JPH07196721A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a polyolefin capable of getting a polymer in high yield per unit catalyst, having high bulk specific gravity, narrow molecular weight distribution and excellent free flowability and moldability and useful for molded article, etc., by (co)polymerizing an olefin using a specific catalyst system. CONSTITUTION:This polyolefin is produced by the (co)polymerization of an olefin such as ethylene using a catalyst system consisting of a combination of (A) a solid catalyst component at least containing a silicon oxide such as SiO2 and/or an aluminum oxide such as Al2O3, a magnesium compound such as methylmagnesium chloride and a titanium compound such as titanium tetrachloride, (B) an inner olefin compound of the formula R<1>CH=CHR<2> (R<1> and R<2> are each a 1-24C alkyl, an aryl, an aralkyl; the substituents form cis- configuration) such as cis-2-butene and (C) an organic metal compound such as trimethylaluminum.

Description

Detailed Description of the Invention

[0001]

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

[Prior Art and Problems to be Solved by the Invention]

Conventionally, in this kind of technical field, many catalysts have been known in which a compound of a transition metal such as titanium or vanadium is carried on an inorganic magnesium solid such as magnesium halide, magnesium oxide or magnesium hydroxide as a carrier. Has been. However, in these known techniques, there is a problem that the polymer yield per solid catalyst and the polymer yield per transition metal are low in the case of homopolymerization of α-olefin or the copolymerization of ethylene and α-olefin. , There is a need for increased activity. Particularly in the case of homopolymerization of ethylene or copolymerization of ethylene with a small amount of α-olefin, the polymer yield per solid catalyst and the polymer yield per transition metal are remarkably low. Therefore, further improvement is required in order to omit the pelletizing step, which has been increasing in demand in recent years, and to directly apply the powdery polymer to a processing machine. In addition, the bulk specific gravity of the obtained polyolefin is generally small, the average particle size is relatively small, and the particle size distribution is generally wide, so there are many fine powder particles, and dust is generated when molding the polymer, and the efficiency during molding is reduced. Since problems such as the above occur, improvements have been strongly desired in terms of productivity and polymer handling. The present inventors have previously filed several patent applications for new catalyst components that have improved the above-mentioned drawbacks (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, Japanese Patent Fair 1-1288, Japanese Patent Fair 1-122
89, JP-A-60-149605, and 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. And the powder polymer cannot be directly applied to the processing machine. The present invention improves these disadvantages and significantly increases the polymer yield per solid catalyst and the transition metal per transition metal in the case of homopolymerization of α-olefins or copolymerization of ethylene and α-olefins. As a result of earnest research aimed at, the present invention has been achieved.

[0003]

That is, the present invention provides a method for polymerizing or copolymerizing an olefin by using a solid catalyst component and an organometallic compound as a catalyst, wherein the solid catalyst component is at least a magnesium compound, a titanium compound and a general formula R ¹ CH = CHR ² (wherein R ¹ and R ² are each a carbon number of 1 to
24 alkyl groups, aryl groups or aralkyl groups, which may be the same or different and are in the cis position, are obtained by contacting internal olefin compounds with each other. It relates to a manufacturing method. The present invention also provides a method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as a catalyst, wherein the solid catalyst component is 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 having 1 to 24 carbon atoms, an aryl group or an aralkyl group, and may be the same or different,
The invention relates to a method for producing polyolefin, which is a substance obtained by bringing internal olefin compounds represented by (cis position) into contact with each other. By using 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,
In particular, homopolymerization of ethylene or a copolymer of ethylene and a small amount of α-olefin can be obtained with extremely high activity, the bulk specific gravity of the produced polyolefin is high, and the free flowing property is also good. In addition, when used as pellets, it can be used for molding in powder form as it is, and there are few troubles during molding, and polyolefin can be produced extremely advantageously.

The present invention will be specifically described below. <1> Solid Catalyst Component The solid catalyst component of the present invention is at least a magnesium compound, a titanium compound and a general formula R ¹ CH═CHR ² (wherein R ¹ and R ² are an alkyl group having 1 to 24 carbon atoms, an aryl group or aralkyl). Group, which may be the same or different, and which are in the cis position, are brought into contact with each other, and the solid catalyst component of the present invention comprises at least silicon oxide and / or Alternatively, an aluminum oxide, a magnesium compound, a titanium compound and a general formula R ¹ CH═CHR ² (wherein R ¹ and R ² represent an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, which may be the same or different). It is a substance obtained by bringing internal olefin compounds represented by (cis position) into contact with each other. (1) Magnesium Compound [Component I] The magnesium compound used in the present invention is not particularly limited, but 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 (wherein R ¹ represents a hydrocarbon residue having 1 to 20 carbon atoms,
X is a halogen atom, and n is 0 ≦ n ≦ 2), and the hydrocarbon residue is preferably one having 1 to 12 carbon atoms, for example, an alkyl group. , Aryl groups, aralkyl groups 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-propoxybromorommagnesium, n-butoxybromomagnesium,
sec-butoxybromo magnesium, tert-butoxy bromo magnesium, dimethoxy magnesium,
Diethoxy magnesium, di n-propoxy magnesium, di iso-propoxy magnesium, n-butoxy magnesium, di sec-butoxy magnesium, di t
Examples thereof include compounds such as ert-butoxymagnesium, and magnesium chloride is particularly preferable. In the present invention, these magnesium compounds are alcohols
It may be one treated with an electron donor such as a phenol, an ester, a ketone, a carboxylic acid, an ether, an amine or a phosphine. In addition, the general formula R ² MgX (wherein R ² is a hydrocarbon group having 1 to 20 carbon atoms, X 2
Is a halogen atom), a so-called Grignard reagent represented by the formula (1) is preferred, and such a hydrocarbon residue preferably has 1 to 12 carbon atoms, and examples thereof include an alkyl group, an aryl group, and an aralkyl group. Examples of the halogen atom include fluorine, chlorine, bromine, iodine, and the like. Specific examples include methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium iodide, 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 Examples thereof include compounds such as bromide, hexyl magnesium iodide, octyl magnesium chloride, octyl magnesium bromide, decyl magnesium chloride, decyl magnesium bromide, phenyl magnesium chloride and phenyl magnesium bromide. Not only these magnesium compounds may be used alone, but also a mixture of a plurality of them 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 (wherein R ³ is a hydrocarbon having 1 to 20 carbon atoms). A residue, X represents a halogen atom, and m is 0 ≦ m ≦ 4), and the hydrocarbon residue is preferably one having 1 to 12 carbon atoms, For example, an alkyl group, an aryl group, an aralkyl group and the like can be mentioned. 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. as aryl group, phenyl group, tolyl group, xylyl group, etc., as aralkyl group , Benzyl group, etc. are exemplified,
Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specifically, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and other tetrahalogenated titanium, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, monoethoxytritoxide. Fluorotitanium, monoethoxytribromotitanium, diethoxydifluorotitanium, diethoxydichlorotitanium, diethoxydibromotitanium, triethoxyfluorotitanium, triethoxychlorotitanium, tetraethoxytitanium, monopropoxytrichlorotitanium, monoisopropoxytrichlorotitanium, di Propoxydichlorotitanium, diisopropoxydichlorotitanium, diisopropoxydibromotitanium, triisopropoxyfluorotitanium, tripropoxychlorotitanium, tetra-n Propoxy titanium, tetraisopropoxy titanium, monobutoxytrichlorotitanium, monoisobutoxytrichlorotitanium, dibutoxydichlorotitanium, tributoxyfluorotitanium, tributoxychlorotitanium, triisobutoxychlorotitanium, tetra n-butoxytitanium, tetraisobutoxytitanium. , Tetra-sec-butoxytitanium, tetra-tert-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, di2-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 is exemplified, and preferably,
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 preferable. In addition to the above tetravalent titanium compounds, trivalent titanium compounds are also preferred. Examples of the trivalent titanium compound include titanium tetrahalide such as titanium tetrachloride and titanium tetrabromide,
A tetravalent halogenated alkoxytitanium compound represented by the general formula Ti (OR ') _{pX4 -P} (wherein R'is 1 to 2 carbon atoms).
0 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 the periodic table I to
Examples thereof include titanium trihalides or trivalent titanium compounds obtained by reduction with a Group III metal organometallic compound. These titanium compounds can be preferably used alone or in a mixture of plural kinds. Further, it is also possible to use a titanium compound and a vanadium compound in combination within a necessary range, as such a vanadium compound, vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, a tetravalent vanadium compound such as tetraethoxyvanadium, Examples thereof include pentavalent vanadium compounds such as vanadium oxytrichloride, ethoxydichlorovanadyl, triethoxyvanadyl and tributoxyvanadyl, and trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide. When using a titanium compound and a vanadium compound in combination, the V / Ti molar ratio 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. Is. The aluminum oxide used in the present invention is a composite oxide of alumina or aluminum and at least one other metal of Group I to VIII of the periodic table. Typical examples of the complex oxides of silicon or aluminum and at least one other metal of Group I to VIII of the Periodic Table are Al ₂ O ₃ .MgO, Al ₂ O ₃ .CaO, and 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,
Examples thereof include various natural or synthetic multiple oxides such as Al ₂ O ₃ .NiO and SiO ₂ .MgO. Here, the above formula represents only the composition, not the molecular formula,
The structure and component ratio of the double oxide used in the present invention are not particularly limited. As a matter of course, the silicon oxide and / or aluminum oxide used in the present invention may be used without any problem even if it absorbs a small amount of water and 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, but the particle size is preferably 1 to
A silica having 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 is desirable. Before use, it is desirable to perform firing treatment at 200 to 800 ° C. in advance by a conventional 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 , in which R ⁴ and R ⁵ have 1 to 2 carbon atoms.
4, preferably 1 to 12 represents an alkyl group, an aryl group or an aralkyl group, which may be the same or different and is a compound in the cis position, and the alkyl group may be a methyl group, an ethyl group, a propyl group, i- Propyl group, butyl group,
Examples include s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group and octyl group. Examples of aryl group include phenyl group, tolyl group, xylyl group and the like, and examples of aralkyl group include benzyl group. The internal olefin compound used in the present invention is a compound that does not substantially polymerize even when contacted with a solid catalyst component obtained by contacting at least a magnesium compound and a titanium compound with a catalyst composed of an organometallic compound. Specific examples of suitable 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 any 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 preferable. Of course, these compounds may be used alone or in combination of two or more kinds. Further, in addition to the cis-type internal olefin described above, a trans-type internal olefin may be used in combination within the range not impairing the present invention. The trans internal olefin is not particularly limited, and examples thereof include the cis isomers.

(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 inorganic compounds have the general formula _{^{Me (YR 6) p R 7}} q X zpq ( wherein Me periodic table I~IV elements of Group, z is the element Me
Valence of 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 represent a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms such as an alkyl group, an aryl group and 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 and a s-butyl group, Examples of the t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, the aryl group include a phenyl group, tolyl group, xylyl group, and the like, and the aralkyl group includes a benzyl group. 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 the above R ⁶ , R ⁷ and X). As a preferable specific example of these, 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
Examples thereof include compounds such as (N (CH ₃ ) ₂ ) ₂ . Of course, these compounds may be used alone or in combination of two or more.

(6) Even if various organic compounds [component VI] are further added to the titanium compound, magnesium compound, internal olefin compound, and in some cases silicon oxide and / or aluminum oxide, they are reacted with each other. Often, examples of such organic compounds include alcohols, phenols, ethers, ketones, aldehydes, esters, amines, nitriles, halogenated hydrocarbons and the like. . Preferred specific examples include alcohols such as 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-pentanol, 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
-Pentanol, 1-nonanol, 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
And 1-eicosanol, benzyl alcohol, methyl cellosolve, or an arbitrary mixture thereof. Among the phenols, phenol, orthocresol, metacresol, paracresol, α-naphthol, β-naphthol, catechol, resorcinol, hydroquinone, orcin, orthochlorophenol, metachlorophenol, parachlorophenol. , Ortho-bromophenol, meta-bromophenol, para-bromophenol, ortho-iodophenol, meta-iodophenol, para-iodophenol, 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 propyl pentyl ether, propyl hexyl 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. Examples thereof include phenyl ketone, dipropyl ketone, propyl butyl ketone, propyl pentyl ketone, propyl hexyl ketone, cyclohexanone and benzophenone. Examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeroaldehyde, capronaldehyde, benzaldehyde and the like. Among the esters, 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, salicylsanpendyl, ethyl α-resorcinate,
Methyl anisate, ethyl anisate, phenyl anisate,
Benzyl anisate, ethyl o-methoxybenzoate, p-
Methyl ethoxybenzoate, methyl p-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. Examples thereof include methyl and ethyl naphthoate.

Examples of amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tribuethylamine, pyridine and piperidine. Examples of the nitriles include acetonitrile, propionitrile, acetonitrile, benzonitrile and the like. Among 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
-Dichloropropane, 1.3-dichloropropane, 1,
1-dichlorobutane, 1,2-dichlorobutane, 1.3
-Dichlorobutane, 1.4-dichlorobutane, phenyl chloride, benzyl chloride and the like can be mentioned.
Of course, these compounds may be used alone or in combination of two or more.

(7) In addition to the above-mentioned titanium compound, magnesium compound, internal olefin compound, and in some cases silicon oxide and / or aluminum oxide, the general formula Al (OR ⁸ ) _p R ⁹ _q X _{3- (p + q )} (R ⁸ and R ⁹ have 1 to 24 carbon atoms, preferably 1 to 1 carbon atoms ₎
2 is a hydrocarbon residue, 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. The hydrocarbon residue preferably has 1 to 12 carbon atoms,
Examples thereof include an alkyl group, an aryl group, an aralkyl group, and the like. Examples of the alkyl group include a methyl group, an ethyl group,
Propyl group, i-propyl group, butyl group, s-butyl group, t-
A butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like, an aryl group, a phenyl group, a tolyl group, a xylyl group, and the like, an aralkyl group, a benzyl group, and the like, a halogen atom, fluorine, chlorine,
Examples include bromine and iodine. Specific examples of these organic aluminum compounds include dimethyl aluminum methoxide, dimethyl aluminum ethoxide, dimethyl aluminum isoproxide, dimethyl aluminum t-butoxide, dimethyl aluminum n-butoxide, dimethyl aluminum sec-butoxide, and diethyl aluminum methoxide. , Diethyl aluminum ethoxide, diethyl aluminum isoproxide, diethyl aluminum n-butoxide, diethyl aluminum sec-butoxide, diethyl aluminum cyclohexyl oxide, diethyl aluminum t-butoxide,
Dipropyl aluminum ethoxide, dipropyl aluminum t-butoxide, dibutyl aluminum t-butoxide, di i-butyl aluminum methoxide, di i-
Butyl aluminum ethoxide, di i-butyl aluminum isopropoxide, di i-butyl aluminum-i
-Butoxide, di-butyl aluminum-t-butoxide, di-t-butyl aluminum 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, Phenylethoxy aluminum chloride, ethyl ethoxy aluminum hydride, ethyl methoxy aluminum chloride, ethyl isopropoxy aluminum dichloride ethyl butoxy aluminum chloride, phenyl aluminum dichloride, diphenyl aluminum chloride, benzyl aluminum dichloride,
Dibenzyl aluminum chloride, dimethyl aluminum chloride, diethyl aluminum fluoride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, di-butyl aluminum chloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, Methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum, tri n-butyl aluminum, triisobutyl aluminum, tri n-hexyl aluminum, tri n-octyl aluminum, or any of these A mixture, etc. 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 kinds.

(8) The reaction ratios of the above components are not particularly limited, but the following quantitative 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.
01-20, preferably 0.1-10, more preferably 0.2-43) [Component IV] / [Component II] (molar ratio) = 0.01-1
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) [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) Production of solid catalyst component In the present invention, at least a magnesium compound and a titanium compound, and optionally a silicon compound and / or an aluminum compound are contacted with each other. The solid catalyst component thus obtained is contacted with an internal olefin which is not substantially polymerized during the production of the component. The order of contacting each component is not particularly limited, but the following order may be mentioned, for example. 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) Contact [Component II] and [Component IV], and then contact [Component I]. {[Component II] + [Component IV]} → [Component I] 4) Simultaneously contact [Component I], [Component II] and [Component IV]. {[Component I] + [Component II] + [Component IV]} 5) [Component III] is contacted with [Component I], then [Component II], and finally [Component IV]. [Component III] → [Component I] → [Component II] → [Component IV] 6) Contact [Component III] and [Component II], then contact [Component IV], and finally [Component I] Contact. [Component III] → [Component II] → [Component IV] → [Component I] 7) Contact [Component III] and [Component IV], then contact [Component I], and finally [Component II] Contact. [Component III] → [Component IV] → [Component I] → [Component II] 8) Contact [Component I] and [Component II], and then [Component
III] and finally [Component IV]. {[Component I] + [Component II]} → [Component III] → [Component I]
V] 9) Contact [Component I] and [Component IV], and then [Component
III] and finally [Component II]. {[Component I] + [Component IV]} → [Component III] → [Component I]
I] 10) [Component I] and [Component IV] are contacted, then [Component III], and finally [Component II]. {[Component I] + [Component IV]} → [Component III] → [Component I]
I] 11) Contacting [Component I], [Component II] and [Component IV], and then contacting [Component III]. {[Component I] + [Component II] + [Component IV]} → [Component II]
I] The inorganic compound ([component V]), organic compound ([component VI]), and organometallic compound ([component VII]), which are optional components, are brought into contact with each other in any order with respect to the contacting order of the above essential components. be able to. Further, the same component may be contacted twice or more.

Among these, the preferred contact order 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 Component IV] → {[Component I] + [Component V] + [Component II]} → [Component VII] →
[Component V]

The reaction method for producing the solid catalyst component in the present invention is not particularly limited, but the above magnesium compound [component I] and titanium compound [in the presence or absence of an inert hydrocarbon solvent]. Ingredients such as Component II] and internal olefin compound [Component IV] and optional components such as inorganic compound [Component V], organic compound [Component VI], organometallic compound [Component VII] are added at a temperature of 0 to 200.
A method of co-milling at a temperature of 30 minutes to 50 hours using a ball mill, a vibration mill, a rod mill, an impact mill or the like may be used, and for example, pentane, cyclohexane, heptane, octane, nonane, decane, Common thiols such as benzene, toluene, xylene, etc., or a mixture thereof.
So-called inactive hydrocarbons that are inactive with respect to the Gral catalyst, the above-mentioned (for example, described in [Component VI]) alcohols, phenol
, Ethers, ketones, esters, amines,
A method may be used in which a mixed heating reaction is carried out 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 a mixture thereof, and then the solvent is removed by evaporation. . However, it is preferable that the organic aluminum compound is brought into contact with the organic solvent. When silicon oxide and / or aluminum oxide [component III] is added as a solid catalyst component and reacted with each other, a method of reacting in the above organic solvent is preferable. Each reaction operation for preparing the solid catalyst component should be carried out 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 above-mentioned solid catalyst component and an organometallic compound, and the organometallic compound is known as one of the components of the Ziegler catalyst. Group 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,
Organoaluminum compounds of RAl (OR) X and R ₃ Al ₂ X ₃ (provided that R is an alkyl group or aryl group having 1 to 20 carbon atoms, X is a halogen atom, and R is the same or different) ) Or the general formula R ₂ Zn (where R
Is an alkyl group having 1 to 20 carbon atoms and may be the same or different from each other, and is represented by an organozinc compound of trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisec-butyl. Aluminum, tri-t
Examples thereof include ert-butyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl aluminum chloride, diisopropyl aluminum chloride, ethyl aluminum sex chloride, diethyl zinc and mixtures thereof. The amount of the organic metal compound used is not particularly limited, but is usually 0.1 to 0.1 with respect to the titanium compound.
It can be used 1000 times. 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 the 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 usually used in an amount of 0.1 to 1 mol, preferably 0.2 to 0.5 mol, relative to 1 mol of the organic metal compound. . When used as an addition compound of an organometallic compound and an organic acid ester, a molar ratio of organometallic compound: organic acid ester of 2: 1 to 1: 2 is preferable.
The organic acid ester used at this time has a carbon number of 1 to 1.
It is an ester of 24 saturated or unsaturated monobasic or dibasic organic carboxylic oxygen 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 acid, methyl anisate, ethyl anisate, phenyl anisate, benzyl anisate, ethyl o-methoxybenzoate, methyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, phenyl p-toluate , O-toluy Acid ethyl, ethyl m- toluic acid,
Mention may be made of methyl p-aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, methyl naphthoate, ethyl naphthoate and the like. Among these, particularly preferred are alkyl esters of benzoic acid, o- or p-threic acid or p-anisic acid, and especially methyl esters thereof.
Ethyl ester is preferred.

<3> Polymerization of Olefin Polymerization of olefin using the catalyst of the present invention is a slurry.
Polymerization, solution polymerization or gas phase polymerization can be performed.
That is, all the reactions are carried out in the presence or absence of an inactive hydrocarbon with oxygen and water being substantially cut off. The polymerization conditions for olefins are temperature 20 to 120
° C., preferably from 50 to 110 ° C., the pressure to from atmospheric pressure 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 it is effectively performed by adding hydrogen to the polymerization system.
Of course, by using the catalyst of the present invention, it is possible to carry out the polymerization reaction in two stages or other stages having different polymerization conditions such as hydrogen concentration and polymerization temperature without any trouble. The method of the present invention is applicable to the polymerization of all olefins which can be polymerized with a Ziegler catalyst, and particularly α-olefins having 2 to 12 carbon atoms are preferable, for example, ethylene, propylene, 1-butene, hexene-1,4- Α-, such as methylpentene-1
Homopolymerization of olefins and ethylene and propylene,
Ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1, etc. and carbon number 3
It is preferably used for the copolymerization of .alpha.-olefin of .about.12, the copolymerization of propylene and 1-butene, the copolymerization of ethylene with two or more kinds of other .alpha.-olefins, and the like. In particular, the homopolymerization of ethylene and the α-olefin content in the ethylene / α-olefin copolymer are usually 20 mol% or less,
It is preferably 0 to 10 mol%, more preferably 0 to 5 mol%. Further, copolymerization with a diene for the purpose of modifying the polyolefin is also preferably carried out. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, and dicyclopentadiene.

[0017]

EFFECTS OF THE INVENTION By using 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, and particularly, homopolymerization of ethylene or ethylene and a small amount of α-olefin can be obtained. The obtained copolymer is extremely highly active, and the bulk density of the produced polyolefin is high, and the free flowability is good, which is very advantageous in the polymerization operation. However, it can be subjected to molding processing, there are few troubles during molding processing, and polyolefin can be manufactured extremely advantageously.

[0018]

EXAMPLES Examples will be given below, but these are for the purpose of carrying out the present invention, and the present invention is not limited thereto. Example 1 (a) Production of solid catalyst component Commercially available anhydrous magnesium chloride 15 g in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls having a diameter of 1/2 inch, Triethoxyaluminum 6.3 g and titanium tetrachloride 9.0
Into a nitrogen atmosphere, g was added and ball milling was performed for 16 hours at room temperature to obtain a solid powder. A three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, to which 20 g of the above solid powder, 100 cc of dehydrated hexane and 1.0 g of ethanol were added, and then 6.2 g of diethylaluminum chloride was added to the mixture at room temperature for 1.5 After reacting for 1 hour, 14.7 g of cis-2-heptene was further added and reacted for 1.5 hours, and then nitrogen blowing was performed under heating to remove the solvent component to obtain a solid catalyst component. 36 g of titanium was contained per 1 g of the obtained solid catalyst component. (B) Slurry Polymerization A stainless steel autoclave with an internal volume of 2 liter equipped with an electromagnetic induction stirrer was well dried, and dried hexane 10
00 ml, 1 mmol of triethylaluminum and 10 mg of the above solid catalyst component were added, and the internal temperature was raised to 90 ° C. The internal pressure becomes 2kg / cm ² , but the total pressure of hydrogen is 5k.
Add 10 g of ethylene to g / cm ^2.
The pressure was increased to / cm ² to initiate polymerization. Total pressure is 10kg /
Ethylene was continuously introduced so as to be cm ² and polymerization was carried out for 1 hour. Then, methanol was added to stop the polymerization, and hexane was removed by evaporation to remove white polyethylene powder 22
0 g was obtained. Polymerization activity is 122,000gPE / gT
i, hr, ethylene pressure, 4,400 g PE / 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 number of branches in the produced polymer was examined by 13 C-NMR, the number was 0.1 or less per 1000 carbons.

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 in Example 1. The obtained solid catalyst component contained 4 per 1 g.
It contained 3 mg of titanium. Slurry polymerization was performed under the same conditions as in Example 1 to obtain white polyethylene powder.
6 g was obtained. Polymerization activity is 91,200gPE / gTi,
hr, ethylene pressure, 3,920 g PE / gcat, h
r, ethylene pressure, catalytic efficiency 455,000 gP
The activity was extremely high with E / gTi. The melt flow rate (MFR) of the produced ethylene polymer was 5.2 g /
After 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 1 g. Slurry polymerization was performed under the same conditions as in Example 1 to obtain 215 g of white polyethylene powder. The polymerization activity was 113,000 gPE / gTi, hr, ethylene pressure, 4,300 gPE / gcat, hr, ethylene pressure, and the catalyst efficiency was 566,000 gPE / gTi, which was a very high activity. The produced ethylene polymer had a melt flow rate (MFR) of 6.1 g / 10 min, a density of 0.9664 g / cm 3, and a bulk density of 0.37 g /
It was cm3. Example 4 (a) Production of solid catalyst component Commercially available anhydrous magnesium chloride 15 g in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls having a diameter of 1/2 inch, Triethoxyaluminum 6.3 g and titanium tetrachloride 9.0
Ball milling was performed at room temperature for 16 hours in a nitrogen atmosphere. To this, 14.0 g of cis-2-heptene was added and further ball milled at room temperature for 16 hours to obtain a solid powder. A three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, to which 20 g of the above solid powder, 100 cc of dehydrated hexane and 1.0 g of ethanol were added, and then 6.2 g of diethylaluminum chloride was added thereto, followed by 1. at room temperature. After reacting for 5 hours, nitrogen blowing was performed under heating to remove the solvent component to obtain a solid catalyst component. This solid catalyst component contained 38 mg of titanium per 1 g. (B) Slurry polymerization 205 g of slurry polymerization was carried out under the same conditions as in Example 1.
Of white polyethylene powder was obtained. Polymerization activity is 107,
000gPE / gTi, 4,100gPE / gca
t, hr, ethylene pressure, catalyst efficiency is 539,00
The activity was extremely high at 0 gPE / gTi. The resulting ethylene polymer has a melt flow rate (MFR) of 6.
It was 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, it was found to be 1
It was 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 1 g. Slurry polymerization was performed under the same conditions as in Example 1 to obtain 123 g of white polyethylene powder. Polymerization activity is 45,000gPE / gTi, 2,5
It was 00 gPE / gcat, hr, ethylene pressure, and the catalyst efficiency was 224,000 gPE / gTi, which was lower than those of Examples 1 to 4. The melt flow rate (MFR) of the produced ethylene polymer was 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
A solid catalyst component was prepared in the same manner as in Example 1 except that was used. The obtained solid catalyst component contained 36 mg of titanium per 1 g. Slurry polymerization was performed under the same conditions as in Example 1 to obtain a white polyethylene powder 85.
g was obtained. Polymerization activity is 47,000 gPE / gTi, h
r, ethylene pressure, 1,700 gPE / gcat, hr,
Ethylene pressure is ri and catalyst efficiency is 236,000 gP
The activity was lower than that of E / gTi and Examples 1 to 4.
Melt flow rate of produced ethylene polymer (MF
R) is 5.4 g / 10 min, and the density is 0.9662 g /
cm ³ , and the bulk density was 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 replaced with nitrogen, and 10 g of commercially available anhydrous magnesium chloride was added to the flask.
It was taken and dried in 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 then 35.5 g of silicon tetrachloride was added dropwise over 10 minutes. After the dropping was completed, the reaction was allowed to proceed for another 1 hour, followed by drying under reduced pressure at 250 ° C. to obtain a white powdery reaction product. 50m of titanium tetrachloride on the obtained white powder
1 was added and reacted at 130 ° C. for 1 hour. After completion of the reaction, washing was carried out with hexane, and washing was repeated until titanium tetrachloride was not found in the washing liquid. Next, 50 ml of hexane and 2.0 g of cis-2-heptene were added, and the mixture was reacted at room temperature for 1.5 hours, then nitrogen was blown under heating to remove the solvent component to obtain a solid catalyst component. 1 in 1 g of the obtained solid catalyst component
It contained 4.5 mg of titanium. (B) Slurry polymerization The same autoclave as in Example 1 was used, in which 1000 ml of dry hexane and 5 m of triethylaluminum were used.
mol and 95 mg of the above solid catalyst component were added, and the internal temperature was raised to 90 ° C. Although the internal pressure was 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 the polymerization. Ethylene was continuously introduced so that the total pressure was 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 white polyethylene powder. Polymerization activity is 138,000g
PE / gTi, hr, ethylene pressure, 2,000gPE /
gcat, hr, ethylene pressure, catalyst efficiency is 13
The activity was extremely high at 8,000 gPE / gTi.
Melt flow rate of 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 number of branches in the produced polymer was examined by ¹³ C-NMR, it was 0.1 or less per 1000 carbons.

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. This solid catalyst component (1 g) contained 15.5 mg of titanium. Slurry polymerization was performed under the same conditions as in Example 1 to obtain 135 g of white polyethylene powder. Polymerization activity is 72,000gPE / gTi, hr, ethylene pressure,
It 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 melt flow rate (MFR) of the produced ethylene polymer was 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 The same procedure as in Example 5 was repeated 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 ingredients were prepared. The obtained solid catalyst component contained 12.4 mg of titanium per 1 g of titanium. Slurry polymerization was performed under the same conditions as in Example 5 to obtain 155 g of white polyethylene powder. The polymerization activity was 132,000 gPE / gTi, hr, ethylene pressure, 1,600 gPE / gcat, hr, ethylene pressure, and the catalyst efficiency was 132,000 gPE / gTi, which was a very high activity. The produced ethylene polymer had 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.
It was g / cm ³ . When the branching in the produced polymer was examined by ¹³ C-NMR, it was found to be 0.
It was 1 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 1 g of titanium. Slurry polymerization was performed under the same conditions as in Example 5 to obtain 97 g of white polyethylene powder.
The polymerization activity was 64,000 gPE / gTi, hr, ethylene pressure, 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 melt flow rate (MFR) of the produced ethylene polymer was 9.1 g / 10 m.
in, the density was 0.9668 g / cm ³ , and the bulk density was 0.33 g / cm ³ . Example 7 (a) Production of solid catalyst component Magnesium oxide (adsorption amount of iodine 18 mg / g MgO)
10 g of the dried product was vacuum dried 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 under vacuum, 50 ml of titanium tetrachloride was added, and the mixture was reacted at 130 ° C. for 1 hour. After completion of the reaction, the washing was repeated with hexane, and the washing was repeated until titanium tetrachloride was not observed in the washing liquid. Next, 50 ml of hexane and 2.0 g of cis-2-heptene were added, and the mixture was reacted at room temperature for 1.5 hours, then nitrogen was blown under heating to remove the solvent component to obtain a solid catalyst component. The solid catalyst component 1 g thus obtained contained 7.
It contained 8 mg of titanium. (B) Slurry polymerization The same autoclave as in Example 1 was used, in which 1000 ml of dry hexane and 5 m of triethylaluminum were used.
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 start the polymerization. Ethylene was continuously introduced so that the total pressure was 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 white polyethylene powder. Polymerization activity is 20,6
00gPE / gTi, hr, ethylene pressure, 320gPE
/ Gcat, hr, ethylene pressure, catalyst efficiency is 4
It was 1,200 gPE / gTi. The melt flow rate (MFR) of the produced ethylene polymer was 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, it was 100
The number 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 obtained solid catalyst component contained 9.8 mg of titanium per 1 g of titanium. Slurry polymerization was performed under the same conditions as in Example 7 to obtain 214 g of 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 produced ethylene polymer has a melt flow rate (MFR) of 18.9 g / 10.
min, the density was 0.9670 g / cm ³ , and the 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 replaced with nitrogen, and 33.3 ml (0.3 mol / l) of a diethyl ether solution of ethylmagnesium bromide was added to the flask. 1
Mol), and with stirring, orthochlorophenol 1
2.9 g (0.1 mol) was added. After reacting for 1 hour under reflux of diethyl ether, 80 ml of titanium tetrachloride
(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, and then a large amount of hexane was added to dilute the solution to precipitate the reaction product. The supernatant was removed by decantation, and fresh hexane was added to wash the reaction product. This washing operation was repeated until free titanium tetrachloride was removed, and then hexane was distilled off to obtain a solid catalyst in the form of fine particles. 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 and then blown with nitrogen under heating to remove the solvent component to obtain a solid catalyst component. 5 g in 1 g of the obtained solid catalyst component.
It contained 3.0 mg of titanium. (B) Slurry polymerization The same autoclave as in Example 1 was used, in which 1000 ml of dry hexane and 5 m of triethylaluminum were used.
mol and 93 mg of the above solid catalyst component were added, and the internal temperature was raised to 90 ° C. Although the internal pressure was 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 the polymerization. Ethylene was continuously introduced so that the total pressure was 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 147 g of white polyethylene powder. Polymerization activity is 29,800gP
E / g Ti, hr, ethylene pressure, 1,600 g PE / g
Cat, hr, ethylene pressure, catalytic efficiency 29,8
The activity was extremely high at 00 gPE / gTi. The produced ethylene polymer had 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 the number} of branches in the produced polymer was examined by ¹³ C-NMR, it was 0.1 or less per 1000 carbons. 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 1 g. Slurry polymerization was performed under the same conditions as in Example 8 to obtain 127 g of 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. The 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. The same autoclave as in Example 1 was used, in which 1000 ml of dry hexane and 5 mmo of triethylaluminum were used.
1 and 10 mg of the above solid catalyst component were added, and the internal temperature was adjusted to 70
Raised to ℃. The internal pressure is 1.5 kg / cm ² , but hydrogen is added to bring the total pressure to 3.0 kg / cm ^2, and 40 g of 1-butene is injected together with ethylene to bring the total pressure to 6 kg / c.
Polymerization was initiated by pressurizing to m ² . Total pressure is 6kg /
Ethylene was continuously introduced so as to be cm ² and polymerization was carried out for 1 hour. Thereafter, methanol was added to stop the polymerization, and hexane was removed by evaporation to remove white polyethylene powder 18
6 g was obtained. Polymerization activity is 172,000gPE / gT
i, hr, ethylene pressure, 6,200 g PE / gcat,
hr, ethylene pressure, catalytic efficiency 517,000 g
The activity was extremely high with PE / gTi. The melt flow rate (MFR) of the produced ethylene polymer was 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 The solid catalyst component was prepared under the same conditions as in Comparative Example 1. Slurry polymerization was performed under the same conditions as in Example 9 to obtain 230 g of white polyethylene powder. Polymerization activity is 139,000
gPE / gTi, hr, ethylene pressure, 7,670 gPE
/ Gcat, hr, ethylene pressure, catalyst efficiency is 41
The activity was 8,000 gPE / gTi, which was lower than that of Example 9. The resulting ethylene polymer had 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 / cm ^3.
It was cm ³ . Example 10 (a) Production of solid catalyst component Commercially available anhydrous magnesium chloride 15 g was placed in a stainless steel pot having an internal volume of 400 ml 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 in a nitrogen atmosphere to obtain a reaction product.
A three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and 100 g of dehydrated butanol and 12.8 g of the reaction product of anhydrous magnesium chloride and triethoxyaluminum described above were placed therein, and the temperature was kept at 80 ° C. for 1 ° C. Reacted for hours.
After cooling to room temperature, 45 g of silica (Fuji Davison, # 955) calcined at 400 ° C. for 3 hours was added, and the mixture was reacted again at 80 ° C. for 2 hours and then dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, 50 g of the above solid powder was put therein, 100 cc of dehydrated hexane and 4.8 g of titanium tetrachloride were added, and the mixture was 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 blow under heating,
The solvent component was removed to obtain a solid catalyst component. The obtained solid catalyst component contained 19 mg of titanium per 1 g of titanium. (B) Gas phase polymerization As a gas phase polymerization apparatus, a stainless steel oak equipped with a stirrer
A loop was made with a blower, a flow controller and a dry cyclone using a toque, and the temperature of the autoclave was adjusted by flowing hot water into the jacket. 250 m of the above solid catalyst component was placed in an autoclave adjusted to 80 ° C.
50 mmol of g / hr and triethylaluminum
/ Hr while supplying each gas while adjusting the hydrogen in the autoclave gas phase to be 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 the produced polymer was intermittently taken out to carry out continuous polymerization for 10 hours. The catalyst efficiency was 305,000 g polymer / gTi, which was a very high activity. 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 . When the branching in the produced polymer was examined by ¹³ C-NMR, it was found to be 0.
It was 1 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 1 g of titanium. Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 10. Catalyst efficiency is 288,000gP
The activity was extremely high with E / gTi. The melt flow rate (MFR) of the produced ethylene polymer was 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 used instead of cis-2-heptene.
Example 1 except 1.2 g of cis stilbene was used
A solid catalyst component was prepared in the same manner as 0. The obtained solid catalyst component contained 14 mg of titanium per 1 g of titanium.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 10. Catalyst efficiency is 253,000 gPE /
The activity was extremely high with gTi. The melt flow rate (MFR) of the produced ethylene polymer was 5.1 g / 10.
min, the density was 0.9669 g / cm ³ , and the 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 an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch. , 6.3 g of triethoxyaluminum, and under a nitrogen atmosphere,
Ball milling was performed for 16 hours at room temperature to obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and 100 g of dehydrated butanol and 12.8 g of the reaction product of anhydrous magnesium chloride and triethoxyaluminum described above were put therein, and reacted at 80 ° C. for 1 hour. It was After cooling to room temperature, add 45 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours, and again at 80 ° C.
React for 2 hours and then add cis-2-heptene 11.6
g was added and reacted at 80 ° C. for 1.5 hours. Then 120
It was dried under reduced pressure at ℃ for 2 hours to obtain a solid powder. A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, 50 g of the above solid powder was put therein, 100 cc of dehydrated hexane and 4.8 g of titanium tetrachloride were added, and the mixture was reacted at 120 ° C. for 1.5 hours. After that, perform a nitrogen blow under heating,
The solvent component was removed to obtain a solid catalyst component. The obtained solid catalyst component contained 17 mg of titanium per 1 g of titanium. (B) Gas phase polymerization Using the above solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 10. Catalyst efficiency is 277,000 gPE /
The activity was extremely high with gTi. The melt flow rate (MFR) of the produced ethylene polymer was 4.9 g / 10.
min, the density was 0.9664 g / cm ³ , and the bulk density was 0.39 g / cm ³ . When the number of branches in the produced polymer was examined by ¹³ C-NMR, it was 0.1 or less per 1000 carbons.

Comparative Example 8 Example 1 except that no cis-2-heptene was used.
A solid catalyst component was prepared in the same manner as 0. The obtained solid catalyst component contained 23.5 mg of titanium per 1 g. Gas phase polymerization was carried out using the above solid catalyst component under the same conditions as in Example 10. Catalyst efficiency is 149000gP
The catalyst efficiency was lower than that of E / gTi and Examples 10 to 13. The produced ethylene polymer had a melt flow rate (MFR) of 4.8 g / 10 min and a density of 0.
9662 g / cm ³ and a bulk density of 0.37 g / c
It was m ³ . Example 14 (a) Production of solid catalyst component Commercially available anhydrous magnesium chloride 15 g was placed in a stainless steel pot with an internal volume of 400 ml containing 25 stainless steel balls each 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 in a nitrogen atmosphere to obtain a reaction product.
A three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and 100 g of dehydrated butanol and 12.8 g of the reaction product of anhydrous magnesium chloride and triethoxyaluminum described above were put therein, and reacted at 80 ° C. for 1 hour. It was After cooling to room temperature, 45 g of silica (Fuji Davison, # 955) calcined at 400 ° C. for 3 hours was added, and the mixture was reacted again at 80 ° C. for 2 hours and then dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, 50 g of the above solid powder was put therein, 100 cc of dehydrated hexane and 5.3 g of diethoxydichlorotitanium were added, and the mixture was refluxed with hexane to give 1.
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 1.6 g was added and the mixture was stirred 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 1 g of titanium. (B) Gas phase polymerization Using the above solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 10. Catalyst efficiency is 292,000g PE /
The activity was extremely high with gTi. The melt flow rate (MFR) of the produced ethylene polymer was 4.3 g / 10.
min, the density was 0.9668 g / cm ³ , and the bulk density was 0.36 g / cm ³ . When the number of branches in the produced polymer was examined by ¹³ C-NMR, it was 0.1 or less per 1000 carbons. Comparative Example 9 Example 1 except that cis-2-heptene was not used.
A solid catalyst component was prepared in the same manner as in 4. The obtained solid catalyst component contained 20.5 mg of titanium per 1 g of titanium. Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 10. Catalyst efficiency 122,000gP
The catalyst efficiency was lower than that of E / gTi and Example 14. The melt flow rate of the produced ethylene polymer (M
FR) is 6.1g / 10min, density is 0.9664g
/ Cm ³ and the bulk density was 0.32 g / cm ³ .

Example 15 (a) Production of solid catalyst component A commercially available anhydrous stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls having a diameter of 1/2 inch was used. Magnesium chloride (10 g) and triethoxyaluminum (4.2 g) were added and subjected to ball milling at room temperature for 16 hours in a nitrogen atmosphere to obtain a reaction product.
A three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, 5 g of the reaction product of anhydrous magnesium chloride and triethoxyaluminum was added, and further 5 g of silica (Fuji Davison, # 952) calcined at 600 ° C. was added. Tetrahydrofuran (100 ml) was added, and the mixture was reacted at 60 ° C for 2 hours and dried under reduced pressure at 120 ° C to remove tetrahydrofuran. Next, after adding 3 ml of silicon tetrachloride and reacting at 60 ° C. for 2 hours, titanium tetrachloride was added to 1.6 ml.
After adding ml, the mixture was 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 the solvent component to obtain a solid catalyst component. . 30 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 carried out under the same conditions as in Example 10. Catalyst efficiency is 334,000 gPE /
The activity was extremely high with gTi. The melt flow rate (MFR) of the produced ethylene polymer was 5.5 g / 10.
min, the density was 0.9672 g / cm ³ , and the bulk density was 0.42 g / cm ³ . When the number of branches in the produced polymer was examined by ¹³ C-NMR, it was 0.1 or less per 1000 carbons. 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 1 g. Gas phase polymerization was carried out using the above solid catalyst component under the same conditions as in Example 15. Catalyst efficiency is 152,000gP
The catalyst efficiency was lower than that of E / gTi and Example 15. The 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) Manufacture of solid catalyst component SiO ₂ (Fuji Davisson, # #), which was calcined at 600 ° C. in a 500 ml three-necked flask equipped with a stirrer and a reflux condenser.
955) 50g was added, and dehydrated hexane 160
ml and titanium tetrachloride (2.2 ml) were added, and the mixture was reacted under a hexane reflux for 3 hours. After cooling, add 3 mmol of a hexane solution of diethylaluminum chloride at 1 mmol / cc.
After adding 0 ml and reacting again with hexane reflux for 2 hours, vacuum drying was performed at 120 ° C. to remove hexane. (Component [I]) Commercially available anhydrous magnesium chloride 10 g and aluminum triethoxide 4 were placed in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch. Into a nitrogen atmosphere, 0.2 g and titanium tetrachloride (2.7 g) were added, and ball milling was performed at room temperature for 16 hours to obtain a reaction product. The reaction product (5.4 g) was dissolved in dehydrated ethanol (160 ml), and the total amount of the solution was added to a three-necked flask containing the component [I] and reacted under ethanol reflux for 3 hours, and then at 150 ° C. for 6 hours. It was dried under reduced pressure. 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 the solvent component to obtain a solid catalyst component. 16 mg in 1 g of the obtained solid catalyst component
It contained titanium. (B) Gas phase polymerization Using the above solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 10. Catalyst efficiency is 314,000 gPE /
The activity was extremely high with gTi. The melt flow rate (MFR) of the produced ethylene polymer was 3.8 g / 10.
min, the density was 0.9665 g / cm ³ , and the bulk density was 0.42 g / cm ³ . When the number of branches in the produced polymer was examined by ¹³ C-NMR, it was 0.1 or less per 1000 carbons. 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 6. The obtained solid catalyst component contained 19 mg of titanium per 1 g of titanium.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 16. 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 in Example 16. 18 g of titanium was contained in 1 g of the obtained solid catalyst component. Using this solid catalyst component, Example 10
Gas phase polymerization was carried out under the same conditions as above. The catalyst efficiency is 301,
The activity was extremely high at 000 gPE / gTi. The produced ethylene polymer had 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 the number} of branches in the produced polymer was examined by ¹³ C-NMR, it was 0.1 or less per 1000 carbons. Comparative Example 12 Example 1 except that cis-2-heptene was not used.
A solid catalyst component was prepared in the same manner as in 7. The obtained solid catalyst component contained 22 mg of titanium per 1 g.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 17. Catalyst efficiency is 149000 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 the bulk density was 0.37 g / cm ³ . ¹³ C
-When the branching in the produced polymer was investigated by NMR,
It was 0.1 or less per 1000 carbons. Example 18 (a) Production of solid catalyst component Commercially available anhydrous magnesium chloride (10 g) , 4.2 g of triethoxyaluminum were charged and subjected to ball milling at room temperature for 16 hours in a nitrogen atmosphere to obtain a reaction product.
A three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and dehydrated 2-methyl-1-pentano-
100 g, 5.0 g of the reaction product of anhydrous magnesium chloride and triethoxyaluminum, and 10.0 g of diethoxydichlorotitanium were added, and the mixture was reacted at 80 ° C. for 1 hour.
After cooling to room temperature, 46 g of silica (Fuji Davison, # 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, and the mixture was stirred at room temperature for 1.5 hours, and then subjected to nitrogen blowing under heating to remove the solvent component to obtain a solid catalyst component. 25 g 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 carried out under the same conditions as in Example 10. Catalyst efficiency is 346,000 gPE /
The activity was extremely high with gTi. The melt flow rate (MFR) of the produced ethylene polymer was 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 number of branches in the produced polymer was examined by ¹³ C-NMR, it was 0.1 or less per 1000 carbons.

Comparative Example 13 Example 1 except that cis-2-heptene was not used.
A solid catalyst component was prepared in the same manner as in No. 8. The obtained solid catalyst component contained 29 mg of titanium per 1 g of titanium.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 18. Catalyst efficiency is 160,000 gPE /
The catalyst efficiency was lower than that of 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-pentanol used in Example 18. 24 g of titanium was contained in 1 g of the obtained solid catalyst component. Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 10. Catalyst efficiency is 331,000gP
The activity was extremely high with E / gTi. The melt flow rate (MFR) of the produced ethylene polymer was 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, it was 100
The number 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 1 g. 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. The 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, 250 mg / wt of the above solid catalyst component was placed in an autoclave adjusted to 80 ° C.
hr and triethylaluminum at 50 mmol / h
at a rate of r, and the butene-1 / ethylene molar ratio in the autoclave gas phase was adjusted to 0.25, and each gas was supplied while adjusting hydrogen to 15% 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 the produced polymer was intermittently withdrawn to carry out continuous polymerization for 10 hours. Catalyst efficiency is 2
The activity was extremely high at 80,000 gPE / gTi. The melt flow rate of the produced ethylene polymer (M
FR) is 1.4g / 10min, density is 0.9218g
/ 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. Gas phase polymerization was carried out using the above solid catalyst component under the same conditions as in Example 20. Catalyst efficiency is 230,000g PE / g
The catalyst efficiency was lower than that of Ti and Example 20. 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
Gas phase polymerization was carried out under the same conditions as above. The catalyst efficiency is 269,
The activity was extremely high at 000 gPE / gTi. 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 the number} of branches in the produced polymer was examined by ¹³ C-NMR, it was 0.1 or less per 1000 carbons. 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 1. The obtained solid catalyst component contained 28 mg of titanium per 1 g.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 21. Catalyst efficiency is 118,000g PE /
The catalyst efficiency was lower than that of gTi and Example 21. Melt flow rate (MFR) of the produced ethylene polymer
6.5g / 10min, density is 0.9669g / c
m ³ , and the bulk density was 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 replaced with nitrogen, and 50 g of silica (Fuji Davison, # 955) calcined at 600 ° C. was put therein. Then, 160 ml of dehydrated hexane and 2.2 ml of titanium tetrachloride were added and reacted for 3 hours under hexane reflux. After cooling, the supernatant was removed by decantation and dried under reduced pressure at 120 ° C to remove hexane. (Component [I]) Commercially available anhydrous magnesium chloride 10 g, triethoxyaluminum 4. in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch. Into a nitrogen atmosphere, 2 g was added, and ball milling was performed at room temperature for 16 hours to obtain a reaction product.
Another 500 ml three-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen, and 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 for 3 hours under the reflux of ethanol. It was After cooling, 50 g of the above component [I] was added, and the mixture was reacted under a reflux of ethanol for 3 hours. After cooling, the supernatant was removed by decantation, and vacuum drying was performed at 150 ° C for 6 hours. Next, 150 ml of hexane and 80 mmol of diethylaluminum chloride were added, and the mixture was reacted under hexane reflux for 1 hour. After that, 24 mmol of methyldimethoxysilane was added and reacted at 40 ° C. for 1 hour, and then 23.4 g of cis-2-heptene was added and stirred at room temperature for 1.5 hours, and then nitrogen blow under heating to remove the solvent component. The solid catalyst component was obtained. 21 g 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 carried out under the same conditions as in Example 10. Catalyst efficiency is 295,000 gPE /
The activity was extremely high with gTi. The melt flow rate (MFR) of the produced ethylene polymer was 6.2 g / 10.
min, the density was 0.9671 g / cm ³ , and the bulk density was 0.44 g / cm ³ . When the number of branches in the produced polymer was examined by ¹³ C-NMR, it was 0.1 or less per 1000 carbons. 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 2. The obtained solid catalyst component contained 25 mg of titanium per 1 g.
Using this solid catalyst component, gas phase polymerization was carried out under the same conditions as in Example 22. 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 drawings]

FIG. 1 is a flow chart showing steps for producing a catalyst of the present invention.

Claims (2)

[Claims] 1. A method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as a catalyst,
The solid catalyst component is at least a magnesium compound, a titanium compound and a general formula R ¹ CH═CHR ² (wherein R ¹ and R ² represent an alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, which may be the same or different). The method for producing polyolefin is characterized in that it is a substance obtained by contacting internal olefin compounds represented by (cis position) with each other. 2. A method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as a catalyst,
The solid catalyst component is 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 (wherein R ¹ and R ² are an alkyl group having 1 to 24 carbon atoms or an aryl group). Alternatively, a method for producing a polyolefin, which is a substance obtained by contacting internal olefin compounds represented by aralkyl groups, which may be the same or different and are in the cis position, with each other.