JP3262662B2 - Method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a novel polyolefin. More particularly, the present invention significantly increases the polymer yield per solid catalyst and the polymer yield per transition metal, thereby eliminating the need for removing catalyst residues in the polymer, The present invention relates to a process for increasing the bulk density and reducing the finely divided portion of the polymer produced to produce good particles having a large average particle size, and at the same time producing a polyolefin having a narrow molecular weight distribution.

2. Description of the Related Art

Heretofore, in this type of technical field, many catalysts have been known in which an inorganic magnesium solid such as magnesium halide, magnesium oxide or magnesium hydroxide is used as a carrier and a transition metal compound such as titanium or vanadium is supported on the solid. Have been. However, in these known techniques, in the case of homopolymerization of α-olefin or in the case of copolymerization of ethylene and α-olefin, there is a problem that the polymer yield per solid catalyst and the polymer yield per transition metal are low. There is a need for improved activity. In particular, in the case of homopolymerization of ethylene or copolymerization of ethylene with a small amount of α-olefin, the yield of polymer per solid catalyst and the yield of polymer per transition metal are extremely low. Therefore, improvement is still needed in order to omit the pelletizing step, which has been increasing in recent years, and to apply the powder polymer to a processing machine as it is. In addition, the bulk specific gravity of the resulting polyolefins is generally small, the average particle size is relatively small, and the particle size distribution is generally wide, so there are many fine powders. Therefore, improvements have been strongly desired in terms of productivity and polymer handling. The present inventors have previously filed several patent applications for a novel catalyst component which has improved the above-mentioned disadvantages (Japanese Patent Publication No. 51-152, Japanese Patent Publication No. 56-54323, Japanese Patent Publication No. 64-404, Japanese Patent Publication No. 10526, Tokuhei 1-
11651, Tokiko 1-1288, Tokiko 1-122
89, JP-A-60-149605, JP-A-62-321
05, JP-A-62-207306, JP-A-3-3500
4, JP-A-3-185004). When these catalyst components are used, the polymer yield per solid catalyst and the polymer yield per transition metal can be increased, and a polymer having a high bulk density and a large average particle size can be obtained. Is omitted, and there is a disadvantage that the powder polymer cannot be directly applied to a processing machine. The present invention improves these disadvantages and significantly increases the polymer yield per solid catalyst and the polymer yield per transition metal in the case of homopolymerization of α-olefin or copolymerization of ethylene and α-olefin. As a result of intensive research for the purpose of the present invention, the present invention has been achieved.

[0003]

That is, the present invention provides a method of polymerizing ethylene by using a solid catalyst component and an organometallic compound as a catalyst, or ethylene and a small amount of α-olefin having 3 to 12 carbon atoms.
In the method of copolymerizing a compound, the solid catalyst component comprises at least a magnesium compound, a titanium compound and a compound of the general formula R
¹ CH = CHR ² (where R ¹ and R ^{2 each} have 1 to 24 carbon atoms)
Represents an alkyl group, an aryl group or an aralkyl group,
An ethylene polymer or ethylene- containing compound obtained by bringing an internal olefin compound represented by
α-olefin copolymer (α-olefin content 20
% Or less) . The present invention is a method for <br/> copolymerized ethylene polymerization or ethylene and a small amount of 3 to 12 carbon atoms α- olefin and an organic metal compound as a solid catalyst component as a catalyst, said solid catalyst component is at least silicon oxide And / or aluminum oxide, magnesium compound, titanium compound and general formula R ¹ CH =
An internal olefin compound represented by CHR ² (where R ¹ and R ² represent an alkyl group, an aryl group or an aralkyl group having 1 to 24 carbon atoms, which may be the same or different, and are located at the cis position), Ethylene polymer or ethylene α-O , characterized in that it is a substance obtained by contact
Lefin copolymer (α-olefin content 20 mol% or less
Lower) relates to the manufacturing method. Ri by <br/> in using the method of the present invention, a copolymer of homopolymer or ethylene and a small amount of α- olefins et styrene is obtained at an extremely high activity,
In addition, the resulting polyolefin has a high bulk specific gravity and a good free-flowing property, so that the polymerization operation is very advantageous.In addition, when used as pellets, it can be used for molding even if it is in powder form. There is little trouble during processing, and polyolefin can be produced very advantageously.

Hereinafter, the present invention will be described specifically. <1> Solid Catalyst Component The solid catalyst component of the present invention comprises at least a magnesium compound, a titanium compound and a general formula R ¹ CH ＝ CHR ² (where R ¹ and R ² are an alkyl group, aryl group or aralkyl having 1 to 24 carbon atoms). Which may be the same or different, and may be the same or different and are in the cis position), and the solid catalyst component of the present invention comprises at least silicon oxide and / or Or an aluminum oxide, a magnesium compound, a titanium compound and a general formula R ¹ CH ＝ CHR ² (where R ¹ and R ² represent an alkyl group, an aryl group or an aralkyl group having 1 to 24 carbon atoms, and may be the same or different. (Often located at the cis position). (1) Magnesium compound [Component I] The magnesium compound used in the present invention is not particularly limited, and examples thereof include magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium sulfate, and magnesium silicate. In addition, a general formula Mg (OR ¹ ) _n X _2-n (where R ¹ represents a hydrocarbon residue having 1 to 20 carbon atoms,
X represents a halogen atom, and n represents 0 ≦ n ≦ 2), and the hydrocarbon residue is preferably one having 1 to 12 carbon atoms, for example, an alkyl group , Aryl group, aralkyl group and the like,
Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specifically, magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, methoxychloromagnesium, ethoxychloromagnesium, n-propoxychloromagnesium, iso
-Propoxychloromagnesium, n-butoxychloromagnesium, sec-butoxychloromagnesium,
tert-butoxychloromagnesium, methoxybromomagnesium, ethoxybromomagnesium, n-propoxybromomagnesium, iso-propoxybromomagnesium, n-butoxybromomagnesium,
sec-butoxybromomagnesium, tert-butoxybromomagnesium, dimethoxymagnesium,
Diethoxymagnesium, di-n-propoxymagnesium, diiso-propoxymagnesium, n-butoxymagnesium, disec-butoxymagnesium, dit
Compounds such as tert-butoxymagnesium can be mentioned, and magnesium chloride is particularly preferable. In the present invention, these magnesium compounds are alcohol-
, An ester, a ketone, a carboxylic acid, an ether, an amine, a phosphine or the like. And a general formula R ² MgX (where R ² is a hydrocarbon group having 1 to 20 carbon atoms;
Is a halogen atom), and the hydrocarbon residue is preferably a group having 1 to 12 carbon atoms, such as an alkyl group, an aryl group and an aralkyl group. And examples of the halogen atom include fluorine, chlorine, bromine and iodine, and specifically, methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium iodide, and n-propyl magnesium chloride , N
-Propyl magnesium bromide, n-propyl magnesium iodide, n-butyl magnesium chloride, n-butyl magnesium bromide, n-butyl magnesium iodide, isobutyl magnesium chloride, isobutyl magnesium bromide, isobutyl magnesium iodide, hexyl magnesium chloride, hexyl magnesium Compounds such as bromide, hexylmagnesium iodide, octylmagnesium chloride, octylmagnesium bromide, decylmagnesium chloride, decylmagnesium bromide, phenylmagnesium chloride, and phenylmagnesium bromide can be given. These magnesium compounds may be used alone, or a mixture of two or more kinds may be preferably used. (2) Titanium compound [Component II] The titanium compound used in the present invention is not particularly limited, but is represented by the general formula Ti (OR ³ ) _m X _4-m (where R ³ is a hydrocarbon having 1 to 20 carbon atoms) Residue, X represents a halogen atom, and m represents 0 ≦ m ≦ 4), and the hydrocarbon residue is preferably a group having 1 to 12 carbon atoms, For example, an alkyl group, an aryl group, an aralkyl group, and the like, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group,
i-propyl group, butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc., aryl groups, phenyl group, tolyl group, xylyl group, etc., aralkyl group , A benzyl group, and the like,
Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specifically, titanium tetrachlorides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, monoethoxytrichlorotitanium Fluorotitanium, monoethoxytribromotitanium, diethoxydifluorotitanium, diethoxydichlorotitanium, diethoxydibromotitanium, triethoxyfluorotitanium, triethoxychlorotitanium, tetraethoxytitanium, monopropoxytrichlorotitanium, monoisopropoxytrichlorotitanium, diethoxy Propoxydichlorotitanium, diisopropoxydichlorotitanium, diisopropoxydibromotitanium, triisopropoxyfluorotitanium, tripropoxychlorotitanium, tetra-n Propoxy titanium, tetraisopropoxy titanium, monobutoxytrichlorotitanium, monoisobutoxytrichlorotitanium, dibutoxydichlorotitanium, tributoxyfluorotitanium, tributoxychlorotitanium, triisobutoxychlorotitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium , Tetrasec-butoxytitanium, tetratert-butoxytitanium, monopentoxytrichlorotitanium, dipentoxydichlorotitanium, tripentoxydimonochlorotitanium, tetra-n-pentyloxytitanium, tetracyclopentyloxytitanium, monooctyloxytrichlorotitanium, Dioctyloxydichlorotitanium, trioctyloxymonochlorotitanium, tetra-n
-Hexyloxytitanium, tetracyclohexyloxytitanium, tetra-n-heptyloxytitanium, tetra-
n-octyloxytitanium, tetra-2-ethylhexyloxytitanium, mono-2-ethylhexyloxytrichlorotitanium, di-2-ethylhexyloxydichlorotitanium, tri-2-ethylhexyloxymonochlorotitanium,
Tetra-nonyloxytitanium, tetradecyloxytitanium, tetraisobornyloxytitanium, tetraoleyloxytitanium, tetraallyloxytitanium, tetrabenzyloxytitanium, tetrabenzhydryloxytitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, Triphenoxychlorotitanium, tri-o-
Xyleneoxychlorotitanium, tetraphenoxytitanium, tetra-o-methylphenoxytitanium, tetra-m
-Methylphenoxytitanium, tetra-1-naphthyloxytitanium, tetra-2-naphthyloxytitanium, or an arbitrary mixture thereof;
Titanium tetrachloride, monoethoxytrichlorotitanium, monobutoxytrichlorotitanium, diethoxydichlorotitanium,
Dibutoxydichlorotitanium, triethoxymonochlorotitanium, tributoxymonochlorotitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-n-hexyloxytitanium, tetra-n-octyloxytitanium, tetra-2 -Ethylhexyloxytitanium and the like are desirable. In addition to the tetravalent titanium compound, a trivalent titanium compound is also preferable. Examples of the trivalent titanium compound include titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide,
A tetravalent halogenated alkoxytitanium compound represented by the general formula Ti (OR ') _{pX4 -P} (where R' has 1 to 2 carbon atoms)
X represents an alkyl group, an aryl group or an aralkyl group, and X represents a halogen atom. p is 0 <p ≦ 4)
With hydrogen, aluminum, titanium or periodic table I to
Titanium trihalide or a trivalent titanium compound obtained by reduction with an organic metal compound of a Group III metal can be used. These titanium compounds can be preferably used alone or as a mixture of two or more kinds. Also, a titanium compound and a vanadium compound can be used in combination within a necessary range.Examples of such a vanadium compound include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxy vanadium; Examples thereof include pentavalent vanadium compounds such as vanadium oxytrichloride, ethoxydichlorvanadyl, triethoxyvanadyl, and tributoxyvanadyl, and trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide. When the titanium compound and the vanadium compound are used in combination, the V / Ti molar ratio when the titanium compound and the vanadium compound are used in combination is preferably in the range of 2/1 to 0.01 /.

(3) Silicon oxide and aluminum oxide [Component III] The silicon oxide used in the present invention is a double oxide of silica or silicon and at least one other metal of Group I to VIII of the periodic table. It is. The aluminum oxide used in the present invention is a double oxide of alumina or aluminum and at least one other metal of Groups I to VIII of the periodic table. Silicon or aluminum and the Periodic Table I~VIII group at least one other typical examples of Al ₂ O ₃ · MgO double oxide of _{metal, Al 2 O 3 · CaO,} Al 2 O
₃ · SiO ₂ , Al ₂ O ₃ · MgO · CaO, Al ₂ O ₃ · Mg
O.SiO ₂ , Al ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ ,
Various natural or synthetic multiple oxides such as Al ₂ O ₃ .NiO and SiO ₂ .MgO can be exemplified. Here, the above formula is not a molecular formula but represents only a composition,
The structure and component ratio of the double oxide used in the present invention are not particularly limited. Needless to say, the silicon oxide and / or aluminum oxide used in the present invention may absorb a small amount of moisture, and may be used without any problem even if it contains a small amount of impurities. The properties of these silicon oxides and / or aluminum oxides are not particularly limited as long as the object of the present invention is not impaired.
Desirably, the silica has a pore size of 200 μm, a pore volume of 0.3 ml / g or more, and a surface area of 50 m ² / g or more. In use, it is desirable to perform a baking treatment in advance at 200 to 800 ° C. by an ordinary method.

(4) Internal olefin compound [Component IV] The internal olefin compound used in the present invention is represented by the general formula R ⁴ CH = CHR ⁵ , wherein R ⁴ and R ^{5 each} have 1 to 2 carbon atoms.
4, preferably 1 to 12 alkyl groups, aryl groups or aralkyl groups, which may be the same or different and are compounds at the cis position, wherein the alkyl group is a methyl group, an ethyl group, a propyl group, an i- Propyl group, butyl group,
The aryl group includes a phenyl group, a tolyl group, an xylyl group and the like, and the aralkyl group includes a benzyl group and the like. The s-butyl group, the t-butyl group, the pentyl group, the hexyl group, the heptyl group and the octyl group. The internal olefin compound used in the present invention is a compound that does not substantially polymerize even when it is brought into contact with a catalyst composed of an organometallic compound and a solid catalyst component obtained by bringing at least a magnesium compound and a titanium compound into contact with each other. Preferred examples of these internal olefins include cis-2-butene, cis-2-pentene, cis-2-hexene, cis-3-hexene, 4-methyl-cis-2-pentene,
Cis-2-heptene, 4-methyl-cis-2-hexene, 5-methyl-cis-2-hexene, cis-3-heptene, 2-methyl-cis-3-hexene, 4,4-dimethyl-cis-2-pentene, cis-2-octene, cis-3-octene, 4-methyl-cis-2-heptene, 5
-Methyl-2-cis-2-heptene, 6-methyl-cis-2-heptene, 4-ethyl-cis-2-hexene,
4,4-dimethyl-cis-2-hexene, 4,5-dimethyl-cis-2-hexene, 5,5-dimethyl-cis-2-hexene, 2-methyl-cis-3-heptene, 5-methyl-cis-3-heptene, cis-4-octene,
Examples thereof include 2,2-dimethyl-cis-3-hexene, 2,5-dimethyl-cis-3-hexene, 6-methyl-cis-3-heptene, cis-stilbene, and an arbitrary mixture thereof. Preferably, cis-2-hexene, 4
-Methyl-cis-2-pentene, cis-2-heptene,
4-methyl-cis-2-hexene, 5-methyl-cis-2-hexene, cis-2-octene, 4-methyl-cis-2-heptene, 5-methyl-2-cis-2-heptene, 6-methyl-cis-2-heptene, 4-ethyl-cis-2-hexene, 4,4-dimethyl-cis-2-hexene, 4,5- Dimethyl-cis-2-hexene, 5,5
-Dimethyl-cis-2-hexene, cis-stilbene and the like are desirable. Of course, these compounds may be used alone or in combination of two or more. In addition, a trans-type internal olefin can be used in addition to the cis-type internal olefin as long as the present invention is not impaired. The trans internal olefin is not particularly limited, and examples thereof include the cis isomer.

(5) The above-mentioned magnesium compound, titanium compound, internal olefin compound, and in some cases, silicon oxide and / or aluminum oxide can be further reacted with various inorganic compounds [Component V]. . Such an inorganic compound has a general formula Me (YR ⁶ ) _p R ⁷ _q X _zpq (where Me is an element of Group I to IV of the periodic table, and z is an element Me
Is usually 1 ≦ z ≦ 4, p and q are 0 ≦ p ≦ z, 0 ≦
q ≦ z, 0 ≦ p + q ≦ z, X represents a halogen atom or a hydrogen atom, and Y represents an oxygen atom or a nitrogen atom. R ⁶ and R ⁷ each represent a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, such as an alkyl group, an aryl group or an aralkyl group, which may be the same or different. expressed. In such a compound, examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a s-butyl group, Aryl groups include phenyl group, tolyl group, xylyl group, etc., and aralkyl groups include benzyl group, etc., as t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. Specifically, NaOR, NaX, Mg (O
R) ₂ , Mg (OR) X, MgX ₂ , Ca (OR) ₂ , C
a (OR) X, CaX ₂ , Zn (OR) ₂ , Zn (OR)
X, ZnX ₂ , Cd (OR) ₂ , Cd (OR) X, CdX
_{2, B (OR) 3,} B (OR) 2 X, B (OR) X 2, BX
_{3, Al (OR) 3,} Al (OR) 2 X, Al (OR)
X ₂ , AlX ₃ , Si (OR) ₄ , Si (OR) ₃ X, Si
(OR) ₂ X ₂ , Si (OR) X ₃ , Si (OR) ₃ R, S
i (OR) ₂ R ₂ , Si (OR) R ₃ , Si (OR) ₂ X
R, Si (NR) ₃ R, Si (NR) ₂ R ₂ , Si (N
R) R ₃ , Si (NR) ₂ XR, Six ₄ , Sn (O
R) ₄ , Sn (OR) ₃ X, Sn (OR) ₂ X ₂ , Sn (O
R) Various compounds represented by X ₃ , SnX _{4 and the} like can be mentioned (R and X in the formula are the same as R ⁶ , R ⁷ and X described above). Preferred examples of these include Mg (O
C ₂ H ₅ ) ₂ , Mg (OC ₂ H ₅ ) Cl, Al (OC
_{H 3) 3, Al (OC} 2 H 5) 3, Al (On-C 3 H 7) 3,
_{Al (Oi-C 3 H 7} ) 3, Al (On-C 4 H 9) 3, Al
_{(Osec-C 4 H 9)} 3, Al (Ot-C 4 H 9) 3, Al
(OCH ₃ ) ₂ Cl, Al (OC ₂ H ₅ ) ₂ Cl, Al (O
_{C 2 H 5) Cl 2,} Al (Oi-C 3 H 7) 2 Cl, Al (O
_{i-C 3 H 7) Cl} 2, AlCl 3, AlCl 3 · OEt 2,
Al (OC ₆ H ₅ ) ₃ , Al (OC ₆ H ₅ ) ₂ Cl, Al (O
C ₆ H ₅ ) Cl ₂ , Al (OC ₆ H ₄ CH ₃ ) ₃ , Al (OC ₆
H ₄ CH ₃ ) ₂ Cl, Al (OC ₆ H ₄ CH ₃ ) Cl ₂ , Al
(OCH ₂ C ₆ H ₃ ) ₃ , Si (OC ₂ H ₅ ) ₄ Si (OC ₂ H ₅ ) ₃ Cl, Si (OC ₂ H ₅ ) ₂ Cl ₂ , S
i (OC ₂ H ₅ ) Cl ₃ , SiCl ₄ , Si (OC
_{6 H 5) 4, Si (} OC 6 H 5) 3 Cl, Si (OC 6 H 5) 2
Cl ₂ , Si (OC ₆ H ₅ ) Cl ₃ , Si (OCH ₂ C
₆ H ₅ ) ₄ and the like. In addition, (CH ₃ ) ₂ Si (OCH ₃ ) ₂ and (CH ₃ ) ₂ Si (OC _{2
H 5) 2, (C 2} H 5) 2 Si (OCH 3) 2, (C 2 H 5) 2 S
i (OC ₂ H ₅ ) ₂ , (CH ₃ ) HSi (OCH ₃ ) ₂ , (C
H ₃ ) ₂ Si (N (CH ₃ ) ₂ ) ₂ , (CH ₃ ) ₂ Si (N
(C ₂ H ₅ ) ₂ ) ₂ , (C ₂ H ₅ ) ₂ Si (N (CH ₃ ) ₂ ) ₂ ,
(C ₂ H ₅ ) ₂ Si (N (C ₂ H ₅ ) ₂ ) ₂ , (CH ₃ ) HSi
Compounds such as (N (CH ₃ ) ₂ ) ₂ can be mentioned. Of course, these compounds can be used alone or in combination of two or more.

(6) The above-mentioned titanium compound, magnesium compound, internal olefin compound, and in some cases, silicon oxide and / or aluminum oxide may be further reacted with each other by adding various organic compounds [Component VI]. Often, such organic compounds include alcohols, phenols, ethers, ketones, aldehydes, esters, amines, nitriles, halogenated hydrocarbons and the like. . Preferred specific examples of alcohols include methanol, ethanol, 1-
Propanol, 2-propanol, 1-butanol, 2
-Methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-
Butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-1-pentanol, 4-methyl- 2-pentanole, 2-ethyl-1
-Butanol, 1-heptanol, 2-heptanol,
3-heptanol, 4-heptanol, 2,4-dimethyl-3-pentanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 3,5- Dimethyl-1-hexanol, 2,2,4-trimethyl-1
-Pentanole, 1-nonanole, 5-nonano-3,5
-Dimethyl-4-heptanol, 2,6-dimethyl-4
-Heptanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, 2,6,8-trimethyl-4-nonano-
1-tridecanol, 1-pentadecanol, 1-
Hexadecanol, 1-heptadecanol, 1-octadecanol, 1-octadecanol, 1-nonadecanol
, 1-eicosanol, benzyl alcohol, methyl cellosolve or any mixture thereof. Phenols include phenol, ortho-cresol, meta-cresol, para-cresol, α-naphthol, β-naphthol, catechol, resorcinol, hydroquinone, orcin, ortho-chlorophenol, meta-chlorophenol, and para-chlorophenol. , Orthobromophenol, metabromophenol, parabromophenol, orthoiodophenol, metaiodophenol, paraiodophenol, 4-chlorometacresol and the like. For ethers, methyl ether,
Methyl ethyl ether, methyl propyl ether, methyl butyl ether, methyl pentyl ether, methyl hexyl ether, methyl phenyl ether, ethyl ether, ethyl propyl ether, ethyl butyl ether, ethyl pentyl ether, ethyl hexyl ether, ethyl phenyl ether, propyl ether, propyl butyl ether, Examples include propylpentyl ether, propylhexyl ether, diphenyl ether, tetrahydrofuran, dioxane, and the like.

Among the ketones, acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl pentyl ketone, methyl hexyl ketone, methyl phenyl ketone, diethyl ketone, ethyl propyl ketone, ethyl butyl ketone, ethyl pentyl ketone, ethyl hexyl ketone, ethyl hexyl ketone, ethyl Examples include phenyl ketone, dipropyl ketone, propyl butyl ketone, propyl pentyl ketone, propyl hexyl ketone, cyclohexanone, and benzophenone. Aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeroaldehyde, caproaldehyde, benzaldehyde and the like. Esters include methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate, di-propyl benzoate, butyl benzoate Hexyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoic acid 4
-Tolyl, methyl salicylate, ethyl salicylate, p-
Methyl oxybenzoate, ethyl p-oxybenzoate, phenyl salicylate, cyclohexyl p-oxybenzoate, salicyl sampenzil, ethyl α-resorcinate,
Methyl anisate, ethyl anisate, phenyl anisate,
Benzyl anisate, ethyl o-methoxybenzoate, p-
Methyl ethoxybenzoate, p-methyl toluate, p-
Ethyl toluate, phenyl p-toluate, ethyl o-toluate, ethyl m-toluate, methyl p-aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, naphthoic acid Methyl, ethyl naphthoate and the like can be mentioned.

Examples of the amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, trifluoroethylamine, pyridine and piperidine. Examples of the nitriles include acetonitrile, propionitrile, acetonitrile, benzonitrile and the like. In the halogenated hydrocarbons, methyl chloride, ethyl chloride, propyl chloride, butyl chloride, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, methyl iodide, ethyl iodide, propyl iodide,
Butyl iodide, 1,1-dichloroethane, 1,2
-Dichloroethane, 1,1-dichloropropane, 1,2
-Dichlorpropane, 1.3-dichloropropane, 1,
1-dichlorobutane, 1,2-dichlorobutane, 1.3
-Dichlorobutane, 1.4-dichlorobutane, phenyl chloride, benzyl chloride and the like.
Of course, these compounds can be used alone or in combination of two or more.

(7) In addition to the above titanium compound, magnesium compound, internal olefin compound, and in some cases, silicon oxide and / or aluminum oxide, a compound of the general formula Al (OR ⁸ ) _p R ⁹ _q X _{3- (p + q} (Wherein R ⁸ and R ⁹ have 1 to 24 carbon atoms, preferably 1 to 1 carbon atoms ₎
R ⁸ and R ⁹ may be the same or different, X represents a hydrogen atom or a halogen atom, and p and q are 0 ≦ p <3, 0 <q ≦ 3. 0 <p + q ≦
The organoaluminum compound [component VII] represented by 3) may be added and reacted with each other. Such hydrocarbon residues are preferably those having 1 to 12 carbon atoms,
For example, an alkyl group, an aryl group, an aralkyl group, and the like, and examples of the alkyl group include a methyl group, an ethyl group,
Propyl, i-propyl, butyl, s-butyl, t-
As a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like, the aryl group is a phenyl group, a tolyl group, a xylyl group, and the like, and the aralkyl group is, for example, a benzyl group. chlorine,
Bromine, iodine and the like can be mentioned. Specific examples of these organoaluminum compounds include dimethylaluminum methoxide, dimethylaluminum ethoxide, dimethylaluminum isoproxide, dimethylaluminum t-butoxide, dimethylaluminum n-butoxide, dimethylaluminum sec-butoxide, and diethylaluminum methoxide. , Diethylaluminum ethoxide, diethylaluminum isoproxide, diethylaluminum n-butoxide, diethylaluminum sec-butoxide, diethylaluminum cyclohexyloxide, diethylaluminum t-butoxide,
Dipropylaluminum ethoxide, dipropylaluminum t-butoxide, dibutylaluminum t-butoxide, dii-butylaluminum methoxide, dii-
Butylaluminum ethoxide, dii-butylaluminum isopropoxide, dii-butylaluminum-i
-Butoxide, di-i-butylaluminum-t-butoxide, di-t-butylaluminum methoxide, di-t-
Butyl aluminum ethoxide, di-t-butyl aluminum t-butoxide, dimethyl aluminum phenoxide, di-n-hexyl aluminum ethoxide, di-n-hexyl aluminum isopropoxide, ethyl ethoxy aluminum chloride, isobutyl ethoxy aluminum chloride, ethyl phenoxy aluminum chloride, Phenylethoxyaluminum chloride, ethylethoxyaluminum hydride, ethylmethoxyaluminum chloride, ethylisopropoxyaluminum dichlorideethylbutoxyaluminum chloride, phenylaluminum dichloride, diphenylaluminum chloride, benzylaluminum dichloride,
Dibenzylaluminum chloride, dimethylaluminum chloride, diethylaluminum fluoride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, dii-butylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide, Methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, trimethylaluminum, triethylaluminum, trin-propylaluminum, trin-butylaluminum, triisobutylaluminum, trin-hexylaluminum, trin-octylaluminum, or any of these Mixtures. Methyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-hexyl aluminum, diethyl aluminum chloride,
Ethyl aluminum sesquichloride and ethyl aluminum dichloride are preferred. Of course, these compounds may be used alone or in combination of two or more.

(8) The reaction ratio of each component is not particularly limited, but the following ratios can be used. 1) [Component II] / [Component I] (molar ratio) = 0.001-
1000, preferably 0.01 to 100, more preferably 0.05 to 102) [Component I] / [Component III] (mmol / g) = 0.
01 to 20, preferably 0.1 to 10, more preferably 0.2 to 43 3) [Component IV] / [Component II] (molar ratio) = 0.01 to 1
000, preferably 0.05 to 100, more preferably 0.1 to 104) [Component V] / [Component I] (molar ratio) = 0.01 to 1
00, preferably 0.05 to 10, more preferably 0.1 to 55 5) [Component VI] / [Component I] (molar ratio) = 0.01 to 1
00, preferably 0.05 to 10, more preferably 0.1 to 56) [Component VII] / [Component II] (molar ratio) = 0.01 to
100, preferably 0.05 to 10, more preferably 0.1 to 5 (9) Preparation of solid catalyst component The present invention provides at least a magnesium compound and a titanium compound, and optionally a silicon compound and / or an aluminum compound, in contact with each other. The solid catalyst component is obtained by contacting an internal olefin that is not substantially polymerized during the production of the component. The order of contact of the components is not particularly limited, and examples thereof include the following order. 1) After contacting [Component I] and [Component II], [Component I]
V]. [Component I] → [Component II] → [Component IV] 2) After contacting [Component I] and [Component IV], [Component I]
I]. [Component I] → [Component IV] → [Component II] 3) After bringing [Component II] and [Component IV] into contact, contact [Component I]. {[Component II] + [Component IV]} → [Component I] 4) Contact [Component I], [Component II] and [Component IV] simultaneously. {[Component I] + [Component II] + [Component IV]} 5) Contact [Component III] with [Component I], then contact [Component II], and finally contact with [Component IV]. [Component III] → [Component I] → [Component II] → [Component IV] 6) Contact [Component III] with [Component II], then contact [Component IV], and finally with [Component I]. Make contact. [Component III] → [Component II] → [Component IV] → [Component I] 7) Contact [Component III] with [Component IV], then contact [Component I], and finally with [Component II] Make contact. [Component III] → [Component IV] → [Component I] → [Component II] 8) Contact [Component I] with [Component II] and then contact [Component
III] and finally with [Component IV]. {[Component I] + [Component II]} → [Component III] → [Component I
V] 9) [Component I] and [Component IV] are brought into contact, and then [Component
III] and finally with [Component II]. {[Component I] + [Component IV]} → [Component III] → [Component I
I] 10) Contact [Component I] with [Component IV], then contact [Component III], and finally contact with [Component II]. {[Component I] + [Component IV]} → [Component III] → [Component I
I] 11) Contact [Component I], [Component II] and [Component IV], and then contact [Component III]. {[Component I] + [Component II] + [Component IV]} → [Component II
I] The inorganic compound ([Component V]), the organic compound ([Component VI]), and the organometallic compound ([Component VII]), which are optional components, are brought into contact with each other in an arbitrary order with respect to the contact order of the above essential components. be able to. The same component may be contacted two or more times.

The preferred order of contact is as follows. 1) [Component I] → [Component V] → [Component II] → [Component IV] 2) [Component I] → [Component V] → [Component V] → [Component II]
→ [Component IV] 3) [Component I] → [Component V] → [Component IV] → [Component II] 4) [Component I] → [Component V] → [Component II] → [Component VI]
I] → [Component IV] 5) [Component I] → [Component V] → [Component V] → [Component II]
→ [Component VII] → [Component IV] 6) [Component I] → [Component V] → [Component II] → [Component VI]
→ [Component VII] → [Component IV] 7) [Component I] → [Component V] → [Component V] → [Component II]
→ [Component II] → [Component IV] 8) [Component I] → [Component VI] → [Component II] → [Component IV] 9) [Component I] → [Component VI] → [Component II] → [Component VI
I] → [Component IV] 10) [Component I] → [Component VI] → [Component V] → [Component I
I] → [Component IV] 11) [Component III] → [Component I] → [Component II] → [Component V]
II] → [Component IV] 12) [Component III] → {[Component I] + [Component V]} →
[Component II] → [Component VII] → [Component IV] 13) [Component III] → {[Component I] + [Component V]} →
[Component II] → [Component V] → [Component VII] → [Component IV] 14) [Component III] → {[Component I] + [Component V]} →
[Component II] → [Component V] → [Component II] → [Component VII] →
[Component IV] 15) [Component III] → {[Component I] + [Component V] + [Component II] + [Component VI]} → [Component VII] → [Component IV] 16) [Component III] → ｛ [Component I] + [Component V] + [Component II] + [Component VI]｝ → [Component VII] → [Component V] →
[Component IV] 17) [Component III] → [Component II] → [Component VII] → {[Component I] + [Component V]} → [Component IV] 18) [Component III] → [Component II] → [Component II] Component IV] → {[Component I] + [Component V] + [Component II]} → [Component VII] →
[Component V]

In the present invention, the reaction method for producing the solid catalyst component is not particularly limited, but the magnesium compound [component I] and the titanium compound [component I] in the presence or absence of an inert hydrocarbon solvent. Essential components such as Component II] and an internal olefin compound [Component IV] and optional components such as an inorganic compound [Component V], an organic compound [Component VI], and an organometallic compound [Component VII] are heated to a temperature of 0 to 200.
For 30 minutes to 50 hours, a method of co-grinding using a ball mill, a vibration mill, a rod mill, an impact mill, or the like may be used. General benzene such as benzene, toluene, xylene, or a mixture thereof
So-called inert hydrocarbons which are inert to the gray catalyst, alcohols described above (for example, as described in [Component VI]), phenols
, Ethers, ketones, esters, amines,
A method of mixing and reacting at a temperature of 0 to 400 ° C., preferably 20 to 300 ° C. for 5 minutes to 10 hours in an organic solvent composed of nitriles or the like or a mixture thereof, and then evaporating and removing the solvent may be used. . However, when the above-mentioned organoaluminum compound is brought into contact, it is preferably carried out in an organic solvent. When a silicon oxide and / or an aluminum oxide [component III] is added as a solid catalyst component and reacted with each other, a method of reacting in an organic solvent is preferable. Each reaction operation relating to the preparation of the solid catalyst component should be performed in an inert gas atmosphere, and it is desirable to avoid moisture as much as possible.

<2> Organometallic Compound The catalyst used in the present invention comprises the solid catalyst component and an organometallic compound, and the organometallic compound is known as one component of a Ziegler catalyst. Group III organometallic compounds can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formulas R ₃ Al, R ₂ AlX, RAlX _{2 ,} R ₂ AlOR,
RAl (OR) X and organoaluminum compounds of R ₃ Al ₂ X ₃ (where R represents an alkyl group or aryl group having 1 to 20 carbon atoms, X represents a halogen atom, and R may be the same or different) ) Or the general formula R ₂ Zn (where R
Is an alkyl group having 1 to 20 carbon atoms, which may be the same or different), and is represented by trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisec-butyl Aluminum, tri-t
Examples thereof include tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sexchloride, diethylzinc and a mixture thereof. The amount of the organometallic compound used is not particularly limited, but is usually 0.1 to
1000 mol times can be used. In the present invention, the organometallic compound component can also be preferably used as a mixture or an addition compound of the organometallic compound and an organic acid ester. At this time, when the organic metal compound and the organic acid ester are used as a mixture, the organic acid ester is used in an amount of usually 0.1 to 1 mol, preferably 0.2 to 0.5 mol, per 1 mol of the organic metal compound. . When the compound is used as an addition compound of an organic metal compound and an organic acid ester, the organic compound preferably has a molar ratio of the organic metal compound: organic acid ester of 2: 1 to 1: 2.
The organic acid ester used at this time has a carbon number of 1 to 1.
It is an ester of a saturated or unsaturated monobasic or dibasic organic carboxylic oxygen having 24 carbon atoms and an alcohol having 1 to 30 carbon atoms. Specifically, methyl formate, ethyl acetate,
Amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate, di-propyl benzoate, butyl benzoate, hexyl benzoate, cyclopentyl benzoate, benzoate Cyclohexyl acid, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, phenyl salicylate, cyclohexyl p-oxybenzoate, salicylsanpendyl, α-resorcinol Ethyl acrylate, methyl anisate, ethyl anisate, phenyl anisate, benzyl anisate, ethyl o-methoxybenzoate, methyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, phenyl p-toluate , O-torui Acid ethyl, ethyl m- toluic acid,
Examples thereof include methyl p-aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, methyl naphthoate, and ethyl naphthoate. Of these, particularly preferred are alkyl esters of benzoic acid, o- or p-tolylic acid or p-anisic acid, and particularly methyl esters of these.
Ethyl esters are preferred.

<3> Polymerization of Olefin Polymerization of olefin using the catalyst of the present invention is carried out by slurry.
It can be carried out by polymerization, solution polymerization or gas phase polymerization.
That is, all reactions are carried out in the presence or absence of inert hydrocarbons with substantially no oxygen, water or the like. The polymerization conditions for the olefin are as follows.
C., preferably 50 to 110 ° C., and the pressure is from normal pressure to 70 kg / cm ² , preferably 2 to 60 kg / cm ² . The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but can be effectively controlled by adding hydrogen to the polymerization system.
Of course, using the catalyst of the present invention, the polymerization reaction in two or more stages having different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any trouble. The method of the present invention Chigura - is applicable to the polymerization of all olefins that can be polymerized with the catalyst, particularly preferably a α- olefin having 2 to 12 carbon atoms, such as ethylene homopolymers and ethylene and propylene, ethylene and 1-butene , ethylene and hexene-1, ethylene and 4-methylpentene-1, etc. of ethylene and co-Polymerization of α- olefins having 3 to 12 carbon atoms, Contact <br/> preliminary ethylene and the other two or more α- olefins It is suitably used for copolymerization with In particular, the homopolymerization of ethylene and the α-olefin content in the ethylene / α-olefin copolymer are usually 20 mol% or less, preferably 0 to 0 mol%.
It is desirable that the content be 10 mol%, more preferably 0 to 5 mol%. Copolymerization with a diene for the purpose of modifying polyolefin is also preferably performed. As the diene compound used at this time, for example, butadiene, 1,
4-hexadiene, ethylidene norbornene, dicyclopentadiene and the like can be mentioned.

[0017]

According to the method of the present invention, a homopolymer of α-olefin or a copolymer of ethylene and α-olefin can be obtained with high activity, particularly, homopolymerization of ethylene or ethylene and a small amount of α-olefin. Is very highly active, and the resulting polyolefin has a high bulk specific gravity and good free-flowing properties, making it very advantageous in polymerization operations. However, it can be used for molding, there is little trouble during molding, and polyolefin can be produced very advantageously.

[0018]

The present invention will be described in more detail with reference to the following Examples, which are merely illustrative of the present invention and are not intended to limit the present invention. Example 1 (a) Production of solid catalyst component 15 g of commercially available anhydrous magnesium chloride was placed in a stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls having a diameter of 1/2 inch. 6.3 g of triethoxyaluminum and 9.0 of titanium tetrachloride
g of the mixture was ball-milled at room temperature for 16 hours in a nitrogen atmosphere to obtain a solid powder. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen. 20 g of the above solid powder, 100 cc of dehydrated hexane and 1.0 g of ethanol were added thereto, and 6.2 g of diethylaluminum chloride was added thereto. After reacting for 1 hour and further adding 14.7 g of cis-2-heptene and reacting for 1.5 hours, nitrogen blowing was carried out under heating to remove the solvent component to obtain a solid catalyst component. 1 mg of the obtained solid catalyst component contained 36 mg of titanium. (B) Slurry polymerization A 2 l stainless steel autoclave equipped with an electromagnetic induction stirrer was thoroughly dried, and dried hexane 10
00 ml, 1 mmol of triethylaluminum and 10 mg of the solid catalyst component were added, and the internal temperature was raised to 90 ° C. Although the internal pressure becomes 2 kg / cm ² , the total pressure of hydrogen is 5 k
g / cm ^2, and then add 10 kg of ethylene.
/ Cm ² to initiate polymerization. Total pressure is 10kg /
Ethylene was continuously introduced so as to obtain cm ^2, and polymerization was carried out for 1 hour. Thereafter, methanol was added to stop the polymerization, hexane was removed by evaporation, and white polyethylene powder 22 was added.
0 g was obtained. Polymerization activity is 122,000 gPE / gT
i, hr, ethylene pressure, 4,400 gPE / gcat,
hr, ethylene pressure, catalyst efficiency 611,000 g
The activity was extremely high with PE / gTi. The produced ethylene polymer is melt-flow rate (MFR) [AST
M-D1238-65T, 190 ° C, 2.16 kg load] is 5.4 g / 10 min, and the density is 0.9663 g /
a cm @ 3, the bulk density was 0.37 g / cm ^3. When the branches in the produced polymer were examined by 13 C-NMR, it was found to be 0.1 or less per 1,000 carbon atoms.

Example 2 A solid catalyst component was prepared in the same manner as in Example 1 except that 7.4 g of cis-2-heptene was used. 4 g / g of the solid catalyst component obtained
It contained 3 mg of titanium. Slurry polymerization was carried out under the same conditions as in Example 1 to obtain a white polyethylene powder of 19%.
6 g were obtained. The polymerization activity was 91,200 gPE / gTi,
hr, ethylene pressure, 3,920 gPE / gcat, h
r, ethylene pressure, catalyst efficiency 455,000 gP
The activity was extremely high with E / gTi. Melt flow rate (MFR) of the produced ethylene polymer was 5.2 g /
At 10 minutes, the density was 0.9661 g / cm3 and the bulk density was 0.36 g / cm3. Example 3 In Example 1, 1 was used instead of cis-2-heptene.
A solid catalyst component was prepared as in Example 1, except that 2.6 g of cis-2-hexene was used. The obtained solid catalyst component contained 38 mg of titanium per gram. Slurry polymerization was carried out under the same conditions as in Example 1 to obtain 215 g of a white polyethylene powder. The polymerization activity was 113,000 gPE / gTi, hr, ethylene pressure and 4,300 gPE / gcat, hr, ethylene pressure, and the catalyst efficiency was extremely high, 566,000 gPE / gTi. The resulting ethylene polymer has a melt flow rate (MFR) of 6.1 g / 10 min, a density of 0.9664 g / cm3 and a bulk density of 0.37 g / cm3.
cm3. Example 4 (a) Production of solid catalyst component 15 g of commercially available anhydrous magnesium chloride was placed in a stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls having a diameter of 1/2 inch. 6.3 g of triethoxyaluminum and 9.0 of titanium tetrachloride
g of the resulting solution was subjected to ball milling at room temperature for 16 hours in a nitrogen atmosphere. 14.0 g of cis-2-heptene was added thereto, and further ball milling was performed at room temperature for 16 hours to obtain a solid powder. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 20 g of the above solid powder, 100 cc of dehydrated hexane and 1.0 g of ethanol were added thereto, followed by 6.2 g of diethylaluminum chloride. After reacting for 5 hours, nitrogen blowing was performed under heating, and the solvent component was removed to obtain a solid catalyst component. The solid catalyst component contained 38 mg of titanium per gram. (B) Slurry polymerization Slurry polymerization was performed under the same conditions as in Example 1 to obtain 205 g.
A white polyethylene powder was obtained. The polymerization activity is 107,
000gPE / gTi, 4,100gPE / gca
t, hr, ethylene pressure, catalyst efficiency 539,00
The activity was extremely high at 0 gPE / gTi. The melt flow rate (MFR) of the produced ethylene polymer is 6.
1 g / 10 min, the density was 0.9665 g / cm ³ , and the bulk density was 0.35 g / cm ³ . ¹³ C-
When the branch in the produced polymer was examined by NMR,
0.1 or less per 000 carbons.

Comparative Example 1 A solid catalyst component was prepared in the same manner as in Example 1 except that cis-2-heptene was not used. The obtained solid catalyst component contained 55 mg of titanium per gram. Slurry polymerization was carried out under the same conditions as in Example 1 to obtain 123 g of a white polyethylene powder. The polymerization activity was 45,000 gPE / gTi, 2,5
The catalyst efficiency was 224,000 gPE / gTi, which was lower than those of Examples 1 to 4, which was 00 gPE / gcat, hr and ethylene pressure. Melt flow rate (MFR) of the produced ethylene polymer is 5.8 g / 10 min,
The density is 0.9660 g / cm ³ and the bulk density is 0.3
It was 5 g / cm ³ . Comparative Example 2 In Example 1, 14.7 g of trans-2-hexene was used.
A solid catalyst component was prepared as in Example 1 except that was used. The obtained solid catalyst component contained 36 mg of titanium per gram. Slurry polymerization was carried out under the same conditions as in Example 1 to obtain a white polyethylene powder 85
g was obtained. The polymerization activity is 47,000 gPE / gTi, h
r, ethylene pressure, 1,700 gPE / gcat, hr,
The ethylene pressure is ri and the catalyst efficiency is 236,000 gP
The activity was lower than E / gTi and Examples 1-4.
Melt flow rate of the produced ethylene polymer (MF
R) is 5.4 g / 10 min, and the density is 0.9662 g /
cm ³ and a bulk density of 0.36 g / cm ³ . Example 5 (a) Production of solid catalyst component A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 10 g of commercially available anhydrous magnesium chloride was placed therein.
And dried under vacuum at 150 ° C. for 3 hours. Then, 33.6 g of ethanol was added, and the mixture was stirred at 100 ° C. to dissolve magnesium chloride, and 35.5 g of silicon tetrachloride was added dropwise over 10 minutes. After the completion of the dropwise addition, the reaction was further performed for 1 hour, followed by drying under reduced pressure at 250 ° C. to obtain a white powdery reaction product. 50m of titanium tetrachloride is added to the obtained white powder.
1 was added and reacted at 130 ° C. for 1 hour. After the completion of the reaction, the resultant was washed with hexane, and the washing was repeated until no titanium tetrachloride was found in the washing solution. Next, 50 ml of hexane and 2.0 g of cis-2-heptene were added, reacted at room temperature for 1.5 hours, and then subjected to nitrogen blowing under heating to remove a solvent component, thereby obtaining a solid catalyst component. 1 g per 1 g of the obtained solid catalyst component
It contained 4.5 mg of titanium. (B) Slurry polymerization Using the same autoclave as in Example 1, 1000 ml of dry hexane and 5 m of triethylaluminum were placed therein.
mol and 95 mg of the solid catalyst component were added, and the internal temperature was raised to 90 ° C. Although the internal pressure became 2 kg / cm ² , hydrogen was added until the total pressure became 6 kg / cm ² , and ethylene was further pressurized to 10 kg / cm ² to start polymerization. Ethylene was continuously introduced so that the total pressure became 10 kg / cm ^2, and polymerization was carried out for 15 minutes. Thereafter, methanol was added to stop the polymerization, and hexane was removed by evaporation to obtain 190 g of a white polyethylene powder. The polymerization activity is 138,000 g
PE / gTi, hr, ethylene pressure, 2,000 gPE /
gcat, hr, ethylene pressure, catalyst efficiency is 13
The activity was extremely high at 8,000 gPE / gTi.
Melt flow rate of the produced ethylene polymer (MF
R) is 10.9 g / 10 min, density is 0.9665 g
/ Cm ³ and the bulk density was 0.36 g / cm ³ . When the branches in the produced polymer were examined by ¹³ C-NMR, it was found to be 0.1 or less per 1,000 carbon atoms.

Comparative Example 3 A solid catalyst component was prepared in the same manner as in Example 5, except that cis-2-heptene was not used. 1 g of this solid catalyst component contained 15.5 mg of titanium. Slurry polymerization was carried out under the same conditions as in Example 1 to obtain 135 g of a white polyethylene powder. The polymerization activity was 72,000 gPE / gTi, hr, ethylene pressure,
Example 5 was 1,100 gPE / gcat, hr, ethylene pressure, and the catalyst efficiency was 72,000 gPE / gTi.
The activity was lower than that of. The resulting ethylene polymer has a melt flow rate (MFR) of 12.8 g / 10 mi.
n, the density was 0.9667 g / cm ³ , and the bulk density was 0.33 g / cm ³ . Example 6 A solid catalyst was prepared in the same manner as in Example 5 except that 50 ml of monoethoxytrichlorotitanium was used instead of titanium tetrachloride and 3.7 g of cis stilbene was used instead of cis-2-heptene. The components were prepared. The obtained solid catalyst component contained 12.4 mg of titanium per gram. Slurry polymerization was carried out under the same conditions as in Example 5 to obtain 155 g of a white polyethylene powder. The polymerization activity was 132,000 gPE / gTi, hr, ethylene pressure, 1600 gPE / gcat, hr, ethylene pressure, and the catalytic efficiency was extremely high, 132,000 gPE / gTi. The resulting ethylene polymer has a melt flow rate (MFR) of 8.5 g / 10 min, a density of 0.9667 g / cm ³ and a bulk density of 0.35.
g / cm ³ . In addition, when the branch in the produced polymer was examined by ¹³ C-NMR, it was found that the number of branches per 1,000 carbons was 0.1.
There was one or less. Comparative Example 4 A solid catalyst component was prepared in the same manner as in Example 6, except that cis stilbene was not used.
The obtained solid catalyst component contained 16.0 mg of titanium per gram. Slurry polymerization was carried out under the same conditions as in Example 5 to obtain 97 g of a white polyethylene powder.
The polymerization activity was 64,000 gPE / gTi, hr, ethylene pressure and 1,020 gPE / gcat, hr, ethylene pressure, and the catalyst efficiency was 64,000 gPE / gTi, which was lower than that of Example 6. The resulting ethylene polymer has a melt flow rate (MFR) of 9.1 g / 10 m.
in, density is 0.9668g / cm ^3, had a bulk density of 0.33g / cm ^3. Example 7 (a) Production of solid catalyst component Magnesium oxide (Iodine adsorption amount 18 mg / g MgO)
And dried under vacuum at 150 ° C. for 1 hour. Then, 50 ml of hexane was added to suspend magnesium oxide in hexane, 5 ml of aluminum chloride diethyl etherate was added, and the mixture was stirred under reflux of hexane for 2 hours. After completion of the reaction, hexane was removed in vacuo, 50 ml of titanium tetrachloride was added, and the mixture was reacted at 130 ° C. for 1 hour. After the completion of the reaction, the resultant was washed with hexane, and the washing was repeated until no titanium tetrachloride was found in the washing solution. Next, 50 ml of hexane and 2.0 g of cis-2-heptene were added, reacted at room temperature for 1.5 hours, and then subjected to nitrogen blowing under heating to remove a solvent component, thereby obtaining a solid catalyst component. In 1 g of the obtained solid catalyst component, 7.
It contained 8 mg of titanium. (B) Slurry polymerization Using the same autoclave as in Example 1, 1000 ml of dry hexane and 5 m of triethylaluminum were placed therein.
mol and 763 mg of the above solid catalyst component were added, and the internal temperature was raised to 90 ° C. The internal pressure becomes 2 kg / cm ² ,
Hydrogen was added until the total pressure reached 6 kg / cm ² , and ethylene was further pressurized to 10 kg / cm ² to initiate polymerization. Ethylene was continuously introduced so that the total pressure became 10 kg / cm ^2, and polymerization was carried out for 30 minutes. Thereafter, methanol was added to stop the polymerization, and hexane was removed by evaporation to obtain 245 g of a white polyethylene powder. Polymerization activity is 20,6
00gPE / gTi, hr, ethylene pressure, 320gPE
/ Gcat, hr, ethylene pressure and catalyst efficiency is 4
It was 1,200 gPE / gTi. The resulting ethylene polymer had a melt flow rate (MFR) of 15.6 g /
10min, density of 0.9668g / cm ^3, bulk density was 0.34 g / cm ^{3. 13} C-NM
When the branch in the produced polymer was examined by R, 100
It was 0.1 or less per 0 carbon.

Comparative Example 5 A solid catalyst component was prepared in the same manner as in Example 7, except that cis-2-heptene was not used. The resulting solid catalyst component contained 9.8 mg titanium / g. Slurry polymerization was carried out under the same conditions as in Example 7 to obtain 214 g of a white polyethylene powder. The polymerization activity was 14,300 gPE / gTi, hr, ethylene pressure, 140 gPE / gcat, hr, ethylene pressure, and the catalyst efficiency was 28,600 gPE / gTi, which was lower than that of Example 7. The resulting ethylene polymer has a melt flow rate (MFR) of 18.9 g / 10
min, density of 0.9670g / cm ^3, bulk density was 0.32 g / cm ^3. Example 8 (a) Production of solid catalyst component A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen. 1
Mol), and add orthochlorophenol 1 with stirring.
2.9 g (0.1 mol) were added. After reacting for 1 hour under reflux of diethyl ether, titanium tetrachloride 80 ml
(0.73 mol) was added. Then, the temperature of the bath was raised to 150 ° C., and the reaction was carried out for 2 hours. The supernatant was removed by decantation, and hexane was newly added to wash the reaction product. After repeating this washing operation until free titanium tetrachloride disappeared, hexane was distilled off to obtain a fine solid catalyst. Next, 50 ml of hexane and 15.3 g of cis-2-heptene were added, and the mixture was reacted at room temperature for 1.5 hours. Thereafter, nitrogen was blown under heating to remove a solvent component, thereby obtaining a solid catalyst component. 5 g are contained in 1 g of the obtained solid catalyst component.
It contained 3.0 mg of titanium. (B) Slurry polymerization Using the same autoclave as in Example 1, 1000 ml of dry hexane and 5 m of triethylaluminum were placed therein.
mol and 93 mg of the solid catalyst component were added, and the internal temperature was raised to 90 ° C. Although the internal pressure became 2 kg / cm ² , hydrogen was added until the total pressure became 6 kg / cm ² , and ethylene was further pressurized to 10 kg / cm ² to start polymerization. Ethylene was continuously introduced so that the total pressure became 10 kg / cm ^2, and polymerization was carried out for 15 minutes. Thereafter, methanol was added to terminate the polymerization, and hexane was removed by evaporation to obtain 147 g of a white polyethylene powder. Polymerization activity is 29,800 gP
E / gTi, hr, ethylene pressure, 1,600 gPE / g
cat, hr, ethylene pressure and catalyst efficiency is 29,8
The activity was extremely high at 00 gPE / gTi. The resulting ethylene polymer has a melt flow rate (MFR) of 9.3 g / 10 min and a density of 0.9669 g / cm ^3.
And the bulk density was 0.34 g / cm ³ . Note that
^When branches in the produced polymer were examined by ¹³ C-NMR, the number was 0.1 or less per 1000 carbon atoms. Comparative Example 6 A solid catalyst component was prepared in the same manner as in Example 8, except that cis-2-heptene was not used. The obtained solid catalyst component contained 74 mg of titanium per gram. Slurry polymerization was carried out under the same conditions as in Example 8 to obtain 127 g of a white polyethylene powder. The polymerization activity was 18,500 gPE / gTi, hr, ethylene pressure, 1,370 gPE / gcat, hr, ethylene pressure, and the catalyst efficiency was 18,500 gPE / gTi, which was lower than that of Example 8. Melt flow rate (MFR) of the produced ethylene polymer was 11.2 g /
10min, density of 0.9665g / cm ^3, bulk density was 0.32 g / cm ^3.

Example 9 A solid catalyst component was prepared under the same conditions as in Example 1. Using the same autoclave as in Example 1, 1000 ml of dry hexane and 5 mmol of triethylaluminum were placed therein.
and the solid catalyst component (10 mg) were added, and the internal temperature was reduced to 70
° C. Although the internal pressure becomes 1.5 kg / cm ² , hydrogen is added to make the total pressure 3.0 kg / cm ^2, and 40 g of 1-butene is injected together with ethylene to make the total pressure 6 kg / cm ^2.
The polymerization was started by applying pressure until the pressure reached m ² . Total pressure 6kg /
Ethylene was continuously introduced so as to obtain cm ^2, and polymerization was carried out for 1 hour. Thereafter, methanol was added to stop the polymerization, hexane was removed by evaporation, and white polyethylene powder 18 was added.
6 g were obtained. Polymerization activity is 172,000 gPE / gT
i, hr, ethylene pressure, 6,200 gPE / gcat,
hr, ethylene pressure, catalyst efficiency 517,000 g
The activity was extremely high with PE / gTi. The melt flow rate (MFR) of the produced ethylene polymer is 1.7 g.
/ 10 min, the density is 0.9228 g / cm ³ ,
The bulk density hs was 0.38 g / cm ³ . Comparative Example 7 A solid catalyst component was prepared under the same conditions as in Comparative Example 1. Slurry polymerization was carried out under the same conditions as in Example 9 to obtain 230 g of a white polyethylene powder. Polymerization activity is 139,000
gPE / gTi, hr, ethylene pressure, 7,670 gPE
/ Gcat, hr, ethylene pressure, and the catalyst efficiency is 41.
The activity was 8,000 gPE / gTi, which was lower than that of Example 9. The resulting ethylene polymer has a melt flow rate (MFR) of 1.9 g / 10 min, a density of 0.9210 g / cm ³ and a bulk density of 0.37 g / cm3.
cm ³ . Example 10 (a) Production of solid catalyst component 15 g of commercially available anhydrous magnesium chloride was placed in a stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls having a diameter of 1/2 inch. Then, 6.3 g of triethoxyaluminum was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product.
A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 100 g of dehydrated butanol and 12.8 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum were placed therein. Allowed to react for hours.
After cooling to room temperature, 45 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, reacted again at 80 ° C. for 2 hours, and dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, 50 g of the above solid powder was added thereto, and 100 cc of dehydrated hexane and 4.8 g of titanium tetrachloride were added thereto and reacted at 120 ° C for 1.5 hours. . After cooling to room temperature, 11.6 g of cis-2-heptene was added, and the mixture was stirred at room temperature for 1.5 hours, and then subjected to nitrogen blowing under heating.
The solvent component was removed to obtain a solid catalyst component. The obtained solid catalyst component contained 19 mg of titanium per gram. (B) Gas phase polymerization As a gas phase polymerization apparatus, a stainless steel oven equipped with a stirrer is used.
A loop was made with a blower, a flow controller and a dry cyclone using a crepe, and the auto crepe was controlled by flowing hot water through the jacket. 250 m of the above solid catalyst component was placed in an autoclave adjusted to 80 ° C.
g / hr and 50 mmol of triethylaluminum
/ Hr, while supplying each gas while adjusting the hydrogen in the autoclave gas phase to 50% of the total pressure, while maintaining the total pressure at 8 kg / cm ² G. The gas in the system was circulated by a blower, and continuous polymerization was carried out for 10 hours while intermittently extracting the produced polymer. The catalyst efficiency was as high as 305,000 g polymer / gTi. The produced ethylene polymer had a melt flow rate (MFR) of 4.5 g / 10 min and a density of 0.966.
It was 5 g / cm ³ , and was a round granular material having a bulk density of 0.39 g / cm ³ . In addition, when the branch in the produced polymer was examined by ¹³ C-NMR, it was found that the number of branches per 1,000 carbons was 0.1.
There was one or less.

Example 11 A solid catalyst component was prepared in the same manner as in Example 10, except that 9.9 g of cis-2-hexene was used instead of cis-2-heptene. The obtained solid catalyst component contained 21 mg of titanium per gram. Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 10. The catalyst efficiency is 288,000 gP
The activity was extremely high with E / gTi. The resulting ethylene polymer has a melt flow rate (MFR) of 5.5 g /
10min, density of 0.9664g / cm ^3, was bulk density 0.38 g / cm ^3. Example 12 In Example 10, 2 was substituted for cis-2-heptene.
Example 1 except that 1.2 g of cis stilbene was used
A solid catalyst component was prepared in the same manner as in Example 1. The obtained solid catalyst component contained 14 mg of titanium per gram.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 10. The catalyst efficiency is 253,000 gPE /
It was very active with gTi. Melt flow rate (MFR) of the produced ethylene polymer is 5.1 g / 10
min, density of 0.9669g / cm ^3, bulk density was 0.37 g / cm ^3. Example 13 (a) Production of solid catalyst component 15 g of commercially available anhydrous magnesium chloride was placed in a stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls having a diameter of 1/2 inch. And 6.3 g of triethoxyaluminum, and under a nitrogen atmosphere,
Ball milling was performed at room temperature for 16 hours to obtain a reaction product. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, into which 100 g of dehydrated butanol and 12.8 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum were added and reacted at 80 ° C. for 1 hour. Was. After cooling to room temperature, 45 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, and the mixture was again heated to 80 ° C.
With cis-2-heptene 11.6.
g was added and reacted at 80 ° C. for 1.5 hours. Then 120
Drying under reduced pressure at 2 ° C. for 2 hours gave a solid powder. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, 50 g of the above solid powder was added thereto, and 100 cc of dehydrated hexane and 4.8 g of titanium tetrachloride were added thereto and reacted at 120 ° C. for 1.5 hours. Then, nitrogen blowing under heating,
The solvent component was removed to obtain a solid catalyst component. The obtained solid catalyst component contained 17 mg of titanium per gram. (B) Gas phase polymerization Using the above solid catalyst component, gas phase polymerization was performed under the same conditions as in Example 10. The catalyst efficiency is 277,000 gPE /
It was very active with gTi. The resulting ethylene polymer has a melt flow rate (MFR) of 4.9 g / 10
min, density of 0.9664g / cm ^3, bulk density was 0.39 g / cm ^3. When the branches in the produced polymer were examined by ¹³ C-NMR, it was found to be 0.1 or less per 1,000 carbon atoms.

Comparative Example 8 Example 1 except that no cis-2-heptene was used.
A solid catalyst component was prepared in the same manner as in Example 1. The obtained solid catalyst component contained 23.5 mg of titanium per gram. Gas phase polymerization was carried out under the same conditions as in Example 10 using the above solid catalyst component. Catalyst efficiency is 149,000 gP
The catalyst efficiency was lower than E / gTi and Examples 10-13. The resulting ethylene polymer has a melt flow rate (MFR) of 4.8 g / 10 min and a density of 0.5 g / min.
9662 g / cm ³ and a bulk density of 0.37 g / c
m ³ . Example 14 (a) Production of solid catalyst component 15 g of commercially available anhydrous magnesium chloride was placed in a stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls having a diameter of 1/2 inch. Then, 6.3 g of triethoxyaluminum was added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product.
The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, into which 100 g of dehydrated butanol and 12.8 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum were added and reacted at 80 ° C. for 1 hour. Was. After cooling to room temperature, 45 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, reacted again at 80 ° C. for 2 hours, and dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen. 50 g of the solid powder was placed in the three-necked flask, and 100 cc of dehydrated hexane and 5.3 g of diethoxydichlorotitanium were added.
After reacting for 5 hours, diethylaluminum chloride 1
5.2 g was added, and the mixture was further reacted under reflux of hexane for 1.5 hours. After cooling to room temperature, cis-2-heptene 1
After adding 1.6 g and stirring at room temperature for 1.5 hours, nitrogen blowing was performed under heating to remove the solvent component to obtain a solid catalyst component. The obtained solid catalyst component contained 15 mg of titanium per gram. (B) Gas phase polymerization Using the above solid catalyst component, gas phase polymerization was performed under the same conditions as in Example 10. The catalyst efficiency is 292,000 gPE /
It was very active with gTi. The resulting ethylene polymer has a melt flow rate (MFR) of 4.3 g / 10
min, density of 0.9668g / cm ^3, bulk density was 0.36 g / cm ^3. When the branches in the produced polymer were examined by ¹³ C-NMR, it was found to be 0.1 or less per 1,000 carbon atoms. Comparative Example 9 Example 1 except that cis-2-heptene was not used.
In the same manner as in Example 4, a solid catalyst component was prepared. The obtained solid catalyst component contained 20.5 mg of titanium per gram. Using this solid catalyst component, gas phase polymerization was performed under the same conditions as in Example 10. Catalyst efficiency is 122,000 gP
The catalyst efficiency was lower than E / gTi and Example 14. Melt flow rate of the produced ethylene polymer (M
FR) is 6.1 g / 10 min, and the density is 0.9664 g.
/ Cm ³ , and the bulk density was 0.32 g / cm ³ .

EXAMPLE 15 (a) Production of a solid catalyst component A stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls each having a diameter of 1/2 inch was placed in a commercially available anhydrous stainless steel pot. 10 g of magnesium chloride and 4.2 g of triethoxyaluminum were added, and ball milling was performed under a nitrogen atmosphere at room temperature for 16 hours to obtain a reaction product.
The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 5 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum was added. After adding 100 ml of tetrahydrofuran and reacting at 60 ° C. for 2 hours, the mixture was dried at 120 ° C. under reduced pressure to remove tetrahydrofuran. Then, after adding 3 ml of silicon tetrachloride and reacting at 60 ° C. for 2 hours, titanium tetrachloride was added in 1.6 ml.
The mixture was added and reacted at 130 ° C. for 2 hours. After cooling to room temperature, 100 ml of hexane and 6.5 g of cis-2-heptene were added, and the mixture was stirred at room temperature for 1.5 hours, and then subjected to nitrogen blowing under heating to remove a solvent component to obtain a solid catalyst component. . 1 mg of the obtained solid catalyst component contained 30 mg of titanium. (B) Gas phase polymerization Using the above solid catalyst component, gas phase polymerization was performed under the same conditions as in Example 10. The catalyst efficiency is 334,000 gPE /
It was very active with gTi. The resulting ethylene polymer has a melt flow rate (MFR) of 5.5 g / 10
min, density of 0.9672g / cm ^3, bulk density was 0.42 g / cm ^3. When the branches in the produced polymer were examined by ¹³ C-NMR, it was found to be 0.1 or less per 1,000 carbon atoms. Comparative Example 10 A solid catalyst component was prepared in the same manner as in Example 15 except that cis-2-heptene was not used. The obtained solid catalyst component contained 40 mg of titanium per gram. Gas phase polymerization was carried out under the same conditions as in Example 15 using the above solid catalyst component. Catalyst efficiency is 152,000gP
The catalyst efficiency was lower than that of E / gTi and Example 15. Melt flow rate of the produced ethylene polymer (M
FR) is 6.2 g / 10 min, and the density is 0.9669 g.
/ Cm ³ and the bulk density was 0.41 g / cm ³ .

EXAMPLE 16 (a) Production of Solid Catalyst Component SiO ₂ (Fuji Devison, # 1) fired at 600 ° C. in a 500 ml three-necked flask equipped with a stirrer and a reflux condenser.
955) 50 g, and further dehydrated hexane 160
Then, 2.2 ml of titanium tetrachloride was added, and the mixture was reacted under hexane reflux for 3 hours. After cooling, a 1 mmol / cc hexane solution of diethylaluminum chloride was added to 3 mL.
After adding 0 ml and reacting again with hexane reflux for 2 hours, hexane was removed by drying under reduced pressure at 120 ° C. (Component [I]) A stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls having a diameter of 1/2 inch, 10 g of commercially available anhydrous magnesium chloride and aluminum triethoxide 4 were added. Then, under a nitrogen atmosphere, ball milling was carried out at room temperature for 16 hours to obtain a reaction product. 5.4 g of the reaction product was dissolved in 160 ml of dehydrated ethanol, and the entire amount of the solution was added to a three-necked flask containing the component [I], and reacted for 3 hours under ethanol reflux, and then at 150 ° C. for 6 hours. Drying under reduced pressure was performed. After cooling to room temperature, 100 ml of hexane and 12.2 g of cis-2-heptene were added, and the mixture was stirred at room temperature for 1.5 hours, and then subjected to nitrogen blowing under heating to remove a solvent component to obtain a solid catalyst component. 16 mg is contained in 1 g of the obtained solid catalyst component.
Of titanium was included. (B) Gas phase polymerization Using the above solid catalyst component, gas phase polymerization was performed under the same conditions as in Example 10. The catalyst efficiency is 314,000 gPE /
It was very active with gTi. Melt flow rate (MFR) of the produced ethylene polymer is 3.8 g / 10
min, density of 0.9665g / cm ^3, bulk density was 0.42 g / cm ^3. When the branches in the produced polymer were examined by ¹³ C-NMR, it was found to be 0.1 or less per 1,000 carbon atoms. Comparative Example 11 Example 1 except that cis-2-heptene was not used.
A solid catalyst component was prepared in the same manner as in No. 6. The obtained solid catalyst component contained 19 mg of titanium per gram.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 16. The catalyst efficiency is 187,000 gPE /
The catalyst efficiency was lower than that of gTi and Example 16. Melt flow rate (MFR) of the produced ethylene polymer
Is 4.2 g / 10 min and the density is 0.9665 g / cm
³ , and the bulk density was 0.40 g / cm ³ .

Example 17 A solid catalyst component was prepared in the same manner as in Example 16, except that 3.6 g of boron triethoxide was used instead of aluminum triethoxide. 1 mg of the obtained solid catalyst component contained 18 mg of titanium. Using this solid catalyst component, Example 10
The gas phase polymerization was carried out under the same conditions as described above. The catalyst efficiency is 301,
000 gPE / gTi, very high activity. The resulting ethylene polymer has a melt flow rate (MFR) of 5.2 g / 10 min and a density of 0.9659 g / cm ^3.
And the bulk density was 0.40 g / cm ³ . Note that
^When branches in the produced polymer were examined by ¹³ C-NMR, the number was 0.1 or less per 1000 carbon atoms. Comparative Example 12 Example 1 except that cis-2-heptene was not used.
In the same manner as in 7, a solid catalyst component was prepared. The obtained solid catalyst component contained 22 mg of titanium per gram.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 17. The catalyst efficiency is 149,000 gPE /
The catalyst efficiency was lower than that of gTi and Example 17. Melt flow rate (MFR) of the produced ethylene polymer
5.3g / 10min, density 0.9657g / c
m ³ and bulk density were 0.37 g / cm ³ . ¹³ C
When examining the branches in the produced polymer by -NMR,
It was 0.1 or less per 1000 carbons. Example 18 (a) Production of solid catalyst component 10 g of commercially available anhydrous magnesium chloride was placed in a stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls having a diameter of 1/2 inch. And 4.2 g of triethoxyaluminum were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product.
The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and dehydrated 2-methyl-1-pentano-
100 g, 5.0 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum, and 10.0 g of diethoxydichlorotitanium were added and reacted at 80 ° C. for 1 hour.
After cooling to room temperature, 46 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, reacted again at 80 ° C. for 2 hours, and dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane and 10.6 g of diethylaluminum chloride were added and reacted at room temperature for 1 hour, and then 23.4 g of cis-2-heptene was added.
After stirring at room temperature for 1.5 hours, nitrogen blowing was performed under heating to remove the solvent component to obtain a solid catalyst component. 1 mg of the obtained solid catalyst component contained 25 mg of titanium. (B) Gas phase polymerization Using the above solid catalyst component, gas phase polymerization was performed under the same conditions as in Example 10. The catalyst efficiency is 346,000 gPE /
It was very active with gTi. Melt flow rate (MFR) of the produced ethylene polymer is 5.0 g / 10
min, the density was 0.9665 g / cm ³ and the bulk density was 0.43 g / cm ³ . When the branches in the produced polymer were examined by ¹³ C-NMR, it was found to be 0.1 or less per 1,000 carbon atoms.

Comparative Example 13 Example 1 was repeated except that cis-2-heptene was not used.
In the same manner as in Example 8, a solid catalyst component was prepared. The obtained solid catalyst component contained 29 mg of titanium per gram.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 18. The catalyst efficiency is 160,000 gPE /
The catalyst efficiency was lower than gTi and Example 18. Melt flow rate (MFR) of the produced ethylene polymer
Is 5.8 g / 10 min and the density is 0.9662 g / cm
³ , and the bulk density was 0.40 g / cm ³ . Example 19 A solid catalyst component was prepared in the same manner as in Example 18 except that 100 ml of ethanol was used instead of 2-methyl-1-pentanole used in Example 18. 1 g of the obtained solid catalyst component contained 24 mg of titanium. Using this solid catalyst component, gas phase polymerization was performed under the same conditions as in Example 10. The catalyst efficiency is 331,000gP
The activity was extremely high with E / gTi. The resulting ethylene polymer has a melt flow rate (MFR) of 4.7 g /
10min, density of 0.9667g / cm ^3, bulk density was 0.44 g / cm ^{3. 13} C-NM
When the branch in the produced polymer was examined by R, 100
It was 0.1 or less per 0 carbon. Comparative Example 14 A solid catalyst component was prepared in the same manner as in Example 19, except that cis-2-heptene was not used. The obtained solid catalyst component contained 28 mg of titanium per gram. Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 19. Catalyst efficiency is 162,000gP
The catalyst efficiency was lower than that of E / gTi and Example 19. Melt flow rate of the produced ethylene polymer (M
FR) is 4.7 g / 10 min, and the density is 0.9666 g
/ Cm ³ and the bulk density was 0.41 g / cm ³ . Example 20 A solid catalyst component was prepared under the same conditions as in Example 19 above. Using the same polymerization apparatus as in Example 10, the autocatalyst adjusted to 80 ° C. was charged with the solid catalyst component at 250 mg /
hr and triethylaluminum at 50 mmol / h
r, and each gas is supplied while adjusting the butene-1 / ethylene molar ratio in the autocrepe gas phase to 0.25 and hydrogen to 15% of the total pressure. The gas in the system was circulated by a blower while maintaining the total pressure at 8 kg / cm ² G, and continuous polymerization was carried out for 10 hours while intermittently extracting the produced polymer. Catalyst efficiency is 2
The activity was extremely high at 80,000 gPE / gTi. Melt flow rate of the produced ethylene polymer (M
FR) is 1.4 g / 10 min, and the density is 0.9218 g.
/ Cm ³ and the bulk density was 0.44 g / cm ³ . Comparative Example 15 A solid catalyst component was prepared under the same conditions as in Comparative Example 14. Using the above solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 20. The catalyst efficiency is 230,000 gPE / g
The catalyst efficiency was lower than that of Example 20 with Ti. The resulting ethylene polymer has a melt flow rate (MFR) of 1.0 g / 10 min and a density of 0.9206 g / cm ^3.
And the bulk density was 0.44 g / cm ³ . Example 21 A solid catalyst component was prepared in the same manner as in Example 18, except that alumina was used instead of silica in Example 18. Using this solid catalyst component, Example 10
The gas phase polymerization was carried out under the same conditions as described above. The catalyst efficiency is 269,
000 gPE / gTi, very high activity. The resulting ethylene polymer has a melt flow rate (MFR) of 6.7 g / 10 min and a density of 0.9666 g / cm ^3.
And the bulk density was 0.34 g / cm ³ . Note that
^When branches in the produced polymer were examined by ¹³ C-NMR, the number was 0.1 or less per 1000 carbon atoms. Comparative Example 16 Example 2 except that cis-2-heptene was not used.
A solid catalyst component was prepared in the same manner as in Example 1. The obtained solid catalyst component contained 28 mg of titanium per gram.
Using this solid catalyst component, gas phase polymerization was performed under the same conditions as in Example 21. The catalyst efficiency is 118,000 gPE /
The catalyst efficiency was lower than gTi and Example 21. Melt flow rate (MFR) of the produced ethylene polymer
6.5g / 10min, density 0.9669g / c
m ³ and bulk density were 0.35 g / cm ³ .

Example 22 (a) Production of solid catalyst component A 500-ml three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 50 g of silica (Fuji Devison, # 955) calcined at 600 ° C. was placed therein. , 160 ml of dehydrated hexane and 2.2 ml of titanium tetrachloride were added and reacted under hexane reflux for 3 hours. After cooling, the supernatant was removed by decantation, and hexane was removed by drying at 120 ° C. under reduced pressure. (Component [I]) 10 g of commercially available anhydrous magnesium chloride and triethoxyaluminum were placed in a stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls having a diameter of 1/2 inch. 2 g was added and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product.
Another 500 ml three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, 7.5 g of the above reaction product and 5.0 g of tetrabutoxytitanium were added to 160 ml of dehydrated ethanol, and the mixture was reacted under reflux of ethanol for 3 hours. Was. After cooling, 50 g of the above-mentioned component [I] was added, and the mixture was reacted for 3 hours under reflux of ethanol. After cooling, the supernatant was removed by decantation, followed by drying under reduced pressure at 150 ° C. for 6 hours. Next, 150 ml of hexane and 80 mmol of diethylaluminum chloride were added, and reacted for 1 hour under hexane reflux. Thereafter, 24 mmol of methyldimethoxysilane was added and reacted at 40 ° C. for 1 hour. After that, 23.4 g of cis-2-heptene was added, and the mixture was stirred at room temperature for 1.5 hours. Then, nitrogen was blown under heating to remove solvent components. Thus, a solid catalyst component was obtained. 21 mg of titanium was contained in 1 g of the obtained solid catalyst component. (B) Gas phase polymerization Using the above solid catalyst component, gas phase polymerization was performed under the same conditions as in Example 10. The catalyst efficiency is 295,000 gPE /
It was very active with gTi. Melt flow rate (MFR) of the produced ethylene polymer is 6.2 g / 10
min, density of 0.9671g / cm ^3, bulk density was 0.44 g / cm ^3. When the branches in the produced polymer were examined by ¹³ C-NMR, it was found to be 0.1 or less per 1,000 carbon atoms. Comparative Example 17 Example 2 except that cis-2-heptene was not used.
A solid catalyst component was prepared in the same manner as in Example 2. The obtained solid catalyst component contained 25 mg of titanium per gram.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 22. The catalyst efficiency is 133,000 gPE /
The catalyst efficiency was lower than that of gTi and Example 22. Melt flow rate (MFR) of the produced ethylene polymer
Is 6.4 g / 10 min and the density is 0.9669 g / cm
³ , and the bulk density was 0.44 g / cm ³ .

[Brief description of the drawings]

FIG. 1 is a flowchart showing a production process of a catalyst of the present invention.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-266107 (JP, A) JP-A-7-82313 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/65-4/658 C08F 10/00-10/14 C08F 110/00-110/14 C08F 210/00-210/18

Claims (2)

(57) [Claims] 1. A method according to claim 1, wherein ethylene is polymerized by using a solid catalyst component and an organometallic compound as a catalyst, or ethylene and a small amount of 3 to
In the method of copolymerizing an α-olefin of ^No. 12 , the solid catalyst component is at least a magnesium compound, a titanium compound and a general formula R ¹ CH ＝ CHR ² (where R ¹ and R ² are an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, an ethylene heavy, wherein may be the same or different, is a substance obtained by the internal olefin compound is brought in contact with each other, represented by some cis)
Copolymer or ethylene / α-olefin copolymer (α-O
Refining content of 20 mol% or less) . 2. Polymerization of ethylene using a solid catalyst component and an organometallic compound as a catalyst or ethylene and a small amount of 3 to 3 carbon atoms.
In the method of copolymerizing an α-olefin of No. 12 , the solid catalyst component comprises at least a silicon oxide and / or an aluminum oxide, a magnesium compound, a titanium compound and a general formula R ¹ CH ＝ CHR ² (where R ¹ and R ² Represents an alkyl group, an aryl group, or an aralkyl group having 1 to 24 carbon atoms, which may be the same or different, and is a cis-position). Characteristic ethylene polymer
Or an ethylene / α-olefin copolymer (α-olefin
(20% by mol or less) .