Polar group-containing olefin copolymer and method for producing the same

Abstract

To provide a novel polar group-containing olefin copolymer and a method for producing the copolymer.SOLUTION: A polar group-containing olefin copolymer contains: a structural unit (A) derived from at least one kind of olefin with carbon number 2 to 20; 0.04 mol% to 10.00 mol% of a structural unit (b-1) expressed by the following general formula (b-1); and at least one kind of a structural unit (c-1) expressed by the following general formula (c-1) and a structural unit (c-2) expressed by the following general formula (c-2), in a main chain. Chemical formula 1 (See the specification for symbols in the general formula (b-1), general formula (c-1) and general formula (c-2).)

Description

[Technical field]

[0001] The present invention relates to a novel polar group-containing olefin copolymer, and more particularly to a novel polar group-containing olefin copolymer having a main chain containing a structure derived from an olefin having 2 to 20 carbon atoms, a vinylene carbonate derivative, and a structure derived from a specific polar group-containing monomer, and a method for producing the same. [Background technology]

[0002] Among resin materials, olefin copolymers are excellent in physical properties such as physical properties and moldability, and are also economically and environmentally friendly, making them an important industrial material that is widely used. However, since olefin copolymers do not have polar groups, it has been difficult to apply them to applications that require physical properties such as adhesion to other materials, printability, or compatibility with fillers. Since the inclusion of polar groups can improve these physical properties, the synthesis of polar group-containing olefin copolymers by radical polymerization has been carried out industrially for many years. On the other hand, polar group-containing olefin copolymers obtained by radical polymerization have many branched structures and are therefore poor in rigidity and durability, so the development of linear polar group-containing olefin copolymers has been desired.

[0003] In this situation, in recent years, active research has been conducted into the introduction of polar groups into the polymer chain of linear polyolefins by copolymerizing olefins with polar vinyl monomers in the presence of late periodic metal complexes (Non-Patent Documents 1 and 2). Among linear polar group-containing olefin copolymers, linear ethylene-vinyl alcohol copolymers (EVOH) are substances for which the establishment of a synthesis method is required. Branched EVOH is industrially produced by radical copolymerization of ethylene and vinyl acetate followed by hydrolysis, but if linear EVOH could be synthesized, it may be possible to synthesize a more durable EVOH.

[0004] As an example of the synthesis of a linear polar group-containing olefin copolymer containing a hydroxyl group, a method has been reported in which ethylene and vinylene carbonate are copolymerized in the presence of a late metal complex and then hydrolyzed (Patent Document 1). In this method, a hydroxyl group is introduced at the vicinal position. On the other hand, it is known that the catalyst used in Patent Document 1 is limited in the polar monomers that can be copolymerized, and for example, ethylene and acrylic esters cannot be copolymerized (Non-Patent Documents 3 and 4). If another polar group can be introduced into a linear polar group-containing olefin copolymer containing a hydroxyl group, it is expected that new functions will be expressed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. WO 00 / 56781 [Non-patent literature]

[0006] [Non-Patent Document 1] Chem. Rev., 2000, 100, 1169-1203. [Non-Patent Document 2] Chem. Rev., 2009, 109, 5215-5244. [Non-Patent Document 3] Organometallics,2004,23,5121-5123. [Non-Patent Document 4] J.Am.Chem.Soc.,2009,131,12613-12622. Summary of the Invention [Problem to be solved by the invention]

[0007] In such a situation, the present application provides a method for producing a linear polyolefin having an OM at a vicinal position. 1The object of the present invention is to provide a novel polar-group-containing olefin copolymer having a structural unit containing a group (hydroxyl group and / or metal alkoxide) and at least one of a structural unit containing a carboxylate group and / or a carboxy group derived from an acrylic ester derivative and a structural unit containing an ester group, and a method for producing the same. [Means for solving the problem]

[0008] As a result of intensive research to achieve the above-mentioned objective, the present researchers discovered that OM is present in the vicinal position in linear polyolefins. 1 The present invention has discovered a polar-group-containing olefin copolymer having a novel structure in which a structural unit containing a group (hydroxyl group and / or metal alkoxide) and at least one of a structural unit containing a carboxylate group and / or a carboxy group derived from an acrylic ester derivative and a structural unit containing an ester group are further introduced, and a method for producing the same has been discovered. That is, the present invention includes the following aspects.

[0009] <1> A structural unit (A) derived from at least one olefin having 2 to 20 carbon atoms; 0.04 mol % to 10.00 mol % of a structural unit (b-1) represented by the following general formula (b-1), At least one of a structural unit (c-1) represented by the following general formula (c-1) and a structural unit (c-2) represented by the following general formula (c-2), A polar group-containing olefin copolymer, characterized in that both of the above are contained in the main chain.

[0010] [ka] (In formula (b-1), R 1 and R 2are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a nitro group, an amino group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, an amido group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, or R 1 and R 2 may be bonded to each other to form a 4- to 10-membered ring. M 1 are each independently a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table.

[0011] [ka] (In formula (c-1), R 3 is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. M 2 is a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table.

[0012] [ka] (In formula (c-2), R 3 R 3 is synonymous with. R 4is a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms which is substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one of an oxygen atom, a sulfur atom, or a nitrogen atom.

[0013] <2> The above-mentioned compound further contains a structural unit (b-2) represented by the following general formula (b-2): <1> 2. The polar group-containing olefin copolymer according to claim 1 .

[0014] [ka] (In formula (b-2), R 1 and R 2 are the above R 1 and R 2 is equivalent to

[0015] <3> R of the structural unit (b-1) 1 and R 2 At least one of the above is a hydrogen atom. <1> or <2> 2. The polar group-containing olefin copolymer according to claim 1 . <4> R in the general formula (c-1) and the general formula (c-2) 3 are each a hydrogen atom. <1> ~ <3> 2. The polar group-containing olefin copolymer according to claim 1 . <5> R of the structural unit (b-1) 1 and R 2 are each a hydrogen atom. <1> ~ <4> 2. The polar group-containing olefin copolymer according to claim 1 . <6> At least one of the olefins having 2 to 20 carbon atoms is ethylene. <1> ~ <5> 2. The polar group-containing olefin copolymer according to claim 1 .

[0016] <7> The total content of the structural unit (c-1) and the structural unit (c-2) is 0.01 mol % to 30.00 mol %. <1> ~ <6> 2. The polar group-containing olefin copolymer according to claim 1 .

[0017] <8> A step of polymerizing at least one olefin having 2 to 20 carbon atoms, at least one monomer represented by the following general formula (1), and at least one monomer represented by the following general formula (2) in the presence of a catalyst containing at least one compound represented by the following general formula (101) to obtain an olefin copolymer; A method for producing a polar group-containing olefin copolymer, comprising the steps of converting at least a portion of the structural units derived from the monomer represented by general formula (1) contained in the olefin copolymer into structural units represented by the following general formula (b-1), and optionally converting at least a portion of the structural units derived from the monomer represented by general formula (2) into structural units represented by the following general formula (c-1):

[0018] [ka] [In general formula (101), M represents a metal atom of Group 10 of the periodic table. Q represents an oxygen atom, a sulfur atom, -S(=O)2-O-, or -C(=O)-O-, and the left side of each of these groups is bonded to A and the right side is bonded to M. A represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. R L represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a ligand coordinated to M. L represents a ligand coordinated to M. R x and R y each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. R L and L and R x and R y may form a ring, R x and A or Ry and A may form a ring.

[0019] [ka] (In formula (1), R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a nitro group, an amino group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, an amido group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, or R 1 and R 2 may be bonded to each other to form a 4- to 10-membered ring.

[0020] [ka] (In formula (2), R 3 is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. R 4 is a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms which is substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one of an oxygen atom, a sulfur atom, or a nitrogen atom.

[0021] [ka] (In formula (b-1), R 1 and R 2 are the above R 1 and R 2 is synonymous with. M 1 are each independently a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table.

[0022] [ka] (In formula (c-1), R 3 R 3 is synonymous with. M 2 is a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table. Effect of the Invention

[0023] According to the present invention, OM is introduced into a linear polyolefin at a vicinal position. 1 The present invention can provide a novel polar-group-containing olefin copolymer having a structural unit containing a group (hydroxyl group and / or metal alkoxide) and at least one of a structural unit containing a carboxylate group and / or a carboxy group derived from an acrylic ester derivative and a structural unit containing an ester group, and a method for producing the same. [Brief description of the drawings]

[0024] [Figure 1] FIG. 1 shows the results of 13C-NMR measurement of the polar group-containing olefin copolymer 2 of Example 2. [Diagram 2] FIG. 2 shows a partially enlarged view of the results of 13C-NMR measurement of the polar group-containing olefin copolymer 2 of Example 2. [Diagram 3]FIG. 3 shows a partially enlarged view of the results of 13C-NMR measurement of the polar group-containing olefin copolymer 2 of Example 2. [Figure 4] FIG. 4 shows the results of 1H-NMR measurement of the polar group-containing olefin copolymer 1 of Example 1. [Diagram 5] FIG. 5 shows a partially enlarged view of the 1H-NMR measurement result of the polar group-containing olefin copolymer 1 of Example 1. [Figure 6] FIG. 6 shows a partially enlarged view of the 1H-NMR measurement results of the polar group-containing olefin copolymer 1 of Example 1. [Figure 7] FIG. 7 shows the results of 1H-NMR measurement of the polar group-containing olefin copolymer 2 of Example 2. [Figure 8] FIG. 8 shows a partially enlarged view of the 1H-NMR measurement results of the polar group-containing olefin copolymer 2 of Example 2. [Figure 9] FIG. 9 shows the results of HSQC measurement of the polar group-containing olefin copolymer 1 of Example 1. [Figure 10] FIG. 10 shows the results of HSQC measurement of the polar group-containing olefin copolymer 2 of Example 2 (hydrogen: around 1.85 ppm to around 2.85 ppm, carbon: around 39 ppm to around 50 ppm). [Figure 11] FIG. 11 shows the results of DEPT135-NMR measurement of the polar group-containing olefin copolymer 2 of Example 2 (from about 40 ppm to about 52 ppm). [Figure 12] FIG. 12 shows the results of HSQC measurement of the polar-group-containing olefin copolymer 2 of Example 2 (hydrogen: from about 3.10 ppm to about 4.80 ppm, carbon: from about 55 ppm to about 82 ppm). [Figure 13] FIG. 13 shows the results of DEPT135-NMR measurement of the polar group-containing olefin copolymer 2 of Example 2 (from about 54 ppm to about 65 ppm). [Figure 14] FIG. 14 shows the results of infrared absorption spectrum analysis of the polar group-containing olefin copolymer 3 of Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] The polar group-containing olefin copolymer of the present invention and its production method will be described in detail below. In this specification, "(meth)acryloyl" means at least one selected from "acryloyl" and "methacryloyl". In the present invention, "monomer" means an unpolymerized compound, and "structural unit" means a structural unit that constitutes a polymer derived from a monomer or a polymerizable compound formed by polymerization of the monomer or the compound. The "structural unit" may be a unit formed directly by a polymerization reaction, or may be a unit that is partially converted into a different structure by treating the polymer. In addition, in this specification, the use of "to" indicating a numerical range means that the numerical values ​​before and after it are included as the lower limit and upper limit, for example, "A to B" means that the range is from A to B. Furthermore, the upper limit and lower limit in a numerical range can be any combination to form a numerical range that is "from the lower limit to the upper limit". In addition, in this specification, "derived from an acrylic acid ester derivative" means "derived from a monomer represented by the above general formula (2)".

[0026] The polar group-containing olefin copolymer of the present invention comprises a structural unit (A) derived from at least one olefin having 2 to 20 carbon atoms, 0.04 mol % to 10.00 mol % of a structural unit (b-1) represented by the following general formula (b-1), At least one of a structural unit (c-1) represented by the following general formula (c-1) and a structural unit (c-2) represented by the following general formula (c-2), The polar group-containing olefin copolymer is characterized in that each of the above is contained in the main chain.

[0027] [ka] (In formula (b-1), R 1 and R 2are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a nitro group, an amino group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, an amido group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, or R 1 and R 2 may be bonded to each other to form a 4- to 10-membered ring. M 1 are each independently a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table.

[0028] [ka] (In formula (c-1), R 3 is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. M 2 is a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table.

[0029] [ka] (In formula (c-2), R 3 R 3 is synonymous with. R 4is a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms which is substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one of an oxygen atom, a sulfur atom, or a nitrogen atom.

[0030] As shown in FIG. 1 and the like, the polar group-containing olefin copolymer of the present invention is a copolymer of an olefin having two or more carbon atoms such as ethylene, which has an OM at a vicinal position in the main chain (the wavy line in the chemical structural formula in the figure represents the main chain of the polymer). 1 The novel polar-group-containing olefin copolymer comprises a structural unit (b-1) containing a group (hydroxyl group and / or metal alkoxide), and at least one of a structural unit (c-1) containing a carboxylate group and / or a carboxyl group derived from an acrylic ester derivative, and a structural unit (c-2) containing an ester group.

[0031] Thus, the polar group-containing olefin copolymer of the present invention has OM at the vicinal position. 1 A specific amount of groups (hydroxyl groups and / or metal alkoxides) and COOM 2 Groups (carboxyl groups and / or carboxylate groups) and COOR 4 Since the copolymer has two or more kinds of polar groups in the main chain, that is, at least one kind of polar group (ester group), it may have better performance and new properties than conventional polar group-containing olefin copolymers.

[0032] The polar group-containing olefin copolymer of the present invention is a polyolefin having 2 or more carbon atoms, such as ethylene, in which OM at the vicinal position is 1 The acrylic ester derivative represented by the general formula (c-1) is represented by the formula (c-2). 2 Group (M 2 may have a hydrogen atom or a metal ion of Group 1, 2, 12 or 13 of the Periodic Table). The polar group-containing olefin copolymer of the present invention is expected to realize functions not found in conventional ethylene copolymers, such as a carboxyl group derived from an ethylene-vicinal hydroxyl group-(meth)acrylic acid ester derivative having a chelating ability to metals. Copolymers having such functions are expected to be used as supports for metal complex catalysts and adsorbents for recovering metal complexes.

[0033] In addition, the polar group-containing olefin copolymer of the present invention is expected to realize functions not found in conventional ethylene copolymers, such as ionic bonding to the carboxylate group derived from a metal alkoxide-(meth)acrylic acid ester derivative at the ethylene-vicinal position. Copolymers having such functions are expected to be used in automobile parts and the like, taking advantage of their excellent compatibility with pigments and fillers and their toughness.

[0034] In addition, it is believed that the polar group-containing olefin copolymer of the present invention can be further functionalized by performing graft polymerization using the different polar groups contained in the structural unit (b-1) or the structural unit (c-1). For example, in the polar group-containing olefin copolymer of the present invention, the hydroxyl group at the vicinal position and the carboxyl group derived from the acrylate derivative have different proton acidities, which allows for different chemical modifications, and different material properties can be expected from conventional olefin-acrylate copolymers. Furthermore, the polar group-containing olefin copolymer of the present invention has linear polyolefins each having different polar groups contained in the structural unit (b-1) or the structural unit (c-1), and therefore has higher heat resistance and rigidity than branched polar group-containing olefin copolymers. Therefore, the copolymer is expected to be used in applications requiring such properties as storage containers and pipes.

[0035] The polar group-containing olefin copolymer of the present invention is a polyolefin having 2 or more carbon atoms, such as ethylene, in which OM at the vicinal position is 1The polar group-containing olefin copolymer of the present invention does not contain the structural unit (c-1) but may contain an ester group derived from an acrylic acid ester derivative represented by the general formula (c-2). When the polar group-containing olefin copolymer of the present invention does not contain the structural unit (c-1) but contains the structural unit (c-2) containing an ester group, it is possible to obtain a polar group-containing olefin copolymer by the OM method while imparting a function due to the structural unit (c-2) containing an ester group. 1 Since the selectivity of the further chemical modification reaction at the group can be improved and side reactions can be suppressed, it is expected that materials suitable for desired applications can be obtained efficiently.

[0036] (1) Structural unit (A) The structural unit (A) is a structural unit derived from at least one olefin having 2 to 20 carbon atoms. The monomer (monomer (A)) used in the present invention from which the structural unit (A) is derived is at least one type of olefin having 2 to 20 carbon atoms. The olefin having 2 to 20 carbon atoms may be a chain olefin or a cyclic olefin, and examples thereof include at least one type selected from the group consisting of α-olefins having 2 to 20 carbon atoms, including ethylene, and cyclic olefins having 4 to 20 carbon atoms.

[0037] The α-olefin having 2 to 20 carbon atoms used in the present invention is an α-olefin having 2 to 20 carbon atoms represented by the structural formula: CH2=CHR (wherein R is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, which may have a linear structure or may be branched), and preferably an α-olefin having 2 to 12 carbon atoms. The cyclic olefin having 4 to 20 carbon atoms is a cyclic olefin having 4 to 20 carbon atoms represented by the structural formula: R'CH=CHR" (wherein R' and R" are bonded to each other to form a ring structure, which is a hydrocarbon group having a total of 2 to 18 carbon atoms and may be branched), and is preferably a cyclic olefin having 4 to 15 carbon atoms.

[0038] Specific examples of the monomer (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, cyclobutene, cyclopentene, and norbornene, etc. From the viewpoint of the production efficiency of the polymer, the monomer (A) is preferably one or more selected from the group consisting of ethylene, propylene, 1-butene, and norbornene, and more preferably ethylene. The structural unit (A) may be one type alone or two or more types. Examples of a combination of two types include structural units derived from ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, ethylene-norbornene, etc. Examples of a combination of three types include structural units derived from ethylene-1-butene-hexene, ethylene-1-butene-1-octene, etc.

[0039] In the present invention, the monomer (A) preferably contains ethylene as an essential component and may further contain one or more α-olefins having 3 to 20 carbon atoms, if necessary. The amount of ethylene in the monomer (A) may be 65 mol % to 100 mol % or 70 mol % to 100 mol % relative to 100 mol % of the entire monomer (A).

[0040] (2) Structural unit (b-1) The structural unit (b-1) is a structural unit represented by the following general formula (b-1).

[0041] [ka] (In formula (b-1), R 1 and R 2are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a nitro group, an amino group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, an amido group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, or R 1 and R 2 may be bonded to each other to form a 4- to 10-membered ring. M 1 are each independently a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table.

[0042] R 1 and R 2 In the above, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 1 and R 2 In the formula, the ester group having 1 to 30 carbon atoms is represented by -COOR a where R a represents a hydrocarbon group having 1 to 30 carbon atoms. The number of carbon atoms in the ester group does not include the number of carbon atoms in the carbonyl group. a The lower limit of the carbon number is 1 or more, and may be 2 or more, and the upper limit of the carbon number is 30 or less, and may be 20 or less, or may be 10 or less.

[0043] R aExamples of the hydrocarbon group having 1 to 30 carbon atoms in the formula (I) include linear, branched, and cyclic saturated or unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Preferred examples of the hydrocarbon group having 1 to 30 carbon atoms include the following examples of alkyl groups having 1 to 30 carbon atoms, as well as alkenyl groups such as ethenyl, propenyl, butenyl, and pentenyl groups; aryl groups such as phenyl, methylphenyl, n-propylphenyl, i-propylphenyl, n-butylphenyl, i-butylphenyl, s-butylphenyl, t-butylphenyl, n-hexylphenyl, trimethylphenyl, pentamethylphenyl, biphenyl, naphthyl, anthracenyl, fluorenyl, and tolyl groups; and aralkyl groups such as benzyl, phenylethyl, phenylpropyl, naphthylmethyl, diphenylmethyl, and triphenylmethyl groups.

[0044] The alkyl group having 1 to 30 carbon atoms may be, for example, linear, branched, or cyclic, and includes, for example, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, a 1-nonyl group, a 1-decyl group, a t-butyl group, a tricyclohexylmethyl group, an isopropyl group, a 1-dimethylpropyl group, a 1,1,2-trimethylpropyl group, a 1,1-diethylpropyl group, an isobutyl group, a 1,1-dimethylbutyl group, a 2-pentyl group, Preferred examples of the aryl group include 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, and norbornyl group.

[0045] The hydrocarbon group may further have a substituent, and examples of the substituent include a halogen atom, an epoxy group, an amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and a hydroxyl group. The number of carbon atoms contained in the substituent is determined by the above-mentioned R a The carbon number in the formula (I) is not included in the carbon number in the formula (I). R a The hydrocarbon group in is preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and even more preferably an unsubstituted hydrocarbon group having 1 to 6 carbon atoms.

[0046] Suitable specific examples of the ester group having 1 to 30 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group, a cyclohexyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a benzyloxycarbonyl group, and a phenoxycarbonyl group.

[0047] R 1 and R 2 In the formula, the acyloxy group having 1 to 30 carbon atoms is represented by -OCOR b where R b represents a hydrocarbon group having 1 to 30 carbon atoms. The number of carbon atoms in the acyloxy group does not include the number of carbon atoms in the carbonyl group. b The lower limit of the carbon number is 1 or more, and may be 2 or more, and the upper limit of the carbon number is 30 or less, and may be 20 or less, or may be 10 or less. The hydrocarbon group having 1 to 30 carbon atoms is the same as R a The same can be mentioned. Suitable specific examples of the acyloxy group having 1 to 30 carbon atoms include an acetyloxy group, a propionyloxy group, a (meth)acryloyloxy group, and a benzoyloxy group.

[0048] R1 and R 2 In the above, the acyl group having 1 to 30 carbon atoms is represented by -COR c where R is a monovalent group represented by the formula: c represents a hydrocarbon group having 1 to 30 carbon atoms. The number of carbon atoms in the acyl group does not include the number of carbon atoms in the carbonyl group. c The lower limit of the carbon number is 1 or more, and may be 2 or more, and the upper limit of the carbon number is 30 or less, and may be 20 or less, or may be 10 or less. R c The hydrocarbon group having 1 to 30 carbon atoms in R a The same can be mentioned. Suitable specific examples of the acyl group having 1 to 30 carbon atoms include an acetyl group, a propionyl group, a (meth)acryloyl group, and a benzoyl group.

[0049] R 1 and R 2 In the formula, the alkoxy group having 1 to 30 carbon atoms is -OR d where R d represents an alkyl group having 1 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. The lower limit of the number of carbon atoms in the alkoxy group may be 1 or more, or may be 2 or more, and the upper limit may be 30 or less, or may be 20 or less, or may be 10 or less. R d The alkyl group having 1 to 30 carbon atoms and the aralkyl group having 7 to 30 carbon atoms in the R a The same can be mentioned. Suitable specific examples of the alkoxy group having 1 to 30 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, an n-hexoxy group, a cyclopropoxy group, a cyclopentoxy group, a cyclohexyloxy group, an n-octoxy group, an n-deoxy group, and a benzyloxy group. In addition, an aryloxy group having 6 to 30 carbon atoms is represented by -OR d’where R d’ represents an aryl group having 6 to 30 carbon atoms. The lower limit of the number of carbon atoms in the aryl group may be 6 or more, or may be 8 or more, and the upper limit may be 30 or less, or may be 20 or less, or may be 12 or less. R d’ The aryl group having 6 to 30 carbon atoms in R a Among these, those corresponding to aryl groups having 6 to 30 carbon atoms can be mentioned. Specific examples of the aryloxy group having 6 to 30 carbon atoms include a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a butylphenoxy group, a naphthyloxy group, a fluorenyloxy group, and an anthracenyloxy group.

[0050] R 1 and R 2 In the above, the alkylthio group having 1 to 30 carbon atoms is -SR e where R e represents an alkyl group having 1 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. The lower limit of the number of carbon atoms in the alkylthio group may be 1 or more, or may be 2 or more, and the upper limit may be 30 or less, or may be 20 or less, or may be 10 or less. R e The alkyl group having 1 to 30 carbon atoms and the aralkyl group having 7 to 30 carbon atoms in R a The same can be mentioned. Suitable specific examples of the alkylthio group having 1 to 30 carbon atoms include a methylthio group, an ethylthio group, and a benzylthio group.

[0051] An arylthio group having 6 to 30 carbon atoms is represented by -SR e’ where R e’ represents an aryl group having 6 to 30 carbon atoms. The lower limit of the number of carbon atoms in the aryl group may be 6 or more, or may be 8 or more, and the upper limit may be 30 or less, or may be 20 or less, or may be 12 or less. Re’ The aryl group having 6 to 30 carbon atoms in R a Among these, those corresponding to aryl groups having 6 to 30 carbon atoms can be mentioned. Specific examples of the arylthio group having 6 to 30 carbon atoms include a phenylthio group and a naphthylthio group.

[0052] R 1 and R 2 In the above, the amino group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms is represented by -N(R f )R g where R f and R g each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The lower limit of the number of carbon atoms in the hydrocarbon group substituted by the substituted amino group may be 1 or more, or may be 2 or more, and the upper limit may be 30 or less, or may be 20 or less, or may be 10 or less. R f and R g The hydrocarbon group having 1 to 30 carbon atoms in R a The same can be mentioned. Suitable specific examples of the amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms include an amino group (-NH2), a monomethylamino group, a dimethylamino group, a monoethylamino group, a diethylamino group, a monoisopropylamino group, a diisopropylamino group, a monophenylamino group, and a diphenylamino group.

[0053] R 1 and R 2 In the above, the silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms is represented by -SiR h R i R j where R h , R i and R jeach independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The lower limit of the number of carbon atoms in the hydrocarbon group substituted with the silyl group may be 1 or more, or may be 2 or more, and the upper limit may be 30 or less, or may be 20 or less, or may be 10 or less. R h , R i and R j The hydrocarbon group having 1 to 30 carbon atoms in R a The same can be mentioned. Suitable specific examples of the silyl group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms include a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a triisopropylsilyl group, and a tert-butyldiphenylsilyl group.

[0054] R 1 and R 2 In the above, the amide group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms is represented by -CONR k R l or -NR k COR l where R k and R l each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The number of carbon atoms in the hydrocarbon group substituted by the substituted amide group does not include the number of carbon atoms in the carbonyl group, and k and R l The lower limit of the carbon number is 1 or more, and may be 2 or more, and the upper limit of the carbon number is 30 or less, and may be 20 or less, or may be 10 or less. R k and R l The hydrocarbon group having 1 to 30 carbon atoms in R a The same can be mentioned. Specific examples of the amide group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms include, for example, -CONH2, -CONH(CH3), -CON(CH3)2, -CONH(C2H5), -CON(C2H5)2, -CONH(i-C3H7), -CON(i-C3H7)2, -CONH(Ph), -CON(Ph)2, -NHCOCH3, -NHCOC2H5, etc. In this specification, Ph represents a phenyl group.

[0055] R 1 and R 2 In the above, the hydrocarbon group having 1 to 30 carbon atoms and substituted with at least one halogen atom (halogen-substituted hydrocarbon group having 1 to 30 carbon atoms) is a group in which at least one hydrogen atom is substituted with a halogen atom. a Among them, an alkyl group and an aryl group are preferable from the viewpoint of availability. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The lower limit of the number of carbon atoms in the halogen-substituted hydrocarbon group having 1 to 30 carbon atoms may be 1 or more, or may be 2 or more, and the upper limit may be 30 or less, or may be 20 or less, or may be 10 or less. Specific examples of the halogen-substituted hydrocarbon group having 1 to 30 carbon atoms include a halomethyl group in which 1 to 3 hydrogen atoms of a methyl group are substituted with halogen atoms, a chloroethyl group, a γ-chloropropyl group, a 3,3′,3″-trifluoropropyl group, a perfluoropropyl group, a perfluorophenyl group, a bromophenyl group, a chlorophenyl group, a fluorophenyl group, a dichlorophenyl group, etc., and examples of the halomethyl group include a chloromethyl group, a bromomethyl group, a fluoromethyl group, a dichloromethyl group, a trifluoromethyl group, etc.

[0056] R 1 and R 2 In the hydrocarbon group having 1 to 30 carbon atoms which may be substituted with at least one substituent selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, the hydrocarbon group having 1 to 30 carbon atoms isa As the hydrocarbon group having 1 to 30 carbon atoms which may be substituted with at least one substituent selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, among others, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group is preferred in terms of production efficiency of the copolymer. Suitable specific examples of the unsubstituted hydrocarbon group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, an ethenyl group, a propenyl group, a butenyl group, and a phenyl group.

[0057] R 1 and R 2 In the above, the number of carbon atoms in the heterocyclic group which may be substituted with a substituent containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom is, for example, 2 or more, and the upper limit may be 8 or less, or may be 6 or less, or may be 5 or less. Specific examples of the heterocyclic group include a pyridyl group, a furanyl group, a thienyl group, an oxazoyl group, an oxazolidinyl group, an isoxazolidinyl group, a thiazolyl group, a dihydrofuranyl group, and a tetrahydrofuranyl group.

[0058] Examples of the substituent containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom include a hydroxyl group, a formyl group, a carboxy group, an epoxy group, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a cyano group, a nitro group, an amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, an amide group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a sulfonyl group having 1 to 30 carbon atoms, a sulfoxide group having 1 to 30 carbon atoms, and a sulfonate ester group having 1 to 30 carbon atoms. The ester group having 1 to 30 carbon atoms, the acyloxy group having 1 to 30 carbon atoms, the acyl group having 1 to 30 carbon atoms, the alkoxy group having 1 to 30 carbon atoms, the aryloxy group having 6 to 30 carbon atoms, the amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, the amide group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, the alkylthio group having 1 to 30 carbon atoms, and the arylthio group having 6 to 30 carbon atoms may be the same as described above.

[0059] The sulfonyl group having 1 to 30 carbon atoms is -SOR m where R m represents a hydrocarbon group having 1 to 30 carbon atoms. The lower limit of the number of carbon atoms in the sulfonyl group may be 1 or more, or may be 2 or more, and the upper limit may be 30 or less, or may be 20 or less, or may be 10 or less. R m The hydrocarbon group having 1 to 30 carbon atoms in R a The same can be mentioned. Specific examples of the sulfonyl group having 1 to 30 carbon atoms include, for example, -SO2CH3 and -SO2Ph.

[0060] The sulfoxide group having 1 to 30 carbon atoms is -SOR n where R n represents a hydrocarbon group having 1 to 30 carbon atoms. With respect to the number of carbon atoms in the sulfoxide group, the lower limit may be 1 or more, or may be 2 or more, and the upper limit may be 30 or less, or may be 20 or less, or may be 10 or less. R n The hydrocarbon group having 1 to 30 carbon atoms in R a The same can be mentioned. Suitable specific examples of the sulfoxide group having 1 to 30 carbon atoms include -SOCH3 and -SOPh.

[0061] The sulfonic acid ester group having 1 to 30 carbon atoms is -OSOR o where R orepresents a hydrocarbon group having 1 to 30 carbon atoms. The lower limit of the number of carbon atoms in the sulfonate ester group may be 1 or more, or may be 2 or more, and the upper limit may be 30 or less, or may be 20 or less, or may be 10 or less. R o The hydrocarbon group having 1 to 30 carbon atoms in R a The same can be mentioned. Specific examples of the sulfonate group having 1 to 30 carbon atoms include, for example, -SO3CH3 and -SO3Ph.

[0062] From the viewpoint of production efficiency of the copolymer, the substituent containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom is preferably at least one selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, and an arylthio group having 6 to 30 carbon atoms, and more preferably at least one selected from the group consisting of an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms.

[0063] In general formula (b-1), R 1 and R 2 are combined with each other to form R 1 and R 2 R may form a 4- to 10-membered ring together with the unsaturated bond to which it is bonded, or may form a 5- or 6-membered ring. 1 and R 2 The ring formed by bonding with each other may be a carbocyclic or heterocyclic ring, and the carbocyclic or heterocyclic ring may be a monocyclic or polycyclic ring. 1 and R 2 may be bonded to each other to form a saturated or unsaturated bond, or may form a -CO-O-CO- group, and may be a non-aromatic ring.

[0064] In the structural unit (b-1), the R 1 and R 2 at least one of which may be a substituent other than a hydrogen atom, is a halogen atom, a hydroxyl group, a formyl group, a carboxy group, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a nitro group, an amino group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, an amide group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one type selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, or R 1 and R 2 may be bonded to each other to form a 4- to 10-membered ring. In addition, R in the general formula (b-1) 1 and R 2 may be the same or different.

[0065] On the other hand, in the structural unit (b-1), from the viewpoint of polymerization activity, 1 and R 2 may be a hydrogen atom, and 1 and R 2 However, each of them may be a hydrogen atom.

[0066] M in general formula (b-1) 1 In the above, examples of metal ions of Groups 1, 2, 12, or 13 of the periodic table include lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, calcium ions, magnesium ions, strontium ions, barium ions, aluminum ions, and zinc ions. M1 In the case where the metal ion is a metal ion of Group 1, 2, 12 or 13 of the periodic table, it is preferably at least one selected from the group consisting of a lithium ion, a sodium ion, a potassium ion, a calcium ion, a magnesium ion, an aluminum ion and a zinc ion, from the viewpoints of ease of obtaining the reagent and economics. In the polar group-containing olefin copolymer of the present invention, M 1 may contain one type or a mixture of two or more types. M 1 When the metal is a divalent or higher metal ion, the counter anion may be an alkoxide or carboxylate of the copolymer, or may be any other anion.

[0067] In the polar group-containing olefin copolymer of the present invention, the structural unit represented by the general formula (b-1) contained as an essential structural unit may be a structural unit derived from a vinylene carbonate derivative, or may be a structural unit derived from at least one type of monomer represented by the following general formula (1).

[0068] [ka] (In formula (1), R 1 and R 2 are the above R 1 and R 2 is equivalent to

[0069] The polar group-containing olefin copolymer of the present invention may contain at least one structural unit selected from the group consisting of the structural unit (b-0) represented by the following general formula (b-0) and the structural unit (b-2) represented by the following general formula (b-2) in addition to the structural unit (b-1) represented by the following general formula (b-1) derived from at least one monomer represented by the general formula (1) or as the structural unit (B). The polar group-containing olefin copolymer of the present invention may contain the structural unit (b-1) represented by the following general formula (b-1) and the structural unit (b-2) represented by the following general formula (b-2) as essential structural units. The polar group-containing olefin copolymer of the present invention may not contain the structural unit (b-0) represented by the following general formula (b-0).

[0070] [ka] (In formula (b-0), formula (b-1), and formula (b-2), R 1 and R 2 are the above R 1 and R 2 is synonymous with. M 1 are the above M 1 is equivalent to

[0071] The structural unit (b-1) may be derived from the structural unit (b-0), as described below.

[0072] The polar group-containing olefin copolymer of the present invention may contain a structural unit (b-2) represented by general formula (b-2) at the terminal. 1 and R 2 The mechanism of formation of the structural unit represented by general formula (b-2) is presumed to be as follows, taking the case where is hydrogen as an example. The structural unit represented by general formula (b-2) is presumed to be formed by the transfer and insertion of vinylene carbonate, followed by β-carbonate elimination, followed by decarboxylation and protonation. In the following scheme, M and Q are respectively defined as M and Q in formula (101) described later. As the structural unit (b-2), R 1 and R2 When at least one of them is not a hydrogen atom, it may contain a ketone structure at its terminal.

[0073] [ka]

[0074] Examples of the monomer (monomer (B)) represented by general formula (1) from which the structural unit (b-1), the structural unit (b-2), and the structural unit (b-0) are derived include, but are not limited to, the following monomers.

[0075] [ka]

[0076] The monomer represented by the general formula (1) can be produced by appropriately combining conventionally known production methods. 1 and R 2 When at least one of the substituents is a substituent other than a hydrogen atom, for example, a silver-catalyzed cyclization reaction of propargyl alcohol with carbon dioxide, or a reaction using an acyloin and a carbonylating agent such as phosgene can be used to introduce the substituent. Substituents can also be introduced by referring to Synlett (2014), 25, P1178-1180., Tetrahedron Lett. (1972), 17, P1701-1704., and Adv. Synth. Catal. (2021), 363, P5129-5137. As the monomer represented by the general formula (1), a commercially available product may be used. The monomer represented by the general formula (1) may be used in combination of two or more kinds.

[0077] The structural unit (b-1), the structural unit (b-2) and the structural unit (b-0) may each be of one type alone or of two or more types.

[0078] (3) Structural unit (c-1) The structural unit (c-1) is a structural unit represented by the following general formula (c-1).

[0079] [ka] (In formula (c-1), R 3 is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. M 2 is a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table.

[0080] R in formula (c-1) 3 In the formula (1), examples of the halogen atom include the same as those described in the formula (1). Examples of the hydrocarbon group having 1 to 10 carbon atoms and substituted with at least one halogen atom include the same as those of the hydrocarbon group having 1 to 30 carbon atoms and substituted with at least one halogen atom described in the formula (1) having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include the same as those of the hydrocarbon group having 1 to 30 carbon atoms and substituted with at least one halogen atom described in the formula (1).

[0081] R in formula (c-1) 3 may be a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 3 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group having 1 to 3 carbon atoms, or may be a hydrogen atom, a halogen atom, a trifluoromethyl group, or a methyl group, or may be a hydrogen atom or a methyl group, in terms of polymerization activity and comonomer content.

[0082] M in formula (c-1) 2 In the formula (b-1), the metal ion of Group 1, 2, 12 or 13 of the periodic table is represented by M 1 Examples of the metal ions include those of Groups 1, 2, 12, and 13 of the periodic table described above. M in formula (c-1) 2 In the above, the metal ion of Group 1, 2, 12 or 13 of the periodic table is preferably at least one selected from the group consisting of a lithium ion, a sodium ion, a potassium ion, a calcium ion, a magnesium ion, an aluminum ion and a zinc ion, from the viewpoints of reagent availability and economy. In the polar group-containing olefin copolymer of the present invention, M 2 may contain one type or a mixture of two or more types. In the polar group-containing olefin copolymer of the present invention, M 2 is M in general formula (b-1). 1 may be the same as or different from. M 2 When the metal is a divalent or higher metal ion, the counter anion may be an alkoxide or carboxylate of the copolymer, or may be any other anion.

[0083] The structural unit (c-1) may be derived from the structural unit (c-2), as described below.

[0084] (4) Structural unit (c-2) The structural unit (c-2) is a structural unit represented by the following general formula (c-2).

[0085] [ka] (In formula (c-2), R 3 R 3 is synonymous with. R 4 is a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms which is substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one of an oxygen atom, a sulfur atom, or a nitrogen atom.

[0086] The structural unit (c-1) may be derived from the structural unit (c-2), and R 3 is the R of the structural unit (c-1) 3 may be the same as

[0087] R in formula (c-2) 4 In the above, the silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, the hydrocarbon group having 1 to 30 carbon atoms which is substituted with at least one halogen atom, and the hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one of an oxygen atom, a sulfur atom, and a nitrogen atom are each independently selected from the group consisting of the above-mentioned R 1 and R 2 Examples of the above-mentioned examples are the same as those described above.

[0088] R in formula (c-2) 4 may be a hydrogen atom, a silyl group which may be substituted with at least one hydrocarbon group having 1 to 6 carbon atoms, a hydrocarbon group having 1 to 6 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 6 carbon atoms which may be substituted with at least one substituent containing at least one of an oxygen atom, a sulfur atom, or a nitrogen atom, or may be a hydrocarbon group having 1 to 6 carbon atoms.

[0089] Examples of monomers from which the structural unit (c-1) and the structural unit (c-2) are derived include monomers (monomers (C)) represented by the following general formula (2).

[0090] [ka] (In formula (2), R 3 and R 4 are the above R 3 and R 4 is equivalent to

[0091] Examples of the monomer represented by the general formula (2) from which the structural unit (c-2) is derived include, but are not limited to, the following monomers.

[0092] [ka]

[0093] [ka]

[0094] The monomer represented by the general formula (2) can be produced by appropriately combining conventionally known production methods. For example, it can be synthesized by the Reppe method in which acetylene is reacted with carbon monoxide and methanol is added. 4 Generally, it can be replaced by transesterification. Substituents can also be introduced by referring to Organometallics (2016), 35, P943-949., J. Org. Chem. (1989), 54, P1006-1012., and Tetrahedron Lett.(2018), 59, P3279-3282. As the monomer represented by the general formula (2), a commercially available product may be used. The monomer represented by the general formula (2) may be used in combination of two or more kinds.

[0095] The structural unit (c-1) and the structural unit (c-2) may each be of one type alone or of two or more types.

[0096] (5) Other structural units The polar group-containing olefin copolymer of the present invention may further contain other structural units different from the structural unit (A), the structural unit (b-1), the structural unit (b-2), and the structural unit (b-0), as well as the structural unit (c-1) and the structural unit (c-2). Examples of the other structural units include structural units derived from other polar group-containing monomers such as vinyl acetate, allyl acetate, 3-butenyl acetate, acrylonitrile, 3-cyanopropene, and vinyl ether.

[0097] (6) Polar group-containing olefin copolymer The polar group-containing olefin copolymer of the present invention is characterized in that it contains, in its main chain, a structural unit (A) derived from at least one olefin having 2 to 20 carbon atoms, 0.04 mol % to 10.00 mol % of the structural unit (b-1) represented by the general formula (b-1), and at least one of the structural unit (c-1) represented by the general formula (c-1) and the structural unit (c-2) represented by the general formula (c-2). The polar group-containing olefin copolymer of the present invention must contain at least one of the structural unit (A), the structural unit (b-1), and at least one of the structural unit (c-1) and the structural unit (c-2), and must contain structural units derived from a total of three or more types of monomers.

[0098] In the present invention, the proportion of the structural unit (A) in the polar group-containing olefin copolymer may be appropriately selected depending on the desired physical properties, but the lower limit is usually 60.00 mol%, and may be 70.00 mol%, 80.00 mol%, 85.00 mol%, 90.00 mol%, 93.80 mol%, 95.00 mol%, 96.00 mol%, 97.00 mol%, or 98.00 mol%, relative to 100 mol% of all structural units. On the other hand, the upper limit is usually 99.95 mol%, and may be 99.93 mol%, 99.92 mol%, 99.90 mol%, 99.80 mol%, 99.60 mol%, 99.50 mol%, 99.40 mol%, 99.00 mol%, or 98.50 mol%.

[0099] The ratio of the structural unit (b-1) in the polar group-containing olefin copolymer may be appropriately selected within the range of 0.04 mol% to 10.00 mol% depending on the average molecular weight and the desired physical properties. The ratio of the structural unit (b-1) is 0.04 mol% at the lower limit relative to the total structural units of 100 mol%, but may be 0.05 mol%, 0.10 mol%, 0.15 mol%, 0.20 mol%, 0.25 mol%, 0.35 mol%, 0.50 mol%, 0.80 mol%, or 1.00 mol%. On the other hand, the upper limit is usually 10.00 mol%, but may be 8.00 mol%, 5.00 mol%, 4.80 mol%, 4.00 mol%, 3.00 mol%, or 2.00 mol%.

[0100] The total ratio of the structural units (b-1) and (b-2) in the polar group-containing olefin copolymer may be appropriately selected according to the average molecular weight and the desired physical properties, and the lower limit is usually 0.04 mol%, may be 0.05 mol%, may be 0.10 mol%, may be 0.15 mol%, may be 0.20 mol%, may be 0.50 mol%, may be 0.80 mol%, based on 100 mol% of the total structural units. On the other hand, the upper limit is usually 10.00 mol%, may be 8.50 mol%, may be 5.50 mol%, may be 5.00 mol%, may be 4.50 mol%, may be 4.00 mol%, may be 3.50 mol%.

[0101] The ratio of the structural unit (c-1) in the polar group-containing olefin copolymer may be appropriately selected according to the average molecular weight and the desired physical properties. The ratio of the structural unit (c-1) may be 0 mol% relative to the total structural units of 100 mol%, but the lower limit is usually 0.01 mol%, may be 0.05 mol%, may be 0.10 mol%, may be 0.15 mol%, may be 0.20 mol%, may be 0.25 mol%, may be 0.50 mol%, or may be 0.80 mol%. On the other hand, the upper limit is usually 30.00 mol%, may be 20.00 mol%, may be 10.00 mol%, may be 5.00 mol%, may be 3.50 mol%, may be 2.50 mol%, may be 2.00 mol%, or may be 1.50 mol%.

[0102] The ratio of the structural unit (c-2) that may be contained in the polar group-containing olefin copolymer may be appropriately selected according to the average molecular weight and the desired physical properties. The ratio of the structural unit (c-2) may be 0 mol% relative to the total structural units of 100 mol%, but the lower limit may be 0.01 mol%, 0.05 mol%, 0.10 mol%, 0.15 mol%, 0.20 mol%, 0.25 mol%, 0.50 mol%, or 0.90 mol%. On the other hand, the upper limit is usually 20.00 mol%, and may be 10.00 mol%, 5.00 mol%, 4.00 mol%, 3.50 mol%, 3.00 mol%, 2.70 mol%, 2.00 mol%, or 1.00 mol%.

[0103] The combination of the contents of the respective structural units may be such that, relative to 100 mol% of all structural units, the structural unit (A) is 80.00 mol% to 99.86 mol%, the structural unit (b-1) is 0.04 mol% to 10.00 mol%, and the total of the structural units (c-1) and (c-2) is 0.10 mol% to 10.00 mol%, or further, the structural unit (A) may be 90.00 mol% to 99.75 mol%, the structural unit (b-1) is 0.10 mol% to 5.00 mol%, and the total of the structural units (c-1) and (c-2) is 0.15 mol% to 5.00 mol%. Furthermore, the structural unit (A) may be 90.00 mol % to 99.60 mol %, the structural unit (b-1) may be 0.20 mol % to 5.00 mol %, and the total of the structural units (c-1) and (c-2) may be 0.20 mol % to 5.00 mol %.

[0104] The combination of the contents of the structural units may be such that, relative to 100 mol% of all structural units, the structural unit (A) is 60.00 mol% to 99.95 mol%, the total of the structural units (b-1) and (b-2) is 0.04 mol% to 10.00 mol%, and the total of the structural units (c-1) and (c-2) is 0.01 mol% to 30.00 mol%, and the structural unit (A) is 60.00 mol% to 99.00 mol%, the structural units (b-1) and (b The total of the structural units (c-1) and (c-2) may be 0.50 mol% to 10.00 mol%, the total of the structural units (c-1) and (c-2) may be 0.50 mol% to 30.00 mol%, the structural unit (A) may be 85.00 mol% to 99.6 mol%, the total of the structural units (b-1) and (b-2) may be 0.20 mol% to 5.00 mol%, the total of the structural units (c-1) and (c-2) may be 0.20 mol% to 10.00 mol%. The structural unit (A) may be 85.00 mol% to 99.5 mol%, the total of the structural units (b-1) and (b-2) may be 0.25 mol% to 5.00 mol%, the total of the structural units (c-1) and (c-2) may be 0.25 mol% to 10.00 mol%. Furthermore, the structural unit (A) may be 90.00 mol% to 99.00 mol%, the total of the structural units (b-1) and (b-2) may be 0.50 mol% to 5.00 mol%, and the total of the structural units (c-1) and (c-2) may be 0.50 mol% to 5.00 mol%.

[0105] As long as at least one of the structural units (c-1) and (c-2) is included, the relationship between the contents of the structural units (c-1) and (c-2) may be arbitrary. For example, the content of the structural unit (c-1) may be 5% or more, 10% or more, or 20% or more larger than the content of the structural unit (c-2) relative to the total content of the structural units (c-1) and (c-2) being 100%. Only one of the structural units (c-1) and (c-2) may be included.

[0106] M in structural unit (c-1) 2 is a hydrogen atom or a metal ion, and the content ratio thereof may be appropriately selected depending on the application, and is not particularly limited. M in structural unit (c-1) 2 The proportion of metal ions (degree of neutralization) relative to 100 mol% of the entire structural unit (c-1), the lower limit may be 0 mol% or more, 5 mol% or more, 10 mol% or more, or 20 mol% or more, and the upper limit may be 100 mol% or less, 90 mol% or less, or 80 mol% or less. In addition, M in the structural unit represented by the general formula (b-1) 1 is a hydrogen atom or a metal ion, and the content ratio thereof may be appropriately selected depending on the application, and is not particularly limited. M in the structural unit represented by formula (b-1) 1 The proportion of metal ions (degree of neutralization) relative to 100 mol% of the entire structural units represented by general formula (b-1), may be 0 mol% at the lower limit, or may be 5 mol% or more, or 10 mol% or more, or may be 20 mol% or more, and the upper limit may be 100 mol%, or may be 90 mol% or less, or may be 80 mol% or less. In the polar group-containing olefin copolymer of the present invention, M 2 and M in the structural unit represented by general formula (b-1) 1 However, the proportion of metal ions (degree of neutralization) is 1 H-NMR and 13 It can be determined by C-NMR. M in the structural unit (c-1) 2 The content of hydrogen atoms and M 2 The ratio of metal ions (M 2 is a metal ion / (M 2 The content of hydrogen atoms + M 2 The content of metal ions (%) to M 2 Similarly, the proportion of M in the structural unit represented by the general formula (b-1) can be calculated. 1 The content of hydrogen atoms and M 1 The ratio of metal ions (M 1 is a metal ion / (M 1The content of hydrogen atoms + M 1 The content of metal ions (%) to M 1 The proportion of metal ions can be calculated.

[0107] The polar group-containing olefin copolymer of the present invention may further contain one or more other structural units. When the polar group-containing olefin copolymer of the present invention contains other structural units, the ratio of the other structural units in the polar group-containing olefin copolymer may be appropriately selected according to the desired physical properties, but the lower limit is usually 0.01 mol%, may be 0.05 mol%, may be 0.10 mol%, or may be 0.50 mol%, based on 100 mol% of the total structural units. On the other hand, the upper limit is usually 35.00 mol%, may be 30.00 mol%, may be 20.00 mol%, or may be 10.00 mol%. In addition, when the polar group-containing olefin copolymer of the present invention further contains the structural unit (b-0), the ratio may be as described above, and in addition to the above, the upper limit value may be 5.00 mol%, 3.50 mol%, 2.50 mol%, 2.00 mol%, or 1.50 mol%.

[0108] A structure derived from one molecule of each monomer is defined as one structural unit in the polar group-containing olefin copolymer. The amount of structural units is the ratio of each structural unit expressed in mol % when the total structural units in the polar group-containing olefin copolymer is taken as 100 mol %.

[0109] The polar group-containing olefin copolymer of the present invention may be a random copolymer, block copolymer, graft copolymer, etc., of at least one of the structural unit (A), the structural unit (b-1), the structural unit (c-1) and the structural unit (c-2), and other structural units that may be included as necessary. Among these, the random copolymer may be one that can contain a large amount of the structural unit (b-1), the structural unit (c-1) and the structural unit (c-2).

[0110] The amount of structural units can be controlled by the selection of catalyst, the amount of monomer (A), monomer (B), monomer (C) and other monomers added during polymerization, and the pressure and temperature during polymerization. Specific means for increasing the amount of structural units derived from monomer (B) and monomer (C) in the copolymer include increasing the amount of monomer (B) and monomer (C) added during polymerization, selecting a catalyst, reducing the olefin pressure during polymerization, and increasing the polymerization temperature. For example, it is necessary to adjust these factors to control the copolymer to the desired region. The adjustment of the amounts of the structural units (c-1) and (c-2) will be described in detail in the production method described below.

[0111] The amount of structural units in the polar group-containing olefin copolymer of the present invention is 1 H-NMR spectrum and 13 The C-NMR spectrum can be measured by the method described in the Examples. Furthermore, the presence of polar groups such as the structural unit (b-1), the structural unit (c-1) and the structural unit (c-2) in the polar group-containing olefin copolymer of the present invention can also be confirmed by analyzing the IR spectrum.

[0112] The weight average molecular weight (Mw) of the polar group-containing olefin copolymer in the present invention is usually 1,000 to 2,000,000, may be 5,000 to 1,500,000, may be 10,000 to 1,000,000, or may be 10,000 to 800,000. A suitable range is 5,000 to 600,000. When Mw is equal to or greater than the lower limit, physical properties such as mechanical strength and impact resistance tend to be sufficient, and when Mw is equal to or less than the upper limit, molding is easy in terms of melt viscosity.

[0113] The number average molecular weight (Mn) of the polar group-containing olefin copolymer of the present invention is usually 1,000 to 2,000,000, may be 3,000 to 1,500,000, may be 3,000 to 1,000,000, or may be 3,000 to 800,000. A suitable range is 3,000 to 600,000. When Mn is equal to or greater than the lower limit, physical properties such as mechanical strength and impact resistance tend to be sufficient, and when Mn is equal to or less than the upper limit, molding is easy in terms of melt viscosity.

[0114] The ratio of Mw to Mn (Mw / Mn) of the polar group-containing olefin copolymer of the present invention is usually 1.0 to 4.0, may be 1.3 to 3.5, or may be 1.4 to 3.3. If Mw / Mn is 1.0 or more, various processability including molding tends to be sufficient, and if it is 4.0 or less, the mechanical properties tend to be good. In the present invention, (Mw / Mn) may be expressed as a molecular weight distribution parameter.

[0115] In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by gel permeation chromatography (GPC). Specifically, the GPC measurement in the present invention can be performed by the method described in the Examples.

[0116] The polar group-containing olefin copolymer of the present invention is 13 The number of methyl branches calculated by C-NMR per 1,000 carbon atoms may be 50 or less, 5 or less, 3 or less, or 2 or less. When the number of methyl branches satisfies this range, the elastic modulus is high and the mechanical strength of the molded article is also high. The number of methyl branches can be controlled by selecting the transition metal catalyst to be used or adjusting the polymerization temperature. As a specific means for reducing the number of methyl branches of the polar group-containing olefin copolymer of the present invention, lowering the polymerization temperature is effective. In order to reduce the number of methyl branches, for example, it is required to adjust these factors to control it to the desired copolymer region.

[0117] The number of methyl branches is as described in [Structure of Polar Group-Containing Olefin Copolymer] in the Examples section described later. 13 Using the C-NMR spectrum, the calculation is performed as follows: 13 The sum of the integrated intensities of the signals from methyl carbons in the range of 20.0 to 19.8 ppm, methine carbons in the range of 33.2 to 33.0 ppm, and methylene carbons in the range of 37.5 to 37.3 ppm in the C-NMR spectrum divided by 4 is I (B1) The number of methyl branches per total of 1,000 carbon atoms (total 1000C) is calculated using the following formula:

[0118] Number of methyl branches (number / total 1000C) = I (B1) ×1000 / I (トータル) Here, I (B1) , I (トータル) are the quantities shown in the following formulas, respectively. I (B1) =(I 20.0~19.8 +I 33.2~33.0 +I 37.5~37.3 ) / 4 I (トータル) =I 180.0~135.0 +I 120.0~2.0 Note that I is the integrated intensity, and the subscripts of I indicate the range of chemical shifts. For example, I 180.0~135.0 indicates the integrated intensity of the signal detected between 180.0 ppm and 135.0 ppm.

[0119] (7) Method for producing polar group-containing olefin copolymer The method for producing the polar group-containing olefin copolymer of the present invention is not particularly limited as long as it can produce the polar group-containing olefin copolymer of the present invention. For example, the present invention includes a step of obtaining an olefin copolymer by polymerizing at least one olefin having 2 to 20 carbon atoms, at least one monomer represented by the following general formula (1), and at least one monomer represented by the following general formula (2) in the presence of a catalyst containing a transition metal, and converting at least a part of the -OCOO- groups contained in the olefin copolymer to -OM at the vicinal positions. 1 Group (where M1 is the above M 1 ) and then -COOR 4 At least a portion of the groups is replaced with -COOM 2 Group (where R 4 and M 2 are the above R 4 and M 2 (which is synonymous with the above).

[0120] Further, the method for producing a polar group-containing olefin copolymer of the present invention includes a step of polymerizing at least one olefin having 2 to 20 carbon atoms, at least one monomer represented by the following general formula (1), and at least one monomer represented by the following general formula (2) in the presence of a catalyst containing at least one compound represented by the following general formula (101) to obtain an olefin copolymer, and a step of converting at least a portion of the structural units derived from the monomer represented by the general formula (1) to structural units represented by the following general formula (b-1), and optionally further converting at least a portion of the structural units derived from the monomer represented by the general formula (2) to structural units represented by the following general formula (c-1). In addition, the at least one kind of olefin having 2 to 20 carbon atoms, the at least one kind of monomer represented by the following general formula (1), and the at least one kind of monomer represented by the following general formula (2) may be the same as those explained as the monomer (A), the monomer (B), and the monomer (C), respectively, and therefore the explanation here will be omitted.

[0121] [ka] (In formula (1), R 1 and R 2 are the above R 1 and R 2 is equivalent to

[0122] [ka] (In formula (2), R 3 and R 4 are the above R 3 and R 4 is equivalent to

[0123] [ka] (In formula (b-1), R 1 and R 2 , and M 1 are the above R 1 and R 2 , and M 1 is equivalent to

[0124] [ka] (In formula (c-1), R 3 and M 2 R 3 and M 2 is equivalent to

[0125] (7-1) Catalyst The polar group-containing olefin copolymer of the present invention may be polymerized in the presence of a catalyst containing a transition metal, from the viewpoint of introducing the monomer (B) and the monomer (C) into the main chain of an olefin polymer having 2 or more carbon atoms in a one-step polymerization reaction, and from the viewpoint of making the molecular structure of the copolymer linear. The catalyst containing a transition metal is not particularly limited as long as it is capable of polymerizing the monomer (A) with the monomer (B) and the monomer (C). For example, a transition metal compound of Groups 5 to 11 of the periodic table having a chelating ligand can be used.

[0126] Specific examples of preferred transition metals include vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, platinum, ruthenium, cobalt, rhodium, nickel, palladium, and copper. Among these, preferred are transition metals of Groups 8 to 11, more preferred are transition metals of Group 10, and examples of the transition metals of Group 10 include nickel, palladium, and platinum, and particularly preferred are nickel (Ni) and palladium (Pd). These metals may be used alone or in combination.

[0127] Chelating ligands have at least two atoms selected from the group consisting of P, N, O, and S, and include ligands that are bidentate or multidentate, and are electronically neutral or anionic. Exemplary structures are given in the review by Brookhart et al. (Chem. Rev., 2000, 100, 1169). Preferred are bidentate anionic P,O ligands such as phosphorus sulfonates, phosphorus carboxylates, phosphorus phenoxides, phosphorus alkoxides, phosphorus enolates, and other bidentate anionic N,O ligands such as pyridine carboxylates, and other diimine, diphenoxide, and diamide ligands.

[0128] As the catalyst containing a transition metal, from the viewpoints of the production efficiency of the polymer, the molecular weight of the polymer, and the copolymerizability of the monomer (A) with the monomer (B) and the monomer (C), a catalyst containing a late transition metal selected from the group consisting of Group 8 to Group 10 transition metals is preferred, and among these, a catalyst containing a Group 10 transition metal is preferred, and further, a catalyst containing a Group 10 transition metal and having a chelating ligand containing one or more phosphorus atoms as a coordination point to the Group 10 transition metal is preferred.

[0129] As the catalyst containing a transition metal, in terms of the production efficiency of the polymer, the molecular weight of the polymer, and the copolymerizability of the monomer (A) with the monomer (B) and the monomer (C), it is particularly preferable that the catalyst containing a Group 10 transition metal is at least one kind of compound represented by the following general formula (101).

[0130] [ka] [In general formula (101), M represents a metal atom of Group 10 of the periodic table. Q represents an oxygen atom, a sulfur atom, -S(=O)2-O-, or -C(=O)-O-, and the left side of each of these groups is bonded to A and the right side is bonded to M. A represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. R L represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a ligand coordinated to M. L represents a ligand coordinated to M. R x and R y each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. R L and L and R x and R y may form a ring, R x and A or R y and A may form a ring.

[0131] In the general formula (101), M represents a metal atom of Group 10 of the periodic table, and among these, Ni or Pd is preferable. Q represents a divalent group represented by -S(=O)2-O-, -C(=O)-O-, -O-, or -S-, and is a site that coordinates one electron to M. The left side of each of the groups is bonded to A, and the right side is bonded to M. Among these, from the viewpoint of catalytic activity, Q is preferably -S(=O)2-O- or -O-, and particularly preferably -O-.

[0132] A is a divalent hydrocarbon group having 1 to 30 carbon atoms which links Q to the phosphorus atom and which may have a substituent. The divalent hydrocarbon group having 1 to 30 carbon atoms may be a divalent hydrocarbon group having 1 to 20 carbon atoms, and preferred examples thereof include an alkylene group, an arylene group, and a combination thereof. For example, the following formulas (a-1) to (a-7) are included. 101 )2] n n in - is an integer of 1 to 3, and -[C(R 101 )2]- indicates the number of repetitions. In the following formula, R 101 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. 101 Adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, in which case the ring has 5 to 8 members and may have a substituent on the ring.

[0133] R 101 The hydrocarbon group having 1 to 20 carbon atoms is R a Among these, the same hydrocarbon groups having 1 to 20 carbon atoms can be mentioned. Of the hydrocarbon groups having 1 to 20 carbon atoms, hydrocarbon groups having 1 to 15 carbon atoms are preferred, and hydrocarbon groups having 1 to 10 carbon atoms are more preferred. As the divalent hydrocarbon group having 1 to 30 carbon atoms for A, the following formula (a-2) or the following formula (a-7) is preferable in terms of catalytic activity.

[0134] [ka]

[0135] Examples of the substituent in A include a halogen atom, OR β , CO2R β , CO2M', CON(R α ) 2, COR β , O.C.(O)R β, S.R. β , SO2R β , SOR β , OSO2R β , PO(OR β ) 2-y (R α ) y , C.N., N.H.R. β , N(R β )2, Si(OR α ) 3-x (R α ) x , OSi(OR α ) 3-x (R α ) x , NO2, SO3M', PO3M'2, P(O)(OR β ) 2M′, or an epoxy-containing group, etc. (wherein R α represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R β represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2). The hydrocarbon group having 1 to 20 carbon atoms is R a Among these, the same hydrocarbon groups having 1 to 20 carbon atoms can be mentioned.

[0136] L represents a ligand coordinated to M. L may be a zero-valent ligand that can be removed from the metal. L is preferably a compound having an electron donating group and capable of stabilizing the metal complex by coordinating to the metal atom M. L may be a hydrocarbon compound having 1 to 20 carbon atoms and having at least one of oxygen, nitrogen, and sulfur atoms as an atom capable of coordinating, or a hydrocarbon compound having a carbon-carbon unsaturated bond capable of coordinating to a transition metal and optionally containing a heteroatom. L preferably has 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms.

[0137] Preferred examples of L include cyclic unsaturated hydrocarbons, phosphines, pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkylnitrile derivatives, arylnitrile derivatives, alcohols, amides, aliphatic esters, aromatic esters, and amines. Examples of L having a sulfur atom include dimethyl sulfoxide (DMSO). Examples of L having a nitrogen atom include trialkylamines having an alkyl group with 1 to 10 carbon atoms, dialkylamines having an alkyl group with 1 to 10 carbon atoms, pyridine, 2-methylpyridine (also known as picoline), 2,6-dimethylpyridine (also known as 2,6-lutidine), aniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, N,N,N',N'-tetramethylethylenediamine (TMEDA), 4-(N,N-dimethylamino)pyridine (DMAP), acetonitrile, benzonitrile, quinoline, and 2-methylquinoline. Examples of L having an oxygen atom include diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane. From the viewpoint of the stability and catalytic activity of the complex, DMSO, pyridine, picoline, 2,6-lutidine, and TMEDA are preferred, and DMSO, picoline, and 2,6-lutidine are more preferred. More preferred examples of L include cyclic olefins, phosphines, pyridines, cyclic ethers, aliphatic esters, and aromatic esters. More preferred examples of L include trialkylphosphines, pyridine, 2,6-lutidine, picolines, R β CO2R β (R β The definition of is as described above.

[0138] In the present invention, R L represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, or a ligand coordinated to M. R LWhen R is a ligand coordinated to M, the same as L can be mentioned, but it may be an anionic ligand rather than a neutral ligand. For example, when the ligand reacts with nickel(0)bis(1,5-cyclooctadiene) (Ni(cod)2) as a transition metal compound, the ligand derived from the transition metal compound is R L and L combine together to form a ring, forming a σ,π-cyclooct-4-enyl group.

[0139] The polymerization reaction in the present invention is carried out by reacting M and R L It is believed that the reaction is initiated by the insertion of an olefin such as ethylene or a copolymerizable monomer thereof into the bond of R L If the number of carbon atoms in R is too large, the initiation reaction tends to be inhibited. L The group preferably has 1 to 16 carbon atoms, excluding the carbon atoms contained in the substituent, and more preferably has 1 to 10 carbon atoms. R L Specific examples of the alkyl group include a hydride group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenyl group, a p-methylphenyl group, a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group. In addition, R L and L may be bonded to each other to form a ring. Examples of such a ring include a σ,π-cyclooct-4-enyl group and an acetylacetonato group, which are also preferred embodiments of the present invention.

[0140] R x and R y each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. R x and R y The hydrocarbon group having 1 to 30 carbon atoms in the above general formula (1) is a The same can be mentioned. R x and Ry The substituent in may be the same as the substituent in A. Also, R x and R y In the above formula, adjacent substituents may be linked to each other to form a 5- to 8-membered heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom.

[0141] R x and R y is in the vicinity of M and exerts steric and / or electronic interactions with the transition metal M. To exert such effects, R x and R y The bulkier the better. x and R y Each of these preferably has 3 to 30 carbon atoms, and more preferably 6 to 20 carbon atoms.

[0142] R x and R y are preferably each independently an alkyl group having 3 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent.

[0143] R x and R yThe alkyl group having 3 to 10 carbon atoms which may have a substituent in the formula (I) includes a linear or branched alkyl group having 3 to 10 carbon atoms which may have a substituent. Examples of the alkyl group having 3 to 10 carbon atoms which may have a substituent include a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, a 1-nonyl group, a 1-decyl group, an i-propyl group, a 1-dimethylpropyl group, a 1,1,2-trimethylpropyl group, a 1,1-diethylpropyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a 1,1-dimethylbutyl group, a 2-pentyl group, a 3-pentyl group, a 2-hexyl group, a 3-hexyl group, a 2-ethylhexyl group, a 2-heptyl group, a 3-heptyl group, a 4-heptyl group, a 2-propylheptyl group, a 2-octyl group, a 3-nonyl group, a methoxymethyl group, an ethoxymethyl group, an i-propoxymethyl group, and a t-butoxymethyl group. The alkyl group having 3 to 10 carbon atoms which may have a substituent may be, among others, a branched alkyl group having 3 to 10 carbon atoms which may have a substituent, and may be an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, or a t-butyl group.

[0144] R x and R y Examples of the cycloalkyl group having 6 to 20 carbon atoms which may have a substituent include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, and the like which may be substituted with a linear or branched alkyl group having 3 to 10 carbon atoms which may contain a hetero atom. Also, it may be, for example, a cycloalkyl group described in paragraphs

[0104] to

[0113] of JP2018-141138A (X in paragraphs

[0104] to

[0113] of JP2018-141138A indicates the bonding position of P (phosphorus atom) in general formula (101) of the present invention). The cycloalkyl group having 6 to 20 carbon atoms which may have a substituent may be, among others, a cyclohexyl group or an adamantyl group substituted with a linear or branched alkyl group having 3 to 10 carbon atoms, and may be a 2-isopropyl-5-methylcyclohexyl group (menthyl group) or an adamantyl group.

[0145] R x and R y Among these, from the viewpoints of controlling the molecular weight of the polymer and controlling the copolymerizability with a polar monomer, it is more preferable that the alkyl group is an aryl group having 6 to 20 carbon atoms which may have a substituent.

[0146] R x and R y In the above, examples of the aryl group having 6 to 20 carbon atoms and which may have a substituent include a phenyl group, a naphthyl group, an anthracenyl group, etc., which may be substituted with a linear or branched alkyl group having 3 to 10 carbon atoms and which may contain a hetero atom. The aryl group having 6 to 20 carbon atoms preferably has a branched alkyl group having 3 to 6 carbon atoms, a silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a substituent containing at least one of an oxygen atom and a nitrogen atom, and more preferably has a substituent containing at least one of an oxygen atom and a nitrogen atom. R x and R y In the case of the aryl group having 6 to 20 carbon atoms which may have a substituent, adjacent substituents may be linked to each other to form a 5-8 membered heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom, and may be, for example, a hydrocarbon group represented by general formula (B) or (C) in JP 2024-052628 A and a hydrocarbon group represented by general formula (B) or (C) in JP 2024-052627 A. When the aryl group having 6 to 20 carbon atoms has a substituent containing at least one of an oxygen atom and a nitrogen atom, the substituent is preferably substituted at the ortho position relative to the carbon bonded to phosphorus in the aryl group. x and R yThis is because at least one of the oxygen atom and the nitrogen atom in the aryl group can be spatially arranged so as to have an interaction with the transition metal M.

[0147] Preferred R x and R ySpecific examples of the aryl group include an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 2-isopropyl-5-methylcyclohexyl group, an adamantyl group, a phenyl group, a 2,6-dimethoxyphenyl group, a 2,4,6-trimethoxyphenyl group, a 2,6-di-t-butylphenyl group, a 2,4,6-tri-t-butylphenyl group, a 2,6-ditrimethylsilylphenyl group, a 4-methyl-2,6-dimethoxyphenyl group, a 4-t-butyl-2,6-dimethoxyphenyl group, phenyl group, 1,3-dimethoxy-2-naphthyl group, 2,6-diethoxyphenyl group, 2,4,6-triethoxyphenyl group, 4-methyl-2,6-diethoxyphenyl group, 4-t-butyl-2,6-diethoxyphenyl group, 1,3-diethoxy-2-naphthyl group, 2,6-diphenoxyphenyl group, 2,4,6-triphenoxyphenyl group, 4-methyl-2,6-diphenoxyphenyl group, 4-t-butyl-2,6-diphenoxyphenyl group, 1,3-diphenoxy-2-naphthyl group, 2,6-dimethoxymethylphenyl group, 2,4,6 -trimethoxymethylphenyl group, 4-methyl-2,6-dimethoxymethylphenyl group, 4-t-butyl-2,6-dimethoxymethylphenyl group, 1,3-dimethoxymethyl-2-naphthyl group, 2,6-diphenoxymethylphenyl group, 2,4,6-triphenoxymethylphenyl group, 4-methyl-2,6-diphenoxymethylphenyl group, 4-t-butyl-2,6-diphenoxymethylphenyl group, 1,3-diphenoxymethyl-2-naphthyl group, 2,6-di(2-methoxyethyl)phenyl group, 2,4,6-tri(2-methoxyethyl)phenyl group, Examples of the phenyl group include a 4-methyl-2,6-di(2-methoxyethyl)phenyl group, a 4-t-butyl-2,6-di(2-methoxyethyl)phenyl group, a 1,3-di(2-methoxyethyl)-2-naphthyl group, a 2,6-di(2-phenoxyethyl)phenyl group, a 2,4,6-tri(2-phenoxyethyl)phenyl group, a 4-methyl-2,6-di(2-phenoxyethyl)phenyl group, a 4-t-butyl-2,6-di(2-phenoxyethyl)phenyl group, and a 1,3-di(2-phenoxyethyl)-2-naphthyl group. Among these, a 2,6-dimethoxyphenyl group is preferable. Furthermore, the preferred R x and R y Specific examples of the above include an "aryl group having a substituent" bonded to P (phosphorus atom) in the ligand described in paragraphs 0058 to 0059 of JP 2024-052628 A, and an "aryl group having a substituent" bonded to P (phosphorus atom) in the ligand described in paragraphs 0058 to 0060 of JP 2024-052627 A.

[0148] R x and R y may be bonded to A to form a ring structure. Specific examples of such structures include those described in paragraphs 0120 to 0121 of JP 2018-141138 A (the examples here are the R x or R y R corresponds to one of 16 and A are bonded to form a ring structure, and P and Q have the same meanings as in the general formula (101) of the present invention.

[0149] Among the compounds represented by general formula (101) of the present invention, a compound represented by the following general formula (102) or a compound represented by the following general formula (103) is preferred in terms of polymer production efficiency.

[0150] [ka] (In general formula (102), M, L, R L , R x and R y are the same as those in the general formula (101), and R 11 , R 12 , R 13 and R 14 R each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. 11 , R 12 , R 13 and R 14Adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. In this case, the ring has 5 to 8 members and may have a substituent on the ring.

[0151] In general formula (102), R 11 , R 12 , R 13 and R 14 The hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and the substituent are the same as those described in A above. 101 It may be similar to the above.

[0152] Among them, R 11 The more bulky the group, the higher the molecular weight of the polymer tends to be. Therefore, the group is preferably a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent, and is preferably a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R 11Specific examples of the hydrocarbon group having 1 to 30 carbon atoms and optionally substituted with a substituent used as the substituent include a methyl group, an ethyl group, a 1-propyl group, an i-propyl group, a 1-butyl group, an i-butyl group, a s-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a norbornyl group, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group, a fluorenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 3,5-dimethylphenyl group, Preferred examples of the phenyl group include a phenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2,3,4-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2-i-propylphenyl group, a 3-i-propylphenyl group, a 4-i-propylphenyl group, a 2-t-butylphenyl group, a 3-t-butylphenyl group, a 4-t-butylphenyl group, a 2,4-di-t-butylphenyl group, a 2,5-di-t-butylphenyl group, a 3,5-di-t-butylphenyl group, a pentamethylphenyl group, and a pentafluorophenyl group.

[0153] Also, R 11 Specific examples of the substituent used as the substituent include an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, a phenoxy group, a p-methylphenoxy group, a p-methoxyphenoxy group, an ethoxycarbonyl group, a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, a t-butylthio group, a phenylthio group, a cyclohexylamino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a cyclohexylamino group, a carbazolyl group, a piperidyl group, a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, a trimethylsilyloxy group, and a trimethoxysiloxy group. Among them, R 11 may be a hydrocarbon group having 4 to 20 carbon atoms which may have a substituent.

[0154] Suitable examples of the compound represented by the general formula (102) include the following compounds, but are not limited thereto. In the chemical formulas below, Ph is a phenyl group, DMP is a 2,6-dimethoxyphenyl group, iPr is an isopropyl group, t-Bu is a t-butyl group, Ad is an adamantyl group, Cy is a cyclohexyl group, Me is a methyl group, TMS is a trimethylsilyl group, and py is a pyridyl group.

[0155] [ka]

[0156] [ka] (In general formula (103), M, L, R L , R x and R y are the same as those in the general formula (101), and R 21 , R 22 , R 23 and R 24 R each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. 21 , R 22 , R 23 and R 24 or a plurality of groups may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. In this case, the ring has 5 to 8 members and may have a substituent on the ring.

[0157] R 21 and R 22 At least one of R is preferably a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent, since this makes it possible to control the direction in which the olefin reacts by stereocontrol and to prevent chain transfer. 21 or R 22 However, if the group is an electron-withdrawing group, the performance as an olefin polymerization catalyst is further improved, which is preferable. As the electron-withdrawing group, a trifluoromethyl group, a pentafluorophenyl group, a methoxycarbonyl group, and the like are preferably used.

[0158] Also, R 21 , R 22 , R 23 and R 24 or when a plurality of groups are linked to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, each ring has 5 to 8 members, but two or more rings may form a condensed ring.

[0159] Suitable examples of the compound represented by the general formula (103) include the following compounds, but are not limited thereto.

[0160] [ka]

[0161] In addition, examples of suitable compounds represented by the general formula (103) include transition metal complexes obtained by reacting the following compounds with Ni(cod)2 or Ni(acac)2. Furthermore, transition metal complexes obtained by reacting at least one of the ligands described in paragraphs 0058-0059 of JP-A-2024-052628 and the ligands described in paragraphs 0058-0060 of JP-A-2024-052627 with Ni(cod)2 or Ni(acac)2 are also included.

[0162] [ka]

[0163] The transition metal complex used in the present invention can be prepared by a conventionally known method. The transition metal-containing catalyst used in the present invention contains the above-mentioned transition metal complex as a main catalytic component, and may be used in combination with an activator, a carrier, etc., if necessary.

[0164] Al(R 31 ) s (OR 31 ) t X (3-(s+t)) In the general formula, R 31 each independently represents a hydrocarbon group having 1 to 20 carbon atoms; X represents a hydrogen atom, a halogen atom, or a siloxy group; s and t each independently represent a number of 0 or more and 3 or less, either s or t being greater than 0, and s+t being 3 or less. R 31 is a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group, alkenyl group, aryl group, aralkyl group, etc. having 1 to 12 carbon atoms. Among these, organoaluminum compounds in which s or t is 3 are preferred because they are good cocatalysts. Specific examples of the organoaluminum compound represented by the above general formula include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and tri-n-octylaluminum; trialkoxyaluminums such as triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, tri-sec-butoxyaluminum, and tri-tert-butoxyaluminum; and halogen- or alkoxy-containing alkylaluminums such as diethylaluminum monochloride and diethylaluminum monomethoxide. Among these, trialkylaluminums or trialkoxyaluminums are preferred, and trialkoxyaluminums are more preferred. The alkyl group of the trialkylaluminum may be the same as described above, and among these, a methyl group, an isobutyl group, and an n-octyl group are preferred, and among these, triisobutylaluminum or tri-n-octylaluminum is preferred. The alkoxy group of the trialkoxyaluminum may be the same as described above, and among them, a methoxy group, an ethoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group are preferable, and among these, triisopropoxyaluminum, triisobutoxyaluminum, trisec-butoxyaluminum, and tritert-butoxyaluminum are preferable.

[0165] As the carrier, any carrier can be used as long as it does not interfere with the gist of the present invention. In general, inorganic oxides and polymer carriers are preferably used. Specifically, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc. or mixtures thereof can be mentioned, and mixed oxides such as SiO2-Al2O3, SiO2-V2O5, SiO2-TiO2, SiO2-MgO, SiO2-Cr2O3 can also be used, and inorganic silicates, polyethylene carriers, polypropylene carriers, polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic acid ester carriers, polyester carriers, polyamide carriers, polyimide carriers, etc. can be used. There are no particular limitations on the particle size, particle size distribution, pore volume, specific surface area, etc. of these carriers, and any one can be used.

[0166] (7-2) Polymerization method for polar group-containing olefin copolymer The polymerization method for the step of obtaining an olefin copolymer by polymerizing at least one olefin having 2 to 20 carbon atoms, at least one monomer represented by the general formula (1), and at least one monomer represented by the general formula (2) in the presence of a catalyst is not limited. The polymerization method used may be solution polymerization in which all of the polymer produced is dissolved in a medium, slurry polymerization in which at least a portion of the polymer produced becomes a slurry in a medium, bulk polymerization in which the liquefied monomer itself is used as a medium, or high pressure ionic polymerization in which at least a portion of the polymer produced is dissolved in a monomer liquefied at high temperature and pressure. The polymerization method may be any of batch polymerization, semi-batch polymerization, and continuous polymerization. Specific manufacturing processes and conditions are disclosed in, for example, JP-A-2010-260913 and JP-A-2010-202647.

[0167] The unreacted monomers and the medium may be separated from the produced polymer and recycled for use. When recycling, these monomers and the medium may be purified and reused, or may be reused without purification. A conventionally known method can be used to separate the produced polymer from the unreacted monomers and the medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.

[0168] The copolymerization temperature, copolymerization pressure and copolymerization time are not particularly limited, but usually, the optimum settings can be made within the following ranges, taking into consideration the productivity and process capacity. That is, the copolymerization temperature is usually -20°C to 290°C, preferably 0°C to 250°C, more preferably 0°C to 200°C, further preferably 10°C to 150°C, and particularly preferably 20°C to 100°C. The copolymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, more preferably 0.5 MPa to 80 MPa, further preferably 1.0 MPa to 70 MPa, and particularly preferably 1.3 MPa to 60 MPa. The copolymerization time can be selected from the range of 0.1 minute to 50 hours, preferably 0.5 minutes to 40 hours, and further preferably 1 minute to 30 hours. In the present invention, the polymerization is generally carried out under an inert gas atmosphere, for example, a nitrogen or argon atmosphere, and preferably a nitrogen atmosphere.

[0169] There is no particular restriction on the supply of catalyst and monomer to the polymerization reactor, and various supply methods can be used depending on the purpose. For example, in the case of batch polymerization, a method can be used in which a predetermined amount of monomer is supplied to a copolymerization reactor in advance and a catalyst is supplied thereto. In this case, additional monomer or additional catalyst may be supplied to the copolymerization reactor. In addition, in the case of continuous polymerization, a method can be used in which a predetermined amount of monomer and catalyst are supplied to a copolymerization reactor continuously or intermittently to perform the copolymerization reaction continuously.

[0170] Regarding the control of the copolymer composition, a method of controlling by changing the monomer supply ratio can be generally used. Other methods include a method of controlling the copolymer composition by utilizing the difference in monomer reactivity ratio due to the difference in catalyst structure, and a method of controlling the copolymer composition by utilizing the polymerization temperature dependency of the monomer reactivity ratio. The molecular weight of the copolymer can be controlled by a conventionally known method, such as a method of controlling the molecular weight by controlling the polymerization temperature, a method of controlling the molecular weight by controlling the monomer concentration, or a method of controlling the molecular weight by controlling the ligand structure in a transition metal complex.

[0171] In this manner, a polar group-containing olefin copolymer can be obtained, which is characterized in that the main chain contains a structural unit (A) derived from at least one olefin having 2 to 20 carbon atoms, a structural unit (b-0) derived from at least one monomer represented by the general formula (1), and a structural unit (c-2) derived from at least one monomer represented by the general formula (2). 4 The copolymer having the -OCOO- group is preferably a copolymer having at least a part of the -OM group at the vicinal position. 1 Group (where M 1 is the above M 1 ) and then -COOR 4 At least a portion of the group is -COOM 2 It functions as a precursor copolymer to be subjected to a process in which it may be converted into a radical.

[0172] (7-3) At least a part of the -OCOO- groups contained in the olefin copolymer is replaced with -OM at the vicinal position. 1 Converted to the -COOR group 4 At least a portion of the groups is -COOM 2 A step of converting This step may convert at least a portion of the structural units derived from the monomer represented by general formula (1) into structural units represented by general formula (b-1) below, and may further convert at least a portion of the structural units derived from the monomer represented by general formula (2) into structural units represented by general formula (c-1) below. At least a part of the -OCOO- groups contained in the olefin copolymer is substituted with -OM at the vicinal positions. 1 Converted to the -COOR group 4 At least a portion of the groups is -COOM 2 The method for converting the -OCOO- groups to hydroxyl groups at the vicinal positions is not particularly limited. 4 Methods for converting at least a portion of the -OCOO- groups to carboxy groups include acid decomposition, hydrolysis, hydrogenation, thermolysis, etc. Also, at least a portion of the -OCOO- groups may be converted to metal alkoxides at the vicinal positions, and then converted to -COOR 4 Examples of methods by which at least a portion of the groups may be converted to carboxylate salt groups include saponification, and a method in which the groups are reacted with a compound containing a metal ion after or during thermal decomposition. The conversion method is -OM 1 Group and / or -COOM 2 The method may be appropriately selected depending on the type and amount of the group, and two or more methods may be combined. For example, at least a part of the -OCOO- groups may be converted into a metal alkoxide and then converted into a hydroxyl group by the above method, or at least a part of the -OCOO- groups may be converted into a hydroxyl group and then neutralized with a metal ion to convert into a metal alkoxide. 4 At least a portion of the groups may be converted to carboxy groups by the above-mentioned method, or -COOR 4 At least a portion of the groups may be converted to carboxy groups and then neutralized with a metal ion to convert them to carboxylate salt groups.

[0173] At least a part of the -OCOO- groups contained in the olefin copolymer is substituted with -OM at the vicinal positions. 1Converted to the -COOR group 4 At least a portion of the groups is -COOM 2 When the hydroxyl group can be converted into the hydroxyl group, a base is used in the saponification, and an acid is used in the acidolysis. In the hydrolysis, a conventionally known acid catalyst or base catalyst may be used as an additive for promoting the reaction. The base or base catalyst is not particularly limited, but examples thereof include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and carbonates of alkali metals or alkaline earth metals such as sodium hydrogencarbonate and sodium carbonate, etc., that can be used appropriately. The acid or acid catalyst is not particularly limited, and examples of the acid or acid catalyst that can be used include solid acids such as montmorillonite, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, acetic acid, benzoic acid, citric acid, paratoluenesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid. From the viewpoint of efficiency, the hydrogenation is preferably carried out under reducing conditions using a metal catalyst, and an example of the metal catalyst is a palladium carbon catalyst. In the method of reacting a compound containing a metal ion after or during the thermal decomposition, the metal ion is selected from the group consisting of the M 1 and M 2 The ions may be the same as the ions of the metal atoms described above.

[0174] The compound containing metal ions used in the neutralization reaction is not particularly limited as long as it contains the ions of the metal atoms, and examples thereof include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and zinc hydroxide, metal carbonates such as sodium bicarbonate, sodium carbonate, lithium carbonate, and zinc carbonate, and metal oxides such as sodium oxide, potassium oxide, lithium oxide, and zinc oxide. These compounds are easy to use because the counter ions of the metal ions are unlikely to remain in the polar group-containing olefin copolymer. The amount of the compound containing metal ions used in the neutralization reaction to be added during the reaction may be appropriately adjusted according to the ratio of conversion to carboxylate (neutralization degree). The reaction conditions in the method for converting the structural unit (c-2) are not particularly limited, and may be appropriately selected from conventionally known methods. For example, the type of alcohol that dissolves the base during saponification and the R 4 It is believed that the selection can be made by combining with the structure of the structural unit (c-2). Specifically, when a methanol solution of potassium hydroxide is used, the R 4 When R is a t-butyl group, only the structural unit (b-1) is produced, and the structural unit (c-1) is not produced. On the other hand, when an ethanol solution of potassium hydroxide is used, R 4 Even if R in the structural unit (c-2) is a t-butyl group, saponification at least partially proceeds, and the structural unit (c-1) is also produced together with the structural unit (b-1). 4 When is a methyl group, saponification proceeds and the structural unit (c-1) is produced together with the structural unit (b-1). EXAMPLES

[0175] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples as long as they do not deviate from the gist of the invention. The physical properties of the polar group-containing olefin copolymer and the like were measured by the following methods. The abbreviations are as follows: cod: cyclooctadiene tBu: tertiary butyl iPr: Isopropyl Et: Ethyl

[0176] [Structure of polar group-containing olefin copolymer] (1) 1 H-NMR and 13 C-NMR analysis Similar compounds of structural units represented by general formula (b-0) and general formula (b-1) 1 H-NMR and 13 The NMR spectrum was assigned with reference to the C-NMR spectrum (spectral database provided by the National Institute of Advanced Industrial Science and Technology), and the structure of the polar group-containing olefin copolymer was determined. Diethyl carbonate (δ 1 Around H=4.2ppm, δ 13 C = 64 ppm), and 2,3-butanediol (δ 1 H=3.8ppm, δ 13 It was verified by two-dimensional NMR that a signal was detected at a position equivalent to the chemical shift value of the cation (around C=71 ppm). The structural units represented by general formula (c-1) and general formula (c-2) were assigned to the NMR spectrum with reference to values ​​calculated using chemical shift prediction software (ACD / Labs (registered trademark) manufactured by Fujitsu Limited), and the structure of the polar group-containing olefin copolymer was determined. Among the structural units represented by general formula (c-1), M 2 =H, δ 1 H=2.4ppm and δ 13 A signal was detected at a chemical shift value of C=45 ppm. 1 H-NMR (Figures 7 and 8) and13 This was confirmed by C-NMR (Figures 1 and 2). 2 =K, δ 1 H=2.4ppm and δ 13 A signal was detected at a chemical shift value of C=46 ppm. 1 H-NMR (Figures 7 and 8) and 13 This was confirmed by C-NMR (Figures 1 and 2). Among the structural units represented by general formula (c-2), R 4 = tBu, δ 1 H=2.3ppm and δ 13 It was confirmed by two-dimensional NMR (HSQC) (Figure 10) and DEPT135-NMR (Figure 11) that a signal was detected at a chemical shift value of C = 47 ppm. 4 = Et, δ 1 H=4.1ppm and δ 13 It was confirmed by two-dimensional NMR (HSQC) (FIG. 12) and DEPT135-NMR (FIG. 13) that a signal was detected at a chemical shift value of C=60 ppm.

[0177] The measurement equipment used was an AV400 NMR device manufactured by Bruker Biospin Co., Ltd. The probe used was a cryoprobe with a diameter of 10 mm. The sample temperature was 120°C.

[0178] [Sample preparation conditions: Examples 1 and 2] 100 mg of the sample was placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 mL of a solvent (o-dichlorobenzene / deuterated bromide benzene (C6D5Br)) and hexamethyldisiloxane as a chemical shift standard substance, and dissolved uniformly in a block heater at 150°C.

[0179] [Measurement conditions: Examples 1 and 2] ( 1 H-NMR) Pulse angle: 4.5° Pulse interval: 2 seconds Number of times accumulated: 1024 Chemical shift: The chemical shift is set to 0.09 ppm for the proton signal of hexamethyldisiloxane, and the chemical shifts of the signals due to other protons are based on this. ( 13 C-NMR) Pulse angle: 90° Pulse interval: 51.5 seconds Number of times accumulated: 1024 Decoupling conditions: Inverse gate decoupling method Chemical shift: The chemical shift was set to 1.98 ppm for the 13C signal of hexamethyldisiloxane, and the chemical shifts of other 13C signals were based on this. (DEPT135-NMR) Pulse angle: 90° Capture time: 2.9 seconds Wait time: 3 seconds Accumulation count: 512 times (1H-DOSY) Number of times: 32 F2 axis data points: 25208 F1 axis data points: 2 (2D-NMR:HSQC) Number of times accumulated: 256 F2 axis data points: 1024 F1 axis data points: 72

[0180] [Sample preparation conditions: Examples 3 and 5] 50-60 mg of the sample was placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 mL of solvent (o-dichlorobenzene / deuterated bromide benzene (C6D5Br)), 50 mg of deuterated tetrachloroethane (TCE), and hexamethyldisiloxane as a chemical shift standard substance, and dissolved uniformly in a block heater at 150°C.

[0181] [Sample preparation conditions: Examples 4 and 6] 50-60 mg of the sample was placed in an NMR sample tube with an inner diameter of 10 mm together with 2.4 mL of a solvent (o-dichlorobenzene / deuterated bromide benzene (C6D5Br)) and hexamethyldisiloxane as a chemical shift standard substance, and dissolved uniformly in a block heater at 150°C.

[0182] [Measurement conditions: Examples 3 to 6] ( 1 H-NMR) Pulse angle: 4.5° Pulse interval: 2 seconds Accumulation count: 2048 times Chemical shift: The chemical shift is set to 0.09 ppm for the proton signal of hexamethyldisiloxane, and the chemical shifts of the signals due to other protons are based on this. ( 13 C-NMR) Pulse angle: 90° Pulse interval: 51.5 seconds Accumulation count: 2048 times Decoupling conditions: Inverse gate decoupling method Chemical shifts: The chemical shifts were set at 1.98 ppm for the 13C signal of hexamethyldisiloxane and 1.98 ppm for other 13 The chemical shifts of the C signals were based on this. (DEPT135-NMR) The conditions were the same as in Examples 1 and 2.

[0183] [Measurement conditions: Examples 3 and 4] (1H-DOSY) The conditions were the same as in Examples 1 and 2.

[0184] <Calculation method for polar group-containing monomer content> (R of structural unit (c-1) and structural unit (c-2) 4 (Calculation method for tBu content) 13 Using the C-NMR spectrum, the content of each monomer in the above structural unit was calculated from the following formula: c The structural unit represented by the general formula (b-0) is VC oindicates a structural unit represented by general formula (b-1). ClK is one of the structural units represented by general formula (c-1), 2 =K. ClH is one of the structural units represented by general formula (c-1), 2 =H. C2tBu is a structural unit represented by the general formula (c-2) 4 =tBu. C2Et is a structural unit represented by general formula (c-2), 4 =Et. C1K amount (mol%)=I(C1K)×100 / [I(VC c )+I(VC o )+I(C2tBu)+I(C2Et)+I(E)+I(C1K)+I(C1H)] C1H amount (mol%)=I(C1H)×100 / [I(VC c )+I(VC o )+I(C2tBu)+I(C2Et)+I(E)+I(C1K)+I(C1H)] C2tBu amount (mol%)=I(C2tBu)×100 / [I(VC c )+I(VC o )+I(C2tBu)+I(C2Et)+I(E)+I(C1K)+I(C1H)] Here, I(VC c ), I(VC o ), I(C2tBu), I(C2Et), I(ClK), I(ClH), and I(E) are the quantities shown in the following formulas. I(VC c )=(I 153.0~154.0 +I 79.5~79.8 ) / 2 I(VC o )=I 74.5~75.5 / 2 I(C2tBu)=I 79.1~79.3 I(C2Et)=I 59.4~59.8 I(ClK)=I 45.9~46.0 I(ClH)=I 45.0~45.8 I(E) = [I2.0~120.0 +I 135.0~200.0 -I(VC c )×3-I(VC o )×2-I(C2tBu)×7-I(C2Et)×5-I(ClK)×3-I(ClH)×3] / 2 I am 13 The integrated intensity of the C-NMR spectrum is shown. The subscript number of I indicates the range of chemical shifts. For example, I 2.0~120.0 indicates the integrated intensity of the signal detected between 2.0 ppm and 120.0 ppm.

[0185] (R of structural unit (b-0), structural unit (b-1), and structural unit (c-2) 4 = Et, and a method for calculating the content of the aldehyde structure in the structural unit (b-2) 1 Using the H-NMR spectrum, the content of each monomer in the above structural unit was calculated from the following formula: Al represents an aldehyde structure among the structures represented by general formula (b-2). VC o Amount (mol%)=I H (VC o )×100 / [I H (VC c )+I H (VC o )+I H (C2tBu)+I H (C2Et)+I H (ClK)+I H (ClH)+I H (E) VC c Amount (mol%)=I H (VC c )×100 / [I H (VC c )+I H (VC o )+I H (C2tBu)+I H (C2Et)+I H (ClK)+I H (ClH)+I H (E) Amount of A1 (mol%) = I H (Al) × 100 / [I H (VC c) + I H (VC o ) + I H (C2tBu) + I H (C2Et) + I H (ClK) + I H (ClH) + I H (E)〕 C2Et amount (mol%) = I H (C2Et) × 100 / [I H (VC c ) + I H (VC o ) + I H (C2tBu) + I H (C2Et) + I H (ClK) + I H (ClH) + I H (E)〕 Here, I H (Al), I H (VC c )、I H (VC o )、I H (C2tBu)、I H (C2Et)、I H (ClK)、I H (ClH)、I H (E) are each the amounts represented by the following formulas. I H (Al) = I H、9.5~9.7 I H (VC c ) = (I H、4.0~4.7 - I H、4.0~4.3 ) / 2 I H (VC o ) = I H、3.3~3.8 / 2 I H (C2tBu) = I H、2.1~2.3 I H (C2Et) = I H、4.0~4.3 / 2 I H (ClK) + I H (ClH) = I H、2.3~2.5 I H (E) = (I H、0.1~6.0 - I H (VC c)×2-I H (VC o )×2-I H (C2tBu)×12-I H (C2Et)×8-(I H (ClK)+I H (ClH))×3) / 4 I H teeth 1 The integrated intensity of the H-NMR spectrum is shown. The numbers to the right of the H readings indicate the range of chemical shifts. For example, I H、0.1~6.0 indicates the integrated intensity of the signal detected between 0.1 ppm and 6.0 ppm.

[0186] (Calculation method of ethylene content) The ethylene content was calculated by dividing the content of the polar group-containing comonomer by 100 mol % of the entire polymer. Ethylene content (mol%) = 100 - (VC c Amount+VC o amount + C2tBu amount + C2Et amount + Al amount + C1K amount + C1H amount)

[0187] (2) Infrared absorption (IR) spectrum analysis The infrared absorption spectrum was measured by weighing 1 mg of the sample, placing it between potassium bromide (KBr) plates, and using a Fourier transform infrared spectrophotometer FT / IR-6600 (DLATGS detector) manufactured by JASCO Corporation, using the transmission method. The measurement wave number range was 400 to 4000 cm -1 The resolution is 4 cm -1 The number of integration times for both background and sample measurements was 16 to 32. Among the structural units represented by general formula (b-1), M 1 For K, the temperature is 3350-3400 cm -1 It was confirmed by the IR spectrum (FIG. 14) that a peak was detected near the M 2 For those with K, the wavelength is 1550-1600 cm -1 It was confirmed by IR spectrum (FIG. 14) that a peak was detected in the vicinity.

[0188] (3) Number average molecular weight and weight average molecular weight The number average molecular weight and the weight average molecular weight were calculated by size exclusion chromatography using polystyrene as a molecular weight standard. The specific measurement method of GPC is as follows. Apparatus: Agilent Technologies PL-GPC 220 Detector: IR detector Column: Resonac AT-806MS (3 columns in series) Mobile phase solvent: orthodichlorobenzene (ODCB) Measurement temperature: 140℃ Flow rate: 1.0mL / min Injection volume: 0.3mL [Sample preparation] The polar group-containing olefin copolymer is dissolved at 1 mg / mL in ODCB containing 0.24 mg / mL TMP (2,4,6-trimethylphenol) at 140° C. for about 1 hour. The retention volume obtained by GPC measurement is converted to molecular weight using a calibration curve prepared in advance using standard polystyrene (PS). The standard polystyrenes used are the following brands manufactured by Tosoh Corporation: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000. A calibration curve is prepared by injecting 0.3 mL of a solution containing 0.24 mg / mL TMP dissolved in ODCB for ethylene (co)polymer so that each is 0.5 mg / mL. A cubic equation obtained by approximating with the least squares method is used for the calibration curve. The viscosity equation used for conversion to molecular weight is [η] = K × M α The following numerical values ​​are used: PS:K = 1.38 x 10 -4 , α=0.700 PP:K = 1.03 x 10 -4 , α=0.780 PE:K = 3.92 x 10 -4 , α=0.733

[0189] [Synthesis example 1] (B27-DM) According to Synthesis Example 4 described in WO 2010 / 050256, the following 2-bis(2,6-dimethoxyphenyl)phosphano-6-pentafluorophenylphenol ligand (B-27DM) was synthesized.

[0190] [ka]

[0191] [Synthesis example 2] (AL-40) According to Synthesis Example 2 described in JP 2024-52628 A, the following 2-[[bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)-4-yl)phosphino]methyl]-1,1,1,3,3,3-hexafluoro-2-propanol ligand (AL-40) was synthesized.

[0192] [ka]

[0193] All the following operations were carried out under a nitrogen atmosphere. Example 1 (1) Preparation of catalyst solution In a 50 mL flask, 10.8 mg (39.3 μmol) of Ni(cod)2 was weighed out and dissolved in 8 mL of toluene. In a separate flask, 16.8 mg (29.8 μmol) of B-27DM obtained from Synthesis Example 1 was weighed out. 6 mL of the toluene solution of Ni(cod)2 was weighed out and added to the flask containing B-27DM. The resulting solution was warmed in a 40°C water bath and stirred for 15 minutes to obtain a catalyst solution.

[0194] (2) Preparation of Precursor Copolymer 1 74 mL of toluene, 1.76 g (20.5 mmol) of vinylene carbonate (VC, Aldrich, 99.5%, acid < 200 ppm, H2O < 100 ppm), 0.6 mL (4.2 mmol) of t-butyl acrylate (tBA), and 0.5 mL of a toluene solution (0.1 M) of Al(OiPr)3 were added to a 0.2 L autoclave equipped with a catalyst cylinder and a killer feeder that had been thoroughly dried and replaced with nitrogen, and the temperature was raised to 90 ° C. High-pressure nitrogen was added to this to make it 0.5 MPa, and then 2.5 MPa of ethylene was added to make the internal pressure 3.0 MPa. Next, 2 mL of the catalyst solution prepared in (1) above was added to the catalyst cylinder, and the catalyst solution was forced into the autoclave with high-pressure nitrogen, and this point was the reaction start time. After that, the catalyst cylinder was washed with 3 mL of toluene, and the washing liquid was forced into the autoclave with high-pressure nitrogen. Thirty minutes after the start of the reaction, 1 mL of a toluene solution of diacetic acid (2 M) was injected through the killer feeder to stop the reaction. The killer feeder was washed with 3 mL of toluene, and then the ethylene was depressurized. The internal temperature of the autoclave was cooled to room temperature, and 100 mL of acetone was added. The precipitated copolymer was collected by filtration, washed twice with 100 mL of acetone, and then dried under reduced pressure. The amount of precursor copolymer 1 thus obtained was 0.96 g (activity 190 kg / mol-Ni / hr). The analytical results of the obtained precursor copolymer 1 are summarized in Tables 1 and 2 as Reference Example 1.

[0195] (3) Preparation of polar group-containing olefin copolymer (at least a part of the -OCOO- groups of the precursor copolymer is converted to -OM at the vicinal positions) 1 Converted to the -COOR group 4 At least a portion of the groups is -COOM 2 (Process for converting to the base) 0.72 g of the precursor copolymer 1 obtained in (2) above was placed in a 100 mL two-necked eggplant flask, dissolved in 7.2 mL of toluene at 110 ° C., and cooled to room temperature. 4.9 mL of potassium hydroxide ethanol solution (0.37 M) was added thereto, a Dean-Stark apparatus was attached, and the mixture was heated at 110 ° C. for 20 minutes. Then, 2.8 mL of toluene was added and the mixture was heated for another 4 hours. After 4 hours, the solvent was completely distilled off, and the precipitated copolymer was washed three times with 10 mL of water. The copolymer was then filtered and recovered using a glass filter. The recovered copolymer was vacuum dried at 90 ° C. for 4 hours, and 0.72 g of polar group-containing olefin copolymer 1 was obtained. The analysis results of the obtained polar group-containing olefin copolymer 1 are summarized in Tables 1 and 2.

[0196] Example 2 0.45 g of the polar group-containing olefin copolymer 1 obtained in Example 1 (3) was placed in a 100 mL two-necked eggplant flask, and 16 mL of toluene and 5.8 mL of a diethyl ether solution of hydrogen chloride (1.0 M) were added at room temperature and stirred for 4 hours. The mixture was then heated to 80 ° C and stirred for 5 hours. After returning to room temperature, 5.8 mL of a diethyl ether solution of hydrogen chloride (1.0 M) was added, and the mixture was heated to 110 ° C and stirred for 5 hours. After 5 hours, the solvent was completely distilled off, and the precipitated copolymer was washed three times with 10 mL of water. The copolymer was then filtered and recovered using a glass filter. The recovered copolymer was vacuum dried at 90 ° C for 4 hours to obtain 0.28 g of a polar group-containing olefin copolymer 2. The analysis results of the obtained polar group-containing olefin copolymer 2 are summarized in Tables 1 and 2.

[0197] Example 3 (1) Preparation of catalyst solution In a flask, 12.9 mg (0.05 mmol) of Ni(acac)2 was weighed out and dissolved in 10 mL of toluene. In a separate flask, 19.4 mg (0.03 mmol) of AL-40 obtained from Synthesis Example 2 was weighed out. 6 mL of the toluene solution of Ni(acac)2 was weighed out and added to the flask containing AL-40. The resulting solution was warmed in a 40°C water bath and stirred for 15 minutes to obtain a catalyst solution.

[0198] (2) Preparation of Precursor Copolymer 2 87 mL of toluene, 3.2 mL (50 mmol) of vinylene carbonate, 0.4 mL (4.2 mmol) of methyl acrylate (MA), and 0.5 mL of a toluene solution (0.1 M) of tri-n-octyl aluminum were added to a 0.2 L autoclave having a catalyst cylinder and a killer feeder that had been thoroughly dried and replaced with nitrogen in advance, and the temperature was raised to 90°C. High-pressure nitrogen was added to this to make the pressure 0.5 MPa, and then 2.5 MPa of ethylene was added to make the internal pressure 3.0 MPa. Next, 2 mL of the catalyst solution prepared in (1) above was added to the catalyst cylinder, and the catalyst solution was forced into the autoclave with high-pressure nitrogen, and this point was the reaction start time. After that, the catalyst cylinder was washed with 3 mL of toluene, and the washing solution was forced into the autoclave with high-pressure nitrogen. 29 minutes after the start of the reaction, 3 mL of a toluene solution (0.2 M) of 1,2-butanediol was forced into the autoclave from the killer feeder to stop the reaction. The killer feeder was washed with 3 mL of toluene, and the washing liquid was injected with high-pressure nitrogen, after which the ethylene was depressurized. The temperature inside the autoclave was cooled to room temperature, and then 100 mL of acetone was added. The precipitated copolymer was collected by filtration, washed twice with 100 mL of acetone, and then dried under reduced pressure. The amount of precursor copolymer 2 thus obtained was 2.99 g (activity 620 kg / mol-Ni / hr). The analytical results of the obtained precursor copolymer 2 are summarized in Tables 1 and 2 as Reference Example 2.

[0199] (3) Production of polar group-containing olefin copolymer 0.97 g of the precursor copolymer 2 obtained in (2) above was placed in a 50 mL two-necked eggplant flask, and 9.7 mL of toluene was added. 1.0 mL of a methanol solution of potassium hydroxide (1.4 M) was added thereto at room temperature, and a Dean-Stark apparatus was attached and heated at 110 ° C for 1 hour. Then, 4.0 mL of toluene was added, and the mixture was heated for another 5 hours and 40 minutes. After heating, the solvent was completely distilled off, and the precipitated copolymer was washed four times with 10 mL of water. The copolymer was then filtered and recovered using a glass filter. The recovered copolymer was vacuum dried at 90 ° C for 4 hours, and 0.97 g of polar group-containing olefin copolymer 3 was obtained. The analysis results of the obtained polar group-containing olefin copolymer 3 are summarized in Tables 1 and 2.

[0200] Example 4 0.72 g of the polar group-containing olefin copolymer 3 obtained in Example 3 (3) was placed in a 100 mL two-necked eggplant flask, and 26 mL of toluene and 5.2 mL of a diethyl ether solution of hydrogen chloride (1.0 M) were added at room temperature and stirred for 35 minutes. The mixture was then heated to 110°C and stirred for 9 hours and 20 minutes. The mixture was then heated to 120°C and stirred for 20 minutes. The mixture was further heated to 130°C and stirred for 2 hours and 15 minutes. The mixture was then returned to room temperature, and the copolymer was washed four times with 15 mL of water. The copolymer was then filtered and collected using a glass filter. The collected copolymer was vacuum dried at 90°C for 3 hours and 40 minutes to obtain 0.68 g of polar group-containing olefin copolymer 4. The analysis results of the obtained polar group-containing olefin copolymer 4 are summarized in Tables 1 and 2.

[0201] Example 5 (1) Preparation of catalyst solution In a flask, 65.8 mg (0.24 mmol) of Ni(cod)2 was weighed out and dissolved in 12 mL of toluene. In a separate flask, 112.7 mg (0.20 mmol) of B-27DM obtained from Synthesis Example 1 was weighed out. 10 mL of the toluene solution of Ni(cod)2 was weighed out and added to the flask containing B-27DM. The resulting solution was warmed in a 40°C water bath and stirred for 15 minutes to obtain a catalyst solution.

[0202] (2)-1 Preparation of Precursor Copolymer 3 79 mL of toluene, 6.6 mL (105 mmol) of vinylene carbonate (VC, Aldrich, 99.5%, acid < 200 ppm, H2O < 100 ppm), 1.8 mL (12.5 mmol) of t-butyl acrylate (tBA), and 6 mL of a toluene solution (0.1 M) of Al(OiPr)3 were added to a 0.2 L autoclave equipped with a catalyst cylinder and a killer feeder that had been thoroughly dried and replaced with nitrogen, and the temperature was raised to 90 ° C. High-pressure nitrogen was added to this to make it 0.5 MPa, and then ethylene was added at 2.5 MPa to make the internal pressure 3.0 MPa. Next, 3 mL of the catalyst solution prepared in (1) above was added to the catalyst cylinder, and the catalyst solution was forced into the autoclave with high-pressure nitrogen, and this point was the reaction start time. After that, the catalyst cylinder was washed with 3 mL of toluene, and the washing liquid was forced into the autoclave with high-pressure nitrogen. 19 minutes after the start of the reaction, 1 mL of catalyst solution was added, and the catalyst solution was forced into the autoclave with high-pressure nitrogen. 32 minutes after the start of the reaction, 1.5 mL of catalyst solution was added, and the catalyst solution was forced into the autoclave with high-pressure nitrogen. 37 minutes after the start of the reaction, 2 mL of catalyst solution was added, and the catalyst solution was forced into the autoclave with high-pressure nitrogen. 50 minutes after the start of the reaction, 3 mL of 1,2-butanediol in toluene solution (0.2 M) was forced into the autoclave from the killer feeder to stop the reaction. Then, ethylene was depressurized, and the internal temperature of the autoclave was cooled to room temperature, and 100 mL of acetone was added. The precipitated copolymer was collected by filtration and dried under reduced pressure. The amount of precursor copolymer 3 thus obtained was 1.55 g (activity 12 kg / mol-Ni / hr). The analysis results of the obtained precursor copolymer 3 are summarized in Tables 1 and 2 as Reference Example 3.

[0203] (2)-2 Preparation of Precursor Copolymer 4 0.91 g of the precursor copolymer 3 was placed in a 50 mL eggplant flask and dissolved in 20 mL of toluene at 110 ° C. 100 mL of acetone was placed in a 200 mL eggplant flask, and the dissolved precursor copolymer 3 was quickly added at room temperature. 5.0 mL of 10% dilute hydrochloric acid was added to this at room temperature, and the mixture was stirred for 1 hour and 15 minutes. The precipitated copolymer was filtered using a glass filter, and the copolymer was collected. This copolymer was also dissolved in 10 mL of toluene at 110 ° C. 50 mL of acetone was placed in a 100 mL eggplant flask, and the dissolved copolymer was quickly added at room temperature. 5.0 mL of 10% dilute hydrochloric acid was added to this at room temperature, and the mixture was stirred for 25 minutes. The precipitated copolymer was filtered using a glass filter and collected. Furthermore, the obtained copolymer was placed in a 100 mL eggplant flask, and 50 mL of acetone and 5.0 mL of 10% dilute hydrochloric acid were added to it at room temperature, and the mixture was stored in a refrigerator overnight. The copolymer was then filtered using a glass filter and collected. The recovered copolymer was vacuum dried for 4 hours and 15 minutes at 90° C. Precursor copolymer 4 thus obtained weighed 0.70 g.

[0204] (3) Production of polar group-containing olefin copolymer 0.60 g of the precursor copolymer 4 obtained in (2)-2 above was placed in a 50 mL two-necked eggplant flask, and 6.0 mL of toluene was added. 1.0 mL of a methanol solution of potassium hydroxide (2.2 M) was added thereto at room temperature, and the mixture was heated at 110 ° C for 1 hour and 35 minutes. Then, 2.0 mL of toluene was added, and the mixture was heated for another 3 hours. After 3 hours, a Dean-Stark apparatus was attached, and the mixture was heated at 110 ° C for 7 hours and 20 minutes. After heating, the solvent was completely distilled off, and the precipitated copolymer was washed 9 times with 10 mL of water. The copolymer was then filtered and recovered using a glass filter. The recovered copolymer was vacuum dried at 90 ° C for 5 hours, and 0.55 g of polar group-containing olefin copolymer 5 was obtained. The analysis results of the obtained polar group-containing olefin copolymer 5 are summarized in Tables 1 and 2.

[0205] Example 6 0.40 g of the polar group-containing olefin copolymer 5 obtained in Example 5 (3) was placed in a 100 mL two-necked eggplant flask, and 14 mL of toluene and 6.8 mL of a diethyl ether solution of hydrogen chloride (1.0 M) were added at room temperature. The mixture was then heated to 110 ° C and stirred for 5 hours. Then, 9.0 mL of toluene was added, and the mixture was heated and stirred at 110 ° C for another 1 hour and 50 minutes. After returning to room temperature, 9.0 mL of toluene and 10 mL of water were added, and the solvent was completely distilled off. The precipitated copolymer was washed three times with 10 mL of water, and the copolymer was filtered and recovered using a glass filter. The recovered copolymer was vacuum dried at 82 ° C for 4 hours and 35 minutes to obtain 0.37 g of polar group-containing olefin copolymer 6. The analysis results of the obtained polar group-containing olefin copolymer 6 are summarized in Tables 1 and 2.

[0206] [Table 1]

[0207] [Table 2]

[0208] In Table 1, "*" means that the sample was not dissolved in the measurement solvent and could not be analyzed. In Table 2, "ND" means that it was not detected in the measurement, and "-" means that it was not contained in the first place. The reason why the samples did not dissolve in the GPC measurement of Examples 3, 5, and 6 in Table 1 is thought to be that in Examples 3 and 5, the ionic nature of the polymer increased and the solubility decreased because the metal alkoxide and carboxylate group were contained in larger amounts than in Example 1. In Example 6, the solubility decreased because the polarity of the polymer increased due to the increased content of hydroxyl groups.

[0209] 1 to 3 show the polar group-containing olefin copolymer 2 of Example 2. 13 4 to 6 show the results of C-NMR measurement of the polar group-containing olefin copolymer 1 of Example 1. 17 and 8 show the results of H-NMR measurement of the polar group-containing olefin copolymer 1 of Example 2. 1 The H-NMR measurement results are shown below. FIG. 9 shows the results of HSQC measurement of the polar group-containing olefin copolymer 1 of Example 1. FIG. 10 shows the HSQC measurement results of the polar group-containing olefin copolymer 2 of Example 2 (hydrogen: around 1.85 ppm to around 2.85 ppm, carbon: around 39 ppm to around 50 ppm), and FIG. 11 shows the DEPT135-NMR measurement results of the polar group-containing olefin copolymer 2 of Example 2 (around 40 ppm to around 52 ppm). FIG. 12 shows the HSQC measurement results of the polar group-containing olefin copolymer 2 of Example 2 (hydrogen: around 3.10 ppm to around 4.80 ppm, carbon: around 55 ppm to around 82 ppm), and FIG. 13 shows the DEPT135-NMR measurement results of the polar group-containing olefin copolymer 2 of Example 2 (around 54 ppm to around 65 ppm). 10 and 12 are HSQC spectra of the polar group-containing olefin copolymer 2. In FIG. 10, the area enclosed in a black frame shows the CH correlation of c2, which is a hydrogen atom derived from the structural unit (c-2). In FIG. 12, the area enclosed in a black frame on the left side shows the CH correlation of e1 and e2, which are hydrogen atoms derived from the structural unit (c-2), and the area enclosed in a black line on the right side shows the CH correlation of g3 and g4, which are hydrogen atoms derived from the structural unit (B).

[0210] As is clear from the NMR measurement results, the polar group-containing olefin copolymers 1 to 6 produced in Examples 1 to 6 were revealed to be novel polar group-containing olefin copolymers containing, in the main chain, specific amounts of structural units (b-1) and (b-2) as structural units (B) derived from an olefin and a vinylene carbonate derivative represented by general formula (1), and at least one of structural units (c-1) and (c-2). Note that although figures are not shown for the 2D NMR and DEPT135-NMR for the structural unit (c-2) in Examples 1, 5, and 6, the structural unit (c-2) in Example 2 was not shown. 1 H-NMR and 13Since there were peaks at the same chemical shifts as in C-NMR, it was confirmed that they contained the same structure. In Table 2, the content (mol %) of each structural unit means the content ratio of each structural unit when all structural units of the copolymer are taken as 100 mol %. In addition, regarding the contents of the structural units (b-1) and (c-1) in Examples 3 and 5, since the polymer did not dissolve in ODCB alone, the polymer was dissolved in a mixed solvent of ODCB and TCE. 1 H-NMR measurements were performed to confirm the 1 , M 2 Only H was detected, and no K was detected. However, IR spectrum analysis revealed that M 1 , M 2 It was confirmed that M was present in Examples 3 and 5. Based on this IR result and the fact that the copolymer was treated with potassium hydroxide in the step immediately prior to obtaining the polar group-containing olefin copolymer as in Example 1, it was confirmed that M 1 , M 2 is judged to be only K, 1 H-NMR measurement 1 , M 2 The results are quantified as H. 1 , M 2 The quantitative result was that it was K. [Industrial Applicability]

[0211] The novel polar group-containing olefin copolymer of the present invention is a copolymer in which OM at the vicinal position is contained in a polyolefin having 2 or more carbon atoms such as ethylene. 1 group (hydroxyl group and / or metal alkoxide) and COOM 2 Groups (carboxyl groups and / or carboxylate groups) and COOR 4 Since two or more polar groups consisting of at least one of the groups (ester groups) are introduced, it is possible to realize functions not found in conventional olefin copolymers, such as chelating coordination. For example, the polar group-containing olefin copolymer of the present invention is expected to be used as a carrier for metal complex catalysts or an adsorbent for recovering metal complexes. In addition, the polar group-containing olefin copolymer of the present invention is expected to realize functions not found in conventional ethylene copolymers, such as ionic bonding with the carboxylate group derived from the metal alkoxide-(meth)acrylic acid ester derivative at the vicinal position of the ethylene-vinylene carbonate derivative. Copolymers having such functions are expected to be used in automobile parts and the like, taking advantage of their excellent compatibility with pigments and fillers and their toughness. In addition, the OM at the vicinal position of the polar group-containing olefin copolymer of the present invention 1 Motoya COOM 2 Further functionality can be achieved by graft polymerization onto the group. For example, in the polar group-containing olefin copolymer of the present invention, the vicinal hydroxyl group derived from the vinylene carbonate derivative and the carboxyl group derived from the acrylate derivative have different proton acidities, which allows for different chemical modifications, and different material properties can be expected from conventional olefin-acrylate copolymers. In addition, the polar group-containing olefin copolymer of the present invention is a linear polyolefin having OM at the vicinal position. 1 group (hydroxyl group and / or metal alkoxide) and COOM 2 Groups (carboxyl groups and / or carboxylate groups) and COOR 4 By containing two or more types of polar groups, i.e. at least one type of branched polar group (ester group), the heat resistance and rigidity are greater than those of branched polar group-containing olefin copolymers, and it is expected that the copolymer will be used in applications such as storage containers and pipes where these properties are required. Furthermore, by copolymerizing a polyolefin having two or more carbon atoms, such as ethylene, with a vinylene carbonate derivative and an acrylic acid ester derivative, carbon dioxide can be fixed.

Claims

1. A structural unit (A) derived from at least one olefin having 2 to 20 carbon atoms; 0.04 mol % to 10.00 mol % of a structural unit (b-1) represented by the following general formula (b-1), At least one of a structural unit (c-1) represented by the following general formula (c-1) and a structural unit (c-2) represented by the following general formula (c-2), A polar group-containing olefin copolymer, characterized in that both of the above are contained in the main chain. 【Chemistry 1】 (In formula (b-1), R １ and R ２ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a nitro group, an amino group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, an amide group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, or １ and R ２ may be bonded to each other to form a 4- to 10-membered ring. M １ are each independently a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table. 【Chemistry 2】 (In formula (c-1), R ３ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. M ２ is a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table. 【Chemistry 3】 (In formula (c-2), R ３ is the R ３ is synonymous with. R ４ is a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms which is substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one of an oxygen atom, a sulfur atom, or a nitrogen atom.

2. The polar group-containing olefin copolymer according to claim 1, further comprising a structural unit (b-2) represented by the following general formula (b-2): 【Chemistry 4】 (In formula (b-2), R １ and R ２ are the above R １ and R ２ (Same meaning as above.)

3. R of the structural unit (b-1) １ and R ２ The polar group-containing olefin copolymer according to claim 1 , wherein at least one of the above is a hydrogen atom.

4. R in the general formula (c-1) and the general formula (c-2) ３ and each of the is a hydrogen atom.

5. R of the structural unit (b-1) １ and R ２ and each of the is a hydrogen atom.

6. The polar group-containing olefin copolymer according to any one of claims 1 to 5, wherein at least one of the olefins having 2 to 20 carbon atoms is ethylene.

7. The polar group-containing olefin copolymer according to any one of claims 1 to 5, wherein the total content of the structural unit (c-1) and the structural unit (c-2) is 0.01 mol% to 30.00 mol%.

8. A step of polymerizing at least one olefin having 2 to 20 carbon atoms, at least one monomer represented by the following general formula (1), and at least one monomer represented by the following general formula (2) in the presence of a catalyst containing at least one compound represented by the following general formula (101) to obtain an olefin copolymer; A step of converting at least a part of the structural units derived from the monomer represented by the general formula (1) contained in the olefin copolymer into structural units represented by the following general formula (b-1), and further converting at least a part of the structural units derived from the monomer represented by the general formula (2) into structural units represented by the following general formula (c-1): The present invention relates to a method for producing a polar group-containing olefin copolymer. 【Chemistry 5】 [In general formula (101), M represents a metal atom of Group 10 of the periodic table. Q is an oxygen atom, a sulfur atom, or -S(=O) ２ It represents —O— or —C(═O)—O—, and the left side of each of the groups is bonded to A and the right side is bonded to M. A represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. R Ｌ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a ligand coordinated to M. L represents a ligand coordinated to M. R ｘ and R ｙ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. R Ｌ and L and R ｘ and R ｙ may form a ring, R ｘ and A or R ｙ and A may form a ring. 【Chemistry 6】 (In formula (1), R １ and R ２ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, a nitro group, an amino group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, an amide group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, or １ and R ２ may be bonded to each other to form a 4- to 10-membered ring. 【Chemistry 7】 (In formula (2), R ３ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with at least one halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. R ４ is a silyl group which may be substituted with at least one hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms which is substituted with at least one halogen atom, or a hydrocarbon group or heterocyclic group having 1 to 30 carbon atoms which may be substituted with at least one substituent containing at least one of an oxygen atom, a sulfur atom, or a nitrogen atom. 【Chemistry 8】 (In formula (b-1), R １ and R ２ are the above R １ and R ２ is synonymous with. M １ are each independently a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table. 【Chemistry 9】 (In formula (c-1), R ３ is the R ３ is synonymous with. M ２ is a hydrogen atom or a metal ion of Group 1, 2, 12, or 13 of the periodic table.

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