Method for producing olefin polymers in the presence of an olefin polymerization catalyst

Abstract

To provide a method for producing an olefin polymer that is performed in the presence of a catalyst for olefin polymerization having excellent activity and exhibiting high selectivity and / or production efficiency of 1-octene in particular with a relatively small amount of a co-catalyst.SOLUTION: A method for producing an olefin polymer is performed in the presence of a catalyst including (A) a chromium compound, (B) an amine compound of a formula (1) and (C) a compound such as (C-2) an organic aluminum oxy compound or the like and includes a step of contacting component (A), component (B) and component (C-2) at a concentration of a component (C-2) in terms of Al atom in a range of 0.05 to 1.5 mol / l. (R1 to R4 represent a group such as a hydrocarbon group or the like; Y represents a structure represented by -CR5R6-; R5 and R6 represent a group such as a hydrogen atom or the like; and Z represents an integer of 1 to 10.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing olefin polymers in the presence of an olefin polymerization catalyst that has excellent activity and high selectivity and / or production efficiency for specific olefin polymers. [Background technology]

[0002] Alpha-olefins are important compounds widely used industrially, for example, as raw materials for polyolefins. 1-Hexene and 1-Octene, for instance, are in high demand as raw materials for polyolefins. Industrialized methods for producing alpha-olefins include those using organoaluminum or transition metal compounds as catalysts. However, these industrialized methods typically yield mixtures of various alpha-olefins. This can make it difficult to respond flexibly to changes in the market prices of each component. Therefore, a manufacturing method with high selectivity for the desired alpha-olefin is desirable.

[0003] In recent years, the present inventors have reported catalysts that can selectively produce 1-hexene by the trimerization reaction of ethylene using transition metal complex compounds having a phenoxyimine ligand (for example, Patent Document 1).

[0004] Furthermore, chromium-based catalysts using ligands containing phosphorus atoms have been disclosed as catalysts for selectively producing 1-octene (for example, Patent Documents 2-4). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2009 / 005003 [Patent Document 2] International Publication No. 2004 / 056479 [Patent Document 3] International Publication No. 2013 / 137676 [Patent Document 4] International Publication No. 2009 / 022770 [Overview of the project] [Problems that the invention aims to solve]

[0006] Our studies have shown that catalysts that yield 1-hexene or 1-octene require alkylaluminoxane compounds as co-catalysts. Furthermore, it has been found that some catalysts require extremely large amounts of alkylaluminoxane relative to the catalyst when reacting with olefins. Alkylaluminoxanes are generally expensive and are dangerous compounds that can spontaneously combust, so a reduction in their usage is desirable.

[0007] Furthermore, it has been reported that, for example, chromium-based catalysts containing phosphorus exhibit excellent effects even when the amount of alkylaluminoxane is reduced by combining alkylaluminoxane and organoaluminum compounds at various concentrations. However, our own investigations suggest that there are catalysts for which such measures are insufficient.

[0008] This invention has been made in view of these problems. That is, the object of this invention is to provide a method for producing olefin polymers in the presence of an olefin polymerization catalyst that has excellent activity, a relatively small amount of co-catalyst, and particularly high selectivity and / or production efficiency for 1-octene. [Means for solving the problem]

[0009] The inventors of the present invention have conducted extensive research to solve the above problems and have found that by including a step of contacting a specific transition metal compound, an amine compound having a specific structure, and a co-catalyst such as an alkylaluminoxane at a specific concentration, a catalyst containing a relatively small amount of alkylaluminoxane (for example, a small ratio of alkylaluminoxane to the transition metal compound) exhibits excellent high activity and / or high selectivity for 1-octene. Furthermore, they have found that in the presence of this catalyst, olefin polymerization reactions, preferably when ethylene is used as the olefin, can be carried out with high efficiency to obtain 1-octene, a tetramer of ethylene, or 1-hexene, a trimer, with high activity, thus completing the present invention. In other words, the present invention is defined as follows.

[0010] [1] A method for producing an olefin polymer, comprising carrying out an olefin polymerization reaction in the presence of an olefin polymerization catalyst containing the following components (A) to (C): A method for producing an olefin polymer, comprising the step of contacting component (A), component (B), and component (C-2) at a concentration range of 0.05 to 1.5 mol / l, where the concentration of component (C-2) in terms of Al atoms is in the range of 0.05 to 1.5 mol / l. (A) Chromium compounds (B) Amine compounds represented by the following general formula (1)

[0011] [ka]

[0012] (In general formula (1), R 1 ~R 4 They may be the same or different from each other. This 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, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked together. Y is a substituent R 5 and R 6 A carbon atom having (-CR5 R 6 -represents a structure). R 5 and R 6 may be the same as or different from each other, and represent 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, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and R 5 and R 6 may be linked to each other, and R 1 ~R 4 may be linked to any one of them. Z represents an integer from 1 to 10.) (C) (C-1) organometallic compound, (C-2) organoaluminum oxy compound, and (C-3) at least one compound selected from the group consisting of compounds that react with a transition metal compound to form an ion pair.

[0013] [2] The method for producing an olefin polymer according to [1], wherein the concentration of the (C-2) component in terms of Al atoms is 0.12 to 0.85 mol / l.

[0014] [3] The method for producing an olefin polymer according to [1], wherein the molar ratio of the (C-2) component (in terms of Al atoms) to the component (A) (in terms of Cr atoms) is 50 to 1500.

[0015] [4] The method for producing an olefin polymer according to [1], further comprising the following component (D) in addition to the components (A) to (C). (D) A carrier for supporting at least one compound selected from the group consisting of the components (A) to (C).

[0016] [5] The method for producing an olefin polymer according to [1], wherein the oligomerization reaction of olefin is carried out in the presence of an antistatic agent.

[0017] [6] The method for producing an olefin polymer according to [1], wherein the olefin is ethylene.

[0018] [7] A method for producing an olefin polymer according to [1], wherein the olefin polymer is 1-octene. [Effects of the Invention]

[0019] The present invention provides a method for producing olefin polymers in the presence of an olefin polymerization catalyst that has excellent activity, and in particular high selectivity for 1-octene and / or production efficiency. [Modes for carrying out the invention]

[0020] The embodiments of the present invention will be described below, but the present invention is not limited thereto. In the present invention, olefin multimerization means converting the olefin into 2 to 10 mers, preferably into trimers to tetramers.

[0021] <Chromium compound (A)> The chromium compound (A) used in the present invention is usually an inorganic salt, organic salt, or metal-organic complex of chromium. Specific examples of chromium compound (A) include chromium(III) chloride, chromium(II) chloride, chromium(III) bromide, chromium(II) bromide, chromium(III) iodide, chromium(II) iodide, chromium(III) fluoride, chromium(II) fluoride, chromium trichloride tristetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetylacetonate, chromium(III) trifluoroacetylacetonate, and chromium(III) hexafluoroacetylacetonate. However, chromium compound (A) is not limited to these. Among these, trivalent chromium compounds are preferred. Chromium compounds containing halogen atoms are also preferred.

[0022] <Amine compound (B)> The amine compound (B) used in the present invention is represented by the following general formula (1).

[0023] [ka]

[0024] In general formula (1), R 1 ~R 4 These may be identical or different from each other, and represent 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, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked together. More specifically, R 1 ~R 4 Preferably, the group is a hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, sulfo group, mercapto group, aluminum-containing group, or hydroxyl group.

[0025] R 1 ~R 4 If at least one of the elements is a halogen atom, specific examples of that halogen atom include fluorine, chlorine, bromine, and iodine. Similarly, specific examples of halogens (atoms) in the following text also include fluorine, chlorine, bromine, and iodine.

[0026] R 1 ~R 4If at least one of the hydrocarbon groups is a hydrocarbon group, specific examples of such hydrocarbon groups include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, more preferably 1 to 10, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20, such as vinyl, allyl, and isopropenyl; linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20, such as ethynyl and propargyl; and cyclopropyl, cyclobutyl, and cyclopentyl Examples include cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20, such as chlorophenyl, cyclohexyl, and adamantyl; cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; alkyl-substituted aryl groups having 1 to 30 carbon atoms, preferably 5 to 10, such as tolyl, isopropylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl; and alkylidene groups having 1 to 30 carbon atoms, preferably 5 to 10, such as benzylidene, methylidene, and ethylidene.

[0027] R 1 ~R 4 If at least one of the groups is a hydrocarbon group, the hydrogen atoms of that hydrocarbon group may be substituted with halogens. Specific examples include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20, such as trifluoromethyl, pentafluorophenyl, and chlorophenyl.

[0028] R 1 ~R 4 If at least one of the groups is a hydrocarbon group, the hydrogen atoms of that hydrocarbon group may be substituted with other hydrocarbon groups. Specific examples include aryl-substituted alkyl groups such as benzyl, cumyl, diphenylethyl, and trityl.

[0029] R 1 ~R4 If at least one of the residues is a hydrocarbon group, then that hydrocarbon group is also a heterocyclic compound residue; oxygen-containing groups such as alkoxy groups, allyloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxyl groups, peroxy groups, and carboxylic acid anhydride groups; nitrogen-containing groups such as amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and ammonium salts of amino groups; and boranediyl groups, borantriyl groups, and diboranyl groups. It may have at least one group selected from the group consisting of sulfur-containing groups such as mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups, thioacyl groups, thioether groups, thiocyanate groups, isothiocyanate groups, sulfone ester groups, sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, and sulfenyl groups; phosphorus-containing groups such as phosphine groups, phosphoryl groups, thiophosphoryl groups, and phosphat groups; silicon-containing groups; germanium-containing groups; and tin-containing groups. In particular, preferred are linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, more preferably 1 to 10, and especially preferably 2 to 10, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, and adamantyl; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents, such as halogen atoms, alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, alkoxy groups, or amino groups, and aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, or allyloxy groups.

[0030] R 1 ~R 4If at least one of the groups is an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, and / or a phosphorus-containing group, specific examples of these groups include those similar to those previously exemplified as substituents that may be included in a hydrocarbon group. Among these, oxygen-containing groups, nitrogen-containing groups, and sulfur-containing groups are preferred, and oxygen-containing groups and nitrogen-containing groups are more preferred.

[0031] Examples of nitrogen-containing groups include amide groups, amino groups, imide groups, and imino groups. Specific examples of amide groups include acetamide, N-methylacetamide, and N-methylbenzamide. Specific examples of amino groups include dimethylamino, ethylmethylamino, and diphenylamino. Specific examples of imide groups include acetimide and benzimide. Specific examples of imino groups include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

[0032] Examples of the sulfur-containing groups include alkylthio groups, arylthio groups, thioester groups, sulfone ester groups, and sulfonamide groups. Specific examples of alkylthio groups include methylthio and ethylthio. Specific examples of arylthio groups include phenylthio, methylphenylthio, and naphthylthio. Specific examples of thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl. Specific examples of sulfone ester groups include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Specific examples of sulfonamide groups include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

[0033] R 1 ~R 4If at least one of the residues is a heterocyclic compound residue, specific examples of such heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine; oxygen-containing compounds such as furan and pyran; sulfur-containing compounds such as thiophene; and groups obtained by further substituting these heterocyclic compound residues with substituents such as alkyl groups and alkoxy groups having 1 to 30, preferably 1 to 20, carbon atoms.

[0034] R 1 ~R 4 If at least one of the groups is a boron-containing group, specific examples of the boron-containing group include those similar to those previously exemplified as substituents that may be included in a hydrocarbon group. Furthermore, alkyl-substituted boron, aryl-substituted boron, boron halides, and alkyl-substituted boron halides can also be mentioned. Examples of alkyl-substituted boron groups include (Et)2B-, (iPr)2B-, (iBu)2B-, (Et)3B, (iPr)3B, and (iBu)3B. Examples of aryl-substituted boron groups include (C6H5)2B-, (C6H5)3B, (C6F5)3B, and (3,5-(CF3)2C6H3)3B. Examples of boron halides include BCl2- and BCl3. Examples of alkyl-substituted boron halides include (Et)BCl-, (iBu)BCl-, and (C6H5)2BCl. Here, Et represents the ethyl group, iPr represents the isopropyl group, and iBu represents the isobutyl group. In addition, trisubstituted boron may exist in a coordinate bond state.

[0035] R 1 ~R 4If at least one of the groups is an aluminum-containing group, specific examples of such aluminum-containing groups include alkyl-substituted aluminum, aryl-substituted aluminum, aluminum halides, and alkyl-substituted aluminum halides. Examples of alkyl-substituted aluminum groups include (Et)2Al-, (iPr)2Al-, (iBu)2Al-, (Et)3Al, (iPr)3Al, and (iBu)3Al. An example of an aryl-substituted aluminum group is (C6H5)2Al-. Examples of aluminum halides include AlCl2- and AlCl3. Examples of alkyl-substituted aluminum halides include (Et)AlCl- and (iBu)AlCl-, where Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group. In addition, trisubstituted aluminum may exist in a coordinate bond state.

[0036] R 1 ~R 4 If at least one of the groups is a silicon-containing group, specific examples of such silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. Examples of hydrocarbon-substituted silyl groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl(pentafluorophenyl)silyl. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, and triphenylsilyl are preferred, and trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are more preferred. An example of a hydrocarbon-substituted siloxy group is trimethylsiloxy.

[0037] R 1 ~R 4 If at least one of these is a germanium-containing group and / or a tin-containing group, specific examples of these groups include those in which the silicon in the silicon-containing group exemplified earlier is replaced with germanium or tin.

[0038] In general formula (1), Y is a substituent R 5 , R 6 A carbon atom having (-CR 5 R 6 R shows the structure represented by -. 5 , R 6 These may be identical or different from each other, and represent a hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group. Examples of each of these groups are given by R 1 ~R 4 This is similar to the example in R. 5 and R 6 They may be connected to each other, and R 1 ~R 4 It may also be linked to this.

[0039] In general formula (1), Z represents an integer from 1 to 10. It is sometimes preferable that Z be from 2 to 10. On the other hand, Z is preferably an integer from 1 to 3, more preferably 1 or 2, and particularly preferably 1. When Z is 2 or greater, multiple Ys may be the same or different from one another.

[0040] In general formula (1), R 1 ~R 4 Two or more of them may be connected to each other. However, R 1 is R 3 and R 4 It is not connected to R 2 is R 3 and R 4 It is preferable that the group is not linked to such a specific group. Examples of preferred amine compounds that are not linked to such a specific group include, for example, amine compounds of the following three embodiments represented by the general formulas (1A) to (1C).

[0041] [ka]

[0042] (In general formula (1A), the definitions of each group are the same as those of each group in general formula (1). However, R 1 ~R 4 Each of these is not linked to any group other than the nitrogen atom.

[0043] [ka]

[0044] (In general formula (1B), the definition of each group is the same as the definition of each group in general formula (1). However, R 1 and R 2 They are connected, R 3 and R 4 They are connected.

[0045] [ka]

[0046] (In general formula (1C), the definition of each group is the same as the definition of each group in general formula (1). However, R 1 and R 2 Each of them is not linked to any group other than the nitrogen atom, R 3 and R 4 They are connected.

[0047] In general formula (1), R 1 ~R 4 R may be a linear or branched group, or a group containing a cyclic structure, 1 ~R 4 Two or more of them may be connected to each other to form a ring structure. For example, R 1 and R 3 , R 2 and R 4 If either of the two is linked (joined), the number of links is preferably 4 or more, R 1 and R 3 , R 2 and R 4When both are connected (bonded), the number of bonds is preferably 3 or more. The number of bonds refers to the number of bonds in the connection from one nitrogen atom to the other nitrogen atom. For example, when R 1 and R 3 are both methylene groups (-CH2-), and they are connected, the number of bonds in the connection from one nitrogen atom containing R 1 to the other nitrogen atom containing R 3 is 3. However, as represented by general formulas (1A) to (1C), R 1 is not connected to R 3 and R 4 , and R 2 is preferably not connected to R 3 and R 4 . Also, each of R 1 to R 4 preferably has no substituent of a cyclic structure, that is, is a linear or branched group. When R 1 to R 4 is a linear or branched group (for example, a linear or branched hydrocarbon group which may have a substituent), the number of carbon atoms of the linear or branched group is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10. Also, in that case, the total number of carbon atoms of R 1 to R 4 is preferably 8 or more. R 1 to R 4 is preferably linear.

[0048] When R 1 to R 4 is any of the above preferred groups, the reaction activity of the olefin tends to be higher, and there is a tendency to more efficiently produce a relatively low-boiling α-olefin which is a dimer to pentamer (preferably trimer to tetramer) of the olefin. Here, when the raw material is ethylene, its trimer to tetramer corresponds to hexene and octene. That is, there is a tendency to be suitable for the production of olefins having 10 or less carbon atoms.

[0049] When an olefin polymerization catalyst containing the amine compound (B) of the present invention is used, the proportion of the amount of olefin polymers produced, i.e., olefin di-pentamers (preferably triper-tetramers), to the total amount of products produced tends to be high. Specifically, this proportion is preferably 85% by weight or more, preferably 88% by weight or more, more preferably 90% by weight or more, and particularly preferably 91% by weight or more. Thus, for example, when the proportion of di-pentamers (preferably triper-tetramers) produced is high, the number of types of polymers produced tends to be small. Also, since the difference in boiling points of each component is relatively large, separation by distillation becomes easy (for example, the boiling point of 1-hexene is 63°C, and the boiling point of 1-octene is 122-123°C). As a result, it is thought that manufacturing costs can be suppressed and it is easier to respond to market fluctuations.

[0050] On the other hand, R 1 and R 2 The two have the same structure, and / or R 3 and R 4 It is also preferable that they have the same structure. In this case, the selectivity for the ethylene tetramer, i.e., 1-octene, may be higher.

[0051] R 1 and R 2 When they are linked to form a ring structure, and / or R 3 and R 4 Even when they are linked to form a ring structure, R 1 and R 2 The two have the same structure, and / or R 3 and R 4 It is preferable that the ring structure is the same. In this case, "same structure" means that the ring structure as seen from N is symmetrical, that is, the ring structure R 1 side (or R 3 The structure of the side, and R 2 side (or R 4 This means that the structure is the same as that of the side. In this case as well, the selectivity for the ethylene tetramer, i.e., 1-octene, may be high.

[0052] Note, R 1 and R 2If they are connected, and / or R 3 and R 4 When connected, in the present invention, R 1 and R 2 The number of carbon atoms in each (and / or R 3 and R 4 The number of carbon atoms in each of these atoms is defined by the point where the number of carbon atoms constituting the linkage structure is 1 / 2 of the total number of carbon atoms. If there is one carbon atom at this 1 / 2 point, the number of carbon atoms in this atom is set to "0.5" and R 1 and R 2 The number of carbon atoms in each (and / or R 3 and R 4 Distribute it to the number of carbon atoms in each of the following. For example, R 1 and R 2 When linked together to form a piperidine 1-yl group with the nitrogen atom, R 1 and R 2 The number of carbon atoms in each of these atoms is "2.5".

[0053] R 1 and R 2 The two have the same structure, and / or R 3 and R 4 The reason why a better effect can be obtained when the structure is the same is not always clear. However, R 1 ~R 4 Since it is thought to be located relatively close to the chromium atom of the central metal chromium compound (A), the R in the above structure is 1 ~R 4 It is speculated that the steric influence of these elements appropriately controls the ease of ethylene coordination to the metallacycle and the activation energy of the insertion reaction.

[0054] In the present invention, the catalytic activity of 1-octene, as described in the examples below, is one of the indicators used to comprehensively evaluate the performance of the catalyst for olefin amplification. The catalytic activity of 1-octene is the amount of 1-octene produced per unit time and per unit amount of catalyst, i.e., the 1-octene production efficiency. Note that this 1-octene production efficiency is a different indicator from the selectivity of 1-octene.

[0055] Furthermore, in each of the preferred embodiments described above, not only is the efficiency of producing ethylene trimers (1-hexene) and tetramers (1-octene) improved, but the reaction activity of ethylene and the efficient production of 1-octene are also favorable.

[0056] In the present invention, when producing ethylene polymers, 1-hexene and 1-octene are the main products. These two are relatively easy to separate by distillation. Therefore, the efficiency of 1-octene production, as described earlier, is considered an important indicator from an industrial standpoint. This is especially important when using manufacturing equipment that produces both 1-hexene and 1-octene simultaneously.

[0057] Specific examples of amine compounds (B) are shown below. However, amine compounds (B) are not limited to these examples.

[0058] [ka]

[0059] [ka]

[0060] In each of the above compounds, Me is a methyl group, Et is an ethyl group, n Pr is a n-propyl group, i Pr represents an isopropyl group, and Ph represents a phenyl group. The number of carbon atoms between the nitrogen atoms in each of the above compounds is 1 or 2, but compounds in which the number of carbon atoms between the nitrogen atoms is changed to 3 or more can also be used.

[0061] As the amine compound (B), a commercially available amine compound may be used. When synthesizing the amine compound (B), for example, it can be obtained by alkylating or arylating a specific amine compound using a general method. Alternatively, the amine compound (B) can also be obtained by reducing an imine compound using a general method. Furthermore, in this invention, multiple types of amine compounds (B) can be used in combination.

[0062] As described above, using an olefin polymerization catalyst containing the amine compound (B) of the present invention tends to efficiently produce 1-octene. For example, in the olefin polymer with 10 or fewer carbon atoms produced, the proportion of 1-octene is preferably 40% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more, particularly preferably 65% ​​by weight or more, and most preferably 70% by weight or more.

[0063] The amine compound (B) and the chromium compound (A) may be added to the reactor separately. However, it is preferable to add a transition metal complex, which has been formed by reacting the amine compound (B) and the chromium compound (A) beforehand, to the reactor. For example, a transition metal complex can be obtained by dissolving the amine compound (B) in a solvent, mixing it with the chromium compound (A), and stirring it under an inert gas atmosphere such as nitrogen or argon at -78°C to room temperature or reflux conditions for about 5 minutes to 48 hours.

[0064] The solvent used in synthesizing transition metal complexes is not particularly limited. Any common solvent known to be usable in such reactions can be used. Specific examples of solvents include polar solvents such as ether and tetrahydrofuran; hydrocarbon solvents such as toluene, methylcyclohexane, and heptane; and halogenated hydrocarbon solvents such as methylene chloride.

[0065] The transition metal complex is obtained dissolved or suspended in a solvent. This solution or suspension of the transition metal complex may be used as is, or the transition metal complex may be isolated and then redissolved or suspended in the solvent before use.

[0066] <Compound (C)> As the compound (C) used in the present invention, an organoaluminum oxy compound (C-2) is used as an essential component, and optionally, at least one compound selected from the group consisting of an organometallic compound (C-1) and a compound (C-3) that reacts with a transition metal compound to form an ion pair may be further used. Hereinafter, these compounds (C-1) to (C-3) will be described. In the following description, the compound (C-3) is referred to as "ionized ionic compound (C-3)".

[0067] [Organometallic Compound (C-1)] As the organometallic compound (C-1), for example, organometallic compounds of Groups 1, 2, 12, and 13 of the periodic table such as the compounds (C-1a), (C-1b), and (C-1c) described below can be used. In the present invention, the organometallic compound (C-1) is assumed not to include the organoaluminum oxy compound (C-2) described later.

[0068] (C-1a): General formula R a m Al(OR b ) n H p X q (In the formula, R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other, X represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3) represents an organoaluminum compound.

[0069] (C-1b): General formula M 2 AlR a 4 (In the formula, M 2 represents Li, Na, or K, and R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) represents a complex alkylate of a Group 1 metal of the periodic table and aluminum.

[0070] (C-1c): General formula R a R b M 3 (In the formula, R a and R b each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other, and M 3 is Mg, Zn or Cd), a dialkyl compound of a Group 2 or Group 12 metal in the periodic table represented by the formula.

[0071] Examples of the organoaluminum compound (C-1a) include, for example, an organoaluminum compound represented by the general formula R a m Al(OR b ) 3-m (In the formula, R a and R b each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other, and m is preferably a number of 1.5 ≦ m ≦ 3.); an organoaluminum compound represented by the general formula R a m AlX 3-m (In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably a number of 0 < m < 3.); an organoaluminum compound represented by the general formula R a m AlH 3-m (In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably a number of 2 ≦ m < 3.); an organoaluminum compound represented by the general formula R a m Al(OR b ) n X q (In the formula, R a and R b each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other, X represents a halogen atom, m is a number of 0 < m ≦ 3, n is a number of 0 ≦ n < 3, q is a number of 0 ≦ q < 3, and m + n + q = 3) can be used.

[0072] Specific examples of the organoaluminum compound (C-1a) include tri(n-alkyl)aluminum such as trimethylaluminum, triethylaluminum, tri(n-butyl)aluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; tribranched-chain alkylaluminum such as triisopropylaluminum, triisobutylaluminum, tri(sec-butyl)aluminum, tri(tert-butyl)aluminum, tri(2-methylbutyl)aluminum, tri(3-methylbutyl)aluminum, tri(2-methylpentyl)aluminum, tri(3-methylpentyl)aluminum, tri(4-methylpentyl)aluminum, tri(2-methylhexyl)aluminum, tri(3-methylhexyl)aluminum, and tri(2-ethylhexyl)aluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritrilylaluminum; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; (iC4H9) x Al y (C5H 10 ) z Alkenyl aluminum such as isoprenyl aluminum, represented by formulas such as (wherein x, y, and z are positive numbers and z ≥ 2x; iC4H9 represents an isobutyl group); alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; for example, R a 2.5 Al(OR b ) 0.5 (In the formula, R a and R bThis represents hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4, which may be the same or different from each other. Partially alkoxylated alkylaluminum having an average composition represented by ); dialkylaluminum allyloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum sesquichloride Examples include alkylaluminum sesquihalides such as cyclolide and ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

[0073] Compounds similar to organoaluminum compounds (C-1a), such as organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom, like (C2H5)2AlN(C2H5)Al(C2H5)2, can also be used.

[0074] Specific examples of the compound (C-1b) include LiAl(C2H5)4 and LiAl(C7H 15 )4 is one example.

[0075] Specific examples of the aforementioned compound (C-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, and butylethylmagnesium.

[0076] Specific examples of organometallic compounds (C-1) other than the compounds (C-1a) to (C-1c) described above include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, and butylmagnesium chloride.

[0077] Compounds that form organoaluminum compounds within the polymerization reaction system, such as a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium, can also be used.

[0078] The organometallic compounds (C-1) described above can be used individually or in combination of two or more. Among the organometallic compounds (C-1) described above, organoaluminum compounds (C-1a) are particularly preferred.

[0079] [Organoaluminum oxy compounds (C-2)] The organoaluminum oxy compound (C-2) may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Publication No. 2-78687. Conventionally known aluminoxanes can be produced, for example, by the following method and are usually obtained as a solution.

[0080] (1) A method of reacting the adsorbed water or crystal water with the organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a suspension containing a compound containing adsorbed water or a salt containing crystal water (for example, magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium chloride hydrate) and a hydrocarbon solvent.

[0081] (2) A method of directly reacting an organoaluminum compound such as trialkylaluminum with water, ice, or water vapor in a solvent such as benzene, toluene, ethyl ether, or tetrahydrofuran.

[0082] (3) A method of reacting organoaluminum compounds such as trialkylaluminum with organotin oxides such as dimethyltin oxide and dibutyltin oxide in a solvent such as decane, benzene, or toluene.

[0083] The aluminoxane may contain small amounts of organometallic components. The solvent and unreacted organoaluminum compounds may be removed from the aluminoxane solution recovered in each of the above methods by distillation, and the aluminoxane may be further redissolved in the solvent or suspended in a poor solvent.

[0084] Specific examples of organoaluminum compounds used for the production of aluminoxanes are the same as the specific examples of organoaluminum compounds (C-1a) described earlier. Organoaluminum compounds can be used individually or in combination of two or more. Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

[0085] For the production of aluminoxanes, examples of solvents that can be used include hydrocarbon solvents and ether-based solvents. Specific examples of hydrocarbon solvents 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; and halides of aromatic hydrocarbons, aliphatic hydrocarbons, or alicyclic hydrocarbons (especially chlorinated or brominated compounds). Specific examples of ether-based solvents include ethyl ether and tetrahydrofuran. Among these, aromatic hydrocarbons and aliphatic hydrocarbons are preferred. When using organoaluminum oxy compounds that are insoluble or sparingly soluble in benzene, the amount of Al component that dissolves in benzene at 60°C is usually 10% or less, preferably 5% or less, and more preferably 2% or less, in terms of Al atoms.

[0086] As the organoaluminum oxy compound (C-2), organoaluminum oxy compounds containing boron, represented by the following general formula (5), can also be used.

[0087] [ka]

[0088] (In general formula (5), R 7 R represents a hydrocarbon group with 1 to 10 carbon atoms, or a halogenated hydrocarbon group with 1 to 10 carbon atoms. 8 (This refers to hydrogen atoms, halogen atoms, and hydrocarbon groups with 1 to 10 carbon atoms, which may be identical or different from each other.)

[0089] A boron-containing organoaluminum oxy compound represented by general formula (5) can be produced, for example, by reacting an alkylboronic acid represented by general formula (6) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of -80°C to room temperature for 1 minute to 24 hours.

[0090] R 7 -B(OH)2···(6) (In general formula (6), R 7 R in the above general formula (5) is 7 (Same group as shown)

[0091] Specific examples of alkylboronic acids represented by general formula (6) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These alkylboronic acids can be used individually or in combination of two or more.

[0092] Specific examples of organoaluminum compounds to be reacted with alkylboronic acid are the same as the specific examples of organoaluminum compounds (C-1a) described earlier. Organoaluminum compounds can be used individually or in combination of two or more. Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are more preferred.

[0093] Among the organoaluminum oxy compounds mentioned above, organoaluminum oxy compounds containing methylaluminoxane and polymethylaluminoxane are particularly preferred examples. The organoaluminum oxy compounds (C-2) described above can be used individually or in combination of two or more.

[0094] [Ionized ionic compounds (C-3)] Ionized ionic compounds (C-3) are compounds that react with transition metal compounds to form ion pairs. Therefore, any compound that has the property of forming ion pairs when in contact with at least a transition metal compound falls under the category of ionized ionic compounds (C-3).

[0095] As ionized ionic compounds (C-3), for example, Lewis acids, ionic compounds, borane compounds, and carborane compounds 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, and U.S. Patent No. 5321106 can be used. Furthermore, heteropoly compounds and isopoly compounds can also be used.

[0096] Examples of the Lewis acid include compounds represented by the general formula BR3 (where R is a phenyl group or fluorine, which may have substituents such as a fluorine, methyl group, or trifluoromethyl group). Specific examples include trifluoroborone, triphenylborone, tris(4-fluorophenyl)borone, tris(3,5-difluorophenyl)borone, tris(4-fluoromethylphenyl)borone, tris(pentafluorophenyl)borone, tris(p-tolyl)borone, tris(o-tolyl)borone, and tris(3,5-dimethylphenyl)borone.

[0097] Specific examples of the aforementioned ionic compounds include, for example, compounds represented by the following general formula (7).

[0098] [ka]

[0099] In general formula (7), R 9+ For example, H + Examples include carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, and ferrocenium cations having transition metals.10 ~R 13 These are organic groups that may be the same or different from each other, preferably aryl groups or substituted aryl groups.

[0100] R 9+ Specific examples of cases where the compound is a carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0101] R 9+ Specific examples of cases where the compound is an ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N,2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0102] R 9+ Specific examples of cases where the cation is a phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0103] R 9+ As such, carbonium cations and ammonium cations are preferred, and triphenylcarbonium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations are more preferred.

[0104] In addition to the compounds represented by the general formula (7) described above, the ionic compounds that can also be used are trialkylsubstituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0105] Specific examples of the aforementioned trialkyl-substituted ammonium salts include triethylammonium tetraphenylborate, tri(n-propyl)ammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o-tolyl)borate, tri(n-butyl)ammonium tetra(pentafluorophenyl)borate, tri(n-propyl)ammonium tetra(o,p-dimethylphenyl)borate, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)borate, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)borate, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)borate, and tri(n-butyl)ammonium tetra(o-tolyl)borate.

[0106] Specific examples of the aforementioned N,N-dialkylanilinium salts include N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, and N,N,2,4,6-pentamethylanilinium tetraphenylborate.

[0107] Specific examples of the aforementioned dialkylammonium salts include di(n-propyl)ammonium tetra(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

[0108] In addition to the salts described above, the following ionic compounds can also be used: triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following general formulas (8) or (9).

[0109] [ka]

[0110] (In general formula (8), Et represents an ethyl group.)

[0111] [ka]

[0112] (In general formula (9), Et represents an ethyl group.)

[0113] Specific examples of the borane compounds include decaborane (14); salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; and salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydridodecaborate)cobaltate (III) and bis[tri(n-butyl)ammonium]bis(dodecahydridodecaborate)nickelate (III).

[0114] Specific examples of the carborane compounds include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbowndecaborane (13), 2,7-dicarbowndecaborane (13), and undecahydride-7,8-dimethyl- 7,8-Dicarboundecaporane, Dodecahydride-11-methyl-2,7-Dicarboundecaporane, Tri(n-butyl)ammonium 1-carbadecaborate, Tri(n-butyl)ammonium 1-carboundecaporate, Tri(n-butyl)ammonium 1-carbadodecaborate, Tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, Tri(n-butyl)ammonium bromo-1-carbadodecaborate, Tri(n-butyl)ammonium 6-carbadecabo Rate (14), tri(n-butyl)ammonium 6-carbadecaborate (12), tri(n-butyl)ammonium 7-carbadecaborate (13), tri(n-butyl)ammonium 7,8-dicalbounddecaborate (12), tri(n-butyl)ammonium 2,9-dicalbounddecaborate (12), tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicalbounddecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7 Salts of anions such as ,9-dicarboxylate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboxylate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxylate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxylate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carboxylate;Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)ferrate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)nickelate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)copperate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)goldate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbowndecaborate)iron Examples of metal carborane anion salts include (III) tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboundecaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboundecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)nickelate (IV).

[0115] The aforementioned heteropoly compounds typically consist of atoms of silicon, phosphorus, titanium, germanium, arsenic, or tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specific examples include phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titaniummolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, and phosphomolybdoniobic acid. Salts of these acids may also be used. Specific examples of salts include salts with metals from Group 1 or 2 of the periodic table (e.g., lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium), organic salts such as triphenylethyl salts, and isopolycompounds.

[0116] The ionized ionic compounds (C-3) described above can be used individually or in combination of two or more.

[0117] Using the above-described catalysts for olefin polymerization, olefin polymers can be obtained with high activity, and in particular, when ethylene is used as the olefin, the selectivity for 1-octene is high. For example, when an organoaluminum oxy compound (C-2) such as methylaluminoxane is used as a co-catalyst component, higher activity is observed for ethylene, and 1-octene can be produced. Furthermore, when an ionized ionic compound (C-3) such as triphenylcarbenium tetrakis(pentafluorophenyl)borate is used as a co-catalyst component, 1-octene can be obtained from ethylene with better activity and higher selectivity.

[0118] <Carrier (D)> The olefin polymerizing catalyst used in the present invention may contain a support (D). The support (D) is an inorganic or organic compound, and is usually a granular or particulate solid. In the present invention, the support (D) supports a chromium compound (A), an amine compound (B), and / or compound (C). As the inorganic compound, porous oxides, inorganic halides, clays, clay minerals, and ion-exchangeable layered compounds are preferred.

[0119] Specific examples of the porous oxide include SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or composites or mixtures containing these (e.g., natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO). Among these, porous oxides mainly composed of SiO2 and / or Al2O3 are preferred. The porous oxide may also contain small amounts of carbonates, sulfates, nitrates, or oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O. The particle size, specific surface area, and pore volume of the porous oxide are not particularly limited and can be appropriately determined according to the type of material and manufacturing method. In the present invention, the particle size of the porous oxide is preferably 0.5 to 300 μm, more preferably 20 to 200 μm, and the specific surface area is preferably 50 to 1000 m². 2 / g, more comfortably 100-700m 2 The density is / g, and the pore volume is preferably 0.3 to 3.0 cm³. 3 The weight is / g. The porous oxide is, if necessary, calcined, preferably at 100-1000°C, more preferably at 150-700°C.

[0120] Specific examples of the inorganic halides include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halides may be used as is, or they may be used after being ground using a ball mill or vibration mill. Alternatively, the inorganic halides may be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

[0121] The aforementioned clay typically contains clay minerals as its main component. The ion-exchangeable layered compound is a compound having a crystalline structure in which planes formed by ionic bonds are stacked parallel to each other with weak bonding forces, and is a compound in which the contained ions are exchangeable. Examples of ion-exchangeable layered compounds that can be used include ionic crystalline compounds having layered crystalline structures such as hexagonal close-packing type, antimony type, CdCl2 type, and CdI2 type. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds can be natural or synthetically synthesized.

[0122] Specific examples of clays and clay minerals include kaolin, bentonite, kibushi clay, gylome clay, allophane, hisingerite, pyrophyllite, mica, montmorillonite, vermiculite, hectorite, teniolite, lyokdiite, palygorskite, kaolinite, nacrite, dickite, and halloysite. Specific examples of ion-exchangeable layered compounds include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, 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. Among these, clay and clay minerals are preferred, and synthetic mica, montmorillonite, vermiculite, hectorite, and teniolite are more preferred.

[0123] The pore volume of clay, clay minerals, and ion-exchangeable layered compounds is preferably 0.1 cc / g or more, more preferably 0.3 to 5 cc / g. This pore volume is determined by mercury intrusion using a mercury porosimeter, with a pore radius of 20 to 3 × 10⁻¹⁰. 4 This volume was measured in the angstrom range. When using a support material with a pore volume of less than 0.1 cc / g for pores with a radius of 20 angstroms or more, it tends to be difficult to obtain high merging activity.

[0124] It is also preferable to subject clay and clay minerals to chemical treatment. Chemical treatments include, for example, surface treatments to remove impurities adhering 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. Acid treatment can not only remove surface impurities but also increase the surface area by dissolving cations such as Al, Fe, and Mg in the crystalline structure. Alkali treatment can change the structure of the clay by destroying its crystalline structure. Salt treatment and organic treatment can change the surface area and interlayer distance by forming ionic complexes, molecular complexes, or organic derivatives.

[0125] Ion-exchangeable layered compounds may also be layered compounds in which the interlayer space has been expanded by exchanging the 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. Introducing another substance into the interlayer space of a layered compound in this way is called intercalation. Specific examples of guest compounds (other substances) 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 is a hydrocarbon group, etc.), and [Al 13 O4(OH) 24 ] 7+ [Zr4(OH) 14 ] 2+ [Fe3O(OCOCH3)6] +Examples of metal hydroxide ions include those listed above. Guest compounds can be used individually or in combination of two or more. When intercalating guest compounds, for example, dimers obtained by hydrolyzing metal alkoxides (where R is a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, or colloidal inorganic compounds such as SiO2 can also be present. Specific examples of pillars include oxides produced by heating and dehydrating after intercalating the above-mentioned metal hydroxide ions between layers.

[0126] Clay, clay minerals, and ion-exchangeable layered compounds may be used as is, or after processing such as ball milling or sieving. They may also be used after adding water for adsorption, or after heat dehydration.

[0127] Examples of the aforementioned organic compounds include granular or particulate solid organic compounds with a particle size of 10 to 300 μm. Specific examples of monomers for the polymers constituting the organic compounds include (co)dimers produced mainly from α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene; (co)dimers produced mainly from vinylcyclohexane and styrene; and modified versions thereof.

[0128] <Organic compound component (E)> The olefin polymerization catalyst used in the present invention may further contain an organic compound component (E) as needed.

[0129] In the present invention, the organic compound component (E) is used, for example, to improve the polymerization performance. Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates. However, the organic compound component (E) is not limited to these.

[0130] The alcohols and phenolic compounds are typically R 14Compounds represented by -OH are used. 14 This represents a hydrocarbon group with 1 to 50 carbon atoms or a halogenated hydrocarbon group with 1 to 50 carbon atoms. As for alcohols, R 14 Compounds in which the group is a halogenated hydrocarbon are preferred. As for phenolic compounds, compounds in which the α,α'-positions of the hydroxyl group are substituted with hydrocarbons having 1 to 20 carbon atoms are preferred.

[0131] The aforementioned carboxylic acid is typically R 15 Compounds represented by -COOH are used. 15 This represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. In particular, R 15 Compounds in which the group is a halogenated hydrocarbon group having 1 to 50 carbon atoms are preferred.

[0132] Preferred phosphorus compounds include phosphates having a POH bond, and phosphates or phosphine oxide compounds having a P-OR bond or a P=O bond.

[0133] As the sulfonate, for example, a compound represented by the following general formula (10) can be used.

[0134] [ka]

[0135] In general formula (10), M 2 These are elements of groups 1-14 of the periodic table, and R 14 is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; t is an integer from 1 to 7; u is an integer 1 ≤ u ≤ 7 and tu ≥ 1.

[0136] <Catalyst for olefin expansion> The olefin polymerizing catalyst used in the present invention contains at least the above-mentioned component (A) (chromium compound (A)), component (B) (amine compound (B)), and component (C-2). The ratios of these components will be described later.

[0137] The olefin polymerization catalyst used in the present invention is a catalyst used in the polymerization reaction of olefins. Specific examples of olefins include vinyl compounds such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, vinylcyclohexene, styrene, 1-octene, and 1-decene, and internal olefins such as 2-butene, cyclopentene, cyclohexene, and norbornene. Among these, ethylene is preferred. Two or more olefins may be copolymerized.

[0138] <Method for producing olefin polymers> The present invention provides a method for producing olefin polymers, which involves carrying out an olefin polymerization reaction (preferably a trimerization to tetramerization reaction, more preferably a tetramerization reaction) in the presence of the olefin polymerization catalyst described above.

[0139] Specific examples of olefins to be polymerized are as described above, with ethylene being particularly preferred. Specifically, it is preferable to produce the polymer by a polymerization reaction of ethylene, more preferably to produce 1-hexene and 1-octene with high selectivity by trimerization and tetramerization reactions of ethylene, and especially preferably to produce 1-octene with high selectivity by tetramerization reaction of ethylene.

[0140] During the mass production process, there are no particular restrictions on the order in which components (A), (B), (C), and other components (e.g., carrier (D), component (E) (organic compound component (E)) are added to the reactor. Specific examples of the addition method are as follows.

[0141] (1) A method of adding component (A) and component (B) to the reactor in any order.

[0142] (2) A method of adding a transition metal complex, which has been formed by contacting component (A) and component (B) in advance, to a reactor.

[0143] (3) A method of adding component (A), component (B), and component (C) to the reactor in any order.

[0144] (4) A method of adding a transition metal complex formed by contacting components (A) and (B) in advance, and component (C) to a reactor in any order.

[0145] (5) A method of adding a catalyst component, which has been in contact with component (C) beforehand, to a reactor, which has been formed by contacting component (A) and component (B) beforehand to a transition metal complex.

[0146] (6) A method of adding a catalyst component, which is formed by contacting component (A) and component (B) with a transition metal complex, with component (C) in a prior contact, and component (C) to a reactor in any order. In this case, each component (C) may be the same or different.

[0147] (7) A method of adding a carrier (D) on which a transition metal complex formed by contacting component (A) and component (B) in advance is supported to a reactor.

[0148] (8) A method of adding a carrier (D) on which a transition metal complex formed by contacting components (A) and (B) in advance is supported, and component (C) to a reactor in any order.

[0149] (9) A method of adding a transition metal complex formed by contacting component (A) and component (B) in advance, and a support (D) carrying component (C), to a reactor.

[0150] (10) A method of adding a transition metal complex formed by contacting components (A) and (B) in advance, and a support (D) carrying component (C), and component (C) to a reactor in any order. In this case, each component (C) may be the same or different.

[0151] (11) A method of adding a carrier (D) supporting component (C), component (A), and component (B) to a reactor in any order.

[0152] (12) A method of adding a carrier (D) supporting component (C) and a transition metal complex formed by pre-contacting components (A) and (B) to a reactor in any order.

[0153] (13) A method of adding a carrier (D) supporting component (C), component (A), component (B), and component (C) to a reactor in any order. In this case, each component (C) may be the same or different.

[0154] (14) A method of adding a carrier (D) supporting component (C), a transition metal complex formed by pre-contacting components (A) and (B), and component (C) to a reactor in any order. In this case, each component (C) may be the same or different.

[0155] (15) A method of adding a support (D) on which a transition metal complex formed by contacting component (A) and component (B) in advance is supported, and a support (D) on which component (C) is supported, to a reactor in any order.

[0156] (16) A method of adding a support (D) on which a transition metal complex formed by contacting components (A) and (B) in advance is supported, a support (D) on which component (C) is supported, and component (C) to a reactor in any order. In this case, each component (C) may be the same or different.

[0157] (17) A method of adding component (A), component (B), and component (E) to the reactor in any order.

[0158] (18) A method of adding a transition metal complex formed by contacting components (A) and (B) in advance, and component (E) to a reactor in any order.

[0159] (19) A method of adding component (A), component (B), component (C), and component (E) to the reactor in any order.

[0160] (20) A method of adding a transition metal complex formed by contacting components (A) and (B) in advance, component (C), and component (E) to a reactor in any order.

[0161] (21) A method of adding a component that has been in contact with component (C) and component (E) in advance, component (A), and component (B) to a reactor in any order.

[0162] (22) A method of adding a component that has been in contact with component (C) and component (E) in advance, and a transition metal complex formed by bringing component (A) and component (B) into contact in advance, to a reactor in any order.

[0163] (23) A method of adding a carrier (D) supporting component (E), component (A), and component (B) to a reactor in any order.

[0164] (24) A method of adding a carrier (D) supporting component (E) and a transition metal complex formed by pre-contacting components (A) and (B) to a reactor in any order.

[0165] (25) A method of adding a carrier (D) supporting components (C) and (E), component (A), and component (B) to a reactor in any order.

[0166] (26) A method of adding a carrier (D) supporting components (C) and (E) and a transition metal complex formed by pre-contacting components (A) and (B) to a reactor in any order.

[0167] (27) A method of adding a catalyst component, which is formed by contacting component (A) and component (B) in advance with component (C) and component (E) to a reactor in any order.

[0168] (28) A method of adding a catalyst component, which is a transition metal complex formed by contacting component (A) and component (B) in advance, to a reactor in any order, component (C), and component (E). In this case, each component (C) may be the same or different.

[0169] (29) A method of adding a catalyst component, which is a transition metal complex formed by contacting component (A) and component (B) in advance and then contacting component (C) in advance, and a component, which is a transition metal complex formed by contacting component (C) and component (E) in advance, to a reactor in any order. In this case, each component (C) may be the same or different.

[0170] (30) A method of adding a support (D) on which a transition metal complex formed by contacting components (A) and (B) in advance, component (C), and component (E) to a reactor in any order.

[0171] (31) A method of adding a support (D) on which a transition metal complex formed by contacting components (A) and (B) in advance is supported, and component (E) to a reactor in any order.

[0172] (32) A method of adding a support (D) on which a transition metal complex formed by pre-contacting components (A) and (B), and components (C) and (E) that have been pre-contacted, to a reactor in any order.

[0173] (33) A method of adding a catalyst component, which has been in contact with component (E) beforehand, to a reactor, which has been formed by contacting component (A) and component (B) beforehand to a transition metal complex.

[0174] (34) A method of adding a catalyst component to a reactor, which is formed by contacting component (A) and component (B) in advance with a transition metal complex, and then contacting component (C) and component (E) in any order in advance.

[0175] (35) A method of adding a catalyst component, which is formed by contacting components (A) and (B) in advance to a transition metal complex, with components (C) and (E) in any order, to a reactor in any order. In this case, each component (C) may be the same or different.

[0176] (36) A method of adding a transition metal complex formed by contacting component (A) and component (B) in advance, and a support (D) carrying component (E), to a reactor.

[0177] (37) A method of adding a transition metal complex formed by contacting component (A) and component (B) in advance, and a support (D) on which component (C) and component (E) are supported, to a reactor.

[0178] (38) A method of adding a transition metal complex formed by contacting components (A) and (B) beforehand, a support (D) carrying components (C) and (E), and component (C) to a reactor in any order. In this case, each component (C) may be the same or different.

[0179] In the present invention, component (C), which is added to the reactor in a single step, contains component (C-2) as an essential component, and may further contain at least one of components (C-1) and (C-3) as needed. When component (C) is added to the reactor in multiple stages, in at least one of the stages, component (C) may contain component (C-2) as an essential component, and may further contain at least one of components (C-1) and (C-3) as needed. In this case, one of the stages of addition may include a stage in which component (C) does not contain component (C-2), but contains at least one of components (C-1) and (C-3). Hereinafter, the present invention is preferably carried out in a temperature range of 0°C to 45°C, and also, (C-2) component In terms of aluminum atoms, in a concentration range of 0.05 mol / l to 1.5 mol / l, at least component (A), component (B), and (C-2) componentThe method is characterized by including a step of bringing the substance into contact (sometimes called a pre-contact step). The preferred lower limit of the temperature is 5°C, more preferably 10°C, and even more preferably 15°C. On the other hand, the preferred upper limit is 40°C, more preferably 37°C, and even more preferably 35°C. The preferred lower limit of the concentration is 0.10 mol / l, more preferably 0.12 mol / l, even more preferably 0.13 mol / l, and particularly preferably 0.14 mol / l. On the other hand, the preferred upper limit of the concentration is 1.2 mol / l, more preferably 1.0 mol / l, even more preferably 0.8 mol / l or 0.85 mol / l, particularly preferably 0.75 mol / l, and especially preferably 0.7 mol / l.

[0180] By meeting these conditions, it is possible to achieve excellent olefin polymer production performance with a relatively low amount of (C-2) component used.

[0181] In the present invention, in the preliminary contact step described above, the molar ratio of component (C-2) to the chromium atom equivalent (M) in component (A) [(C-2) / M] is usually 50 to 1500. The preferred lower limit is 60, more preferably 80, and particularly preferably 100. On the other hand, the preferred upper limit is 1200, more preferably 1000, even more preferably 800, particularly preferably 700, and especially preferably 600. The ratio of component (A) to component (B) will be described later.

[0182] In the present invention, by going through the process of contacting components (A) to (C) within the specific concentration and temperature ranges described above, excellent olefin polymerization performance can be achieved even with a relatively small amount of component (C-2). Specifically, the olefin polymerization performance can be improved by increasing reaction activity, low polyethylene by-product rate, high octene selectivity, and high octene production efficiency. Furthermore, when the molar ratio of component (C-2) to the chromium atom equivalent (M) in component (A) [(C-2) / M] satisfies the above-mentioned higher preferred range, the selectivity of octene tends to increase.

[0183] The above preliminary contact step may be carried out in the presence of an olefin. In that case, it is preferable that the concentration and pressure of the olefin be lower than those of the polymerization reaction step described later. However, it is generally preferable to carry out the step in the absence of an olefin.

[0184] The reason for these effects is not yet known, but the inventors speculate that the following possibilities may be at play.

[0185] The catalyst according to the present invention has the ability to yield 1-hexene and 1-octene through a metalacycle mechanism as described later. It is believed that an activation step by the action of (C-2) components is necessary for the catalyst to actually exhibit catalytic performance. This activation (sometimes referred to as pre-activation) likely requires a certain amount of contribution from multiple (C-2) components to chromium. Therefore, under low concentration conditions, a certain amount of (C-2) components is required to obtain a sufficient contribution from the (C-2) components.

[0186] However, under conditions of high (C-2) component concentrations within a specific range, activation or pre-activation may be possible even with small amounts of (C-2) component, and once activated, subsequent contact with large amounts of (C-2) component may not necessarily be an essential step.

[0187] Furthermore, according to the present invention, if the above conditions are met, the selectivity for 1-octene tends to be relatively increased. This is presumed to be because the activation by the (C-2) component forms a structure favorable for 1-octene production. Based on this idea, it can also be explained that the molar ratio of the (C-2) component in terms of Al atoms to the component (A) in terms of chromium atoms may be preferable within a specific molar ratio range.

[0188] Furthermore, when considering the importance of the above activation or pre-activation, it is also preferable to use the (C-1) component in combination with the (C-2) component. Generally, the activation or pre-activation of a chromium catalyst that gives 1-hexene or 1-octene by a metallacycle mechanism as described later is considered to involve the alkylation of chromium, and it is considered that the alkylation of chromium is promoted by using the (C-1) component together with the (C-2) component.

[0189] In the present invention, in the pre-contact step, the molar ratio [(C-1) / M] of the (C-1) component used in combination with the (C-2) component to the chromium atom conversion (M) in the component (A) is usually 3 to 500. The preferable lower limit of this molar ratio is 5, more preferably 10, and particularly preferably 20. On the other hand, it is used in an amount such that the preferable upper limit of this molar ratio is 400, more preferably 300, and even more preferably 200.

[0190] In the present invention, an olefin multimer is obtained by polymerizing an olefin in the presence of the olefin polymerization catalyst described above. The polymerization can be carried out by any of a liquid-phase reaction method such as a solution reaction or a suspension reaction, and a gas-phase reaction method. Preferably, it is a liquid-phase reaction method.

[0191] In the liquid-phase reaction method, usually, an inert hydrocarbon medium is used. Specific examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, and tetralin; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. Among them, linear saturated hydrocarbons having 5 to 7 carbon atoms such as pentane, n-hexane, and n-heptane; and alicyclic saturated hydrocarbons such as methylcyclohexane are preferable.

[0192] When producing 1-hexene or 1-octene mainly by the trimerization or tetramerization reaction of ethylene using a catalyst for olefin oligomerization, the chromium atoms in component (A) are usually 10 -12 ~10 -2 moles, preferably 10 -10 ~10 -3 moles per liter of the reaction volume. In the present invention, even when component (A) is used at a relatively low concentration, highly active olefin oligomers can be obtained.

[0193] Component (B) is used in an amount such that the molar ratio [(B) / M] with the chromium atoms (M) in component (A) is usually 0.1 to 10, preferably 0.5 to 2.

[0194] Among component (C), component (C-1) is used in an amount such that the molar ratio [(C-1) / M] between component (C-1) and the chromium atoms (M) in component (A) is usually 0.01 to 100000, preferably 0.05 to 50000.

[0195] Component (C-2) is used in an amount such that the molar ratio [(C-2) / M] between the aluminum atoms in component (C-2) and the chromium atoms (M) in component (A) is usually 50 to 2000, preferably 60 to 1500, more preferably 80 to 1200, particularly preferably 100 to 1000, and especially preferably 100 to 600. The molar ratio between the above-mentioned component (C-1) and the chromium atoms of component (A), and the molar ratio between component (C-2) and the chromium atoms of component (A) are the specifications of the amount ratio including each component used during the preliminary activation.

[0196] Component (C-3) is used in an amount such that the molar ratio [(C-3) / M] between component (C-3) and the chromium atoms (M) in component (A) is usually 1 to 10, preferably 1 to 5.

[0197] The amounts of components (C-1) to (C-3) used above include the amounts of components (C-1) to (C-3) used in the preliminary contact step described above. That is, components (C-1) to (C-3) can also be used additionally, for example, under low-concentration conditions in the presence of an olefin for a polymerization reaction, separate from the preliminary contact step. When these components (C-1) to (C-3) are used additionally, it is preferable to use them after the preliminary contact step described above.

[0198] Component (D) is used in such an amount that the ratio (g / mol) of the mass (g) of component (D) to the molars of chromium atoms (M) in component (A) is usually 100 to 10000, preferably 1000 to 5000.

[0199] When component (C) is used as component (C), component (E) is used in an amount such that the molar ratio [(E) / (C-1)] is usually 0.01 to 10, preferably 0.1 to 5. When component (C) is used as component (C), component (E) is used in an amount such that the molar ratio [(E) / (C-2)] between component (E) and aluminum atoms in component (C-2) is usually 0.001 to 2, preferably 0.005 to 1. When component (C) is used as component (C), component (E) is used in an amount such that the molar ratio [(E) / (C-3)] is usually 0.01 to 10, preferably 0.1 to 5.

[0200] The reaction temperature for polymerization is typically -50 to 200°C, preferably 0 to 170°C, more preferably 40 to 130°C, and particularly preferably 50 to 120°C. The most preferred lower limit is 60°C, and the most preferred upper limit is 100°C. The catalyst of the present invention tends to be advantageous at higher reaction temperatures because it suppresses the by-production of high molecular weight polymers such as polyethylene, and efficiently produces the target olefin polymer (especially 1-hexene and 1-octene when ethylene is reacted). Moreover, the efficiency of 1-octene production also tends to be higher. For example, the reaction to selectively produce 1-hexene and 1-octene from ethylene is known to proceed via a metallacycle mechanism. The reason why higher reaction temperatures are more effective is presumed to be that, in addition to the catalyst of the present invention having a structure that easily produces 1-hexene and 1-octene, higher temperatures are advantageous for forming a metallacycle mechanism, and the overall reaction activity increases, thus suppressing the by-production of polyethylene.

[0201] The reaction pressure is typically atmospheric pressure to 10 MPa, preferably atmospheric pressure to 6 MPa, and more preferably atmospheric pressure to 5 MPa. The lower limit is preferably 0.5 MPa, more preferably 0.9 MPa, and particularly preferably 1.5 MPa. The most preferred upper limit is 4 MPa. The catalyst of the present invention tends to produce 1-octene more efficiently at higher reaction pressures. It is presumed that 1-octene is obtained via metallacyclononane, which is formed by the coordination of two molecules of ethylene to metallacyclopentane, followed by the concerted (or sequential) insertion of ethylene. The reason why higher reaction pressures are more effective is not entirely clear, but it is presumed that the structure of the catalyst of the present invention is such that the coordination of two molecules of ethylene to metallacyclopentane becomes more favorable at higher pressures.

[0202] The multimerization reaction can be carried out using batch, semi-continuous, or continuous methods.

[0203] The polymerization reaction may be carried out with the addition of an antistatic agent. Specific examples of antistatic agents include polypropylene glycol, polypropylene glycol distearate, ethylenediamine-PEG-PPG-block copolymer, stearyldiethanolamine, lauryldiethanolamine, alkyldiethanolamide, and polyoxyalkylene (e.g., polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer (PEG-PPG-PEG)). Among these, polyoxyalkylene (e.g., PEG-PPG-PEG) is preferred. The antistatic agent is used in an amount such that the ratio (g / mol) of the mass (g) of chromium atoms (M) in component (A) to the molars is usually 100 to 10000, preferably 100 to 1000.

[0204] The polymerization reaction may be carried out by adding hydrogen. The hydrogen pressure in the reaction is usually 0.01 MPa to 5 MPa, preferably 0.01 MPa to 1 MPa. [Examples]

[0205] The present invention will be described in detail below based on synthesis examples and embodiments, but the present invention is not limited to these embodiments.

[0206] The structure of the compound obtained in the synthesis example is 270MHz 1 The determination was made using instruments such as 1H NMR (JEOL, instrument name GSH-270) and ICP emission spectrometer (Agilent Technologies, instrument name 720-ES).

[0207] The yield of the reaction product and the selectivity of 1-hexene and 1-octene were analyzed using gas chromatography (Shimadzu GC-14A, J&W Scientific DB-5 column).

[0208] [Catalytic activity] Catalytic activity was determined by dividing the mass of the reaction product obtained per unit time by the atomic weight (millimoles) of the transition metal in the transition metal catalyst component used for amplification.

[0209] [Selectivity of 1 - hexene or 1 - octene] The selectivity of 1 - hexene or 1 - octene was determined according to the following formula. S(%) = Wp / Wr×100 S(%): Selectivity of 1 - hexene or 1 - octene (mass fraction) Wr (mass): Total mass of products composed of 4 or more carbon atoms generated by the reaction Wp (mass): Mass of 1 - hexene or 1 - octene generated by the reaction

[0210] The following shows synthesis examples of amine compounds and examples of ethylene oligomerization.

[0211] (1) Synthesis examples of amine compounds [Synthesis Example 1] 2.7 mL (26.9 mmol) of N - methylpropylamine, 0.40 g (13.5 mmol) of paraformaldehyde, and 1.8 mL of diethyl ether were charged into a sufficiently dried 20 mL reactor and stirred at room temperature. After 116 hours, the solvent of the reaction solution was distilled off under reduced pressure, and the obtained crude product was distilled under reduced pressure to obtain 0.95 g (yield 45%) of an amine compound represented by the following formula (B - 1) (hereinafter referred to as compound (B - 1)). 1 H - NMR(270MHz,CD3COCD3): 2.79(2H,s), 2.31(4H,t,J = 7.3Hz), 2.16(6H,s), 1.44(4H,sext,J = 7.3Hz), 0.86(6H,t,J = 7.3Hz)ppm

[0212]

Chemical formula

[0213] [Synthesis Example 2] In a thoroughly dried 20 mL reactor, 2.8 mL (26.9 mmol) of N-methylisopropylamine, 0.40 g (13.3 mmol) of paraformaldehyde, and 1.8 mL of diethyl ether were charged and stirred at room temperature. After 118 hours, the solvent was removed from the reaction mixture under reduced pressure, and the resulting crude product was subjected to vacuum distillation to obtain 1.01 g (48% yield) of the target compound (hereinafter referred to as compound (B-2)) shown in the following formula (B-2). 1 H-NMR(270MHz,CD3COCD3):3.00(2H,s),2.97(2H,quint,J=6.8Hz),2.13(6H,s),0.94(12H,d,J=6.8Hz)ppm

[0214] [ka]

[0215] (2) Organoaluminum compounds In the following examples, the following organoaluminum compounds were used. TMA: Trimethylaluminum TEA: Triethylaluminum TIBAL: Triisobutyl Aluminum TNOA: Trin-Octyl Aluminum

[0216] (3) Ethylene increase [Example 1] In a thoroughly dried 100 mL Schlenk tube, 0.58 g (3.66 mmol) of amine compound (B-1), 1.31 g (3.39 mmol) of chromium trichloride tristetrahydrofuran, and 68 mL of dichloromethane were added and stirred under an argon atmosphere at room temperature (20-25°C) for 20 hours. After concentrating the reaction mixture under reduced pressure to approximately 1 / 10 of its original volume, 15 mL of n-hexane was added and stirred for a while, and the insoluble matter was filtered off using a glass filter. After washing with 20 mL of n-hexane, 0.93 g of the chromium compound was obtained by drying under reduced pressure.

[0217] In a 25 mL Schlenk tube, which had been thoroughly dried, 6.3 mg of the above chromium compound and 10 mL of toluene were placed under a nitrogen atmosphere. 9.95 mmol (in terms of aluminum atoms) of Albemarle's 19.6 wt% polymethylaluminoxane (hereafter sometimes referred to as MAO) toluene solution (Al concentration = 2.97 mmol / mL) was added, and the mixture was stirred at room temperature for 5 minutes to prepare the catalyst solution (aluminum concentration during this process: 0.5 mmol / mL). Next, 29.6 mL of methylcyclohexane was placed in a 100 mL autoclave that had been thoroughly purged with nitrogen, and 0.03 mmol (in terms of aluminum atoms) of triisobutylaluminum toluene solution (Al concentration = 0.1 mmol / mL) was added. Subsequently, 0.10 mL (0.0001 mmol in terms of chromium atoms) of the previously prepared catalyst solution was added, and the reaction was started by pressurizing with ethylene (0.8 MPa-G). The reaction was carried out at 60°C for 60 minutes while supplying ethylene at the same pressure, and then the reaction was stopped by adding a small amount of isopropanol. After the reaction was complete, the reaction solution was washed with 0.1 N hydrochloric acid solution and pure water, and the low-boiling point components (components with 10 or fewer carbon atoms) were separated from the high-boiling point components and polyethylene using a liquid nitrogen trap under reduced pressure, and analyzed by gas chromatography. The amount of low-boiling point components produced (components with 10 or fewer carbon atoms) was 703 mg, and the amount of polyethylene produced was 6 mg. The catalytic activity calculated from the total amount of these products was 7.2 kg-product / (mmol-Cr·hr). Among the low-boiling point components, the selectivity for 1-hexene was 50.2 mass%, the selectivity for 1-octene was 46.6 mass%, and the catalytic activity of 1-octene was 3.4 kg-product / (mmol-Cr·hr). The results are shown in Table 1.

[0218] [Examples 2 and 3] The reaction was carried out in the same manner as in Example 1, except that the amount of polymethylaluminoxane used was changed. The results are shown in Table 1.

[0219] [Examples 4-7] The reaction was carried out in the same manner as in Example 3, except that polymethylaluminoxane was added during the preparation of the catalyst solution, followed by the addition of each organoaluminum compound shown in Table 1. The results are shown in Table 1.

[0220] [Example 8] In a thoroughly dried 100 mL Schlenk tube, 0.22 g (1.39 mmol) of amine compound (B-2), 0.47 g (1.25 mmol) of chromium trichloride tristetrahydrofuran, and 24 mL of dichloromethane were added and the mixture was stirred under an argon atmosphere for 23 hours. After concentrating the reaction mixture under reduced pressure to approximately half its volume, 15 mL of n-hexane was added and the mixture was stirred for a while, and the insoluble matter was filtered off using a glass filter. After washing with 20 mL of n-hexane, the mixture was dried under reduced pressure to obtain 0.20 g of the chromium compound.

[0221] The reaction was carried out in the same manner as in Example 1, except that the above-mentioned chromium compound was used. The results are shown in Table 1.

[0222] [Comparative Example 1] The reaction was carried out in the same manner as in Example 1, except that the amount of polymethylaluminoxane used was changed as shown in Table 1. The results are shown in Table 1.

[0223] [Reference example 1] In a thoroughly dried 100 mL Schlenk tube, 0.58 g (3.66 mmol) of amine compound (B-1), 1.31 g (3.39 mmol) of chromium trichloride tristetrahydrofuran, and 68 mL of dichloromethane were added and the mixture was stirred under an argon atmosphere for 20 hours. After concentrating the reaction mixture under reduced pressure to approximately 1 / 10 of its original volume, 15 mL of n-hexane was added and the mixture was stirred for a while. The insoluble matter was filtered off using a glass filter. After washing with 20 mL of n-hexane, the mixture was dried under reduced pressure to obtain 0.93 g of the chromium compound. Toluene was added to this chromium compound to prepare a toluene solution (catalyst solution) with a chromium atom concentration of 0.001 mmol / mL.

[0224] 29.6 mL of methylcyclohexane was placed in a 100 mL autoclave that had been thoroughly purged with nitrogen, and 0.5 mmol (in terms of aluminum atoms) of polymethylaluminoxane (Tosoh Finechem MMAO-3A, ​​5.7% by mass in hexane solution) was added. Subsequently, 0.10 mL (0.0001 mmol (in terms of chromium atoms) of the previously prepared catalyst solution was added, and the reaction was started by pressurizing with ethylene (0.8 MPa-G). The reaction was carried out at 60°C for 60 minutes while supplying ethylene at the same pressure, and then the reaction was stopped by adding a small amount of isopropanol. After the reaction was complete, the reaction solution was washed with 0.1 N hydrochloric acid water and pure water, and the low-boiling point components (components with 10 or fewer carbon atoms) were separated from the high-boiling point components and polyethylene using a liquid nitrogen trap under reduced pressure, and the analysis was performed by gas chromatography. The amount of low-boiling point components (components with 10 or fewer carbon atoms) produced was 1002 mg, and the amount of polyethylene produced was 7 mg. The catalytic activity calculated from the total amount of these products was 10.3 kg-product / (mmol-Cr·hr). Among the low-boiling point components, the selectivity for 1-hexene was 51.7 mass%, the selectivity for 1-octene was 44.8 mass%, and the catalytic activity of 1-octene was 4.6 kg-product / (mmol-Cr·hr). The results are shown in Table 2.

[0225] [Reference example 2] The reaction was carried out in the same manner as in Reference Example 1, except that 0.03 mmol (in terms of aluminum atoms) of triisobutylaluminum toluene solution (Al concentration = 0.1 mmol / mL) was added to the autoclave, and the polymethylaluminoxane used was changed to Albemarle's 19.6 wt% polymethylaluminoxane toluene solution (Al concentration = 2.97 mmol / mL), with the amounts as shown in Table 2. The results are shown in Table 2.

[0226] [Comparative Example 2] The reaction was carried out in the same manner as in Reference Example 1, except that 0.03 mmol (in terms of aluminum atoms) of triisobutylaluminum toluene solution (Al concentration = 0.1 mmol / mL) was added to the autoclave, and the polymethylaluminoxane used was changed to Albemarle's 19.6 wt% polymethylaluminoxane toluene solution (Al concentration = 2.97 mmol / mL), with the amount of the solution changed. The results are shown in Table 2.

[0227] [Comparative Example 3] In a thoroughly dried 100 mL Schlenk tube, 0.22 g (1.39 mmol) of amine compound (B-2), 0.47 g (1.25 mmol) of chromium trichloride tristetrahydrofuran, and 24 mL of dichloromethane were added and the mixture was stirred under an argon atmosphere for 23 hours. After concentrating the reaction mixture under reduced pressure to approximately half its volume, 15 mL of n-hexane was added and the mixture was stirred for a while, and the insoluble matter was filtered off using a glass filter. After washing with 20 mL of n-hexane, 0.20 g of the chromium compound was obtained by drying under reduced pressure. Toluene was added to this chromium compound to prepare a toluene solution (catalyst solution) with a chromium atom concentration of 0.001 mmol / mL.

[0228] The reaction was carried out in the same manner as in Comparative Example 2, except for the use of the catalyst solution described above. The results are shown in Table 2.

[0229] [Table 1]

[0230] [Table 2]

[0231] [Example 9] The reaction was carried out in the same manner as in Example 1, except that the same polymethylaluminoxane as in Reference Example 1 (Tosoh Finechem MMAO-3A, ​​5.7% by mass hexane solution (Al concentration, 1.61 mmol / mL)) was used. The results obtained in this example, along with the results in Example 1, are shown in Table 3.

[0232] [Table 3]

[0233] [Examples 10, 11] The reaction was carried out in the same manner as in Example 2, except that polymethylaluminoxane was added during the preparation of the catalyst solution, followed by the addition of the organoaluminum compounds shown in Table 4. The results obtained in this example, along with the results from Example 2, are shown in Table 4.

[0234] [Table 4]

[0235] [Example 12] The reaction was carried out in the same manner as in Example 4, except that the amount of organoaluminum compound was changed during the preparation of the catalyst solution. The results obtained in this example, along with the results from Examples 3 to 5, are shown in Table 5.

[0236] [Table 5]

[0237] [Example 13] The reaction was carried out in the same manner as in Example 6, except that the organoaluminum compound was replaced with TNOA during the preparation of the catalyst solution. The results obtained in this example, along with the results from Examples 6 and 7, are shown in Table 6.

[0238] [Table 6]

Claims

1. A method for producing an olefin polymer, comprising carrying out an olefin polymerization reaction in the presence of an olefin polymerization catalyst containing the following components (A) to (C): A method for producing an olefin polymer, comprising the step of contacting component (A), component (B), and component (C-2) described below, such that the concentration of component (C-2) in terms of Al atoms is in the range of 0.05 to 1.5 mol / l. (A) Chromium compounds (B) Amine compounds represented by the following general formula (1) 【Chemistry 1】 (In general formula (1), R １ ~R ４ They may be the same or different from each other. This 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, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked together. Y is a carbon atom having substituents R ５ and R ６ (a structure represented by -CR ５ R ６ -). R ５ and R ６ may be the same as or different from each other, and represent 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, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. R ５ and R ６ may be linked to each other, and may also be linked to any one of R １ to R ４ . Z is 1. (C) (C-1) organometallic compound, (C-2) Organoaluminum oxy compounds, and A compound that is selected from the group consisting of (C-3) compounds that react with transition metal compounds to form ion pairs, and that contains at least the (C-2) component.

2. The method for producing an olefin polymer according to Claim 1, characterized in that the (C-2) component includes one or more selected from the group consisting of methylaluminoxane and polymethylaluminoxane.

3. The method for producing an olefin polymer according to claim 1, characterized in that the concentration of the (C-2) component on an Al atom basis is 0.12 to 0.85 mol / l.

4. A method for producing an olefin polymer according to claim 1, characterized in that the molar ratio of component (C-2) (in terms of Al atoms) to component (A) (in terms of Cr atoms) is 50 to 1500.

5. A method for producing an olefin polymer according to claim 1, comprising the following component (D) in addition to components (A) to (C). (D) A carrier for supporting at least one compound selected from the group consisting of components (A) to (C).

6. A method for producing an olefin polymer according to claim 1, wherein the polymerization reaction of an olefin is carried out in the presence of an antistatic agent.

7. A method for producing an olefin polymer according to claim 1, wherein the olefin is ethylene.

8. A method for producing an olefin polymer according to claim 1, wherein the olefin polymer is 1-octene.

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