CS235326B2 - A process for preparing a catalyst for the α-olefin polymerization - Google Patents

Abstract

The method for producing a catalyst for the polymerization of alpha-olefins according to the invention consists in reacting one molar part of an organic aluminum compound β with 0.1 to 8 molar parts of an electron donor in a solvent at a temperature of -20 to 200 °C, thereby obtaining a solid product (I), then this solid product (I) is allowed to react with titanium tetrachloride at a temperature of 0 to 100 °C at a ratio of the number of aluminum atoms to the number of titanium atoms of 0.05 to 10, then the liquid part of the resulting material is removed by washing, thereby obtaining a solid product (II), free of free TiCl., then 100 parts by weight of this solid product (II) is allowed to react with 10 to 1,000 parts by weight of an allotron donor and 10 to 1,000 parts by weight of an electron acceptor at a temperature of 40 to 200 °C, thereby obtaining a solid product (III), with molar and mass parts related to each other as moles and grams.

Description

The present invention relates to a process for the production of a catalyst for the polymerization of alpha-olefins, which allows in particular gas-phase polymerization and further a modification of this gas-phase polymerization consisting in a combination of suspension or block polymerization and gas-phase polymerization.

It is well known that alpha-olefins are polymerized using so-called Ziegler-Natta catalysts, containing a compound of transition metals of groups IV to VI of the periodic table and an organometallic compound of metals of groups I to III of the periodic table and further modified catalysts obtained by further addition of an electron donor and the like. Of this group of catalysts, catalysts containing titanium chloride are most often used, since this transition metal compound is widely used for the preparation of highly crystalline polymers, for example propylene, 1-butene, etc.

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

1. A compound obtained by reducing sulfur trichloride with hydrogen followed by ball milling for activation. This substance is known as titanium trichloride (HA)

2. A compound obtained by reducing sulfur dioxide with metallic aluminum, followed by ball milling for activation. This substance is expressed by the general formula TiClyl/3 AlCl^ and is designated titanium trichloride (AA).

3. A compound obtained by reducing sulfur tetrachloride with an organoaluminum compound and subsequent heat treatment.

Since none of the above titanium trichlorides is completely satisfactory, numerous modifications have been proposed. Among others, a production method has been proposed in which titanium trichloride, obtained by reducing sulfur trichloride with an organoaluminum compound, is allowed to react with an electron donor and titanium tetrachloride, thereby increasing the efficiency of the catalyst and reducing the amount of amorphous polymer by-product (see, for example, Japanese Patent Application Laid-Open No. 34,478/1972). A disadvantage of the catalysts thus obtained is their lower thermal stability.

Furthermore, a method has been proposed in which titanium tetrachloride and an organoaluminum compound are separately mixed with a certain amount of a complexing agent (e.g., an electron donor), and the two liquid mixtures obtained are mixed and reacted to obtain a solid catalytic component (Japanese Patent Application Laid-Open No. 9296/1978). This method also has the disadvantage of reduced thermal stability, as the catalyst was described in the aforementioned Japanese Patent Application Laid-Open No. 34,478/1972.

Furthermore, a process has been disclosed in which a uniform liquid material consisting of an organoaluminum compound and an ether is added to titanium tetrachloride or the latter is added to said liquid to obtain a titanium tetrachloride-containing liquid (Japanese Patent Application Laid-Open No. 115 7-7/1977), and a process in which the above liquid material is heated to a temperature of 150°C or lower to precipitate fine particles of titanium tetrachloride (Japanese Patent Application Laid-Open No. 47 594/1977, etc.).

However, these processes also had the consequence of reduced thermal stability of the obtained catalysts.

On the other hand, there are known processes for the polymerization of alpha-olefins using Ziegler-Natta catalysts in which alpha-olefins are in a different phase in suspension polymerization using a solvent such as n-hexane and the like (for example, Japanese Patent Publication No. 10,596/1957), and in which the polymerization is carried out using a liquefied alpha-olefin monomer such as liquefied propylene (for example, Japanese Patent Publication No. 6,

686/1961 and 14,041/1963), and the polymerization is carried out in the gas phase using gaseous propylene (for example, Japanese Patent Publications Nos. 14,812/1964 and 17,487/1967, etc.). A method of block polymerization followed by gas phase polymerization has been known for a long time (for example, Japanese Patent Publication No. 14,862/1974, Japanese Patent Application Laid-Open No. 135,987/1976, etc.). Among the above polymerization methods, gas phase polymerization is preferable because it eliminates the need for regeneration and reuse of the solvent during polymerization, as in the suspension polymerization method, and the need for regeneration and reuse of the liquefied monomer, such as liquefied propylene, as in the block polymerization method. Therefore, the cost of obtaining the solvent or monomer is low and the equipment for producing poly-alpha-olefins is simplified. In the case of a gas phase polymerization process, however, non-uniform catalyst particles in the gas phase are prone to form non-uniform polymer particles.

This then causes the polymer particles to agglomerate and clog the outlet of the polymerization vessel or the conveying line, which causes difficulties in long-term stabilized continuous operation and the quality of the polymer dispersion is coarser.

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

The inventors continued their studies, and the result of their efforts is a new catalyst.

It has been found that when this catalyst is used for the polymerization of alpha-olefins, better polymerization results can be achieved compared to previous catalysts. In this case, it is possible to overcome to a large extent the disadvantages of the conventional gas phase polymerization processes.

The essence of the present invention is a method for producing a catalyst for the polymerization of alpha-olefins with uniform particle size, high storage life and thermal stability of the catalyst. When using this catalyst, the above-mentioned disadvantages of gas phase polymerization do not occur. At the same time, the advantages of gas phase polymerization can be sufficiently demonstrated.

The method for producing a catalyst according to the invention is characterized in that the reaction product (I) of a defined organoaluminum compound (AI) with the electron donor (B1) used, with titanium tetrachloride (C), is allowed to react to form a solid product (II), this solid product (II) is allowed to react further with a defined electron donor (B2) with a defined electron acceptor (E), to form a solid product (III), and the solid product (III) is bound with a defined organoaluminum compound (A2) to obtain a catalyst.

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

The method for producing the catalyst according to the invention is described in more detail below.

The catalyst is prepared by producing a solid product (III) which is bound with an organoaluminum compound, or the resulting compound is further reacted with an alpha-olefin to obtain a preactivated catalyst as mentioned above.

The production of the solid product (III) proceeds 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 solid product (II).

The reaction of the organoaluminum compound (AI) with the electron donor (B1) is carried out in a solvent (D), at a temperature of -20 to 200 °C, preferably -10 to 100 °C for 30 seconds to 5 hours. The procedure for adding the components (AI), (B1) and (D) is not limited and the ratio of the reactants ranges 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 2 liters of solvent per mole of the organoaluminum compound. Aliphatic hydrocarbons are preferably used as solvents. In this way, the reaction product (I) is obtained. The reaction product (I) can be subjected to further reaction in the liquid state after the reaction is completed (this liquid will be hereinafter referred to as the 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 a period of 5 minutes to 8 hours. Although the reaction is preferably carried out without the use of a solvent, aliphatic or aromatic hydrocarbons can be used. The addition of components (I), (C) and the solvent can be carried out in any order and the mixing of the total amount is preferably completed within 5 hours. The reactants are used in the following amounts: solvent, 0 to 3,000 ml per mole of titanium tetrachloride, the 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 the reaction is complete, the liquid portion is separated and removed by filtration or decantation, followed by repeated washing with solvent, thereby obtaining a solid product (II), which can be used in the next step in the state in which it is suspended in the solvent or can be dried for a longer period and used in the next step in the form of a solid product.

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

Although this reaction can be carried out without the use of a solvent, advantageous results are obtained when aliphatic hydrocarbons are used. Preferably, 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 used, all based on 100 g of solid product (II). It is preferable to mix these three or four substances at a temperature of -10 to 40 ° C for 30 seconds to 60 minutes and allow them to react at a temperature of 40 to 200 ° C, preferably 50 to 100 ° C for 30 seconds to 5 hours. The order of addition of the solid product (II), the component (B2), the component (E) and the solvent is not particularly limited, (B2) and (E) may be reacted in advance before being mixed 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. After the reaction of the reaction product (II), (B2) and (E) is completed, the liquid portion is separated and removed by filtration or decantation, followed by repeated washing, thereby obtaining the solid product (III), which is used in the next process after drying and taking out in the form of a solid or in a state of being suspended in a solvent

The solid product (III) thus prepared is in the form of spherical particles with a diameter of from 2 to 100 µm, preferably 10 to 70 µm, and these particles have a narrow particle size distribution close to the average size indicated above. When observing the solid product (III) under a microscope, channels are visible. The specific surface area of the solid product (III) is in the range of 125 to 200 m ² /g. In contrast, the specific surface area of the solid 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 complete product (III), a broad and strong diffraction is observed near the lattice, where d = 48.5.10“^m, while no diffraction corresponding to the surface, where d =· 58.5.10”^m, is observed.

According to the measurement of the infrared spectrum of the surface of the solid product (III), no absorption due to the hydroxyl group was observed near 3,450 cm ^-1 . The solid product (III) has a special feature in 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 will be described below, the high thermal stability being based on the aforementioned structure of the solid product (III), the structure of which is formed under the reaction conditions of the present invention.

The obtained product (III) is mixed with an organoaluminum compound in a ratio of 0.1 to 500 g of this compound per 1 g of solid product (III), to form a catalyst, and optionally this catalyst is allowed to react further with an alpha-olefin to form a preactivated catalyst.

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

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 a halogen, such as fluorine, chlorine, bromine or iodine, and n and n' always denote any number given by the relationship , O < n+n' 3,

Specific examples of these compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri-n-hexyaluminum, triisohexyaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum and the like, dialkylaluminum monohalides such as diethylaluminum monochloride, di-n-propylaluminum monochloride, diisobutylaluminum monochloride, diethylaluminum monofluoride, distylaluminum monobromide, diethylaluminum monoiodide and the like, alkylaluminum hydrides such as diethylaluminum hydride, and alkylaluminum halides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride and the like. Alkoxyaluminums such as monoethoxydiethylaluminum, diethoxyanoethylaluminum and the like may also be used. These organoaluminum compounds may be used as mixtures of one or more of these compounds. The organoaluminum compound (A1) for producing the solid product (I) may be the same as or different from the organoaluminum compound (A2) used for binding with the solid product (III).

As electron donors, it is possible to use various types of substances mentioned above in the process according to the invention, although it is preferable that the electron donors consist solely or predominantly (more than 50% molar, based on the total number of moles of donor) of ethers, or that substances other than ethers are used together with ethers. As for the electron donors used, it is possible to use 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, thiourea, isocyanates, azo compounds, phosphines, phosphites, phosphinities, thioethers, thioalcohol, etc. Specific examples include ethers such as diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexyl ether, 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, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluylate, ethyl toluylate, 2-ethylhexyl toluylate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenyl acetate; aldehydes such as acetaldehyde, benzaldehyde; fatty acids such as formic acid, acetic acid, propionic acid, lactic acid, oxalic acid, succinic acid, acrylic acid, oleic 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, triethacholamine, beta-(N,N-dimethylamino)ethanol, pyridine, quinoline, alpha-picoline, N,N,N',N'-tetramethylhexaethylenediamin, aniline, dimethylaniline; amides such as formamide, hexamethylphosphoric acid amide, N,N,N ^/ ,N-pentaethyl-N'-beta-dimethylaminoethylphosphoric acid triamide, octamethylpyrophosphoric acid; ureas such as N,N,N',N'-tetramethylurea; isocyanates such as phenyl isocyanate, tolyl isocyanate; azo compounds such as azobenzene; phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide; phosphites such as dimethylphosphite, di-n-octylphosphite, triethylphosphite, tri-n-butylphosphite, triphenylphosphite; dialkylphosphoric acid derivatives such as ethyldiethylphosphonate, ethyldibutylphosphonate, phenyldiphenylphosphonate; thioesters such as diethylthioether, diphenylthioether, ethylphenylthioether, ethylene sulfide, propylene sulfide; and thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol. These electron donors may be used in a mixture. The electron donor (B1) for preparing the reaction product (I) may be the same as or different from the electron donor (B2) for reacting with the solid product (II).

The electron acceptors used in this invention are represented by halides of elements of groups III to VI of the periodic table of elements. Specific examples include anhydrous aluminum chloride, silicon chloride, tin chloride, tin tetrachloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium chloride, antimony tetrachloride and the like. These compounds may be used in a mixture. Titanium tetrachloride is most preferred.

As solvents, aliphatic hydrocarbons such as n-heptane, n-octane, isooctane and the like can be used. Alternatively, instead of aliphatic hydrocarbons or together with them, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloroethylene, trichloroethylene, tetrachloroethylene and the like can be used. Alternatively, aromatic compounds such as aromatic hydrocarbons, for example naphthalene, and their derivatives substituted with alkyl substituents such as acetylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene,

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

The solid product (III) thus obtained is mixed for a longer time with an organo-aluminum compound, thereby obtaining a catalyst which can be used in a known manner for the polymerization of alpha-olefins, or it is allowed to react further with an alpha-olefin, thereby obtaining a pre-activated catalyst which can also be used for the polymerization of alpha-olefin.

In the case of suspension or bulk polymerization, the catalyst obtained by the addition of the solid product (III) with an organo-aluminum compound also exhibits sufficient activity. In the case of gas-phase polymerization, it is more advantageous to use a pre-activated catalyst obtained by reaction with an alpha-olefin, since the catalyst thus activated exhibits higher activity. In the case of suspension or bulk polymerization followed by gas-phase polymerization, it is possible to use the original (unactivated) catalyst, since in this case the necessary reaction with the alpha-olefin occurs before the gas-phase polymerization occurs, so that the resulting catalyst is similar to the pre-activated catalyst and has better activity.

The previous activation is preferably carried out using 0.1 to 500 g of organoaluminum compound, 0 to 50 liters of solvent, 0 to 1,000 ml of hydrogen and 0.05 to 5,000 g, and preferably 0.05 to 3,000 g of alpha-olefin based on 1 g of the product (III), the reaction of the alpha-olefin being carried out at a temperature of from 0 to 100 ° C for 1 minute to 20 hours, when 0.01 to 2,000 g, preferably 0.05 to 200 g of alpha-olefin reacts.

The reaction of the alpha-olefin to the previous activation can be carried out in a solvent formed by aliphatic or aromatic hydrocarbons, or in a liquefied alpha-olefin, such as liquefied propylene, liquefied 1-butene, etc. Furthermore, it is also possible to carry out the reaction of the alpha-olefin, such as ethylene, propylene, etc. in the gas phase. It is also possible to carry out the activation in the presence of a poly-alpha-olefin prepared in advance or hydrogen.

There are various catalyst activation procedures, such as

1. a process in which the reaction is carried out in suspension, in a bulk or in the gas phase in such a way that the alpha-olefin is brought into contact with a catalyst prepared by binding the solid product (III) with an organoaluminum compound, or

2. the solid product (III) binds with an organoaluminum compound in the presence of an alpha-olefin, it is also possible

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

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

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

After completion of the previous activation, the solvent and unreacted alpha-olefin are removed, for example by distillation under reduced pressure, and after drying, the obtained powder is used for subsequent polymerization, or alternatively, the solid product can be suspended in a solvent in an amount of 80 liters or less per 1 g of solid product and the obtained suspension used for subsequent polymerization.

The thus obtained preactivated catalyst can be used for the polymerization of alpha-olefins in suspension, carried out in a hydrocarbon solvent such as n-hexane, n-octane, benzene, toluene and the like, or for the bulk polymerization carried out in a liquefied monomer alpha-olefin, for example in liquefied propylene, liquefied butene, etc., but can preferably be used for gas phase polymerization. The desired catalyst efficiency is also achieved in the case of a modification of the gas phase polymerization, that is, when using suspension polymerization followed by gas phase polymerization, or bulk polymerization followed by gas phase polymerization.

The polymerization of alpha-olefins in the gas phase can be carried out without the presence of a solvent such as n-hexane, n-heptane, etc., and can also be carried out in the presence of a solvent in an amount of 0 to 500 g per 1 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 such a way that the fluidization is controlled by stirring elements. The polymerization can also be carried out using vertical or horizontal type impeller blades.

The polymerization of alpha-olefin in suspension or bulk polymerization followed by gas phase polymerization can be carried out in batches. For example, there is a process (,) in which after the polymerization in suspension or bulk polymerization, the solvent or liquefied alpha-olefin is removed, and gas phase polymerization is carried out gradually, while supplying gaseous alpha-olefin; in process (2), the polymerization in suspension or bulk polymerization is carried out, and while the polymerization continues without removing the solvent or alpha-olefin, the solvent or liquefied alpha-olefin is embedded in the polymer particles, while the liquid portion is lost, and therefore the previous form of polymerization is continuously changed to gas phase polymerization;

in process (3), suspension polymerization or bulk 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, feeding the alpha-olefin into the gas phase, etc.

This multi-stage polymerization, consisting of a combination of suspension or bulk polymerization with gas phase polymerization, results in the desired results, especially in the case of continuous polymerization. According to some of the methods mentioned, for example, it is possible to carry out a suspension or bulk polymerization in the first stage, wherein this polymerization is continued until a polymer containing 30% or less of solvent or liquefied alpha-olefin is obtained, optionally the solvent or liquefied alpha-olefin is removed and then the alpha-olefin is polymerized in the gas phase, in a second stage, while simultaneously fluidizing the polymer particles.

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

As for the conditions of the polymerization of alpha-olefins, it is possible to carry out any known polymerization in suspension, bulk polymerization or gas phase polymerization under conditions where the polymerization of alpha-olefins takes place at a temperature from room temperature (20 °C) to 200 °C, at a polymerization pressure from atmospheric pressure (100 kPa) to a pressure of 5 MPa and usually for a period of 5 minutes to 10 hours. During the polymerization, it is possible to add an appropriate amount of hydrogen in a conventional manner to adjust the molecular weight.

As alpha-olefins, it is possible to use for the polymerization according to the invention straight-chain monoolefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc., branched monoolefins such as 4-methyl-1-pentene, 2-methyl-1-pentene, 3-methyl-1-butene, etc., diolefins such as butadiene, isoprene, chloroprene, etc., styrene and the like. These olefins can be homopolymerized or copolymerized in combination with each other, for example in combination of propylene with ethylene, butene with ethylene, or propylene with 1-butene. In this case, it is possible to carry out the polymerization of a mixture of monomers or in multiple stages using different alpha-olefins in the first stage, when polymerization is carried out in suspension or block polymerization, followed by a second stage in a similar polymerization in the gas phase.

The first advantage of the process according to the invention is that the average diameter of the polymer particles is small and the particle face is close to spherical, while the particle size distribution is small and the amount of large and too small particles is reduced. 1 In the case of gas phase polymerization, the flow of polymer particles is smooth and a long-term stabilized continuous process is possible. Therefore, the advantage of gas phase polymerization is shown. In the case of gas phase polymerization alone, it is possible to reduce the cost of solvent and monomer regeneration. In addition, in the case of suspension polymerization or bulk 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 suspension polymerization or bulk polymerization, and to evaporate the unreacted monomer by heating the polymerization reaction mixture in the successive gas phase.

The second advantage of the process according to the invention is that the storage stability of the catalyst is increased. For example, when the solid product (III) was left at a temperature of about 30 °C for 4 months, there was no significant decrease in the polymerization activity. This means that there is no need for a special storage facility, for example, for storing the solid product (III) at a temperature of 0 °C. Even if the solid product (III) is left at a high concentration of 1.0% or more at a temperature of 30 °C or more for one week after the solid product (III) is exposed to the ergane aluminum compound without polymerization starting, the fine powdering caused by stirring in the catalyst container hardly occurs. The shape of the polymer particles was not degraded and the polymerization efficiency was not reduced. This advantage is further enhanced by prior activation of the catalyst with an alpha-olefin.

The third advantage of the process according to 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 ground into fine powder and, in the case of suspension polymerization, are not moistened with a solvent. 1 It follows from the above that the usable temperature range for controlling the temperature in the polymerization vessel during polymerization is expanded, resulting in long-term stabilized operation.

A fourth advantage of the present invention is that polymer particles with a high bulk density are obtained. The bulk density of the polymer is 0.45 to 0.52, which allows the use of a small volume of polymerization vessel or container for a given weight of polymer.

The 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 of parts 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, especially the rigidity of the polymer, are not reduced even without the separation of the atactic polymer. This allows the elimination of further steps.

This invention will be explained by way of examples.

Example)

1. Preparation of catalyst n-Hexane (60 ml), diethylaluminum monochloride (DEAC) (0.05 mol) and diisoayl 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 obtain reaction liquid (I) (the molar ratio of diisoayl ether to diethylaluminum monochloride was 2.4). TiCl^ in an amount of 0.4 mol was introduced into a reactor purged with nitrogen and heated to 35°C. The entire amount of the above reaction liquid (I) was added dropwise to the reaction mixture. The addition took 30 minutes and the reaction mixture was maintained at the same temperature for another 30 minutes, after which the reaction temperature was raised to 75°C and the reaction was continued for one hour. Then, the reaction mixture was cooled to room temperature to remove the upper layer, and the procedure was repeated by adding 400 ml of n-hexane and the upper layer was removed by decantation. This procedure was repeated four times to obtain 19 g of solid product (II). The entire amount of product (II) was suspended in 300 ml of n-hexane, and 16 g of diisoamyl ether and 35 g of TiCl^ were added to the resulting suspension at 20 °C. The addition took about one minute. Then, the reaction was continued at 65 °C for one hour. After the reaction was completed, the resulting substance was cooled to room temperature (20 °C), and the upper layer was decanted by adding 400 ml of n-hexane five times, the reaction mixture was stirred for <0 minutes, and after standing, the upper layer was separated, and then dried under reduced pressure to obtain solid product (III).

2. Method of producing pre-activated catalyst

A 2-liter stainless steel reactor equipped with a beveled blade was purged with nitrogen. 20 ml of n-hexane, 420 mg of diethylaluminum monochloride and 30 mg of solid product (111) were charged into the reactor at room temperature. 150 ml of hydrogen was then introduced and the reaction was carried out under a partial pressure of propylene of 500 kPa for 5 minutes.

Then, unreacted propylene, hydrogen and n-hexene were removed under reduced pressure to obtain a pre-activated catalyst in powder form (reacted propylene: 80.0 g per solid product (III)).

3. Method of polymerization of propylene

300 ml of hydrogen was introduced into the reactor containing the previously activated catalyst mentioned above, and polymerization was carried out in the gas phase at a partial propylene pressure of 2.5 MPa and a polymerization temperature of 70 °C for 2 hours. After the reaction was completed, 5 g of ethanol was added, the reaction mixture was heated at 70 °C for 30 minutes, and then cooled to room temperature. 156 g of polymer was obtained by drying. The polymer yield was 5,200 g per g of solid product (III); isotactic index 99.8; and bulk specific gravity 0.50. The shape of the polymer particles was close to spherical. 97.4% of the polymer particles had a size between 1,410 and 234 μm, and neither fine powder nor lumps were observed.

No colored polymer was detected and the Saltiness 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 by the procedure of Example 1, except that isoamyl ether was not used in the reaction of the solid product (I) (the solid products for mixing with the organoaluminum compound, obtained by the procedures given in the comparative examples, will hereinafter be referred to as the final solid product (III) and this final solid product will hereinafter be referred to collectively as the solid catalyst component). The final solid product was pre-activated by the procedure of Example 1. Using this activated catalyst, propylene was polymerized by the procedure of Example 1.

Comparative example 3

Example 1 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 the solid product (11).

Comparative example 4

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

Comparative example 5

The procedure according to Example 1 was repeated with the difference that in the formation of the solid product (II) according to Example 1, diisoamyl ether was not used.

Comparative example 6

Example 1 was repeated except that the solid product (II) of Example 1 was replaced by the product obtained by adding 0.05 mol of diethylaluminum chloride to a solution of 0.4 mol of TiCl^ and 0.12 mol of diisoamyl ether at 35°C. The addition was carried out over a period of 30 minutes, while maintaining the mixture 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 with the difference that unreacted TiCl2 was not removed from the reaction mixture after the formation of 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 following reaction.

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

Table, Example Yield poles-* Isotactic. Bulk meter Share passing _RTT x) _(Iz xx) number of meru on g index mass by eye by eye solid components 1,410 4,699 cat. until jUffl 234 yuan (») (») 1 5 200 99.8 0.50 97.4 0 4.2 3.0

Comparative

examples 1 1 100 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 4.3 12.6 7 1 900 95.0 0.41 54.0 22 3.5 9.0

Explanation to Tables 1 and 13:

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

Example 2

The procedure described in Example 1 was repeated except that in the preparation of the solid product (II) and Example 1, the TiCl2 was maintained at 12°C while the reaction liquid (I) was added dropwise 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 except that in the production of solid product (11) according to Example 1, the temperature increase to 75°C after dropwise addition of reaction liquid (I) to TiCl2 was changed to 65°C. The resulting product (III) was brown in color.

Example 4

Instead of reacting dilsoamyl ether and TiCl^ with solid product (II) according to Example 1, 38 g of dilsoamyl ether, 12 g of SiCl^ and 17 g of TiCl^ were added to 200 l of n-hexane at room temperature (20 °C) within one minute, after which solid product (II) (19 g) was added and the reaction was carried out for 2 hours at 75 °C. Then the reaction mixture was washed with n-hexane, dried and the result was solid product (III). Catalyst activation and propylene polymerization were carried out according to the procedure given in Examples 1, 2 and 3.

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

Table 2

Example Pollen yield- Zeatakt air number per g solids index catal.

Bulk specific gravity.

Share passing by eye by eye 1,410 4,699 until 7" 234 ^um (») (*)

IZ«>

2 5 100 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 1 l of n-heptane, 0.16 mol of di-n-butylamine 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 give the reaction liquid (I). The entire amount of this product (I) was added dropwise over 60 minutes to a mixture consisting of 50 l of toluene and 0.64 mol of TiCl^ while maintaining the reaction mixture at 45°C. Then the temperature was raised to 85°C and the reaction continued for 2 hours. Then the temperature of the reaction mixture was lowered to room temperature to remove the upper layer and 300 ml of n-heptane were added twice and the upper layer of the components was removed by decantation. In this way, 49 g of solid product (II) was 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 TiCl^ were added to the suspension obtained at room temperature over a period of 2 minutes. The subsequent reaction was carried out at a temperature of 90 °C for 2 hours, then the reaction mixture was cooled, decanted, saturated with n-heptane and dried, thereby obtaining a solid product (III). The subsequent activation of the catalyst and polymerization of propylene were carried out according to the procedure described in examples 1, 2 and 3.

Comparative example 8

The procedure according to Example 5 was repeated, with the difference that instead of the solid product (III), the solid product (II) according to Example 5 was used.

Example

0.057 vol of diethyl aluinium chloride and 0.15 vol of diisoayl ether were added dropwise to 40 vol of n-hexane at 18 °C for 5 min, and the mixture was allowed to react at 35 °C for 30 min. The resulting reaction liquid was added dropwise to 0.5 vol of TiCl* at 35 °C for 180 min, the reaction continued at 35 °C for 60 min, then the temperature was increased to 75 °C and the mixture was heated for 60 min, then the temperature was reduced to room temperature (20 °C), the upper layer was removed, 400 vL of n-hexane was added twice each time, and the upper layers were removed by decantation. In the above procedure, a solid product (II) was obtained in an amount of 24 g. The entire amount of the obtained product was suspended in 100 µl of n-hexane and 12 g of diisopropyl ether was added to the resulting suspension and the reaction was continued at 35°C for one hour.

Next, 12 g of diisoayl ether and 72 g of TiCl2 were added in 2 turns at a temperature of 35 °C, the temperature was increased to 65 °C and the reaction continued for one hour, then the reaction mixture was cooled to room temperature (20 °C), decanted, washed with n-hexane and dried, to obtain a solid product (III). The subsequent preparation of the activated catalyst and the polymerization of propylene were carried out by the procedure described in Example 1.

Example 7

The procedure of Example 6 was repeated with the difference that in the preparation of reaction product (1) 0.06 vol of diisopropylaluminium monochloride was allowed to react with 0.14 vol of di-n-octyl ether.

Example

The procedure of Example 6 was repeated with the difference that in the preparation of solid product (II) 0.72 vol of TiCl2 was used for the reaction with solid product (I).

Example 9 g of solid product (II), obtained by the procedure of Example 6 was suspended in 200 ml of toluene and to the resulting suspension were added 10 g of TlCl^ and 26 g of di-n-butyl ether and the reaction was carried out at 50 °C for 180 minutes, after which the reaction mixture was cooled to room temperature (20 °C), decanted, filtered with n-hexane and solidified, thereby obtaining solid product (III). Subsequent preparation of the activated catalyst and polymerization of propylene were carried out according to the procedure of Example 1.

Example 10

0.03 aol of trileobutylaluminum and 0.07 aol of di-n-dodecyl ether were allowed to react in 100 aol of n-hexane at 20 °C for 30 min. The resulting reaction liquid was added dropwise to 0.15 aol of TiCl^ for 120 min at 20 °C, and then the temperature was maintained at 30 °C for 30 min. Then the temperature was raised to 50 °C and the reaction was continued for 60 min. After the reaction was completed, decantation was carried out to remove the upper layer, n-hexane, and drying was carried out, thereby obtaining 23 g of solid product (II), which was then suspended in 50 ml of n-heptane. 21 g of di-n-butyl ether and 40 g of TiClj were added to the resulting suspension, and the reaction was continued at 50 °C for 140 min. Then the reaction mixture was cooled, the upper layer was removed by decantation, the residue was washed with n-hexane and evaporated to obtain a solid product (III). The subsequent preparation of the pre-activated catalyst for the polymerization of propylene was carried out according to the procedure described in Example 1.

Example if

0.07 mol of triethylaluminum 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 was continued at the same temperature for 30 minutes, thereby obtaining the reaction product (1), which was further added dropwise over 4 hours at 32 °C to 0.6 mol of TiCl^ and the temperature was maintained at 35 °C for one hour, after which it was increased to 78 °C and the reaction was continued for 2 hours, then the reaction mixture was cooled to 20 °C, the upper layer was removed by repeated addition of 400 ml of n-hexane and decantation (5 times), which was confirmed by the absence of TiCl^, followed by filtration and drying, thereby obtaining 23 g of solid product (XI).

mol of di-n-pentyl ether and 5 g of anhydrous AlCl.J were added to 300 ml of n-heptane and the reaction was carried out at 80 °C for 2 hours, whereby AlCl was dissolved. The reaction mixture was then cooled to 30 °C, 23 g of the above solid product (11) was added, 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, whereby the solid product (III) was obtained.

The subsequent preparation of the pre-activated catalyst and the polymerization of propylene were carried out according to the procedure given in Examples 1, 2 and 3.

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

Table 3

Example number Polymer yield per g of catalyst solids laotakt. index Bundle specific gravity Share passing (iž) by eye 1 410 to 234 μ» (») eye 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 the solid product (III) obtained by the procedure of Example 1 and 5 g of polypropylene powder were mixed in the reactor described in Examples 1 and 2, after which the n-pentene was removed under reduced pressure. The gas phase reaction was carried out under a partial overpressure of propylene of 80 kPa at 30 °C for 20 minutes, while the catalyst was fluidized with the propylene. Then, the unreacted propylene was removed, thereby obtaining a pre-activated catalyst (the ratio of reacted propylene per g of solid product (III) was 1.8 g). The use of the obtained catalyst and propylene polymer in the gas phase was carried out according to the procedure described in Examples 1 and 3.

23532»

Example 13 '

At 20°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, after which the unreacted propylene was removed, thereby obtaining a powdery preactivated catalyst (reacted propylene per g of solid product (111):120 g). The use of the resulting catalyst and the gas phase polymerization were carried out according to the procedure described in Examples 1 and 3.

Example 14

The procedure of Example 1 was repeated with the difference that ethylene was used instead of propylene in the activation of the catalyst according to Example 1. The ethylene was allowed to react with a partial ethylene overpressure of 100 kPa at 35 °C for 10 minutes (ratio of ethylene reacted per g of solid product (111):2.4 g).

Example 15

Example 1 was repeated with the difference that instead of propylene, 1-butene was used for the circular activation from Example 1, and the reaction was carried out under a partial overpressure of 1-butene of 50 kPa at 35 °C for 10 minutes (proportion of reacted 1-butene per g of solid product (111): 0.3 g).

Example 16

Example 1 was repeated except that instead of 420 mg of diethylaluminum monochloride in Examples 1 and 2, 380 mg of diisopropylaluminum monochloride was used.

Example 17

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

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

Table 4

Example Yield polynumber of air per g

Ieotactic.

index

Bulk moderate Proportion passing through the eye of the ocean

ΗΤΤ ^χ ) IŽ ^{* 1} *) solid catalyst components

410 4 699 to pa

234 yuan (%) (») (»)

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 18

The catalyst was pre-activated by the procedure described in Example 1, (1) and (2). 1000 l of n-hexane and 150 ml of hydrogen were added to the resulting catalyst. The suspension polymerization reaction was then carried out under a partial propylene pressure of 1.2 HPa at 70 °C for 2.5 hours, after which the n-hexane was removed by steam stripping. The polymer was obtained by the procedure described above.

Example 19

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

Example 20

The powdery, pre-activated catalyst was prepared in the reactor described in Example 1, (1) and (2). After feeding 300 l of hydrogen and 200 g of propylene, block polymerization was carried out at a partial propylene overpressure of 2.6 HPa at 60 °C for 30 minutes, thereby obtaining 35 g of reacted propylene. Subsequently, the resulting suspension containing unreacted propylene was fed to a fluidized bed having a diameter of 20 cm and a volume of 20 liters and equipped with stirrers, while propylene was circulated at a flow rate of 5 cal/a to fluidize the polymer, and gas-phase polymerization was carried out at a partial propylene overpressure of 2.1 HPa at a reaction temperature of 70 °C for 2 hours. Additional processing to obtain the polymer was carried out by the method described in Example 1.

Example 21

The block polymerization was carried out as in Example 8 under a pressure of 2.6 HPa for 30 minutes at 60°C. Then, the unreacted liquefied propylene was transferred to a separate feed tank connected to the reactor. The reactor temperature was raised to 72°C and, while propylene was fed from the feed tank to the reactor, a gas phase polymerization was carried out for 2 hours to create a polymerization pressure of 2.6 HPa. The subsequent post-processing was carried out as described in Example 1 to obtain a polymer.

Example 22

The bulk polymerization was carried out under a pressure of 2.6 MPa at 60 °C for 30 minutes according to the procedure described in Example 20. Then the polymerization temperature was increased to 70 °C, thereby obtaining a polymerization pressure of 3' MPa. If the polymerization was left without intervention, the pressure decreased to 2.6 MPa within 40 minutes. This means that the bulk polymerization was continuously converted to gas-phase polymerization. When propylene was fed in an amount corresponding to a pressure of 2.6 MPa for 60 minutes, the polymerization proceeded in the gas phase. Additional processing to obtain the polymer was carried out according to the procedure described in Example 1.

Example 23

000 ml of n-hexene, 320 mg of diethylaluminum monochloride and i8 mg of the solid product (111), obtained according to the procedure of Example 5, were allowed to react with propylene under a partial propylene pressure of 120 kPa at 20 °C for 10 minutes, in order to pre-activate the catalyst (ratio of reacted propylene per g of solid product (111): 0.6 g). Unreacted propylene was removed and 120 ml of hydrogen was introduced. Polymerization in suspension was carried out under a partial propylene pressure of 1.0 MPa at 70 °C for 2.5 hours.

The n-Hexane was subsequently removed by steam stripping to obtain the polymer.

Example 24 ml of n-pentane, 280 mg of diethylaluminium monochloride and 25 mg of the solid product (III) obtained by the procedure of Example 5 were reacted. Propylene was allowed to react at 15°C, while its partial overpressure was increased. The overpressure was increased to 500 kPa in 5 minutes (100 kPa/min). The catalyst was pre-activated for 5 minutes (ratio of reacted propylene per g of solid product (III):3.2 g).

Unreacted propylene was removed and 200 ml of hydrogen was introduced into the reaction mixture.

The suspension polymerization was carried out under a partial pressure of propylene of 1.0 MPa at 70 °C for 60 minutes (reacted propylene: 63 g). The resulting suspension containing the solvent was fed into a fluidized bed equipped with stirrers, after which the propylene was polymerized in the gas phase according to the procedure given 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 allowed to react without prior activation, 120 ml of hydrogen were introduced and the subsequent suspension polymerization was carried out under a partial overpressure of propylene of 10 MPa at 70 °C for 2.5 hours. Then, the n-hexane was removed by steam stripping, whereby the polymer was obtained.

Example 26

Using the catalyst without prior activation, propylene was polymerized in suspension by the procedure described in Example 25. Unreacted propylene and hydrogen were subsequently removed, and n-hexane was distilled off under reduced pressure to an n-hexane content of 30% in the polymer. This polymer, containing the solvent, was fed into a fluidized bed equipped with stirrers, as described in Example 20. Then, 450 ml of hydrogen was fed in and polymerization was carried out in the gas phase, at a partial propylene pressure of 2.1 MPa at 70°C for 2 hours, as described in Example 20. Subsequent processing to obtain the polymer was carried out by the procedure described in Example 1.

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

Table 5

Example Number Polymer yield per g of catalyst solids leotakt. index Bundle specific gravity Share passing _RTT x) _(Iz xx) eye 1,410 to 234 μα (») eye 4 699 JiTB (») 18 5,400 99.8 0.48 97.6 0 2.6 2.3 19 5,000 99.6 0.47 95.0 0 2.9 2.8 20 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 22 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 27

The block copolymerization of propylene β ethylene was carried out by the procedure described in Example 26 β with the difference that in the first stage, propylene polymerization was carried out in suspension and in the second stage, polymerization was carried out in the gas phase under a partial hydrogen pressure of 800 kPa and a partial ethylene pressure of 1.2 kPa at 70 °C for 2 hours to achieve ethylene polymerization.

Example 28

Example 20 was repeated except that instead of 200 g of propylene, an alpha-olefin mixture containing 200 g of propylene and 20 g of ethylene was used. A copolymer of propylene and ethylene was obtained by the above procedure.

Example 29

Example 28 was repeated 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, with the difference that when using a pre-activated catalyst, the polymerization of ethylene was carried out under a hydrogen overpressure of 1.2 MPa and a partial ethylene overpressure of 1.2 MPa at 85 °C, instead of using 300 ml of hydrogen and a partial propylene overpressure of 2.5 MPa at 70 °C.

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

Table 6

Example number Polymer yield per g of catalyst solids Isotactic index Bundle specific gravity Share passing RTT ^x) I ₍ xx) from 1,410 to 234 ua («) eye 4 699 jam (*) 27 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. Then, polymerization was carried out by the procedure described in Example 1, (2) and (3).

Comparative examples 9 to l2

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

Comparative Example 9: Solid product (XI), obtained in Example 1

Comparative Example 10: Final solid product obtained in Comparative Example 4.

Comparative Example 11: Final solid product obtained in Comparative Example 6.

Comparative Example 12: 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 Polymer yield per g of catalyst solids Isotactic index Bundle specific gravity Share passing HTT ^x) IŽ«> by 1,410 to 234 pm (#) eye . 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 3.8 16

Example 32

300 mg of solid product (III) obtained according to the procedure of Example 1 and 3,000 mg of diethylaluminum monochloride were suspended in 200 ml of n-hexane, followed by reaction under a partial overpressure of propylene of 130 kPa at 20 °C for 10 minutes, then the unreacted propylene was removed and the residue was stored under stirring at 30 °C for one week. The resulting catalyst suspension containing 25 mg of solid product (III) was fed to a polymerization vessel, where polymerization was carried out in suspension and in the gas phase.

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, after which the polymerization of propylene was carried out.

Comparative Example 13: Solid product obtained in Example 1

Comparative Example 14: Final solid product obtained in Comparative Example 4

Comparative Example 15: Final solid product obtained in Comparative Example 6

Comparative Example 16: 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 6number Polymer yield per g of catalyst solids Isotactic index Bundle specific gravity Share of visitors| BTT ³ ^ _(Iz xx) windows 1,410 to 234 Jun (%) by the way 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 22 4.3 13 15 @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 suspension polymerization with gas phase polymerization was carried out according to the procedure of Example 24, with the difference that the suspension polymerization was carried out at 78 °C using the solid product (III) obtained in Example 1, instead of the suspension polymerization at 70 °C using the solid product (III) obtained in the procedure of Example 5.

Comparative example 18

Using the solid product (II) obtained by the procedure of Example 1 instead of the solid product (III) obtained in Example 1, slurry polymerization was carried out at 78°C, followed by gas phase polymerization as described in Example 33. In the stage where the propylene slurry polymerization was carried out at 78°C, the polymer was swollen with n-pentane, while 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, propylene was subjected to suspension polymerization at 78°C, followed by gas phase polymerization as described in Example 33. In the suspension polymerization step carried out at 78°C, the polymer was swollen with n-pentane, and in the gas phase polymerization step, the polymer did not undergo fluidization because it formed lumps.

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

Table 9

Example number Polymer yield per g of catalyst solids Isotactic index Bundle specific gravity Share passing RTT ^x) IŽ ³ “* by 1,410 to 234 pa (») eye 4 699 pa (*) 33 5,950 98.2 0.49 91.0 0 2.9 2.0 Comparative examples 18 400 92.0 - - - 2.3 >20 19 180 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 surface area and infrared spectrum measurements, X-ray diffraction, Al, Ti, Cl and diaminoamyl ether analysis and optical microscope observation. The results are shown in Table 10 and the infrared spectra in Fig. 1.

(1) measurement of specific surface area:

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

(2) measurement of the infrared spectrum of the surface:

The diffusion reflectance spectrum of the sandwiches 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 by powder method using a goniometer (PMQ-82) from Rigaku Denki Kabushiki Kaiaha and using Cu K alpha line (lambda » 15.4.10 ^-9 m) and Ni as filter, at 40 KV and 20 aA.

(4) composition analysis:

The weighed samples were dissolved in water, and then Al and Ti were analyzed by atomic absorption. The electron donors were extracted with n-hexane, and then measured by gas chromatography. The content was calculated from the calibration curve.

(5) observation with an optical microscope:

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

Comparative example 20

For comparison, measurements were made on the catalytic complex prepared by the procedure described in Example 1 described in Japanese Patent Application Laid-Open No. 47-34478/1972 (USP 4,210,738). The results are shown in Table 10 and the infrared spectra in Fig. 2.

Figures 1 and 2 show the results of measurements performed 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 rays 1 138 no 4.85 2.7) 2.15 1.77 1.70 1.48 m,width 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 a 1.70 w Example Composition analysis mg/g Channel number AI Those Cl Electric sink 1 0.89 252 541 100 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 2.5 271 600 75 no

Intensity: s> m> ww

Comparative example 21

Unlike the procedure described in Example 1, the catalyst complex obtained in Comparative Example 20 was used in the polymerization of propylene instead of the solid product (III). The polymer yield per g of catalyst complex was 3,000 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 in a nitrogen atmosphere at 55°C for 4 days, then cooled and propylene polymerization was carried out according to Example 1. The solid product (III) obtained in Example 1 showed better thermal stability and the decrease in polymer yield was 5% or less, while in the case of using the catalyst complex obtained by the procedure of Comparative Example 20, the decrease in polymer yield was 71%.

The results are shown in Table 1 1.

That lump 11

Example Poly-yield Isotactic. Bulk meter Share passing number eru on g index mass by eye by eye solid pro- 1,410 4,699 duct (III) until 234 jum <*) (*)

LIP

x)

I ₍ 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.