CS235326B2 - Method of catalyst production for alpha-olefins polymerization - Google Patents

Abstract

Process for preparing a catalyst for polymerization alpha-olefins according to the invention in that one is allowed to react one molar part of organic aluminum salt β 0,1 aS 8 molar parts of electron donor in solvent at a temperature of from -20 to 200 ° C, to obtain a solid product (I) then this solid product (I) reacts with titanium tetrachloride at room temperature 0 to 100 ° C with the number of aluminum atoms to a number of titanium atoms from 0.05 to 10, then removing the liquid portion of the resulting material washing to give a solid product (II), free of TiCl 100% by weight 10 parts by weight of this solid product (II) 1000 parts by weight of alotrone donor and 10 to 1000 parts by weight of an acceptor electrons at temperatures from 40 to 200 ° C, thereby obtaining a solid product (III) wherein molar and weight parts are combined like moles and grams.

Description

The present invention relates to a process for the preparation of a catalyst for alpha-olefin polymerization, which permits in particular a gas phase polymerization and a modification of the gas phase polymerization by combining slurry or block polymerization and gas phase polymerization.

It is well known that alpha and olefins are polymerized using so-called Ziegler-Natta catalysts containing a transition metal compound IV. to VI. groups of the Periodic Table of the Elements and an organometallic compound of metals I · to III. groups of the Periodic Table of the Elements and further modified catalysts obtained by the further addition of an electron donor and the like. Of these catalysts, titanium tetrachloride catalysts are most commonly used, since this transition metal compound is widely used for the preparation of highly crystalline polymers such as propylene, 1-butene, etc.

The titanium tetrachloride can be divided into three types according to the production method:

CLAIMS 1. A compound obtained by reducing hydrogen chloride titanium tetrachloride followed by milling in a ball mill for activation. This substance is known as titanium tetrachloride (HA)

2. A compound obtained by reducing aluminum titanium dioxide, followed by milling in a ball mill for activation. It is represented by the general formula TiClyl / 3 AlCl 4 and is referred to as titanium tetrachloride (AA).

3. A compound obtained by reducing organoaluminium titanium tetrachloride compound followed by heat treatment.

Since none of these titanium tetrachlorides is entirely satisfactory, numerous modifications have been proposed. Among other things, a process has been proposed in which titanium tetrachloride obtained by reducing titanium tetrachloride with an organoaluminum compound is reacted with an electron donor and titanium tetrachloride, thereby increasing catalyst efficiency and reducing the amount of amorphous polymer by-product (see e.g. 34 478/1972). A disadvantage of the catalysts thus obtained is their lower thermal stability.

Further, a process has been proposed in which titanium tetrachloride and organoaluminum compound are mixed separately with some amount of a complexing agent (e.g. an electron donor), and the resulting two liquid mixtures are mixed with a reaction to obtain a solid catalyst component (Japanese Published Patent Application 9296). 1978). This process also has the disadvantage of reduced thermal stability as a catalyst has been described in the aforementioned Japanese Patent Application No. 34478/1972.

Further, a process has been disclosed in which a uniform liquid material consisting of an organoaluminum compound and an ether is added to or added to the titanium tetrachloride to obtain a titanium tetrachloride-containing liquid (Japanese Patent Application Publication No. 115 77/777). and a process in which the aforementioned liquid material is heated to a temperature of 150 ° C or lower to achieve precipitation of fine titanium tetrachloride particles (Japanese Patent Application Publication No. 47 594/1977, etc.).

However, these processes have also resulted in reduced thermal stability of the catalysts obtained.

On the other hand, there are known processes for the polymerization of alpha-olefins with the use of Ziegler-Natta catalysts in which alpha-olefins are in a different phase in suspension polymerization using a binder such as n-hexane and the like (e.g. The foolish polymerization takes place using a liquefied alpha-olefin monomer, such as liquefied propylene (for example, Japanese Patent Specifications 6).

686/1961 and 14 041/1963), and the polymerization ae is carried out in the gas phase using propylene gas (for example, Japanese Patent Nos. 14 812/1964 and 17 487/1967, etc.). Further, a method of blocked polymerization followed by gas phase polymerization is known (for example, Japanese Patent Specification No. 14,862/1974, Japanese Patent Application Publication No. 135,987 / 1976, and the like). there is no need to regenerate and reuse the solvent in the polymerization, such as in the slurry polymerization process, to recover and reuse the liquefied monomer, such as liquefied propylene, as in the bulk polymerization process. Therefore, the cost of obtaining a solvent or monomer is small and the equipment for producing poly-alpha-olefins is simplified. However, in the case of a gas phase polymerization process, but unequal gas phase catalyst particles, unequal catalyst particles are prone to form unequal polymer particles.

This in turn causes sintering of the polymer particles and clogging of the exit of the polymerization vessel or conveyor line, causing difficulties in long-term stabilized continuous operation and the quality of the polymer dispersion is coarser.

The present inventors have proposed a polymerization process which is not burdened by the above drawbacks, even in the case of gas phase polymerization, i.e., a process for producing polyalpha-olefins using a catalyst prepared by reacting an electron donor reaction product with an organoaluminum compound and titanium tetrachloride. the presence of an aromatic compound to form a solid product, or by reacting the solid product further with an electron donor to form a solid product and combining the thus obtained solid product with an organoaluminum compound.

The inventors have continued to study and the result of their efforts is a new catalyst.

It has been found that by using this catalyst to polymerize alpha-olefins, better polymerization results can be achieved compared to prior art catalysts. In this case, the disadvantages encountered in conventional processes are largely overcome in gas-phase polymerization.

The present invention relates to a process for the preparation of a catalyst for the polymerization of alpha-olefins of uniform particle size, high shelf life and thermal stability of the catalyst. When using this catalyst, the above-mentioned disadvantages do not occur with gas-phase polymerization. In doing so, Be can sufficiently show the advantages of gas-phase polymerization.

The process for the preparation of the catalyst according to the invention is characterized by reacting the reaction product (I) of the defined organoaluminum compound (A1) with the electron donor (B1) used, with titanium tetrachloride (C), to form a solid product (II), this solid product. (II) is further reacted with a defined electron donor (B2) with a defined electron acceptor (E) to form a solid product (III) and the solid product (III) binds with a defined organoaluminum compound (A2) to obtain a catalyst.

Better efficiency is obtained when the polymerization of the alpha-olefins of the invention is carried out in the presence of a pre-activated catalyst obtained by binding the solid product (III) with an organoaluminum compound as defined above and then reacting the alpha-olefin with the resulting combination. Said polymerization may be carried out in gas phase, in suspension or as bulk polymerization. Particularly in the case of gas phase polymerization or a combination of suspension or block polymerization with gas phase polymerization as a modification of the gas phase or bulk state polymerization, the advantages resulting from the gas phase polymerization are fully realized.

The production method of the catalyst according to the invention is described in more detail below.

The preparation of the catalyst proceeds by producing a solid product (III) which binds with an organoaluminum compound, or by reacting the resulting compound with an alpha-olefin to obtain a pre-activated catalyst as mentioned above.

The solid product (III) is produced as follows:

The organoaluminum compound is first reacted with an electron donor to form reaction product (I), which is reacted with titanium tetrachloride and then further with an electron donor and an electron acceptor to form a solid product (II).

The reaction of the organoaluminum compound (A1) with the electron donor (B1) is carried out in solvents (D), at a temperature of from -20 to 200 ° C, preferably from -10 to 100 ° C for 30 seconds to 5 hours. The process of adding the components (A1), (B1) and (D) is not limited and the ratio of the reactants is from 0.1 to 8 moles, preferably from 1 to 4 moles of electron donor and 0.5 to 5 liters, preferably 0.5 to 5 moles. 2 liters of solvent per mole of organoaluminum compound. Preferred solvents are aliphatic hydrocarbons. In this way, reaction product (I) is obtained. The reaction product (I) may be subjected to another reaction in the liquid state after completion of the reaction (this liquid will hereinafter be referred to as reaction liquid -CI)), without separating the solid product (I).

The reaction of the reaction product (I) with titanium tetrachloride (CC) is carried out at a temperature of from 0 to 200 ° C, preferably from 10 to 90 ° C, for 5 minutes to 8 hours. Although the reaction proceeds preferably without the use of a solvent, aliphatic or aromatic hydrocarbons may be used. Addition of component (I), (C) and solvent may be carried out in any order and mixing of the total amount is preferably complete within 5 hours. The reactants are used in the following amounts: solvent, 0 to 3000 ml per mole of titanium tetrachloride, ratio (Al / Ti) of the number of aluminum atoms in (I) to the number of titanium atoms in titanium tetrachloride; is 0.05 to 10, preferably 0.06 to 0.2. After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, followed by repeated washing with solvent to give a solid product (II) which can be used in the next step as suspended in the solvent or can be dried for longer used as a solid product.

The solid product (II) is then reacted with an electron donor (B2) and an electron acceptor (E).

Although this reaction may be carried out without the use of a solvent, advantageous results are obtained using aliphatic hydrocarbons. 10 to 1000 g, preferably 50 to 200 g of component (B2), 10 to 1000 g, preferably 20 to 500 g of component (E) and 0 to 3000 ml, preferably 100 to 1000 ml of solvent are preferably used, all based on 100 g of solid product (II). It is preferred to mix the three or four substances at a temperature of from -10 to 40 ° C for 30 seconds to 60 minutes and to react at 40 to 200 ° C, preferably 50 to 100 ° C for 30 seconds to 5 hours. The order of addition of the solid product (II), component (B2), component (E) and the solvent is not particularly limited, (B2) and (E) may be reacted beforehand before mixing with the solid product (II). The reaction of (B2) with (E) is carried out at a temperature of from 10 to 100 ° C for 30 minutes to 2 hours and the resulting product is cooled to 40 ° C or lower and used. Upon completion of the reaction of reaction product (II), (B2) and (E), the liquid fraction is separated and removed by filtration or decantation followed by repeated washing to give a solid product (III), which is used in the next drying and removal procedure. as a solid or suspended in a solvent

The solid product (III) thus prepared is in the form of spherical particles having a diameter of from 2 to 100 µm, preferably 10 to 70 µm, which particles have a narrow particle size distribution close to the average value of the aforementioned size. When the solid product (III) is observed in a microscope, channels are seen. The specific surface area of the solid product (III) is in the range of from 125 to 200 m ² / g. In contrast, the specific surface area of the inventive product XII) is in the range of 100 to 120 m ² / g. The above-mentioned higher specific surface area of the solid product (III) was achieved by reacting the electron donor (B2) and the electron acceptor (E) with the solid product (II). In the X-ray diffraction spectrum of the coating product (III), a broad and strong diffraction is observed near the lattice where d = 48.5.10 < -1 >

Absorption caused by the hydroxyl group near 3.450 cm ^-1 was not observed by measuring the infrared spectrum of the solid product surface (III). The solid product (III) has the special feature that it is thermally stable and even when stored at high temperatures of 30 to 50 ° C the properties of the resulting catalyst do not deteriorate as described below, the high thermal stability being based on said solid product structure ( III), the structure of which is formed under the reaction conditions of the invention.

The product (III) obtained is mixed with an organoaluminum compound in a ratio of 0.1-500 g of this compound per g of solid product (III) to form a catalyst, and optionally allowed to further react with an alpha-olefin to form a pre-activated catalyst. .

The organoaluminum compounds used in the process of this invention are represented by the general formula ^A1 V'n ^X 3- (n ₊ n '), wherein

R and R * each represent a hydrocarbon group such as an alkyl group, an aryl group, an alkaryl group, a cycloalkyl group, etc., or an alkoxy group,

X denotes halogen, such as fluorine, chlorine, bromine or iodine, and n and n 'denote any number given by the formula O <n + n' 3,

Particular examples of such compounds include trialkylaluminum such as trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-iso-butyl aluminum, tri-n-hexylaluminum, triisohexylaluminum, tri-2-methylpentyl aluminum, tri-n -oktylhliník, tri-n-decylhliník and the like, dialkylaluminiummonohalogenidy such as diethylaluminum monochloride, di-n-propylaluminum diisobutylaluminiummonochlorid, diethylaluminiuramonofluorid, disthylaluminiummonobromid, diethylaluminiummonojodid and the like, alkylaluminum such as diethylaluminum, and alkylaluminum halides,. such as methylaluminum, ethylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride and the like. Further, they can use alkoxy aluminum such as monoethoxydiethyl aluminum, diethoxyaonoethyl aluminum and the like. These organoaluminum compounds can be used as mixtures of one or more compounds of this kind. The organoaluminum compound (A1) to produce the solid product (I) may be the same or different from the organoaluminum compound (A2) used to bind with the solid product (III).

Different types of substances mentioned above can be used as electron donors in the process of the invention, however, it is preferred that the electron donors consist solely or predominantly (more than 50 mol%, based on the total number of moles of the donor) of ethers, or were used together with ethers. With respect to the electron donors used, organic compounds containing at least one oxygen, nitrogen, sulfur and phosphorus atom such as ethers, alcohols, esters, aldehydes, fatty acids, aromatic acids, ketones, nitriles, amines, amides, urea can be used. , thiourea, isocyanates, azo compounds, phosphines, phosphites, phosphinites, thioethers, thioalcohol, etc. Specific examples are ethers such as diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-pentylether, di-n-hexylether, di-isohexyl ether, di-n-octyl ether, diisooctyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol, monomethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran; alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, cresol, xylenol, ethylphenol, naphthol; esters such as ethyl methacrylate, ethyl acetate, butyl formate, amyl acetate, vinyl lactate, vinyl acetate, ethylbenzoate, propylbenzoate, butylbenzoate, octylbenzoate, 2-ethylhexylbenzoate, methyltoluylate, ethyltoluylate, methylethylhexyltoluylate, methylanisate, ethyllanisate2, ethylanisate6, ethylanisate6, ethylanisate 6 propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethylphenylacetate; aldehydes such as acetaldehyde, benzaldehyde; fatty acids such as formic acid, acetic acid, propionic acid, lactic acid, oxalic acid, succinic acid, acrylic acid, aaleic acid; aromatic acids such as benzoic acid; ketones such as methyl ethyl ketone, methyl isobutyl ketone, benzophenone; nitriles such as acetonitrile; amines such as methylamine, diethylamine, tributylamine, triethakolamine, beta- (N, N-dimethylamino) ethanol, pyridine, quinoline, alpha-picoline, Ν, Ν, Ν ', Ν'-tetranethylhexaethylenediamine, aniline, dimethylaainiline; amides such as formamide, hexamethyl phosphoric triamide, N, N, N ^/, N-N'-pentaaethyl beta dimethylaminoethylfosforečná, oktamethylpyrofosforaaid; ureas such as Ν, Ν, Ν ', Ν'-tetramethylurea; ioocyanates such as phenyl isocyanate, toluyl isocyanate; azo compounds such as azobenzene; phosphines such as etphaylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide; phosphites such as dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, triphenyl phosphite; dialkyl phosphinic acid derivatives such as ethyldiethylphosphonate, ethyldibulylphosphonate, phenyldiphenylphosphonate; thioesters such as diethylthioether, diphenylthioether, ethylphenylthioether, ethylenaulfide, propylenaulfide; and thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol. These electron donors can be used in a mixture. The electron donor (B1) for preparing the reaction product (I) may be the same or different from the electron donor (B2) to react with the solid product (II).

The electron acceptors used in this invention are represented by halides of elements III. to VI. groups of the Periodic Table of the Elements. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, tin tetrachloride, titanium tetrachloride, zirconium chloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, anti-thionium chloride and the like. These compounds can be used in admixture. Most preferred is titanium tetrachloride.

As solvents, aliphatic hydrocarbons such as n-heptane, n-octane, isoctane and the like can be used. In addition, aliphatic hydrocarbons or halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloroethylene, trichlorethylene, tetrachlorethylene and the like may be used instead. In addition, aromatic compounds such as aromatic hydrocarbons such as naphthalene and derivatives thereof substituted with alkyl substituents such as aesitylene, sulphate, ethylbenzene, isopropylhenzene, 2-ethylnaphthalene,

1-phenylnaphthalene and the like, and halides such as name chlorobenzene, o-dichlorobenzene etc.

The solid product (III) thus obtained is further mixed with the organoaluminum compound to give a catalyst which can be used in a manner known per se for the polymerization of alpha-olefins, optionally further reacted with an alpha-olefin to obtain a pre-activated catalyst, which can further be used to polymerize an alpha-olefin.

In the case of suspension polymerization or block polymerization, the catalyst obtained by contacting the solid product (III) with an organo-lithium compound also exhibits sufficient activity. In the case of gas-phase polymerization, it is preferable to use a pre-activated catalyst obtained by reaction with alpha-olefin, since the activated catalyst exhibits a higher efficiency. In the case of slurry or block polymerization followed by gas phase polymerization, the original (unactivated) catalyst may be used, in which case the necessary reaction with alpha-olefin will occur before the gas phase polymerization takes place. so that the resulting catalyst is similar to the pre-activated catalyst and my better performance.

Pre-activation is preferably carried out using 0.1-500 g of an organoaluminum compound, 0-50 liters of solvent, 0-1000 ml of hydrogen and 0.05-5000 g, and preferably 0.05-3000 g of elpholefin based on per 1 g of product (III), wherein the reaction of the alpha-elefin is carried out at a temperature of from 0 to 100 ° C for 1 minute to 20 hours, when 0.01 to 2000 g, preferably 0.05 to 200 g of alpha is reacted. -olefin.

The reaction of the alpha-olefin to the previous activation may take place in a solvent formed of aliphatic or aromatic hydrocarbons, or in a liquefied alpha-olefin, such as liquefied propylene, liquefied 1-butene and the like. It is also possible to carry out the reaction of alpha-olefin, such as ethylene, propylene, etc. in the gas phase. It is also possible to perform activation in the presence of a pre-prepared poly-alpha-olefin or hydrogen.

There are various catalyst activation procedures, such as

1. a process in which a slurry, block or gas phase reaction is carried out by contacting an alpha-olefin with a catalyst prepared by binding the solid product (III) to an organoaluminum compound, or

2. the solid product (III) binds with an organoaluminium compound in the presence of an alpha-olefin;

3. use the method of (1) or (2) in the presence of a poly-alpha-olefin,

4. the process is carried out using any one of (1), (2) or (3), in the presence of hydrogen, etc.

Of the alpha-olefins, straight chain monoolefins such as ethylene, propylene, 1-butene, 1-hexene, t-heptene, 1-octene, 1-decene and the like can be used for prior activation of branched chain monoolefins such as 4-methyl-1-pentene, 2-methyl-1-pentene, 3-methyl-1-butene etc. and styrene. These alpha-olefins may be the same or different from the olefins to be polymerized to be used for the previous activation of the catalyst, or may be used in a mixture.

Upon completion of the previous activation, the solvent and unreacted alpha-olefin are removed, for example by distillation under reduced pressure, and after drying, the powder obtained is used for subsequent polymerization or the solid product may be suspended in solvent at 80 liters or less per g of solid product. the suspension obtained for subsequent polymerization.

The pre-activated catalyst thus obtained may be used for slurry polymerization of alpha-olefins carried out in a hydrocarbon solvent such as n-hexane, n-octane, benzene, toluene and the like, or for bulk polymerization carried out in a liquefied monomeric alpha-olefin, for example on liquefied propylene, liquefied butene, etc., but may preferably be used for gas phase polymerization. The desired activity of the catalyst is also achieved in the case of modification of the gas phase polymerization, i.e. using slurry polymerization, followed by gas phase polymerization, or block polymerization, followed by gas phase polymerization.

The gas phase polymerization of alpha-olefins may be carried out in the absence of a solvent such as n-hexane, n-heptane, etc., and may also be carried out in the presence of solvent in an amount of 0 to 500 g per kg of poly-alpha-olefin particles. The polymerization can be carried out continuously or in batches. The polymerization can also be carried out in a fluidized bed or in that the fluidization is controlled by the mixing elements. The polymerization can also be carried out using vertical or horizontal type blades of the stirrer blades.

Slurry or block polymerization of alpha-olefin followed by gas phase polymerization may be carried out in batches. For example, the process ()) may be removed in which the solvent or liquefied alpha-olefin is removed after slurry or bulk polymerization, and the gas phase polymerization is successively carried out, feeding the gaseous alpha-olefin; In process (2), a slurry or block polymerization is carried out and while the polymerization proceeds without removal of the solvent or alpha-olefin, the solvent or liquefied alpha-olefin is contained in the polymer particles, losing the liquid portion and hence the previous form of polymerization. continuously changes in gas phase polymerization;

in process (3), the slurry or block polymerization is continued until the solvent or alpha-olefin content per kg of polymer particles is 500 g or less, followed by gas phase polymerization, gas phase alpha-olefin feed, etc.

This multistage polymerization consisting of a combination of slurry or block polymerization with gas phase polymerization results in the desired results, especially in the case of continuous polymerization. For example, slurry or block polymerization may be carried out in the first step until a polymer containing 30% or less of solvent or liquefied alpha-olefin is obtained, or the solvent or liquefied alpha-olefin is removed and then the gas phase alpha-olefin polymerization is carried out in the second stage while fluidizing the polymer particles.

The catalyst of the first stage is used in the gas phase polymerization of the second stage, but even the addition of fresh catalyst in this second stage does not prevent the activity of the invention. The two-stage polymerization is preferably carried out so that the weight ratio of the slurry or block polymerization polymer to the gas phase polymerization polymer in the final polymer is 0.1 to 100 parts of the latter polymer to 1 part of the former polymer.

With respect to the alpha-olefin polymerization conditions, any of the known slurry, block, or gas phase polymerizations can be carried out under conditions where the alpha-olefin polymerization is carried out at room temperature (20 ° C) to 200 ° C. , at a polymerization pressure of atmospheric pressure (100 kPa) to a pressure of 5 MPa and usually for 5 minutes to 10 hours. In the polymerization, a suitable amount of hydrogen can be added in a conventional manner to adjust the molecular weight.

As the alpha-olefins, straight chain monoolefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc., branched chain monoolefins such as 4-methyl-1-ol may be used for the polymerization of the invention. pentene, 2-methyl-1-pentene, 3-methyl-1-butene etc., diolefins such as butadiene, isoprene, chloroprene etc., styrene and the like. These olefins may be homopolymerized or copolymerized in combination with each other, for example, in the combination of propylene with ethylene, butene with ethylene, or propylene with 1-butone. In this case, it is possible to polymerize the monomer mixture or in several stages using different alpha-olefins in the first stage in suspension or block polymerization, followed by a second stage in the form of a gas-phase polymerization.

A first advantage of the process according to the invention is that the average diameter of the polymer particles is small and the face of the particles approaches spherical, with the particle size distribution being small and the amount of large and too small particles being reduced. In the case of gas-phase polymerization, the polymer particle stream is continuous and a long-term stabilized continuous process is possible. Therefore, gas-phase polymerization is preferred. In the case of gas-phase polymerization alone, the cost of solvent and monomer recovery can be reduced. In addition, in the case of slurry or block polymerization followed by gas phase polymerization, it is possible to achieve a concentration of solvent or liquefied alpha-olefin contained in the polymer of 30% or less based on the first stage of slurry or block polymerization and evaporate the unreacted monomer. of the reaction mixture in a sequential gas phase.

A second advantage of the process according to the invention is that the storage stability of the catalyst is increased. For example, if the solid product (III) was left at a temperature of about 30 ° C for 4 months, there was no significant decrease in polymerization activity. As a result, no special storage device is needed, for example for storing the solid product (III) at 0 ° C. Although the solid product (III) is left at a high concentration of 1.0% or higher at 30 ° C or higher, for one week for scanning the solid product (III) with the erganoaluminum compound without starting polymerization, grinding to a fine powder caused by agitation in the catalyst container hardly occurs. The shape of the polymer particles was not degraded and the polymerization efficiency was not reduced. This advantage will further increase the prior activation of the alpha-olefin catalyst.

A third advantage of the process of the invention is the improved thermal stability of the catalyst during polymerization. Even if the polymerization is carried out at a relatively high temperature of 70 ° C or higher, the resulting polymer particles are not comminuted to a fine powder and, in the case of suspension polymerization, are not wetted by the solvent. It follows that the applicable temperature range to control the temperature in the polymerization vessel during polymerization is extended, resulting in a long-term stabilized operation.

a fourth advantage of the present invention is that polymer particles having a high bulk density are obtained. The bulk density of the polymer is 0.45 to 0.52, allowing the use of a small volume of polymerization vessel or container at a given polymer weight.

A fifth advantage of the process according to the invention is that a highly crystalline poly-alpha-olefin is obtained. For example, in the production of polypropylene, the isotactic index (the ratio by weight of isotactic polypropylene insoluble in n-hexane (at 20 ° C) to 100 parts by weight of the total amount of polymer formed) is 98 to 99.8, and the physical properties, particularly the rigidity of the polymer, without separation of the atactic polymer. As a result, further steps can be omitted.

The present invention will be illustrated by way of examples.

Example)

1. Preparation of Catalyst n-Hexane (60 mL), diathylaluminum monochloride (DEAC) (0.05 mol) and diisoaoyl ether (0.12 mol) were stirred at 25 ° C for one minute and then allowed to react for 5 minutes at the same temperature to give reaction liquid (I) (the molar ratio of diisoamyl ether to diethylaluminum monochloride was 2.4). To the reactor purged with nitrogen and heated to 35 ° C was added TiCl 2 in an amount of 0.4 mol. The entire amount of the above reaction liquid (I) was added dropwise to the reaction mixture. The addition lasted 30 minutes and the reaction mixture was maintained at the same temperature for an additional 30 minutes, after which the reaction temperature was raised to 75 ° C and the reaction continued for one hour. The reaction mixture was cooled to room temperature to remove the top layer, then the procedure was repeated with 400 ml of n-hexane and the top layer was removed by decantation. This procedure was repeated four times to give 19 g of solid product (II). The entire amount of product (II) was suspended in 300 ml of n-hexane, and to the resulting suspension was added 16 g of diisoamyl ether and 35 g of TiCl 2 at 20 ° C. The addition took about one minute. Then the reaction was continued at 65 ° C for one hour. After completion of the reaction, the resulting material was cooled to room temperature (20 ° C), then the top layer was decanted by adding 400 ml of n-hexane five times, stirring the reaction mixture for <0 minutes and standing on top to separate the top layer. drying under reduced pressure gave the solid product (III).

2. A process for producing a pre-activated catalyst

Stainless steel reactor! 2 liters of steel, equipped with slanted blades, was purged with nitrogen. 20 ml of n-hexane, 420 mg of diethyl aluminum ammonium chloride and 30 mg of solid product (111) were introduced into the reactor at room temperature. Further, 150 ml of hydrogen were introduced and the reaction was carried out under a partial pressure of propylene of 500 kPa for 5 minutes.

Unreacted propylene, hydrogen and n-hexene were then removed under reduced pressure to give a pre-activated catalyst in powder form (reacted propylene: 80.0 g on solid product (III)).

3. Propylene polymerization process

300 ml of hydrogen were introduced into the reactor containing the pre-activated catalyst mentioned above and gas phase polymerization was carried out under a propylene partial pressure of 2.5 MPa and a polymerization temperature of 70 ° C for 2 hours. After completion of the reaction, 5 g of ethanol were added, the reaction mixture was heated at 70 ° C for 30 minutes and then cooled to room temperature. Drying gave 156 g of polymer. The polymer yield was 5200 g per g solid product (III); isotactic index 99.8; and a bulk density of 0.50. The shape of the polymer particles was spherical. 97.4% of the polymer particles had a size between 1410 and 234 µm, with no fine powder or lumps being observed.

The presence of a colored polymer was not detected and the Sulfur Index was 3.0.

Comparative Example 1

Example 1 was repeated except that solid product (II) was used instead of solid product (III).

Comparative Example 2

The solid product, corresponding to the solid product (III), was prepared according to the procedure of Example 1 except that isoamylether was not used in the reaction of the solid product (I) (the solid products to be mixed with the organoaluminum compound obtained according to the procedures given in the comparative examples) hereinafter referred to as the final solid product (III) and this final solid product hereinafter referred to collectively as the solid catalyst component). The final solid product was pre-activated according to Example 1. Using this activated catalyst, proplylene was polymerized according to Example 1.

Comparative Example 3

Example t was repeated except that diisoamyl ether (0.12 mol, 19 g) was not used in the preparation of reaction product (I), but this amount of 19 g was added to 16 g of diisoamyl ether used in the subsequent reaction and solid product (11). ).

Comparative Example 4

Example 1 was repeated except that TiCl * was not used for the reaction and solid product (II) in the preparation of the solid product (III) of Example 1.

Comparative example 5

The procedure of Example 1 was repeated except that diisoamyl ether was not used in the formation of the solid product (II) of Example 1.

Comparative example 6

Example 1 was repeated to make the solid (II) of Example 1 replaced by the product obtained by adding 0.05 mol of diethylaluminium chloride to a solution of 0.4 mol of TiCl 2 and 0.12 mol of diisoamyl ether at 35 ° C. The addition was carried out for 30 minutes, and the mixture was maintained at the same temperature. The temperature was then raised to 75 ° C and the reaction continued for a total of one hour.

Comparative example 7

Example 1 was repeated β except that unreacted TiCl 2 was not removed from the reaction mixture after formation of the solid product (II), but the volume of the reaction mixture was made up to 400 mL with n-hexane and the resulting mixture was used for the next reaction.

The results of Example 1 and Comparative Examples 1 and 7 are shown in Table 1.

Table, Example Yield of Poles- * Isotact. Bulk specific Share passing _RTT x) _Iž xx) mer number per g index wt. okem okem solid components 1 410 4 699 katsl. to jUffl 234 jua (») 1 200 99.8 0.50 97.4 0 4.2 3.0

Comparative

examples 1 1 100 ALIGN! 98.5 0.40 60.0 30 3.9 17.5 2 80 96.5 0.25 60.0 34 4.3 ? 20 3 50 4 2 800 95.0 0.40 80.0 12 4,5 8.8 5 1 800 98.0 0.40 58.3 10 4.1 9.9 6 1 400 96.0 0.40 56.0 15 Dec 4.3 12.6 7 1 900 95.0 0.41 54.0 22nd 3.5 9.0

Explanation of Table 1 and Table 13:

^X ^ BTT «melt flow rate (according to ASM D-1238 (D)« index of torsion (according to JIS K7103)

Example 2

The procedure of Example 1 was repeated except that in the preparation of the solid product (II) and Example 1, TiCl 2 and the dropwise addition of reaction liquid (I) were maintained at 12 ° C for 45 minutes and the resulting mixture was maintained. at 35 ° C for 60 minutes. The resulting solid product (III) was brown in color.

Example 3

The procedure of Example 1 was repeated with the difference that in the production of the solid product (11) of Example 1, the temperature increase to 75 ° C after the dropwise addition of reaction liquid (I) to TiCl 2 was changed to 65 ° C. The resulting product (III) was brown in color.

Example 4

Instead of reacting dilsoamyl ether and TiCl4 with the solid product (II) of Example 1, 38 g of dilsoamyl ether, 12 g of SiCl4 and 17 g of TiCl4 were added to 200 [mu] l of n-hexane at alatnoate (20 [deg.] C.) over one minute. solid product (II) (19 g) was added and the reaction was allowed to proceed at 75 ° C for 2 hours. Thereafter, the reaction mixture was washed with n-hexane, dried to give a solid product (III). Activation of the catalyst and propylene polymerization was carried out as described in Examples 1, 2 and 3.

The results of Examples 2 to 4 are shown in Table 2.

Table 2

Example Pollen yield - Aeroact number per g index of the solid component cat.

Bulk density.

Share passing okem okem 1 410 4 699 to 7 " 234 µm (») (*)

IŽ «>

2 5 100 ALIGN! 98.9 0.49 96.5 0 4.3 3.0 3 5 000 98.5 0.50 98.0 0 4.2 3.1 4 5 200 99.2 0.50 92.0 0 4.3 3.0

Example 5 al n-heptane, 0.16 mol of di-n-butylamino and monochloride and 0.10 mol of di-n-butyl ether were mixed at 30 ° C for 3 minutes and allowed to react for 20 minutes to the reaction liquid (I). The entire amount of this product (I) was added dropwise over 60 minutes to a solution consisting of 50 µl of toluene and 0.64 mol of TiCl 2 while maintaining the reaction mixture at 45 ° C. The temperature was then raised to 85 ° C and the reaction continued for 2 hours. After the temperature of the reaction mixture was lowered to room temperature, an additional upper layer was added and 300 ml of n-heptane was added twice, and the upper layer of the components was removed by decantation. 49 g of solid product (II) were obtained. The total amount of this product (II) was suspended in 300 ml of n-heptane, and 20 g of di-n-butyl ether and 150 g of TiCl2 were added at room temperature for 2 minutes. Subsequent reaction was carried out at 90 ° C for 2 hours, then the reaction mixture was cooled, decanted, washed with n-heptane and dried to give the solid product (III). Subsequent activation of the catalyst and propylene polymerization proceeded as described in Examples 1, 2 and 3.

Comparative example 8

The procedure of Example 5 was repeated except that the solid product (II) of Example 5 was used instead of the solid product (III).

Example no

0.057 aol of diethylaluainine monochloride and 0.15 vol of diisoavylether were added dropwise to 40 [mu] l of n-hexane at 18 [deg.] C. for 5 minutes, then allowed to react at 35 [deg.] C. for 30 minutes. The resulting reaction liquid was added dropwise to 0.5 vol TiCl * at 35 ° C for 180 windings, the reaction continued at 35 ° C for 60 windings, after the temperature rose to 75 ° C and the temperature was heated for 60 windings, then the temperature was lowered to the temperature of temperature (20 ° C), the upper layer was removed, 400 µl of n-hexane was added twice, and the upper layers were removed by decantation. The entire product was suspended in 100 µl of n-hexane and 12 g of diisoavylether was added to the resulting slurry and the reaction was continued at 35 ° C for one hour.

Next, 12 g of diisoavylether and 72 g of TiCl 3 were added at 35 ° C, the temperature was raised to 65 ° C and the reaction continued for one hour, after which the reaction mixture was cooled to room temperature (20 ° C), decanted. , washing with n-hexane and drying to obtain a solid product (III). Subsequent preparation of the activated catalyst prenes and propylene polymerization was carried out as described in Example 1.

Example 7

The procedure of Example 6 was repeated except that in the preparation of the reaction product (1) 0.06 vol of diisopropylaluvinone monochloride was reacted with 0.14 vol of di-n-octyl ether.

Example

The procedure of Example 6 was repeated except that 0.72 vol TiCl4 was used to prepare the solid product (II) for the reaction and the solid product (I).

EXAMPLE 9 g of the solid product (II) obtained in Example 6 were suspended in 200 ml of toluene and 10 g of TlCl4 and 26 g of di-n-butyl ether were added thereto, and the reaction was carried out at 50 DEG C. for 180 minutes. after which the reaction was cooled to the heat of temperature (20 ° C), decanted, washed with n-hexane reinforcement to give the solid product (III). Subsequent preparation of activated catalyst feeds and propylene polymerization were carried out as in Example 1.

Example 10

0.03 aol of trlieobutyl aluminum and 0.07 aol of di-n-dodecyl ether were reacted in 100 [mu] l of n-hexane at 20 [deg.] C. for 30 minutes. The resulting reaction liquid was added dropwise to 0.15 aol of TiCl 2 for 120 minutes at 20 ° C and then maintained at 30 ° C for 30 minutes. The temperature was then raised to 50 ° C and the reaction continued for 60 minutes. After completion of the reaction, decantation was performed to remove the top layer, sweeping n-hexane and drying to give 23 g of solid product (II), which was then suspended in 50 ml of n-heptane. To the resulting suspension was added 21 g of di-n-butyl ether and 40 g of TiCl 3, the reaction was continued at 50 ° C for 140 minutes. After this, the reaction mixture was cooled, the upper layer removed by decantation, the remainder was n-hexanes washed and the solid obtained (III). Subsequent preparation of the preactivated propylene polymerization catalyst was carried out as described in Example 1.

Example li

0.07 mol of triethyl aluminum and 0.15 mol of dl-n-propyl ether were mixed with 45 ml of octane at 20 ° C for 2 minutes and the reaction continued at the same temperature for 30 minutes to give reaction product (1) which was added dropwise over 4 hours at 32 ° C to 0.6 mol of TiCl 2 and held at 35 ° C for one hour, then raised to 78 ° C and the reaction continued for 2 hours, after which the reaction mixture was cooled to 20 ° C, the top layer was removed by repeated addition of 400 mL of n-hexane and decanting (5 times), confirmed by the absence of TiCl 2, followed by filtration and drying, yielding 23 g of solid product (XI).

mole of di-n-pentylether and 5 g of anhydrous AlCl 1 was added to 300 ml of n-heptane and the reaction was carried out at 80 ° C for 2 hours while the AlClp was expanded and the reaction mixture was cooled to 30 ° C. of the solid (11), the reaction continued for 2 hours at 80 ° C, then the reaction mixture was cooled to room temperature, the upper layer was removed three times by adding 300 ml of n-hexane and decanting, followed by filtration and drying of the residue. (III).

Subsequent preparation of the pre-activated catalyst and propylene polymerization was carried out as described in Examples 1, 2 and 3.

The results of Examples 5-11 and Comparative Example 8 are shown in Table 3.

Table 3

Example number Yield of polymer per g of solid catalyst component laotakt. index Bulk density Share passing iž «) okem 1 410 to 234 μ » okem 4,699 pm (*) rtt * ' 5 5 100 99.6 0.50 94.8 0 3. « 2.9 8 3 100 98.6 0.40 80.0 12 4,5 8.1

Comparative examples

6 5 900 99.0 0.50 96.8 0 3.6 1,8 7 5 000 98.4 0.46 90.0 0 3.8 3.1 8 5 600 99.0 0.48 95.0 0 3.6 2,0 9 5 200 99.0 0.50 93.8 0 3.3 2.1 10 5 000 98.6 0.45 92.1 0 3.8 3.1 11 5 100 99.5 0.50 94.8 0 4.1 3.5

Example.

ml of n-pentane, 160 mg of diethylaluminum monochloride, 32 mg of solid product (III) obtained according to Example 1 and 5 g of polypropylene powder were fried in the reactor described in Examples 1 and 2, after which n-pentene was removed under reduced pressure. The gas-phase reaction was carried out under a partial pressure of propylene of 80 kPa at 30 ° C for 20 minutes while the catalyst was fluidized peopylene. Thereafter, unreacted propylene was removed to give a pre-activated catalyst (the ratio of reacted propylene per g of solid product (111) was 1.8 g). Use of the obtained catalyst and propylene polymer in the gas phase was carried out as described in Examples 1 and 3.

23532 »

Example 1 a d 13 '

At 20 DEG C., 120 mg of di-n-butylaluminum chloride and 25 mg of the solid product (III) obtained from Example 5 were added to 30 g of propylene, and the reaction was carried out under a partial pressure of propylene of 980 kPa for 10 minutes, then unreacted propylene. removed to give a pulverulent pre-activated catalyst (reacted propylene per g solid product (111): 120 g). The use of the resulting catalyst and gas phase polymerization was carried out as described in Examples 1 and 3.

Example 14

The procedure of Example 1 was repeated except that ethylene was used in place of propylene when activating the catalyst of Example 1. Ethylene was allowed to react with a partial pressure of ethylene of 100 kPa at 35 ° C for 10 minutes (ratio of reacted ethylene per g solid product (111): 2.4 g).

Example 1

Example 1 was repeated except that 1-butene was used instead of propylene for the orbital activation of Example 1, the reaction being carried out under 1-butene partial pressure of 50 kPa at 35 ° C for 10 minutes (the proportion of 1-btitene converted to g of solid product (111): 0.3 g).

Example 16

Example 1 was repeated with the difference that instead of 420 mg of diethylaluminum monochloride in the example. 1 and 2, 380 mg of diisopropylaluminum monochloride was used.

Example 17

The pre-activation according to Examples 1 and 2 was repeated except that 320 mg of triethyl aluminum was used instead of 420 mg of diethylaluminum monochloride used in Examples 1 and 2. Subsequently, the polymerization of Example 1 (3) was repeated except that the ethylene was polymerized under a hydrogen overpressure of 1.2 MPa and a partial overpressure of ethylene of 1.2 MPa at 85 ° C.

The results obtained in Examples 12-17 are shown in Table 4.

Table 4

Example Yield polyether aer per g

Ieotakt.

index

Loose moderate Percentage passing through the eye's eye

Pevná ^χ ) I ^{* 1} *) solid catalyst components

410 4 699 to pa

234 jua (») (»)

17

100 5,000 5,000 5,100 5,000 5,800

99.3

99.0

98.8

98.9

99.5

0.48

0.46

0.45

0.45

0.48

0.46

90.8

92.5 92.0 92.0

96.5 92.0

4.3

3.8

3.8

3.6

3.8

4.1

2.9

2.8

2.8

2.9

2.9

2.3

Example 1 a d 18

Pre-activation of the catalyst was carried out according to the procedure of Example 1, (1) and (2). 1,000 al n-hexane and 150 ml hydrogen were added to the resulting catalyst. The polyyaerial reaction in suspension was then carried out under a partial pressure of propylene of 1.2 HPa at 70 ° C for 2.5 hours, and the n-hexane was removed by stripping with steam. The process ee obtained the polymer.

Example 19

The pre-activated catalyst was prepared according to the procedure of Example I, (1) and (2), and the block polymerization was carried out after addition of 300 ml of hydrogen and 600 g of propylene under propylene partial pressure of 3.1 HPa at 70 ° C for 1 hour. After completion of the reaction, unreacted propylene was depleted and the polymer was further processed as described in Example 1.

Example 20

The pulverulent, pre-activated catalyst was prepared in the reactor described in Example 1, (1) and (2). After introducing 300 [mu] l of hydrogen and 200 g of propylene, block polyaeration was carried out at a partial pressure of propylene of 2.6 HPa at 60 [deg.] C. for 30 minutes to obtain 35 g of reacted propylene. Subsequently, the resulting unreacted propylene slurry was introduced into a fluid bed having a diameter of 20 cm and a volume of 20 liters and equipped with stirrers, while propylene was circulated to fluidize the polymer at a flow rate of 5 ca / a and gas phase polyaeration was performed at propylene partial pressure. 2.1 HPa at a reaction temperature of 70 ° C for 2 hours. The post-treatment to obtain the polymer was carried out as described in Example 1.

Example 21

The block polyaeration was carried out as in Example 8 under a pressure of 2.6 HPa for 30-30 minutes at 60 ° C. The unreacted liquefied propylene was transferred to a separate feed tank connected to the reactor. The temperature of the reactor was raised to 72 ° C and gas phase polyaeration was carried out for 2 hours while propylene was fed from the feed tank to the talp reactor to produce a polyaeration overpressure of 2.6 HPa. Subsequent processing was carried out as described in Example I to obtain a polyaer.

Example 22

The block polymerization was carried out at a pressure of 2.6 MPa at 60 ° C for 30 minutes as described in Example 20. Thereafter, the polymerization temperature was raised to 70 ° C to obtain a polymerization pressure of 3 MPa. If the polymerization was left untreated, the pressure was reduced to 2.6 MPa in 40 minutes. That is, the block polymerization was continuously converted to a gas phase polymerization. The propylene feed was carried out in an amount corresponding to an overpressure of 2.6 MPa for 60 minutes, gas phase polymerization. The post-treatment to obtain the polymer was carried out as described in Example 1.

Example 23

000 ml of n-hexene, 320 mg of diethylaluminum monochloride and 18 mg of the solid product (111) obtained according to Example 5 were reacted with propylene under a partial pressure of propylene of 120 kPa at 20 ° C for 10 minutes to pre-activate the catalyst ( ratio of propylene reacted per g solid product (111): 0.6 g). Unreacted propylene was removed and 120 ml hydrogen was introduced. The slurry polymerization was carried out at a partial pressure of propylene of 1.0 MPa at 70 ° C for 2.5 hours.

The n-hexane was then removed by steam stripping to obtain the polymer.

EXAMPLE 24 ml of n-pentane, 280 mg of diethylaliminium monochloride and 25 mg of solid product (III) obtained according to Example 5 were reacted. The propylene was allowed to react at 15 ° C and its partial pressure increased. The pressure increase to 500 kPa took place in 5 minutes (100 kPa / min). Pre-activation of the catalyst was performed for 5 minutes (ratio of propylene reacted per g solid product (111): 3.2 g).

Unreacted propylene was removed and 200 ml of hydrogen was transferred to the reaction mixture.

The slurry polymerization was carried out at a partial pressure of propylene of 1.0 MPa at 70 ° C for 60 minutes (reacted propylene: 63 g). The resulting solvent-containing slurry was introduced into a fluidized bed equipped with stirrers, followed by gas phase polymerization of propylene as described in Example 20.

Example 25

000 ml of n-hexane, 320 mg of diethylaluminum monochloride and 30 mg of the solid product (III) obtained in Example 5 (1) were reacted without prior activation by introducing 120 ml of hydrogen and subsequent slurry polymerization under a partial pressure of propylene of 10 MPa at 70 ° C, for 2.5 hours. Then, n-hexane was removed by steam stripping to obtain a polymer.

Example 26

Using the catalyst without prior activation, propylene slurry polymerization was carried out as described in Example 25. Subsequently, unreacted prooylene and hydrogen were removed, and n-hexane was distilled off under reduced pressure to a n-hexane content of 30% polymer. containing the solvent was introduced into a fluidized bed equipped with the stirrers described in Example 20. Thereafter, 450 ml of hydrogen were introduced and gas-phase polymerization was performed at a propylene partial pressure of 2.1 MPa at 70 ° C for 2 hours as described in Example 20. The following treatment to obtain the polymer was carried out as described in Example 1.

The results obtained in Examples 18-26 are shown in Table 5.

Table 5

Example Number Yield of polymer per g of solid catalyst component leotact. index Bulk density Share passing _RTT x) _Iž xx) okem 1 410 to 234 μα (») okem 4 699 JiTB (») 18 5 400 99.8 0.48 97.6 0 2.6 2.3 19 Dec 5 000 99.6 0.47 95.0 0 2.9 2.8 20 May 5 800 99.3 0.48 93.6 0 2.6 . 2.9 21 5 900 99.2 0.46 94.5 0 2.8 2.1 22nd 5 700 99.2 0.48 93.6 0 2.8 2.4 23 5 300 99.6 0.50 93.2 0 1,8 2.6 24 5 800 99.0 0.49 92.0 0 a, 4 2.8 25 4 500 98.2 0.45 91.0 0 1.6 3.5 26 5 980 98.5 0.45 90.0 0 1,8 2.1

Example 1 and d 27

Propylene β ethylene · block copelyaeration was carried out as described in Example 26, except that in the first stage propylene slurry polymerization was carried out and in the second stage gas phase polymerization under a partial hydrogen overpressure of 800 kPa and a partial overpressure of ethylene was carried out. 2 KPa at 70 ° C for 2 hours to effect ethylene polymerization.

Example 28

Example 20 was repeated except that an alpha-olefin containing 200 g propylene and 20 g ethylene was used instead of 200 g propylene. A propylene-ethylene copolymer was obtained.

Example 29

Example 28 was repeated β except that 30 g of i-butane was used instead of 20 g of ethylene to obtain a copolymer of propylene and 1-butane.

Example 30

Example 1 was repeated to obtain the polymer except that using a pre-activated catalyst, ethylene was polymerized at a hydrogen pressure of 1.2 MPa and a partial pressure of ethylene of 1.2 MPa at 85 ° C, instead of using 300 mL of hydrogen and a partial pressure of propylene 2.5 MPa at 70 ° C.

The results of Examples 27-30 are shown in Table 6.

Table 6

Example number Yield of polymer per g of solid catalyst component Isotact. index Bulk density Share passing RTT ^x) I _ž xx) ekem 1 410 to 234 ua okem 4 699 jam (*) 27 Mar: 5 900 98.0 0.45 90.0 0 1.6 2.3 28 5 900 98.1 0.46 91, 5 0 3.6 2.1 29 5 800 98.5 0.46 90.0 0 3.8 2,0 30 5 300 - 0.45 90.0 0 *, 2 2.5

Example 31

The solid product obtained in Example 1 was stored at 30 ° C for 4 months. The polymerization was then carried out as described in Example 1, (2) and (3).

Comparative Examples 9 to 12

The solid products obtained in the following example and the comparative examples were stored for 4 months at 30 ° C. Then, using these compounds instead of the solid product (111), the propylene activation activation and polymerization was carried out as described in Example 1, (2), (3).

Comparative Example 9: The solid product (XI) obtained in Example 1

Comparative Example 10: The final solid product obtained in Comparative Example 4.

Comparative Example 11: The final solid product obtained in Comparative Example 6.

Comparative Example 12: The final solid product obtained in Comparative Example 7.

The results of Example 31 and Comparative Examples 9 to 12 are shown in Table 7.

Table 7

Example number Yield of polymer per g of solid catalyst component Isotact. index Bulk density Share passing HTT ^x) IŽ «> okem 1 410 to 234 pm okem. 4 699 (»1 31 4 600 99.0 0.45 91.8 0 4.1 3.0 Comparative examples 9 600 98.0 0.40 55.0 25 4.3 18 10 1 200 95.0 0.40 75.0 18 4.1 14 11 700 96.0 0.40 53.0 18 4.3 18 12 900 95.1 0.40 52.0 19 Dec 3.8 16

Example 32

300 mg of the solid product (III) obtained according to Example 1 and 3000 mg of diethylaluminum monochloride were suspended in 200 ml of n-hexane, followed by a reaction at partial pressure of propylene of 130 kPa at 20 ° C for 10 minutes, after which unreacted propylene was removed. and the residue stored with stirring at 30 ° C for one week. The resulting catalyst slurry containing 25 mg of solid product (III) was fed to a polymerization vessel for slurry and gas phase polymerization.

Comparative Examples 13 to 16

Using the following solid products instead of the solid product (III) obtained in Example 1, the catalyst suspensions were stored at 30 ° C for one week as described in Example 32, followed by polymerization of propylene.

Comparative Example 13: Solid product obtained in Example 1

Comparative Example 14: The final solid product obtained in Comparative Example 4

Comparative Example 15: The final solid product obtained in Comparative Example 6

Comparative Example 16: The final solid product obtained in Comparative Example 7.

The results of Example 32 and Comparative Examples 13 to 16 are shown in Table 8.

Table 8

Example 6 číslo Yield of polymer per g of solid catalyst component Isotact. index Bulk density Share passing through BTT ³ ^ _Iž xx) windows 1 410 to 234 jun (%) okem 4 699 R (%) 32 4 900 98.5 0.45 90.0 0 2.3 2.9 Comparative examples 13 700 97.5 0.32 50.0 28 4.2 18 14 1 300 94.8 0.30 61.0 22nd 4.3 13 15 Dec @ 00 95.8 0.31 62.0 24 4.2 17 16 1 280 94.8 0.29 49.0 35 3.8 12

The combination of slurry polymerization and gas phase polymerization was carried out as in Example 24, except that slurry polymerization at 78 ° C was performed using the solid product (III) obtained in Example 1, instead of slurry polymerization at 70 ° C. using the solid product (III) obtained in Example 5.

Comparative example 18

Using the solid product (II) obtained in Example 1 instead of the solid product (III) obtained in Example 1, slurry polymerization was performed at 78 ° C, followed by the gas phase polymerization described in Example 33. In the step of For example, when the polymerization of propylene in suspension was carried out at 78 ° C, the polymer was swollen with n-pentane, and in the gas-phase polymerization stage the polymer could not be fluidized because it formed lumps.

Comparative example 19

Using the final solid product obtained in Comparative Example 7 instead of the solid product (III) obtained in Example 1, polymerization of propylene in suspension was performed at 78 ° C followed by gas phase polymerization as described in Example 33. slurry polymerization performed at 78 ° C, the polymer was swollen with n-pentane and in the gas phase polymerization step, did not undergo fluidization as it formed lumps.

The results of Example 33 and Comparative Examples 18 and 19 are shown in Table 9.

Table 9

Example number Yield of polymer per g of solid catalyst component Isotact. index Bulk density Share passing RTT ^x) UP TO ³ “* okem 1 410 to 234 pa okem 4 699 Bye (*) 33 5 950 98.2 0.49 91.0 0 2.9 2.0 Comparative examples 18 400 92.0 - - - 2,3> 20 19 Dec 180 90.0 - 2,1> 20

Example 34 and Comparative Example 20

Example 34

The solid products (III) obtained in Examples 1, 4, 6 and II were subjected to specific surface and infrared surface measurement, X-ray diffraction, Al, Ti, Cl and diiaoamylether analysis and optical microscopy observations. The results are shown in Table 10 and the infrared spectra in Figure 1.

(1) surface area measurement:

The specific surface area was measured at liquid nitrogen temperature, according to the BST procedure, and using an automatic adjustment of 2,200 for micrometer measurement of the specific surface area.

(2) infrared surface measurement:

Diffusion reflection of the sandwich spectrum between KRS-5 plates was measured using a Fourier transform spectrophotometer (JIR-400) from Nihon Denshi Kabushiki Kaisha.

(3) X-ray diffraction:

X-ray diffraction was performed using a powder process using a Rigaku Denki Kabushiki Kaiaha (PMQ-82) goniometer and using the Cu K alpha line (lambda »15.4.10 ^-9 m) and Ni as a filter at 40 KV and 20 aA.

(4) composition analysis:

The weighed samples were dissolved in water and Al and Ti were analyzed according to the atom absorption method. Electron donors were extracted with n-hexane, followed by gas chromatography measurements. The content was calculated from the calibration curve.

(5) observation by optical microscope:

Sandwich samples placed between the glass plates were observed with an optical microscope (manufactured by Olympus Kogaku Co.).

Comparative Example 20

For comparison, the measurement of the catalyst complex prepared by the procedure described in Example 1 described in Japanese Patent Application Publication No. 47-34478 / 1972 (USP 4,210,738) was performed. The results are shown in Table 10 and the infrared spectra in Figure 2.

Figures 1 and 2 show the results of measurements taken under the following conditions: sampling rate: 1.00, resolution: 4.00 and timing: 300.

Table 10

Example number Specific surface area m ² / g Hydroxy- group X-ray diffraction. beams 1 138 No 4.85 2.7) 2.15 1.77 1.70 1.48 m, broad. 8 w m w ww 4 142 No 4.90 2.73 2.13 2.00 1.78 1.49 3 3 and w m w 6 135 No 4.87 2.71 2.15 1.77 1.70 1.48 8 8 m m w 11 130 No 5.02 2.72 2.13 1.98 1.78 1.48 with 8 & « m «

Comparative

example 20 180 Yes 5.85 m 5.27 2.97 2.71 m w s 1.77 and 1.70 w Example Analysis of mg / g composition Channel number AI Ti Cl Ponor elektr. 1 0.89 252 541 100 ALIGN! Yes 4 0.60 254 245 120 Yes 6 0.60 256 548 115 Yes 11 1.00 265 589 90 Yes Comparative example 20 May 2.5 271 600 75 No

Intensity: s> m> ww

Comparative example

In contrast to the procedure of Example 1, the catalyst complex obtained in Comparative Example 20 was used instead of the solid product (III) in propylene polymerization. The yield of polymer per g of catalyst complex was 3000 g.

Example 35 and Comparative Example 22

The solid product (III) obtained in Example 1 and the catalyst complex obtained in Comparative Example 20 were heated under nitrogen atmosphere at 55 ° C for 4 days, after which they were cooled and polymerized propylene according to Example 1. The solid product (III) Example 1 exhibited better thermal stability and a polymer yield reduction of 5% or less, while using the catalyst complex obtained in Comparative Example 20, the polymer yield reduction was 71 #.

The results are shown in Table 11.

Ta bulka 11

Example Yield Poles- Isotact. Bulk specific Share passing číelo eru to g index wt. okem okem fixed pro- 1 410 4 699 duct (III) to 234 jum (*)

LIP

(x)

I _ž xx)

Comparative example

21 3 000 98.0 0.45 93.0 0 35 4,980 99.6 0.50 97.0 0 Comparative example 22 S70 93.0 0.45 93.5 0

3.2

4.1

3.8

8.6

3.0

16.0

Claims (12)

CLAIMS 1. A process for the preparation of an alpha-olefin polyaeration catalyst comprising reacting one molar part of an organic aluminum compound with 0.1 to 8 molar parts of an electron donor in a solvent at a temperature of from -20 DEG C. to 200 DEG C. obtaining a solid product (I), then reacting the solid product (I) with titanium tetrachloride at a temperature of 0 to 100 ° C at an aluminum to titanium ratio of 0.05 to 10, then evaporating the liquid portion of the resulting material washing to give a solid product (II) free of free TiCl ^, then reacting 100 parts by weight of the solid product (II) and 10 to 1000 parts by weight of an electron donor and 10 to 1000 parts by weight of an electron acceptor at a temperature of 40 to 200 ° C to give a solid product (III), with molar and parts by weight as moles and grams. 2. A process according to claim 1, wherein the catalyst is pre-activated by polymerization reaction with alpha-olefin. . 3. The process of claim 2 wherein the activating polymerization with alpha-olefin is carried out in the gas phase. 4. Process according to claim 1 or 2, characterized in that the activation polymerisers and alpha-olefin are carried out in suspension and then in the gas phase. 5. A process according to claim 1 or 2, wherein the alpha-olefin activating polymerization is carried out in bulk and then in gas phase. 6. The method of claim 1, wherein the organic aluminum compound is a compound of formula - "V * n ' ^X 3- (n + n') in which R and R * are each alkyl, aryl, alkaryl, cycloalkyl or alkoxy, X denotes fluorine, chlorine, bromine or iodine, and n and n 'each denote a number optimal within the relation 0 <n + n ‘* 3. 7. The method of claim 1, wherein the electron donors may be the same or different and comprise at least one member of the group consisting of ethers, alcohols, esters, aldehydes, fatty acids, aromatic acids, ketones, nitriles, amines, amides, urea, thiourea, isocyanates, azo compounds, phosphines, phosphites, phosphinites, thioethers and thioalcohols. 8. A method according to claim 1, wherein the electron donors may be the same or different and consist solely or predominantly of ethers, and for longer time with compounds other than ethers, but used with ethers. 8. The method of claim 1, wherein the electron acceptor comprises at least one member selected from the group consisting of anhydrous aluminum chloride, silica chloride, cesium chloride, magnesium chloride, titanium tetrachloride, zirconium chloride, phosphorus trichloride, phosphorus trichloride, vanadium chloride and chloride. antiaonočitý. 10. The process of claim 1 wherein the solvent is an aliphatic hydrocarbon. 11. A process according to claim 1, wherein the reaction of the solid product (II) with the electron donor and the electron acceptor is carried out in an aliphatic hydrocarbon. 12. The process of claim 1 wherein the reaction of the solid product (II) with an electron donor and an electron acceptor is carried out by first allowing the electron donor and electron acceptor to react at a temperature of from 10 to 100 [deg.] C for 30 minutes to 2 hours, then the reaction product is cooled and the cooled reaction product is reacted with the solid product (II). 13. A process according to any one of the preceding claims, characterized in that one molar part of the organic aluminum compound is reacted with 1 to 4 molar parts of an electron donor in 0.5 to 5 parts by volume of an aliphatic hydrocarbon solvent at a temperature of -10 to 100. ° C to obtain the solid product (I), the solid product (I) is then reacted with titanium tetrachloride at a temperature of from 10 to 90 ° C, in a ratio of aluminum to titanium of 0.06 to 0.2, thereafter removing the liquid fraction from the obtained material by washing to obtain a solid product (II) free of titanium tetrachloride, then reacting 100 parts by weight of this solid product (II) with 50- 200 parts by weight of an electron donor and 20 to 500 parts by weight of an electron acceptor in 0.1 to 1 part by volume of an aliphatic hydrocarbon solvent at a temperature of from 50 to 100 ° C to obtain a solid product (III), wherein molar, mass and volume parts are to each other as moths, grams and liters.