Process for producing olefin polymers

Abstract

To provide a method that suppresses by-production of an olefin polymer and enables selective production of an olefin multimer with high activity and, particularly when using ethylene, to provide a method that enables efficient production of 1-octene (a tetramer).SOLUTION: An olefin multimerization reaction is performed in the presence of an olefin multimerization catalyst that comprises: a chromium compound (A); an amine compound (B) of general formula (1); and a compound (C) obtained by contacting a magnesium halide compound with an alcohol, which are thereafter contacted with an organic aluminum. (R1-R4 each denote a group such as a hydrocarbon group, Y is a structure represented by -CR5R6-, R5 and R6 each denote a group such as a hydrogen atom, Z is an integer of 1-10).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] α-Olefins are important compounds that are widely used industrially, for example, as raw materials for polyolefins. For example, 1-hexene and 1-octene are in high demand as raw materials for polyolefins. Industrialized methods for producing α-olefins include those that use organoaluminum or transition metal compounds as catalysts. However, industrialized methods usually produce a mixture of many types of α-olefins. For this reason, it may be difficult to respond flexibly to changes in the market conditions of each component. Therefore, a highly selective production method for the desired α-olefin is desired.

[0003] Recently, the present inventors have reported a catalyst capable of selectively producing 1-hexene by the trimerization reaction of ethylene, utilizing a transition metal complex compound having a phenoxyimine ligand (for example, Patent Document 1).

[0004] Furthermore, chromium-based catalysts using a ligand containing a phosphorus atom have been disclosed as catalysts for selectively producing 1-octene (eg, Patent Documents 2 to 4). The present applicant also discloses an olefin multimerization method using a chromium-based catalyst (Patent Document 5). [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 [Patent Document 5] International Publication No. 2019 / 009390 Summary of the Invention [Problem to be solved by the invention]

[0006] According to the study by the present inventors, many of the conventional catalysts show high efficiency and olefin selectivity, but the selectivity of α-olefins may decrease (the amount of ethylene polymer produced as a by-product may increase) depending on the reaction conditions. Therefore, it is desirable to prepare catalysts and olefin polymerization methods that have high selectivity to α-olefins under various reaction conditions. Preferably, a method that has high selectivity to 1-octene is desired.

[0007] Like 1-hexene, 1-octene is an important component of polyolefin feedstocks, especially for the production of high-performance polyolefins, and may also be important as a feedstock for lubricants.

[0008] The present invention has been made in view of the above-mentioned problems. That is, an object of the present invention is to provide a method for producing olefin polymers having excellent activity, and particularly high selectivity and / or production efficiency of 1-octene. [Means for solving the problem]

[0009] As a result of intensive research by the present inventors to solve the above problems, they found that a catalyst containing a specific transition metal compound, an amine compound having a specific structure, and a cocatalyst prepared by a specific method has excellent high activity and / or high 1-octene selectivity, that an olefin polymerization reaction can be suitably carried out in the presence of this catalyst, and that in particular, when ethylene is used as the olefin, 1-octene, which is a tetramer of ethylene, can be obtained with high activity, and thus completed the present invention. That is, the present invention is characterized by the following features.

[0010] [1] A process for producing olefin polymers, comprising carrying out an olefin polymerization reaction in the presence of an olefin polymerization catalyst comprising the following components (A) to (C): (A) Chromium compounds (B) An amine compound represented by the following general formula (1):

[0011] [ka]

[0012] (In general formula (1), R 1 ~R 4 may be the same or different 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 to each other.

[0013] Y is a substituent R 5 and R 6 Carbon atom with (-CR 5 R 6 R 5 and R 6 may be the same or different and each 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; R 5 and R 6 may be linked to each other, and R 1 ~R 4 may be linked to any of the following: Z represents an integer from 1 to 10.

[0014] (C) A component obtained by contacting a magnesium halide with an alcohol having 1 to 20 carbon atoms and then contacting the resulting mixture with an organoaluminum compound represented by the following general formula (α):

[0015] [ka]

[0016] (In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom or a hydrogen atom, and n is a real number of 1 to 3. When there are multiple Rs, each R may be the same or different, and when there are multiple Xs, each X may be the same or different.)

[0017] [2] In the general formula (1), R 1 is R 3 and R 4 It is not connected to R 2 is R 3 and R 4 The method for producing an olefin multimer according to [1], wherein an amine compound (B) that is not linked to

[0018] [3] The method for producing an olefin multimer according to [1], wherein an amine compound (B) in which Z is an integer of 1 to 3 in the general formula (1) is used. [4] The method for producing an olefin multimer according to [1], wherein an amine compound (B) in which Z is 1 in the general formula (1) is used.

[0019] [5] The method for producing olefin polymers according to [1], wherein the catalyst for olefin polymerization contains the following component (D) in addition to the components (A) to (C): (D) A support for supporting at least one compound selected from the group consisting of components (A) to (C).

[0020] [6] The method for producing an olefin polymer according to [1], wherein an olefin polymerization reaction is carried out in the presence of an antistatic agent. [7] The method for producing an olefin multimer according to [1], wherein the olefin is ethylene. [8] The method for producing an olefin multimer according to [1], wherein the olefin multimer is 1-octene. Effect of the Invention

[0021] The present invention can provide a method for producing olefin polymers in the presence of an olefin polymerization catalyst which has excellent activity even at a low reaction temperature, and in particular has high selectivity and / or production efficiency for 1-octene. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto. In the present invention, the oligomerization of an olefin means converting an olefin into a dimer to a decamer, and preferably into a trimer to a tetramer.

[0023] <Chromium compounds (A)> The chromium compound (A) used in the present invention is usually an inorganic salt, an organic salt or a metal-organic complex of chromium. Specific examples of the chromium compound (A) include chromium chloride (III), chromium chloride (II), chromium bromide (III), chromium bromide (II), chromium iodide (III), chromium iodide (II), chromium fluoride (III), chromium trichloride tristetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetylacetonate, chromium (III) trifluoroacetylacetonate, and chromium (III) hexafluoroacetylacetonate. However, the chromium compound (A) is not limited to these. Among these, trivalent chromium compounds are preferred. Also preferred are chromium compounds containing halogen atoms.

[0024] <Amine Compound (B)> The amine compound (B) used in the present invention is represented by the following general formula (1).

[0025] [ka]

[0026] In the general formula (1), R 1 ~R 4may be the same or different, and each 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 to each other. More specifically, R 1 ~R 4 is preferably a hydrogen atom, a halogen atom, a hydrocarbon group, a residue of a heterocyclic compound, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester group, an amido group, an imido group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group, a carboxyl group, a sulfo group, a mercapto group, an aluminum-containing group, or a hydroxy group.

[0027] R 1 ~R 4 When at least one of is a halogen atom, specific examples thereof include fluorine, chlorine, bromine, and iodine. R 1 ~R 4When at least one of the groups is a hydrocarbon group, specific examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, 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, preferably 2 to 20, carbon atoms, such as vinyl, allyl, and isopropenyl; linear or branched alkynyl groups having 2 to 30, preferably 2 to 20, carbon atoms, such as ethynyl and propargyl; cyclopropyl, cyclobutyl, cyclopentyl, and the like. cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentadienyl, indenyl, fluorenyl, etc.; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc.; alkyl-substituted aryl groups such as tolyl, isopropylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, etc.; and alkylidene groups having 1 to 30 carbon atoms, preferably 5 to 10 carbon atoms, such as benzylidene, methylidene, ethylidene, etc.

[0028] R 1 ~R 4 When at least one of the groups is a hydrocarbon group, the hydrogen atom of the hydrocarbon group may be substituted with a halogen. Specific examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as trifluoromethyl, pentafluorophenyl, and chlorophenyl.

[0029] R 1 ~R 4 When at least one of is a hydrocarbon group, the hydrogen atom of the hydrocarbon group may be substituted with another hydrocarbon group, specific examples of which include aryl-substituted alkyl groups such as benzyl, cumyl, diphenylethyl, and trityl.

[0030] R 1 ~R4 When at least one of the above is a hydrocarbon group, the hydrocarbon group may further include a heterocyclic compound residue; an oxygen-containing group such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, or a carboxylic anhydride group; a nitrogen-containing group such as an amino group, an imino group, an amido group, an imido group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, or an amino group that has become an ammonium salt; a boranediyl group, a boranetriyl group, The compound may have a boron-containing group such as a diboranyl group; a sulfur-containing group such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate group, an isothiocyanate group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, or a sulfenyl group; a phosphorus-containing group such as a phosphido group, a phosphoryl group, a thiophosphoryl group, or a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Among these, preferred are linear or branched alkyl groups having 1 to 30, preferably 1 to 20, more preferably 1 to 10, and particularly preferably 2 to 10, carbon atoms, 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, preferably 6 to 20, carbon atoms, 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, preferably 1 to 20, carbon atoms, alkoxy groups, or amino groups, or aryl groups or aryloxy groups having 6 to 30, preferably 6 to 20, carbon atoms.

[0031] R 1 ~R 4When at least one of is an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group and / or a phosphorus-containing group, specific examples of such groups include those exemplified above as the substituents that may be contained in the hydrocarbon group. Among them, the oxygen-containing group, the nitrogen-containing group and the sulfur-containing group are preferred, and the oxygen-containing group and the nitrogen-containing group are more preferred.

[0032] The nitrogen-containing group may be, for example, an amide group, an amino group, an imido group, or an imino group. Specific examples of the amide group include acetamide, N-methylacetamide, and N-methylbenzamide. Specific examples of the amino group include dimethylamino, ethylmethylamino, and diphenylamino. Specific examples of the imido group include acetimide and benzimide. Specific examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

[0033] The sulfur-containing group includes, for example, an alkylthio group, an arylthio group, a thioester group, a sulfone ester group, and a sulfonamide group. Specific examples of the alkylthio group include methylthio and ethylthio. Specific examples of the arylthio group include phenylthio, methylphenylthio, and naphthylthio. Specific examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl. Specific examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Specific examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

[0034] R 1 ~R 4When at least one of the above is a heterocyclic compound residue, specific examples of the heterocyclic compound residue include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, as well as groups in which these heterocyclic compound residues are further substituted with a substituent having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as an alkyl group or an alkoxy group.

[0035] R 1 ~R 4 When at least one of the groups is a boron-containing group, specific examples of the boron-containing group include those exemplified above as the substituents that may be contained in the hydrocarbon group. In addition, alkyl group-substituted boron, aryl group-substituted boron, boron halide, and alkyl group-substituted boron halide groups are also included. Examples of alkyl group-substituted boron groups include (Et)2B-, (iPr)2B-, (iBu)2B-, (Et)3B, (iPr)3B, and (iBu)3B. Examples of aryl group-substituted boron groups include (C6H5)2B-, (C6H5)3B, (C6F5)3B, and (3,5-(CF3)2C6H3)3B. Examples of boron halide groups include BCl2- and BCl3. Examples of alkyl-substituted boron halide groups include (Et)BCl-, (iBu)BCl-, and (C6H5)2BCl. Here, Et is an ethyl group, iPr is an isopropyl group, and iBu is an isobutyl group. Tri-substituted boron may be in a coordinate bond state.

[0036] R 1 ~R 4When at least one of the above is an aluminum-containing group, specific examples of the aluminum-containing group include alkyl group-substituted aluminum, aryl group-substituted aluminum, aluminum halide, and alkyl group-substituted aluminum halide. Examples of alkyl group-substituted aluminum groups include (Et)2Al-, (iPr)2Al-, (iBu)2Al-, (Et)3Al, (iPr)3Al, and (iBu)3Al. Examples of aryl group-substituted aluminum groups include (C6H5)2Al-. Examples of aluminum halide groups include AlCl2- and AlCl3. Examples of alkyl group-substituted aluminum halide groups include (Et)AlCl- and (iBu)AlCl-. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group. In addition, tri-substituted aluminum may be in a coordinate bond state.

[0037] R 1 ~R 4 When at least one of the above is a silicon-containing group, specific examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Examples of the hydrocarbon-substituted silyl group 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. Examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

[0038] R 1 ~R 4 When at least one of the groups is a germanium-containing group and / or a tin-containing group, specific examples of such groups include those in which the silicon of the silicon-containing groups exemplified above is substituted with germanium or tin.

[0039] In the general formula (1), Y is a substituent R 5 , R 6 Carbon atom with (-CR 5 R 6 R 5 , R 6 may be the same or different, and each 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. Examples of each of these groups are R 1 ~R 4 This is similar to the example in R. 5 and R 6 may be linked to each other, and R 1 ~R 4 may be linked to

[0040] In general formula (1), Z represents an integer of 1 to 10. In some cases, Z is preferably an integer of 2 to 10. On the other hand, Z is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1. When Z is 2 or more, multiple Y's may be the same or different from each other.

[0041] In the general formula (1), R 1 ~R 4 Two or more of R may be linked to each other. 1 is R 3 and R 4 It is not connected to R 2 is R 3 and R 4 Such preferred amine compounds not linked to a specific group include, for example, the amine compounds of three embodiments represented by the following general formulas (1A) to (1C).

[0042] [ka] In the general formula (1A), the definition of each group is the same as that of the general formula (1). However, R 1 ~R 4 is not linked to any group.)

[0043] [ka] In the general formula (1B), the definition of each group is the same as that of the general formula (1). However, R 1 and R 2 is concatenated, R 3 and R 4 are connected.)

[0044] [ka] In the general formula (1C), the definition of each group is the same as that of the general formula (1). However, R 1 and R 2 is not linked to any group, and R 3 and R 4 are connected.)

[0045] In the general formula (1), R 1 ~R 4 may be a linear or branched group or a group containing a cyclic structure, R 1 ~R 4 Two or more of the groups may be linked together to form a ring structure. For example, R 1 and R 3 , R 2 and R 4 When either one of them is linked (bonded), the number of bonds is preferably 4 or more, and R 1 and R 3 , R 2 and R 4 When both are linked (bonded), the number of bonds is preferably 3 or more. However, as represented by general formulas (1A) to (1C), 1 is R 3 and R 4 It is not connected to R 2 is R 3 and R4 It is preferable that R is not linked to 1 ~R 4 Each of R preferably does not have a substituent having a cyclic structure, i.e., is a linear or branched group. 1 ~R 4 When R is a linear or branched group (for example, a linear or branched hydrocarbon group which may have a substituent), the number of carbon atoms in the linear or branched group is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10. 1 ~R 4 The total number of carbon atoms in R is preferably 8 or more. 1 ~R 4 is preferably linear.

[0046] R 1 ~R 4 When is any one of the above preferred groups, the reaction activity of the olefin tends to be higher, and it tends to be easier to produce α-olefins having a relatively low boiling point, which are dimers to pentamers (preferably trimers to tetramers) of olefins, more efficiently. Here, when the raw material is ethylene, the trimers to tetramers correspond to hexene and octene. That is, it tends to be suitable for producing olefins having 10 or less carbon atoms.

[0047] When the olefin multimerization catalyst containing the amine compound (B) of the present invention is used, the ratio of the amount of olefin multimers, i.e., olefin dimers to pentamers (preferably trimers to tetramers) produced to the amount of all products produced tends to be high. Specifically, this ratio is desirably 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 ratio of the amount of dimers to pentamers (preferably trimers to tetramers) produced is high, the types of multimers produced tend to be fewer. In addition, the difference in boiling points between the components is relatively large, making it easy to separate them by distillation (for example, the boiling point of 1-hexene is 63°C, and the boiling point of 1-octene is 122 to 123°C). As a result, it is thought that the production cost can be suppressed and it is easy to respond to the influence of market conditions.

[0048] On the other hand, R 1 and R 2 and / or R 3 and R 4 It is also preferable that R have the same structure. In this case, the selectivity for the tetramer of ethylene, i.e., 1-octene, may be increased. For example, among the amine compounds (B) used in the examples described below, R 1 ~R 4 The amine compounds (B-1) and (B-11) in which all of are methyl groups correspond to this case.

[0049] R 1 and R 2 are linked together to form a ring structure, and / or R 3 and R 4 When R is linked to form a ring structure, 1 and R 2 and / or R 3 and R 4 In this case, the "same structure" means that the ring structure is symmetrical when viewed from N, that is, the R 1 Side (or R 3 side) structure and R 2 Side (or R 4 This means that the structure of the ethylene tetramer (R side) is the same as that of the ethylene tetramer (R side). In this case, the selectivity of 1-octene may be increased. For example, among the amine compounds (B) used in the examples described later, 1 and R 2 is connected and R 3 and R 4 and R 1 and R 2 is connected and R 3 and R 4 The amine compound (B-10) in which the following are linked to form a 6-membered ring corresponds to this case.

[0050] In addition, R 1 and R 2 If are connected, and / or R 3 and R4 In the present invention, when R 1 and R 2 The number of carbon atoms in each of (and / or R 3 and R 4 The number of carbon atoms in each of the amine compounds (B) is defined as a boundary at a point where the number of carbon atoms constituting the linking structure is half. For example, among the amine compounds (B) used in the examples described later, R 1 ~R 4 Each of the carbon atoms of each of the amine compounds (B-3) is 3. 1 and R 3 The number of carbon atoms in each of these is 3.5, R 2 and R 4 Each of these has 2.5 carbon atoms.

[0051] R 1 and R 2 and / or R 3 and R 4 It is not entirely clear why the effect is superior when R 1 ~R 4 is considered to be located relatively close to the chromium atom of the central metal, chromium compound (A), so R in the above structure 1 ~R 4 It is speculated that the steric influence of the ethylene moiety may appropriately control the ease of ethylene coordination to the metallacycle and the activation energy of the insertion reaction.

[0052] In the present invention, one of the indices for comprehensively judging the performance of an olefin multimerization catalyst is the catalytic activity of 1-octene described in the examples below. The catalytic activity of 1-octene is the amount of 1-octene produced per unit time and per unit amount of catalyst, that is, the efficiency of 1-octene production. Note that this efficiency of 1-octene production is an index different from the selectivity of 1-octene.

[0053] Furthermore, in each of the preferred embodiments described above, not only is the production efficiency of ethylene trimers (1-hexene) and tetramers (1-octene) improved, but it is also preferable in terms of the reaction activity of ethylene and the efficient production of 1-octene.

[0054] In the present invention, when ethylene polymers are produced, 1-hexene and 1-octene are the main products. These products can be relatively easily separated by distillation. Therefore, the production efficiency of 1-octene described above is considered to be an important indicator from an industrial viewpoint. In particular, when a production facility for co-producing 1-hexene and 1-octene is used, this may be an important item.

[0055] Specific examples of the amine compound (B) are shown below, however, the amine compound (B) is not limited thereto.

[0056] [ka]

[0057] [ka]

[0058] In the above compounds, Me is a methyl group, Et is an ethyl group, n Pr is a normal propyl group. i Pr is an isopropyl group, and Ph is a phenyl group. The number of carbon atoms between N and N in each of the above compounds is 1 or 2, but compounds in which the number of carbon atoms between N and N is changed to 3 or more can also be used.

[0059] A commercially available amine compound may be used as the amine compound (B). When synthesizing the amine compound (B), for example, a specific amine compound can be alkylated or arylated by a general method to obtain the amine compound (B). The amine compound (B) can also be obtained by reducing an imine compound by a general method. In the present invention, multiple types of amine compounds (B) can also be used in combination.

[0060] As described above, the use of the olefin multimerization catalyst containing the amine compound (B) of the present invention tends to efficiently produce 1-octene. For example, the proportion of 1-octene in the produced olefin multimers having 10 or less carbon atoms is desirably 40% by weight or 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.

[0061] The amine compound (B) and the chromium compound (A) may be added separately to the reactor. However, it is preferable to add a transition metal complex formed in advance by reacting the amine compound (B) with the chromium compound (A) to the reactor. For example, the transition metal complex can be obtained by dissolving the amine compound (B) in a solvent, mixing this with the chromium compound (A), and stirring the mixture under an inert gas atmosphere such as nitrogen or argon at -78°C to room temperature or under reflux for about 5 minutes to 48 hours.

[0062] The solvent used in synthesizing the transition metal complex is not particularly limited. Any common solvent known to be usable in such a reaction can be used. Specific examples of the solvent include polar solvents such as ether and tetrahydrofuran; hydrocarbon solvents such as toluene, methylcyclohexane, and heptane; and halogenated hydrocarbon solvents such as methylene chloride.

[0063] The transition metal complex is obtained in a state of being dissolved or suspended in a solvent. This solution or suspension of the transition metal complex may be used as it is, or the transition metal complex may be isolated once and then dissolved or suspended again in a solvent before use.

[0064] <Compound (C)> In the process for producing an olefin polymer of the present invention, the compound (C) obtained by the method described below is used in combination with the above-mentioned chromium compound (A) and amine compound (B).

[0065] Compound (C) is a component obtained by contacting magnesium halide with an alcohol having 1 to 20 carbon atoms, and then contacting the resulting mixture with an organoaluminum compound represented by the following general formula (α).

[0066] [ka] (In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom or a hydrogen atom, and n is a real number of 1 to 3. When there are multiple Rs, each R may be the same or different, and when there are multiple Xs, each X may be the same or different.)

[0067] The method for obtaining the compound (C) of the present invention will be described below. The compound (C) of the present invention can be obtained by contacting a magnesium halide with an alcohol having 1 to 20 carbon atoms (hereinafter, this contact may be referred to as the "first contact"), and then contacting the organoaluminum compound represented by the general formula (α) (hereinafter, this contact may be referred to as the "second contact"). The method is described in more detail below, but is not limited to this method.

[0068] As the magnesium halide, magnesium chloride and magnesium bromide are preferably used. Such magnesium halides may be used as they are as commercially available products or may be prepared separately from alkyl magnesium, and in the latter case, the magnesium halide may be used without isolation.

[0069] Examples of the alcohol having 1 to 20 carbon atoms include alcohols corresponding to the alkoxy group having 1 to 20 carbon atoms. For example, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-pentanol, i-amyl alcohol, n-hexanol, n-heptanol, 2-ethylhexanol, n-octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethanol, cumyl alcohol, i-propylbenzyl alcohol, and the like; halogen-containing alcohols such as trichloromethanol, trichloroethanol, and trichlorohexanol; and lower alkyl group-containing phenols such as phenol, cresol, ethylphenol, nonylphenol, cumylphenol, and naphthol. Among these, methanol, ethanol, propanol, butanol, pentanol, i-amyl alcohol, hexanol, heptanol, 2-ethylhexanol, octanol, and dodecanol are preferred.

[0070] When magnesium halide is contacted with an alcohol having 1 to 20 carbon atoms, the contact may be carried out in the presence of a solvent. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene dichloride, chlorobenzene, and dichloromethane; and mixtures of these.

[0071] The contact is usually preferably carried out under heating. When heating, the temperature can be selected as long as it is up to the boiling point of the solvent used. The heating time depends on the temperature and the ratio of the magnesium compound to the alcohol, but for example, when the molar ratio of magnesium compound / alcohol is about 1 / 3 and n-decane is used as the solvent, the solution can be obtained in about 4 hours under the condition of a heating temperature of 130°C. In addition, it is preferable to use a stirring device when preparing the solution.

[0072] The contact product of magnesium halide and alcohol having 1 to 20 carbon atoms thus prepared (hereinafter, sometimes referred to as "first contact product") may be used after removing the solvent used during the contact, or may be used without distilling off the solvent. Usually, it is used in the next step without distilling off the solvent.

[0073] The first contact product obtained by the above method is then contacted (=second contact) with an organoaluminum compound represented by the following general formula (α).

[0074] [ka]

[0075] In the general formula (α), R is a hydrocarbon group having 1 to 20 carbon atoms, specifically Examples of the organoaluminum compound include methyl, ethyl, propyl, butyl, hexyl, octyl, and decyl groups. X represents a halogen atom such as a chlorine atom or a bromine atom, or a hydrogen atom. n represents a real number of 1 to 3, and is preferably 2 or 3. When there are a plurality of Rs, each R may be the same or different, and when there are a plurality of Xs, each X may be the same or different. Specific examples of the organoaluminum compound include the following compounds. Examples of organoaluminum compounds that satisfy these requirements include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethyl ... Examples of the aluminum sesquihalides include alkylaluminum sesquihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide, and other alkylaluminum dihalides; and alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride. Of these, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and diisobutylaluminum hydride are preferred.

[0076] The contact method in the second contact is not particularly limited, but is usually carried out by adding the organoaluminum compound represented by the general formula (α) to the first contact product under stirring. In this case, the first contact product may be diluted with a solvent, and as such a solvent, any hydrocarbon that does not have active hydrogen can be used without particular limitation, but it is usually efficient to use the solvent used in the first contact as it is as the solvent for the second contact without distilling it off. The organoaluminum compound to be added to the first contact product may be diluted in a solvent or may be added without diluting it in a solvent, but is usually used in a form diluted in an aliphatic saturated hydrocarbon such as n-decane or n-hexane, or an aromatic hydrocarbon solvent such as toluene or xylene. When the organoaluminum compound is added, it is usually added to the first contact product over a period of 5 minutes to 5 hours. If the heat removal capacity in the contact system is sufficient, it can be completed in a short period of time, while if the capacity is insufficient, it is preferable to add it over a long period of time. The organoaluminum compound may be added all at once, or may be added in several divided portions. When split additions are made, the organoaluminum compound in each addition may be the same or different, and the temperature of the first contact product in each addition may be the same or different.

[0077] The amount of the organoaluminum compound represented by the general formula (α) used in the second contact is usually 0.1 to 50 times by mole, preferably 0.5 to 30 times by mole, more preferably 1.0 to 20 times by mole, further preferably 1.5 to 15 times by mole, and particularly preferably 2.0 to 10 times by mole, of aluminum atoms relative to the amount of magnesium atoms in the first contact product.

[0078] Preferred examples of the method and conditions for the second contact are described below. When the first contact product is contacted with the organoaluminum compound represented by the general formula (α), for example, means by reaction of two liquid substances such as contacting a hydrocarbon-diluted solution of a magnesium compound with an organoaluminum compound diluted in a hydrocarbon solvent is preferred. The amount of the organoaluminum compound used at that time varies depending on its type and contact conditions, but it is preferably usually 2 to 10 moles per 1 mole of the magnesium compound. From the viewpoint of the reactivity of the resulting compound (C) and also from the viewpoints of the shape and particle size of the solid product that may be generated in this step, the contact of these components is preferably carried out under mild conditions. For example, when the magnesium compound and the organoaluminum compound are contacted and mixed in a liquid state with each other to form a solid product by mutual reaction, after mixing both at a low temperature such that a rapid change does not occur due to their contact, the temperature is raised and the reaction is gradually allowed to proceed. According to this method, when it becomes solid, it is easy to obtain a granular or spherical solid product with a relatively narrow particle size distribution, and it is easy to obtain a component having a homogeneous reactivity.

[0079] The above compound (C) may be in a solid state, and in that case, it can also be used as a carrier for the olefin polymerization catalyst of the present invention. When the above compound (C) is in a solid state, it preferably contains both a magnesium atom, an aluminum atom and an alkoxy group having 1 to 20 carbon atoms, is insoluble in a hydrocarbon solvent, and has an average particle size of 3 to 80 μm. The molar ratio (Mg / Al) of the magnesium atom to the aluminum atom in the carrier component is in the range of 1.0 < Mg / Al ≦ 300.0, and the molar ratio (OR / Al) of the alkoxy group to the aluminum atom is preferably 0.05 < OR / Al < 2.0.

[0080] Note that being insoluble in a hydrocarbon solvent means that the dissolved amount of the magnesium atom is 0.5% by weight or less even when stirred in at least one solvent selected from hexane, decane and toluene for 1 minute to 1 hour in the temperature range from 0 °C to the inherent boiling point of the solvent under normal pressure, and that the dissolved amounts of the aluminum atom and the alkoxy group are each 1% by weight or less even when stirred in at least one solvent selected from hexane, decane and toluene for 1 minute to 1 hour at room temperature under normal pressure.

[0081] The compound (C) of the present invention may contain other metal atoms and other organic groups in addition to the above-mentioned magnesium, aluminum, and alkoxy groups. Preferably, it does not contain Group 4 transition metal atoms such as titanium, zirconium, and hafnium. If such components are contained, the olefin polymer may be replicated during the olefin polymerization reaction described below.

[0082] When the compound (C) is a solid component as described above, the total amount of magnesium atoms, aluminum atoms, and alkoxy groups having 1 to 20 carbon atoms is usually in the range of 10 to 90% by weight, and is preferably in the range of 15 to 60% by weight, particularly preferably in the range of 20 to 40% by weight, from the viewpoint of the olefin polymerization activity of the polymerization catalyst containing the carrier component described later and the powder properties of the polyolefin obtained as a result of polymerization. Among the components other than magnesium atoms, aluminum atoms, and alkoxy groups having 1 to 20 carbon atoms in the carrier component, halogen atoms account for the largest weight. When the halogen atoms are chlorine atoms, the amount of chlorine atoms in the carrier component reaches about 20% by weight in the smallest case and about 80% by weight in the large case. In addition, the compound (C) may also contain alcohols corresponding to alkoxy groups having 1 to 20 carbon atoms, hydrocarbon compounds used as dispersion media (sometimes called solvents), etc.

[0083] When the compound (C) is a solid as described above, the alkoxy group having 1 to 20 carbon atoms therein is a group derived from the alcohol having 1 to 20 carbon atoms used as a raw material component during the preparation of the carrier component described later. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentoxy group, i-amyloxy group, n-hexoxy group, n-heptoxy group, 2-ethylhexoxy group, n-octoxy group, dodecoxy group, octadecyloxy group, oleoyloxy group, benzyloxy group, phenylethoxy group, cumyloxy group, i-propylbenzyloxy group, etc., halogen-containing alkoxy groups such as trichloromethoxy group, trichloroethoxy group, trichlorohexoxy group, and lower alkyl group-containing phenoxy groups such as phenoxy group, cresoxy group, ethylphenoxy group, nonylphenoxy group, cumylphenoxy group, naphthoxy group, etc. Among these, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, i-amyloxy group, hexoxy group, heptoxy group, 2-ethylhexoxy group, octoxy group, dodecoxy group are preferred.

[0084] When the compound (C) is a solid as described above, the molar ratio (Mg / Al) of magnesium atoms to aluminum atoms therein is usually in the range of 1.0 < Mg / Al ≦ 300.0, and from the viewpoints of olefin polymerization activity and the powder properties of the produced polyolefin, it is preferably in the range of 30.0 < Mg / Al ≦ 250.0, more preferably in the range of 30.0 < Mg / Al ≦ 200.0, still more preferably in the range of 35.0 < Mg / Al ≦ 200.0, and particularly preferably in the range of 40.0 < Mg / Al ≦ 150.0. The molar ratio (OR / Al) of the alkoxy group to aluminum atoms is usually 0.05 < OR / Al < 2.0, and from the point of further enhancing the olefin polymerization activity, it is preferably in the range of 0.1 ≦ OR / Al < 1.8, and particularly preferably in the range of 0.2 ≦ OR / Al < 1.0.

[0085] In the case of the solid compound (C) as described above, the average particle size is preferably 3 to 80 μm, more preferably 3 to 50 μm, since the by-produced olefin polymer described later tends to be granular and may not adhere to the inner wall of the reactor, or to piping or a cooling device during the reaction process. The size of the microcrystals is usually 3 to 80 (Å), preferably 10 to 75 (Å), more preferably 12 to 70 (Å), even more preferably 15 to 60 (Å), and particularly preferably 20 to 55 (Å).

[0086] In addition to the above-mentioned compounds, the following compounds can be used in combination as the compound (C) used in the present invention, so long as the purpose of the present invention is not adversely affected. It is at least one compound selected from the group consisting of organometallic compounds (C-1), organoaluminum oxy compounds (C-2), and compounds (C-3) that react with transition metal compounds to form ion pairs. These compounds (C-1) to (C-3) are explained below. In the following description, compound (C-3) is referred to as "ionizing ionic compound (C-3)".

[0087] [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. These compounds also include the compounds represented by the general formula (α) above. In the present invention, the organometallic compound (C-1) does not include the organoaluminum oxy compound (C-2) described below.

[0088] (C-1a): General formula R a m Al(OR b ) n H p X q (In the formula, R a and R brepresents 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), and is an organoaluminum compound represented by the formula.

[0089] (C-1b): General formula M 2 AlR a 4 (wherein 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), and is a complex alkyl compound of a Group 1 metal of the periodic table and aluminum.

[0090] (C-1c): General formula R a R b M 3 (wherein R a and R b represent hydrocarbon groups 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), and is a dialkyl compound of a Group 2 or 12 metal of the periodic table.

[0091] Examples of the organoaluminum compound (C-1a) include an organoaluminum compound represented by the general formula R a m Al(OR b ) 3-m (wherein R a and R b represent hydrocarbon groups 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 where 1.5 ≦ m ≦ 3). An organoaluminum compound represented by the general formula R a m AlX 3-m (wherein 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 where 0 < m < 3). An organoaluminum compound represented by the general formula R a m AlH 3-m (wherein R arepresents 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 (wherein R a and R b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, 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.

[0092] Specific examples of the organoaluminum compound (C-1a) include tri(n-alkyl)aluminums such as trimethylaluminum, triethylaluminum, tri(n-butyl)aluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tri-branched chain alkylaluminums 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, tri(2-ethylhexyl)aluminum; tricycloalkylaluminums such as tricyclohexylaluminum, tricyclooctylaluminum; triarylaluminums such as triphenylaluminum, tritolylaluminum; dialkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride; (iC4H9) x Al y (C5H 10 ) z(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; a 2.5 Al(OR b ) 0.5 (In the formula, R a and R bare the same or different hydrocarbon groups having 1 to 15, preferably 1 to 4, carbon atoms.) partially alkoxylated alkylaluminum having an average composition represented by the formula: dialkylaluminum aryloxides 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) and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum sesquichloride, etc. partially halogenated alkylaluminums such as alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; dialkylaluminum hydrides, such as diethylaluminum hydride, dibutylaluminum hydride; partially hydrogenated alkylaluminums such as alkylaluminum dihydrides, such as ethylaluminum dihydride, propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminums, such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide.

[0093] Compounds similar to the organoaluminum compound (C-1a), for example, organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms, such as (C2H5)2AlN(C2H5)Al(C2H5)2, can also be used.

[0094] Specific examples of the compound (C-1b) include LiAl(C2H5)4, LiAl(C7H 15 )4 are examples. Specific examples of the compound (C-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, and butylethylmagnesium.

[0095] Specific examples of the organometallic compound (C-1) other than the compounds (C-1a) to (C-1c) explained above include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, butyl magnesium bromide, and butyl magnesium chloride.

[0096] It is also possible to use a compound which forms an organoaluminum compound in the polymerization reaction system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium.

[0097] The organometallic compounds (C-1) described above can be used alone or in combination of two or more. Among the organometallic compounds (C-1) described above, the organoaluminum compounds (C-1a) are particularly preferred.

[0098] [Organoaluminum oxy compound (C-2)] The organoaluminum oxy compound (C-2) may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution.

[0099] (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a suspension containing a compound containing adsorbed water or a salt containing water of crystallization (e.g., magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium chloride hydrate) and a hydrocarbon solvent, thereby reacting the adsorbed water or the water of crystallization with the organoaluminum compound.

[0100] (2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a solvent such as benzene, toluene, ethyl ether or tetrahydrofuran.

[0101] (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a solvent such as decane, benzene or toluene.

[0102] The aluminoxane may contain a small amount of an organometallic component. The solvent and the unreacted organoaluminum compound may be distilled off from the aluminoxane solution recovered in each of the above methods, and the aluminoxane may be further redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0103] Specific examples of the organoaluminum compound used for producing aluminoxane are the same as those of the organoaluminum compound (C-1a) described above. The organoaluminum compound can be used alone or in combination of two or more. Among them, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

[0104] Examples of the solvent used for producing aluminoxane include hydrocarbon solvents and ether solvents. Specific examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel; and aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbon halides (particularly chlorinated or brominated compounds). Specific examples of the ether solvent include ethyl ether and tetrahydrofuran. Among these, aromatic hydrocarbons and aliphatic hydrocarbons are preferred. When using an organoaluminum oxy compound that is insoluble or poorly soluble in benzene, the amount of Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, and more preferably 2% or less in terms of Al atom.

[0105] As the organoaluminum oxy compound (C-2), a boron-containing organoaluminum oxy compound represented by the following general formula (5) can also be used.

[0106] [ka] (In general formula (5), R 7 R represents a hydrocarbon group having 1 to 10 carbon atoms. 8 represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different.

[0107] The boron-containing organoaluminum oxy compound represented by the general formula (5) can be produced, for example, by reacting an alkylboronic acid represented by the following 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.

[0108] [ka] (In general formula (6), R 7 is R in the above general formula (5). 7 (represents the same group as

[0109] 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 them, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These alkylboronic acids can be used alone or in combination of two or more.

[0110] Specific examples of the organoaluminum compound to be reacted with alkylboronic acid are the same as the specific examples of the organoaluminum compound (C-1a) described above. The organoaluminum compound can be used alone or in combination of two or more. Among them, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are more preferred. The organoaluminum oxy compounds (C-2) explained above can be used singly or in combination of two or more.

[0111] [Ionized ionic compounds (C-3)] The ionizing ionic compound (C-3) is a compound that reacts with a transition metal compound to form an ion pair. Therefore, at least a compound that has the property of forming an ion pair when contacted with a transition metal compound corresponds to this ionizing ionic compound (C-3).

[0112] Examples of the ionized ionic compound (C-3) that can be used include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Patent No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds can also be used.

[0113] The Lewis acid may be, for example, a compound represented by the general formula BR3 (R is fluorine or a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group). Specific examples thereof include trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.

[0114] Specific examples of the ionic compound include compounds represented by the following general formula (7).

[0115] [ka]

[0116] In general formula (7), R 9+ For example, H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. 10 ~R 13 are the same or different organic groups, preferably aryl groups or substituted aryl groups.

[0117] R 9+Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0118] R 9+ Specific examples of the 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.

[0119] R 9+ Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0120] R 9+ As the cation, a carbonium cation or an ammonium cation is preferable, and a triphenylcarbonium cation, an N,N-dimethylanilinium cation or an N,N-diethylanilinium cation is more preferable.

[0121] In addition to the compound represented by the general formula (7) explained above, the ionic compound may further include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0122] Specific examples of the trialkyl-substituted ammonium salt 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.

[0123] Specific examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, and N,N,2,4,6-pentamethylanilinium tetraphenylborate.

[0124] Specific examples of the dialkylammonium salt include di(n-propyl)ammonium tetra(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

[0125] In addition to the salts described above, the ionic compound may also be triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, or a boron compound represented by the following general formula (8) or (9).

[0126] [ka] (In the general formula (8), Et represents an ethyl group.)

[0127] [ka] (In the general formula (9), Et represents an ethyl group.)

[0128] Specific examples of the borane compound 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(dodecahydridedodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)nickelate(III).

[0129] Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbanonaborane (14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbanoundecaborane (13), 2,7-dicarbanoundecaborane (13), undecahydride-7,8-dimethyl- 7,8-Dicarbaundecaborane, Dodecahydride-11-methyl-2,7-dicarboxaundecaborane, Tri(n-butyl)ammonium 1-carbadecaborate, Tri(n-butyl)ammonium 1-carbaundecaborate, 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-carbadecaborate acrylate (14), tri(n-butyl)ammonium 6-carbadecaborate (12), tri(n-butyl)ammonium 7-carbaundecaborate (13), tri(n-butyl)ammonium 7,8-dicarbaundecaborate (12), tri(n-butyl)ammonium 2,9-dicarbaundecaborate (12), tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7 ,9-dicarboxecaporate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboxecaporate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxecaporate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxecaporate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate;Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)iron Examples of the salts of metal carborane anions include tri(n-butyl)ammonium bis(undecahydride-7-carboundecaborate)chromate(III), tri(n-butyl)ammonium bis(undecahydride-7-carboundecaborate)cobaltate(III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)chromate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)manganate(IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)cobaltate(III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)nickelate(IV).

[0130] The heteropoly compound is usually composed of an atom of silicon, phosphorus, titanium, germanium, arsenic or tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten.Specific examples thereof 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.Also, it may be a salt of each of these acids. Specific examples of salts include salts with metals of 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 isopoly compounds.

[0131] The ionized ionic compounds (C-3) explained above can be used singly or in combination of two or more kinds. The above compounds (C-1), (C-2) and (C-3) are used in an amount of preferably 10 moles or less, more preferably 1 mole or less, even more preferably 0.5 moles or less, and particularly preferably 0.1 moles or less, calculated as aluminum atoms per mole of magnesium atoms of the magnesium compound (C).

[0132] <Carrier (D)> The olefin multimerization catalyst of 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 the chromium compound (A), the amine compound (B) and / or the compound (C). As the inorganic compound, a porous oxide, an inorganic halide, a clay, a clay mineral, or an ion-exchangeable layered compound is preferred.

[0133] Specific examples of the porous oxide include SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or a composite or mixture containing these (e.g., natural or synthetic zeolite, 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 contain a small amount of carbonate, sulfate, nitrate, or oxide component such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, or Li2O. The particle size, specific surface area, and pore volume of the porous oxide are not particularly limited and may be appropriately determined depending on the type of material and the 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 m. 2 / g, more preferably 100 to 700m 2 / g, and the pore volume is preferably 0.3 to 3.0 cm 3 The porous oxide is preferably fired at 100 to 1000°C, more preferably 150 to 700°C, as necessary.

[0134] Specific examples of the inorganic halide include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halide may be used as is, or may be used after being pulverized by a ball mill or a vibration mill. In addition, the inorganic halide may be dissolved in a solvent such as alcohol, and then precipitated into fine particles by a precipitating agent.

[0135] The clay usually contains a clay mineral as a main component. The ion-exchangeable layered compound is a compound having a crystal structure in which the planes formed by ionic bonds are stacked in parallel with each other with weak bonding force, and the ions contained therein are exchangeable. As the ion-exchangeable layered compound, for example, ionic crystalline compounds having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl2 type, CdI2 type, etc. can be used. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds can be not only natural but also artificially synthesized compounds.

[0136] Specific examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, mica, montmorillonite, vermiculite, hectorite, taeniolite, ryokudeite, palygorskite, kaolinite, nacrite, dickite, and halloysite.Specific examples of ion-exchangeable layered compounds include crystalline acid 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 taeniolite are more preferred.

[0137] The pore volume of the clay, clay mineral, and ion-exchangeable layered compound is preferably 0.1 cc / g or more, more preferably 0.3 to 5 cc / g. This pore volume is measured by a mercury intrusion method using a mercury porosimeter with a pore radius of 20 to 3×10 4 When a carrier having a pore volume of less than 0.1 cc / g with a radius of 20 angstroms or more is used, it tends to be difficult to obtain high polymerization activity.

[0138] It is also preferable to subject clay and clay minerals to chemical treatment. Examples of chemical treatment include surface treatment to remove impurities attached to the surface and treatment to affect the crystal structure of the clay. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment not only removes surface impurities, but also increases the surface area by dissolving cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment can destroy the crystal structure of clay and change the structure of clay. Salt treatment and organic treatment can change the surface area and interlayer distance by forming ion complexes, molecular complexes, or organic derivatives.

[0139] The ion-exchangeable layered compound may be a layered compound in which the interlayer space has been expanded by exchanging the exchangeable ions between the layers with other large bulky ions. These bulky ions act as supports to support the layered structure and are usually called pillars. The introduction of another substance between the layers of the layered compound in this way is called intercalation. Specific examples of guest compounds (other substances) to be intercalated include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides (R is a hydrocarbon group, etc.) such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3, and [Al 13 O4(OH) 24 ] 7+ , [Zr4(OH) 14 ] 2+ , [Fe3O(OCOCH3)6] + Examples of the guest compounds include metal hydroxide ions such as those mentioned above. The guest compounds can be used alone or in combination of two or more. When the guest compounds are intercalated, for example, dimers obtained by hydrolysis of metal alkoxides (R is a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, and colloidal inorganic compounds such as SiO2 can also be allowed to coexist. Specific examples of the pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

[0140] The clay, clay mineral, and ion-exchangeable layered compound may be used as is, or may be used after treatment such as ball milling or sieving. In addition, they may be used after newly adding water to adsorb it, or may be used after heat dehydration treatment.

[0141] The organic compound may be, for example, a granular or fine particle solid organic compound having a particle size of 10 to 300 μm.Specific examples of monomers of polymers constituting the organic compound 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 modifications thereof.

[0142] <Organic compound component (E)> The olefin polymerisation catalyst of the present invention may further contain an organic compound component (E) as required.

[0143] In the present invention, the organic compound component (E) is used for the purpose of, for example, improving the polymerizability. As such an organic compound, for example, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates can be used. However, the organic compound component (E) is not limited thereto.

[0144] The alcohols and phenolic compounds are generally selected from the group consisting of R 14 Compounds represented by -OH are used. 14 represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. 14 is a halogenated hydrocarbon. As the phenolic compound, a compound in which the α,α'-positions of a hydroxyl group are substituted with a hydrocarbon having 1 to 20 carbon atoms is preferred.

[0145] The carboxylic acid is usually R 15 The compound represented by -COOH is used. 15represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. In particular, R 15 is a halogenated hydrocarbon group having 1 to 50 carbon atoms.

[0146] The phosphorus compound is preferably a phosphoric acid having a POH bond, or a phosphate or phosphine oxide compound having a P-OR bond or a P=O bond. As the sulfonate, for example, a compound represented by the following general formula (10) can be used.

[0147] [ka]

[0148] In general formula (10), M 2 is an element in groups 1 to 14 of the periodic table, and R 14 represents hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Z represents 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 represents an integer of 1 to 7; u represents an integer satisfying 1≦u≦7 and tu≧1.

[0149] <Catalyst for olefin polymerization> The olefin polymerization catalyst of the present invention is a catalyst used in the polymerization reaction of olefins. Specific examples of the 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 them, ethylene is preferred. Two or more olefins may be co-polymerized.

[0150] <Method for producing olefin polymer> The method for producing an olefin polymer of the present invention is a method for carrying out an olefin polymerization reaction (preferably a trimerization to tetramerization reaction, more preferably a tetramerization reaction) in the presence of the above-described olefin polymerization catalyst.

[0151] Specific examples of the olefin to be polymerized are as described above, and among them, ethylene is preferred. Specifically, it is preferred to produce a polymer by the polymerization reaction of ethylene, it is more preferred to produce 1-hexene and 1-octene with high selectivity by the trimerization and tetramerization reaction of ethylene, and it is particularly preferred to produce 1-octene with high selectivity by the tetramerization reaction of ethylene.

[0152] In the case of polymerization, the order of adding the chromium compound (A), the amine compound (B), the compound (C) and other components (e.g., the carrier (D) and the organic compound component (E)) to the reactor is not particularly limited. Specific examples of the addition method are as follows.

[0153] (1) A method in which component (A) and component (B) are added as they are to a reactor in any order. (2) A method in which component (A) and component (B) are contacted in advance to form a transition metal complex, and the resulting complex is added to a reactor. (3) A method in which components (A), (B) and (C) are added as they are to a reactor in any order. Additionally, the method described in Patent Document 5 can be exemplified.

[0154] In the present invention, olefin polymers are obtained by polymerizing olefins in the presence of the above-described olefin polymerizing catalyst. Polymerization can be carried out by either a liquid phase reaction method such as a solution reaction or a suspension reaction, or a gas phase reaction method.

[0155] In the liquid phase reaction method, an inert hydrocarbon medium is usually 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 these, 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 preferred.

[0156] When 1-hexene or 1-octene is produced, for example, by the trimerization or tetramerization of ethylene using an olefin multimerization catalyst, the chromium atom in component (A) is usually 10 -12 ~10 -2 Molar, preferably 10 -10 ~10 -3 In the present invention, even when the component (A) is used in a relatively low concentration, it is possible to obtain olefin polymers with high activity.

[0157] Component (B) is used in an amount such that the molar ratio to the chromium atoms (M) in component (A) [(B) / M] is usually 0.1-10, preferably 0.5-2. The molar ratio of aluminum atoms in component (C) to chromium atoms (M) in component (A) is usually such that the Al / Cr ratio is 0.01 to 100,000, preferably 0.05 to 50,000.

[0158] Component (D) is used in an amount such that the ratio (g) of the mass (g) of component (D) per mole of chromium atoms (M) in component (A) (g / mol) is usually 100 to 10,000, preferably 1,000 to 5,000.

[0159] The components (C) and (E) are used in such amounts that the (E) / Al molar ratio is usually 0.01-10, preferably 0.1-5. The reaction temperature for polymerization is usually in the range of -50 to 200°C, preferably 0 to 170°C, and more preferably 20 to 120°C. In the olefin polymerization reaction of the present invention, it may be preferable to carry out the reaction at a relatively low temperature. In the case of the polymerization reaction of ethylene, the amount of by-product of ethylene polymers is small and the selectivity for the production of 1-octene, which is a tetramer of ethylene, tends to be high at a temperature more preferably in the range of 0 to 50°C, and even more preferably in the range of 10 to 40°C.

[0160] According to the studies of the present inventors, in the case of known olefin polymerization catalysts, the amount of olefin polymer by-produced tends to increase as the reaction temperature decreases. Although the cause of such a tendency is unclear, the present inventors consider it as follows.

[0161] In the conventional olefin polymerization catalyst containing a chromium compound (A), an amine compound (B), and one or more components selected from the above-mentioned (C-1), (C-2), and (C-3), the interaction between the so-called promoter components such as the above-mentioned (C-1), (C-2), and (C-3), the chromium compound (A), and the amine compound (B) becomes weak at low reaction temperatures. For example, the reaction via the metallacycle mechanism that selectively produces 1-hexene or 1-octene from ethylene becomes less likely to proceed, and the production of polymers may become relatively dominant.

[0162] On the other hand, it is speculated that compound (C) of the present invention exhibits good reaction activity and α-olefin selectivity because the (finely dispersed) magnesium component contained therein acts to adjust the reactivity of the organoaluminum compound and the magnesium component acts to support the interaction between the chromium compound (A), the amine compound (B), and the organoaluminum compound even at relatively low temperatures, making it easier for the reaction to proceed via the metallacycle mechanism.

[0163] In the olefin multimerization reaction of the present invention, the reaction pressure is usually normal pressure to 10 MPa, preferably normal pressure to 6 MPa, more preferably normal 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 preferable upper limit is 4 MPa.

[0164] The polymerization reaction can be carried out in any of a batch, semi-continuous, and continuous manner. The polymerization reaction may be carried out by adding an antistatic agent. Specific examples of the antistatic agent 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 them, polyoxyalkylene (e.g., PEG-PPG-PEG) is preferred. The antistatic agent is used in an amount such that the ratio (g) of the mass per mole of chromium atoms (M) in component (A) is usually 100 to 10,000, preferably 100 to 1,000 (g / mol).

[0165] 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. The α-olefins obtained by the olefin oligomerization reaction of the present invention, preferably 1-hexene and 1-octene, can be used without any restriction in applications where conventional α-olefins are used, for example, as main monomer components or comonomer components in the production of olefin polymers, and can also be used as raw materials for the synthesis of various organic compounds by utilizing the reactivity of their double bonds. EXAMPLES

[0166] The present invention will be specifically described below based on Synthesis Examples and Examples, but the present invention is not limited to these Examples.

[0167] [Quantitative analysis of reaction products] The reaction products were quantified by gas chromatography (Shimadzu GC-14A instrument, J&W Scientific DB-5 column) using nonane as an internal standard.

[0168] [Catalytic activity] The catalytic activity was determined by dividing the mass of the reaction product obtained per unit time by the amount (mmol) of transition metal atoms in the transition metal catalyst component used for polymerization.

[0169] [Selectivity for 1-hexene or 1-octene] The selectivity for 1-hexene or 1-octene was calculated according to the following formula. S(%)=Wp / Wr×100 S(%): 1-hexene or 1-octene selectivity (mass fraction) Wr (mass): The total mass of products produced by the reaction that have 4 or more carbon atoms Wp (mass): Mass of 1-hexene or 1-octene produced by the reaction Examples of catalyst synthesis and ethylene oligomerization are given below.

[0170] [Synthesis Example 1] (Preparation of Chromium Compounds)

[0171] [ka]

[0172] In a thoroughly dried 100mL Schlenk flask, 0.698g (3.829mmol) of the compound (B1) specified by the above structural formula, 1.305g (3.483mmol) of chromium trichloride tristetrahydrofuran, and 70mL of dichloromethane were added and stirred for 16 hours under an argon atmosphere. The reaction solution was concentrated under reduced pressure to about 1 / 7 in weight ratio, and then 15mL of diethyl ether was added. After stirring for a while, the insoluble matter was filtered out with a glass filter, washed with 20mL of diethyl ether, and dried under reduced pressure to obtain 0.67g of chromium compound (I).

[0173] [Synthesis Example 2] (Preparation of magnesium chloride-alcohol reactant (C1)) 95.2 g (1.0 mol) of anhydrous magnesium chloride, 242 ml of decane, 260.4 g (2.0 mol) of 2-ethylhexyl alcohol, and 298.6 g (1.0 mol) of 2-octyldodecanol were reacted at 155° C. for 4 hours to obtain a homogeneous solution [component (C1)].

[0174] [Synthesis Example 3] (Preparation of Mg-containing carrier component (C1-1)) In a 1000 ml flask that has been thoroughly purged with nitrogen, add the components ( C 1) 50 ml (50 mmol in terms of magnesium atom) and 400 ml of decane were charged, and while stirring at 500 rpm using a three-one motor, 52 mmol of triethylaluminum diluted with decane was added dropwise over 30 minutes while maintaining the liquid temperature at 20°C. The liquid temperature was then raised to 80°C over 3.5 hours, and reacted for 1 hour. Next, while maintaining the temperature at 80°C, 98 mmol of triethylaluminum diluted with decane was added dropwise again over 30 minutes, and then the reaction was continued for another 1 hour. After the reaction was completed, the solid portion was collected by filtration, thoroughly washed with toluene, and 100 ml of toluene was added to make a toluene slurry of the solid catalyst component (C1-1).

[0175] [Example 1] (Ethylene Polymerization) 30 mL of toluene 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 was added. Furthermore, a toluene slurry of Mg-containing carrier component (C1-1) was added so that the amount was 0.4 mmol in terms of magnesium atoms. After the gas phase was purged with ethylene, the slurry liquid was heated to 30°C. Separately, under an argon atmosphere, 0.02 mmol (in terms of chromium atoms) of the chromium compound (I) obtained in Synthesis Example 1 and 19.5 mL of toluene were added to a Schlenk flask that had been thoroughly dried, and 0.5 mL of a 1 mol / L triethylaluminum / toluene solution (0.5 mmol in terms of aluminum atoms) was contacted, and 0.5 mL of the mixture (0.5 μmol in terms of chromium atoms) was added to the autoclave. The pressure in the reactor was maintained at 0.8 MPa-G while ethylene was supplied, and the temperature was maintained at 30°C for 60 minutes. The pressure was then reduced to remove unreacted ethylene, and a small amount of isopropanol was added to stop the reaction. After the reaction was completed, the reaction solution was washed with 0.1 N hydrochloric acid and pure water, and low boiling point components (components with 10 or less carbon atoms) were separated from 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 (components with 10 or less carbon atoms) produced was 636 mg, and the amount of polyethylene produced was 50 mg. The catalytic activity calculated from the total amount of these products was 1370 (g / mmol-Cr·hr). The selectivity for 1-hexene was 5.4 mass%, the selectivity for 1-octene was 86.8 mass%, and the catalytic activity for 1-octene was 1190 (g / mmol-Cr·hr).

[0176] [Example 2] The reaction was carried out under the same conditions as in Example 1, except that the reaction temperature was 25°C instead of 30°C. The amount of low-boiling point components (the amount of components having 10 or less carbon atoms) produced was 764 mg, and the amount of polyethylene produced was 79 mg. The catalytic activity calculated from the total amount of these products was 1690 (g / mmol-Cr hr). The selectivity for 1-hexene was 4.2 mass%, the selectivity for 1-octene was 86.0 mass%, and the catalytic activity for 1-octene was 1450 (g / mmol-Cr hr).

[0177] [Comparative Example 1] The reaction was carried out under the same conditions as in Example 1, except that the toluene slurry of the Mg-containing carrier component (C1-1) was not added. The amount of low boiling point components (the amount of components having 10 or less carbon atoms) produced was 92 mg, and the amount of polyethylene produced was 62 mg. The catalytic activity calculated from the total amount of these products was 310 (g / mmol-Cr hr). The selectivity for 1-hexene was 31.7 mass%, the selectivity for 1-octene was 27.4 mass%, and the catalytic activity for 1-octene was 85 (g / mmol-Cr hr).

[0178] [Comparative Example 2] 30 mL of toluene was placed in a 100 mL autoclave that had been thoroughly purged with nitrogen, and 0.5 mmol of methylaluminoxane (Tosoh Finechem MMAO-3A, ​​5.7 mass% hexane solution) was added in terms of aluminum atoms. After the gas phase was replaced with ethylene, the slurry liquid was heated to 25°C. Separately, under an argon atmosphere, the chromium compound (I) obtained in Synthesis Example 1 was dissolved in toluene in a thoroughly dried Schlenk flask to prepare a toluene solution (catalyst solution) of 0.001 mmol / mL in terms of chromium atoms. 0.1 mL of this solution (0.1 μmol in terms of Cr atoms) was added to the autoclave. The reaction was held at 25°C for 60 minutes while supplying ethylene so that the pressure inside the reactor was maintained at 0.8 MPa-G. Thereafter, the product was analyzed in the same manner as in Example 1. The amount of low boiling point components (components with 10 or less carbon atoms) produced was 147 mg, and the amount of polyethylene produced was 59 mg. The catalytic activity calculated from the total amount of these products was 2060 (g / mmol-Cr hr). The selectivity for 1-hexene was 3.2 mass%, the selectivity for 1-octene was 67.6 mass%, and the catalytic activity for 1-octene was 1390 (g / mmol-Cr hr).

[0179] From the above results, it is clear that the method for producing an olefin polymer of the present invention can selectively produce an olefin polymer with little by-production of olefin polymers. In particular, it tends to be suitable for producing 1-octene, which is a tetramer in the polymerization reaction of ethylene. [Industrial Applicability]

[0180] The process for producing olefin polymers of the present invention has excellent reaction activity even at relatively low temperatures, produces little by-production of olefin polymers, i.e., has a high selectivity for the production of olefin polymers, and is therefore extremely useful in the production of olefin polymers. In addition, in the case of the polymerization reaction of ethylene, the selectivity for 1-octene, which is a tetramer, tends to be high. Therefore, the present invention is of extremely high industrial value.

Claims

1. A process for producing olefin polymers by carrying out an olefin polymerization reaction in the presence of an olefin polymerization catalyst comprising the following components (A) to (C): (A) Chromium compounds (B) An amine compound represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), R 1 ~R 4 may be the same or different 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 to each other. Y is a substituent R 5 and R 6 A carbon atom having a carbon atom (-CR 5 R 6 R 5 and R 6 may be the same or different and each 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; R 5 and R 6 may be linked to each other, and R 1 ~R 4 may be linked to any of the following: Z represents an integer of 1 to 10. (C) A component obtained by contacting a magnesium halide with an alcohol having 1 to 20 carbon atoms and then contacting the resulting mixture with an organoaluminum compound represented by the following general formula (α): 【Chemistry 2】 (In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom or a hydrogen atom, and n is a real number of 1 to 3. When there are multiple Rs, each R may be the same or different, and when there are multiple Xs, each X may be the same or different.)

2. In the general formula (1), R 1 is R 3 and R 4 It is not connected to R 2 is R 3 and R 4 2. The method for producing an olefin multimer according to claim 1, wherein the amine compound (B) is not linked to the olefin multimer.

3. 2. The process for producing an olefin multimer according to claim 1, wherein the amine compound (B) represented by the general formula (1) is an integer of 1 to 3.

4. 2. The process for producing an olefin multimer according to claim 1, wherein an amine compound (B) in which Z is 1 in the general formula (1) is used.

5. The method for producing olefin polymers according to claim 1, wherein the catalyst for olefin polymerization contains the following component (D) in addition to the components (A) to (C): (D) A support for supporting at least one compound selected from the group consisting of components (A) to (C).

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

7. 2. The process for producing an olefin polymer according to claim 1, wherein the olefin is ethylene.

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

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