction was repeated under the conditions of Example 1 and the results are shown in Table 1.

Table 1.

Comparative Example 1

3 g (0.032 mol) of MgCl ₂ and 50 ml of n-decane are put together in a 1 liter reactor, and stirred at room temperature for 1 hour under a nitrogen atmosphere. Then, 15 ml (0.1 mol) of 2-ethyl-1-hexanol is slowly added thereto. The solution was heated to 120 ° C. and reacted for 2 hours, 0.5 ml of ethyl benzoate was added thereto, followed by reaction for 1 hour to obtain a homogeneous solution. After the temperature was lowered to room temperature and 20 ml of TiCl ₄ was added dropwise, the reaction temperature was slowly raised to 90 ° C. and reacted for 2 hours to form a solid carrier. Then, 1 ml of diisobutyl phthalate was added to the reaction for 1 hour. The solid was collected by filtration and washed sufficiently with purified hexane until no free titanium tetrachloride was detected in the wash. After purifying heptane was added to the carrier, 40 ml of TiCl ₄ was added dropwise thereto over 1 hour, and the reaction mixture was heated at 100 ° C. for 2 hours, and then the free titanium component of the prepared solid catalyst was detected with purified hexane. After washing, the solid is dried and stored under nitrogen atmosphere. The manufactured solid complex titanium component contained 4.6 weight% of titanium atoms.

When propylene was polymerized in the same manner as in Example 1 using the same amount of solid complex as converted to titanium atom, 48.0 g of polypropylene was obtained as a white powder. This polymer had a boiling n-heptane extraction residue of 94.2%, an apparent density of 0.32 g / ml and a melt index of 1.7.

Comparative Example 2

3 g (0032 mol) of MgCl ₂ and 50 ml of n-decane are put together in a 1 liter reactor, and 15 ml (0.1 mol) of Daeup 2-ethyl-1-hexanol, which is stirred under nitrogen atmosphere at room temperature for 1 hour, is slowly added thereto. The solution was heated to 120 ° C. for 2 hours, and then 1 ml of diisobutylphthalate was added thereto, followed by reaction for 1 hour to obtain a homogeneous solution. After the temperature was lowered to room temperature and 20 ml of TiCl ₄ was added dropwise, the reaction temperature was slowly raised to 90 ° C. and reacted for 2 hours to form a solid carrier. Then, 1 ml of diisobutyl phthalate was added to the reaction for 1 hour. The solid was collected by filtration and washed sufficiently with purified hexane until no free titanium tetrachloride was detected in the wash. After purifying heptane was added to the carrier, 40 ml of TiCl ₄ was added dropwise thereto over 1 hour, and the reaction mixture was heated at 100 ° C. for 2 hours, and then the free titanium component of the prepared solid catalyst was detected with purified hexane. After washing, the solid is dried and stored under nitrogen atmosphere. The manufactured solid complex titanium component contained 5.7 weight% of titanium atoms.

Propylene was polymerized in the same manner as in Example 1 using the same amount of solid complex in terms of titanium atom to give 66.5 g of a polypropylene white powder. This polymer had a boiling n-heptane extraction residue ratio of 96.5%, an apparent density of 0.33 g / ml and a melt index of 2.7.

Claims (1)

In the catalyst for α-olefin polymerization composed of solid titanium containing magnesium, titanium, halogen and electron donors and organometallic compounds of Groups 1 to 3 metals of the periodic table, the electron donor is monoethyleneglycol monobenzoate, mono Ethylene glycol dibenzoate, diethylene glycol monobenzoate, diethylene glycol dibenzoate, triethylene glycol monobenzoate, triethylene glycol dibenzoate, monopropylene glycol monobenzoate, dipropylene glycol monobenzoate, dipropylene A catalyst for α-olefin polymerization selected from glycol dibenzoate, tripropylene glycol monobenzoate and mixtures thereof.