KR920004804B1 - Alpha-olefin polymerization catalyst composition and process for polymerization olefins - Google Patents

Abstract

A catalyst composition for polymerizing alph-aolefin comprises (A) a solid catalyst ingredient obtained by dissolving magnesium compound of formula Mg(OR)nX2-n 0 <= n <= 2 (where R is hycrocarbon group and X is halogen atom) in a mixture of hydrocarbon solution and at least one compound selected from alcohols, esters and alkoxy organic aluminum, and subsequently adding titanium compound of formula TiX4 (where X is halogen atom), (B) organic metal compound selected from I-III group in the periodic table, and (C) organic silicone compound containing Si-O-C bond. The catalyst composition gives a high stereoregular product at high yield.

Description

Catalyst composition and polymerization method for preparing α-olefin polymer

The present invention relates to a process for preparing α-olefin polymers. More specifically, the present invention relates to α-olefins having high crystallinity and good particle shape by using a preactivated catalyst suitable for polymerization of α-olefins, especially slurry polymerization or bulk polymerization. It relates to a catalyst composition for producing α-olefin polymer and a polymerization method for producing a polymer in high yield.

In particular, the present invention relates to a method for preparing a large amount of high-stereospecific specific olefin polymers by α-olefin polymerization having three or more carbon atoms. (alpha) -olefin consists of the transition metal compound of group IV-VI of the periodic table, and the organometallic compound of group I-II, and also contains what was denatured by adding an electron donor etc. It is well known to carry out by what is called a Ziegler-Natta catalyst.

Α prepared by reacting a halogen containing a titanium compound with a reaction product of a silicon compound or a metal compound of a metal belonging to Groups I to II of the Periodic Table of the Elements and an electron donor compound containing magnesium halides and active hydrogen atoms A number of polymerization catalysts are known which exhibit high activity and stereospecificity in stereoregular polymerization of alpha-olefins with catalyst components suitable for the polymerization of -olefins.

Essential components for the preparation of these catalysts are alkyl halides and magnesium halides, which are partially supported on alkyl halides and magnesium aluminum compounds, which form complexes of electron donor compounds, preferably titanium halides in the form of complexes with electron donor compounds. Among them, titanium trichloride obtained by reducing titanium tetrachloride as an organoaluminum compound is treated with an electron donor and titanium tetrachloride to increase the catalytic activity and at the same time reduce the formation of amorphous polymers. However, the thermal stability of the catalyst is insufficient. There is a drawback.

In addition, a method of preparing a high catalyst catalyst component by mixing and reacting two reaction liquids, which are prepared by separately mixing titanium tetrachloride and an organoaluminum compound with a predetermined amount of a complex generating agent (an electron donor is also a kind thereof), also includes a thermal stability of the catalyst. There is a deficiency that is lacking

Furthermore, a method of preparing a liquid product containing titanium trichloride and adding the homogeneous liquid material composed of an organoaluminum compound and ether to titanium tetrachloride or the reverse order, and heating the liquid to below 150 ° C. The method of precipitating titanium trichloride also has a drawback that the thermal stability of the catalyst is deficient.

On the other hand, in a polymerization method for an α-olefin phase using a Ziegler-Natta catalyst, slurry polymerization in a solvent such as η-hexane, gas phase polymerization in a gas monomer such as bulk polymerization gas phase propylene in a liquefied monomer such as liquefied propylene It is well known and also known is a method of vapor phase polymerization after bulk polymerization.

Among them, the gas phase polymerization method cannot recover and reuse the solvent used for the polymerization, nor can it recover and reuse the liquefied monomer such as propylene, and the recovery cost of the solvent or monomer is low. However, in the gas phase polymerization method, since the monomer in the polymerizer is present in the gas phase, the monomer concentration is relatively low compared to the slurry polymerization method and the bulk polymerization method, so that the reaction rate is slow and the amount of polymer per catalyst is increased. In order to increase the retention period and to increase the reactor, or to increase the catalytic activity, trialkyl aluminum is modified to reduce the stereoregularity of the polymer.

In addition, in the gas phase polymerization method, uneven catalyst particles tend to cause uneven polymer particles.

This can lead to agglomeration of polymer particles or to a polymer discharge of a polymerizer or to a waste of a transport line or to a particle by an unreacted α-olefin in a polymerizer, and is difficult to maintain a long-term stable continuous operation. This results in a lot happening.

The present invention improves the high activity and high solids specificity, which is useful for preparing particle olefin polymers with controlled particle size distribution, and the resulting polymer is reduced in stereospecificity even when the melt index of the polymer is changed using a molecular weight modifier such as hydrogen. Little or no is shown, a granular polymer having a high bulk density in the slurry polymerization method and mostly containing particles of a suitable size can be obtained.

In particular, the catalyst of the present invention is an active catalyst of stereoregular control ability. Since the catalytic activity is not reduced even in the presence of hydrogen used as a molecular weight regulator during the polymerization reaction, there is no need for the troublesome operation of removing the catalyst residue from the polymer produced at the end of the reaction. In addition, even when slurry polymerization is performed at a higher temperature using a catalyst having further improved thermal stability of the catalyst, the particle size of the polymer is uniform, the catalytic activity is high, the formation rate of the amorphous polymer is low, and the stereoregularity of the polymer is increased. It is to provide a method for producing an α-olefin polymer that can be easily controlled.

The present invention briefly describes an α-olefin using a solid catalyst product obtained by treating a support compound, which is a reaction product of a magnesium compound, a chloride compound, and a silicon compound, as a carrier, with a titanium compound to produce a solid component, and treating an electron donor. To polymerize the α-olefin in the presence of a catalyst which is pre-activated by polymerizing a part or all of the catalyst in the presence of the final solid catalyst product, the organoaluminum compound and the external electron donor. to be.

In the present invention, "polymerization treatment" means the polymerization of α-olefin by contacting a small amount of α-olefin with a solid catalyst product under mild conditions that can be polymerized. The catalyst component is coated with a polymer by such catalyst preactivation polymerization treatment. In the future, this polymerization will affect the polymer properties and catalyst yield.

The present invention relates to a method for producing a catalyst suitable for prepolymerization and a method for preparing α-olefin polymerization such as prepolymerization conditions for improving catalyst yield and polymer properties during prepolymerization. In addition, the characteristics of the present invention have been disclosed a method of removing the solvent by decanting or filtration of the prepolymerized catalyst after the prepolymerization treatment, but the present invention can be carried out immediately without the removal of the solvent and unreacted monomer in the prepolymerized catalyst High yield, high stereoregularity and high bulk density can be obtained, and it is a prepolymerization method that can simplify the process due to the heat resistance of the catalyst.

From the viewpoint of improving the stereospecificity of the catalyst, it is preferable to use an aromatic ester mixed with a small amount of phenol, especially ortho-substituted phenol. It is preferable to react with the electron donating compound carrier before the reaction with the titanium compound.

However, it is possible to react both the compound and the carrier with the electron donating compound at the same time. It is also possible to react the titanium compound with the carrier and then to treat the solid reaction product with the electron donating compound. The titanium compound can be reacted with the electron donating compound in the form of an inorganic compound.

The above reaction is carried out under the condition that the amount of the electron donating compound present in bound form in the solid product separated from the reaction mixture is 1 mole or less per gram atom of magnesium, in particular 0.1 to 0.3 mole per gram atom of magnesium. Proceed.

The molar ratio between the electron donating compound and the titanium compound is 0.2 to 2, preferably 0.5 to 1.5.

The reaction between the compound containing the Mg-OR bond of the carrier and the halogenated titanium compound produces a halide of magnesium in which the Ti compound is chemically immobilized.

This reaction proceeds under conditions where this reaction is as complete as possible.

The reaction between a carrier, a titanium halide compound, for example titanium tetrachloride, and an electron donating compound yields a halide of magnesium composed of a titanium compound and an electron donating compound chemically immobilized on a halide. The fact that the titanium compound and the electron donor compound are chemically bonded to magnesium on the halide can be proved by various methods, including infrared analysis and Raman analysis.

In other respects, it has been found that the product between the titanium compound and the carrier does not vary the form of the carrier and the surface area of 100 to 900 m ² / g regardless of the presence of the electron donor compound.

The processing rate is somewhat high, in the range of 0.5 to 0.7 (g / cc bulk density).

Among the catalyst components of the present invention, those suitable for stereospecifically polymerizing alpha α-olefins,

a) titanium compound

b) the carrier described above, and

c) prepared by reaction with the titanium compound and an electron donating compound (or Lewis salt) capable of forming an additional compound.

Particularly suitable for the stereospecific polymerization of alpha-olefins, the present catalyst component is

a) a titanium compound selected from halogenated compounds containing at least one titanium halogen bond, in particular tetravalent titanium halogen bond.

b) a carrier having a surface area of 10 to 100 m ² / g, a bulk density of 0.5 to 0.7 g / cc, and a particle size of at least 50% of from 10 to 50 microns, particularly 10 to 40 microns, composed of a compound of the general formula:

XnMg (OR) 2-n '

n

2, 특히 0

n'

=1 이고, X는 Cl 및 Br에서 선정된 할로겐 원자, R는 탄소원자수 1 내지 12개의 알킬, 시클로알킬 및 아릴기이다.0 in the above formula

n

2, especially 0

n '

= 1, X is a halogen atom selected from Cl and Br, R is an alkyl, cycloalkyl and aryl group having 1 to 12 carbon atoms.

c) reaction products between electron and donor compounds selected from esters of organic and inorganic oxygenated acids, in particular esters of aromatic acids.

Particularly suitable titanium halide compounds for preparing the present catalyst components are titanium tetrahalides, in particular titanium tetrachloride. However, halogen-alcoholates and halogen-phenolates such as Ti (0-n-C4H9) 2C12, TiOC2H5C13, Ti (OC6H5) 2C12 can also be used. Examples of non-halogenated titanium compounds are tetraalcoholates such as Ti (0-n-C4H9). Non-halogenated titanium compounds are generally used for the production of ethylene polymerization catalysts. Compounds of the general formula XnMg (OR) 2-n containing one or more Mg-OR bonds are represented by magnesium as alcohol and monohalogen alcoholates.

Examples of these compounds include Mg (OC2H5) 2, Mg (0-i-C4Hg) 2, Mg (OC6H5) 2, Mg (OC6H4CH3) 2, Mg (OC6H4C2H5), Mg (OCH3), (OCH2C6H6), C2H4OMgCl, C4H9OMgCl, CH3C6H5O-MgCl, (CH3) 2C6H3OMgCl.

Magnesium alcohol salts can also be used in the form of complexes with alcohol salts of other metals such as alcohol salts of Al, B, Zn, and Zr. The reaction between the carrier, the titanium halide compound, for example titanium tetrachloride, and the electron donating compound yields a halide of magnesium composed of a titanium compound and an electron donating compound chemically immobilized on the halide. The fact that the titanium compound and the electron donating compound are chemically bonded to magnesium on the halide can be proved by various methods, including infrared extraction and Raman analysis, which are solvent extraction methods.

In another aspect of the present invention, it was found that the product between the titanium compound and the carrier did not change the form of the carrier and the surface area of 90 to 770 m ² / g regardless of the presence or absence of the electron donating compound.

In the present invention, the magnesium compound used in the preparation of the solid titanium catalyst component is preferably a magnesium compound having no reducing ability, that is, a compound having no magnesium-carbon bond or magnesium-hydrogen bond.

Such magnesium compound may be derived from a magnesium compound having a reducing ability.

Examples of magnesium compounds having no reducing ability are magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride: alkoxy magnesium, for example ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium And 1-C10 alkoxy magnesium, such as 2-ethylhexoxy magnesium: alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride and octoxy magnesium chloride C10 alkoxymagnesium halides: phenoxy magnesium halides which may be optionally substituted by lower alkyl groups such as acetyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxy magnesium chloride, for example aryloxymagnesium Uh, phenoxy magnesium optionally substituted by lower alkyl groups: and magnesium salts of carboxylic acids, for example magnesium salts of aliphatic carboxylic acids having 1-20 carbon atoms such as magnesium laurate and magnesium stearate There is this. The magnesium compound may be in the form of a complex or mixture with another metal.

Halogen-containing magnesium compounds, all of the above magnesium chloride. Alkoxy magnesium chloride and aryloxy magnesium chloride are preferred among these magnesium compounds.

As the solvent used, various hydrocarbon solvents may be used. Examples include aliphatic hydrocarbons such as hexane, heptane, pentaneoctane, decane, dodecane, teradecan and kerosene and halogelated hydrocarbons such as dichloroethane, difluoropropane, trichloroethylene, carbon tetrachloride and chlorobenzene cyclopentane, methyl Aliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, cyclooctane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and cyene belong.

Specific examples of the titanium compounds include titanium tetrahalides such as TiC14, TiBr4 and TiI4, Ti (OCH3) 3Cl, Ti (OC2H5) 3Cl, Trialcititan onohalides such as Ti (On-C4H9) 3Cl and Ti (OC2H5) 3Br, Alkoxytitanium dihalide Ti (OCH2) Cl3, Ti (OC2H5) Cl3, Ti (On-C4H9) Cl3, such as Ti (OCH3) 2C12, Ti (OC2H5) 2C12, Ti (On-C4H9) 2C12 and Ti (OC2HS) 2Br2 Alkoxy titanium trihalides such as Ti (OC2H5) Br3 and Ti (0-iso-C4H9) NBr3, tetraalkoxytitanium such as Ti (OC2H5) 4, Ti (OC2H5) 4 and Ti (On-C4H9) 4; Mixtures thereof, and mixtures thereof with other metal compounds such as hydrogen halides, halogens, aluminum compounds or silicon compounds, or sulfur compounds.

Of these, halogen-containing titanium compounds are preferred. Titanium tetrahalide, all of the above titanium tetra chloride are particularly preferred.

The electron donor may be ether, monocarboxylic acid ester, aliphatic carboxylic acid, carboxylic anhydride, organosilicon compound having Si-0-C bond, ketone, aliphatic carbonate, alkoxy group-containing alcohol, aryl-oxy group-containing alcohol And organophosphorus compounds having a P-0-C bond.

Examples of preferred electron donors include C4-Cl4 aliphatic ethers, C4-C2O monocarboxylic acid esters. Cl-C2O preferably Cl-C4 aliphatic carboxylic acid, C4-C1O carboxylic anhydride, organosilicon compounds having Si-0-C bonds having 1 to 10 carbon atoms in organic group, C4-C2O canton, C4- Cl4 aliphatic carbonates, C4-C2O alkoxy group-containing alcohols, C4-C2O aryloxy group-containing alcohols, and compounds wherein the organic group is organic having a P-0-C bond having 1 to 10 carbon atoms. Specific examples of aliphatic ethers include methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, ethyl benzyl ether, ethylene glycol, dibutyl ether and anisole.

Specific examples of the mono carboxylic acid esters are methylbenzoate, ethylbenzoate, propylbenzoate. Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl fluorate, ethyl fluorate. Amyl fluate, ethyl benzoate, methyl an acetate, ethyl an acetate and ethyl ethoxy benzoate methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, iso-butyl acetate, t-butyl acetate, octyl acetate. Cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl maleate, ethyl pyrunate, ethyl methylate, ethyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, methylcyclohexane carboxylate Belongs.

Specific examples of aliphatic carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid and biliric acid. Specific examples of the carboxylic anhydrides include acetic anhydride, maleic anhydride, benzoic anhydride phthalic anhydride, trivelic anhydride and tetrahydro phthalic anhydride.

Particular examples of organosilicon compounds having Si-0-C bonds are methylsilicate, ethylsilicate and diphenyldimethoxy silane. Organosilicon compounds of the formula RnSi (OR ′) 4-n include phenyltriethoxysilane, phenyltri-iso-butoxysilane, phenyltri-iso-pentoxysilane, diphenyl diethoxysilane, diphenyl di-iso- Pentoxysilane, diphenylisooctylsilane, triphenylmethoxysilane, triphenyl ethoxysilane and triphenyl isopentoxysilane methyltrimethoxysilane, methyltriethoxysilane, methyl triethoxysilane, methyl tri-n -Butoxysilane, methyltri-iso-pentoxysilane, methyltri-n-hexoxysilane, methyltri-iso-octoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, Tetra-n-butoxysilane, tetra-iso-pentoxysilane, tetra-n-hexoxysilane, dimethyl diethoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-iso-pentoxysilane. Trimethyl mexoxysilane, trimethyl ethoxysilane, trimethyl isobutoxysilane, ethyltriethylethoxysilane, ethyltri-iso-propoxysilane, ethyltri-iso-pentoxysilane, diethyl diethoxysilane, diethyldi- Iso-pentoxysilane, triethyl isopropoxysilane, tri-n-propylethoxysilane, tri-n-butylethoxysilane, tri-iso-pentyl ethoxysilane, n-butyltriethoxysilane, isobutyl Triethoxysilane, isopentyl triethoxysilane. Isopentyltri-n-butoxysilane, di-n-butyldiethoxysilane, di-iso-butyl di-iso-pentoxysilane.

Specific examples of kenones are acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl n-butyl ketone, acetophenone, benzophenone cyclohexanone and benzoquinone. Specific examples of the alkoxy group-containing alcohols are butyne cellosolve (ethylene glycol monobutyl ether) and ethyl cellosolve (ethylene glycol monoethyl ether). Specific examples of aliphatic carbonates are dimethyl carbonate, diethyl carbonate and ethylene carbonate.

Specific examples of organophosphorus compounds having a P-0-C bond are trimethyl phosphite and triethyl phosphite.

Among these electron donors. Preference is given to monocarboxylic acid esters, aliphatic carboxylic acids, carboxylic anhydride ketones, alkoxy group-containing alcohols and organosilicon compounds having Si-0-C bonds. Monocarboxylic esters and carboxylic anhydrides are particularly preferred. Specific examples of preferred polycarboxylic acid esters include diethylmethyl succinate, diisobutyl alpha-methylglutarate, diethylmethyl malonate, diethylethyl malonate, diethyl isopropyl malonate, diethylbutyl malonate , Diethylphenyl malonate. Diethylphenyl malonate, diethyl diethyl malonate, diethyl dibutyl malonate, monoisooryl, maleate, diisooctyl maleate, diisobutyl maleate, diisobutylbutyl maleate, diisopropyl beta Methylglutarate, diaryl succinate di-2-ethylhexyl fumarate, diisooctyl citraconate and esters of long chain dicarboxylic acids (e.g. diethyl adipate, diisobutyl dimate. Diiso C5-C30 aliphatic polycarboxylic acid esters such as propyl sebate, di-n-butyl sebate, di-n-octyl sebate and di-2-ethylhexyl sebate: diethyl 1,2-cyclohexane carboxyl C10-C30 substituted polycarboxylic acid esters, such as the rate and diisobutyl 1,2-cyclohexane, carboxylate, monoethyl phthalate, dimethyl phthalate, methylethylphthalate, monoisobutyl phthalate Diethyl phthalate, ethylisobutyl phthalate di-n-propyl phthalate diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di- C10-C30 aromatic polycarboxylic acid esters such as n-octyl phthalate dineopentyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylic acid and dibutyl naphthalene dicarboxylic acid and 3 C8-C30 heterocyclic polycarboxylic acid esters such as esters of, 4-furandicarboxylic acid.

The organoaluminum compound used in the present invention is a general formula AIRnR 'nX3- (n + n') (wherein R and R represent a hydrocarbon group or an alkoxy group such as an alkyl group, an aryl group, an alkali group, a cycloalkyl group, and X represents fluorine). , Halogen of chlorine, bromine and iodine, n, n 'is an arbitrary integer of 0 &lt; n + n = 3), specific examples are triethyl aluminum, trimethyl aluminum, tri-propyl aluminum, tri n- Trialkyl aluminums, such as butyl aluminum, tri i-butyl aluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, tri 2-methylbenzyl aluminum, tri n-octyl aluminum, and tri n-mesyl aluminum, ethyl aluminum dichloride and monoalkyl aluminum dihalides such as i-butylaluminum chloride; alkoxy alkyl aluminums such as monoethoxy diethyl aluminum diethoxy monoethylaluminum, and diethyl alumina Dialkyl aluminum monohalides such as monochloride, di n-propyl aluminum monochloride, di i-butyl aluminum monochloride, dienyl aluminum fluoride, diethyl aluminum monobromide, diethyl aluminum mono iodide, di Dialkyl aluminum hydrides, such as ethyl aluminum hydride, alkyl aluminum seski halides, such as methyl aluminum sesquichloride and ethyne aluminum sesquichloride, can be used.

Such organoaluminum can also be used in mixture of 2 or more types. In particular, the present invention relates to a method for producing an olefin polymer by polymerizing olefins in the presence of a catalyst system consisting of the following components (A), (B) and (C).

(A) an ester selected from the group consisting of esters of polycarboxylic acids and esters of polyhydroxy compounds. Solid titanium catalyst component containing magnesium, titanium and halogen, the catalyst component contacting a hydrocarbon solution with a titanium compound and a magnesium compound To obtain a solid, which is produced by monocarboxylic ester, aliphatic carboxylic acid, carboxylic anhydride, ketone, aliphatic ether, aliphatic carbonate, alkoxy group-containing alcohol, aryl Is carried out in the presence of at least one electron donor (C) selected from the group consisting of oxy-containing alcohols, organosilicon compounds having Si-0-C bonds and organophosphorus compounds having P-0-C bonds, (B) An organometallic compound of a metal selected from the group of metals of groups I-II of the periodic table.

The present invention also relates to the solid titanium catalyst component described above. Magnesium so far. Various techniques have been proposed for the production of solid catalyst components which must contain titanium, halogens and electron donors. When this solid catalyst compound is used in the polymerization of α-olefins having three or more carbon atoms, It is known that it can be produced. However, many of the foregoing techniques are still desired to be further refined with regard to the activity of the catalyst component and the steric properties of the polymer. For example, in order to obtain a high quality olefin polymer without processing it after polymerization, the proportion of the stereospecific polymer produced should be very high and the yield of polymer per unit amount of transition metal should be sufficiently high.

From this point of view, the prior art may be at a fairly high level for certain types of polymers, but is almost unsatisfactory for the halogen content remaining in the polymers causing corrosion of the molding machine. In addition, many catalyst components produced by the prior art have the drawback of significantly reducing yield and stereospecificity.

This drawback is 0.1g to 500g, preferably 0.5 to 50g of organoaluminum compound and reaction product with respect to 1g of the final solid catalyst product which is preactivated by adding α-olefin and polymerizing some or all of the catalyst components in the present invention. By polymerizing a part or all of the catalyst components using 0.01 to 5000 g, preferably 0.05 to 3000 g, of the α-olefin in the presence of at least the final solid product and the organic aluminum compound in the 0.05 to 10 g catalyst component.

Prepolymerization conditions are 1 minute to 20 hours at 0 ° C. to 100 ° C., preferably 10 ° C. to 70 ° C., and the propylene atmosphere is 0.1 kg / cm ² to 8 kg / cm ² preferably 0.1 kg / cm ² -4 kg / Under the condition of cm ^2, the alkylaluminum to titanium molar ratio is 0-500, preferably 50-200. The molar ratio of alkylaluminum and electron donor components is 0-200, preferably 5-50, and the electron donor to titanium molar ratio is 0-100, preferably 1-40.

The? -olefin is preferably polymerized in an amount of 0.01 to 2000 g, preferably 0.05 to 200 g, per 1 g of the final solid catalyst product. Further, 50 L or less solvent may be used for preactivation. Examples of the solvent include hydrocarbon solvents such as protane, butane, n-pentane, n-hexane, n-heptane, benzene and toluene.

Α-olefins used for preactivation are ethylene, propylene, butene-1, hexane-1, heptene-1, octene-1, deken-1, other linear monoolefins, 4-methyl-heptene-1, 2 Condensed chain monoolefins such as -methylheptene-1 and 3-methyl-heptene-1, styrene and the like.

In this way, the α-olefin is the same as or different from the α-olefin to be polymerized or is not related in any case. The polymerization treatment is carried out in hydrocarbon solutions such as propane, butane, n-heptane, n-hexane, n-heptane, n-octane, benzene, toluene, and in liquefied α-olefins such as liquefied propylene and liquefied butene-1. It may be carried out and hydrogen may coexist during the polymerization treatment.

The amount of each material used for preparing the preactivation catalyst is 0.5 to 500 g, preferably 1 to 50 g, 1 to 20 g of reaction product, 5000 g or less, preferably 0.1 to 20 g, of trialkyl aluminum, per 1 g of the solid catalyst product. 1000 g, 0-10 L of hydrogen, 0-80 L of solvent.

Addition of the catalyst component, alpha-olefin, etc. which perform preactivation including a polymerization process, and reaction are performed at 0-100 degreeC, Preferably it is 10-70 degreeC. The polymerization treatment reacts the α-olefins with 0.1 to 500 g per gram of solid catalyst product. The polymerization treatment time is preferably 1 minute to 5 hours.

The polymerization treatment can be carried out in the presence of 0 to 5000 g of α-olefin polymer particles per gram of solid catalyst product. In the case of preactivation, in the case of addition mixing or polymerization of each catalyst component, stirring is performed as necessary.

The effect of the present invention is that the activity of the catalyst obtained is very high and the α-olefin polymer can be obtained in high yield. In other words. Polymer yield per gram of solid product amounts to 5,000 to 20,000 g in slurry polymerization, bulk polymerization.

Therefore, since the catalyst can be reduced in the slurry polymerization bulk polymerization, the catalyst or polymer purification after the completion of the polymerization can be simplified, and there is no coloring of the polymer, and no damage to physical properties of the polymer or rusting of the mold during polymer molding. The purification of polymers can be simplified.

The effect of the present invention is that the transition metal can be used very effectively, and the molecular weight distribution can be narrowly adjusted, so that a good shape of the particles during polymerization can be obtained. High polymer yields can be expected. There is no need to remove the amorphous polymer and the catalyst residues in the polymer.

Describe the specific number of definitions or measuring methods used in the examples below.

(1) BD (g / cm ³ )

As apparent specific gravity of the polymer, g number of the apparent volume 1 cm ³ .

(2) Total I. I (%)

After the completion of the polymerization, the polymer was filtered to obtain an atactic polymer dissolved in hexane, which is called an atactic polymer (I) dissolved in hexane, and 8 g of a hexane-insoluble polymer was extracted from boiling 100 m1 of boiling normal butane for 10 hours and then separated by filtration. The polymer was divided into polymer (II) (atactic polypropylene) of the normal plywood solubles and polymer (iscactic polypropylene) of the normal heptane insoluble, respectively, and dried, and the total formula was calculated as follows. Find I

(3) Particle size distribution (%)

100 g of polymer is placed in a standard mesh and shaken for 15 minutes to determine the amount of polymer separated in each standard mesh.

Example 1

(1) Preparation of solid titanium catalyst component

Substituting a 500m1 round bottom flask equipped with a stirrer and a reflux condenser sufficiently with nitrogen gas, 6.9 g of magnesium ethoxide and 100 ml of decane were placed in a reactor, and stirred at room temperature for 30 minutes, followed by 5.1 ml of phenyl triethoxysilane and 20 m1 of decane. After adding over time and reacting at 80 ° C. for 2 hours, 28.9 ml of titanium tetrachloride was added to this solution for 1 hour, and then heated to 130 ° C. and then diisobunyl. 3.4 ml of phthalate and 20 ml of decane were added dropwise, followed by reaction for 2 hours, followed by washing with hexane to obtain a solid component. After adding titanium tetrachloride 170m1 to this solid component, it reacts at 130 degreeC for 2 hours, and wash | cleans enough until a free titanium compound is not detected with hexane, and a solid titanium catalyst component is obtained.

The solid catalyst component used in the polymerization was slurried in hexane, and the rest was dried under reduced pressure and dried to obtain a powdery catalyst. As a result of component analysis, 3.4% wt titanium per gram catalyst was included.

(2) Prepolymerization (Preparation of Preactivation Catalyst)

A 2 liter stainless steel autoclave, fully substituted with nitrogen gas, was made into a propylene atmosphere. Then, 1 liter of purified hexane was added, 7.65 m mole of triethylaluminum and 0.76 m mole of phenyltriethoxysilane were added, followed by stirring for 5 minutes. The titanium catalyst component thus prepared was converted to titanium atoms, and 0.03 m mole was added thereto, followed by injecting propylene gas at 2 kg / cm ² g and prepolymerizing at 30 ° C. for 20 minutes.

(3) Polymerization of Propylene

The reactor containing the preactivated catalyst was heated, 0.4 kg / cm ² g of hydrogen was injected at 65 ° C., and polymerization was performed at 70 ° C. for 2 hours. The yield of the total polymer dried after the end of the polymerization was 350g, the polymer (I.I) not extracted in boiling normal heptane is 97.3%. The polymerization activity is 299 kg / PP / g-Ti.

Example 2-4

Prepolymerization is carried out using the solid titanium catalyst component prepared in Example 1, prepolymerization is carried out while varying the amount of triethyl aluminum in the prepolymerization conditions, and the remaining conditions are carried out in the same manner as in Example 1. Each condition and result is shown in Table 1.

Example 5-10

Prepolymerization is carried out using the solid titanium catalyst component prepared in Example 1, prepolymerization is carried out while varying the amount of phenyltriethoxysilane in the prepolymerization conditions, and the remaining conditions are carried out in the same manner as in Example 1. Each condition and results are shown in Table 2.

Example 11-14

Prepolymerization is carried out using the solid titanium catalyst component prepared in Example 1, prepolymerization is carried out while changing the propylene pressure in the prepolymerization conditions, and the remaining conditions are carried out in the same manner as in Example 1. Each condition and result is shown in Table 3.

Example 15-19

Prepolymerization is carried out using the solid titanium catalyst component prepared in Example 1, prepolymerization is carried out while changing the prepolymerization time of the prepolymerization conditions, and the remaining conditions are carried out in the same manner as in Example 1. Each condition and result is shown in Table 4.

Example 20-24

Prepolymerization is carried out using the solid titanium catalyst component prepared in Example 1, prepolymerization is carried out while changing the prepolymerization temperature among the prepolymerization conditions, and the remaining conditions are performed in the same manner as in Example 1. Each condition and result is shown in Table 5.

Example 25

In the preparation of the solid titanium catalyst component, the same procedure as in Example 1 was performed except that 3.4 ml of trimethyl methoxysilane was added instead of 5 ml of phenyltriethoxysilane in Example 1. Prepolymerization and this polymerization were the same as in Example 1, and the results are shown in Table 6.

Example 26

The preparation of the solid titanium catalyst component was the same as that in Example 1 except that 2.3 ml of diphenyl phthalate was added instead of 3.4 ml of diisobutyl phthalate. The results are shown in Table 6.

Example 27

The preparation was carried out in the same manner as in Example 1, except that 34.7 ml of titanium tetrachloride was added in the preparation of the solid titanium catalyst component. The results are shown in Table 6.

Example 28

Ethylene was polymerized using the solid titanium catalyst component prepared in Example 1. Titanium catalyst component was converted into titanium atom, 0.03m mole and triethylaluminum 7.65m mole were added, and then the temperature was elevated. 2 kg / cm g of hydrogen was injected at 65 ° C., and polymerization was performed at 70 ° C. for 8 hours with 8 kg / cm G of ethylene. After completion, the yield of the dried total polymer was 260 g.

Example 29

In Example 28, polymerization was performed by replacing with diethylaluminum chloride instead of triethyl aluminum to obtain 210 g.

Example 30

(1) Preparation of solid titanium catalyst component

13.8g of di-iso-butoxymagnesium was added to 200m1 tetrahydrofuran instead of magnesium ethoxide using the apparatus used in Example 1, and stirred at room temperature for 30 minutes, and then ethane was used as an electron donor instead of phenyltriethoxysilane. 5.8 ml was injected over 3 hours, heated to 80 ° C., and reacted for 1 hour to form alkoxy organoaluminium-magnesium complex, followed by dropwise addition of 19 ml of ethyl aluminum dichloride over 5 hours, followed by reaction at 80 ° C. for 3 hours. Let's do it. After the reaction, the unreacted compound was removed with boiling hexane, and 25 ml titanium tetrachloride was added dropwise to the alkoxy organoaluminium-magnesium complex obtained above for 2 hours, and after 2 hours, the mixture was washed sufficiently with hexane until no free titanium component was detected. Titanium catalyst component is prepared.

(2) prepolymerization

Under the prepolymerization condition of Example 1, triethyl aluminum 100m mole and the solid catalyst were added 0.03m mole as a titanium component, followed by stirring for 5 minutes, propylene 2kg / cm ² G, and prepolymerization at 30 ° C. for 20 minutes. .

(3) propylene polymerization

The polymerization is carried out under the conditions of the first embodiment. The yield of the total polymer dried after the completion of the polymerization was 200g, 90% of the polymer (I.I) not extracted in boiling normal heptane and the polymerization activity was 139kg PP / g-Ti

Example 31

Ethylene polymerization was carried out using the solid catalyst prepared in Example 30. 1 L of hexane, 100 m mole of triethyl aluminum and 0.01 m mole of titanium as a titanium component were added thereto, and 2.5 kg / cm g of hydrogen was added thereto. Ethylene injection and total pressure were 8 kg / cm g, and polymerization was carried out for 2 hours to obtain 3309. The bulk density of the polymer was 0.39.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

TABLE 6

Claims (4)

The catalyst composition polymerization method for alpha-olefin polymer manufacture consisting of the following (A), (B), and (C). (A) A solid catalyst component obtained by adding one or two or more of alcohols, esters and alkylaluminum to a magnesium compound and a hydrocarbon solution to obtain a magnesium complex of alkoxy organoaluminum and contacting with a titanium compound. (B) organometallic compounds selected from Groups I to III of the Periodic Table. (C) Si-0-C bonded organic silicon compound. The catalyst composition for producing an α-olefin polymer according to claim 1, wherein the magnesium compound is a magnesium compound of the following formula. Mg (OR) nX _2-n 0

n

2 (R is a hydrocarbon group, X is a halogen atom) The catalyst composition for producing an α-olefin polymer according to claim 1, wherein the titanium compound is a titanium compound of the following formula. Mg (OR) nX2-n 0≤n≤4 (R is a hydrocarbon group, X is a halogen atom) The composition according to claim 1, wherein the composition having an alkyl-to-titanium mole ratio of 50-200, a titanium-to-electron donor component mole ratio of 5 to 50 in the catalyst composition of claim 1 is 0.1-6kg / cm ² g, temperature 5 A catalyst composition for producing an α-olefin polymer, characterized in that the α-olefin is polymerized into a final solid product obtained by prepolymerization under a condition of ˜40 ° C. and a time of 2 to 40 minutes.