JP7382798B2 - Polar group-containing olefin copolymer and polar group-containing olefin copolymer composition - Google Patents

Description

The present disclosure relates to a novel polar group-containing olefin copolymer, and specifically relates to a novel polar group-containing olefin copolymer in which a specific polar group is selectively introduced at the terminal.

Terminal-functionalized polyolefins, in which functional groups are introduced at the ends of polyolefins, are expected to improve the properties of polyolefins and are desired by industry.
For example, when a terminally functionalized polyolefin is mixed with a regular polyolefin, functional groups tend to appear at the polyolefin interface as a result of hydrophobic interactions. As a result, the functionalized polyolefin interface improves processing, molding, painting, and other properties that have traditionally been considered weak points of polyolefins. Furthermore, when terminally functionalized polyolefins are applied to compounds, more stable compounds can be formed due to the presence of an interface that firmly holds fillers, fibers, and additives. Thus, end-functionalized polyolefins can extend the scope and/or route of production of polyolefin compounds.

Additionally, the terminally functionalized polyolefin can be a raw material for diblock polymers. Different types of resins can be joined by initiating polymerization of different types from the terminal functional groups of the terminally functionalized polyolefin. For example, a polyolefin into which a halogen is introduced at the end serves as an initiator for radical polymerization, and an acrylic resin or polystyrene can be bonded to the end of the polyolefin. Furthermore, the diblock polymer thus obtained can be used in the production of polyolefin compounds, such as by mixing with polyolefins to improve the properties of the polyolefins, as described above.

Conventional methods for selectively introducing functional groups into the terminals of polyolefins include, for example, reacting the double bonds at the terminals of polyolefins with a highly reactive organometallic reagent to create active terminals, and then converting them into desired terminals. Examples include a method of reacting with a compound having a functional group (for example, Patent Document 1).
However, this method has problems in that it involves too many steps, is uneconomical because it consumes a large amount of organometallic reagent, and further has a poor yield.

Other methods for selectively introducing functional groups into the terminals of polyolefins include a method of performing living polymerization of polyolefins and then reacting the growing terminals with a compound having a desired functional group (for example, a method in which the growing terminals are reacted with a compound having a desired functional group). Patent Document 1).
However, there is a problem in that such living polymerization is not suitable for industrialization of polyolefins in the first place. There are almost no known catalysts that can perform living polymerization of olefins, and all of them are not far superior in productivity to non-living polymerization catalysts, are expensive, and the range of polyolefins that can be produced from them is very narrow.

Furthermore, Non-Patent Document 2 discloses that olefin polymerization was performed using 2-vinylfuran as a chain transfer agent to obtain a polyolefin having a furyl group at the end. However, in Non-Patent Document 2, the introduction of a furyl group to the terminal end of a polyolefin is only successful. Furyl-terminated polyolefins are not sufficient as end-functionalized polyolefins to improve the properties of polyolefins required by industry as described above.

On the other hand, Non-Patent Document 3 discloses that polyalkoxycarbonylmethylene was obtained by performing homopolymerization using alkyl diazoacetate (N ₂ = CHCOOR, R = ethyl group, or methyl group) as a polymerization monomer. ing.
In addition, in Non-Patent Document 4, by copolymerizing a carbene with a specific structure (N ₂ = CHCOOR, R = ethyl group) and ethylene in the presence of a rhodium-based catalyst, a small amount of discloses that an ethylene-carbene copolymer was obtained.

US Patent No. 7,897,709

Macromolecules 2003, 36, 3085-3100 Angew. Chem. Int. Ed. 2016, 55, 14378-14383 Macromolecules 2003, 36, 36-41 Dalton Trans. 2013, 42, 9058-9068

As described above, conventional methods for selectively introducing functional groups into the terminals of polyolefins have problems because they are multi-step, low-efficiency, and complicated. Further, in simple random copolymerization of an olefin and a polar group-containing monomer, the polar monomer is not selectively introduced at the terminal. That is, in random copolymerization of an olefin and a polar group-containing monomer, the olefin is also introduced into the main chain, making it difficult to control the molecular structure.
There is a need for a novel polar group-containing olefin copolymer in which functional groups useful for improving the properties of polyolefins as described above are selectively introduced at the terminal ends.

In view of the state of the prior art, the present application aims to provide a novel polar group-containing olefin copolymer in which a specific polar group is selectively introduced at the terminal.

The polar group-containing olefin copolymer of the present disclosure is
A structural unit (A) derived from one or more monomers selected from ethylene and olefins having 3 to 20 carbon atoms;
One or more monomers selected from the polar group-containing olefin monomer (b-1) represented by the following general formula (1) and the polar group-containing olefin monomer (b-2) represented by the following general formula (2). The derived structural unit (B) and
It is characterized by containing a structural unit (C) derived from one or more monomers selected from polar group-containing carbene monomers represented by the following general formula (3).

（一般式（１）中、Ｒ^１とＲ^２は、それぞれ独立して、水素原子、炭素数１～３０のエステル基、炭素数１～３０のアシルオキシ基、炭素数１～３０のアルコキシ基、炭素数６～３０のアリールオキシ基、シアノ基、炭素数１～３０の炭化水素基で置換されていても良いアミノ基、炭素数１～３０の炭化水素基で置換されていても良いアミド基、炭素数１～３０の炭化水素基で置換されていても良いイミノ基、炭素数１～３０のハロゲン置換炭化水素基、又は、酸素原子、硫黄原子、窒素原子及びリン原子からなる群より選ばれる少なくとも１種を含む官能基で置換されていても良い炭素数１～３０の炭化水素基であり、Ｒ^１とＲ^２の少なくとも一つは、酸素原子及び窒素原子の少なくとも１種を含む基である。）

(In general formula (1), R ¹ and R ² are each independently a hydrogen atom, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Aryloxy group having 6 to 30 carbon atoms, cyano group, amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, amide group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms , an imino group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 30 carbon atoms, or an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. A hydrocarbon group having 1 to 30 carbon atoms which may be ^substituted with a functional group containing at least one ^of )

（一般式（２）中、Ｒ^３～Ｒ^１０は、それぞれ独立して、水素原子、ハロゲン原子、又は、炭素数１～２０の炭化水素基である。ｎは０又は正の整数を示し、ｎが２以上の場合には、Ｒ^７～Ｒ^１０は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。Ｒ^１１～Ｒ^１４は、それぞれ独立して、水素原子、炭素数１～３０のエステル基、炭素数１～３０のアシルオキシ基、炭素数１～３０のアルコキシ基、炭素数６～３０のアリールオキシ基、シアノ基、炭素数１～３０の炭化水素基で置換されていても良いアミノ基、炭素数１～３０の炭化水素基で置換されていても良いアミド基、炭素数１～３０の炭化水素基で置換されていても良いイミノ基、又は、酸素原子、硫黄原子、窒素原子及びリン原子からなる群より選ばれる少なくとも１種を含む官能基で置換されていても良い炭素数１～３０の炭化水素基であり、Ｒ^１１～Ｒ^１４の少なくとも一つは、酸素原子及び窒素原子の少なくとも１種を含む基である。Ｒ^１１及びＲ^１２、並びに、Ｒ^１３及びＲ^１４は、各々一体化して２価の有機基を形成してもよく、Ｒ^１１又はＲ^１２と、Ｒ^１３又はＲ^１４とは、互いに環を形成していてもよい。）

(In general formula (2), R ³ to R ¹⁰ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. n represents 0 or a positive integer, When n is 2 or more, R ⁷ to R ¹⁰ may be the same or different in each repeating unit. R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, a carbon number Substituted with an ester group having 1 to 30 carbon atoms, an acyloxy 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, or a hydrocarbon group having 1 to 30 carbon atoms. 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 imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, or an oxygen atom, A hydrocarbon group having 1 to 30 carbon atoms that may be substituted with a functional group containing at least one selected from the group consisting of sulfur atom, nitrogen atom, and phosphorus atom, and at least one of R ¹¹ to R ¹⁴ is , is a group containing at least one of an oxygen atom and a nitrogen atom. R ¹¹ and R ¹² and R ¹³ and R ¹⁴ may each be combined to form a divalent organic group, and R ¹¹ or R ¹² and R ¹³ or R ¹⁴ may mutually form a ring.)

（一般式（３）中、ＸとＹは、それぞれ独立して、ハロゲン原子、炭素数１～３０のエステル基、炭素数１～３０のアシルオキシ基、炭素数１～３０のアルコキシ基、炭素数６～３０のアリールオキシ基、炭素数１～３０のアルキルチオ基、シアノ基、炭素数１～３０の炭化水素基で置換されていても良いアミノ基、炭素数１～３０の炭化水素基で置換されていても良いアミド基、炭素数１～３０の炭化水素基で置換されていても良いイミノ基、又は、酸素原子、硫黄原子、窒素原子及びリン原子からなる群より選ばれる少なくとも１種を含む官能基で置換されていても良い炭素数１～３０の炭化水素基であり、ＸとＹの少なくとも一つは酸素原子及び窒素原子の少なくとも１種を含む基である。ＸとＹは環を形成してよく、その場合に形成される環は５～７員環である。）

(In general formula (3), X and Y each independently represent a halogen atom, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Substituted with an aryloxy group having 6 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, a cyano group, an amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms an amide group which may be substituted with an amide group, an imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, or at least one member selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom. It is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a functional group, and at least one of X and Y is a group containing at least one of an oxygen atom and a nitrogen atom. may be formed, in which case the ring formed is a 5- to 7-membered ring.)

In the polar group-containing olefin copolymer of the present disclosure, containing 20 mol% or more of the terminal of the structural unit (C) with respect to the total 100 mol% of the terminal structural units further chemically converts the terminal of the polymer. This is preferable from the viewpoint of conversion efficiency.

In the polar group-containing olefin copolymer of the present disclosure, containing the structural unit (C) in an amount of 0.001 mol% or more and 5 mol% or less with respect to 100 mol% of the entire structural unit is a terminus of the terminal derived from the structural unit (C). This is preferable from the viewpoint of keeping the ratio high.

In the polar group-containing olefin copolymer of the present disclosure, it is preferable that 50 mol% or more of the structural unit (C) be located at the terminal from the viewpoint of conversion efficiency when further chemically converting the terminal of this polymer. .

In the polar group-containing olefin copolymer of the present disclosure, the mol fraction [A] of the structural unit (A) and the mol fraction [B] of the structural unit (B) are such that [A]≧{([A ]+[B])×80%} is preferably satisfied in order for the copolymer to maintain the properties as an olefin, such as hydrophobicity.

In the polar group-containing olefin copolymer of the present disclosure, in the general formula (3), X and Y are each independently substituted with an ester group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms. An amino group, a cyano group, an alkoxy group having 1 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms, which may be substituted, is preferable from the viewpoint of copolymer production efficiency and chain transfer efficiency. .

In the polar group-containing olefin copolymer of the present disclosure, the polar group-containing carbene monomer represented by the general formula (3) is at least one selected from monomers represented by the following general formulas (100) to (103). A carbene monomer derived from one type is preferable from the viewpoint of ease of handling.

（一般式（１００）～一般式（１０３）中、ＸおよびＹは前記一般式（３）と同義であり、Ｌはハロゲン原子を示す。）

(In general formulas (100) to (103), X and Y have the same meanings as in general formula (3) above, and L represents a halogen atom.)

In the polar group-containing olefin copolymer of the present disclosure, in the general formulas (100) to (103), X and Y each independently represent an ester group having 1 to 30 carbon atoms, an ester group having 1 to 30 carbon atoms, The amino group, cyano group, alkoxy group having 1 to 30 carbon atoms, or aryloxy group having 6 to 30 carbon atoms, which may be substituted with a hydrocarbon group, improves copolymer production efficiency and chain transfer. Preferable from the point of view of efficiency.

In the polar group-containing olefin copolymer of the present disclosure, the polar group-containing carbene monomer represented by the general formula (3) is dimethyl 2- diazomalonate , diethyl 2- diazomalonate , 2- diazomalonate , Dipropyl malonate, dibutyl 2- diazomalonate , methyl 2 - diazocyanoacetate , ethyl 2-diazocyanoacetate, propyl 2- diazocyanoacetate , butyl 2- diazocyanoacetate , and 2- diazomalononitrile A carbene monomer derived from at least one selected from the group consisting of is preferred from the viewpoint of ease of availability and ease of handling.

In the polar group-containing olefin copolymer of the present disclosure, in the general formula (1), R ¹ is a hydrogen atom, which improves the production efficiency of the copolymer, the molecular weight of the copolymer, and the monomer (A). It is also preferable from the viewpoint of copolymerizability with the monomer (C).

In the polar group-containing olefin copolymer of the present disclosure, in the general formula (1), R ¹ is a hydrogen atom, and R ² is an ester group having 1 to 30 carbon atoms, a cyano group, a cyanomethyl group, a cyanoethyl group , An acyloxymethyl group or an acyloxyethyl group is preferable from the viewpoint of production efficiency of the copolymer, molecular weight of the copolymer, and copolymerizability with the monomer (A) and the monomer (C).

In the polar group-containing olefin copolymer of the present disclosure, the polar group-containing olefin monomer (b-1) represented by the general formula (1) is methyl acrylate, ethyl acrylate, propyl acrylate, or butyl acrylate. , vinyl acetate, allyl acetate, 3-butenyl acetate, acrylonitrile, and 3-cyanopropene. It is preferable from the viewpoint of copolymerizability with A) and the monomer (C).

In the polar group-containing olefin copolymer of the present disclosure, in the general formula (2), n is 0 or 1, and R ³ to R ¹⁰ are each independently a hydrogen atom or a methyl group. It is preferable from the viewpoint of polymer production efficiency, molecular weight of the copolymer, and copolymerizability with the monomer (A) and the monomer (C).

In the polar group-containing olefin copolymer of the present disclosure, the polar group-containing olefin monomer (b-2) represented by the general formula (2) is methyl 5-norbornene-2-carboxylate, 5-norbornene-2 - ethyl carboxylate, propyl 5-norbornene-2-carboxylate, butyl 5-norbornene-2-carboxylate, dimethyl 5-norbornene-2,3-dicarboxylate, 5-norbornene-2,3-dicarboxylic anhydride, 2-Hydroxy-5-norbornene, 5-norbornene-2-methanol, 5-norbornene-2-methylamine, 2-acetoxy-5-norbornene, 2-cyanomethyl-5-norbornene, and 5-norbornene-2-carbonitrile At least one selected from the group consisting of is preferable from the viewpoint of copolymer production efficiency, copolymer molecular weight, and copolymerizability with the monomer (A) and the monomer (C).

The polar group-containing olefin copolymer composition of the present disclosure contains at least one transition metal selected from the group consisting of nickel, palladium, and platinum, and the polar group-containing olefin copolymer of the present disclosure.

According to the present disclosure, it is possible to provide a novel polar group-containing olefin copolymer in which a specific polar group is selectively introduced at the end.

FIG. 1 shows the results of ¹ H-NMR measurement of polar group-containing olefin copolymer 5 of Example 5.

1. Polar Group-Containing Olefin Copolymer Hereinafter, the polar group-containing olefin copolymer of the present disclosure will be described in detail for each item. In addition, in this specification, "(meth)acrylic acid" indicates each of acrylic acid and methacrylic acid, and "(meth)acryloyl" indicates each of acryloyl and methacryloyl. Furthermore, in this specification, "~" indicating a numerical range is used to include the numerical values written before and after it as a lower limit value and an upper limit value.

The polar group-containing olefin copolymer of the present disclosure includes a structural unit (A) derived from one or more monomers selected from ethylene and olefins having 3 to 20 carbon atoms;
One or more monomers selected from the polar group-containing olefin monomer (b-1) represented by the following general formula (1) and the polar group-containing olefin monomer (b-2) represented by the following general formula (2). The derived structural unit (B) and
It is characterized by containing a structural unit (C) derived from one or more monomers selected from polar group-containing carbene monomers represented by the following general formula (3).
In the polar group-containing olefin copolymer of the present disclosure, the structural unit (A) and the structural unit (B) further include one or more monomers selected from polar group-containing carbene monomers represented by the following general formula (3). It is a novel multi-component polar group-containing olefin copolymer having a structural unit (C) derived from
In the polar group-containing olefin copolymer of the present disclosure, the structural unit (C) derived from one or more monomers selected from the polar group-containing carbene monomers is likely to be selectively introduced into the terminal of the polyolefin. Specifically, the structural unit (C) located at the terminal is preferably 50 mol% or more, more preferably 65 mol% or more, and even more preferably It is possible to obtain an olefin polymer containing a polar group of 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, 95 mol% or more, or 99 mol% or more. Furthermore, with respect to a total of 100 mol% of the structural units (C) contained in the polymer, the structural unit (C) located at the polymerization termination terminal is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably An olefin polymer containing polar groups of 70 mol % or more, more preferably 80 mol % or more can be obtained.
Moreover, since the structural unit (C) is likely to be selectively introduced into the terminal end of the polyolefin, a high proportion of the specific polar group that the structural unit (C) has is likely to be introduced into the terminal end of the polyolefin. Specifically, a polar group-containing olefin copolymer containing 20 mol% or more, further 30 mol% or more of the terminal of the structural unit (C) with respect to a total of 100 mol% of the structural units at the ends (both ends) of the polymer, It is possible to obtain a polar group-containing olefin copolymer containing 50 mol % or more of the terminal of the structural unit (C) with respect to a total of 100 mol % of the structural unit of the polymerization termination terminal (one terminal of the polymer).

The polar group-containing carbene monomer used in the production of the polar group-containing olefin copolymer of the present disclosure has two substituents on the carbene carbon, and at least one of the two substituents contains a disubstituted polar group. It's carbene. When such a disubstituted carbene is inserted into a polymer (polymer chain) by coordinating (polymerization reaction) with the transition metal of a catalyst containing a transition metal during polymerization, steric hindrance caused by the quaternary carbon of the disubstituted carbene occurs. Therefore, it is thought that the next monomer coordination becomes difficult to occur, and chain transfer (β-hydrogen elimination, etc.) occurs faster than the next monomer coordination. Due to such a mechanism, the polar group-containing carbene monomer of the disubstituted carbene used in the present disclosure is thought to function as a chain transfer agent and also as a terminal modifying agent.
The polar group-containing carbene monomer used in the present disclosure is characterized in that it undergoes a 1,1-addition reaction. In the case of such a 1,1-addition reaction, compared to the case of the 1,2-addition reaction of 2-vinylfuran as described in Non-Patent Document 2, the compound has a functional group that causes greater steric hindrance. It is believed that the coordination and insertion reactions of the monomer proceed, while the coordination and insertion reactions of the next monomer are suppressed. As a result, β-hydrogen elimination occurs after insertion of the carbene monomer, and it is believed that the polar group derived from the carbene monomer can be more reliably introduced to the end (polymerization terminated end) of the olefin copolymer.
According to the present disclosure, a specific polar group is selectively introduced at the end of a polyolefin by performing normal olefin polymerization and reacting the growing end with a disubstituted carbene, which is a chain transfer agent having a desired polar group. Since it can be introduced with higher efficiency than before, it is possible to efficiently produce an olefin copolymer containing a terminal polar group.

The polar group-containing carbene monomer used in the present disclosure is a disubstituted carbene that has two substituents on the carbene carbon and at least one of the two substituents contains a polar group. In this case, two polar groups can be introduced at the same time at the terminal. That is, in the polar group-containing olefin copolymer of the present disclosure, the terminal polar group-containing olefin copolymer has -C(X)(Y) (here, X and Y are synonymous with the general formula (3) described later) at the terminal. Polymers can be obtained.

Furthermore, the terminal furan ring in Non-Patent Document 2 of the prior art is considered to have extremely poor chemical reactivity and therefore is unlikely to become a starting point for inducing other functional groups. On the other hand, the polar group-containing olefin copolymer of the present disclosure can appropriately select and introduce a polar group suitable for improving processing, molding, painting, etc. properties, which were conventionally considered weak points of polyolefins. It is expected to be applied in many fields, such as expanding the range and/or production route of polyolefin compounds and as a raw material for diblock polymers.

(1) Structural unit (A)
The structural unit (A) is a structural unit derived from one or more monomers (A) selected from ethylene and olefins having 3 to 20 carbon atoms.
The monomer (A) used in the present disclosure is at least one selected from ethylene and olefins having 3 to 20 carbon atoms. The olefin having 3 to 20 carbon atoms may be a chain olefin or a cyclic olefin, and includes at least one selected from α-olefins having 3 to 20 carbon atoms and cyclic olefins having 4 to 20 carbon atoms. It will be done.
The α-olefin having 3 to 20 carbon atoms used in the present disclosure is an α-olefin having 3 to 20 carbon atoms represented by the structural formula: CH ₂ =CHR ¹⁸ (R ¹⁸ is a hydrocarbon group having 1 to 18 carbon atoms). and may have a linear structure or a branched structure), and more preferably an α-olefin having 3 to 12 carbon atoms.
Examples of the cyclic olefin having 4 to 20 carbon atoms include cyclobutene, cyclopentene, cyclohexene, and norbornene.
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, and norbornene. From the viewpoint of polymer production efficiency, the monomer (A) is preferably one or more selected from the group consisting of ethylene, propylene, 1-butene, and norbornene, and more preferably ethylene. is preferred.
Further, the structural unit (A) may be used alone or in combination of two or more types.

The two combinations include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, propylene-1-octene, and ethylene-norbornene. Examples include structural units derived from.
The three combinations include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene. Examples include structural units.

In the present disclosure, the monomer (A) used in the structural unit (A) preferably essentially contains ethylene, and may further contain one or more α-olefins having 3 to 20 carbon atoms as necessary. good.
Ethylene in the monomer (A) may be 65 to 100 mol%, or 70 to 100 mol%, based on 100 mol% of the entire monomer (A).

(2) Structural unit (B)
The structural unit (B) is composed of a polar group-containing olefin monomer (b-1) represented by the following general formula (1) and a polar group-containing olefin monomer (b-2) represented by the following general formula (2). It is a structural unit derived from one or more selected monomers (B).

（一般式（１）中、Ｒ^１とＲ^２は、それぞれ独立して、水素原子、炭素数１～３０のエステル基、炭素数１～３０のアシルオキシ基、炭素数１～３０のアルコキシ基、炭素数６～３０のアリールオキシ基、シアノ基、炭素数１～３０の炭化水素基で置換されていても良いアミノ基、炭素数１～３０の炭化水素基で置換されていても良いアミド基、炭素数１～３０の炭化水素基で置換されていても良いイミノ基、炭素数１～３０のハロゲン置換炭化水素基、又は、酸素原子、硫黄原子、窒素原子及びリン原子からなる群より選ばれる少なくとも１種を含む官能基で置換されていても良い炭素数１～３０の炭化水素基であり、Ｒ^１とＲ^２の少なくとも一つは、酸素原子及び窒素原子の少なくとも１種を含む基である。）

(In general formula (1), R ¹ and R ² are each independently a hydrogen atom, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Aryloxy group having 6 to 30 carbon atoms, cyano group, amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, amide group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms , an imino group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 30 carbon atoms, or an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a functional group containing at least one kind of functional group, and at least one of R ¹ and R ² is a group containing at least one kind of an oxygen atom and a nitrogen atom. )

（一般式（２）中、Ｒ^３～Ｒ^１０は、それぞれ独立して、水素原子、ハロゲン原子、又は、炭素数１～２０の炭化水素基である。ｎは０又は正の整数を示し、ｎが２以上の場合には、Ｒ^７～Ｒ^１０は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。Ｒ^１１～Ｒ^１４は、それぞれ独立して、水素原子、炭素数１～３０のエステル基、炭素数１～３０のアシルオキシ基、炭素数１～３０のアルコキシ基、炭素数６～３０のアリールオキシ基、シアノ基、炭素数１～３０の炭化水素基で置換されていても良いアミノ基、炭素数１～３０の炭化水素基で置換されていても良いアミド基、炭素数１～３０の炭化水素基で置換されていても良いイミノ基、又は、酸素原子、硫黄原子、窒素原子及びリン原子からなる群より選ばれる少なくとも１種を含む官能基で置換されていても良い炭素数１～３０の炭化水素基であり、Ｒ^１１～Ｒ^１４の少なくとも一つは、酸素原子及び窒素原子の少なくとも１種を含む基である。Ｒ^１１及びＲ^１２、並びに、Ｒ^１３及びＲ^１４は、各々一体化して２価の有機基を形成してもよく、Ｒ^１１又はＲ^１２と、Ｒ^１３又はＲ^１４とは、互いに環を形成していてもよい。）

(In general formula (2), R ³ to R ¹⁰ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. n represents 0 or a positive integer, When n is 2 or more, R ⁷ to R ¹⁰ may be the same or different in each repeating unit. R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, a carbon number Substituted with an ester group having 1 to 30 carbon atoms, an acyloxy 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, or a hydrocarbon group having 1 to 30 carbon atoms. 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 imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, or an oxygen atom, A hydrocarbon group having 1 to 30 carbon atoms that may be substituted with a functional group containing at least one selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom, and at least one of R ¹¹ to R ¹⁴ is , is a group containing at least one of an oxygen atom and a nitrogen atom.R ¹¹ and R ¹² and R ¹³ and R ¹⁴ may each be combined to form a divalent organic group, and R ¹¹ or R ¹² and R ¹³ or R ¹⁴ may mutually form a ring.)

(2-1) Polar group-containing olefin monomer (b-1)
In the general formula (1), the ester group having 1 to 30 carbon atoms is a monovalent group 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, and refers to the number of carbon atoms in the above ^Ra , and the lower limit may be 1 or more, it may be 2 or more, and the upper limit is 30 or less. The number may be 20 or less, or 10 or less.
Examples of the hydrocarbon group having 1 to 30 carbon atoms in R ^a include linear, branched, cyclic saturated or unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. In addition to the following examples of alkyl groups having 1 to 30 carbon atoms, alkenyl groups such as ethenyl group, propenyl group, butenyl group, pentenyl group, phenyl group, methylphenyl group, n-propylphenyl group, i-propylphenyl group, n -butylphenyl group, i-butylphenyl group, s-butylphenyl group, t-butylphenyl group, n-hexylphenyl group, trimethylphenyl group, pentamethylphenyl group, biphenyl group, naphthyl group, anthracenyl group, fluorenyl group, Preferred examples include tolyl group and benzyl group.
Further, the alkyl group having 1 to 30 carbon atoms may be linear, branched, or cyclic, and may be a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, tricyclohexylmethyl group, isopropyl group, 1-dimethylpropyl group, 1,1,2- Trimethylpropyl group, 1,1-diethylpropyl group, isobutyl group, 1,1-dimethylbutyl group, 2-pentyl group, 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, Preferred examples include a cycloheptyl group, a cyclooctyl group, a cyclododecyl group, a 1-adamantyl group, a 2-adamantyl group, a norbornyl group, and the like.
The hydrocarbon group may further have a substituent, and examples of the substituent include a halogen atom, an epoxy group, an amino group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms, Examples include an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and a hydroxyl group. Note that the number of carbon atoms included in the substituent is not included in the number of carbon atoms mentioned above.
The hydrocarbon group in R ^a is preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and an unsubstituted hydrocarbon group having 1 to 6 carbon atoms. A hydrocarbon group is even more preferred.
Specific examples of ester groups having 1 to 30 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, and cyclohexyloxycarbonyl group. Preferred examples include 2-ethylhexyloxycarbonyl group, benzyloxycarbonyl group, and phenoxycarbonyl group.

In the general formula (1), the acyloxy group having 1 to 30 carbon atoms is a monovalent group 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, and refers to the number of carbon atoms in the above R ^b , and the lower limit may be 1 or more, it may be 2 or more, and the upper limit is 30 or less. The number may be 20 or less, or 10 or less.
Examples of the hydrocarbon group having 1 to 30 carbon atoms include those mentioned above for R ^a .
Preferred examples of the acyloxy group having 1 to 30 carbon atoms include acetyloxy group, propionyloxy group, (meth)acryloyloxy group, and benzoyloxy group.

In the general formula (1), the alkoxy group having 1 to 30 carbon atoms is a monovalent group represented by -OR ^c , where R ^c represents an alkyl group having 1 to 30 carbon atoms. The number of carbon atoms in the alkoxy group may have a lower limit of 1 or more, or 2 or more, and an upper limit of 30 or less, 20 or less, or 10 or less. good.
Examples of the alkyl group having 1 to 30 carbon atoms in R ^c include the same ones as in R ^a above.
Specific examples of the alkoxy group having 1 to 30 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, and t-butoxy group. Preferred examples include n-pentoxy group, n-hexoxy group, cyclopropoxy group, cyclopentoxy group, cyclohexyloxy group, n-octoxy group, n-detoxy group and the like.
Furthermore, the aryloxy group having 6 to 30 carbon atoms is a monovalent group represented by -OR ^c' , where R ^c' represents an aryl group having 6 to 30 carbon atoms. The number of carbon atoms in the aryl group may have a lower limit of 6 or more, and may be 8 or more, and an upper limit of 30 or less, 20 or less, or 12 or less. good.
Examples of the aryl group having 6 to 30 carbon atoms in R ^c' include those corresponding to the aryl group having 6 to 30 carbon atoms among the above R ^a .
Specific examples of the aryloxy group having 6 to 30 carbon atoms include phenoxy group, methylphenoxy group, ethylphenoxy group, butylphenoxy group, naphthyloxy group, fluorenyloxy group, anthracenyloxy group, etc. be able to.

In general formula (1), the amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms is a monovalent group represented by -NR ^d R ^e , where R ^d and R ^e are Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The lower limit of the carbon number of the hydrocarbon group substituted with the substituted amino group may be 1 or more, and may be 2 or more, and the upper limit may be 30 or less, and may be 20 or less. It may be 10 or less.
The hydrocarbon group having 1 to 30 carbon atoms in R ^d and R ^e can be the same as those mentioned in R ^a above.
Specific examples of the amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms include, for example, an amino group (-NH ₂ ), a monomethylamino group, a dimethylamino group, a monoethylamino group, a diethylamino group, Preferred examples include a monoisopropylamino group, a diisopropylamino group, a monophenylamino group, and a diphenylamino group.

In the general formula (1), the amide group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms is a monovalent group represented by -CONR ^f R ^g or -NR ^f COR ^g , where R ^f and R ^g each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The lower limit of the carbon number of the hydrocarbon group substituted with the substituted amide group may be 1 or more, and may be 2 or more, and the upper limit may be 30 or less, and may be 20 or less. It may be 10 or less.
The hydrocarbon group having 1 to 30 carbon atoms in R ^f and R ^g can be the same as those mentioned in R ^a above.
Specific examples of the amide group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms include -CONH ₂ , -CONH(CH ₃ ), -CON(CH ₃ ) ₂ , -CONH(C ₂ H ₅ ), -CON(C ₂ H ₅ ) ₂ , -CONH(i-C ₃ H ₇ ), -CON(i-C ₃ H ₇ ) ₂ , -CONH(Ph), -CON(Ph) ₂ , -NHCOCH ₃ , -NHCOC ₂ H ₅ and the like can be preferably mentioned. In addition, in this specification, Ph represents a phenyl group.

In the general formula (1), the imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms is a monovalent group represented by -N=CR ^h R ⁱ , where R ^h and R Each ⁱ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The lower limit of the carbon number of the hydrocarbon group substituted with the substituted imino group may be 1 or more, and may be 2 or more, and the upper limit may be 30 or less, and may be 20 or less. It may be 10 or less.
The hydrocarbon group having 1 to 30 carbon atoms in R ^h and R ⁱ can be the same as those mentioned in R ^a above.
Specific examples of the imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms include -N=CH(CH ₃ ), -N=CHC ₂ H ₅ and the like. .

In the general formula (1), the halogen-substituted hydrocarbon group having 1 to 30 carbon atoms is a hydrocarbon group having 1 to 30 carbon atoms in which at least one hydrogen atom is substituted with a halogen. Examples of the hydrocarbon group having 1 to 30 carbon atoms include those mentioned above for R ^a . Examples of halogen include fluorine atom, chlorine atom, bromine atom, and 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, and may be 2 or more, and the upper limit may be 30 or less, and may be 20 or less. It may be 10 or less.
Specific examples of the halogen-substituted hydrocarbon group having 1 to 30 carbon atoms include, for example, a halomethyl group in which 1 to 3 of the hydrogen atoms of the methyl group are substituted with halogen atoms, a γ-chloropropyl group, and a 3,3' , 3''-trifluoropropyl group, perfluorophenyl group, dichlorophenyl group, etc., and examples of the halomethyl group include chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, trifluoromethyl group, etc. .

In general formula (1), the number of carbon atoms in the hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a functional group containing at least one kind selected from the group consisting of oxygen atom, sulfur atom, nitrogen atom and phosphorus atom. Examples of the 1-30 hydrocarbon group include the same ones as R ^a above.
Examples of the functional group containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom include a hydroxyl group, an epoxy group, an ester group having 1 to 30 carbon atoms, and an acyloxy group having 1 to 30 carbon atoms. group, alkoxy group having 1 to 30 carbon atoms, aryloxy group having 6 to 30 carbon atoms, cyano group, amino group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms, carbonized group having 1 to 30 carbon atoms Amide group which may be substituted with a hydrogen group, imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, alkylthio group, thioester group having 1 to 30 carbon atoms, sulfonyl having 1 to 30 carbon atoms group, a sulfoxide group having 1 to 30 carbon atoms, a sulfonic acid ester group having 1 to 30 carbon atoms, a phosphite group having 1 to 30 carbon atoms, a phosphate group having 1 to 30 carbon atoms, a phosphorus ylide group having 1 to 30 carbon atoms, etc. can be mentioned.

Ester group having 1 to 30 carbon atoms, acyloxy group having 1 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, aryloxy group having 6 to 30 carbon atoms, cyano group, hydrocarbon group having 1 to 30 carbon atoms Regarding the amino group which may be substituted, the amide group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, and the imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, the above-mentioned It may be the same as.

The alkylthio group having 1 to 30 carbon atoms is a monovalent group represented by -SR ^s , where R ^s represents an alkyl group having 1 to 30 carbon atoms. The number of carbon atoms in the alkylthio group may have a lower limit of 1 or more, or 2 or more, and an upper limit of 30 or less, 20 or less, or 10 or less. good.
The alkyl group having 1 to 30 carbon atoms in R ^s can be the same as those mentioned in R ^a above.
Preferred examples of the alkylthio group having 1 to 30 carbon atoms include methylthio group and ethylthio group.

The thioester group having 1 to 30 carbon atoms is a monovalent group represented by -C(=S)OR ^j or -C(=O)SR ^k , where R ^j and R ^k each have 1 carbon number. Shows ~30 hydrocarbon groups. The number of carbon atoms in the thioester group does not include the number of carbon atoms in the thiocarbonyl group or carbonyl group, and refers to the number of carbon atoms in the above R ^j or R ^k , and the lower limit may be 1 or more, and may be 2 or more. The upper limit value may be 30 or less, may be 20 or less, or may be 10 or less.
The hydrocarbon group having 1 to 30 carbon atoms in R ^j and R ^k can be the same as those mentioned in R ^a above.
Specific examples of thioester groups having 1 to 30 carbon atoms include -C(=S)OCH ₃ , -C(=O)SCH ₃ , -C(=S)OPh, -C(=O)SPh, etc. can be mentioned suitably.

The sulfonyl group having 1 to 30 carbon atoms is a monovalent group represented by -SO ₂ R ¹ , where R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms. The number of carbon atoms in the sulfonyl group may have a lower limit of 1 or more, or 2 or more, and an upper limit of 30 or less, 20 or less, or 10 or less. good.
The hydrocarbon group having 1 to 30 carbon atoms in R ¹ can be the same as those mentioned in R ^a above.
Specific examples of the sulfonyl group having 1 to 30 carbon atoms include -SO ₂ CH ₃ and -SO ₂ Ph.

The sulfoxide group having 1 to 30 carbon atoms is a monovalent group represented by -SOR ^m , where R ^m represents a hydrocarbon group having 1 to 30 carbon atoms. The number of carbon atoms in the sulfoxide group may have a lower limit of 1 or more, or 2 or more, and an upper limit of 30 or less, 20 or less, or 10 or less. good.
The hydrocarbon group having 1 to 30 carbon atoms in R ^m can be the same as those mentioned in R ^a above.
Preferred examples of the sulfoxide group having 1 to 30 carbon atoms include -SOCH ₃ and -SOPh.

The sulfonic acid ester group having 1 to 30 carbon atoms is a monovalent group represented by -OSO ₂ R ⁿ , where R ⁿ represents a hydrocarbon group having 1 to 30 carbon atoms. The lower limit of the number of carbon atoms in the sulfonic acid ester group may be 1 or more, or 2 or more, and the upper limit may be 30 or less, 20 or less, or 10 or less. It's okay.
The hydrocarbon group having 1 to 30 carbon atoms in R ⁿ can be the same as those mentioned in R ^a above.
Specific examples of the sulfonic acid ester group having 1 to 30 carbon atoms include -SO ₃ CH ₃ and -SO ₃ Ph.

The phosphite group having 1 to 30 carbon atoms is a monovalent group represented by -P(OR ^o ) ₂ , where R ^o each independently represents a hydrocarbon group having 1 to 30 carbon atoms. The lower limit of the number of carbon atoms in the phosphite group may be 1 or more, or 2 or more, and the upper limit may be 30 or less, 20 or less, or 10 or less. Good too.
The hydrocarbon group having 1 to 30 carbon atoms in R ^o can be the same as those mentioned in R ^a above.
Preferred examples of the phosphite group having 1 to 30 carbon atoms include -P(OPh) ₂ and -P(OCH ₃ ) ₂ .

The phosphate group having 1 to 30 carbon atoms is a monovalent group represented by -P(=O)(OR ^p ) ₂ , where R ^p is each independently a hydrocarbon group having 1 to 30 carbon atoms. shows. The lower limit of the number of carbon atoms in the phosphate group may be 1 or more, or 2 or more, and the upper limit may be 30 or less, 20 or less, or 10 or less. good.
The hydrocarbon group having 1 to 30 carbon atoms in R ^o can be the same as those mentioned in R ^a above.
Specific examples of the phosphate group having 1 to 30 carbon atoms include -P(=O)(OPh) ₂ and -P(=O)(OCH ₃ ) ₂ , for example.

The phosphorus ylide group having 1 to 30 carbon atoms is a monovalent group represented by -P=CR ^q R ^r , where R ^q and R ^r each independently represent a hydrogen atom or a phosphorus ylide group having 1 to 30 carbon atoms. Indicates a hydrocarbon group, at least one of which is the hydrocarbon group. The number of carbon atoms in the hydrocarbon group substituted with the phosphorus ylide group does not include the number of carbon atoms in P=C, but refers to the number of carbon atoms in R ^q or R ^r , and the lower limit may be 1 or more, and 2 or more. The upper limit value may be 30 or less, may be 20 or less, or may be 10 or less.
The hydrocarbon group having 1 to 30 carbon atoms in R ^o can be the same as those mentioned in R ^a above.
Specific examples of the phosphorus ylide group having 1 to 30 carbon atoms include -P=CHCH ₃ , -P=CHPh, -P=CHCH ₂ Ph, and the like.

At least one of R ¹ and R ² is a group containing at least one of an oxygen atom and a nitrogen atom. Examples of the group containing at least one of an oxygen atom and a nitrogen atom include an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and a 6 to 30 carbon atom group. An aryloxy group, a cyano 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, and a cyano group having 1 to 30 carbon atoms. Examples include an imino group which may be substituted with 30 hydrocarbon groups, and a hydrocarbon group having 1 to 30 carbon atoms which is substituted with a substituent containing at least one of an oxygen atom and a nitrogen atom. The substituents containing at least one of an oxygen atom and a nitrogen atom of the hydrocarbon group having 1 to 30 carbon atoms include a hydroxyl group, an epoxy group, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, Alkoxy group having 1 to 30 carbon atoms, aryloxy group having 6 to 30 carbon atoms, cyano group, amino group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms, 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 imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, a thioester group having 1 to 30 carbon atoms, a sulfonyl group having 1 to 30 carbon atoms, and a sulfonyl group having 1 to 30 carbon atoms. -30 sulfoxide groups, sulfonic acid ester groups having 1 to 30 carbon atoms, phosphite groups having 1 to 30 carbon atoms, and phosphate groups having 1 to 30 carbon atoms.

As the polar group-containing olefin monomer (b-1) represented by the general formula (1), for example, (meth)acrylic acid ester is suitably used.
Specific examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. , isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate hydroxyethyl acid, hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, polyethylene glycol (meth)acrylate ester, (meth)acrylic acid Dimethylaminoethyl, diethylaminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, (meth)acrylic acid Glycidyl, trifluoromethyl (meth)acrylate, -2-trifluoromethylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, 4-(1,2,2,6,6-pentamethylpiperidyl) Examples include acrylate.
Further, as the polar group-containing olefin monomer (b-1) represented by the general formula (1), (meth)acrylamide, (meth)acrylonitrile, vinylamide, vinyl acetate, allyl acetate, 3-butenyl acetate, 3- Cyanopropene, methyl vinyl ether, 3-chloropropene, N-propylideneethenamine, 3-(methylthio)-1-propene, 3-(methylsulfinyl)-1-propene, 3-(methylsulfonyl)-1-propene, Examples include methyl 2-propene-1-sulfonate and dimethyl 2-propenylphosphonate.

In the general formula (1), when R ¹ is a hydrogen atom, from the viewpoint of production efficiency of the polymer, molecular weight of the polymer, and copolymerizability with the monomer (A) and the monomer (C). preferable.
Further, in the general formula (1), R ¹ is a hydrogen atom, and R ² is an ester group having 1 to 30 carbon atoms, a cyano group, a cyanomethyl group, a cyanoethyl group , an acyloxymethyl group, or an acyloxyethyl group. , is preferable from the viewpoint of production efficiency of the polymer, molecular weight of the polymer, and copolymerizability with the monomer (A) and the monomer (C).

The polar group-containing olefin monomer (b-1) represented by the general formula (1) has, among others, a high weight ratio of heteroatoms, a small side effect on later transition metal catalysts, and a high polymer content. From the viewpoint of production efficiency, molecular weight of the polymer, and copolymerizability with the monomer (A) and the monomer (C), methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, vinyl acetate, acetic acid Preferably, it is at least one selected from the group consisting of allyl, 3-butenyl acetate, acrylonitrile, and 3-cyanopropene.

(2-2) Polar group-containing olefin monomer (b-2)
In the general formula (2), examples of the halogen atoms in R ³ to R ¹⁰ include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group having 1 to 20 carbon atoms in R ³ to R ¹⁰ include the same hydrocarbon groups having 1 to 20 carbon atoms among the above R ^b in general formula (1). Among them, alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group and propenyl group, and the like.
n represents 0 or a positive integer, preferably 2 or less, and preferably 1 or less.

In general formula (2), in R ¹¹ to R ¹⁴ , an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a cyano group, and a cyano group having 1 to 30 carbon atoms. Amino group optionally substituted with a hydrocarbon group, amide group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms, imino group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms , or a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a functional group containing at least one member selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom, each having the general formula ( It may be the same as that explained for R ¹ and R ² in 1).

In general formula (2), at least one of R ¹¹ to R ¹⁴ is a group containing at least one of an oxygen atom and a nitrogen atom, but also for a group containing at least one of an oxygen atom and a nitrogen atom, It may be the same as that explained for R ¹ and R ² in general formula (1).

R ¹¹ and R ¹² and R ¹³ and R ¹⁴ may each be combined to form a divalent organic group. Here, the organic group refers to a group containing at least a carbon atom. When they are combined to form a divalent organic group, it is preferably a divalent hydrocarbon group, and the hydrocarbon groups include -CO-, -O(CO)-, -COO- , -C(=O)OC(=O)-, -C(=O)NR ^f C(=O)-, -SO ₂ -, -O-, and other linking groups may be included. Note that R ^f here is the same as above.

R ¹¹ or R ¹² and R ¹³ or R ¹⁴ may each be bonded to each other to form a ring, or may form a carbocycle or a heterocycle, and the carbocycle or heterocycle is It may be monocyclic or polycyclic. For example, R ¹¹ or R ¹² and R ¹³ or R ¹⁴ may each be bonded to each other to form a -CO-O-CO- group.

In the general formula (2), it is preferable that n is 0 or 1 and R ³ to R ¹⁰ are hydrogen atoms or methyl groups from the viewpoint of ease of synthesis of the polar monomer itself.

The polar group-containing olefin monomer (b-2) represented by the general formula (2) has, among others, a low side effect on the later transition metal catalyst, polymer production efficiency, polymer molecular weight, and, From the viewpoint of copolymerizability with the monomer (A) and the monomer (C), methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, propyl 5-norbornene-2-carboxylate, Butyl 5-norbornene-2-carboxylate, dimethyl 5-norbornene-2,3-dicarboxylate, 5-norbornene-2,3-dicarboxylic anhydride, 2-hydroxy-5-norbornene, 5-norbornene-2-methanol , 5-norbornene-2-methylamine, 2-acetoxy-5-norbornene, 2-cyanomethyl-5-norbornene, and 5-norbornene-2-carbonitrile. Furthermore, methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, propyl 5-norbornene-2-carboxylate, butyl 5-norbornene-2-carboxylate, 5-norbornene-2,3- Preferably, it is at least one selected from the group consisting of dicarboxylic acid anhydride and 5-norbornene-2-methanol.

(3) Structural unit (C)
The structural unit (C) is a structural unit derived from one or more monomers (C) selected from polar group-containing carbene monomers represented by the following general formula (3).

（一般式（３）中、ＸとＹは、それぞれ独立して、ハロゲン原子、炭素数１～３０のエステル基、炭素数１～３０のアシルオキシ基、炭素数１～３０のアルコキシ基、炭素数６～３０のアリールオキシ基、炭素数１～３０のアルキルチオ基、シアノ基、炭素数１～３０の炭化水素基で置換されていても良いアミノ基、炭素数１～３０の炭化水素基で置換されていても良いアミド基、炭素数１～３０の炭化水素基で置換されていても良いイミノ基、又は、酸素原子、硫黄原子、窒素原子及びリン原子からなる群より選ばれる少なくとも１種を含む官能基で置換されていても良い炭素数１～３０の炭化水素基であり、ＸとＹの少なくとも一つは酸素原子及び窒素原子の少なくとも１種を含む基である。ＸとＹは環を形成してよく、その場合に形成される環は５～７員環である。）

(In general formula (3), X and Y each independently represent a halogen atom, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Substituted with an aryloxy group having 6 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, a cyano group, an amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms an amide group which may be substituted with an amide group, an imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, or at least one member selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom. It is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a functional group, and at least one of X and Y is a group containing at least one of an oxygen atom and a nitrogen atom. may be formed, in which case the ring formed is a 5- to 7-membered ring.)

In the general formula (3), a halogen atom, an ester group having 1 to 30 carbon atoms, an acyloxy 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 1 to 30 carbon atoms, -30 alkylthio group, cyano group, amino group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms, amide group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms, 1 carbon group ~30 imino groups optionally substituted with hydrocarbon groups, or carbon atoms optionally substituted with functional groups containing at least one selected from the group consisting of oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms The number 1 to 30 hydrocarbon groups may be the same as those explained for R ¹ and R ² in general formula (1), respectively.

X and Y may form a ring, in which case the ring formed is a 5- to 7-membered ring. Preferred examples of such a structure include those shown by the following structures.

In X and Y, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms; An amino group which may be substituted, an amide group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, an imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, or oxygen The number of carbon atoms in the hydrocarbon group having 1 to 30 carbon atoms, which may be substituted with at least one functional group selected from the group consisting of atom, sulfur atom, nitrogen atom, and phosphorus atom, is determined by the production efficiency of the polymer and Among them, the number is preferably 1 to 10, more preferably 1 to 6, because subsequent chemical conversion is easier.

The polar group-containing carbene monomer represented by the general formula (3) is a carbene monomer derived from at least one monomer selected from the monomers represented by the following general formulas (100) to (103). Preferred from the viewpoint of ease of availability and ease of handling, and particularly preferred is a carbene monomer derived from at least one compound selected from the compounds represented by the following general formula (100).

（一般式（１００）～一般式（１０３）中、ＸおよびＹは前記一般式（３）と同義であり、Ｌはハロゲン原子を示す。）

(In general formulas (100) to (103), X and Y have the same meanings as in the above general formula (3), and L represents a halogen atom.)

The halogen atom in L may be the same as that explained for R ¹ and R ² in general formula (1).

In the general formulas (100) to (103), among others, X and Y may be each independently substituted with an ester group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms. When an amino group, a cyano group, an alkoxy group having 1 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms is introduced at the end of the polyolefin, subsequent chemical conversion is easier; In addition, it is preferable from the viewpoint of polymer production efficiency and chain transfer efficiency.
Combinations of X and Y include an ester group having 1 to 30 carbon atoms, a cyano group and an ester group having 1 to 30 carbon atoms, a cyano group, and an ester group having 1 to 30 carbon atoms, and an ester group having 1 to 30 carbon atoms. An amino group which may be substituted with a hydrocarbon group, an ester group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms , a cyano group and an alkoxy group having 1 to 30 carbon atoms, a cyano group and an aryloxy group having 6 to 30 carbon atoms, both an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, etc. In particular, when an ester group with 1 to 30 carbon atoms, a cyano group and an ester group with 1 to 30 carbon atoms, both cyano groups are introduced at the end of a polyolefin, the subsequent Preferable from the viewpoint of chemical conversion efficiency.

Specific examples of the polar group-containing carbene monomer represented by the general formula (3) include dimethyl 2- diazomalonate , diethyl 2- diazomalonate , dipropyl 2- diazomalonate , and 2-diazomalonate. Dibutyl zomalonate, methyl 2 - diazocyanoacetate , ethyl 2- diazocyanoacetate , propyl 2-diazocyanoacetate, butyl 2- diazocyanoacetate , 2- diazomalononitrile , methyl 2- diazopropionate , ethyl 2-diazopropionate, butyl 2- diazopropionate , methyl 2- diazobutanoate , ethyl 2- diazobutanoate , butyl 2- diazobutanoate , dimethyl 2,2-difluoromalonate, Diethyl 2,2-difluorocyanoate, dibutyl 2,2-difluoromalonate, methyl 2,2-difluorocyanoacetate, ethyl 2,2-difluorocyanoacetate, butyl 2,2-difluorocyanoacetate, 2,2-difluoro malononitrile, methyl 2,2-difluoropropionate, ethyl 2,2-difluoropropionate, butyl 2,2-difluoropropionate, methyl 2,2-difluorobutanoate, ethyl 2,2-difluorobutanoate, 2, Examples include carbene monomers derived from butyl 2-difluorobutanoate, tetra(methoxycarbonyl)ethylene, tetra(ethoxycarbonyl)ethylene, tetracyanoethylene, dicyanodi(methoxycarbonyl)ethylene, dicyanodi(ethoxycarbonyl)ethylene, and the like.

Examples of the polar group-containing carbene monomer represented by the general formula (3) include dimethyl 2- diazomalonate , diethyl 2- diazomalonate , dipropyl 2- diazomalonate , and 2- diazomalonate. At least one member selected from the group consisting of dibutyl acid, methyl 2- diazocyanoacetate , ethyl 2- diazocyanoacetate , propyl 2- diazocyanoacetate , butyl 2- diazocyanoacetate , and 2- diazomalononitrile . A carbene monomer derived from is preferred from the viewpoint of ease of availability and ease of handling.

(4) Polar group-containing olefin copolymer The polar group-containing olefin copolymer of the present disclosure has a structural unit (A) derived from one or more monomers (A) selected from ethylene and olefins having 3 to 20 carbon atoms. , a structural unit (B) derived from one or more monomers (B) selected from the specific polar group-containing olefin monomers, and 1 selected from the polar group-containing carbene monomers represented by the general formula (3). It contains a structural unit (C) derived from more than one type of monomer (C).
Monomer (A), monomer (B), and monomer (C) may be used alone or in a mixture of two or more.
That is, the polar group-containing olefin copolymer of the present disclosure contains one or more types of each of the structural unit (A), the structural unit (B), and the structural unit (C), and may contain a total of three or more types of monomer units. is necessary.

In the present disclosure, 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 mol% or more with respect to 100 mol% of the entire structural unit. It is preferably 65.5 mol% or more, more preferably 76 mol% or more, and still more preferably 87 mol% or more. On the other hand, the upper limit is usually 99.989 mol% or less, preferably 99.945 mol% or less, more preferably 99.89 mol% or less, even more preferably 99.45 mol% or less.
The structural unit (B) in the polar group-containing olefin copolymer may be appropriately selected depending on the desired physical properties, but the lower limit is usually 0.01 mol% or more with respect to 100 mol% of the entire structural unit. , preferably 0.05 mol% or more, more preferably 0.1 mol% or more, still more preferably 0.5 mol% or more. On the other hand, the upper limit is usually 35 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less.
The structural unit (C) in the polar group-containing olefin copolymer may be appropriately selected depending on the average molecular weight and desired physical properties, but the lower limit is usually 0.001 mol% with respect to 100 mol% of the entire structural unit. The content is preferably 0.005 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.05 mol% or more. On the other hand, the upper limit is usually 5 mol% or less, preferably 4.5 mol% or less, more preferably 4 mol% or less, even more preferably 3 mol% or less.

Note that a structure derived from one molecule of each of the monomer (A), the monomer (B), and the monomer (C) is defined as one structural unit in the polar group-containing olefin copolymer.
The structural unit amount is the ratio of each structural unit expressed in mol% when the total structural units in the polar group-containing olefin copolymer is 100 mol%.

Examples of the polar group-containing olefin copolymer of the present disclosure include random copolymers, block copolymers, and graft copolymers of structural units (A), (B), and (C). Among these, random copolymers that can contain a large amount of the structural unit (B) may be used.

In the polar group-containing olefin copolymer of the present disclosure, it is preferable that the terminal of the structural unit (C) is contained in an amount of 20 mol% or more, and more than 20 mol%, based on a total of 100 mol% of the structural units at the terminal (both terminals). is more preferable, and more preferably 25 mol% or more, 28 mol% or more, or 30 mol% or more.

Moreover, in the polar group-containing olefin copolymer obtained by the production method of the present disclosure, it is preferable that 50 mol% or more of the structural unit (C) is located at the terminal. Furthermore, it is preferable that 65 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more of the structural unit (C) is located at the terminal.

Further, in the polar group-containing olefin copolymer of the present disclosure, the mol fraction [A] of the structural unit (A) and the mol fraction [B] of the structural unit (B) are such that [A]≧{( [A]+[B])×80%} is preferably satisfied in order for the copolymer to maintain the properties as an olefin, such as hydrophobicity.

Further, in the polar group-containing olefin copolymer of the present disclosure, the total of the terminals derived from the structural unit (C) and the terminals derived from the structural unit (B) is 30 mol% or more with respect to 100 mol% of the entire terminals. It is preferably at least 35 mol%, and even more preferably at least 40 mol%.

Further, in the polar group-containing olefin copolymer of the present disclosure, it is preferable that the unsaturated terminals of the structural unit (C) are contained in an amount of 50 mol% or more, and more than 50 mol%, based on a total of 100 mol% of the unsaturated terminal structural units. More preferably, the content is 55 mol% or more, more preferably 65 mol% or more. The unsaturated terminal is a structure formed when β-hydrogen elimination occurs after monomer insertion and polymerization is terminated, and corresponds to a polymerization terminated terminal. In the present disclosure, it is preferable that a large number of unsaturated terminals derived from the structural unit (C) exist in the unsaturated terminals of the entire polymer. Note that the polymerization initiation terminal is usually a saturated terminal.
The polar group-containing olefin copolymer of the present disclosure preferably contains 50 mol% or more of the polymerization termination terminal of the structural unit (C) with respect to a total of 100 mol% of the structural unit of the polymerization termination terminal (one terminal), It is more preferable to contain it in an amount exceeding 50 mol%, and even more preferably to contain it in an amount of 55 mol% or more, and more preferably 65 mol% or more.

Further, in the polar group-containing olefin copolymer of the present disclosure, the total of the unsaturated terminals derived from the structural unit (C) and the unsaturated terminals derived from the structural unit (B) is 100 mol in total of the structural units of the unsaturated terminals. %, it is preferably 65 mol% or more, and more preferably 70 mol% or more.

The amount of structural units can be controlled by selecting a catalyst, the amounts of monomer (A), monomer (B), and monomer (C) 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, Reducing the olefin pressure and increasing the polymerization temperature are effective. For example, it is required to control these factors to achieve a desired copolymer region.

The amount of structural units in the polar group-containing olefin copolymer in the present disclosure is determined using ¹ H-NMR spectrum and ¹³ C-NMR spectrum. NMR spectra are measured by the following method.
A polar group-containing olefin copolymer is heated and dissolved in 1,1,2,2-tetrachloroethane-d2, and the homogeneous solution is subjected to NMR measurement. ^{The 1} H-NMR spectrum is based on a 5% by mass solution of the polar group-containing olefin copolymer, and the ¹³ C-NMR spectrum is based on a 15% by mass solution of the polar group-containing olefin copolymer.
The NMR measurement is performed at 120° C. using, for example, Ascend 500 manufactured by BRUKER Co., Ltd.
^13C -NMR was measured using chromium (III) acetylacetonate as a relaxing reagent and a reverse gated decoupling method (90° pulse of 9.0 microseconds, spectral width: 31 kHz, relaxation time: 10 seconds, Acquisition time: 10 seconds, FID integration number of 5,000 to 10,000 times), and quantitative analysis is performed.

The weight average molecular weight (Mw) of the polar group-containing olefin copolymer in the present disclosure is usually 1,000 to 2,000,000, preferably 10,000 to 1,500,000, more preferably 20,000 to 1 ,000,000, preferably in the range of 31,000 to 800,000, and more preferably in the range of 35,000 to 800,000. If Mw is less than 1,000, physical properties such as mechanical strength and impact resistance may not be sufficient, and if Mw exceeds 2,000,000, the melt viscosity will be extremely high, making molding difficult. There is.

The number average molecular weight (Mn) of the polar group-containing olefin copolymer in the present disclosure is usually 1,000 to 2,000,000, preferably 5,000 to 1,500,000, more preferably 10,000 to 1 ,000,000, preferably in the range of 10,000 to 800,000, and more preferably in the range of 20,000 to 600,000. If Mn is less than 1,000, physical properties such as mechanical strength and impact resistance may not be sufficient, and if Mn exceeds 2,000,000, the melt viscosity will be extremely high, making molding difficult. There is.

The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) of the polar group-containing olefin copolymer in the present disclosure is usually 1.5 to 4.0, preferably 1.6 to 3. 3, more preferably in the range of 1.7 to 3.0. If Mw/Mn is less than 1.5, various processability including molding may not be sufficient, and if it exceeds 4.0, mechanical properties may be poor.
Further, in the present disclosure, (Mw/Mn) may be expressed as a molecular weight distribution parameter.

The weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure are determined by gel permeation chromatography (GPC).
An example of the GPC measurement method in the present disclosure is as follows.
The number average molecular weight and weight average molecular weight were determined using a high-temperature GPC device manufactured by Tosoh Corporation equipped with a TSKgel GMHHR-H(S)HT column (two 7.8 mm ID x 30 cm in series) manufactured by Tosoh Corporation; It can be calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145 degrees) using polystyrene as a molecular weight standard using HLC-8321GPC/HT.

The melting point (Tm, °C) observed by differential scanning calorimetry (DSC) of the polar group-containing olefin copolymer in the present disclosure is not particularly limited. The melting point is preferably more than 50°C and 140°C or less, more preferably 60°C to 138°C, even more preferably 70°C to 135°C. When this range is satisfied, heat resistance, impact resistance, adhesiveness, etc. will be excellent.
The melting point can be determined, for example, by using "EXSTAR 6000" manufactured by Seiko Electronics Co., Ltd., isothermally at 40°C for 1 minute, increasing the temperature from 40°C to 160°C at 10°C/min, isothermally at 160°C for 10 minutes, and at 10°C/min. It can be determined by lowering the temperature from 160°C to 10°C in minutes, isothermal at 10°C for 5 minutes, and then increasing the temperature from 10°C to 160°C at a rate of 10°C/min.

(5) Method for producing a polar group-containing olefin copolymer (5-1) Catalyst The polar group-containing olefin copolymer in the present disclosure requires the presence of a catalyst containing a transition metal from the viewpoint of making the molecular structure linear. It may be polymerized below.
The transition metal-containing catalyst used in the present disclosure is particularly one that can polymerize the monomer (A) and the monomer (B) using the monomer (C) as a chain transfer agent. Examples include, but are not limited to, transition metal compounds of Groups 5 to 11 having a chelating ligand.
Specific examples of preferred transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom, Examples include copper atoms. Among these, transition metals of Groups 8 to 11 are preferred, and transition metals of Group 10 are more preferred, and examples of the Group 10 transition metals include nickel, palladium, and platinum, and particularly preferred are transition metals of Group 10. are nickel (Ni) and palladium (Pd). These metals may be used alone or in combination.
The chelating ligand has at least two atoms selected from the group consisting of P, N, O, and S, and is bidentate or multidentate. Contains a ligand and is electronically neutral or anionic. Its structure is illustrated in the review by Brookhart et al. (Chem. Rev., 2000, 100, 1169).
Preferably, bidentate anionic P,O ligands include, for example, phosphorus sulfonic acid, phosphocarboxylic acid, phosphophenol, and phosphorus enolate; other bidentate anionic N,O ligands include, for example, salicyl. Examples include aldoiminates and pyridine carboxylic acids, and other examples include diimine ligands, diphenoxide ligands, and diamide ligands.

The transition metal-containing catalyst used in the method for producing a polar group-containing olefin polymer of the present disclosure is characterized by polymer production efficiency, polymer molecular weight, and copolymerization with the monomer (A) and the monomer (C). From the viewpoint of properties, a catalyst containing a later period transition metal selected from Group 8 to Group 10 transition metals is preferable, and a catalyst containing a Group 10 transition metal is particularly preferable, and a catalyst containing a Group 10 transition metal is particularly preferable. It is a catalyst containing a Group 10 transition metal, and preferably has a chelate ligand containing one or more phosphorus atoms as a coordination point to the Group 10 transition metal.

The transition metal-containing catalyst used in the method for producing a polar group-containing olefin copolymer of the present disclosure is selected based on the production efficiency of the polymer, the molecular weight of the polymer, and the coexistence with the monomer (A) and the monomer (C). From the viewpoint of polymerizability, the catalyst is preferably a catalyst containing a Group 10 transition metal, and at least one selected from compounds represented by the following general formula (104).

（一般式（１０４）中、Ｍは第１０族遷移金属を示し、ＱはＡ［－Ｓ（＝Ｏ）_２－Ｏ－］Ｍ、Ａ［－Ｃ（＝Ｏ）－Ｏ－］Ｍ、Ａ［－Ｏ－］Ｍ、又はＡ［－Ｓ－］Ｍの「［ ］」の中に示される２価の基を示す（ただし、両側のＡ、Ｍは基の結合方向を示すために記載している）。Ａは、Ｑとリン原子を連結する炭素数１～３０の２価の炭化水素基で官能基を有していてもよく、Ｌは金属から脱離可能な０価の配位子を示し、Ｒ^１５とＲ^１６とＲ^１７は官能基を有していてもよい炭素数１～３０の炭化水素基を示す。Ｒ^１５とＬは環を形成してもよく、Ｒ^１６とＲ^１７は環を形成してもよく、Ｒ^１６又はＲ^１７はＡと結合して環を形成してもよい。）

(In general formula (104), M represents a Group 10 transition metal, and Q represents A[-S(=O) ₂ -O-]M, A[-C(=O)-O-]M, A Indicates a divalent group shown in [ ] of [-O-]M or A[-S-]M (However, A and M on both sides are written to indicate the bonding direction of the group. A is a divalent hydrocarbon group having 1 to 30 carbon atoms that connects Q and the phosphorus atom, and may have a functional group, and L is a zero-valent coordination group that can be detached from the metal. R ¹⁵ , R ¹⁶ and R ¹⁷ represent a hydrocarbon group having 1 to 30 carbon atoms which may have a functional group. R ¹⁵ and L may form a ring, and R ¹⁶ and R ¹⁷ may form a ring, and R ¹⁶ or R ¹⁷ may combine with A to form a ring.)

In the general formula (104), M represents a Group 10 transition metal, and among them, Ni and Pd are preferable.
Q represents a divalent group represented by -S(=O) ₂ -O-, -C(=O)-O-, -P(=O)(-OH)-O-, or -S- This is a site that coordinates one electron to M. The left side of each of the above formulas is connected to Q, and the right side is connected to M. Among these, -S(=O) ₂ -O- is particularly preferred from the viewpoint of catalytic activity.

A is a divalent hydrocarbon group having 1 to 30 carbon atoms that connects Q and the phosphorus atom, and the hydrocarbon group may have a functional group.
The divalent hydrocarbon group having 1 to 30 carbon atoms is preferably a divalent hydrocarbon group having 1 to 12 carbon atoms, preferably an alkylene group, an arylene group, etc., especially an arylene group. is preferred.

Examples of the functional group of the hydrocarbon group in A include a halogen atom, -OR ^u , -CO ₂ R ^u , -CO ₂ M', -CON(R ^t ) ₂ , -COR ^u , -SR ^u , -SO ₂ R ^u , -SOR ^u , -OSO ₂ R ^u , -PO(OR ^u ) _2-y (R ^t ) _y , -CN, -NHR ^u , -N(R ^u ) ₂ , -Si(OR ^t ) _3-x (R ^t ) _x , -OSi(OR ^t ) _3-x (R ^t ) _x , -NO ₂ , -SO ₃ M', -PO ₃ M' ₂ , -P(O) (OR ^u ) ₂ M', or an epoxy-containing group (where R ^t represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ^u represents a hydrocarbon group having 1 to 20 carbon atoms). , M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2).
Examples of the hydrocarbon group having 1 to 20 carbon atoms here include the same ones as R ^a in the general formula (1).

Examples of the divalent hydrocarbon group having 1 to 30 carbon atoms in A include the following formulas (a-1) to (a-7). In the following formula, R ¹⁰⁴ is each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a functional group. The hydrocarbon group having 1 to 30 carbon atoms in R ¹⁰⁴ can be the same as R ^a in the general formula (1). The hydrocarbon group having 1 to 30 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 1 to 10 carbon atoms.
Among the divalent hydrocarbon groups having 1 to 30 carbon atoms in A, especially the divalent hydrocarbon groups having 1 to 30 carbon atoms in Q, from the viewpoint of catalytic activity, the following formula (a-7 ) is preferable.

L represents a zero-valent ligand that can be detached from the metal.
L is preferably a compound that has an electron-donating group and can coordinate to the metal atom M to stabilize the metal complex. L is a hydrocarbon compound having 1 to 20 carbon atoms that has oxygen, nitrogen, sulfur, or phosphorus as an atom that can coordinate, or a hydrocarbon compound that has a carbon-carbon unsaturated bond that can coordinate to a transition metal. (which may contain heteroatoms) can also be used. Preferably, L has 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms.

Preferred examples of L include pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkyl nitrile derivatives, aryl nitrile derivatives, alcohols, amides, aliphatic esters, and aromatic esters. amines, phosphines, phosphine oxides, phosphites, phosphinic esters, phosphonous esters, phosphonic esters, phosphites, phosphoric esters, cyclic unsaturated hydrocarbons There are many types.
Examples of L having a sulfur atom include dimethyl sulfoxide (DMSO). Those having a nitrogen atom include trialkylamines having an alkyl group having 1 to 10 carbon atoms, dialkylamines having an alkyl group having 1 to 10 carbon atoms, pyridine, 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), Examples include acetonitrile, benzonitrile, quinoline, 2-methylquinoline and the like. Examples of those having an oxygen atom include diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane. Those having a phosphorus atom include triphenylphosphine, tributylphosphine, triphenylphosphine oxide, and tributylphosphine oxide. From the viewpoint of complex stability and catalytic activity, dimethyl sulfoxide (DMSO), pyridine, 2,6-dimethylpyridine (also known as 2,6-lutidine), N,N,N',N'-tetramethylethylenediamine (TMEDA) ) is preferred, and dimethyl sulfoxide (DMSO) and 2,6-dimethylpyridine (also known as 2,6-lutidine) are more preferred.
Note that R ¹⁵ and L may form a ring. As such an example may be mentioned the cyclooct-1-enyl group, which is also a preferred embodiment in the present disclosure.

R ¹⁵ , R ¹⁶ and R ¹⁷ represent a hydrocarbon group having 1 to 30 carbon atoms which may have a functional group.
Examples of the hydrocarbon group having 1 to 30 carbon atoms in R ¹⁵ , R ¹⁶ , and R ¹⁷ include those similar to R ^a in the general formula (1).
The functional groups in R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same as the functional group in Q above.

R ¹⁵ is preferably a hydrocarbon group having 1 to 20 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with an alkoxy group or an aryloxy group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10. Specifically, R ¹⁵ is more preferably an alkyl group having 1 to 3 carbon atoms, a benzyl group, a trifluoromethyl group, a pentafluorophenyl group, a 1-(methoxymethyl)ethyl group, or a 1-(ethoxymethyl) group. ) ethyl group, 1-(phenoxymethyl)ethyl group, or 1-(2,6-dimethylphenoxymethyl)ethyl group, and even more preferably a methyl group or a benzyl group.
In general formula (104), R ¹⁵ may be present in either the cis or trans position with respect to P, and is preferably in the cis position.

R ¹⁶ and R ¹⁷ are in the vicinity of the transition metal M and interact with the transition metal M sterically and/or electronically. In order to exert such an effect, it is preferable that R ¹⁶ and R ¹⁷ be bulky. The carbon number of R ¹⁶ and R ¹⁷ is preferably 3 to 30, more preferably 6 to 20.

R ¹⁶ and R ¹⁷ each represent an alkyl group having 3 to 10 carbon atoms which may have a functional group, a cycloalkyl group having 6 to 20 carbon atoms which may have a functional group, or a functional group. An aryl group having 6 to 20 carbon atoms is preferable.
The alkyl group having 3 to 10 carbon atoms in R ¹⁶ and R ¹⁷ is preferably an n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or t-butyl group.

The cycloalkyl group having 6 to 20 carbon atoms which may have a functional group in R ¹⁶ and R ¹⁷ is a linear or branched alkyl group having 3 to 10 carbon atoms which may have a functional group. Examples include an optionally substituted cyclohexyl group, cycloheptyl group, and cyclooctyl group.
Furthermore, for example, the cycloalkyl group described in paragraphs 0104 to 0113 of JP2018-141138A (X in paragraphs 0104 to 0113 of JP2018-141138A is P in the general formula (104) of the present disclosure) (indicates the bonding position of a phosphorus atom)).
R ¹⁶ and R ¹⁷ are preferably a cyclohexyl group optionally substituted with a linear or branched alkyl group having 3 to 10 carbon atoms, from the viewpoint of controlling the polymer molecular weight and polar monomer copolymerizability. Preferably, a cyclohexyl group substituted with a straight chain or branched alkyl group having 3 to 10 carbon atoms is more preferable. Among these, 2-isopropyl-5-methylcyclohexyl group (menthyl group) is preferred.

Further, as the aryl group having 6 to 20 carbon atoms which may have a functional group in R ¹⁶ and R ¹⁷ , the aryl group having 6 to 20 carbon atoms which may have a functional group may be a linear or branched aryl group having 3 to 10 carbon atoms. Examples include a phenyl group, a naphthyl group, an anthracenyl group, and the like, which may be substituted with an alkyl group. The aryl group having 6 to 20 carbon atoms is preferably substituted with a group containing at least one of an oxygen atom and a nitrogen atom. When the aryl group having 6 to 20 carbon atoms is substituted with a group containing at least one of an oxygen atom and a nitrogen atom, the functional group is substituted at the ortho position to the carbon bonded to phosphorus. It is preferable. This is because by doing so, a spatial arrangement can be taken such that at least one of the oxygen atoms and nitrogen atoms in R ¹⁶ and R ¹⁷ interacts with the transition metal M.

Preferred specific examples of R ¹⁶ and R ¹⁷ include 2,6-dimethoxyphenyl group, 2,4
, 6-trimethoxyphenyl group, 4-methyl-2,6-dimethoxyphenyl group, 4-t-butyl-2,6-dimethoxyphenyl group, 1,3-dimethoxy-2-naphthyl group, 2,6-dimethoxyphenyl group, Ethoxyphenyl 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 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, 4-methyl-2,6-di(2-methoxyethyl)phenyl group, 4-t-butyl-2,6-di(2 -methoxyethyl) phenyl group, 1,3-di(2-methoxyethyl)-2-naphthyl group, 2,6-di(2-phenoxyethyl)phenyl group, 2,4,6-tri(2-phenoxyethyl) ) phenyl group, 4-methyl-2,6-di(2-phenoxyethyl)phenyl group, 4-t-butyl-2,6-di(2-phenoxyethyl)phenyl group, 1,3-di(2- Examples include phenoxyethyl)-2-naphthyl group.

R ¹⁶ or R ¹⁷ may be combined with A to form a ring structure. Specifically, for example, the structure described in paragraphs 0120 to 0121 of JP-A No. 2018-141138 (in this example, the substituent R ¹⁶ and A are bonded to form a ring structure) and P and Q are synonymous with general formula (104) of the present disclosure.).

Among the compounds represented by the general formula (104) of the present disclosure, a compound represented by the following general formula (105) is preferred from the viewpoint of polymer production efficiency.

（一般式（１０５）中、Ｍ、Ｌ、Ｒ^１５、Ｒ^１６及びＲ^１７は、それぞれ前記一般式（１０４）と同義であり、Ｒ^１１１、Ｒ^１１２、Ｒ^１１３及びＲ^１１４はそれぞれ独立に、水素原子、炭素数１～３０の炭化水素基、又は官能基である。）

(In general formula (105), M, L, R ¹⁵ , R ¹⁶ and R ¹⁷ each have the same meaning as in the above general formula (104), and R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ each independently, A hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a functional group.)

In the general formula (105), the hydrocarbon group having 1 to 30 carbon atoms and the functional group in R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ may be the same as those explained in A above.
Among them, the bulkier R ¹¹¹ tends to give a polymer with a higher molecular weight, such as t-butyl group, trimethylsilyl group, phenyl group, 9-anthracenyl group, 4-t-butylphenyl group, 2,4- Functional groups such as di-t-butylphenyl group and pentafluorophenyl group may be selected as appropriate.

The transition metal complex used in the present disclosure can be prepared by a conventionally known method.
Further, the transition metal-containing catalyst used in the present disclosure has the above-mentioned transition metal complex as a main catalyst component, and an activator, a carrier, etc. can be used in combination, if necessary. Examples of the activator include alkylalumoxane and boron-containing compounds, which are cocatalysts used in metallocene catalysts.

Further, as the carrier, any carrier can be used as long as it does not impair the gist of the present invention. In general, inorganic oxides and polymer carriers can be suitably used.
Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof are mentioned, and SiO ₂ -Al ₂ O ₃ , SiO ₂ -V ₂ O ₅ , SiO ₂ -TiO ₂ , SiO ₂ -MgO, SiO ₂ -Cr ₂ O ₃ and other mixed oxides can also be used, inorganic silicates, polyethylene carriers, polypropylene carriers, Polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic ester carriers, polyester carriers, polyamide carriers, polyimide carriers, etc. can be used. These carriers are not particularly limited in particle size, particle size distribution, pore volume, specific surface area, etc., and any carrier can be used.

(5-2) Polymerization method used in the production method of polar group-containing olefin copolymer:
The method of polymerizing the polar group-containing olefin copolymer in the present disclosure is not limited.
Solution polymerization in which all of the produced polymer is dissolved in the medium, slurry polymerization in which at least part of the produced polymer becomes slurry in the medium, bulk polymerization in which the liquefied monomer itself is used as the medium, or monomer liquefied at high temperature and high pressure. High-pressure ionic polymerization or the like is used in which at least a portion of the produced polymer is dissolved.
The polymerization format may be batch polymerization, semi-batch polymerization, or continuous polymerization.
Specific manufacturing processes and conditions are disclosed in, for example, Japanese Patent Laid-Open Nos. 2010-260913 and 2010-202647.

Unreacted monomers and media may be separated from the produced polymer and recycled for use. During recycling, these monomers and media may be purified and reused, or may be reused without being purified. Conventional known methods can be used to separate the produced polymer from unreacted monomers and the medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.

Although there are no particular restrictions on the copolymerization temperature, copolymerization pressure, and copolymerization time, optimal settings can usually be made from the following ranges in consideration of 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, even more preferably 10°C to 150°C, particularly preferably 20°C to 100°C. be. The copolymerization pressure is from 0.1 MPa to 100 MPa, preferably from 0.3 MPa to 90 MPa, more preferably from 0.5 MPa to 80 MPa, even more preferably from 1.0 MPa to 70 MPa, particularly preferably from 1.3 MPa to 60 MPa. The copolymerization time can be selected from the range of 0.1 minutes to 50 hours, preferably 0.5 minutes to 40 hours, and more preferably 1 minute to 30 hours.
In the present invention, polymerization is generally carried out under an inert gas atmosphere. For example, a nitrogen or argon atmosphere can be used, and a nitrogen atmosphere is preferably used.

There are no particular restrictions on the supply of the 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, it is possible to supply a predetermined amount of monomer to a copolymerization reactor in advance, and then supply a catalyst thereto. In this case, additional monomers and additional catalysts may be supplied to the copolymerization reactor. Further, in the case of continuous polymerization, a method can be adopted in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to a copolymerization reactor to carry out the copolymerization reaction continuously.

Regarding the control of the composition of the copolymer, a method of controlling by changing the monomer supply ratio can generally be used. Other methods include controlling the copolymerization composition by utilizing differences in the monomer reactivity ratio due to differences in catalyst structure, and controlling the copolymerization composition by utilizing the polymerization temperature dependence of the monomer reactivity ratio. .
Conventionally known methods can be used to control the molecular weight of the copolymer. That is, examples include a method of controlling the molecular weight by controlling the polymerization temperature, a method of controlling the molecular weight by controlling the monomer concentration, and a method of controlling the molecular weight by controlling the ligand structure in the transition metal complex.
In the present disclosure, in particular, since the monomer (C) is used as a chain transfer agent, a method of controlling the content of the monomer (C), a method of controlling the molecular weight by controlling the ligand structure in the transition metal complex, By controlling the molecular weight by controlling the polymerization temperature, and by combining these methods, it is possible to appropriately adjust the terminal modification content of specific functional groups and to control the molecular weight.

2. Polar group-containing olefin copolymer composition The polar group-containing olefin copolymer composition of the present disclosure contains at least one transition metal selected from the group consisting of nickel, palladium, and platinum, and the polar group-containing composition of the present disclosure. Contains an olefin copolymer.
The polar group-containing olefin copolymer of the present disclosure is preferably produced using a transition metal catalyst, and may contain residual catalyst depending on the purification conditions, and when containing a transition metal. There is.
The polar group-containing olefin copolymer of the present disclosure is preferably produced using a transition metal catalyst containing at least one transition metal selected from the group consisting of nickel, palladium, and platinum. The polar group-containing olefin copolymer composition of the present disclosure contains at least one transition metal selected from the group consisting of nickel, palladium, and platinum, and the polar group-containing olefin copolymer of the present disclosure.

In the polar group-containing olefin copolymer composition of the present disclosure, at least one transition metal selected from the group consisting of nickel, palladium, and platinum derived from the residual catalyst is based on 100% by mass of the polar group-containing olefin copolymer. It is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. The lower limit of the transition metal content in the polar group-containing olefin copolymer composition of the present disclosure may be the detection limit of the method for measuring the transition metal.
Methods for measuring the transition metal in the polar group-containing olefin copolymer composition of the present disclosure include energy dispersive X-ray fluorescence spectroscopy (EDX), wavelength dispersive X-ray fluorescence spectrometry (WDX), and inductively coupled plasma emission spectrometry (ICP- Known methods include AES), inductively coupled plasma mass spectrometry (ICP-MS), and atomic absorption spectrometry. Among these, it is more preferable to use inductively coupled plasma optical emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) in terms of accuracy. In any case, it is desirable to remove organic substances by treating the polymer with a pretreatment method such as ashing or extraction.
Further, the transition metal content in the polar group-containing olefin copolymer composition of the present disclosure can also be estimated as follows from the polymerization activity and the amount of catalyst charged. For example, "Number of moles of catalyst used in polymerization (mol) x Atomic weight of transition metal in catalyst (g/mol) ÷ Yield of polymer obtained from polymerization (g) = Metal content contained in polymer (mass%)" In this way, we can obtain a theoretical value based on the law of conservation of mass.
The lower limit of the transition metal content depends on the lower measurement limit of the analyzer, but is 0.00005% by mass, 0.0001% by mass, or 0.001% by mass based on 100% by mass of the polar group-containing olefin copolymer. Examples include mass %.

Next, the present disclosure will be concretely explained using Examples, but the present disclosure is not limited by these Examples unless it departs from the gist thereof. The physical properties of the polar group-containing olefin copolymer and the like were measured by the following methods.

[Amount of structural units in polar group-containing olefin copolymer]
The structure of the polar group-containing olefin copolymer was determined by ¹ H-NMR and ¹³ C-NMR analysis using Ascend 500 manufactured by BRUKER.
For NMR measurement, 1,1,2,2-tetrachloroethane-d2 was used as a solvent, and the polymer concentration for ¹ H-NMR measurement was 5% by mass, and the polymer concentration for ¹³ C-NMR was 15% by mass. I went at a degree.
A part of ¹³ C-NMR was measured using chromium (III) acetylacetonate as a relaxing reagent and reverse gated decoupling method (90° pulse of 9.0 microseconds, spectral width: 31 kHz, relaxation time: 10 seconds, acquisition time: 10 seconds, FID integration number of 5,000 to 10,000 times), and quantitative analysis was performed.

[Number average molecular weight and weight average molecular weight]
Using a high-temperature GPC device, HLC-8321GPC/HT, manufactured by Tosoh Corporation, equipped with a TSKgel GMHHR-H(S)HT column (two 7.8 mm ID x 30 cm in series) manufactured by Tosoh Corporation, polystyrene was used. Calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145 degrees) using as a molecular weight standard.
[Analysis of metal content in polymer]
The metal content in the polymer of this application is calculated as follows: "Number of moles of catalyst used in polymerization x atomic weight of transition metal in catalyst (g/mol) ÷ Yield of polymer obtained from polymerization (g) x 100 = Metal contained in polymer It was determined from the calculated value of "Content (mass%)".

[Synthesis of transition metal complex]
(Synthesis example 1)
In the following chemical formula (A), the transition metal complex (I) in which R is both 2-methoxyphenyl and Lut is 2,6-dimethylpyridine was synthesized as described in JP-A No. 2007-046032. .

(Synthesis example 2)
Transition metal complex (II) in which R is cyclohexyl and Lut is 2,6-dimethylpyridine in the chemical formula (A) was synthesized as described in JP-A No. 2011-068881.

(Synthesis example 3)
In the chemical formula (A), the transition metal complex (III) in which both R are menthyl (2-isopropyl-5-methylcyclohexyl) and Lut is 2,6-dimethylpyridine is disclosed in JP-A No. 2017-031300. Synthesized as described.

(Example 1)
In a 50 mL autoclave in a nitrogen atmosphere, transition metal complex (I) (6.5 mg, 0.010 mmol) as a catalyst, toluene (8 mL) as a solvent, and dimethyl-2 as a chain transfer agent (monomer (C)) were added. -Diazomalonate (316.2 mg, 2.0 mmol) and allyl acetate (monomer (B)) (2 mL) as a polar group-containing monomer were successively added. The autoclave was pressurized with ethylene (monomer (A)) (3.0 MPa) and stirred at a reaction temperature of 80° C. for 12 hours. The autoclave was returned to room temperature and methanol (20 mL) was added. The precipitated solid was collected by filtration, washed with methanol, and dried under reduced pressure. The amount of polar group-containing olefin copolymer 1 obtained was 165 mg. Pd was contained in an amount of 0.65% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 1 are shown in Tables 1 and 2.

(Example 2)
The same procedure as in Example 1 was carried out except that methyl acrylate (2.0 mL) was used as the monomer (B). The amount of polar group-containing olefin copolymer 2 obtained was 610 mg. Pd was contained in an amount of 0.18% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 2 are shown in Tables 1 and 2.

(Example 3)
The same procedure as in Example 1 was carried out except that the catalyst was transition metal complex (II) (5.8 mg, 0.010 mmol) and the monomer (B) was methyl acrylate (2.0 mL). The amount of polar group-containing olefin copolymer 3 obtained was 1188 mg. Pd was contained in an amount of 0.096% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 3 are shown in Tables 1 and 2.

(Example 4)
Everything was carried out in the same manner as in Example 1 except that transition metal complex (II) (5.8 mg, 0.010 mmol) was used as the catalyst. The amount of polar group-containing olefin copolymer 4 obtained was 274 mg. Pd was contained in an amount of 0.39% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 4 are shown in Tables 1 and 2.

(Example 5)
The same procedure as in Example 1 was carried out except that the catalyst was transition metal complex (III) (6.9 mg, 0.010 mmol). The amount of polar group-containing olefin copolymer 5 obtained was 78 mg.
Various analysis results of the polar group-containing olefin copolymer 5 are shown in Tables 1 and 2. Pd was contained in an amount of 1.40% by mass based on 100% by mass of the polar group-containing olefin copolymer.
FIG. 1 shows the results of ¹ H-NMR measurement of polar group-containing olefin copolymer 5 of Example 5.

(Example 6)
The catalyst was transition metal complex (III) (6.9 mg, 0.010 mmol), the solvent was toluene (5 mL), the monomer (C) was dimethyl-2- diazomalonate (158.1 mg, 1.0 mmol), and the monomer (B) was ) was changed to allyl acetate (5.0 mL), but the same procedure as in Example 1 was carried out. The amount of polar group-containing olefin copolymer 6 obtained was 56 mg. Pd was contained in an amount of 1.90% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 6 are shown in Tables 1 and 2.

(Example 7)
All except that the catalyst was transition metal complex (III) (6.9 mg, 0.010 mmol), the monomer (C) was dimethyl-2- diazomalonate (158.1 mg, 1.0 mmol), and the reaction temperature was 50°C. It was carried out in the same manner as in Example 1. The amount of polar group-containing olefin copolymer 7 obtained was 230 mg. Pd was contained in an amount of 0.47% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 7 are shown in Tables 1 and 2.

(Example 8)
The catalyst was transition metal complex (III) (6.9 mg, 0.010 mmol), the monomer (C) was dimethyl-2- diazomalonate (158.1 mg, 1.0 mmol), and the monomer (B) was allyl chloride (2. 0 mL), and the reaction temperature was 50°C, but the same procedure as in Example 1 was carried out. The amount of polar group-containing olefin copolymer 8 obtained was 103 mg. Pd was contained in an amount of 1.00% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 8 are shown in Tables 1 and 2.

(Example 9)
The catalyst was transition metal complex (III) (6.9 mg, 0.010 mmol), the monomer (C) was dimethyl-2- diazomalonate (158.1 mg, 1.0 mmol), and the monomer (B) was allyl chloride (2. Everything was carried out in the same manner as in Example 1 except that the volume was changed to 0 mL). The amount of polar group-containing olefin copolymer 9 obtained was 84 mg. Pd was contained in an amount of 1.30% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 9 are shown in Tables 1 and 2.

(Example 10)
The catalyst was transition metal complex (III) (6.9 mg, 0.010 mmol), the monomer (C) was dimethyl-2- diazomalonate (158.1 mg, 1.0 mmol), and the monomer (B) was methyl acrylate (2 The same procedure as in Example 1 was carried out except that the volume was changed to .0 mL). The amount of polar group-containing olefin copolymer 10 obtained was 449 mg. Pd was contained in an amount of 0.24% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 10 are shown in Tables 1 and 2.

(Example 11)
The catalyst was transition metal complex (III) (6.9 mg, 0.010 mmol), the solvent was toluene (5.0 mL), the monomer (C) was dimethyl-2- diazomalonate (158.1 mg, 1.0 mmol), and the monomer Everything was carried out in the same manner as in Example 1 except that (B) was replaced with methyl acrylate (5.0 mL). The amount of polar group-containing olefin copolymer 11 obtained was 450 mg. Pd was contained in an amount of 0.24% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 11 are shown in Tables 1 and 2.

(Example 12)
The catalyst was transition metal complex (III) (6.9 mg, 0.010 mmol), the solvent was toluene (5.0 mL), the monomer (C) was dimethyl-2- diazomalonate (158.1 mg, 1.0 mmol), and the monomer The same procedure as in Example 1 was repeated except that (B) was replaced with 3-butenyl acetate (5.0 mL). The amount of polar group-containing olefin copolymer 12 obtained was 203 mg. Pd was contained in an amount of 0.53% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer 12 are shown in Tables 1 and 2.

(Comparative example 1)
Except that the catalyst was transition metal complex (II) (5.0 mg, 0.010 mmol), the solvent was toluene (12.0 mL), the monomer (C) was not used, and the monomer (B) was allyl acetate (3.0 mL). were carried out in the same manner as in Example 1. The amount of the obtained polar group-containing olefin copolymer C1 was 1740 mg. Pd was contained in an amount of 0.061% by mass based on 100% by mass of the polar group-containing olefin copolymer.
Various analysis results of the polar group-containing olefin copolymer C1 are shown in Tables 1 and 2.

In Table 1, AAc is allyl acetate, MA is methyl acrylate, AC is allyl chloride, and 3BA is 3-butenyl acetate.

In each table, "<1" was set as "0" and ">99" was set as "100" for calculation of each numerical value. In addition, the numerical value is rounded to the nearest whole number. %).

In addition, in Tables 1 and 2,
"Structural unit (C)/total structural unit" refers to the structural unit (C ) means the content ratio.
"Structural unit (B)/total structural units" means the content ratio of the structural unit (B) when the total structural units of the polymer are 100 mol%.
"Structural unit (C) saturated terminal/total structural unit (C)" refers to the saturated terminal derived from structural unit (C) when the total of structural units (C) contained in the polymer is 100 mol%. It means the content ratio.
"Structural unit (C) unsaturated terminal/total structural unit (C)" refers to unsaturated terminals derived from structural unit (C) when the total of structural units (C) contained in the polymer is 100 mol%. It means the content ratio of terminals.
"Structural unit (C) saturated terminal/total saturated terminal of the polymer" refers to the structural unit (C) located at the terminal of the polymer when the total of the saturated terminal structural units contained in the polymer is 100 mol%. It means the content ratio of saturated ends derived from.
"Structural unit (B) saturated terminal/total saturated terminal of the polymer" refers to the structural unit (B) located at the terminal of the polymer when the total of the saturated terminal structural units contained in the polymer is 100 mol%. It means the content ratio of saturated ends derived from.
"Structural unit (A) saturated terminal/total saturated terminal of the polymer" refers to the structural unit (A) located at the terminal of the polymer when the total of the saturated terminal structural units contained in the polymer is 100 mol%. It means the content ratio of saturated ends derived from.
"Structural unit (C) unsaturated terminal/total unsaturated terminal" refers to the structural unit (C) located at the terminal of the polymer when the total of structural units of unsaturated terminal contained in the polymer is 100 mol%. means the content of unsaturated terminals derived from
"Structural unit (B) unsaturated terminal/total unsaturated terminal" refers to the structural unit (B) located at the terminal of the polymer when the total of structural units of unsaturated terminal contained in the polymer is 100 mol%. means the content of unsaturated terminals derived from
"Structural unit (A) unsaturated terminal/total unsaturated terminal" refers to the structural unit (A) located at the terminal of the polymer when the total of the structural units of unsaturated terminal contained in the polymer is 100 mol%. means the content of unsaturated terminals derived from
"Terminal/terminus derived from structural unit (C)" refers to the terminus derived from structural unit (C) located at the terminal of the polymer when the total of terminal structural units contained in the olefin copolymer is 100 mol%. It means the content ratio of terminals. (Calculated as (saturated end content ratio + unsaturated end content ratio)/2.)
"Terminal/terminus derived from structural unit (B)" refers to the terminus derived from structural unit (B) located at the terminal of the polymer when the total of terminal structural units contained in the olefin copolymer is 100 mol%. It means the content ratio of terminals.
"Terminal/terminus derived from structural unit (A)" refers to the terminus derived from structural unit (A) located at the terminal of the polymer when the total of terminal structural units contained in the olefin copolymer is 100 mol%. It means the content ratio of terminals.

According to the present disclosure, by performing normal olefin polymerization and reacting the growing terminal with a disubstituted carbene, which is a chain transfer agent having a desired polar group, a specific polar group is selectively transferred to the terminal in a high proportion. It was shown that it is possible to provide a novel polar group-containing olefin polymer introduced in
According to the present disclosure, it is possible to obtain a polar group-containing olefin copolymer having desired polar groups in an amount exceeding half of the polymerization terminated ends, and further, having desired polar groups in 99 mol% of the polymerization termination ends. It is also possible to obtain polar group-containing olefin copolymers.

The novel polar group-containing olefin polymers in which specific polar groups are selectively introduced at the terminals of the present disclosure are effective in improving the properties of polyolefins and expanding the production range and/or production route of polyolefin compounds. It is expected to be used in a wide range of fields, including as a raw material for diblock polymers.

Claims (13)

A structural unit (A) derived from one or more monomers selected from ethylene and olefins having 3 to 20 carbon atoms;
One or more monomers selected from the polar group-containing olefin monomer (b-1) represented by the following general formula (1) and the polar group-containing olefin monomer (b-2) represented by the following general formula (2). The derived structural unit (B) and
A polar group-containing olefin copolymer comprising a structural unit (C) derived from one or more monomers selected from polar group-containing carbene monomers represented by the following general formula (3).

(In general formula (1), R ¹ and R ² are each independently a hydrogen atom, an ester group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Aryloxy group having 6 to 30 carbon atoms, cyano group, amino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, amide group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms , an imino group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 30 carbon atoms, or an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. A hydrocarbon group having 1 to 30 carbon atoms which may be ^substituted with a functional group containing at least one ^of )

(In general formula (2), R ³ to R ¹⁰ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. n represents 0 or a positive integer, When n is 2 or more, R ⁷ to R ¹⁰ may be the same or different in each repeating unit. R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, a carbon number Substituted with an ester group having 1 to 30 carbon atoms, an acyloxy 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, or a hydrocarbon group having 1 to 30 carbon atoms. 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 imino group which may be substituted with a hydrocarbon group having 1 to 30 carbon atoms, or an oxygen atom, A hydrocarbon group having 1 to 30 carbon atoms that may be substituted with a functional group containing at least one selected from the group consisting of sulfur atom, nitrogen atom, and phosphorus atom, and at least one of R ¹¹ to R ¹⁴ is , is a group containing at least one of an oxygen atom and a nitrogen atom. R ¹¹ and R ¹² and R ¹³ and R ¹⁴ may each be combined to form a divalent organic group, and R ¹¹ or R ¹² and R ¹³ or R ¹⁴ may mutually form a ring.)

(In general formula (3), X and Y are each independently an ester group having 1 to 30 carbon atoms, an amino group optionally substituted with a hydrocarbon group having 1 to 30 carbon atoms, a cyano group, or An alkoxy group having 1 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms .) The polar group-containing olefin according to claim 1, wherein the polar group-containing olefin copolymer contains 20 mol% or more of the terminal structural unit (C) with respect to a total of 100 mol% of the terminal structural units. Copolymer. The polar group-containing olefin copolymer according to claim 1 or 2, wherein the polar group-containing olefin copolymer contains the structural unit (C) in an amount of 0.001 mol% or more and 5 mol% or less based on 100 mol% of the entire structural units. Group-containing olefin copolymer. The polar group-containing olefin copolymer according to any one of claims 1 to 3, wherein 50 mol% or more of the structural unit (C) in the polar group-containing olefin copolymer is located at a terminal. Polymer. The polar group-containing olefin copolymer is
The mol fraction [A] of the structural unit (A) and the mol fraction [B] of the structural unit (B) satisfy [A]≧{([A]+[B])×80%} The polar group-containing olefin copolymer according to any one of claims 1 to 4, characterized by: The polar group-containing carbene monomer represented by the general formula (3) is a carbene monomer derived from at least one monomer selected from the monomers represented by the following general formulas (100) to (103). The polar group-containing olefin copolymer according to any one of claims 1 to 5 .

(In general formulas (100) to (103), X and Y have the same meanings as in general formula (3) above, and L represents a halogen atom.) The polar group-containing carbene monomer represented by the general formula (3) is dimethyl 2- diazomalonate , diethyl 2-diazomalonate, dipropyl 2- diazomalonate , dibutyl 2- diazomalonate , - A carbene derived from at least one member selected from the group consisting of methyl diazocyanoacetate , ethyl 2- diazocyanoacetate , propyl 2- diazocyanoacetate , butyl 2- diazocyanoacetate , and 2- diazomalononitrile . The polar group-containing olefin copolymer according to any one of claims 1 to 6 , which is a monomer . The polar group-containing olefin copolymer according to any one of claims 1 to 7 , wherein in the general formula (1), R ¹ is a hydrogen atom. In the general formula (1), R ¹ is a hydrogen atom, and R ² is an ester group having 1 to 30 carbon atoms, a cyano group, a cyanomethyl group, a cyanoethyl group , an acyloxymethyl group, or an acyloxyethyl group. The polar group-containing olefin copolymer according to any one of claims 1 to 8 . The polar group-containing olefin monomer (b-1) represented by the general formula (1) is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, vinyl acetate, allyl acetate, 3-butenyl acetate, acrylonitrile. The polar group-containing olefin copolymer according to any one of claims 1 to 9 , characterized in that it is at least one selected from the group consisting of , and 3-cyanopropene. According to any one of claims 1 to 10, wherein in the general formula (2), n is 0 or 1, and R ³ to R ¹⁰ are each independently a hydrogen atom or a methyl group. The polar group-containing olefin copolymer described above. The polar group-containing olefin monomer (b-2) represented by the general formula (2) is methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, or 5-norbornene-2-carboxylic acid. Propyl, butyl 5-norbornene-2-carboxylate, dimethyl 5-norbornene-2,3-dicarboxylate, 5-norbornene-2,3-dicarboxylic anhydride, 2-hydroxy-5-norbornene, 5-norbornene-2 - At least one member selected from the group consisting of methanol, 5-norbornene-2-methylamine, 2-acetoxy-5-norbornene, 2-cyanomethyl-5-norbornene, and 5-norbornene-2-carbonitrile. The polar group-containing olefin copolymer according to any one of claims 1 to 11 , characterized by: A polar group-containing olefin copolymer comprising at least one transition metal selected from the group consisting of nickel, palladium, and platinum and the polar group-containing olefin copolymer according to any one of claims 1 to 12 . Polymer composition.