JP6739186B2 - Process for producing olefin polymer - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention can produce an olefin polymer with high activity, can effectively prevent contamination of the inside of the polymerization vessel such as the polymerization vessel wall and stirring blade, and can operate stably for a long period of time. The present invention relates to a method for producing an olefin polymer.

In chemical equipment such as petroleum distilling and refining plants and polyolefin manufacturing plants, fouling causes problems such as reduced heat exchange capacity of the plants and blockage of pipes, resulting in unstable manufacturing operation and the worst case. In the case of, the operation may be stopped. Specifically, it is known that, for example, polymer lumps or sheet-like substances are generated in the polymerization vessel, or the polymer is attached to the stirring blades or the polymerization vessel wall.

As a method for solving these problems, for example, Patent Documents 1 and 2 disclose a method of adding a surfactant in a polymerization vessel, and Patent Document 3 discloses a method of adding a surfactant to a solid catalyst in which olefin is prepolymerized. A method of using a supported catalyst for polymerization is disclosed. However, these methods have a problem that the activity of the polymerization catalyst is lowered and the catalyst cost is increased. Therefore, in recent years, methods for improving the polymerization activity and reducing the occurrence of various problems such as fouling have been proposed (Patent Documents 4 to 7).

JP, 2000-313717, A JP 2000-327707 A JP, 2000-297114, A JP, 2004-277677, A International Publication No. 2010/114069 International Publication No. 2010/123033 Special table 2012-514685 gazette Japanese Patent Publication No. 2015-526583

As a result of examination by the present inventors, in the methods proposed in Patent Documents 4 to 7, there are cases where the fouling is insufficiently suppressed under relatively harsh conditions such as a high production rate or large-scale production. I came to the knowledge that there is. And as a result of further studies by the present inventors, the cause is that the mixing ratio or the supply amount ratio is difficult to stabilize when the compounds to be introduced for fouling suppression are plural kinds, and the solid state and In the case of a suspension, it was thought that the stability of the supply or the dispersibility in the polymerization vessel might decrease. In fact, U.S. Pat. No. 6,037,849 discloses supply instability.

The present invention has been made in view of the above-mentioned new problems of the prior art. That is, an object of the present invention is to produce an olefin polymer with high activity, and to effectively prevent fouling inside the polymerization vessel such as a polymerization vessel wall or a stirring blade, which enables stable operation for a long period of time. An object of the present invention is to provide a method for producing an olefin polymer that can be used.

The present invention is specified by the following matters.

[1] (A) Solid catalyst component for olefin polymerization, and
(B) In the presence of an amide compound represented by the following general formula (I),
A method for producing an olefin polymer , which comprises (co)polymerizing at least one olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms in a polymerization vessel ,

(In formula (I), R ¹ and R ² are each a hydrocarbon group having 1 to 32 carbon atoms and may be the same or different, and R ³ , R ⁴ and R ⁵ are each a hydrogen atom or a carbon number. It is a hydrocarbon group of 1 or more and 18 or less, an oxygen-containing hydrocarbon group or a sulfur-containing hydrocarbon group, which may be the same or different from each other, and a and b are each an integer of 0 or more and may be the same or different from each other. , A+b is 1 or more.)

Ingredient (A)
(A-1) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton,
(A-2) (a) organometallic compound,
(B) an organoaluminum oxy compound, and
(C) A compound selected from a Lewis acid, an ionic compound, a borane compound, a carborane compound, a heteropoly compound and an isopoly compound, which reacts with (A-1) to form an ion pair.
At least one compound selected from
(A-3) Fine particle carrier
Consists of
A method for producing an olefin polymer, comprising:
[2] The method for producing an olefin polymer according to [1], wherein in the general formula (I), R ³ , R ⁴ and R ⁵ are hydrogen atoms or hydrocarbon groups having 1 to 18 carbon atoms.
[3] The method for producing an olefin polymer as described in [1] or [2], wherein in the general formula (I), a+b is 1.
[4] The method for producing an olefin polymer according to any one of [1] to [3], wherein the component (B) is supplied in an amount of 0.1 ppm or more and 500 ppm or less with respect to the olefin polymer yield.
[5] The method for producing an olefin polymer according to any one of [1] to [4], wherein the olefin is ethylene alone or ethylene and an α-olefin having 3 to 20 carbon atoms.
[6] The method for producing an olefin polymer according to any one of [1] to [5], wherein the olefin (co)polymerization is performed in a suspension or in a gas phase.

According to the present invention, the decrease in the polymerization activity of olefins is reduced, the fluidity inside the polymerization vessel is effectively ensured without decreasing the production rate, and the adhesion of the polymer to the polymerization vessel wall or the stirring blade is prevented. Since this can be prevented, stable operation with high activity can be performed for a long period of time, and an olefin polymer having excellent particle properties can be produced.

[Solid catalyst component (A) for olefin polymerization]
As the solid catalyst component (A) for olefin polymerization used in the present invention, for example, a solid catalyst component containing a compound of a transition metal selected from Groups 3 to 12 of the periodic table is preferable. Specific examples thereof include a carrier-supported transition metal complex catalyst component in which a transition metal compound of Groups 4 to 6 of the Periodic Table is supported on a particulate carrier, and a solid titanium catalyst component and an organoaluminum compound. Examples thereof include a titanium-based catalyst component and a Phillips catalyst component in which an arbitrary chromium compound capable of being oxidized to chromium trioxide is supported on an inorganic oxide solid such as silica.

Among them, the carrier-supported metallocene catalyst component belonging to the carrier-supported transition metal complex catalyst component is preferable, and the carrier-supported metallocene catalyst component comprising the following components (A-1) to (A-3) Is more preferable.
(A-1) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton,
(A-2) (a) organometallic compound,
(B) an organoaluminum oxy compound, and
(C) Compound that reacts with (A-1) to form an ion pair
At least one compound selected from
(A-3) Fine particle carrier

The group 4 to 6 transition metal compound of the periodic table used for the carrier-supported transition metal complex-based catalyst component may be a group 4 to 6 transition metal compound having a known olefin polymerization ability, for example, the periodic table. Group 4-6 transition metal halides, transition metal alkylates, transition metal alkoxides, non-crosslinkable or crosslinkable metallocene compounds can be used. In particular, a transition metal compound of Group 4 of the periodic table is preferable. Specific examples include titanium tetrachloride, dimethyltitanium dichloride, tetrabenzyl titanium, tetrabenzyl zirconium, and tetrabutoxy titanium. Further, from the viewpoint of polymerization activity and the like, non-crosslinkable or crosslinkable metallocene compounds are particularly preferable. The metallocene compound is a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, and is represented by, for example, the following general formula (II).

ML _X ...(II)
(In the formula (II), M is a transition metal of Group 4 of the periodic table (specifically, zirconium, titanium or hafnium), L is a ligand (group) coordinated to the transition metal, and at least 1 L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom. , A trialkylsilyl group, —SO ₃ R (R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen) or a hydrogen atom, and x is a valence of the transition metal. Indicates the number of L.)

Specific examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group; methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group , Pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopenta Examples thereof include alkyl-substituted cyclopentadienyl group such as dienyl group and hexylcyclopentadienyl group; indenyl group; 4,5,6,7-tetrahydroindenyl group; and fluorenyl group. These groups may have a substituent such as a halogen atom and a trialkylsilyl group.

As the ligand having a cyclopentadienyl skeleton, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula (II) contains two or more groups having a cyclopentadienyl skeleton, the two groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene; It may be bonded via an alkylidene group such as lidene or diphenylmethylene; a silylene group; a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group or a methylphenylsilylene group. Further, the groups having two or more cyclopentadienyl skeletons are preferably the same.

Specific examples of the hydrocarbon group having 1 to 12 carbon atoms, which is a ligand other than the ligand having a cyclopentadienyl skeleton, include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a pentyl group. And the like; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; and aralkyl groups such as benzyl group and neofil group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group and the like. Specific examples of the aryloxy group include a phenoxy group. Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of —SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.

When the valence of the transition metal is 4, the compound represented by the general formula (II) is more specifically represented by the following general formula (II′).

MR ^a R ^b R ^c R ^d ...(II′)
(In the formula (II′), M is zirconium, titanium or hafnium, R ^a is a group having a cyclopentadienyl skeleton, and R ^b , R ^c and R ^d may be the same or different from each other, A group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, —SO ₃ R (R is a substituent such as halogen. Optionally a hydrocarbon group having 1 to 8 carbon atoms) or a hydrogen atom).

As the component (A-1), a transition metal compound in which one of R ^b , R ^c and R ^{d in} the general formula (II′) is a group having a cyclopentadienyl skeleton is particularly preferable. For example, in the case where R ^a and R ^b are groups having a cyclopentadienyl skeleton, the groups having these cyclopentadienyl skeletons can be bonded to each other via an alkylene group, a substituted alkylene group, an alkylidene group, a silylene group, a substituted silylene group or the like. It may be combined. In this case, R ^c and R ^d are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, —SO ₃ R or a hydrogen atom.

Below, the specific compound is illustrated about the transition metal compound whose M is zirconium. Bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromide, bis(indenyl)zirconium bis(p-toluenesulfonato),bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, bis(fluorenyl) Zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl) ) Zirconium bis(methane sulfonate), ethylene bis(indenyl) zirconium bis(p-toluene sulfonate), ethylene bis(indenyl) zirconium bis(trifluoromethane sulfonate), ethylene bis(4,5,6,7-tetrahydro) Indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis(cyclopentadienyl) zirconium dichloride, dimethylsilylene Bis(methylcyclopentadienyl)zirconium dichloride, dimethylsilylene bis(dimethylcyclopentadienyl)zirconium dichloride, dimethylsilylene bis(trimethylcyclopentadienyl)zirconium dichloride, dimethylsilylene bis(indenyl)zirconium dichloride, dimethylsilylene bis( Indenyl)zirconium bis(trifluoromethanesulfonato), rac-dimethylsilylenebis{1-(2-methyl-4,5-acenaphthocyclopentadienyl)}zirconium dichloride, rac-dimethylsilylenebis{1-(2- Methyl-4,5-benzoindenyl)}zirconium dichloride, rac-dimethylsilylenebis{1-(2-methyl-4-isopropyl-7-methylindenyl)}zirconium dichloride, rac-dimethylsilylenebis{1-( 2-Methyl-4-phenylindenyl)}zirconium dichloride, rac-dimethylsilylenebis{1-(2-methylindenyl)}zirconium dichloride, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium Jiku Lolid, dimethyl silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenyl silylene bis(indenyl) zirconium dichloride, methylphenyl silylene bis(indenyl) zirconium dichloride, bis(cyclopentadienyl) zirconium dichloride, bis(cyclopentadienyl) ) Zirconium dibromide, bis(cyclopentadienyl)methyl zirconium monochloride, bis(cyclopentadienyl)ethyl zirconium monochloride, bis(cyclopentadienyl)cyclohexyl zirconium monochloride, bis(cyclopentadienyl)phenyl zirconium Monochloride, bis(cyclopentadienyl)benzyl zirconium monochloride, bis(cyclopentadienyl)zirconium monochloride monohydride, bis(cyclopentadienyl)methylzirconium monohydride, bis(cyclopentadienyl)dimethylzirconium, Bis(cyclopentadienyl)diphenylzirconium, bis(cyclopentadienyl)dibenzylzirconium, bis(cyclopentadienyl)zirconium methoxy chloride, bis(cyclopentadienyl)zirconium ethoxy chloride, bis(cyclopentadienyl) Zirconium bis(methanesulfonato), bis(cyclopentadienyl)zirconium bis(p-toluenesulfonato), bis(cyclopentadienyl)zirconium bis(trifluoromethanesulfonato), bis(methylcyclopentadienyl)zirconium Dichloride, bis(dimethylcyclopentadienyl) zirconium dichloride, bis(dimethylcyclopentadienyl) zirconium ethoxy chloride, bis(dimethylcyclopentadienyl) zirconium bis(trifluoromethanesulfonato), bis(ethylcyclopentadienyl) Zirconium dichloride, bis(methylethylcyclopentadienyl)zirconium dichloride, bis(propylcyclopentadienyl)zirconium dichloride, bis(methylpropylcyclopentadienyl)zirconium dichloride, bis(butylcyclopentadienyl)zirconium dichloride, bis (Methylbutylcyclopentadienyl)zirconium dichloride, bis(methylbutylcyclopentadienyl)zirconium bis(methanesulfonato),bis(trimethylcyclopentadienyl) ) Zirconium dichloride, bis(tetramethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(hexylcyclopentadienyl)zirconium dichloride, bis(trimethylsilylcyclopentadienyl)zirconium dichloride, etc. ..

In each of the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including. The alkyl group such as propyl and butyl includes isomers such as n-, i-, sec-, and tert-.

Further, in each of the above zirconium compounds, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used. In addition to titanium compounds and hafnium compounds having the same three-dimensional structure, and further bromide, iodide, etc., for example, JP-A-3-9913, JP-A-2-131488, JP-A-3-21607, Transition metal compounds such as those described in Kaihei 3-106907, Japanese Patent Application Laid-Open No. 3-188092, Japanese Patent Application Laid-Open No. 4-69394, Japanese Patent Application Laid-Open No. 4-3008887, International Publication No. 2001/27124, etc. Can be mentioned.

Further, as the transition metal compound, a transition metal compound represented by the following general formula (IV) as described in JP-A No. 11-315109 can also be mentioned.

(In the formula (III), M represents a transition metal atom of Groups 4 to 6 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different from each other, and are hydrogen. Represents an atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. , Two or more of these may be linked to each other to form a ring, and when m is 2 or more, two groups of R ^{1 to} R ⁶ may be linked ( However, R ¹ is not bonded to each other), n is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or boron. A group containing a group, an aluminum containing group, a phosphorus containing group, a halogen containing group, a heterocyclic compound residue, a silicon containing group, a germanium containing group, or a tin containing group, and when n is 2 or more, a plurality of groups represented by X The groups may be the same or different from each other, and plural groups represented by X may be bonded to each other to form a ring.)

The component (A-2) constituting the carrier-supported transition metal complex-based catalyst component reacts with the organometallic compound (a), the organoaluminumoxy compound (b), and (A-1) to form an ion pair. Is at least one compound selected from the compound (c).

As the organometallic compound (a), for example, organometallic compounds of groups 1 and 2 and groups 12 and 13 of the periodic table represented by the following general formulas (IV), (V) and (VI) can be used. ..

R ^a _m Al(OR ^b ) _n H _p X _q ... (IV)
(In formula (IV), R ^a and R ^b may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0<m≦3, n is 0≦n<3, p is 0≦p<3, q is a number 0≦q<3, and m+n+p+q=3.)
An organoaluminum compound represented by. Specific examples of this compound include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, and diisobutyl aluminum hydride.

M ² AlR ^a ₄ (V)
(In the formula (V), M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
A complex alkyl compound of a Group 1 metal of the periodic table and aluminum. Specific examples of this compound include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

R ^a R ^b M ³ ... (VI)
(In formula (VI), R ^a and R ^b may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. is there.)
A dialkyl compound of a metal of Group 2 or Group 12 of the periodic table represented by:

Among the above organometallic compounds, organoaluminum compounds are preferred. The organometallic compounds may be used alone or in combination of two or more.

A known aluminoxane can be used as the organoaluminum oxy compound (b). Specifically, for example, compounds represented by the following general formulas (VII) and (VIII) can be used.

(In the formulas (VII) and (VIII), R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.)

As the organoaluminum oxy compound (b), in the above formulas (VII) and (VIII), methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is suitably used. These aluminoxanes may be mixed with some organoaluminum compounds. It may also be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. The organoaluminum oxy compound described in JP-A-2-167305 and the aluminoxane having two or more kinds of alkyl groups described in JP-A-2-24701 and JP-A-3-103407 are also suitable. Available.

Such an aluminoxane can be produced, for example, by the following methods (1) to (3) and is usually obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension described above to react the organoaluminum compound with adsorption water or crystallization water.
(2) A method in which water, ice, or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.
(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

Aluminoxanes may contain small amounts of organometallic components. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-. Trialkyl aluminum such as butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide Dialkyl aluminum halides such as diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; Dialkyl aluminum aryloxides such as diethyl aluminum phenoxide. To be Of these, trialkylaluminum and tricycloalkylaluminum are preferable.

Furthermore, as the organoaluminum compound, isoprenylaluminum represented by the following general formula (IX) can also be used.

_{(I-C 4 H 9)} x Al y (C 5 H 10) z ··· (IX)
(In the formula (IX), x, y, and z are positive numbers, and z≧2x)

The organoaluminum compounds may be used alone or in combination of two or more.

Specific examples of the solvent used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane. Of hydrocarbons, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons. Hydrocarbon solvents such as halides, especially chlorides and bromides, are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these, aromatic hydrocarbons are preferable.

Examples of the compound (c) that reacts with (A-1) to form an ion pair (hereinafter referred to as “ionized ionic compound (c)”) are disclosed in JP-A-1-501950 and JP-A-1-502036. Lewis acids, ionic compounds described in JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, and the like. Examples include borane compounds and carborane compounds, as well as heteropoly compounds and isopoly compounds. The ionized ionic compound (c) may be used alone or in combination of two or more.

The organometallic compound (a), the organoaluminum oxy compound (b), and the ionized ionic compound (c), which are the components that can be used as the component (A-2), have been described above. It is preferable to use b) as the component (A-2).

Examples of the particulate carrier (A-3) include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , and mixtures containing these (eg, Inorganic metal oxide carriers such as SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO), Inorganic chloride carriers such as MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ , and organic carriers such as polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, and styrene-divinylbenzene copolymer. .. Clay, its components, clay minerals, ion-exchangeable layered compounds, and the like can also be used as the inorganic carrier.

The average particle size of the carrier using an inorganic compound is preferably 1 to 300 μm, more preferably 3 to 200 μm. Such a carrier is used after firing at 100 to 1000° C., preferably 150 to 700° C., if necessary.

The inorganic chloride may be used as it is, or may be used after being crushed by a ball mill or a vibration mill. Further, it is also possible to use the one obtained by dissolving the inorganic chloride in a solvent such as alcohol and then depositing it in the form of fine particles with a depositing agent.

Clay-based carriers are usually composed mainly of clay minerals. Further, the carrier using the ion-exchangeable layered compound has a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak binding forces, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. Further, these clays, clay minerals, and ion-exchange layered compounds are not limited to naturally-occurring ones, and artificial synthetic products can also be used. Further, as the clay, clay mineral or ion-exchange layered compound, clay, clay mineral, or ion crystalline compound having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingelite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdee group, palygorskite, kaolinite, nacrite, Examples include dickite and halloysite. Examples of the ion-exchange layered compound include α-Zr(HAsO ₄ ) ₂ ·H ₂ O, α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) ₂ 3H ₂ O, α-Ti(HPO _{4 ).} ) ₂ , α-Ti(HAsO ₄ ) ₂ ·H ₂ O, α-Sn(HPO ₄ ) ₂ ·H ₂ O, γ-Zr(HPO ₄ ) ₂ , γ-Ti(HPO ₄ ) ₂ , γ-Ti. Examples thereof include crystalline acidic salts of polyvalent metals such as (NH ₄ PO ₄ ) ₂ ·H ₂ O. It is also preferable to chemically treat clay and clay minerals. As the chemical treatment, any of surface treatment for removing impurities adhering to the surface, treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment.

The ion-exchangeable layered compound may be a layered compound in which the interlayer is expanded by utilizing the ion-exchange property and exchanging the exchangeable ion between layers with another large bulky ion. Such bulky ions play a pillar-like role for supporting the layered structure, and are usually called pillars. In addition, the introduction of another substance between the layers of the layered compound is called intercalation. Examples of the guest compounds to be intercalated _compound, TiCl 4, ZrCl cationic inorganic compound such as _{4, Ti (OR) 4,} Zr (OR) 4, PO (OR) 3, B (OR) 3 or the like of the metal alkoxide ( R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O(OCOCH ₃ ) ₆ ] ^{+ and} other metal hydroxide ions, etc. Can be mentioned. These compounds may be used alone or in combination of two or more. In addition, when these compounds were intercalated, they were obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group or the like) such as Si(OR) ₄ , Al(OR) ₃ , Ge(OR) ₄ . Polymers, colloidal inorganic compounds such as SiO _{2 and the} like can also be present together. Examples of the pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them. Among these, preferred are clays and clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

Examples of the organic compound used for the organic carrier include granular or particulate solids having a particle size in the range of 1 to 300 μm. Specifically, as exemplified above, the (co)weight produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene. Included are polymer or vinylcyclohexane, (co)polymers produced based on styrene, and their modified forms.

In addition, the components (A-2) described above are prepared by the methods described in JP-A Nos. 11-140113, 2000-38410, 2000-95810, and International Publication No. 2010/55652. It is also possible to use a solid component obtained by insolubilizing the above) as the particulate carrier (A-3). In this case, contact with the component (A-2) is not essential in the method for preparing a carrier-supported metallocene catalyst component described below.

A method for preparing a carrier-supported metallocene catalyst component, which is one of the solid catalyst components (A) for olefin polymerization, will be described. The carrier-supported metallocene-based catalyst component is a catalyst component in which a metallocene-based transition metal compound is supported on a carrier, and preferably the component (A-1) and the component (A-2) described above are particularly preferable. Is a catalyst component containing the component (b)] and the component (A-3). This carrier-supported metallocene catalyst can be prepared, for example, by mixing and contacting the component (A-1), the component (A-2) and the component (A-3). The contact order of each component is arbitrary.

An inert hydrocarbon solvent is preferably used for the preparation of the carrier-supported metallocene catalyst component. Specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclopentane and other alicyclic hydrocarbons; benzene, toluene, Aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or a mixture thereof.

When preparing the carrier-supported metallocene catalyst component, the transition metal compound (A-1) is usually 0.001 to 1.0 mmol, preferably 1 to 10 g, per 1 g of the particulate carrier (A-3) in terms of transition metal atom. Used in an amount of 0.005-0.5 mmol. The organoaluminum oxy compound (b) is used in an amount of usually 0.1 to 100 mmol, preferably 0.5 to 20 mmol in terms of aluminum atom. When an organoaluminum compound is used, the organoaluminum compound is generally used in an amount of 0.001 to 1000 mmol, preferably 2 to 500 mmol, per 1 g of the particulate carrier (A-3).

The temperature at which the above components are mixed and contacted is usually −50 to 150° C., preferably −20 to 120° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes.

In the carrier-supported metallocene catalyst component thus obtained, the transition metal compound (A-1) is converted to about 5×10 ⁻⁶ to 10 ^{−10 in} terms of transition metal atom per 1 g of the fine particle carrier (A-3). ^-3 mol, preferably 10 ^{−5 to} 3×10 ⁻⁴ mol, and the organoaluminum oxy compound (b) is approximately 10 ⁻³ to 10 ⁻¹ mol, preferably 2×10 ⁻ , in terms of aluminum atom. It is desirable that the carrier be supported in an amount of ^{3 to} 5×10 ⁻² mol.

The solid catalyst component (A) for olefin polymerization may be a prepolymerized catalyst component in which olefin is prepolymerized. The prepolymerization catalyst component is formed from an olefin polymerization catalyst and, if necessary, an olefin polymer produced by prepolymerization. The prepolymerization catalyst contains a transition metal compound (A-1), a component (A-2) such as an organoaluminum oxy compound (b), and a particulate carrier (A-3), and if necessary, prepolymerization. The olefin polymer (D) produced by As a method for preparing the prepolymerization catalyst, for example, a solid catalyst component obtained by mixing and contacting the components (A-1), (A-2) and (A-3) in an inert hydrocarbon solvent or an olefin medium. There is a method of prepolymerizing a small amount of olefin. Specific examples of the inert hydrocarbon solvent used for preparing the prepolymerization catalyst include the same inert hydrocarbon solvents as those used for preparing the carrier-supported metallocene catalyst described above.

The olefin used in the prepolymerization is 100 to 0 mol% of ethylene, 0 to 49 mol% of propylene, and 0 to 100 mol% of olefin having 4 or more carbon atoms, preferably 100 to 0 mol% of ethylene, Propylene is 0 to 20 mol% and olefin having 4 or more carbon atoms is in the range of 0 to 100 mol%, more preferably 100 to 20 mol% ethylene, 0 to 20 mol% propylene and olefin having 4 or more carbon atoms. Is preferably in the range of 0 to 80 mol %, particularly preferably 100 to 20 mol% of ethylene and 0 to 80 mol% of an olefin having 4 or more carbon atoms.

Specific examples of the olefin having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 Examples include α-olefins having 4 to 20 carbon atoms such as hexadecene, 1-octadecene, and 1-eicosene. Furthermore, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a- Octahydronaphthalene, styrene, vinylcyclohexane, dienes and the like can also be used.

When preparing the prepolymerization catalyst, the transition metal compound (A-1) is usually 0.001 to 1.0 mmol, preferably 0.005 to 1 g of the particulate support (A-3) in terms of transition metal atom. Used in an amount of 0.5 mmol. The organoaluminum oxy compound (b) is used in an amount of usually 0.1 to 100 mmol, preferably 0.5 to 20 mmol in terms of aluminum atom.

In the prepolymerization catalyst obtained as described above, about 5×10 ⁻⁶ to 10 ⁻³ mol of the transition metal compound (A-1) in terms of transition metal atom per 1 g of the fine particle carrier (A-3), The amount is preferably 10 ^{−5 to} 3×10 ⁻⁴ mol, and the organoaluminum oxy compound (b) is about 10 ⁻³ to 10 ⁻¹ mol, preferably 2×10 ^{−3 to} 5×, in terms of aluminum atom. The olefin polymer (D), which is supported in an amount of 10 ⁻² mol and is produced by prepolymerization, is supported in an amount of about 0.1 to 500 g, preferably 0.3 to 300 g, and particularly preferably 1 to 100 g. Is desirable.

The solid catalyst component (A) for olefin polymerization may contain other components useful for polymerization in addition to the components described above. Further, the carrier-supported metallocene catalyst component may optionally contain an organoaluminum compound and a surfactant as needed during catalyst synthesis or prepolymerization.

[Amide compound (B)]
The amide compound (B) used in the present invention is an amide compound represented by the following general formula (I). By using such a specific amide compound as an additive during olefin polymerization, an olefin polymer can be produced with high activity and various problems such as fouling can be suppressed. Specifically, since the amide compound (B) used in the present invention can effectively suppress the occurrence of various problems with a relatively small amount as compared with conventional additives, the degree of decrease in the polymerization activity due to the addition of the additives. As a result, the olefin polymer can be produced with high activity.

(In formula (I), R ¹ and R ² are each a hydrocarbon group having 1 to 32 carbon atoms and may be the same or different, and R ³ , R ⁴ and R ⁵ are each a hydrogen atom or a carbon number. It is a hydrocarbon group of 1 or more and 18 or less, an oxygen-containing hydrocarbon group or a sulfur-containing hydrocarbon group, which may be the same or different from each other, and a and b are each an integer of 0 or more and may be the same or different from each other. , A+b is 1 or more.)

R ¹ and R ² (hydrocarbon group having 1 to 32 carbon atoms) in the general formula (I) may be saturated or unsaturated, may be aliphatic or aromatic, and may be linear, branched or cyclic. .. For example, any of an aliphatic hydrocarbon group such as an alkyl group and an alkenyl group and an aromatic hydrocarbon group can be used. Preferred specific examples include an alkyl group or an alkenyl such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group and an oleoyl group. Groups. Other examples include cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group. Particularly, a hydrocarbon group having 1 to 18 carbon atoms is preferable, and an alkyl group and an alkenyl group having 1 to 18 carbon atoms are more preferable.

In the case where R ³ , R ⁴ and R ⁵ in the general formula (I) are hydrocarbon groups having 1 to 18 carbon atoms, preferable specific examples thereof include those similar to the above hydrocarbon groups. When R ³ , R ⁴ and R ⁵ are oxygen-containing hydrocarbon groups having 1 to 18 carbon atoms, specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an ethanol group and a propionic acid group. In the case of a sulfur-containing hydrocarbon group having 1 to 18 carbon atoms, specific examples thereof include methylthio group and methanethiol group. As R ³ , R ⁴ and R ⁵ , a hydrogen atom and a hydrocarbon group having 1 to 18 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable.

In the general formula (I), a and b are each an integer of 0 or more, a+b is 1 or more, preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and most preferably 1 (ie One of a and b is 1 and the other is 0). For example, when a=1 and b=0, the compound is an N-acyl sarcosine compound (N-acyl-N-alkylglycine compound) represented by the following general formula (I-1), and when a=0 and b=1 Is a carboxylic acid N-alkylethanolamide compound represented by the following general formula (I-2). Both are suitable compounds as the component (B).

(In the formula (I-1) and ^{(I-2), R 1} ~R 5 is the same as ^R 1 to R ⁵ of formula (I).)

As R ¹ and R ² in the general formulas (I-1) and (I-1), a hydrocarbon group having 1 to 18 carbon atoms is preferable, and an alkyl group and an alkenyl group having 1 to 18 carbon atoms are more preferable. .. Furthermore, as R ² , an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. R ³ , R ⁴ and R ⁵ are preferably hydrogen atoms and hydrocarbon groups having 1 to 18 carbon atoms, more preferably hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, and hydrogen atoms and 1 or more carbon atoms. Alkyl groups of 2 or less are particularly preferred, with hydrogen atoms being most preferred.

Specific examples of the compound represented by the general formula (I-1) include N-capryloylsarcosine, N-lauroylsarcosine, N-myristoylsarcosine, N-palmitoylsarcosine, N-stearoylsarcosine, N-oleoylsarcosine, N-lauroyl-N-ethylglycine, N-lauroyl-N-propylglycine, N-lauroyl-N-butylglycine, N-lauroyl-N-cyclohexylglycine, N-lauroyl-N-phenylglycine, N-lauroyl-N -Benzylglycine, N-lauroyl-N-methylalanine, N-lauroyl-N-methylaspartic acid, N-lauroyl-N-methylcysteine, N-lauroyl-N-methylglutamic acid, N-lauroyl-N-methylleucine, N-lauroyl-N-methylisoleucine, N-lauroyl-N-methylmethionine, N-lauroyl-N-methylphenylalanine, N-lauroyl-N-methylserine, N-lauroyl-N-methylthreonine, N-lauroyl-N- Examples include methyltyrosine and N-lauroyl-N-methylvaline. Among them, compounds in which R ² is a methyl group and R ³ is a hydrogen atom are preferable, and N-lauroyl sarcosine, N-oleoyl sarcosine, N-capryloyl sarcosine, N-myristoyl sarcosine, and N-stearoyl sarcosine are more preferable.

Specific examples of the compound represented by the general formula (I-2) include caprylic acid N-methylethanolamide, capric acid N-methylethanolamide, lauric acid N-methylethanolamide, myristic acid N-methylethanolamide, Palmitic acid N-methylethanolamide, stearic acid N-methylethanolamide, oleic acid N-methylethanolamide, linoleic acid N-methylethanolamide, linolenic acid N-methylethanolamide, coconut oil fatty acid N-methylethanolamide, laurin Acid N-ethylethanolamide, lauric acid N-propylethanolamide, lauric acid N-butylethanolamide, lauric acid N-phenylethanolamide, lauric acid N-benzylethanolamide, lauric acid N-methylisopropanolamide, lauric acid N -Methylisobutanolamide. Among them, compounds in which R ² is a methyl group and R ⁴ and R ⁵ are hydrogen atoms are preferable, and particularly coconut oil fatty acid N-methylethanolamide, lauric acid N-methylethanolamide, stearic acid N-methylethanolamide, oleic acid. N-methylethanolamide is more preferred.

In addition, specific examples of the compound represented by the general formula (I) include ethylene glycol N-lauroyl sarcosinate, polyoxyethylene N-lauroyl sarcosinate, polyoxypropylene N-lauroyl sarcosinate and polyoxy. Also included are ethylene coconut oil fatty acid N-methyl ethanolamide and polyoxypropylene coconut oil fatty acid N-methyl ethanolamide.

[Production of olefin polymer]
In the method for producing an olefin polymer of the present invention, the olefin polymer is selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of the solid catalyst component (A) for olefin polymerization and the amide compound (B) described above. (Co)polymerize one or more of the olefins mentioned in the polymerizer. In the present invention, the term "(co)polymerization" is used to include both polymerization and copolymerization. In the present invention, the terms “polymerization” and “polymer” may be used to include not only homopolymerization and homopolymer but also copolymerization and copolymer.

At the time of (co)polymerization, the addition method of the solid catalyst component (A) for olefin polymerization and the amide compound (B) is arbitrary, and the component (B) may be added after the addition of the component (A). However, the component (A) may be added after the component (B) is added, or the component (A) and the component (B) may be mixed and brought into contact with each other.

The polymerization can be carried out either in suspension, in solution or in gas phase, and particularly preferably in suspension or in gas phase by slurry polymerization or gas phase polymerization. Specific examples of the inert hydrocarbon medium used in slurry polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane. Alicyclic hydrocarbons such as benzene; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or a mixture thereof. Of these, aliphatic hydrocarbons and alicyclic hydrocarbons are preferable.

The polymerization temperature is usually -50 to 150°C, preferably 0 to 100°C in the case of slurry polymerization, and usually 0 to 120°C, preferably 20 to 100°C in the case of gas phase polymerization. The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. The molecular weight of the obtained olefin polymer can also be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.

Specific examples of ethylene and α-olefins having 3 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1 -Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene. These may be used alone or in combination of two or more. Further, in addition to ethylene and α-olefin having 3 to 20 carbon atoms, another copolymerization monomer may be used in combination for copolymerization. Examples of the copolymerization monomer include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, Examples include 5,8,8a-octahydronaphthalene. Further, styrene, vinylcyclohexane, and diene can be used.

As the olefin, it is preferable to use ethylene alone or ethylene and an α-olefin having 3 to 20 carbon atoms. In particular, it is preferable to use 100 to 0 mol% of ethylene, 0 to 49 mol% of propylene and 0 to 100 mol% of an olefin having 4 or more carbon atoms, and 100 to 0 mol% of ethylene and 0 of propylene. To 20 mol% and α-olefins having 4 or more carbon atoms are more preferably used within the range of 0 to 100 mol%, ethylene is 100 to 20 mol%, propylene is 0 to 20 mol% and carbon atoms are 4 or more. It is particularly preferable to use the α-olefin in the range of 0 to 80 mol %, most preferably 100 to 20 mol% of ethylene and the α-olefin of 4 or more carbon atoms in the range of 0 to 80 mol %. .. Further, in the present invention, it is preferable to produce an ethylene-based polymer having ethylene as a main monomer. The ethylene-based polymer contains an ethylene component in an amount of 50 mol% or more and, if necessary, has an α of 4 to 10 carbon atoms. -(Co)polymers containing olefin components are preferred.

In the polymerization, the olefin polymerization catalyst (A) is usually 10 ⁻⁸ to 10 ⁻³ mol, preferably 10 ⁻⁷ to 10 mol per 1 l of the polymerization volume in terms of the transition metal atom in the transition metal compound (A-1). It is desirable to use it in an amount of 10 ⁻⁴ mol. The organoaluminum oxy compound (A-2) is generally used in an amount of 10 to 500 mol, preferably 20 to 200 mol, per mol of the transition metal atom in the transition metal compound (A-1) in terms of aluminum atom. desirable. The amide compound (B) is preferably used in an amount of 0.1 ppm or more and 500 ppm or less with respect to the olefin polymer yield. When the amide compound (B) is used in an amount of 0.1 ppm or more, the effect of suppressing the occurrence of various problems such as fouling tends to be sufficiently obtained. On the other hand, when it is used in an amount of 500 ppm or less, it tends to be possible to suppress the recovery of the polymerization solvent and the gas, the increase in the load on the purification treatment, and the deterioration of the catalyst performance. The amount of the amide compound (B) used is more preferably 0.5 ppm or more and 200 ppm or less, and particularly preferably 1 ppm or more and 100 ppm or less.

The present invention will be described more specifically by the following examples. However, the present invention is not limited to the description of the examples below.

[Preparation Example 1] (Preparation of solid catalyst component (X-1))
Using a stirrer with an internal volume of 270 L, under a nitrogen atmosphere, silica gel (manufactured by Fuji Silysia Chemical Ltd., average particle size 70 μm, specific surface area 340 m ² /g, pore volume 1.3 cm ³ /g, 10 at 250° C.) (Time drying) 10 kg was suspended in 77 L of toluene and then cooled to 0 to 5°C. While maintaining the system temperature at 0 to 5° C., 19.4 L of a toluene solution of methylaluminoxane (3.5 mol/L in terms of Al atom) was added dropwise to this suspension over 30 minutes. After each additive component was contacted for 30 minutes, the temperature in the system was raised to 95°C over 1.5 hours, and subsequently contacted at 93 to 97°C for 4 hours. Then, the temperature was lowered to room temperature, the supernatant liquid was removed by decantation, and further washed twice with toluene to obtain a total amount of 115 L of a toluene slurry of a solid carrier. When a part of this slurry was collected and analyzed, the solid content concentration was 123 g/L.

12.2 L (1.50 kg as a solid content) of the obtained slurry was charged into a reactor equipped with a stirrer with an internal volume of 114 L under a nitrogen atmosphere, and toluene was further added so that the total amount became 28 L. Then, a solution prepared by dissolving 23.5 g of bis(1,3-n-butylmethylcyclopentadienyl)zirconium dichloride (54.2 mmol in terms of Zr atom) in 5.0 L of toluene was pressure-fed to the reactor. The system was contacted at a temperature of 20 to 25° C. for 1 hour. The supernatant was removed by decantation and washed with hexane three times. Thereafter, hexane was further added to adjust the total amount to 30 L to obtain a hexane slurry of the solid catalyst component (X-1).

[Preparation Example 2] (Preparation of prepolymerized solid catalyst component (XP-1))
30 L of a hexane slurry of the solid catalyst component obtained in Preparation Example 1 was cooled to 10°C, and 2.89 mol of diisobutylaluminum hydride (DiBAl-H) was added thereto. While maintaining the temperature inside the system at 10 to 15°C, ethylene was continuously fed into the system under normal pressure for several minutes, and then 70 ml of 1-hexene was added. After that, ethylene supply was started at 1.46 kg/h, and preliminary polymerization was carried out at an internal temperature of 32 to 37°C. 70 ml of 1-hexene was added 5 times every 30 minutes after starting the prepolymerization, and the ethylene supply was stopped when the ethylene supply reached 4.37 kg 180 minutes after the start of the prepolymerization. Then, the supernatant was removed by decantation, and washed with hexane four times. Then, hexane was further added to adjust the total amount to 30 L to obtain a hexane slurry of the prepolymerized solid catalyst component (XP-1).

Next, the hexane slurry was inserted into an evaporator/dryer with a stirrer having an internal volume of 43 L under a nitrogen atmosphere, the pressure was reduced to −68 kPaG over about 60 minutes, and when it reached −68 kPaG, vacuum drying was performed for about 4.3 hours. The volatile components in the hexane and the prepolymerized catalyst component were removed. The pressure was further reduced to -100 kPaG, and when it reached -100 kPaG, it was vacuum dried for 8 hours to obtain 6.20 kg of the prepolymerized solid catalyst component (XP-1).

[Example 1]
(Polymerization evaluation (i): Evaluation of autoclave wall state during polymerization)
500 ml of n-heptane was charged into a 1-liter stainless steel autoclave that had been sufficiently replaced with nitrogen, and the system was replaced with ethylene, 10 ml of 1-hexene, the prepolymerized solid catalyst component (XP-1) obtained in Preparation Example 2. 250 mg was added and the temperature was raised to 55°C. It took about 10 minutes from the addition of the prepolymerized solid catalyst component (XP-1) to 55°C. Then, 0.20 ml of a toluene solution (10 g/L) of N-oleoyl sarcosine (manufactured by Wako Pure Chemical Industries, Ltd.) as component (B) (2.0 mg as N-oleoyl sarcosine) and a prepolymerized solid catalyst component ( 200 mg of XP-1) was added and the temperature in the system was raised to 73°C. Then, the polymerization was started by introducing ethylene, and the pressure was maintained at 8.0 kg/cm ² -G while continuously supplying ethylene, and the polymerization was performed for 90 minutes. After the completion of the polymerization, the pressure was released, the polymer was removed, and the state of the autoclave was confirmed. As a result, no adhesion of the polymer to the vessel wall of the autoclave or the stirring blade was observed.

(Polymerization evaluation (ii): Polymerization activity evaluation)
500 ml of n-heptane was charged into a 1-liter stainless steel autoclave that had been sufficiently replaced with nitrogen, the system was replaced with ethylene, and 20 ml of 1-hexene and a decane solution of triisobutylaluminum (1.0 mol/L) 0.06 ml. Was charged and kept at room temperature for 5 minutes. Then, 0.20 ml of a toluene solution (10 g/L) of N-oleoyl sarcosine (manufactured by Wako Pure Chemical Industries, Ltd.) as component (B) (2.0 mg as N-oleoyl sarcosine) and a prepolymerized solid catalyst component ( XP-1) 160 mg was added and the temperature in the system was raised to 73°C. Then, the polymerization was started by introducing ethylene, and the pressure was maintained at 8.0 kg/cm ² -G while continuously supplying ethylene, and the polymerization was performed for 90 minutes. After completion of the polymerization, the pressure was released, the polymer was filtered, washed, and dried under reduced pressure at 80° C. for 10 hours to obtain 98.7 g of a polymer.

[Examples 2 to 5]
Polymerization evaluation (i) and polymerization evaluation (ii) were carried out in the same manner as in Example 1 except that the compound of component (B) and the addition amount were changed to the conditions shown in Table 1. The results are shown in Table 1.

[Comparative Examples 1 to 7]
Polymerization evaluation (i) and polymerization evaluation (ii) were carried out in the same manner as in Example 1 except that the compound of component (B) and the addition amount were changed to the conditions shown in Table 1. The results are shown in Table 1.

The chemical formula of the main compound of the component (B) used in Examples and Comparative Examples is as follows.

As is clear from Table 1, the component (B) used in Examples 1 to 5 was able to suppress the adhesion of the polymer to the vessel wall of the autoclave and the stirring blade with a relatively small addition amount. Therefore, it can be understood that the olefin polymer can be stably produced with high polymerization activity.

[Preparation Example 3] (Preparation of prepolymerized solid catalyst component (XP-2))
In a reactor with an inner volume of 200 ml equipped with a stirrer, 10.0 g of the prepolymerized solid catalyst component (XP-1) obtained in Preparation Example 2 was charged under a nitrogen atmosphere, and hexane was added so that the total amount became 50 ml. Next, the temperature in the system was raised to 35° C., and then, as component (B), 5.0 ml (N-) of a hexane solution of N-oleoyl sarcosine (manufactured by Wako Pure Chemical Industries, Ltd.). 50 mg of oleoyl sarcosine) was added, followed by contact at 32 to 37° C. for 2 hours to obtain a hexane slurry of the prepolymerized solid catalyst component (XP-2). The hexane slurry was transferred to a glass Schlenk tube having an internal volume of 100 ml, and hexane was distilled off under reduced pressure at 25° C. to obtain 10.1 g of a prepolymerized solid catalyst component (XP-2).

[Example 6]
(Polymerization evaluation (i): Evaluation of autoclave wall state during polymerization)
500 ml of n-heptane was charged into a 1 L stainless steel autoclave that had been sufficiently replaced with nitrogen, and the system was replaced with ethylene, 10 ml of 1-hexene, the prepolymerized solid catalyst component (XP-2) obtained in Preparation Example 3. 250 mg was added and the temperature was raised to 55°C. It took about 10 minutes from the addition of the prepolymerized solid catalyst component (XP-2) to 55°C. Then, 200 mg of the prepolymerized solid catalyst component (XP-2) was further charged, and the temperature in the system was raised to 73°C. Then, the polymerization was started by introducing ethylene, and the pressure was maintained at 8.0 kg/cm ² -G while continuously supplying ethylene, and the polymerization was performed for 90 minutes. After the completion of the polymerization, the pressure was released, the polymer was removed, and the state of the autoclave was confirmed. As a result, no adhesion of the polymer to the vessel wall of the autoclave or the stirring blade was observed.

(Polymerization evaluation (ii): Polymerization activity evaluation)
500 ml of n-heptane was charged into a 1-liter stainless steel autoclave that had been sufficiently replaced with nitrogen, the system was replaced with ethylene, and 20 ml of 1-hexene and a decane solution of triisobutylaluminum (1.0 mol/L) 0.06 ml. Was charged and kept at room temperature for 5 minutes. Then, 160 mg of the prepolymerized solid catalyst component (XP-2) was added, and the temperature in the system was raised to 73°C. Then, the polymerization was started by introducing ethylene, and the pressure was maintained at 8.0 kg/cm ² -G while continuously supplying ethylene, and the polymerization was performed for 90 minutes. After the completion of the polymerization, the pressure was released, the polymer was filtered, washed, and dried under reduced pressure at 80° C. for 10 hours to obtain 93.6 g of a polymer.

[Example 7]
(Polymerization evaluation (iii): Evaluation of drivability by gas phase polymerization)
Copolymerization of ethylene and 1-hexene was carried out using a gas phase fluidized bed polymerization apparatus. The polymerization pressure was 1.7 MPaG, and the polymerization temperature was 80°C. The prepolymerized solid catalyst component (XP-1) prepared in Preparation Example 2 was fed into the polymerization reactor at 5.0 g/hr. N-oleoyl sarcosine (manufactured by Wako Pure Chemical Industries, Ltd.) was supplied as a component (B) into the circulating gas line so that it was present in an amount of 50 wtppm with respect to the mass of the polymer. The gas composition in the gas-phase polymerizer was such that ethylene partial pressure=1.0 MPa, hydrogen/ethylene=4.8×10 ⁻⁴ molar ratio, and 1-hexene/ethylene=0.022 molar ratio so that ethylene and hydrogen were obtained. , 1-hexene and isopentane were continuously fed to produce a polymer at a rate of 6.0 kg/hr. The residence time was 4 hours. At this time, the polymer density was 916 kg/m ³ , and the melt flow rate was 3.8 g/10 min. The melt flow rate was measured according to ASTM D1238-65T under conditions of 190° C. and 2.16 kg load.

The operation was carried out for 18 hours under the above conditions, but no heat spots were found in all places such as the polymerization vessel and the piping, and stable polymerization could be carried out.

[Comparative Example 8]
The amount of the prepolymerized solid catalyst component (XP-1) fed was 4.2 g/hr, and the component (B) was not fed in the same manner as in Example 7, except that the weight of the solid polymer component was 6.0 kg/hr. Produced a coalesce. As a result of operating under these conditions, a heat spot was generated in the polymerization vessel and the like and the operation could not be continued in 4 hours.

According to the present invention, the decrease in the polymerization activity of olefins is reduced, the fluidity inside the polymerization vessel is effectively ensured without decreasing the production rate, and the adhesion of the polymer to the polymerization vessel wall or the stirring blade is prevented. Since it can be prevented, stable operation with high activity is possible for a long period of time, and it is very suitable in the field where it is important to produce an olefin polymer having excellent particle properties.

Claims (6)

(A) Solid catalyst component for olefin polymerization, and
(B) In the presence of an amide compound represented by the following general formula (I),
A method for producing an olefin polymer , which comprises (co)polymerizing at least one olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms in a polymerization vessel ,

(In formula (I), R ¹ and R ² are each a hydrocarbon group having 1 to 32 carbon atoms and may be the same or different, and R ³ , R ⁴ and R ⁵ are each a hydrogen atom or a carbon number. It is a hydrocarbon group of 1 or more and 18 or less, an oxygen-containing hydrocarbon group or a sulfur-containing hydrocarbon group, which may be the same or different from each other, and a and b are each an integer of 0 or more and may be the same or different from each other. , A+b is 1 or more.)
Ingredient (A)
(A-1) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton,
(A-2) (a) organometallic compound,
(B) an organoaluminum oxy compound, and
(C) a compound selected from a Lewis acid, an ionic compound, a borane compound, a carborane compound, a heteropoly compound and an isopoly compound, which reacts with (A-1) to form an ion pair,
At least one compound selected from
(A-3) Fine particle carrier
Consists of
A method for producing an olefin polymer, comprising: The method for producing an olefin polymer according to claim 1, wherein in the general formula (I), R ³ , R ⁴ and R ⁵ are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. The method for producing an olefin polymer according to claim 1 or 2, wherein in the general formula (I), a+b is 1. The method for producing an olefin polymer according to claim 1, wherein the component (B) is supplied in an amount of 0.1 ppm or more and 500 ppm or less with respect to the olefin polymer yield. The method for producing an olefin polymer according to any one of claims 1 to 4, wherein the olefin is ethylene alone or ethylene and an α-olefin having 3 to 20 carbon atoms. The method for producing an olefin polymer according to claim 1, wherein the olefin (co)polymerization is carried out in a suspension or in a gas phase.