JPH1143513A - Production of ethylene-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyethylene having a wide molecular-weight distribution, excellent extrusion, high melt tension and high bulk density, by polymerizing ethylene using a specific catalyst component obtained by prepolymerization. SOLUTION: Ethylene is polymerized by using both (C) a prepolymerization solid catalytic component obtained by prepolymerizing a 2-20C α olefin in the presence of both (A) a solid catalytic component obtained by halogenating a partially or wholly homogeneous hydrocarbon solution containing a magnesium compound of formula I (R<1> is an alkyl, etc. ; X is a halogen; (k) is 0-2) and a polyalkyl titanate compound of formula II (R' is an alkyl, etc.; (1) is 2-20) as essential components and optionally an alcohol compound of the formula R<4> OH (R<4> is an alkyl, etc.), in the presence or absence of a titanium compound of formula III (R<3> is an alkyl, etc.; (m) is 1-4) and (B) a halogen-containing organoaluminum compound and (D) an organoaluminum compound to give the objective ethylene-based polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an ethylene polymer having novel characteristics. More specifically, extrudability suitable for hollow molding and inflation molding, etc.,
It is possible to produce polyethylene having high melt tension and large bulk density with high productivity.Ethylene is produced using a catalyst system consisting of a prepolymerized solid catalyst component and an organoaluminum compound, which has been prepolymerized using a halogen-containing organoaluminum compound. And a method for producing an ethylene-based polymer, characterized by homopolymerizing ethylene or copolymerizing ethylene with another olefin.

[0002]

2. Description of the Related Art Polyethylene is widely and generally used as a molding material, but the required characteristics vary depending on the application and the molding method. For example, polyethylene having a narrow molecular weight distribution and relatively low molecular weight is suitable for products manufactured by the injection molding method. On the other hand, for products manufactured by inflation molding or hollow molding, polyethylene having a wide molecular weight distribution and relatively high molecular weight is suitable.
Especially in the case of hollow molding, for example, when molding large containers, in order to prevent drawdown of the parison or to secure uniform stretchability when molding products with complicated shapes, from the viewpoint of resin molding and physical properties, It is necessary to select polyethylene having high resin extrudability and high melt tension.

However, when the molecular weight distribution is widened to improve the extrudability and the melt tension, the productivity in production usually decreases in many cases. For example, a method for producing an olefin polymer having a wide molecular weight distribution and a high melt tension has been proposed in Japanese Patent Application Laid-Open No. Sho 52-24292. However, in Japanese Patent Application Laid-Open No. 52-24292, although the effect of improving the melt tension and the like is recognized to some extent, the effect of improving the melt tension and the like is not sufficient in a region having high productivity in manufacturing. Further, the polymerization method of the publication has a disadvantage that fish eyes cannot be eliminated unless strong kneading conditions are selected. Therefore, Japanese Patent Application Laid-Open No. 5-230136 proposes a method which does not rely on the two-stage polymerization method in order to overcome the above problems. However, even in this publication, it is necessary to improve various performances of the catalyst including the activity of the solid catalyst component. Further, the polyethylene obtained by these conventional methods has a disadvantage that the bulk density is small and the powder properties are poor, so that the handleability is poor.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, to have a wide molecular weight distribution, excellent extrudability, high melt tension, large bulk density, and ordinary kneading. An object of the present invention is to provide a production method capable of producing a polyethylene capable of eliminating fish eyes under high conditions with high productivity.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a pre-polymerized solid catalyst component obtained by pre-polymerizing a solid catalyst component described below using a specific organoaluminum compound is used. By using, it has a wide molecular weight distribution, high extrudability, melt tension, bulk density,
The present inventors have found a formulation that can produce fisheye erasable polyethylene under ordinary kneading conditions with high productivity, and have completed the present invention. That is, the present invention relates to (I) (a) a magnesium compound represented by the general formula Mg (OR ¹ ) _k X _2-k (R ¹ : an alkyl group, an aryl group, a cycloalkyl group,
X: halogen, k = 0, 1, 2) (b) General formula

[0006]

Embedded image

A polyalkyl titanate compound represented by the formula (R ^2, which represents an alkyl group, an aryl group or a cycloalkyl group and may be the same or different, 1 = 2 to 20) as an essential component; (OR ³ ) a titanium compound represented by _m X _4-m (R ³ : an alkyl group, an aryl group, a cycloalkyl group,
X: In the presence or absence of halogen, m = 1, 2, 3, 4), if necessary, represented by the general formula (d) R ⁴ OH (R ⁴ : alkyl group, aryl group, cycloalkyl group) The solid catalyst component obtained by treating a hydrocarbon solution containing an alcohol compound and leaving a homogeneous or partially heterogeneous portion with a halogenating agent is converted to a solid catalyst component having 2 to 2 carbon atoms in the presence of (II) a halogen-containing organoaluminum compound. (III) a prepolymerized solid catalyst component obtained by prepolymerizing an α-olefin of No. 20;
(IV) A method for producing an ethylene polymer, characterized by homopolymerizing ethylene or copolymerizing ethylene with another olefin using a catalyst system comprising a combination of an organoaluminum compound.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The magnesium compound (a) used for producing the solid catalyst component (I) of the present invention has a general formula Mg
(OR ¹ ) _k X _2-k (R ¹ : alkyl group, aryl group,
A compound represented by a cycloalkyl group, X: halogen, k = 0, 1, 2) is used. Specifically, R ¹ is methyl, ethyl, propyl, butyl, pentyl, hexyl,
It is an alkyl, aryl, or cycloalkyl group having up to about 15 carbon atoms such as octyl, tolyl, xylyl, cyclohexyl and the like, and X is chlorine, bromine or iodine. Examples include diethoxymagnesium, ethoxymagnesium chloride, diphenoxymagnesium, magnesium chloride and the like. In the production of a normal solid catalyst component, the particle size is controlled in the halogenation step described later so that the particle size can be arbitrarily controlled according to the applicable process.In such a case, the raw material before the halogenation step is prepared in a hydrocarbon solvent. It is preferably in a homogeneous solution state. In such a case, dialkoxymagnesium, which is a compound in which k = 2, is preferable. On the other hand, the halogenation step can be performed in a non-uniform state by using a raw material magnesium compound having a controlled particle size. As the polyalkyl titanate compound (b), a compound represented by the following general formula is used.

[0009]

Embedded image

(Where R^Two Is alkyl, aryl or
Represents a cycloalkyl group, which may be the same or different.
1 is an integer of 1 to 20. ) R in the above formula^Two Is R¹ The ones exemplified in
It is. Specifically, OR^Two Is a butoxy group, and l is
Compounds which are 2, 4, 7, 10 ^Two But professional
Compounds which are oxy groups and 1 is 2, 4, 7, 10 respectively
And the like. Among them, l is 4, 7, and 10, respectively.
Compounds are preferred. Furthermore, tetraalkoxy titanium (described later)
A small amount of H_Two Obtained by reacting O
Condensates of tetraalkoxy titanium can also be used
You. OR^Two Also used are compounds in which some of them have been replaced with halogens
I can do it.

Further, in order to adjust the halogenation rate and the liquid viscosity in the later-described halogenation step, a titanium compound (c) represented by the following general formula is usually used as necessary.

[0012]

(C) General formula Ti (OR ³ ) _m X _4-m

[0013] (R ^3: an alkyl group, an aryl group, may be the same or different a cycloalkyl group, X: halogen, m = 1, 2, 3, 4) said R ¹ is as R ^3, X, Those exemplified for X can be similarly mentioned. Specifically, tetraethoxytitanium, tetrapropoxytitanium, tetra-n-
Triethoxymonochlorotitanium, tripropoxymonochlorotitanium, m = 3 compounds such as butoxytitanium,
Triethoxy-dichlorotitanium, dipropoxydichlorotitanium, di-n-butoxydichlorotitanium, etc. as compounds with m = 2, ethoxytrichlorotitanium, propoxytrichlorotitanium, n as compounds with m = 1, such as tri-n-butoxymonochlorotitanium -Butoxytrichlorotitanium and the like, but compounds with m = 4 and 3 are preferred. Among them, tetra-n-butoxytitanium with m = 4, tri-n-butoxymonochlorotitanium with m = 3 and the like are preferable.

If necessary, an alcohol compound (d) represented by the following general formula is used for adjusting the affinity between the above-mentioned magnesium compound, polyalkyl titanate compound, titanium compound and a hydrocarbon solvent.

[0015]

(D) R ⁴ OH (where R ⁴ represents an alkyl, aryl or cycloalkyl group)

As R ⁴ , those exemplified for R ¹ can be similarly mentioned. Specific examples include ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-octyl alcohol and the like.

The solid catalyst component used in the production of the polyethylene of the present invention uses the above-mentioned magnesium compound, polyalkyl titanate compound, optionally a titanium compound, and if necessary, an alcohol compound, and uses a solution in a hydrocarbon solvent (optionally). May leave some insoluble parts). As the hydrocarbon solvent used for this, hexane, heptane, aliphatic hydrocarbons such as octane,
Alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene are used. In particular, non-halogenated hydrocarbons are desirable. In preparing the solution in the hydrocarbon solvent, the order of catalytic addition of the magnesium compound, the polyalkyl titanate compound, the titanium compound in some cases, and the alcohol to be added as necessary is not particularly limited and can be appropriately selected. In order to obtain the above-mentioned hydrocarbon solution, it is preferable to heat the mixture in a temperature range of usually 20 to 170 ° C, more preferably 70 to 150 ° C, after adding and mixing the raw materials. If the temperature is lower than the above range, the solubility of the raw material may be extremely deteriorated, and the properties of the catalyst particles may be deteriorated. If the temperature is higher than the above range, the polyalkyl titanate compound (b) may be deteriorated, which is not preferable. The amount of the solvent used is the above magnesium compound (a), polyalkyl titanate compound (b),
The required amount is added so that the total molar amount of the titanium compound (c) satisfies the following range with respect to the solvent used.

0.01 (mol / L) ≦ {total molar amount of (a), (b) and (c)} (mol) / solvent amount (L) ≦ 4 (mol / L), preferably 0.01 (Mol / L) ≦ {total molar amount of (a), (b) and (c)} (mol) / solvent amount (L) ≦ 2 (mo
1 / L)

## EQU1 ## If the concentration is below the above range, the yield of the catalyst per used amount of the solvent is extremely low, which is not practical. Also,
If the concentration is higher than the above range, the liquid viscosity of the hydrocarbon solution increases, which may hinder handling. In some cases, any of a magnesium compound, a polyalkyl titanate compound, and a titanium compound may be added after the heating treatment.

In order to obtain the target performance, the charge ratio of each raw material is usually charged within the following molar ratio range. 0 ≦ titanium compound (c) / magnesium compound (a) ≦
5 0.25 ≦ polyalkyl titanate compound (b) / magnesium compound (a) ≦ 4, preferably 0 ≦ titanium compound (c) / magnesium compound (a) ≦
2 0.25 ≦ polyalkyl titanate compound (b) / magnesium compound (a) ≦ 2 More preferably, 0.25 ≦ titanium compound (c) / magnesium compound (a) ≦ 1 0.25 ≦ polyalkyl titanate compound ( b) / magnesium compound (a) ≦ 1.5

## EQU1 ## Outside the above range, the polymerization activity may be reduced, the molecular weight distribution may not be broadened, the extrudability and melt tension may be insufficient, and the molding may not be suitable for large-sized hollow molding.
Subsequently, the homogeneous hydrocarbon solution or suspension obtained as described above is treated with a halogenating agent to obtain a solid catalyst component. The halogenating agent is not particularly limited as long as it has the action, and usually includes halides of Group III, IV, V and VI elements, hydrogen halides, and the like. Specific examples include titanium tetrachloride and tetrachloride. Examples thereof include chlorides such as silicon, tin tetrachloride and vanadium tetrachloride, and chlorine-containing compounds such as hydrogen chloride. Among them, a single product or a mixture of two or more thereof may be used. Among them, titanium tetrachloride, silicon tetrachloride and the like are preferable.

The method of treating with these halogenating agents is not particularly limited, but the treatment is usually performed at a temperature in the range of 20 to 200 ° C, preferably 80 to 130 ° C. If the treatment is carried out at a temperature below the above, halogenation may be extremely insufficient, which is not preferable. If the treatment is carried out at a temperature higher than the above, the polyalkyl titanate (b) may deteriorate, which is not preferable. The halogenation treatment may be performed once or may be repeated twice or more.

The solid catalyst component produced as described above is separated and washed with a hydrocarbon solvent to obtain a solid catalyst component to be finally subjected to prepolymerization. Further, in the present invention, a small amount of an electron donating compound may be allowed to coexist at any stage before the solid catalyst component is generated, or after the solid catalyst component is generated, it is treated with a small amount of the electron donating compound. May be. Such electron donating compounds generally include phosphorus-containing compounds, oxygen-containing compounds, sulfur-containing compounds, nitrogen-containing compounds, and the like. Of these, an oxygen-containing compound is preferably used. As the oxygen-containing compound, for example, the following formula

[0024]

[Image Omitted] R ⁵ OR ⁶ , R ⁵ COR ⁶ , R ⁵ (COOR
⁶ ) _p

(Wherein, R ⁵ and R ⁶ each represent a hydrocarbon group which may be substituted with an alkoxy group, and may be mutually bonded to form a cyclic group; and p is an integer of 1 to 3. Is shown.)
In particular, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, aromatic carboxylic acid esters such as diheptyl phthalate, or a metal salt of an aromatic carboxylic acid, ethyl phenylacetate, benzoic acid Carboxylic esters such as methyl, ethyl benzoate, methyl toluate, methyl anisate, ethyl anisate, methyl ethoxybenzoate, ethyl cinnamate, and silicon-containing carboxylic esters such as benzoic acid-β-trimethoxysilylethyl And the like. The amount of the electron-donating compound is not particularly limited, but is usually 10 mol or less, preferably 0.1 mol, per 1 mol of the magnesium compound.
It is chosen to be between 01 and 1 mol.

The solid catalyst component prepared through the prepolymerization above steps is subjected to prepolymerization. The prepolymerization is usually carried out by bringing the solid catalyst component into contact with the amount of the halogen-containing organoaluminum compound in a hydrocarbon solvent and supplying an α-olefin having a molecular weight of 2 to 20 carbon atoms in the presence of hydrogen if necessary.

Specifically, butane as a hydrocarbon solvent,
Aliphatic hydrocarbons such as pentane, isopentane, hexane, heptane, and octane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene are used. The used solid catalyst component is supplied so as to have a concentration of 5 to 80 (g-solid catalyst component / L-hydrocarbon solvent) per the hydrocarbon solvent. If the concentration of the solid catalyst component is lower than the above range, the productivity is lowered and is not practical. On the other hand, if the solid catalyst component concentration is higher than the above range, handling such as transfer of the prepolymerized catalyst may be impaired, which is not preferable.

The halogen-containing organoaluminum compound has a general formula

Embedded image AlR ⁷ _q R ⁸ _r X _s

(Wherein R ⁷ and R ⁸ represent an alkyl, allyl or cycloalkyl group and may be the same or different. X
Represents a halogen atom. Also, 0 <s <3, q + r + s
= 3 is satisfied. )

The compound represented by the following formula is used. R ⁷ , R
⁸ is the same as exemplified for R ¹ . X is chlorine, bromine, iodine or the like. Specific examples include diethylaluminum monochloride, dimethylaluminum monochloride, ethylaluminum sesquichloride, methylaluminum sesquichloride, ethylaluminum dichloride, methylaluminum dichloride and the like. Further, the halogen-containing organoaluminum compound used is preferably 0.1 to 5 (mmol
/ G-solid catalyst component), more preferably from 0.5 to
4 (mmol / g-solid catalyst component). When these halogen-containing organoaluminum compounds are used, a polymer having a wide molecular weight distribution and a high melt tension can be obtained. When the supply amount is too small, the activation of the solid catalyst component becomes insufficient, and when the supply amount is too large, the melt tension of the produced polymer tends to decrease.

The prepolymerization temperature is usually in the range of 0 to 110 ° C., preferably 10 to 90 ° C. When the pre-polymerization temperature is lower than the above range, the pre-activation of the solid catalyst component is insufficient, and sufficient activity may not be exhibited during the main polymerization, which is not preferable. On the other hand, when the prepolymerization temperature is higher than the above range, the prepolymerized polymer dissolves and slurry-like solid catalyst particles cannot be obtained, which is not practical for handling.

The prepolymerization time is usually in the range of 1 to 600 minutes,
It is preferably carried out in the range of 10 to 300 minutes. When the prepolymerization time is less than the above range, the contact time with the halogen-containing organoaluminum compound is small and the activation of the solid catalyst component is insufficient, and when the prepolymerization time is longer than the above range, the solid catalyst component may be overreduced. Yes, it is not preferable because it may not be practically suitable. The supply of the α-olefin is performed within the above prepolymerization time. The supply method may be from the gas phase part or the liquid phase part of the hydrocarbon solvent. The α-olefin used has 2 to 20 carbon atoms, specifically, ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1, 4-methylpentene-1, 3-methylbutene-1, Such as styrene,
It may be used alone or in combination. Among them, ethylene, propylene, styrene and the like are preferred.

The α-olefin may be supplied continuously or intermittently at time intervals. Further, if necessary, in order to adjust the molecular weight of the prepolymerized polymer, the reaction may be carried out in a hydrocarbon solvent in the presence of hydrogen. The prepolymerization yield of the solid catalyst component is 0.05 to 100 (g-polymer / g-solid catalyst component). If the prepolymerization yield is less than the above range, the protection effect of the solid catalyst component by the prepolymerized polymer becomes insufficient, and the solid catalyst component may be crushed during the main polymerization and fine powder may be generated, which may cause a problem in the process. When the pre-polymerization yield is above the above range, the amount of solid catalyst component in the pre-polymerized solid catalyst component is reduced. Is not realistic.

In this prepolymerization, an antistatic agent can be supplied as necessary to prevent the solid catalyst component from being charged. The prepolymerized solid catalyst component contains an unreacted halogen-containing organoaluminum compound in the hydrocarbon solvent of the cleaning solution, and is usually washed with a hydrocarbon solvent. As the washing solvent, those listed as the solvent for the prepolymerization are used, and the same solvent as used at this time or a different solvent may be used. Also,
The pre-polymerized solid catalyst component after washing can be used either in a slurry state in a solvent or in a dry state after removing the solvent and drying.

The prepolymerized solid catalyst component obtained as described above is used for homopolymerization of ethylene and copolymerization with an α-olefin in the presence of an organoaluminum compound. The polymerization form is not particularly limited as long as a target product can be obtained, but a slurry polymerization method in which an ethylene monomer is dissolved in a hydrocarbon solvent to carry out polymerization is usually used.

Hereinafter, a specific description will be given. The organoaluminum compound used may or may not be halogen containing. Typical examples are trialkylaluminums such as triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum, and dialkylaluminum halides such as diethylaluminum chloride. And the like. Of these organoaluminums, trialkylaluminums are preferred,
Triethylaluminum, triisobutylaluminum and the like are preferred. Further, two or more kinds of organoaluminum compounds may be used in combination.

The amount of the organoaluminum compound used is in the range of 0.01 to 5 mmol / L, preferably 0.1 to 5 mmol / L, in the case of slurry polymerization and solution polymerization using a hydrocarbon solvent. 0
In the range of 2 to 0.4 mmol / L, more preferably 0.0
It is in the range of 2 to 0.3 mmol / L. When the use ratio of the organoaluminum compound is above the above range, the molecular weight distribution of the obtained polymer is narrow, the melt tension is lowered, and when large-sized hollow molding is performed, there is a problem in that the moldability such as uniform stretchability is poor. On the other hand, below the above range, sufficient polymerization activity cannot be obtained, which is not practical.

The α-olefin usually has 2 to 20 carbon atoms and includes propylene, butene-1, pentene-1, hexene-1, octene-1, 4-methylpentene-1, 3-methylbutene-1, and styrene. . Dienes can also be used. As described above, the polymerization reaction can be carried out by solution polymerization in addition to slurry polymerization performed in an inert hydrocarbon solvent. At this time, aliphatic hydrocarbons such as butane, pentane, isopentane, hexane, heptane and octane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene are used as the hydrocarbon solvent. . Furthermore, it can be carried out by gas phase polymerization in the absence of an inert hydrocarbon solvent.

The polymerization reaction is usually selected from a temperature range of 20 to 200 ° C. and a pressure range of 1 to 100 (kgf / cm ² ). In the present invention, a polymer having a desired molecular weight can be obtained by allowing hydrogen to be present in the polymerization reaction zone. Further, in the main polymerization, not only the one-stage polymerization method but also the polymerization
A multi-stage polymerization method involving more than two stages may be employed. According to the present invention, a polyethylene polymer having a wide molecular weight distribution and excellent extrudability of a resin, having a high melt tension and a large bulk density and capable of eliminating fish eyes under ordinary kneading conditions is supplied with higher productivity. it can.

[0040]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. In addition, various physical property values in the examples were determined by the following methods.

(1) Polymerization activity of catalyst KK = (polymer produced (g)) / (catalyst amount (g)) · (polymerization time (hr)) · (partial pressure of olefin (kgf / cm)
² ))

(2) Melt index The melt index is ASTM-D-1238-57T.
Measured at 190 ° C. under a load of 21.6 kg.
LMI was set (unit: g / 10 minutes).

(3) Outflow ratio Outflow ratio as a measure of molecular weight distribution (hereinafter referred to as SS)
Is a value indicating the dependence of melt viscosity on decay stress, and ASTM-D
21.6kg load and 5kg according to -1238-57T
Expressed by the outflow ratio under load. The larger the SS, the better (usually 23 or more). If the SS is insufficient, the molecular weight distribution is narrow and the extrudability during resin extrusion for large-sized hollow molding deteriorates.

(4) Melt Tension The melt tension (hereinafter, referred to as MT) was measured using a 30 mmφ single screw extruder, and a pelletized sample with a full flight screw was used under the following conditions using a melt tension tester manufactured by Toyo Seiki Co., Ltd. Was measured. The measurement condition is 1mmφ,
It was measured in units of (g) using a 5 mmL, 60 ° inflow nozzle at 190 ° C., an extrusion speed of 0.44 g / min, and a take-up speed of 0.94 m / min. Furthermore, the above 21.6
The melt index (HLMI) of kg load is 5.5
(G / 10 minutes), but the MT at this time
(Hereinafter, this is referred to as an M value) The conversion formula of M value = MT + 10 · Log (HLMI / 5.5) was used.

Generally, the M value is preferably 12 g or more.
If this is insufficient, the parison draws down during hollow molding, especially when molding a large container, or when a product having a complicated shape is molded, uniform stretchability deteriorates. In addition, if the physical properties of the product are insufficient, fire resistance deteriorates.

(5) Fish Eye Determination Fish eye was determined using a 30 mmφ single screw extruder.
The sample pelletized by the full flight screw was formed into a sheet by a pressure press, and the sheet was heated and vacuum formed into a hat shape to determine the presence or absence of fish eyes. (6) Bulk density The bulk density was measured based on JIS K6721.

Example 1 (1) Preparation of Solid Catalyst Component (Catalyst I) After sufficiently replacing the ₂ L autoclave with induction stirring with nitrogen, 7.44 g (65.0 mmol) of Mg (OEt) ₂ was added.
l), 11.06 g (32.5 mm) of Ti (OBu) ₄
ol), and tetramer-tetrabutoxytitanium represented by the following formula (hereinafter referred to as T-TBT)

[0048]

Embedded image

55.21 g (56.88 mmol) of
Further, 386 ml of sufficiently dehydrated NHX is charged. Thereafter, the mixture is treated at 105 ° C. for 3 hours with stirring to obtain uniform N
An HX solution was obtained. Next, after cooling the solution to room temperature, 50 ° C.
, (TiCl ₄ / NHX) = (50/50) volume% TiCl ₄ diluent is added in the following order.

1) Initial stage (0 to 1 hour after addition): 22.8 ml of diluent (11.4 ml as TiCl ₄ (19.
68g)) 2) Mid-term (1-2 hours after addition): 45.6 ml of diluent
(22.8 ml (39.35 g) as TiCl ₄ ) 3) Late (2 to 3 hours after addition): 387.3 m of diluent
1 (193.7 ml as TiCl ₄ (334.24
g)) Then, after performing a heat treatment at 105 ° C. for 5 hours, the resultant was washed several times with NHX at room temperature to obtain 40.0 g of a solid catalyst component.

(2) Preliminary polymerization After sufficiently replacing the 2 L autoclave with induction stirring with nitrogen, 1 L of NHX and 15 parts of the solid catalyst component obtained in (1) were added.
g, after charging 19.8 mg of the antistatic agent Stadis 425, 2 KG of hydrogen was introduced. After heating to 80 ° C, diethyl aluminum monochloride (DEAC)
Of 3.62 g (30.0 mmol; DEAC = 2 mmol)
1 / g-solid catalyst component) and simultaneously
g was continuously supplied from the liquid phase nozzle over 30 minutes. After the completion of the reaction, NHX washing was repeated several times at room temperature to obtain 30.0 g of a prepolymerized solid catalyst component. The prepolymerization yield was 1.0 g-polymer / g-solid catalyst component per solid catalyst component.

(3) Polymerization After sufficiently replacing the 2 L autoclave with induction stirring with nitrogen, 1 L of NHX, 60 mg of the prepolymerized solid catalyst component obtained in (2) (30 mg as a solid catalyst component), and antistatic agent Stadis 450 were added. After charging 9.9 mg, the gas phase was replaced with hydrogen several times, and 10.9 kgf of hydrogen was added at 90 ° C.
/ Cm ² be on the lookout. Thereafter, 25.78 mg (0.13 mmol) of triisobutylaluminum (TiBAL)
/ L) at the same time as feeding ethylene through the liquid phase feed nozzle to reduce the ethylene partial pressure to 7.0 kgf / cm ^2.
To keep. After continuously supplying ethylene at 90 ° C. for 2 hours, 30 ml of ethyl alcohol was added to deactivate the catalyst, unreacted ethylene was purged at room temperature, NHX was separated and dried, and 242.8 g of a produced polymer was obtained. . The polymerization activity K of the catalyst was 578. The bulk density ρ _B of the resulting polymer was 0.33. HLM of sample pelletized with full flight screw using 30mmφ single screw extruder
I is 6.48 g / 10 min, SS is 27.3, MT is 1
2.1 g (M value: 12.8 g). No fish eyes were observed by the hat method observation. A polymer having a high SS, a high M value and a high ρ _B was obtained while maintaining high activity.

Example 2 (1) Preliminary Polymerization In the prepolymerization of Example 1, the amount of DEAC used was set to 0.1.
91 g (7.5 mmol; DEAC = 0.5 mmol /
g-solid catalyst component) to obtain 30 g of a prepolymerized solid catalyst component. The prepolymerization yield was 1.0 g-polymer / g-solid catalyst component per solid catalyst component. (2) Polymerization In the polymerization of Example 1 using the above prepolymerized catalyst, the same operation was carried out except that the filling hydrogen pressure was 10.6 kgf / cm ² , to obtain 223.0 g of a produced polymer. The polymerization activity K of the catalyst was 531. Bulk density ρ of formed polymer
_B was 0.32. Using a 30mmφ single screw extruder,
H of sample pelletized with full flight screw
LMI was 7.21 g / 10 min, SS was 23.8, and MT was 11.8 g (M value: 13.0 g). No fish eyes were observed by the hat method observation. Example 1
Similarly, while maintaining high activity, high SS, high M value, high ρ
A polymer of _B was obtained.

<Example 3> (1) Preliminary polymerization In the prepolymerization of Example 1, the amount of DEAC used was changed to 7.
The same operation was conducted except that the amount was 23 g (60 mmol; DEAC = 4 mmol / g-solid catalyst component), thereby obtaining 30 g of a prepolymerized solid catalyst component. The prepolymerization yield was 1.0 g-polymer / g-solid catalyst component per solid catalyst component. (2) Polymerization In the polymerization of Example 1 using the above prepolymerized catalyst, the same operation was carried out except that the filling hydrogen pressure was 8.9 kgf / cm ^2, and 250.7 g of a produced polymer was obtained. The polymerization activity K of the catalyst was 597. The bulk density ρ _B of the resulting polymer was 0.34. HLM of sample pelletized with full flight screw using 30mmφ single screw extruder
I is 7.02 g / 10 min, SS is 29.1, MT is 1
1.3 g (M value: 12.4 g). No fish eyes were observed by the hat method observation. Example 1
Similarly, while maintaining high activity, high SS, high M value, high ρ
A polymer of _B was obtained.

Example 4 (1) Prepolymerization In the prepolymerization of Example 1, the organoaluminum compound was replaced with ethyl aluminum sesquichloride (Al (Et)).
_1.5 Cl _1.5; EASC abbreviated) of 3.71 g (30.
0 mmol; EASC = 2 mmol / g-solid catalyst component), and 30 g of a prepolymerized solid catalyst component was obtained. The prepolymerization yield was 1.0 g-polymer / g-solid catalyst component per solid catalyst component. (2) Polymerization In the polymerization of Example 1 using the above prepolymerized catalyst, the same operation was carried out except that the filling hydrogen pressure was 11.4 kgf / cm ^2, and 245.7 g of a produced polymer was obtained. The polymerization activity K of the catalyst was 585. Bulk density ρ of formed polymer
_B was 0.31. Using a 30mmφ single screw extruder,
H of sample pelletized with full flight screw
The LMI was 6.71 g / 10 min, the SS was 26.8, and the MT was 12.3 g (13.1 g in M value). No fish eyes were observed by the hat method observation. As in Example 1, a polymer having a high SS, a high M value and a high ρ _B was obtained while maintaining high activity.

Comparative Example 1 (1) Preliminary Polymerization In the preliminary polymerization of Example 1, 3.43 g (30.0 mmol; TEA = TEA) of triethylaluminum (TEA) was used.
The same operation was performed except that the amount was 2 mmol / g-solid catalyst component) to obtain 30 g of a prepolymerized solid catalyst component. The prepolymerization yield was 1.0 g-polymer / g- per solid catalyst component.
It was a solid catalyst component. (2) Polymerization In the polymerization of Example 1 using the above catalyst, 3.2 kgf / cm ^{2 of} hydrogen and 17.85 mg of TiBAL were used.
(0.09 mmol / L), 7.0 kg of ethylene partial pressure
The operation was carried out in exactly the same manner except that f / cm ² was obtained, to obtain 242 g of a produced polymer. The polymerization activity K of the catalyst was 576. The bulk density ρ _B of the resulting polymer was 0.26. 3
Using a 0 mmφ single screw extruder, the HLMI of the sample pelletized with a full flight screw was 5.20, SS was 15.5, and MT was 9.4 (M value 9.1). No fish eyes were observed by the hat method observation. Polymerization activity was as high as in Example 1, but low SS,
The polymer had a low M value and a low ρ _B.

Comparative Example 2 (1) Preliminary Polymerization In the preliminary polymerization of Example 1, 0.86 g (7.5 mmol; TEA = TEA) of triethylaluminum (TEA) was used.
The operation was performed in exactly the same manner except that 0.5 mmol / g-solid catalyst component) was obtained, to obtain 30 g of a prepolymerized solid catalyst component. The prepolymerization yield was 1.0 g-polymer / solid catalyst component.
g-solid catalyst component. (2) Polymerization In the polymerization of Example 1 using the above catalyst, 8.2 kgf / cm ^{2 of} hydrogen and 25.74 mg of TiBAL were used.
(0.13 mmol / L), 7.0 kg of ethylene partial pressure
The operation was carried out in exactly the same manner except that the flow rate was changed to f / cm ² , to obtain 214.2 g of a produced polymer. The polymerization activity K of the catalyst was 510. The bulk density ρ _B of the resulting polymer was 0.25.
The HLMI of the sample pelletized with a full flight screw using a 30 mmφ single screw extruder is 5.77, SS
Was 23.5 and MT was 9.1 (M value: 9.3).
No fish eyes were observed by the hat method observation. The polymerization activity and SS were as high as in Example 1, but the polymer was low M value and low ρ _B.

Comparative Example 3 (1) Preliminary Polymerization In the preliminary polymerization of Example 1, 6.84 g (60 mmol; triethylaluminum (TEA); TEA = 4.
The operation was performed in exactly the same manner except that the amount was 0 mmol / g-solid catalyst component) to obtain 30 g of a prepolymerized solid catalyst component. The prepolymerization yield was 1.0 g-polymer / g- per solid catalyst component.
It was a solid catalyst component. (2) Polymerization In the polymerization of Example 1 using the above catalyst, 2.4 kgf / cm ^{2 of} hydrogen and 17.85 mg of TiBAL were used.
(0.09 mmol / L), 7.0 kg of ethylene partial pressure
The same operation was conducted except that the flow rate was changed to f / cm ^2, and 252 g of a produced polymer was obtained. The polymerization activity K of the catalyst was 600. The bulk density ρ _B of the resulting polymer was 0.23. 3
The HLMI of the sample pelletized with a full flight screw using a 0 mmφ single screw extruder was 5.65, SS was 13.8, and MT was 8.8 (8.9 in M value). No fish eyes were observed by the hat method observation. Polymerization activity was as high as in Example 1, but low SS,
The polymer had a low M value and a low ρ _B.

Comparative Example 4 (1) Preliminary Polymerization In the preliminary polymerization of Example 1, 5.94 g (30.0 mmol; triisobutylaluminum (TiBAL)) was used.
The same operation was conducted except that TiBAL = 2 mmol / g-solid catalyst component), and 30 g of the prepolymerized solid catalyst component was used.
Obtained. The prepolymerization yield was 1.0 g-polymer / g-solid catalyst component per solid catalyst component. (2) Polymerization In the polymerization of Example 1 using the above catalyst, 3.3 kgf / cm ^{2 of} hydrogen and 17.85 mg of TiBAL were used.
(0.09 mmol / L), 7.0 kg of ethylene partial pressure
The operation was carried out in exactly the same manner except that the flow rate was changed to f / cm ² to obtain 245 g of a produced polymer. The polymerization activity K of the catalyst was 583.
The bulk density ρ _B of the resulting polymer was 0.26. 30m
Using an mφ single screw extruder, the HLMI of the sample pelletized with a full flight screw was 5.87, and SS was 1
At 5.3, the MT was 9.0 (9.3 in M value). Also,
No fish eyes were observed by hat method observation. Polymerization activity was as high as in Example 1, but low SS and low M
Value, low ρ _B polymer.

Example 5 (1) Preparation of Solid Catalyst Component (Catalyst II) In the preparation of the solid catalyst component of Example 1, Ti (OB
u) ₄ is removed from the raw materials, and Mg (OEt) ₂ and TT
BT is charged in the same amount. 30X more fully dehydrated NHX
Charge 5 ml. Thereafter, the mixture was treated at 105 ° C. for 3 hours with stirring to obtain a uniform NHX solution. Next, after cooling the solution to room temperature, at 50 ° C., (TiCl ₄ / NHX) = (5
0/50)% by volume of TiCl ₄ diluent is added in the following order:

1) Initial stage (0 to 1 hour after addition): 19.2 ml of diluent (9.6 ml (16.5 ml as TiCl ₄ ))
7g)) 2) Mid-term (1-2 hours after addition): 38.4 ml of diluent
(19.2 ml (33.14 g) as TiCl ₄ ) 3) Late stage (2 to 3 hours after addition): 326.4 m of diluent
1 (163.2 ml (281.68 as TiCl ₄ )
g)) Then, after performing a heat treatment at 105 ° C. for 5 hours, the resultant was washed several times with NHX at room temperature to obtain 40.0 g of a solid catalyst component.

(2) Prepolymerization The amount of DEAC to be used was 3.62 g (30 mmol; DEAC =
(2.0 mmol / g-solid catalyst component) to obtain 30 g of a prepolymer solid catalyst component. The prepolymerization yield was 1.0 g-polymer / g-solid catalyst component per solid catalyst component. (3) Polymerization In the polymerization of Example 1 using the above prepolymerized catalyst, the same operation was carried out except that the filling hydrogen pressure was 11.2 kgf / cm ² , to obtain 248.2 g of a produced polymer. The polymerization activity K of the catalyst was 591. Bulk density ρ of formed polymer
_B was 0.31. Using a 30mmφ single screw extruder,
H of sample pelletized with full flight screw
LMI was 7.23 g / 10 minutes, SS was 24.1, and MT was 11.2 g (M value: 12.4 g). No fish eyes were observed by the hat method observation. Example 1
Similarly, while maintaining high activity, high SS, high M value, high ρ
A polymer of _B was obtained.

Comparative Example 5 (1) Preliminary Polymerization In the preliminary polymerization of Example 5, 3.43 g (30.0 mmol; triethylaluminum (TEA); TEA =
The same operation was performed except that the amount was 2 mmol / g-solid catalyst component) to obtain 30 g of a prepolymerized solid catalyst component. The prepolymerization yield was 1.0 g-polymer / g- per solid catalyst component.
It was a solid catalyst component. (2) Polymerization In the polymerization of Example 1 using the catalyst described above, 3.5 kgf / cm ^{2 of} hydrogen and 17.85 mg of TiBAL were used.
(0.09 mmol / L), 7.0 kg of ethylene partial pressure
The same operation was carried out except that f / cm ² was used, to obtain 241.1 g of a produced polymer. The polymerization activity K of the catalyst was 574. The bulk density ρ _B of the resulting polymer was 0.26.
Using a 30 mmφ single screw extruder, the HLMI of the sample pelletized with a full flight screw was 5.21, SS
Was 17.1 and MT was 9.1 (8.9 in M value).
No fish eyes were observed by the hat method observation. Polymerization activity was as high as in Example 7, but low SS,
The polymer had a low M value and a low ρ _B.

Example 6 (1) Preparation of Solid Catalyst Component (Catalyst III) In the preparation of the solid catalyst component of Example 1, the M
g (OEt) ₂ was changed commercial anhydrous MgCl ₂ 6.1
9 g (65.0 mmol) were charged, and Ti (OBu) ₄
And T-TBT are charged in equal amounts. More fully dehydrated NH
Prepare 224 ml of X and call. Then, with stirring, 10
Treated at 5 ° C. for 3 hours, suspended N
An HX solution was obtained. Next, after cooling the solution to room temperature, at 50 ° C., (TiCl ₄ / NHX) = (50/50)% by volume of T
The iCl ₄ dilution was added in the following order.

1) Initial stage (0 to 1 hour after addition): 19.2 ml of diluent (9.6 ml (16.5 ml as TiCl ₄ ))
7g)) 2) Mid-term (1-2 hours after addition): 38.4 ml of diluent
(19.2 ml (33.14 g) as TiCl ₄ ) 3) Late stage (2 to 3 hours after addition): 326.4 m of diluent
1 (163.2 ml (281.68 as TiCl ₄ )
g)) Then, after performing a heat treatment at 105 ° C. for 5 hours, the resultant was washed several times with NHX at room temperature to obtain 40.0 g of a solid catalyst component.

(2) Prepolymerization The amount of DEAC to be used was 3.62 g (30 mmol; DEAC =
(2.0 mmol / g-solid catalyst component) to obtain 30 g of a prepolymerized solid catalyst component. The prepolymerization yield was 1.0 g-polymer / g-solid catalyst component per solid catalyst component. (3) Polymerization In the polymerization of Example 1 using the above prepolymerized catalyst, the same operation was carried out except that the filling hydrogen pressure was changed to 11.1 kgf / cm ² , thereby obtaining 218.8 g of a produced polymer. The polymerization activity K of the catalyst was 521. Bulk density ρ of formed polymer
_B was 0.31. Using a 30mmφ single screw extruder,
H of sample pelletized with full flight screw
LMI was 6.96 g / 10 min, SS was 23.0, and MT was 11.5 g (12.5 g in M value). No fish eyes were observed by the hat method observation. As in Example 1, a polymer having a high SS, a high M value and a high ρ _B was obtained while maintaining high activity.

Comparative Example 6 (1) Preliminary Polymerization In the preliminary polymerization of Example 6, 3.43 g (30.0 mmol; TEA =
The same operation was performed except that the amount was 2 mmol / g-solid catalyst component) to obtain 30 g of a prepolymerized solid catalyst component. The prepolymerization yield was 1.0 g-polymer / g- per solid catalyst component.
It was a solid catalyst component. (2) Polymerization In the polymerization of Example 1 using the above catalyst, 3.7 kgf / cm ^{2 of} hydrogen and 17.85 mg of TiBAL were used.
(0.09 mmol) and a partial pressure of ethylene of 7.0 kgf /
The same operation as in Example ² was carried out except that cm ² was used.
23.0 g were obtained. The polymerization activity K of the catalyst was 531. The bulk density ρ _B of the resulting polymer was 0.26. 3
The HLMI of the sample pelletized with a full flight screw using a 0 mmφ single screw extruder was 5.73, SS was 14.1, and MT was 8.5 (M value: 8.7). No fish eyes were observed by the hat method observation. Polymerization activity was as high as in Example 8, but low SS,
The polymer had a low M value and a low ρ _B.

<Comparative Example 7> The procedure of Example 1 was repeated, except that the prepolymerization was not carried out, to obtain 187 g of a produced polymer. The polymerization activity K of the catalyst was 445. The bulk density ρ _B of the resulting polymer was 0.23.
Using a 30 mmφ single screw extruder, the HLMI of the sample pelletized with a full flight screw was 13.3, SS
Was 18.6 and MT was 9.1 (M value: 12.8). No fish eyes were observed by the hat method observation. Polymerization activity is low, a low SS, was a polymer of low [rho _B.

Example 7 (1) Prepolymerization In the prepolymerization of Example 1, the amount of DEAC used was 1
2.7 g (105 mmol; DEAC = 7 mmol / g)
-Solid catalyst component), except that 30 g of a prepolymerized solid catalyst component was obtained. The prepolymerization yield was 1.01 g-polymer / g-solid catalyst component per solid catalyst component. (2) Polymerization In the polymerization of Example 1 using the above prepolymerized catalyst, the same operation was carried out except that the filling hydrogen pressure was 9.5 kgf / cm ^2, and 231 g of a produced polymer was obtained. The polymerization activity K of the catalyst was 551. The bulk density ρ _B of the resulting polymer was 0.34. HLM of sample pelletized with full flight screw using 30mmφ single screw extruder
I: 4.01 g / 10 min, SS: 29.1, MT: 1
0.9 (8.9 in M value). No fish eyes were observed by the hat method observation.

[0070]

[Table 1]

[0071]

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention.

Claims (2)

[Claims] (I) (a) The general formula Mg (OR ¹ ) _k X
A magnesium compound represented by _2-k (R ¹ : an alkyl group, an aryl group, a cycloalkyl group,
X: halogen, k = 0, 1, 2) (b) General formula A polyalkyl titanate compound represented by the formula (R ² : an alkyl group, an aryl group, or a cycloalkyl group, which may be the same or different and 1 = 2 to 20) is an essential component, and (c) a general formula Ti (OR ³ ) A titanium compound represented by _m X _4-m (R ³ : an alkyl group, an aryl group, a cycloalkyl group,
X: In the presence or absence of halogen, m = 1, 2, 3, 4), if necessary, represented by the general formula (d) R ⁴ OH (R ⁴ : alkyl group, aryl group, cycloalkyl group) The solid catalyst component obtained by treating a hydrocarbon solution containing an alcohol compound and leaving a homogeneous or partially heterogeneous portion with a halogenating agent is converted to a solid catalyst component having 2 to 2 carbon atoms in the presence of (II) a halogen-containing organoaluminum compound. (III) a prepolymerized solid catalyst component obtained by prepolymerizing an α-olefin of No. 20;
(IV) A method for producing an ethylene-based polymer, comprising homopolymerizing ethylene or copolymerizing ethylene with another olefin using a catalyst system obtained by combining an organoaluminum compound. 2. The method for producing an ethylene-based polymer according to claim 1, wherein the amount of the halogen-containing organoaluminum compound used in the prepolymerization is 0.1 to 5 (mmol / g-solid catalyst component).