JPH1143507A - Production of solid catalytic component for ethylene polymerization and production of ethylene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalytic component capable of developing high polymerization activity in an industrially sufficient economical scale, producing a polyethylene having a wide molecular weight distribution in high productivity, by halogenating a magnesium compound, etc., using a nonaromatic hydrocarbon solvent. SOLUTION: A solution of (A) a magnesium compound of the formula Mg(OR<1> )k X2-k (R<1> is an alkyl, etc.; X is a halogen; (k) is 0-2) such as diethoxy magnesium and (B) a polyalkyl titanate of the formula (R<2> is an alkyl, etc.; (1) is 2-20) such as tetramer of tetrabutoxy titanium as essential components in the presence or absence of (C) a titanium compound of the formula Ti(OR<3> )m X4-m (R<3> is an alkyl, etc.; (m) is 1-4) in a uniform or a partially uniform nonaromatic hydrocarbon solvent (including a halide) containing (D) an alcohol compound of the formula OR<4> OH (R<4> is an alkyl, etc.), is treated with a halogenating agent to give the objective catalytic component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a solid catalyst component for obtaining an ethylene polymer having novel characteristics, and a method for producing an ethylene polymer using the catalyst component. More specifically, a method for producing a solid catalyst component, which is suitable for hollow molding and inflation molding, is capable of producing polyethylene having excellent extrudability, high melt tension, and large bulk density with high productivity, and the solid catalyst. The present invention relates to a method for producing the ethylene polymer using the components.

[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.

[0003] In particular, in the case of molding a large container in blow molding, in order to prevent drawdown of a parison or to secure uniform stretchability when molding a product having a complicated shape, it is necessary to improve the resin molding process and physical properties. Therefore, 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 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, although the effect of improving the melt tension and the like is recognized in JP-A-52-24292, the effect of improving the melt tension and the like is not sufficient in a region having high productivity.
Further, the polymerization method of the publication has a disadvantage that fish eyes cannot be eliminated unless strong kneading conditions are selected.

[0004] For this reason, a prescription that overcomes the above problems is
It is proposed in Japanese Patent Application Laid-Open No. 5-230136. However, even in the proposal of this publication, there is still a need to improve the performance of the catalyst including the polymerization 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.

[0005] The inventors of the present invention have been studying the performance improvement of the catalyst, and in particular, have scaled up the production scale of the solid catalyst component from a flask scale up to that time to a closed pressure vessel such as a bench scale or a pilot scale. At that time, they faced a problem that the polymerization activity of the catalyst system using the obtained solid catalyst component was remarkably reduced, and worked diligently to solve these problems.

[0006]

An object of the present invention is to provide a solid catalyst capable of stably exhibiting a high polymerization activity when producing the solid catalyst component of the present invention on an industrially sufficient economic scale. A polyethylene having a wide molecular weight distribution, good extrudability, high melt tension, and a large bulk density using the solid catalyst component, and capable of eliminating fish eyes under ordinary kneading conditions. Is to provide a production method capable of producing a high productivity.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have clarified the cause of the decrease in activity due to scale-up, and reached the present invention. That is,
Unlike the production in a glass flask, the production of a scaled-up solid catalyst component is generally performed in a closed system using a pressure vessel, but in the production of the solid catalyst component of the present invention, an aromatic solvent is used as a solvent. When hydrocarbons are used, alkyl halides produced by the reaction between the solid catalyst component raw materials cause a Friedel-Crafts reaction with these aromatic hydrocarbons to generate hydrogen halides, which accumulate in a closed container. It has been found that it acts as a deactivator for the solid catalyst component.

In the study using a glass flask, a reflux condenser is usually installed to prevent the pressurization of the system, and the reaction is carried out by flowing nitrogen gas. The activity was reduced and there was no problem of activity reduction. On the other hand, in a closed system reaction using a pressure vessel, when an aromatic hydrocarbon is used for the production of a solid catalyst component, hydrogen halide generated by the above-described Friedel-Crafts reaction accumulates in the system and forms a catalyst. Had been deactivated. In order to solve these deactivation problems, as a recipe that can be easily conceived, a reflux condenser is installed in the same way as a flask scale, and an inert gas such as argon or nitrogen is blown into the system to remove hydrogen halide from the system. Forcible discharge may be considered. The present inventors have also conducted intensive studies on these ideas, but did not achieve good results.

The present inventors have conducted intensive studies to solve these problems, and based on the above findings, completed the present invention by making the reaction solvent non-aromatic. Was. That is, the present invention provides: (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

[0010]

Embedded image

A polyalkyl titanate compound represented by the formula (R ² : an alkyl group, an aryl group, a cycloalkyl group, which may be the same or different and 1 = 2 to 20) is 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) When a solid catalyst component is obtained by treating a solution of a hydrocarbon solvent (including a halide) containing an alcohol compound and leaving a homogeneous or partially heterogeneous portion with a halogenating agent, a non-aromatic solvent is used as the hydrocarbon solvent. An object of the present invention is to provide a method for producing a solid catalyst component for ethylene polymerization, which comprises using a hydrocarbon solvent (including a halide).

[0012]

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 halogen such as chlorine, bromine or iodine. For example, diethoxymagnesium,
Ethoxy magnesium chloride, diphenoxy magnesium, magnesium chloride and the like can be mentioned. 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.

[0013]

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.

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.

[0016]

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

[0017] (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.

[0019]

(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 hydrocarbon solvent used in the production of the solid catalyst component of the present invention is not particularly limited as long as it is not an aromatic hydrocarbon solvent that causes a Friedel-Crafts reaction, and includes a halogenated hydrocarbon solvent. Usually, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclohexane; halogenated aliphatic hydrocarbons such as dichloroethane, tetrachloroethane, butyl chloride and decalin; halogens An alicyclic hydrocarbon is used. Preferably, hexane,
Heptane, octane, cyclohexane and the like are used.
To these hydrocarbon solvents, add the above-mentioned magnesium compound, polyalkyl titanate compound, titanium compound in some cases, and alcohol compound as necessary, and leave a solution in the hydrocarbon solvent (in some cases, leave a part insoluble part). Is prepared). In preparing a solution in a hydrocarbon solvent, the order of catalytic addition of a magnesium compound, a polyalkyl titanate compound, and in some cases, a titanium compound and, if necessary, an alcohol is not particularly limited.
To obtain the above-mentioned hydrocarbon solution, usually 2
Within a temperature range of 0 to 170 ° C, more preferably 70 to 1 ° C.
It is preferable to heat in a temperature range of 50 ° C. If the temperature is lower than the above range, the dissolution 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 solvent used is added in a necessary amount so that the total molar amount of the magnesium compound (a), the polyalkyl titanate compound (b) and 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 is reduced, the molecular weight distribution is not broadened, the extrudability and the melt tension are insufficient, and the composition is unsuitable for large hollow molding and the like. Then, the uniform (in some cases, non-uniform) obtained as described above
By treating a hydrocarbon solution with a halogenating agent,
A solid catalyst component is obtained. The halogenating agent is not particularly limited as long as it has the action, but usually, III, IV, V,
Group VI element halides, hydrogen halides and the like, specifically, titanium tetrachloride, silicon tetrachloride, tin tetrachloride,
Chloride such as vanadium tetrachloride and the like, and chlorine-containing compounds such as hydrogen chloride and the like can be mentioned. Of these, 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 heat treatment temperature of these halogen-containing compounds is usually 20 to 200 ° C., preferably 90 to 115 ° C.
More preferably, it is carried out at 100 to 110 ° C. When the heat treatment temperature is lower than the above range, the solid catalyst component is insufficiently halogenated, and the obtained ethylene polymer cannot obtain a high melt tension. In addition, when the heat treatment temperature is above the above range, the detailed reaction mechanism is unknown, but even if a non-aromatic hydrocarbon solvent is used, a phenomenon of decreasing the activity of the solid catalyst component is observed, which is not practically appropriate. . The halogenation treatment may be performed once or may be repeated twice or more.

The solid catalyst component produced as above is separated and washed with a hydrocarbon solvent to obtain a solid catalyst component to be finally subjected to preliminary polymerization. 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

[0028]

[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, being subjected to the preliminary polymerization is desired. The pre-polymerization is usually carried out by contacting the solid catalyst component with the organoaluminum compound in a hydrocarbon solvent and, if necessary, in the presence of hydrogen.
-By feeding olefins.

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 amount of the solid catalyst component used is supplied at 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 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. Specifically, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum,
Trioctylaluminum, diethylaluminum monochloride, dimethylaluminum monochloride, ethylaluminum sesquichloride, methylaluminum sesquichloride, ethylaluminum dichloride, methylaluminum dichloride and the like can be mentioned.
Among them, diethyl aluminum monochloride which is a halogen-containing organic aluminum, dimethyl aluminum monochloride, ethyl aluminum sesquichloride,
Preferred are methylaluminum sesquichloride, ethylaluminum dichloride, methylaluminum dichloride and the like.

Further, the halogen-containing organoaluminum compound to be used is supplied in a range of 0.1 to 5 (mmol / g-solid catalyst component), preferably in a range of 0.5 to 4 (mmol / g-solid catalyst component). Is done. When the supply amount is less than the above range, the activation of the solid catalyst component becomes insufficient. On the other hand, if the supply amount is more than the above range, the melt tension of the resin to be produced decreases, which is not preferable.

The prepolymerization is carried out in a temperature range of usually from 0 to 110 ° C., preferably from 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,
More preferably, it is carried out in the range of 10 to 300 minutes. When the prepolymerization time is shorter than the above range, the contact time with the organoaluminum compound is short, and the activation of the solid catalyst component becomes insufficient. If the prepolymerization time is longer than the above range, the solid catalyst component may be overreduced, which is not practical. The α-olefin feed 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 carbon atoms.
~ 20, specifically ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1,
4-methylpentene-1, 3-methylbutene-1, styrene, etc., which 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 intervals of time. In order to adjust the molecular weight of the prepolymerized polymer, if necessary, the reaction is 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 needed to prevent the solid catalyst component from being charged. The prepolymerized solid catalyst component contains an unreacted 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. Further, 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 a halogen-containing product. 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 in the above range or more, the molecular weight distribution of the obtained polymer is narrow and the melt tension is reduced.When large-sized hollow molding is performed, the moldability such as uniform stretchability is deteriorated. . Further, in the use range described below, 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 a single-stage polymerization method but also a multi-stage polymerization method can be employed. According to the present invention, a polyethylene polymer having a wide molecular weight distribution, excellent extrudability of a resin, a high melt tension, a large bulk density and capable of eliminating fish eyes under ordinary kneading conditions is supplied with high productivity. be able to.

[0045]

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. Usually, 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) Judgment of fish eye Judgment of fish eye was made 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 After a ₂ L autoclave with induction stirring was sufficiently purged 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)

[0052]

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 (30 mg as a solid catalyst component) of the prepolymerized solid catalyst component obtained in (2), and an 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. Then, 25.78 mg (0.13 mmol) of triisobutylaluminum (TiBAL)
Simultaneously with the supply of l), ethylene is supplied from a liquid phase feed nozzle to maintain the ethylene partial pressure at 7.0 kgf / cm ² . 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 resulting polymer has a bulk density ρ _B of 0.
34. Using a 30 mmφ single screw extruder, the HLMI of the sample pelletized with a full flight screw was 6.48 g / 10 min, SS was 27.3, and MT was 12.1 g.
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) Preparation of solid catalyst component In the preparation of the solid catalyst component of Example 1, the same operation was performed except that the heat treatment temperature after the addition of the TiCl ₄ diluent was 100 ° C. Thus, 31.0 g of a solid catalyst component was obtained.

(2) Preliminary polymerization Except that the solid catalyst component obtained above was used, the same operation as in the prepolymerization of Example 1 was carried out.
0.0 g was obtained. The prepolymerization yield is 1. per solid catalyst component.
It was 0 g-polymer / g-solid catalyst component. (3) Polymerization In the polymerization of Example 1 using the above prepolymerized catalyst, the filling hydrogen pressure was 8.8 kgf / cm ² and the TiBAL was 21.
The same operation was performed except that the amount was 81 mg (0.11 mmol), and 216.3 g of a produced polymer was obtained. The polymerization activity K of the catalyst was 515. 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 6.31 g / 10 min, SS is 22.0, MT is 1
It was 1.4 g (12.0 g in M value). No fish eyes were observed by the hat method observation. Example 1
Although the activity was slightly decreased as compared with, a polymer having a high SS, a high M value and a high SS was obtained.

<Example 3> (1) Preparation of solid catalyst component In the preparation of the solid catalyst component of Example 1, the same operation was performed except that the heat treatment temperature after adding the TiCl ₄ diluent was 110 ° C. Thus, 46.0 g of a solid catalyst component was obtained.

(2) Prepolymerization Except for using the solid catalyst component obtained above, the same operation as in the prepolymerization of Example 1 was carried out.
0.0 g was obtained. The prepolymerization yield is 1. per solid catalyst component.
It was 0 g-polymer / g-solid catalyst component. (3) Polymerization In the polymerization of Example 1 using the above pre-polymerization catalyst, the filling hydrogen pressure was 12.0 kgf / cm ² , and the TiBAL was 2
The same operation was conducted except that the amount was changed to 8.75 mg (0.145 mmol), thereby obtaining 228.9 g of a produced polymer. The polymerization activity K of the catalyst was 545. The bulk density ρ _B of the resulting polymer was 0.32. Using a 30 mmφ single screw extruder, the HLMI of the sample pelletized with a full flight screw was 5.21 g / 10 min, SS was 24.5, M
T was 12.6 g (M value: 12.4 g). Also,
No fish eyes were observed by hat method observation. As in Example 1, while maintaining high activity, high SS and high M
A polymer having a high ρ _B value was obtained.

<Comparative Example 1> (1) Preparation of solid catalyst component 73.2 g of solid catalyst component was prepared in exactly the same manner as in Example 1 except that the hydrocarbon solvent used was changed to toluene. I got

(2) Preliminary polymerization Except that the solid catalyst component obtained above was used, the same operation as in the prepolymerization of Example 1 was carried out to prepare the prepolymerized solid catalyst component.
2.5 g were obtained. The prepolymerization yield was 0.1 per solid catalyst component.
It was 5 g-polymer / g-solid catalyst component. (3) Polymerization After sufficiently replacing the 5 L autoclave with induction stirring with the above pre-polymerized catalyst with nitrogen, 3 L of NHX, 135 mg of the pre-polymerized solid catalyst component (90 m as a solid catalyst component)
g) After charging 29.7 mg of the antistatic agent Stadis450, the gas phase was replaced several times with hydrogen, and then 25.0 kgf / cm ^{2 of} hydrogen was introduced at 90 ° C. Then, TiBA
At the same time as supplying 193.35 mg (0.975 mmol) of L, ethylene is supplied from a liquid phase part feed nozzle, and the ethylene partial pressure is maintained at 10.0 kgf / cm ² . 90
After continuously supplying ethylene at 2 ° C. for 2 hours, 63.0 g of a produced polymer was obtained. The polymerization activity K of the catalyst was 35. ASTM-D-1238 due to small sample volume
190 ° C with a melt indexer based on -57T, 2
The powder was melted to a strand under a load of 1.6 kg, and then cut to obtain pellets. The HLMI of the sample was 5.07 g / 10 min, SS was 27.5, and MT was 12.4.
g (M value: 12.0 g) and bulk density ρ _B were 0.26. No fish eyes were observed by the hat method observation. Compared with Example 1, although the SS and M values were at target levels, ρ _B was low and the polymerization activity was extremely low.

Reference Example 1 (1) Preparation of Solid Catalyst Component In the preparation of the solid catalyst component of Comparative Example 1, the container used was a 500 ml glass flask equipped with a reflux condenser, and the charged raw material ratio was reduced to １ ／. Except for dropping, the same operation was carried out to obtain 36.0 g of a solid catalyst component.

(2) Preliminary polymerization Except for using the solid catalyst component obtained above, the same operation as in the prepolymerization of Example 1 was carried out.
0.0 g was obtained. The prepolymerization yield is 1. per solid catalyst component.
It was 0 g-polymer / g-solid catalyst component. (3) Polymerization In the polymerization of Example 1 using the above prepolymerized catalyst, the filling hydrogen pressure was 9.1 kgf / cm ² , and the TiBAL was 53.
The same operation was performed except that the amount was changed to 53 mg (0.27 mmol) to obtain 218.8 g of a produced polymer. The polymerization activity K of the catalyst was 521. Using a 30mmφ single screw extruder,
H of sample pelletized with full flight screw
LMI was 5.31 g / 10 min, SS was 25.1, MT was 13.1 g (M value 12.9 g), and bulk density was 0.28. No fish eyes were observed by the hat method observation. Even when a toluene solvent was used, a polymer having high activity, high SS, and high M value was obtained as in Example 1 by using a glass flask with a reflux condenser.

[0065]

[Table 1]

[0066]

[Brief description of the drawings]

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

Claims (4)

[Claims] (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 A polyalkyl titanate compound represented by the following formula (R ² : an alkyl group, an aryl group, or a cycloalkyl group, which may be the same or different, l = 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) When a solid catalyst component is obtained by treating a solution of a hydrocarbon solvent (including a halide) containing an alcohol compound and leaving a homogeneous or partially heterogeneous portion with a halogenating agent, a non-aromatic solvent is used as the hydrocarbon solvent. A process for producing a solid catalyst component for ethylene polymerization, comprising using a hydrocarbon solvent (including a halide). 2. The temperature for treating with a halogenating agent is 9
The method for producing a solid catalyst component according to claim 1, wherein the temperature is in the range of 0 to 115 ° C. 3. A method for producing a solid catalyst component, wherein the reactor for producing the solid catalyst component is a closed system. 4. An α-alkyl having 2 to 20 carbon atoms using the solid catalyst component (I) according to claim 1 and an organoaluminum compound.
-Homopolymerizing ethylene or copolymerizing ethylene with another olefin using a catalyst obtained by combining (II) a prepolymerized solid catalyst component obtained by prepolymerizing an olefin and (III) an organoaluminum compound. A method for producing an ethylene polymer, comprising: