JP2000044621A - Catalyst for polymerization of ethylene polymer and production of ethylene polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst exhibiting high activity at high temperature, affording ethylene polymers having narrow molecular weight distribution and compositional distribution, and a production method of ethylene polymers using this catalyst. SOLUTION: This manufacturing method for ethylene polymer utilizes the catalyst for polymerization of ethylene obtained by bringing (A) an organic aluminum compound into contact with (B) an organic magnesium compound soluble in hydrocarbon solvent, (C) a titanium compound soluble in hydrocarbon solvent, (D) a halogenated hydrocarbon and (E) an alcohol including a halogen, an ether including a halogen or methanol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing an ethylene-based polymer and a method for producing an ethylene-based polymer using the catalyst. More specifically, the present invention relates to an ethylene-based polymer such as a linear low-density polyethylene by high-temperature solution polymerization. The present invention relates to a catalyst for producing an ethylene polymer which is suitably used for the production of a coalescence, and a method for producing an ethylene polymer using the catalyst.

[0002]

2. Description of the Related Art Hitherto, as a method for producing a linear low-density polyethylene, a high-pressure ion method, a gas-phase polymerization method, a suspension polymerization method, and a high-temperature solution polymerization method are known. Among these methods, the high-temperature solution polymerization method is characterized in that a polymer having a narrow molecular weight distribution is obtained because the produced polymer is uniformly dissolved in a solvent, and a low-density product can be efficiently produced. Has features.

[0003] In the solution polymerization method, the produced polymer is dissolved in a solvent, and the liquid viscosity of the polymerization system becomes high.
For the operation of the apparatus, it is desirable to carry out the polymerization at as high a temperature as possible (155 ° C. or higher). However, all of the catalysts used in the conventional solution polymerization method have insufficient activity at high temperatures, and the physical properties of the obtained copolymer have not yet been satisfactory.

Some proposals have hitherto been made for the purpose of obtaining a catalyst having high activity at a high temperature. For example, Japanese Patent Publication No. 46-31968 and Japanese Patent Publication No. 50-391
No. 17 proposes a catalyst which can achieve a relatively high activity without preparing a catalyst in advance. However, none of them can express sufficiently high activity in any of these cases. Further, when the molecular weight distribution (Mw / Mn) of the produced polymer is wide and the produced polymer is a copolymer, However, there are disadvantages such as that the composition is also non-uniform, and the characteristics of the solution polymerization method tend to be destroyed.

Japanese Patent Laid-Open Publication No. Sho 60-42405 proposes using an alcohol as an activator in order to improve the activity. However, sufficient effects have not been obtained in terms of balance between activity, narrowing of molecular weight distribution and narrowing of composition distribution. Further, Japanese Unexamined Patent Publication No.
No. 10 employs a simple catalyst preparation method,
A method for narrowing the molecular weight distribution (Mw / Mn) and the composition distribution has been proposed. However, this method requires a long polymerization time because sufficient activity cannot be obtained in a short time (within 10 minutes). As a result, there is a problem that the molecular weight distribution and the composition distribution do not become sufficiently narrow.

[0006] In addition to the above problems, in recent years, there has been an increasing demand for higher performance of linear low-density polyethylene resins, and further improvement in activity, narrowing of molecular weight distribution, narrowing of composition distribution, and the like are desired. .

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above, and has a sufficiently high activity even at a high temperature, does not require a complicated preparation step, and shows a sufficiently high activity with a short residence time. In addition, it is an object of the present invention to provide a catalyst for producing an ethylene polymer which has a sufficiently narrow molecular weight distribution and composition distribution and does not require washing and removing catalyst residue components, and a method for producing an ethylene polymer using the catalyst. It is the purpose.

[0008]

Means for Solving the Problems The present inventors have made intensive studies and found that (A) an organoaluminum compound and (B)
Organic magnesium compounds soluble in hydrocarbon solvents, (C)
The activity is improved by a catalyst for producing an ethylene polymer obtained by contacting a titanium compound soluble in a hydrocarbon solvent, (D) a halogenated hydrocarbon and (E) a halogen-containing alcohol, a halogen-containing ether or methanol, The present invention was found to be very effective in narrowing the molecular weight distribution and the composition distribution, and completed the present invention.

That is, the present invention provides the following catalyst for producing an ethylene polymer and a method for producing an ethylene polymer using the catalyst. 1. (A) organoaluminum compound, (B) organomagnesium compound soluble in hydrocarbon solvent, (C) titanium compound soluble in hydrocarbon solvent, (D) halogenated hydrocarbon and (E) halogen-containing alcohol, halogen A catalyst for producing an ethylene-based polymer, which is brought into contact with a contained ether or methanol. 2. The catalyst for producing an ethylene-based polymer according to the above 1, wherein (A), (B) and (C) are represented by the following general formulas (I), (II) and (III), respectively. R ¹ _m AlX ¹³ _3-m (I) wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
Represents an aryl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and X ¹ represents a halogen atom. M is a real number satisfying 0 <m ≦ 3. When a plurality of R ¹ are present, each R ¹ may be the same or different. MgR ² R ³ ... (II) wherein R ² represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and R ³ represents 1 to 18 carbon atoms.
An alkyl group, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom. ] _{^{Ti (OR 4) n X 2}} 4-n ··· (III) wherein, R ⁴ is an alkyl group having 1 to 18 carbon atoms, 5 carbon atoms
X ² represents a cycloalkyl group or an aryl group having 6 to 18 carbon atoms, and X ² represents a halogen atom. N is 0
It is a real number satisfying ≦ n ≦ 4. ] 3. The catalyst for producing an ethylene-based polymer according to the above 1, wherein (A), (B) and (C) are represented by the following general formulas (IV), (V) and (VI), respectively. R ¹ _1.5 AlX ¹ _1.5 (IV) wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
Represents an aryl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and X ¹ represents a halogen atom. MgR ² R ³ ... (V) wherein R ² and R ³ represent an alkyl group having 1 to 18 carbon atoms. ] _{^{Ti (OR 4) n ··· (}} VI) wherein, R ⁴ is an alkyl group having 1 to 18 carbon atoms, 5 carbon atoms
Represents a cycloalkyl group having from 18 to 18 or an aryl group having from 6 to 18 carbon atoms. N is a real number satisfying 0 ≦ n ≦ 4. ] 4. 4. The catalyst for producing an ethylene-based polymer according to any one of the above items 1 to 3, wherein (E) is a fluorine-containing alcohol or a chlorine-containing ether. 5. 4. The catalyst for producing an ethylene-based polymer according to any one of the above items 1 to 3, wherein (E) is 2,2,2-trifluoroethanol, chloromethylmethyl ether or chloromethylethyl ether. 6. A method for producing an ethylene-based polymer, comprising using the catalyst for producing an ethylene-based polymer according to any one of the above 1 to 5 and copolymerizing ethylene and an α-olefin under a condition in which a produced polymer is dissolved in a reaction medium.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below. 1. Catalyst for Ethylene Polymer Production The catalyst of the present invention comprises (A) an organic aluminum compound, (B) an organic magnesium compound soluble in a hydrocarbon solvent, (C) a titanium compound soluble in a hydrocarbon solvent,
(D) halogenated hydrocarbon and (E) halogen-containing alcohol, halogen-containing ether or methanol.

As the component (A), the following general formula (I)
The organic aluminum compound represented by these is mentioned. R¹ _mAlX¹ _3-m... (I) [wherein, R¹Is an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
To 20 aryl groups and 1 to 20 carbon alkoxy groups.
Or an aryloxy group having 6 to 20 carbon atoms;¹Is
Indicates a halogen atom. Also, m is an actual value satisfying 0 <m ≦ 3.
Is a number. Note that R¹Is more than one each R¹Is the same
May be different. And an organoaluminum compound represented by the general formula (I)
For example, the general formula R¹ _ThreeAl, R¹ _TwoAlX¹, R¹ A
1X¹ _Two, R¹ _TwoAlOR^Five, R¹Al (OR^Five ) X ¹, (OR
^Five )_Three Al [where R^Five Is alkyl having 1 to 20 carbon atoms
A group or an aryl group having 6 to 20 carbon atoms. I want
Is R¹ _ThreeAl_Two X¹ _ThreeThe compound represented by these is mentioned.

More specifically, these compounds include triethylaluminum, tripropylaluminum, tributylaluminum, triamylaluminum, trioctylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, diisopropylaluminum monochloride. , Diisobutylaluminum monochloride, dioctylaluminum monochloride, ethylaluminum dichloride, isopropylaluminum dichloride, butylaluminum dichloride, octylaluminum dichloride, aluminum triethoxide, aluminum triisopropoxide, aluminum triisobutoxide, diethylaluminum monoethoxide, di Propyl aluminum monoethoxide, monoethyl Monoethoxy aluminum chloride, monoethyl-isopropoxy aluminum chloride, ethyl aluminum sesquichloride, propyl aluminum sesquichloride, butyl aluminum sesquichloride and the like. Among these organoaluminum compounds, such as diethyl aluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctyl aluminum monochloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum sesquichloride, etc. Preferably, In particular, R ¹ ₂ compounds represented by AlX ^1, for example, compounds represented by diethylaluminum monochloride and _{^{R 1 3 Al 2 X 1 3}} , for example, ethylaluminum sesquichloride preferred.

In the catalyst of the present invention, the component (B) includes a hydrocarbon-soluble organomagnesium compound represented by the following general formula (II). MgR ² R ³ ... (II) wherein R ² represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and R ³ represents 1 to 18 carbon atoms.
An alkyl group, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom. Specific examples of the hydrocarbon-soluble organomagnesium compound include diethylmagnesium, di-n-butylmagnesium, diisobutylmagnesium, n-butyloctylmagnesium, isobutyloctylmagnesium, diamylmagnesium, dihexylmagnesium, and the like.
Dioctyl magnesium, ethyl-n-butyl magnesium, ethyl isobutyl magnesium, dialkyl magnesium such as n-butyl isopropyl magnesium, diaryl magnesium such as diphenyl magnesium, alkyl aryl magnesium such as ethyl phenyl magnesium, alkyl such as n-butyl magnesium isopropoxide Examples include aryl magnesium alkoxides such as magnesium alkoxide and phenyl magnesium propoxide; alkyl magnesium halides such as butyl magnesium chloride and amyl magnesium chloride; and aryl magnesium halides such as phenyl magnesium chloride. Of these, dialkylmagnesium is preferred, and specifically, ethylbutylmagnesium, dibutylmagnesium, dihexylmagnesium, n-butyloctylmagnesium and the like are particularly preferred. Among them, ethyl-n-butylmagnesium is particularly preferred. These organomagnesium compounds may be used alone or as a mixture of two or more of the above. Magnesium compounds other than the above-mentioned organomagnesium compound,
For example, when magnesium chloride or the like is used, sufficient catalytic activity cannot be obtained.

The hydrocarbon solvent may have 5 to 5 carbon atoms.
18, aliphatic hydrocarbon compounds, alicyclic hydrocarbon compounds,
And aromatic hydrocarbon compounds. These hydrocarbon compounds may be used alone or as a mixture of two or more. Specifically, for example, n-pentane, i-
Pentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene, xylene and the like can be mentioned. In the present invention, the organomagnesium compound preferably dissolves in the hydrocarbon compound at normal temperature. Room temperature is 10-30 ° C
And dissolving means that a homogeneous solution is obtained. When an organic magnesium compound that does not dissolve in a hydrocarbon compound is used, sufficient activity may not be obtained.

The component (C) in the present invention includes a hydrocarbon-soluble titanium compound represented by the following general formula (III). _{^{Ti (OR 4) n X 2}} 4-n ··· (III) wherein, R ⁴ is an alkyl group having 1 to 18 carbon atoms, 6 carbon atoms
X ² represents a cycloalkyl group or an aryl group having 6 to 18 carbon atoms, and X ² represents a halogen atom. N is a real number satisfying 0 ≦ n ≦ 4. ] Here, the general formula (III) titanium compound represented by the above, when n is 0, the general formula TiX ² ₄ wherein, X ² are as defined above. ] It is a titanium tetrahalide represented by these. Specifically, for example, TiCl ₄ , T
iBr ₄ and TiI ₄ .

When n is 1, the general formula T
i (OR^Four) X^Two _Three[Wherein, R^Four And X ^Two Is the same as above
). Specifically,
If (CH_Three O) TiCl_Three, (C_Two H_FiveO) TiCl_Three,
(C_Three H₇ O) TiCl_Three, (N-C_Four H₉ O) TiCl
_Three Etc or X^Two A corresponding bird in which is bromine or iodine
Halogenated alkoxytitanium or trichlorocyclo
Cycloalkyl trihalides such as hexoxytitanium
Toxic titanium or trichlorophenoxytitanium
Rehalogenated aryloxy titanium.

When n is 2, the general formula Ti
(OR^Four)_Two X^Two _Two[Wherein, R^Four And X ^Two Is the same as above
). Specifically,
If (CH_Three O) TiCl_Two, (C_TwoH_FiveO) TiCl_Two,
(C_ThreeH₇O) TiCl_Two, (N-C_Four H₉ O) TiCl
_Two Etc or X^Two Is bromine or iodine
Dialkoxytitanium or dichlorodicyclo
Dihalogenated dicycloalkyloxy such as oxotitanium
Dihae such as titanium or dichlorodiphenoxytitanium
And diaryloxytitanium logen.

If n is 3, the general formula Ti
(OR^Four)_Three X^Two[Wherein, R^Four And X ^Two Is the same as above
). Specifically,
If (CH_Three O)_Three TiCl, (C_TwoH_FiveO)_Three TiC
l, (C_ThreeH₇O)_Three TiCl, (n-C_FourH₉O)_Three 
TiCl or X^Two Is bromine or iodine
Monohalogenated trialkoxy titanium or
Monohalogenated compounds such as lolotricyclohexoxytitanium
Licycloalkyloxytitanium or monochlorotri
Monohalogenated triaryloxy such as phenoxytitanium
And titanium.

When n is 4, the general formula Ti
(OR ⁴ ) ₄ wherein R ⁴ is the same as defined above. Specifically, for example, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-titanium
Examples thereof include tetraalkoxytitanium such as n-butoxytitanium and tetraisobutoxytitanium; tetracycloalkyloxytitanium such as tetracyclohexoxytitanium; and tetraaryloxytitanium such as tetraphenoxytitanium.

Of these, the general formula Ti (OR ⁴ )
Tetraalkoxytitanium and TiX ₄ represented by ₄
Are particularly preferable, and tetra-n-butoxytitanium and tetrachlorotitanium are particularly preferable. These various titanium compounds may be used alone or as a mixture of two or more of the above.

The hydrocarbon solvent is the same as the above-mentioned hydrocarbon compound. In the present invention, the titanium compound is preferably dissolved in the hydrocarbon compound at normal temperature. Normal temperature refers to 10 to 30 ° C., and dissolving refers to a uniform solution. When an organic titanium compound that does not dissolve in a hydrocarbon compound is used, sufficient activity may not be obtained in some cases.

The component (D) in the catalyst of the present invention is a halogenated hydrocarbon compound. Specific examples include an aliphatic halogenated hydrocarbon compound having 1 to 18 carbon atoms, an alicyclic hydrocarbon compound having 5 to 18 carbon atoms, or an aromatic halogenated hydrocarbon compound having 6 to 15 carbon atoms. . (D)
More specifically as a component, for example, dichloromethane;
Chloroform; carbon tetrachloride; dichloroethane; trichloroethane; tetrachloroethane; pentachloroethane; n
-Propyl chloride; isopropyl chloride; 1,3-dichloropropane; 1,2-dichloropropane; n-butyl chloride; isobutyl chloride; sec-butyl chloride; t-butyl chloride; 1,4-dichlorobutane; n-amyl chloride ;
Aliphatic chlorinated hydrocarbon compounds such as isoamyl chloride; 1,5-dichloropentane; n-hexyl chloride; 1,6-octyl chloride; n-decyl chloride, and corresponding brominated, iodinated or fluorinated hydrocarbons Compounds. Chlorobenzene, o-chlorotoluene, p
Aromatic chlorinated hydrocarbon compounds such as -chlorotoluene, p-chloroethylbenzene, o-dichlorobenzene, p-dichlorobenzene; 3,4-dichlorotoluene; benzyl chloride; p-chlorobenzyl chloride; benzotrichloride and the like. Corresponding brominated, iodinated or fluorinated hydrocarbon compounds are mentioned. Of these halogenated hydrocarbon compounds, 1,2-dichloroethane; 1,2-dichloropropane; isopropyl chloride and t-butyl chloride are preferred, and isopropyl chloride is particularly preferred.

The component (E) in the catalyst of the present invention is a halogen-containing alcohol, a halogen-containing ether or methanol. The halogen-containing alcohol is a compound in which one or two or more hydrogen atoms other than a hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule are substituted with a halogen atom. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms. Specifically, 2-chloroethanol, 1-chloro-
2-propanol, 3-chloro-1-propanol, 1
-Chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6
-Chloro-1-hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-
Chlorbenzhydrol, (m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro-
(M, p) -cresol, 6-chloro- (m, o) -cresol, 4-chloro-1-naphthol, (m, o,
p) -chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-chlororesorudin, 2-
Bromoethanol, 3-bromo-1-propanol, 1
-Bromo-2-propanol, 1-bromo-2-butanol, 1-bromo-2-naphthol, 2-bromo-p-cresol, 6-bromo-2-naphthol, (m, o,
p) -bromophenol, 4-bromoresorcinol,
(M, o, p) -fluorophenol, p-iodophenol, 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro- 1- (α-chloromethyl) -1-
Propanol, 2,3-dibromo-1-propanol,
1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4-dibromo-1-naphthol,
2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, β, β, β-trichloro-
tert-butanol, 2,3,4-trichlorophenol, 2,4,5-trichlorophenol, 2,4,6
-Trichlorophenol, 2,4,6-tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,2,2-trifluoroethanol, α, α,
α-trifluoro-m-cresol, 2,4,6-triiodophenol, 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2
2,3,3-tetrafluoro-1-propanol, 2,
3,5,6-tetrafluorophenol, tetrafluororesorcin and the like.

Of these, halogen-containing alcohols having a high electron-withdrawing property as a substituent are preferred.
For example, fluorine-containing alcohols and the like can be mentioned. Among the fluorine-containing alcohols, aliphatic alcohols are preferred.
Particularly, 2,2,2-trifluoroethanol is preferred.

A halogen-containing ether is a C.sub.1 group in which one or more hydrogen atoms have been replaced by halogen atoms.
—OC bond-containing compound. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms. Specifically, chloromethyl methyl ether, chloromethyl ethyl ether, bromomethyl methyl ether, 2,2-dichloroethyl methyl ether, 2-chloroethyl methyl ether, 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether, 2-chloroethyl ethyl ether, α, α-dichloromethyl methyl ether, 1-chloro-2,2,2-trifluoroethyl difluoromethyl ether, 2-chloro-1,1,2-trifluoroethyl difluoromethyl ether, Difluoromethyl-2,
2,2-trifluoroethyl ether, 2-chloro-
1,1,2-trifluoroethyl methyl ether, 2,
2-dichloro-1,1-difluoroethyl methyl ether, 2-bromo-1,1,2-trifluoroethyl ethyl ether, 2-chloro-1,1,2-trifluoroethyl ethyl ether, ethyl-1,1 , 2,2-tetrafluoroethyl ether, heptafluoropropyl-
1,2,2,2-tetrafluoroethyl ether, n-
Butyl-1,1,2,2-tetrafluoroethyl ether, 4-bromophenyltrifluoromethyl ether,
Tetrahydrofurfuryl chloride, 2-bromofuran,
3-bromofuran, perfluoro-2-butyltetrahydrofuran, bis (4-fluorophenyl) ether,
2-bromoethyl ether, 2-chloroethyl ether, 1,2-dichloroethyl ethyl ether, pentafluoroanisole, 2,3,5,6-pentafluoroanisole, 2,4,6-tribromoanisole, 2,
3,4-trichloroanisole, 2,4,6-trichloroanisole, 2,4,5-trifluoroanisole,
2-bromo-4-fluoroanisole, 4-bromo-2
-Fluoroanisole, 2,4-dibromoanisole,
α, 4-dichloroanisole, 2,3-dichloroanisole, 2,4-difluoroanisole, 2-bromoanisole, 2-chloroanisole, 2-fluoroanisole, 2-iodoanisole, benzyl-3-bromopropylether Can be

Among them, the one in which the halogen is chlorine is
Ter is preferred, and among chlorine-containing ethers, aliphatic ones are preferred. Particularly, chloromethyl methyl ether and chloromethyl ethyl ether are preferred. The catalyst of the present invention is obtained by bringing the above-mentioned catalyst components (A) to (E) into contact. When contacting, it is preferable to dissolve the above-mentioned catalyst components (A) to (E) in the above-mentioned hydrocarbon solvent.

As for the order of contact, (A) and (B) were mixed, and the resulting mixture (*) was added to (C),
(D) and (E) may be contacted in this order to form a catalyst. In this case, (*), (C),
The order of contact of (D) and (E) does not matter. That is,
The contact may be made in the order of (*), (C), (D), (E), the contact may be made in the order of (*), (D), (C), (E), Other contact orders may be used. Also,
Any of the components (*), (C), (D) and (E) may be preliminarily contact-mixed and then contacted with other components.

The order of contact between (E) and other components is not particularly limited, and (E) and (A), (B),
After contacting with at least one of the components (C) and (D), it can be used by contacting with the remaining other components. For example, after the mixture obtained by contacting (A) and (E) is brought into contact with (B) and then brought into contact with (C) and (D), the mixture may be used, and (*), (C) and (C) The mixture obtained by contacting D) may be used in contact with (E). Preferably, the mixture obtained by contacting (A) and (E) and (B) and (C) are brought into contact in this order, and then introduced into the reactor, and (D) is introduced into the reactor through another line. I do.

The method for preparing the catalyst of the present invention is not particularly limited as long as it follows the above-mentioned order of contact, and may be a method of preparing in a catalyst preparation tank or a method of preparing in a supply pipe (line) to a reactor. , In a reactor, or a combination of these methods. When the catalyst components are prepared in a catalyst preparation tank, the catalyst components (A) to (E) are prepared in accordance with the above-mentioned contact sequence.
Is contact mixed. In this case, according to the contact order described above,
Contact mixing may be performed in one catalyst preparation tank, or contact mixing may be performed in two or more catalyst preparation tanks.

When the catalyst components are prepared in the supply pipe (line) to the reactor, the catalyst components (A) to (E) are contact-mixed in accordance with the above-mentioned contact order. In this case, according to the contact order described above, contact mixing may be performed in one line,
Contact mixing may be performed in two or more lines. Preferably,
In this method, (C) is prepared so as to be in contact with (*) or the contact mixture of (*) and (D) on the same line. (C)
If is prepared in a line that is not the same as (*) or the contact mixture of (*) and (D), the activity may decrease.

When the catalyst components are prepared in a reactor, the catalyst components (A) to (E) are contact-mixed in accordance with the above-mentioned order of contact. In this case, the catalyst components (A) to (E) may be supplied to the reactor in one line, or may be supplied to the reactor in two or more lines, and each component may be supplied to the reactor in a separate line. May be supplied. Also, when preparing in a combination of the above preparation method,
It is only necessary that the catalyst components (A) to (E) and the contact mixture thereof be contact-mixed in accordance with the above-mentioned contact sequence. Preferably, (C) is (*) or (*) and (D)
Is a method of preparing so as to be in contact with the contact mixture on the same line. If (C) is prepared in a line that is not the same as (*) or the contact mixture of (*) and (D), the activity may be reduced.

Among these, a preferable preparation method is a preparation method in a supply pipe (line) to the reactor, and a preparation method combining the method and the preparation method in the reactor. Particularly preferred is a method of preparing in a supply pipe (line) to the reactor. In the line, ethylene or another α-olefin may or may not be present. Preferably, no ethylene or other α-olefin is present.

With respect to the mixing ratio of the catalyst components (A) to (E), (B) / (C) [atomic ratio of Mg / Ti] =
0.1-30 is preferable, and 0.5-20 are more preferable.
It is. Outside this range, catalyst activity tends to decrease. (A) / (C) [atomic ratio of Al / Ti]
= 1 to 120, more preferably 5 to 80. If this ratio is less than 1, the catalytic activity is low, and if it exceeds 120, the activity corresponding to the amount added is not sufficiently improved,
Physical properties of the obtained ethylene polymer (film formability)
Of the catalyst and increase of the catalyst residue in some cases. Also,
(E) / (C) [atomic ratio of halogenated alcohol or halogenated ether or methanol / Ti] = 0.1 to 2
00 is preferable, and more preferably 0.2 to 100. Particularly preferably, it is 0.5 to 50. This ratio is 0.
If it is less than 1, the effect of addition (narrowing of the molecular weight distribution and narrowing of the composition distribution) is not sufficient, and if it exceeds 200, the activity may decrease. Further, (D) / (A) [atomic ratio of halogenated hydrocarbon / Al] is preferably 0.001 to 5.0, more preferably 0.01 to 2.0. If this ratio is less than 0.001, the effect of addition (narrowing of molecular weight distribution and narrowing of composition distribution) is not sufficient, and if it exceeds 5.0, the activity may decrease.

When the above-mentioned catalyst components (A) to (E) are brought into contact, the temperature is preferably in the range of 0 to 100 ° C, more preferably 10 to 50 ° C. The contact time is preferably within 60 minutes, more preferably within 30 minutes. Particularly preferably, it is within 10 minutes. In addition, the concentration is preferably 0.005 to 10 mmol / 1L, and more preferably 0.01 to 1mmol / 1L, per 1L of the solvent and per Ti atom. The other components may be in accordance with the above mixing ratio.

2. Method for Producing Ethylene Polymer The method for producing an ethylene polymer of the present invention is produced by copolymerizing ethylene and α-olefin using the above-mentioned catalyst. The polymerization reaction is performed in a solvent, and is performed under heating conditions under which the produced polymer is dissolved in the solvent. Further, the polymerization reaction may be carried out continuously or batchwise.

The α-olefin to be copolymerized with ethylene includes a linear or branched monoolefin having 3 to 18 carbon atoms, a monoolefin substituted with an aromatic nucleus, or a polyunsaturated compound (conjugated diene, non-conjugated diene). ) And the like. Specifically, as the monoolefin, propylene, 1-butene, 1-hexene, 1-octene, 1-
Linear monoolefins such as nonene, 1-decene, 1-undecene and 1-dodecene, and 3-methyl-1-butene;
Substitution with a branched monoolefin such as 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene or an aromatic nucleus such as styrene Monoolefins. Specific examples of the polyunsaturated compound include butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 1,7.
-Octadiene, 1,9-decadiene and the like.

Examples of the solvent include an aliphatic hydrocarbon compound having 5 to 18 carbon atoms, an alicyclic hydrocarbon compound having 5 to 18 carbon atoms, and an aromatic hydrocarbon compound having 6 to 20 carbon atoms. Specific examples include n-pentane, i-pentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene, xylene and the like. These hydrocarbon compounds may be used alone or as a mixture of two or more. Preferred are aliphatic hydrocarbon compounds having 5 to 18 carbon atoms, and among them, hexane is preferred.

The polymerization temperature is a temperature at which the produced polymer dissolves in the solvent, usually 140 ° C. or higher, preferably 160 to 220 ° C.
Perform at ° C. Particularly preferably, it is 170 to 190 ° C.
The catalyst concentration is usually 0.001 to 10 mmol in titanium concentration
/ L, preferably 0.005 to 5.0 mmol / L. Particularly preferably, 0.01 to 1.0 mmol / L
It is.

The polymerization pressure is usually 1 to 15 MPa, preferably 2 to 12 MPa. Particularly preferably, 3 to 10
MPa. Further, a molecular weight regulator such as hydrogen may be present in the polymerization reaction system. The polymerization time is usually 1 to 60
Minutes, preferably 2 to 30 minutes, particularly preferably 5 to 20 minutes.

[0040]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Methods for measuring various physical properties measured in Examples and Comparative Examples are as follows. (1) It was measured under the following measurement conditions in accordance with MI JIS K-7210. Measurement conditions: load = 2160 g, temperature = 190 ° C. (2) Density Measured according to JIS K-7112 D method. (3) Molecular weight distribution (Mw / Mn) As a scale representing the molecular weight distribution of the copolymer, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC),
Mw / Mn was determined. (4) Composition distribution of copolymer (fraction k) As a scale representing the composition distribution of the copolymer, a melting curve obtained by using a differential scanning calorimeter (DSC) is 35.
110-130 ° C for the total amount of melting at -130 ° C
The fraction k of the amount of melting in was determined. If the total melting amount is the same, a smaller fraction k indicates that the composition distribution is narrower. (5) Molding of cast film The obtained copolymer was kneaded and granulated by a single screw extruder having a diameter of 20 mmφ. Next, a cast film was formed with an extruder having a diameter of 20 mmφ under the following conditions. Screw: Full flight type L / D = 20, air gap 1cm, rotation speed 60rpm, dice: coat hanger type 170m in width
m, lip width 0.8 mm Resin temperature: 210 ° C., discharge 2 kg / hr, take-off speed 6 m / min. Film thickness: 40 μm (6) Film impact The film impact conforms to ASTM-D3420,
It was measured with a film impact tester manufactured by Toyo Seiki Seisaku-sho, Ltd. The diameter of the impact head was set to 1/2 inch.

Example 1 After thoroughly replacing the inside of a dry polymerization reactor with an internal volume of 1 L with a stirrer with argon, 430 mL of dry n-hexane, 70 mL of 1-octene,
Hydrogen was charged at a gauge pressure of 0.02 MPa and the temperature was raised to 171 ° C. Ethyl aluminum sesquichloride 0.28m
mol (in terms of the molar amount of Al), 0.084 mmol of 2,2,2-trifluoroethanol, and 0.07 mmol of n-butylethylmagnesium were charged into the catalyst preparation device in this order, mixed, and then prepared in advance. A mixed solution of 0.015 mmol of tetrabutoxytitanium and 0.1155 mmol of isopropyl chloride was added, and then introduced into the above-mentioned polymerization reactor at the same time as ethylene gas, and polymerization was carried out at 171 ° C. for 5 minutes while maintaining the total pressure at 3.1 MPa. As a result, 60.0 g of an ethylene-1-octene copolymer was obtained. The physical properties of this copolymer were evaluated by the above-mentioned measurement methods. The results are shown in Table 1. The molecular weight distribution and composition distribution of this copolymer were very narrow. Example 2 After thoroughly replacing the inside of a dry polymerization reactor with a stirrer having an inner volume of 1 L with argon, 430 mL of dried n-hexane, 70 mL of 1-octene, and 0.02 MPa of hydrogen at a gauge pressure were charged to 171 ° C. The temperature rose. 0.28 mmol of ethyl aluminum sesquichloride (Al
), N-butylethylmagnesium 0.0
After adding 7 mmol to the catalyst preparation device in this order and mixing, 0.01 mmol of tetrabutoxytitanium prepared in advance was prepared.
5 mmol, 0.084 m of chloromethyl methyl ether
mol, and a mixed solution of 0.1155 mmol of isopropyl chloride was added. Then, the mixture was introduced into the polymerization reactor at the same time as ethylene gas, and polymerization was carried out at 171 ° C. for 5 minutes while maintaining the total pressure at 3.1 MPa. 46.8 g of an octene copolymer was obtained. The physical properties of this copolymer were evaluated by the above-mentioned measurement methods. The results are shown in Table 1.
The molecular weight distribution and composition distribution of this copolymer were very narrow. Example 3 The same procedure as in Example 2 was carried out except that chloromethyl methyl ether was replaced with chloromethyl ethyl ether. The results are shown in Table 1. The molecular weight distribution of this copolymer,
The composition distribution was narrow. Example 4 Example 4 was repeated except that 2,2,2-trifluoroethanol was replaced with methanol. The results are shown in Table 1. The molecular weight distribution and composition distribution of this copolymer were narrow. [Example 5] 2,2,2-trifluoroethanol was replaced with methanol, and the addition order was ethyl aluminum sesquichloride and n-butylethyl magnesium 0.07.
The procedure of Example 1 was repeated except that mmol was added to the catalyst preparing device in this order and mixed, and then a previously prepared mixed solution of tetrabutoxytitanium, methanol and isopropyl chloride was added. The results are shown in Table 1. The molecular weight distribution and composition distribution of this copolymer were narrow. Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that 2,2,2-trifluoroethanol was not added. The results are shown in Table 1. This copolymer had a broader molecular weight distribution and composition distribution than that of Example 1. Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that ethanol was used instead of 2,2,2-trifluoroethanol. The results are shown in Table 1. This copolymer was prepared in Example 1
The molecular weight distribution and the composition distribution were wider than those of the above. Comparative Example 3 Chloromethyl methyl ether was replaced with methyl-t
Polymerization was carried out in the same manner as in Example 2 except that -butyl ether was used. The results are shown in Table 1. This copolymer had a wider molecular weight distribution than that of Example 2. Example 6 In a catalyst supply line connected to a 1 L continuous reaction vessel, 7.5 L / hour of dried n-hexane and 1.666 mmol of ethyl aluminum sesquichloride were added.
/ H, methanol 0.499 mmol / h, n-
After butylethylmagnesium was completely mixed at a rate of 0.398 mmol / hour, tetrabutoxytitanium was further introduced into the catalyst supply line at a rate of 0.018 mmol / hour and isopropyl chloride at a rate of 0.716 mmol / hour. At the same time, 640 g / h of ethylene and 0.1 g of hydrogen were added.
02 g / h, 1-octene was used to obtain a copolymer having a density of 0.9.
The reaction was continuously supplied at a rate of 200 to 500 g / hour at a rate of about 14 g / cm3, at a reaction temperature of 175 ° C and a reaction pressure of 7
The polymerization reaction was carried out under the condition of 0 kg / cm2G with an average residence time of 0.11 hour to obtain an ethylene 1-octene copolymer. The physical properties of this copolymer were evaluated by the above-mentioned measurement methods. The results are shown in Table 1. The molecular weight distribution and composition distribution of this copolymer were very narrow. As a result, a film having a very high impact was obtained. Comparative Example 4 A copolymer was produced in the same manner as in Example 6 except that methanol was not added. The results are shown in Table 1.
This copolymer had a broader molecular weight distribution and composition distribution than that of Example 6. As a result, only a low impact film was obtained. Comparative Example 5 A copolymer was produced in the same manner as in Example 6 except that methanol was replaced with isostearyl alcohol. The results are shown in Table 1. This copolymer had a broader molecular weight distribution and composition distribution than that of Example 6. As a result, only a low impact film was obtained.

[0042]

[Table 1]

[0043]

The catalyst for producing an ethylene polymer of the present invention and the method for producing an ethylene polymer using the catalyst,
Various ethylene-based polymers can be efficiently produced. In particular, it is possible to efficiently produce a linear low-density ethylene-based polymer having a very narrow molecular weight distribution and composition distribution and excellent transparency and uniformity at a high temperature with a small amount of comonomer, and a high polymer yield. Can be achieved. Ethylene polymer obtained by the present invention is excellent in mechanical strength, transparency, and heat sealability, heat seal strength, etc., packaging film, food film, tape film, container, daily necessities, It can be used for various applications such as pipes and tubes.

Continued on the front page F-term (reference) 4J028 AA01A AB01A AC06A AC07A BA02B BB01B BC05B BC06B BC15B BC16B BC17B BC19B BC24B CB23C CB26C CB30C EB02 EB04 EB05 EB07 EB08 EB09 EB10 GA05 GA03 A02 GA03 AA04Q AA09Q AA15Q AA16Q AA17Q AA18Q AA19Q AA21Q AB02Q AR22Q AS01Q AS02Q AS03Q AS15Q CA01 CA04 FA09

Claims (6)

[Claims] (A) an organoaluminum compound, (B)
Organic magnesium compounds soluble in hydrocarbon solvents, (C)
A catalyst for producing an ethylene-based polymer, which is obtained by contacting a titanium compound soluble in a hydrocarbon solvent, (D) a halogenated hydrocarbon and (E) a halogen-containing alcohol, a halogen-containing ether or methanol. 2. The catalyst for producing an ethylene polymer according to claim 1, wherein (A), (B) and (C) are represented by the following general formulas (I), (II) and (III), respectively. R ¹ _m AlX ¹³ _3-m (I) wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
Represents an aryl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and X ¹ represents a halogen atom. M is a real number satisfying 0 <m ≦ 3. When a plurality of R ¹ are present, each R ¹ may be the same or different. MgR ² R ³ ... (II) wherein R ² represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and R ³ represents 1 to 18 carbon atoms.
An alkyl group, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom. ] _{^{Ti (OR 4) n X 2}} 4-n ··· (III) wherein, R ⁴ is an alkyl group having 1 to 18 carbon atoms, 5 carbon atoms
X ² represents a cycloalkyl group or an aryl group having 6 to 18 carbon atoms, and X ² represents a halogen atom. N is 0
It is a real number satisfying ≦ n ≦ 4. ] 3. The catalyst according to claim 1, wherein (A), (B) and (C) are represented by the following formulas (IV), (V) and (VI), respectively. R ¹ _1.5 AlX ¹ _1.5 (IV) wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
Represents an aryl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and X ¹ represents a halogen atom. MgR ² R ³ ... (V) wherein R ² and R ³ represent an alkyl group having 1 to 18 carbon atoms. ] _{^{Ti (OR 4) n ··· (}} VI) wherein, R ⁴ is an alkyl group having 1 to 18 carbon atoms, 5 carbon atoms
Represents a cycloalkyl group having from 18 to 18 or an aryl group having from 6 to 18 carbon atoms. N is a real number satisfying 0 ≦ n ≦ 4. ] 4. The catalyst for producing an ethylene polymer according to claim 1, wherein (E) is a fluorine-containing alcohol or a chlorine-containing ether. 5. The ethylene polymer according to claim 1, wherein (E) is 2,2,2-trifluoroethanol, chloromethylmethyl ether or chloromethylethyl ether. Production catalyst. 6. An ethylene-based copolymer which uses the catalyst for producing an ethylene-based polymer according to claim 1 and copolymerizes ethylene and an α-olefin under conditions in which a produced polymer is dissolved in a reaction medium. A method for producing a polymer.