JP3773979B2 - Solid material for ethylene polymer, solid catalyst component and method for producing ethylene polymer using the same - Google Patents

Description

【００４２】
【発明の効果】
以上に示したように、エチレン系重合体用触媒の担体となる固体物質を特定の粒径にすることで、エチレン系重合体を成形加工したフィルムやシートにフィッシュアイの発生を抑え、外観を向上できる。また、重合用触媒の活性を向上することもできる。
【図面の簡単な説明】
【図１】 図１は、本発明における固体物質にチタン化合物等を接触させる調製工程に関するフローチャートである。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a method for producing an ethylene polymer, and more specifically, a solid material used for preparing a solid catalyst component for an ethylene copolymer, a solid catalyst component using the solid material, and an ethylene system using the solid material. The present invention relates to a method for producing a polymer.
[0002]
[Prior art]
An olefin polymerization catalyst generally called a Ziegler catalyst is generally composed of a transition metal compound component and an organometallic compound. Among these, in the preparation of the former transition metal compound component, a technique using magnesium chloride or magnesium dialkoxide as a carrier has been widely practiced, and there are many related techniques.
[0003]
Further, this magnesium compound is often used after being subjected to a treatment such as mechanical grinding.
[0004]
[Problems to be solved by the invention]
However, the technology using these magnesium compounds as a carrier for olefin polymerization catalysts is for improving the activity as a catalyst and controlling the particle size of the produced polymer, and improving the appearance of films and sheets formed by molding the produced polymer. In particular, the examination from the viewpoint of reducing the occurrence of fish eyes is not disclosed.
[0005]
In addition, there are fish eyes in films and sheets molded from the current ethylene-based copolymer, and not only the problem of poor appearance, but also the problem of tube breakage when processing thin films with the inflation molding method. There is a strong demand for improvement.
[0006]
[Means for Solving the Problems]
Accordingly, the present inventors have intensively studied a catalyst system for improving the appearance of a film or sheet obtained by molding an ethylene polymer, particularly for reducing the generation of fish eyes, and as a result, produced a solid as a carrier for a polymerization catalyst. It has been found that by making the product a specific particle size, it is possible to suppress the generation of fish eyes and improve the appearance and the activity of the catalyst in a film or sheet obtained by molding an ethylene copolymer. The present invention has been accomplished by solving the above problems.
[0007]
  According to the present invention, the following means are provided.
(1) A solid substance containing a magnesium compound used for the preparation of a solid catalyst component for an ethylene polymer,Magnesium chloride, magnesium fluoride, magnesium bromide, magnesium iodide, magnesium halide treated with an electron donor, magnesium halide treated with alcohol, and then reacted with an organoaluminum compound or silicon tetrachloride , Magnesium dialkoxide (excluding magnesium alkoxide dispersion (Liogel)), one obtained by reacting metallic magnesium and alcohol under reflux, and 0.0001 gram atom or more per mole of metallic magnesium, alcohol and metallic magnesium At least one solid substance selected from those obtained by reacting a halogen-containing compound containing an amount of halogen;A solid substance having an average particle size of 10 μm or less and a maximum particle size of 15 μm or less.
(2) A solid catalyst component for an ethylene polymer obtained by bringing a titanium compound into contact with the solid substance of (1).
(3) A solid catalyst component for an ethylene polymer obtained by bringing a halogen-containing silicon compound, an alcohol, and a titanium compound into contact with the solid substance of (1).
(4) A method for producing an ethylene polymer in which ethylene or ethylene and an α-olefin are polymerized using a catalyst system comprising the solid catalyst component according to (2) or (3) and an organoaluminum compound.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The solid substance of the present invention contains at least a magnesium compound, and various compounds or compositions having a function as a catalyst support or the catalyst itself can be employed. This is used for the preparation of a solid catalyst component for an ethylene polymer.
[0009]
    As the solid substance containing at least a magnesium compound, first, substantially anhydrous magnesium chloride, magnesium fluoride, bromine magnesium, magnesium iodide, magnesium dialkoxide are used.(Excluding magnesium alkoxide dispersion (Riogel))Can be mentioned.TheAs a magnesium dialkoxide, what has a C1-C6 alkyl group is preferable. In particular, magnesium dialkoxide obtained from metallic magnesium and alcohol is preferably used.
[0010]
The metal magnesium is not particularly limited in shape and the like, and metal magnesium having an arbitrary particle size, for example, magnesium in a granular shape, a ribbon shape, a powder shape, or the like can be used. Moreover, although it does not specifically limit also to the surface state of metallic magnesium, The thing by which coating | covers, such as magnesium oxide, are not produced | generated on the surface is preferable.
[0011]
Although arbitrary things can be used as alcohol, it is preferable to use a C1-C6 lower alcohol. In particular, it is preferable to use ethanol because the solid substance that remarkably improves the expression of the catalyst performance can be obtained. Although it is not particularly limited to the purity and water content of the alcohol, if an alcohol having a high water content is used, magnesium hydroxide is produced on the surface of the metal magnesium, so an alcohol having a water content of 1% or less, particularly 2000 ppm or less. It is preferable to use it.
[0012]
Although it does not ask | require about the quantity of alcohol, Preferably it is 2-100 mol with respect to 1 mol of metal magnesium, Most preferably, it is 5-50 mol. When there is too much alcohol, the yield of a solid substance with good morphology may be reduced, and when it is too little, stirring in the reaction vessel may not be performed smoothly. However, it is not limited to the molar ratio.
[0013]
The reaction itself between magnesium metal and alcohol can be carried out in the same manner as a known method. For example, a solid material is obtained by reacting metal magnesium and alcohol under reflux until generation of hydrogen gas is not observed. In an inert gas (for example, nitrogen gas, argon gas) atmosphere, it is preferable to use an inert organic solvent (for example, a saturated hydrocarbon such as n-hexane) in some cases. Regarding the addition of magnesium metal and alcohol, it is not necessary to add the entire amount to the reaction vessel from the beginning, and they may be added separately. A particularly preferred form is a method in which the whole amount of alcohol is added from the beginning and metal magnesium is added in several portions.
[0014]
Further, a solid material obtained from metallic magnesium, alcohol, and halogen and / or a halogen-containing compound can also be preferably used.
Any metal magnesium can be used and is the same as described above.
Any alcohol can be used and is the same as described above.
The type of halogen is not particularly limited, but chlorine, bromine, or iodine is preferable. In particular, iodine can be preferably used. Moreover, there is no restriction | limiting in particular as a halogen-containing compound, As long as it is a compound containing a halogen atom, any of an inorganic or organic compound may be sufficient. Specifically, MgCl₂, MgI₂Mg (OEt) I, Mg (OEt) Cl, MgBr₂, CaCl₂Halogen-containing inorganic compounds such as NaCl, KBr, CH_ThreeI, CH₂I₂, CHI_Three, CH_ThreeCl, CH₂Cl₂, CHCl_Three, CH_ThreeBr, C₂H_FiveA halogen-containing organic compound such as I can be preferably used. Among these, especially MgCl₂, MgI₂Is preferred. The state, shape, particle size, etc. of this compound are not particularly limited, and any compound may be used. For example, it can be used in the form of a solution in an alcohol solvent such as ethanol.
[0015]
Although it does not ask | require about the quantity of alcohol, Preferably it is 2-100 mol with respect to 1 mol of metal magnesium, Most preferably, it is 5-50 mol. When there is too much alcohol, the yield of a solid substance with good morphology may be reduced, and when it is too little, stirring in the reaction vessel may not be performed smoothly. However, it is not limited to the molar ratio.
[0016]
The amount of halogen used is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 0.001 gram atom or more, per 1 gram atom of metal magnesium. The halogen-containing compound is used in an amount of 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 0.001 per 1 gram atom of metal magnesium. More than gram atoms.
[0017]
Each of the halogen and the halogen-containing compound may be used alone or in combination of two or more. Further, a halogen and a halogen-containing compound may be used in combination. In this case, the amount of all halogen atoms is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 0.001 gram atom or more with respect to 1 gram atom of metal magnesium. The upper limit of the amount of halogen and / or halogen-containing compound used is not particularly defined and may be appropriately selected within the range in which the target solid substance can be obtained. In general, the amount of all halogen atoms is 1 gram atom of magnesium metal. Is preferably less than 0.06 gram atoms.
[0018]
The reaction itself between magnesium metal, alcohol, halogen and / or halogen-containing compound can be carried out in the same manner as in a known method. For example, a solid material is obtained by reacting metallic magnesium, an alcohol, and a halogen and / or a halogen-containing compound under reflux until generation of hydrogen gas is not observed (usually 20 to 30 hours). Specifically, for example, when iodine is used as the halogen, a method in which solid iodine is introduced into an alcohol containing metal magnesium and then heated to reflux, and an alcohol solution of iodine is added dropwise to the alcohol containing metal magnesium. Examples thereof include a method of heating to reflux and a method of dropping an alcoholic solution of iodine while heating an alcohol containing metallic magnesium. In any method, it is preferable to carry out using an inert organic solvent (for example, saturated hydrocarbon such as n-hexane) in an inert gas (for example, nitrogen gas, argon gas) atmosphere.
[0019]
Regarding the charging of magnesium metal, alcohol, halogen, and / or halogen-containing compound, it is not necessary to put all the amounts into the reaction vessel from the beginning, and they may be added in portions. A particularly preferred form is a method in which the whole amount of alcohol is added from the beginning and metal magnesium is added in several portions. In such a case, a temporary mass generation of hydrogen gas can be prevented, which is very desirable from the viewpoint of safety. In addition, the reaction vessel can be reduced in size. Furthermore, it becomes possible to prevent entrainment of alcohol, halogen and / or halogen-containing compounds caused by temporary large-scale generation of hydrogen gas. The number of times of division may be determined in consideration of the scale of the reaction vessel, and is not particularly limited. However, in view of the complexity of the operation, 5 to 10 times is usually preferable. The reaction itself may be either a batch type or a continuous type. Further, as a modified method, an operation in which a small amount of magnesium metal is first charged into the alcohol that has been charged in its entirety from the beginning, the product produced by the reaction is separated and removed in a separate tank, and then a small amount of metal magnesium is charged again. It is also possible to repeat.
[0020]
Further, as a solid substance of the present invention, magnesium halide treated with an electron donor such as ester, ketone, carboxylic acid, ether, amine and phosphine, or magnesium halide pretreated with alcohol, and then an organoaluminum compound Or what was made to react with silicon tetrachloride etc. is also employable.
[0021]
The particle size of the solid substance is adjusted by a pulverization method as described below. If necessary, the particle size is adjusted by a classification method as described below.
In the present invention, the average particle size of the solid substance needs to be 10 μm or less, preferably 6 μm or less, and the maximum particle size needs to be 15 μm or less. When the average particle size exceeds 10 μm, the resulting catalyst is not sufficiently active, and when the maximum particle size exceeds 15 μm, the appearance of films and sheets made of an ethylene polymer produced using this solid material as a solid catalyst component deteriorates. (Fresh fish eyes). This particle size was measured with a particle size distribution analyzer CIS-1 manufactured by GALAI using a laser scan analysis method.
[0022]
The pulverization method is not particularly limited, but using a normal ball mill, pearl mill, disper mill or the like, a dry method performed in an inert gas atmosphere such as nitrogen or argon, saturated hydrocarbons (for example, n-hexane, etc.) The wet method performed in an inert organic solvent can be employed. Moreover, there is no restriction | limiting in the apparatus which performs this grinding | pulverization, Both a batch type and a continuous type may be sufficient. The pulverization conditions may be appropriately selected according to the respective pulverization methods, such as the pulverization time, so that the above particle diameter is obtained.
[0023]
The classification method is not particularly limited, but a normal method such as using a sieve or a cyclone and a dry method performed under an inert gas atmosphere such as nitrogen or argon, or a saturated hydrocarbon or the like (for example, n-hexane or the like) A wet method performed in an active organic solvent can be employed. Moreover, there is no restriction | limiting in the apparatus which performs this grinding | pulverization, Both a batch type and a continuous type may be sufficient.
Among the above solid substances, (1) reaction products of metal magnesium and alcohol or (2) reaction products of metal magnesium, alcohol, halogen and / or halogen-containing compounds are used as solid catalyst components. (2) is more preferable from the viewpoint of the catalytic activity of the film and the appearance of the resulting film or sheet made of an ethylene polymer.
The solid substance obtained as described above can be washed and dried as necessary to obtain a product.
[0024]
In the present invention, the solid catalyst component is obtained by contacting at least a titanium compound with the solid substance.
As the titanium compound of the solid catalyst component, the general formula (I)
TiX¹ _n(OR¹)_4-n... (I)
(Where X¹Is preferably a halogen atom, particularly a chlorine atom, R¹Is a hydrocarbon group having 1 to 10 carbon atoms, particularly a linear or branched alkyl group, and R¹When a plurality of are present, they may be the same as or different from each other. n is an integer of 0-4. ) Can be used. Specifically, Ti (O-i-C_ThreeH₇)_Four, Ti (O-C_FourH₉)_FourTiCl (O-C₂H_Five)_ThreeTiCl (O-i-C_ThreeH₇)_ThreeTiCl (O-C_FourH₉)_ThreeTiCl₂(OC_FourH₉)₂TiCl₂(Oi-C_ThreeH₇)₂TiCl_FourEtc.
[0025]
In addition, the solid catalyst component of the present invention may be obtained by contacting the above-mentioned solid substance with a halogen-containing silicon compound, an alcohol, and a titanium compound.
The titanium compound as the solid catalyst component is the same as in the general formula (I).
Further, the halogen-containing silicon compound of the solid catalyst component may be represented by the general formula (II)
X² _nSi (OR²)_4-n... (II)
(Where X²Is preferably a halogen atom, particularly a chlorine atom or bromine, and R²Is an alkyl group having 1 to 8 carbon atoms, preferably a methyl group, an ethyl group or a propyl group. n is an integer of 1-4. ) Can be used. Specifically, SiCl_Four, SiBr_Four, SiCl_Three(OCH_Three), SiCl₂(OC₂H_Five)₂These can be used alone or as a mixture.
[0026]
In addition, as the alcohol of the solid catalyst component, a linear or branched aliphatic or alicyclic alcohol can be used. Preferably, it is a C1-C8 primary or secondary alcohol. Specific examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, octanol, and cyclopentanol.
[0027]
These solid catalyst components are prepared as follows.
First, when the solid catalyst component is obtained by using the solid substance and at least a titanium compound, the solid substance is dispersed in an inert solvent. The inert solvent is not particularly limited as long as it is inert with the solid substance and the solid catalyst component, and various solvents such as aliphatic hydrocarbons and alicyclic hydrocarbons can be used. Specifically, butane, pentane, hexane, heptane, cyclohexane and the like are preferable. The amount of the solid substance added is not particularly limited, but is preferably 50 to 500 g per liter of the solvent for the convenience of operation.
[0028]
Next, the titanium compound as the solid catalyst component is added to the dispersion, and the reaction is carried out with stirring at a temperature of 0 to 200 ° C., preferably 50 to 150 ° C. under normal pressure or pressure. The addition amount of the titanium compound is at least equimolar, preferably excessive, with respect to the solid substance (number of moles of magnesium). Specifically, it is 1 to 20 times mol or more, preferably 1.5 to 10 times mol. Although depending on the reaction temperature, the reaction time is usually 5 minutes to 10 hours, preferably 30 minutes to 8 hours. In the case of solventless reaction, mechanical mixing with a ball mill or the like may be performed at the above temperature and time.
[0029]
In the case where the solid catalyst component of the present invention is obtained by contacting the solid substance with a halogen-containing silicon compound, alcohol, and titanium compound, the solid substance is dispersed in an inert solvent. This inert solvent is the same as described above. Next, the halogen-containing silicon compound and alcohol as the solid catalyst component are reacted with the dispersion at a predetermined temperature and time to modify the solid substance. The amount of the halogen-containing silicon compound added is such that the halogen / magnesium (atomic ratio) is 1 or less with respect to the solid substance. Preferably, this ratio is in the range of 0.2 to 1, more preferably 0.5 to 1. If this ratio exceeds 1, the amount of fine polyethylene particles (105 μm or less) produced is undesirably high. Moreover, the addition amount of alcohol shall be 0.1 times the number of moles with respect to a solid substance (mole number of magnesium). The upper limit of this addition amount is not particularly limited, but since a large amount of use is a waste of the titanium compound, it is usually based on an equivalent mole of halogen contained in silicon. When the amount of alcohol used is less than this lower limit, it is not possible to expect sufficient improvement in polymerization activity or improvement in the bulk density of the polymer. This reaction temperature is usually 0 to 150 ° C, preferably 20 to 100 ° C. The reaction time depends on the reaction temperature, but is usually 5 minutes to 5 hours, preferably 30 minutes to 3 hours. In addition, the contact order of the three types of solid catalyst components in the above reaction is not particularly limited to this. First, the solid substance is reacted with the halogen-containing silicon compound, and then the alcohol is added to the reaction system. It may be performed in two stages. As described above, the reaction using a solvent is a preferred embodiment of the present invention, but it can also be carried out in the absence of a solvent. In this case, for example, a solid product, a halogen-containing silicon compound, and an alcohol may be directly mechanically mixed by a ball mill or the like at a predetermined ratio.
[0030]
After modifying the solid substance, a titanium compound is further added, and the reaction is carried out with stirring under a temperature condition of 0 to 200 ° C., preferably 50 to 150 ° C. under normal pressure or pressure. The addition amount of the titanium compound is at least equimolar, preferably excessive, with respect to the solid substance (number of moles of magnesium). Specifically, it is 1 to 20 times mol or more, preferably 1.5 to 10 times mol. Although depending on the reaction temperature, the reaction time is usually 5 minutes to 10 hours, preferably 30 minutes to 5 hours. In the case of solventless reaction, mechanical mixing with a ball mill or the like may be performed at the above temperature and time. After performing the above reaction, the solid catalyst component is separated and washed from the reaction product. The washing at this time is performed using an inert hydrocarbon solvent having 5 to 10 carbon atoms, such as pentane, hexane, cyclohexane, heptane and the like. The washed solid catalyst component may be used as it is, or may be used as a catalyst component dispersed at an appropriate concentration in an inert hydrocarbon solvent in an inert gas.
[0031]
What is obtained by reacting metal magnesium and alcohol, which are suitable as solid substances, or metal halide, alcohol, and a halogen-containing compound containing halogen in an amount of 0.0001 gram atom or more per mole of metal magnesium. In such a case, a combination of contacting these with a halogen-containing silicon compound, an alcohol, and a titanium compound is preferable.
In the production of the ethylene polymer of the present invention, a catalyst system comprising the above solid catalyst component and an organoaluminum compound can be suitably used.
[0032]
As this organoaluminum compound, the general formula (III)
AlR^Three _nX^Three _3-n... (III)
(Wherein R^ThreeIs an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group, and X^ThreeIs a halogen atom, preferably a chlorine atom or a bromine atom. n is an integer of 1 to 3. ) Are widely used. Specific examples include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, diethylaluminum monoethoxide, ethylaluminum sesquichloride and the like. These may be used alone or in combination of two or more.
[0033]
Specifically, the dispersion of the solid catalyst component and the organoaluminum compound are added as a catalyst to the polymerization reaction system, and then ethylene or α-olefin is introduced.
The α-olefin used for copolymerization with ethylene is selected from linear or branched α-olefins having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. Specifically, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, 4-methylpentene-1, and mixtures thereof It is. The amount of α-olefin introduced is usually in the range of 0.2 to 5% by weight of ethylene.
[0034]
The polymerization method and its conditions are not particularly limited, and any of solution polymerization, suspension polymerization, and gas phase polymerization can be applied, and either continuous polymerization or discontinuous polymerization is possible.
Taking solution polymerization or suspension polymerization as an example, the catalyst component is added in an amount of 0.0005 to 10 mmol / liter, preferably 0.001 to 1 mmol / liter, as titanium atoms of the solid catalyst component. The compound is used so that the Al / Ti atomic ratio is 5 to 1000, preferably 15 to 200. The ethylene pressure in the reaction system is usually normal pressure to 100 kg / cm.², Preferably 5-50 kg / cm²The reaction temperature is usually 20 to 200 ° C., preferably 50 to 150 ° C., and the reaction time is usually 5 minutes to 10 hours, preferably 30 minutes to 5 hours. The molecular weight can be adjusted during the polymerization to some extent depending on the polymerization conditions such as polymerization temperature, catalyst concentration, and catalyst molar ratio, but it is more effective to carry out in the presence of hydrogen.
[0035]
【Example】
Next, although an example and a comparative example show the present invention concretely, the present invention is not limited to the following example.
Incidentally, the ethylene / α-olefin copolymerization conditions in this example are set so that fisheye is easily generated in order to easily evaluate the effect of reducing fisheye in the solid material of the present invention. If an appropriate polymerization condition is selected, the absolute number thereof is reduced as a whole, but the superiority of the present invention is maintained.
[Example 1]
(1) Preparation of solid material
A glass reactor (with an internal volume of 0.5 liter) equipped with a stirrer was sufficiently replaced with nitrogen gas, and then 8 g of metal magnesium, 121 g of ethanol and 0.1 g of iodine were added, and the system was refluxed with stirring. The reaction was continued until generation of hydrogen gas ceased to obtain a solid product. The reaction solution containing this solid product was dried under reduced pressure to put 25 g of the solid product and 200 ml of hexane in a stainless steel ball mill (internal volume 400 ml, 100 stainless steel balls having a diameter of 1.2 cm) for 10 hours. Grinding was performed. After the hexane was distilled off under reduced pressure, the particle size of the obtained solid substance was measured by the above measuring method. As a result, the average particle size was 4.4 μm and the maximum particle size was 11.0 μm.
(2) Preparation of solid catalyst component
15 g of the solid material obtained above and 350 ml of dehydrated hexane were added to a glass three-necked flask (with an internal volume of 0.5 liter) sufficiently substituted with nitrogen gas, and 3.8 ml of silicon tetrachloride and ethanol 3 under stirring. .8 ml was added and reacted at 70 ° C. for 2 hours. Next, 20 ml of titanium tetrachloride was added and reacted at 70 ° C. for 6 hours, and then washed with hexane to obtain a solid catalyst component. The titanium content per gram of the solid catalyst component was measured by a colorimetric method and found to be 44 mg.
[0036]
(3) Copolymerization of ethylene and α-olefin
Polyethylene obtained by adding 2.7 liters of dehydrated hexane, 4.9 mmol of triethylaluminum, and 0.16 mmol of the solid catalyst component in terms of titanium atom to a SUS autoclave (internal volume 7 liters) sufficiently substituted with nitrogen gas Was measured such that the intrinsic viscosity [η] = 0.5 dl / g and ethylene was continuously supplied so that the total pressure of the reactor was 0.65 MPa, and the reaction was conducted while stirring at 80 ° C. for 60 minutes. Then, the temperature was lowered to 40 ° C.
The reactor was then depressurized and after adding 2.3 liters of dehydrated hexane, the additional polyethylene weighed to give MI = 0.05 g / 10 min, 25 g of butene-1 and Ethylene was continuously supplied so that the total pressure in the reactor was 0.30 MPa, and the reaction was carried out with stirring at 80 ° C. for 30 minutes.
After completion of the reaction, the obtained ethylene / butene-1 copolymer was dried and formed into a film by an inflation molding method (thickness = 6 μm, blow ratio = 1.5). Three 10 × 10 cm films were sampled from the film and evaluated by visually counting the total number of fish eyes.
Table 1 shows the particle size, titanium content, catalytic activity, and fish eye evaluation results of the solid substance.
A film having high catalytic activity and a low fish eye level was obtained.
[0037]
[Example 2]
(1) Preparation of solid material
A solid material was prepared in the same manner as in Example 1 (1) except that magnesium chloride was used instead of iodine in Example 1 (1). The obtained product had an average particle size of 5.5 μm and a maximum particle size of 12.6 μm.
(2) Preparation of solid catalyst component
Using the solid material obtained in (1), a solid catalyst component was obtained in the same manner as in Example 1 (2). The titanium content per gram of the solid catalyst component was measured by a colorimetric method and found to be 46 mg.
(3) Copolymerization of ethylene and α-olefin
Using the solid catalyst component obtained in (2), polymerization was carried out in the same manner as in Example 1 (3). The results are shown in Table 1.
A film having high catalytic activity and a low fish eye level was obtained.
[0038]
Example 3
(1) Preparation of solid material
A solid material was prepared in the same manner as in Example 1 (1) except that the ball milling time was 2 hours in Example 1 (1). What was obtained had an average particle size of 6.2 μm and a maximum particle size of 13.5 μm.
(2) Preparation of solid catalyst component
Using the solid material obtained in (1), a solid catalyst component was obtained in the same manner as in Example 1 (2). The titanium content per gram of the solid catalyst component was measured by a colorimetric method and found to be 43 mg.
(3) Copolymerization of ethylene and α-olefin
Using the solid catalyst component obtained in (2), polymerization was carried out in the same manner as in Example 1 (3). The results are shown in Table 1.
A film with a low fish eye level was obtained, although the catalytic activity was not very high.
[0039]
[Comparative Example 1]
(1) Preparation of solid material
A solid material was prepared in the same manner as in Example 1 (1) except that the ball milling time was 30 minutes in Example 1 (1). What was obtained had an average particle size of 22.0 μm and a maximum particle size of 33.5 μm.
(2) Preparation of solid catalyst component
Using the solid material obtained in (1), a solid catalyst component was obtained in the same manner as in Example 1 (2). The titanium content per gram of the solid catalyst component was measured by a colorimetric method and found to be 45 mg.
(3) Copolymerization of ethylene and α-olefin
Using the solid catalyst component obtained in (2), polymerization was carried out in the same manner as in Example 1 (3). The results are shown in Table 1.
Since the average particle size and the maximum particle size of the solid material were large, only a film with extremely large fish eyes could be obtained.
[0040]
[Comparative Example 2]
(1) Preparation of solid material
A solid material was prepared in the same manner as in Example 1 (1) except that the ball milling time was 1 hour in Example 1 (1). The obtained product had an average particle size of 5.6 μm and a maximum particle size of 15.4 μm.
(2) Preparation of solid catalyst component
Using the solid material obtained in (1), a solid catalyst component was obtained in the same manner as in Example 1 (2). The titanium content per gram of the solid catalyst component was measured by a colorimetric method and found to be 44 mg.
(3) Copolymerization of ethylene and α-olefin
Using the solid catalyst component obtained in (2), polymerization was carried out in the same manner as in Example 1 (3). The results are shown in Table 1.
Since the maximum particle size of the solid material was large, only a film with extremely large fish eyes could be obtained.
[0041]
[Table 1]

[0042]
【The invention's effect】
As shown above, by making the solid material that becomes the carrier of the catalyst for the ethylene polymer into a specific particle size, the generation of fish eyes on the film or sheet molded from the ethylene polymer is suppressed, and the appearance is improved. It can be improved. In addition, the activity of the polymerization catalyst can be improved.
[Brief description of the drawings]
FIG. 1 is a flowchart relating to a preparation process in which a titanium compound or the like is brought into contact with a solid substance in the present invention.

Claims (5)

A solid substance containing a magnesium compound used for the preparation of a solid catalyst component for an ethylene polymer, wherein magnesium chloride, magnesium fluoride, magnesium bromide, magnesium iodide, magnesium halide are treated with an electron donor, Pre-treated magnesium halide with alcohol, then reacted with organoaluminum compound or silicon tetrachloride, magnesium dialkoxide (excluding magnesium alkoxide dispersion (riogel)), and obtained by reacting magnesium metal with alcohol and metallic magnesium, at least one solid substance selected halogen-containing compound containing a halogen in an amount of more than 0.0001 g atom to alcohol and metallic magnesium 1 mole from those obtained by reacting, Solid material, wherein the average particle size of 10μm or less and a maximum particle size of 15μm or less. A solid substance obtained by reacting metal magnesium with alcohol, or obtained by reacting metal magnesium, alcohol, and a halogen-containing compound containing 0.0001 gram atom or more of halogen with respect to 1 mole of metal magnesium. The solid substance according to claim 1, wherein A solid catalyst component for an ethylene polymer obtained by bringing a titanium compound into contact with the solid substance according to claim 1. A solid catalyst component for an ethylene polymer obtained by bringing a halogen-containing silicon compound, an alcohol, and a titanium compound into contact with the solid substance according to claim 1. Ethylenic polymer production method of using a catalyst system comprising a solid catalyst component and an organoaluminum compound according to claim 3 or 4 to polymerize ethylene or ethylene and α- olefin.

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