JPS6340806B2 - - Google Patents

Description

[Detailed description of the invention]

[] Object of the Invention The present invention relates to a method for producing an ethylene polymer, which comprises homopolymerizing ethylene or copolymerizing ethylene and α-olefin using a novel catalyst system. More specifically, the treated product obtained by treating (A) (1) (a) a solid component containing at least a magnesium atom, a halogen atom, and a titanium atom using (b) an alkyl aluminum compound; 2) A solid catalyst component obtained by treating a chain ether compound and (B)
This relates to a method for producing an ethylene polymer, characterized by homopolymerizing ethylene or copolymerizing ethylene and α-olefin using a catalyst system obtained from an organoaluminum compound, and the catalyst system has extremely high polymerization activity. The purpose is to produce ethylene polymers using [] Background of the Invention It has been known that a catalyst system obtained from a solid catalyst component containing a magnesium atom, a halogen atom, and a titanium atom and an organoaluminum compound is a highly active olefin polymerization catalyst. When ethylene is homopolymerized or ethylene and α-olefin are copolymerized using the above catalyst system, the polymerization activity of the catalyst system is not always sufficient, and therefore, the catalyst remaining in the polymer after polymerization is If the residue is not removed, the catalyst residue may damage equipment used in post-treatment processes such as drying the polymer, kneading it with additives or other polymers, and molding the polymer or its composition. This may cause rusting, discoloration and deterioration of the resulting molded product. Therefore, it cannot be said that it is possible to completely omit the catalyst residue removal step. On the other hand, there is an increasing need to reduce construction and manufacturing costs by simplifying processes. For these reasons, there is a desire for a catalyst system that does not cause rusting of the equipment or coloring and deterioration of molded products even if the step of removing catalyst residue after polymerization is omitted. There is also a need for a catalyst system that produces a polymer with excellent powder properties during copolymerization of ethylene and α-olefin. In other words, it is desired to provide a polymer having a particularly small angle of repose. This greatly improves the feeding and falling effect of the obtained polymer powder from the hopper and the like. [] Structure of the Invention From the above, the present inventor has determined that it is possible to produce an ethylene polymer without the above-mentioned problems, and that the above-mentioned problems (including during molding of the polymer) can be produced. As a result of various searches to obtain a polymer free of ) and (b) a treated product obtained by treatment using an alkyl aluminum compound and (2) "chain-like ether compound having a total number of carbon atoms of 6 to 18" (hereinafter "ether compound") These can be obtained by homopolymerizing ethylene or copolymerizing ethylene and α-olefin using a solid catalyst component obtained by treating (B) and a catalyst system obtained from an organoaluminum compound. It has been discovered that an ethylene polymer can be obtained that has improved all of the above problems, and the present invention has been achieved. [] Effects of the Invention When ethylene is homopolymerized or ethylene and α-olefin are copolymerized using the catalyst system used in the present invention, the following characteristics (effects) are exhibited. (1) The polymerization activity of the catalyst system is extremely high. Therefore, even if the catalyst residue remaining in the polymer is not removed after the production of this polymer, rusting of the equipment used in the post-treatment, kneading and molding processes of the polymer can be significantly reduced. Not only can this be suppressed, but also the discoloration and deterioration of molded products can be significantly improved. (2) The resulting polymer has good powder properties. That is, the angle of repose of the resulting polymer powder is small. This means that when the resulting polymer powder is transported with compressed nitrogen, the feeding through the transport pipe is smooth, nitrogen pressure fluctuations are small, and the powder falls easily from the hopper, making it difficult to cause blitzing or surging. . [] Detailed Description of the Invention (A) Treated Product The treated product used to produce the solid catalyst component of the present invention can be obtained by treating the solid component with an alkyl aluminum compound. (1) Solid component The solid component used to produce the treated product contains magnesium atoms, halogen atoms, and titanium atoms. The solid component is obtained by treating a magnesium-containing compound and a tetravalent titanium compound. In this treatment, only the magnesium compound and the titanium compound may be treated, but the magnesium compound and the electron-donating organic compound may be treated in advance, and the resulting treated product and the titanium compound may be treated. Furthermore, a magnesium compound, a titanium compound, and an electron-donating organic compound may be treated. (They may be processed simultaneously or separately). Furthermore, the magnesium-based compound and the electron-donating organic compound may be treated in advance, and the resulting compound may be treated with the titanium-based compound and the electron-donating organic compound. Preferred examples of the magnesium compound used to produce the solid component include magnesium compounds represented by the following formulas [formula () and formula ()], as well as magnesium oxide and magnesium hydroxide. ^Mg ₍ ^{OR 1 )} _{m _} . R ¹ and R ² are hydrogen atoms or hydrocarbon groups selected from the group ^consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbons, and aromatic hydrocarbon groups having at most 16 carbon atoms;
X ² is a halogen atom. In formulas () and (), R ¹ and R ² are preferably hydrogen atoms, alkyl groups having at most 12 carbon atoms, and phenyl groups, and X ¹ and X ² are chlorine atoms, bromine atoms, and iodine atoms. Atoms are preferred, especially chlorine and bromine atoms. Among the magnesium compounds represented by formula (1), representative examples of preferred compounds include magnesium chloride, magnesium bromide, magnesium ethylate, magnesium butyrate, and hydroxymagnesium chloride. Further, among the magnesium compounds represented by the formula (), representative examples of suitable compounds include butyl ethylmagnesium, dibutylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, phenylmagnesium chloride, ethylmagnesium bromide, butylmagnesium bromide, and Examples include phenylmagnesium bromide. Furthermore, the titanium-based compound used to produce the solid catalyst component is a compound containing tetravalent titanium. A typical example is ()
Examples include tetravalent titanium compounds represented by the formula. Ti ⁽ _OR ^{3 )} l A hydrocarbon group selected from the group consisting of a hydrogen group and an aromatic hydrocarbon group. In formula (), R ³ is preferably an alkyl group having at most 6 carbon atoms, and X ³ is preferably a chlorine atom or a bromine atom, particularly preferably a chlorine atom. Among the tetravalent titanium compounds represented by the formula (), representative examples of suitable compounds include titanium tetrachloride, methoxytitanium trichloride,
Ethoxytitanium trichloride, butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride,
Mention may be made of triethoxytitanium trichloride, tetraethoxy and tetrabutoxytitanium. In producing the solid component used in the present invention, compounds such as electron-donating organic compounds and the inorganic compounds and organic compounds described below are not necessarily required, but
In producing the solid component, the electron-donating organic compound is an organic compound having at least one polar group, generally referred to as a Lewis base. This electron-donating organic compound is well known as a modifier for polymerization activity, crystallinity, etc. for obtaining an olefinic polymerization catalyst. Representative examples of the electron-donating organic compounds include the following saturated or unsaturated aliphatic, alicyclic, or aromatic compounds. The compound is preferably a chain or cyclic ether compound [having at most 24 carbon atoms]. (for example, diethyl ether, di-n-butyl ether, di-isoamyl ether, dihexyl ether, ethoxybenzene, diphenyl ether)], carboxylic acid compounds [preferably those having at most 18 carbon atoms (for example, benzoic acid, lactic acid, acetic acid, stearic acid)], monohydric or polyhydric alcohol compounds or phenolic compounds [those having at most 18 carbon atoms are preferred (for example, ethyl alcohol, n-
butyl alcohol, phenol, p-methylphenol, ethylene glycol)], anhydrides of the carboxylic acid compounds (e.g., acetic anhydride, phthalic anhydride, benzoic anhydride)], the carboxylic acid compounds and alcohol compounds, or phenols. ester compounds (for example, ethyl benzoate, γ-butyl lactone, phenyl acetate, ethyl acetate, butyl benzoate), aldehyde compounds [preferably those with at most 18 carbon atoms] For example, benzaldehyde, butyraldehyde, acrylaldehyde, cinnamaldehyde)]. Ketone compounds [preferably those with a total carbon number of at most 24 (e.g., acetone, benzophenone, acetophenone, cyclohexanone)], halide compounds of the above carboxylic acids (e.g., acetyl chloride, benzoyl chloride, benzoyl bromide) , cyclohexanecarbonyl chloride), silicate ester compounds containing at most 24 carbon atoms (e.g., tetramethyl silicate, tetraethyl silicate, tetracresyl silicate,
trichloromethylsilicate)] mono- or polysiloxanes (preferably those with a total silicon number of at most 1000), amine compounds [preferably those with a total carbon number of at most 36 (for example, tributylamine, butylamine, aniline, N,N-dimethylaniline)], amide compounds [even if the total number of carbon atoms is large
36 is preferred (e.g. N, N
-dimethylbenzamide, acetamide,
N,N-dimethylhexanoxamide)], phosphate ester compounds or phosphite ester compounds [preferably those having at most 24 carbon atoms (for example, triphenyl phosphite, diphenyl phosphate chloride, triethyl phosphate, triphenyl phosphate), etc. Furthermore, any compound other than the electron-donating organic compound used to produce the solid component may be used as long as it does not poison the catalyst of the solid component. Among these compounds, inorganic compounds include halides of Groups or Groups of the periodic table (for example, aluminum, silicon,
halides such as zinc), sulfates, nitrates,
Examples include sulfites and nitrites. In order to produce the solid component, the magnesium compound and the titanium compound or these compounds and the electron-donating organic compound may be treated by mechanically crushing these compounds (hereinafter referred to as "compound"). (hereinafter referred to as "grinding method") and a method of contacting in an inert solvent or in the absence of an inert solvent (when the processed material is liquid) (hereinafter referred to as "contact method")
), etc. As the co-pulverization method, a commonly used method of co-pulverizing a magnesium-based compound and a titanium-based compound or these compounds and an electron-donating organic compound to produce a solid catalyst component for olefin polymerization may be applied. Generally, co-pulverization may be carried out using a pulverizer such as a ball mill, a vibratory ball mill, an impact pulverizer, or a colloid mill at around room temperature in an atmosphere of an inert gas (eg, nitrogen, argon). Normally, it is not necessary to perform measures such as cooling, but if heat generation is significant due to this co-pulverization, cooling may be performed for convenience of operation. Although the time required for co-pulverization cannot be absolutely defined depending on the performance of the crusher, etc., it is necessary to at least make the material to be crushed fine enough to withstand use. Although the resulting pulverized material can be used even if it is not in a completely uniform state, it is preferable that it be in a uniform state. Therefore, the co-milling time is generally between 5 minutes and 24 hours. In addition, the contact method is a method of processing in the presence or absence of an inert solvent (when one of the processed materials is a liquid and can be stirred as a liquid). The inert solvent used in this process is dry (contains no water), typically with a boiling point of 10 to
300℃ aliphatic hydrocarbons (e.g., n-hexane, n-heptane, n-octane), alicyclic hydrocarbons (e.g., cyclohexane,
dimethylcyclohexane), aromatic hydrocarbons (e.g. benzene, toluene, xylene)
and halides of these hydrocarbons (eg, tetrachlorinated hydrocarbons, trichloroethylene, chlorobenzene). In this contact method, although the treatment can be carried out in an inert solvent as described above, at least one of the above-mentioned electron-donating organic compounds, titanium-based compounds, and magnesium-based compounds is a liquid. If stirring is possible, the treatment can also be carried out in the absence of an inert solvent. In the contact method, the ratio of solid to liquid in the treatment system is at most 500 g. The contact temperature is usually room temperature (20°C) to 250°C, although it varies depending on the type and proportion of the contact material, contact time, and other conditions. Contact time is determined by the type and proportion of the contact object,
Although it varies depending on the contact temperature and other conditions, it is generally from 5 minutes to 24 hours. In either of the above co-pulverization methods and contact methods, the ratio of titanium-based compound to 1 mol of magnesium-based compound is generally
It is 0.02 to 20 moles. Further, when an electron-donating organic compound is used, the ratio of the electron-donating organic compound to 1 mol of the magnesium compound is usually at most 50 mol. The solid component obtained in the above manner is treated using an inert solvent used in the treatment method.
Purified by washing until titanium-based compounds, magnesium-based compounds and electron-donating organic compounds (if used) remaining in the solid components are no longer found in the washing solution, and removing the used inert solvent. . This washing method may be carried out by removing the supernatant by decanting or filtering. The content of titanium atoms in the solid component obtained as described above is generally 0.01 to 30% by weight. In addition, the content of magnesium atoms is 0.1~
30% by weight, and the content of halogen atoms is at most 90% by weight. (2) Alkylaluminum compounds Among the alkylaluminum compounds, preferred ones have the following general formula [()
The following formula can be mentioned. R ⁴ _a Al ⁽ _OR ⁵ ₎ ^b _H c preferred), R ⁵
is an aliphatic or aromatic hydrocarbon group having at most 15 carbon atoms (particularly preferably a hydrocarbon group having at most 8 carbon atoms), and X ⁶ is a halogen atom. a is 0<a≦3, b is 0≦b<3, and c is 0≦c<3
, d is 0≦d<3, and a+b
+c+d is 3. (As the alkyl aluminum compound represented by the formula, triethyl aluminum,
Trialkylaluminum compounds such as tributylaluminum, triisopropylaluminum and trihexylaluminum, trialkenylaluminum compounds such as triisoprenylaluminum, dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum, ethylaluminum sesquiethoxide and butylaluminum butoxide In addition to alkylaluminum sesquialkoxides such as R ⁴ _2.5 Al(OR ⁵ ) _0.5 , partially alkoxylated alkyl aluminum compounds with an average composition such as diethyl aluminum chloride, dibutyl aluminum chloride and diethylaluminium bromide are also used. Dialkyl aluminum halogenides such as ethyl aluminum sesquichloride, alkyl aluminum sesquihalogenides such as butyl aluminum sesquichloride and ethyl aluminum sesquibromide, alkyl aluminum dichlorides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dichloride and butyl aluminum dibromide. Partially halogenated alkyl aluminum such as dihalogenide, dialkyl aluminum hydride such as diethylaluminum hydride and dibutyl aluminum hydride, partially hydrogen such as ethyl aluminum dihydride, propyl aluminum hydride and butyl aluminum dihydride. and partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride and ethylaluminum ethoxybromide. (3) Treatment ratio In producing the treated product, the amount of the alkylaluminum compound used is generally determined by the ratio of the metal-alkyl group bond that the alkylaluminium compound has to the titanium atoms present in the solid component. The amount is from the same amount to 500 equivalents, and particularly preferably from the same amount to 50 equivalents. (4) Treatment method The treatment of solid components with an alkyl aluminum compound is generally carried out in an inert solvent. In this case, the inert solvent may be the same as that used in the contact method in the production of the solid component (it may be the same as the inert solvent used in the contact method,
may be of the opposite sex). Magnesium-based compounds, titanium-based compounds and electron-donating organic compounds (if used) used in the production of the solid components, as well as inert solvents used in the contacting process and solid components and alkyl aluminum compounds used in the production of the solid catalyst components. In addition, the inert solvent (if used) may be used alone or in combination of two or more. The treatment temperature varies depending on the type of solid component and alkyl aluminum compound used, their ratio, and their concentration relative to the inert solvent, but is generally between -20 and 140 °C.
℃, particularly preferably from 0 to 100℃. The concentration of the alkylaluminum compound in the inert solvent is generally 0.01 mol or more, preferably 0.1 mol or more, per inert solvent. Further, the treatment time varies depending on the type of the treated materials, their treatment ratios, their ratios to the inert solvent, and the treatment time, but generally 30 minutes to 24 hours is sufficient. (5) Purification (post-treatment) The treated product obtained as described above is generally purified to a dilution rate of 1/10 by decanting or filtering the supernatant using an inert solvent.
It can be obtained by washing to 0 or more. The content of titanium atoms in the thus purified treated product is generally 0.01 to 20% by weight. (B) Solid catalyst component The solid catalyst component of the present invention can be produced by treating the treated product obtained as described above with an ether compound. (1) Ether compound The ether compound used to produce the solid catalyst component has a total carbon number of 6 to 18.
It is a chain-like ether compound. Among these ether compounds, those having a total carbon number of 6 to 12 are particularly desirable. Desirable representative examples include di-n-propyl ether, di-isopropyl ether, di-n-butyl ether,
Mention may be made of di-isobutyl ether, di-isoamyl ether, di-allyl ether, dibenzyl ether, benzyl methyl ether and dicyclohexyl ether. Among them, di-n-butyl ether,
Diisobutyl ether and diisoamyl ether are preferred. (2) Treatment ratio The ratio of the ether compound to 1 gram equivalent of the metal of the alkyl aluminum compound in the treated product is generally 0.1 to 1000 mol, preferably 0.1 to 100 mol, and especially
0.5-30 mol is suitable. If the treatment ratio of the ether compound to 1 gram equivalent of metal in the alkyl aluminum compound is 0.1 mol or less, the effects of the present invention, particularly the polymerization activity, cannot be sufficiently exhibited.
On the other hand, if the amount is 1000 moles or more, not only is it not expected to further improve the effects of the present invention, but it is also unfavorable in terms of manufacturing the solid catalyst component. (3) Treatment method The treatment of the treated product and the ether compound is generally carried out in an inert solvent, but if the treatment system can be sufficiently stirred, there is no inert solvent present. It is also possible to carry out under certain conditions. If this treatment is carried out in an inert solvent,
Inert solvents are used in the production of the solid components mentioned above.
The same inert solvent as used in the contacting method may be used (it may be the same as the inert solvent used in the contacting method, or it may be different). Magnesium-based compounds, titanium-based compounds, and electron-donating organic compounds (if used) used in the production of solid components, solid components, alkyl aluminum compounds and inert solvents used in the production of treated products, and solid catalyst components The treated product, ether compound, and inert solvent (if used) used in the production of may be used alone or in combination of two or more. If a viscous solid substance is formed when the ether compound and the treated substance are brought into contact, and it becomes impossible to stir the treatment system, the solid substance can be fixed by using an aromatic hydrocarbon as an inert solvent. You can avoid creating kimonos. The treatment temperature varies depending on the type of treated product and ether compound used, their ratio, and their concentration relative to the inert solvent, but is generally in the temperature range of -20 to 140°C, particularly 0 to 100°C. A temperature range of is preferred. Further, when an inert solvent is used, the treatment concentration is generally 0.01 mol or more, particularly preferably 0.1 mol or more, of the ether compound per inert solvent. Further, the treatment time varies depending on the type of the treated materials, their treatment ratios, their ratios to the inert solvent, and the treatment time, but generally 30 minutes to 24 hours is sufficient. (4) Purification (post-treatment) The solid catalyst component obtained as described above is generally washed until the dilution ratio is 1/100 or more by decanting or filtering the supernatant using an inert solvent. It can be obtained by doing. The content of titanium atoms in the solid catalyst component thus purified is generally 0.01 to 20% by weight. (C) Organoaluminum compound Among the organoaluminum compounds used in the homopolymerization of ethylene or the copolymerization of ethylene and α-olefin in the present invention, the general formulas of typical ones are as follows [Formula (), Formula ()] and () expression]. Al R ⁸ R ⁹ R ¹⁰ () R ¹¹ R ¹² Al-O-Al R ¹³ R ¹⁴ () Al R ¹⁵ _1.5 X ⁶ _1.5 () In () formula, () formula and () formula,
R ⁸ , R ⁹ and R ¹⁰ may be the same or different, and are an aliphatic, alicyclic or aromatic hydrocarbon group having at most 12 carbon atoms, a halogen atom or a hydrogen atom, but at least one of them are the hydrocarbon groups, R ¹¹ , R ¹² , R ¹³ and
R ¹⁴ may be the same or different, and is the aforementioned hydrocarbon group, R ¹⁵ is the aforementioned hydrocarbon group, and X ⁶ is a halogen atom. Among the organoaluminum compounds represented by the formula (), representative examples include trialkylaluminum such as triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum, diethylaluminum hydride and diisobutylaluminum hydride. Examples include alkyl aluminum hydrides such as diethyl aluminum chloride and diethyl aluminum bromide. Further, among the organoaluminum compounds represented by the formula (), representative examples include alkyldialumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane. Further, among the organoaluminum compounds represented by the formula (), ethylaluminum sesquichloride is a typical example. In carrying out the present invention, the solid catalyst component and the organoaluminum compound, or the reactant or mixture of these and the electron-donating organic compound may be separately introduced into the reactor (polymerization vessel), but only two of them may be introduced into the reactor (polymerization vessel). Some or all of them may be mixed in advance. Alternatively, it may be used after being diluted in advance with an inert solvent used as a solvent in the polymerization described later. (D) Polymerization (1) Amount of solid catalyst component and organoaluminum compound used In carrying out the polymerization of the present invention, there is no restriction on the amount of the solid catalyst component and organoaluminum compound obtained as described above, but Preferred proportions are 1 mg to 1 g of solid catalyst component and 0.1 to 10 mmol of organoaluminum compound per 1 inert organic solvent used in the polymerization. Further, the amount of the organoaluminum compound used is generally in the range of 1 to 1000 mol per 1 atomic equivalent of titanium metal contained in the solid catalyst component. (2) α-Olefin When carrying out the present invention, ethylene may be homopolymerized, or ethylene and α-olefin may be copolymerized. α-olefin is a hydrocarbon having a double bond at the end, and has at most 12 carbon atoms. Representative examples include propylene, butyne-1,4-methylpentene-1, hexene-1 and octene-1. Butene-1 used in the present invention is so-called spent B-1 obtained by naphtha cracking.
A B fraction can be used. The copolymerization ratio of the above α-olefin in the obtained ethylene polymer is generally at most 30 mol%.
and is preferably 20 mol% or less, particularly 15
It is preferably less than mol%. (3) Other polymerization conditions Polymerization is carried out with ethylene alone or with ethylene and α-
This is carried out by dissolving the olefin in an inert solvent, but if necessary, a molecular weight regulator (generally hydrogen) may be present in the coexistence. Polymerization temperature is generally -10℃ to 200℃
In practical terms, the temperature is 170° above room temperature (25°C).
below ℃. In addition, the conditions used in the production of general ethylene polymers may be applied to the type of polymerization solvent and the ratio of ethylene alone or ethylene and α-olefin. Furthermore, the configuration of the polymerization reactor, the method of controlling polymerization, the post-treatment method, the ratio of monomer (ethylene or ethylene and α-olefin) to the inert organic solvent used in polymerization, the ratio of organoaluminum compound, inert Regarding the type of organic solvent and the post-treatment method after completion of polymerization, there are no limitations specific to this catalyst system, and all known methods can be applied. [] Examples and Comparative Examples The present invention will be explained in more detail below using Examples. In addition, in the examples and comparative examples, melt
The index (hereinafter referred to as "MI") is JIS K-
According to 6760, temperature is 190℃ and load is 2.16
Measured under Kg conditions. In addition, the High Road Melt Index (hereinafter referred to as "HLMI")
Measurements were made in accordance with JIS K-6760 at a temperature of 190°C and a load of 21.6 kg. Furthermore, the density is
Measured according to JIS K-6760. In addition, in each Example and Comparative Example, each compound used in the production and polymerization of the solid component and solid catalyst component (for example, inert solvent, ethylene, α-olefin, titanium compound, ether compound, magnesium compound, Alkylaluminum compounds, solid components, organoaluminum compounds) were used after substantially removing water in advance. Also, the solid components and solid catalyst components and the polymerization were essentially moisture-free and conducted under a nitrogen atmosphere. Example 1 [(A) Production of solid component (1)] Anhydrous magnesium chloride (commercially available anhydrous magnesium chloride was heated at about 500°C in a dry nitrogen stream)
(obtained by heating and drying for 15 hours)
20.0 g and 7.0 g of titanium tetrachloride were placed in a vibrating ball mill container (stainless steel, cylindrical, internal volume: 1
, the apparent volume of a porcelain ball mill with a diameter of 10 mm.
50% filling). This was attached to a vibrating ball mill with an amplitude of 6 mm and a frequency of 30 Hz, and co-pulverized for 8 hours until a uniform co-pulverized product [Titanium atom content
6.58% by weight, magnesium atom content 18.7% by weight, chlorine atom content 74.7% by weight, hereinafter referred to as "solid component"
(1)'' was obtained. [(B) Production of solid catalyst component (A)] Put 15.0 g of this solid component (1) into a 500 ml flask, add 100 ml of n-heptane to suspend it, and let it cool to room temperature (approximately 25°C). ), 20.6 ml of a solution of triethylaluminum (as an alkyl aluminum compound) in n-hexane (concentration: 1 mol/mol) was added dropwise over 2 hours with sufficient stirring.
After the addition was completed, the temperature of the treatment system was raised to 60°C, and the mixture was stirred at this temperature for 2 hours. Then, the treatment system was again cooled to room temperature, 200 ml of n-heptane was added, and the mixture was thoroughly stirred. Next, this treatment system was left standing, and the supernatant liquid was
I pulled out 200ml. By repeating this operation four times, a solid substance [hereinafter referred to as "treated product (a)"] was obtained. Then, 20.6 ml of a solution of isoamyl ether (as an ether compound) in n-heptane (concentration: 1 mol/mole) was added, and the mixture was stirred at room temperature (approximately 25°C) for 2 hours to carry out ether treatment. Next, this treated solution was thoroughly washed with n-heptane, and then dried under reduced pressure at a temperature of 60°C for 3 hours to obtain a solid substance [hereinafter referred to as "solid catalyst component (A)"]. . [(C) Polymerization of ethylene] The solid catalyst component obtained as described above was placed in a 3.0 stainless steel autoclave as the main catalyst.
8.8 mg of (A) was added, and further 0.54 g of triethylaluminum (as an organic aluminum compound) was added, and 1 kg of isobutane was further added as an inert solvent. Then, the autoclave was closed and the internal temperature was raised to 80°C. Partial pressure of hydrogen in the reaction system
Feed up to 3.0Kg/cm ² (gauge pressure) and further 3.5
Kg/cm ² (gauge pressure) of ethylene was injected. Homopolymerization of ethylene was carried out for 40 minutes while maintaining this ethylene partial pressure. The polymerization was then terminated by discharging the contained gas to the outside of the system. The obtained ethylene homopolymer was dried at a temperature of 60° C. under reduced pressure for 12 hours. As a result, 310 g of polymer was obtained.
That is, the polymerization activity is 15100 g/g - solid catalyst component (A), time, ethylene partial pressure [Kg/cm ² (gauge pressure)]
It is. The MI of this polymer is 3.3g/10min,
HLMI/MI was 39.5. Also, the bulk density is
It was 0.38g/cc. The angle of repose of this polymer was measured using a three-wheeled cylindrical rotating machine (manufactured by Tsutsui Rikagakuki Kikai) and was found to be 30 degrees. Examples 2 to 4, Comparative Examples 1 to 3 In producing the solid component (1) of (A) of Example 1, 2.0 g of diphenyl ether (as an electron donating compound) was further used, and titanium tetrachloride was also used. Co-pulverization was carried out under the same conditions as in Example 1, except that the amount used was changed to 4.0 g, and a uniform co-pulverized product [hereinafter referred to as "solid component (2)"] was obtained. Instead of the solid component (1) used in Example 1 (B), the same amount (15.0 g)
Example 1 (B ) was treated under the same conditions.
Next, the treatment was carried out in the same manner as in (B) of Example 1, except that 12.2 ml of a n-heptane solution of butyl ether was used instead of the isoamyl ether used as the ether compound used in (B) of Example 1. After washing and drying, a solid substance [hereinafter referred to as "solid catalyst component (B)"] was obtained (Example 2). The treated product (a) obtained in Example 1 (B) was thoroughly washed with n-heptane without being treated with an ether compound, and then dried under reduced pressure at a temperature of 60°C for 3 hours, A solid substance [hereinafter referred to as "solid catalyst component (C)"] was obtained (Comparative Example 1). The solid component (1) obtained in Example 1 (A) was treated with an ether compound, washed and dried under the same conditions as in Example 1 (B) without being treated with an alkyl aluminum compound. A solid substance [hereinafter referred to as "solid catalyst component (D)"] was obtained (Comparative Example 2). 20.0 g of anhydrous magnesium chloride used in (A) of Example 1 and 2.0 g of tetraethyl silicate were co-pulverized in the same manner as in (A) of Example 1 (titanium tetrachloride was not used). Of the co-pulverized products obtained
Take 15.0g and combine it with 5.0g of titanium tetrachloride.
The mixture was poured into 50 ml of toluene and stirred at a temperature of 60° C. for 2 hours. Next, the solid material [hereinafter referred to as "solid component"] was thoroughly washed with n-heptane and dried under reduced pressure at 60°C.
(3)'' was obtained. Instead of solid component (1) used in Example 1 (B), 15.0 g of solid component
(3), and 8.0 ml of n-hexane solution of diethylaluminum chloride (concentration 1 mol/) was used instead of triethylaluminum used as the alkylaluminum compound.
The treatment was carried out in the same manner as in Example 1. Next, the amount of the isoamyl ether compound used as the ether compound in (B) of Example 1 was changed to 32.0 ml, and the treatment was carried out at a temperature of 60°C for 2 hours. By washing and drying in the same manner, a solid substance [hereinafter referred to as "solid catalyst component (E)"]
was obtained (Example 3). 11.4 g of magnesium ethylate was placed in a 500 ml flask, and then 17.0 g of titanium tetrabutyrate was added. The treatment system was heated to a temperature of 170°C and stirred at this temperature for 3 hours.
The treatment system was allowed to cool to approximately room temperature, 200 ml of hexane was added, and 63.5 g of ethylaluminum bromide was added dropwise over 3 hours. After dropping, turn off the treatment system.
The temperature was increased to 50°C and stirring was carried out for 2 hours at this temperature. The treatment system was allowed to cool to approximately room temperature, and the product was thoroughly washed with n-hexane until no titanium atoms were observed in the washing solution, and then dried in the same manner as for solid component (1) in Example 1. did. As a result, a solid product [hereinafter referred to as "solid component (4)"]
was gotten. Of the solid component (4) obtained as above,
After putting 15.0g into a 500ml flask, 100ml of n
- Added heptane. Suspend the treatment system and add 10.0ml of triisobutylaluminum with stirring.
It dripped over time. After dropping, the treatment system is heated to 60℃.
and stirred at this temperature for 2 hours. The treatment system was cooled to room temperature again and treated in the same manner as in (B) of Example 1 to obtain a solid substance [hereinafter referred to as “treated product (b)”].
I got it. Next, add 10.0ml to this treated product (b).
n-heptane solution of ethyl octyl ether (as an ether compound) (concentration 1 mol/)
A solid substance [hereinafter referred to as "solid catalyst component (F)"] was obtained by processing, washing and drying under the same conditions as in Example 1 (B) (Example 4). Instead of isoamyl ether used as the ether compound in Example 1 (B), 20.6 ml
n-heptane solution of diethyl ether (conc.
The ether treatment was carried out under the same conditions as in Example 1 (B) except that 1 mol/) was used. Then, by washing and drying in the same manner as in Example 1 (B), a solid substance [hereinafter referred to as "solid catalyst component (G)"] was obtained.
was obtained (Comparative Example 3). 3.0 stainless steel autoclaves were charged with each of the solid catalyst components (B) to (G) obtained in the above manner as the main catalyst in the amounts shown in Table 1-1, and 0.54 g of triethylaluminum ( As an organoaluminium compound, co-catalyst)
was added and 1 Kg of isobutane was further added as an inert solvent. Then, each autoclave was closed and the internal temperature was raised to 80°C. Next, add hydrogen in the amount shown in Table 1-1, and add the α-olefin to the
Add or do not add ethylene as shown in Table 1, and feed 3.5 kg/cm ² (gauge pressure) of ethylene as shown in Table 1. While maintaining the ethylene partial pressure at 3.5 kg/cm ² , Homopolymerization of ethylene or ethylene and α-
Copolymerization with olefin was carried out. The polymerization was then terminated by discharging the contained gas to the outside of the system. Each of the obtained ethylene homopolymers or copolymers of ethylene and α-olefin was dried at 60° C. under reduced pressure for 12 hours. The yield and calculated polymerization activity of each homopolymer or copolymer were determined in the first step.
It is shown in Table 1. In addition, the MI of each homopolymer,
HLMI/MI, bulk density and angle of repose were measured. The results are shown in Table 1-2.

【table】

[Table] Example 5 7.0 ml of the solid catalyst component (A) obtained in (B) of Example 1 was placed as the main catalyst in a 3.0 mm stainless steel autoclave, and 0.54 g of triethylaluminum (as an organic aluminum compound) was added.
820 g of isobutane as an inert solvent and 180 g of a so-called spent fraction (content of butene-1 20.5% by weight) substantially free of water and butadiene were further added. Then, the autoclave was closed and the internal temperature was raised to 80°C. Hydrogen was fed into the reaction system to a partial pressure of 1.0 kg/cm ² (gauge pressure), and ethylene was further pressurized at 3.5 kg/cm ² (gauge pressure). While maintaining this ethylene partial pressure,
Copolymerization of ethylene and butene-1 was carried out for 1 minute. The polymerization was then terminated by discharging the contained gas to the outside of the system. The obtained copolymer of ethylene and butene-1 was dried at a temperature of 60° C. under reduced pressure for 12 hours. As a result, 320 g of polymer was obtained.
That is, polymerization activity 26100g/g・solid catalyst component
(A)・Time・Ethylene partial pressure [Kg/cm ² (gauge pressure)]
It is. The MI of this polymer is 4.6 g/10 min,
HLMI/MI was 39.0. Also, the bulk density is
It was 0.38g/cc. The angle of repose of this polymer was measured using a three-wheeled cylindrical rotating machine (manufactured by Tsutsui Rikagaku Kikai Co., Ltd.) and was found to be 30 degrees. From the results of the above Examples and Comparative Examples, it is clear that when homopolymerization of ethylene or copolymerization of ethylene and α-olefin is carried out using a catalyst system obtained from the solid catalyst component and organoaluminum compound used in the present invention. It is clear that not only the polymerization activity of the catalyst system is high, but also the bulk density of the obtained homopolymer and copolymer is relatively high, and the powder properties are good because the angle of repose of the polymer powder is small. be. FIG. 1 shows a process for preparing a catalyst used in the method for producing an ethylene polymer of the present invention.

[Brief explanation of the drawing]

FIG. 1 is a flowchart of the steps for preparing a catalyst used in the method for producing an ethylene polymer of the present invention.

Claims (1)

[Claims] 1 (A)(1)(a) Magnesium-based compound and ()
Ti (OR ^{3 )} _{l _} ^_ A hydrocarbon group selected from the group consisting of ] (b) Alkylaluminum compound represented by the formula () R ⁴ _a Al (OR ⁵ ) _b H _c X ⁴ _d () [R ⁴ is an alkyl group having at most 15 carbon atoms, and R ⁵ is a carbon at most 15 aliphatic or aromatic hydrocarbon groups;
X ⁴ is a halogen atom, and a is 0<a≦
3, b is 0≦b<3, and c is 0
≦c<3, d is 0≦d<3,
And a+b+c+d is 3. ] and (2) a solid catalyst component obtained by treating a chain-like ether compound having a total carbon number of 6 to 18; ) A method for producing an ethylene polymer, which comprises homopolymerizing ethylene or copolymerizing ethylene and α-olefin using a catalyst system obtained from an organoaluminum compound.