JPH0710930A - Production of ethylene polymer or copolymer - Google Patents

Abstract

PURPOSE:To obtain an ethylene (co)polymer having a narrow mol.wt. distribution, suppressed in smoking, and improved in the hand of a molded product thereof by using a catalyst system wherein a specific solid catalyst component is used in combination with an organometallic compd. and a specific compd. CONSTITUTION:Ethylene or ethylene and a 3C or higher alpha-olefin are polymerized using a catalyst system comprising the following components [A] to [C]. The component [A] is a solid catalyst component comprising the following ingredients (I) and (II). The ingredient (I) is a solid ingredient prepd. by bringing Mg into contact with a halogenated hydrocarbon, a compd. of the following formula: XnM(OR)m-n (wherein X is a hydrogen atom, a halogen atom, or a 1-20C hydrocarbon group; M is B, C, Al, Si, or P; R is a 1-20C hydrocarbon group; (m) is the valence of M; and m>n>=0), and a halogen-contg. alcohol. The ingredient (II) is a titanium halide compd. The component [B] is an organometallic compd. The component [C] is a compd. of the following formula: R<1>R<2>R<3>C-(-Y-(CR<4>R<5>ml)nl-R<6> (wherein Y is an amine or ether bond represented by NR<7> or O; R<1> to R<7> are each H or a 1-5C hydrocarbon group; m1 is 1 to 4; and n1 is 1 to 5).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an ethylene polymer or an ethylene-α-olefin copolymer using a high performance catalyst.

[0002]

2. Description of the Related Art Magnesium is used as a transition metal component such as titanium.
Magnesium-supporting olefin supported on a carrier containing a compound
In-polymerization catalysts are known. Carrier used here
Is often used after mechanical crushing, in this case
The resulting polymerization catalyst, and thus the polymer particle shape, is not uniform
Will be Recently, attempts have been made to improve the particle shape of the carrier.
It has been fixed. For example, an aqueous solution of magnesium chloride
Or dissolved magnesium chloride hydrate (MgCl₂・ 6
H ₂(O) is spray-dried into spherical particles (Patent Document 1)
49-65999, 52-38590, 54-
41985), magnesium metal, halogenated carbon
Contact electron donating compounds such as hydrogen fluoride and alcohol
Method (JP-A-51-64586), organic magnet
How to react sium compounds with orthosilicic acid ester
Method, magnesium metal, orthosilicic acid ester and ha
Method of reacting rogenated hydrocarbons with each other (JP-A-5353)
No. 146,292) has been proposed, but
Although the particle shape of the body and catalyst is improved to some extent,
The media activity is unsatisfactory. In addition, the inventors of the present invention previously described the metal mug.
Nesium, halogenated hydrocarbons and general formula X_mC (O
R)_4-mBy contacting the compound of
A solid magnesium-containing solid that serves as a complete carrier for olefin polymerization
It was found that a body can be obtained (JP-A-56-12540).
No. 7) discloses the polymerization activity of a catalyst prepared using this solid.
There is still a problem with sex. Furthermore, the present inventors
Sium, halogenated hydrocarbon, general formula X_mM (OR)
_4-mContact with the compound and alcohol containing halogen
To provide a method for producing a catalyst carrier for olefin polymerization.
I proposed it (Japanese Patent Laid-Open No. 63-264608), but
Polyolefin produced using a catalyst prepared from the body
Is a lot of wax that causes smoke
There is a problem. Further magnesium halogen compounds
And (b) inclusion of an alkoxy group in a metal of groups I to IV of the periodic table
Contact the product with (C) alcohol compound.
Components consisting of soot, organoaluminum compounds and compounds
Ethylene and carbon number in catalyst system consisting of combination of cyclic compounds
By contacting 3 or more olefins under solvent-free conditions
Mar density 0.900 to 0.945 g / cm³Ethylene
-Although a method for producing an olefin copolymer is also known,
(JP-A-61-271310), the copolymer obtained
Has a problem in terms of molecular weight distribution.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an ethylene (co) polymer that suppresses the generation of smoke as described above and has an improved texture (feel) of the molded product. To do.

[0004]

[Means for Solving the Problems] That is, according to the present invention, a catalyst system comprising the following components (A) to (C) is contacted with ethylene, or ethylene and an α-olefin having 3 or more carbon atoms to obtain a molecular weight. A method for producing an ethylene polymer or an ethylene copolymer characterized by obtaining an ethylene polymer or an ethylene copolymer having a narrow distribution is summarized as follows: (A) From the following components (I) and (II) Solid catalyst component (I) consisting of magnesium, a halogenated hydrocarbon and a compound represented by the general formula X _n M (OR) _mn (where X is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M, and m> n ≦ 0) is contacted with a halogen-containing alcohol. Teruna Component (II) a titanium halide compound (B) an organometallic compound (C) the general formula ^{(I) R 1 R 2 R} 3 C - (- Y- (CR 4 R 5) m1) n1 -R 6 ··· ( I) (wherein Y is an amine or ether represented by NR ⁷ or O, R ^{1 to} R ⁷ represent H or a hydrocarbon group having 1 to 5 carbon atoms, and R ^{1 to} R ³ and R ^{4 to} R ⁶ At least two of them may be linked to each other to form a cyclic compound, m ₁
1 to 4 and n ₁ is 1 to 5) (hereinafter referred to as the amine or ether compound).

Raw Material for Preparation of Catalyst Component (a) Metallic Magnesium Metallic magnesium may be of any type, but powdery or chip-like ones are particularly preferable. In using these magnesium metal, after washing with an inert hydrocarbon, for example, a saturated aliphatic, alicyclic or aromatic hydrocarbon having 6 to 8 carbon atoms, an inert gas such as nitrogen is used. It is desirable to heat-dry in the presence of.

(B) Halogenated hydrocarbons Halogenated hydrocarbons are mono- or poly-halogen substitution products of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. Specific examples of those compounds include, in aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride,
Carbon tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromethane, 1,2-diiodoethane, methylchloroform, methylbromoform, methyliodoform, 1,1 , 2-trichloroethylene, 1,
1,2-tribromoethylene, 1,1,2,2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride,
1,2-dichloropropane, hexachloropropylene,
Octachloropropane, decabromobutane, and chlorinated paraffins, alicyclic compounds include chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, and hexachlorocyclohexane; aromatic compounds include chlorobenzene, bromobenzene, and o-dichlorobenzene. , P-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p
-Chlorobenzotrichloride and the like can be mentioned. These compounds may be used alone or in combination of two or more.

(C) General formula X _n M (OR) _{mn In the} formula, M, X, R, m and n are as defined above. Further, X may be a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms. When X is a hydrocarbon group, X and R may be the same or different. Hereinafter, the compound of the above general formula is simply referred to as an alkoxy compound. The hydrocarbon groups represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl, (Pr), i-propyl (i.
-Pr), butyl (Bu), i-butyl (i-Bu),
Alkyl groups such as hexyl (He) and octyl (Oct), cycloalkyl groups such as cyclohexyl (cyHe) and methylcyclohexyl, alkenyl groups such as allyl, propenyl and butenyl, phenyl (Ph), tolyl, aryl groups such as xylyl group, Examples thereof include phenethyl and aralkyl such as 3-phenylpropyl. Among these,
Particularly, an alkyl group having 1 to 10 carbon atoms is desirable. Less than,
Specific examples of the alkoxy group-containing compound will be given.

Compounds where M is carbon C (OR)_FourIncluded in C (OMe)_Four, C (OE
t)_Four, C (OPr) _Four, C (OBu)_Four, C (Oi-
Bu)_Four, C (OHe)_Four, C (OOct)_Four: Formula X
C (OR)₃HC (OMe) contained in₃, HC (OE
t)₃, HC (OPr)_3,HC (OBu)₃, HC
(OHe)₃, HC (OPh)₃MeC (OM
e)₃, MeC (OEt)₃, EtC (OMe)₃ , E
tC (OEt)₃, CyHeC (OEt)₃, PhC
(OMe)₃, PhC (OEt)₃, CH₂ClC (O
Et)₃, MeCHBrC (OEt)₃, MeCHCl
C (OEt) ₃; ClC (OMe)₃, ClC (OE
t)₃, ClC (Oi-Bu)₃, BrC (OE
t)₃Formula X₂C (OR)₂Included in MeCH (O
Me)₂, MeCH (OEt)₂, CH₂(OM
e)₂, CH₂(OEt)₂, CH₂ClCH (OE
t)₂, CHCl₂CH (OEt)₂, CCl₃CH
(OEt)₂, CH ₂BrCH (OEt)₂, PhCH
(OEt)₂.

Compound when M is silicon Si (OMe) ₄ , Si contained in the formula Si (OR) ₄
(OEt) ₄ , Si (OBu) ₄ , Si (Oi-Bu)
₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (O
Ph) ₄ : HSi (O contained in the formula XSi (OR) ₃
Et) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ ,
HSi (OPh) ₃ ; MeSi (OMe) ₃ , MeSi
(OEt) ₃ , MeSi (OBu) ₃ , EtSi (OE
t) ₃ , PhSi (OEt) ₃ , EtSi (OP
h) ₃ ; ClSi (OMe) ₃ , ClSi (OE
t) ₃ , ClSi (OBu) ₃ , ClSi (OP
h) ₃ , BrSi (OEt) ₃ ; Formula X ₂ Si (OR)
₂ contained in Me ₂ Si (OMe) ₂ and Me ₂ Si (O
Et) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (O
Et) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ S
iH (OEt) ₂ ; MeBuSi (OEt) ₂ : X ₃ S
Me ₃ SiOMe, Me ₃ SiOE contained in iOR
t, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ Si
OEt, Ph ₃ SiOEt.

Compounds where M is boron Formula B (OR)₃Included in B (OEt)₃, B (OB
u)₃, B (OHe) ₃, B (OPh)₃.

Compound when M is aluminum Al (OMe) ₃ , Al contained in the formula Al (OR) ₃
(OEt) ₃ , Al (OPr) ₃ , Al (Oi-Pr)
₃ , Al (OBu) ₃ , Al (Ot-Bu) ₃ , Al
(OHe) ₃ , Al (OPh) ₃ .

Compounds where M is phosphorus P (OR)₃Included in P (OMe)₃, P (OE
t)₃, P (OBu) ₃, P (OHe)₃, P (OP
h)₃.

(D) Halogen-containing alcohol As the halogen-containing alcohol, any one or two or more hydrogen atoms other than the hydroxyl group in the mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule is used. It means a compound substituted with a halogen atom. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and chlorine atom is preferable.

Examples of these compounds are 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-chlorobenzhydrol,
(M, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol,
6-chloro- (m, o) -cresol, 4-chloro-
3,5-dimethylphenol, chlorohydroquinone,
2-benzyl-4-chlorophenol, 4-chloro-1
-Naphthol, (m, o, p) -chlorophenol, p
-Chlor-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-
Chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol,
1-bromo-2-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-
Naphthol, (m, o, p) -bromophenol, 4-
Bromresorcin, (m, o, p) -fluorophenol, p-iodophenol: 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3- Chlor-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, 2,3,5-tribrom-4-
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, 2,2,3,3-tetrafluoro-1-
Propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin and the like can be mentioned.

Preparation of Solid Component The solid component is obtained by bringing a halogen-containing alcohol into contact with a contact product of metallic magnesium, a halogenated hydrocarbon and the alkoxy compound. (1) Contact of Metal Magnesium, Halogenated Hydrocarbon and the Alkoxy Compound The contact method of the three is not particularly limited, and any method may be used. That is, a method of contacting the three simultaneously, a compound obtained by contacting metal magnesium and a halogenated hydrocarbon in advance, or a compound obtained by contacting these compounds in advance, for example, ClMgCH ₃ , which is known as a so-called Grignard reagent, C
lMgC ₂ H ₅ , ClMgC ₃ H ₇ , ClMgC
_{4 H 9, ClMgi-C 4} H 9, ClMgC 6 H 13, C
1MgC ₈ H ₁₇ , BrMgC ₂ H ₅ , BrMgC
_{4 H 9, BrMgi-C 4} H 9, IMgC 4 H 9, Cl
A method in which a compound represented by MgC ₂ H ₅ , BrMgC ₆ H ₅ or the like is brought into contact with the alkoxy compound, or a solution of a halogenated hydrocarbon is added to a suspension of metallic magnesium in a solution of the alkoxy compound and then contacted. It is possible to carry out, for example, a method of bringing the alkoxy compound into contact with the halogenated hydrocarbon, and then adding metal magnesium to bring them into contact with each other.

In the above-mentioned three-way contact, a small amount of the Grignard reagent may be present in the reaction system. The use ratio of the alkoxy compound and metallic magnesium is
The number of OR ¹ groups in the alkoxy compound is preferably 1 or more, particularly 3 to 5 per 1 atom of magnesium in the metal magnesium. For example, in the case of an alkoxy compound represented by X ¹ ₂ C (OR ¹ ) ₂ , the amount of the alkoxy compound is 0.5 mol or more, preferably 1.5 to 2.5 mol per gram atom of magnesium. ¹ C (O
In the case of the alkoxy compound represented by R ¹ ) ₃ , 1 /
The amount is preferably 3 mol or more, and more preferably 1 to 5/3 mol.
Also, the halogenated hydrocarbon is preferably used in an amount of 1 to 2 mol per 1 gram atom of magnesium.

These catalytic reactions have a contact temperature of 0 to 250.
C, preferably 30 to 120 C, contact time 0.5 to 10
It is achieved by stirring under conditions of time. or,
This reaction can be carried out in the presence of the inert hydrocarbon previously used for drying the metal magnesium, for example, an aliphatic, alicyclic or aromatic hydrocarbon having 6 to 8 carbon atoms. In order to efficiently carry out the reaction, it is desirable to carry out in the presence of ether. As the ether, diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di2-ethylhexyl ether, diallyl ether, diphenyl ether, anisole and the like can be used. Further, for the purpose of accelerating these reactions, iodine, alkyl iodide or inorganic halides such as calcium chloride, copper chloride, manganese chloride and hydrogen halide can be used. The solid thus prepared by the reaction is then contacted with a halogen-containing alcohol, but it may be contacted with the alcohol as it is in the same reaction system, or separated from the reaction system prior to contact with the alcohol. It may be washed with a suitable detergent such as the above-mentioned inert hydrocarbon, and may be dried if necessary.

(2) Contact with Halogen-Containing Alcohol The contact between the magnesium-containing solid obtained in (1) above and the halogen-containing alcohol may be carried out by mixing and stirring in the presence of an inert medium. As an inert medium, pentane,
Hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene, 1,
Halogenated hydrocarbons such as 2-dichloroethane, 1,2-dichloropropane, carbon tetrachloride, butyl chloride, isoamyl chloride, bromobenzene and chlorotoluene can be used. The contact between the two is usually 0.1 at -20 to + 150 ° C.
~ 100 hours. When the contact is accompanied by heat generation, it is possible to adopt a method in which the both are gradually contacted at a low temperature first, the temperature is raised when the mixing of the entire amount is completed, and the contact is continued. The halogen-containing alcohol is usually used in an amount of 0.05 to 20 gram moles, preferably 0.1 to 10 gram moles, per 1 gram atom of magnesium in the solid. The solid component according to the present invention is obtained as described above, and the solid component can be washed with an inert hydrocarbon, if necessary, and further dried if necessary.

The solid component according to the present invention is composed of particles having a narrow particle size distribution and a uniform shape, and the specific surface area measured at the adsorption temperature of liquid nitrogen by the BET method is 1,000.
m ² / g or less, preferably 30~600m ² / g, a pore volume of 1.00 cm ³ / g or less, preferably 0.03
0.7 cm ³ / g. In addition, the composition is such that the magnesium atom is 5 to 25% by weight, the halogen atom is 3 to 70% by weight, and the rest is an organic compound or the like.

Preparation of catalyst component A solid catalyst component obtained by supporting a titanium halide compound known as a catalyst component for olefin polymerization on this solid component is
Exhibits excellent catalytic performance. Moreover, when preparing a catalyst component using this solid, a metal oxide such as silica and alumina, a polyolefin such as polyethylene and polypropylene, and other inert solid substances can also be used.

The titanium halide compound is a divalent, trivalent, or tetravalent titanium halide compound,
Examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxy titanium, trichloro butoxy titanium,
Examples thereof include dichlordiethoxytitanium, dichlorodibutoxytitanium, dichlorodiphenoxytitanium, chlorotriethoxytitanium, chlortoribtoxytitanium, tetrabutoxytitanium, titanium trichloride and the like. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxy titanium, dichlorodibutoxy titanium, and dichlorodiphenoxy titanium are preferable, and titanium tetrachloride is particularly preferable.

(Co) polymerization of ethylene The catalyst component obtained as described above is used in combination with an organometallic compound and the amine or ether compound and, if necessary, an electron-donating compound, to homopolymerize ethylene or other compounds. It is useful as a catalyst for copolymerization with the above-mentioned mono-olefin or a di-olefin having 3 to 10 carbon atoms, and in particular, an ethylene polymer or ethylene-α-olefin copolymer having a narrow molecular weight distribution can be produced. Along with this, the amount of wax that causes smoke is reduced. Further, when the molecular weight distribution is narrowed, the density of the obtained (co) polymer is decreased, and the feel (feel) of a molded article using the (co) polymer, for example, a nonwoven fabric is improved.

Organometallic compounds which can be used are organic compounds of metals of groups I to III of the periodic table. As the compound, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly preferable. Organoaluminum compounds that can be used include those represented by the general formula R ⁸ _n1 A
lX ′ _3-n1 (wherein R ⁸ is an alkyl group or an aryl group,
X ′ represents a halogen atom, an alkoxy group or a hydrogen atom, and n ₁ is an arbitrary number within the range of 1 ≦ n ₁ ≦ 3. ), For example, a trialkylaluminum, a dialkylaluminum monohalide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, a dialkylaluminum monoalkoxide, a dialkylaluminum monohydride, etc., having 1 to 18 carbon atoms, preferably a carbon atom. Particularly preferred are alkylaluminum compounds of the number 2 to 6 or mixtures or complex compounds thereof. Specifically, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, and trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide. Dialkyl aluminum monohalides such as diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, monobutyl aluminum dihalides such as isobutyl aluminum dichloride, ethyl aluminum aluminum Alkyl aluminum sesquihalides such as sesquichloride, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, dialkyl aluminum monoalkoxides such as diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum Hydride, dipropyl aluminum hydride,
Dialkyl aluminum hydrides such as diisobutyl aluminum hydride can be mentioned. Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable.
These trialkylaluminums are combined with other organoaluminum compounds such as diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof which are industrially easily available. Can be used together.

Also, two or more via oxygen or nitrogen atoms
Organo-aluminum compound with aluminum
It can be used. Examples of such compounds include (C
₂H_Five)₂AlOAl (C₂H_Five)₂, (C_FourH₉)₂
AlOAl (C_FourH ₉)₂,

[Chemical 1] Etc. can be illustrated.

The amount of the organometallic compound used relative to the above catalyst component is usually 1 per 1 gram atom of titanium in the catalyst.
˜2,000 gram moles, especially 20-500 gram moles are desirable.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride and diethylzinc, and LiAl (C
Examples thereof include compounds such as ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . In addition to the organometallic compound, the following general formula (I), R ¹ R ² R ³ C-(-Y- (CR ⁴ R ⁵ ) _{m 1} ) _{n 1} -R ⁶ ... (I) (wherein Y is NR ⁷ Alternatively, an amine or ether represented by O, R ^{1 to} R ⁷ are H or a compound represented by C 1 to C 4) to form the catalyst system of the present invention. In this general formula, m ₁ is 1 to 4 and n ₁ is 1 to 5
And preferably m ₁ is ₁ to 2 and n ₁ is ₁ to 2. Further, the more the number of alkyl groups of the substituent R is, the more preferable that the number of H is 2 or less, more preferably all of them are alkyl groups, and each of R ^{1 to} R ³ and R ^{4 to} R ⁶ is one. It is also possible to use a compound that is bonded to form a cyclic compound. Although the polymerization activity tends to decrease and the molecular weight distribution tends to narrow as the amount of the compound added is increased, the amount added is preferably 0.005 in terms of molar concentration ratio with respect to the organometallic compound added as a cocatalyst. ~ 0.
6 has a sufficient effect, and more preferably, 0.
When added in an amount of 01 to 0.06, there is little decrease in the polymerization activity and a sufficient effect can be obtained.

Examples of the amine or ether compound include the following. Amines (a) One nitrogen atom n-Bu ₂ NH, n-Bu ₂ NMe, i-Bu ₂ NH,
i-Bu ₂ NMe, t-Bu ₂ NH, t-Bu ₂ NM
e, n-Pr ₂ NH, i-Pr ₂ NH, piperidine,

[0028]

[Chemical 2]

(B) Two nitrogen atoms

[Chemical 3]CH₃NHCH₂CH₂NHCH₃, CH₃N (C
H₃) CH₂CH₂N (CH₃) CH₃, CH₃CH₂
N (CH₃) CH₂CH₂NHCH₃, CH₃CH ₂N
HCH₂CH₂NHCH₃, Piperazine.

(C) Three nitrogen atoms

[Chemical 4]

Ethers (a) One oxygen atom n-Bu ₂ O, i-Bu ₂ O, t-Bu ₂ O, n-Pr
₂ O, i-Pr ₂ O, tetrahydrofuran (THF),
Cineole,

[0032]

[Chemical 5]

(B) Two oxygen atoms

[Chemical 6]

(C) Three oxygen atoms

[Chemical 7]

The electron-donating compound which can be combined with the above-mentioned catalyst component, the amine or ether compound and the organometallic compound as the case requires, is an ordinary electron-donating compound used in this type of polymerization reaction. Is appropriately selected from That is, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines, amides,
Examples thereof include nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic acid esters and the like. Of these, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols and ethers are preferably used.

Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid and other aliphatic monocarboxylic acids, and malonic acid. , Succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, tartaric acid and other aliphatic oxycarboxylic acids, cyclohexanemonocarboxylic acid, cyclohexenemonocarboxylic acid, cis-1,2- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,
Alicyclic carboxylic acids such as 2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, aromatic monocarboxylic acids such as p-tertiary butyl benzoic acid, naphthoic acid and cinnamic acid, phthalic acid, isophthalic acid, Terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid,
Examples thereof include aromatic polycarboxylic acids such as mellitic acid. As the carboxylic acid anhydride, acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above-mentioned carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, pivalic acid. Isobutyl, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate,
Monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, p
-Ethyl tertiary butyl benzoate, ethyl p-anisate,
Ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, phthalic acid Diallyl, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromelliticate, tetraethyl pyromelliticate, tetrabutyl pyromelliticate. Etc.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used,
Specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride,
Butyric acid bromide, butyric acid iodide, pivalic acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid bromide, Succinic acid chloride, succinic acid bromide,
Glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride,
Sebacic acid bromide, maleic acid chloride, maleic acid bromide, fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, 1-
Cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid bromide, benzoyl chloride,
Benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide, α-naphthoic acid chloride, cinnamic acid chloride,
Examples thereof include cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Also, a monoalkyl halide of a dicarboxylic acid such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, phthalic acid butyl chloride may be used.

Alcohols are represented by the general formula R ⁹ OH. In the formula, R ⁹ is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol,
Examples include isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol.

The ethers are represented by the general formula R ¹⁰ OR ¹¹ . In the formula, R ¹⁰ and R ¹¹ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R ¹⁰ and R ¹¹ may be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether,
Examples include diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethyl phenyl ether. Two or more kinds of these electron donating compounds may be used. Further, these electron donating compounds may be used when an organometallic compound is used in combination with a catalyst component, or may be used after being brought into contact with the organometallic compound in advance.

The ratio of the organometallic compound to the electron donating compound used as necessary is 0.1 mol of the organometallic compound as aluminum to 1 mol of the electron donating compound.
~ 40, preferably selected in the range of 1 to 25 gram atoms.

The (co) polymerization reaction may be carried out in either a gas phase or a liquid phase. In the case of polymerizing in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene,
It can be carried out in an inert hydrocarbon such as toluene or xylene, and in a liquid monomer. The polymerization temperature is usually -80 ° C.
To + 150 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres.

[0043]

EXAMPLES The present invention will be specifically described with reference to examples and application examples. The percentages (%) in the examples are by weight unless otherwise specified. Polymer melt index (MI) was measured according to ASTM-D 1238. Bulk density was measured according to ASTM-D 1895-69 Method A.

Example 1 Preparation of Magnesium-Containing Solid Component In a 1-liter reaction vessel equipped with a reflux condenser, under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity: 99.
5%, average particle size 1.6 mm) 12.8 g (0.53 mol)
Then, 250 ml of n-hexane was added, the mixture was stirred at 68 ° C. for 1 hour, metallic magnesium was taken out, and dried under reduced pressure at 65 ° C. to obtain preactivated metallic magnesium.
Next, ethyl orthoformate [H
88 ml (0.53 mol) of C (OC ₂ H ₅ ) ₃ ] and 0.5% of a 10% solution of methyl iodide in iodine as a promoter.
The suspension added in ml was kept at 55 ° C, and n-hexane 1 was added.
A solution of 80 ml (0.8 mol) of n-butyl chloride in 00 ml was added dropwise at first 5 ml, and after stirring for 50 minutes, 8
The remaining solution was added dropwise in 0 minutes. The reaction was carried out at 70 ° C. for 4 hours with stirring to obtain a solid reaction product. The reaction product was washed 6 times with 300 ml of n-hexane at 50 ° C. 60 times.
After drying under reduced pressure at 0 ° C. for 1 hour, 55.6 g of a magnesium-containing solid consisting of white powder was recovered. This solid contained 22.5% magnesium and 34.0% chlorine.

Contact with 2,2,2-trichloroethanol
300 ml equipped with contact reflux condenser, stirrer and dropping funnel
Into the reaction vessel of No. 2, 6.3 g of magnesium-containing solid and 50 ml of n-heptane were put in a nitrogen gas atmosphere to make a suspension, and 2,2,2-trichloroethanol 2 was stirred with stirring at room temperature.
A mixed solution of 0 ml (0.02 mmol) and 11 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes and further stirred at 80 ° C for 1 hour. The obtained solid was filtered, washed with 100 ml of n-hexane at room temperature 6 times, and dried under reduced pressure at room temperature for 1 hour to prepare 8.1 g of a solid component according to the present invention. This solid component contains 14.2% magnesium and 47.
The content was 5%, the specific surface area was 162 m ² / g, and the pore volume was 0.21 cm ³ / g.

Preparation of catalyst component In a 300 ml reaction vessel equipped with a reflux condenser and a stirrer,
Under a nitrogen gas atmosphere, 6.3 g of the solid component obtained as described above and 40 ml of toluene were put into a suspension, 60 ml of titanium tetrachloride was added thereto, and the mixture was stirred at 120 ° C. for 2 hours. The obtained solid substance was separated by filtration at 110 ° C. and washed 7 times with 100 ml of n-heptane at room temperature to obtain 5.7 g of a catalyst component having a titanium content of 3.8%.

An ethylene polymerization stirrer with an internal volume of 1.5 liters of stainless steel (S
US Pat. No. 32) in an autoclave under a nitrogen gas atmosphere, 10 mg of the catalyst component obtained above, 1 mmol / l of triisobutylaluminum and 700 parts of isobutane.
ml and 2,2,5,5-tetramethylpiperidine 0.0
2 mmol / l was charged and the temperature of the polymerization system was raised to 85 ° C. Next, hydrogen was introduced until the hydrogen partial pressure reached 1 kgG, and then ethylene was introduced until the ethylene partial pressure reached 5 kgG. To keep the total pressure of the polymerization system constant at 21 kgG,
Polymerization was carried out for 60 minutes while continuously supplying ethylene. After the completion of the polymerization, the polymerization solvent and unreacted ethylene were purged, and the white powdery polymer was taken out and the temperature was reduced to 70 ° C.
After drying for 10 hours, MI 0.19 (dg / mi
n), and 182 g of polyethylene powder having a density of 0.9520 (g / cc) was obtained. The polymer obtained is 17600 active.
g / g-cat. The Mw / Mn was 4.4.

(Comparative Example 1) In Example 1, 2, 2,
Polymerization was similar except that 5,5-tetramethylpiperidine was not used. The polymer obtained is 21100 active.
(G / g-cat.), MI 0.30 (dg / mi)
n), the density was 0.9527 (g / cc), and the Mw / Mn was 7.1.

Other examples and comparative examples are summarized in Table 1 below. The added amount of the compound of the general formula (I) is 0.02 mmol / liter.

[Table 1]

[0050]

Industrial Applicability According to the method of the present invention, the molecular weight distribution is narrowed, the wax content causing smoke is reduced to suppress smoke, and at the same time, the texture of the obtained ethylene (co) polymer molded article ( Texture) can be improved.

[Brief description of drawings]

FIG. 1 is a flow chart diagram illustrating the method of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiya Saito 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Inventor Hiroyuki Furuhashi Nishitsuruoka-oka, Oi-cho, Saitama 3-3-1 Tonen Co., Ltd. Research Institute (72) Inventor Satoshi Ueki 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Research Institute

Claims (1)

[Claims] 1. A catalyst system comprising the following components (A) to (C), or ethylene, or ethylene and α-containing 3 or more carbon atoms:
A method for producing an ethylene polymer or an ethylene copolymer, which comprises contacting an olefin to obtain an ethylene polymer or an ethylene copolymer having a narrow molecular weight distribution. (A) Solid catalyst component consisting of the following components (I) and (II): (I) magnesium, a halogenated hydrocarbon and a compound represented by the general formula X _n M (OR) _mn (where X is a hydrogen atom, Halogen atom or hydrocarbon group having 1 to 20 carbon atoms, M is boron, carbon, aluminum, silicon or phosphorus atom, R is hydrocarbon group having 1 to 20 carbon atoms, m is valence of M, and m> solid component obtained by contacting a halogen-containing alcohol with (n ≧ 0) (II) titanium halide compound (B) organometallic compound (C) general formula (I) R ¹ R ² R ³ C-(-Y _{^{- (CR 4 R 5) m1}} ) n1 -R 6 ··· (I) ( wherein Y is an amine or ether represented by NR ⁷ or O, R ¹ ~R ⁷ is H or a 1 to 5 carbon atoms It represents a hydrocarbon group, R ¹ to R ³ and R ⁴ to R ⁶ are linked to each other between at least two parties It may also form a Jo compound .m
₁ is 1 to 4 and n ₁ is 1 to 5)