Method for producing olefin polymers

Abstract

The present invention provides a method for producing olefin polymers that can effectively prevent contamination of the polymer chamber walls, stirring blades, and other internal components, and can also achieve greater operational stability and polymerization activity of the manufacturing apparatus. [Solution] A method for producing an olefin polymer, characterized by polymerizing ethylene and at least one olefin selected from 3 to 20 carbon atoms α-olefins in a polymerizer in the presence of two or more of the following components (A) and (B), and further in the presence of a compound containing a specific poly(alkyleneoxy) unit which is component (C). Component (A): Solid catalyst component for olefin polymerization, Component (B): Polyoxyethylene alkylamine compound represented by the following general formula (I) TIFF2026059256000014.tif29161 [In general formula (I), R is a hydrocarbon group having 1 to 30 carbon atoms, and m and n are independent integers of 1 or more.]

Description

Technical Field

[0001] The present invention relates to a method for producing an olefin polymer that can prevent fouling inside a polymerization vessel such as a polymerization vessel wall and stirring blades, and can achieve further improvement in the stability and polymerization activity in the operation of a production apparatus.

Background Art

[0002] In chemical apparatuses such as petroleum distillation and refining plants and polyolefin production plants, problems such as a decrease in the heat exchange capacity of the plant due to fouling and blockage of pipes occur. As a result, the production operation becomes unstable, and in the worst case, the operation may stop. Specific problems include, for example, the generation of polymer lumps and sheet-like substances in the polymerization vessel and the adhesion of polymers to the stirring blades and the polymerization vessel wall.

[0003] As a method for solving these problems, Patent Document 1 discloses a method of adding an alkyldiethanolamine compound into a polymerization vessel for olefin polymerization by a gas phase method using a solid catalyst. Further, Patent Document 2 discloses a method for producing an olefin polymer using a charge control agent-containing prepolymerization catalyst obtained by contacting a charge control agent with a prepolymerization catalyst obtained by prepolymerizing an olefin in the presence of a solid catalyst and then prepolymerizing the olefin again. Patent Document 2 discloses that as the charge control agent, (C-1) a polyalkylene oxide block, (C-2) a higher aliphatic amide, (C-3) a polyalkylene oxide, (C-4) a polyalkylene oxide alkyl ether, and (C-5) an alkyldiethanolamine can be used.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

[0005] Olefin polymers are important industrial products widely used in a wide variety of applications, and there is a need for further improvements in their productivity. The object of the present invention is to provide a method for producing olefin polymers that can prevent contamination of the polymer chamber walls, stirring blades, and other internal components, and achieve further improvements in the operational stability of the manufacturing equipment and polymerization activity. [Means for solving the problem]

[0006] The inventors have found that, in order to further improve the productivity of olefin polymers, by using two or more polyoxyethylene alkylamine compounds when polymerizing olefins in the presence of a solid catalyst, and further by supplying a combination of compounds containing specific poly(oxyalkylene) units to the polymerizer, it is possible to prevent contamination of the polymerizer walls, stirring blades, and other parts of the polymerizer, and to achieve further improvements in the operational stability of the manufacturing equipment and polymerization activity. The present invention is based on these new findings of the inventors. The gist of the present invention is as follows.

[0007] [1] A method for producing an olefin polymer, characterized by polymerizing ethylene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms in a polymerizer in the presence of the following component (A) and two or more components (B). Component (A): Solid catalyst component for olefin polymerization, Component (B): Polyoxyethylene alkylamine compound represented by the following general formula (I)

[0008] [ka] [In general formula (I), R is a hydrocarbon group having 1 to 30 carbon atoms, and m and n are independent integers of 1 or more.]

[0009] [2] A method for producing an olefin polymer according to [1] above, characterized by polymerizing an olefin in the presence of component (A), two or more components (B), and the following component (C). Component (C): A compound containing poly(oxyalkylene) units.

[0010] [3] A method for producing an olefin polymer according to [2] above, characterized in that component (C) is selected from the following. (Ca) polyoxyalkylene block compounds, (Cb) polyoxyalkylene alkyl ether compounds, and (Cc) Polyoxyalkylene alkyl ester compound

[0011] [4] A method for producing an olefin polymer according to [2] above, characterized in that component (C) is a compound having a poly(oxyethylene) block and a poly(oxypropylene) block.

[0012] [5] Supply of component (A) to the polymerizer, and Supply of two or more components (B) to the polymerizer, A method for producing an olefin polymer as described in [1] above, characterized by performing each of these steps separately. [6] Supply of component (A) to the polymerizer, and, Supply of two or more components (B) and (C) to the polymerizer, A method for producing an olefin polymer as described in [2] above, characterized by performing each of these steps separately. [7] A method for producing an olefin-based polymer according to any one of the above [1] to [6], characterized in that the polymerization of the olefin is carried out in a suspension or in the gas phase. [8] Component (A) is (A-1) A transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, (A-2)(A-2a) organometallic compound, (A-2b) Organoaluminum oxy compounds, and (A-2c) Compound that reacts with component (A-1) to form an ion pair. at least one compound selected from the group consisting of and, (A-3) A particulate carrier and A method for producing an olefin polymer according to any one of the above [1] to [6], characterized by containing [Effects of the Invention]

[0013] The method for producing olefin polymers according to the present invention prevents contamination of the polymer chamber walls, stirring blades, and other internal components, and also achieves improved operational stability and polymerization activity of the production apparatus. [Modes for carrying out the invention]

[0014] The present invention provides a method for producing olefin polymers using the above-mentioned components (A) and (B), and more preferably, component (C) is also used. The following describes these components (A), (B), and (C).

[0015] Component (A): Solid catalyst component for olefin polymerization As component (A), a solid catalyst component for olefin polymerization is preferred, for example, a solid catalyst component containing a transition metal compound selected from Group 3 to Group 12 of the periodic table. Specific examples include a carrier-supported transition metal complex catalyst component in which a transition metal compound from Groups 4 to 6 of the periodic table is supported on a particulate carrier, a solid titanium-based catalyst component containing a solid titanium catalyst component and an organoaluminum compound, and a Phillips catalyst component in which any chromium compound that can be oxidized to chromium trioxide is supported on an inorganic oxide solid such as silica.

[0016] The Group 4-6 transition metal compounds used in the carrier-supported transition metal complex catalyst component can be any known Group 4-6 transition metal compounds with olefin polymerization ability. Examples of such transition metal compounds include Group 4-6 transition metal halides, transition metal alkylates, transition metal alkoxyates, and non-crosslinkable or crosslinkable metallocene compounds. Group 4 transition metal compounds are particularly preferred. Among these, supported metallocene catalyst components belonging to supported transition metal complex catalyst components are preferred, and supported metallocene catalyst components containing the following components (A-1) to (A-3) are more preferred. (A-1) Transition metal compounds of Group 4 of the periodic table having a cyclopentadienyl skeleton, (A-2) At least one compound selected from the group consisting of the following components (A-2a) to (A-2c), (A-2a) organometallic compound, (A-2b) Organoaluminum oxy compounds, and (A-2c) A compound that reacts with component (A-1) to form an ion pair. (A-3) Particulate carrier.

[0017] Specific examples of transition metal compounds in Group 4 of the periodic table include titanium tetrachloride, dimethyltitanium dichloride, tetrabenzyl titanium, tetrabenzyl zirconium, and tetrabutoxytitanium. Furthermore, non-crosslinkable or crosslinkable metallocene compounds are particularly preferred from the viewpoint of polymerization activity, which indicates the activity in the polymerization reaction of the catalyst (yield of olefin polymer per gram of catalyst). Metallocene compounds are transition metal compounds in Group 4 of the periodic table having a cyclopentadienyl skeleton, and are represented, for example, by the following general formula (II).

[0018] ML d ...(II) [In general formula (II), M is a transition metal of Group 4 of the periodic table (specifically zirconium, titanium, or hafnium). L is a ligand (group) that coordinates to the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton. L other than ligands having a cyclopentadienyl skeleton are hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, allyloxy groups, halogen atoms, trialkylsilyl groups, -SO3R' (where R' is a hydrocarbon group having 1 to 8 carbon atoms, which may have substituents such as halogens), or hydrogen atoms. d is the valence of the transition metal and indicates the number of L atoms.]

[0019] Specific examples of ligands having a cyclopentadienyl skeleton include cyclopentadienyl groups; alkyl-substituted cyclopentadienyl groups such as methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, ethylcyclopentadienyl, methylethylcyclopentadienyl, propylcyclopentadienyl, methylpropylcyclopentadienyl, butylcyclopentadienyl, methylbutylcyclopentadienyl, and hexylcyclopentadienyl; indenyl groups; 4,5,6,7-tetrahydroindenyl groups; and fluorenyl groups. These groups may have substituents such as halogen atoms and trialkylsilyl groups.

[0020] Among ligands having a cyclopentadienyl skeleton, alkyl-substituted cyclopentadienyl groups are particularly preferred. When a compound represented by general formula (II) contains two or more groups having a cyclopentadienyl skeleton, two of these groups may be bonded via alkylene groups such as ethylene and propylene; alkylidene groups such as isopropylidene and diphenylmethylene; silylene groups; substituted silylene groups such as dimethylsilylene, diphenylsilylene, and methylphenylsilylene. Furthermore, it is preferable that the two or more groups having a cyclopentadienyl skeleton are identical.

[0021] 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 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; aryl groups such as phenyl group, tolyl group; aralkyl groups such as benzyl group, neophyl group. Specific examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, butoxy group. Specific examples of the aryloxy group include phenoxy group. Specific examples of the halogen atom include fluorine, chlorine, bromine, iodine. Specific examples of -SO3R' include p-toluenesulfonate group, methanesulfonate group, trifluoromethanesulfonate group. When there are a plurality of ligands other than the ligand having a cyclopentadienyl skeleton, these ligands may be the same or different, and may also have one or more combinations of different ligands.

[0022] When the valence of the transition metal is 4, for example, the compound represented by the general formula (II) is more specifically represented by the following general formula (II'). MR 1 R 2 R 3 R 4 ···(II') [In the general formula (II'), M is zirconium, titanium or hafnium. R 1 is a group having a cyclopentadienyl skeleton. R 2 , R 3 and R 4 are each independently 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, -SO3R' (R' is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as a halogen), or a hydrogen atom.]

[0023] Particularly, as the component (A-1), in the general formula (II'), R 2 , R 3 and R 4A transition metal compound in which one of the groups has a cyclopentadienyl skeleton is preferred. For example, R 1 and R 2 If R is a group having a cyclopentadienyl skeleton, these groups having a cyclopentadienyl skeleton may be bonded via alkylene groups, substituted alkylene groups, alkylidene groups, silylene groups, substituted silylene groups, etc. Note that in this case R 3 and R 4 These are alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, allyloxy groups, halogen atoms, trialkylsilyl groups, -SO3R', or hydrogen atoms. Specific examples of these groups can be similarly listed for formula (II) above.

[0024] The following are examples of transition metal compounds in which M is zirconium. Bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromide, bis(indenyl)zirconium bis(p-toluenesulfonate), bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl) Methyl zirconium monochloride, ethylene bis(indenyl) zirconium bis(methanesulfonate), ethylene bis(indenyl) zirconium bis(p-toluenesulfonate), ethylene bis(indenyl) zirconium bis(trifluoromethanesulfonate), ethylene bis(4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium Mudiclorides, dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(dimethylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(trimethylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium bis(trifluoromethanesulfonate), 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,Dimethylsilylene bis(4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene bis(indenyl) zirconium dichloride, methylphenylsilylene bis(indenyl) zirconium dichloride, bis(cyclopentadienyl) zirconium dichloride, bis(cyclopentadienyl) zirconium dibromide, bis(cyclopentadienyl) methyl zirconium monochloride, bis(cyclopentadienyl) ethyl zirconium dibromide Conium monolith, bis(cyclopentadienyl)cyclohexylzirconium monolith, bis(cyclopentadienyl)phenylzirconium monolith, bis(cyclopentadienyl)benzylzirconium monolith, bis(cyclopentadienyl)zirconium monolith monohydride, bis(cyclopentadienyl)methylzirconium monohydride, bis(cyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)diphenylzirconium, bis(cyclopentadienyl)dibenzylzirconium Zirconium, bis(cyclopentadienyl)zirconium methoxychloride, bis(cyclopentadienyl)zirconium ethoxycyclochloride, bis(cyclopentadienyl)zirconium bis(methanesulfonate), bis(cyclopentadienyl)zirconium bis(p-toluenesulfonate), bis(cyclopentadienyl)zirconium bis(trifluoromethanesulfonate), bis(methylcyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadienyl) Zirconium ethoxycyclochloride, bis(dimethylcyclopentadienyl)zirconium bis(trifluoromethanesulfonate), 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(methanesulfonate), bis(trimethylcyclopentadienyl)zirconium dichloride, bis(tetramethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(hexylcyclopentadienyl)zirconium dichloride, bis(trimethylsilylcyclopentadienyl)zirconium dichloride, etc.

[0025] In the above examples, disubstituted cyclopentadienyl rings include 1,2- and 1,3-substituted compounds, and trisubstituted compounds include 1,2,3- and 1,2,4-substituted compounds. Furthermore, alkyl groups such as propyl and butyl include isomers such as n-, i-, sec-, and tert-.

[0026] Furthermore, in each of the above zirconium compounds, transition metal compounds in which zirconium metal is substituted with titanium metal or hafnium metal can also be used. In addition to titanium compounds and hafnium compounds having similar stereostructures, as well as bromides, iodides, etc., other examples of transition metal compounds can be found, such as those described in Japanese Patent Publication No. 3-9913, Japanese Patent Publication No. 2-131488, Japanese Patent Publication No. 3-21607, Japanese Patent Publication No. 3-106907, Japanese Patent Publication No. 3-188092, Japanese Patent Publication No. 4-69394, Japanese Patent Publication No. 4-300887, and International Publication No. 2001 / 27124.

[0027] Other examples of transition metal compounds include those represented by the following general formula (III), as described in Japanese Patent Publication No. 11-315109.

[0028] [ka]

[0029] [In general formula (III), M 1 R represents transition metal atoms in groups 4-6 of the periodic table. f represents an integer from 1 to 6. 11 ~R 16Each of these independently represents a hydrogen 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. 11 ~R 16 Two or more of these may be linked to each other to form a ring. When f is 2 or greater, R 11 ~R 16 In multiple units having these groups, each of these groups is defined independently in the same manner as above. Also, when f is 2 or greater, R 11 ~R 16 Two of the groups may be linked together (however, multiple R 11 (They cannot be joined together). e is M 1 It is a number that satisfies the given valency. X represents a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group. When e is 2 or greater, multiple groups represented by X are each defined independently in the same manner as above. The multiple groups represented by X may be identical or different, or the multiple groups represented by X may include one or more different combinations of groups. Furthermore, the multiple groups represented by X may bond to each other to form a ring. Specific examples of substituents as X include the groups disclosed in Japanese Patent Publication No. 11-315109.

[0030] The component (A-2) constituting the support-type transition metal complex catalyst component is at least one compound selected from organometallic compounds (A-2a), organoaluminum oxy compounds (A-2b), and compounds (A-2c) that react with component (A-1) to form an ion pair.

[0031] As organometallic compounds (A-2a), for example, organometallic compounds of groups 1, 2 and 12, 13 of the periodic table represented by the following general formulas (IV), (V), and (VI) can be used.

[0032] R 5 g Al(OR 6 ) h H i X 1 j ···(IV) [In general formula (IV), R 5 and R 6 each independently represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. X 1 represents a halogen atom. g is a number where 0 < g ≦ 3, h is a number where 0 ≦ h < 3, i is a number where 0 ≦ i < 3, j is a number where 0 ≦ j < 3, and g + h + i + j = 3.] An organoaluminum compound represented by this formula. As this hydrocarbon group, an alkyl group is preferred. Specific examples of the compound represented by general formula (IV) include trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride.

[0033] M 2 AlR 7 4···(V) [In general formula (V), M 2 represents Li, Na or K, and R 7 represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.] An organometallic complex compound of a Group 1 metal of the periodic table and aluminum represented by this formula. As the above hydrocarbon group, an alkyl group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, is preferred. Specific examples of the compound represented by general formula (V) include LiAl(C2H5)4, LiAl(C7H 15 )4.

[0034] R 8 R 9 M 3 ···(VI) [In general formula (VI), R 8 and R 9 may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. M3 [It is Mg, Zn, or Cd.] Organometallic compounds of Group 2 or Group 12 metals in the periodic table, represented by [the specified formula]. Alkyl groups are preferred as this hydrocarbon group.

[0035] Among the organometallic compounds mentioned above, organoaluminum compounds are preferred. Furthermore, organometallic compounds may be used individually or in combination of two or more.

[0036] As the organoaluminum oxy compound (b), known aluminoxanes can be used. Specifically, for example, at least one of the compounds represented by the following general formulas (VII) and (VIII) can be used.

[0037] [ka]

[0038] [ka]

[0039] [In general formulas (VII) and (VIII), R 21 ~R 24 Each of the following independently represents a hydrocarbon group with 1 to 10 carbon atoms, and k and p independently represent integers of 2 or more.

[0040] As for organoaluminum oxy compound (b), in the above general formulas (VII) and (VIII), R 21 ~R 24Methyl aluminoxanes in which the group is a methyl group, with k and p values ​​of 3 or higher, preferably 10 or higher, are suitably used. These aluminoxanes may contain some organoaluminum compounds. Furthermore, the organoaluminum oxy compound (b) may be a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Publication No. 2-78687. Organoaluminum oxy compounds described in Japanese Patent Publication No. 2-167305, aluminoxanes having two or more alkyl groups described in Japanese Patent Publication No. 2-24701 and Japanese Patent Publication No. 3-103407 are also suitably used.

[0041] Such aluminoxanes can be produced, for example, by the methods (1) to (3) below, and are usually obtained as a solution in a hydrocarbon solvent.

[0042] (1) A method of reacting an organoaluminum compound such as trialkylaluminum with adsorbed water or crystal water by adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium containing a compound or salt containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerium chloride hydrate. (2) A method of directly reacting organoaluminum compounds such as trialkylaluminum with water, ice, or water vapor in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. Law. (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.

[0043] Aluminoxane may contain small amounts of organometallic components. Alternatively, the recovered aluminoxane solution may be redissolved in the solvent after removing the solvent or unreacted organoaluminum compounds by distillation.

[0044] Specific examples of organoaluminum compounds used in the preparation of aluminoxanes include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; and dialkylaluminum allyloxides such as diethylaluminum phenoxide. Among these, trialkylaluminum and tricycloalkylaluminum are preferred.

[0045] Furthermore, isoprenylaluminum, represented by the following general formula (IX), can also be used as an organoaluminum compound for aluminoxane preparation.

[0046] (i-C4H9) r Al s (C5H 10 ) t ...(IX) [In general formula (IX), r, s, and t are positive numbers, and t ≥ 2r.]

[0047] Organoaluminum compounds for aluminoxane preparation may be used individually or in combination of two or more types.

[0048] Specific examples of solvents used in the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel fuel; or hydrocarbon solvents such as halogenated compounds of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, particularly chlorinated compounds and brominated compounds. Other ethers such as ethyl ether and tetrahydrofuran can also be used. Among these, aromatic hydrocarbons are preferred.

[0049] Examples of compounds (c) that react with component (A-1) to form an ion pair (hereinafter also referred to as "ionized ionic compound (c)") include Lewis acids, ionic compounds, borane compounds and carborane compounds, as well as heteropoly compounds and isopoly compounds, as described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Publication No. 3-179005, Japanese Patent Publication No. 3-179006, Japanese Patent Publication No. 3-207703, Japanese Patent Publication No. 3-207704, U.S. Patent No. 5321106, etc. The fact that the ionized ionic compound (c) acts as an activator for metallocene catalysts is disclosed, for example, in Japanese Patent No. 5295501. The ionized ionic compound (c) may be used alone or in combination of two or more types.

[0050] The organometallic compounds (A-2a), organoaluminum oxy compounds (A-2b), and ionized ionic compounds (A-2c) that can be used as component (A-2) have been described above. However, it is preferable to use either organoaluminum oxy compounds (A-2b) alone, or a combination of organoaluminum compounds (A-2a) and organoaluminum oxy compounds (A-2b) as component (A-2).

[0051] Examples of particulate carriers (A-3) include inorganic carriers made of inorganic materials and organic carriers made of organic materials. Examples of inorganic carriers include inorganic metal oxide carriers such as SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, and mixtures containing two or more of these (e.g., SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO), and inorganic chloride carriers such as MgCl2, MgBr2, MnCl2, and MnBr2. Clay, clay minerals which are its components, and ion-exchangeable layered compounds can also be used as inorganic carriers. Examples of organic carriers include organic polymer carriers such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymers.

[0052] The average particle size of the inorganic support is preferably 1 to 300 μm, more preferably 3 to 200 μm. Such a support is used after being calcined at 100 to 1000°C, preferably 150 to 700°C, as needed.

[0053] Inorganic chlorides may be used as is, or they may be used after being ground using a ball mill or vibratory mill. Alternatively, inorganic chlorides can be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

[0054] Clay-based carriers are typically composed primarily of clay minerals. Carriers using ion-exchangeable layered compounds have a crystalline structure in which planes formed by ionic bonds are stacked parallel to each other with weak bonding forces, allowing for ion exchange. Most clay minerals are ion-exchangeable layered compounds. Furthermore, these clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural sources; artificially synthesized materials can also be used. Examples of clays, clay minerals, or ion-exchangeable layered compounds include clays, clay minerals, and ionic crystalline compounds having layered crystalline structures such as hexagonal close packing type, antimony type, CdCl2 type, and CdI2 type. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gillome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, lyokdiite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchangeable layered compounds include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O. It is also preferable to chemically treat clay and clay minerals. Chemical treatments can be used, including surface treatments to remove impurities attached to the surface and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment.

[0055] Ion-exchangeable layered compounds may also be layered compounds in which the interlayers are expanded by utilizing ion exchange properties to exchange exchangeable ions between layers with other large, bulky ions. These bulky ions play a supporting role in the layered structure and are usually called pillars. The process of introducing another substance between the layers of a layered compound in this way is called intercalation. Guest compounds used for intercalation include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR")4, Zr(OR")4, PO(OR")3, and B(OR")3 (where R" independently represents a hydrocarbon group, etc.), and [Al 13 O4(OH) 24 ] 7+ [Zr4(OH) 14 ] 2+ [Fe3O(OCOCH3)6] +Examples include metal hydroxide ions. These compounds can be used individually or in combination of two or more. Furthermore, when intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides such as Si(OR")4, Al(OR")3, and Ge(OR")4 (where R" independently represents a hydrocarbon group, etc.), colloidal inorganic compounds such as SiO2, can also be present. Furthermore, examples of pillars include oxides produced by intercalating the above-mentioned metal hydroxide ions between layers and then heating and dehydrating them. Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, pectolite, teniolite, and synthetic mica are particularly preferred.

[0056] Examples of organic carriers include granular or particulate solids with a particle size in the range of 1 to 300 μm. Specific examples of polymers forming the organic carrier include, as previously exemplified, (co)polymers produced mainly from ethylene or α-olefins with 3 to 14 carbon atoms, such as propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane or styrene, and their modified forms.

[0057] Furthermore, a solid component obtained by insolubilizing component (A-2) as described above by the method described in Japanese Patent Publication No. 11-140113, Japanese Patent Publication No. 2000-38410, Japanese Patent Publication No. 2000-95810, International Publication No. 2010 / 55652, etc., can also be used as a particulate carrier (A-3). In this case, contact with component (A-2) is not essential in the method for preparing the carrier-supported metallocene catalyst component described below.

[0058] A method for preparing a support-supported metallocene catalyst component, which is preferably used as a solid catalyst component (A) for olefin polymerization, is described below. This support-supported metallocene catalyst can be prepared by mixing and contacting components (A-1) to (A-3). The contact order of each component is arbitrary. In addition, each of these components (A-1) to (A-3), or at least one of (A-2a), (A-2b), and (A-2c) as component (A-2), may be used in multiple contacts with each component.

[0059] For the preparation of carrier-supported metallocene catalyst components, it is preferable to use an inert hydrocarbon solvent. Specifically, these include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof.

[0060] When preparing a support-supported metallocene catalyst component, the transition metal compound (A-1) is typically used in an amount of 0.001 to 1.0 mmol, preferably 0.005 to 0.5 mmol, per gram of particulate support (A-3) in terms of transition metal atoms. The organoaluminum oxy compound (b) is typically used in an amount of 0.1 to 100 mmol, preferably 0.5 to 20 mmol, in terms of aluminum atoms. When using an organoaluminum compound, it is typically used in an amount of 0.001 to 1000 mmol, preferably 2 to 500 mmol, per gram of particulate support (A-3).

[0061] The temperature at which the above components are mixed and brought into contact 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.

[0062] The carrier-supported metallocene catalyst component obtained in this way contains, per gram of particulate carrier (A-3), a transition metal compound (A-1) preferably amounting to about 5 × 10¹⁶ atoms in terms of transition metal atoms. -6 ~10 -3 Mole, Comfortable 10 -5 ~3×10 -4 It is carried in mole quantities. Furthermore, per 1 g of particulate carrier (A-3), the amount of organoaluminum oxy compound (b) is preferably about 10 in terms of aluminum atoms. -3 ~10 -1 Moles, more preferably 2 × 10 -3 ~5×10 -2 It is carried in mole quantities.

[0063] The solid catalyst component for olefin polymerization, which is component (A), may be a prepolymerization catalyst component in which monomers for preparing olefin polymers are prepolymerized. One form of the prepolymerization catalyst component includes a solid catalyst component for olefin polymerization and, if necessary, an olefin polymer produced by prepolymerization. A preferred form of the prepolymerization catalyst includes a transition metal compound (A-1), component (A-2), particulate carrier (A-3), and, if necessary, an olefin polymer (D) produced by prepolymerization. One method for preparing a prepolymerization catalyst is to prepolymerize a small amount of monomer for olefin polymer formation in the presence of a solid catalyst component obtained by mixing and contacting components (A-1) to (A-3) in an active hydrocarbon solvent or in a medium containing monomers for olefin polymer preparation. As mentioned above, the contact order of components (A-1) to (A-3) is not particularly limited. Furthermore, at least one of these components may be contacted in multiple separate steps. Specific examples of inert hydrocarbon solvents used in the preparation of prepolymerization catalysts include those similar to those used in the preparation of the support-supported metallocene catalysts described earlier.

[0064] As monomers used in prepolymerization to prepare olefin-based polymers, ethylene, propylene, and at least one olefin with 4 to 20 carbon atoms can be used. The olefin for prepolymerization preferably has the following composition (AA). • Composition (AA): Ethylene: 100-0 mol%, Propylene: 0-49 mol%, and α-olefins with 4 or more carbon atoms: 0-100 mol%. Furthermore, the following composition (BB) is considered a more preferable composition, and the following composition is considered an even more preferable composition. The following composition (DD) is a particularly preferred composition of (CC). ·Composition (BB): Ethylene: 100-0 mol%, Propylene: 0-20 mol%, and α-olefins with 4 or more carbon atoms: 0-100 mol%. ·Composition (CC): Ethylene: 100-20 mol%, Propylene: 0-20 mol%, and α-olefins with 4 or more carbon atoms: 0-80 mol%. ·Composition (DD): Ethylene: 100-20 mol%, and α-olefins with 4 or more carbon atoms: 0-80 mol%. (In each of the above compositions, the sum of the mole percent of ethylene, the mole percent of propylene, and the mole percent of olefins having 4 or more carbon atoms shall be 100%.)

[0065] Examples of α-olefins with 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Furthermore, monomers that can be copolymerized with α-olefins include 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, and dienes.

[0066] When preparing the prepolymerization catalyst, the transition metal compound (A-1) is used in an amount of typically 0.001 to 1.0 mmol, preferably 0.005 to 0.5 mmol, per gram of particulate support (A-3) in terms of transition metal atoms. The organoaluminum oxy compound (b) is used in an amount of typically 0.1 to 100 mmol, preferably 0.5 to 20 mmol, per gram of particulate support (A-3) in terms of aluminum atoms.

[0067] The prepolymerization catalyst obtained as described above contains, per 1 g of particulate support (A-3), preferably about 5 × 10⁶ transition metal compounds (A-1) in terms of transition metal atoms. -6 ~10 -3 Mole, Comfortable 10 -5 ~3×10 -4 The material is supported in molar quantities. The amount of organoaluminum oxy compound (b) per 1 g of particulate carrier (A-3) is preferably about 10 units in terms of aluminum atoms. -3 ~10 -1 Moles, more preferably 2 × 10 -3 ~5×10 -2 The polymer is supported in molar quantities. It is desirable that the olefin polymer (D) produced by prepolymerization is supported on the particulate carrier (A-3) in an amount of about 0.1 to 500 g, preferably 0.3 to 300 g, and particularly preferably 1 to 100 g.

[0068] Furthermore, component (A), a solid catalyst component for olefin polymerization, may optionally contain other components useful for polymerization, such as surfactants other than component (B) represented by general formula (I) and component (C) represented by general formula (II), during catalyst synthesis or prepolymerization, in addition to the components described above.

[0069] Component (B): Polyoxyethylene alkylamine compound The polyoxyethylene alkylamine compound, which is component (B), is a compound represented by the following general formula (I), and two or more such compounds are used in the present invention.

[0070] [ka]

[0071] (In general formula (I), R is a hydrocarbon group having 1 to 30 carbon atoms, and m and n are independent integers of 1 or more.)

[0072] The hydrocarbon group R in general formula (I) may be saturated or unsaturated. Furthermore, this hydrocarbon group may be linear, branched, or cyclic, and may have two or more of these structures. This hydrocarbon group may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group having at least two of these groups. Examples of aliphatic hydrocarbon groups include alkyl groups and alkenyl groups. Preferred specific examples of hydrocarbon groups include alkyl or alkenyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, and oleoyl groups. Other examples include cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and neophyll groups. Among these, alkyl groups with 8 to 18 carbon atoms are preferred.

[0073] In general formula (I), m and n are each integers greater than or equal to 1. m and n are each independently preferably between 1 and 5. m+n is preferably between 2 and 10.

[0074] Specific examples of polyoxyethylene alkylamine compounds, which are component (B) represented by general formula (I), include lauryldiethanolamine, stearyldiethanolamine, polyoxyethyleneoctylamine, polyoxyethylenedecylamine, polyoxyethylenelaurylamine, polyoxyethylenestearylamine, polyoxyethylene coconut oil alkylamine, polyoxyethylene tallowamine, and polyoxyethylene hydrogenated tallowamine. Among these, lauryldiethanolamine, stearyldiethanolamine, polyoxyethylenelaurylamine, polyoxyethylenestearylamine, and polyoxyethylene coconut oil alkylamine are preferred.

[0075] As combinations of components (B) using at least two types, there are combinations of compounds in which the number of carbon atoms in R in general formula (I) differs by 4 to 12, and / or the number of m+n differs by 2 to 8. As an example of such a combination, Capryl diethanolamine and lauryl diethanolamine, Capryl diethanolamine and stearyl diethanolamine, Capryl diethanolamine and behenyl diethanolamine, Lauryl diethanolamine and stearyl diethanolamine, Lauryl diethanolamine and behenyl diethanolamine, Stearyldiethanolamine and behenyldiethanolamine There are several combinations, and among them, the combination of lauryldiethanolamine and stearyldiethanolamine is preferred.

[0076] In the method for producing olefin polymers of the present invention, it is desirable to polymerize the olefin in the presence of component (A) and component (B) as described below. Component (C) is a compound containing a specific poly(oxyalkylene) unit, which is described below.

[0077] Component (C): Compound containing poly(oxyalkylene) units Compounds containing the poly(oxyalkylene) unit, which is component (C), are, for example, compounds selected from (Ca), (Cb), and (Cc) below. (Ca) polyoxyalkylene block compounds, (Cb) polyoxyalkylene alkyl ether compounds, and (Cc) Polyoxyalkylene alkyl ester compound

[0078] Such compounds include those commonly used as nonionic surfactants and can be used without any restrictions. Among these, it is preferable to use a compound selected from (Ca) polyoxyalkylene block compounds and (Cb) polyoxyalkylene alkyl ether compounds, and among these, compounds having poly(oxyethylene) blocks and poly(oxypropylene) blocks are preferably used. The following describes each compound.

[0079] (Ca) polyoxyalkylene block compounds Polyoxyalkylene blocking compound of component (Ca) can be cited as polyoxyethylene polyoxypropylene glycol.

[0080] <Polyoxyethylene polyoxypropylene glycol> Polyoxyethylene polyoxypropylene glycol is an ABA-type block polymer nonionic surfactant containing both oxyethylene and oxypropylene units.

[0081] The polyoxyethylene polyoxypropylene glycol preferably contains 10 to 80% by weight of oxyethylene units, and particularly preferably 10 to 30% by weight, when the total percentage of parts by weight of oxyethylene units and parts by weight of oxypropylene units is taken as 100%. The polyoxyethylene polyoxypropylene glycol preferably has an average molecular weight in the range of 1,000 to 50,000, and is particularly preferably in the range of 1,000 to 5,000. The aforementioned polyoxyethylene polyoxypropylene glycol is preferably found in a 1% by mass aqueous solution at a temperature of 10°C or higher, and particularly preferably in the range of 10°C to 80°C.

[0082] The polyoxyethylene polyoxypropylene glycol used in this invention is commercially available from companies such as ADEKA Corporation, Sanyo Chemical Industries, Ltd., Aoki Oil & Fat Co., Ltd., NOF Corporation, Kao Corporation, etc., and is readily available.Specific examples include L-31, F-34, F-38, L-42, L-43, L-44, L-61, L-62, L-63, L-64, P-65, F-68, L-71, L-72, P-75, F-77, L-81, P-84, P-85, F-87, F-88, L-92, P-94, F-98, L-101, P-103, P-104, P-105, F-108, L- 121, L-122, P-123, F-127, TR-304, TR-501, TR-504, TR-701, TR-702, TR-704, TR-707, TR-904, TR-908 , TR-1101, TR-1102, TR-1104, TR-1301, TR-1302, TR-1304, TR-1307, TR-1501, TR-1504, TR-1508 etc. Examples include Newpol PE-34, Newpol PE-61, Newpol PE-62, Newpol PE-64, Newpol PE-68, Newpol PE-71, Newpol PE-74, Newpol PE-75, Newpol PE-78, and Newpol PE-108 from Sanyo Chemical Industries, Ltd. Examples include Brownon P-101M, Brownon P-171, Brownon P-172, Brownon P-201, and Brownon P-301 from Aoki Oil & Fat Co., Ltd. Examples include Pronon #124P, Pronon #188P, Pronon #201, Pronon #202, Pronon #204, Pronon #208, Pronon #238, Pronon #184R, and Pronon #188 from NOF Corporation Examples include Emulgen PP-290 from Kao Corporation.

[0083] Furthermore, the polyoxyethylene polyoxypropylene glycol used in the present invention may also be represented by the following general formula (X) or (XI).

[0084] [ka]

[0085] [ka] In general formulas (X) and (XI), a, b, and c represent their respective average chain lengths. When the repeating unit represents the average chain length of the portion consisting of oxyethylene units represented by -CH2CH2O-, each is independently selected from the range of 1 to 100, preferably 1 to 50, and more preferably 1 to 20. When the repeating unit represents the average chain length of the portion consisting of oxypropylene units represented by -CH2CH(CH3)O-, each is selected from the range of 1 to 100, preferably 3 to 60, and more preferably 4 to 40.

[0086] (Cb) Polyoxyalkylene alkyl ether compound Examples of polyoxyalkylene alkyl ether compounds for component (Cb) include polyoxyethylene alkyl ethers.

[0087] <Polyoxyethylene alkyl ether> Polyoxyethylene alkyl ethers are ether-type nonionic surfactants containing oxyethylene units.

[0088] The HLB value (Hydrophile-lipophile balance value) of the polyoxyethylene alkyl ether is preferably 7.0 or higher, and more preferably in the range of 8.0 or higher and less than 20.

[0089] The polyoxyethylene alkyl ether used in this invention is commercially available from companies such as ADEKA Corporation, Sanyo Chemical Industries, Ltd., Aoki Oil & Fat Co., Ltd., NOF Corporation, and Kao Corporation, and is readily available. Specific examples include LA-675B, LA-775, LA-875, LA-975, LA-1275, and OA-7 from ADEKA Corporation; Emarumin 40, Emarumin 50, Emarumin 70, Emarumin 140, Emarumin 180, Emarumin 200, Emarumin 240, Emarumin L-90-S, Emarumin LS-80, Emarumin LS-90, Emarumin NL-70, Emarumin NL-80, Emarumin NL-90, Emarumin NL-100, NL-110, and Emarumin CCE-130 from Aoki Oil & Fat Industry Co., Ltd. 1507, Brownon EL-1509P, Brownon EL-1512P, Brownon EL-1515, Brownon EL-1521, Brownon EL-1540P, Brownon CH-305, Brownon CH-310L, Brownon CH-315L, Brownon CH-320L, Brownon CH-330L, Brownon CH-340, Brownon CH-640, Brownon SR-705, Brownon SR-707, Brownon SR-711, Brownon SR-715, Brownon SR-720, Brownon SR-730, Brownon EN-1504, Brownon EN-1507, Brownon EN-1509, Brownon EN-1513.5. Examples include Braunon EN-1520A, Braunon EN-905, Braunon EN-909, Braunon EN-914, Braunon EN-920PL, Braunon BE-5, and Braunon BE-10, as well as NOF Corporation's Nonion K-204, Nonion K-220, Nonion K-230, Nonion K-2100W, Nonion P-208, and Nonion Examples include Nonion P-210, Nonion P-213, Nonion E-202, Nonion E-202S, Nonion E-205, Nonion E-205S, Nonion E-212, Nonion P-215, Nonion E-230, Nonion S-202, Nonion S-207, Nonion S-215, Nonion S-220, and Nonion S-250, all manufactured by Kao Corporation. Examples include Emulgen 104P, Emulgen 105, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 147, Emulgen 150, Emulgen 210, Emulgen 220, Emulgen 306P, Emulgen 320P, Emulgen 350, Emulgen 404, Emulgen 408, Emulgen 409P, Emulgen 420, Emulgen 430, Emulgen 707, Emulgen 709, Emulgen 1108, Emulgen 1118S-70, Emulgen 1135S-70, Emulgen 1150S-60, Emulgen 4085, Emulgen LS-106, Emulgen LS-110, Emulgen LS-114, and Emulgen MS-110.

[0090] Furthermore, the polyoxyethylene alkyl ether used in this invention may also be represented by the following general formula (XII).

[0091] [ka]

[0092] In general formula (XII), R wis a hydrocarbon group having 1 to 30 carbon atoms, preferably an octyl group, decyl group, lauryl group, myristyl group, cetyl group, stearyl group, or behenyl group. In general formula (3), a represents the average chain length of the portion consisting of oxyethylene units, and is selected from the range of 2 to 100, preferably 2 to 60, and more preferably 3 to 40.

[0093] (Cc) Polyalkylene oxide alkyl ester compound Polyalkylene oxide alkyl ester compounds are compounds in which polyoxyalkylene and alkyl groups are linked by an ester bond, and polyoxyethylene fatty acid esters are preferably used.

[0094] <Polyoxyethylene fatty acid ester> The HLB value of the polyoxyethylene fatty acid ester is preferably 7.0 or higher, and more preferably in the range of 8.0 or higher and less than 20. The polyoxyethylene fatty acid esters used in this invention are commercially available and readily obtainable from companies such as Sanyo Chemical Industries, Ltd., Aoki Oil & Fat Co., Ltd., NOF Corporation, and Kao Corporation. Specific examples include Ionet MS-400, Ionet MS-1000, Ionet MO-200, Ionet MO-400, and Ionet MO-600 from Sanyo Chemical Industries, Ltd.; Braunon L-400, Braunon S-300A, Braunon O-200SA, Braunon O-400SA, and Braunon O-600SA from Aoki Oil & Fat Co., Ltd.; and Noni Examples include ON L-2, NONION L-4, NONION S-2, NONION S-4, NONION S-6, NONION S-15, NONION S-15K, NONION S-15.4, NONION S15.4V, NONION S-40, NONION O-2, NONION O-3, NONION O-4, and NONION O-6, as well as EMANON 1112, EMANON 3199VB, and EMANON 4110 manufactured by Kao Corporation. Furthermore, the polyoxyethylene fatty acid ester used in this invention may also be represented by the following general formula (4).

[0095] [ka]

[0096] In general formula (XIII), R x is a hydrocarbon group having 1 to 30 carbon atoms, preferably 5 to 27 carbon atoms, and more preferably 7 to 25 carbon atoms. In general formula (XIII), a represents the average chain length of the portion consisting of oxyethylene units, and is selected from the range of 2 to 100, preferably 2 to 60, and more preferably 3 to 40.

[0097] Component (C) is a polyoxyethylene alkylamine compound represented by general formula (I), which is component (B). [ka] Excluding the following: [In general formula (I), R is a hydrocarbon group having 1 to 30 carbon atoms, and m and n are each independent integers of 1 or more.] Furthermore, it is more preferable that component (C) is not an amine compound.

[0098] Production of olefin polymers The present invention provides a method for producing an olefin polymer, comprising the step of (co)polymerizing one or more olefins selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms in a polymerizer, in the presence of two or more of the above-described components (A) (solid catalyst component for olefin polymerization) and (B) (polyoxyethylene alkylamine compound), and more preferably, in addition to the above-described specific component (C) (compound containing poly(alkyleneoxy) units).

[0099] In this invention, the term "(co)polymerization" is used to encompass both polymerization and copolymerization. Furthermore, in this invention, "polymerization" and "polymer" may be used to encompass not only "homopolymerization" and "homopolymer," but also "copolymerization" and "polymer," respectively.

[0100] The method of supplying component (A), two or more components (B), and component (C) to the polymerizer during (co)polymerization is arbitrary and not particularly limited. Component (A), two or more components (B), and component (C) may be supplied to the polymerizer individually in any order. Alternatively, a mixture of two of the components (A), two or more components (B), and component (C) may be pre-mixed and brought into contact, and the remaining components may be added to the polymerizer in any order.

[0101] Alternatively, a mixture of component (A), two or more components (B), and component (C) obtained by pre-mixing and contacting them may be added to the polymerizer. Furthermore, two or more of these supply methods may be combined. Component (A) may also be added to the polymerizer as a pre-polymerization solid catalyst component. Furthermore, in any of the above, two or more types of component (C) may be used.

[0102] A suitable method for supplying component (A) and two or more components (B) to a polymerizer. In the method for producing olefin polymers of the present invention, the following method is preferred for supplying component (A) and two or more components (B) to the polymerizer. (1) Supply of component (A) to the polymerizer, Supply of two or more components (B) to the polymerizer A method of doing each of these separately. (2) Component (A) and two or more components (B) Supply of mixture a' obtained by contact to the polymerizer How to do it. (3) Component (A) and two or more components (B) The mixture a' obtained by contact is supplied to the polymerizer. And, Supply of two or more components (B) to the polymerizer, A method of performing one action first and the other action later. In (1) above, one embodiment is to mix two or more components (B) to form a mixture a and supply it. Also in (2) and (3), one embodiment is to mix two or more components (B) to form a mixture a and then bring it into contact with (A) or to supply mixture a to a polymerizer. In these supply methods, each supply is performed at at least one of the following timings: before polymerization begins in the polymerizer, at the start of polymerization, or during polymerization. The order in which component (A) is supplied to the polymerizer and the two or more components (B) in method (1) is not particularly limited. They may be supplied to the polymerizer simultaneously, or one may be supplied to the polymerizer first, followed by the other. The order in which mixture a' is supplied to the polymerizer and the two or more components (B) are supplied to the polymerizer in method (3) is not particularly limited. After starting the supply of one component, the supply of the other component may be started while the supply of the first component is still being supplied, and both components may be supplied simultaneously. It is preferable to supply mixture a' to the polymerizer first, followed by the supply of two or more components (B). In this case, the supply of the two or more components (B) to the polymerizer after the supply of mixture a' can be performed at at least one timing: before the start of polymerization in the polymerizer, at the start of polymerization, or during the polymerization reaction. In methods (1), (2), and (3), when component (A) and two or more components (B) are supplied to the polymerizer, at least one of them may be supplied to the polymerizer in multiple batches. Furthermore, in a preferred embodiment, there is a method for producing an olefin polymer in which, after supplying a mixture obtained by contacting component (A) and two or more components (B) to a polymerizer, the olefin is polymerized while or after further supplying two or more components (B) to the polymerizer. In this embodiment, the two or more components (B) further supplied may be partially or entirely different from the two or more components (B) in the mixture already supplied, but it is preferable that they be the same. Furthermore, it is preferable to use a prepolymerization catalyst component obtained by prepolymerizing a monomer for olefin polymerization in the presence of a solid catalyst component for olefin polymerization as component (A). Component (A) may be supplied to the polymerizer in multiple batches.

[0103] A suitable method for supplying component (A), two or more components (B), and component (C) to a polymerizer. In the method for producing olefin polymers of the present invention, the following method is preferred for supplying component (A), two or more components (B), and component (C) to the polymerizer. (4) Supply of component (A) to the polymerizer, Supply of two or more components (B) to the polymerizer, and Supply of component (C) to the polymerizer A method of doing each of these separately. In this (4), one embodiment is to mix two or more components (B) and component (C) to form mixture b, which is then supplied to the polymerizer. (5) Component (A), two or more components (B), and component (C) Supply of mixture b' obtained by contact to the polymerizer How to do it. In this (5), one embodiment is to mix two or more components (B) and component (C) to form a mixture b, and then bring it into contact with component (A). (6) Component (A), two or more components (B), and component (C) The mixture b' obtained by contact is supplied to the polymerizer. and Supply of two or more components (B) and (C) to the polymerizer. A method of performing one action first and the other later, or a method of performing both actions together. In this (6), one embodiment is to mix two or more components (B) and component (C) to form mixture b, and then bring it into contact with component (A) or supply it to the polymerizer. In these supply methods, each supply is performed at at least one of the following timings: before polymerization starts in the polymerizer, at the start of polymerization, or during polymerization. Note that in method (4) Supply of component (A) to the polymerizer, Supply of two or more components (B) to the polymerizer, and Supply of component (C) to the polymerizer The order in which these are supplied is not particularly limited. They may be supplied to the polymerizer simultaneously. Furthermore, in method (6) Component (A), two or more components (B), and component (C) The mixture b' obtained by contact is supplied to the polymerizer. and Supply of two or more components (B) and (C) to the polymerizer. The order in which they are supplied is not particularly limited. They may be supplied to the polymerizer simultaneously, or one may be supplied to the polymerizer first, followed by the other. Also, after supplying mixture b' to the polymerizer first, Supply of two or more components (B) and (C) to the polymerizer. It is preferable to do so. In this case, the supply of two or more components (B) to the polymerizer after the supply of mixture b' can be carried out at at least one timing before polymerization begins, at the start of polymerization, or during the polymerization reaction. In methods (4), (5), and (6), when supplying component (A) and mixture b' to the polymerizer, at least one of them may be supplied to the polymerizer in multiple portions. Furthermore, in a preferred embodiment, there is a method for producing an olefin polymer in which, after supplying a mixture obtained by contacting component (A), two or more components (B), and component (C) to a polymerizer, the olefin is polymerized while or after further supplying two or more components (B) and component (C) to the polymerizer. In this embodiment, the two or more components (B) and component (C) further supplied may be partially or entirely different from the two or more components (B) and component (C) in the mixture already supplied, but it is preferable that they be the same. Furthermore, it is preferable to use a prepolymerization catalyst component obtained by prepolymerizing a monomer for olefin polymerization in the presence of a solid catalyst component for olefin polymerization as component (A).

[0104] In this invention, by using component (A) in combination with two or more components (B), or even further by using component (C) in combination, it is possible to effectively prevent fouling inside the polymerizer, such as on the polymerizer walls and stirring blades, and to achieve greater operational stability of the manufacturing equipment and further improvement of polymerization activity.

[0105] The inventors surmise that the reason such effects are obtained is that two or more components (B), or even component (C), form an interacting compound, thereby maintaining the aforementioned anti-fouling effect while enabling stable operation of the manufacturing equipment and further improving polymerization activity.

[0106] There are no particular restrictions on the ratio of the multiple components (B) present in the polymerization chamber. For example, if component (B) consists of two types, component (B-1) and component (B-2), the ratio can preferably be selected from the range of component (B-1):component (B-2) = 99:1 to 1:99. More preferably, this ratio can be selected from the range of 95:5 to 5:95, and particularly preferably from the range of 90:10 to 10:90. The mass ratio of the total amount of component (B) to component (C) can preferably be selected from the range of total amount of component (B):component (C) = 100:0.1 to 100:100. This ratio is more preferably selected from the range of 100:0.1 to 100:50, and particularly preferably from the range of 100:0.1 to 100:30. The ratio (mass ratio) of component (A) to the total amount of multiple components (B) can be selected from the range of component (A):total amount of multiple components (B) = 100:0.05 to 100:30. It is more preferable to select this ratio from the range of 100:0.1 to 100:25, and particularly preferable to select it from the range of 100:0.2 to 100:20. The ratio (mass ratio) of the total amount of multiple components (B) and the total mass of component (C) to component (A) can be selected from the range of component (A): total amount of multiple components (B) + total mass of component (C) = 100:0.05 to 100:30. It is more preferable to select this ratio from the range of 100:0.1 to 100:25, and particularly preferable to select it from the range of 100:0.2 to 100:20.

[0107] Polymerization can be carried out in a suspension, solution, or gas phase, and is particularly preferably carried out in a suspension or gas phase by slurry polymerization or gas phase polymerization. Specific examples of inert hydrocarbon media used in slurry polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. Among these, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred.

[0108] The polymerization temperature is typically -50 to 150°C, preferably 0 to 100°C, for slurry polymerization, and typically 0 to 120°C, preferably 20 to 100°C, for gas-phase polymerization. The polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out by batch, semi-continuous, or continuous methods.

[0109] Polymerization can also be carried out in two or more stages with different reaction conditions. The molecular weight of the resulting olefin polymer can also be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature.

[0110] As raw materials for polymerization, ethylene and at least one selected from α-olefins having 3 to 20 carbon atoms are used. Specific examples of these α-olefins 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-eicosene. These can be used individually or in combination of two or more types. In addition to ethylene and α-olefins having 3 to 20 carbon atoms, other copolymerization monomers may also be used in combination. Examples of copolymerization monomers include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4:5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene. Styrene, vinylcyclohexane, and dienes can also be used.

[0111] As the olefin used as a raw material for polymerization, any olefin having one of the compositions (AA), (BB), (CC), or (DD) previously exemplified for prepolymerization can be used. Furthermore, in the present invention, it is preferable to produce an ethylene-based polymer with ethylene as the main monomer. As the ethylene-based polymer, a (co)polymer containing 50 mol% or more of ethylene and optionally an α-olefin component having 4 to 10 carbon atoms is preferred. The olefins used in the present invention, such as ethylene, α-olefin, and the above copolymer monomers, may also include biomass-derived monomers (ethylene, α-olefin, copolymer monomer). The monomers constituting the polymer may consist solely of biomass-derived monomers, or they may contain both biomass-derived monomers and fossil fuel-derived monomers. Biomass-derived monomers are monomers made from any renewable natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, which are plant-derived or animal-derived, and which contain 10¹⁴C isotopes as carbon. -12It contains biomass carbon (pMC) in a proportion of approximately 100 pMC, as measured in accordance with ASTM D 6866. Biomass-derived monomers are obtained by conventionally known methods. It is preferable that the olefin polymer according to the present invention contains biomass-derived monomers from the viewpoint of reducing environmental impact (mainly greenhouse gas reduction). If the polymer production conditions such as polymerization catalyst, polymerization process, and polymerization temperature are equivalent, even if the raw material monomer contains biomass-derived monomers, the 14C isotope can be 10 -12 ~10 -14 Aside from the small proportions it contains, its molecular structure is equivalent to that of olefin polymers composed of fossil fuel-derived monomers. Therefore, its performance is considered to be the same. Furthermore, the olefins used in the present invention, such as ethylene, α-olefin, and the above-mentioned copolymer monomers, may also contain monomers derived from chemical recycling (ethylene, α-olefin, copolymer monomer). The monomers constituting the polymer may consist solely of monomers derived from chemical recycling, or they may contain monomers derived from chemical recycling, monomers derived from fossil fuels, and / or monomers derived from biomass. Monomers derived from chemical recycling can be obtained by conventionally known methods. It is preferable for the olefin polymer according to the present invention to contain monomers derived from chemical recycling from the viewpoint of reducing environmental impact (mainly waste reduction). Even if the raw material monomers contain monomers derived from chemical recycling, since monomers derived from chemical recycling are monomers obtained by depolymerizing polymers such as waste plastics back to monomer units such as ethylene through depolymerization, thermal decomposition, etc., and monomers produced using such monomers as raw materials, if the polymer production conditions such as polymerization catalyst, polymerization process, and polymerization temperature are the same, the molecular structure is equivalent to that of an olefin polymer consisting of monomers derived from fossil fuels. Therefore, the performance is also considered to be unchanged.

[0112] During polymerization, the olefin polymerization catalyst (A) is typically 10 per liter of polymerization volume, calculated in terms of transition metal atoms in the transition metal compound (A-1). -8 ~10 -3 moles, preferably 10 -7 ~10 -4It is preferable to use the compounds in molar quantities. The organoaluminum oxy compound (A-2) is preferably used in an amount of 10 to 500 moles, and more preferably 20 to 200 moles, per mole of transition metal atoms in the transition metal compound (A-1), in terms of aluminum atoms.

[0113] Examples The present invention will be further described by the following examples. However, the present invention is not limited to the following examples. The component (B) used in the examples and comparative examples is as follows: Ingredients (B-1): Lauryl diethanolamine [Electro Stripper (registered trademark) EA (manufactured by Kao Corporation)] Ingredient (B-2): Stearyldiethanolamine [CAS number 10213-78-2, manufactured by Tokyo Chemical Industry Co., Ltd.] The polyoxyethylene polyoxypropylene glycol [component (C)] used in the examples and comparative examples is as follows: Ingredients (C-1): ADEKA Pluronic® L-71 (manufactured by ADEKA Corporation)

[0114] [Preparation Example 1] (Preparation of Solid Catalyst Component (X-1)) Using a 270 L reactor with a stirrer, 10 kg of silica gel (manufactured by Fuji Silysia Chemical Co., Ltd., average particle size 70 μm, specific surface area 340 m² / g, pore volume 1.3 cm³ / g, dried at 250 °C for 10 hours) was suspended in 77 L of toluene under a nitrogen atmosphere, and then cooled to 0-5 °C. While maintaining the system temperature at 0-5 °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. After contacting each additive component for 30 minutes, the system temperature was raised to 95 °C over 1.5 hours, and then contact was maintained at 93-97 °C for 4 hours. After that, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the mixture was washed twice with toluene to obtain a toluene slurry of a solid support carrying methylaluminoxane in total volume 115 L. When a portion of this slurry was taken and analyzed, the solid content concentration was found to be 123 g / L.

[0115] Of the obtained slurry, 12.2 L (1.50 kg as solid content) was charged into a 114 L stirrer under a nitrogen atmosphere, and toluene was added until the total volume was 28 L. Next, a solution of 23.5 g (54.2 mmol in terms of Zr atoms) of bis(1,3-n-butylmethylcyclopentadienyl)zirconium dichloride dissolved in 5.0 L of toluene was pumped into the reactor and contacted for 1 hour at a system temperature of 20-25°C. The supernatant was removed by decantation and washed three times with hexane. Then, hexane was added to bring the total volume to 30 L to obtain a hexane slurry of the solid catalyst component (X-1).

[0116] [Preparation Example 2] (Preparation of prepolymerization solid catalyst component (XP-1)) 30 L of 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. While maintaining the system temperature at 10-15°C, ethylene was continuously supplied to the system under atmospheric pressure for several minutes, and then 70 ml of 1-hexene was added. Subsequently, ethylene supply was started at 1.46 kg / h, and prepolymerization was carried out at a system temperature of 32-37°C. 70 ml of 1-hexene was added a total of 5 times at 30-minute intervals from the start of prepolymerization, and when the ethylene supply reached 4.37 kg after 180 minutes from the start of prepolymerization, the ethylene supply was stopped. The supernatant was then removed by decantation and washed four times with hexane. Then, hexane was added to bring the total volume to 30 L, obtaining a hexane slurry of the prepolymerized solid catalyst component (XP-1).

[0117] Next, the hexane slurry was placed in a 43 L evaporative dryer with a stirrer under a nitrogen atmosphere, and the pressure was reduced to -68 kPaG over approximately 60 minutes. Once -68 kPaG was reached, it was vacuum-dried for approximately 4.3 hours to remove volatile components from the hexane and prepolymerization catalyst. The pressure was further reduced to -100 kPaG, and once -100 kPaG was reached, it was vacuum-dried for 8 hours to obtain 6.20 kg of prepolymerization solid catalyst component (XP-1).

[0118] [Example 1] (Polymerization evaluation (i): Evaluation of the autoclave wall condition during polymerization) 500 ml of n-heptane was charged into a 1 L stainless steel autoclave that had been thoroughly purged with nitrogen, and the system was purged with ethylene. 10 ml of 1-hexene and 250 mg of the prepolymerization solid catalyst component (XP-1) obtained in Preparation Example 2 were added, and the temperature was raised to 55°C. It took approximately 10 minutes from the addition of the prepolymerization solid catalyst component (XP-1) to the temperature reaching 55°C. Subsequently, a mixture of 4.50 mg of component (B-1) and 0.50 mg of component (B-2) [component (B-1):component (B-2) = 90:10 (mass ratio)] was added, diluted in 5 ml of toluene. Next, 200 mg of the prepolymerization solid catalyst component (XP-1) was added, and the temperature in the system was raised to 73°C. Polymerization was then started by introducing ethylene, and polymerization was carried out for 90 minutes while continuously supplying ethylene and maintaining a pressure of 8.0 kg / cm2-G. After polymerization was complete, the pressure was released and the polymer was removed. Upon checking the condition of the autoclave, no polymer was found to be adhering to the autoclave walls or stirring blades.

[0119] (Polymerization evaluation (ii): Polymerization activity evaluation) 500 ml of n-heptane was placed in a 1 L stainless steel autoclave that had been thoroughly purged with nitrogen, and the system was purged with ethylene. 20 ml of 1-hexene and 0.06 ml of decane solution of triisobutylaluminum (1.0 mol / L) were added, and the system was held at room temperature for 5 minutes. Then, a mixture of 4.50 mg of component (B-1) and 0.50 mg of component (B-2) [component (B-1):component (B-2) = 90:10 (mass ratio)] was added, diluted in 5 ml of toluene. Subsequently, 180 mg of prepolymerization solid catalyst component (XP-1) was added, and the temperature in the system was raised to 73°C. Polymerization was then started by introducing ethylene, and polymerization was carried out for 90 minutes while continuously supplying ethylene and maintaining a pressure of 8.0 kg / cm2-G. After polymerization was complete, the pressure was removed, the polymer was filtered and washed, and dried under reduced pressure at 80°C for 10 hours to obtain 83.3 g of polymer. The total amount of components (B-1) and (C-1) relative to polymer yield (g) was 60 ppm (by mass), and the polymer yield (polymerization activity) per 1 g of catalyst was 463 (g-PE / g-cat).

[0120] [Examples 2-6 and Comparative Example 1] As shown in Table 1, polymerization evaluation (i) and polymerization evaluation (ii) were performed in the same manner as in Example 1, except that the types and amounts of components (B-1), (B-2), and (C-1) were changed. The results are shown in Table 1.

[0121] [Table 1]

[0122] As is clear from Table 1, in Examples 1-3, which used components (B-1) and (B-2), and in Examples 4-6, which used components (B-1), (B-2), and (C-1), the adhesion of polymers to the autoclave walls and stirring blades was suppressed. In Comparative Example 1, which did not use any of components (B-1), (B-2), or (C-1), polymer adhesion to the autoclave walls and stirring blades was observed. Furthermore, Examples 1-6 showed higher polymerization activity than Comparative Example 1. In other words, in Examples 1-6, olefin polymers could be produced with higher polymerization activity and more stably compared to Comparative Example 1.

[0123] [Preparation Example 3] (Preparation of Prepolymerization Solid Catalyst Component (XP-2)) In a 3000 ml stirrer-equipped reactor, 400.0 g of the prepolymerization solid catalyst component (XP-1) obtained in Preparation Example 2 was charged under a nitrogen atmosphere, and hexane was added until the total volume reached 1600 ml. Next, the temperature in the system was raised to 35°C, and then 4.0 g of lauryldiethanolamine (B-1) as component (B), diluted in 50 ml of toluene, was added. The mixture was then contacted at 32-37°C for 2 hours to obtain a hexane slurry of the prepolymerization solid catalyst component (XP-2). This hexane slurry was transferred to a 2000 ml glass Schlenk tube, and the hexane was removed by distillation under reduced pressure at 25°C to obtain 404.0 g of the prepolymerization solid catalyst component (XP-2).

[0124] [Example 7] (Polymerization evaluation (iii): Evaluation of operability by gas-phase polymerization) Copolymerization of ethylene and 1-hexene was carried out using a fluidized bed polymerizer. The polymerization pressure was set to 1.7 MPaG and the polymerization temperature to 80°C. The prepolymerization solid catalyst component (XP-2) prepared in Preparation Example 3 was supplied to the polymerization reactor at a rate of 3.0 g / hr. Components (B-1) and (B-2) were mixed in a mass ratio of 50:50 and supplied to the circulating gas line so that the total amount of components (B-1) and (B-2) relative to the mass of the polymer was 4 ppm (by mass). The gas composition in the vapor-phase polymerizer was maintained by continuously supplying ethylene, hydrogen, 1-hexene, and isopentane so that the ethylene partial pressure was 1.0 MPa, the hydrogen / ethylene ratio was 6.0 × 10⁻⁴ molars, and the 1-hexene / ethylene ratio was 0.025 molars, producing polymer at a rate of 6.0 kg / hr. The residence time was 4 hours. The polymer density at this time was 913 kg / m³, and the melt flow rate was 3.6 g / 10 min. The melt flow rate was measured at 190°C and under a 2.16 kg load, according to ASTM D1238-65T. Under the above conditions, the system was operated for 12 hours, and no heat spots were observed in any part, including the polymerizer and piping, indicating stable polymerization. The polymer yield (polymerization activity) per gram of catalyst was 2000 (g-PE / g-cat).

[0125] [Example 8] (Polymerization evaluation (iii): Evaluation of operability by gas-phase polymerization) Copolymerization of ethylene and 1-hexene was carried out using a fluidized bed polymerizer. The polymerization pressure was set to 1.7 MPaG and the polymerization temperature to 80°C. The prepolymerization solid catalyst component (XP-2) prepared in Preparation Example 3 was supplied to the polymerization reactor at a rate of 3.0 g / hr. Components (B-1) and (B-2) were mixed in a mass ratio of 70:30 and supplied to the circulating gas line so that the total amount of components (B-1) and (B-2) relative to the mass of the polymer was 5 ppm (by mass). The gas composition in the vapor-phase polymerizer was maintained by continuously supplying ethylene, hydrogen, 1-hexene, and isopentane so that the ethylene partial pressure was 1.0 MPa, the hydrogen / ethylene ratio was 5.6 × 10⁻⁴ molars, and the 1-hexene / ethylene ratio was 0.026 molars, producing polymer at a rate of 5.5 kg / hr. The residence time was 4.4 hours. The polymer density at this time was 915 kg / m³, and the melt flow rate was 3.5 g / 10 min. The melt flow rate was measured at 190°C and under a 2.16 kg load, according to ASTM D1238-65T.

[0126] Under the above conditions, the system was operated for 20 hours, and no heat spots were observed in any part, including the polymerizer and piping, indicating stable polymerization. The polymer yield (polymerization activity) per gram of catalyst was 1833 (g-PE / g-cat).

[0127] [Table 2] [Industrial applicability]

[0128] According to the present invention, it is possible to provide a method for producing olefin polymers that prevents contamination of the polymerizer walls, stirring blades, and other internal components of the polymerizer, and that can achieve further improvements in the operational stability and polymerization activity of the manufacturing equipment. The present invention will therefore greatly contribute to improving the productivity of catalyst-based olefin polymers.

Claims

1. A method for producing an olefin polymer, characterized by polymerizing ethylene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms in a polymerizer in the presence of the following component (A) and two or more components (B). Component (A): Solid catalyst component for olefin polymerization, Component (B): Polyoxyethylene alkylamine compound represented by the following general formula (I) 【Chemistry 1】 [In general formula (I), R is a hydrocarbon group having 1 to 30 carbon atoms, and m and n are each independent integers of 1 or more.]

2. A method for producing an olefin polymer according to claim 1, characterized by polymerizing an olefin in the presence of component (A), two or more components (B), and the following component (C). Component (C): A compound containing poly(oxyalkylene) units.

3. A method for producing an olefin polymer according to claim 2, characterized in that component (C) is selected from the following. (C-a) Polyoxyalkylene block compound, (C-b) polyoxyalkylene alkyl ether compounds, and (C-c) Polyoxyalkylene alkyl ester compound

4. The method for producing an olefin polymer according to claim 2, characterized in that component (C) is a compound having a poly(oxyethylene) block and a poly(oxypropylene) block.

5. Supply of component (A) to the polymerizer, and Supply of two or more components (B) to the polymerizer, A method for producing an olefin polymer according to claim 1, characterized in that each of these steps is performed separately.

6. Supply of component (A) to the polymerizer, and Supply of two or more components (B) and (C) to the polymerizer, A method for producing an olefin polymer according to claim 2, characterized in that each of these steps is performed separately.

7. A method for producing an olefin-based polymer according to any one of claims 1 to 6, characterized in that the polymerization of the olefin is carried out in a suspension or in the gas phase.

8. Component (A) is (A-1) A transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, (A-2) (A-2a) organometallic compound, (A-2b) Organoaluminum oxy compounds, and (A-2c) A compound that reacts with component (A-1) to form an ion pair. at least one compound selected from the group consisting of and, (A-3) A particulate carrier and A method for producing an olefin polymer according to any one of claims 1 to 6, characterized by including the following:

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