JPS591408B2 - Method for producing solid catalyst component for olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a solid catalyst component for olefin polymerization.

More specifically, the present invention relates to a novel method for producing a solid catalyst component for olefin polymerization, which can yield a polymer having extremely high polymerization activity and excellent mechanical properties and moldability. [I] Background of the present invention In recent years, transition metal halides (particularly titanium halides) have been used as ethylene polymerization catalysts in preparation with carriers [particularly compounds of divalent metals (particularly magnesium)] or compounds on carriers. A proposal to dramatically improve the polymerization activity (catalytic activity) per catalyst by supporting it on the treated product obtained by the treatment, and to substantially omit the step of removing catalyst residue remaining in the polymerization system after the completion of polymerization. Many things have been done.

These carriers include magnesium-containing compounds such as magnesium hydroxychloride, magnesium oxide, magnesium alcoholade, magnesium hydroxide and magnesium dihalide.

Furthermore, it has been proposed that these magnesium-containing compounds are pretreated with compounds such as water, alcohols, aldehydes, ketones, esters, ethers, and carboxylic acids. However, although these carriers or carriers pretreated with the above-mentioned compounds had significantly improved polymerization activity, when polymerizing ethylene or ethylene with other olefins,
This cannot be said to be practically satisfactory.

In other words, the problems are: (1) Polymerization activity is not always sufficient, and although the activity is relatively high in a short period of time, it is severely deactivated, resulting in poor productivity in long-term polymerization. ) is low.

(2) The bulk specific gravity (density) of the resulting polymer is too low,
Productivity of the polymerization equipment decreases.

(3) When a molecular weight modifier (generally hydrogen) is used to adjust the melt flow index of the resulting polymer, the effectiveness of the molecular weight modifier is relatively small and therefore the molecular weight modifier is used in a relatively large amount. Polymers with a high melt flow index cannot be obtained unless hydrogen is used (high hydrogen partial pressure if hydrogen is used) or polymerized at high temperatures.

(4) Poor reactivity of other olefins (as comonomers) in copolymerization, thus requiring high comonomer concentrations.

That is, since the polymerization conversion rate of the comonomer is lower than that of ethylene, the comonomer is wasted. (5) When copolymerizing ethylene and other olefins, the homogeneity of the branching degree distribution of the copolymer is insufficient (for low molecular weight polymers, the branching force is distributed as desired; Since the branches are hardly distributed in the polymer, it is impossible to exhibit sufficient performance as a copolymer.

etc. can be mentioned.

In the high-density polyethylene industry, copolymers of ethylene and other olefins are widely produced, and copolymers are mostly used in molding fields such as blow molding, stretch molding, and film molding.

The basic physical properties of such copolymers are largely determined by the amount of comonomer introduced into the ethylene chain and its distribution.
In particular, the number of short chain branches present in the high molecular weight part is determined by the spherulite structure,
It has a great influence on the basic properties of the polymer such as crystallinity, crystallization rate and melting point.

Furthermore, from the point of view of practical physical properties, it influences many aspects such as environmental stress resistance, film strength, flexibility, and formability. From the above, controlling the number and distribution of short chain branches in a copolymer is very important for improving practical physical properties.

The degree of branching distribution in copolymers is thought to be largely influenced by factors such as copolymerization reactivity with comonomers and ease of chain transfer by molecular weight modifiers (particularly hydrogen); The short chain branching of copolymers of ethylene and olefins obtained by catalyst systems such as organoaluminum compounds (e.g., trialkylaluminum)-titanium trichloride and organoaluminum compound monotetrachloride systems has low molecular weight. unnecessarily lowering the density of the copolymer in order to concentrate it in the copolymer, thereby significantly changing the basic properties of the polymer such as melting point and crystallization rate simply by increasing the hydrocarbon soluble content. was impossible.

Furthermore, the reactivity of the comonomer in copolymerization is thought to be closely related to the above-mentioned branching degree distribution, but especially in the case of copolymerization with olefins having 4 or more carbon atoms, the degree of conversion of the comonomer depends on the degree of conversion of the comonomer. ``Accounts for a large proportion of manufacturing costs.

When examining the performance of the prior art, which is based on supporting a titanium halide using a magnesium-containing compound pretreated with an electron donor as a carrier, as a catalyst for the copolymerization of ethylene and olefin, it was found that Although the homogeneity of the branching degree distribution and the reactivity with comonomers are considerably improved compared to catalyst systems in which the transition metal compound is not supported on a carrier, it cannot be said that they are necessarily satisfactory. In particular, the phenomenon in which the polymerization activity decreases (ie, deactivation) with the polymerization time is severe, and significant improvements including this point are required.

The problem with using catalyst systems with high initial polymerization activity and severe deactivation on an industrial scale is that even if the average polymerization time is simply lengthened, the product yield (production amount per unit catalyst) increases. Not only is this not possible, but it also poses major obstacles to the process, such as the risk of runaway polymerization and the difficulty of controlling the reaction temperature.

Moreover, among the above-mentioned carriers, many methods using magnesium alcoholade have been proposed.

Examples of this method include the following. (1) A method using a reaction product of magnesium alcoholade and a tetravalent titanium compound as a solid catalyst component.

(2) A method in which a magnesium alcoholade is brought into contact with an alkyl aluminum halide and then reacted with a transition metal halide. (3) A method in which a titanium tetraalkoxide is reacted with a magnesium alcoholade, and this reaction product is reacted with silicon tetrachloride. (4) A method in which a halogenating agent is applied to magnesium alcoholade and then a transition metal compound is supported on the finger body. In the case of homopolymerization of ethylene or copolymerization of ethylene with other olefins in the presence of a catalyst system, the above-mentioned problems cannot be completely solved, so it cannot be said to be practically satisfactory.

As mentioned above, ethylene polymers (especially copolymers of ethylene and olefins) are used in a wide range of fields, and although they are occupying an increasingly important position in industrial production, There are still few proposals regarding catalyst systems suitable for the production of ethylene-based copolymers that improve their basic performance.

[]Objects and effects of the present invention (a) Objects of the present invention As a result of various explorations by the present inventors to solve the above problems, (A) (1) Aluminum halide (2) or a cyclic ether-based compound" (hereinafter referred to as "ether-based compound") and (3) a solid product obtained by contacting with a magnesium alcoholade (B).
A solid catalyst component for polymerization obtained by supporting a "tetravalent titanium compound having at least one halogen atom" (hereinafter referred to as a "titanium compound") and an organoaluminum compound as a cocatalyst. The inventors have discovered that olefin-based polymers with high polymerization activity can be obtained by polymerizing olefins using a catalyst system such as the above, and have arrived at the present invention.

(b) Effects of the present invention In the present invention, the effects (characteristics) when ethylene is homopolymerized or ethylene and other olefins are copolymerized in the presence of the catalyst system obtained as described above are as follows.

(1) Catalytic system activity.

Therefore, since the content of catalyst residues in the polymer produced after completion of polymerization is extremely small, the step of removing catalyst residues from the polymer can be substantially omitted. (2) Since the bulk specific gravity (density) of the obtained polymer is relatively large,
The productivity of the polymerization process, drying process of the obtained polymer, and transport process is excellent. (3) Due to the low deactivation of the catalyst system used, it is possible to use the catalyst system for a fairly long time. (4) When producing a polymer with excellent melt flow index using a molecular weight modifier (e.g., hydrogen),
Since the effect of the molecular weight regulator is excellent, even if a relatively small amount of the molecular weight regulator is used, the effect can be sufficiently exhibited. (5) Since the soluble content in the polymerization solvent is small, there are relatively few deposits in the equipment during the polymerization process, so it is possible to produce the polymer without difficulty.

Furthermore, the characteristics of copolymerizing ethylene and other olefins are as follows. (1) Since the branching degree distribution of the resulting copolymer is relatively homogeneous regardless of the molecular weight of the polymer, the environmental stress cracking resistance of this copolymer is good.

(2) Since the copolymerizability of other olefins (comonomers) is excellent, the polymerization conversion rate of comonomers is higher than that of other catalyst systems. (3) Relatively low density (approximately 0.9207/
Slurry polymerization of the ethylene polymer Cc) is possible at a relatively low temperature (generally 100° C. or lower).

Therefore, the resulting polymer can be easily recovered. []
DETAILED DESCRIPTION OF THE INVENTION (a) Production of solid product (1) Aluminum halide The aluminum halide used in the present invention is anhydrous, and representative examples thereof include aluminum chloride, aluminum fluoride, and aluminum bromide. given,
Particularly preferred is aluminum chloride.

(!1) Ether Compound The ether compound used in the present invention has at most 40 carbon atoms and has aliphatic, cycloaliphatic, and aromatic hydrocarbon groups (which may be partially substituted with halogen).
Typical examples include dimethyl ether, methyl ethyl ether, diethyl ether, di-propyl ether,
Di-isopropyl ether, di-n-butyl ether, di-iso-butyl ether, di-iso aluminum ether, dioctyl ether, didodecyl ether, diallyl (AllyI) ether, iso-butyl vinyl ether, polyethylene glycol, polypropylene glycol, ethylene glycol dimethyl ether, diethyl Linear aliphatic ethers such as Cellosolp and benzyl methyl ether, diphenyl ethers, di-p-tolyl ether, linear aromatic ethers such as anisole, ethoxybenzene and dimethoxybenzene, and ethylene oxide, propylene oxide, trioxane. Mention may be made of cyclic ethers such as furan, tetrahydrofuran, dioxane, coumaron, coumaran and tetrahydrobilane.

Among these ether compounds, aliphatic or aromatic linear ethers are preferred, and those whose general formula is represented by the following formula [Formula (1)] are particularly desirable.

R1-0-R2() In formula (1), R1 and R2 may be the same or different, and are selected from alkyl groups, aryl groups, and aralkyl groups having at most 10 carbon atoms.

In particular, in formula (1), it is preferable that R1 and R2 have 8 or less carbon atoms. Suitable ones include ethyl phenyl ether, (phenetol), methyl phenyl ether (anisole), diphenyl ether, diethyl ether, diisoamyl ether and dipropyl ether. (111) Magnesium Alcolade Furthermore, among the magnesium compounds used in the present invention, the general formula of a typical one is represented by the following formula [formula ()].

Mg(0R3)2 () In the formula, R3 is selected from the group consisting of an alkyl group having at most 8 carbon atoms, a cycloalkyl group, a cycloalkyl group having an alkyl group, an aryl group, and an aralkyl group. It is an exposed hydrocarbon group.

Representative examples of these magnesium alcoholates include magnesium methylate, magnesium ethylate, magnesium (n-propylate), (isopropylate) magnesium butyrate, magnesium hexylate, magnesium phenolade, and magnesium cyclohexanolate. , magnesium pencil alcoholade and magnesium cresolate.

Among these magnesium alcoholades, those in which R3 in the above formula is represented by an alkyl group or phenyl group having at most 3 carbon atoms are desirable.

These suitable magnesium alcoholades include magnesium ethylate, magnesium methylate and magnesium phenolate.

(1V) Reaction ratio In producing the solid product, the reaction ratio of aluminum halide to 1 mol of the magnesium alcoholade is generally from 0.1 to 10 mol, in particular:
0.2 to 2 mol is preferred.

If the reaction ratio of aluminum halide to 1 mol of magnesium alcoholade is less than 0.1 mol, the polymerization activity of the resulting catalyst system will be low, while if it is 10 mol or more,
The bulk specific gravity of the ethylene polymer produced is 0.18 or less, resulting in a decrease in productivity.

Further, the reaction ratio of the ether compound to 1 mol of magnesium alcoholade is generally 0.1 to 10 mol, preferably 0.2 to 2 mol.

A particularly important factor in this reaction is the reaction ratio of aluminum halide and ether compound, and the reaction ratio of aluminum halide to 1 mole of ether compound is usually 0.25 to 4 moles, and in particular, 0.
5 to 1.5 mol is suitable.

This reaction ratio is important because it changes the effectiveness of the molecular weight regulator and also changes the polymerization activity. (v) Reaction conditions and post-treatment The methods for producing this solid product include a sequential reaction method in which the aluminum halide and the ether compound are reacted in advance, and then the resulting reaction product is reacted with magnesium alcoholade; Although there is a simultaneous reaction method in which the two components are simultaneously mixed and reacted, either method may be employed to produce a solid product.

This reaction is carried out under a dry (moisture-free) atmosphere of inert gas (eg, nitrogen, argon).

Furthermore, this reaction is usually carried out in an organic solvent that is liquid at room temperature. Representative examples of this organic solvent include aliphatic hydrocarbons (e.g., n-hexane, n-heptane), alicyclic hydrocarbons (e.g., cyclohexane, methylcyclohexane), and aromatic hydrocarbons (e.g.,
benzene, toluene) and halides of these hydrocarbons (for example, carbon tetrachloride, trichloroethylene), but these organic solvents may be used alone or in combination of two or more. In particular, the reaction between aluminum halide and an ether compound is an exothermic reaction, and toluene, benzene, and methylcyclohexane are preferred from the standpoint of removing the reaction heat and producing a reaction mixture that is not necessary for producing a solid product. Furthermore, the amount of organic solvent used per 1V of magnesium alcoholade is generally from 3 to 50 ml, preferably from 5 to 30 ml. In the sequential reaction method, when reacting aluminum halide with an ether compound, the reaction temperature is
Generally, the temperature is room temperature (2'C) to 150°C, and preferably room temperature to 100°C.

Further, in the simultaneous reaction method, the temperature is generally room temperature to 150°C, particularly preferably 50 to 100°C. Furthermore, the reaction time is usually 10 minutes to 3 hours, especially 30 minutes.
~90 minutes is appropriate.

In particular, a solid product can be obtained by reacting for 30 to 90 minutes at a temperature range of 50 to 10'C, taking into account both the above reaction temperature and reaction time. The supernatant liquid of the reaction product (precipitate) obtained by the above two methods is extracted using the organic solvent used during the reaction or another hydrocarbon solvent.

Then a new hydrocarbon solvent (maybe a different type of hydrocarbon)
The hydrocarbon-insoluble solid product can be purified by repeating several times the operation of adding, stirring and washing, and then removing the supernatant liquid (so-called decanting method). The solid product (composite carrier) purified in this way varies in color depending on the type of ether compound used in the reaction, ranging from dark green to an ocher pick color, and is in powder form. .
Atomic absorption analysis reveals that it is a composite carrier containing magnesium and aluminum. (b) Production of solid component The solid component, which is the object of the present invention, can be produced by reacting the purified solid product obtained by the above method with the titanium compound described below. can.

(1) Titanium compound The titanium compound used to produce the solid component is a tetravalent titanium compound having at least one halogen atom, and its general formula is represented by the following formula [formula ()]. It is something.

TlXm(0R4)4-n1 () In the formula, X is a chlorine atom, a bromine atom or an iodine atom, and R
4 is an aliphatic, alicyclic or aromatic hydrocarbon group having at most 12 carbon atoms, and m is a number from 1 to 4.

Typical examples of titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, dimethoxytitanium dichloride, trimethoxytitanium chloride, ethoxytitanium trichloride, diethoxytitanium dichloride, and triethoxytitanium. Mention may be made of chloride, propoxytitanium trichloride and butoxytitanium trichloride.

Among these titanium compounds, in formula (), R4
is an alkyl group having at most 6 carbon atoms, and m is preferably 3 or 4, particularly titanium tetrachloride,
Methoxytitanium trichloride, ethoxytitanium trichloride and butoxytitanium trichloride are preferred, and titanium tetrachloride is particularly preferred.

(4) Reaction ratio Although the reaction ratio between the solid product and the titanium compound described above varies depending on the content of magnesium in the solid product, in general, the solid product supports as much of the titanium compound as possible. The reaction ratio of the titanium compound per 1 atom of magnesium in the solid product is usually selected from the range of 0.1 to 200 mol (preferably 0.2 to 100 mol). force (can vary depending on reaction temperature, concentration and time).

Appropriate conditions may be selected such that the amount of titanium atoms supported on the solid product (composite support) containing aluminum, silicon and magnesium is generally 1 to 10% by weight. (111) Reaction conditions and purification (post-treatment)
The solid component can be produced by reacting the solid product and the titanium compound in the inert hydrocarbon solvent used to produce the solid product or in the absence of a solvent. I can do it.

The reaction temperature in this reaction varies depending on reaction conditions such as the reaction ratio of titanium compound to magnesium in the solid product and the type of solid product and titanium compound, but when the reaction is carried out in the presence of a solvent, is generally room temperature to 150°C, especially 50°C.
~120°C is preferred.

If the reaction occurs below room temperature, the reaction will be insufficient. On the other hand, although the desired product can be obtained even if the reaction is carried out at a reaction temperature of 150° C. or higher, it is not necessary. On the other hand, when the reaction is carried out in the absence of a solvent, it is desirable to carry out the reaction at a higher temperature than in the reaction in the presence of a solvent, and the preferred reaction temperature range is 80 to 140°C. Further, although the reaction time varies depending on the reaction conditions and reaction temperature, it is generally 10 minutes to 3 hours.
It is desirable to react for 30 minutes to 2 hours from the viewpoint of zeta activity.

If the reaction time is less than 10 minutes, the reaction is insufficient. Further, even if the reaction is allowed to proceed for 3 hours or more, the reaction may not proceed further and the resulting catalyst system may be deactivated. The solid component obtained by the above method is generally purified by the following method. That is, the mixture of solid components and unreacted substances is obtained by decanting the supernatant liquid using the hydrocarbon solvent used during the reaction or another hydrocarbon solvent (preferably one with a relatively low boiling point). It is desirable to remove the titanium compound by a filtration method and repeat the washing until the presence of titanium-based compounds is no longer recognized in the washing liquid.

The hydrocarbon solvent may be used for washing, and the resulting slurry containing solid components (substantially free of unreacted titanium compounds) may be supplied to the polymerization vessel described below. is also possible. Alternatively, after the hydrocarbon solvent used for washing is removed under reduced pressure, the solid component can be matted into a polymerization vessel. [] Confirmation of the use of the solid catalyst component and the effects of the present invention The solid catalyst component obtained as described above and the catalyst system obtained from the organic-luminium compound, etc. were brought into contact with Oufine and polymerized, thereby producing the present invention. You can check the effect of

1) Organoaluminum compound The organoaluminum compound used to obtain the solid catalyst component and catalyst system obtained by the present invention is well known as a Ziegler type 1 catalyst.

Typical general formulas thereof are shown by the following formulas [formula (), formula (V), and ()]. In formulas (), (), and (), R5, R6, R7, R8 and P, RlO, Rll, and Rl2 may be the same or different, and R5R6 and R7 are hydrogen atoms, halogen atoms, or have as many carbon atoms as possible. 8 alkyl or alkoxy groups, R8 is an alkyl group having at most 8 carbon atoms, R9, RlO and Rll are alkyl groups having at most 8 carbon atoms, and Rl2 is a halogen atom or It is an alkyl group having at most 8 carbon atoms, and X is a halogen atom.

At least one of R5, R6 and R7 is an alkyl group. Representative examples of these include trialkylaluminums such as triethylaluminum, triisobutylaluminum and trihexylaluminum;
Alkylaluminum halides such as diethylaluminum chloride, ethylaluminum sesquichloride and dibutylaluminum chloride, dialkylaluminum hydrides such as diethylaluminum hydride, alkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum methoxide, and diethylaluminum diethyl Examples include alkyl aluminum amides such as amide.

Among these organoaluminum compounds, trialkylaluminums are preferred, and trialkylaluminums in which the alkyl group has at most 6 carbon atoms (eg, triethylaluminum, triisobutylaluminum) are particularly preferred. Aluminum halide, ether compound used for production according to the present invention,
Each of the magnesium alcoholade, titanium-based compound, and organoaluminum compound may be used alone, or two or more types may be used in combination.

(b) Olefin The olefin polymerized using the catalyst system obtained as described above is usually an olefin having at most 12 carbon atoms, typical examples of which are ethylene, propylene, butene-1,4-methyl Benzene-1, Hexene-1
and octene-1.

In polymerization, these olefins may be used alone or in combination of two or more. The catalyst system obtained from the solid catalyst component obtained by the present invention and the organoaluminum compound is particularly effective in the homopolymerization of ethylene or in combination with ethylene in a small amount (generally,
0% by weight or less) with other olefins. (c) Polymerization conditions, etc. Polymerization is carried out by dissolving one olefin or two or more olefins in an inert solvent, or without using an inert solvent. ) may coexist.

The polymerization temperature is generally from -10°C to 200°C, and practically from room temperature (25°C) to 170°C.

In addition, the type of polymerization solvent and the proportion used relative to olefin are known in the production of olefin polymers (eg, ethylene homopolymers, ethylene copolymers, propylene polymers).

Furthermore, the configuration of the polymerization reactor, polymerization control method, post-treatment method, proportion of monomer and organoaluminum compound to inert organic solvent used in polymerization, type of inert organic solvent, and Regarding the post-treatment method, there are no limitations inherent to this catalyst system, and all known methods can be applied.

[] Implementation F7ll. COMPARATIVE EXAMPLES AND APPLIED EXAMPLES The present invention will be explained in more detail below using examples and applied examples.

In addition, in the Examples and Comparative Examples, the melt index (hereinafter referred to as "M.IJ") was measured according to JISK-6760.

True density was measured according to JISK-6760. Furthermore, bulk density was measured according to JISK-6721. Further, bending rigidity (stiffness) was measured according to ASTM D-747, and tensile test (yield strength, cutting strength, and elongation) was measured according to JISK-6760. The method for measuring short chain branching by infrared absorption spectroscopy uses the absorption of 4255a1-1 determined by infrared absorption spectroscopy as an internal standard, and from the absorption of the methyl group of 1378an-1,
Measured by the method of A.H. WillbOrn [A.H.
urn), Journal of Polymer Science (JO
urnalOfPOlymerScience) No. 34
vol., p. 569, (1959)].

In addition, in each example and comparative example, each compound used in the production and polymerization of the catalyst component (inert organic solvent, ethylene, other olefins, aluminum halides, titanium compounds, organoaluminum compounds, ether compounds, hydrogen etc.) were all substantially free of moisture, and the preparation and polymerization of each catalyst component were conducted substantially in the absence of moisture and under a nitrogen atmosphere.

Example 1 [Production of solid catalyst (4)] 4.75y (35.6 mmol) of commercially available anhydrous aluminum chloride, which had been previously ground in an agate pot under a nitrogen atmosphere, was weighed into a 200 ml three-necked flask, and then 357
111 of toluene was added and thoroughly stirred.

5.657 (35.7 mmol) of isoamyl ether (hereinafter referred to as "compound sacrifice 1" as an ether compound) was weighed out using a syringe, and added dropwise little by little while stirring. Addition of aluminum chloride suspended in toluene caused an exothermic reaction. After the exotherm had ended, stirring was continued for 15 minutes at room temperature (approximately 25° C.). After adding 2.01 V (17.6 mmol) of magnesium ethylate to this reaction system,
The temperature of the reaction solution was raised to 90°C, and the reaction was carried out for 1.5 hours. At this time, the reaction solution was a white slurry-like liquid. After cooling the reaction solution to about 40°C, the supernatant liquid was extracted, and after washing by adding n-hexane (approximately 30 ml) (12.5 ml per 1y of magnesium), the supernatant liquid was extracted by decanting. . This wash was repeated three more times. The obtained solid product (composite carrier) was dried at about 50° C. under reduced pressure. As a result, 1,957 white powdery solid products were obtained. This collective product 1.86y
Weigh out, put it in a 200ml flask, and add 8.8
3 ml of titanium tetrachloride (80.6 mmol) were added.
The reaction was carried out at 90° C. for 1.5 hours with stirring.

After cooling the reaction system to approximately room temperature, the soil clear liquid was extracted.
Three washes were carried out in the same manner as the solid product was washed.
As a result, a 1.95y white powdery solid catalyst [hereinafter referred to as "solid catalyst (A)"] was obtained. This solid catalyst (A) was dried at about 5-0°C under reduced pressure for about 10 hours. This dried solid catalyst (4) was subjected to atomic absorption analysis and titration analysis. Titanium content is 4.3% by weight
, the aluminum content is 2.5% by weight,
The chlorine content was 55% by weight. Application example 1 [Polymerization of ethylene] 0.7 mmol of triisobutylaluminum (
0.5 mol/TO) n-heptane solution (1.4 m0) was added, 21.0 w of the solid catalyst (A) obtained in Example 1 was added, and a liquid of isobutane as a solvent was added at the polymerization temperature (85°C). The phase was charged at room temperature through a flow meter so that it occupied 700 ml.

After removing the nitrogen gas in the system by blowing a small amount and completely sealing the reaction system, the temperature was raised to the polymerization temperature.
After the polymerization temperature was reached, using a micro cylinder, pressure was introduced into the reaction system until the partial pressure of the reaction system reached 2 atmospheres (gauge pressure), and then pressure was introduced until the partial pressure of ethylene reached 10 atmospheres (gauge EL). React (polymerization) while stirring for 40 minutes while continuously supplying ethylene to keep the total pressure of the reaction system constant.
I did this. After the polymerization was completed, the solvent and unreacted monomer (ethylene) in the reaction system were purged. As a result, a white powdery polymer was obtained. This polymer was dried at a temperature of 80°C for about 2 hours under reduced pressure without being purified.
43.77 of a polymer (ethylene monopolymer) was obtained.
In other words, the specific activity is 1,7397,7J [solid catalyst (
A)・Time・Pressure (ethylene pressure). The bulk density of this polymer was 0.297/Cml, and the bulk density of this polymer was 0.297/Cml. I. is 0.
It was 557/10 minutes. H. L. M is 17.87/1
0 minutes (i.e. I]I, MI/M-1. is 32.4)
The true density was 0.95357/Cml. Application example 2 Application example 1 was used except that the amount of solid catalyst (A) used in the autoclave used in application example 1 was changed to 15.6 w.
Isobutylaluminum and isobutane were added in the same manner as above.

The partial pressure of ethylene in the reaction system is 5k9/CTii and the partial pressure of hydrogen is 0.23k9/? Instead, ethylene and butene-1 were copolymerized and dried in the same manner as in Application Example 1, except that 2.52% by weight of butene-1 based on ethylene was added using a micro bomb. As a result, 27
A 2.8y copolymer of ethylene and butene-1 was obtained. That is, the specific activity is 3,2887/7 - solid catalyst (
A)・Time・Pressure. The bulk density of this copolymer is 0
．． 317/c, true density is 0,9274y/CT
It was iI. Moreover, HLM was 0.76y/10min. Examples 2 to 6, Comparative Examples 1 and 2 Instead of compound (1) used as the ether compound in Example 1, diphenyl ether [hereinafter referred to as "compound (2)]" and diethyl ether [hereinafter referred to as "compound (2)"] were used. Compound (3)], anisole [hereinafter referred to as "Compound (4)]"
co-phenetol [hereinafter referred to as "compound (5)"]
and dipropyl ether [hereinafter referred to as L compound (6)] were changed as shown in Table 1-1, and the amounts of aluminum chloride, toluene and magnesium ethylate were changed as shown in Table 1-1. After carrying out each reaction, washing and drying were performed in the same manner as in Example 1 (Comparative Example 1 did not use an ether compound, and Comparative Example 2 did not use aluminum chloride. ).

The reactions were carried out under the same conditions as in Example 1, except that the amounts of each solid product (composite carrier) and titanium tetrachloride used were changed as shown in Table 1-2, and then washed and Drying was performed to obtain solid catalysts. The yield of each solid catalyst obtained, their abbreviations, and the titanium (Ti) aluminum (At
) and chlorine (Ct) content are shown in Table 1-2. Application Examples 3 to 7 The usage amount, polymerization temperature, polymerization time, and partial pressure of ethylene and hydrogen of each solid catalyst obtained in Examples 2, 3, and 4 and Comparative Examples 1 and 2 are shown in Table 2-1. Homopolymerization of ethylene was carried out in the same manner as in Application Example 1, except for the changes as shown.

The yield and specific activity of each ethylene monopolymer obtained, as well as the bulk density, true density, M. 9 and HLMI are shown in Table 2-2. Application Examples 8 to 14 The amount of each solid catalyst obtained in Examples 1 to 6, the polymerization temperature, the polymerization time, the amount of butene-1 to ethylene, and the partial pressures of ethylene and hydrogen were Copolymerization of ethylene and butene-1 was carried out in the same manner as in Application Example 2 except for the changes shown in Table 1.

The yield and specific activity of each copolymer of ethylene and butene-1 obtained, as well as the bulk density, true density, and M. I. and HLMI are shown in Table 3-2. Application example 15 Same as application example 9 except that the amount of solid catalyst (8) used was changed to 11.57f9, and 23% by weight of hexene-1 based on ethylene was used instead of Z-butene-1. Copolymerization of ethylene and hexene-1 was carried out.

After the copolymerization was completed, the solvent and unreacted monomers (ethylene and hexene-1) were purged. As a result, 204.77
A white powder (copolymer) was obtained. The bulk density of this copolymer was 0.307/d. Moreover, the M. I. was 0.127/10 min and HLMI was 667/10 min (i.e. HLM/M.I.
55). 100 parts by weight of the ethylene monopolymer or copolymer obtained in Application Example 3 and Application Example 14 and 0.1 part by weight of 2,6-di-tert-butyl-p-cresonol as a stabilizer; 0.05 parts by weight of distearyl thiodipropionate and 0.1 parts by weight of calcium stearate were mixed in an extruder with an inner diameter of 20 mm (C1 temperature 150°C, C2 temperature 170°C, die temperature 1800°C).
C) was used to prepare pellets while kneading.

Each pellet obtained was preheated for 5 minutes using a press set at 165°C, then 100k9/? 5 under the pressure of
After pressing for a minute, use a water-cooled press machine to press 100 kg.
Pressing was carried out for 3 minutes at a pressure of /0fi1. The bending rigidity of the press plate made of the ethylene monopolymer composition obtained in Application Example 3 is 10,800 kg/C! l, and the yield strength is 3
It was 28k9/Crit.

Moreover, the cutting strength was 350k9/(1-JmoVt), and the elongation rate was 840%. The bending rigidity of the press plate was 9,400k9/?

Further, the yield strength was 299k9/CTiL, and the elongation rate was 10%. The ethyl branch of this copolymer is 100
There were 0 carbon atoms and 32 atoms. From the above examples, comparative examples, and reference examples, it is clear that when ethylene homopolymerization or copolymerization of ethylene and other olefins is carried out using a catalyst system obtained using the solid catalyst component obtained by the present invention as a catalyst component, the polymerization ratio is A powdered polymer with high activity and high bulk density can be obtained, has high copolymerizability, has little deactivation even after long polymerization, and has a very high melt index to a low melt index. It is clear that even polymers with high activity can be obtained.

Claims (1)

[Scope of Claims] 1 (A) A solid product obtained by contacting (1) aluminum halide (2) a chain or cyclic ether compound and (3) magnesium alcoholate with (B)
A method for producing a solid catalyst component for olefin polymerization, which comprises supporting a tetravalent titanium compound having at least one halogen atom.