New regulations for compounds

Abstract

To provide a compound to be a ligand of a transition metal compound, which shows unconventional characteristics in stereoregular control, molecular weight control and the like, in the polymerization of propylene as well as the polymerization of ethylene.SOLUTION: The present invention discloses, specifically, a fluorenyl group-containing phenol derivative: for example, the following compound 4.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to novel compounds, and more specifically to novel compounds that can be used as ligands for novel transition metal compounds that can be used as catalysts for olefin polymerization. [Background technology]

[0002] Catalysts consisting of metallocene compounds and co-catalysts such as organoaluminum oxy compounds are known to be used as catalysts for producing olefin polymers such as ethylene-α-olefin copolymers and propylene polymers.

[0003] Various types of transition metal compounds, such as metallocene compounds, have been actively developed as catalysts. For example, Patent Document 1 describes a transition metal compound (A) represented by the following general formula:

[0004] [ka] (In the formula, M represents a transition metal of Group 4 of the periodic table such as Ti, L represents a monovalent anionic ligand in which an element of Group 15 of the periodic table acts as the coordinating atom, X represents halogens, etc., m represents an integer from 1 to 3, R 1 ~R 5 The following describes a method for producing a cyclic olefin copolymer in which ethylene and / or an α-olefin having 3 to 20 carbon atoms copolymerizes with at least one cyclic olefin compound in the presence of a polymerization catalyst comprising (A) (where represents hydrogen, halogen, or alkyl group having 1 to 20 carbon atoms) and one or more activators (B) selected from organoaluminum oxy compounds and organoboron compounds, and a specific example of the transition metal compound (A) is CpTi(t-Bu2C=N)Cl2, and a comparative example is Cp * Ti(2,6- i Pr2PhO)Cl2 is mentioned (Cp is a cyclopentadienyl group, Cp * is η 5 - Represents a pentamethylcyclopentadienyl group.

[0005] On the other hand, Patent Document 2 states that Cp * An example of the production of ultra-high molecular weight polyethylene using a complex having a [t-BuPN]Cl2 skeleton has been disclosed.

[0006] Furthermore, there are disclosures that use metallocene compounds having cyclopentadienyl and fluorenyl structures of a specific structure as components of catalysts for olefin polymerization (Patent Documents 3 and 4). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2007-63409 [Patent Document 2] Special Publication No. 2016-534165 [Patent Document 3] International Publication No. 01 / 027124 [Patent Document 4] International Publication No. 2004 / 029062 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, the transition metal compounds described in Patent Documents 1 and 2 primarily disclose polymerization reactions of ethylene and copolymerization reactions of ethylene with cyclic olefins. Catalysts for olefin polymerization containing transition metal compounds that can polymerize ethylene are often also capable of polymerizing α-olefins such as propylene. In other words, if a catalyst polymerizes propylene, it is generally also capable of polymerizing ethylene. On the other hand, in the case of polymerization reactions of α-olefins such as propylene, olefin polymerization catalysts containing transition metal compounds are sometimes required to control more functions than those for ethylene, such as controlling stereoregularity, regioregularity, and molecular weight in conjunction with these. For example, conventional atactic polypropylene is known for its use as an elastomer in rubber and other applications such as shoe soles, but it has been difficult to obtain atactic polypropylene with high molecular weight, which has limited its applications. One suitable method for obtaining such novel olefin polymers is to improve the catalyst for olefin polymerization, particularly the structure of the ligand of the transition metal complex used in the catalyst. However, no transition metal complex or ligand structure suitable for producing the above-mentioned polymers is currently known.

[0009] From the above perspective, the object of the present invention is to provide a compound suitable as a raw material for a ligand of a transition metal compound that exhibits unprecedented characteristics in the polymerization of ethylene as well as propylene, such as the control of stereoregularity and molecular weight, and a method for producing the same. [Means for solving the problem]

[0010] As a result of investigations in view of the above-mentioned problems, the present inventors have found that compounds having a specific structure can serve as ligands for transition metal compounds, for example, and that catalysts for olefin polymerization containing transition metal complexes using such compounds as ligand raw materials have unique stereoregularity control and molecular weight control capabilities, particularly as catalysts for α-olefin polymerization such as propylene, and have completed the present invention. That is, the present invention has the following configuration. [1] A compound represented by the following general formula (A-1).

[0011]

Chemical formula

[0012] <00003OB>

[0012] [2] The compound according to [1] wherein n is 4 or 5. [3] The compound according to [1] wherein the ring structure formed by R 3 , R 4 is an aromatic ring.

Advantages of the Invention

[0013] The compounds of the present invention are suitable, for example, as ligands for transition metal compounds. Olefin polymerization catalysts containing transition metal compounds using the compounds of the present invention as ligands exhibit high activity in the polymerization and copolymerization of ethylene and olefins having 3 or more carbon atoms, and are characterized by yielding high molecular weight polymers. Furthermore, by selecting the structure of the transition metal compound, it is possible to produce polymers with different stereoregularities such as atactic and isotactic, and polymers with high molecular weights regardless of stereoregularity. [Modes for carrying out the invention]

[0014] The compounds of the present invention are represented by the following general formula (A-1) and are identified by satisfying the following requirements.

[0015] [ka] In equation (A-1), R 1 These are group 16 atoms of the periodic table. Specifically, examples include oxygen (O-), sulfur (S-), selenium (Se-), tellurium (Te-), etc. More preferably, selected from oxygen and sulfur atoms, and even more preferably oxygen.

[0016] R 2 is, -(Q(R l )2) x -A substituent in the structure, where Q is a carbon atom or a silicon atom. Q is preferably a carbon atom. Here x is an integer from 0 to 5. The preferred upper limit of x is 4, more preferably 3, and even more preferably 2. When x is 0, specifically the fluorenyl structure of formula (A-1) and R 3 ,R 4 This is a configuration in which the ring structure formed by the ring is directly bonded by covalent bonds. 2 ga-(C(R l )2) x - If it is a substituent in the structure, there may be multiple R l The groups may bond to each other to form a ring structure, or they may bond to adjacent carbon atoms. l They may also bond directly to each other to form a carbon-carbon double bond (-C=C-).l Specific examples of the basis will be discussed later.

[0017] R 2 The structure allows for control of the conformation, such as the distance and angle between the aromatic ring structure and the fluorenyl structure of formula (A-1). By controlling this conformation, as described later, the olefin polymerization catalyst containing a transition metal complex with the compound of the present invention as a ligand may be able to control the stereoregularity of the resulting olefin polymer in polymerization reactions of propylene and other materials.

[0018] R 3 ,R 4 is -C(R m )2-A substituent in the formula, and there are multiple R m These are different R m They may bond to each other to form a ring structure, or they may directly bond to form a covalent bond and thus a ring structure. A preferred example of the aforementioned direct bonding is R bonded to an adjacent carbon atom. m One example is a structure in which two atoms directly bond to each other, forming a carbon-carbon double bond (-C=C-).

[0019] n is an integer between 2 and 10. If n is greater than or equal to 2, there are multiple R's. 4 The groups represented by may be the same or different from each other. A preferred lower limit for n is 2, more preferably 4. On the other hand, a preferred upper limit is 8, more preferably 6, and even more preferably 5.

[0020] The aforementioned R 3 , R 4 The ring structure formed is R of equation (A-1). 2 Alternatively, it can bond with a fluorenyl structure and an aromatic ring structure, but these two groups are different R groups. 3 or multiple R 4 It is preferable to bond with a group selected from R. 3 and R 2 and are joined together, R 4 This is an embodiment in which the aromatic ring structure is bonded to the aforementioned R 3 Instead, R bonds to the aromatic ring structure.4 A different R 4 and R 2 An example of a structure in which and are combined can be given.

[0021] R 3 , R 4 As shown in equation (A-1), it forms a ring structure. This ring structure links the aromatic ring structure and the fluorenyl structure of (A-1), and by creating a rigid ring structure, as will be described later, when the compound of the present invention is used as a catalyst for olefin polymerization, it may exhibit favorable effects in stereocontrolling the reaction and controlling the molecular weight.

[0022] For example, R 3 , R 4 The ring formed by this molecule connects the aromatic ring structure and the fluorenyl structure to create a rigid structure, which reduces structural changes during the olefin polymerization reaction. This results in a more uniform direction in which the olefin coordinates to the olefin polymerization catalyst, narrowing the distribution of stereoregularity and copolymerizability, and making it easier to obtain polymers with a more uniform structure. Furthermore, the reduced structural changes during polymerization make chain transfer reactions less likely, which may make it easier to obtain polymers with high molecular weights.

[0023] A preferred example of this ring structure is one in which n is 5 and R is bonded to an adjacent carbon. m One example is the so-called aromatic ring structure, which includes carbon-carbon double bonds directly bonded to each other. Because aromatic ring structures are rigid, they may exhibit effects such as increased polymerization rates due to electronic effects from resonance structures.

[0024] R 5 ~R 7 , R l , R m Each of these is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene-based divalent derivative group.

[0025] R 5 ~R7 , R l , R m Preferably, each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. 5 ~R 7 , R l , R m This group includes multiple groups, and they may bond to each other to form a ring structure.

[0026] Examples of the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, chain-like unsaturated hydrocarbon groups having 2 to 20 carbon atoms, and cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms.

[0027] Examples of alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decanyl groups, and branched saturated hydrocarbon groups such as isopropyl, isobutyl, s-butyl, t-butyl, t-amyl, neopentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl, and cyclopropylmethyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 6.

[0028] Examples of cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, 1-adamantyl, and 2-adamantyl groups, as well as groups in which the hydrogen atoms of these cyclic saturated hydrocarbon groups are replaced by hydrocarbon groups having 1 to 17 carbon atoms, such as 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-cyclohexylcyclohexyl, and 4-phenylcyclohexyl groups. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 5 to 11.

[0029] Examples of chain-like unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as the ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group), and alkynyl groups such as the ethynyl group, 1-propynyl group, and 2-propynyl group (propargyl group). The number of carbon atoms in the chain-like unsaturated hydrocarbon group is preferably 2 to 4.

[0030] Examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclopentadienyl, norborneyl, phenyl, naphthyl, indenyl, azurenyl, phenanthryl, and anthracenyl groups. Other examples include 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-ethylphenyl, 4-t-butylphenyl, 4-cyclohexylphenyl, biphenylyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, and 2,4,6-trimethylphenyl (mesityl), which are groups in which the hydrogen atoms of these cyclic unsaturated hydrocarbon groups are replaced by hydrocarbon groups having 1 to 15 carbon atoms. Other examples include benzyl and cumyl groups, which are groups in which the hydrogen atoms of linear or branched saturated hydrocarbon groups are replaced by cyclic saturated or cyclic unsaturated hydrocarbon groups having 3 to 19 carbon atoms. The number of carbon atoms in the cyclic unsaturated hydrocarbon groups is preferably 6 to 10.

[0031] Examples of alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, dimethylmethylene (isopropylidene), ethylmethylene, 1-methylethylene, 2-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, and n-propylene. The alkylene group preferably has 1 to 6 carbon atoms.

[0032] Examples of arylene groups having 6 to 20 carbon atoms include o-phenylene groups, m-phenylene groups, p-phenylene groups, and 4,4'-biphenylene groups. The number of carbon atoms in the arylene group is preferably 6 to 12.

[0033] Examples of aryl groups include those derived from aromatic compounds, such as phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenantrenyl, tetracerenyl, chrysenyl, pyrenyl, indenyl, azurenyl, pyrrolyl, pyridyl, furanyl, and thiophenyl groups, although these overlap somewhat with the previously mentioned examples of cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms.

[0034] Examples of the aforementioned aromatic compounds include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene.

[0035] Examples of substituted aryl groups include those that partially overlap with the examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms mentioned above, but also include groups in which one or more hydrogen atoms of the aryl group are substituted by substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups. Specifically, these include 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), 3-ethylphenyl group, 4-ethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, biphenylyl group, 4-(trimethylsilyl)phenyl group, and 4-aminophenyl group. Examples of substituted aryl groups include 4-(dimethylamino)phenyl group, 4-(diethylamino)phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-phenoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3-(trifluoromethyl)phenyl group, 4-(trifluoromethyl)phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, and 2-(6-methyl)pyridyl group. Furthermore, "electron-donating group-containing substituted aryl groups," described later, can also be mentioned as substituted aryl groups.

[0036] Examples of silicon-containing groups include alkylsilyl groups such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, and triisopropylsilyl, which are hydrocarbon groups having 1 to 20 carbon atoms in which carbon atoms are replaced by silicon atoms; arylsilyl groups such as dimethylphenylsilyl, methyldiphenylsilyl, and t-butyldiphenylsilyl; pentamethyldisilanyl; and trimethylsilylmethyl. The number of carbon atoms in alkylsilyl groups is preferably 1 to 10, and the number of carbon atoms in arylsilyl groups is preferably 6 to 18.

[0037] Examples of nitrogen-containing groups include amino groups, nitro groups, N-morpholinyl groups, and, in the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms or silicon-containing groups, groups in which the =CH- structural unit is replaced by a nitrogen atom, groups in which the -CH2- structural unit is replaced by a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or groups in which the -CH3 structural unit is replaced by a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded or a nitrile group, such as dimethylamino groups, diethylamino groups, dimethylaminomethyl groups, cyano groups, pyrrolidinyl groups, piperidinyl groups, and pyridinyl groups. Dimethylamino groups and N-morpholinyl groups are preferred as nitrogen-containing groups.

[0038] Oxygen-containing groups include hydroxyl groups, the aforementioned hydrocarbon groups with 1 to 20 carbon atoms, silicon-containing groups, or nitrogen-containing groups in which the -CH2- structural unit is replaced by an oxygen atom or a carbonyl group, or in which the -CH3 structural unit is replaced by an oxygen atom to which a hydrocarbon group with 1 to 20 carbon atoms is bonded, such as methoxy groups, ethoxy groups, t-butoxy groups, phenoxy groups, trimethylsiloxy groups, methoxyethoxy groups, hydroxymethyl groups, methoxymethyl groups, ethoxymethyl groups, t-butoxymethyl groups, and 1-hydroxyethyl groups. Examples of oxygen-containing groups include 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxyl group, methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl group, carbamoylmethyl group, furanyl group, and pyranyl group. Methoxyethyl group is preferred as the oxygen-containing group.

[0039] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, which are elements of Group 17.

[0040] Examples of halogen-containing groups include trifluoromethyl, tribromomethyl, pentafluoroethyl, and pentafluorophenyl groups, which are hydrocarbon groups, silicon-containing groups, nitrogen-containing groups, or oxygen-containing groups having 1 to 20 carbon atoms, in which a hydrogen atom is substituted by a halogen atom.

[0041] The aforementioned multiple R 5 At least one of the substituents is preferably a substituent other than hydrogen, more preferably a hydrocarbon group, and even more preferably an aromatic hydrocarbon group.

[0042] The above R 1 ~R 7 There are no particular restrictions regarding the relative positions of R 5 If R is a substituent other than hydrogen, preferably a hydrocarbon group having 1 to 20 carbon atoms, 1 And, R 5 And, R 3 Or R 4 The preferred positional relationship between (A-1) and the aromatic ring structure is R 1 and R 5 It is preferable that the positions are in an ortho position relationship, R 1 And, R 3 or R 4 It is preferable that the positions are in an ortho relationship. Also, the relationship between the aromatic ring structure of formula (A-1) and the fluorenyl structure is R 3 , R 4 The positional relationship to the ring structure formed by R 3 , R 4 When forming an aromatic ring structure, it is preferable that the position is in an ortho position.

[0043] With such a desirable structure as described above, the ligand structure is compact, making it easier to control the coordination direction of the olefin during the olefin polymerization reaction, and enabling unique stereocontrol.

[0044] Examples of the halogens mentioned above include fluorine, chlorine, bromine, and iodine, but chlorine or bromine is preferred.

[0045] In the present invention, these substituents are preferably hydrocarbon groups having 1 to 20 carbon atoms, more preferably hydrocarbon groups having 1 to 4 carbon atoms, and even more preferably selected from methyl groups and ethyl groups, and particularly methyl groups.

[0046] Specific examples of the compounds of the present invention are shown below, but the transition metal compounds of the present invention are not limited to these.

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] The compounds of the present invention can be synthesized by appropriately selecting and combining known synthetic methods. Among them, various coupling reactions can be suitably used for the synthesis of the compounds of the present invention. Numerous methods have been disclosed for such coupling reactions that generate various carbon-carbon bonds. For example, the methods described in Tetrahedron Letters, 1979, 3437-3440; Journal of the Chemical Society, Chemical Communications, 1977, 683-684; Chemistry Letters, 1977, 301-302, etc. can be cited.

[0056] More specifically, an organic metal compound (for example, an organic boron compound, an organic zinc compound, an organic tin compound) containing a ring structure including R 1 , R 5 can be mentioned, and a method of bonding it to a halide or triflate of a ring structure including R 3 , R 4 by a coupling reaction can be cited (see the following formula (1)).

[0057]

Chemical formula

[0058]

Chemical formula

[0059] <Synthesis of Halides> R 3 , R 4 Halides with a ring structure containing fluorenes can be synthesized by reacting fluorenes with a base or organometallic reagent and then substituting them with an alkyl halide (see formula (3) below). Examples of bases include inorganic bases such as potassium hydroxide, sodium hydroxide, and potassium tert-butoxide, and organic bases such as diazabicycloundecene and 1,4-diazabicyclo[2,2,2]octane. Examples of organometallic reagents include n-butyllithium and methyllithium.

[0060] [ka] In equation (3), X represents iodine, bromine, and chlorine.

[0061] <Triflat compounds> R 3 , R 4 Triflate compounds with a ring structure containing can be synthesized by a Friedel-Crafts reaction of phenols and fluorenes using an acid catalyst, followed by a reaction with a triflating agent (see formula (4) below). Examples of acid catalysts include aluminum chloride and sulfuric acid. Examples of triflating agents include trifluoromethanesulfonic anhydride and N-phenyltrifluoromethanesulfonimide.

[0062] [ka] In equation (4), X represents an OH group, iodine, bromine, or chlorine.

[0063] As described later, the compounds of the present invention can be used, for example, as ligands to obtain transition metal compounds (complexes) or catalysts for olefin polymerization containing them, and polymers with various stereoregularities can be obtained in the polymerization of α-olefins using these catalysts. Furthermore, it may be possible to produce mixtures of polymers with different stereoregularities in a single polymerization step. In addition, these catalysts may exhibit unique properties, such as a tendency to easily produce polymers with higher molecular weights compared to conventional catalysts.

[0064] The above-mentioned transition metal compounds can be synthesized, for example, by known methods of anionizing the compound of the present invention with an organolithium compound and reacting it with the corresponding halogen-containing transition metal compound. The transition metal compound has, for example, the following structure.

[0065] [ka]

[0066] R in the above structural formula 1 ~R 7 And n are as defined in formula (A-1) above, and M is an atom of group 4 of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom. These atoms are elements that are considered to have high anionic (coordination) polymerizability. Among these, titanium and zirconium are preferred, and titanium is more preferred. Also, R 8 , R 9 R 5 ~R 7 It is a substituent similar to that of [another substituent].

[0067] The following describes a typical application of the compound of the present invention: a catalyst for olefin polymerization.

[0068] Examples of the above olefin polymerization catalyst include a mode in which a transition metal compound obtained using the compound of the present invention as a ligand is combined with at least one compound selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the above transition metal compound to form an ion pair. Examples of each of these components used in the above olefin polymerization catalyst are as follows.

[0069] ((B-1) Organometallic compound) Specific examples of the organometallic compound (B-1) used in the present invention include compounds containing at least one element of Groups 1, 2, 12, and 13 of the periodic table represented by the following general formulas (B-1a) to (B-1c):

[0070] R a p Al(ОR b ) q H r Y s ···(B-1a) (In the general formula (B-1a), R a and R b may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is a number where 0 < p ≤ 3, q is a number where 0 ≤ q < 3, r is a number where 0 ≤ r < 3, s is a number where 0 ≤ s < 3, and m + n + p + q = 3.) An organoaluminum compound represented by;

[0071] M 3 AlR c 4···(B-1b) (In the general formula (B-1b), M 3 represents Li, Na or K, and R c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.) A complex alkyl compound of an alkali metal of Group 1 of the periodic table and aluminum represented by;

[0072] R d R e M 4 ···(B-1c) (In the general formula (B-1c), Rd and R e may be the same as or different from each other and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 4 is an alkaline earth metal of Group 2 or a metal of Group 12 of the periodic table represented by Mg, Zn or Cd. A dialkyl compound with a metal of Group 2 or Group 12 of the periodic table represented by ().

[0073] Examples of the organoaluminum compound belonging to the general formula (B-1a) include the following compounds:

[0074] R a p Al(ОR b ) 3-p ···(B-1a-1) (In the formula (B-1a-1), R a and R b may be the same as or different from each other and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number satisfying 1.5 ≤ p ≤ 3.) An organoaluminum compound represented by

[0075] R a p AlY 3-p ···(B-1a-2) (In the formula (B-1a-2), R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number satisfying 0 < p < 3.) An organoaluminum compound represented by

[0076] R a p AlH 3-p ···(B-1a-3) (In the formula (B-1a-3), R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number satisfying 2 ≤ p < 3.) An organoaluminum compound represented by

[0077] R a p Al(ОR b ) q Y s···(B-1a-4) (In formula (B-1a-4), R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is a number where 0 < p ≤ 3, q is a number where 0 ≤ q < 3, s is a number where 0 ≤ s < 3, and p + q + s = 3.) An organoaluminum compound represented by

[0078] More specifically, as the organoaluminum compound belonging to the general formula (B-1a), tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc.; Tri-branched chain alkylaluminum such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum, etc.; Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, etc.; Triarylaluminum such as triphenylaluminum, tritolylaluminum, etc.; Dialkylaluminum hydride such as diisobutylaluminum hydride; (i-C4H9) x Al y (C5H 10 ) z (In the formula, x, y, and z are positive numbers, and z ≥ 2x.) Trialkenylaluminum such as triisoprenylaluminum represented by etc.; 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; R a 2.5 Al(OR) b ) 0.5 Partially alkoxylated alkylaluminum having an average composition represented by the formula (wherein R a and R b These may be identical or different from each other, and represent hydrocarbon groups having 1 to 15, preferably 1 to 4, carbon atoms. Dialkylaluminum allyloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), 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; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides, ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

[0079] Compounds similar to (B-1a) can also be used in the present invention, and examples of such compounds include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2.

[0080] Compounds belonging to the general formula (B-1b) include LiAl(C2H5)4 and LiAl(C7H 15 Examples include 4.

[0081] Examples of compounds belonging to the general formula (B-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, bis(pentafluorophenyl)zinc, dimethylcadmium, and diethylcadmium.

[0082] In addition, other organometallic compounds (B-1) that can be used include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, and butylmagnesium chloride.

[0083] Furthermore, compounds such as a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium, which form the above-mentioned organoaluminum compound within the polymerization system, can also be used as the organometallic compound (B-1).

[0084] Among organometallic compounds (B-1), organoaluminum compounds are preferred from the viewpoint of catalytic activity. The organometallic compounds (B-1) described above can be used individually or in combination of two or more.

[0085] ((B-2) Organoaluminum oxy compounds) The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or it may be a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Application Publication No. 2-78687.

[0086] Conventionally known aluminoxanes can be produced by methods such as those described below, and are usually obtained as solutions in a hydrocarbon solvent.

[0087] (1) A method of reacting the adsorbed water or crystal water with the organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium containing a compound or salt containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerium chloride hydrate.

[0088] (2) A method of reacting an organoaluminum compound such as trialkylaluminum directly with water, ice, or water vapor in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

[0089] (3) A method of reacting organoaluminum compounds such as trialkylaluminum with organotin oxides such as dimethyltin oxide and dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0090] The aluminoxane may contain a small amount of organometallic components. Alternatively, after removing the solvent or unreacted organoaluminum compounds from the recovered aluminoxane solution by distillation, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.

[0091] Specific examples of organoaluminum compounds used in preparing aluminoxanes include those similar to those exemplified as organoaluminum compounds belonging to the general formula (B-1a) above. Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

[0092] The organoaluminum compounds described above can be used individually or in combination of two or more.

[0093] Solvents used in the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel fuel; or halogenated compounds of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, particularly chlorinated and brominated hydrocarbon solvents. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred. These solvents can be used individually or in combination.

[0094] The organoaluminum oxy compound (B-2) according to the present invention includes aluminoxanes selected from at least one of aluminoxanes having a structure represented by the following general formula (B-2a) or (B-2b), and aluminoxanes having a repeating unit represented by the following general formula (B-2c) and a repeating unit represented by the following general formula (B-2d) as part of their structure.

[0095] [ka]

[0096] In the general formula, R c Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specific examples of hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, and ethylphenyl group. Among these examples, methyl group, ethyl group, and isobutyl group are preferred, and methyl group is particularly preferred, and in the general formulas (B-2a), (B-2b), and (B-2c), R c A portion of it may be substituted with halogen atoms such as chlorine or bromine, and the halogen content may be 40% by weight or less.

[0097] In the general formulas (B-2a) and (B-2b) above, r represents an integer between 2 and 500, preferably between 6 and 300, and particularly preferably between 10 and 100.

[0098] In the above general formulas (B-2c) and (B-2d), s and t each represent an integer of 1 or greater. The aluminoxane having the repeating unit represented by the general formula (B-2c) and the repeating unit represented by the general formula (B-2d) is preferably such that its molecular weight, measured by the freezing point depression method of benzene, is in the range of 200 to 2000.

[0099] Furthermore, the benzene-insoluble organoaluminum oxy compounds used in the present invention are preferably those in which the Al component that dissolves in benzene at 60°C is typically 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms; in other words, they are preferably insoluble or sparingly soluble in benzene.

[0100] In the present invention, the organoaluminum oxy compound (B-2) can also be an organoaluminum oxy compound containing boron represented by the following general formula (B-2e).

[0101] [ka]

[0102] In general formula (B-2e), R 15 This indicates a hydrocarbon group with 1 to 10 carbon atoms, and four R 16 These may be identical or different from each other, and each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0103] The boron-containing organoaluminum oxy compound represented by the general formula (B-2e) can be produced by reacting an alkylboronic acid represented by the general formula (B-2f) 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.

[0104] R 15 -B(OH)2···(B-2f) In general formula (B-2f), R 15 R in the above general formula (B-2e) is 15 It shows the same base.

[0105] Specific examples of alkylboronic acids represented by the general formula (B-2f) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These can be used individually or in combination of two or more.

[0106] Specific examples of organoaluminum compounds that react with such alkylboronic acids include organoaluminum compounds similar to those exemplified as organoaluminum compounds belonging to the general formula (B-1a) above.

[0107] The organoaluminum compounds mentioned above are preferably trialkylaluminum and tricycloalkylaluminum, and particularly preferably trimethylaluminum, triethylaluminum, and triisobutylaluminum. These can be used individually or in combination of two or more.

[0108] When an organoaluminum oxy compound (B-2), such as methylaluminoxane, is used in combination with the aforementioned transition metal compound as a co-catalyst component, it exhibits very high polymerization activity towards olefin compounds.

[0109] The organoaluminum oxy compounds (B-2) described above can be used individually or in combination of two or more.

[0110] ((B-3) Compounds that react with the aforementioned transition metal compounds to form ion pairs) Examples of compounds (B-3) used in the present invention that react with the transition metal compound to form an ion pair (hereinafter referred to as "ionized ionic compound") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Application Publication No. 3-179005, Japanese Patent Application Publication No. 3-179006, Japanese Patent Application Publication No. 3-207703, Japanese Patent Application Publication No. 3-207704, US-5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

[0111] Specifically, examples of the Lewis acid include compounds represented by BR3 (where R is a phenyl group or fluorine which may have substituents such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroborone, triphenylborone, tris(4-fluorophenyl)borone, tris(3,5-difluorophenyl)borone, tris(4-fluoromethylphenyl)borone, tris(pentafluorophenyl)borone, tris(p-tolyl)borone, tris(o-tolyl)borone, and tris(3,5-dimethylphenyl)borone.

[0112] Examples of the ionized ionic compounds include compounds represented by the following general formula (B-3a).

[0113] [ka]

[0114] In general formula (B-3a), R 17 is H + R is a carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, or ferrocenium cation having a transition metal. 18 ~R 21 These may be the same or different from each other, and are organic groups, preferably aryl groups or substituted aryl groups.

[0115] Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0116] Examples of the aforementioned ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium 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.

[0117] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0118] R 17 As such, carbonium cations and ammonium cations are preferred, and triphenylcarbonium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations are particularly preferred.

[0119] Other examples of ionic compounds include trialkylsubstituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0120] Specific examples of the aforementioned trialkyl-substituted ammonium salts include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0121] Specific examples of the aforementioned N,N-dialkylanilinium salts include, for example, N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

[0122] Examples of the aforementioned dialkylammonium salts include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

[0123] Furthermore, as ionized ionic compounds, examples include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formulas (B-3b) or (B-3c).

[0124] [ka] In formula (B-3b), Et represents an ethyl group.

[0125] [ka] In formula (B-3c), Et represents an ethyl group.

[0126] Examples of ionized ionic compounds (compound (B-3)) specifically include borane compounds such as decaborane; 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; Examples include 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). Examples of ionized ionic compounds include, specifically, carborane compounds such as 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbowndecaborane, 2,7-dicarbowndecaborane, and undecahydride-7,8-dimethyl Tyl-7,8-dicarboundecaporane, dodecahydride-11-methyl-2,7-dicarboundecaporane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, 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, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7-carbound decaborate, tri(n-butyl)ammonium 7,8-dicalbound decaborate, tri(n-butyl)ammonium 2,9-dicalbound decaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicalbound decaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dical Salts of anions such as bounce decaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dic bounce decaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dic bounce decaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dic bounce decaborate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carb bounce decaborate; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)ferrate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)niclate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)copperate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)goldate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbowndecaborate)ferric acid Examples include salts of metal carborane anions such as salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboundecaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboundecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)nickelate (IV).

[0127] Heteropoly compounds, which are examples of ionized ionic compounds, are compounds containing an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specifically, these include, but are not limited to, 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, phosphomolybdotungstovanadic acid, phosphomolybdoniobic acid, and salts of these acids. Furthermore, examples of the salts include salts of the acid with alkali metals from Group 1 or alkaline earth metals from Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0128] Isopoly compounds, which are examples of ionized ionic compounds, are compounds composed of a metal ion of one atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered as molecular ionic species of metal oxides. Specifically, examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Furthermore, examples of the salts include salts of the acids with metals from Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0129] The ionized ionic compounds described above (compounds that react with the transition metal compounds to form ion pairs (B-3)) can be used individually or in combination of two or more types.

[0130] Furthermore, the catalyst for olefin polymerization according to the present invention may also optionally include the following support (C) along with the above-mentioned transition metal compound (hereinafter sometimes abbreviated as "component (A)") and at least one compound (B) selected from the group consisting of organometallic compounds (B-1), organoaluminum oxy compounds (B-2), and ionized ionic compounds (B-3).

[0131] [(C) Carrier] The carrier (C) used in the present invention is an inorganic or organic compound, and is in the form of granular or fine particulate solids. By supporting the above-mentioned transition metal compound and compound (B) on the carrier (C), a polymer with good morphology can be obtained.

[0132] The inorganic compound is preferably a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral, or an ion-exchangeable layered compound.

[0133] Specifically, the porous oxide can be SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or composites or mixtures containing these. Furthermore, natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc., can be used. Among these, porous oxides mainly composed of SiO2 and / or Al2O3 are preferred.

[0134] Furthermore, the porous oxide may contain small amounts of carbonates, sulfates, nitrates, and oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.

[0135] Such porous oxides have different properties depending on the type and manufacturing method, but the porous oxides preferably used in the present invention have a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of ​​50 to 1000 m². 2 / g, preferably 100-700m 2 It is in the range of / g, and the pore volume is 0.3-3.0 cm³. 3 It is desirable that the value be within the range of / g. Such porous oxides are used after being calcined at 100-1000°C, preferably 150-700°C, as needed.

[0136] The solid aluminoxane compound mentioned above is an aluminoxane selected from at least one of the aluminoxanes shown in (B-2a) to (B-2d).

[0137] The solid aluminoxane used in the present invention differs from conventionally known olefin polymerization catalyst supports in that it does not contain inorganic solid components such as silica or alumina, or organic polymer components such as polyethylene or polystyrene, and is solidified with alkylaluminum compounds as the main component. In the present invention, "solid" means that the aluminoxane component (B-2) maintains a substantially solid state in the reaction environment in which it is used. More specifically, for example, when preparing a solid catalyst component for olefin polymerization by contacting component (A) and component (B) as described later, it means that component (B) is in a solid state in an inert hydrocarbon solvent such as hexane or toluene used in the reaction, under a specific temperature and pressure environment. Furthermore, for example, when performing suspension polymerization using a solid catalyst component for olefin polymerization prepared using component (B) as described later, it is also a necessary requirement that component (B) contained in the catalyst component is in a solid state in a hydrocarbon solvent such as hexane, heptane, or toluene, under a specific temperature and pressure environment. The same applies to bulk polymerization, where polymerization is carried out in liquefied monomer instead of a solvent, and gas-phase polymerization, where polymerization is carried out in monomer gas.

[0138] Under the above-described environment, visual inspection is the simplest way to determine whether component (B) is in a solid state; however, visual inspection is often difficult, for example, during polymerization. In such cases, it is possible to determine this from, for example, the properties of the polymer powder obtained after polymerization or its adhesion to the reactor. Conversely, if the polymer powder has good properties and minimal adhesion to the reactor, even if some of component (B) dissolves under polymerization conditions, the present invention will not deviate from its purpose. Indicators for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymers; however, polymer bulk density is preferred from the viewpoint of quantitative accuracy. In the present invention, the bulk density is usually 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

[0139] The solid aluminoxane used in this invention dissolves in n-hexane held at a temperature of 25°C in a range of typically 0 to 40 mol%, preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol%.

[0140] The dissolution ratio of the solid aluminoxane used in this invention in n-hexane was determined by adding 2 g of solid aluminoxane support to 50 ml of n-hexane maintained at 25°C, stirring for 2 hours, then separating the solution using a G-4 glass filter, and measuring the aluminum concentration in the filtrate. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

[0141] As the solid aluminoxane according to the present invention, any known solid aluminoxane can be used without limit. Examples of known manufacturing methods include those described in Japanese Patent Publication No. 7-42301, Japanese Patent Application Publication No. 6-220126, Japanese Patent Application Publication No. 6-220128, Japanese Patent Application Publication No. 11-140113, Japanese Patent Application Publication No. 11-310607, Japanese Patent Application Publication No. 2000-38410, Japanese Patent Application Publication No. 2000-95810, and WO201055652.

[0142] The average particle size of the solid aluminoxane according to the present invention is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1,000 μm, and particularly preferably 1 to 200 μm.

[0143] The average particle size of solid aluminoxane is determined by observing the particles with a scanning electron microscope, measuring the particle sizes of 100 or more particles, and weight-averaging them. The particle size of solid aluminoxane was measured from the particle image using the Pythagorean method to determine the maximum length. That is, the length of the particle image enclosed by two parallel lines was measured in both the horizontal and vertical directions, and the particle size was calculated using the following formula. Particle size = ((horizontal length)) 2 + (vertical length) 2 ) 0.5

[0144] The weight-average particle size of solid aluminoxane can be calculated using the particle size obtained above, according to the following formula. Average particle size=Σnd 4 / Σnd 3 (where n is the number of particles and d is the particle size)

[0145] The solid aluminoxane preferably used in the present invention has a specific surface area of ​​50 to 1000 m². 2 / g, preferably 100-800m 2 The density is / g, and the pore volume is 0.1-2.5 cm³. 3 It is preferable that the value be / g.

[0146] Examples of inorganic halides include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halides may be used as is, or they may be used after being ground using a ball mill or vibration mill. Alternatively, the inorganic halides may be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

[0147] The aforementioned clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystalline structure in which planes formed by ionic bonds are stacked parallel to each other with weak bonding forces, and the ions it contains are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Furthermore, these clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural sources; artificially synthesized materials can also be used.

[0148] Furthermore, examples of clay, clay minerals, or ion-exchangeable layered compounds include ionic crystalline compounds having layered crystalline structures such as hexagonal close-packing type, antimony type, CdCl2 type, and CdI2 type.

[0149] Furthermore, clays and clay minerals include kaolin, bentonite, kibushi clay, gylome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, lyokdiite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchangeable layered compounds include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O.

[0150] Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc / g or more, and particularly preferably 0.3 to 5 cc / g, as measured by the mercury intrusion method for pores with a radius of 20 Å or more. Here, the pore volume is measured in the range of pore radii from 20 to 30,000 Å by the mercury intrusion method using a mercury porosimeter.

[0151] When using a support material with a pore volume of less than 0.1 cc / g and a radius of 20 Å or more, it tends to be difficult to obtain high polymerization activity.

[0152] It is also preferable to subject the clay and clay minerals used in this invention to chemical treatment. Chemical treatments can include surface treatments to remove impurities adhering to the surface, and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment removes surface impurities and increases the surface area by dissolving cations such as Al, Fe, and Mg in the crystalline structure. Alkali treatment destroys the crystalline structure of the clay, leading to a change in its structure. Salt treatment and organic treatment can form ionic complexes, molecular complexes, and organic derivatives, thereby altering the surface area and interlayer distance.

[0153] The ion-exchangeable layered compound used in this invention may be a layered compound in which the interlayers are expanded by utilizing ion exchange properties and exchanging the exchangeable ions between layers with other large, bulky ions. Such bulky ions play a supporting role in the layered structure and are usually called pillars. The introduction of another substance between the layers of a layered compound in this way is called intercalation. Possible guest compounds for intercalation include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), and [Al 13 O4(OH) 24 ] 7+ [Zr4(OH) 14 ] 2+ [Fe3O(OCOCH3)6] + Examples include metal hydroxide ions. These compounds can be used individually or in combination of two or more. Furthermore, when intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides (where R represents a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, or colloidal inorganic compounds such as SiO2 can also be present. In addition, as pillars, oxides produced by heating and dehydrating after intercalating the above-mentioned metal hydroxide ions between layers can also be used.

[0154] The clay, clay minerals, and ion-exchangeable layered compounds used in this invention may be used as is, or after being subjected to treatments such as ball milling or sieving. They may also be used after being newly treated with water adsorption or heat dehydration. Furthermore, they may be used individually or in combination of two or more.

[0155] Of these, clay or clay minerals are preferred, with montmorillonite, vermiculite, pectolite, teniolite, and synthetic mica being particularly preferred.

[0156] As mentioned above, the support (C) is an inorganic or organic compound, but examples of organic compounds include granular or particulate solids with a particle size in the range of 10 to 300 μm. Specifically, examples include (co)polymers produced mainly from α-olefins with 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane and styrene, and modified versions thereof.

[0157] The olefin polymerization catalyst described above may also optionally contain the following specific organic compound component (D) along with the transition metal compound, compound (B), and optionally a support (C).

[0158] [(D) Organic compound component] In the present invention, the organic compound component (D) is used, if necessary, to improve the polymerization performance of the olefin polymerization catalyst of the present invention and the physical properties of the resulting polymer (for example, the molecular weight of the resulting polymer) (in the case of molecular weight, to increase the molecular weight). Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

[0159] The alcohols and phenolic compounds are typically R 22 -The one represented by OH is used, where R22 This indicates a hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols).

[0160] As for alcohols, R 22 It is preferable that the halogenated hydrocarbon group is present. Furthermore, as for the phenolic compound, it is preferable that the α,α'-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms.

[0161] The above carboxylic acids are typically R 23 -The one represented by COOH is used. 23 This represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, with halogenated hydrocarbon groups having 1 to 50 carbon atoms being particularly preferred.

[0162] Preferably, the phosphorus compounds used are phosphates having a P-O-H bond, phosphates having a P-OR or P=O bond, and phosphine oxide compounds. Examples of the above-mentioned sulfonates include those represented by the following general formula (Da).

[0163] [ka] In the general formula (Da), M 5 These are atoms from groups 1-14 of the periodic table, and R 24 is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; t is an integer from 1 to 7; u is an integer from 1 to 7; and tu ≥ 1.

[0164] <Method for producing olefin polymers> An olefin polymer can be obtained by including a step of polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above. As described above, in this specification, the olefin refers to any compound having a polymerizable double bond.

[0165] In the polymerization, the usage method of each component constituting the catalyst of the present invention and the addition order to the polymerization reactor can be arbitrarily selected, and the following methods are exemplified.

[0166] (1) A method of adding the transition metal compound alone to the polymerization reactor. (2) A method of adding the transition metal compound and compound (B) to the polymerization reactor in any order. (3) A method of adding a catalyst component in which the transition metal compound is supported on a carrier (C) and compound (B) to the polymerization reactor in any order. (4) A method of adding a catalyst component in which compound (B) is supported on a carrier (C) and the transition metal compound to the polymerization reactor in any order. (5) A method of adding a catalyst component in which the transition metal compound and compound (B) are supported on a carrier (C) to the polymerization reactor. (6) A method of adding a catalyst component in which the transition metal compound and compound (B) are supported on a carrier (C), and compound (B) to the polymerization reactor in any order. In this case, the compound (B) supported on the carrier (C) and the compound (B) added alone may be the same or different. In addition, an olefin polymer can be produced using known methods.

[0167] In the solid catalyst component in which the transition metal compound is supported on the above carrier (C) and the solid catalyst component in which the transition metal compound and compound (B) are supported on the carrier (C), the olefin may be prepolymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

[0168] In the present invention, (co)polymerization can be carried out by either liquid-phase polymerization methods such as dissolution polymerization or suspension polymerization, or by gas-phase polymerization methods. Specifically, examples of inert hydrocarbon media used in liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. The olefin itself can also be used as the solvent for (co)polymerization.

[0169] When polymerizing olefins using the above-described catalyst for olefin polymerization, the transition metal compound is typically used in amounts of 10 per liter of reaction volume. -12 ~10 -2 moles, preferably 10 -10 ~10 -3 It is used in quantities that equal moles.

[0170] The organometallic compound (B-1) is used in an amount such that the molar ratio [(B-1) / M] of the organometallic compound (B-1) to the total transition metal atoms (M) in the transition metal compound is typically 0.01 to 100,000, preferably 0.05 to 50,000. The organoaluminum oxy compound (B-2) is used in an amount such that the molar ratio [(B-2) / M] of the aluminum atoms in the organoaluminum oxy compound (B-2) to the total transition metal (M) in the transition metal compound is typically 10 to 500,000, preferably 20 to 100,000. The compound (ionized ionic compound) (B-3) that reacts with the transition metal compound to form an ion pair is used in an amount such that the molar ratio [(B-3) / M] of the ionized ionic compound (B-3) to the transition metal atoms (M) in the transition metal compound is typically 1 to 50, preferably 1 to 30, more preferably 1 to 20.

[0171] The organic compound component (D) is used in an amount such that its molar ratio [(D) / (B-1)] with the organometallic compound (B-1) is typically 0.01 to 10, preferably 0.1 to 5. The organic compound component (D) is used in an amount such that its molar ratio [(D) / (B-2)] with the organoaluminum oxy compound (B-2) is typically 0.001 to 2, preferably 0.005 to 1. The organic compound component (D) is used in an amount such that its molar ratio [(D) / (B-3)] with the ionized ionic compound (B-3) is typically 0.01 to 10, preferably 0.1 to 5.

[0172] Furthermore, the polymerization temperature of olefins using such olefin polymerization catalysts is typically in the range of -50 to +200°C, preferably 0 to 170°C. The polymerization pressure is typically atmospheric pressure to 100 kg / cm². 2 -G, preferably at atmospheric pressure ~50 kg / cm² 2 Under the conditions of -G, the polymerization reaction can be carried out using batch, semi-continuous, or continuous methods. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions.

[0173] The molecular weight of the resulting olefin polymer can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of compound (B) used.

[0174] The hydrogen mentioned above acts as a chain transfer agent and is a component that lowers molecular weight. When used in combination with olefin polymerization reactions, it tends to have little effect on polymerization activity. The olefin polymerization catalyst containing the transition metal compound of this application exhibits the property of easily producing components with high molecular weight, and therefore has the advantage of offering a high degree of freedom in molecular weight adjustment.

[0175] The olefins that can be polymerized by the olefin polymerization catalyst of the present invention are not particularly limited as long as they have polymerizable double bonds, but include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20, more preferably 2 to 10, such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; Examples of cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20, and more preferably 3 to 10, include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0176] The olefin polymerization catalyst of the present invention is more preferably used for the homopolymerization of ethylene, or the copolymerization of ethylene with an olefin having 3 to 20 carbon atoms, preferably a linear or branched α-olefin having 3 to 10 carbon atoms, the homopolymerization of propylene, or the copolymerization of propylene with an olefin selected from ethylene or an α-olefin having 4 to 20 carbon atoms. The α-olefin may be used alone or in combination of two or more types.

[0177] In the copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, the α-olefin (hereinafter also referred to as olefin A) is not particularly limited as long as it achieves the effects of the present invention, but for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and 1-decene are preferred. These α-olefins may be used individually or in combination of two or more. Among these, it is more preferable that at least one selected from 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene is used.

[0178] When ethylene is used as the α-olefin and the above-mentioned olefin A is used, the ratio of ethylene to the above-mentioned olefin A used is typically 1:10 to 5000:1, preferably 1:5 to 1000:1, in terms of ethylene:the above-mentioned olefin A (molar ratio).

[0179] The ratio of propylene to olefin B, selected from ethylene and α-olefins having 4 to 20 carbon atoms, is typically 1:10 to 5000:1, preferably 1:5 to 1000:1, in molar ratio. A preferred example of olefin B is the same as olefin A, excluding propylene.

[0180] The olefin polymerization catalyst of the present invention may (co)polymerize known chain-like unsaturated hydrocarbons having polar groups (for example, carbonyl groups, hydroxyl groups, ether-bonding groups, etc.).

[0181] Furthermore, the olefin polymerization catalyst of the present invention may be used to (co)polymerize vinylcyclohexane, diene, or polyene, etc.

[0182] Examples of the diene or polyene include cyclic or chain-like compounds having 4 to 30 carbon atoms, preferably 4 to 20, and possessing two or more double bonds. Specifically, these include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, and dicyclopentadiene. 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadien, 5,9-dimethyl-1,4,8-decatriene; Furthermore, aromatic vinyl compounds, such as mono- or polyalkylstyrenes including styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene; Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like can be mentioned.

[0183] As described above, the transition metal compound of the present invention has a novel structure containing a ligand in which a fluorenyl structure and an aromatic ring structure are crosslinked. It has a novel structure in which a specific substituent is introduced at a specific position of the metallocene skeleton, and the olefin polymerization catalyst of the present invention containing the compound (A) has better copolymerizability of α-olefins than a conventional transition metal compound having a metallocene skeleton (not having a specific substituent at a specific position), shows a good balance of olefin polymerization activity-copolymerizability, has a sufficient molecular weight, and can produce a low-density ethylene copolymer.

[0184] In addition, when propylene is polymerized using the olefin polymerization catalyst containing the transition metal compound of the present invention, a ultra-high molecular weight isotactic polymer or an atactic polymer can be produced. With conventional catalysts, it has been difficult to increase the molecular weight of an atactic polymer of propylene, and there has been a tendency to obtain a polymer with a relatively low molecular weight. This is presumably because an isotactic structure propylene polymer tends to accelerate the polymerization rate by forming a helical structure, but this effect cannot be obtained with an atactic structure.

[0185] Surprisingly, the transition metal compound of the present invention can obtain a polymer with a high molecular weight with high activity even for atactic polypropylene. Also, it may show an unexpected performance that α-olefin polymers with different stereoregularities can be obtained depending mainly on the structure of R2 in the formula (A-1). <​​​​​​The presence of allows the spacing between the aromatic ring structure and the fluorenyl structure to be wider overall compared to typical metallocenes, making it easier for even olefins with a large number of carbon atoms to approach the catalytic reaction active species (which is thought to be formed around M in equation (A-1)), and also R 1 Since the aromatic ring structure and the active species can form a resonance structure, it is thought that the reactivity of the active species will increase and the polymerization rate will improve. Also, R 3 , R 4 The ring structure formed by this compound strongly links the aromatic ring structure and the fluorenyl structure, resulting in less structural change during the reaction. This may suppress chain transfer, which can occur during olefin reactions, and thus facilitate an increase in molecular weight. Based on these two effects, it is thought that this compound exhibits high activity and high molecular weight properties.

[0187] On the other hand, especially R 2 Structure and R 3 , R 4 By selecting the ring structure formed, it is possible to adjust the spacing between the aromatic ring structure and the fluorenyl structure, as well as the angle between the aromatic ring structure and the fluorenyl structure. It is thought that this selection and control may allow for the acquisition of isotactic polymers and atactic polymers. 2 , R 3 , R 4 Depending on the choice of structure, mixtures and compositions of polymers with different stereoregularities may also be prepared in situ.

[0188] Based on the above inferences, the olefin polymerization catalyst containing the transition metal compound of this application likely exhibits unique properties that allow for a wide degree of freedom in controlling stereoregularity and molecular weight.

[0189] [Olefin polymer] According to the present invention, by polymerizing an olefin selected from one or more α-olefins having 2 to 30 carbon atoms in the presence of a useful catalyst for olefin polymerization having the specific structure described above and containing the transition metal compound, it is possible to efficiently produce high molecular weight olefin polymers with various stereoregularities by homopolymerizing ethylene, copolymerizing ethylene with at least one olefin A selected from olefins having 3 to 20 carbon atoms, or polymerizing α-olefins such as propylene.

[0190] One embodiment of the olefin polymer is an ethylene-based polymer containing ethylene-derived structural units in a range of preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 90 to 100 mol%. The ethylene-based polymer contains olefin A-derived structural units in a range of preferably 0 to 50 mol%, more preferably 0 to 30 mol%, and even more preferably 0 to 10 mol% in total. However, the sum of the content of ethylene-derived structural units and the content of olefin A-derived structural units is 100 mol%. The ethylene-based polymer in which the olefin A-derived structural units are within the above range exhibits excellent moldability. In addition, other structural units may be included without departing from the spirit of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy, or by infrared spectroscopy if a reference substance is available.

[0191] Among these polymers, ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-1-octene polymer, ethylene-1-hexene polymer, ethylene-4-methyl-1-pentene polymer, ethylene-propylene-1-octene polymer, ethylene-propylene-1-hexene polymer, and ethylene-propylene-4-methyl-1-pentene polymer are particularly preferred. The above copolymers are usually random copolymers, but they may also be so-called block copolymers (impact copolymers) obtained by mixing or continuously producing two or more polymers selected from these polymers.

[0192] Among the polymers having the constituent units described above, α-olefin polymers consisting substantially only of constituent units derived from α-olefins having 2 to 20 carbon atoms are preferred. "Substantially" means that the proportion of constituent units derived from α-olefins having 2 to 20 carbon atoms is 95% by weight or more of the total constituent units.

[0193] In the case of α-olefin polymers, isotactic polymers and atactic polymers can be obtained with high molecular weights.

[0194] In the aforementioned olefin polymer, the weight-average molecular weight measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 10,000 to 5,000,000, more preferably 10,000 to 2,000,000, and particularly preferably 20,000 to 1,000,000. The molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), is not particularly limited, but is preferably 1 to 10, more preferably 1 to 7.

[0195] In the case of the olefin polymer, in the case of an ethylene-based polymer, the density is not particularly limited, but is 875 kg / m³. 3 More than 975kg / m 3 The following is preferable:

[0196] In the olefin polymer, the intrinsic viscosity [η] in decalin at 135°C is not particularly limited, but is preferably 0.1 to 40 dl / g, more preferably 0.5 to 15 dl / g, and most preferably 1 to 10 dl / g.

[0197] In the olefin polymer, the melt mass flow rate (MFR; in units of g / 10 min) measured under conditions of 190°C and a 2.16 kg load, or 230°C and a 2.16 kg load, according to ASTM D1238-89, is not particularly limited, but is preferably 0.001 g / 10 min or more and 300 g / 10 min or less, and more preferably 0.001 g / 10 min or more and 200 g / 10 min or less.

[0198] Furthermore, it is preferable that the value obtained by dividing the MFR value measured under conditions of 190°C or 230°C and a 10kg load, in accordance with ASTM D1238-89, by the MFR value measured under the conditions of 190°C and a 2.16kg load (I10 / I2) is 5.0 or more and less than 300. The details of the measurement conditions for the above physical properties are as described in the examples.

[0199] The compounds of the present invention can be used not only as catalysts for olefin polymerization as described above, but also for other applications. For example, they can be used as intermediate compounds for pharmaceuticals and agrochemicals, or as special surfactants. [Examples]

[0200] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0201] [Measurement method] [Structure of the compound] The structure of the compound synthesized below is: 1 The determination was made using 1H-NMR spectroscopy (270 MHz, JEOL GSH-270) and FD-MS (JEOL JMS-T100GC).

[0202] <Reference example 1> Compound 1, represented by the following formula, was synthesized by the following method.

[0203] [ka]

[0204] In a thoroughly dried and nitrogen-purged 300 mL reactor, 24.50 g (143.9 mmol) of orthophenylphenol, 15.8 mL (172.7 mmol) of dihydropyran, 3.62 g (14.4 mmol) of pyridinium p-toluenesulfonic acid, and 50 mL of dichloromethane were added and stirred overnight at room temperature. 20 mL of 1 M aqueous sodium hydroxide solution was added, and the soluble components were extracted with dichloromethane. The resulting organic layer was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was distilled off to quantitatively obtain compound 1 as a colorless, transparent liquid. 1 Compound 1 was identified by 1H-NMR (CDCl3) measurement. The obtained compound 1 was used directly in the next step.

[0205] 1 H NMR(270 MHz, CDCl3, δ in ppm) 7.58-7.54 (2H, m), 7.43-7.21 (6H, m), 7.07 (1H, td, J = 7.3, 1.6 Hz), 5.40 (1H, t, J = 2.9 Hz), 3.80 (1H, td, J = 10.7, 2.9 Hz), 3.58-3.54 (1H, m), 1.84-1.49 (6H, m).

[0206] <Reference example 2> Compound 2, represented by the following formula, was synthesized by the following method.

[0207] [ka]

[0208] In a thoroughly dried and nitrogen-purged 300 mL reactor, 24.47 g (161.6 mmol) of ortho-tert-butylphenol, 22.2 mL (242.3 mmol) of dihydropyran, 4.07 g (16.2 mmol) of pyridinium-p-toluenesulfonic acid, and 50 mL of dichloromethane were added and stirred overnight at room temperature. 20 mL of 1 M aqueous sodium hydroxide solution was added, and the soluble components were extracted with dichloromethane. The resulting organic layer was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was distilled off to quantitatively obtain compound 2 as a colorless, transparent liquid. 1 Compound 2 was identified by 1H-NMR (CDCl3) measurement. The obtained compound 2 was used directly in the next step.

[0209] 1 H NMR(270 MHz, CDCl3, δ in ppm) 7.29 (1H, dd, J = 8.1, 1.4 Hz), 7.20-7.12 (2H, m), 6.93-6.90 (1H, m), 5.48 (1H, t, J = 2.8 Hz), 3.97-3.89 (1H, m), 3.68-3.64 (1H, m), 2.05-1.60 (6H, m), 1.42 (9H, s).

[0210] <Reference example 3> Compound 3, represented by the following formula, was synthesized by the following method.

[0211] [ka]

[0212] In a thoroughly dried and nitrogen-purged 500 mL reactor, 16.85 g (101.4 mmol) of fluorene and 150 mL of THF were charged and stirred. After cooling to -78°C, 63.4 mL of n-butyllithium solution (hexane solution, 1.6 M, 101.4 mmol) was added and the mixture was stirred at room temperature for 2 hours. In a thoroughly dried and nitrogen-purged 1000 mL reactor, 25.35 g (101.4 mmol) of orthobromobenzyl bromide in a THF (100 mL) solution cooled to -78°C was slowly added dropwise. After stirring overnight at room temperature, saturated ammonium chloride aqueous solution was added and the solvent was removed as much as possible by distillation. The soluble components were extracted from the remaining solution with ethyl acetate, and the resulting organic layer was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was distilled off to quantitatively obtain compound 3 as a white solid. 1 Compound 3 was identified by 1H-NMR (CDCl3) measurement. The obtained compound 3 was used directly in the next step.

[0213] 1 H NMR(270 MHz, CDCl3, δ in ppm) 7.77 (2H, d, J = 7.6 Hz), 7.67 (1H, d, J = 7.6 Hz), 7.36 (2H, t, J = 7.3 Hz), 7.31-7.14 (7H, m), 4.42 (1H, t, J = 7.7 Hz), 3.16 (2H, d, J = 7.6 Hz).

[0214] [Example 1] Compound 4, represented by the following formula, was synthesized by the following method.

[0215] [ka]

[0216] In a thoroughly dried and nitrogen-purged 1000 mL reactor, 36.60 g (143.9 mmol) of compound 1 and 300 mL of THF were charged. After cooling to -78°C, 93.9 mL of n-butyllithium solution (hexane solution, 1.6 M, 150.2 mmol) was added, and the mixture was stirred at room temperature for 2 hours. 16.9 mL (151.3 mmol) of trimethoxyborane was added at -78°C, and the mixture was stirred overnight at room temperature. 2 M HCl was added, and after removing as much of the solvent as possible, the soluble components were extracted with tert-butyl methyl ether. The resulting organic layer was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was removed by distillation to obtain a white solid compound. 10.89 g (50.9 mmol) of the crude product obtained, 18.76 g (56.0 mmol) of compound 3, 0.11 g (0.50 mmol) of palladium acetate, 25.93 g (122.14 mmol) of tripotassium phosphate, 0.41 g (1.0 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 100 mL of THF, and 15 mL of water were added to a thoroughly dried, nitrogen-purged 500 mL reactor and stirred at 75 °C for 7 hours. After removing as much of the solvent as possible, the soluble components were extracted from the remaining solution with dichloromethane, and the resulting organic layer was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was removed by distillation. The resulting residue was purified by silica gel column chromatography to obtain compound 4 as a white solid in 18% yield. 1 Compound 4 was identified based on the results of 1H-NMR (CDCl3) measurement.

[0217] 1 H NMR(270 MHz, toluene-d8, δ in ppm) 7.50 (2H, d, J = 7.3 Hz), 7.41 (2H, dd, J = 8.1, 1.2 Hz), 7.21-6.89 (15H, m), 6.79 (1H, t, J = 7.6 Hz), 4.85 (1H, s), 3.88 (2H, t, J = 7.5 Hz), 2.99 (2H, dd, J = 17.3, 7.5 Hz).

[0218] [Example 2] Compound 5, represented by the following formula, was synthesized by the following method.

[0219] [ka]

[0220] In a thoroughly dried and nitrogen-purged 300 mL reactor, 2.34 g (10.0 mmol) of compound 2 and 30 mL of THF were charged. After cooling to -78 °C, 6.6 mL of n-butyllithium solution (hexane solution, 1.6 M, 10.5 mmol) was added, and the mixture was stirred at 0 °C for 1.5 hours. 1.2 mL (10.5 mmol) of trimethoxyborane was added at 0 °C, and the mixture was stirred overnight at room temperature. To this reaction mixture, 3.42 g (10.2 mmol) of compound 3, 45 mg (0.20 mmol) of palladium acetate, 5.31 g (25 mmol) of tripotassium phosphate, 160 mg (0.40 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, and 15 mL of water were added, and the mixture was stirred at 75 °C for 7 hours. After removing as much of the solvent as possible, the soluble components were extracted with dichloromethane, and the resulting organic layer was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was removed to obtain the crude product. The obtained crude product, 0.20 g (0.80 mmol) of pyridinium p-toluenesulfonic acid, and 50 mL of ethanol were thoroughly dried and charged into a 300 mL nitrogen-purged reactor, which was stirred at 55°C. After stirring overnight, saturated sodium bicarbonate aqueous solution was added, and after removing as much of the solvent as possible, the soluble components were extracted with dichloromethane, and the resulting organic layer was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was removed to obtain a residue which was purified by silica gel column chromatography to obtain compound 5 as a white solid in 40% yield. 1 Compound 5 was identified based on the results of 1H-NMR (CDCl3) measurement.

[0221] 1H NMR(270 MHz, CDCl3, δ in ppm) 7.68 (2H, d, J = 7.6 Hz), 7.45-7.40 (3H, m), 7.31-7.26 (4H, m), 7.18-7.09 (2H, m), 7.01 (1H, dd, J = 7.6, 1.3 Hz), 6.90-6.83 (2H, m), 6.74 (1H, d, J = 7.3 Hz), 4.97 (1H, s), 3.82 (1H, t, J = 7.4 Hz), 3.12 (1H, dd, J = 13.8, 6.6 Hz), 2.77 (1H, dd, J = 13.8, 8.6 Hz), 1.43 (9H, s).

[0222] [Example 3] Compound 6, represented by the following formula, was synthesized by the following method.

[0223] [ka]

[0224] In a thoroughly dried, nitrogen-purged 3000 mL reactor, 24.07 g (220 mol) of p-cresol and 240 ml of dichloromethane were added and stirred. After cooling in an ice bath, 13 ml of concentrated sulfuric acid was slowly added. In another thoroughly dried, nitrogen-purged flask, 40.55 g (220 mol) of 9-fluorenol was added, followed by 1200 ml of dichloromethane, and the mixture was stirred to prepare the solution. This solution was slowly added dropwise to the reactor cooled in an ice bath, and the mixture was stirred at room temperature for 2 hours. Saturated sodium bicarbonate aqueous solution was added to quench the reaction, and then sodium hydroxide aqueous solution (2 M) was added until the reaction mixture became neutral. 800 ml of ethyl acetate was added, stirred, and allowed to stand, after which the organic layer and aqueous layer were separated. The organic layer was washed with water and saturated brine, and then concentrated using a rotary evaporator to obtain 64.57 g of crude product. The crude product was purified by silica gel column chromatography to obtain compound 6 in 32% yield. 1 Compound 6 was identified based on the results of 1H-NMR (CDCl3) measurement.

[0225] 1 H NMR(270 MHz, CDCl3, δ in ppm) 7.83-7.80 (2H, m), 7.43-7.37 (4H, m), 7.30-7.25 (3H, m), 6.94-6.67 (3H, m), 5.33 (1H, brs) 2.19(3H, brs).

[0226] <Reference example 4> Compound 7, represented by the following formula, was synthesized by the following method.

[0227] [ka]

[0228] In a thoroughly dried, nitrogen-purged 3000 mL reactor, 14.09 g (51.7 mmol) of compound 6 and 130 ml of dichloromethane were added and stirred. While cooling the reactor in an ice bath, 8.8 ml (109 mmol) of pyridine was added. Next, a solution was prepared by mixing 10.1 ml (59.4 mmol) of trifluoromethanesulfonic acid anhydride and 24 ml of dichloromethane, and this solution was slowly added dropwise to the reactor, which had been cooled in an ice bath. After addition, the temperature was raised to room temperature and stirred for 1.5 hours at room temperature. After quenching with 40 ml of 2 M hydrochloric acid solution, the mixture was extracted with 600 ml of tert-butyl methyl ether. After separating the organic layer and the aqueous layer, the organic layer was washed with saturated sodium bicarbonate solution, then saturated brine, and dried with anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the filtrate was concentrated in a rotary evaporator to obtain 18.8 g of crude product. The crude product was purified by silica gel column chromatography to obtain compound 7 in 78% yield. 1 Compound 7 was identified based on the results of 1H-NMR (CDCl3) measurement.

[0229] 1H NMR(270 MHz, CDCl3, δ in ppm) 7.84-7.80 (2H, m), 7.44-7.24 (8H, m), 7.07 (1H, dd, J = 8.5, 2.0 Hz), 6.30(1H, brs), 5.44(1H, brs), 2.09(3H, brs).

[0230] [Example 4] Compound 8, represented by the following formula, was synthesized by the following method.

[0231] [ka]

[0232] In a 200 ml three-necked flask, 3.80 g (14.9 mmol) of compound 1, 6.00 g (14.8 mmol) of compound 7, 7.60 g (35.8 mmol) of tripotassium phosphate, 33 mg (0.15 mmol) of palladium acetate, 122 mg (0.30 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, and 60 ml of THF were added, and the system was purged with nitrogen. After adding 12 ml of water, the temperature was raised to 60 °C and stirring was continued for 2 hours. After adding aqueous hydrochloric acid (2 M) and quenching, the reaction mixture was extracted with tert-butyl methyl ether. The organic layer was separated with water and saturated brine and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and the organic layer was concentrated using a rotary evaporator to obtain 9.89 g of crude product. The crude product was purified by silica gel column chromatography to obtain 3.67 g of a mixture containing compound 8.

[0233] The mixture was added to a 500 ml flask, and 0.20 g (1.1 mmol) of p-toluenesulfonic acid monohydrate, 150 ml of methanol, and 50 ml of tert-butyl methyl ether were added. The mixture was stirred overnight at room temperature. Saturated sodium bicarbonate aqueous solution was added to quench the mixture, and it was extracted with ethyl acetate. The organic layer was washed with water and saturated brine and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and the organic layer was concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography to obtain compound 8 in 48% yield. 1 Compound 8 was identified based on the results of 1H-NMR (CDCl3) measurement.

[0234] 1 H NMR(270 MHz, CDCl3, δ in ppm) 7.78-7.11 (18H, m),6.30 (1H, brs), 5.41(1H, brs), 5.17(1H, brs), 2.11(3H, brs).

[0235] The following describes the preparation of a catalyst for olefin polymerization using the aforementioned compound and an example of a method for polymerizing olefins.

[0236] [Stereoregularity of polymers] The stereoregularity of polymers (triad isotacticity (mm)) is 13 The result was obtained from 13C-NMR spectroscopy measurements.

[0237] [Weight-average molecular weight (Mw), molecular weight distribution (Mw / Mn) of polymers] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). The calculations were performed using the molecular weight distribution curve obtained from a Tosoh Corporation "HLC-8321GPC-HT" gel permeation chromatograph (high-temperature size exclusion chromatograph), under the following operating conditions.

[0238] <Equipment and conditions used> Measuring device: Gel permeation chromatograph HLC-8321GPC-HT model (manufactured by Tosoh Corporation) Analysis software; Chromatography data system Empower3 (trademark, Waters Inc.) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (Inner diameter 7.5 mm x length 30 cm, Tosoh Corporation) Mobile phase: o-dichlorobenzene [ODCB] (Wako Pure Chemical Industries, Special Grade Reagent) Detector; differential refractometer (built into the device) Column temperature: 140°C Flow rate; 1.0 mL / min Injection volume; 400 μL Sampling time interval: 0.5 seconds Sample concentration: 0.15% (w / v) Molecular weight calibration; monodisperse polystyrene (Tosoh Corporation) / molecular weight from 495 to 20.6 million Molecular weight conversion; PS conversion / standard conversion method

[0239] [Production of transition metal compounds] <Synthesis of transition metal compound (A1)> The transition metal compound (A1) represented by the following formula was synthesized by the following method.

[0240] [ka]

[0241] In a thoroughly dried, nitrogen-purged 100 mL reactor, 424 mg (1.0 mmol) of compound (4) and 25 mL of diethyl ether were charged. After cooling to -78°C, 1.31 mL of n-butyllithium solution (hexane solution, 1.6 M) was added, and the mixture was stirred at room temperature for 1.5 hours. To this solution, 0.7 mL of methylmagnesium bromide (diethyl ether solution, 3.0 M) was added at -78°C, and the mixture was stirred at room temperature for 1.5 hours. In a thoroughly dried, nitrogen-purged 100 mL reactor, 1.0 mL of tetrachlorotitanium solution (toluene solution, 1.0 M) and 12 mL of pentane were added. After cooling to -78°C, 37 mL of diethyl ether was added, and the mixture was stirred for 1.5 hours. To this solution, the ligand n-butyllithium / methylmagnesium bromide mixed solution was added at -78°C, and the mixture was stirred overnight at room temperature. After removing the reaction solution by distillation, dichloromethane was added to the solid obtained in the glove box to prepare a suspension, and insoluble matter was removed by filtration through a membrane filter with a pore size of 0.45 μm. After removing the solvent by distillation, the same filtration treatment was performed with toluene and cyclohexane, and the cyclohexane suspension was filtered off with a glass filter to obtain the target product (A1), an orange solid, in a yield of 6%. 1 The target substance (A1) was identified based on the results of 1H-NMR (CDCl3) and FD-MS measurements.

[0242] 1 H NMR(270 MHz CDCl3, δ in ppm) 8.26 (1H, d, J = 8.2 Hz), 7.95 (3H, dq, J = 11.3, 3.9 Hz), 7.49-7.07 (13H, m), 6.91 (2H, td, J = 6.5, 3.4 Hz), 6.55-6.49 (1H, m), 4.16 (2H, dd, J = 21.4, 14.5 Hz), -0.36 (3H, s), -0.76 (3H, s).FD-MS:m / z=500.2(M + )

[0243] (Polymerization example p1) Under a nitrogen atmosphere, 2.0 mg (4.0 μmol) of transition metal compound (A1) was placed in a Schlenk tube, and 8.0 mL of toluene was added to prepare a catalyst solution with a transition metal compound (A1) concentration of 0.0005 M.

[0244] In a 15 mL stainless steel autoclave with a volume of SUS (stainless steel) that had been thoroughly purged with nitrogen, 0.2 mL (0.05 M) of a heptane solution of triisobutylaluminum (10 μmol) and 2.9 mL of heptane as a polymerization solvent were added, and the mixture was stirred at 600 rpm. The resulting solution was heated to 60 °C, and then the autoclave was pressurized with propylene until the total pressure reached 7 bar.

[0245] Polymerization was started by adding 0.1 mL of the catalyst solution (concentration of transition metal compound (A1) at 0.0005 M, volume at 0.05 μmol), 0.1 mL (0.005 M) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl) borate (0.5 μmol), and then 0.7 mL of heptane to the autoclave. Polymerization was started at 60°C for 11 minutes, after which a small amount of isobutyl alcohol was added to stop the polymerization. 1 mL (1 M) of hydrochloric acid was added to the obtained polymer solution, the aqueous layer was washed three times with hexane, the solvent was removed from the recovered organic layer, and the mixture was dried under reduced pressure at 130°C for 10 hours to obtain 0.51 g of propylene polymer. NMR analysis of the propylene polymer showed that its stereoregularity was mm / mr / rr = 29 / 44 / 27, its weight-average molecular weight (Mw) was 303,000, and its molecular weight distribution index, Mw / Mn, was 2.1.

[0246] (Comparative polymerization example p1) The transition metal compound (A4) represented by the following formula was synthesized using the method described in WO2001-027124.

[0247] [ka]

[0248] Next, under a nitrogen atmosphere, 2.0 mg (4.0 μmol) of transition metal compound (A4) was placed in a Schlenk tube, and 7.2 mL of toluene and 0.8 mL (0.8 mmol, 1 M) of triisobutylaluminum toluene solution were added. The mixture was stirred at room temperature for at least 10 minutes to prepare a catalyst solution with a transition metal compound (A4) concentration of 0.0005 M.

[0249] In a 15 mL stainless steel autoclave with a volume of SUS (stainless steel) that had been thoroughly purged with nitrogen, 0.2 mL (0.05 M) of a heptane solution of triisobutylaluminum (10 μmol) and 2.9 mL of heptane as a polymerization solvent were added, and the mixture was stirred at 600 rpm. The resulting solution was heated to 60°C, and then the autoclave was pressurized with propylene until the total pressure reached 7 bar.

[0250] Polymerization was started by adding 0.1 mL of the catalyst solution (with a transition metal compound (A4) concentration of 0.0005 M and a volume of 0.05 μmol), 0.1 mL (0.005 M) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl) borate (0.5 μmol), and then 0.7 mL of heptane to the autoclave. Polymerization was started at 60°C for 10 minutes, after which a small amount of isobutyl alcohol was added to stop the polymerization. 1 mL (1 M) of hydrochloric acid was added to the obtained polymer solution, the aqueous layer was washed three times with hexane, the solvent was removed from the recovered organic layer, and the mixture was dried under reduced pressure at 130°C for 10 hours to obtain 0.12 g of propylene polymer. NMR analysis of the propylene polymer showed that its stereoregularity was mm / mr / rr = 92 / 5 / 3, its weight-average molecular weight (Mw) was 22,800, and its molecular weight distribution index, Mw / Mn, was 1.7.

[0251] [Reference example 5] Compound 9, represented by the following formula, was synthesized by the following method.

[0252] [ka]

[0253] In a 500 ml three-necked flask under a nitrogen atmosphere, 200 ml of anhydrous dichloromethane, 25 g (0.163 mol) of 2-tert-butylphenol, 0.12 g (0.47 mmol) of pyridinium p-toluenesulfonate, and 22.1 ml (0.24 mol) of 3,4-dihydro-1H-pyran were added and stirred overnight at room temperature. Saturated sodium bicarbonate solution was added to quench the mixture, and the organic layer was separated. The organic layer was washed with saturated brine and separated again. The organic layer was concentrated using a rotary evaporator to obtain 38.29 g of crude product. The obtained crude product was used directly in the next step. 1 Compound 9 was identified based on the results of 1H-NMR (CDCl3) measurement.

[0254] 1 H NMR(270 MHz, CDCl3, δ in ppm) 7.33-7.11 (3H, m), 6.96-6.87 (1H, m), 5.52-5.46 (1H, m), 3.98-3.86 (1H, m), 3.70-3.61 (1H, m), 2.12-1.58 (6H, m),1.42 (9H, s).

[0255] [Reference example 6] Compound 10, represented by the following formula, was synthesized by the following method.

[0256] [ka]

[0257] In a thoroughly dried 500 ml three-necked flask under a nitrogen atmosphere, 19.0 g (81 mmol) of compound 9 and 100 ml of anhydrous THF were added and stirred while cooling in an ice bath. 61 mL of n-butyllithium solution (hexane solution, 1.6 M, 97 mmol) was slowly added dropwise. After stirring for 1 hour, the mixture was cooled to -78°C. 12.9 ml (122 mmol) of trimethyl borate was slowly added dropwise. After addition, the temperature was gradually raised to room temperature and stirred overnight. The flask was cooled in an ice bath, quenched with 2 mol / L hydrochloric acid solution, and the organic layer was separated by adding water. The organic layer was separated by saturated ammonium chloride aqueous solution, saturated sodium bicarbonate aqueous solution, and saturated brine to obtain 21.7 g of crude product. The obtained boronic acid (compound 10) was used in the next step without any special purification.

[0258] [Example 5] Compound 11, represented by the following formula, was synthesized by the following method.

[0259] [ka]

[0260] In a 200 ml three-necked flask, 15.5 g (55.6 mmol) of the previously synthesized boronic acid (compound 10), 15.0 g (37 mmol) of compound 7, 18.9 g (89 mmol) of tripotassium phosphate, 166 mg (0.74 mmol) of palladium acetate, 609 mg (1.48 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, and 150 ml of THF were added and stirred. After adding 30 ml of water, the reaction mixture was heated and stirred under reflux for 2 hours. The flask was cooled in an ice bath and quenched with 2 mol / L hydrochloric acid aqueous solution. 100 ml of tert-butyl methyl ether was added, and the organic layer was separated. The organic layer was washed with saturated ammonium chloride aqueous solution, saturated sodium bicarbonate aqueous solution, and saturated brine, and dried over magnesium sulfate. The organic layer was concentrated using a rotary evaporator to obtain 31.0 g of crude product. The product was purified by silica gel column chromatography (eluent:hexane:dichloromethane = 20:1) to obtain 19.8 grams of the product.

[0261] The obtained product was added to a 100 ml three-necked flask, and 0.77 g of p-toluenesulfonic acid monohydrate, 25 ml of dichloromethane, and 25 ml of methanol were added. The mixture was stirred at room temperature for 3 hours. The mixture was quenched with saturated sodium bicarbonate aqueous solution, and dichloromethane was added, allowing the organic layer to separate. The organic layer was washed with saturated sodium bicarbonate aqueous solution, water, and saturated brine, and concentrated using a rotary evaporator to obtain 10.3 g of the product. The product was purified by silica gel column chromatography to obtain 4.986 g (12.3 mmol) of the target product. 1 Compound 11 was identified based on the results of 1H-NMR (CDCl3) measurement.

[0262] 1 H NMR(270 MHz, CDCl3, δ in ppm) 7.84-7.77 (2H, m), 7.43-7.08 (10H, m), 7.05-6.93 (1H, m), 6.32(1H, br, s), 5.34(1H, br, s), 5.01(1H, br, s), 2.11(3H, br, s), 1.44(9H, br, s).

Claims

1. A compound represented by the following general formula (A-1). 【Chemistry 1】 [In formula (A-1), R 1 It is a group 16 atom in the periodic table, R 2 is, -(Q(R l ) 2 ) x - A substituent in the structure, where Q is a carbon atom or a silicon atom. R 3 , R 4 is a substituent of the -C(R m ) 2 - structure. In the formula, when there are multiple Rs m , different Rs m may combine with each other to form a ring structure, or may directly combine to form a covalent bond to form a ring structure R 5 ~R 7 , R l , R m These are, respectively, a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene-based divalent derivative group. n is an integer between 2 and 10. x is an integer between 0 and 5 (excluding 0).

2. The compound according to claim 1, wherein n is 4 or 5.

3. R 3 , R 4 The compound according to claim 1, wherein the ring structure formed is an aromatic ring.

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