NL8202923A - PROCESS FOR PREPARING ALPHA-OLEGIN POLYMERS - Google Patents

Description

v N.O. 31236 1

Process for preparing α-olefin polymers.

The present invention relates to a process for preparing α-olefin polymers. More particularly, the invention relates to a process for preparing α-olefin polymers, which are highly crystalline and have good particle shape, with good yield, by using a new catalyst suitable for α olefin polymerization, in particular gas phase polymerization, and further combinations of gas phase polymerization with suspension polymerization or mass polymerization, as modifications of gas phase polymerization.

It is known that α-olefins are polymerized in the presence of the so-called Ziegler-Natta catalysts, which are a compound of transition metals of groups IV to VI of the periodic table and an organometallic compound of the metals of groups I to III of the periodic table and including those catalysts which have been rhodified by the addition of an electron donor, etc. Furthermore, for the preparation of highly crystalline polymers of propylene, butene-1, etc., titanium trichloride is most commonly used for the aforementioned transition metal compound as a component of the catalysts. The titanium trichloride is classified into the following three types according to its preparation: (1) a product obtained by reduction of TiCl4 with hydrogen, followed by grinding in a ball mill for activation (which product is called titanium trichloride (HA)); (2) a product obtained by reduction of TiCl4 with aluminum metal, followed by grinding in a ball mill for activation, ie a compound expressed by the general formula TiCl3 · V3-AICI3 (the so-called titanium trichloride (AA)) ; and (3) a product obtained by reduction of TiCl 2 with an organoaluminum compound, followed by heat treatment.

However, these types of titanium trichloride are not entirely satisfactory and various improvements have been considered and attempted. As one such improved method, a method has been proposed in which TiCl4 is reduced with an organoaluminum compound to obtain a titanium trichloride, which is then treated with an electron donor and TiCl4, thereby increasing the activity of the resulting catalyst and also the amount of amorphous polymer formed is reduced (e.g., Japanese Patent Application 47-34478 / 1972). However, such a method has the drawback that the catalyst falls short in heat stability.

Furthermore, another method has been proposed in which TiCl 2 and an organoaluminum compound are respectively mixed and reacted separately and reacted with a certain amount of complexing agent (including electron donors) beforehand to obtain two separated reaction liquids, which are then mixed with are mixed together and reacted to prepare a solid catalyst component (Japanese Patent Application 53-9296 / 1978). Such a process also has the same drawback as in the aforementioned Japanese patent application 10 47-34478 / 1972, in that the catalyst lacks heat stability.

Furthermore, a method has been proposed in which a uniform liquid material consisting of an organoaluminum compound and an ether is added to ΤΙΟΙή, or the order is reversed to prepare a liquid material containing titanium trichloride (Japanese patent application 52 115797/1977) and a method, wherein the aforementioned liquid material is heated to a temperature of 150 ° C or less to deposit a fine particulate titanium trichloride. However, such processes have the same drawback as mentioned above, in that the catalyst lacks heat stability.

On the other hand, with respect to the phase of α-olefins, in which they are polymerized in the presence of the Ziegler-Natta catalysts, are suspension polymerization, which is carried out in a solvent such as n-hexane (eg Japanese Patent 32-10596 / 1957), bulk polymerization, which is conducted in a liquefied monomer, such as liquefied propylene (Japanese Patent 36-6686 / 1961 and 38-14041 / 1963), and gas phase polymerization, which is conducted in a gaseous monomer, such as gaseous propylene (Japanese Pat. Nos. 39-14812 / 1964 and 42-17487 / 1967) are well known. Furthermore, a process for carrying out mass polymerization followed by gas phase polymerization is also known (e.g., Japanese Patent Specification 49-14862 / 1974 and Japanese Patent Application 51-135987 / 1976). Under these processes, gas phase polymerization is effective in that recovery and reuse of solvent used for polymerization as in the case of slurry polymerization are not necessary; recovery and reuse of liquefied monomer used for polymerization such as in the case of mass polymerization are not necessary; the recovery cost of solvent or monomer is low; 40 equipment for the preparation of α-olefins is simplified; etc.

8202923? -3 1 3 'On the other hand, gas phase polymerization is not effective because, since the monomer is present in the gas phase reaction vessel, the monomer concentration is lower than in the case of the suspension polymerization process or the mass polymerization process, so that the reaction speed decreases; consequently, in order to increase the polymer efficiency per unit weight of catalyst, it is necessary to extend the retention time or therefor to increase the reaction kettle or to increase the catalyst activity it is necessary to use a modified trialkyl aluminum, the stereo regularity of the polymer is reduced. Furthermore, according to the gas phase polymerization, uneven polymer particles are likely to be formed as a result of uneven catalyst particles.

Bit is responsible for causing agglomeration of polymer particles, clogging at the polymer discharge opening of the polymerization kettle or in the transport line or clogging due to fine particles accompanying unreacted arolefin from the polymerization kettle, whereby a long-term stabilized, continuous operation is made difficult and the quality of dispersion is increased.

Applicants have previously found as a polymerization process, which does not have the disadvantages described above, even in the case of gas phase polymerization, a process for the preparation of α-olefin polymers, in which a reaction product of an organo-aluminum compound with an electron donor is converted with TiCl 2 to obtain a solid, which is reacted with an electron donor and an electron acceptor to obtain a solid product, which is combined with an organo-aluminum compound to obtain a catalyst, in the presence of which α olefins are polymerized (Japanese Patent Application 55-12875 / 1980, which will be referred to hereinafter as "prior invention A").

This earlier invention A is characterized in that a long-term stabilized gas phase polymerization can be carried out; the catalyst has high storage stability and heat stability during the polymerization; the polymer efficiency in the gas phase polymerization is 5000 to 6000 g / g (solid product) and the amount of amorphous polymer formed is reduced. However, the storage stability of the catalyst at high temperatures above 35 ° C is insufficient and the heat stability of the catalyst must also be higher.

Applicants have conducted further studies to improve the catalyst and as a result have found that when the aforementioned solid obtained by reacting an 8202923 4 reaction product of an organoaluminum compound with an electron donor with HCl 4 is subjected to polymerization treatment with an α-olefin and the solid thus treated is reacted with an electron donor and an electron acceptor, it is then possible to further improve the storage stability and heat stability of the catalyst (first aspect). Furthermore, as a process which does not have the aforementioned drawbacks, even in the case of gas phase polymerization, applicants have previously found a process for the preparation of α-olefins, wherein a reaction product of an organoaluminium compound with an electron donor is reacted with TiCl4 to obtain a solid material, which is then reacted with an electron donor and an electron acceptor to obtain a solid product, which is then combined with an organo-aluminum compound and a reaction product (G) of an α olefin and an organoaluminum compound with an electron donor to obtain a pre-activated catalyst and α-olefins are polymerized in the presence of the pre-activated catalyst (Japanese Patent Application 55-23785 / 1980; this application will be cited below) as "previous invention B").

The aforementioned prior invention B of applicants is characterized in that no polymer lump is formed in the gas phase polymerization; long-term stabilized operation is possible even in the case of gas phase polymerization; the polymer efficiency in the gas phase polymerization is 7000 to 12000 g / g (solid product) and the amount of amorphous polymer formed is reduced; without an increase in the amount of atactic polymer, it is possible to control the stereoregularity of polymer and it is also possible to control the toughness, in particular the flexural modulus of the polymer and the storage stability and the heat stability of the polymer. catalyst are 30 better. On the other hand, such problems have arisen that when the catalyst is stored at a high temperature of 35 ° C or higher, reduction in the catalyst activity is observed; long-term storage of the catalyst mixture obtained by adding an organoaluminum compound and a reaction product (G) of an α-olefin, an organoaluminum compound and an electron donor to the solid product presents a problem and in the case of a high polymerization At a temperature of 90 ° C or higher, the resulting polymer has an inferior shape and the percentage of amorphous polymer formed increases.

Applicants have continued further studies for improvement, and as a result have found that when a solid product 8202923 'f! 5 subjected to polymerization treatment with an α-olefin in each of the steps for the preparation of the solid product is used in place of the solid product (III) used in the previous inventions A or B, then it is possible the storage stability and the heat -5 improve catalyst stability. In this way, a first or second aspect of the present invention is achieved.

The object of the present invention with the first and second aspects is to provide a process for the preparation of α-olefin polymers, using a catalyst with further improved storage stability and heat stability, even when gas phase polymerization, suspension polymerization or mass polymerization is carried out at a temperature higher than that of the previous inventions A and B, the polymer obtained has a uniform particle size; the catalyst activity is greater; the percentage of amorphous polymer formed is lower; in particular, the advantages of the gas phase polymerization can be fully demonstrated and, moreover, the stereoregularity of the polymer can be easily controlled in the second aspect.

Summary of the invention.

The present invention briefly relates to a process for preparing α-olefin polymers, characterized by polymerizing an α-olefin in the presence of a pre-activated catalyst obtained by reaction of a reaction product (I) of an organo-olefin. aluminum compound (A ^) with an electron donor (B · ^), with TiCl ^ (C) to obtain a solid product (II), then converting this solid product (II) with an electron donor (B2) and an electron acceptor (E) for obtaining a solid product (III), the during and / or after the reaction step to obtain the solid product (II) and / or during and / or after the reaction step to obtain the solid product (III), subjecting the solid product (II) or (III) to a polymerization treatment with an α-olefin and combining the obtained solid end product with an organo-aluminum compound (A2) or an organo-aluminum compound ( A2) and a reaction product ( G) of an organoaluminum compound (A3) with an electron donor (B3) to obtain a pre-activated catalyst and preferably in this combination, then subjecting part or all of the pre-8202923 6 activated catalyst to a polymerization treatment with an α-olefin in the presence of the solid end product and the organo-aluminum compound (A2) to obtain another preactivated catalyst.

The "polymerization treatment" means that a small amount of an α-olefin is contacted with catalyst components (ie solid product (II), solid product (III) or solid end product), under polymerizable conditions of the α-olefin for polymerizing the α-olefin and this polymerization treatment produces a state where the catalyst components are coated with polymer.

Detailed description of the preferred embodiments.

The preparation of the catalyst used in the present invention will first be described below.

The aforementioned solid end product is prepared as follows.

First, an organo-aluminum compound is reacted with an electron donor to obtain a reaction product (I), which is then treated with TiCl4 to obtain a solid product (II), which is then reacted with an electron donor and a Electron acceptor for obtaining a solid product (III) and wherein in either or both steps of obtaining the solid product (II) or (III), one or more of the solid product (II) during its formation , the formed solid product (II) or the solid product (III) are subjected to a polymerization treatment with an α-olefin to obtain a solid final product. The reaction of an organo-aluminum compound (A ^) with an electron donor (Bi) is carried out in solvent (D) at a temperature of -20 ° C to 200 ° C, preferably -10 ° C to 100 ° C, for a time period from 30 seconds to 5 hours. The order of addition of (A ^) 30 (B- ^) and (D) has no particular limitation and suitable proportions of their amounts used are 0.1 to 8 moles, preferably 1 to 4 moles of the electron donor and 0, 5 to 5 L, preferably 0.5 to 2 L of solvent, each based on 1 mole of the organoaluminum compound.

The solvent should preferably be an aliphatic hydrocarbon. In this way a reaction product (I) is obtained. This reaction product (I) can be subjected to the following reaction without separating the product, i.e. in a liquid state in which the reaction is completed (this liquid state will hereinafter be referred to as reaction liquid (1)).

The method of subjecting the solid product (II) or 8202923'y * 7 (III) to a polymerization treatment with an α-olefin during and / or after the reaction step to obtain the solid product (II) and / or during and / or after the reaction step to obtain the solid product (III), 5 (1) comprises a process in which an α-olefin is added at any time during the reaction of the reaction liquid (I) with TiCl 2 (C) to subject the solid product (II) to a polymerization treatment during its formation, (2) a process in which, upon completion of the reaction of the reaction liquid (I) with TiCl4, an α-olefin is added to subject the solid product (II) to polymerization treatment, (3) a process in which a solid product (II) obtained after filtering or decanting and then washing or subjecting the solid product (II) to polymerization treatment obtained according to the methods mentioned above (1 ) or (2), is combined with an organo-aluminum compound, followed by addition of an α-olefin to subject the combination to a polymerization treatment, (4) a process, during which the solid product (II) step whether the solid product (II) subjected to polymerization treatment obtained by the method (1) or (2) is reacted with an electron donor and an electron acceptor to obtain a solid product (III), becomes an α-olefin added to carry out the polymerization treatment and (5) a method in which a solid product (III) obtained after filtering or decanting and then washing is combined with an organo-aluminum compound, followed by addition of an α-olefin to subject the combination to a polymerization treatment.

In the case of the polymerization treatment with an α-olefin according to method (1) or (2), an α-olefin is passed under atmospheric pressure or added such that a pressure of 980 kPa or lower is obtained at a reaction temperature of 30 ° C to 90 ° C for 5 minutes to 10 hours. Regarding the amount of α-olefin added, it is preferable from 10 to 5000 g of α-olefin per 100 g of the solid product (II) to be formed or to be formed or the solid product (III) to be formed or formed. and polymerize 0.05 to 100 g thereof. After completion of the polymerization treatment with α-olefin, unreacted olefin is flushed and the resulting material is used for the next step, in the suspension state in solvent or in the form of solid product obtained after drying the suspension.

8202923 8

In case the polymerization treatment with an α-olefin is applied to the solid product (II) or the solid product (III) obtained after filtering or decanting and then washing, or the solid product (II) subjected to polymerization treatment, obtained By the process (1) or (2), it is preferable to add 10 to 2000 ml of a solvent and 5 to 500 g of an organoaluminum compound to 100 g of the solid product (II) or the solid product (III) and adding 10 to 5000 g of an α-olefin under 0 to 980 k ^ a at a reaction temperature of 0 to 90 ° C for 5 minutes to 10 hours to obtain 0.05 to 100 g of the alkene polymerize. The solvent is preferably an aliphatic hydrocarbon and the organoaluminum compound can be the same or a different compound than used for the reaction liquid (I). After the polymerization treatment with an α-olefin, unreacted α-olefin is rinsed out and the resulting material is filtered off or decanted and then washed with a solvent. It is then used in the next step in a state in which it is suspended in a solvent or obtained in the form of a solid product after drying the suspension.

The reaction of the reaction product (I) with TiCl4 (C) is carried out at 0 20 to 200 ° C, preferably 10 to 90 ° C for 5 minutes to 10 hours. Although solvent is preferably not used, aliphatic or aromatic hydrocarbons can be used. The mixing of (I), (C) and solvent can be performed in any order and it is preferable to complete the mixing treatment of the total amount within 5 hours. Even during the mixing treatment, the reaction is carried out, and after mixing the total amount, it is preferable to continue the reaction within 5 hours. With respect to the respective amounts used for the reaction, the solvent is used in an amount of 0 to 3000 ml per 30 moles of TiCl 2 and the reaction product (I) is used in a ratio of the number of Al atoms in (I) to the number of Ti atoms in TiCl 3 (Al / Ti) from 0.05 to 10, preferably from 0.06 to 0.3. It is also possible to add an α-olefin at any time during the reaction of (I) with (C) to carry out the polymerization treatment. After completion of the reaction, a solid product (II) obtained by filtering or decanting a liquid portion, followed by repeated washing with a solvent, or a solid product (II) subjected to a polymerization treatment with an α-olefin, in the next step be used in the state in which the product (II) 40 is suspended in a solvent or obtained in the form of solid product after drying the suspension. The aforementioned solid product (II) or the solid product (II), which has been subjected to polymerization treatment, can be further combined with an organoaluminum compound, followed by addition of an α-olefin to the obtained com-5 combination to carry out the polymerization treatment. After the polymerization treatment with an α-olefin, the obtained material is subjected to filtration or decantation and then washing and used in the next step in the state in which it is suspended in a solvent or in the form of solid product obtained after drying the suspension.

The aforementioned solid product (II) or the solid product (II), which has been subjected to a polymerization treatment, is then reacted with an electron donor (B £) and an electron acceptor (E). Although this reaction can be run without a solvent, the use of aliphatic hydrocarbons gives preferred results. Furthermore, an α-olefin can be added at this step to carry out a polymerization treatment. The amounts used are 10 to 1000 g, preferably 50 to 200 g (B2), 10 to 1000 g, preferably 20 to 500 g (E), 0 to 3000 ml, preferably 100 to 1000, respectively. ml of solvent and 0 to 5000 g of an α-olefin, each based on 100 g of the solid product (II) or the solid product (II) subjected to a polymerization treatment. These four or five substances are preferably mixed at -10 ° C to 40 ° C for 30 seconds for up to 60 minutes and at 40 to 200 ° C, preferably 50 ° C for 25 seconds to 100 ° C for up to 5 seconds. hours converted. The order of mixing the solid product (II), (B2)> (E), the solvent and the oc olefin has no particular limitation. (B2) and (E) can be converted to each other before mixing with the aforementioned solid product (II) or the solid product (II) subjected to a polymerization treatment, and in this case ( B2) reacted with (E) at 10 to 100 ° C for 30 minutes to 2 hours, followed by cooling to 40 ° C or less before use. After completion of the reaction of the solid product (II) or the solid product (II) subjected to a polymerization treatment (B2) and (E), a liquid portion is separated and removed by filtration or decantation, followed by repeated washing with a solvent to obtain a solid product (III). This solid product (III) can then be combined with an organoaluminum coating followed by addition of an α-olefin to carry out a polymerization treatment. After the polymerization treatment with an α-olefin 8202923, the product obtained is filtered or decanted, followed by washing to obtain a solid end product. This final solid product is used in the next step in the state in which it is suspended in a solvent or in the form of a solid product obtained after drying the suspension. In the case where the solid product (III) is not subjected to the polymerization treatment with an α-olefin, the solid product (III) corresponds to the solid final product. In this case, the polymerization treatment should be carried out at least at the solid product (II) step.

The solid end product thus obtained is then combined with an organo-aluminum compound (A2) or an organo-aluminum compound (A2) and a reaction product (G) of an organo-aluminum compound (A3) with an electron donor (B3), or at further preferably, an α-olefin is added to the resulting combination to obtain a preactivated catalyst. By appropriate selection of the reaction product (G) at the time of the combination, it is possible to control the stereoregularity of the resulting polymer. This pre-activation will be described in detail later.

The organoaluminum compounds used in the present invention are represented by the general formula AlRnR, nX3 "(n + n ')> wherein R and R' each represent a hydrocarbon group such as an alkyl group, aryl group, alkaryl group, cycloalkyl group, etc. or alkoxy group, X represents a halogen atom such as fluorine, chlorine, bromine or iodine and n and n 'each represent an arbitrary number of 0 <n + n' ^ 3 and as concrete examples trialkylaluminum compounds such as trimethylaluminum , triethyl aluminum, tri-n-propylaluminum, tri-n-butyl aluminum, tri-iso-butyl aluminum, tri-n-hexyl aluminum, tri-iso-hexyl aluminum, tri-2-methylpentyl aluminum, tri-n-octyl aluminum , tri-n-decyl aluminum, etc., dialkyl aluminum ammonium halides, such as diethyl aluminum monochloride, di-n-propyl aluminum monochloride, di-iso-butyl aluminum monochloride, diethyl aluminum monofluoride, diethyl aluminum monobromide, diethyl aluminum. ethyl aluminum hydride and alkyl aluminum halides, such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, etc. In addition, alkoxyalkyl aluminum compounds, such as monoethoxydiethyl aluminum, diethoxymonoethyl aluminum, etc., can also be used. These organo-aluminum compounds can be used as a mixture of two or more compounds. The organoaluminum compound 40 (A ^) to obtain the solid product (I), the organoaluminum 8202923 11 aluminum compound (A2) to be combined with the solid end product and (A3) to obtain the reaction product (G) can be the same or different from each other.

With regard to the electron donors used in the present invention, several types are explained below, but it is preferred that electron donors consisting essentially of ethers be used as (B1) and (B2) and others electron donors are used in conjunction with ethers.

With respect to the electron donors used, organic compounds containing terrestrial oxygen, nitrogen, sulfur and phosphorus atoms, such as ethers, alcohols, esters, aldehydes, fatty acids, aromatic acids, ketones, nitriles, amines, amides , urea, thiourea, isocyanates, azo compounds, phosphines, phosphites, phosphinites, H 2 S, thioethers, thio alcohols, etc. With respect to concrete examples, ethers such as diethyl ether, di-n-propyl ether, di-n-butyl ether, di-isoamyl ether, di-n-pentyl ether, di-n-hexyl ether, di-iso-hexyl ether, di- n-octyl ether, di-iso-octyl 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; phenols such as phenol, cresol, xylenol, ethyl phenol, naphthol esters such as methyl methacrylate, ethyl acetate, butyl formate, amyl acetate, vinyl lactate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, 2-ethylhexyl benzoate 2-ethylhexyl toluylate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenyl acetate; aldehydes such as acetaldehyde, benzaldehyde; fatty acids such as formic, acetic, propionic, lactic, oxalic, succinic, acrylic, maleic; aromatic acids such as benzoic acid; ketones such as methyl-30 ethyl ketone, methyl isobutyl ketone, benzophenone; nitriles such as acetonitrillin amines such as methylamine, diethylamine, tributylamine, triethanolamine, 3- (N, N-dimethylatnino) ethanol, pyridine, quinoline, a-picoline, 2,4,6-trimethylpyridine, Ν, Ν, Ν ', Ν tetramethylhexaethylenediamine, aniline, dimethylaniline; amides such as formamide, hexamethylphosphoric triamide, Ν, Ν, Ν Ν, N ', N ”pentamethyl-N'-3” dimethylaminoethyl phosphoric triamide, octamethylpyrophosphoroamide; ureas such as Ν, Ν, Ν ', N'tetramethyl urea; isocyanates such as phenyl isocyanate, toluyl isocyanate; azo compounds such as azobenzene; phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenyl-40phosphine oxide; phosphites such as dimethyl phosphite, di-n-octyl phosphite, 8202923 12 triethyl phosphite, tri-n-butyl phosphite, triphenyl phosphite; phosphinites such as ethyl diethyl phosphinlet, ethyl dibutyl phosphinite, phenyldiphenyl phosphinlet; thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide, propylene sulfide; and thioalcohols such as ethyl-5 thioalcohol, n-propylthioalcohol, thiophenol. These electron donors can be used as mixtures. The electron donor (B ^) to obtain the reaction product (I), to convert (B2) with the solid product (II) or the solid product (II) subjected to polymerization treatment and (B3) to obtain the reaction product 10 (G) can be the same or different from each other.

The electron acceptors (E) used in the present invention are represented by halides of elements from group III to group VI of the periodic table. As concrete examples, anhydrous AICI3, organo-aluminum compounds are represented by the al-15 common formula AlRnX3_n (0 <η <„2), SiCl ^, SnC ^, SnCl ^, ΤΙΟΙή, ZrCl ^, PCI3 {PCI5, VCI4, SbCl ^ , etc. listed. They can be used as a mixture. TiCl 2 is most preferred.

With regard to the solvent, the following solvents are used:

With regard to aliphatic hydrocarbons, n-pentane, n-hexane, n-heptane, n-octane, iso-octane, etc. are listed. Furthermore, instead of the aliphatic hydrocarbons or together halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloroethene, trichlorethylene, tetrachlorethylene, etc., may also be used.

With regard to aromatics, aromatic hydrocarbons such as naphthalene and as their derivatives are alkyl substituted derivatives such as mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, 1-phenylnaphthalene, etc .; and halides such as mono-chlorobenzene, chlorotoluene, chloroxylene, dichlorobenzene, bromobenzene, etc.

With respect to the α-olefins used for the polymerization treatment, straight-chain monoalkenes such as ethylene, propylene, butene-1, pentene-1, hexene-1, hepten-1, etc .; branched chain monoalkenes such as 4-methylpentene-1, 2-methylpentene-1, 3-methylpentene-1, etc. Styrene can also be used. These α-olefins can be equal to or different from the α-olefins used for the prior activation or those α-olefins used for regular polymerization and they can be used as a mixture.

Next, a process for combining the solid end product, an organo-aluminum compound (A2) and the reaction product (G) of an organo-aluminum compound (A3) with an electron donor 5 (B3) for the preparation of catalyst, in the second aspect of the present invention and a preferred method for further carrying out the previous activation with an o-olefin for the preparation of the catalyst, in the first and second aspects of the present invention, described in detail below.

The organoaluminum compounds (A2) and (A3) which form the catalyst used in the present invention need not be the same as (Αχ) used to form the reaction liquid (I), but ( Αχ), (A2) and (A3) can be the same or different.

The most preferred organoaluminum compounds are dialkylaluminum monohalides such as (Αχ) and (A2) and tri-alkylaluminum compounds such as (A3).

The electron donor (B3) used for the preparation of the reaction product (G) can be selected from that in the same region as described in the reaction to obtain the solid final product, but does not necessarily require the same compound as used to obtain the final solid product. The reaction product (G) is usually obtained by reacting 1 mole of an organoaluminum compound (A3) with 0.01 to 5 moles of an electron donor in the presence of a solvent such as n-hexane, n-heptane, in an amount of 10 to 5000 ml based on 1 g of the organoaluminum compound (A3) and based on 1 g of the electron donor, at -30 ° to 100 ° C for 10 minutes to 10 hours. Usually the reaction is carried out by the dropwise addition of the electron donor diluted with the solvent to the organoaluminum compound (A3) diluted with the solvent.

In the case where the solid end product is combined with the organoaluminum compound (A2) and in the second aspect of the present invention, for the reaction product (G) to obtain the catalyst, the organoaluminum compound (A2) is used in an amount of 0.1 to 500 g, preferably 0.5 to 500 g, and the reaction product (G), in an amount of 0.5 to 10 g, each per g of the solid final product and they can be combined together in random order to obtain the catalyst. For example, 40 may be the order of combination (A2) »the solid end product (G) or 8202923 14 (A2)> (G) and the solid end product.

Another preferred method of the present invention is the method of adding an α-olefin to the catalyst components to subject some or all of the catalyst components to a polymerization treatment prior to activation. A method of combining the solid end product, the organo-aluminum compound (A2), the α-olefin (F) and in the second aspect of the present invention, further the reaction product (G), for prior activation, will be described in detail below .

The preliminary activation can be carried out by part or all of the catalyst components of 1 g of the solid end product, 0.1 to 500 g, preferably 0.5 to 5 g of an organoaluminum compound (A2) and in the second aspect of the invention, further subjecting 0.05 to 10 g of the reaction product (G) to a polymerization treatment at least in the presence of the solid end product and the organoaluminum compound (A2) with 0.01 to 5000 g, preferably 0.05 to 3000 g of an α-olefin. With regard to the polymerization treatment conditions, it is preferable that the temperature is in the range of 0 ° to 100 ° C, preferably 10 ° to 70 ° C, the time in the range is from 1 minute to 20 hours and the α-olefin to be polymerized is in an amount of 0.01 to 2000 g, preferably 0.05 to 200 g, per g of the solid end product. 101 or less hydrogen may be present in the polymerization treatment. 50 l or less of solvent may be used in the prior activation. The solvent can be a hydrocarbon solvent such as propane, butane, n-pentane, n-hexane, n-heptane, benzene, toluene, etc., and the preliminary activation can be performed in a liquid alpha olefin, such as liquefied propylene, liquid made butene-1, etc. or in gaseous ethylene or propylene.

Before the activation, polymer particles obtained by slurry, bulk or gas phase polymerization can be made existing simultaneously. Such a polymer can be equal to or different from the α-olefin polymers as the object of polymerization. The amount of such a polymer, which must be capable of existing co-existence, can be in the range of 0 to 5000 g per g of the solid final product.

The solvent or α-olefin used in the pre-activation can be removed by distillation under reduced pressure, filtration or the like, halfway during the pre-activation or after completion of the activation. Furthermore, to suspend the solid product in a solvent, · 80 1 or less per g of the solid product, solvent may be added.

Various methods exist for the prior activation.

With regard to the. main embodiments thereof are explained the following: (1) a method in which solid end product is combined with an organo-aluminum compound (A2) and α-olefin (F) is added before the polymerization treatment is carried out, followed in the second aspect of the present invention by further adding reaction product (G); (2) a method, wherein solid end product is combined with (A2) in the presence of (F) to carry out the polymerization treatment with (F), followed in the second aspect of the present invention by further addition of (G); (3) a method, in which solid end product is combined with (A2) and in the second aspect of the present invention further (G) is added, followed by polymerization treatment with (F) and (4) a method, wherein, after the polymerization treatment of the present invention according to (3), (G) is further added.

In the foregoing embodiments, (G) is of course not added in the case of the first aspect of the present invention.

With regard to the methods (1) and (2) of pre-activation, the following concrete methods are further explained: (1-1) a method in which solid end product is combined with (A2) and the obtained combination is subjected to a polymerization treatment with (F) in the vapor phase or in liquefied cralene or in a solvent, followed by removal of unconverted (F) or unconverted (F) and solvent and in the second aspect of the present invention, further addition of (G); (1-2) a method, wherein (G) is added without removing unreacted (F) or unreacted (F) and solvent, at (1-1); (1-3) a process in which (G) is added and then unconverted (F) or unconverted (F) and solvent is removed, in (1-2); (1-4) a method according to (1-1) - (1-3), wherein obtained α-olefin polymer is added beforehand; (1-5) a method according to (1-1) - (1-4), wherein after prior activation, solvent or unreacted (F) and solvent are removed to obtain a catalyst in the form of powder; 8202923 16 (2-1) a method, wherein (A £) is combined with solid end product in the presence of oralkene, dissolved in a solvent or a liquefied α-olefin or α-olefin gas, to carry out the polymerization treatment with α- olefin, followed in the second aspect of the present invention by further addition of (G); (2-2) a process, wherein (2-1) is carried out in the presence of pre-obtained α-olefin polymer and (2-3) a process, wherein after prior activation, unconverted (F) and solvent under reduced pressure removed to obtain a catalyst in the form of powder.

In processes (1) and (2), it is possible that a component obtained by reacting solid end product and (A2) with (F) is not mixed with (G) at the time of catalyst preparation, but that it is just before polymerization are mixed together. Furthermore, in methods (1) - (4) it is possible to use hydrogen together with (F). Whether the catalyst is prepared in the form of a suspension or in the form of a powder makes no essential difference.

The catalyst obtained by combining the solid end product (A2) and in the second aspect of the present invention further (G), as described above, or the pre-activated catalyst obtained by further reaction with an α-olefin, is used for the preparation of α-olefin polymers.

The polymerization can be carried out by slurry polymerization in a hydrocarbon solvent or by mass polymerization in a liquefied α-olefin monomer, but in the present invention, since the catalyst has a high activity, gas phase polymerization of α-olefins has a particularly remarkable effectiveness. and suspension or bulk polymerization, followed by gas phase polymerization as a modification of the gas phase polymerization, also shows a desirable effectiveness.

The gas phase polymerization of α-olefins can be carried out not only in the absence of solvent, such as n-hexane, n-heptane, but 00k in a state where 0 to 500 g of solvent per kg of a-olefin polymer is present. Furthermore, the gas phase polymerization can be carried out by continuous or discontinuous polymerization. Furthermore, the gas phase polymerization can be carried out in a fluidized bed or in a fluidized manner by means of stirring elements or by stirring by means of a blade of the vertical or horizontal type.

With respect to the process of slurry or bulk polymerization followed by gas phase polymerization of cc olefins, the following 8202923.

17 explained: in the case, for example, of discontinuous polymerization, a process in which oralkene is polymerized in a solvent or a liquefied α-olefin monomer and then the solvent or α-olefin monomer is removed so that it is present in an amount of 500 g or less per kg of polymer particles, followed by polymerization of α-olefin in the vapor phase and a process, wherein polymerization of α-olefin continues without removal of solvent or a liquefied α-olefin and proceeds to gas phase polymerization without the addition of one or other operation since the solvent or the liquefied α-olefin is absorbed into the resulting polymer. A multi-stage polymerization, consisting of a combination of bulk or suspension polymerization with gas phase polymerization, shows a desirable result, especially in the case of continuous polymerization. This multi-stage polymerization can be carried out as follows: In the first stage, suspension or bulk polymerization is carried out, the polymerization being continued to a suspension concentration of [(polymer (kg)) / (polymer (kg) + solvent or liquefied ce-olefin ( kg)) x 100%] of 70% or higher, or the polymerization is carried out until the suspension concentration reaches 30 to 50% and then 20 solvent or liquefied α-olefin is removed to obtain a suspension concentration of 70% or higher; and in the second stage, α-olefin is subjected to vapor phase polymerization. In this process, the catalyst is fed at the time of first stage slurry or bulk polymerization, and in the gas phase polymerization, which is then conducted, the first stage catalyst can be sufficiently used as such, but fresh catalyst can be the stairs should also be added. Regarding the ratio of the weight of polymer formed by slurry or bulk polymerization and that of polymer formed by gas phase polymerization, it is preferred that the ratio be in the range of 0.1 to 100 parts by weight polymer of gas phase polymerization. based on a polymer part of suspension or bulk polymerization.

With respect to the polymerization conditions of α-olefins, slurry polymerization, bulk polymerization and gas phase polymerization 35 can be performed at a polymerization temperature from room temperature (20 ° C) to 200 ° C under a polymerization pressure from atmospheric pressure (0 kPa) to about 5000 kPa and usually for 5 minutes to 20 hours. In the polymerization, the addition of an appropriate amount of hydrogen for molecular weight control and the like are carried out in the usual manner.

8202923 18

With respect to the α-olefins used in the polymerization of the present invention, straight chain monoalkenes such as ethylene, propylene, butene-1, hexene-1, octene-1, etc .; branched chain monoalkenes such as 4-methylpentene-1,2-methylpentene-1,3-methylpen-5-toe-1, etc .; diolefins such as butadiene, isoprene, chloroprene, etc. are listed. Styrene can also be used. These olefins can be homopolymerized or copolymerized in combination, for example, a combination of propylene with ethylene, butene with ethylene, and propylene with butene-1. In this case, they can be polymerized as a mixture of monomers or in a plurality of steps, wherein different α-olefins can be used in the first stage slurry or bulk polymerization and the second stage gas phase polymerization.

The main effectiveness of the present invention consists in that according to the first and second aspects of the present invention a strong crystalline polymer is obtained with a good powder form with a high polymer yield by using the catalyst with an improved storage stability. and heat stability, even in the case of gas phase polymerization, wherein the monomer concentration is relatively low and also that according to the second aspect of the present invention, high temperature polymerization is possible and yet it is easily possible to achieve the stereoregularity of the polymer obtained with a small amount of amorphous polymer formed.

The effectiveness of the present invention will be described in more detail below.

The first effectiveness of the present invention is that the storage stability of the solid end product and the catalyst is further improved. For example, even when the solid end product is stored at a high temperature of about 40 ° C for about 4 months, there is no reduction in the polymerization activity; consequently, no special storage equipment for storing the solid end product is necessary and even when the solid end product is combined with an organoaluminum compound and in the second aspect of the present invention further the reactle product (G) and then the obtained combination at a high concentration of the final solid product of 1.0% or more, stored at 40 ° G or higher for 1 week until polymerization is initiated, no reduction in polymerization activity occurs; fine pulverization of catalyst brought about by stirring in the catalyst reservoir hardly takes place and the shape of the polymer particles does not deteriorate.

8202923 19

The second effectiveness of the present invention is that since the resulting catalyst has a very high activity, a high polymer efficiency is of course obtained in the suspension or bulk polymerization; For example, in the gas phase polymerization, where the monomer concentration is relatively low, the polymer efficiency per gram of solid end product is 6200 to 9000 g (polymer) in the case of the first aspect of the present invention and 9000 to 15000 g (polymer) in the case of the first aspect of the present invention. second aspect of the present invention.

The third effectiveness of the present invention is that since the polymer is obtained with a high yield even when the amounts of alcohol, alkylene oxide, steam, etc., which are used to deactivate the catalyst after the production of α-olefin polymers or purification of the polymer are further reduced, the polymer does not color and has a yellowing index of 0 to 2.0; furthermore, development of a corrosive gas having a bad effect, such as degradation of physical properties of polymer or rusting of the mold at the time of polymer formation, does not occur: even, for example, in the case where the polymer is heated to 200 ° C heated, acid gas evolution, which changes the color of a 20 kongo red test paper, is not observed.

The fourth effectiveness of the present invention is that the percentage of amorphous polymer formed is reduced at the time of preparation of α-olefin polymers, and such effectiveness is also high, especially at the time of preparation of copolymer. For example, in the preparation of propylene polymer, the amount of isotactic propene as n-hexane insoluble product (20 ° C) is 98 to 99.8% expressed as isotactic index and that of atactic polypropylene as n-hexane soluble product is only 0.2 up to 2% expressed in atactic index. Thus, even when atactic polymer 30 is not removed, disadvantages such as degradation of polymer physical properties such as stiffness, heat stability, etc. are overcome, whereby the atactic polymer propagation step can be omitted, resulting in a simplification of the preparation process of the polymer.

The fifth effectiveness of the present invention is that polymer particles of good shape are obtained and that the average particle size is also small, ie 90 to 99% of the polymer is within the range of 0.25 to 0, 50 mm. The shape of the particles is almost spherical; the amounts of large particles and fine particles are reduced and the particle size distribution is narrow. Furthermore, the bulk density of the polymer is in the range of 0.45 to 0.52, and a small area of the storage tank per unit weight of polymer may be sufficient, therefore it is possible to compact the polymer production plant. Neither clogging difficulties caused by cohesion of polymer particles nor transport difficulties caused by fine particles occur; consequently, especially in gas phase polymerization, it is possible to perform a long-stabilized, continuous operation, since the amount of fine particles entrained in the unreacted α-olefin gas discharged from the polymerization kettle is reduced.

The first effectiveness, which is specific to the second aspect of the present invention, is that the high heat stability of the catalyst has allowed the polymerization of α-olefins to be carried out at high temperatures. Thus far, polymerization at high temperatures above 90 ° C has often degraded the powder form and has also increased the percentage of amorphous polymer formed, whereas according to the present invention, even when the polymerization is carried out above 90 ° C, the polymer obtained has a uniform powder and has a small percentage of amorphous polymer formed. Due to the fact that such a high temperature polymerization is possible, a large difference between the polymerization temperature and the cooling water temperature could be provided to increase the heat removal capacity and also the production capacity of the polymerization kettle.

The second effectiveness, which is specific to the second aspect of the present invention, is that it is possible to control the stereoregularity of the polymer without increasing the amount of atactic polymer as an n-hexane soluble product. For example, in the case of polypropylene, it is possible, if desired, the stereoregularity of homopolymers in the range of 0.88 to 0.96 expressed as absorbance ratio of that at 995 cm * to that at 974 cm *. - measured by the infrared absorption method (which ratio will be expressed below by IR-T) and thus control the stereoregularity of copolymer in the range of 0.83 to 0.95 without increasing the amount of atactic polymer. So far, when the stereoregularity of homopolymer is reduced, or when copolymers are prepared, to improve the physical properties of molded polymer product, such as stiffness, impact strength, heat sealing temperature, etc., is the amount of atactic polymer increases.

According to the present invention, it has become possible to omit the atactic polymer removal step and still control the stereoregularity of polymer, if desired, depending on the areas of application of the polymer in polymer preparation.

Example I

(1) Preparation of solid final product. 60 ml of n-Hexane, 0.05 mole diethylaluminum monochloride (DEAC) and 0.12 mole diisoamyl ether were mixed together at 25 ° C for 1 minute and then reacted at the same temperature for 5 minutes to obtain a reaction liquid (I) (molar ratio di-IQ isoamyl ether / DEAC: 2.4). 0.4 mole of TiCl4 was charged to a reactor which had been purged with nitrogen gas and heated to 35 ° C and the total amount of the aforementioned reaction liquid (I) was added dropwise over 180 minutes, followed by maintaining the product obtained at the same temperature for 15 60 minutes, raising the temperature at 80 ° C, carrying out further reaction for 1 hour to form a solid product (II), cooling at 50 ° C, adding 2.85 g propylene and carrying out the polymerization treatment at 50 ° C for 2 hours. After the treatment, the liquid was heated to 70 ° C and the supernatant was removed, followed by repeating 4 times a method of adding 400 ml of n-hexane and removing the supernatant by decanting to obtain a solid product (II) subjected to the polymerization treatment (20.4 g i.e. solid product (11) (19.0 g) plus polymer (1.4 g)). The total amount of this (II) was suspended in 25 ml of 25 n-hexane and to the suspension obtained were added 16 g of diisamyl ether and 35 g of TiCl 2 at 20 ° C for about 1 minute, followed by reaction for 1 hour at 70 ° C. After completion of the reaction, the obtained product was cooled to room temperature (20 ° C) and the supernatant was removed by decantation, followed by repeating the method of adding 400 ml of n-hexane 5 times, stirring for 10 minutes, storing and removing the supernatant and drying under reduced pressure to obtain a solid product (III).

(2) Preparation of pre-activated catalyst.

A 2 L stainless steel reactor fitted with inclined blades was charged with nitrogen gas and to this reactor were added 20 ml of n-hexane, 414 mg of diethylaluminum monochloride and 28 mg of the solid product (III) at room temperature added. Then the reaction was carried out at 40 ° C under a partible pro-40 carrot pressure of 200 kPa for 10 minutes (converted propylene per g solid p-8202923 22 product (III): 16.3 g), followed by removal of unreacted pro carrot and n-hexane under reduced pressure to obtain a preactivated catalyst.

(3) Polymerization of propylene.

300 ml of hydrogen were charged to the reactor, which contained the catalyst after completion of the pre-activation, and the gas phase polymerization was carried out under a partial propylene pressure of 2500 kPa at a polymerization temperature of 70 ° C for 2 hours. After the completion of the reaction, 5 g of methanol were added and the deactivation reaction was carried out at 70 ° C for 30 minutes, followed by cooling to room temperature (20 ° C) and drying of the obtained polymer, whereby 182.8 g of polymer were obtained were. The polymer yield per g of solid product (III) was 6.528 g, the isotactic index (n-hexane insoluble product at 20 ° C (%)), 99.8, bulk density of polymer 0.50 and the polymer particles had a almost spherical in shape, with 98% thereof having dimensions between 0.5 and 0.25 mm and 0.2% having dimensions smaller than 0.1 fl ™ ·. No polymer discoloration was observed and the yellowing index was 2, 0.

Example II

The solid product (III) obtained in Example I was stored for 4 months at 40 ° C and then a propylene polymerization was carried out as in steps (2) and (3) of Example I.

Comparative example 1

The solid product (II) obtained in Example I was stored for 4 months at 40 ° C as in Example II and then a propylene polymerization was carried out.

Comparative example 2

The solid product (II) subjected to polymerization treatment obtained in Example 1 was stored at 40 ° C for 4 months as in Example II, then a propylene polymerization was performed.

Comparative example 3

A propylene polymerization was carried out as in Example 1, except that the solid product (III) was obtained by reacting diiso-amyl ether with TiCl 2 without subjecting the solid product (II) to a polymerization treatment.

Example III

A pre-activated catalyst was obtained as in steps (1) and (2) of Example 1 and 1500 ml of n-hexane and 200 ml of hydrogen were introduced, followed by suspension polymerization under a partial propylene pressure of 8202923. 1000 kPa at 70 ° C for 4 hours. After completion of the polymerization, n-hexahah was removed by steam stripping to obtain a polymer.

Example IV

A propylene slurry polymerization was carried out as In for Example III, except that the polymerization was performed at 82 ° C instead of 70 ° G. The particle shape, bulk density and isotactic index of the polymer were almost unchanged from that of Example III .

10 Comparative example 4

The solid product (II) was reacted with diisoamyl ether and TiCl4 as in Example I, but without subjecting the solid product (II) to a polymerization treatment, to obtain a solid product (III) and a propylene polymerization was carried out at 82 ° G performed as in example IV. The resulting polymer swelled in n-hexane.

Comparative example 5 '

Using the solid product (II) obtained in Example I, a propylene polymerization was conducted at 82 ° C as in Example IV. The resulting polymer swelled in n-hexane.

20 Comparative example 6

Using the solid product (II), which was subjected to polymerization treatment, obtained in Example I, a propylene polymerization was performed at 82 ° C as in Example IV. The resulting polymer swelled in n-hexane.

The results of the previous examples and comparative examples are shown in Table A.

8202923 24

TABLE A

Number of Polymer- Iso- Landfill- How Much- Pas- 1 2

the pre-yield tac-weight held by MFR YI

image and (g) per g of the measurement 0.1 comparison fixed pro-index poly- 0.25-0.5 mm example duct (III) more (%) (%)

Example I 6528 99.8 0.50 98 0.2 4.1 2.5

Example II 6200 99.0 0.50 96 0.4 3.8 3.0

Compare 1 1000 98.0 0.45 60 2.4 3.8 18.0

Compare 2 1100 98.2 0.44 65 1.8 3.6 17.5

Compare 3 4 100 98.5 0.49 92.0 1.0 4.3 8.0

Example III 6800 99.0 0.50 96.0 0.6 4.2 2.0

Example IV 7200 98.0 0.49 96.0 0.8 4.1 1.8

Compare 4 - - -

Compare 5 - ~ - "~

Compare 6 - - - 8202923

Melt flow rate (according to ASTM D-1238 (L)) 2

Comparison index (according to JIS K7103)

The symbol (-) in the table means "not measurable" 25

Example V

40 ml of n-heptane, 0.05 mole diethylaluminum monochloride, 0.09 mole diisoamyl ether and 0.05 mole di-n-butyl ether were reacted at 18 ° C for 30 minutes to obtain a reaction liquid dropwise to 0.275 mole ΤίΟΙή at 40 ° C in 300 minutes was added, followed by reaction reaction mixture at the same temperature as above for 1.5 hours, raising the temperature to 65 ° G, further reaction mixture for 1 hour, removing the supernatant and repeating the procedure of adding 200 ml of n-hexane 6 times and removing the supernatant by decanting to obtain 18 g of solid product (II), which were then suspended in 500 ml n-hexane, followed by addition of 2 g diethylaluminum monochloride and addition of 1 g propene at 60 ° C for 1 hour for reaction, to obtain a solid product (II) 15 subjected to polymerization treatment (amount of converted propene: 0 , 3 g). After the reaction, the supernatant was removed, followed by repeating the procedure of adding 300 ml of n-hexane twice and removing the supernatant by decantation. 18.3 g of the solid product (II) subjected to polymerization treatment were then suspended in 40 ml of n-hexane, followed by addition of 18 g of TiCl4 and 18 g of n-butyl ether and reaction of the mixture for 3 hours at 60 ° C. After the reaction, the supernatant was removed by decantation, followed by repeating the method of adding 200 ml of n-hexane 3 times, stirring for 5 minutes, storing the mixture and removing the supernatant and then drying of the obtained material under reduced pressure to obtain a solid product (III). Using this product, a propylene polymerization was carried out as in steps (2) and (3) of Example I.

Example VI

80 ml of n-octane, 0.05 mole of diisopropylaluminum monochlorida and 0.11 mole of di-n-octyl ether were reacted at 35 ° C for 4 hours to obtain a reaction liquid, which was added dropwise to 0.25 mole of TiCl4 at 31 ° C C in 120 minutes, followed by reaction of the mixture at 40 ° C for 30 minutes, raising the temperature to 85 ° C, further conversion of the mixture for 30 minutes, addition of 20 g of propene at the same temperature as before, conversion of the mixture for 30 minutes, removal of the liquid by filtration, 2 repeated steps of a method of adding 300 ml of n-octane, stirring the mixture for 5 minutes and filtering off-40, to obtain a solid product (II), subjected to S 2 0 2 9 2 3 26 polymerization treatment (solid product (II): 17.5 g) (amount of converted propene: 0.1 g). To this solid product, subjected to polymerization treatment, 40 ml of n-octane, 22 g of diisoamyl ether and 14 g of TiCl4 were added, followed by reaction of the mixture at 85 ° C for 30 minutes, filtration, 4 times repeated treatment of the method of adding 100 ml of n-pentane, stirring for 30 minutes and filtering and drying to obtain a solid product (III). Propylene polymerization was then carried out as in steps (2) and (3) of Example I.

Example VII

A solid product (III) was prepared as in Example I, except that 0.04 mol of di-n-butylaluminum monochloride was used instead of 0.05 mol of diethylaluminum monochloride, to obtain a reaction liquid (I), which was added dropwise 45 ° C was added to TiCl4. The propylene polymerization was carried out using the solid product (III).

Example VIII

Example I was repeated, except that 22 g of diisoamyl ether, 20 g of TiCl 4 and 18 g of silicon tetrachloride were added to the solid product (II) subjected to polymerization treatment to obtain a solid product (III). A propylene polymerization was performed using this product.

Example IX

Example I was repeated, except that 28 g of di-n-pentyl ether and 5 g of anhydrous aluminum trichloride were added to 100 ml of n-heptane, followed by reaction of the mixture by heating at 80 ° C for 2 hours to obtain a solution, to which 20.4 g of a solid product (II) subjected to polymerization treatment, as in Example 1, was added, followed by reaction of the mixture at 80 ° C for 2 hours to obtain a solid product (III) . below

a propylene polymerization was carried out using this product. Example X.

Example V was repeated except that 35 g of TiCl 4, 12.0 g of diisoamyl ether and 6 g of di-n-butyl ether were added to 18.3 g of the solid product (II), subjected to polymerization treatment, to obtain a solid product (III). A propylene polymerization was performed using this product.

Example XI

0.03 mol of Triisobutylalurium was reacted with 0.07 mol of di-n-dead-40-ethyl ether in 100 ml of n-hexane at 20 ° C for 40 minutes before obtaining a reaction liquid, which was then added dropwise to 0.18 mol TiCl4 at 20 ° C for 2 hours, followed by addition of 4 g of propylene, reaction of the mixture at 30 ° C for 30 minutes and further at 50 ° C for 60 minutes, removal of the liquid portion by filtration and n-hexane washes to give 23.8 g of a solid product (II) subjected to polymerization treatment (amount of propylene converted. * 0.8 g). To this product were added 50 ml of n-heptane, 21 g of di-n-butyl ether and 40 g of TiCl4, followed by reaction of the mixture at 50 ° C for 140 minutes, filtering, washing with n-hexane and drying, whereby solid product (III) was obtained. Using this product, a propylene polymerization was carried out as in Example I.

Example XII

0.07 mol of Triethylaluminum was reacted with 0.18 mol of diisoamyl ether 15 in 45 ml of n-hexane at 40 ° C for 4 hours to obtain a reaction liquid, which was then added dropwise to 0.84 mol of HCl at 32 ° C for 4 hours, followed by maintaining the temperature at 35 ° C for 1 hour, adding 10 g of propene, increasing the temperature at 78 ° C, reacting the mixture at this temperature for 2 hours, filtering, washing with n hexane and drying to give 24 g of a solid product (II) subjected to polymerization treatment (amount of propylene converted: 1.0 g). This product was added to a reaction liquid obtained by reaction of 40 ml of n-hexane, 27 g of diisoamyl ether and 20 g of TiCl 4 at 35 ° C for 30 minutes, followed by reaction of the mixture for 1 hour at 75 ° C, filtration, washing with n-hexane and drying, yielding a solid product (III). Using this product, a propylene polymerization as in Example 1 was performed.

Example XIII

A solid product (III) was obtained as in Example 1, except that 6 g of butene-1 were used instead of 2.85 g of propene, 20.9 g of a solid product (II) being subjected to polymerization treatment slings were obtained (amount of converted butene-1: 0.9 g). Using the solid product (III), a propylene polymerization was carried out as in Example I.

Example XIV

A solid product (III) was obtained as in Example XIII, except that 4.0 g of ethylene was used instead of butene-1 to obtain 20.6 g of a solid product subjected to polymerization treatment (amount converted ethylene: 0.6 g). Using the solid product (III) 8202923 28, a propylene polymerization was performed.

Example XV

Into the same reactor as in step (2) of Example I, 4 ml of n-pentane, 160 mg of diethylaluminium monochloride, 28 mg of the solid product (III) obtained from Example 1 and 5 g of polypropylene powder were charged and mixed together, followed by removal of n-pentane under reduced pressure, carrying out the gas phase reaction while the previously obtained catalyst was fluidized, with propylene gas under a partial propylene pressure of 80 kFa at 30 ° C for 20 minutes and then removal of unreacted propylene for obtaining a pre-activated catalyst (amount of converted propylene per g of the solid product (III): 1.6 g). Using this catalyst, a gas phase polymerization was carried out as in step (3) of Example I.

Example XVI

120 mg of Di-n-butylaluminum monochloride and 28 mg of the solid product (III) obtained from Example XI were placed in 30 g of propylene at 20 ° C, followed by reaction of the mixture under 980 kpa for 10 minutes and removal of unreacted propylene, whereby a preactivated catalyst is obtained in the form of powder 20 (amount of converted propene per g of the solid product (III): 1.1 g). Using this catalyst, a gas phase polymerization of propylene was carried out as in step (3) of Example I.

Example XVII

Example I was repeated, except that in the precooked activation of step (2) of Example I ethylene was used instead of propylene and ethylene was reacted under a partial ethylene pressure of 100 kxa at 35 ° C for 10 minutes (amount ethylene converted per g of the solid product (III): 2.4 g).

Example XVIII

Example I was repeated, except that in the previous activation of Example I, butene-1 was used instead of propylene and butene-1 was converted under a partial butene pressure of 50 kPa at 35 ° C for 10 minutes (amount of butene-1 converted per g of the solid product (III): 0.3 g).

35 Example XIX

Example I was repeated, except that 380 mg of diisopropyl aluminum monochloride was used instead of 420 mg of diethyl aluminum mono chloride in step (2) of Example I.

Example XX

40 Pre-activation was performed as in step (2) of 8202923 29 Example I, except that 320 mg of triethyl aluminum were used instead of 420 mg of diethyl aluminum monochloride and polymer was obtained as in step (3) of Example I, except that ethylene was polymerized under a hydrogen pressure of 1200 kPa and a partible ethylene-5 pressure of 1200 kpa at 85 ° C.

Example XXI

After a preactivated catalyst was prepared as in steps (1) and (2) of Example I, 300 ml of hydrogen and then 600 g of propylene were introduced, followed by mass polymerization under a partial propylene pressure of 3100 k 2 a at 70 ° C for 1 hour. After completion of the reaction, unreacted propylene was rinsed out and the post-treatment was carried out as in Example 1 to obtain a polymer.

The results of Examples V to XXI are included in Table B.

8202923 30

TABLE B

Number of Polymer- Iso- Landfill- How Much- Pass- * **

the pre-yield tac- weight ad- ministration MFR YI

image and (g) per measurement of the measurement 0.1 comparison fixed pro-index poly- 0.25-0.5 mm example duct (III) more ®m (%) (%)

Example V 6400 99.6 0.50 98.2 0.3 4.2 2.8

Example VI 6200 99.3 0.50 98.0 0.4 4.1 2.8

Example VII 6300 99.0 0.48 95.0 0.2 4.8 2.5

Example VIII 6400 98.0 0.48 98.0 0.3 4.1 2.8

Example IX 6200 98.0 0.46 98.0 0.4 4.9 2.8

Example X 6800 99.6 0.50 98.0 0.3 3.8 2.0

Example XI 6200 98.0 0.48 95.0 0.5 3.2 2.8

Example XII 6300 99.0 0.50 94.0 0.4 3.8 2.5

Example XIII 6500 99.0 0.50 96.0 0.2 3.8 2.5

Example XIV 6200 99.0 0.50 95.0 0.3 3.2 2.8

Example XV 6520 99.0 0.50 96.0 0.2 3.4 2.5

Example XVI 6400 99.0 0.49 94.0 0.2 3.8 2.6

Example XVII 6200 98.5 0.46 92.0 0.6 3.4 2.9

Example XVIII 6450 99.0 0.50 96.0 0.5 4.3 2.6

Example XIX 6200 98.5 0.48 92.0 0.6 4.2 2.9

Example XX 6900 - 0.46 92.0 0.4 4.1 2.0

Example XXI 6400 99.0 0.50 98.0 0.2 4.3 2.2 8202 923 31

Example XXII

A pre-activated powder catalyst was prepared in a reactor as in steps (1) and (2) of Example I followed by the feed. of 300 ml of water and 200 g of propylene and then mass polymerization under a partial propylene pressure of 2600 kPa at 60 ° C for 30 minutes (amount of polymerized propylene: 35 g). Thereafter, the resulting slurry, which contained unreacted propylene, was rinsed in a fluidized bed with a diameter of 20 cm and a volume of 20 l, provided with stirring elements, while poly-10 was more fluidized with propylene gas, which circulated with a flow speed of 5 cm / sec to carry out the gas phase polymerization at a reaction temperature of 70 ° C under a partial propylene pressure of 2100 kPa for 2 hours. The post-treatment was then carried out as in Example I to obtain a polymer.

Example XXIII

Mass polymerization was performed under a partial propylene pressure of 2600 kPa at 60 ° C for 30 minutes as in Example XXI, followed by transferring unconverted liquefied propylene to a separate feed tank connected to the reactor. raising the temperature of the reactor to 72 ° C and conducting the gas phase polymerization for 2 hours, while propylene was fed from the feed tank to give a polymerization pressure of 2600 kPa. Then, the same treatment as in Example 1 was carried out to obtain a polymer.

Example XXIV

Mass polymerization was performed under 2600 kPa at 60 ° C for 30 minutes as in Example XXI. The polymerization temperature was then raised to 70 ° C to obtain a polymerization pressure of 3100 kPa. When the polymerization was continued as such, the pressure dropped to 2600 kPa in 40 minutes. Therefore, the bulk polymerization was continuously transferred to the gas phase polymerization. Gas phase polymerization was further conducted while propylene was fed for 60 minutes to maintain the pressure at 2600 kPa. The post-treatment was carried out as in Example I to obtain a polymer.

Example XXV

1000 ml of n-Hexane, 320 mg of diethylaluminum monochloride and 13 mg of solid product (III) obtained in Example V were fed and propylene was reacted under partial propylene pressure of 120 kPa at 20 ° G for 10 min-40 to pre-activate (amount of converted pro 8202923 32 carrots per g of solid product (III): 0.6 g). Unreacted propylene was rinsed out and 120 ml of hydrogen were introduced, followed by suspension polymerization under a partial propylene pressure of 1000 kPa at 70 ° C for 2.5 hours. Then n-hexane was removed by steam stripping to obtain a polymer.

Example XXVI

80 ml of n-Pentane, 280 mg of diethylaluminum monochloride and 25 mg of solid product (III) were added. Then propylene was reacted at 15 ° C while increasing its partial pressure, ie by bringing its pressure to 500 kPa (100 kPa / min) in 5 minutes to perform a pre-activation (amount converted propene per g of the solid product (III): 3.2 g). Unreacted propylene was rinsed out and 200 ml of hydrogen were introduced, followed by suspension polymerization under a partial propylene pressure of 1000 kPa at 70 ° C for 60 minutes (amount of polymerized propylene: 63 g). The resulting suspension containing the solvent was introduced into a fluidized bed equipped with stirring elements, followed by propylene gas phase polymerization, as in Example XXII.

Example XXVII

1000 ml of n-Hexane, 320 mg of diethylaluminum monochloride and 30 mg of the solid product (III) obtained in Example V were introduced and 120 ml of hydrogen were introduced without pre-activation, followed by suspension polymerization under a partial propylene pressure of 1000 kPa at 70 ° C for 2.5 hours. Then n-hexane was removed by steam stripping to obtain a polymer.

Example XXVIII

Propene was subjected to a suspension polymerization using the non-preactivated catalyst as in Example XXVII, followed by rinsing unreacted propylene and hydrogen and distillation of n-hexane under reduced pressure to n-hexane in the polymer in an amount of 30 % was present. This solvent-containing polymer was placed in the fluidized bed, which was equipped with stirring elements as used in Example XXII and 450 ml of hydrogen was introduced to carry out a gas phase polymerization under a parallel propylene pressure of 2100 kPa at 70 ° C for 2 hours as in Example XXII. Aftertreatment was then carried out as in Example 1 to obtain a polymer.

Example XXIX

A propylene-ethylene block copolymerization was performed as in Example XXVIII, except that the suspension polymerization of the first stage 8202923 33 was carried out with propylene and if the gas phase polymerization of the second stage ethylene polymerization was conducted under a partial hydrogen pressure of 800 kPa and a partial ethylene pressure of 1200 kPa at 70 ° C for 2 hours.

5 Example XXX

Example XXII was repeated, except that an α-olefin mixture of 200 g of propylene with 20 g of ethylene was used instead of using 200 g of propylene to obtain a polymer (propylene-ethylene copolymer).

Example XXXI

Example XXX was repeated except that 30 g of butene-1 was used instead of using 20 g of ethylene to obtain a polymer (propylene-butene-1 copolymer).

Example XXXII

A polymer was obtained as in Example 1, except that the ethylene polymerization was carried out under a hydrogen pressure of 1200 kPa and a partial ethylene pressure of 1200 kPa at 85 ° C, using the pre-activated catalyst, instead of running of a propylene polymerization using 300 ml of hydrogen, under a partial propylene pressure of 2500 kPa at 70 ° C.

Example XXXIII

300 mg of the solid product (III) obtained in Example I and 3000 mg of diethylaluminum monochloride were suspended in 200 ml of n-hexane, followed by reaction under a partial propylene pressure of 130 kPa at 20 ° C for 10 rainutes, rinsing out unreacted propylene, storing the obtained material under stirring at 30 ° C for 1 week, introducing the obtained catalyst slurry containing 25 mg of the solid product (III) into a polymerization kettle and then conducting a slurry polymerization and subsequent gas-phase polymerization as in Example XXVI.

Comparative Examples 7, 8 and 9

Using each of the following solid products in place of the solid product (III) obtained in Example I, the respective obtained catalyst suspensions were stored for 1 week as in Example XXXIII:

Comparative Example 7: The solid product (II) obtained in "Example I.

Comparative Example 8: The solid product (II) subjected to polymerization treatment obtained in Example I.

8202923 34

Comparative Example 9: The solid product (III) obtained according to Comparative Example 3.

The results of Examples XXII to XXXIII and Comparative Examples 7 to 9 are shown in the following Table C.

8202923 35

TABLE C

Number of Polymer- Iso- Landfill- How Much- Pass- * **

the pre-yield tac-weight held by MFR YI

image and (g) per g of the measurement 0.1 comparison fixed pro-index poly- 0.25-0.5 mm example duct (III) more (%) (%)

Example XXII 7200 99.2 0.49 95.0 0.3 2.6 2.0

Example XXIII 7400 99.0 0.49 96.0 0.2 2.9 1.5

Example XXIV 7100 99.2 0.50 96.0 0.3 3.8 2.2

Example XXV 6700 99.4 0.50 94.0 0.3 3.8 2.1

Example XXVI 7100 99.0 0.49 96.0 0.2 3.8 2.0

Example XXVII 6200 99.0 0.45 91.0 0.2 3.4 3.0

Example XXVIII 7400 98.5 0.45 90.0 0.2 3.6 1.5

Example XXIX 7500 98.0 0.45 90.0 0.2 3.4 1.5

Example XXX 7600 98.0 0.46 91.4 0.2 3.2 1.4

Example XXXI 7500 98.0 0.46 92.0 0.2 3.8 '1.8

Example XXXII 6600 - 0.45 90.0 0.3 4.1 2.4

Example XXXIII 6200 98.5 0.46 90.0 0.9 2.9 3.0

Compare 7 600 98.5 0.45 90.0 4.8 2.9 20

Compare 8 700 98.5 0.45 92.0 4.2 2.9 20

Compare 9 4200 98.5 0.45 93.0 2.2 2.9 4.0 8202923 36

Example XXXIV

(1) Preparation of solid product (III)

A solid product (III) (a solid final product) is obtained in the same manner as in step (I) of Example I.

(2) Preparation of a pre-activated catalyst

A 2 L stainless steel reactor fitted with inclined blades, purged with nitrogen gas and 20 ml of n-hexane, 414 mg of diethyl aluminum monochloride and 22 mg of the final solid product were charged to this reactor at room temperature. The reaction was then carried out at 40 ° C under a partial propylene pressure of 200 kPa for 10 minutes (converted propylene per g of solid end product: 16.3 g), followed by rinsing unreacted propylene and then adding of a reaction product (G) obtained by reacting 23 mg of triethyl aluminum with 30.3 mg of methyl p-toluylate in 20 ml of 15 n-hexane at 25 ° C for 30 minutes to obtain a pre-activated catalyst.

(3) Polymerization of propylene

Into the reactor, which contained the catalyst upon completion of the preactivation, 150 ml of u / a was introduced and the gas phase polymerization was carried out under partial propylene pressure of 2200 kPa at a polymerization temperature of 80 ° C for 2 hours. After the completion of the reaction, 3 g of methanol were introduced and the deactivation reaction was carried out at 70 ° C for 30 minutes, followed by cooling to room temperature (20 ° C) and drying the resulting polymer, 25 h / hour 260 g of polymer obtained u / ers. The polymer yield per g solid end product u / as 13000 g, the isotactic index (insoluble in n-hexane at 20 ° C (%), 99.2, polymer bulk density, 0.50 and the polymer particles had a substantially spherical shape, u / e of 99% having dimensions between 0.25 and 0.50 mm and particles passing through a sieve of 0.1 mm 30 0.1% or less h / s. No polymer staining u / er u / a and the yellowing index u / axis 0.5 further u / er due to the degree of polymer corrosion corroded by the degree of u / arm stability of the catalyst after the deactivation u / u Please note, polymer is heated / depleted at a certain temperature and whether acid gas is easily or difficult to decolve / decreate / be affected by the presence or absence of congo red color change (according to JIS K -6723) As a result, no color change is observed.

The polymer was allowed to anneal at 135 ° C for 120 minutes according to the methods of J.P. Luongo (Journal of Applied Polymer Science, 3, (1960) 40 302), obtained an IR-Z of 0.94 h / min.

8202923 37

Example XXXV

Steps (1) and (2) of Example XXXIV u / er were repeated to obtain a preactivated catalyst. 1500 ml n-Hexane and 200 ml h / atester were then introduced and the slurry polymerization carried out 5 h / h under a partial propylene pressure of 1000 kEa at 70 ° C; for 4 hours. After completion of the polymerization, n-hexane is removed by steam stripping to obtain a polymer.

Example XXXVI

Example XXXV u / e repeated, except that the propylene slurry polymerization u / e was carried out at 92 ° C instead of 70 ° C. The particle shape, bulk density and isotactic index of the polymer obtained hours are virtually unchanged from that of Example XXXV.

Reference example 10

A propylene polymerization was carried out as for example XXXVI, * 15 except that the reaction product (G) was not used. The polymer obtained obtained from zu / ol in n-hexane.

Reference example 11

Diisoamyl ether and TiCl 2 u / er reacted with the solid product (II) as in Example XXXIV, but without subjecting the solid product (II) to -20 u / er on a polymerization treatment with propylene to obtain a solid final product, followed by propylene polymerization as in Example XXXVI, equil / el at 52 ° C. The bulk density and isotactic index of the obtained polymer are both lower.

Comparative Example 12 A propylene polymerization was carried out using the solid product (II) as obtained in Example XXXIV in the same manner as in Example XXXVI, equally at 92 ° C. The polymer obtained was sol / ol in n-hexane.

Comparative Example 13 A propylene polymerization carried out using the solid product (II), subjected to polymerization treatment obtained in Example XXXIV, in the same manner as in Example XXXVI, equally at 92 ° C. The polymer obtained will dissolve in n-hexane in n-hexane.

Example XXXVII

The solid end product obtained, for example, XXXIV hours per month at 40 ° C. A propylene polymerization was carried out as in steps (2) and (3) of Example XXXIV.

Reference example 14

The solid product (II) obtained, for example, XXXIV / hr for 40 months at 40 ° C, as in Example XXXVII. A propylene polymerization 8202923 * 38 was then performed.

Reference example 13

The solid praduct (II), subjected to polymerization treatment, obtained, for example, XXXIV / 1, was stored at 40 ° C for 4 months, such as 5, for example, XXXVII. Then a propylene polymerization was carried out.

Reference example 16

A propylene polymerization was carried out as in Example XXXVII, except that the solid product (II), without being subjected to a polymerization treatment, was reacted with diisoamyl ether and TiCl 2 to obtain a solid final product.

Reference example 17

A polymerization was performed without addition of the reaction product (G) in Example XXXVII.

Example XXXVIII

A pre-activated catalyst was prepared as in Example XXXV, except that 15 mg of methyl p-toluylate were used to prepare the reaction product (G). Propylene polymerization was performed using this catalyst.

Example XXXIX

A preactivated catalyst was prepared as in Example XXXV, except that 7.5 mg of methyl p-toluylate were used to prepare the reaction product (G). Propylene polymerization was performed using this catalyst.

Example XL

A pre-activated catalyst was prepared as in Example XXXV, except that 4.7 mg of methyl p-toluylate were used to prepare the reaction product (G). Propylene polymerization was performed using this catalyst.

Example XLI

A preactivated catalyst was prepared as in Example XXXV, except that 60 mg of methyl p-toluylate were used to prepare the reaction product (G). Propylene polymerization was performed using this catalyst.

Comparative Example 18 A pre-activated catalyst was prepared as in Example XXXV, except that 23 mg of triethyl aluminum were used in place of the reaction product (G) to prepare the catalyst. Propylene polymerization was performed using the catalyst. The amount of atactic polymer increased markedly.

8202923 39

Reference examples 19 and 20

A preactivated catalyst was prepared as in Example XXXV, except that 30.3 g of methyl p-toluylate (Comparative Example 19) or 7.5 mg (Comparative Example 20) were used in place of the reaction product (G). Propylene polymerization was carried out using the catalyst. The value of IR-t "was unchanged.

Example XLII

A pre-activated catalyst was prepared as in Example XXXIV, except that 50 mg of triisobutyl aluminum and 38 mg of ethyl benzoate were used to prepare the reaction product (G). A propylene polymerization was carried out using the catalyst.

Example XLIII

A pre-activated catalyst was prepared as in Example XXXIV, except that 40 mg of tri-n-butyl aluminum and 55 mg of ethyl p-anisate were used to prepare the reaction product (G). Propylene polymerization was performed using the catalyst.

Example XLIV

40 ml of n-heptane, 0.05 mole of diethylaluminum monochloride, 0.09 mole of di-isoamyl ether and 0.05 mole of di-n-butyl ether were reacted at 18 ° C for 30 minutes to obtain a reaction liquid which was added dropwise was added to 0.275 mol TiCl 4 at 40 ° C for 300 minutes, followed by a reaction of the mixture at the same temperature as before for 1.5 hours, raising the temperature to 65 ° C, further conversion of the mixture for 1 hour , removing the supernatant and repeating the method of adding 200 ml n-hexane 6 times and removing the supernatant by decanting to obtain 18 g of a solid product (II), which was then suspended in 500 ml of n-hexane, followed by addition of 2 g of diethylaluminum monochloride and addition of 1 g of propylene at 60 ° C for 1 hour in the reaction to obtain a solid product (II), subjected to polymerization treatment (amount of put propene: 0.3 g). After the reaction, the supernatant was removed, followed by repeating the procedure of adding 300 ml of n-hexane twice and removing the supernatant by decantation. 18.3 g of the solid product (II), subjected to polymerization treatment, were then suspended in 40 ml of n-hexane, followed by addition of 18 g of TiCl 2 and 18 g of n-butyl ether and reaction of the mixture for - 3 hours at 60 ° C. After the reaction, the supernatant was removed by decantation, followed by repeating the method of adding 200 ml of n-hexane 3 times, stirring for 5 minutes, keeping the mixture 8202923 and removing the supernatant and then drying the obtained material under reduced pressure to obtain a solid final product. Using this product, a propylene polymerization was carried out as in steps (2) and (3) of Example 5 XXXIV.

Example XLV

80 ml of n-octane, 0.05 mole of diisopropylaluminum monochloride and 0.11 mole of di-n-octyl ether were reacted at 35 ° C for 4 hours to obtain a reaction liquid, which was added dropwise to 0.25 mole of TiCl ^ at 31 ° C for 120 minutes, followed by reaction of the mixture for 30 minutes at 40 ° C, raising the temperature to 85 ° C, further conversion of the mixture for 30 minutes, adding 20 g of propylene to the same temperature as before, reaction of the mixture for 30 minutes, removal of the liquid by filtration, 2 repeats of the method of adding 300 ml of n-octane, stirring of the mixture for 5 minutes and filtration to obtain a solid product (II), subjected to polymerization treatment (solid product (II): 17.5 g) (amount of converted propene: 0.1 g). To this solid product, subjected to polymerization treatment, 40 ml of n-octane, 22 g of diisoamyl ether and 14 g of TiCl 2 were added, followed by reaction of the mixture for 30 minutes at 85 ° C, filtering off 4 times. method of adding 100 ml of n-pentane, stirring for 10 minutes and filtering and drying to obtain a solid product (III). This product 25 (17 g) was then suspended in 100 ml of n-pentane, followed by addition of 2.4 g of diethylaluminum monochloride, addition of 3 g of propene and reaction of the mixture for 2 hours at 45 ° C (amount of converted propylene : 0.6 g). After the reaction, filtration, washing and drying were performed to obtain a solid final product from which a pre-activated catalyst was prepared as in Example XXXIV. Propylene polymerization was performed using this catalyst.

Example XLVI

A solid final product was prepared as in Example XLV, except that 0.04 mole of di-n-butylaluminum monochloride was used instead of 0.05 mole of diisopropylaluminum monochloride to obtain a reaction liquid (I) dropwise at 45 ° C was fed to TiCl 2. Propylene polymerization was performed using this solid end product.

8202923 41

Example XL VII

60 ml n-Hexane, 0.05 mol diethylaluminum monochloride (DEAC) and 0.12 mol diisoamyl ether were mixed at 25 ° C for 1 minute and then the mixture was reacted at the same temperature as above for 5 minutes to obtain a reaction liquid (I) (the molar ratio diisoamyl ether to DEAC: 2.4). 0.5 mole TiCl 2 / ug into a nitrogen gas purged reactor heated to 35 ° C, followed by the dropwise addition to the mixture of the total amount of the reaction liquid (I) obtained above for 120 minutes, maintaining the temperature at the same temperature as before for 30 minutes, raising the temperature to 75 ° C, further conversion for 1 hour, cooling to room temperature, removing the supernatant and repeating 4 times the method of adding 400 ml of n-hexane and removing the supernatant by decanting to obtain a solid product (11) (19 g). The total amount of this solid product (II) u / s suspended in 300 ml n-hexane, followed by addition of 16 g diisoamyl ether and 35 g TiCl 2 at room temperature (20 ° C) for about 1 minute and conversion of the mixture for 1 hour at 65 ° C. After the reaction, the liquid was cooled to room temperature (20 ° C) followed by removal of the supernatant by decantation, repeating the method of adding 400 times ml of n-hexane, stirring for 10 minutes, stirring the mixture and removing the supernatant and drying under reduced pressure to obtain a solid product (III). A portion of 25 (10 g) of this solid product (III) is slurried in 200 ml of n-hexane, followed by addition of 0.7 g of diethylaluminum monochloride, further addition of 2 g of propylene, reaction of the mixture at 25 ° C for 10 minutes, filter off u / ann 1 g propene u / ash converted, 2 times u / axes with 200 ml n-hexane and drying under reduced pressure to obtain a solid end product, u / from a pre-activated catalyst u / obtained as for example XXXIV. Propylene polymerization was carried out using this catalyst.

Example XLVIII

Example XXXIV is repeated, except that 22 g of diisoamyl ether, 20 g of 35 TiCl 2 and 18 g of silicon tetrachloride are added to the solid product (II), under polymerization treatment, to obtain a solid final product. A propylene polymerization was carried out using this product.

Example IL

40 Example XXXIV u / e repeated, except that 28 g of di-n-pentyl ether 8202923 42 and 5 gv / anhydrous aluminum trichloride are added to 100 ml of n-heptane, followed by reaction of the mixture by heating at 80 ° C for 2 hours to obtain. of a solution, u / o solid product (II), subjected to polymerization treatment (20.4 g), such as 5 in Example XXXIV, u / u added, followed by reaction of the mixture at 80 ° C for 2 hours before obtaining a solid end product. A propylene polymerization was carried out using this product.

Example L

Example XLIV was repeated, except that 35 g of TiCl 2, 12.0 g of diisO-10 amyl ether and 6 g of di-n-butyl ether were added to 18.3 g of the solid product (II) under polymerization treatment, for obtaining a solid end product. A propylene polymerization was performed four times using this product.

Example LI

0.03 mole Triisobutylaluminum was reacted with 0.07 mole di-n-dodecyl ether in 100 ml n-hexane at 20 ° C for 40 minutes to obtain a reaction liquid, which was then added dropwise to 0.18 mole TiCl 2 at 20 ° C for 2 hours, followed by addition of 4 g of propylene, reaction of the mixture at 30 ° C for 30 minutes and further for 60 minutes at 50 ° C, removal of the liquid portion by filtration and washing with n-hexane to obtain a solid product (II), subjected to polymerization treatment (23.8 g) (amount of converted propene: 0.8 g). To this product, 50 ml of n-heptane, 21 g of di-n-butyl ether and 40 g of TiCl 2 were added, followed by reaction of the mixture at 50 ° C for 140 minutes, filtering, u / ases with n- hexane and drying to obtain a solid final product.

A propylene polymerization was carried out using this product as in Example XXXIV.

Example LII

0.07 mol of Triethylaluminum was reacted with 0.18 mol of diisoamyl ether in 45 ml of n-hexane at 40 ° C for 4 hours to obtain a reaction liquid, which was then added dropwise to 0.84 mol of TiCl 2 at 32 ° C for 4 hours, followed by maintaining the temperature for 1 hour at 35 ° C, adding 10 g of propylene, increasing the temperature at 78 ° C, reacting the mixture at this temperature for 2 hours, filtering , v / axes with n-hexane and drying to obtain a solid product (II), subjected to polymerization treatment (24 g) (amount of propylene converted: 1.0 g). This product was added to a reaction liquid obtained by reaction of 40 ml of n-hexane, 27 g of diisoamyl ether and 20 g of TiCl 2 at 35 ° C for 8202923 ° C for 30 minutes, followed by reaction of the mixture at 75 ° C for 1 hour, filtering, u / axes with n-hexane and drying to obtain a solid final product. Using this product, a propylene polymerization was carried out as for example XXXIV.

5 Example LIU

A solid final product was obtained as in Example XXXIV, except that 6 g of butene-1 was used instead of 2.85 g of propylene to obtain a solid product (II) subjected to polymerization treatment (20). 1.9 g) (amount of converted butene-1: 0.9 g). Using this solid final product, a propylene polymerization was carried out as in Example XXXIV.

Example LIV

A solid final product was obtained as in Example LIII, except that 4.0 g of ethylene was used instead of 6 g of butene-1 to obtain a solid product (II), subjected to polymerization treatment (20.6 g) (amount of converted ethylene: 0.6 g). Propylene polymerization was carried out using this solid end product.

Example LV

Into the same reactor as in step (2) of Example XXXIV, 4 ml of n-pentane, 160 mg of diethylaluminum monochloride, 22 mg of solid end product obtained from Example XXXIV and 5 g of polypropylene powder were mixed and mixed together, followed by removal of n-pentane under reduced pressure, carry out the gas phase reaction while the catalyst obtained above is fluidized, with propylene gas under a partial propylene pressure of 80 kPa at 30 ° C for 20 minutes and then removal of unreacted propylene for obtaining a pre-activated catalyst (amount of converted propylene per g of solid end product: 1.8 g). Using this catalyst, a gas-phase polymerization is carried out as in step (3) of Example XXXIV.

Example LVI

120 mg of Di-n-butylaluminum monochloride and 28 mg of the solid end product obtained, for example, XLIV hours were placed in 30 g of propylene at 20 ° C, followed by reaction of the mixture under 980 kPa for 10 minutes and removal of non converted propylene to obtain a preactivated powdered catalyst (amount of converted propene per g of the solid end product: 100 g). Using this catalyst, the gas phase polymerization of propylene is carried out as in step (3) of Example XXXIV.

8202923 44

Example LVII

Example XXXIV is repeated except that in the pre-activation of step (2) of Example XXXIV ethylene is used instead of propylene and ethylene converted under partial ethylene pressure of 100 kPa at 35 ° C for 10 minutes (amount of converted ethylene per g of the solid final product: 2.4 g).

Example LVIII

Example XXXIV u / s repeated, except that in the prior activation of Example XXXIV, butene-1 / ud is used instead of propylene 10 and butene-1 u / t is converted under a partial butene pressure of 50 kPa at 35 ° C for 10 minutes (amount of converted butene-1 per g of the solid end product: 0.3 g).

Example LI'XX

Example XXXIV is repeated except that 380 mg of diisopropylaluminum monochloride are used instead of 414 mg of diethylaluminum monochloride in step (2) of Example XXXIV.

Example LX

Preliminary activation was carried out as in step (2) of Example XXXIV, except that 320 mg of triethylaluminum were used instead of 414 mg of diethylaluminum monochloride and polymer obtained as in step (3) of Example XXXIV, except that ethylene is polymerized under a hydrogen pressure of 1200 kPa and a partial ethylene pressure of 1200 kPa at 85 ° C.

Example LXI

After a pre-activated catalyst prepared u / as as in steps (1) and (2) of Example XXXIV, u / u 300 ml u / ater and then 600 g of propylene were introduced, followed by mass polymerization under partial propylene pressure of 3100 kf? a at 70 ° C for 1 hour. After completion of the reaction, unreacted propylene was rinsed out and the post-treatment was carried out as for example XXXIV to obtain a polymer.

Example LXII

A pre-activated powdered catalyst prepared in a reactor, as in steps (1) and (2) of Example XXXIV, followed by introduction of 300 ml of u / ater and 200 g of propylene and then running mass polymerization under a partial propylene pressure of 2600 kpa at 60 ° C for 30 minutes (amount of polymerized propylene: 35 g). Thereafter, the resulting slurry, which contained unreacted propylene, was rinsed in a fluidized bed with a diameter of 40 cm and a volume of 20 l, provided with stirring elements, while fluidized with propylene gas, which circulated at a flow rate of 5 cm / sec to carry out a gas phase polymerization at a reaction temperature of 70 ° C under a partial propylene pressure of 2100 kPa a for 2 hours. The post-treatment was then carried out as for example XXXIV to obtain a polymer.

Example LXIII

Mass polymerization was carried out under a partial propylene pressure of 2600 kpa at 60 ° C for 30 minutes as in Example LXII, followed by transfer of unreacted liquefied propylene to a separate feed tank connected to the reactor, increasing the temperature of the reactor at 72 ° C and carrying out a gas phase polymerization for 2 hours, while propylene was fed from the feed tank to give a polymerization pressure of 2600 kPa. Then the same treatment was carried out as in Example 15 XXXIV to obtain a polymer.

Example LXIV

Mass polymerization was performed under 600 kfla at 60 ° C for 30 minutes as in LXII, for example. The polymerization temperature was then raised to 70 ° C to obtain a polymerization pressure of 3100 kpa. When the polymerization was continued as such, the pressure dropped to 2600 kPa in 40 minutes. Thus, the bulk polymerization was continuously moved to the gas phase polymerization. The gas phase polymerization was continued while propylene was fed for 60 minutes to maintain the pressure at 2600 kBa. The post-treatment 25 was carried out as for example XXXIV to obtain a polymer.

Example LXV

1000 ml of n-Hexane, 320 mg of diethylaluminum monochloride and 30 mg of the final solid product obtained in step (1) of Example XXXIV were placed in a reactor and without activating them, the reaction product (G) was used in step (2) ) of Example XXXIV. Subsequently, a suspension polymerization was carried out under a partial propylene pressure of 1000 kPa at 85 ° C for 3 hours, followed by removal of n-hexane by steam stripping to obtain a polymer.

Example LXVI

Propene was slurried polymerized using the non-preactivated catalyst such as LXV, followed by rinsing unreacted propylene and hydrogen and distillation of n-hexane under reduced pressure until n-hexane was present in the 8202923 46 polymer. an amount of 30%. This solvent-containing polymer was placed in a fluidized bed equipped with stirring elements, as used in Example XXIX, and 450 ml of hydrogen was introduced to conduct a gas phase polymerization under a partial propylene pressure of 2100 kBa at 70 ° C for 2 hours as for example LXII. The post-treatment was then carried out as for example XXXIV to obtain a polymer.

Example LXVII

A propylene-ethylene block copolymerization was carried out as in Example LXVI, except that the first stage slurry polymerization was carried out with propylene and if the second stage gas phase polymerization was the ethylene polymerization carried out under a partial hydrogen pressure of 800 kBa and a partial ethylene pressure of 1200 kpa at 70 ° C for 2 hours.

15 Example. LXVIII

Example LXII was repeated, except that a 00 olefin mixture of 200 g of propylene and 20 g of ethylene was used instead of using 200 g of propylene to obtain a polymer (propylene-ethylene copolymer).

20 Example LXIX

Example LXVIII was repeated, except that 30 g of butene-1 were used instead of 20 g of ethylene to obtain a polymer (propylene-butene-1 copolymer).

Example LXX

300 mg of the final solid product obtained, for example, XXXIV and 3000 mg of diethylaluminum monochloride, were slurried in 200 ml of n-hexane, followed by reaction under a partial propylene pressure of 1300 kpa at 20 ° C for 10 minutes, rinsing from unreacted propylene, maintaining the obtained material with stirring at 40 ° C for 1 week, introducing the obtained catalyst slurry, containing 25 mg of the final solid product, into a polymerization kettle, followed by conducting slurry polymerization and subsequent gas phase polymerization as for example LXVI.

Comparative Examples 21, 22 and 23 Using each of the following solid products in place of the solid final product obtained in Example XXXIV, the resulting catalyst suspensions were stored for 1 week as in Example LXX:

Comparative Example 21: The solid product (II) obtained at

40 example XXXIV

8202923 47

Comparative Example 22: the solid product (II) subjected to

polymerization treatment obtained, for example, XXXIV

Comparative Example 23: The solid end product obtained in Comparative Example 11,

The results of the previous examples and comparative examples are included in Table D.

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Example LXXI

15 g of a solid product (III), obtained as in Example 1, except that the solid product (II) without subjecting it to a polymerization treatment with propylene. reacted with diisoamyl ether 5 and Ticph, suspended in 500 ml n-hexane and 5 g propene and further 2.4 g diethyl aluminum monochloride were added. Then the reaction was run for 10 hours at 15 ° C, followed by filtration, repeating the procedure of adding 400 ml of n-hexane 3 times, washing and filtering and drying under reduced pressure to obtain 10 a solid product (III) subjected to polymerization treatment (15.2 g) (polymer: 0.2 g). Using this solid product, subjected to polymerization treatment (30 mg) and diethylaluminum monochloride (480 mg), a propylene polymerization was performed as in step (3) of Example I.

15 Example LXXII

10 g of a solid product (III) obtained as in Example I were suspended in 200 ml of n-heptane. 3 g of diethyl aluminum monochloride and 8 g of propylene were added and the reaction was conducted at 20 ° C for 3 hours, followed by filtration, washing and drying to obtain 10.3 g of a solid product (III) subjected to polymerization treatment ( polymer: 0.3 g). Using 20 mg of this solid product and 420 mg of diethylaluminum monochloride, a propylene polymerization was carried out as in step (3) of Example I.

Example LXXIII

80 ml of n-hexane, 0.05 mole of diethylaluminum monochloride and 0.13 mole of diisoamyl ether were mixed together at 35 ° C for 30 minutes and reacted to obtain a reaction liquid (I), which was then at 38 ° C for 4 hours ° C was added dropwise to 0.45 mol TiCl 4, followed by maintaining the mixture at the same temperature as above for 90 minutes, raising the temperature to 76 ° C, further conversion for 1.5 hours before obtaining a solid product (II) which is then filtered off, washed with n-hexane, filtered off and suspended in 50 ml of n-hexane. 15 g of diisoamyl ether, 16 g of TiCl 3 and 3 g of propene 35 were added, followed by reaction at 68 ° C for 2 hours.

After the completion of the reaction, filtration, washing and drying were performed to obtain a solid final product. Using this product, a propylene polymerization was carried out as in steps (2) and (3) of Example I.

£ 202923 λ 53

Example LXXIV

A solid final product was obtained as in Example LXXIII, except that in Example LXXIII, 4 g of ethyl aluminum dichloride were used instead of 16 g of TiCl 2 added for reaction with the solid product (II). A propylene polymerization is then carried out.

Example LXXV

60 ml of n-Hexane, 0.05 mole of diethylaluminum monochloride and 0.12 mole of diisoamyl ether were mixed together and reacted at 35 ° C for 30 minutes and 0.5 g of propylene was dissolved in the resulting reaction liquid. followed by the dropwise addition of the liquid to 0.4 mol TiCl 2 at 38 ° C for 180 minutes, keeping the mixture at the same temperature for 60 minutes, raising the temperature to 80 ° C and its further reaction for 1 hour to obtain a solid product (II), subjected to polymerization treatment, which is then filtered and heated at 70 ° C.

The total amount of this solid product is then suspended in 25 ml of n-hexane and 16 g of diisoamyl ether and 35 g of TiCl 2 are added, followed by reaction for 1 hour at 70 ° C. After the reaction is filtered off , folded / ashed and dried to obtain a solid product (III). A propylene polymerization is then carried out as in steps (2) and (3) of Example I.

8202923 54

TABLE E

Number of Polymer- Iso- Landfill- How Much- Pass-

the pre-yield tac-weight held by MFR YI

image (g) per g of the measurement 150 fixed pro-index poly- 32 to 60 mm duct (III) more mm (%) (%)

Example LXXI 6200 99.0 0.50 94 0.2 3.9 3.1

Example LXXII 6400 99.2 0.50 92 0.2 4.1 2.8

Example LXXIII 6200 98.8 0.49 94 0.6 4.2 3.0

Example LXXIV 6300 98.8 0.49 93 0.6 4.1 3.0

Example LXXV 6200 98.5 0.49 90 0.8 3.9 3.1

Example LXXVI

15 g of a solid product (III) obtained as in example I, except that the solid product (II), without subjecting it to a polymerization treatment with propylene, was reacted with diisoamyl ether and 5 TiCl 2 .mu. / s suspended in 500 ml n-hexane. 5 g of propylene and 2.4 g of diethylaluminum monochloride were added to the suspension obtained and the mixture was reacted for 10 hours at 15 ° C, followed by filtration and repeating the method of adding 400 ml 3 times. n-hexane, washing and filtering, and drying under reduced pressure to obtain a solid product (III) (a solid final product) (15.2 g) (polymer: 0.2 g). A propylene polymer was obtained as in Example I, except that 30 mg of the previous solid end product, 480 mg of diethyl aluminum monochloride and a reaction product (G) obtained by reacting 23 mg of triethyl aluminum with 3.0 g of methyl 15 p-toluylate in 20 ml of n-hexane at 25 ° C for 5 hours, introduced h / s and 150 ml h / ater / h added, followed by gas phase polymerization under a propylene partial pressure of 2200 kpa at a polymerization temperature of 80 ° C for 2 hours.

Example LXXVII

A pre-activated catalyst is obtained as in steps (2) and (3) of Example 1, except that the solid end product obtained in Example LXXVI uses u / s. A propylene polymerization was then carried out.

8202923 55

Example LXXVIII

10 g of a solid product (III) obtained as in Example 1 were suspended in 200 ml of n-heptane and 3 g of diethylaluminum monochloride and 8 g of propylene were added, followed by reaction for 5 hours at 20 ° C and then filtering off, washing and drying to obtain a solid product (III), subjected to polymerization treatment (a solid final product) (10.3 g) (polymer: 0.3 g). A propylene polymerization is then carried out as in steps (2) and (3) of Example I.

Example LXXIX

80 ml of n-hexane, 0.05 mole of diethylaluminum monochloride and 0.13 mole of diisoamyl ether were mixed together at 35 ° C for 30 minutes and reacted to obtain a reaction liquid (I), which was then added dropwise added to 0.45 mol TiCl 4 at 38 ° C for 4 hours, followed by maintaining the mixture at the same temperature for 30 minutes, raising the temperature at 76 ° C and further conversion for 1.5 hours to obtain of a solid product (II), which was then filtered off, washed and suspended in 50 ml of n-hexane. To the obtained suspension were added 15 g of diisoamyl ether, 16 g of TiCl 2 and 3 g of propene, followed by reaction for 2 hours at 68 ° C. After the reaction, the mixture was filtered off, washed and dried to obtain a solid final product. Using this product, a propylene polymerization was carried out as in steps (2) and (3) of Example I.

Example LXXX

A solid final product was obtained as in Example LXXIX, except that in Example LXXIX 4 g of ethylaluminum dichloride was added instead of 16 g of TiCl 2 for reaction with the solid product (II). Propylene polymerization was then performed using the solid end product.

30 Example LXXXI

60 ml n-Hexane, 0.05 mole diethylaluminum monochloride and 0.12 mole diisoamyl ether were mixed and reacted at 35 ° C for 30 minutes and 0.5 g propylene was dissolved in the reaction liquid, followed by the dropwise addition of the liquid to 0.4 mole 35 TiCl 3 at 38 ° C for 180 minutes, maintaining the mixture at the same temperature for 60 minutes, increasing the temperature at 80 ° C and further reaction for 1 hour to obtain a solid product (II), subjected to polymerization treatment, which was then filtered off and washed at 70 ° C. The total amount of the product was suspended in 25 ml of n-hexane 8202923 56 and 16 g of diisoamyl ether and 35 g of TiCl 2 were added to the resulting suspension, followed by reaction at 70 ° C for 1 hour. After the reaction, filtered, washed and dried to obtain a solid product (III). (Using this product, a propylene-5 polymerization was carried out as in steps (2) and (3) of Example I.

Example LXXX11

Using 10 g of the solid product (III) obtained in example LXXXI, a solid final product, subjected to polymerization treatment, was obtained as in example LXXVIII. Using this product, a propylene polymerization was carried out as for example LXXVI.

Example LXXXIII

A pre-activated catalyst was obtained as in the 15 steps (1) and (2) of Example 1 and 600 g of butene-1 was introduced, followed by polymerization of butene-1 at 70 ° C.

Verqeli.jkinq example 24

Using the solid product (III), not subjected to a polymerization treatment, obtained in Example XIV, a propylene polymerization was carried out as in Example III. The bulk density of the resulting polymer decreased and its isotactic index also decreased.

Comparative example 25

In Example LXXVIII, a solid end product was obtained without the addition of propylene (3 g). Then a propylene polymerization was performed at 92 ° C as in Example III. The bulk density of the obtained polymer decreased and its isotactic index also decreased.

Comparative Example 26 A propylene polymerization was carried out as in Example III, except that in Example LXXXI a solid product (III) was obtained without dissolving propylene (0.5 g). The bulk density of the obtained polymer decreased and its isotactic index also decreased.

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Claims (42)

A process for the preparation of olefin polymers, characterized in that (a) 1 mol of an organoaluminum compound (A ^) with 0.1 to 8 mol of an electron donor (B ^) in a solvent at a convert temperature from -20 ° to 200 ° C to obtain a reaction product (I), (b) convert this reaction product (I) with TiCl 3 at a temperature of 0 to 200 ° C in a ratio of the number of Al atoms to that of Ti atoms from 0.05 to 10 to form a solid product (II), 10 (c) convert 100 g of this solid product (II) with 10 to 1000 g of an electron donor (B2) and 10 up to 1000 g of an electron acceptor at a temperature of 40 ° to 200 ° C to obtain a solid product (III), (d) during and / or after the reaction step (b) and / or during and / or after the reaction step (c), the solid product (II) or (III) is subjected to a polymerization treatment by contacting the product (II) or (III) with 10 to 5000 g of an <ol> olefin at 100 g of the solid product (II) or (III), under atmospheric pressure or adding the 20 ol olefin to the solid product (II) or (III) to create a pressure of 1000 kPa or less and at a reaction temperature of 50 ° C to 90 ° C to obtain a solid end product and (e) a {& -olefin polymerizes in the presence of a catalyst containing a combination of the solid end product with an organo-aluminum compound ( A £) Method according to claim 1, characterized in that after completion of the reaction of the reaction product (I) with TiCl 2, this polymerization treatment is carried out by removing the liquid part obtained, suspending it. of the obtained solid product (II) in a solvent to form a slurry and add an organoaluminum compound and an Ok olefin under 0 to 1000 kpa to the slurry to polymerize the Ot olefin. Method according to claim 1, characterized in that after completion of the reaction of the solid product (II) with an electron donor and an electron acceptor, this polymerization treatment is carried out by removing the liquid part obtained, suspending the resulting solid product (III) in a solvent to form a slurry and adding an organoaluminum compound and a <& -> olefin at 0 to 1000 kPa to the slurry to polymerize the O 2 -olefin. 8202923 Process according to claim 2, characterized in that amounts of the organoaluminum compound and the vt-olefin are added in the range from 5 to 500 g and in the range from 10 to 5000 g, respectively, based on 100 g of the solid product (II) and that a reaction temperature is used in the range from 30 ° to 90 ° C. Process according to claim 3, characterized in that amounts of the organoaluminum compound and the 66-olefin are added in the range of 5 to 500 g and in the range of 10 to 5000 g, respectively, based on 100 g of the solid end product and that a reaction temperature is used in the range from 30 ° to 90 ° C, Process according to claim 1, characterized in that the reaction product (I) is used in the form of a liquid obtained by reacting an organo-aluminum compound with an electron donor as such in the subsequent reaction. Process according to claim 1, characterized in that the cL-olefin polymerization is carried out by gas phase polymerization. 8. Process according to claim 1, characterized in that the β-olefin polymerization is carried out by suspension polymerization followed by gas phase polymerization. 2. Process according to claim 1, characterized in that the olefin polymerization is carried out by mass polymerization followed by gas phase polymerization. 10. Process according to claim 1, characterized in that organo-aluminum compounds (A ^) and {k ^) are used, represented by the general formula AIR R ', X,, nn n1 3- (n + n') ) R and R 1 each are alkyl, aryl, alkaryl ,. cycloalkyl or alkoxy, X represents fluorine, chlorine, bromine or iodine, and n and n 'each represent an integer 30, satisfying the relationship 0 <n + n' ^ * 3. Process according to claim 1, characterized in that electron donors (B. ^) are used which are the same or different and each are selected from the group consisting of ethers, alcohols, esters, aldehydes, fatty acids, aromatic acids, ketones, nitriles, amines, amides, ureas, thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, sulfur sulfide, thioethers and thio alcohols, the organic compounds each containing 1 to 15 carbon atoms . Method according to claim 1, characterized in that electron donors (B1) and (B2) are used which are the same or different and consist exclusively or mainly of ethers and those electron donors which are 8202923 AV other than ethers have been used together with ethers. Method according to claim 1, characterized in that at least one compound is used as the electron acceptor selected from the group consisting of u / an free AlCl, SiCl, SnCl, SnCl, TiCl, ZrCl, 5 Pcl, VC14 and SbCl5. 14. Process according to claim 1, characterized in that an aliphatic carbon / hydrogen substance is used as the solvent. Method according to claim 1, characterized in that the reaction of the solid product (II) with an electron donor and an electron acceptor is carried out in an aliphatic carbon / hydrogen. Method according to claim 1, characterized in that the reaction of the product (II) with an electron donor (B2) and an electron acceptor is carried out by previously converting the electron donor with the electron acceptor at a temperature of 10 ° to 100 ° C for a period of time from 30 minutes to 2 hours, the resulting reaction product cools to 40 ° C or less and this reaction product reacts with the solid product (II). Process according to claim 1, characterized in that the catalyst is pre-activated by further reaction of an α-olefin with the combination of the solid end product with an organo-aluminum compound (A2) and the resulting pre-activated catalyst for an olefin polymerization. Method according to claim 17, characterized in that the activation is carried out in advance using 0.1 to 500 g of an organo-aluminum compound (A2), 0 to 50 l of solvent, 0 to 1000 ml h / hydrogen and 0.05 to 5000 g of <6-olefin, each based on 1 g of the final solid product and converting the oC-olefin at a temperature of 0 ° to 100 ° C to form 0.01 to 2000 g of the converted c olefin based on 1 g of the final solid product. 19. Process for preparing olefin polymers, characterized in that (a) 1 mol of an organoaluminum compound (A ^) is reacted with 1 to 4 mol of an electron donor (B ^) in 0.5 to 5 l of an aliphatic carbon / hydrogen solvent at a temperature of -10 ° to 100 ° C to obtain a reaction product (I), (b) reacting this reaction product (I) with TiCl 2 at a temperature of 10 ° to 90 ° C in a ratio of the number of Al atoms to that of Ti atoms from 0.06 to 0.3 to form a solid product (II), (c) convert 100 g of this solid product (II) by 50 to 200 g of 40 an electron donor (B2) and 20 to 500 g of an electron acceptor (E) 8. Q 2 9 2 3 at a temperature of 50 ° to 100 ° C to obtain a solid product (III), (d) during and / or after step (b) and / or during and / or after the reaction step (c), the solid product (II) or (III) is subjected to a polymerization treatment by contacting the product (II) or (III) with 10 to 5000 g of an «i-olefin based on 100 g of the solid product (II) or (III), under atmospheric pressure or addition of the o6-olefin to the solid product (II) or (III) to create a pressure of 1000 kPa or lower and a reaction temperature of from 30 to 90 ° C to obtain a solid final product, and (e) polymerizes a £ olefin or oG olefins in the presence of a catalyst containing a combination of the solid final product with a organic compound (Ag). 20. Process for the preparation of olefin olymers, characterized in that (a) 1 mol of an organoaluminum compound (A · ^) is reacted with 0.1 to 8 mol of an electron donor (B ^) in a solvent at a temperature of -20 ° to 200 ° C, to obtain a reaction product (I), (b) react this reaction product (I) with TiCl 2 at a temperature of 20 ° to 200 ° C in a ratio of the number of Al atoms to that of Ti atoms from 0.05 to 10, forming a solid product (II), (c) 100 g of this solid product (II) converts with 10 to 1000 g of an electron donor (B ^) and 10 to 1000 g of an electron acceptor at a temperature of 40 ° to 200 ° C, to obtain a solid product (III), (d) during and / or after the reaction step (b) and / or after the reaction step (c) subjects the solid product (II) or (III) to a polymerization treatment by contacting the product (II) or (III) with 10 to 5000 g of an olefin based from 100 g of h The solid product (II) or (III), under atmospheric pressure or addition of oi-olefin to the solid product (II) or (III) to create a pressure of 1000 kPa or less and at a reaction temperature of 30 ° to 90 ° C to obtain a solid final product, combine 35 (e) 1 g of the solid final product with 0.1 to 500 g of an organoaluminum compound ^), (f) to the combination of step (e ) 0.05 to 10 g of a reaction product (G) obtained by reacting 1 mole of an organoaluminum compound (A ^) with 0.01 to 5 moles of an electron donor (Bj), which reaction is carried out at a temperature of -30 ° C to 20 ° C, up to 100 ° C, is effected on a polymerization treated catalyst and (g) polymerizes an olefin or carbonolefins upon reaction. absence of this polymerization treated catalyst. 21. Process according to claim 20, characterized in that the polymerization-treated catalyst is subjected to a pre-activation treatment with 0.01 to 5000 g of olefin. Method according to claim 20, characterized in that after completion of the reaction of the reaction product (I) with TiCl 2, this polymerization treatment is carried out by removing the obtained liquid portion, suspending the obtained solid product (II) in a solvent to form a slurry and add an organoaluminum compound and an it-olefin at 0 to 1000 kPa to the slurry to polymerize the i-olefin. Method according to claim 20, characterized in that after completion of the reaction of the reaction product (II) with an electron donor and an electron acceptor, this polymerization treatment is carried out by removing the liquid part obtained, suspending the solid product (III) obtained in a solvent to form a slurry and an organoaluminum compound and an olefin under 0 to 1000 kPa to the slurry to polymerize the (olefin). Process according to claim 21, characterized in that the amounts of the organoaluminum compound and the olefin are added in the range from 5 to 500 g and in the range from 10 to 5000 g, each involved to 100 g of the solid product (II) and that a reaction temperature is used in the range from 30 ° to 90 ° C. 25. Process according to claim 23, characterized in that the amounts of organoaluminium compound and olefin are added in the range from 5 to 500 g or in the range from 10 to 5000 g, each based on 100 g. of the solid product (III) and that a reaction temperature is used in the range from 30 ° to 90 ° C. 26. Process according to claim 20, characterized in that the reaction product (I) is used in the form of a liquid obtained by reaction of an organo-aluminum compound with an electron donor as such in the subsequent reaction. 27. Method according to claim 20, characterized in that the o2. -olefin polymerization carried out by gas phase polymerization. 28. Process according to claim 20, characterized in that the 40 06 olefin polymerization is carried out by slurry polymerization followed by 8202923 · 63 gas phase polymerization. 29. Process according to claim 20, characterized in that the olefin polymerization is carried out by mass polymerization, followed by gas phase polymerization. 30. Process according to claim 20, characterized in that organoaluminium compounds (A ^) are used, which are represented by the general formula AIR R x., Nn '3- (n + n'). ) R and R 'each represent alkyl, aryl, alkaryl, cycloalkyl or alkoxy, X represents fluorine, chlorine, bromine or iodine and n and n' each represent a number satisfying the relationship 0 <n + n '= 3. 31. Process according to claim 20, characterized in that electron donors (B1) and (B2) are used which are the same or different and are each at least selected from the group consisting of ethers, alcohols, esters, aldehydes, fatty acids, aromatic acids, ketones, nitriles, amines, amides, ureas, thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, u / hydrogen sulfide, thioethers and thioalcohols, the organic compounds each containing 1 to 15 carbon atoms. 32. Method according to claim 20, characterized in that electron donors (B1) and (B2) are used which are mixed or different and consist exclusively or mainly of ethers, and the compounds other than ethers used together with ethers. 33. Method according to claim 20, characterized in that the electron acceptor used is at least one compound selected from the group consisting of u / a free AlCl 2, SiCl 2, SnC 2, SnCl 2, TiCl 2, ZrCl 2, PCl. ^, VC14 and SbCl5. 34. Process according to claim 20, characterized in that an aliphatic carbon substance is used as the solvent. 35. Process according to claim 20, characterized in that the reaction of the reaction product (II) with an electron donor and an electron acceptor is carried out in an aliphatic carbon / hydrogen. 36. Method according to claim 20, characterized in that the reaction of the product (II) with an electron donor and an electron acceptor is carried out by pre-converting the electron donor with the electron acceptor at a temperature of 10 ° to 100 ° C for a period of time from 30 minutes to 2 hours, the resulting reaction product cools to 40 ° C or less and this reaction product reacts with the solid product (II). 37. Process according to claim 21, characterized in that the 8202923 -6ff activation treatment is carried out in advance using 0.1 to 500 g of an organoaluminum compound, 0 to 50 l of solvent, 0 to 1000 ml of hydrogen and 0.05 to 5000 g of an o6 olefin, each based on 1 g of the final solid product and converting the 06 olefin at a temperature of 0 ° 5 to 100 ° C to form 0.01 to 2000 g converted ού -olefin based on 1 g of the solid final product. 38. Process according to claim 20, characterized in that a reaction temperature at step (b) is used in the range from 10 to 90 ° C. 39. Process according to claim 20, characterized in that the combination of 1 g of the solid end product with 0.1 to 500 g of an organo-aluminum compound {h ^) is subjected to a preliminary activation treatment according to steps (e). with 0.01 to 5000 g of an ol-olefin and then add the reaction product (G). 40. Process according to claim 20, characterized in that the solid end product obtained by the polymerization treatment and consisting of the organo-aluminum compound (Ag) and a polymer of t-6-olefin and the reaction product (G) are stored separately and just prior to the polymerization of step (f) mixing together and used as a catalyst. 41. Process according to claim 20, characterized in that the polymerization treatment is carried out in such a way that the polymerized amount of C olefin at step (d) is 0.01 to 2000 g per g of the solid product (II) or ( III). 8202923