Solid catalyst for olefin polymerization and method for producing olefin polymer using the same

Abstract

To provide a solid catalyst for olefin polymerization that prevents the inside of a polymerizer from getting dirty, such as a polymerizer wall and an agitation blade, and achieves the stable operation of production equipment, and a method for producing an olefin polymer using the same.SOLUTION: The (co) polymerization of olefins is performed in the presence of a solid catalyst for olefin polymerization including (A) a solid catalyst component for olefin polymerization and (B) a carboxylic acid compound represented by general formula (I). [In the general formula (I), R is a hydrocarbon group having one or more and 30 or less carbon atoms].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a solid catalyst for olefin polymerization which can prevent fouling of the inside of a polymerization vessel, such as the walls of the polymerization vessel or the stirring blades, and thereby achieve stable operation of the production apparatus, and to a method for producing an olefin copolymer using the same. [Background technology]

[0002] Olefin polymers are important industrial products that are widely used in a wide variety of applications, and there is a demand for improving the productivity thereof. Various catalysts have been studied for use in producing olefin polymers. Patent Document 1 discloses an olefin prepolymerization catalyst formed by prepolymerizing an olefin using a catalyst comprising a solid catalyst component having a transition metal compound of Group IVB of the periodic table supported on a carrier and an aluminoxane, as a catalyst for producing an ethylene polymer or an ethylene-α-olefin copolymer having excellent powder properties and narrow molecular weight distribution and / or composition distribution with excellent polymerization activity. Patent Document 1 discloses that carboxylic acids may be added to the catalyst as electron donors. On the other hand, in chemical plants such as petroleum distillation and refining plants and polyolefin manufacturing plants, problems such as a drop in the heat exchange capacity of the plant and blockage of piping can occur due to fouling, which can result in unstable production operations and, in the worst case, operation shutdown. Specific problems include, for example, the generation of polymer lumps or sheet-like matter in a polymerization vessel, and the adhesion of polymer to the stirring blades and walls of the polymerization vessel.

[0003] As a method for solving these problems, Patent Document 2 discloses a method of adding an alkyldiethanolamine compound to a polymerization vessel in which olefin polymerization is performed by a gas phase method using a solid catalyst. Furthermore, Patent Document 3 discloses a method for producing a prepolymerized solid catalyst for olefin polymerization, which comprises contacting an antistatic agent with a first prepolymerized catalyst obtained by prepolymerizing an olefin in the presence of a solid catalyst, and then prepolymerizing an olefin again in the presence of the first prepolymerized catalyst containing an antistatic agent to obtain a second prepolymerized catalyst. Patent Document 3 discloses that (C-1) polyalkylene oxide block, (C-2) higher aliphatic amide, (C-3) polyalkylene oxide, (C-4) polyalkylene oxide alkyl ether, and (C-5) alkyldiethanolamine can be used as the antistatic agent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 63-152608 [Patent Document 2] JP 2000-313718 A [Patent Document 3] JP 2001-048912 A Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a solid catalyst for olefin polymerization which can prevent fouling of the inside of a polymerization vessel, such as the walls of the polymerization vessel or the stirring blades, and thereby achieve stable operation of the production apparatus, and a process for producing an olefin polymer using the same. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors have found that, in order to further improve the productivity of olefin polymers, it is possible to achieve stable operation of a production apparatus by allowing a carboxylic acid compound to coexist when polymerizing an olefin in the presence of a solid catalyst, thereby preventing fouling of the inside of a polymerization vessel, such as the walls of the polymerization vessel or the stirring blades. Patent Document 1 discloses that a carboxylic acid may be added as an electron donor to a catalyst consisting of a solid catalyst supporting a transition metal compound and an aluminoxane. However, Patent Document 1 does not describe or suggest at all that the carboxylic acid has a function of preventing fouling inside a polymerization vessel. In addition, although Patent Documents 2 and 3 disclose that antistatic agents such as alkyldiethanolamines have a function of preventing contamination inside a polymerization vessel, there is no description or suggestion whatsoever that a carboxylic acid compound has a function of preventing contamination inside a polymerization vessel. The present invention has been made based on the new findings of the present inventors. The gist of the present invention is as follows.

[0007] [1] A solid catalyst for olefin polymerization, comprising: (A) a solid catalyst component for olefin polymerization; and (B) a carboxylic acid compound represented by the following general formula (I):

[0008] [ka]

[0009] [In the above general formula (I), R is a hydrocarbon group having 1 to 30 carbon atoms.]

[0010] [2] The solid catalyst for olefin polymerization according to [1], which comprises component (A) and component (B). [3] Component (A) is (A-1) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton; (A-2) at least one compound selected from the group consisting of (a) organometallic compounds, (b) organoaluminum oxy-compounds, and (c) compounds that react with component (A-1) to form an ion pair; (A-3) a fine particle carrier; The solid catalyst for olefin polymerization according to [1], [4] A method for producing an olefin polymer, comprising (co)polymerizing ethylene and one or more olefins selected from the group consisting of α-olefins having 3 to 20 carbon atoms in the presence of the solid catalyst for olefin polymerization according to any one of [1] to [3]. [5] The method for producing an olefin polymer according to [4], wherein the (co)polymerization of olefins is carried out in a suspension or in a gas phase. Effect of the Invention

[0011] According to the process for producing an olefin polymer of the present invention, it is possible to prevent the interior of the polymerization vessel, such as the walls of the polymerization vessel and the stirring blades, from becoming dirty, thereby achieving stable operation of the production apparatus. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] [Solid catalyst component for olefin polymerization (A)] The solid catalyst component (A) for olefin polymerization [component (A)] is preferably, for example, a solid catalyst component containing a compound of a transition metal selected from Groups 3 to 12 of the periodic table. Specific examples thereof include a support-supported transition metal complex catalyst component in which a transition metal compound of Groups 4 to 6 of the periodic table is supported on a particulate support, a solid titanium 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.

[0013] The transition metal compound of Groups 4 to 6 of the periodic table used in the carrier-supported transition metal complex catalyst component may be any known transition metal compound of Groups 4 to 6 of the periodic table having olefin polymerization ability. For example, transition metal halides, transition metal alkylates, transition metal alkoxylates, and non-bridged or bridged metallocene compounds of Groups 4 to 6 of the periodic table can be used as such transition metal compounds. In particular, transition metal compounds of Group 4 of the periodic table are preferred. Among these, a carrier-supported metallocene catalyst component belonging to the carrier-supported transition metal complex catalyst components is preferred, and a carrier-supported metallocene catalyst component containing the following components (A-1) to (A-3) is more preferred. (A-1) a transition metal compound 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) to (c): (a) organometallic compound, (b) organoaluminum oxy-compounds, and (c) a compound that reacts with component (A-1) to form an ion pair; (A-3) Microparticle carrier.

[0014] Specific examples of the transition metal compound of Group 4 of the periodic table include titanium tetrachloride, dimethyltitanium dichloride, tetrabenzyltitanium, tetrabenzylzirconium, and tetrabutoxytitanium. Furthermore, from the viewpoint of polymerization activity (yield of olefin polymer per 1 g of catalyst) in the polymerization reaction of the catalyst, non-bridged or bridged metallocene compounds are particularly preferred. The metallocene compound is a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, and is represented, for example, by the following general formula (II).

[0015] 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) 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 is a hydrocarbon group having 1 to 12 carbon atoms, 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. d is the valence of the transition metal and indicates the number of L.]

[0016] Specific examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, an alkyl-substituted cyclopentadienyl group such as a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, an ethylcyclopentadienyl group, a methylethylcyclopentadienyl group, a propylcyclopentadienyl group, a methylpropylcyclopentadienyl group, a butylcyclopentadienyl group, a methylbutylcyclopentadienyl group, or a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, or a fluorenyl group. These groups may have a substituent such as a halogen atom or a trialkylsilyl group.

[0017] As the ligand having a cyclopentadienyl skeleton, an alkyl-substituted cyclopentadienyl group is particularly preferred. When the compound represented by the general formula (II) contains two or more groups having a cyclopentadienyl skeleton, the two groups having a cyclopentadienyl skeleton may be bonded via an alkylene group such as ethylene or propylene; an alkylidene group such as isopropylidene or diphenylmethylene; a silylene group; or a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group. In addition, it is preferable that the groups having two or more cyclopentadienyl skeletons are the same.

[0018] Specific examples of the hydrocarbon group having 1 to 12 carbon atoms other than the ligand having a cyclopentadienyl skeleton include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and pentyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and neophyl. Specific examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, and butoxy. Specific examples of the aryloxy group include phenoxy. Specific examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Specific examples of -SO3R' include p-toluenesulfonato, methanesulfonato, and trifluoromethanesulfonato. When there are a plurality of ligands other than the ligand having a cyclopentadienyl skeleton, these ligands may be the same or different, and one or more combinations of different ligands may be present.

[0019] The compound represented by general formula (II), for example when the transition metal has a valence of 4, 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. 1 R is a group having a cyclopentadienyl skeleton. 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.

[0020] In particular, the component (A-1) is a compound represented by the general formula (II′): 2 , R 3 and R 4A transition metal compound in which one of R is a group having a cyclopentadienyl skeleton is preferred. For example, R 1 and R 2 When R is a group having a cyclopentadienyl skeleton, the group having a cyclopentadienyl skeleton may be bonded via an alkylene group, a substituted alkylene group, an alkylidene group, a silylene group, a substituted silylene group, or the like. 3 and R 4 is 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', or a hydrogen atom. Specific examples of these groups include the same groups as those listed above for formula (II).

[0021] Specific examples of transition metal compounds in which M is zirconium are given below: bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromide, bis(indenyl)zirconium bis(p-toluenesulfonato), bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride, ethylene bis(indenyl)zirconium dichloride, ethylene bis(indenyl)zirconium dibromide, ethylene bis(indenyl)dimethylzirconium, ethylene bis(indenyl)diphenylzirconium, ethylene bis(indenyl)diphenylzirconium, and ethylene bis(indenyl)zirconium dichloride. 1,3-Dimethylcyclopentadiene (cyclopentadienyl)zirconium monochloride, 1,3-diethyl-2,4-dimethylphenyl ether (cyclopentadienyl)zirconium bis(methanesulfonate), 1,3-diethyl-2,4-dimethylphenyl ether (cyclopentadienyl)zirconium bis(p-toluenesulfonate), 1,3-diethyl-2,4-dimethylphenyl ether (cyclopentadienyl)zirconium bis(trifluoromethane ... Dimethylsilylene bis(cyclopentadienyl)zirconium dichloride, dimethylsilylene bis(methylcyclopentadienyl)zirconium dichloride, dimethylsilylene bis(dimethylcyclopentadienyl)zirconium dichloride, dimethylsilylene bis(trimethylcyclopentadienyl)zirconium dichloride, dimethylsilylene bis(indenyl)zirconium dichloride, dimethylsilylene bis(indenyl)zirconium bis(trifluoromethanesulfonate), rac-dimethylsilylene bis {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)methylzirconium monochloride, bis(cyclopentadienyl)ethylzirconium dichloride zirconium monochloride, bis(cyclopentadienyl)cyclohexylzirconium monochloride, bis(cyclopentadienyl)phenylzirconium monochloride, bis(cyclopentadienyl)benzylzirconium monochloride, bis(cyclopentadienyl)zirconium monochloride 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(methanesulfonate), bis(cyclopentadienyl)zirconium bis(p-toluenesulfonate), bis(cyclopentadienyl)zirconium bis(trifluoromethanesulfonate), bis(methylcyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadienyl)zirconium dichloride, bis(dimethylcyclopentadiene)zirconium dichloride, 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.

[0022] In the above examples, di-substitutions of the cyclopentadienyl ring include 1,2- and 1,3-substitutions, tri-substitutions include 1,2,3- and 1,2,4-substitutions, and alkyl groups such as propyl and butyl include isomers such as n-, i-, sec-, and tert-.

[0023] In addition, in the above zirconium compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.In addition to titanium compounds and hafnium compounds having similar steric structures, as well as bromides and iodides, transition metal compounds such as those described in JP-A-3-9913, JP-A-2-131488, JP-A-3-21607, JP-A-3-106907, JP-A-3-188092, JP-A-4-69394, JP-A-4-300887, and International Publication No. 2001 / 27124 can be mentioned.

[0024] Further, examples of the transition metal compound include transition metal compounds represented by the following general formula (III) as described in JP-A-11-315109.

[0025] [ka]

[0026] [In general formula (III), M 1 represents a transition metal atom in Groups 4 to 6 of the periodic table. f represents an integer of 1 to 6. R 11 ~R 16R each 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 the groups may be linked together to form a ring. When f is 2 or more, R 11 ~R 16 Between multiple units having the same structure, these groups are each independently defined as above. 11 ~R 16 Two of the groups may be linked together (provided that multiple R 11 (e is M 1 X represents 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, a silicon-containing group, a germanium-containing group, or a tin-containing group. When e is 2 or more, the multiple groups represented by X are each independently defined as above. The multiple groups represented by X may be the same or different, or the multiple groups represented by X may contain one or more combinations of different groups. In addition, the multiple groups represented by X may be bonded to each other to form a ring.] Specific examples of the substituent as X include the groups disclosed in JP-A-11-315109.

[0027] Component (A-2) constituting the carrier-supported transition metal complex catalyst component is at least one compound selected from the group consisting of organometallic compounds (a), organoaluminum oxy compounds (b), and compounds (c) that react with component (A-1) to form an ion pair.

[0028] As the organometallic compound (a), for example, organometallic compounds belonging to Groups 1 and 2, and Groups 12 and 13 of the periodic table, represented by the following general formulas (IV), (V) and (VI), can be used.

[0029] R 5g Al(OR 6 ) h H i X 1 j ···(IV) [In general formula (V), 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. As this hydrocarbon group, an alkyl group is preferred. Specific examples of the compound represented by general formula (V) include trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride.

[0030] 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. 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 and LiAl(C7H 15 )4.

[0031] 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. M 3 is Mg, Zn, or Cd.] An organometallic compound of a metal of Group 2 or 12 of the periodic table, represented by the following formula: The hydrocarbon group is preferably an alkyl group.

[0032] Among the above organometallic compounds, organoaluminum compounds are preferred. The organometallic compounds may be used alone or in combination of two or more.

[0033] As the organoaluminum oxy compound (b), a known aluminoxane can be used. Specifically, for example, at least one of the compounds represented by the following general formulas (VII) and (VIII) can be used.

[0034] [ka]

[0035] [ka]

[0036] [In general formulas (VII) and (VIII), R 21 ~R 24 each independently represents a hydrocarbon group having 1 to 10 carbon atoms, and k and p each independently represent an integer of 2 or greater.

[0037] As the organoaluminum oxy compound (b), there may be mentioned a compound represented by the general formulas (VII) and (VIII), in which R 21 ~R 24Methylaluminoxanes in which k is a methyl group and k and p are 3 or more, preferably 10 or more, are preferably used. A small amount of an organoaluminum compound may be mixed into these aluminoxanes. The organoaluminum oxy compound (b) may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. The organoaluminum oxy compounds described in JP-A-2-167305 and the aluminoxanes having two or more alkyl groups as described in JP-A-2-24701 and JP-A-3-103407 are also preferably used.

[0038] Such aluminoxanes can be produced, for example, by the following methods (1) to (3), and are usually obtained as a solution in a hydrocarbon solvent.

[0039] (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the organoaluminum compound with the adsorbed water or water of crystallization. (2) A method in which water, ice or water vapor is directly reacted with an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0040] The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the aluminoxane may be redissolved in a solvent.

[0041] Specific examples of the organoaluminum compound used in preparing the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; tricycloalkylaluminums 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 aryloxides such as diethylaluminum phenoxide. Among these, trialkylaluminums and tricycloalkylaluminums are preferred.

[0042] Furthermore, isoprenylaluminum represented by the following general formula (IX) can also be used as an organoaluminum compound for preparing aluminoxane.

[0043] (i-C4H9) r Al s (C5H 10 ) t (IX) [In the general formula (X), r, s, and t are positive numbers, and t≧2r.]

[0044] The organoaluminum compounds for preparing the aluminoxane may be used alone or in combination of two or more.

[0045] Specific examples of the solvent used in preparing the aluminoxane 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, and halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, particularly chlorinated and brominated hydrocarbons. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these, aromatic hydrocarbons are preferred.

[0046] Examples of the compound (c) that reacts 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, described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, U.S. Patent No. 5,321,106, and the like. The fact that the ionizing ionic compound (c) acts as an activator for metallocene catalysts is disclosed, for example, in Japanese Patent No. 5295501. The ionizing ionic compound (c) may be used alone or in combination of two or more kinds.

[0047] The organometallic compound (a), the organoaluminum oxy-compound (b), and the ionizing ionic compound (c) that can be used as component (A-2) have been described above. However, it is preferable to use, as component (A-2), the organoaluminum oxy-compound (b) alone or a combination of the organoaluminum compound (a) and the organoaluminum oxy-compound (b).

[0048] The particulate carrier (A-3) may be an inorganic carrier made of an inorganic material or an organic carrier made of an organic material. Examples of the inorganic carrier 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 that are components of clay, ion-exchangeable layered compounds, and the like may also be used as the 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 copolymers.

[0049] The inorganic carrier has an average particle size of preferably 1 to 300 μm, more preferably 3 to 200 μm. If necessary, such a carrier is fired at 100 to 1000° C., preferably 150 to 700° C. before use.

[0050] The inorganic chloride may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill.In addition, the inorganic chloride may be dissolved in a solvent such as alcohol and then precipitated into fine particles by a precipitating agent.

[0051] A carrier using clay is usually composed of a clay mineral as a main component. A carrier using an ion-exchangeable layered compound has a crystal structure in which the planes formed by ionic bonds or the like are stacked in parallel with each other with weak bonding force, and the ions contained therein are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and artificial synthetic products can also be used. Examples of clays, clay minerals, and ion-exchangeable layered compounds include clays, clay minerals, and ionic crystalline compounds having layered crystal 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, gairome clay, allophane, hisinger stone, pyrophyllite, unmo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchangeable layered compounds include crystalline acid 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 subject clay and clay minerals to chemical treatment. As chemical treatment, any of surface treatments that remove impurities attached to the surface and treatments that affect the crystal structure of clay can be used. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

[0052] The ion-exchangeable layered compound may be a layered compound in which the space between layers is expanded by utilizing the ion exchangeability and exchanging the exchangeable ions between layers with other large bulky ions. Such bulky ions play a role of supporting the layered structure and are usually called pillars. The introduction of another substance between layers of a layered compound in this way is called intercalation. Examples of guest compounds for intercalation include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR″4, Zr(OR″4, PO(OR″3, B(OR″3) (each R″ independently represents a hydrocarbon group, etc.), [Al 13 O4(OH) 24 ] 7+ , [Zr4(OH) 14 ] 2+ , [Fe3O(OCOCH3)6] + Metal hydroxide ions such as these can be used alone or in combination of two or more of these compounds. When these compounds are intercalated, polymers obtained by hydrolysis of metal alkoxides such as Si(OR″4), Al(OR″3, Ge(OR″4) (R″ each independently represents a hydrocarbon group, etc.), and colloidal inorganic compounds such as SiO2 can also be used. Examples of pillars include oxides produced by intercalating the above-mentioned metal hydroxide ions between layers and then dehydrating them with heat. Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, taeniolite, and synthetic mica.

[0053] The organic carrier may be a granular or particulate solid having a particle size in the range of 1 to 300 μm. Specific examples of the polymer forming the organic carrier include, as exemplified above, (co)polymers produced mainly from α-olefins having 3 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane and styrene, and modified products thereof.

[0054] Also, a solid component obtained by insolubilizing the above-described component (A-2) by the method described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, WO 2010 / 55652, etc. can be used as the fine particle support (A-3). In this case, contact with the component (A-2) in the preparation method of the support-supported metallocene catalyst component described below is not essential.

[0055] A method for preparing a carrier-supported metallocene catalyst component preferably used as the solid catalyst component (A) for olefin polymerization is described below. This carrier-supported metallocene catalyst can be prepared by mixing and contacting components (A-1) to (A-3). The components may be contacted in any order. Each of the components (A-1) to (A-3), or at least one of the components (a) to (c) as component (A-2), may be used in multiple separate contacts.

[0056] In the preparation of the carrier-supported metallocene catalyst component, it is preferable to use an inert hydrocarbon solvent, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, etc., alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, etc., or mixtures thereof.

[0057] When preparing the carrier-supported metallocene catalyst component, the transition metal compound (A-1) is used in an amount of usually 0.001 to 1.0 millimoles, preferably 0.005 to 0.5 millimoles, per gram of the particulate carrier (A-3) calculated as transition metal atoms. The organoaluminum oxy compound (b) is used in an amount of usually 0.1 to 100 millimoles, preferably 0.5 to 20 millimoles, calculated as aluminum atoms. When an organoaluminum compound is used, the organoaluminum compound is used in an amount of usually 0.001 to 1000 millimoles, preferably 2 to 500 millimoles, per gram of the particulate carrier (A-3).

[0058] The temperature when the above components are mixed and contacted is usually −50 to 150° C., preferably −20 to 120° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes.

[0059] The thus obtained carrier-supported metallocene catalyst component contains the transition metal compound (A-1) in an amount of preferably about 5×10 in terms of transition metal atom per gram of the fine particle carrier (A-3). -6 ~10 -3 moles, more preferably 10 -5 ~3×10 -4 The amount of the organoaluminum oxy-compound (b) is preferably about 10 moles in terms of aluminum atom per gram of the fine particle carrier (A-3). -3 ~10 -1 moles, more preferably 2×10 -3 ~5×10 -2 It is supported in molar amounts.

[0060] The solid catalyst component (A) for olefin polymerization may be a prepolymerized catalyst component in which a monomer for preparing an olefin polymer is prepolymerized. One form of the prepolymerized catalyst component contains the solid catalyst component for olefin polymerization and, if necessary, an olefin polymer produced by prepolymerization. A preferred form of the prepolymerized catalyst contains a transition metal compound (A-1), a component (A-2), a fine particle support (A-3), and, if necessary, an olefin polymer (D) produced by prepolymerization. As a method for preparing the prepolymerization catalyst, for example, in the presence of a solid catalyst component obtained by mixing and contacting components (A-1) to (A-3) in an inert hydrocarbon solvent or in a medium containing a monomer for preparing an olefin polymer, a small amount of a monomer for forming an olefin polymer is prepolymerized. As mentioned above, the order of contacting components (A-1) to (A-3) is not particularly limited. In addition, at least one of these components may be contacted in multiple batches. Specific examples of the inert hydrocarbon solvent used in the preparation of the prepolymerized catalyst include the same inert hydrocarbon solvents as those used in the preparation of the carrier-supported metallocene catalyst described above.

[0061] The monomer for preparing an olefin polymer used in the prepolymerization can be at least one of ethylene, propylene, and an olefin having a carbon number of 4 to 20. The olefin for the prepolymerization preferably has the following composition (A). Composition (A): Ethylene: 100 to 0 mol%, Propylene: 0 to 49 mol %, and α-Olefins having 4 or more carbon atoms: 0 to 100 mol %. Furthermore, the following composition (B) can be mentioned as a more preferable composition, the following composition (C) as an even more preferable composition, and the following composition (D) as an especially preferable composition. ·Composition (B): Ethylene: 100 to 0 mol%, Propylene: 0 to 20 mol %, and α-Olefins having 4 or more carbon atoms: 0 to 100 mol %. ·Composition (C): Ethylene: 100 to 20 mol%, Propylene: 0 to 20 mol %, and α-olefins having 4 or more carbon atoms: 0 to 80 mol %. ·Composition (D): Ethylene: 100 to 20 mol %, and α-olefins having 4 or more carbon atoms: 0 to 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 is 100%).

[0062] Specific examples of α-olefins having 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, 1-eicosene, etc. Furthermore, as monomers to be 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, etc. can also be used.

[0063] In preparing the prepolymerization catalyst, the transition metal compound (A-1) is used in an amount of usually 0.001 to 1.0 mmol, preferably 0.005 to 0.5 mmol, per gram of the particulate carrier (A-3) calculated as transition metal atoms. The organoaluminum oxy compound (b) is used in an amount of usually 0.1 to 100 mmol, preferably 0.5 to 20 mmol, per gram of the particulate carrier (A-3) calculated as aluminum atoms.

[0064] The prepolymerized catalyst obtained as described above contains the transition metal compound (A-1) in an amount of preferably about 5×10 in terms of transition metal atom per gram of the fine particle support (A-3). -6 ~10 -3 moles, more preferably 10 -5 ~3×10 -4 The organoaluminum oxy compound (b) is supported in an amount of preferably about 10 moles in terms of aluminum atom per gram of the fine particle support (A-3). -3 ~10 -1 moles, more preferably 2×10 -3 ~5×10 -2 The olefin polymer (D) produced by prepolymerization is desirably supported on the fine particle support (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.

[0065] In addition, the solid catalyst component (A) for olefin polymerization may contain other components useful for polymerization in addition to the above-described components. In addition, the carrier-supported metallocene catalyst component may optionally contain additives such as surfactants during catalyst synthesis or prepolymerization, as necessary.

[0066] [Carboxylic acid compound (B)] The carboxylic acid compound [component (B)] is a compound represented by the following general formula (I).

[0067] [ka]

[0068] In the general formula (I), R is a hydrocarbon group having 1 to 30 carbon atoms. The number of carbon atoms in this hydrocarbon group is preferably 7 to 21 carbon atoms, more preferably 9 to 19 carbon atoms, and particularly preferably 11 to 17 carbon atoms. The hydrocarbon represented by R may be linear or branched, and may be saturated or unsaturated. Examples of saturated hydrocarbons include alkyl groups. Examples of unsaturated hydrocarbons include hydrocarbon groups having a double bond, such as an alkenyl group having one double bond. Specific examples of the carboxylic acid compound (B) represented by the general formula (I) include caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid. Among these, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid are more preferred. As the carboxylic acid compound (B), at least one selected from the group consisting of compounds represented by general formula (I) can be used. The present inventors speculate that the reason why the addition of the carboxylic acid compound (B) to the solid catalyst for olefin polymerization acts as a polymerization stabilizer that prevents fouling of the inside of the polymerization vessel, such as the walls of the polymerization vessel and the stirring blades, thereby enabling stable operation of the production equipment, is that the adhesion of the carboxylic acid to the surfaces of the solid catalyst for olefin polymerization to the walls of the polymerization vessel and the stirring blades is suppressed.

[0069] [Solid catalysts for olefin polymerization] The solid catalyst for olefin polymerization contains a solid catalyst component for olefin polymerization (A) and a carboxylic acid compound (B) represented by general formula (I) as a stabilizer for stabilizing the operation of a production apparatus, and preferably comprises the solid catalyst component for olefin polymerization (A) and the carboxylic acid compound (B) represented by general formula (I). The solid catalyst for olefin polymerization can be prepared by contacting a solid catalyst component for olefin polymerization (A) with a carboxylic acid compound (B). When the metallocene catalyst component containing the above-mentioned components (A-1) to (A-3) is used as a solid catalyst component for olefin polymerization, the carboxylic acid compound (B) may be added when the metallocene catalyst component is produced using these components according to the above-mentioned production method. The timing of adding the carboxylic acid compound (B) is not particularly limited. In addition, when a prepolymerization catalyst component using a metallocene catalyst component is used as the solid catalyst component for olefin polymerization (A), the carboxylic acid compound (B) may be added when the prepolymerization catalyst component is produced according to the above-mentioned production method. The timing of adding the carboxylic acid compound (B) is not particularly limited. It is preferable to obtain a prepolymerization catalyst containing the carboxylic acid compound (B) by contacting the carboxylic acid compound (B) with the prepolymerization catalyst obtained by using the solid catalyst component for olefin polymerization prepared using the components (A-1) to (A-3) and a monomer for prepolymerization. For example, a solid catalyst component for olefin polymerization is prepared using the component (A-1), the component (b) (organoaluminum oxy compound) as the component (A-2), and the component (A-3), and the component (a) (organometallic compound) is added to the solid catalyst component as the component (A-2) to perform prepolymerization, and the carboxylic acid compound (B) is contacted with the prepolymerization catalyst obtained, thereby preparing a solid catalyst for olefin polymerization as a prepolymerization catalyst containing the carboxylic acid compound (B).

[0070] The amount of the carboxylic acid compound (B) added to the solid catalyst for olefin polymerization is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the solid catalyst component (A) for olefin polymerization.

[0071] [Production of olefin polymers] The method for producing an olefin polymer of the present invention comprises a step of (co)polymerizing ethylene and one or more olefins selected from the group consisting of α-olefins having 3 to 20 carbon atoms in a polymerization vessel in the presence of the above-described solid catalyst for olefin polymerization. In the present invention, the term "(co)polymerization" is used in a sense that includes both polymerization and copolymerization. Furthermore, in the present invention, "polymerization" and "polymer" may be used in a sense that includes not only "homopolymerization" and "homopolymer", but also "copolymerization" and "copolymer", respectively.

[0072] In the (co)polymerization, the method of supplying the components (A) and (B) to the polymerization vessel is arbitrary and is not particularly limited. The components (A) and (B) may be added to the polymerization vessel individually in any order. Alternatively, the components (A) and (B) may be mixed and contacted in advance and then added to the polymerization vessel. Furthermore, two or more of these addition methods may be combined.

[0073] The polymerization can be carried out in any of suspension, solution or gas phase, and is preferably carried out in suspension or gas phase by slurry polymerization or gas phase polymerization.Specific examples of the inert hydrocarbon medium used in slurry polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, etc.; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, etc., or mixtures thereof.Among these, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred.

[0074] The polymerization temperature is usually -50 to 150°C, preferably 0 to 100°C, in the case of slurry polymerization, and usually 0 to 120°C, preferably 20 to 100°C, in the case of gas phase polymerization. The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out by any of a batch method, a semi-continuous method, and a continuous method.

[0075] The polymerization can be carried out in two or more stages with different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by making hydrogen present in the polymerization system or by changing the polymerization temperature.

[0076] At least one selected from ethylene and α-olefins having 3 to 20 carbon atoms is used as a raw material for polymerization. Specific examples of the 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-eicosene. These can be used alone or in combination of two or more. In addition to ethylene and α-olefins having 3 to 20 carbon atoms, other copolymerization monomers may be used in combination for copolymerization. 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.

[0077] As the olefin as a raw material for polymerization, an olefin having any of the compositions (A) to (D) exemplified above for the preliminary polymerization can be used. Furthermore, in the present invention, it is preferable to produce an ethylene-based polymer having ethylene as the main monomer. As the ethylene-based polymer, a (co)polymer containing 50 mol % or more of an ethylene component and, if necessary, containing an α-olefin component having 4 to 10 carbon atoms is preferable.

[0078] In the polymerization, the olefin polymerization catalyst (A) is used in an amount of usually 10 -8 ~10 -3 Molar, preferably 10 -7 ~10 -4 The organoaluminum oxy compound (A-2) is desirably used in an amount of usually 10 to 500 mol, preferably 20 to 200 mol, per mol of transition metal atom in the transition metal compound (A-1) calculated as aluminum atom. EXAMPLES

[0079] The present invention will be described in more detail with reference to the following examples, although the present invention is not limited to the description of the following examples.

[0080] The present invention will be described in more detail with reference to the following examples, although the present invention is not limited to the description of the following examples.

[0081] [Stabilizer] The stabilizer (B) [component (B)] used in the examples and reference examples is as follows: "B-1": Lauric acid [CAS number 143-07-7, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] "B-2": Lauryldiethanolamine [Electrostripper (registered trademark) EA, manufactured by Kao Corporation] "B-3": Caprylic acid [CAS number 124-07-2, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] "B-4": Myristic acid [CAS number 544-63-8, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] "B-5": Palmitic acid [CAS number 57-10-3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] "B-6": Stearic acid [CAS number 57-11-4, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] "B-7": Oleic acid [CAS number 112-80-1, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] "B-8": Linoleic acid [CAS number 60-33-3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]

[0082] [Preparation Example 1] (Preparation of solid catalyst component (X-1)) A 270 L reactor equipped with a stirrer was used, and silica gel (manufactured by Fuji Silysia Chemical Ltd., average particle size 70 μm, specific surface area 340 m / g, pore volume 1.3 cm) was added under a nitrogen atmosphere. 3 10 kg of methylaluminoxane (100 g, dried at 250°C for 10 hours) was suspended in 77 L of toluene and then cooled to 0-5°C. While maintaining the temperature in the system at 0-5°C, 19.4 L of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) was dropped into this suspension over 30 minutes. After contacting each added component for 30 minutes, the temperature in the system was raised to 95°C over 1.5 hours, and then contacted 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 total of 115 L of toluene slurry of a solid carrier carrying methylaluminoxane. A part of this slurry was sampled and analyzed, and the solid concentration was 123 g / L. Of the obtained slurry, 12.2 L (1.50 kg as solid content) was charged into a 114 L reactor equipped with a stirrer under a nitrogen atmosphere, and toluene was added to bring the total volume to 28 L. Next, a solution of 23.5 g (54.2 mmol in terms of Zr atom) 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 to 25°C. The supernatant liquid was removed by decantation and washed three times with hexane. Then, hexane was further added to bring the total volume to 30 L, and a hexane slurry of solid catalyst component (X-1) was obtained.

[0083] [Preparation Example 2] (Preparation of prepolymerized solid catalyst component (XP-1)) 30L of hexane slurry of the solid catalyst component (X-1) obtained in Preparation Example 1 was cooled to 10°C, and 2.89mol of diisobutylaluminum hydride (DiBAl-H) was added thereto. While maintaining the temperature in the system at 10-15°C, ethylene was continuously fed into the system under normal pressure for several minutes, and then 70ml of 1-hexene was added. Then, ethylene feeding was started at 1.46kg / h, and prepolymerization was performed at a system temperature of 32-37°C. 70ml of 1-hexene was added five times in total every 30 minutes after the start of prepolymerization, and when the ethylene feeding reached 4.37kg 180 minutes after the start of prepolymerization, the ethylene feeding was stopped. Then, the supernatant liquid was removed by decantation, and washed four times with hexane. Then, hexane was further added to make the total amount 30L, and a hexane slurry of the prepolymerized solid catalyst component (XP-1) was obtained. Next, the hexane slurry was introduced into a 43 L agitator-equipped evaporator under nitrogen atmosphere, and the pressure was reduced to -68 kPaG over about 60 minutes. When the pressure reached -68 kPaG, the mixture was vacuum-dried for about 4.3 hours to remove hexane and volatile matters in the prepolymerized catalyst component. The pressure was further 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 a prepolymerized solid catalyst component (XP-1).

[0084] [Preparation Example 3] (Preparation of prepolymerized solid catalyst component (XP-2)) In a 200 ml reactor equipped with a stirrer, 10.0 g of the prepolymerized solid catalyst component (XP-1) obtained in Preparation Example 2 was charged under a nitrogen atmosphere, and hexane was added so that the total amount became 50 ml. Next, the temperature in the system was raised to 35°C, and then 100.0 mg of lauric acid (B-1) was diluted with 5 ml of toluene as component (B) and charged, and the mixture was contacted at 32 to 37°C for 2 hours to obtain a hexane slurry of the prepolymerized solid catalyst component (XP-2). This hexane slurry was transferred to a 100 ml glass Schlenk flask, and hexane was distilled off under reduced pressure at 25°C to obtain 10.1 g of the prepolymerized solid catalyst component (XP-2).

[0085] [Example 1] (Polymerization evaluation (i): Evaluation of 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, the system was purged with ethylene, 10 ml of 1-hexene and 250 mg of the prepolymerized solid catalyst component (XP-2) obtained in Preparation Example 2 were 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) until the temperature reached 55°C. Then, 200 mg of the prepolymerized solid catalyst component (XP-2) was further added, and the temperature in the system was raised to 73°C. Next, polymerization was started by introducing ethylene, and the pressure was increased to 8.0 kg / cm while continuously supplying ethylene. 2 The polymerization was carried out for 90 minutes while maintaining the temperature at -G. After the polymerization was completed, the pressure was released, the polymer was removed, and the condition of the autoclave was checked. No adhesion of the polymer to the autoclave walls or the stirring blades was observed, and the polymerization was stable.

[0086] (Polymerization evaluation (ii): Polymerization activity evaluation) 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. 20 ml of 1-hexene and 0.06 ml of a decane solution of triisobutylaluminum (1.0 mol / L) were then added and held at room temperature for 5 minutes. Then, 180 mg of prepolymerized solid catalyst component (XP-2) was added and the temperature in the system was raised to 73°C. Next, polymerization was started by introducing ethylene, and the pressure was increased to 8.0 kg / cm while continuously supplying ethylene. 2 The polymerization was carried out for 90 minutes while maintaining the temperature at -G. After the polymerization was completed, the pressure was released, and the polymer was filtered, washed, and dried at 80°C under reduced pressure for 10 hours to obtain 120.2 g of polymer. The polymer yield per 1 g of catalyst (polymerization activity) was 668 (g-PE / g-cat).

[0087] [Preparation Examples 4 to 10] (Preparation of Prepolymerized Solid Catalyst Components (XP-3) to (XP-9)) Prepolymerized solid catalyst components (XP-3) to (XP-9) were prepared in the same manner as in Preparation Example 3, except that stabilizers (B-2) to (B-8) were used instead of the stabilizer (B-1).

[0088] [Examples 2 to 7, Comparative Example 1 and Reference Example 1] Polymerization evaluation (i) and polymerization evaluation (ii) were carried out in the same manner as in Example 1, except that the solid catalyst component used was changed as shown in Table 1. The results are shown in Table 1.

[0089] [Table 1]

[0090] As is clear from Table 1, in Example 1, which used component (B-1), adhesion of the polymer to the autoclave vessel wall and stirring blades was suppressed compared to Comparative Example 1, which did not use component (B). Furthermore, the polymerization activity was higher than in Reference Example 1, which used component (B-2), an amine compound, instead of component (B-1), a carboxylic acid. That is, in Example 1, as compared with Comparative Example 1 and Reference Example 1, an olefin polymer could be produced stably with high polymerization activity. Furthermore, in Examples 2 to 7, in which components (B-3) to (B-8) were used instead of component (B-1), adhesion of the polymer to the autoclave walls and stirring blades was suppressed and polymerization activity was high, as compared with Comparative Example 1 and Reference Example 1.

[0091] [Example 8] (Polymerization evaluation (iii): Operability evaluation by gas phase polymerization) Copolymerization of ethylene and 1-hexene was carried out using a gas-phase fluidized bed polymerization apparatus. The polymerization pressure was 1.7 MPaG, and the polymerization temperature was 80°C. The prepolymerized solid catalyst component (XP-2) prepared in Preparation Example 3 was fed into the polymerization reactor at 3.7 g / hr. Furthermore, lauryldiethanolamine was fed as a stabilizer into the circulation gas line so that it was present in an amount of 30 ppm (mass basis) relative to the mass of the polymer. The gas composition in the gas-phase polymerization reactor was ethylene partial pressure = 1.0 MPa, hydrogen / ethylene = 4.8 x 10 -4Ethylene, hydrogen, 1-hexene and isopentane were continuously fed so that the molar ratio of 1-hexene / ethylene was 0.022, and a polymer was produced at a rate of 6.0 kg / hr. The residence time was 4 hours. The polymer density at this time was 916 kg / m 3 The melt flow rate was 3.8 g / 10 min. The melt flow rate was measured at 190° C. under a load of 2.16 kg in accordance with ASTM D1238-65T. The operation was carried out for 48 hours under the above conditions, and no heat spots were observed in any parts such as the polymerization vessel or piping, and stable polymerization was possible. The polymer yield per gram of catalyst (polymerization activity) was 1622 (g-PE / g-cat).

[0092] [Reference example 2] A polymer was produced at a rate of 6.0 kg / hr in the same manner as in Example 8, except that the prepolymerized solid catalyst component (XP-3) was used instead of the prepolymerized solid catalyst component (XP-2). Operation was carried out for 48 hours under these conditions, and no heat spots were observed in any part, such as the polymerization vessel or piping, and stable polymerization was carried out. The polymer yield (polymerization activity) per gram of catalyst was 1250 (g-PE / g-cat). [Industrial Applicability]

[0093] According to the present invention, it is possible to provide a solid catalyst for olefin polymerization which can prevent fouling of the inside of a polymerization vessel, such as the walls of the polymerization vessel or the stirring blades, and thereby achieve stable operation of the production apparatus, and a production method for an olefin polymer using the same, and the present invention greatly contributes to improving the productivity of olefin polymers using a catalyst.

Claims

1. (A) a solid catalyst component for olefin polymerization; and (B) a carboxylic acid compound represented by the following general formula (I), and does not contain an amine compound, The (B) carboxylic acid compound is contained in an amount of 1 to 4 parts by mass per 100 parts by mass of the (A) solid catalyst component for olefin polymerization, The component (A) is (A-1) a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl skeleton; (A-2) at least one compound selected from the group consisting of (a) organometallic compounds, (b) organoaluminum oxy compounds, and (c) compounds that react with component (A-1) to form an ion pair; (A-3) a fine particle carrier; A solid catalyst for olefin polymerization comprising: 【Chemistry 1】 [In the above general formula (I), R is a hydrocarbon group having 9 to 30 carbon atoms.]

2. 2. The solid catalyst for olefin polymerization according to claim 1, which comprises the component (A) and the component (B).

3. 3. The method for producing a solid catalyst for olefin polymerization according to claim 1, wherein (B) a carboxylic acid compound is added during the production of (A) the solid catalyst component for olefin polymerization.

4. A method for producing an olefin polymer, comprising (co)polymerizing ethylene and one or more olefins selected from the group consisting of α-olefins having from 3 to 20 carbon atoms in the presence of the solid catalyst for olefin polymerization according to claim 1 or 2.

5. The process for producing an olefin polymer according to claim 4, wherein the (co)polymerization of olefins is carried out in a suspension or in a gas phase.

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