JP2006523741A - Ziegler-Natta type catalyst composition and method for producing the same - Google Patents

Abstract

The present invention relates to a Ziegler-Natta type catalyst composition, a method of producing the Ziegler-Natta type catalyst composition, a method of using the Ziegler-Natta type catalyst composition for olefin polymerization, and the Ziegler of the present invention. -It relates to a copolymer of ethylene that can be produced using a Natta-type catalyst composition.

Description

  The present invention relates to a Ziegler-Natta type catalyst composition, a method for producing the same, and a method for using the catalyst composition for olefin polymerization.

Ziegler-Natta type catalyst compositions have been known for some time. This composition is used in particular for the polymerization of C ₂ -C ₁₀ alk-1-enes and contains in particular a polyvalent titanium compound, an aluminum halide and / or an alkylaluminum together with a suitable carrier material. The preparation of a Ziegler-Natta catalyst is usually performed in two steps. First, a titanium-containing solid component is prepared, which is then reacted with a cocatalyst. Thereafter, polymerization is carried out using the catalyst thus obtained.

  When using an oxide carrier material, it is common to first apply the magnesium compound to the carrier and then add the titanium component in a later step. Such a processing method is described in Patent Document 1, for example.

  When further using a Lewis base, it is common to apply the magnesium component first and then the titanium component to the support material. Patent document 2 has described the manufacturing method of the Ziegler catalyst, for example. In Patent Document 2, an inorganic oxide is reacted with alkylmagnesium and a halogenating agent in an arbitrary order, and the resulting intermediate is reacted with a Lewis base and titanium tetrachloride in an arbitrary order. This catalyst can then be used for the polymerization of olefins together with alkylaluminum and other Lewis bases.

  There are only a few references describing a process of adding a titanium component first and then a magnesium compound.

  Patent Document 3 discloses a method for producing a Ziegler-Natta catalyst in which silica gel is silylated, then brought into contact with a titanium compound, and the intermediate thus obtained is reacted with an alkylmagnesium alkoxide. Lewis base is not used.

  Another method for producing a Ziegler-Natta catalyst is disclosed in US Pat. In the production method of Patent Document 4, an oxide carrier material is brought into contact with a titanium compound, the intermediate thus obtained is reacted with an alkylmagnesium compound, and then hydrogen chloride, hydrogen bromide, water, acetic acid, A reactant selected from the group consisting of alcohol, carboxylic acid, phosphorus pentachloride, silicon tetrachloride, acetylene and mixtures thereof is added. In the production method described in Patent Document 4, no other Lewis base is used.

EP-A594915 EP-A014523 WO99 / 46306 EP-A027733

Accordingly, an object of the present invention is to develop a Ziegler catalyst that exhibits a high productivity and a good comonomer introduction property, while at the same time providing a polymer with a high bulk density. The comonomer incorporation behavior of various catalyst compositions is demonstrated under conditions where the ratio of ethylene to comonomer in the reactor is constant by forming a relatively low density copolymer. It is. Furthermore, the copolymers formed have a low content of extractable substances, especially in the low density range. Copolymers produced with Ziegler catalysts usually have a very high proportion of extractable material, ie low molecular weight material, in particular in the density range of 0.91 to 0.93 g / cm ³ .

The inventors of the present invention have the following steps A) to D):
A) contacting the inorganic metal oxide with a tetravalent titanium compound;
B) The intermediate obtained in step A) is converted into a magnesium compound MgR ¹ _n X ¹ _2-n [wherein X ¹ are independently of each other fluorine, chlorine, bromine, iodine, hydrogen, NR ^X ₂ , OR ^X , SR ^X , SO ₃ R ^X or OC (O) R ^X , wherein R ¹ and R ^X are each independently a linear, branched or cyclic C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl having 1 to 10 carbon atoms in the alkyl moiety, alkyl aryl having 6 to 20 carbon atoms in the aryl part, or C ₆ -C ₁₈ aryl, and n is 1 or 2 Represents. A step of contacting with
C) comprising a step of contacting the intermediate obtained in step B) with a halogenating agent, and D) contacting the intermediate obtained in step C) with a donor compound. It has been found that this can be achieved by a method for producing a Natta-type catalyst composition.

  Furthermore, the present invention provides a Ziegler-Natta type catalyst composition produced by the method of the present invention, a prepolymerized catalyst composition, and at least one catalyst composition of the present invention and, optionally, an aluminum compound as a cocatalyst. Provides a process for polymerizing or copolymerizing olefins under conditions of 20 to 150 ° C. and a pressure of 1 to 100 bar.

  As inorganic metal oxides, for example, silica gel, aluminum oxide, hydrotalcite, medium porous materials and aluminosilicates, in particular silica gel, can be used.

  The reaction of step A) can be carried out after the inorganic metal oxide is partially or completely modified. The support material can be treated at 100 to 1000 ° C. under oxidizing or non-oxidizing conditions, for example, in the presence of a fluorinating agent such as ammonium hexafluorosilicate, if necessary. In this way, for example, the water content and / or the OH group content can be changed. The support material is preferably dried under reduced pressure at 100 to 800 ° C., preferably 150 to 650 ° C. for 1 to 10 hours and then used in the method of the present invention. If the inorganic metal oxide is silica, it is not treated with organosilane prior to step A).

In general, the inorganic metal oxide has an average particle size of 5 to 200 μm, preferably 10 to 100 μm, particularly preferably 20 to 70 μm, 0.1 to 10 ml / g, particularly 0.8 to 4.0 ml / g, particularly preferred. Has an average pore volume of 0.8 to ^2.5 ml / g and a specific surface area of 10 to 1000 m ² / g, in particular 50 to 900 m ² / g, particularly preferably 100 to 600 m ² / g. The inorganic metal oxide may be spherical or granular, and is preferably spherical.

  The specific surface area and average pore volume are determined by the BET method as described in, for example, Journal of the American Chemical Society, 60, (1939), pages 309-319 by S. Brunauer, P. Emmett and E. Teller et al. Measured by nitrogen absorption.

In another embodiment, spray-dried silica gel is used as the inorganic metal oxide. In general, the primary particles of spray-dried silica gel have an average particle size of 1 to 10 μm, in particular 1 to 5 μm. The primary particles are porous, granular silica gel particles, which are obtained from the SiO ₂ hydrogel by grinding and optionally subsequent sieving. The spray-dried silica gel can be obtained by spray-drying primary particles slurried with water or an aliphatic alcohol. However, commercially available silica gel may be used. The spray-dried silica gel thus obtained has pores or grooves having an average diameter of 1 to 10 μm, particularly 1 to 5 μm, and the macroscopic ratio of the pores or grooves in the whole particle is 5 to 5 in terms of volume. It is in the range of 20%, in particular in the range of 5-15%. Porosities and grooves usually have a positive impact on the monomer-promoter diffusion-controlled access and therefore also on the polymerization rate.

In step A), the inorganic metal oxide is first reacted with a tetravalent titanium compound. In this step, the formula (R ³ O) _t X ² _4-t Ti [wherein the group R ³ is synonymous with R, X ² is synonymous with X, and t is 0 to 4 is represented. ] The tetravalent titanium compound represented by this can be used. Examples of suitable compounds are tetraalkoxy titanium (t is 4), for example tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium or titanium (IV) -2-ethylhexoxide. Trialkoxytitanium halides (t is 3 and X ² is a halide), for example titanium chloride triisopropoxide, and titanium tetrahalides (t is 0 and X ² is halogen). Preference is given to titanium compounds in which X ² represents chlorine or bromine, particularly preferably chlorine. Particular preference is given to using titanium tetrachloride.

Step A) can be carried out in an aprotic solvent. Particularly useful solvents are aliphatic and aromatic hydrocarbons titanium compound is dissolved, for example, pentane, hexane, heptane, octane, dodecane, benzene or C ₇ -C ₁₀ alkylbenzene, for example toluene, xylene or ethylbenzene. A particularly preferred solvent is ethylbenzene.

  It is common to slurry inorganic metal oxides in aliphatic and aromatic hydrocarbons and add titanium compounds thereto. It is also possible to add the titanium compound as a pure substance or as a solution of an aliphatic or aromatic hydrocarbon, preferably pentane, hexane, heptane or toluene. However, for example, it is also possible to add a solution of an organometallic compound to the dried inorganic metal oxide. It is preferred that the titanium compound is mixed with a solvent and then added to the suspended inorganic metal oxide. The titanium compound is preferably soluble in the solvent. Reaction step A) can be carried out at 0 to 150 ° C, preferably 20 to 80 ° C.

  The amount of the titanium compound is usually in the range of 0.1 to 20 mmol, preferably in the range of 0.5 to 15 mmol, particularly preferably in the range of 1 to 10 mmol with respect to 1 g of the inorganic metal oxide. Selected.

  In step A), it is also possible to add only a part of the titanium compound, for example 50 to 99% by weight with respect to the total amount of titanium compound, and add the rest during one or more other steps. It is preferred to add the total amount of organometallic compound in step A).

In step B), the intermediate obtained from step A) is usually subjected to the magnesium compound MgR ¹ _n X ¹ _2-n [wherein X ¹ independently of each other without any post-treatment or isolation, Each represents fluorine, chlorine, bromine, iodine, hydrogen, R ^x , NR ^x ₂ , OR ^x , SR ^x , SO ₃ R ^x or OC (O) R ^x , wherein R ^x and R ¹ are independently of each other; each linear, branched or cyclic C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, the alkyl moiety of 1-10 carbon atoms and the aryl portion of alkylaryl number of 6 to 20 carbon atoms, or Represents C ₆ -C ₁₈ aryl and n is 1 or 2; ] To react. It is also possible to use a mixture of the individual magnesium compounds MgR ¹ _n X ¹ _2n as the magnesium compound MgR ¹ _n X ¹ _2-n .

X ¹ has the same meaning as X above. X ¹ preferably represents chlorine, bromine, methoxy, ethoxy, isopropoxy, butoxy or acetate.

R ^X and R ¹ have the same meanings as R described above. In particular, R ¹ is independently of each other methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, phenyl or 1-naphthyl.

Magnesium compounds which can be used are, in particular, alkyl halides magnesium, alkyl magnesium and aryl magnesium are further magnesium alkoxides and alkyl magnesium aryloxides compound, di- (C ₁ -C ₂₀ alkyl) magnesium compound, in particular di ( It preferred to use C ₁ -C ₁₀ alkyl) magnesium compound.

In a particularly preferred embodiment, the magnesium compound MgR ¹ ₂ can be used, for example dimethylmagnesium, diethylmagnesium, dibutylmagnesium, dibenzylmagnesium, (butyl) (ethyl) magnesium or (butyl) (octyl) magnesium. These are particularly useful because they exhibit good solubility in nonpolar solvents. (N-Butyl) (ethyl) magnesium and (butyl) (octyl) magnesium are particularly preferred. In mixed compounds such as (butyl) (octyl) magnesium, the group R ¹ may be present in various proportions, for example, preferably using (butyl) _1.5 (octyl) _0.5 magnesium.

Suitable solvents for step B) are the same solvents as in step A). Particularly useful solvents are aliphatic and aromatic hydrocarbons magnesium compound is dissolved, for example, pentane, hexane, heptane, octane, isooctane, nonane, dodecane, cyclohexane, benzene or C ₇ -C ₁₀ alkylbenzene, such as toluene, xylene Or ethylbenzene. A particularly preferred solvent is heptane.

  It is common for the intermediate obtained by step A) to be slurried in aliphatic and / or aromatic hydrocarbons and to which the magnesium compound is added. It is also possible to add the magnesium compound as a pure substance or preferably as a solution of an aliphatic or aromatic hydrocarbon such as pentane, hexane, heptane or toluene. However, it is also possible to add the magnesium compound solution to the intermediate obtained in step A). The reaction is generally performed in the range of 0 to 150 ° C, preferably 30 to 120 ° C, particularly preferably 40 to 100 ° C.

  The magnesium compound is generally used in an amount of 0.1 to 20 mmol, preferably 0.5 to 15 mmol, particularly preferably 1 to 10 mmol, relative to 1 g of the inorganic metal oxide. In general, the molar ratio of the titanium compound used to the magnesium compound used is in the range from 10: 1 to 1:20, preferably in the range from 1: 1 to 1: 3, particularly preferably 1: 1. .1 to 1: 2.

  The intermediate obtained from step B) is reacted with the halogenating agent in step C), preferably without intermediate isolation.

Usable halogenating agents include compounds capable of halogenating the magnesium compound used, such as hydrogen halides (eg HF, HCl, HBr and HI), silicon halides (eg tetrachlorosilane, trichloromethylsilane, dichloro). Dimethylsilane or trimethylchlorosilane), halides of carboxylic acids (eg acetyl chloride, formyl chloride or propionyl chloride), boron halides, phosphorus pentachloride, thionyl chloride, sulfuryl chloride, phosgene, nitrosyl chloride, mineral acids (inorganic acids) Halides, chlorine, bromine, chlorinated polysiloxanes, alkylaluminum chlorides, aluminum trichloride, ammonium hexafluorosilicate, and the formula R ^Y _s -CY _4-s [wherein R ^Y is hydrogen or linear , C ₁ -C ₂₀ alkyl branched or cyclic For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n- Represents nonyl, n-decyl or n-dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, and the group R ^Y may be substituted with chlorine or bromine; Represents chlorine or bromine, and s is 0, 1, 2 or 3; ] It is a halogenated alkyl compound represented by this.

Halogenating agents (halogenating reagents) such as titanium tetrahalide (eg titanium tetrachloride) are not suitable. It is preferred to use a chlorinating agent. Preferred halogenating agents are alkyl halide compounds of the formula R ^Y _s -C-Cl _4-s such as methyl chloride, ethyl chloride, n-propyl chloride, n-butyl chloride, tert-butyl chloride, dichloromethane, Chloroform or carbon tetrachloride. Formula R ^Y —C—Cl ₃ wherein R ^Y is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl Or n-hexyl is preferred. An alkyl halide compound represented by the formula: As a result, a catalyst exhibiting particularly high productivity is obtained. Chloroform is highly preferred.

  Suitable solvents for the reaction with the halogenating agent are in principle the same as those used in step A). The reaction is usually performed in the range of 0 to 200 ° C, preferably in the range of 20 to 120 ° C.

  In general, the molar ratio of the halogenating agent used to the magnesium compound used is in the range of 4: 1 to 0.05: 1, preferably in the range of 3: 1 to 0.5: 1. A range of ˜1: 1 is particularly preferred. In this way, the magnesium compound can be partially or fully halogenated. The magnesium compound is preferably fully halogenated.

  It is common to react the intermediate obtained from step C) with one or more donor compounds, preferably one donor compound, without intermediate isolation.

  Suitable donor compounds have at least one atom of group 15 and / or 16 of the periodic table of the elements, for example monofunctional or polyfunctional carboxylic acids, Carboxylic anhydrides and carboxylic acid esters, as well as ketones, ethers, alcohols, lactones, organophosphorus compounds and organosilicon compounds. Preference is given to using donor compounds containing at least one nitrogen atom, preferably one nitrogen atom, such as mono- or polyfunctional carboxamides, amino acids, ureas, imines or amines. Preference is given to using one nitrogen-containing compound or a mixture of nitrogen-containing compounds.

Formula NR ⁴ ₂ R ^{5 wherein} R ⁴ and R ⁵ are independently of each other the following groups:
Linear, branched or cyclic C ₁ -C ₂₀ alkyl, for example methyl, ethyl, n-propyl, isopropyl, n- butyl, sec- butyl, isobutyl, tert- butyl, n- pentyl, sec- pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl,
C ₂ -C ₂₀ alkenyl, which may be linear, cyclic or branched and the double bond may be internal or terminal, such as vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl , Cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl,
C ₆ -C ₂₀ aryl optionally having an alkyl group as a substituent, for example, phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2 , 5- or 2,6-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4 5-trimethylphenyl or arylalkyl optionally having other alkyl groups as substituents, for example benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, and R ⁴ And R ⁵ may be combined to form a 5-membered or 6-membered ring, and the organic groups R ⁴ and R ⁵ may be substituted with a halogen such as fluorine, chlorine or bromine, or R ⁴ and R ⁵ represent SiR ⁶ ₃ . ] The amine represented by these is preferable. Further, R ⁴ may be hydrogen. Amines in which one R ⁴ is hydrogen are preferred. In the organosilicon group SiR ⁶ ₃ , usable R ⁶ is the same group as described in detail above for R ⁵ , in which case two R ⁶ are combined with each other to form a 5-membered ring or a 6-membered ring. It is also possible to form a ring.

Suitable examples of organosilicon groups are trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, triallylsilyl, triphenylsilyl and dimethylphenylsilyl. In particularly preferred embodiments, amines of the formula HN (SiR ⁶ ₃ ) ₂ , in particular R ⁶ is linear, branched or cyclic C ₁ -C ₂₀ alkyl, such as methyl, ethyl, n-propyl, isopropyl. , N-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, cyclo Amines representing propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl can be used. Hexamethyldisilazane is highly preferred.

Other preferred donor compounds are those of formula R ⁷ —CO—OR ⁸ , wherein R ⁷ and R ⁸ are each the following groups:
Linear, branched or cyclic C ₁ -C ₂₀ alkyl, for example methyl, ethyl, n-propyl, isopropyl, n- butyl, sec- butyl, isobutyl, tert- butyl, n- pentyl, sec- pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, cyclopropyl (cyclopropane), cyclobutyl (cyclobutane), cyclopentyl (cyclopentane), cyclohexyl (cyclohexane), cycloheptyl ( Cycloheptane), cyclooctyl (cyclooctane), cyclononyl (cyclononane) or cyclododecyl (cyclododecane),
C ₂ -C ₂₀ alkenyl, which may be linear, cyclic or branched and the double bond may be internal or terminal, such as vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl , Cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl,
C ₆ -C ₂₀ aryl optionally having other alkyl groups as a substituent, for example, phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4- 2,5- or 2,6-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3, 4,5-trimethylphenyl, or arylalkyl optionally having other alkyl groups as substituents, for example benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, and R ⁷ and R ⁸ may be substituted with halogen such as fluorine, chlorine or bromine, or R ⁷ and R ⁸ represent SiR ⁹ ₃ . ] The carboxylic acid ester represented by this. Further, R ⁷ may be hydrogen. In the organosilicon group SiR ⁹ ₃ , usable R ⁹ is the same group as described in detail above for R ⁷ , and two R ⁷ are combined with each other to form a 5-membered or 6-membered ring. It is also possible to do. Suitable examples of organosilicon groups are trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, triallylsilyl, triphenylsilyl and dimethylphenylsilyl.

In particularly preferred embodiments, the formula R ⁷ —CO—OR ⁸ , wherein R ⁷ and R ⁸ are each linear or branched C ₁ -C ₈ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n -Represents butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, n-heptyl or n-octyl. ] Can be used. Very particular preference is given to acetates, in particular C ₁ -C ₆ alkyl acetates, such as methyl acetate, ethyl acetate, propyl acetate or isopropyl acetate. With the carboxylic acid ester, a catalyst having high productivity is obtained particularly in the gas phase.

Suitable solvents for the reaction with the donor compound are the same solvents as used in step A). Particularly useful solvents are aliphatic and aromatic hydrocarbons, such as pentane, hexane, heptane, octane, dodecane, benzene or C ₇ -C ₁₀ alkylbenzene, for example toluene, xylene or ethylbenzene. A particularly preferred solvent is ethylbenzene. The donor compound is preferably soluble in the solvent. The reaction is generally performed in the range of 0 to 150 ° C, preferably in the range of 0 to 100 ° C, particularly preferably in the range of 20 to 70 ° C.

  It is common to slurry the intermediate obtained in step C) in a solvent, to which the donor compound is added. However, it is also possible, for example, to dissolve the donor compound in a solvent and then add this solution to the intermediate obtained in step C). The donor compound is preferably soluble in the solvent.

  The molar ratio of titanium compound to donor compound used is generally in the range of 1: 100 to 1: 0.05, preferably in the range of 1:10 to 1: 0.1, and 1: 1 to 1 : 0.4 is particularly preferable.

The catalyst obtained from step D) or a modified variant thereof may be further reacted with another reactant (reagent) as necessary, for example, the formula R ² —OH [wherein R ² is linear, branched or cyclic C _1- C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, alkyl aryl having 1 to 10 carbon atoms in the alkyl moiety and 6 to 20 carbon atoms in the aryl moiety, or C _{6 to} C ₁₈ aryl. ] And / or an organometallic compound of an element belonging to Group 3 of the periodic table.

  Suitable examples of alcohols are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-ethylhexanol, 2,2-dimethyl. Ethanol or 2,2-dimethylpropanol, especially ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol or 2-ethylhexanol.

  Suitable solvents for the reaction with the alcohol are the same solvents as used in step A). The reaction is generally carried out in the range of 0 to 150 ° C, preferably in the range of 20 to 100 ° C, particularly preferably in the range of 60 to 100 ° C.

  When alcohol is used during the above preparation, the molar ratio of alcohol used to magnesium compound used is generally in the range of 0.01: 1 to 20: 1, and 0.05: 1 to 10: 1. : 1 range is preferred, and a range of 0.1: 1 to 1: 1 is particularly preferred.

Further, the catalyst obtained in step D) or a reaction product thereof with another reactant is converted into an organometallic compound MR _m X _3-m of a metal of Group 3 of the periodic table of the elements, provided that X is mutually independent. Each represents fluorine, chlorine, bromine, iodine, hydrogen, NR ^x ₂ , OR ^x , SR ^x , SO ₃ R ^x or OC (O) R ^x , wherein R ^x and R are independently of each other, linear, branched or cyclic C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, the alkyl moiety of 1-10 carbon atoms and the aryl portion of alkylaryl number of 6 to 20 carbon atoms, or C Represents ₆ to _C18 aryl, M represents a metal of Group 3 of the periodic table, preferably B, Al or Ga, particularly preferably Al, and m is 1, 2 or 3. It is also possible to make it contact.

R, independently of one another, each a straight-chain, branched or cyclic C ₁ -C ₂₀ alkyl, for example methyl, ethyl, n-propyl, isopropyl, n- butyl, sec- butyl, isobutyl, tert- butyl, n -Pentyl, sec-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or Cyclododecyl,
C ₂ -C ₁₀ alkenyl, which may be linear, cyclic or branched and the double bond may be internal or terminal, such as vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl , Cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl,
An alkylaryl having 1 to 10 carbon atoms in the alkyl moiety and 6 to 20 carbon atoms in the aryl moiety, such as benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, or C ₆ -C ₁₈ aryl optionally substituted with other alkyl groups such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3 -Phenanthryl, 4-phenanthryl and 9-phenanthryl, 2-biphenyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylphenyl, 2, 3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, and two groups R may be combined to form a 5-membered or 6-membered ring, and the organic machine R may be substituted with a halogen such as fluorine, chlorine or bromine.

X is independently of each other fluorine, chlorine, bromine, iodine, hydrogen, amide NR ^x ₂ , alkoxide OR ^x , thiolate SR ^x , sulfonate SO ₃ R ^x or carboxylate OC (O) R ^x [where R ^X is synonymous with R. ]. NR ^X ₂ may be for example dimethylamino, diethylamino or diisopropylamino, OR ^X may be for example methoxy, ethoxy, isopropoxy, butoxy, hexoxy or 2-ethylhexoxy, SO ₃ R ^X is For example, it may be methyl sulfonate, trifluoromethyl sulfonate or toluene sulfonate, and OC (O) R ^x may be, for example, formate, acetate or propionate.

As an organometallic compound of an element belonging to Group 3 of the periodic table, an aluminum compound AlR _m X _3-m [wherein each symbol has the same meaning as described above. ] Is preferably used. Suitable examples of aluminum compounds include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum or tributylaluminum, halides of dialkylaluminum such as dimethylaluminum chloride, diethylaluminum chloride or dimethylaluminum fluoride, alkylaluminum dihalide. , For example, a mixture of methylaluminum dichloride or ethylaluminum dichloride, or methylaluminum sesquichloride. It is also possible to use a reaction product of an alkylaluminum and an alcohol. An aluminum compound in which X is chlorine is preferred. Of these aluminum compounds, compounds in which m is 2 are particularly preferred. Dialkylaluminum halide AlR ₂ X [wherein X represents halogen, in particular chlorine, and R represents in particular linear, branched or cyclic C ₁ -C ₂₀ alkyl. ] Is preferably used. Very particular preference is given to using dimethylaluminum chloride or diethylaluminum chloride.

A suitable solvent for the reaction with the organometallic compound MR _m X _3-m of the metal of Group 3 of the periodic table is the same as that used in step A). Particularly useful solvents are aliphatic and aromatic hydrocarbons organometallic compounds of 3 elements of the periodic table is dissolved, for example, pentane, hexane, heptane, octane, dodecane, benzene or C ₇ -C ₁₀ alkyl benzenes, e.g. Toluene, xylene or ethylbenzene. A particularly preferred solvent is ethylbenzene. The reaction is generally carried out in the range of 20 to 150 ° C, preferably in the range of 40 to 100 ° C.

  When an organometallic compound of a group 3 metal of the periodic table is used during the above production, it is in the range of 0.005 to 100 mmol, preferably 0.05 to 5 mmol, with respect to 1 g of inorganic metal oxide. It is common to use amounts in the range, particularly preferably in the range of 0.1 to 1 mmol.

After or during the reaction with the various reactants, the catalyst composition or intermediate thus obtained is converted to an aliphatic or aromatic hydrocarbon such as pentane, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, benzene or C ₇ -C ₁₀ alkylbenzene, such as toluene, may be washed one or more times with xylene or ethylbenzene. Preference is given to using aliphatic hydrocarbons, in particular pentane, n-hexane or isohexane, n-heptane or isoheptane. This is usually carried out at 0 to 200 ° C., preferably 0 to 150 ° C., particularly preferably 20 to 100 ° C., for 1 minute to 20 hours, preferably 10 minutes to 10 hours, particularly preferably 30 minutes to 5 hours. . In this treatment, the catalyst is slurried with a solvent and then filtered. It is possible to repeat this process several times. As an alternative to multiple successive washing steps, it is also possible to wash the catalyst by extraction, for example in a Soxhlett apparatus, thereby achieving continuous washing.

  After the step D) or the reaction carried out as necessary or the final washing step, it is preferable to carry out a drying step for removing all or part of the residual solvent. The novel catalyst composition thus obtained can be completely dried or can have a predetermined residual moisture content. However, the amount of the volatile component needs to be 20% by mass or less, particularly 10% by mass or less with respect to the catalyst composition.

  A method comprising step A), step B), step C) and step D) is preferred. Preferred embodiments of the compounds and the respective reaction steps also apply to these preferred methods.

  The novel catalyst composition thus obtained or a preferred embodiment thereof is 0.1 to 30% by weight, preferably 0.5 to 10% by weight, particularly preferably 0.7 to 3% by weight of titanium. It is advantageous to have a content and a magnesium content of 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 0.8 to 6% by weight.

The catalyst composition is first prepolymerized with an α-olefin, preferably a linear C ₂ -C ₁₀ -1-alkene, in particular ethylene or propylene, and the resulting prepolymerized solid catalyst is It can also be used in actual polymerization. The molar ratio of the solid catalyst used in the prepolymerization to the monomer polymerized on the solid catalyst is generally in the range of 1: 0.1 to 1: 200.

  In addition, a small amount of an olefin as a modifying component, preferably an α-olefin, such as vinylcyclohexane, styrene or phenyldimethylvinylsilane, an antistatic agent or a suitable inert compound (eg, wax or oil) is added to the supported catalyst composition. It can be added as an additive during or after preparation. The molar ratio of additive to transition metal compound B) is generally in the range of 1: 1000 to 1000: 1, preferably in the range of 1: 5 to 20: 1.

  The process for polymerizing or copolymerizing olefins in the presence of at least one catalyst composition according to the invention and optionally an aluminum compound as cocatalyst is carried out under conditions of 20 to 150 ° C. and a pressure of 1 to 100 bar. .

  The process according to the invention for polymerizing olefins can be combined with all industrially known polymerization processes under conditions of pressures ranging from 20 to 150 ° C. and from 1 to 100 bar, in particular from 5 to 50 bar. it can. For example, the advantageous temperature and pressure ranges for carrying out the process of the invention are highly dependent on the polymerization process. Thereby, the catalyst composition used according to the present invention can be used in all known polymerization processes in known forms in bulk, suspension, gas phase or supercritical medium in the general reactors used for the polymerization of olefins. For example, suspension polymerization method, solution polymerization method, stirred gas phase method or gas phase fluidized bed method. The process according to the invention can be carried out batchwise or preferably continuously in one step (one step) or more.

  Among the above polymerization methods, gas phase polymerization methods, particularly gas phase polymerization methods in gas phase fluidized bed reactors, solution polymerization methods and suspension polymerization methods, particularly in loop reactors and tank reactors with agitators. The suspension polymerization method is preferred. Suitable gas phase fluidized bed processes are described in detail, for example, in EP-A004645, EP-A089691, EP-A120503 or EP-A241947. Vapor phase polymerization can also be carried out by a condensation or supercondensation method in which a portion of the circulating gas is cooled below the dew point and returned to the reactor as a two-phase mixture. It is also possible to use a reactor having two or more polymerization zones. In a preferred reactor, the two polymerization zones are interconnected and the polymer is alternately passed through these two zones (which may have different polymerization conditions) multiple times. Such a reactor is described, for example, in WO 97/04015. Different polymerization processes (polymerization processes) or even the same polymerization processes can be combined in series as necessary to form a polymerization cascade, for example a polymerization cascade such as the Hostalen process. It is also possible to carry out two or more identical or different treatments in the reactor in parallel.

  The production of the Ziegler catalyst of the present invention may be performed using a combination method, and the polymerization activity of the Ziegler catalyst of the present invention is tested using the combination method.

  The molar mass of the polyalk-1-ene formed in this way can be controlled and adjusted over a wide range by the addition of regulators common in polymerization techniques, for example hydrogen. Furthermore, other common additives such as antistatic agents can be used for the polymerization. Furthermore, the output of the product can be changed by the amount of Ziegler catalyst metered in. Thereafter, the (co) polymer produced thereby can be transported to a deodorizing or deactivating container, where it can be subjected to general and known treatments with nitrogen and / or water vapor.

  The low-pressure polymerization method is generally carried out at a temperature that is at least several degrees below the softening temperature of the polymer. In particular, in this polymerization method, a temperature in the range of 50 to 150 ° C, preferably in the range of 70 to 120 ° C is set. In the suspension polymerization process, the polymerization is generally carried out in the suspending medium, preferably in an inert hydrocarbon such as isobutane, or else in the monomer itself. The polymerization temperature is generally in the range of 20 to 115 ° C., and the pressure is generally in the range of 1 to 100 bar, in particular in the range of 5 to 40 bar. The solids content of the suspension is usually in the range of 10-80%.

A variety of olefinically unsaturated compounds can be polymerized by the process of the present invention; in the present case, the term polymerization includes copolymerization. Usable olefins are ethylene and linear or branched α-olefins having 3 to 12 carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene. 1-decene, 1-dodecene or 4-methyl-1-pentene, as well as non-conjugated and conjugated dienes such as butadiene, 1,5-hexadiene or 1,6-heptadiene, cyclic olefins such as cyclohexene, cyclopentene or norbornene, And polar monomers such as acrylate, acrylamide, acrolein, acrylonitrile, methacrylic acid, vinyl ether, allyl ether and vinyl acetate ester derivatives or amide derivatives. It is also possible to polymerize mixtures of various α-olefins. It is also possible to polymerize aromatic vinyl compounds such as styrene by the method of the present invention. It is preferable to polymerize at least one α-olefin selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene, particularly ethene. . It is also possible to copolymerize a mixture of three or more olefins. In a preferred embodiment of the process according to the invention, ethylene is polymerized or ethylene is co-polymerized with a mixture of C ₃ -C ₈ -α-monoolefin, in particular ethylene and C ₃ -C ₈ -α-monoolefin. Polymerize. In another preferred embodiment of the process according to the invention, ethylene is copolymerized together with an α-olefin selected from propene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. .

Some of the catalyst compositions of the present invention exhibit little or no polymerization activity by themselves, so that aluminum can be used as a cocatalyst so that good polymerization activity can be exhibited. Contact with compound. Suitable aluminum compounds as cocatalysts are in particular the formula AlR ⁷ _m X ³ _3-m , wherein R ⁷ is as defined above for R, X ³ is as defined above for X and m is Represents 1, 2 or 3. It is a compound represented by this. In addition to trialkylaluminum, compounds in which one or two alkyl groups are substituted with alkoxy groups, in particular C ₁ -C ₁₀ dialkylaluminum alkoxides (eg diethylaluminum ethoxide), or one or two halogens Compounds substituted with atoms such as chlorine or fluorine, in particular dimethylaluminum chloride, methylaluminum dichloride, methylaluminum sesquichloride or diethylaluminum chloride are useful as cocatalysts. Preference is given to using trialkylaluminum compounds having 1 to 15 carbon atoms in the alkyl group, for example trimethylaluminum, methyldiethylaluminum, triethylaluminum, triisobutylaluminum, tributylaluminum, trihexylaluminum or trioctylaluminum. It is also possible to use an aluminoxane type cocatalyst, in particular methylaluminoxane MAO. Aluminoxanes are produced, for example, by controlled addition of water to alkylaluminum compounds, particularly trimethylaluminum. Aluminoxane preparations suitable as cocatalysts are commercially available.

  The amount of aluminum compound used depends on its effectiveness as a cocatalyst. Since many cocatalysts are used simultaneously to remove the catalyst poison (ie, act as a scavenger), the amount used will vary depending on the degree of contamination of other starting materials. However, the optimal amount can be determined by one of ordinary skill in the art using simple experimentation. The cocatalyst has an atomic ratio of aluminum in the aluminum compound used as the cocatalyst to titanium in the catalyst composition of the present invention in the range of 10: 1 to 800: 1, particularly in the range of 20: 1 to 200: 1. It is preferably used in such an amount.

  The various aluminum compounds can be used as cocatalysts, separately or as a mixture of two or more components in any order. Accordingly, these aluminum compounds acting as cocatalysts can act continuously or jointly on the catalyst composition according to the invention. The catalyst composition of the present invention can be contacted with one or more promoters before or after contacting with the olefin to be polymerized. It is also possible to preactivate with one or more cocatalysts before mixing with the olefin, and to add the same or other cocatalysts after contacting the preactivated mixture with the olefin. The preactivation is usually carried out under conditions of a temperature of 0 to 150 ° C., in particular 20 to 80 ° C. and a pressure of 1 to 100 bar, in particular 1 to 40 bar.

  To obtain a wide range of products, the catalyst composition of the present invention can be used in combination with at least one catalyst common to olefin polymerization. Catalysts which can be used in the context of the present invention are in particular Phillips catalysts based on chromium oxide, metallocenes (eg EP-A 129368), tight geometric complexes (eg EP-A 0416815 or EP-A 0420436), nickel And a palladium biimine composition (for this production see WO-A 98/03559), an iron and cobalt pyridine biimine compound (for this production see WO-A 98/27124) or chromium amide (see eg 95 JP-170947) is there. Other suitable catalysts are cyclopentadienyl or at least one based on heterocyclopentadienyl having a condensed heterocycle (preferably aromatic and containing nitrogen and / or sulfur). It is a metallocene having the following ligand. Such compounds are described, for example, in WO-A 98/22486. Other suitable catalysts are chromium-substituted monocyclopentadienyl, monoindenyl, monofluorenyl or heterocyclopentadienyl complexes, in which at least one of the substituents on the cyclopentadienyl ring is a donor It has the function of

  Furthermore, in addition to the above catalyst, it is possible to add another cocatalyst, which can make the catalyst active for olefin polymerization. This catalyst is preferably a cation-forming compound (cation-forming compound). Suitable cation-forming compounds are the following compounds: for example aluminoxane type compounds, strong non-charged Lewis acids, in particular tris (pentafluorophenyl) borane, ionic compounds having a Lewis acid cation or ionic compounds comprising Blensted acid as the cation N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and especially N, N-dimethylcyclohexylammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate . By combining in this way with a catalyst, for example, a bimodal (bimodal distribution) product can be produced, or a comonomer can be produced in situ. In this case, it is preferred to use the catalyst composition of the present invention in the presence of at least one catalyst common to olefin polymerization and optionally one or more promoters. Catalysts common to olefin polymerization can be applied to the same inorganic metal oxide or fixed to separate support materials and used simultaneously with the catalyst composition of the invention or in any order.

  According to the method of the present invention, an olefin polymer having a molar mass in the range of about 10,000 to 5,000,000, preferably in the range of 20,000 to 1,000,000 can be produced. In this case, the molar mass (mass average) of the polymer is 20,000 to 400,000. It is particularly preferable that the above range.

The catalyst composition of the present invention is particularly suitable for the production of ethylene homopolymers and copolymers of ethylene and α-olefins. For example, a homopolymer of ethylene or a copolymer of ethylene and a C _{3 to} C ₁₂ -α-olefin (including 10% by mass or less of a comonomer in the copolymer) can be produced. Preferred copolymers are 0.3 to 1.5 mol% 1-hexene or 1-butene, particularly preferably 0.5 to 1.0 mol% 1-hexene or 1-butene, based on the polymer. Contains.

  The bulk density of the ethylene homopolymer and the ethylene / α-olefin copolymer thus obtained is in the range of 240 to 590 g / L, and preferably in the range of 245 to 550 g / L.

In particular, ethylene homopolymers having a density in the range of 0.95~0.96g / cm ^3, and density of 0.92~0.94g / cm ^3, 3~8, preferably in the range of from 4.5 to 6 Copolymers of ethylene and C ₄ -C ₈ -α-olefins, particularly ethylene-hexene copolymers and ethylene-butene copolymers, having a polydispersity M _w / M _n in the range of It can be obtained using a composition. The proportion of the substance that can be extracted from ethylene homopolymers and copolymers by low-temperature heptane (cold heptane) is preferably in the range of 0.01 to 3% by weight, based on the ethylene polymer used. Is in the range of 0.05 to 2% by weight.

  The polymers produced according to the invention can also form mixtures with other olefin polymers, in particular ethylene homopolymers and copolymers. This mixture can be produced by the simultaneous polymerization described above with a plurality of catalysts or simply by subsequently blending the polymer produced according to the invention with other ethylene homopolymers or copolymers.

  Polymers, ethylene copolymers, polymer mixtures and blends are known auxiliaries and / or additives such as processing stabilizers, stabilizers against the action of light and heat, conventional additives such as lubricants, An oxidizing agent, an antiblock forming agent and an antistatic agent, and if necessary, a coloring agent can be further contained. Those skilled in the art are familiar with the types and amounts of these additives.

  The polymers produced according to the invention can subsequently be modified by grafting, crosslinking, hydrogenation or other functionalization reactions known by those skilled in the art.

  Olefin polymers and copolymers, particularly ethylene homopolymers and copolymers, produced using the catalyst composition of the present invention, due to their good mechanical properties, are suitable for films, fibers and molded articles. It is particularly suitable for production.

  The catalyst composition of the present invention is extremely useful for the production of ethylene homopolymers and copolymers. With this catalyst composition, high productivity is obtained even under high polymerization temperature conditions. The polymer produced using the catalyst composition of the present invention has a high bulk density and a low content of components that can be extracted using low temperature heptane. The catalyst of the present invention exhibits good comonomer incorporation and the molar mass of the polymer can be easily adjusted using hydrogen.

[Examples and Comparative Examples]
The parameters listed in the following table were determined based on the following measurement methods:
Density: Conforms to ISO 1183,
MI: Melt flow index (190 ° C / 2.16) according to ISO 1133.

  The Staudinger index (η: eta value) [dl / g] was measured at 130 ° C. using decalin as a solvent and an automatic Ubbellote viscometer (Lauda PVS 1) (at ISO 1628, 130 ° C. , 0.001 g / ml decalin).

  The bulk density (BD) [g / l] was measured according to German Industrial Standard 53468.

The molar mass distribution and the average M _n , M _w and M _w / M _n derived therefrom are determined by the method according to German Industrial Standard 55672 (DIN 55672), solvent: 1,2,4-trichlorobenzene, flow rate: 1 ml / min, temperature: 140 ° C., performed using high temperature gel permeation chromatography (GPC) under conditions calibrated with PE standards.

  Low temperature heptane extractability was measured by stirring 10 g of polymer powder in 50 ml of heptane at 23 ° C. for 2 hours. The polymer was filtered from the extract thus obtained and washed with 100 ml of heptane. The heptane layer was collected to remove the solvent and dried to constant weight. The residue was weighed and made low temperature heptane extractable.

  The particle size was measured by a method based on ISOWD 13320 particle size analysis using a Malvern Mastersizer 2000 (Small Volume MS1) under an inert gas atmosphere.

[Measurement of elemental content of magnesium and aluminum]
The elemental contents of magnesium and aluminum were measured using an inductively coupled plasma atomic spectrometer (ICP-AES) manufactured by Spectro (Klave, Germany). In the case of magnesium, the spectral line of 277.982 nm and aluminum In the case of 309.271 nm spectral line in samples digested in a mixture of concentrated nitric acid, phosphoric acid and sulfuric acid. Titanium content was measured in samples digested in a mixture of 25% sulfuric acid and 30% hydrogen peroxide using a 470 nm spectral line.

[Example 1]
In the first step, 147 g of finely divided spray-dried silica gel ES70X from Crossfield dried at 660 ° C. is suspended in ethylbenzene and mixed with 19.11 ml of a solution of titanium tetrachloride with stirring. did. The suspension thus obtained was stirred at 100 ° C. for 2 hours, cooled to room temperature, the solid was filtered and washed twice with ethylbenzene. The solid thus obtained was resuspended in ethylbenzene and mixed with 200.12 ml of (n-butyl) _1.5 (octyl) _0.5 magnesium (0.875 M in n-heptane). The suspension was stirred at 80 ° C. for 1 hour, cooled to room temperature, the solid was filtered and washed twice with ethylbenzene. The solid was resuspended in ethylbenzene, 28.3 ml of chloroform was added and the mixture was then stirred at 80 ° C. for 1.5 hours. The suspension thus obtained was cooled to room temperature, the solid was filtered and washed twice with ethylbenzene. The solid thus obtained was resuspended in ethylbenzene and mixed with 15.4 ml hexamethyldisilazane. The solid thus obtained was filtered, washed with heptane and dried at 60 ° C. under reduced pressure. Thereby, the magnesium content is 2.5% by mass, the aluminum content is less than 0.1% by mass, and the chlorine content is 9.9% by mass with respect to the finished catalyst composition. Thus, 179.9 g of a catalyst composition having a titanium content of 2.0% by mass was obtained.

[Example 2]
In the first step, 147 g of finely divided spray-dried silica gel ES70X from Crossfield, dried at 600 ° C., was suspended in ethylbenzene and mixed with 19.11 ml of a solution of titanium tetrachloride with stirring. The suspension thus obtained was stirred at 100 ° C. for 2 hours, cooled to room temperature, the solid was filtered and washed twice with ethylbenzene. The solid thus obtained was resuspended in ethylbenzene and mixed with 200.12 ml of (n-butyl) _1.5 (octyl) _0.5 magnesium (0.875 M in n-heptane). The suspension was stirred at 80 ° C. for 1 hour, cooled to room temperature, the solid was filtered and washed twice with ethylbenzene. This solid was resuspended in ethylbenzene, 28.3 ml of chloroform was added and the mixture was then stirred at 80 ° C. for 1.5 hours. The suspension thus obtained was cooled to room temperature, the solid was filtered and washed twice with ethylbenzene. The solid thus obtained was resuspended in ethylbenzene and mixed with 7.35 ml of ethyl acetate. The solid thus obtained was filtered, washed with heptane and dried at 60 ° C. under reduced pressure. Thereby, the magnesium content is 2.3% by mass, the aluminum content is less than 0.1% by mass, and the chlorine content is 10.5% by mass with respect to the finished catalyst composition. 188 g of a catalyst composition having a titanium content of 2.1% by mass was obtained.

[Example 3] (Comparative Example)
In the first step, 51.8 g of a finely divided spray-dried silica gel ES70X from Crossfield, dried at 600 ° C., was suspended in ethylbenzene and mixed with 6.86 ml of a solution of titanium tetrachloride with stirring. . The suspension thus obtained was stirred at 100 ° C. for 2 hours, cooled to room temperature, the solid was filtered and washed twice with ethylbenzene. The solid thus obtained was resuspended in ethylbenzene and mixed with 72.52 ml of (n-butyl) _1.5 (octyl) _0.5 magnesium (0.875 M in n-heptane). The suspension was stirred at 80 ° C. for 1 hour, cooled to room temperature, the solid was filtered and washed twice with ethylbenzene. This solid was resuspended in ethylbenzene and 10.36 ml of chloroform was added, then the mixture was stirred at 80 ° C. for 1.5 hours. The solid thus obtained was filtered, washed with heptane and dried at 60 ° C. under reduced pressure. Thereby, the magnesium content is 2.2% by mass, the aluminum content is less than 0.1% by mass, and the chlorine content is 11.75% by mass with respect to the finished catalyst composition. Thus, 102 g of a catalyst composition having a titanium content of 3.0% by mass was obtained.

[Example 4] (Comparative Example)
100.3 g of particulate spray-dried silica gel ES70X from Crossfield, dried at 600 ° C., was suspended in ethylbenzene and mixed with 13.23 ml of a solution of titanium tetrachloride with stirring. The suspension thus obtained was stirred at 100 ° C. for 1.5 hours, cooled to room temperature, the solid was filtered and washed twice with ethylbenzene. The solid thus obtained was resuspended in ethylbenzene and mixed with 137.6 ml of (n-butyl) _1.5 (octyl) _0.5 magnesium (0.875 M in n-heptane). The suspension was stirred at 80 ° C. for 1 hour, cooled to room temperature, the solid was filtered and washed twice with ethylbenzene. This solid was resuspended in ethylbenzene, 27.63 ml of tetrachlorosilane was added and then stirred at 80 ° C. for 1.5 hours. The solid thus obtained was filtered, washed with pentane and dried at 60 ° C. under reduced pressure. Thereby, the magnesium content is 2.15% by mass, the aluminum content is less than 0.1% by mass, and the chlorine content is 10.05% by mass with respect to the finished catalyst composition. Thus, 129.9 g of a catalyst composition having a titanium content of 3.1% by mass was obtained.

[Examples 5 and 6]
[polymerization]
The polymerization was carried out in a 10 L autoclave with a stirrer. Under nitrogen, 1 g of TEAL (triethylaluminum) was introduced into the autoclave together with 4 L of isobutane and 1 L of butene at room temperature. The autoclave was then pressurized with 4 bar H ₂ and 16 bar ethylene, the mass of catalyst shown in Table 1 was introduced, and the polymerization was carried out for 1 hour at 70 ° C. reactor internal temperature conditions. The reaction was stopped by draining. Table 1 shows the productivity of the catalyst compositions obtained from Examples 1 and 4 and the density and η value of the ethylene-butene copolymers obtained in both Example 5 and Comparative Example 6 according to the present invention. Shows about.

[Example 7]
[polymerization]
The catalyst of Example 3 (C) was polymerized as described in Examples 5 and 6 under the same conditions. With the catalyst of Example 3, an ethylene copolymer having a bulk density of 254 g / L and an η value of 1.48 dl / g was obtained.

[Examples 8 and 9]
[polymerization]
200 mg of triisobutylaluminum (dissolved in hexane) and 18 ml of hexane were introduced into a 1.4 L stirrer autoclave initially charged with 150 g of polyethylene and rendered inert with argon. Thereafter, the mass of catalyst shown in Table 2 is introduced, the autoclave is pressurized with 9 bar N ₂ , 1 bar H ₂ and 10 bar ethylene, the reaction mixture is brought to 110 ° C. and the reaction at 110 ° C. Polymerization was carried out for 1 hour under the internal temperature conditions. The reaction was stopped by draining.

  Table 2 below shows the productivity of the catalyst used in both Example 8 and Comparative Example 9 of the present invention.

Claims (12)

The following steps A) to D):
A) contacting the inorganic metal oxide with a tetravalent titanium compound;
B) The intermediate obtained in step A) is converted into a magnesium compound MgR ¹ _n X ¹ _2-n [wherein X ¹ are independently of each other fluorine, chlorine, bromine, iodine, hydrogen, NR ^X ₂ , OR ^X , SR ^X , SO ₃ R ^X or OC (O) R ^X , wherein R ¹ and R ^X are each independently a linear, branched or cyclic C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl having 1 to 10 carbon atoms in the alkyl moiety, alkyl aryl having 6 to 20 carbon atoms in the aryl part, or C ₆ -C ₁₈ aryl, and n is 1 or 2 Represents. A step of contacting with
C) comprising a step of contacting the intermediate obtained in step B) with a halogenating agent, and D) contacting the intermediate obtained in step C) with a donor compound. A method for producing a Natta-type catalyst composition. The process for producing a catalyst composition according to claim 1, wherein the magnesium compound MgR ¹ ₂ is used in step B).   The method for producing a catalyst composition according to claim 1 or 2, wherein the halogenating agent used in step C) is chloroform.   The method for producing a catalyst composition according to any one of claims 1 to 3, wherein the inorganic metal compound used in step A) is silica gel.   The method for producing a catalyst composition according to any one of claims 1 to 4, wherein the tetravalent titanium compound used in step A) is titanium tetrachloride.   The process for producing a catalyst composition according to any one of claims 1 to 5, wherein the donor compound used in step D) contains at least one nitrogen atom.   A Ziegler-Natta type catalyst composition produced by the method according to claim 1. A prepolymerized composition comprising the catalyst composition according to claim 7 and linear C ₂ -C ₁₀ -1-alkene polymerized to the composition in a mass ratio in the range of 1: 0.1 to 1: 200. Catalyst composition.   9. Polymerizing or copolymerizing olefins in the presence of at least one catalyst composition according to claim 7 or 8 and optionally an aluminum compound as cocatalyst under conditions of 20 to 150 ° C. and a pressure of 1 to 100 bar. Method.   The olefin polymerization method or copolymerization method according to claim 9, wherein a trialkylaluminum compound having 1 to 15 carbon atoms in each alkyl group is used as the aluminum compound. 11. The olefin polymerization method or copolymerization method according to claim 9, wherein ethylene or a mixture of ethylene and a C ₃ -C ₈ -α-monoolefin is (co) polymerized. 11.   A method of using the catalyst composition according to claim 7 or 8 for polymerization or copolymerization of olefins.