Compounds, metal complexes, methods for producing metal complexes, catalysts for olefin polymerization, and methods for producing (co)polymers

Abstract

To provide a transition metal complex catalyst having high catalytic activity and realizing a high-content olefin / polar monomer copolymer, a method of producing the transition metal complex catalyst, and a method of producing the copolymer.SOLUTION: The invention provides a compound represented by the general formula [I] in the figure, where Y is -OR12 or -NR13R14; and R1 to R14 and Z are each independently H, halogen, a heteroatom-containing group, or an organic group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compounds, metal complexes, methods for producing metal complexes, catalysts for olefin polymers, and methods for producing (co)polymers. [Background technology]

[0002] Olefin polymers possess excellent mechanical properties and are used in various fields such as molded articles and films. Meanwhile, methods for introducing polar groups into olefin polymers to impart various functionalities are continuously being developed. A typical method involves radical polymerization of olefins and polar group-containing vinyl monomers (hereinafter referred to as "polar monomers") under high temperature and pressure to obtain polar group-containing olefin copolymers, resulting in the synthesis of ethylene-acrylic acid ester copolymers and ethylene-vinyl acetate copolymers. Furthermore, techniques for introducing polar groups through post-modification have also been developed, and chlorinated polypropylene and maleic anhydride-modified polypropylene are known examples. However, because the synthesis of these polar group-containing polymers utilizes radical reactions, many branches exist in the main chain, and it is generally difficult to control the position and amount of branching.

[0003] As a method for obtaining polar group-containing olefin polymers without using radical reactions, copolymerization reactions of olefins and polar monomers using transition metal complexes as catalysts are known. For example, Brookhart et al. have reported a method for copolymerizing olefins such as ethylene with polar monomers such as olefins containing acrylic acid esters and long-chain esters using a palladium diimine complex (Non-Patent Literature 1). Also, Grubbs et al. have reported a method for copolymerizing ethylene with polar group-containing norbornene using a nickel phenoxyimine complex (Non-Patent Literature 2).

[0004] It is generally known that polar groups in polar monomers interact with the central metal, reducing the catalytic activity of copolymerization reactions or even deactivating the catalyst. The magnitude of the interaction between polar groups in polar monomers and the central metal is known to be greatly influenced by the type and valency of the central metal. Generally, early transition metal complex catalysts tend to deactivate due to their high affinity for donor atoms such as oxygen and nitrogen, forcing the use of methods such as having bulky substituents on the polar groups or adding large amounts of alkylaluminum to protect the polar groups [Non-patent documents 3, 4].

[0005] On the other hand, because high-period transition metal complex catalysts have a lower affinity for polar groups than lower-period transition metal complex catalysts, they can utilize more common polar monomers. For example, nickel phosphine phenolate catalysts are known to promote copolymerization of ethylene / acrylic acid esters and propylene / acrylic acid esters (Patent Documents 1-4, Non-Patent Documents 5, 6). However, copolymerization of olefins and polar monomers still tends to have lower activity compared to homopolymerization using olefins alone. Against this backdrop, there is a desire for the development of olefin / polar monomer copolymerization catalysts that have polymerization activity suitable for industrial scale and can efficiently incorporate polar groups, as well as for the emergence of manufacturing methods, and vigorous research has continued to this day.

[0006] Previous studies have reported that nickel or palladium complexes containing bidentate ligands exhibit catalytic activity in olefin / polar monomer copolymerization reactions, and α-carbonylimine ligands are one such example. Brookhart et al. reported copolymerization of ethylene and polar monomers using a nickel complex catalyst containing an α-carbonylimine ligand, achieving a catalytic reaction of 1.18 × 10⁻¹⁰ in the copolymerization of ethylene and hexyl acrylate. 4 The highest activity is observed at g / mol·h, and the highest content is 2.2 mol% (Patent Document 5). Furthermore, in the copolymerization of ethylene and ethyl undecenoate, 1.26 × 10 4The highest activity was observed at g / mol·h, with a content of 7.4 mol%. In 2020, Changle Chen et al. reported copolymerization of ethylene with various polar monomers using a nickel complex catalyst with an α-carbonylimine ligand, and in the copolymerization reaction of ethylene with methyl undecenoate, the activity was 1.75 × 10⁻⁶. 5 A polymer with a content of 6.3 mol% g / mol·h has been reported (Non-Patent Document 7). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2010 / 050256 [Patent Document 2] U.S. Patent No. 6,559,326 [Patent Document 3] Japanese Patent Publication No. 2005-307021 [Patent Document 4] Japanese Patent Publication No. 2018-24646 [Patent Document 5] Special publication 2004-517933 [Non-patent literature]

[0008] [Non-Patent Document 1] M. Brookhart et. al. J. Am. Chem. Soc. 1995, 117, 6414 [Non-Patent Document 2] R.H. Grubbs et al. Science 2000, 287, 460 [Non-Patent Document 3] R.H. Grubbs et al. Science 2000, 287, 460 [Non-Patent Document 4] J. Imuta et al. J. Am. Chem. Soc. 2002, 124, 1176 [Non-Patent Document 5] J. Heinicke et al. Chem. Eur. J. 2003, 9, 6093 [Non-Patent Document 6] J. Heinicke et al. Eur. J. Inorg. Chem. 2000, 3, 431 [Non-Patent Document 7] J. Heinicke et al. Eur. J. Inorg. Chem. 2000, 3, 431 [Overview of the initiative] [Problems that the invention aims to solve]

[0009] In the above-mentioned literature, the catalytic activity is not considered sufficient for industrial-scale application, and further improvement in activity is desired. The object of the present invention is to provide a transition metal complex catalyst for copolymerizing an olefin and a polar monomer, which has high catalytic activity and yields an olefin / polar monomer copolymer having a high content of polar groups, and a method for producing said copolymer. [Means for solving the problem]

[0010] The present inventors, through diligent research to solve the above problems, synthesized a nickel complex catalyst having a carbonylimine compound as a ligand, obtained by a 1:1 imine condensation of an α-ketoester or α-ketoamide with a naphthylamine compound. They also discovered that this catalyst enables copolymerization of highly active olefins and polar monomers. Furthermore, this invention has been found to yield a copolymer of olefins and polar monomers that is more active and of higher content than nickel catalysts having carbonylimine ligands that have been reported in the past, thus completing the present invention.

[0011] In other words, the gist of this invention is as follows: [1] Compounds represented by the following general formula [I]. [ka] (wherein R 1 to R 11 are each independently hydrogen, halogen, a group containing a heteroatom or an organic group; Y is -OR 12 or -NR 13 R 14 , and R 12 to R 14 are each independently hydrogen, halogen, a group containing a heteroatom or an organic group; Z is hydrogen, halogen, a group consisting of a heteroatom or an organic group.)

[0012] [2] A metal complex represented by the following general formula [II].

Chemical formula

[0013] [4] The metal complex according to the above [2], which is the metal complex represented by the following general formula [III] wherein L is an allyl ligand, and R 15 is hydrogen, halogen, a group containing a heteroatom or an organic group.

Chemical formula

[0014] [5] A method for producing a metal complex, which comprises producing the metal complex represented by general formula [II] by bringing a compound represented by general formula [I] into contact with a transition metal compound containing nickel or palladium. [6] A catalyst for olefin polymerization, comprising the metal complex according to any one of the above [2] to [4]. [7] A method for producing a (co)polymer, comprising (co)polymerizing an olefin in the presence of the polymerization catalyst described in [6] above. [8] A method for producing a copolymer, comprising copolymerizing an olefin with a polar group-containing vinyl monomer in the presence of the polymerization catalyst described in [6] above. [9] The method for producing the copolymer according to [8] above, wherein the polar group-containing vinyl monomer contains an oxygen atom and / or a nitrogen atom. [Effects of the Invention]

[0015] According to the present invention, a transition metal complex catalyst for copolymerizing an olefin and a polar monomer is provided, which has high catalytic activity and yields an olefin / polar monomer copolymer having a high content of polar groups, as well as a method for producing the copolymer. [Modes for carrying out the invention]

[0016] The embodiments of the present invention will be described in detail below. Note that the following description is merely an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents unless it exceeds the essence of the invention.

[0017] The present invention relates to a reaction product obtained by contacting a compound (ligand) [I] represented by general formula [I] with a nickel or palladium compound, namely a metal complex represented by general formula [II], and to a method for producing an olefin (co)polymer or olefin / polar monomer copolymer using the metal complex as a catalyst in the presence of a catalyst. In this invention, "polymerization" refers collectively to the homopolymerization of one type of monomer and the copolymerization of multiple types of monomers. When there is no need to distinguish between the two, the term "polymerization" is used collectively.

[0018] 1. Metal complex and method for producing metal complex The metal complex [II] of the present invention is obtained by reacting a compound represented by the following general formula [I] (hereinafter referred to as "α-carbonylimine compound") with a transition metal compound containing nickel or palladium.

[0019] [ka]

[0020] In general formula (I), R 1 ~R 11 These are, independently, groups or organic groups containing hydrogen, halogen, and heteroatoms. Y is -OR 12 , -NR 13 R 14 And R 12 ~R 14 Each of these is independently a group or organic group containing hydrogen, a halogen, or a heteroatom. Z is a group or organic group consisting of hydrogen, a halogen, or a heteroatom.

[0021] [ka]

[0022] In general formula (II), R 1 ~R 11 Y and Z are the same as those described in general formula [I]. M is nickel or palladium, L is a monoanionic ligand, and X is a counteranion.

[0023] The α-carbonylimine compound and the transition metal compound containing nickel or palladium (hereinafter sometimes referred to as "nickel-palladium compound") are reacted by mixing them, but the mixing conditions are not particularly limited. Furthermore, X represents the counteranion site necessary for the overall solution to become neutral in conjunction with the cationic complex, and may be derived from the nickel-palladium compound used to form the complex, or from the anion exchange reagent. The anion exchange reagent may be reacted with the complex represented by general formula [II], or it may be added simultaneously when forming the complex of general formula [II]. Preferably, the anion reagent is added simultaneously when forming the complex of general formula [II] to obtain the [II] complex having the desired counteranion. Here, "mixing" refers to either directly mixing these compounds or mixing them in a solution using a solvent. In particular, using a solvent is preferable from the viewpoint of achieving uniform mixing. While it is believed that the metal complex given by general formula [II] is produced by the reaction described above, this does not negate the possibility that metal complexes having structures other than those shown in [II] can be used in the production of polymers in the same way as the metal complex shown in general formula [II].

[0024] In general formulas [I] and [II], R 1 ~R 11 We will explain Y, Z, and M, L, and X in general formula [II]. R 1 ~R 11 Each of these is independently (i) hydrogen, (ii) halogen, (iii) a group containing a heteroatom, or (iv) an organic group. Here, (iii) may be a group consisting of a heteroatom or a group containing a heteroatom. Also, (iv) the organic group may have a heteroatom. Note that (iii) and (iv) are not identical.

[0025] (ii) Examples of halogens include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, among which fluorine atoms and chlorine atoms are preferred in terms of improving activity and suppressing side reactions during synthesis. Examples of heteroatoms in (iii) include halogens such as oxygen, nitrogen, phosphorus, sulfur, selenium, silicon, fluorine, and chlorine, as well as boron. Of these heteroatoms, fluorine, chlorine, oxygen, nitrogen, sulfur, and silicon are preferred in terms of improving activity. Furthermore, "groups containing heteroatoms" specifically include OR 17 CO2R 17 CO2M', C(O)N(R 17 )2, C(O)R 17 , SR 17 SO2R 17 SOR 17 OSO2R 17 , P(O)(OR 17 ) 2-y (R 16 ) y , CN, NHR 17 , N(R 17 )2, Si(OR 16 ) 3-x (R 16 ) x , OSi(OR 16 ) 3-x (R 16 ) x , NO2, SO3M', PO3M'2, P(O)(OR 17 Examples include 2M' and epoxy-containing groups. Here, R 16 R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. 17 is a hydrocarbon group having 1 to 20 carbon atoms. M' is an alkali metal, alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x is an integer from 0 to 3, and y is an integer from 0 to 2.

[0026] In (iv), the organic group which may have a heteroatom has a total carbon number of carbon atoms of each substituent which is preferably 1 to 30, more preferably 1 to 20, and even more preferably 4 to 15. Examples of organic groups include linear alkyl groups, acyclic alkyl groups, alkenyl groups, cycloalkyl groups which may have side chains, aryl groups, arylalkyl groups, and alkylaryl groups. The organic group in (iv) may be substituted with a group consisting of a heteroatom and / or a group containing a heteroatom, as shown in (iii).

[0027] Note, R 1 ~R 11 Multiple groups appropriately selected from these may be linked together to form an alicyclic ring, an aromatic ring, or a heterocycle containing a heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur. In this case, the number of ring members is 5 to 8, and the ring may or may not have substituents. Also, R 1 Multiple groups contained within are linked to each other, R 1 A ring may be formed on top. 2 ~R 11 The same applies if any of the elements include multiple groups.

[0028] R 1 ~R 11 Each of these groups is independently preferred, and examples include (i) hydrogen atoms; (ii) fluorine atoms, chlorine atoms; (iii) methoxy groups, ethoxy groups, phenoxy groups, nitrile groups, trimethylsilyl groups, triethylsilyl groups, dimethylphenylsilyl groups, trimethoxysilyl groups, triethoxysilyl groups, trimethylsilyloxy groups, trimethoxysiloxy groups, cyclohexylamino groups, sodium sulfonate, potassium sulfonate, sodium phosphate, potassium phosphate, etc. Also, (iv) methyl groups, ethyl groups, isopropyl groups, butyl groups, phenyl groups, trifluoromethyl groups, pentafluorophenyl groups, carbazolyl groups, naphthyl groups, anthracenyl groups, 3,5-dimethylphenyl groups, diphenylmethyl groups, etc. In particular, R 1Regarding these, preferred options include (i) a hydrogen atom; and (iv) an organic group such as the 3,5-dimethylphenyl group or the diphenylmethyl group. 8 , R 10 Among these, preferred options include (i) a hydrogen atom or (iv) an organic group, specifically a methyl group.

[0029] Y is OR 12 , NR 13 R 14 And R 12 ~R 14 Each of these is independently (i) hydrogen, (ii) halogen, (iii) a group containing a heteroatom (a group consisting of a heteroatom and / or a group containing a heteroatom), and (iv) an organic group which may have a heteroatom. (iii) The heteroatom is the R 1 ~R 11 As explained above, the preferred range is also the same. Specifically, "groups containing heteroatoms" include CO2R 17 CO2M', C(O)N(R 17 )2, C(O)R 17 SO2R 17 SOR 17 , P(O)(OR 17 ) 2-y (R 16 ) y , Si(OR 16 ) 3-x (R 16 ) x ,SO3M',PO3M'2,P(O)(OR 17 Examples include 2M' and epoxy-containing groups. Here, R 16 R represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. 17 represents a hydrocarbon group with 1 to 20 carbon atoms. M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, where x is an integer from 0 to 3 and y is an integer from 0 to 2.

[0030] (iv) The organic group which may have a heteroatom is the above R 1 ~R11 it is the same as that described above, and the preferred range is also the same. R 12 ~R 14 As preferred examples of , the above R 1 ~R 11 it is the same as that described in .

[0031] Z is (i) hydrogen, (ii) halogen, (iii) a group consisting of a heteroatom and / or a group containing a heteroatom, and (iv) an organic group optionally having a heteroatom. The halogen in (ii), the heteroatom in (iii), and the organic group optionally having a heteroatom in (iv) correspond to the above R 1 ~R 11 it is the same as (ii) to (iv) described in , and the preferred range is also the same. Further, a plurality of groups contained in Z may be linked to each other to form a ring on Z.

[0032] Each Z is independently, preferably, (i) a hydrogen atom; (ii) a fluorine atom or a chlorine atom; (iii) a methoxy group, an ethoxy group, a phenoxy group, etc.; (iv) a methyl group, an ethyl group, an isopropyl group, a butyl group, a phenyl group, and the like. Among these, preferred are (i) a hydrogen atom; and (iv) a methyl group and a phenyl group.

[0033] A plurality of selected substituents present in Y and Z may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from the group consisting of oxygen, nitrogen and sulfur. In this case, the number of ring members is 5 to 8, and the ring may or may not have a substituent. Such a structure is preferably the structure of general formula [IV] shown below.

[0034]

Chemical Formula

[0035] Here, R 22 ~R 25Each of these independently consists of (i) hydrogen, (ii) halogen, (iii) a heteroatom and / or a group containing a heteroatom, and (iv) an organic group which may have a heteroatom. Y' is O, S, NR 26 And R 26 (i) hydrogen, (iii) a group consisting of and / or containing a heteroatom, and (iv) an organic group which may have a heteroatom. Particularly preferred, R 22 ~R 25 is hydrogen, and Y' is NMe.

[0036] In general formula (II), M is either nickel or palladium. Furthermore, L is a monoanionic ligand, and one atom may coordinate to the metal, or two or more atoms may coordinate to the metal. Preferably, the ligand is the η3-allyl ligand shown in the following general formula [V], and R 15 (i) hydrogen, (ii) halogen, (iii) a group containing a heteroatom (a group consisting of a heteroatom and / or a group containing a heteroatom), and (iv) an organic group. Of these, hydrogen is particularly preferred.

[0037] [ka]

[0038] In general formula (II), X is a counteranion that pairs with a cationic complex and neutralizes general formula [II]. X may be an atomic anion, a molecular anion, a polymeric anion, or an anionic support surface. Furthermore, the anion is not limited to a monoanion; it may also be a dianion or a higher-order anion, but in this case, the amount of anion present should be such that the entire general formula [II] becomes neutral. Preferably, it is tetrakis[3,5-bis(trifluoromethyl)phenyl]borate or tetrakis[pentafluorophenyl]borate.

[0039] The transition metal compounds used in this invention are those that can react with compounds represented by general formula [I] to form polymerizable complexes. These are sometimes called precursors. For example, [Ni(allyl)X]2 is a nickel-containing transition metal complex. The anion exchange reagent used in this invention is one that can react with a transition metal complex of general formula [I] to form a polymerizable complex. For example, M[tetrakis[3,5-bis(trifluoromethyl)phenyl]borate](M=alkali metal).

[0040] This reaction forms a complex represented by general formula [II]. This reaction is preferably carried out quantitatively, but may not proceed completely in some cases. After the reaction is complete, in addition to the complex represented by general formula [II], components that are replicated by anion exchange reactions will be present. When carrying out the polymerization or copolymerization reaction of the present invention, these other components may or may not be removed.

[0041] In this invention, the complex formation reaction may be carried out in advance in a container separate from the reactor used for polymerization, and the resulting complex of general formula [II] may be subjected to polymerization. Alternatively, the complex formation reaction may be carried out in the polymerization vessel, and in this case, the components present in the container during polymerization may or may not be present at the time of complex formation. Furthermore, the components represented by general formulas [I] and [II] may be used individually, or multiple components may be used in combination. In particular, the use of multiple components is useful for broadening the molecular weight distribution and comonomer distribution.

[0042] 2. Metal complex catalyst components for polymerization The catalyst component in the olefin polymerization catalyst of the present invention is characterized by containing the above-mentioned metal complex or a metal complex obtained by the above-mentioned manufacturing method. In the present invention, a metal complex represented by general formula [II] can be used as a catalyst component for polymerization. As described above, the metal complex represented by general formula [II] can be formed by the reaction of a compound represented by general formula [I] with a transition metal complex component. When using the metal complex represented by general formula [II] as a catalyst component, it may be used in an isolated form or generated in the polymerization reaction system. Furthermore, the metal complex may be supported on a carrier, and the support may be carried out in the reactor used for polymerization, in the presence or absence of these monomers, or in a container separate from the reactor.

[0043] Any carrier can be used as the carrier, as long as it does not impair the spirit of the present invention. Generally, inorganic oxides and polymer carriers are preferably used. Specifically, examples include SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or mixtures thereof. Mixed oxides such as SiO2-Al2O3, SiO2-V2O5, SiO2-TiO2, SiO2-MgO, and SiO2-Cr2O3 can also be used. Inorganic silicates, polyethylene carriers, polypropylene carriers, polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic acid ester carriers, polyester carriers, polyamide carriers, and polyimide carriers can also be used. There are no particular restrictions on particle size, particle size distribution, pore volume, specific surface area, etc., for these carriers, and any carrier can be used.

[0044] Inorganic silicates that can be used include clay, clay minerals, zeolites, and diatomaceous earth. These may be synthetic or naturally occurring minerals. Specific examples of clay and clay minerals include allophane group minerals such as allophane, kaolin group minerals such as dickite, nacrite, kaolinite, and anochite, halloysite group minerals such as metahaloysite and halloysite, serpentine group minerals such as chrysotile, lizardite, and antigorite, smectite minerals such as montmorillonite, sauconite, beidelite, nontronite, saponite, and hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, and erythrolite, attapulgite, sepiolite, pygorskite, bentonite, kibushi clay, gylome clay, hisingerite, pyrophyllite, and lyokdeite group minerals. These may form mixed layers. Examples of synthetic materials include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite. Among these specific examples, preferred are kaolin group minerals such as dickite, nacrite, kaolinite, and anochite; halloysite group minerals such as metahaloysite and halloysite; serpentine group minerals such as chrysotile, lizardite, and antigorite; smectite minerals such as montmorillonite, sauconite, beidelite, nontronite, saponite, and hectorite; vermiculite minerals such as vermiculite; mica minerals such as illite, sericite, and erythritol; synthetic mica; synthetic hectorite; synthetic saponite; and synthetic teniolite. Particularly preferred are smectite minerals such as montmorillonite, sauconite, beidelite, nontronite, saponite, and hectorite; vermiculite minerals such as vermiculite; synthetic mica; synthetic hectorite; synthetic saponite; and synthetic teniolite.

[0045] These carriers may be used as is, or they may be subjected to acid treatment with hydrochloric acid, nitric acid, sulfuric acid, etc., and / or salt treatment with LiCl, NaCl, KCl, CaCl2, MgCl2, Li2SO4, MgSO4, ZnSO4, Ti(SO4)2, Zr(SO4)2, Al2(SO4)3, etc. In this treatment, the corresponding acid and base may be mixed to produce a salt in the reaction system. Shape control such as crushing or granulation, or drying treatment may also be performed.

[0046] 3. Catalyst components for polymerization The olefin polymerization catalyst of the present invention contains the above-mentioned metal complex catalyst component, but only one type of metal complex may be used, or two or more types of metal complexes may be used in combination. Multiple types of metal complexes may be used to broaden the molecular weight distribution. In addition to the metal complex catalyst, the following components (A) and (B) may be included as co-catalysts or additives. When components (A) or (B) are added, mixing with the polymerization catalyst component may be carried out in the reactor used for polymerization, in or out of the presence of these monomers, or in a container separate from the reactor.

[0047] Component (A): A compound that reacts with a metal complex catalyst component to form an ion pair, or an ion-exchange layered silicate. Component (B): Organoaluminum compound

[0048] One example of component (A) is an organoaluminum oxy compound. Organoaluminum oxy compounds have Al-O-Al bonds in their molecules, and the number of these bonds is usually in the range of 1 to 100, preferably 1 to 50. Such organoaluminum oxy compounds are usually products obtained by reacting an organoaluminum compound with water. The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). Suitable inert hydrocarbons include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene, as well as alicyclic hydrocarbons and aromatic hydrocarbons. However, the use of aliphatic or aromatic hydrocarbons is preferred.

[0049] Any organoaluminum compound represented by the following general formula can be used in the preparation of organoaluminum oxy compounds, but trialkylaluminum is preferred. (R 30 ) t Al(Q 1 ) (3-t) (In the formula, R 30Q represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms. 1 (where 't' represents a hydrogen atom or a halogen atom, and 't' represents an integer between 1 and 3.) The alkyl group of trialkylaluminum can be any of the following: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, or dodecyl groups, but methyl and isobutyl groups are preferred, and methyl groups are particularly preferred. Two or more of the above organoaluminum compounds can also be used in combination.

[0050] The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly 0.5 / 1 to 1 / 1. The reaction temperature is usually in the range of -70 to 100°C, preferably -20 to 20°C. The reaction time is usually selected from 5 minutes to 24 hours, preferably 10 minutes to 5 hours. Of the organoaluminum oxy compounds mentioned above, those obtained by reacting alkylaluminum with water are generally called aluminoxanes, and methylaluminoxane (including those substantially composed of methylaluminoxane (MAO)) is particularly suitable as an organoaluminum oxy compound. Solid dry methylaluminoxane (DMAO) obtained by distilling off the solvent from an MAO solution is also suitable. As the organoaluminum oxy compound, two or more of the above-mentioned organoaluminum oxy compounds can be used in combination, or a solution obtained by dissolving or dispersing the organoaluminum oxy compound in the aforementioned inert hydrocarbon solvent may be used.

[0051] An example of an organoaluminum compound used as component (B) is represented by the following general formula. Al(R 32 ) a (Q 2 ) (3-a) In the general formula, R 32 (Q) is a hydrocarbon group having 1 to 20 carbon atoms.2 ) represents hydrogen, halogen, alkoxy group, or siloxy group, and a represents a number greater than 0 and less than or equal to 3.

[0052] Specific examples of organoaluminum compounds represented by the above general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and tri(n-octyl)aluminum, as well as halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monolide and diethylaluminum monomethoxide. Among these, tri(n-octyl)aluminum is preferred. Furthermore, two or more of the above organoaluminum compounds may be used in combination. Furthermore, the above aluminum compounds may be modified with alcohol, phenol, etc. Examples of these modifying agents include methanol, ethanol, 1-propanol, isopropanol, butanol, phenol, 2,6-dimethylphenol, and 2,6-di-t-butylphenol, with preferred specific examples being 2,6-dimethylphenol and 2,6-di-t-butylphenol.

[0053] In the method for preparing the catalyst for olefin polymerization according to the present invention, the metal complex catalyst component is essential, and components (A) and (B) are added as needed. For example, metal complex catalysts are represented by the general formula [II], but when L is a substituent that initiates polymerization, such as an alkyl group, aryl group, or allyl group, components (A) and (B) are not necessarily required. On the other hand, when L is a substituent that does not initiate polymerization, it is necessary to introduce a polymerization initiator on the metal complex by adding components (A) and (B). Furthermore, even if L is the substituent that initiates polymerization, (A) or (B) may be added as additives to change the molecular weight or copolymerization ratio.

[0054] 4. Polymerization reaction One embodiment of the method for producing an olefin polymer of the present invention involves polymerizing or copolymerizing (a) an olefin in the presence of the above-mentioned polymerization catalyst component. In this invention, component (a) is ethylene, or the general formula: CH2=CHR 33 This is an olefin represented by . Here, R 33 R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may have branching, ring, and / or unsaturated bonds. 33 If the number of carbon atoms is greater than 20, sufficient polymerization activity tends not to be exhibited. For this reason, preferred components (a) are ethylene and R 33 Examples include α-olefins, which are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms. Further preferred components (a) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, vinylcyclohexene, and styrene. Note that components (a) may be used individually or in combination of multiple components (a).

[0055] Another embodiment of the method for producing the α-olefin polymer of the present invention involves copolymerizing (a) an olefin and (b) a polar monomer in the presence of the above-mentioned polymerization catalyst component. (a) The component is as described above, and may be a single component (a) or multiple components (a). The polar monomers of component (b) of the present invention are (i) vinyl monomer, (ii) (meth)acrylic acid ester monomer, and (iii) allyl monomer.

[0056] (i) The vinyl monomer has polar groups such as halogen, nitrogen, oxygen, and sulfur, and is particularly a vinyl monomer containing halogen, hydroxyl, amino, nitro, carboxyl, formyl, ester, epoxy, and nitrile groups. Specifically, examples include 5-hexen-1-ol, 2-methyl-3-buten-1-ol, methyl 10-undecenoate, ethyl 10-undecenoate, 10-undecenoic acid, 12-tridecen-2-ol, 10-undecanoic acid, methyl-9-decenate, t-butyl-10-undecenoate, 1,1-dimethyl-2-propen-1-ol, 9-decen-1-ol, 3-butenic acid, 3-buten-1-ol, N-(3-buten-1-yl)phthalimide, 5-hexenoic acid, methyl 5-hexenoate, 5-hexen-2-one, acrylonitrile, methacrylonitrile, vinyl acetate, etc. Among these, methyl 10-undecenoate and ethyl 10-undecenoate are particularly preferred.

[0057] Examples of (meth)acrylic acid ester monomers in (ii) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, and phenyl (meth)acrylate.

[0058] Examples of allyl monomers in (iii) include allyl monomers having 3 carbon atoms (propenyl monomers) and allyl monomers having 4 or more carbon atoms and containing an allyl group. Preferred allyl monomers are those having polar groups such as halogen-containing, nitrogen-containing, oxygen-containing, or sulfur-containing groups, and vinyl monomers containing halogen, hydroxyl group, amino group, nitro group, carboxyl group, formyl group, ester group, epoxy group, nitrile group, etc. Preferred specific examples include allyl acetate, allyl alcohol, allylamine, N-allylaniline, Nt-butoxycarbonyl-N-allylamine, N-benzyloxycarbonyl-N-allylamine, N-allyl-N-benzylamine, allyl chloride, allyl bromide, allyl ether, diallyl ether, and the like.

[0059] In the present invention, there are no particular restrictions on the polymerization method. Slurry polymerization, in which at least a portion of the resulting polymer becomes a slurry in the medium; bulk polymerization, using the liquefied monomer itself as the medium; gas-phase polymerization, carried out in vaporized monomer; or high-pressure ionic polymerization, in which at least a portion of the resulting polymer dissolves in monomer liquefied at high temperature and pressure, are preferably used. Batch polymerization, semi-batch polymerization, or continuous polymerization may also be used. When this polymerization reaction is carried out using a solvent, the solvent may be a hydrocarbon solvent such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, or methylcyclohexane, or a liquid such as liquefied α-olefin, or a polar solvent such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropyl alcohol, or ethylene glycol, either in the presence or absence of such solvents. A mixture of the liquid compounds described herein may also be used as a solvent. Furthermore, ionic liquids can also be used as solvents.

[0060] While there are no particular restrictions on polymerization temperature, polymerization pressure, and polymerization time, the optimal settings can usually be selected from the following ranges, taking into account productivity and process capabilities. Specifically, the polymerization temperature can be selected from a range of -20°C to 290°C, preferably 0°C to 250°C; the polymerization pressure from 0.1 MPa to 300 MPa, preferably 0.3 MPa to 250 MPa; and the polymerization time from 0.1 minutes to 10 hours, preferably 0.5 minutes to 7 hours, and more preferably 1 minute to 6 hours.

[0061] In this invention, polymerization is generally carried out under an inert gas atmosphere. For example, nitrogen, argon, or carbon dioxide atmospheres can be used, with a nitrogen atmosphere being preferred. A small amount of oxygen or air may be present. There are no particular restrictions on the supply of catalysts and monomers to the polymerization reactor, and various supply methods can be used depending on the purpose. For example, in batch polymerization, it is possible to supply a predetermined amount of monomer to the polymerization reactor in advance and then supply the catalyst to it. In this case, additional monomers or additional catalysts may be supplied to the polymerization reactor. In the case of continuous polymerization, a predetermined amount of monomer and catalyst can be supplied to the polymerization reactor continuously or intermittently, and the polymerization reaction can be carried out continuously.

[0062] In particular, copolymers containing polar groups obtained by the present invention exhibit good paintability, printability, antistatic properties, inorganic filler dispersibility, adhesion to other resins, and compatibility with other resins due to the effects of the polar groups in the copolymer. These properties allow the copolymers of the present invention to be used in a variety of applications. For example, they can be used as films, sheets, adhesive resins, binders, compatibilizers, waxes, and the like. [Examples]

[0063] The present invention will be described in more detail in the following examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, the following synthesis examples and examples were performed under a purified nitrogen atmosphere, and dehydrated and deoxygenated solvents were used.

[0064] 1. Evaluation Method (1) Weight-average molecular weight Mw, number-average molecular weight Mn, and molecular weight distribution Mw / Mn The following GPC measurements were used. Specifically, the procedure was as follows: First, approximately 20 mg of the sample was placed in a vial for the PL-SP 260VS high-temperature GPC pretreatment device manufactured by Polymer Laboratory Co., Ltd. O-dichlorobenzene containing BHT (BHT concentration = 0.5 g / L) was added as a stabilizer to adjust the polymer concentration to 0.1% by mass. The polymer was heated to 135°C in the PL-SP 260VS high-temperature GPC pretreatment device to dissolve it, and the sample was prepared by filtering through a glass filter. In the GPC measurement in this invention, no polymer was captured on the glass filter. Next, GPC measurements were performed using a TSKgel GMH-HT column (30 cm x 4) manufactured by Tosoh Corporation and a Waters GPCV 2000 equipped with an RI detector. The measurement conditions were as follows: sample solution injection volume: approximately 520 μL, column temperature: 135°C, solvent: o-dichlorobenzene, flow rate: 1.0 mL / min. The molecular weight was calculated as follows: A commercially available monodisperse polystyrene was used as a standard sample. A calibration curve relating retention time and molecular weight was created from the viscosity formulas of the polystyrene standard sample and the ethylene polymer, and the molecular weight was calculated based on this calibration curve. The viscosity formula used was [η] = K × Mα, and for polystyrene, K = 1.38E -4 Using α=0.70, for ethylene polymers, K=4.77E -4 Using α=0.70, for propylene polymers, K=1.03E -4 We used α=0.78.

[0065] (2) Catalytic activity The catalytic activity (Vp) is given by the following formula (i), using the amount of polymer obtained by the polymerization reaction (g), the amount of catalyst used in the polymerization reaction (unit: mol), and the polymerization reaction time (h).

[0066]

number

[0067] (3) Content of ethyl undecenoate component in the polymer The content (Xm) of ethyl undecenoate in the polymer is given by the following formula (ii).

[0068]

number

[0069] The amounts of ethylene and ethyl undecenoate in the polymer 1 This was determined by 1H-NMR measurement. 1 For the 1H-NMR measurement, approximately 30 mg of the sample was dissolved in orthodichlorobenzene d4 while heating at 130°C, and the NMR measurement was performed at 130°C.

[0070] 2. Ligand synthesis (Synthesis Example 1): Synthesis of Amine Compound X-94 Amine compound X-94 was synthesized according to the following reaction equation.

[0071] [ka]

[0072] (1) Synthesis of compound 2 1-Naphthylamine (1 in the reaction equation) (50 g, 349.2 mmol, 49.0 mL, 1 equiv.) and picolinic acid (1A in the reaction equation) (47.29 g, 384.12 mmol, 1.1 equiv.) were dissolved in dichloromethane (30 mL). To this solution, HATU (O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate) (146.05 g, 384.12 mmol, 1.1 equiv.) and DIEA (N,N-diisopropylethylamine) (90.26 g, 698.40 mmol, 121.65 mL, 2 equiv.) were added, and the reaction solution was stirred at 20°C for 12 hours under nitrogen. The reaction solution was poured into water (500 mL) and extracted with dichloromethane (twice with 500 mL). The collected organic layer was washed with brine (500 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated, and the resulting solid was washed with alkyl hydroxide (10 mL) to obtain the crude product of compound 2 (86.7 g).

[0073] (2) Synthesis of compound 4 Compound 2 (20 g, 80.55 mmol, 1 equiv.), 3,5-dimethyl-1-iodobenzene (3) (73.09 g, 314.97 mmol, 45.40 mL, 3.9 equiv.), silver acetate (20.17 g, 120.83 mmol, 6.19 mL, 1.5 equiv.), and palladium acetate (1.17 g, 5.21 mmol) were mixed and stirred at 140°C for 24 hours. Dichloromethane (200 mL) was added to suspend the mixture, which was then filtered and washed with dichloromethane (twice with 100 mL). The resulting solid was dried to obtain the crude product. The crude product was purified by silica gel column chromatography (using petroleum ether / ethyl acetate 10:1 as the developing solvent) to obtain a brown solid of Compound 4 (28 g, 79.45 mmol, 99%).

[0074] (3) Synthesis of amine compound X-94 Compound 4 was heated under reflux at 90°C in an aqueous solution of NaOH ethanol (ethanol: 200 mL, water: 24 mL, NaOH: 31.78 g, 794.49 mmol). The reaction solution was cooled to room temperature and the solvent was concentrated. The residue was suspended in dichloromethane (150 mL) and filtered. The filtrate was washed with water (3 times with 200 mL) and brine (200 mL), and the organic layer was dried over anhydrous sodium sulfate. The organic layer was concentrated to obtain X-94 before purification. The obtained solid was washed with hexane:siRNA (10:1, 2 times with 77 mL) to obtain purified X-94 (6.0 g, 24.28 mmol, 29%). 1 The identification results by H-NMR are shown below. 1 H NMR (CDCl3, δ, ppm): 2.36 (s, 6H), 3.87 (brs, 2H), 6.62 (dd, J = 6.9, 1.5 Hz, 1H), 7.03-7.07 (m, 3H), 7.12 (dd, J = 6.7, 1.4 Hz, 1H), 7.23-7.40 (m, 3H), 7.75 (dd, J = 8.3, 1.4 Hz, 1H).

[0075] (Synthesis Example 2): Synthesis of Amine Compound X-95 Amine compound X-95 was synthesized according to the following reaction equation.

[0076] [ka] (1) X-95 synthesis In a 50 mL flask, X-94 (2 g, 8.09 mmol, 1 equiv.) and diphenylmethanol (2.98 g, 16.17 mmol, 2 equiv.) were mixed and heated at 120°C. A concentrated hydrochloric acid solution of zinc chloride (551.08 mg, 4.04 mmol) (796 mg, 8.09 mmol, 37%, 0.5 equiv.) was added to the flask. Immediately after addition, exothermic reaction and vigorous foaming were observed. When the reaction solution was heated at 160°C for 90 minutes, it turned into a brown solution. The reaction solution was cooled to room temperature, and dichloromethane (100 mL) was added to suspend it. The organic layer was removed, washed with water (twice with 100 mL) and brine (50 mL), dried over anhydrous sodium sulfate, and then the organic layer was concentrated to obtain the crude product. Purified X-95 was obtained by preparative column chromatography (3.00 g, 5.17 mmol, 64%). 1 The identification results by H-NMR are shown below. 1 H NMR (CDCl3, δ, ppm): 2.32 (s, 6H), 3.75 (brs, 2H), 5.46 (s, 1H), 6.08 (s, 1H), 6.36 (s, 1H), 6.90-7.00 (m, 9H), 7.02 (s, 2H), 7.05-7.20 (m, 13H), 7.27 (m, 1H), 7.91 (d, J = 8.4 Hz, 1H).

[0077] (Synthesis Example 3): Synthesis of Amine Compound X-96 Amine compound X-96 was synthesized according to the following reaction equation. [ka]

[0078] (1) Synthesis of compound 5 Under an argon atmosphere, X-94 (4 g, 16.17 mmol, 1 equiv.) was placed in a flask, dissolved in dichloromethane (50 mL), and cooled to -78°C. Zirconium chloride (37.69 mg, 161.72 μmol) was added to the flask, followed by the dropwise addition of a dichloromethane solution (20 mL) of NBS (N-bromosuccinimide) (3.17 g, 17.79 mmol, 1.1 equiv.). The reaction solution was stirred at -78°C for 1 hour and turned into a brown solution. Saturated sodium bicarbonate aqueous solution (100 mL) was added to the flask, and then the mixture was extracted with dichloromethane (three times with 150 mL each). The collected organic layer was washed with brine, dried over anhydrous sodium sulfate, and the organic layer was concentrated to obtain the crude product. By purification using a silica gel column (eluent: petroleum ether:ethyl acetate 50:1), compound 5 (3.8 g, 11.65 mmol, 72%) was obtained as a yellow oil.

[0079] (2) Synthesis of X-96 Compound 5 (4.8 g, 14.71 mmol, 1 equiv.) was placed in a flask and dissolved in toluene (100 mL). An ethanol solution (20 mL) of 3,5-dimethylphenylboronic acid (6) (3.31 g, 22.07 mmol, 1.5 equiv.) was added to the flask. A 2 M aqueous sodium carbonate solution (28 mL) was then added to the flask. The flask was purged with argon, and Pd(PPh3) (1.02 g, 882.81 μmol, 6 mol%) was added. The mixture was heated at 90°C under nitrogen for 12 hours. The solvent was removed by distillation to obtain the crude product. The crude product was dissolved in dichloromethane (200 mL), washed with water (3 times with 100 mL), and brine (100 mL), dried over anhydrous sodium sulfate, and the organic layer was concentrated to obtain the crude product. Purified X-96 was obtained by preparative column chromatography (2.8 g, 7.97 mmol, 54%). 1 The identification results by H-NMR are shown below. 1H NMR (CDCl3, δ, ppm): 2.32 (s, 6H), 2.34 (s, 6H), 4.08 (brs, 2H), 6.94 (s, 1H), 7.00 (s, 1H), 7.04 (s, 2H), 7.07 (s, 2H), 7.13 (dd, J = 7.0, 1.5 Hz, 1H), 7.24 (d, J = 8.2 Hz, 1H), 7.32 (d, J = 8.2 Hz, 1H), 7.37 (dd, J = 8.1, 6.9 Hz, 1H), 7.76 (dd, J = 8.3, 1.3 Hz, 1H).

[0080] (Synthesis Example 4): Synthesis of amine compound X-116 Amine compound X-116 was synthesized according to the following reaction equation. [ka]

[0081] (1) Synthesis of compound 8 Compound 2 (25 g, 100.69 mmol, 1 equiv.), 3,5-dichloro-1-iodobenzene (compound 7.109.92 g, 402.77 mmol, 4 equiv.), silver acetate (25.21 g, 7.50 mmol, 1.5 equiv.), and palladium acetate (1.13 g, 5.03 mmol, 0.05 equiv.) were added to a flask and heated at 140°C for 72 hours to obtain a brown suspension. The reaction solution was cooled to room temperature. Dichloromethane (300 mL each, three times) was added to the flask to suspend the mixture, and the solid was collected by filtration. Purified compound 8 was obtained by silica gel column chromatography (eluent: petroleum ether:ethyl acetate = 5:1) and recrystallization (dichloromethane:hexane).

[0082] (2) Synthesis of compound 9 Compound 8 (12 g, 30.51 mmol, 1 equiv.) was placed in a flask, and ethanol (45 mL), water (4.5 mL), and potassium hydroxide (17.12 g, 305.14 mmol, 10 equiv.) were added. The mixture was heated at 130°C for 4 hours to obtain a brown suspension. The reaction solution was cooled to room temperature, and the solvent was removed by distillation. The residue was suspended in dichloromethane (300 mL three times) and filtered to obtain the crude product. Compound 9 was obtained by silica gel column chromatography (eluent: petroleum ether:ethyl acetate = 20:1).

[0083] (3) Synthesis of compound 10 Compound 9 (7.5 g, 26.03 mmol, 1 equiv.) was placed in a flask and dissolved in anhydrous dichloromethane (200 mL). The solution was cooled to -78°C, zirconium chloride (60.65 mg, 260 μmol, 0.01 equiv.) was added, followed by the addition of a 150 mL dichloromethane solution of NBS (3.94 g, 22.12 mmol, 0.85 equiv.) dropwise under a nitrogen atmosphere. The reaction solution was stirred at -78°C for 2 hours and turned into a brown solution. The temperature was raised to room temperature, the reaction was stopped with saturated sodium carbonate aqueous solution (400 mL), and the solution was extracted with dichloromethane (three times with 600 mL). The organic layer was collected, washed with brine (400 mL), dried over anhydrous sodium sulfate, and the organic layer was concentrated to obtain a brown crude product. Compound 10 (10.6 g, 28.88 mmol, 55%) was obtained as a yellow solid using a silica gel column (eluent: petroleum ether:ethyl acetate = 50:1).

[0084] (4) Synthesis of X-116 Compound 10 (1.0 g, 2.72 mmol) was placed in a flask and dissolved in anhydrous toluene (20 mL). Next, ethanol solution of 3,5-dimethylphenylboronic acid (408 mg, 2.72 mmol, 1 equiv.) (5 mL) and 2 M aqueous sodium carbonate solution (5 mL) were added to the flask. The two-layer reaction solution was purged with nitrogen, Pd(PPh3)4 (188.89 mg, 163.46 μmol, 0.06 equiv.) was added, and the mixture was heated under nitrogen at 90°C for 12 hours to obtain a brown solution. The reaction solution was cooled to room temperature, and the solvent was removed by distillation. The residue was redissolved in dichloromethane (50 mL three times), washed with water (50 mL) and brine (50 mL), and dried over anhydrous sodium sulfate. The organic layer was concentrated to obtain the crude product. A yellow solid of compound X-116 (0.6 g, 1.53 mmol, 56%) was obtained by silica gel column chromatography (eluent: petroleum ether:ethyl acetate = 50:1). 1 The identification results by H-NMR are shown below. 1 H NMR (CDCl3, δ, ppm): 2.34 (s, 6H), 3.89 (brs, 2H), 6.97 (s, 1H), 7.04 (s, 2H), 7.13 (dd, J = 7.3, 1.3 Hz, 1H), 7.28 (d, J = 8.2 Hz, 1H), 7.34-7.40 (m, 5H), 7.81 (dd, J = 8.3, 1.2 Hz, 1H).

[0085] (5) Synthesis of IM-4C IM-4C was synthesized according to the following reaction equation.

[0086] [ka]

[0087] Methyl pyruvate (290 mg, 2.84 mmol) and X-96 (500 mg, 1.42 mmol) were dissolved in dichloromethane (5 mL), and a few drops of formic acid were added. The mixture was heated under reflux for 8 hours. The solvent was removed by distillation to obtain the crude product of IM-4C. The product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate gradient) (580 mg, 1.33 mmol, 94%). 1 The identification results by H-NMR are shown below. 1 H NMR (CDCl3, δ, ppm): 1.41 (s, 3H), 2.19 (s, 3H), 2.23 (s, 6H), 2.37 (s, 3H), 3.59 (s, 3H), 6.51 (s, 1H), 6.81 (s, 1H), 6.83 (s, 1H), 6.94 (s, 2H), 7.12 (s, 1H), 7.25 (m, 1H), 7.45 (m, 2H), 7.71 (d, J = 8.2 Hz, 1H), 7.83 (d, J = 8.4 Hz, 1H).

[0088] (6) IM-5C IM-5C was synthesized according to the following reaction equation.

[0089] [ka]

[0090] Methyl pyruvate (210 mg, 2.05 mmol) and X-95 (600 mg, 1.03 mmol) were dissolved in dichloromethane (5 mL), and a few drops of formic acid were added. The mixture was heated under reflux for 8 hours, and the solvent was removed by distillation to obtain the crude product of IM-5C. The product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate gradient) (606 mg, 0.914 mmol, 89%). 1 The identification results by H-NMR are shown below. 1H NMR (CDCl3, δ, ppm): 0.61 (s, 3H), 2.23 (s, 3H), 2.35 (s, 3H), 3.63 (s, 3H), 5.43 (s, 1H), 6.19 (s, 1H), 6.64 (s, 1H), 6.70 (s, 1H), 6.7-7.4 (m, 24H), 8.00 (d, J = 8.5 Hz, 1H).

[0091] (7) IM-3D IM-3D was synthesized according to the following reaction equation.

[0092] [ka]

[0093] 1-Methyl isatin (456 mg, 2.83 mmol) and X-94 (700 mg, 2.83 mmol) were dissolved in dichloromethane (5 mL), and a few drops of formic acid were added. The mixture was heated under reflux for 15 hours, and the solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate gradient) to obtain IM-3D (718 mg, 1.84 mmol, 65%).

[0094] (8) IM-4D IM-4D was synthesized according to the following reaction equation.

[0095] [ka]

[0096] 1-Methyl isatin (229 mg, 1.42 mmol) and X-96 (500 mg, 1.42 mmol) were dissolved in dichloromethane (5 mL), and a few drops of formic acid were added. The mixture was heated under reflux for 40 hours. The product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate gradient) to obtain IM-4D (581 mg, 1.20 mmol, 85%). 1 The identification results by H-NMR are shown below. 1H NMR (CDCl3, δ, ppm): 1.59 (s, 3H), 2.11 (s, 6H), 2.39 (s, 3H), 3.02 (s, 3H), 5.9-7.9 (m, 15H).

[0097] (9) IM-5D IM-5D was synthesized according to the following reaction equation. [ka]

[0098] 1-Methyl isatin (166 mg, 1.03 mmol) and X-95 (600 mg, 1.03 mmol) were dissolved in dichloromethane (5 mL), and a few drops of formic acid were added. The mixture was heated under reflux for 40 hours. The product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate gradient) to obtain IM-5D (598 mg, 0.922 mmol, 90%). 1 The identification results by H-NMR are shown below. 1 H NMR (CDCl3, δ, ppm): 1.82 (s, 3H), 2.43 (s, 3H), 3.02 (s, 3H), 5.24 (d, J = 8.1 Hz), 5.62 (s, 1H), 5.87 (s, 1H), 6.1-8.1 (m, 29H).

[0099] (10) IM-6D IM-6D was synthesized according to the following reaction equation.

[0100] [ka]

[0101] 1-Methyl isatin (166 mg, 1.03 mmol) and X-116 (600 mg, 1.61 mmol) were dissolved in toluene (5 mL), and a small amount of p-toluenesulfonic acid was added. The mixture was heated at 100 °C for 12 hours. The solvent was removed by distillation, and the solution was purified using a silica gel column (eluent: hexane, ethyl acetate, gradient) to obtain IM-6D (689 mg, 1.29 mmol, 80%). 1 The identification results by H-NMR are shown below. 1 H NMR (CDCl3, δ, ppm): 1.61 (s, 3H), 2.35 (s, 3H), 3.21 (s, 3H), 4.02 (s, 1H), 6.77 (s, 1H), 6.8-7.0 (m, 5H), 7.09 (t, J = 2.0 Hz, 1H), 7.24 (t, J = 2.0 Hz, 1H), 7.27-7.33 (m, 2H), 7.44 (d, J= 8.3 Hz, 1H), 7.63 (s, 1H), 7.78 (d, J = 8.3 Hz, 1H), 7.93 (d, J = 8.6 Hz, 1H).

[0102] (11) IM-4I IM-4I was synthesized according to the following reaction equation.

[0103] [ka]

[0104] N,N-dimethyl-2-oxopropanamide (196 mg, 1.70 mmol) and X-96 (500 mg, 1.42 mmol) were dissolved in toluene (5 mL), and a small amount of p-toluenesulfonic acid was added. The mixture was heated under reflux for 86 hours. The solvent was removed by distillation, and the solution was purified using a silica gel column (eluent: hexane, dichloromethane, gradient) to obtain IM-4I (226 mg, 0.504 mmol, 30%). 1 The identification results by H-NMR are shown below. 1H NMR (CDCl3, δ, ppm): 1.38 (s, 3H), 2.26 (s, 6H), 2.30 (s, 3H), 2.31 (s, 3H), 2.68 (s, 3H), 2.79 (s, 3H), 6.78 (s, 1H), 6.84 (s, 2H), 6.88 (s, 3H), 7.25 (d, J = 7.1 Hz, 1H), 7.39 (d, J = 8.4 Hz, 1H), 7.45 (t, J = 7.5 Hz, 1H), 7.70 (d, J = 8.3 Hz, 1H), 7.84 (d, J = 8.3 Hz, 1H).

[0105] (12) IM-5I IM-5I was synthesized according to the following reaction equation.

[0106] [ka]

[0107] N,N-dimethyl-2-oxopropanamide (196 mg, 1.70 mmol) and X-95 (800 mg, 1.38 mmol) were dissolved in toluene (5 mL), and a small amount of p-toluenesulfonic acid was added. The mixture was heated under reflux for 86 hours. The solution was purified by silica gel column chromatography (eluent: hexane, dichloromethane, gradient) to obtain IM-5I (380 mg, 0.561 mmol, 34%). 1 The identification results by H-NMR are shown below. 1 H NMR (CDCl3, δ, ppm): 1.13 (s, 3H), 2.26 (s, 3H), 2.30 (s, 3H), 2.76 (s, 3H), 3.02 (s, 3H), 5.32 (s, 1H), 6.18 (s, 1H), 6.65 (s, 1H), 6.71 (s, 1H), 6.78-6.87 (m, 6H), 6.95-7.04 (m, 4H), 7.05-7.25 (m, 13H), 7.33 (dd, J = 8.2, 7.0 Hz, 1H), 7.96 (d, J = 8.5 Hz, 1H).

[0108] 3. Complex Synthesis Metal complex (III) was synthesized by the method described below.

[0109] [ka]

[0110] Ligands, [Ni(allyl)Cl]2 and NaBArF (BArF=3,5-(CF3)2C6H3), were placed in separate flasks, and 5 mL of dichloromethane was added to each. The ligand and NaBArF solutions were pre-mixed, and the mixed solutions were added to the flask containing [Ni(allyl)Cl]2. After stirring at room temperature for 1 hour, the mixture was filtered using Celite. The solvent was removed by distillation to obtain a metal complex (carbonylimine complex). For each metal complex, (IM-4C)Ni(allyl)BArF, (IM-5C)Ni(allyl)BArF, (IM-3D)Ni(allyl)BArF, (IM-4D)Ni(allyl)BarF, (IM-5D)Ni(allyl)BArF, (IM-6D)Ni(allyl)BArF, (IM-4I)Ni(allyl)BArF, and (IM-5I)Ni(allyl)BArF, the respective yields and 1 The identification results by H-NMR are shown below.

[0111] (14)(IM-4C)Ni(allyl)BArF 84% yield 1¹H NMR (CDCl₃, δ, ppm): 1.58 (s, 3H), 2.14 (s, 3H), 2.16 (d, J = 14 Hz, 1H), 2.30 (s, 6H), 2.34 (d, J = 14 Hz, 1H), 2.47 (s, 3H), 2.70 (m, 1H), 3.20 (m, 1H), 3.72 (s, 3H), 5.77 (m, 1H), 6.49 (s, 1H), 6.96 (s, 1H), 6.99 (s, 2H), 7.01 (s, 1H), 7.47-7.53 (m, 6H), 7.63 (t, J = 8.0 Hz, 1H), 7.70 (s, 8H), 7.80 (s, 1H), 7.98 (d, J = 8.2 Hz, 1H), 7.99 (d, J = 8.4 Hz, 1H).

[0112] (15)(IM-5C)Ni(allyl)BArF 90% yield 1 ¹H NMR (CDCl₃, δ, ppm): 1.34 (s, 3H), 2.17 (s, 3H), 2.44 (s, 3H), 3.81 (s, 3H), 5.43 (s, 1H), 5.53 (m, 1H), 6.22 (s, 1H), 6.59 (s, 1H), 6.75-6.88 (m, 5H), 6.91-7.00 (m, 5H), 7.13-7.25 (m, 12H), 7.32 (d, J = 7.1 Hz, 1H), 7.45-7.55 (m, 6H), 7.70 (s, 8H), 8.14 (d, J = 8.7 Hz, 1H).

[0113] (16)(IM-3D)Ni(allyl)BArF 91% yield 1¹H NMR (CDCl₃, δ, ppm): 1.61 (s, 3H), 2.21 (d, J = 13.4 Hz, 1H), 2.31 (d, J = 13.4 Hz, 1H), 2.55 (s, 3H), 2.78 (d, J = 7.2 Hz, 1H), 3.05 (d, J = 6.8 Hz, 1H), 3.08 (s, 3H), 5.77 (m, 1H), 6.23 (s, 1H), 6.86-7.0 (m, 4H), 7.09 (d, J = 7.2 Hz, 1H), 7.45-7.53 (m, 7H), 7.65 (t, J = 8.1 Hz, 1H), 7.70 (s, 8H), 7.77 (s, 1H), 7.99 (d, J = 8.2 Hz, 2H).

[0114] (17)(IM-4D)Ni(allyl)BArF 88% yield 1 ¹H NMR (CDCl₃, δ, ppm): 1.68 (s, 3H), 2.10 - 2.25 (m, 2H), 2.22 (s, 6H), 2.47 (s, 3H), 2.80 (brs, 1H), 2.99 (s, 3H), 3.19 (brs, 1H), 5.47 (m, 1H), 6.13 (s, 1H), 6.42 (d, J = 7.4 Hz, 1H), 6.73 (d, J = 8.1 Hz, 1H), 6.84-6.91 (m, 3H), 6.96 (d, J = 11.9 Hz, 1H), 7.37 (t, J = 7.9 Hz, 1H), 7.43 (d, J = 7.0 Hz, 1H), 7.49 (s, 4H), 7.54-7.58 (m, 2H), 7.62 (t, J = 7.8 Hz, 1H), 7.70 (s, 8H), 7.99 (d, J = 7.8 Hz, 1H), 8.03 (d, J = 8.7 Hz, 1H).

[0115] (18)(IM-5D)Ni(allyl)BArF 87% yield 11H NMR (CDCl3, δ, ppm): 1.63 (s, 3H), 2.00 (d, J = 12.0 Hz, 1H), 2.22 (d, J = 14.0 Hz, 1H), 2.48 (s, 3H), 2.87 (brs, 1H), 3.02 (s, 3H), 3.13 (brs, 1H), 5.58 (m, 1H), 5.72 (s, 1H), 6.07 (s, 1H), 6.10 (d, J = 7.7 Hz, 1H), 6.26 (s, 1H), 6.65-6.74 (m, 3H), 6.75-6.89 (m, 7H), 6.93-7.02 (m, 5H), 7.15-7.26 (m, 9H), 7.28 (d, J = 6.9 Hz, 1H), 7.34 (t, J = 7.8 Hz, 1H), 7.47 (t, J = 7.8 Hz, 1H), 7.49 (s, 4H), 7.70 (s, 8H), 8.14 (d, J = 8.4 Hz, 1H).

[0116] (19) (IM-6D)Ni(allyl)BArF 95% yield 1 1H NMR (CDCl3, δ, ppm): 1.57-2.13 (br, 3H), 2.48 (s, 3H), 3.38 (s, 3H), 5.64 (m, 1H), 6.38 (m, 1H), 6.52 (m, 1H), 6.91 (t, J = 7.6 Hz, 1H), 7.10 (d, J = 7.9 Hz, 1H), 7.12 (m, 1H), 7.30 (m, 1H), 7.43 (t, J = 8.1 Hz, 1H), 7.48-7.56 (m, 5H), 7.60-7.75 (m, 11H), 7.84 (m, 1H), 7.93-8.0 (m, 2H), 8.05 (m, 1H).

[0117] (20) (IM-4I)Ni(allyl)BArF 90% yield 1H NMR (CDCl3, δ, ppm): 1.70 (s, 3H), 2.18 (s, 3H), 2.31 (s, 6H), 2.45 (s, 3H), 2.79 (s, 3H), 2.81 (s, 3H), 5.49 (m, 1H), 6.59 (s, 1H), 6.94-7.08 (m, 3H), 7.45-7.58 (m, 6H), 7.6-7.74 (m, 11H), 7.98 (d, J = 8.6 Hz), 7.99 (d, J = 8.6 Hz, 1H).

[0118] (21)(IM-5I)Ni(allyl)BArF 90% yield 1 H NMR (CDCl3, δ, ppm): 1.01 (brs, 3H), 2.17 (brs, 3H), 2.46 (s, 3H), 2.84 (s, 3H), 2.88 (s, 3H), 5.58-5.86 (m, 2H), 6.23 (s, 1H), 6.59-6.87 (m, 5H), 6.88-7.07 (m, 6H), 7.10-7.36 (m, 14H), 7,47 (t, J = 8.1 Hz, 1H), 7.52 (s, 4H), 7.70 (s, 8H), 8.14 (d, J = 8.6 Hz, 1H).

[0119] 4. The combination of エチレン / ウンデセン acid エチル (Examples 1A~6A) A 2 L induction-stirred autoclave was purged with nitrogen, and anhydrous toluene (400 mL), TNOA (tri-n-octyl aluminum) (100 μmol, 1 mL, 0.1 M toluene solution), and anhydrous ethyl undecenoate (73 mL, 300 mmol) were introduced. A complex catalyst (20 μmol) consisting of the complexes listed in Table 1, diluted in dichloromethane (5 mL), was added to the catalyst feeder. The autoclave was heated to 70°C, and the catalyst solution was introduced using ethylene gas during the heating process. The mixture was stirred at 70°C for 1 hour, during which time ethylene was added as needed to maintain an ethylene pressure of 1 MPa. After the reaction, the mixture was cooled to room temperature, and the polymer was precipitated by adding ethanol to the resulting suspension. The mixture was filtered by suction, the solid was washed with ethanol and acetone, and the polymer was obtained by heating and drying. The weight of the obtained polymer was weighed using a balance, and the catalytic activity was calculated based on the above calculation formula (i). Furthermore, the weight-average molecular weight Mw and molecular weight distribution Mw / Mn were measured using the method described above, and the content was determined using the calculation formula (ii) described above. These results are shown in Table 1.

[0120] (Examples 7A-10A) Polymers were obtained by polymerization under the same conditions as in the experimental formulations of Examples 1A to 6A described above, except that TNOA was not added. The results are shown in Table 1.

[0121] (Example 11A) Polymerization was carried out under the same conditions as in the experimental formulations of Examples 1A to 6A described above, except that TNOA was not added and ethyl undecenoate was changed to 202 mL (829 mmol), and polymers were obtained. The results are shown in Table 2.

[0122] (Example 12A) Polymerization was carried out under the same conditions as in the experimental formulations of Examples 1A to 6A described above, except that TNOA and toluene were omitted and ethyl undecenoate was changed to 403 mL (1658 mmol), and polymers were obtained. The results are shown in Table 2.

[0123] [Table 1]

[0124] [Table 2]

[0125] As can be seen from Table 1, it can be confirmed that the activity, molecular weight, and copolymerization amount change significantly by changing the ligand structure. In particular, as can be seen in Examples 2A, 5A, 7A, and 8A, the activity changed by 2 to 3 × 10 when using IM-5C and IM-5D. 6 Approximately g / mol·h has been confirmed. This is more than 15 times the activity of copolymers of ethylene and methyl undecenoate, and ethyl undecenoate, as shown in Patent Document 5 and Non-Patent Document 7. Furthermore, comparing Examples 2A and 7A, or 5A and 8A, it was confirmed that the content improved by approximately 0.7 mol% when TNOA was not added. From this, it was confirmed that the presence of alkylaluminum such as TNOA affects the amount of polar monomer incorporated.

[0126] As can be seen from Table 2, comparing Examples 8A and 11A, increasing the concentration of ethyl undecenoate did not decrease the activity, but the molecular weight was halved and the content increased by 1.2 mol%. In other words, it can be seen that increasing the concentration of polar monomers is sufficient to increase the content of polar monomers. Furthermore, in Example 12A, when the polymerization reaction was examined under neat conditions without adding a solvent, the activity was 4.55 × 10⁻⁶. 5 Although the concentration decreased, a copolymer with a content of 10.9 mol% was obtained. In ethylene / polar monomer copolymerization using a nickel catalyst having a carbonylimine ligand, there are no examples in conventional or non-patent literature of reactions carried out under neat conditions, making this the first example of polymerization activity being exhibited even in the presence of very high concentrations of polar monomers.

[0127] The metal complex having a carbonylimine ligand of the present invention exhibits excellent catalytic activity even in the presence of polar monomers, and maintains its activity even under conditions of high polar monomer concentrations, thereby achieving high uptake of polar monomers. This demonstrates its significant technical importance. [Industrial applicability]

[0128] By using the metal complex of the present invention, it becomes possible to produce novel functional polyolefins that exhibit characteristics due to the presence of polar groups, making them highly useful industrially, especially in applications where adhesion and aesthetic appeal are required.

Claims

1. A compound represented by the following general formula [I]. 【Chemistry 1】 (wherein R １ to R １１ each independently represent (i) hydrogen, (ii) halogen, (iii) a group containing a heteroatom, or (iv) an organic group. Y is -OR １２ , -NR １３ R １４ , and R １２ to R １４ each independently represent (i) hydrogen, (ii) halogen, (iii) a group containing a heteroatom, or (iv) an organic group. Z is (i) hydrogen, (ii) halogen, (iii) a group containing a heteroatom, or (iv) an organic group. Here, the (ii) halogen in R １ to R １１ is selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; the (iii) group containing a heteroatom is selected from a methoxy group, an ethoxy group, a phenoxy group, a nitrile group, a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, a trimethylsilyloxy group, a trimethoxysiloxy group, a cyclohexylamino group, sodium sulfonate, potassium sulfonate, sodium phosphate, and potassium phosphate; the (iv) organic group is selected from a methyl group, an ethyl group, an isopropyl group, a butyl group, a phenyl group, a trifluoromethyl group, a pentafluorophenyl group, a carbazolyl group, a naphthyl group, an anthracenyl group, a 3,5-dimethylphenyl group, and a diphenylmethyl group. The heteroatom in the group containing a heteroatom (iii) specified by Y and the group containing a heteroatom (iii) specified by Z is selected from oxygen, nitrogen, phosphorus, sulfur, selenium, silicon, fluorine, chlorine, and boron, and the total number of carbon atoms in the organic group (iv) specified by Y and Z is 1 to 30. A plurality of selected substituents present on Y and Z may be linked to each other to form a heterocyclic ring containing 5 to 8 ring members and a heteroatom selected from the group consisting of oxygen and nitrogen.)

2. A metal complex represented by the following general formula [II]. 【Chemistry 2】 (In the formula, R １ ~R １１ Y and Z are the same as those described in general formula [I]. M is nickel or palladium, L is a monoanionic ligand, and X is a counteranion.

3. The metal complex according to claim 2, wherein the monoanionic ligand L coordinates to the metal center with multiple atoms.

4. The above L is a metal complex according to the following general formula [III], where L is an allyl ligand, and R １５ The metal complex according to claim 2, wherein is hydrogen or halogen. 【Transformation 3】 (In the formula, R １ ~R １１ Y, Z, M, and X are the same as those described in general formula (II).

5. A method for producing a metal complex, comprising contacting a compound represented by general formula [I] as described in claim 1 with a transition metal compound containing nickel or palladium to produce a metal complex represented by general formula [II] as described in claim 2.

6. A catalyst for olefin polymerization comprising the metal complex described in any one of claims 2 to 4.

7. A method for producing a (co)polymer, comprising (co)polymerizing an olefin in the presence of the polymerization catalyst described in claim 6.

8. A method for producing a copolymer, comprising copolymerizing an olefin with a polar group-containing vinyl monomer in the presence of the polymerization catalyst described in claim 6.

9. The method for producing a copolymer according to claim 8, wherein the polar group-containing vinyl monomer contains an oxygen atom and / or a nitrogen atom.

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