Porous material for olefin polymerization catalyst, olefin polymerization catalyst, and method for producing olefin polymer

Abstract

To provide a porous coordination polymer capable of producing an olefin polymer with high polymerization activity when used as a catalyst for olefin polymerization.SOLUTION: There is provided a porous material (A) for a catalyst for olefin polymerization satisfying the following requirements (α-1) and (α-2), which is a porous coordination polymer comprising a transition metal ion cluster of Group 4 of the Periodic Table and an organic ligand (L). (α-1) The specific surface area by the BET multipoint method is 500 m2 / g or more and 4000 m2 / g or less. (α-2) The molar ratio of halogen atoms to transition metal atoms in Group 4 of the Periodic Table (halogen atoms / transition metal atoms in Group 4 of the Periodic Table) as measured by X-ray photoelectron spectroscopy (XPS) is 0.20 or more and 1.0 or less and the halogen atom is a chlorine atom and / or a bromine atom.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a porous material for use as a catalyst for olefin polymerization, and more particularly to a porous coordination polymer for use as a catalyst for olefin polymerization and its use. [Background technology]

[0002] Porous coordination polymers (PCPs) are materials with porous structures formed by coordination bonds between metal ions and organic substances, and their use in fields such as adsorbents and catalysts is being investigated.

[0003] For example, there have been reports of porous coordination polymers being used as catalysts for olefin polymerization. Patent Document 1 describes a reaction product between an MOF using a Group 4 metal such as hafnium and a single-site zirconium-benzyl derivative, and a method for polymerizing an alkene by contacting this reaction product with the alkene. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2016 / 25624 Summary of the Invention [Problem to be solved by the invention]

[0005] However, conventional olefin polymerization methods using porous coordination polymers as catalysts have room for further improvement in terms of polymerization activity. In view of the above-mentioned conventional techniques, an object of the present invention is to provide a novel porous coordination polymer for use as an olefin polymerization catalyst, which can produce an olefin polymer with high polymerization activity when used as an olefin polymerization catalyst. [Means for solving the problem]

[0006] The present invention relates to, for example, the following [1] to [8]. [1] A porous material (A) for use as an olefin polymerization catalyst is a porous coordination polymer composed of a Group 4 transition metal ion cluster and an organic ligand (L), and satisfies the following requirements (α-1) and (α-2). (α-1) Specific surface area measured by the BET multipoint method is 500m 2 / g or more 4000m 2 / g or less. (α-2) The molar ratio of halogen atoms to Group 4 transition metal atoms of the periodic table (halogen atoms / Group 4 transition metal atoms of the periodic table) measured by X-ray photoelectron spectroscopy (XPS) is 0.20 or more and 1.0 or less, and the halogen atoms are chlorine atoms and / or bromine atoms.

[0007] [2] The porous material (A) for use as an olefin polymerization catalyst according to [1] above, wherein at least one of the organic ligands (L) is a ligand having two or more carboxy groups in one molecule.

[0008] [3] The porous material (A) for an olefin polymerization catalyst according to the above [1] or [2] further satisfies the following requirement (α-3): (α-3) The molar ratio of oxygen atoms to transition metal atoms of Group 4 of the periodic table (oxygen atoms / transition metal atoms of Group 4 of the periodic table) measured by X-ray photoelectron spectroscopy (XPS) is 2.5 or more and 4.5 or less.

[0009] [4] The specific surface area is 1000m 2 / g or more 4000m 2 The porous material (A) for an olefin polymerization catalyst according to any one of the above [1] to [3], wherein the porous material (A) has a molecular weight of 1000 or less.

[0010] [5] An olefin polymerization catalyst comprising the porous material (A) for an olefin polymerization catalyst according to any one of [1] to [4] above.

[0011] [6] The olefin polymerization catalyst according to [5] above, further comprising at least one component (B) selected from the group consisting of the following (β-1) and (β-2): (β-1) An organoaluminum compound represented by the following general formula (BI): R a m Al(OR b ) n H p X q ···(BI) [In general formula (BI), R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, X is a halogen atom, m is an integer of 1 to 3, n is an integer of 0 to 2, p is an integer of 0 to 2, q is an integer of 0 to 2, and m+n+p+q=3. (β-2) Organoaluminum oxy compounds

[0012] [7] A method for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the olefin polymerization catalyst of [5] or [6] above.

[0013] [8] The method for producing an olefin polymer according to [7] above, wherein the step of polymerizing an olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene with a linear or branched α-olefin having from 3 to 30 carbon atoms. [Effects of the Invention]

[0014] When the porous material (A) for an olefin polymerization catalyst of the present invention is used as an olefin polymerization catalyst, an olefin polymer can be produced with a higher polymerization activity than in olefin polymerization using a conventional porous coordination polymer as a catalyst. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will now be described in further detail. [Porous materials for olefin polymerization catalysts (A)] The porous material (A) for an olefin polymerization catalyst of the present invention (hereinafter also simply referred to as "porous material (A)") is a porous coordination polymer used in olefin polymerization, which is composed of a Group 4 transition metal ion cluster and an organic ligand (L), and satisfies the requirements (α-1) and (α-2) described below.

[0016] <Periodic Table Group 4 Transition Metal Ion Cluster> Examples of the Group 4 transition metals contained in the Group 4 transition metal ion cluster (hereinafter also simply referred to as "metal ion cluster") include titanium (Ti), zirconium (Zr), and hafnium (Hf), and zirconium (Zr) and hafnium (Hf) are preferred because they facilitate the production of porous coordination polymers with stable structures. These may be used alone or in combination of two or more.

[0017] An example of the structure of the metal ion cluster is MO 8-x (OH) x (M is a transition metal atom ion of Group 4 of the periodic table, and x is an integer of 0 to 8.) and the structure described in Coordination Chemistry Reviews 359 (2018) 80-101. Specific examples of the former include M6(μ 3 -O)4(μ 3 —OH)4 (wherein M is a transition metal atom ion of Group 4 of the periodic table).

[0018] <Organic ligand (L)> The organic ligand (L) is an organic ligand that bonds the metal ion clusters together, and examples thereof include polycarboxylic acids such as dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids, which may be used alone or in combination of two or more.

[0019] (dicarboxylic acid) Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-diaminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4-(4-carboxyphenyl)-3-fluorobenzoic acid, 4,4'-(ethyne-1,2-diyl)dibenzoic acid, [1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid, 2',5'-dimethyl-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid, 2,2'-bipyridine-5,5'-dicarboxylic acid, fumaric acid, malonic acid, adipic acid, and derivatives thereof. These may be used alone or in combination of two or more.

[0020] Among the above-mentioned compounds, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-(ethyne-1,2-diyl)dibenzoic acid, [1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid, and derivatives thereof, such as 4-(4-carboxyphenyl)-3-fluorobenzoic acid and 2',5'-dimethyl-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid, are preferred from the viewpoint of polymerization activity during olefin polymerization, which will be described later.

[0021] (tricarboxylic acid) Examples of tricarboxylic acids include biphenyl-3,4',5-tricarboxylic acid, 1,3,5-tris(4'-carboxy[1,1'-biphenyl]-4-yl)benzene, 1,3,5-tris(4-carboxyphenyl)benzene, 1,3,5-benzenetricarboxylic acid, 5'-(4-carboxyphenyl)-2',4',6'-trimethyl-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid, 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tricarboxylic acid, and derivatives thereof. These may be used alone or in combination of two or more.

[0022] (Tetracarboxylic acid) Examples of tetracarboxylic acids include p-terphenyl-3,3',5,5'-tetracarboxylic acid (also known as 5,5'-(1,4-phenylene)bisisophthalic acid), 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayl)tetrabenzoic acid, and derivatives thereof. These may be used alone or in combination of two or more.

[0023] (amine compounds) Examples of the organic ligand (L), in addition to the above-mentioned dicarboxylic acids, include imidazoles such as imidazole, 2-methylimidazole, and 2-phenylimidazole and derivatives thereof; compounds having a pyridine ring such as 4,4'-bipyridine, 1,4-bis(4-pyridyl)benzene, 2,2'-dimethyl-4,4'-bipyridine, 1,4-bis(4-pyridyl)butadiyne, 1,2-bis(4-pyridyl)ethane, and 3,6-di(4-pyridyl)-1,2,4,5-tetrazine and derivatives thereof; compounds having a pyrazine ring such as pyrazine and 2,5-dimethylpyrazine and derivatives thereof; and cyclic amines such as 1,4-diazabicyclo[2.2.2]octane and derivatives thereof other than those mentioned above.

[0024] Among these organic ligands (L), the above-mentioned dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids are preferred, and dicarboxylic acids are more preferred, because they make it easier to obtain a porous coordination polymer having a stable structure.

[0025] [Porous coordination polymer] The porous coordination polymer is a porous crystalline material composed of an organic ligand (L) and a metal ion cluster occupying the central position of the structure to which the organic ligand (L) is coordinated, and is also called a metal organic framework (MOF).

[0026] Since the metal ion cluster has a positive charge, the organic ligand (L) is not necessarily in the state of the above-mentioned compound itself. For example, in the case of a carboxylic acid, the carboxy group is in a deprotonated state and coordinated to the metal ion cluster, more specifically, to the transition metal ion of Group 4 of the periodic table that constitutes the metal ion cluster. In the porous coordination polymer, a monocarboxylic acid that may be used in the manufacturing process may be coordinated to a transition metal ion of Group 4 of the periodic table.

[0027] [Requirements (α-1)~(α-3)] The porous material (A) according to the present invention satisfies the following requirements (α-1) and (α-2).

[0028] Requirements (α-1): Requirement (α-1) is that the specific surface area measured by the BET multipoint method is 500m 2 / g or more 4000m 2 The specific surface area is preferably 1000 m / g or less. 2 / g or more 4000m 2 / g or less, more preferably 1000m 2 / g or more 3000m 2 / g or less.

[0029] Requirements (α-2): Requirement (α-2) is that the molar ratio of halogen atoms to Group 4 transition metal atoms of the periodic table ((halogen atoms / Group 4 transition metal atoms of the periodic table) measured by X-ray photoelectron spectroscopy (XPS) is 0.20 or more and 1.0 or less, and the halogen atoms are chlorine atoms and / or bromine atoms (hereinafter, the molar ratio will also be referred to as the "(Cl+Br) / M ratio"). The (Cl+Br) / M ratio is preferably 0.20 or more and 0.70 or less, and more preferably 0.20 or more and 0.50 or less.

[0030] That is, it is believed that the porous material of the present invention contains the halogen atoms, and that the halogen atoms are bonded to some of the Group 4 transition metal atoms of the periodic table. The halogen atom is a chlorine atom and / or a bromine atom, preferably a chlorine atom or a chlorine atom and a bromine atom, and more preferably a chlorine atom. The porous material (A) preferably further satisfies the following requirement (α-3).

[0031] Requirements (α-3): Requirement (α-3) is that the molar ratio of oxygen atoms to Group 4 transition metal atoms (oxygen atoms / Group 4 transition metal atoms, hereinafter also referred to as "O / M ratio") measured by X-ray photoelectron spectroscopy (XPS) is 2.5 or more and 4.5 or less. The O / M ratio is preferably 3.0 or more and 4.5 or less, and more preferably 3.3 or more and 4.5 or less.

[0032] <Method for measuring O / M ratio and (Cl+Br) / M ratio> Measurement of the O / M ratio and the (Cl+Br) / M ratio by X-ray photoelectron spectroscopy (XPS) is carried out as follows.

[0033] The measurement sample is handled under a nitrogen atmosphere, and monochromated AlKα is used as the X-ray source. Charge correction and neutralization are performed during measurement. The oxygen atomic concentration (Atomic %) is calculated from the peak area of ​​the O1s narrow spectrum, the chlorine atomic concentration (Atomic %) from the peak area of ​​the Cl2s narrow spectrum, and the bromine atomic concentration (Atomic %) from the peak area of ​​the Br3d narrow spectrum.

[0034] Regarding the atomic concentration (Atomic%) of transition metals in Group 4 of the periodic table, the titanium atomic concentration (Atomic%) is calculated from the peak area of ​​the Ti2p narrow spectrum, the zirconium atomic concentration (Atomic%) is calculated from the peak area of ​​the Zr3d narrow spectrum, and the hafnium atomic concentration (Atomic%) is calculated from the peak area of ​​the Hf4f narrow spectrum.

[0035] Based on these atomic concentrations, the O / M ratio and the (Cl+Br) / M ratio are calculated using the following formula. O / M ratio = oxygen atomic concentration / periodic table group 4 transition metal atomic concentration (Cl + Br) / M ratio = (chlorine atom concentration + bromine atom concentration) / periodic table group 4 transition metal atom concentration

[0036] Examples of the form of the porous material (A) include powder and molded bodies. Examples of the shape of the molded body include a sphere, a pellet, a cylinder, a ring, a wheel, and a granule.

[0037] (Method for producing porous material (A)) As a method for producing the porous material (A) of the present invention, a conventionally known method for producing a porous coordination polymer can be appropriately adopted, except that the production conditions are adjusted so as to satisfy the above requirements (α-1) to (α-2), and preferably also the above requirement (α-3). Examples of such a production method include: A method in which two types of solutions, one containing a Group 4 transition metal ion of the periodic table and the other containing the organic ligand, are gradually diffused and reacted at the liquid-liquid interface; a method in which the organic ligand or a solution thereof is added to a solution containing a transition metal ion of Group 4 of the periodic table and reacted with the organic ligand while stirring; A method for reacting a solution containing a transition metal ion of Group 4 of the periodic table and the above-mentioned organic ligand in a pressure vessel Examples include:

[0038] Sources of transition metals of Group 4 of the periodic table include chlorides (titanium chloride, zirconium chloride, hafnium chloride), bromides (zirconium bromide, titanium bromide), oxychlorides (titanium oxychloride, zirconium oxychloride, hafnium oxychloride, and hydrates thereof).

[0039] In these methods, the value of the specific surface area in the above requirement (α-1) can be adjusted by changing the type of organic ligand. Furthermore, in order to satisfy the above requirement (α-2), and preferably also the requirement (α-3), a source of oxygen atoms and a source of chlorine atoms or bromine atoms are first required. Examples of the oxygen atom source include organic ligands having oxygen atoms, such as dicarboxylic acid compounds, tricarboxylic acid compounds, and tetracarboxylic acid compounds, monocarboxylic acid compounds described below, solvents consisting of compounds having oxygen atoms, and water. Examples of the chlorine atom or bromine atom source include chlorides, bromides, and oxychlorides of transition metals of Group 4 of the periodic table, as well as hydrogen chloride, hydrogen bromide, or aqueous solutions thereof.

[0040] Next, by shortening the time for reacting the raw material of the transition metal of Group 4 of the periodic table with the organic ligand, the (Cl+Br) / M ratio in the above requirement (α-2) tends to increase. More specific examples of manufacturing methods include: Step (i) of mixing a raw material of a transition metal of Group 4 of the periodic table, a solvent (e.g., N,N-dimethylformamide), and hydrochloric acid to prepare a solution containing a transition metal ion of Group 4 of the periodic table; a step (ii) of mixing the solution with an organic ligand and a solvent (e.g., N,N-dimethylformamide) and stirring the resulting mixed solution, for example, at 25 to 250°C, preferably 50 to 200°C, for example, for 1 to 15 hours, preferably 3 to 10 hours, to react the Group 4 transition metal ion with the organic ligand; and (iii) optional post-treatment steps such as washing, drying, calcination, etc. The porous material (A) of the present invention can be produced by a method comprising the steps of:

[0041] When preparing the mixed solution in step (ii), a monocarboxylic acid is preferably mixed as the organic ligand in addition to the organic ligand (L). The addition of the monocarboxylic acid promotes the formation of a Group 4 transition metal ion cluster. The monocarboxylic acid can be removed by washing in the post-treatment step (iii).

[0042] Examples of monocarboxylic acids include formic acid (which can be produced in step (i) by reacting N,N-dimethylformamide with hydrochloric acid), acetic acid, benzoic acid, biphenylcarboxylic acid, and derivatives thereof. These may be used alone or in combination of two or more.

[0043] In the post-treatment step (iii), for example, a solid component is separated from the reaction solution by centrifugation or the like, washed, and then dried or calcined at normal or reduced pressure, at room temperature or with heating, to remove the solvent, water, monocarboxylic acid, excess organic ligand (L), and the like contained in the porous material. The lower the pressure or temperature at which drying or calcination is carried out, or the lower the molecular weight of the components contained, the smaller the O / M ratio in the above requirement (α-3) tends to be.

[0044] [Olefin polymerization catalyst] The olefin polymerization catalyst according to the present invention comprises the porous material (A) according to the present invention, and preferably further comprises at least one component (B) selected from the group consisting of the following (β-1) and (β-2): (β-1) An organoaluminum compound represented by the following general formula (BI): R a m Al(OR b ) n H p X q ···(BI) [In general formula (BI), R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, X is a halogen atom, m is an integer of 1 to 3, n is an integer of 0 to 2, p is an integer of 0 to 2, q is an integer of 0 to 2, and m+n+p+q=3. (β-2) Organoaluminum oxy compounds The olefin polymerization catalyst of the present invention may further contain (C) a carrier, and may further contain (D) an organic compound, if necessary.

[0045] 《Organoaluminum Compound (β-1)》 Examples of organoaluminum compound (β-1) (hereinafter also referred to as "component (β-1)") include: Tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, and tri2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; Triarylaluminums such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; Dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; partially halogenated alkylaluminums, such as alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminums (other than dialkylaluminum hydrides), such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide Examples include: The organoaluminum compound (β-1) may be used alone or in combination of two or more kinds.

[0046] 《Organoaluminum oxy compound (β-2)》 As the organoaluminum oxy compound (β-2) (hereinafter also referred to as "component (β-2)"), a conventionally known aluminoxane can be used as it is. Specifically, aluminoxanes represented by the following general formula [B-II1] can be used.

[0047] [ka]

[0048] and / or the following general formula [B-II2]

[0049] [ka]

[0050] (wherein R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more), benzene-insoluble organoaluminum oxy compounds described in JP-A Nos. 2-78687 and 2-167305, and aluminoxanes having two or more types of alkyl groups described in JP-A No. 3-103407. Further, examples of the organoaluminum oxy compound (β-2) include modified methylaluminoxanes represented by the following general formula [B-II3].

[0051] [ka]

[0052] (In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer of 2 or greater.) This modified methylaluminoxane is prepared using trimethylaluminum and alkylaluminums other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAOs can be prepared by the methods described in U.S. Patent Nos. 4,960,878 and 5,041,584. Further, the organoaluminum oxy compound (β-2) may also include a boron-containing organoaluminum oxy compound represented by the following general formula [B-II4].

[0053] [ka]

[0054] (In the formula, R c represents a hydrocarbon group having 1 to 10 carbon atoms. d may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. As the organoaluminum oxy-compound (β-2), commercially available methylaluminoxane and MMAO prepared from trimethylaluminum and triisobutylaluminum are preferred. Of these, MMAO is particularly preferred due to its improved solubility in various solvents and storage stability. The organoaluminum compound (β-2) may be used alone or in combination of two or more kinds.

[0055] (Carrier (C)) The support (C) is an inorganic or organic compound, and is a granular or fine particle solid. Supports conventionally used in olefin polymerization using a transition metal compound and a support as catalyst components, such as those described in paragraphs

[0220] to

[0235] of JP 2012-72365 A, can be used.

[0056] (Organic compound component (D)) An organic compound component (D) may be used as a constituent of the olefin polymerization catalyst, if necessary. The organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the resulting polymer. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0057] [Production method of olefin polymer] The process for producing an olefin polymer of the present invention is characterized by polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst of the present invention.

[0058] In the method for producing an olefin polymer of the present invention, an olefin homopolymer may be produced by polymerizing one type of olefin, or an olefin copolymer may be produced by copolymerizing two or more types of olefins. In this specification, polymerization and copolymerization are not particularly distinguished from each other and are also referred to as "polymerization," and olefin homopolymers and olefin copolymers are not particularly distinguished from each other and are also referred to as "olefin polymers."

[0059] The method of using each component constituting the olefin polymerization catalyst of the present invention and the order of adding them to a polymerization vessel can be selected arbitrarily, but examples include the following: Hereinafter, the porous material (A), component (B), carrier (C), and organic compound component (D) will also be referred to as "components (A) to (D)," respectively. (1) Component (A) is added alone to a polymerization reactor. (2) A method in which component (A) and component (B) are added to a polymerization reactor in any order. (3) A method in which a catalyst component in which component (A) is supported on component (C) and component (B) are added to a polymerization vessel in any order. (4) A method in which a catalyst component in which component (B) is supported on component (C) and component (A) are added to a polymerization reactor in any order. (5) A method in which a catalyst component in which component (A) and component (B) are supported on component (C) is added to a polymerization reactor.

[0060] In each of the above methods, component (D) may be added at any stage. In each of the above methods, at least two of the catalyst components may be contacted in advance. In the above methods (4) and (5) in which component (B) is supported, unsupported component (B) may be added in any order, if necessary. In this case, the components (B) may be the same or different. Furthermore, the solid catalyst component in which component (A) is supported on component (C) and the solid catalyst component in which components (A) and (B) are supported on component (C) may be prepolymerized with an olefin, or the prepolymerized solid catalyst component may have further catalyst components supported thereon.

[0061] In the present invention, olefin polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Specific 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, and mixtures thereof. Furthermore, the olefin (monomer) itself to be (co)polymerized can also be used as the solvent.

[0062] When olefin polymerization is carried out using the above-mentioned olefin polymerization catalyst, the porous material (A) is usually 1×10 per liter of reaction volume in terms of transition metal atoms in the porous material (A). -12 ~1×10 -1 mol, preferably 1 x 10 -10 ~1×10 -1 It is used in molar amounts.

[0063] The organoaluminum compound (β-1) is used in an amount such that the molar ratio [(β-1) / M] of the organoaluminum compound (β-1) to the total transition metal atoms (M) in the porous material (A) is generally 0.01 to 100,000, preferably 0.05 to 50,000.

[0064] The organoaluminum oxy compound (β-2) is used in an amount such that the molar ratio [(β-2) / M] of aluminum atoms in the organoaluminum oxy compound (β-2) to the total transition metal atoms (M) in the porous material (A) is generally 10 to 500,000, preferably 20 to 100,000.

[0065] The polymerization temperature of olefins using such an olefin polymerization catalyst is usually in the range of −50 to +200° C., preferably 0 to 170° C. The polymerization pressure is usually normal pressure to 100 kgf / cm. 2 -G, preferably normal pressure to 50 kgf / cm2 Under the conditions of -G, the polymerization reaction can be carried out in any of batch, semi-continuous, and continuous modes. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0066] The molecular weight of the resulting olefin polymer can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature, and can also be adjusted by the amount of compound (B) used.

[0067] <Olefin> The process for producing an olefin polymer of the present invention is a process for polymerizing an olefin in the presence of the olefin polymerization catalyst of the present invention.

[0068] A preferred embodiment of the method for producing an olefin polymer of the present invention is A method for producing an olefin polymer, comprising a step of homopolymerizing ethylene in the presence of the olefin polymerization catalyst of the present invention; A method for producing an olefin polymer, comprising a step of copolymerizing ethylene with a linear or branched α-olefin having from 3 to 30 carbon atoms in the presence of the olefin polymerization catalyst of the present invention. Examples include:

[0069] When copolymerization is carried out in the method for producing an olefin polymer of the present invention, the amount of each monomer fed is appropriately set depending on the composition of the olefin polymer to be produced. The α-olefins include Examples of linear or branched α-olefins having 3 to 30, preferably 3 to 20, and more preferably 3 to 10 carbon atoms include propylene, 1-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.

[0070] These may be used alone or in combination of two or more. In addition, together with ethylene and the above-mentioned α-olefin, a small amount (for example, 1 mol % or less) of other monomers (for example, cyclic olefins, non-conjugated polyenes) may be copolymerized.

[0071] The olefin polymer produced by the process for producing an olefin polymer of the present invention has a high molecular weight and a broad molecular weight distribution. When the porous material (A) of the present invention is used as an olefin polymerization catalyst, an olefin polymer can be produced with higher polymerization activity than when a conventional MOF is used as an olefin polymerization catalyst. The reason for this is not entirely clear, but is presumed to be as follows.

[0072] First, the porous material (A) has a large specific surface area, as indicated by requirement (α-1), and therefore has a high contact efficiency with olefin monomers, and contains many Group 4 transition metal atoms that serve as polymerization active centers, as indicated by requirement (α-2). Furthermore, by preferably satisfying requirement (α-3), i.e., by containing many coordinatively unsaturated Group 4 transition metal atoms, the reactivity (acidity) of the entire metal ion cluster is enhanced. For these reasons, it is believed that when the porous material (A) according to the present invention is used as an olefin polymerization catalyst, olefin polymers can be produced with high polymerization activity. [Example]

[0073] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples in any way.

[0074] [Measurement method] The various measurement methods are as follows:

[0075] (Measurement of porous materials) ≪Specific surface area≫ The specific surface area of ​​the porous material was measured by measuring the adsorption / desorption isotherm using nitrogen gas adsorption (Microtrac-Bell "BELSORP-max") at liquid nitrogen temperature. The specific surface area was calculated using the multipoint method specified in JIS Z8830:2013.

[0076] <O / M ratio and (Cl+Br) / M ratio> The O / M and (Cl + Br) / M ratios of the porous materials were calculated from the oxygen, chlorine, and metal atomic concentrations measured by X-ray photoelectron spectroscopy (XPS) (measurement device: KRATOS AXIS-NOVA). The samples were handled under a nitrogen atmosphere and measured using a monochromated AlKα X-ray source. Charge compensation and neutralization were performed using the charge neutralization function of the measurement device. The oxygen atomic concentration (atomic %) was determined from the peak area of ​​the O1s narrow spectrum, the chlorine atomic concentration (atomic %) from the peak area of ​​the Cl2s narrow spectrum, the zirconium atomic concentration (atomic %) from the peak area of ​​the Zr3d narrow spectrum, and the hafnium atomic concentration (atomic %) from the peak area of ​​the Hf4f narrow spectrum. The oxygen atom (O) / Group 4 transition metal (Zr, Hf) atomic ratio and the chlorine atom (Cl) / Group 4 transition metal (Zr, Hf) atomic ratio were then calculated.

[0077] (Measurement of olefin polymers) ≪Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)≫ The weight average molecular weight (Mw), number average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). Specifically, they were calculated from the molecular weight distribution curve obtained using a Waters "Alliance GPC 2000" gel permeation chromatograph (high temperature size exclusion chromatograph), and the operating conditions were as follows: Analysis software: Chromatography data system Empower (Waters) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2 (Inner diameter 7.5mm x length 30cm, Tosoh Corporation) Mobile phase: o-dichlorobenzene Detector: differential refractometer (built-in) Column temperature: 140°C Flow rate; 1.0mL / min Injection volume: 400μL Sampling time interval: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibration: Monodisperse polystyrene (Tosoh Corporation) / molecular weight 495 to 20.6 million

[0078] Melting point (Tm) Using an SII RDC220 differential scanning calorimeter, approximately 5 mg of sample was heated from 30°C to 200°C at a heating rate of 50°C / min under a nitrogen atmosphere and held at that temperature for 10 minutes. The sample was then cooled to 30°C at a heating rate of 10°C / min, held at that temperature for 5 minutes, and then heated to 200°C at a heating rate of 10°C / min. The endothermic peak observed during this second heating was taken as the melting peak, and the temperature at which the melting peak (the highest peak if multiple peaks were present) appeared was determined as the melting point (Tm).

[0079] [Preparation of porous materials, etc.] <Raw materials> The following metal sources (M-1) to (M-3) containing transition metals of Group 4 of the periodic table and the following organic ligands (L-1) to (L-7) were used as raw materials for the porous material. In addition to the raw materials for the porous material, the following metal source (M-4) was also prepared. Metal source (M-1): Fujifilm Wako Pure Chemical Industries, Ltd. Zirconium(IV) chloride Metal source (M-2): Fujifilm Wako Pure Chemical Industries, Ltd. Zirconium oxide chloride octahydrate, Wako special grade Metal source (M-3): Aldrich hafnium(IV) chloride 99.9% trace metals basis Metal source (M-4): Fujifilm Wako Pure Chemical Industries, Ltd. Zirconium oxide nanoparticles (10 nm) ·Organic ligand (L-1): Tokyo Chemical Industry Co., Ltd. 4,4'-Biphenyldicarboxylic Acid ·Organic ligand (L-2): Combi-Blocks 4-(4-Carboxyphenyl)-3-fluorobenzoic acid Organic Ligand (L-3): Fujifilm Wako Pure Chemical Industries, Ltd. Terephthalic Acid, Wako Grade 1 ·Organic ligand (L-4): Combi-Blocks 4,4'-(Ethyne-1,2-diyl)dibenzoic acid Organic ligand (L-5): 2',5'-dimethyl-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid, synthesized by the method described in J. Am. Chem. Soc. 2012, 134, 36, 14690-14693 ·Organic ligand (L-6): BLDpharm 4,4',4'',4'''-(Pyrene-1,3,6,8-tetrayl)tetrabenzoic acid Monocarboxylic acid: Fujifilm Wako Pure Chemical Industries, Ltd. Acetic acid, reagent grade

[0080] Example A1 A 200 mL reactor was charged with a rotor, 201 mg of metal source (M-1), 15 mL of N,N-dimethylformamide, and 1.5 mL of hydrochloric acid (35-37%), and then ultrasonically irradiated for 10 minutes. 270 mg of organic ligand (L-1) and 30 mL of N,N-dimethylformamide were added, and then ultrasonically irradiated for 10 minutes. The mixture was heated to 80 °C while stirring with the rotor and continued for 5 hours. The mixture was then cooled to room temperature and the stirring was stopped. The liquid and solid components in the reactor were transferred to a centrifuge tube and centrifuged, after which the supernatant was removed by decantation. After further washing with N,N-dimethylformamide and ethanol, the solid components were transferred to a Schlenk flask and dried under reduced pressure at 200 °C for 4 hours. The mixture was then cooled to room temperature under a nitrogen atmosphere, yielding 110 mg of porous material (A-1).

[0081] Example A2 115 mg of porous material (A-2) was prepared in the same manner as in Example A1, except that 290 mg of organic ligand (L-2) was used instead of 270 mg of organic ligand (L-1).

[0082] Example A3 75 mg of porous material (A-3) was prepared in the same manner as in Example A1, except that 185 mg of organic ligand (L-3) was used instead of 270 mg of organic ligand (L-1).

[0083] Example A4 142 mg of porous material (A-4) was prepared in the same manner as in Example A1, except that 300 mg of organic ligand (L-4) was used instead of 270 mg of organic ligand (L-1).

[0084] Example A5 266 mg of porous material (A-5) was prepared in the same manner as in Example A1, except that 395 mg of organic ligand (L-5) was used instead of 270 mg of organic ligand (L-1) and the mixture was stirred at 80°C for 8 hours.

[0085] Example A6 192 mg of porous material (A-6) was prepared in the same manner as in Example A1, except that 195 mg of organic ligand (L-6) was used instead of 270 mg of organic ligand (L-1).

[0086] Example A7 113 mg of porous material (A-7) was prepared in the same manner as in Example A1, except that 270 mg of organic ligand (L-1) was replaced with 270 mg of organic ligand (L-1) and 273 mg of acetic acid.

[0087] Example A8 150 mg of porous material (A-8) was prepared in the same manner as in Example A1, except that 261 mg of metal source (M-2) was used instead of 201 mg of metal source (M-1).

[0088] Example A9 162 mg of porous material (A-9) was prepared in the same manner as in Example A1, except that 276 mg of metal source (M-3) was used instead of 201 mg of metal source (M-1).

[0089] <Comparative Example a1> 238 mg of porous material (A'-1) was prepared in the same manner as in Example A1, except that the stirring time after raising the temperature to 80°C was changed to 20 hours.

[0090] <Comparative example a2> 263 mg of porous material (A'-2) was prepared in the same manner as in Example A6, except that the stirring time after raising the temperature to 80°C was changed to 20 hours.

[0091] <Comparative example a3> The metal source (M-4) was transferred to a Schlenk tube and dried under reduced pressure at 200°C for 4 hours, and then cooled to room temperature under a nitrogen atmosphere to prepare a material (hereinafter also referred to as the "porous material" for convenience) (A'-3).

[0092] The production conditions, yield, specific surface area, O / M ratio, and (Cl+Br) / M ratio of the porous materials (A-1) to (A-9) and (A'-1) to (A'-3) are shown in Table 1. Since the porous materials (A-1) to (A-9) and (A'-1) to (A'-2) have a high specific surface area, they are all metal ion clusters (the basic structure is M6(μ 3 -O)4(μ 3 It can be said that a porous coordination polymer is formed, which is represented by (—OH)4 (M is Zr or Hf).) and organic ligands (L).

[0093] [Table 1]

[0094] [Production of olefin polymers] <Example P1> 500 mL of heptane was added to a 1-liter stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) and 50 mg of the porous material (A-1) obtained in Example A1 were charged into the reactor. The temperature and pressure were then increased to 80°C and 0.8 MPaG using ethylene, and a polymerization reaction was carried out for 60 minutes at a rotation speed of 350 rpm. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain an olefin polymer having the properties shown in Table 2.

[0095] <Examples P2 to P9> A polymerization reaction was carried out in the same manner as in Example P1, except that 50 mg of each of the porous materials (A-2) to (A-9) obtained in Examples A2 to A9 was used instead of the porous material (A-1). After the reaction was completed, the contents in the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain an olefin polymer having the physical properties shown in Table 2.

[0096] <Comparative examples p1~p3> Polymerization reaction was carried out in the same manner as in Example P1, except that 50 mg of each of the porous materials (A'-1) to (A'-3) obtained in Comparative Examples a1 to a3 was used instead of the porous material (A-1). After the reaction was completed, the contents in the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain an olefin polymer having the physical properties shown in Table 2.

[0097] <Example P10> A polymerization reaction was carried out in the same manner as in Example P1, except that 0.375 mL of a decane solution of triethylaluminum (1.0 mol / L in terms of Al) was used instead of the decane solution of triisobutylaluminum. After completion of the reaction, the contents in the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain an olefin polymer having the physical properties shown in Table 2.

[0098] <Example P11> A polymerization reaction was carried out in the same manner as in Example P1, except that 0.375 mL of a toluene solution of methylaluminoxane (MAO) (1.0 mol / L in terms of Al) was used instead of the decane solution of triisobutylaluminum. After completion of the reaction, the contents in the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain an olefin polymer having the physical properties shown in Table 2.

[0099] <Example P12> 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al), and 50 mg of the porous material (A-1) obtained in Example A1 were added to the reactor. The temperature and pressure were then increased to 80°C and 0.8 MPaG using ethylene, and the polymerization reaction was carried out for 60 minutes at a rotation speed of 350 rpm. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain an olefin polymer having the properties shown in Table 2.

[0100] <Example P13> 500 mL of heptane was added to a 1-L stainless steel autoclave reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor. Next, 0.375 mL of a decane solution of triisobutylaluminum (1.0 mol / L in terms of Al) and 50 mg of the porous material (A-1) obtained in Example A1 were added to the reactor. The reactor was then heated to 80°C and pressurized to 0.8 MPaG using an ethylene / hydrogen mixed gas with a hydrogen concentration of 0.10 vol%, and the polymerization reaction was carried out for 60 minutes at 350 rpm. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain an olefin polymer with the properties shown in Table 2.

[0101] [Table 2]

Claims

1. a porous coordination polymer composed of a Group 4 transition metal ion cluster and an organic ligand (L); Contains halogen atoms, Satisfy the following requirements (α-1) and (α-2), The periodic table group 4 transition metal ion cluster is M 6 O 8-x (OH) x (M is a transition metal atom ion of Group 4 of the periodic table, and x is an integer of 0 to 8.) It has a structure represented by At least one of the organic ligands (L) is selected from a ligand having two or more carboxy groups in one molecule and an amine compound; the amine compound is selected from imidazole, 2-methylimidazole, 2-phenylimidazole, 4,4′-bipyridine, 1,4-bis(4-pyridyl)benzene, 2,2′-dimethyl-4,4′-bipyridine, 1,4-bis(4-pyridyl)butadiyne, 1,2-bis(4-pyridyl)ethane, 3,6-di(4-pyridyl)-1,2,4,5-tetrazine, pyrazine, 2,5-dimethylpyrazine, and 1,4-diazabicyclo[2.2.2]octane; Porous material for olefin polymerization catalyst (A). (α-1) Specific surface area measured by the BET multipoint method is 500 m 2 / g or more 4000m 2 / g or less. (α-2) The molar ratio of halogen atoms to Group 4 transition metal atoms of the periodic table (halogen atoms / Group 4 transition metal atoms of the periodic table) measured by X-ray photoelectron spectroscopy (XPS) is 0.20 or more and 1.0 or less, and the halogen atoms are chlorine atoms and / or bromine atoms.

2. The porous material (A) for an olefin polymerization catalyst according to claim 1, further satisfying the following requirement (α-3): (α-3) The molar ratio of oxygen atoms to transition metal atoms of Group 4 of the periodic table (oxygen atoms / transition metal atoms of Group 4 of the periodic table) measured by X-ray photoelectron spectroscopy (XPS) is 2.5 or more and 4.5 or less.

3. The specific surface area is 1000 m 2 / g or more 4000m 2 The porous material (A) for an olefin polymerization catalyst according to claim 1 or 2, wherein the molecular weight of the porous material (A) for an olefin polymerization catalyst is 1 / g or less.

4. An olefin polymerization catalyst comprising the porous material (A) for an olefin polymerization catalyst according to any one of claims 1 to 3.

5. The olefin polymerization catalyst according to claim 4, further comprising at least one component (B) selected from the group consisting of the following (β-1) and (β-2): (β-1) An organoaluminum compound represented by the following general formula (BI): R a m Al(OR b ) n H p X q ・・・(B-I) [In general formula (BI), R a and R b are each independently a hydrocarbon group having 1 to 15 carbon atoms, X is a halogen atom, m is an integer of 1 to 3, n is an integer of 0 to 2, p is an integer of 0 to 2, q is an integer of 0 to 2, and m+n+p+q=3. (β-2) Organoaluminum oxy compound

6. A method for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 4 or 5.

7. 7. The method for producing an olefin polymer according to claim 6, wherein the step of polymerizing an olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene with a linear or branched α-olefin having from 3 to 30 carbon atoms.

Images