JP2021161292A - Method of producing olefinic polymer - Google Patents

Abstract

To provide a method of producing an olefinic polymer which can achieve further enhancement of polymerization activity and stable operation of a production device by effectively preventing dirt inside a polymerization vessel such as on a polymerization vessel wall and a mixing impeller.SOLUTION: In the production method, an amine compound (B) and a carboxylic acid compound (C) that are represented by specific general formulas coexist in performing (co)polymerization of one or more olefins, selected from the group consisting of ethylene and C3-20 α-olefins, in a polymerization vessel in the presence of an olefin polymerization solid catalyst component (A).SELECTED DRAWING: None

Description

INDUSTRIAL APPLICABILITY The present invention is an olefin-based polymer capable of achieving stable operation of a manufacturing apparatus and further improvement of polymerization activity by effectively preventing stains inside the polymer such as a polymer wall and a stirring blade. Regarding the manufacturing method.

In chemical equipment such as petroleum distillation refining plants and polyolefin manufacturing plants, fouling causes problems such as reduced heat exchange capacity of the plant and blockage of pipes, resulting in unstable manufacturing operation, which is the worst. In the case of, the operation may be stopped. Specifically, for example, it is known that a polymer lump or a sheet-like substance is generated in the polymerizer, or the polymer adheres to the stirring blade or the polymerizer wall.

As a method for solving these problems, Patent Document 1 discloses a method of adding an alkyldiethanolamine compound into a polymer that performs olefin polymerization by a vapor phase method using a solid catalyst, and Patent Document 2 discloses a polyoxyalkylene alkyl. A method for carrying out olefin polymerization by a vapor phase method using a solid catalyst in the presence of an amine compound is disclosed.

Japanese Unexamined Patent Publication No. 2000-313718 Japanese Unexamined Patent Publication No. 2019-157019

Olefin-based polymers are important industrial products that are widely used in a wide variety of applications, and further improvement in their productivity is required. An object of the present invention is an olefin-based weight capable of achieving stable operation of a manufacturing apparatus and further improvement of polymerization activity by effectively preventing stains inside the polymer such as a polymer wall and a stirring blade. The purpose is to provide a method for producing coalescence.

In order to further improve the productivity of the olefin-based polymer, the present inventors carry out olefin polymerization using a solid catalyst for olefin polymerization in the presence of a combination of a specific amine compound and a carboxylic acid compound. By doing so, it is possible to achieve stable operation of the manufacturing apparatus and further improvement of the polymerization activity by effectively preventing the inside of the polymer such as the polymer wall and the stirring blade from becoming dirty. I got a lot of knowledge. The present invention has been made based on the new findings of the present inventors. The gist of the present invention is as follows.

[1] (A) Solid catalyst component for olefin polymerization,
(B) an amine compound represented by the following general formula (I), and (C) a carboxylic acid compound represented by the following general formula (II).
In the presence of, one or more olefins selected from the group consisting of ethylene and α-olefins having 3 or more and 20 or less carbon atoms are (co) polymerized in a polymerizer.
A method for producing an olefin polymer.

[In the above general formula (I), R is a hydrocarbon group having 1 to 30 carbon atoms, and R'is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of R's, the plurality of R's are independently defined in the same manner as described above. m and n are independently integers of 0 or more, and m + n is 1 or more. ]

[In the above general formula (II), R ² represents a hydrocarbon group having 1 or more and 30 or less carbon atoms. ]

[2] The method for producing an olefin polymer according to [1], wherein the component (B) is supplied in an amount of 0.1 mass ppm or more and 500 mass ppm or less with respect to the yield of the olefin polymer.
[3] The method for producing an olefin-based polymer according to [1] or [2], wherein the olefin is ethylene alone or an α-olefin having 3 or more and 20 or less carbon atoms with ethylene.
[4] The method for producing an olefin-based polymer according to any one of [1] to [3], wherein the olefin (co) polymerization is carried out in a suspension or a gas phase.
[5] Ingredient (A) is
(A-1) A transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton,
(A-2) (a) Organometallic compound,
(B) Organoaluminium oxy compounds and
(C) At least one compound selected from the group consisting of compounds that react with (A-1) to form an ion pair, and
(A-3) Fine particle carrier and
The method for producing an olefin polymer according to any one of [1] to [4], which comprises.

According to the method for producing an olefin-based polymer according to the present invention, stable operation of the production apparatus and further improvement of polymerization activity by effectively preventing stains inside the polymer such as the polymer wall and stirring blades. Can be achieved.

[Solid catalyst component for olefin polymerization (A)]
As the solid catalyst component (A) for olefin polymerization, for example, a solid catalyst component containing a transition metal compound selected from Group 3 to Group 12 of the periodic table is preferable. Specific examples thereof include a carrier-supported transition metal complex-based catalyst component in which group 4 to 6 transition metal compounds of the periodic table are supported on a particulate carrier, and a solid state containing a solid titanium catalyst component and an organic aluminum compound. Examples thereof include a titanium-based catalyst component and a Phillips catalyst component in which an arbitrary chromium compound that can be oxidized to chromium trioxide is supported on an inorganic oxide solid such as silica.

Among them, the carrier-supported metallocene-based catalyst component belonging to the carrier-supported transition metal complex-based catalyst component is preferable, and the carrier-supported metallocene-based catalyst component containing the following components (A-1) to (A-3) is preferable. 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) Organoaluminium oxy compounds and
(C) At least one compound selected from the group consisting of compounds that react with the component (A-1) to form an ion pair, and
(A-3) Fine particle carrier.

The transition metal compounds of Groups 4 to 6 of the Periodic Table used for the carrier-supported transition metal complex-based catalyst component may be any transition metal compounds of Groups 4 to 6 of the Periodic Table having known olefin polymerization ability. As such a transition metal compound, for example, a transition metal halide, a transition metal alkylated product, a transition metal alkoxide, a non-crosslinkable or cross-linkable metallocene compound of Groups 4 to 6 of the Periodic Table can be used. In particular, a transition metal compound of Group 4 of the periodic table is preferable. Specific examples of the transition metal compounds of Group 4 of the periodic table include titanium tetrachloride, dimethyltitanium dichloride, tetrabenzyl titanium, tetrabenzyl zirconium, and tetrabutoxytitanium. Further, a non-crosslinkable or crosslinkable metallocene compound is particularly preferable from the viewpoint of polymerization activity showing activity in the polymerization reaction of the catalyst (yield of olefin polymer per 1 g of catalyst). 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 ... (III)
[In formula (III), 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 one L is a ligand having a cyclopentadienyl skeleton. L other than the ligand having a cyclopentadienyl skeleton has a hydrocarbon group having 1 or more and 12 or less carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, and -SO ₃ R (R is halogen, etc.). It is a hydrocarbon group having 1 or more and 8 or less carbon atoms which may have a substituent (1) or a hydrogen atom. x is the valence of the transition metal and indicates the number of L. )

Specific examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group; a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, and a tetramethylcyclopentadienyl group. , Pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopenta Alkyl-substituted cyclopentadienyl groups such as dienyl group and hexylcyclopentadienyl group; indenyl group; 4,5,6,7-tetrahydroindenyl group; fluorenyl group can be mentioned. These groups may have a substituent such as a halogen atom or 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 (III) contains two or more groups having a cyclopentadienyl skeleton, the group having two cyclopentadienyl skeletons is an alkylene group such as ethylene or propylene; isopropi. 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, it is preferable that the groups having two or more cyclopentadienyl skeletons are the same.

Specific examples of the hydrocarbon group having 1 or more and 12 or less 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 and a butyl group. Alkyl groups such as pentyl groups; 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 neofil group can be mentioned. Specific examples of the alkoxy group include an alkoxy group having 1 or more and 4 or less carbon atoms, such as a methoxy group, an ethoxy group, and a butoxy group. Specific examples of the allyloxy group include a phenoxy group. Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of -SO 3 _R, p-toluenesulfonate group, methanesulfonate sulfonato group, and a trifluoromethane sulfonato group. When there are a plurality of ligands other than those having a cyclopentadienyl skeleton, these ligands may be the same or different, or may have one or more combinations of different ligands. good.

The compound represented by the general formula (III) is more specifically represented by the following general formula (III') when the valence of the transition metal is 4, for example.
MR ^a R ^b R ^c R ^d ... (III')
[In formula (III'), M is zirconium, titanium or hafnium. ^Ra is a group having a cyclopentadienyl skeleton. R ^b , R ^c and R ^d are independent groups 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, and the like. -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. ]

In particular, as the component (A-1) ^{, a transition metal compound in which one of R b} , R ^c and R ^{d in} the general formula (III') is a group having a cyclopentadienyl skeleton is preferable. For example, when ^Ra and R ^b are groups having a cyclopentadienyl skeleton, the groups having a cyclopentadienyl skeleton are via an alkylene group, a substituted alkylene group, an alkylidene group, a silylene group, a substituted silylene group and 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. As a specific example of these groups, each group mentioned above with respect to the formula (III) can be similarly mentioned.

Hereinafter, specific compounds of transition metal compounds in which M is zirconium will be illustrated. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromid, 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 dibromid, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloroid, ethylenebis (indenyl) ) Zirconium bis (methane sulfonato), ethylene bis (indenyl) zirconium bis (p-toluene sulfonato), ethylene bis (indenyl) zirconium bis (trifluoromethane sulfonato), ethylene bis (4,5,6,7-tetrahydro) Indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylene Bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis ( Indenyl) Zirconium bis (trifluoromethanesulfonato), rac-dimethylsilylenebis {1- (2-methyl-4,5-acenaftcyclopentadienyl)} 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 Zirconium Lolide, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylcilylenebis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) ) Zirconium dibromid, bis (cyclopentadienyl) methylzirconium monoclonal, bis (cyclopentadienyl) ethylzirconium monolide, bis (cyclopentadienyl) cyclohexylzirconium monolyde, bis (cyclopentadienyl) phenylzirconium Monomonolide, bis (cyclopentadienyl) benzyl zirconium monohydride, bis (cyclopentadienyl) zirconium monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, Bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxychloride, 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 ethoxychloride, 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 di-substituted cyclopentadienyl ring contains 1,2- and 1,3-substituted products, and the tri-substituted product contains 1,2,3- and 1,2,4-substituted products. include. Alkyl groups such as propyl and butyl contain isomers such as n-, i-, sec- and tert-.

Further, in each of the above zirconium compounds, a transition metal compound in which the zirconium metal is replaced with a titanium metal or a hafnium metal can also be used. Further, in addition to titanium compounds and hafnium compounds having a similar three-dimensional structure, as well as bromides and iodides, for example, JP-A-3-9913, JP-A-2-131488, JP-A-3-21607, etc. Transition metal compounds as described in Kaihei 3-106907, JP-A-3-188092, JP-A-4-69394, JP-A-4-300878, 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-11-315109 can also be mentioned.

[In general formula (IV), M represents a transition metal atom of Groups 4-6 of the Periodic Table. m represents an integer of 1 to 6. R ^{11 to} R ¹⁶ are independently hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, and silicon. Indicates a containing group, a germanium-containing group, or a tin-containing group. Two or more of R ^{11 to} R ¹⁶ may be connected to each other to form a ring. Further, m is 2 or more in the case R ¹¹ 2 amino groups which may be coupled out of to R ¹⁶ (where there is no possibility that among the plurality of R ¹¹ are attached). n is a number that satisfies the valence of M. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, and a silicon-containing group. Indicates a group, a germanium-containing group, or a tin-containing group. The plurality of groups represented by X when n is 2 or more are independently defined in the same manner as described above. The plurality of groups represented by X may be the same or different, or the plurality of groups represented by X may contain one or more combinations of different groups. Further, the plurality of groups represented by X may be bonded to each other to form a ring. ]
Specific examples of the substituent as X include each group disclosed in JP-A-11-315109.

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

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

^{_{R e m Al (OR f)}} n H p X q ··· (V)
[In the general formula (V), ^Re and R ^f independently represent hydrocarbon groups having 1 or more and 15 or less carbon atoms, preferably 1 or more and 4 or less. X represents a halogen atom. m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is the number 0 ≦ q <3, and m + n + p + q = 3. ]
Organoaluminium compound represented by. As the hydrocarbon group, an alkyl group is preferable. Specific examples of the compound represented by the general formula (V) include trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride.

M ² AlRg ₄ ... (VI)
[In the general formula (VI), M ² represents Li, Na or K, and Rg represents a hydrocarbon group having 1 or more and 15 or less carbon atoms, preferably 1 or more and 4 or less. ]
Periodic table represented by Organized metal complex compound of Group 1 metal and aluminum.
As the above-mentioned hydrocarbon group, an alkyl group having 1 or more and 15 or less carbon atoms, preferably 1 or more and 4 or less is preferable. Specific examples of the compound represented by the general formula (VI) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

R ^h R ⁱ M ³ ... (VII)
[In the general formula (VII), R ^h and ^Ri may be the same or different from each other, and represent hydrocarbon groups having 1 or more and 15 or less carbon atoms, preferably 1 or more and 4 or less. M ³ is Mg, Zn or Cd. ]
An organometallic compound of a Group 2 or Group 12 metal of the periodic table represented by.
An alkyl group is preferable as the hydrocarbon group.

Among the above organometallic compounds, organoaluminum compounds are preferable. Further, the organometallic compound may be used alone or in combination of two or more.

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

[In the general formulas (VIII) and (IX), R ^{21 to} R ²⁴ independently represent hydrocarbon groups having 1 or more and 10 or less carbon atoms, and n represents an integer of 2 or more. )

As the organoaluminum oxy compound (b), in the above general formulas (VIII) and (IX), ^{methylaluminoxane having R 21 to} R ²⁴ as a methyl group and n of 3 or more, preferably 10 or more is preferably used. Will be done. It does not matter if some organoaluminum compounds are mixed in these aluminoxans. Further, the organoaluminum oxy compound (b) may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. Organoaluminium oxy compounds described in JP-A-2-167305, and aluminoxane having two or more types of alkyl groups described in JP-A-2-24701 and JP-A-3-103407 are also preferably used. Available.

Such aluminoxane can be produced, for example, by the methods (1) to (3) below, 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, first cerium chloride hydrate, etc. A method in which an organic aluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension of the above, and the organic aluminum compound is reacted with adsorbed water or water of crystallization.
(2) A method in which water, ice or water vapor is allowed to act directly 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.

Alminoxane may contain a small amount of organometallic components. Further, the solvent or the unreacted organoaluminum compound may be distilled and removed from the recovered solution of aluminoxane, and then redissolved in the solvent.

Specific examples of the organic aluminum compound used in preparing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum, and tritert-. Trialkylaluminum such as butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide , Dialkylaluminum halides such as diisobutylaluminum chloride; Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; Dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; Be done. Of these, trialkylaluminum and tricycloalkylaluminum are preferable.

Further, isoprenyl aluminum represented by the following general formula (X) can also be used as the organoaluminum compound for preparing aluminoxane.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z ... (X)
[In the general formula (X), x, y, and z are positive numbers, and z ≧ 2x. ]

The organoaluminum compound for preparing aluminoxane may be used alone or in combination of two or more.

Specific examples of the solvent used in the preparation of alminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and simen, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Hydrocarbons, cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, gasoline, kerosene, light oil and other petroleum distillates, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons Examples include hydrocarbon solvents such as halides, especially chlorinated and brominated. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these, aromatic hydrocarbons are preferable.

Examples of the compound (c) (hereinafter referred to as “ionized ionic compound (c)”) that reacts with the component (A-1) to form an ion pair include JP-A-1-501950 and JP-A-1-50206. Lewis acid and 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. , Bolan 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 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 fine particle carrier (A-3) include an inorganic carrier made of an inorganic material and an organic carrier made of an organic material. Examples of the inorganic carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , and a mixture containing two or more of these (for example, SiO). Inorganic metal oxide carriers such as _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), MgCl 2.} Inorganic chloride carriers such as MgBr ₂ , MnCl ₂ , and MnBr _{2 can be mentioned.} Further, clay, clay minerals as its components, ion-exchangeable layered compounds and the like can also be used as an inorganic carrier.
Examples of the organic carrier include organic polymer carriers such as polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, and styrene-divinylbenzene copolymer.

The average particle size of the inorganic carrier is preferably 1 to 300 μm, more preferably 3 to 200 μm. Such a carrier is used by 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 pulverized by a ball mill or a vibration mill. Further, it is also possible to use a solvent in which an inorganic chloride is dissolved in a solvent such as alcohol and then precipitated in the form of fine particles with a precipitant.

Carriers using clay are usually composed mainly of clay minerals. Further, the carrier using the ion-exchangeable layered compound has a crystal structure in which the surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used. Furthermore, clays, as clay minerals or ion-exchangeable layered compound, clay, clay minerals also, hexagonal close packing type, antimony type, CdCl ₂ type, ionic crystalline compounds having a layered crystal structure of type _2, etc. CdI It can be exemplified. Examples of such clays and clay minerals include kaolin, bentonite, knot clay, gailome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, rhokudei stone group, parigolskite, kaolinite, nacrite, etc. Examples include clayite and halloysite. The ion-exchange layered compounds such as _{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 (NH ₄ PO ₄ ) ₂ · H ₂ O and other crystalline acidic salts of polyvalent metals can be mentioned. It is also preferable to chemically treat clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a 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, organic substance treatment and the like.

The ion-exchangeable layered compound may be a layered compound in a state in which the layers are expanded by utilizing the ion-exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation. Guest compounds for intercalation include cationic inorganic compounds such as _{TiCl 4} , ZrCl ₄ , and metal alkoxides such as _{Ti (OR) 4} , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) _3. (R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^+, etc. Can be mentioned. These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were _{obtained by hydrolyzing metal alkoxides such as Si (OR) 4} , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). A polymer, a colloidal inorganic compound such as SiO2, or the like can coexist. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them. Of these, preferred are clays or clay minerals, with particular preference being montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

Examples of the organic carrier include granular or fine particle solids having a particle size in the range of 1 to 300 μm. Specifically, as the polymer forming the organic carrier, as exemplified above, ethylene or α-olefin having 3 or more and 14 or less carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene and the like. Examples thereof include (co) polymers or vinylcyclohexanes produced having styrene as a main component, (co) polymers produced having styrene as a main component, and variants thereof.

Further, the components (A-2) described above by the methods described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, International Publication No. 2010/55652 and the like. ) Can be insolubilized and the solid component obtained can be used as the fine particle carrier (A-3). In this case, contact with the component (A-2) is not essential in the method for preparing the carrier-supported metallocene catalyst component described below.

A method for preparing a carrier-supported metallocene-based catalyst component, which is one of those preferably used as the solid catalyst component (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 above-described components (A-1) and (A-2) [particularly. It is preferably a catalyst component containing the organic aluminum oxy compound (b) [component (b)] and the component (A-3). This carrier-supported metallocene catalyst can be prepared, for example, by mixing and contacting components (A-1) to (A-3). The contact order of each component is arbitrary.

It is preferable to use an inert hydrocarbon solvent for the preparation of the carrier-supported metallocene-based catalyst component. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, toluene, Aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof.

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

The temperature at which each of the above components is 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-based catalyst component thus obtained, the transition metal compound (A-1) is preferably about 5 × 10 ^{− per 1 g of the fine particle carrier (A-3) in terms of transition metal atoms.} It is supported in an amount of ⁶ to ^10-3 mol, more preferably ^{10-5 to} 3 × 10 ^{-4 mol. Further, the organoaluminum oxy compound (b) is preferably about 10-3} to ^10-1 mol, more preferably 2 × 10 ^{-3 to} 5 × 10 in terms of aluminum atoms per 1 g of the fine particle carrier (A-3). It is supported in an amount of ^{-2 mol.}

The solid catalyst component (A) for olefin polymerization may be a prepolymerization catalyst component in which an olefin is prepolymerized. The prepolymerization catalyst component is formed of a catalyst for olefin polymerization 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 fine particle carrier (A-3), and is prepolymerized as necessary. Contains the olefin-based polymer (D) produced by. As a method for preparing the prepolymerization catalyst, for example, a small amount of olefin is added to the solid catalyst component obtained by mixing and contacting the components (A-1) to (A-3) in an inert hydrocarbon solvent or an olefin medium. There is a method of prepolymerizing. Specific examples of the inert hydrocarbon solvent used for preparing the prepolymerization catalyst include the same as the inert hydrocarbon solvent used for preparing the carrier-supported metallocene catalyst described above.

As the olefin used in the prepolymerization, at least one of ethylene, propylene and an olefin having 4 or more and 20 or less carbon atoms can be used. The olefin for prepolymerization preferably has the following composition (A).
-Composition (A):
Ethylene: 100-0 mol%,
Propene: 0-49 mol%, and α-olefin having 4 or more carbon atoms: 0-100 mol%.
Further, the following composition (B) can be mentioned as a more preferable composition, the following composition (C) can be mentioned as a more preferable composition, and the following composition (D) can be mentioned as a particularly preferable composition.
-Composition (B):
Ethylene: 100-0 mol%,
Propene: 0 to 20 mol%, and α-olefin having 4 or more carbon atoms: 0 to 100 mol%.
-Composition (C):
Ethylene: 100-20 mol%,
Propene: 0 to 20 mol%, and α-olefin having 4 or more carbon atoms: 0 to 80 mol%.
-Composition (D):
Ethylene: 100 to 20 mol%, and α-olefin having 4 or more carbon atoms: 0 to 80 mol%.
(In each of the above compositions, the total of mol% of ethylene, mol% of propylene, and mol% of olefin having 4 or more carbon atoms is taken as 100%.)

Specific examples of α-olefins having 4 or more and 20 or less carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. , 1-Tetradecene, 1-Hexadecene, 1-Octene, 1-Eikosen and the like. Furthermore, as monomers copolymerized with α-olefins, 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 0.005 to 1 g of the fine particle carrier (A-3) in terms of transition metal atoms. It is used in an amount of 0.5 mmol. The organic aluminum oxy compound (b) is usually used in an amount of 0.1 to 100 mmol, preferably 0.5 to 20 mmol per 1 g of the fine particle carrier (A-3) in terms of aluminum atoms.

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

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-based catalyst component may optionally contain an organoaluminum compound or a surfactant at the time of catalyst synthesis or prepolymerization, if necessary.

[Amine compound (B)]
The amine compound (B) is a compound represented by the following general formula (I).

[In the formula (I), R is a hydrocarbon group having 1 to 30 carbon atoms, and R'is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of R's, the plurality of R's are independently defined in the same manner as described above. m and n are each independently an integer of 0 or more. m and n may be the same or different from each other. m + n is 1 or more. )

The hydrocarbon group as R in the general formula (I) may be saturated or unsaturated. Further, the hydrocarbon group may be linear, branched or cyclic, and may have two or more of these structures. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group having both of these groups. As the hydrocarbon group, 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 of the hydrocarbon group include 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. Examples include an alkyl group or an alkenyl group. In addition, 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 neofil group can also be mentioned. Of these, an alkyl group having 8 or more and 18 or less carbon atoms is preferable.

R'in the general formula (I) is a hydrogen atom or a hydrocarbon group having 1 or more and 20 or less carbon atoms. When R'is a hydrocarbon group having 1 or more carbon atoms and 20 or less carbon atoms, a preferable specific example thereof is the same as the hydrocarbon group as R in the general formula (I). Among them, a hydrogen atom and an alkyl group having 1 or 2 carbon atoms are preferable, and a hydrogen atom and a methyl group are more preferable.

M and n in the general formula (I) are integers of 0 or more, respectively. m + n is 1 or more. m and n are independent of each other, preferably 0 to 10. m + n is preferably 1 to 20.

Specific examples of the amine compound (B) represented by the general formula (I) include lauryldiethanolamine, stearyldiethanolamine, polyoxyethylene octylamine, polyoxyethylene decylamine, polyoxyethylene laurylamine, and polyoxyethylene octadecylamine. Examples thereof include polyoxyethylene coconut oil alkylamine, polyoxyethylene beef fat amine, polyoxyethylene hydrogenated beef fat amine, polyoxypropylene laurylamine, polyoxypropylene coconut oil alkylamine, and polyoxypropylene beef fat amine. Of these, polyoxyethylene octylamine, polyoxyethylene decylamine, polyoxyethylene laurylamine, polyoxyethylene coconut oil alkylamine, and polyoxypropylene coconut oil alkylamine are preferable.

As the amine compound (B), at least one selected from the group consisting of the amine compounds represented by the general formula (I) can be used.

[Carboxylic acid compound (C)]
The carboxylic acid compound (C) is a compound represented by the following general formula (II).

[In the above general formula (II), R ² represents a hydrocarbon group having 1 or more and 30 or less carbon atoms. ]
In the general formula (II), R ² is a hydrocarbon group having 1 or more and 30 or less carbon atoms. The number of carbon atoms of this hydrocarbon group is preferably 7 or more and 21 or less, and more preferably 7 or more and 17 or less. Specific examples of the carboxylic acid compound (C) represented by the general formula (II) include caprylic acid, lauric acid, stearyl acid, and the like.
As the carboxylic acid compound (C), at least one selected from the group consisting of the compounds represented by the general formula (II) can be used.

[Production of olefin polymer]
The method for producing an olefin polymer of the present invention comprises ethylene and carbon atoms of 3 or more and 20 in the presence of the solid catalyst component (A) for olefin polymerization, the amine compound (B) and the carboxylic acid compound (C) described above. It has a step of (co) polymerizing one or more olefins selected from the group consisting of the following α-olefins in a polymerizer. In the present invention, the term "(co) polymerization" is used to include both polymerization and copolymerization. Further, in the present invention, "polymerization" and "polymer" may be used in the sense of including not only homopolymerization and homopolymer but also copolymer and copolymer.

(Co) Solid catalyst component (A) [component (A)] for olefin polymerization, amine compound (B) [component (B)] and carboxylic acid compound (C) [component (C)] during polymerization The method of addition to the polymerizer is arbitrary and is not particularly limited. The components (A) to (C) may be individually added to the polymerizer in any order. Alternatively, a mixture in which two of the components (A) to (C) are previously mixed and contacted, and the remaining components may be added to the polymer in any order. Alternatively, a mixture in which the components (A) to (C) are previously mixed and contacted may be added to the polymerizer. Further, two or more of these addition methods may be combined. The component (A) may be added to the polymerizer as a prepolymerized solid catalyst component.

The polymerization can be carried out in suspension, in solution or in gas phase, and is preferably carried out by slurry polymerization or gas phase polymerization in particular in suspension or gas phase. 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, and methylcyclopentane. Aliphatic hydrocarbons such as benzene, toluene, xylene and the like; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, or mixtures thereof. Of these, aliphatic hydrocarbons and alicyclic hydrocarbons are preferable.

The polymerization temperature is usually −50 to 150 ° C., preferably 0 to 100 ° C. for slurry polymerization, and usually 0 to 120 ° C., preferably 20 to 100 ° C. for vapor 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 a batch type, a semi-continuous type and a continuous type.

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

Ethylene and α-olefin having 3 or more and 20 or less carbon atoms are used as raw materials for polymerization. Specific examples of this α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-. Hexadecene, 1-octadecene, and 1-eikosen can be mentioned. These can be used alone or in combination of two or more. Further, in addition to ethylene and an α-olefin having 3 or more and 20 or less carbon atoms, another monomer for copolymerization may be used in combination for copolymerization. Examples of the monomer for copolymerization include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4: 5,8-dimethano-1,2,3,4, Examples thereof include 4a, 5,8,8a-octahydronaphthalene. Further, styrene, vinylcyclohexane and dienes can also be used.

As the olefin as a raw material for polymerization, an olefin having any of the compositions (A) to (D) exemplified above for prepolymerization can be similarly used. Further, in the present invention, it is preferable to produce an ethylene-based polymer containing ethylene as a main monomer. As the ethylene-based polymer, a (co) polymer containing 50 mol% or more of an ethylene component and, if necessary, an α-olefin component having 4 to 10 carbon atoms is preferable.

^{During polymerization, the olefin polymerization catalyst (A) is usually 10-8} to ^10-3 mol, preferably ^10-7 to 3 mol, per liter of polymerization volume in terms of transition metal atoms in the transition metal compound (A-1). It is desirable to use in an amount of ^{10-4 mol.} The organic aluminum oxy compound (A-2) is usually used in an amount of 10 to 500 mol, preferably 20 to 200 mol, per 1 mol of the transition metal atom in the transition metal compound (A-1) in terms of aluminum atom. desirable.

The amine compound (B) is preferably used in an amount of 0.1 mass ppm or more and 500 mass ppm or less with respect to the yield of the olefin polymer. When the amine compound (B) is used in an amount of 0.1 mass 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 mass ppm or less, it tends to be possible to suppress the recovery of the polymerization solvent and gas, the increase in the load on the purification treatment, and the deterioration of the catalyst performance. The amount of the amine compound (B) used is more preferably 0.5 mass ppm or more and 200 mass ppm or less, and particularly preferably 1 mass ppm or more and 100 mass ppm or less.

By using the carboxylic acid compound (C) in addition to the amine compound (B), it is possible to prevent the inside of the polymer such as the polymer wall and the stirring blade from becoming dirty and to improve the polymerization activity at the same time. It is possible to improve the productivity of the olefin-based polymer. The reason why such an effect can be obtained is that the tendency to suppress the polymerization activity of the basic amine compound (B) can be suppressed by adding an acid, and further, the carboxylic acid represented by the general formula (II) as an acid can be suppressed. The present inventors presume that the above-mentioned antifouling effect and improvement of polymerization activity could be achieved by specially selecting the compound.

The compounding ratio (molar ratio) of the carboxylic acid compound (C) and the amine compound (B) is preferably selected from the range of (B) :( C) = 100: 1 to 100: 100. This blending ratio is more preferably selected from the range of 100: 5 to 100:50, and particularly preferably selected from the range of 100: 15 to 100:35.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the description of the following examples.

[Stabilizer]
The amine compound (B) [component (B)] as the stabilizer used in Examples and Comparative Examples is as follows.
"B-1": Lauryl diethanolamine [Electro Stripper (registered trademark) EA, manufactured by Kao Corporation]
"B-2": Stearyldiethanolamine [CAS No. 10213-78-2, manufactured by Tokyo Chemical Industry Co., Ltd.]
"B-3": Polyoxyalkylene alkylamine compound [Amit (registered trademark) 102, manufactured by Kao Corporation] (Analysis results of the types and composition ratios of the contained compounds are disclosed in Table 1 of Patent Document 2. .)
"B-4": Polyoxyalkylene alkylamine compound [Amit (registered trademark) 105, manufactured by Kao Corporation]
"B-5": Alkyldiethanolamine compound [Atmer (registered trademark) 163, manufactured by Croda Japan Co., Ltd.] (Analysis results of the types and composition ratios of the contained compounds are disclosed in Table 1 of Patent Document 2).

"Carvone acids"
The carboxylic acid compound [component (C)] used in Examples and Comparative Examples is as follows.
"C-1": Octanoic acid (CAS No. 124-07-2, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
"C-2": Lauric acid (CAS number 143-07-7, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
"C-3": Stearic acid (CAS No. 57-11-4, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)

[Preparation Example 1] (Preparation of solid catalyst component (X-1))
Using a reactor with a stirrer with an internal volume of 270 L, 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 0-5 ° C. While maintaining the in-system temperature at 0 to 5 ° C., 19.4 L of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) was added dropwise to this suspension over 30 minutes. Then, after contacting each of the added components for 30 minutes, the temperature inside the system was raised to 95 ° C. over 1.5 hours, and then contacted at 93 to 97 ° C. for 4 hours. Then, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the mixture was further washed twice with toluene to obtain a toluene slurry of a solid carrier carrying a total amount of 115 L of methylaluminoxane. When a part of this slurry was collected and analyzed, the solid content concentration was 123 g / L.
Of the obtained slurry, 12.2 L (1.50 kg as a solid content) was charged into a reactor with a stirrer having an internal volume of 114 L under a nitrogen atmosphere, and toluene was further added so that the total amount became 28 L. Next, a solution prepared by dissolving 23.5 g (54.2 mmol of Zr atom equivalent) of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride in 5.0 L of toluene was pressure-fed to the above reactor. , The contact was carried out at an in-system temperature of 20 to 25 ° C. for 1 hour. The supernatant was decanted and washed 3 times with hexane. After that, hexane was further added to bring the total volume to 30 L, and a hexane slurry of the solid catalyst component (X-1) was obtained.

[Preparation Example 2] (Preparation of Prepolymerized Solid Catalyst Component (XP-1))
30 L of the hexane slurry of the solid catalyst component (X-1) 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 supplied into the system for several minutes under normal pressure, and then 70 ml of 1-hexene was added. After that, ethylene supply was started at 1.46 kg / h, and prepolymerization was performed at an in-system temperature of 32 to 37 ° C. 70 ml of 1-hexene was added 5 times every 30 minutes after the start of 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 4 times with hexane. After that, hexane was further added to bring the total volume to 30 L, and a hexane slurry of the prepolymerized solid catalyst component (XP-1) was obtained.
Next, the hexane slurry was inserted into an evaporation dryer with 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, it was vacuum dried for about 4.3 hours. , Hexane and volatiles in the prepolymerization catalyst component were removed. Further, the pressure was reduced to -100 kPaG, and when the pressure reached -100 kPaG, the mixture 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 the wall condition of the autoclave during polymerization)
500 ml of n-heptane was charged into a 1 L stainless steel autoclave sufficiently substituted with nitrogen, the inside of the system was replaced with ethylene, 10 ml of 1-hexene, and 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 the temperature reaching 55 ° C. Then, 5.0 mg of lauryldiethanolamine (B-1) as the component (B) and 0.4 mg of octanoic acid (C-1) as the component (C) [Component (B-1): Component (C) = 100: 15 ( The mixture of [molar ratio)] was diluted with 5 ml of toluene and added. Subsequently, 200 mg of the prepolymerized solid catalyst component (XP-1) was added to raise the temperature in the system 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 carried out for 90 minutes. After completion of the polymerization, the pressure was depressurized, the polymer was removed, and the state of the autoclave was confirmed. As a result, no adhesion of the polymer was observed on the wall of the autoclave or the stirring blade.

(Polymerization evaluation (ii): Polymerization activity evaluation)
500 ml of n-heptane was charged into a 1 L stainless autoclave sufficiently nitrogen-substituted, the inside of the system was replaced with ethylene, 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, 5.0 mg of lauryldiethanolamine (B-1) as the component (B) and 0.4 mg of octanoic acid (C-1) as the component (C) [Component (B-1): Component (C) = 100: 15 ( The mixture of [molar ratio)] was diluted with 5 ml of toluene and added. Subsequently, 180 mg of the prepolymerized solid catalyst component (XP-1) was added to raise the temperature in the system 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 carried out for 90 minutes. After completion of the polymerization, the polymer was decompressed, the polymer was filtered and washed, and dried under reduced pressure at 80 ° C. for 10 hours to obtain 88.7 g of the polymer. The amount of the component (B-1) with respect to the polymer yield (g) was 56 mass ppm, and the polymer yield (polymerization activity) per 1 g of the catalyst was 493 (g-PE / g-cat).

[Examples 2 to 8 and Comparative Examples 1 to 7]
As shown in Table 1, the polymerization evaluation was carried out in the same manner as in Example 1 except that the type of stabilizer (component (B)) and the type and amount of the carboxylic acid compound (component (C)) were changed. i) and polymerization evaluation (ii) were carried out. The results are shown in Table 1.

As is clear from Table 1, in Examples 1 and 2 in which the component (B-1) and the component (C-1) were used, the adhesion of the volimmer to the instrument wall and the stirring blade of the autoclave was suppressed, and the component ( The polymerization activity was higher than that of Comparative Example 1 in which only B-1) was used in the same amount of addition and Comparative Example 2 in which only the component (C-1) was used in the same amount of addition.
That is, in Examples 1 and 2, an olefin polymer could be produced stably with higher polymerization activity as compared with Comparative Examples 1 and 2.
Further, even in Examples 3 to 4 in which the component (B-1) and the component (C-2) or the component (C-3) were used, the polymerization activity was higher than that in Comparative Example 1.
In Examples 5 to 8 in which the components (B-2) to (B-5) and the component (C-1) were used instead of the component (B-1), the components (B-2) to (B-5) were used. The polymerization activity was higher than that of Comparative Examples 3 to 6 using only.

[Preparation Example 3] (Preparation of Prepolymerized Solid Catalyst Component (XP-2))
10.0 g of the prepolymerized solid catalyst component (XP-1) obtained in Preparation Example 2 was charged into a reactor with a stirrer having an internal volume of 200 ml under a nitrogen atmosphere, and hexane was added so that the total volume became 50 ml. Next, the temperature in the system was raised to 35 ° C., and then 10.0 mg of lauryldiethanolamine (B-1) as the component (B) and 18.5 mg of octanoic acid (C-1) as the component (C) [component (component (B-1)). A mixture of B-1): component (C) = 100: 35 (molar ratio)] was diluted with 5 ml of toluene and added, and subsequently contacted at 32 to 37 ° C. for 2 hours to obtain a prepolymerized solid catalyst component (prepolymerized solid catalyst component). A hexane slurry of XP-2) was obtained. This 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. under reduced pressure to obtain 10.1 g of a prepolymerized solid catalyst component (XP-2).

[Example 9]
(Polymerization evaluation (i): Evaluation of the wall condition of the autoclave during polymerization)
500 ml of n-heptane was charged into a 1 L stainless steel autoclave sufficiently substituted with nitrogen, the inside of the system was replaced with ethylene, 10 ml of 1-hexene, and 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 reaching 55 ° C. Then, 200 mg of the prepolymerized solid catalyst component (XP-2) was further added to raise the temperature in the system 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 carried out for 90 minutes. After completion of the polymerization, the pressure was depressurized, the polymer was removed, and the state of the autoclave was confirmed. As a result, no adhesion of the polymer was observed on the wall of the autoclave or the stirring blade.

(Polymerization evaluation (ii): Polymerization activity evaluation)
500 ml of n-heptane was charged into a 1 L stainless autoclave sufficiently nitrogen-substituted, the inside of the system was replaced with ethylene, 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, 180 mg of the prepolymerized solid catalyst component (XP-2) was added to raise the temperature in the system 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 carried out for 90 minutes. After completion of the polymerization, the polymer was decompressed, the polymer was filtered and washed, and dried under reduced pressure at 80 ° C. for 10 hours to obtain 123.5 g of the polymer. The polymer yield (polymerization activity) per 1 g of the catalyst was 686 (g-PE / g-cat).

[Preparation Example 4] (Preparation of Prepolymerized Solid Catalyst Component (XP-3))
10.0 g of the prepolymerized solid catalyst component (XP-1) obtained in Preparation Example 2 was charged into a reactor with a stirrer having an internal volume of 200 ml under a nitrogen atmosphere, and hexane was added so that the total volume became 50 ml. Next, the temperature in the system was raised to 35 ° C., and then 10.0 mg of lauryl diethanolamine (B-1) as the component (B) was diluted with 5 ml of toluene and added, followed by contact at 32-37 ° C. for 2 hours. Then, a hexane slurry of the prepolymerized solid catalyst component (XP-3) was obtained. This 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. under reduced pressure to obtain 10.1 g of a prepolymerized solid catalyst component (XP-3).

[Comparative Example 8]
(Polymerization evaluation (i): Evaluation of the wall condition of the autoclave during polymerization)
500 ml of n-heptane was charged into a 1 L stainless steel autoclave sufficiently substituted with nitrogen, the inside of the system was replaced with ethylene, 10 ml of 1-hexene, and the prepolymerized solid catalyst component (XP-3) obtained in Preparation Example 4 were charged. 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-3) to the temperature of 55 ° C. Then, 200 mg of the prepolymerized solid catalyst component (XP-3) was further added to raise the temperature in the system 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 carried out for 90 minutes. After completion of the polymerization, the pressure was depressurized, the polymer was removed, and the state of the autoclave was confirmed. As a result, no adhesion of the polymer was observed on the wall of the autoclave or the stirring blade.

(Polymerization evaluation (ii): Polymerization activity evaluation)
500 ml of n-heptane was charged into a 1 L stainless autoclave sufficiently nitrogen-substituted, the inside of the system was replaced with ethylene, 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, 180 mg of the prepolymerized solid catalyst component (XP-3) was added to raise the temperature in the system 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 carried out for 90 minutes. After completion of the polymerization, the polymer was decompressed, the polymer was filtered and washed, and dried under reduced pressure at 80 ° C. for 10 hours to obtain 110.8 g of the polymer. The polymer yield (polymerization activity) per 1 g of the catalyst was 616 (g-PE / g-cat).

[Example 10]
(Polymerization evaluation (iii): operability evaluation by vapor 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 supplied into the polymerization reactor at 4.8 g / hr. A mixture of lauryl diethanolamine (B-1) as the component (B) and octanoic acid (C-1) as the component (C) at a molar ratio of 100:35 was added to the mass of the polymer in the circulating gas line. (B-1) was supplied so as to be present in an amount of 30 mass ppm. The gas composition in the gas phase polymerizer is ethylene, hydrogen so that ethylene partial pressure = 1.0 MPa, hydrogen / ethylene = 4.8 × 10 ^-4 molar ratio, 1-hexene / ethylene = 0.022 molar ratio. , 1-Hexene and Isopentane were continuously supplied to produce a polymer at a ratio 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 ASTMD1238-65T under the conditions of 190 ° C. and a weight of 2.16 kg.
Although the operation was carried out for 48 hours under the above conditions, no heat spots were observed in all the places such as the polymerizer and the piping, and stable polymerization could be carried out.

[Comparative Example 9]
The supply amount of the prepolymerized solid catalyst component (XP-1) was set to 4.8 g / hr, and the same as in Example 6 except that the mixture of the component (B-1) and the component (C-1) was not supplied. A polymer was produced at a rate of 6.0 kg / hr. As a result of the operation under these conditions, heat spots were generated in the polymerizer and the like, and the operation could not be continued in 4 hours.

According to the present invention, an olefin-based polymer capable of achieving stable operation of a manufacturing apparatus and further improvement of polymerization activity by effectively preventing stains inside the polymer such as a polymer wall and a stirring blade. A production method can be provided, and the present invention greatly contributes to the improvement of the productivity of the olefin-based polymer using the catalyst.

Claims (5)

(A) Solid catalyst component for olefin polymerization,
(B) an amine compound represented by the following general formula (I), and (C) a carboxylic acid compound represented by the following general formula (II).
In the presence of, one or more olefins selected from the group consisting of ethylene and α-olefins having 3 or more and 20 or less carbon atoms are (co) polymerized in a polymerizer.
A method for producing an olefin polymer.

[In the above general formula (I), R is a hydrocarbon group having 1 to 30 carbon atoms, and R'is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of R's, the plurality of R's are independently defined in the same manner as described above. m and n are independently integers of 0 or more, and m + n is 1 or more. ]

[In the above general formula (II), R ² represents a hydrocarbon group having 1 or more and 30 or less carbon atoms. ] The method for producing an olefin polymer according to claim 1, wherein the component (B) is supplied in an amount of 0.1 mass ppm or more and 500 mass ppm or less with respect to the yield of the olefin polymer. The method for producing an olefin-based polymer according to claim 1 or 2, wherein the olefin is ethylene alone or ethylene and an olefin having 3 or more and 20 or less carbon atoms. The method for producing an olefin-based polymer according to any one of claims 1 to 3, wherein the olefin (co) polymerization is carried out in a suspension or a gas phase. Ingredient (A) is
(A-1) A transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton,
(A-2) (a) Organometallic compound,
(B) Organoaluminium oxy compounds and
(C) At least one compound selected from the group consisting of compounds that react with the component (A-1) to form an ion pair, and
(A-3) Fine particle carrier and
The method for producing an olefin polymer according to any one of claims 1 to 4, which comprises.