Process for preparing catalyst component for the polymerization of olefines

The invention relates to the production of titanium-containing compounds suitable for use as a component of Ziegler transition metal catalysts. It is concerned with the production of Ziegler-type catalyst components for the polymerization of α-olefins with considerably high stereoregularity or crystallinity and polymerization activity using solid components containing magnesium halides, electron donors and titanium compounds.

Ziegler catalysts are known as stereospecific polymerization of α-olefins. Various methods have been proposed to further increase the activity and stereoregulatory efficiency of these catalysts. One of these improved processes, which is considerably more efficient in particular with respect to activity, is a process for producing a solid catalyst component by introducing a magnesium compound into a Ziegler catalyst component comprising a transition metal (as described in Japanese Patent Publication Nos. 41,676/1972). and 46 269/1972). However, these processes have been designed mainly for the production of highly active ethylene polymerization catalysts and, when used as alpha-olefin polymerization catalysts such as propylene, have extremely high activity but at the same time greatly reduce the stereoregularity of the resulting polymer while being practical. These catalysts as stereospecific polymerization catalysts are greatly reduced, as is also known.

For these reasons, various methods have been proposed to improve the stereoregularity of α-olefin polymerization polymers using Ziegler catalysts with a solid transition component containing a magnesium compound (for example, in the disclosures of Japanese Laid-open Patent Applications Nos. 9,342/1972, 12,659/1975 and 57 789/1976). A general characteristic of these methods is that an electron donor such as an amine or an ester is introduced into the solid Ziegler catalyst component containing the titanium compound and the magnesium halide.

Further, as is known from the disclosures of Japanese Patent Laid-open Nos. 16,986/1973, 16,987/1973, and 16,988/1973, methods for introducing an electron donor into both the intermediate and the trialkylaluminum component of the Ziegler catalyst (by addition and complexing) have been proposed. in a similar way). By introducing an electron donor into the intermediate component of the Ziegler catalyst containing magnesium halide, the stereoregularity of the prepared polymer is greatly increased.

However, the stereoregularity of the polymers prepared by the methods described above is still insufficient. It is therefore necessary to remove atactic fractions from the α-olefin polymers obtained using the described catalytic systems to obtain a polymer with commonly desired physical properties, thereby complicating the polymer production process.

In addition, there are certain catalyst systems that have a high activity on a titanium atom but do not necessarily have a high activity on a solid catalyst component. Again, it is desirable to find improvements.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a process for the production of a titanium catalyst component which, by stereospecific polymerization of [alpha] -olefins, will have a very high activity on the titanium atom and at the same time make it possible to obtain a polymer with very high stereoregularity. This object is solved by exposing the solid composition comprising the reaction product of a magnesium halide, an electron donor and a titanium halogen compound to an interhalogen compound or halogen.

Accordingly, the present invention provides a process for the production of a catalyst component for olefin polymerization, wherein the solid composition prepared by the interaction of a magnesium halide, an electron donor and a titanium halogen compound is exposed to an interhalogen compound or halogen.

The term "exposure to magnesium halide, electron donor and titanium halogen compound" not only refers to the simultaneous contact of the three compounds but also to the interaction of the three compounds in any order in degrees, including: washing and other intermediate steps.

A preferred embodiment of the process according to the invention consists of the following steps:

1. Effect of electron donor on magnesium halide.

2. Grinding or crushing a mixture comprising the magnesium halide so obtained and the titanium halogen compound in liquid form substantially in the absence of an inactive solvent.

3. Treatment of the mixture containing the magnesium halide so treated with an interhalogen compound or halogen.

4. Treatment of the magnesium halide or the magnesium halide containing mixture with or without reacting the organic solvent with or without carrying out step 3. The words "grinding" and "crushing" are used interchangeably herein.

The described preferred embodiment consists of a combination of several stages, but there are many practical ways depending on the order of execution of stages 3 and 4, as will be described in more detail below. One of these practical methods is that an inert organic solvent is present in the reaction of the mixture containing the magnesium halide, electrons and the titanium halogen compound (i.e., the product formed after step 2) with the interhalogen compound or halogen.

Another practical method is to first expose the composition to an interhalogen compound or halogen and then to an inert organic solvent.

Although it is not known precisely in what form the magnesium halide exists in the product described above, steps 1, 2 and 3, the product of steps 1, 2 and 3 will hereinafter be referred to as the "magnesium halide-containing composition".

A characteristic feature of the titanium compound Ziegler catalyst produced by this method is the excellent stereoregularity of the resulting polymer. In addition, the action of the interhalogen compound or halogen has an effect not only on improving the stereoregularity of the polymer, but also allows an increase in activity per unit of titanium content. In addition, the preferred method described above, which involves the use of an inert organic solvent, achieves high activity per unit of solid catalyst component.

Thus, using the titanium composition of the present invention exhibiting high stereoregularity and high activity for the industrial scale production of α-olefin polymers, stereoregular α-olefin polymers can be obtained with numerous technological advantages such as simplification of operation, reduced monomer consumption and reduced consumption · Auxiliaries, electricity and steam.

The nature, applicability and other features of the invention will become more apparent from the following detailed description, beginning with an analysis of the general aspects of the invention and ending with exemplary embodiments that include preferred embodiments of the invention.

The titanium composition of the invention, i.e., the olefin polymerization catalyst component, comprises a product obtained by treating an interhalogen compound or halogen with a solid mixture obtained by reacting a magnesium halide, an electron donor, and a titanium halogen compound. The terms “action” or “reaction” have the same meaning as above.

1. Solid mixture

1] Ingredients

(i) Magnesium halide

As the magnesium halide, halogen halides such as magnesium chloride, magnesium bromide and magnesium iodide can be used. Magnesium chloride is preferred. In addition, it is preferred that the magnesium halide be substantially anhydrous so as not to adversely affect the function of the catalyst.

In the production of the solid component according to the invention, it is not necessary for the magnesium halide and the other components ii) or iii) to use mechanical contact methods such as grinding by grinding, but in the absence of grinding it is appropriate that the magnesium halide is ground crushed in advance.

(ii) Electron donor

An electron donor suitable for the purpose of the invention is selected from different compounds, each containing at least one atom selected from oxygen, nitrogen and phosphorus atoms in the molecule.

Examples include ethers, esters, ⁷tons, amines and phosphorus compounds. Typical examples are:

1) monoethers, diethers, triethers of 2 to 12 carbon atoms, such as diethyl ether, di-n-butyl ether, di-n-amyl ether, ethylene glycol dimethyl or dibutyl ether;

2) carboxylic acid esters derived from a carboxylic acid having 1 to 12 carbon atoms and an alcohol having 1 to 12 carbon atoms. Examples are aliphatic carboxylate esters such as ethyl acetate, vinyl acetate, methyl acrylate, methyl methacrylate, ethyl methacrylate and octyl laurate, aromatic carboxylate esters such as methylbenzoate, ethylbenzoate, phenylbenzoate, methyltoluylate, ethyltoluylate, ethylanisate, diethyl phthalate;

3) ketones having 2 to 12 carbon atoms, such as acetone, methyl ethyl ketone and acetophenone;

4) amines of 1 to 12 carbon atoms such as trimethylamine, diethylamine, octylamine and urea;

5) phosphorus compounds such as tributylphosphine, triphenylphosphine, triphenylphosphate, triphenylphosphite and hexamethylphosphoric triamide.

These compounds can be used in combinations of two or more. For example, ethyl benzoate and n-butyl ether can be used (Example A4J.

The most preferred of these compounds are esters and especially esters derived from carboxylic acids having 1 to 12 carbon atoms and alcohols having 1 to 12 carbon atoms. Typical examples are given. above. Most preferred esters are lower alkyl methacrylates (C 1 -C 6) and lower alkyl benzoates (C 1 -C 6).

iii) A titanium halogen compound

Generally, a halogen compound of the titanium defined by the formula Ti (OR) mXn-m (where R is an alkyl group, preferably alkyl of 1 to 6 carbon atoms, X is halogen, n is 3 or 4, m is zero or an integer from 1 up to 4 and m).

Typical examples of tetravalent titanium halogen compounds are:

1) titanium tetrahalides, for example titanium tetrachloride, titanium bromide and titanium iodide;

2] alkoxytitanium trihalides, for example methoxytitanium trichloride, ethoxyttitanium trichloride and n-butoxytitanium trichloride;

3] dialkoxytite dihalides, for example dimethoxytitamum dichloride and di-n-butoxythiianium dichloride;

4] trialkoxytite monohalides, for example trimethoxytitanium chloride and tri-n-butoxynitrite chloride.

Examples of titanium trivalent halogen compounds are:

1) titanium tri-b1alpha-iodides, for example titanium tetrachloride, titanite bromide and titanium iodide;

2) alkoxide dihalides, for example methoxytitanium dichloride and n-butoxytitanium dichloride;

3) dialkoxytitanium halides, for example dimethoxyethane^,id and di-n-butoxytitanium chloride.

Among these halogen compounds of titanium, halides, i.e. T1X4 or T1X3, in particular TCl4, titanium tetrachloride and the like are preferred.

In the preferred embodiment described above, the halogenated titanium compound is used in liquid form. Generally, liquid titanium halogen compounds represented by the formula TiXn (where X is halogen and n is 3 or 4) or complexes thereof are used. Of the chlorine, bromine and iodine halogens, chlorine is most preferred. Halogenated titanium compounds which are present in solid form,. they must be used after conversion to the liquid complex with a complexing agent such as ether, ketone, amine, amide and the like.

iv) Interhalogen compound and halogen

The interhalogen compound and halogen used according to the invention are defined by the general formula XYn (wherein n = 2 when X = Y, and n = 1, 3, 5 or 7 when X = Y, wherein X and Y are halogens).

Typical examples are C1F, BrF, LF, BrCl, IC1, IBr, C1F3, BrF3, IF3, IC13 (or I2Cl6), CIF5, BrFs, IFs, IF7, CI2, Brz and I2. Particularly preferred are IC1, ICl3, Cl2 and I2.

v) Inert organic solvent

Although the inert organic solvent is unlikely to be considered as a component of the solid catalyst component of the invention, it is a necessary substance in a preferred embodiment of the invention.

Aliphatic, alicyclic and aromatic hydrocarbons or their halogenated derivatives are used in the process according to the invention. Preferred are solvents composed of halogenated hydrocarbons and aromatic hydrocarbons. Typical examples are hexane, heptane, benzene, toluene, xylene, mesitylene, cyclohexane, methylcyclohexane, 1,2-dichloroethane, propylchloride, butyl chloride, chlorobenzene and brobenzene.

2) Preparation of a solid catalyst component

One practical embodiment of the invention consists in first preparing a solid mixture by the interaction of a magnesium halide, an electron donor and a titanium halogen compound, and treating the mixture with an interhalogen or a halogen.

1) Preparation of solid mixture

The solid mixture is formed by the interaction of the components i), li) and iii) described above. The term "formed by the interaction" of the components herein means obtaining a solid mixture by bringing the three necessary components and, optionally, the auxiliary component described above, into contact with each other either simultaneously or sequentially. The solid composition of the invention formed by the interaction of the above components may exist in various forms including a mere mixture of these components and a form in which the components are partially or completely in a state in which they exhibit some kind of interaction or have reacted .

A number of specific examples of preparation of this composition will be set forth below, but it should be emphasized that the invention is not limited to these methods of preparation.

(a) The anhydrous magnesium halide which has been ground or crushed is suspended in an inert solvent and the resulting titanium halogen compound and an electron donor are added to the resulting suspension.

b) The anhydrous magnesium halide and electron donor are ground or crushed, then suspended in an inert solvent and the titanium compound is added to the suspension.

c) The electron donor is added at the same time when the titanium compound is added in method b].

d) The magnesium halide is pretreated with an electron donor and then ground or comminuted with a titanium halogen compound substantially in the absence of an inert solvent.

e) A titanium-electron donor complex is prepared beforehand, the resulting complex is preferably isolated, then mixed and crushed with anhydrous magnesium halide.

f) The anhydrous magnesium halide, electron donor and titanium halogen compound are simultaneously mixed and comminuted.

g) The anhydrous magnesium halide and the electron donor are mixed and comminuted together, while separately mixing and comminuting the titanium halogen compound and the other portion of the electron donor, then mixing and comminuting the resulting separately obtained mixtures.

h) Anhydrous magnesium halide is hot exposed to an electron donor in another solvent to give a solid that swells and is converted to fine particles, followed by the addition of a titanium halogen compound. If desired, the solid is further crushed after this addition.

1) The anhydrous magnesium halide is dissolved in a solvent such as an alcohol and the solution is evaporated to dryness to give a fine solid. A titanium halogen compound and an electron donor are added thereto. If desired, the solid is then further crushed.

The grinding or crushing of the methods is generally carried out for 2 hours or more. The crushing time is usually 10 to 48 hours. It is desirable that the crushing is carried out in an inert atmosphere. In the production processes a) and 1J it is also possible to add a crushing aid such as SiCl 2 or a hydrocarbon halide (as described, for example, in Japanese Laid-Open Patent No. 39 287/1972) to improve the particle properties of the solid mixture obtained. In addition, an inorganic solid such as silica or an organic solid such as naphthalene, anthracene and hexachlorobenzene may be mixed in the solid mixture to reduce the chlorine content of the solid mixture.

(2) Mixture

The proportions of the three components, i.e. i) magnesium halide, il) electron donor, and iii) titanium halogen compounds contained in the solid mixture are not limited and can be chosen arbitrarily as long as desired results are obtained. Typical molar ratios of these components, expressed in series i) magnesium halide, ii) electron donor, iii) titanium halogen compound, are (1000 to 3): (10 to 0.1): 1, preferably (500 to 5): ( 5 to 0.5): 1.

Magnesium halide, electron donor and titanium halogen compound are essential components of the solid mixture, but the mixture may additionally contain auxiliary components. Examples of auxiliary components are inorganic halides, for example silicon tetrachloride and tin tetrachloride, and hydrocarbon halides, for example dichloroethane and n-butyl chloride.

(3) Contacting the solid mixture with an interhalogen compound or halogen

When the solid mixture obtained as described above is contacted with an interhalo-

With a gene compound or halogen, the titanium composition of the present invention is obtained, i.e. the catalyst component for olefin polymerization.

The amounts of halogen compounds used are of the order of 0.001 to 20, preferably 0.005 to 10, in terms of the molar ratio based on the titanium compound in the solid mixture.

When the halogen compounds are in liquid or solid form, for example, they can be contacted with the solid mixture by mechanical means, such as grinding or crushing, and then washed with an inert organic solvent. Typically, however, the halogen compounds are contacted with the solid mixture after a period of the order of 30 minutes to 5 hours and at a temperature of the order of from room temperature to 150 ° C in the presence of an inert organic solvent. After this operation, it is advantageous to perform a thorough wash.

As an inert organic solvent, an aliphatic, alicyclic or aromatic hydrocarbon or halogenated hydrocarbon may be used in this case. A preferred solvent is a hydrocarbon halide.

Reaction with halogen compounds has a considerable effect on both the activity and the stereoregularity achieved by the action of the solid catalyst component.

(4) 'Příprvaa ýýoodne titanoé - kornooziee

As mentioned above, a preferred embodiment of the invention is that the magnesium halide is treated with an electron donor, the magnesium halide thus treated is milled or crushed together with the liquid titanium halogen compound substantially in the absence of an inert solvent, and the resulting foam is treated with an intermediate foam. a compound or a halogen and simultaneously or subsequently an inert organic solvent.

(1) Preparation of a solid catalyst component (i) Contacting a magnesium halide with an electron donor

The method of contacting a magnesium halide with electron supervision, which may be described as a pretreatment, since it is carried out prior to contacting the titanium compound, can conveniently be carried out in the presence or absence of an inert solvent. For example, one of the different mills (in the absence of an inert solvent) can be used to bring the magnesium halide into contact with the electrons. Alternatively, a method of exposing the halogen to the magnesium and electron donor by heating (to a temperature of the order of 60-150 ° C) in an inert solvent (which may be the same as the solvent specified in Section V above) may be used. solvents.

(ii) Grinding or crushing with the titanium compound

The crushing of the solid thus obtained together with the titanium compound is carried out on condition that substantially no inert solvent is present. Therefore, in the absence of an inert solvent, the pretreatment can be carried out immediately and without any treatment by treating the reaction mixture with the halogenated titanium compound. However, when the above-described pre-contact was in the presence of an inert solvent, it is important to remove substantially all of the solvent at a time, and the pre-dry solid can be contacted with the titanium halogen compound.

The grinding of the preformed solid together with the titanium halogen compound is carried out by means of a mill, for example in a rotary ball mill or a vibrating ball mill or in some other crushing plant.

(iiij Treatment of an interhalngenone compound or halogen and treatment with an inert organic solvent

Exposure of the described solid mixture to the interhalogenated compound or halogen in an inert solvent achieves the high activity of the present invention. However, the duration of treatment with the ether compound or halogen is not necessarily the same as that of the inert organic solvent. For example, the reaction with an idalohalone compound or halogen may be performed prior to treatment with an inert organic solvent.

The reason for the high effect of solvent action in the process of the invention is not clear. However, a reduction in the titanium content of the solid mixture before and after the solvent treatment has been observed, and therefore some extraction or elution of the titanium compound by the solvent can be considered at least in part. However, the present invention is not limited by this supposed reason.

A number of typical embodiments are given below; it should be noted, however, that the invention is not limited thereto.

(a) Magnesium halide and donor. The electrons are exposed to a heat treatment in an inert solvent, the solvent is removed by evaporation to dryness, and a dry solid mass (referred to herein as a "preformed solid") is formed. A titanium halogen compound is added to this preformed solid, and the materials are mixed and comminuted to produce a material referred to herein as a & quot; mixed milled solid & quot ;. The mixed crushed solid is exposed in an inert organic solvent to an interhalogen compound or halogen.

b) The magnesium halide and electron donor are mixed and crushed in a mill to form a preformed solid to which is further added the titanium halogen compound and mixing and crushing are continued. The mixed crushed solid obtained is subjected to the same treatment as in the process and the like.

c) The introduction of the interhalogen compound or halogen is carried out at the time of the formation of the preformed solid in processes a) and b) and the mixed crushed solid is exposed in an inert organic solvent to the interhalogen compound or halogen.

d) The introduction of the interhalogen compound or halogen is carried out in the step of contacting the titanium halogen compound and treating the mixed crushed solid, as in process c), with both an inert organic solvent and an interhalogen compound or halogen.

(4) Quantity of ingredients

The amounts in which the various components are used to produce the solid catalyst component are chosen arbitrarily and are not to be limited by anything other than the condition to achieve the desired results.

The amount of electron donor used to form the preformed solid is usually 0.05 to 1: 1, preferably 0.1 to 0.5: 1, in terms of the molar ratio based on the amount of magnesium halide.

The titanium halogen compound may be used in an amount of 0.005 to 8: 1 in terms of molar ratio based on the amount of magnesium halide and in an amount of 0.1 to 8: 1, preferably 0.2 to 2: 1 in terms of molar ratio based on the amount of electron donor contained in a preformed solid. As mentioned above, the titanium content decreases by the action of an inert organic solvent, but the amount reported herein. the halogen titanium compound refers to the value prior to treatment with an inert organic solvent. The amount of titanium contained by elution due to solvent treatment is 5 to 95 weight percent (such as metallic titanium) of the titanium content before the solvent treatment, and the titanium content in the solid after solvent treatment is usually 5 weight percent or less (such as metallic titanium).

The amount of interhalogen compound or halogen used is 0.001 to 20: 1, preferably 0.005 to 10: 1 in terms of the molar ratio based on the amount of the titanium halogen compound used to produce the solid catalyst component.

The molar ratio of (1) the magnesium halide (ii) of the electron donor to (iii) the titanium halogen compound to (iv) the interhalogen compound or halogen is (1000 to 3): (10 to 0.1): 1: (0.001 to 20) .

(5) Preparation conditions of the solid catalyst component (i) Contact of a magnesium halide and an electron donor

Where the formation of the preformed solid is carried out in an inert solvent, it is desirable to be carried out at high temperature and for as long as possible in order to ensure sufficient contact between the electron donor and the magnesium halide. This reaction is usually carried out in an inert solvent boiling in the range of 60 to 150 ° C for 2 to 5 hours at reflux temperature. In addition, after the reaction, the solvent is removed by distillation to dry the residue, which is then contacted with the titanium halogen compound.

In the case where the preformed solid is formed without the use of an inert solvent, the magnesium halide and electron donor are generally mixed and crushed in a mill for 2 to 48 hours. It has been found that if this crushing time is too long, the properties of the catalyst and the resulting polymer deteriorate (e.g. bulk density and static friction angle).

(ii) Crushing with a titanium halogen compound

The chemical reaction of the preformed solid and the titanium halogen compound is undoubtedly a complexing reaction of the electron donor bound to the magnesium halide and the titanium halogen compound and is believed to proceed immediately and simultaneously with the introduction of the titanium halogen compound. This is inferred from the phenomenon that, in many cases, when the preformed solid is brought into contact with the titanium halogen compound, the solid becomes yellow or green.

Thus, although contact of the titanium halogen compound with the preformed solid can be achieved by mere mixing, it is desirable, after mixing and contacting, for grinding in the mill to be thoroughly mixed after mixing and contacting, thereby thoroughly mixing the titanium halogen compound and the preformed solid. substances. A grinding time of the order of 24 to 48 hours is sufficient for this stage.

(iii) Treatment with an inert organic solvent

By treatment with an inert organic solvent, the material is typically exposed at a temperature of the order of room temperature to 150 degrees Celsius for 30 minutes and 5 hours with stirring. It is desirable to perform a thorough wash after the operation.

In particular, when the inert organic solvent is a hydrocarbon halide, this operation can be carried out at a temperature from room temperature to 100 ° C for 1 to 3 hours using 50 to 100 ml hydrocarbon halide per approximately 10 g of crushed solid. When an aromatic hydrocarbon is used as the inert organic solvent, the operation can be carried out under similar conditions and at a temperature of 50 to 140 ° C. In both cases, however, temperature does not have a decisive effect on the change in catalytic efficiency.

It has been observed that the action of an inert organic solvent results in a decrease in the titanium content of the solid mixture. For this reason, it can be stated that the final point of action of the inert organic solvent is the point in time at which a satisfactory decrease in the titanium content has been achieved. The optimum value for the decrease in titanium content varies with various factors, such as the type and amount of electron donor and the titanium halogen compound used, the type and amount of inert organic solvent used, and the temperature and duration of solvent treatment, but can be readily determined experimentally.

(iv) effecting the intercolouric compounds δ or halogen

By treatment with an ether compound or halogen, the material may be exposed to substantially the same conditions as those used in the present invention. described for the action of an inert organic solvent.

2. Polymerization of spheres

The titanium composition produced as a transient component of the Ziegler catalyst as described above is contacted with a reducing compound of Group I, II or III of the Periodic Table of the Elements, in particular with a compound of the formula AlRnX3._:](wherein n is 1, 2 or 3, X is halogen and R is hydrogen or a hydrocarbon radical of 1 to 10 carbon atoms) to form a catalyst for stereospecific polymerization of wolefins.

Examples of suitable organic compounds are tri-aluminum, tri-butyl-aluminum, tri-aluminum-aluminum, tris-aluminum, di-aluminum-aluminum-hydride, di-butyl-aluminum-aluminum-oxide, and di-butyl-aluminum-chloride. The compound is used in an amount of 1 to 300: 1, preferably 1 to 100: 1 in terms of the weight ratio to the titanium atom in the titanium composition.

Examples of possible pslymerization methods include slurry polymerization using a hydrocarbon such as hexane, heptane or cyclohexane, liquid phase polymerization using a liquid monomer, and gas phase polymerization where the monomer is present in the liquid phase. gas phase.

The polymerization process can be carried out continuously or batchwise. The polymer temperature is of the order of 30 to 120 ° C, preferably 40 to 80 ° C, and the polymerization pressure is of the order of atmospheric pressure to 10 MPa, preferably of the order of atmospheric pressure to 5 MPa.

The catalyst containing the titanium composition according to the invention is highly active when used in the hopsopsomerization or copolymerization of an olefin such as ethylene, propylene, 1-butene, HH^^ H^ l^ ^p ent ent and the like.

The titanium composition of the invention is particularly effective as a catalyst component for propylene polymeram and copolymerization of propylene with 1 to 15% by weight (based on proplene) ethylene. The molecular weight adjustment can be carried out by known methods, such as using hydrogen.

Examples

Example AI

1) Preparation of titanium composition g of anhydrous magnesium chloride, obtained by heating commercially available anhydrous magnesium chloride in an argon stream to 300 ° C. ^OC for 5 hours, and 12 ml of ethnobenzoate are placed in a 1-liter vibration mill (containing 12.7 mm stainless steel balls (JIS, SUS-27) (apparent volume of 800 ml)) with an argon atmosphere. and milled for 24 hours at a frequency of 1410 vibrations per minute and an amplitude of 3.5 mm.

The solid mixture (I) was obtained by placing 5 g of the resultant ground solid in a 200 mL flask, adding 50 mL of n-hexane, which was dried and degassed, and 10 mL of TlCl4, by reacting the mixture for 2 hours at reflux temperature. and washing the product 10 times with 70 ml of n-hexane by decantation.

To this solid mixture was added 50 ml of dried and degassed 1,2-dichloroethane and 0.6 g of iodine trichloride (ICl 3), dissolved in 1,2-dichloroethane, and the resulting material was kept at reflux for 2 hours. The resulting solid is then washed with 2 times 70 ml of 1,2-dichloroethane and 3 times with n-hexane by decantation to give the titanium composition. which is used in a further polymerization in the form of a suspension in hexane containing about 10 wt. % Solids.

The concentration of titanium contained in the titanium composition suspension is determined by colorimetry with color development with hydrogen peroxide. The following polymerization test was performed:

2) Polymerization of proplene (in liquid phase)

A 1 liter internal mixer with a stirrer was charged with 30 ml of tripotassium aluminum and then 2.27 ml of a suspension of the thitanium composition (containing 0.5 mg of titanium) in a propylene gas atmosphere, followed by 700 ml of liquefied monomer propylene. The polymerization is carried out in an autoclave at 70 ° C for 1 hour.

After polymerization and purification of the remaining monomer, 165 g of polymer (pp) are obtained. The yield, based on the amount of titanium atoms (gpp / gTi), was 330,000. The stereospecificity or crystallinity of the polymer (hereinafter referred to as total Π-isotacticity index) was 97.0% as determined by the polymer extraction assay with n-heptane boiling.

Comparative Example A 1

In order to confirm the effect of IC13 treatment, it is prepared. suspension of the solid composition as in Example A1, but contact with IC13 is omitted. The polymerization was carried out with 1.16 ml of the resulting solid composition suspension (containing 1 mg of titanium) in the same manner as in Example A1, except that 40 mg of triethyl aluminum was used.

179 g of polymer are obtained. The yield based on titanium (gpp / gTi) was 179,000, total II was 92.9%.

Example A2

A slurry of the titanium composition was prepared under the same conditions as in Example A1, but IC13 was used in an amount of 0.3 g.

The polymerization was carried out under the same conditions as in Example Ais using 4.54 ml of the resulting suspension of the titanium composition (containing 1 mg of titanium) and 40 mg of triethyl aluminum.

155 g of polymer are obtained. The yield on titanium is 155,000 and the total II is 98.5%.

Example A 3

Titanium slurry. the composition was prepared under the same conditions as in Example A1, but using 0.1 g IC13.

The polymerization was carried out under the same conditions as in Example Ais using 5.00 ml of the resulting slurry of titanium composition (containing 0.8 mg of titanium) and 32 mg of triethyl aluminum.

104. g of polymer. The yield based on titanium is 130,000 and the total II is 98.5 percent.

Example A 4

A titanium composition suspension is prepared using titanium tetrachloride as follows: 5 g of a ground solid consisting of anhydrous magnesium chloride and ethyl benzoate, prepared as in Example A1, is placed in a flask and 50 ml of 1,2-dichloroethane is added. and 12.4 ml titanium tetrachloride solution (containing 1.62 g TiCl 3). The resulting mixture was stirred at room temperature for 2 hours.

The titanium tetrachloride solution described was prepared by reduction of TiCl 2 with AlEt 2 Cl. in a conventional manner, by converting the obtained TiCl 3 to γ-TiCl 3 by heat transfer and milling the substance. To 10 g of the ground product was added 50 ml of 1,2-dichloroethane and 11.8 ml of n-butyl ether with stirring to form a dissolved complex.

After contact with the titanium tetrachloride solution, the mixture is washed 3 times with 50 ml of 1,2-dichloroethane by decantation and then treated with ICl 3.

The ICI3 treatment is carried out by adding to the resulting solid mixture 50 ml of 1,2-dichloroethane and 0.5 g of ICI3 (dissolved in

1,2-dimethylethyl) and the resulting material is heated to reflux for 2 hours. After the reaction, the product was washed by decantation (2 times 1,2-dichloroethane and 5 times n-hexane) to give a slurry of the titanium composition (in n-hexane).

The polymerization was carried out under the same conditions as in Example Ais using 1.39 ml of a titanium composition suspension (containing 1 mg of titanium) and 40 mg of triethyl aluminum.

173 g of polymer are obtained. The yield based on titanium is 173,000 and the total II is 93.0 percent.

Comparative example A 2

To confirm the effect of IC13 treatment, a solid mixture was prepared in the same manner as in Example A 4 and polymerization was carried out as in Example Ais using a 0.42 ml suspension of the solid composition (containing

1 mg of titanium) not contacted with ICl 3 and 40 mg of triethylelin. A polymerization temperature of 75 ° C was used.

minutes after the start of the polymerization, the polymerization reaction is interrupted because the polymer formed in the autoclave forms a lumpy mass and stirring cannot be continued.

232 g of sticky polymer are obtained. The yield based on titanium is 232,000 and total

II is '67.0 ° / o.

Example A 5

40 g of anhydrous magnesium chloride and 14.2 g of ethylbenzoate titanium tetrachloride complex in an argon atmosphere are charged to a 1 liter vibration mill, and the mixture is mixed and milled under the same conditions as in Example A1.

The titanium tetrachloride ethylbenzoate complex was prepared by dropwise addition of an n-hexane solution of ethylbenzoate (molar ratio ethylene enStSt / TiCl 3 = 1) to an n-hexane solution of TiCl 2 at 0 ° C, aging the mixture at room temperature and washing and drying. to give a yellow crystalline solid. Place the mixed and ground solids. into a 200 ml flask and then 50 ml of 1,2-dichloroethane and 0.6 g of iodine trichloride (dissolved in 1,2-dichloroethane) are added. The substances are then maintained at reflux temperature for 2 hours. After reaction, the resulting solid was washed by decantation (2 times 70 ml 1,2-dichloroethane and 3 times n-hexane) to give a slurry of the titanium composition (in n-hexane).

The polymerization is carried out at. using the same conditions as in Example Ais using a 0.61 µm suspension of the titanium composition (containing 0.3 mg of titanium) and 20 mg of triethyl aluminum.

157 g of polymer are obtained. The yield based on titanium is 523,000 and the total II is 83.5 percent.

Comparative Example A 3

About 2.2 g of the ground solid obtained as in Example A 5 was used to prepare a suspension of the ground solid (in 100 ml n-hexane as solvent). The polymerization was carried out in the same manner as in Example A1 using 0.61 ml of the obtained suspension (containing 0.5 mg of titanium) and 40 mg of triethyl aluminum. The polymerization is interrupted 37 minutes from the start, since the polymer forms a lumpy material in the autoclave and stirring cannot be continued. 178 g of a clay-like consistency are obtained. The yield based on titanium is 356,000 and the total II is 47.9%.

Comparison of the results of Example A 5 with the results of Comparative Example A 3 clearly shows the effect of IC13 treatment on the total II.

Example A6

40 g of anhydrous magnesium chloride and 12.6 g of ethylbenzoate titanium tetrachloride complex in an argon atmosphere are charged into a 1-liter vibration mill. The mixture is then mixed and milled under the same conditions as in Example A1.

The ethylbenzoate complex was prepared by adding ethylbenzoate at room temperature to a dissolved titanium trichloride complex prepared under the same conditions as in Example A 4, and washing and drying the obtained green-gray crystals. Place 5 g of the mixed and ground solids in a 200 mL flask and add 50 mL of 1,2-dichloroethane and 0.5 g of iodine trichloride (dissolved in 1,2-dichloroethane). The mixture was refluxed for 2 hours. After the reaction, the solid obtained is washed by decantation to obtain a slurry of the titanium composition.

The polymerization was carried out under the same conditions as in Example Ais using 0.71 ml of a titanium composition suspension (containing 0.5 mg of titanium) and 20 mg of triethyl aluminum.

117 g of polymer are obtained. The yield based on titanium is 234,000 and the total II is 90.3 percent.

Comparative Example A 4

About 2.3 g of the ground solid obtained as in Example A6 was used to prepare a suspension of the ground solid (in 100 ml of hexane used as solvent). The polymerization was carried out in the same manner as in Example Ais using 0.81 ml of a slurry (containing 0.5 mg of titanium) and 20 mg of triethyl aluminum.

The polymerization is discontinued 50 minutes after initiation since the polymer formed forms a mass in the autoclave. 180 g of polymer are obtained. The yield based on titanium is 360,000 and the total II is 59.9%. The difference between the total II values ​​in Example A 6 and the comparative ones. Example A 4 is clearly evident.

Example A 7

In this example, SiC14 is used as the grinding additive. 40 g of anhydrous magnesium chloride, 12 ml of ethyl benzoate and 5.4 ml of SiCl4 are charged into a vibrating mill vessel. These were treated under the same conditions as in Example A1 (where the grinding time was 16 hours) and a ground solid was prepared. The mixture is then reacted with TlCl4 and contacted with ICl3 under the same conditions as in Example A1.

The polymerization was carried out in the same manner as in Example Ais using 2.94 ml of the obtained titanium composition suspension (containing 0.5 mg of titanium) and 40 mg of triethyl aluminum.

145 g of polymer are obtained. The yield based on titanium is 290,000 and the total II is 95.6 percent.

Example A 8

The grinding is carried out under the same conditions as in Example Ais except that 40 g of anhydrous magnesium chloride and 9.0 ml of methyl methacrylate in an argon atmosphere are introduced into a 1-liter vibrating mill vessel and the grinding is carried out for 16 hours.

g of the obtained milled solid is placed in a 200 ml flask. Reaction with TiCl4 and contact with ICl3 (where 0.5 g ICl3 is used) are carried out in the same manner as in Example Ala to obtain a slurry of the titanium composition.

The polymerization was carried out as in Example Ais using 3.18 ml of the obtained titanium composition suspension (containing 2.0 mg of titanium) and 80 mg of triethyl aluminum.

61 g of polymer are obtained. The yield based on titanium is 30,500 and the total II is 98.1%.

Example A9

The procedure of Example A1 was repeated until the reaction system was contacted with TiCl4, and then the system was contacted with IC1 (iodine chloride). To the solid mixture (I) is added 50 ml of 1,2-dichloroethane as solvent and 0.093 ml

IC1 (0.3 g). The mixture was maintained at reflux for 2 hours. After the reaction, the solid obtained is washed by decantation to obtain a slurry of the titanium composition.

The polymerization was carried out under the same conditions as in Example A1 using 1.85 ml of a titanium composition suspension (containing 0.5 mg of titanium) and 25 mg of triethyl aluminum.

107 g of polymer are obtained. The yield based on titanium is 214,000 and the total II is

96,3 %.

Example A 10

The procedure of Example A1 is repeated until the reaction system is contacted with TIC14 and then the system is contacted with iodine (I2). 50 ml of 1,2-dichloroethane as solvent and 0.5 g of I2 are added to the solid mixture. The mixture was then maintained at reflux temperature for 2 hours. After this reaction, the solid obtained is washed by decantation to obtain a slurry of the titanium composition.

The polymerization was carried out under the same conditions as in Example Ais using 1.15 ml of a titanium composition suspension (containing 0.5 mg of titanium) and 30 mg of triethyl aluminum.

62 g of polymer are obtained. The yield based on titanium is 124,000 and the total II is 97.6 percent.

Example A 11

A slurry of the titanium composition was prepared in the same manner as in Example A10, except that 0.35 g of bromine (Brz) was used instead of 0.5 g of I2.

The polymerization was carried out under the same conditions as in Example Ais using 1.92 ml of the obtained titanium composition suspension (containing 1 mg of titanium) and 40 mg of triethyl aluminum.

138 g of polymer are obtained. The yield based on titanium is 138,000 and the total II is 96.4 percent.

Example A 12

The solid component (A) was prepared by mixing and grinding 20 g of anhydrous magnesium chloride and 6 ml of ethyl benzoate for 48 hours as in Example A1 (1).

Separately prepare the solid component (B) by mixing and grinding 20 g of titanium tetrachloride (titanium tetrachloride reduced with aluminum) and 14.4 ml of ethyl benzoate for 48 hours in the same manner.

A solid component (C) is then prepared by mixing and grinding 15.8 g of component (A) and 4.2 g of component (B) for 5 hours.

g of solid component (C) is placed in a 200 ml flask and 100 ml of n-hexane and 0.4 g of ICl3 are added, and the mixture is refluxed for 4 hours.

The solid obtained is washed after decantation to give a titanium composition.

The polymerization was carried out as in Example A1 using 3.27 ml of the obtained titanium composition suspension (containing 1 mg of titanium) and 80 milligrams of triethyl aluminum.

186 g of polymer are obtained. The yield based on titanium (gpp / gTi) is 186,000 and total

II is 94.2%.

Example A 13

The solid component (A) was prepared by mixing and grinding 20 g of anhydrous magnesium chloride and 6 ml of ethyl benzoate for 48 hours as described in Example A 1 d).

Separately prepare the solid component (8) by mixing and grinding 20 g of titanium tetrachloride (titanium tetrachloride reduced with aluminum) and 11.5 ml of ethyl benzoate for 48 hours in the same manner.

A solid component (C) is then prepared by mixing and grinding 16.08 g of solid component (A) and 3.92 g of solid component (B) for 5 hours.

g of solid component (C) is placed in a 200 ml flask and 100 ml of n-hexane and 0.18 g of ICl3 are added. The mixture was refluxed for 4 hours.

After the reaction, the solid obtained is washed by decantation to give a titanium composition.

The polymerization was carried out as in Example A1 using 4.42 ml of the obtained titanium composition suspension (containing 1 mg of titanium) and 80 mg of triethyl aluminum. The polymerization was stopped after 20 minutes.

184 g of polymer are obtained. The yield based on titanium is 184,000 over a polymerization time of 20 minutes and the total II is 94.5%.

Comparative Example A 5

In this example, 2.79 g of the solid component (C) obtained as in Example A 13 was used to prepare a catalyst slurry (in 100 mL hexane as solvent). The polymerization was carried out as in Example Ais using 2.87 ml of a slurry (containing 2.36 mg of titanium) and 80 mg of triethyl aluminum. The polymerization was interrupted after 10 minutes.

257 g of polymer are obtained. The yield, based on titanium, was 109,000 over 10 minutes and the total II was 76.1%.

Example Β 1

1) Preparation of titanium composition g of anhydrous magnesium chloride and 9.0 ml of ethyl benzoate (ethylbenzoate / magnesium chloride molar ratio = 0.3) is placed in a 500 ml three-necked flask and suspended in 300 ml of 1,2-dichloroethane. The mixture is then maintained at reflux temperature for 3 hours with stirring.

After the reaction, 1,2-dichloroethane was distilled off under a stream of argon until almost complete removal, and then the system was dried under reduced pressure to give a white powder (preformed solid).

All the white powder obtained and 6.92 ml of TiCl4 (molar ratio of ethyl benzoate / TiCl = =) 1.0) are placed in a 1 liter internal vibration mill (containing stainless steel balls (JIS, SUS-27) (12.7 mm diameter (app. 800 ml))] and blended. It can be observed that once the white powder was contacted with TiCl 4, it turned into a yellow powder (which can be attributed to the complexing reaction of TIC 14 with ethyl benzoate).

The mixture is milled for 24 hours in a mill vessel at a frequency of 1410 vibrations per minute and an amplitude of 3.5 mm. About 9 g of the obtained milled solid is placed in a 200 ml flask.

50 ml of 1,2-dichloroethane as an inert organic solvent and 0.1 g of ICl 3 (dissolved in 1,2-dichloroethane) as an interhalogen are placed in a flask and stirred at 75 ° C for 2 hours. The solid obtained is washed by decantation (6 times with 100 ml of n-hexane) to give a titanium mixture (catalyst component of the invention).

The titanium concentration of the titanium composition suspension is determined colorimetrically with color development with hydrogen peroxide. The suspension of the composition is used in the following polymerization assay (titanium concentration in the suspension is 0.938 mg / ml). The solid titanium composition was also analyzed and a 1.82 wt% titanium content was found.

2) Polymerization of propylene (in liquid phase)

13 mg of triethyl aluminum (TEA) was charged to a 1 liter internal mixer with a stirrer, and then 0.426 .mu.l of a titanium composition suspension (containing 0.4 mg of titanium, an AltTi molar ratio of 13.6) was added under a propylene gas atmosphere. 850 ml of liquefied propylene monomer is added. The polymerization is then started and carried out for 1 hour at 70 ° C.

After the polymerization was completed and the remaining monomer was purified, 222.5 g of polymer (pp) was obtained. The yield based on titanium (gpp / gTi) is 556,200 'and the yield based on titanium composition (gpptg of the titanium composition) is 10,000 (these results are calculated from the titanium content of the titanium composition).

An extraction assay of the polymer with boiling n-heptane revealed a stereospecificity of the polymer (total II) of 95.7%.

Examples B1 to BIO

In accordance with the procedure of titanium. compositions of Example příkladu 1 were prepared to prepare solids of different composition with respect to a preformed solid mixture (ethylbenzoate (EB) / MgCl 2 ratio) and milled solid mixture (ethylbenzoatet TiCl 2 ratio), and exposed to IG13. The reaction with IC13, the type of solvent, the reaction conditions and the washing procedure are the same as in Example B1.

The polymerization of propylene is carried out as in Example B1; the results are given in Table I.

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Comparative Examples B1, B2 and B3

These examples are given to illustrate that when the ground solid alone obtained by the process of preparing the catalyst component of Example B1 is used as a catalyst, a very low catalytic effect is obtained.

Preformed and ground solids were prepared with the composition shown in Table II and the procedure outlined in Example B. 1. The channel ground solid was used without further treatment to prepare a slurry in n-hexane. Polymerization is carried out using the suspension, the results of which are given in Table II.

Examples zřejmé 1 to B 10 and Comparative Examples B 1, B 2 and B 3 show that the yield based on titanium, the yield based on the titanium composition and the total II is considerably higher due to interhalogen or halogen on the ground solid. in an inactive organic solvent.

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Example В И

1) Preparation of the titanium composition

This example illustrates the preparation of a preformed solid without using an inert solvent.

In an argon atmosphere, 20 g of anhydrous MgCl 2 and ethyl benzoate are charged to the above vibration mill vessel and contacted. In this case, the ethyl benzoate is added to the mill vessel in two 4.5 ml portions and is milled for 16 hours after each portion. The molar ratio of total ethylbenzoate / MgCl2 is 0.3.

7.7 ml of TiCl 2 (ethylbenzoate / TiCl 4 = 0.9 molar ratio) was added to the previously prepared solid. Once the white) preformed solid was contacted with TlCl4, it switched to a yellow solid. This can be attributed to the complexing reaction with the ester. The mixture was milled for 24 hours to give a milled solid.

About 10 g of the ground solid is placed in a 200 ml three-necked flask and 100 ml of 1,2-dichloroethane and 0.1 g of 1С1з are added, and the mixture is maintained at 75 ° C for 2 hours. After the reaction, the solid obtained is washed with hexane (100 ml) by decantation to give a titanium composition.

The titanium content in the titanium composition was found to be 1.68 wt. %.

2) Polymerization of propylene (in liquid phase)

The polymerization was carried out under the conditions and method of Example 1 (wherein the titanium content was 0.35 mg, the TEA content was 12 mg and the Al / Ti molar ratio = 14.4) using a suspension of the obtained titanium composition. 260 g of polymer are obtained. The yield based on titanium (gpp / gTi) is 743,000 and the yield based on titanium composition (gpp / g titanium composition) is 12,500. The total II, determined by the boiling n-heptane extraction test, is

96,3 %.

Examples В 12 to В 26

For the preparation of the solids according to the process for preparing the titanium composition in Example V11, different compositions of preformed solids (ethylbenzoate / MgCl 2 ratio; ethylbenzoate is added in two portions as in Example V11) and ground solids are then applied to the material 1С1з. Propylene polymerizations are carried out using the titanium compositions obtained, the results of which are shown in Table III.

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This example illustrates the case where the reaction with an interhalogen compound or halogen is carried out during the preparation of a preformed solid.

A method for preparing the titanium composition is used, but iodine (Ia) is added during the preparation of the preformed solid. A preformed solid is obtained using 20 g of anhydrous magnesium chloride, 10.5 ml of ethyl benzoate (molar ratio EB / MgCl2 = 0.35), 2.66 g of iodine (I2 / MgCl2 = 0.05) and 300 ml of ethyl acetate. , 2-dichloroethane.

The milled solid is obtained under the conditions and method of Example B1, but prior to grinding 8.1 ml of TiCl4 (molar ratio EB / T1Cl4 - 1.0) is added. About 10 g of the milled solid and 50 ml of 1,2-dichloroethane were treated at 75 ° C for 2 hours.

The polymerization is carried out as in Example B1 using a suspension of the obtained titanium composition; the following results are obtained:

yield based on titanium 490,000 yield based on titanium composition 8,800 total II 95.0%

The titanium composition was prepared by further adding 0.2 g of ICl3 after the milled solid in Example B27 was exposed to 1,2-dichloroethane. The reaction is carried out in the presence of ICl 2 and I 2 in 1,2-dichloroethane. In other words, the procedure is as in Example B27, but in addition to 1,2-dichloroethane, 0.2 g of IC13 is added.

The polymerization is carried out as in Example B1 using a suspension of the thus prepared titanium composition; the following results are obtained:

Yield based on titanium 515,000 Yield based on titanium composition 8,000 total II 97.2% Examples B 29, B 30 and B 31

In accordance with the data in Table IV, titanium compositions are prepared by treating various milled organic solvents with a ground solid in the presence of ICl 3 and polymerizing with these titanium compositions. The results are also shown in Table IV.

Table IV

<td rowspan="2">Example</td><td rowspan="2">Preparation of the ground solid</td><td rowspan="2">Solvent g ICl3, ° C / h</td><td rowspan="2">Ti content in titanium composition (mass, ⁰/O)</td><td colspan="3">Results of polymerization ^C&gt; ^(x)</td>

<td>yield based on titanium</td><td>yield based on the titanium composition</td><td>total II</td>

<td>B 29</td><td>a) x)</td><td>toluene 0,1 75/2</td><td> 2,01</td><td> 505 000</td><td> 10 200</td><td> 93,6</td>

<td>B 30</td><td>b) x)</td><td>mesitylene 0,1 75/2</td><td> 2,11</td><td> 378 000</td><td> 8 000</td><td> 93,8</td>

<td>B 31</td><td>and) ^(x)</td><td>chlorobenzene</td><td> 1,82</td><td> 743 000</td><td> 13 500</td><td> 93,3</td>

0,1 75/2

(x) (a) preparing a ground solid according to Example B 6 tb) preparing a ground solid according to Example B 5

c) The polymerization is carried out according to the method of Example 1 (Ti = 0.4 mg, TEA = 14 mg, Al / Ti molar ratio = 14.7).