Copolymer and method for producing copolymer

Abstract

To provide a polymer having an acetylene group in a side chain, which can be a base for producing a polymer having various substituents.SOLUTION: According to the present invention, there is provided a polymer comprising a first monomer unit 1A derived from a first monomer and a second monomer unit derived from a second monomer, wherein the first monomer unit 1A is a monomer unit having an acetylene group in a side chain.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a copolymer and a method for producing the copolymer. [Background technology]

[0002] In recent years, there has been a demand for polymers with various functions, and there is a demand for polymers into which desired substituents can be introduced depending on the application, as well as polymers that can serve as raw materials for such polymers. For example, polymers having acetylene groups in their side chains may serve as a stepping stone for producing polymers that can have various substituents. For example, Non-Patent Document 1 describes an example of the use of an acrylic monomer having acetylene in its side chain. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Zhengyuan Zhang, Free radical polymerization of acrylates bearing acetylene for preparation of clickable polymers, Polymer, Volume 228, 16 July 2021, 123906 Summary of the Invention [Problem to be solved by the invention]

[0004] However, monovinylacetylene, which can be used as a raw material for polymers having acetylene groups in their side chains, has a low boiling point, is explosive, and is difficult to handle, making it difficult to obtain polymers having acetylene groups in their side chains.

[0005] The present invention has been made in view of the above circumstances, and provides a polymer having an acetylene group in a side chain, which can serve as a stepping stone for producing polymers that can have various substituents. [Means for solving the problem]

[0006] According to the present invention, there is provided a copolymer comprising a first monomer unit 1A derived from a first monomer and a second monomer unit derived from a second monomer, wherein the first monomer unit 1A is a monomer unit having an acetylene group in a side chain.

[0007] Various embodiments of the present invention will be described below as examples, and the embodiments described below can be combined with each other. [1] A copolymer comprising a first monomer unit 1A derived from a first monomer and a second monomer unit derived from a second monomer, wherein the first monomer unit 1A is a monomer unit having an acetylene group in a side chain. [2] The copolymer according to [1], wherein the first monomer unit 1A is a unit represented by the following formula (1-A): [ka] (In formula (1-A), R 1 is any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, hydroxyl, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group; R 2 , R 3 , R 4 are each independently any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group. [3] The copolymer according to [1] or [2], wherein the copolymer has a molecular weight of 1000 or more, and the molecular weight of the copolymer is measured in a deuterated chloroform solvent. 13A copolymer having a peak β in the range of 190 to 220 ppm in a C-NMR spectrum. [4] The copolymer according to [3], wherein the copolymer has an allene structure in at least one of the main chain and the side chain. [5] The copolymer according to [4], further comprising at least one selected from a first monomer unit 1B derived from a first monomer and a first monomer unit 1C derived from a first monomer, wherein the first monomer unit 1B is represented by the following formula (1-B), and the first monomer unit 1C is represented by the following formula (1-C). [ka] (In formula (1-B), R 101 is any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, hydroxyl, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group; R 102 , R 103 , R 104 are each independently any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group. [ka] (In formula (1-C), R 201is any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, hydroxyl, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group; R 203 , R 204 are each independently any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group. [6] The copolymer according to [2], wherein R 1 is hydrogen, copolymer. [7] The copolymer according to any one of [1] to [6], wherein the second monomer is a monomer having a radical polymerizable group, and includes at least one selected from the group consisting of a styrene-based monomer, a (meth)acrylic-based monomer, a diene-based monomer, a vinyl ether-based monomer, and an unsaturated nitrile-based monomer. [8] The copolymer according to any one of [1] to [7], wherein the content of the first monomer units 1A is 1 to 99 mol % relative to a total of 100 mol % of the first monomer units derived from the first monomer contained in the copolymer, the second monomer units, and other monomer units. [9] The copolymer according to any one of [1] to [8], wherein a single glass transition is observed in a differential scanning calorimetric curve of the copolymer; The glass transition temperature of the copolymer is Tp±10% [K], where Tp [K] is the theoretical glass transition temperature of the copolymer; The copolymer is composed of monomer units derived from n types of monomers, Tp [K] is a copolymer that satisfies the following formula (1), where T1 [K] is the glass transition temperature of a homopolymer of a first monomer, C1 is the mass fraction of the copolymerization amount of the first monomer unit relative to 100 parts by mass of the copolymer, T2 [K] is the glass transition temperature of a homopolymer of a second monomer, C2 is the mass fraction of the copolymerization amount of the second monomer unit relative to 100 parts by mass of the copolymer, Tk [K] is the glass transition temperature of a homopolymer of a k-th monomer, and Ck is the mass fraction of the copolymerization amount of the k-th monomer unit relative to 100 parts by mass of the copolymer.

number

[10] The copolymer according to any one of [1] to [9], which is used as a raw material for the Huisgen reaction with an azide compound.

[11] A method for producing a copolymer, comprising a polymerization step, in which raw material monomers including a first monomer and a second monomer are copolymerized to obtain the copolymer including first monomer units 1A derived from the first monomer and second monomer units derived from the second monomer, wherein the first monomer units 1A are monomer units having an acetylene group in a side chain.

[12] A method for producing a copolymer according to

[11] , wherein the first monomer is represented by the following formula (2): [ka] (In formula (2), R 1 is any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, hydroxyl, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group; R 2 , R 3 , R 4are each independently any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group.

[13] A method for producing the copolymer according to

[11] or

[12] , wherein the second monomer is a monomer having a radical polymerizable group, and includes at least one selected from the group consisting of a styrene-based monomer, a (meth)acrylic-based monomer, a diene-based monomer, a vinyl ether-based monomer, and an unsaturated nitrile-based monomer. [Effects of the Invention]

[0008] The copolymer according to the present invention can be used as a starting point for producing polymers that can have various substituents. For example, by using the copolymer according to the present invention as a raw material and carrying out a Huisgen reaction with an azide compound, a polymer having a desired amount of triazole rings with desired substituents can be obtained. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 shows the 13C-NMR spectrum of the copolymer of Example 10. [Figure 2] FIG. 2 shows the differential scanning calorimetry curve of the copolymer according to Example 10. [Figure 3] FIG. 3 shows the IR spectrum of the copolymer according to Example 10. [Figure 4] FIG. 4 shows the differential scanning calorimetry curve of the copolymer according to Example 11. [Figure 5] FIG. 5 shows the differential scanning calorimetry curve of the copolymer according to Example 12. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below by illustrating embodiments of the present invention. The present invention is not limited by these descriptions in any way. The features of the embodiments of the present invention described below can be combined with each other. Furthermore, each feature can be an invention independently. Any number of "0"s (for example, one or two) may be added to the end of the numerical values ​​disclosed in the following description. For example, one or two "0"s may be added after "1.4" to make it "1.40" or "1.400."

[0011] 1.Copolymer A copolymer according to one embodiment of the present invention comprises a first monomer unit 1A derived from a first monomer and a second monomer unit 1A derived from a second monomer.

[0012] 1.1 First monomer unit In the present invention, a monomer unit derived from a first monomer is referred to as a first monomer unit. In this specification, the term "first monomer unit" refers to a concept that includes all monomer units derived from the first monomer, and first monomer unit 1A, and the later-described first monomer unit 1B and first monomer unit 1C refer to subordinate concepts. The copolymer according to the present invention contains first monomer unit 1A. 1.1.1 First Monomer Unit 1A The first monomer unit 1A is a monomer unit having an acetylene group in the side chain. The acetylene group may have a substituent. The first monomer unit 1A can be a monomer unit derived from a monomer containing a monovinylacetylene skeleton. The first monomer unit 1A can be a unit represented by the following formula (1-A).

[0013] [ka]

[0014] In formula (1-A), R 1R can be any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group. 1 is preferably hydrogen. R 1 An example where R is a substituted or unsubstituted ether group is shown below. 1 is a substituted or unsubstituted ether group, R 1 can contain a substituent containing an ether group (ether bond) via C, and can contain a substituent to which an ether group (ether bond) is directly bonded without via C. [ka]

[0015] Similarly, R 1 is a substituted or unsubstituted mercapto group, R 1 can contain a substituent containing -S- via C, and can contain a substituent to which -S- is directly bonded without via C. [ka]

[0016] Similarly, R 1 is a substituted or unsubstituted amino group, R 1 can contain a substituent containing —NH— via C, and can also contain a substituent to which —NH— is directly bonded without via C. [ka]

[0017] In formula (1-A), R 2 , R 3 , R 4R is each independently any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group. 2 , R 3 , R 4 is preferably hydrogen. Specific examples of the substituted or unsubstituted mercapto group, the substituted or unsubstituted ether group, and the substituted or unsubstituted amino group are R 1 It can be the same as:

[0018] Examples of the alkyl group and alkenyl group include alkyl groups and alkenyl groups having 1 to 10 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the heterocyclyl group include groups in which some of the carbon atoms of an aryl group have been replaced with heteroatoms (for example, oxygen, sulfur, or nitrogen).

[0019] Examples of the substituent that the alkyl group, alkenyl group, aryl group, mercapto group, heterocyclyl group, silyl group, and ether group may have include an alkyl group, a hydroxyl group, a halogen group, an amino group, a sulfo group, a carboxyl group, a cyano group, a nitro group, and a nitrile group.

[0020] A specific example of the first monomer unit 1A is R 1 , R 2 , R 3 , R 4 are each hydrogen. The copolymer according to an embodiment of the present invention may have an allene structure in at least one of the main chain and the side chain. That is, the copolymer according to an embodiment of the present invention may include a monomer unit having an allene structure. The monomer unit having an allene structure will be described in detail below.

[0021] 1.1.2 First Monomer Unit 1B The copolymer according to one embodiment of the present invention may further include at least one selected from a first monomer unit 1B derived from a first monomer and a first monomer unit 1C derived from a first monomer. The copolymer according to one embodiment of the present invention may include a first monomer unit 1B. The first monomer unit 1B can be a unit represented by the following formula (1-B).

[0022] [ka]

[0023] In formula (1-B), R 101 is R 1 and can be any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group. R 101 is preferably hydrogen. Specific examples of the substituted or unsubstituted mercapto group, the substituted or unsubstituted ether group, and the substituted or unsubstituted amino group are R 1 It can be the same as:

[0024] In formula (1-B), R 102 , R 103 , R 104 is R 2 , R 3 , R 4and each independently represents one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group. 102 , R 103 , R 104 is preferably hydrogen. Specific examples of the substituted or unsubstituted mercapto group, the substituted or unsubstituted ether group, and the substituted or unsubstituted amino group are R 1 It can be the same as:

[0025] Examples of the alkyl group and alkenyl group include alkyl groups and alkenyl groups having 1 to 10 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the heterocyclyl group include groups in which some of the carbon atoms of an aryl group have been replaced with heteroatoms (for example, oxygen, sulfur, or nitrogen).

[0026] Examples of the substituent that the alkyl group, alkenyl group, aryl group, mercapto group, heterocyclyl group, silyl group, and ether group may have include an alkyl group, a hydroxyl group, a halogen group, an amino group, a sulfo group, a carboxyl group, a cyano group, a nitro group, and a nitrile group.

[0027] A specific example of the first monomer unit 1B is R 101 , R 102 , R 103 , R 104 are each hydrogen.

[0028] 1.1.3 First Monomer Unit 1C The copolymer according to one embodiment of the present invention may include a first monomer unit 1C. The first monomer unit 1C can be a unit represented by the following formula (1-C).

[0029] [ka]

[0030] In formula (1-C), R 201 is R 1 and can be any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group. R 201 is preferably hydrogen. Specific examples of the substituted or unsubstituted mercapto group, the substituted or unsubstituted ether group, and the substituted or unsubstituted amino group are R 1 It can be the same as:

[0031] In formula (1-C), R 203 , R 204 is R 3 , R 4 and each independently represents one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group. 203 , R 204 is preferably hydrogen. Specific examples of the substituted or unsubstituted mercapto group, the substituted or unsubstituted ether group, and the substituted or unsubstituted amino group are R 1 It can be the same as:

[0032] Whether the copolymer according to one embodiment of the present invention has the first monomer unit 1A, the first monomer unit 1B, and / or the first monomer unit 1C can be determined, for example, by: 13 This can be confirmed by obtaining a C-NMR spectrum, and specifically, by the method described in the Examples. A copolymer according to one embodiment of the present invention includes first monomer unit 1B and / or first monomer unit 1C in addition to first monomer unit 1A having an acetylene group in its side chain. Therefore, for example, first monomer unit 1A having an acetylene group can be used as a functionalization site for introducing a specific substituent, and first monomer unit 1B and / or first monomer unit 1C can be used as a functionalization site for introducing another substituent.

[0033] 1.2 Second monomer unit The second monomer can be a monomer having a radically polymerizable group. The second monomer unit may be a monomer unit different from the first monomer. The second monomer unit may have no acetylene group in the side chain and may have no monovinylacetylene skeleton. The second monomer preferably contains at least one selected from the group consisting of styrene-based monomers, (meth)acrylic monomers, diene-based monomers, vinyl ether-based monomers, and unsaturated nitrile-based monomers. These may be used alone or in combination. The content of the second monomer units in the copolymer, and the ratio of the amounts when multiple types of second monomers are contained, can be appropriately set depending on the target polymer.

[0034] The styrene-based monomer unit is a unit derived from a styrene-based monomer such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene, and α-methyl-p-methylstyrene.

[0035] Examples of the (meth)acrylic monomer unit include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, normal propyl acrylate, normal propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, secondary butyl acrylate, secondary butyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, normal octyl acrylate, normal octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, normal The units are derived from (meth)acrylic monomers such as isononyl acrylate, normal nonyl methacrylate, isononyl acrylate, isononyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, ethoxydiethylene glycol acrylate, ethoxydiethylene glycol methacrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isobornyl acrylate, and isobornyl methacrylate. Note that the (meth)acrylic monomer (unit) refers to an acrylic monomer (unit) and a methacrylic monomer (unit).

[0036] The diene monomer unit is, for example, a unit derived from a conjugated diene monomer such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, or chloroprene.

[0037] The vinyl ether monomer unit is, for example, a unit derived from a vinyl ether monomer such as vinyl acetate, vinyl propionate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, vinyl methyl ether, vinyl butyl ether, and vinyl octyl ether.

[0038] The unsaturated nitrile monomer unit is a unit derived from an unsaturated nitrile monomer such as acrylonitrile, methacrylonitrile, ethacrylonitrile, or phenylacrylonitrile.

[0039] 1.3 Amount of each monomer unit in the copolymer The content of the first monomer unit in the copolymer may be appropriately set depending on the desired function of the polymer, and may be, for example, 1 to 99 mol% relative to the total 100 mol% of the moles of each monomer unit contained in the copolymer (100 mol% total of the first monomer unit, second monomer unit, and other monomer units). The content of the first monomer unit may be, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 mol%, or may be within a range between any two of the values ​​exemplified here. The "content of first monomer unit" referred to here can include all monomer units derived from the first monomer, specifically, can include first monomer unit 1A, first monomer unit 1B, and first monomer unit 1C, and can be the total content of first monomer unit 1A, first monomer unit 1B, and first monomer unit 1C.

[0040] Similarly, the content of the second monomer unit in the copolymer may be appropriately set depending on the desired function of the polymer, and may be, for example, 1 to 99 mol% relative to the total 100 mol% of the moles of each monomer unit contained in the copolymer (100 mol% total of the first monomer unit, second monomer unit, and other monomer units). The content of the second monomer unit may be, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 mol%, or may be within a range between any two of the values ​​exemplified here.

[0041] The copolymer may have a structure other than the first monomer unit and the second monomer unit. The content of structures other than the first monomer unit and the second monomer unit relative to the total 100 mol% of the moles of each monomer unit contained in the copolymer (100 mol% in total of the first monomer unit, the second monomer unit, and other monomer units) can be 50 mol% or less. The content of structures other than the first monomer unit and the second monomer unit may be, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 mol%, and may be within a range between any two of the values ​​exemplified here.

[0042] The content of the first monomer units 1A in the copolymer can be appropriately set depending on the desired function of the polymer, and can be, for example, 1 to 99 mol % relative to the total 100 mol % of the moles of each monomer unit contained in the copolymer (100 mol % in total of the first monomer units, second monomer units, and other monomer units). The content of the first monomer units 1A can be, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 mol %, or can be within a range between any two of the values ​​exemplified here.

[0043] Similarly, the content of the first monomer units 1B in the copolymer can be set appropriately depending on the desired function of the polymer, but can be, for example, 0.01 to 30 mol % relative to the total 100 mol % of the moles of each monomer unit contained in the copolymer (100 mol % in total of the first monomer units, second monomer units, and other monomer units). The content of the first monomer units 1B can be, for example, 0.01, 0.1, 1, 5, 10, 15, 20, 25, or 30 mol %, and may be within a range between any two of the values ​​exemplified here.

[0044] The content of the first monomer unit 1C in the copolymer can be appropriately set depending on the desired function of the polymer, and can be, for example, 0.01 to 30 mol % relative to the total 100 mol % of the moles of each monomer unit contained in the copolymer (100 mol % in total of the first monomer unit, second monomer unit, and other monomer units). The content of the first monomer unit 1C can be, for example, 0.01, 0.1, 1, 5, 10, 15, 20, 25, or 30 mol %, or can be within a range between any two of the values ​​exemplified here.

[0045] The total content of first monomer units 1B and 1C in the copolymer (the content of monomer units containing an allene structure) can be set appropriately depending on the desired function of the polymer, but can be, for example, 0.01 to 30 mol % of the total moles of each monomer unit contained in the copolymer (100 mol % of the first monomer units, second monomer units, and other monomer units). The total content of first monomer units 1B and 1C can be, for example, 0.01, 0.1, 1, 5, 10, 15, 20, 25, or 30 mol %, and may be within a range between any two of the values ​​exemplified here.

[0046] By adjusting the amount of each monomer unit, it is possible to change the type, number and amount of functional groups in a polymer obtained by introducing specific functional groups into each first monomer unit. The presence or absence and content of each monomer unit can be controlled by adjusting the production conditions of the copolymer, for example, by adjusting the temperature and pressure during polymerization. For example, increasing the temperature during polymerization can increase the amount of the allene structure-containing monomer units (first monomer unit 1B and first monomer unit 1C) bonded together, while decreasing the polymerization pressure can decrease the amount of the first monomer unit 1A, first monomer unit 1B, and first monomer unit 1C bonded together. The presence or absence and content of each monomer unit can be determined, for example, as follows: 13 In the C-NMR spectrum, the amount of a peak can be calculated based on the presence or absence of a peak appearing at a specific peak position, the peak intensity, the peak area, the amount of the compound charged, etc. Alternatively, it can be confirmed by infrared spectroscopy (IR) based on the absorption associated with each functional group. Specific examples are shown in the Examples.

[0047] 1.4 Copolymer characteristics The copolymer according to one embodiment of the present invention is measured in deuterated chloroform solvent. 13 In the C-NMR spectrum, a peak β can be present in the range of 190 to 220 ppm. Here, peak β can be a peak derived from an allene structure, and is thought to be associated with the first monomer unit 1B and / or 1C described above. Peak β can be observed at, for example, 190, 192, 194, 196, 198, 200, 202, 204, 206, 208, 210, 212, 214, 216, 218, 220 ppm, or within a range between any two of the values ​​exemplified herein. It should be noted that a plurality of peaks β may be observed, for example, two peaks (peak β1 and peak β2) may be observed. Peak β1 can be observed at, for example, 190, 192, 194, 196, 198, or 200 ppm, and may be within a range between any two of the values ​​exemplified here. Peak β2 can be observed at, for example, 200, 202, 204, 206, 208, 210, 212, 214, 216, 218, or 220 ppm, or may be within a range between any two of the values ​​exemplified here.

[0048] The copolymer according to one embodiment of the present invention is measured in deuterated chloroform solvent. 13 In the C-NMR spectrum, a peak α can be present in the range of 60 to 90 ppm. Here, peak α can be a peak derived from an acetylene structure, and is thought to be associated with the first monomer unit 1A described above. Peak α may be observed at, for example, 60, 62, 64, 66, 68, 70, 72, 74, 75, 76, 78, 80, 82, 84, 86, 88, 90 ppm, or may be within a range between any two of the values ​​exemplified herein. It should be noted that a plurality of peaks α may be observed, or two peaks α (peak α1 and peak α2) may be observed. Peak α1 may be observed at, for example, 60, 62, 64, 66, 68, 70, 72, 74, 75, or 76 ppm, or may be within a range between any two of the values ​​exemplified here. Peak α1 may be a peak based on a triple bond carbon to which hydrogen is bonded. Peak α2 may be observed at, for example, 70, 72, 74, 75, more than 75, 76, 78, 80, 82, 84, 86, 88, or 90 ppm, or may be within a range between any two of the values ​​exemplified here. Peak α2 may be a peak based on triple bond carbon to which carbon is bonded.

[0049] Furthermore, the copolymer according to one embodiment of the present invention has a viscosity measured in a deuterated chloroform solvent. 13 In the C-NMR spectrum, the peak intensity or peak area of ​​peak β relative to the peak intensity or peak area of ​​peak α is preferably 1% to 15%. The ratio of the peak intensity or area of ​​peak β to the peak intensity or area of ​​peak α can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15%, and may be within a range between any two of the values ​​exemplified here.

[0050] 13 The presence or absence of peaks in the C-NMR spectrum and their peak intensities (peak areas) can be confirmed by the methods described in the Examples or methods analogous thereto.

[0051] The copolymer according to one embodiment of the present invention preferably exhibits a single glass transition in a differential scanning calorimetry curve obtained by subjecting the copolymer to differential scanning calorimetry (DSC).

[0052] The observation of a single glass transition means that there is one step shift in the baseline in the differential scanning calorimetry curve obtained by differential scanning calorimetry (DSC). Furthermore, when one step shift in the baseline is observed in the differential scanning calorimetry curve, the copolymer is considered to be neither a block copolymer nor a mixture of homopolymers, but a random copolymer.

[0053] The method for obtaining a differential scanning calorimetry curve can be as described in the Examples. The glass transition temperature can be the midpoint glass transition temperature (Tmg) measured in accordance with JIS K 7121.

[0054] The glass transition temperature can be adjusted by, in particular, the glass transition temperatures of the homopolymers of the first monomer, the second monomer, and the other monomers, and the blending ratios thereof. The glass transition temperature of the copolymer is preferably Tp±10% [K] (ie, Tp±0.1×Tp [K]), where Tp [K] is the theoretical glass transition temperature of the copolymer. Here, when a copolymer is composed of monomer units derived from n types of monomers, Tp [K] can be such that the following formula (1) is satisfied when T1 [K] is the glass transition temperature of a homopolymer of a first monomer, C1 is the mass fraction of the copolymerization amount of the first monomer unit relative to 100 parts by mass of the copolymer, T2 [K] is the glass transition temperature of a homopolymer of a second monomer, C2 is the mass fraction of the copolymerization amount of the second monomer unit relative to 100 parts by mass of the copolymer, Tk [K] is the glass transition temperature of a homopolymer of a kth monomer, and Ck is the mass fraction of the copolymerization amount of the kth monomer unit relative to 100 parts by mass of the copolymer.

number

[0055] The copolymer according to one embodiment of the present invention may be a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, or the like. The copolymer according to one embodiment of the present invention may be a random copolymer, and the fact that it is a random copolymer can be confirmed by the observation of a single glass transition between the glass transition temperatures of the homopolymers constituting the copolymer in a differential scanning calorimetry curve. When the copolymer is composed of a first monomer unit and a second monomer unit, the fact that it is a random copolymer can be confirmed by the observation of a single glass transition between the glass transition temperature of the homopolymer of the first monomer and the glass transition temperature of the homopolymer of the second monomer.

[0056] The weight average molecular weight of the copolymer according to one embodiment of the present invention can be 1,000 to 2,000,000. The weight average molecular weight of the copolymer can be, for example, 1,000, 5,000, 10,000, 50,000, 100,000, 500,000, 1,000,000, or 2,000,000, and may be within a range between any two of the numerical values ​​exemplified here. The weight average molecular weight can be a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and can be, for example, a value measured under the measurement conditions described below. Device name: HLC-8320 (Tosoh Corporation) Column: Three TSKgel GMHHR-H columns in series Temperature: 40℃ Detection: Differential refractive index Solvent: tetrahydrofuran Calibration curve: Can be prepared using standard polystyrene (PS).

[0057] The copolymer according to one embodiment of the present invention can serve as a stepping stone for producing polymers that may have various substituents. As an example, the copolymer according to one embodiment of the present invention can be used as a raw material for the Huisgen reaction with an azide compound. For example, by subjecting an acetylene group contained in the copolymer to the Huisgen reaction with an azide compound (R-N3) having a substituent R, a compound having a triazole ring having a substituent R can be obtained. This makes it possible to obtain the desired compound with high efficiency and high accuracy, while suppressing the production of by-products.

[0058] 2. Copolymer manufacturing method A method for producing a copolymer according to one embodiment of the present invention includes a polymerization step in which raw material monomers including a first monomer and a second monomer are copolymerized to obtain a copolymer, and the first monomer unit 1A has an acetylene group in its side chain.

[0059] 2.1 First Monomer The first monomer can be represented by the following formula (2): [ka]

[0060] R in the above formula (2) 1 , R 2 , R 3 and R 4 is the same as in the above formula (1-A). 1 , R 2 , R 3 and R 4 is R in formula (1-B) 101 , R 102 , R 103 , R 104 The same can be said as R in the above formula (2). 1 , R 3 and R 4 is R in formula (1-C) 201 , R 203 , R 204 It can be the same as:

[0061] 2.2 Second Monomer The second monomer can be a monomer having a radically polymerizable group. The second monomer preferably includes at least one selected from the group consisting of a styrene-based monomer, a (meth)acrylic-based monomer, a diene-based monomer, a vinyl ether-based monomer, and an unsaturated nitrile-based monomer. These may be used alone or in combination.

[0062] The styrene-based monomer is, for example, a styrene-based monomer such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene, and α-methyl-p-methylstyrene.

[0063] Examples of the (meth)acrylic monomer include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, normal propyl acrylate, normal propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, secondary butyl acrylate, secondary butyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, normal octyl acrylate, normal octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, Examples of (meth)acrylic monomers include normal nonyl acrylate, normal nonyl methacrylate, isononyl acrylate, isononyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, ethoxydiethylene glycol acrylate, ethoxydiethylene glycol methacrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isobornyl acrylate, and isobornyl methacrylate. Note that the term "(meth)acrylic monomer (unit)" refers to an acrylic monomer (unit) and a methacrylic monomer (unit).

[0064] The diene monomer is, for example, a unit derived from a conjugated diene monomer such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, or chloroprene.

[0065] Examples of the vinyl ether monomer include vinyl acetate, vinyl propionate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, vinyl methyl ether, vinyl butyl ether, and vinyl octyl ether.

[0066] The unsaturated nitrile monomer is an unsaturated nitrile monomer such as acrylonitrile, methacrylonitrile, ethacrylonitrile, or phenylacrylonitrile.

[0067] 2.3 Charge amount of first monomer and second monomer, etc. In the polymerization step according to one embodiment of the present invention, when the total amount of the raw material monomers used in the polymerization step is taken as 100 parts by mass, the amount of the first monomer charged can be 1 to 99 parts by mass. The amount of the first monomer charged can be, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 parts by mass, and may be within a range between any two of the numerical values ​​exemplified here. In the polymerization step according to one embodiment of the present invention, when the total amount of the raw material monomers used in the polymerization step is 100 parts by mass, the amount of the second monomer charged can be 1 to 99 parts by mass. The amount of the second monomer charged is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 parts by mass, and may be within a range between any two of the numerical values ​​exemplified here. In the polymerization step according to one embodiment of the present invention, when the total amount of the raw material monomers used in the polymerization step is 100 parts by mass, the amount of monomers other than the first monomer and the second monomer charged can be 50 parts by mass or less, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts by mass, and may be within a range between any two of the numerical values ​​exemplified here.

[0068] The polymerization step can be a radical polymerization of the first monomer and the second monomer using an initiator. The polymerization initiator is not particularly limited, but examples thereof include azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile; and organic peroxides such as benzoyl peroxide, t-butyl peroxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexanoate, di-t-butyl peroxide, dicumyl peroxide, ethyl-3,3-di-(t-butylperoxy)butyrate, and 1,1,3,3-tetramethylbutoxyperoxy-2-ethylhexanoate. These may be used alone or in combination of two or more. The amount of the polymerization initiator used is not particularly limited, but may be, for example, 0.0, 0.2, 0.3, 0.4, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0 mol% relative to 100 mol% of all monomer units, and may be within a range between any two of the numerical values ​​exemplified here.

[0069] A chain transfer agent can be used in the polymerization step. Examples of the chain transfer agent include, but are not limited to, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, α-methylstyrene dimer, ethyl thioglycolate, limonene, and terpinolene. The amount of chain transfer agent used is not particularly limited as long as it is within a range that allows the target molecular weight to be obtained. For example, the amount of chain transfer agent used is 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 mol% relative to 100 mol% of all monomer units, and may be within a range between any two of the values ​​exemplified here.

[0070] In the polymerization process, first, the second monomer, the initiator, and the chain transfer agent are added to a solvent, and the gas phase is replaced with an inert gas such as nitrogen. Then, the first monomer is pumped with the inert gas and heated under pressure to polymerize the mixture. The polymerization conditions can be adjusted depending on the types of raw material monomers and the desired properties of the polymer. For example, the pressure can be 0.005 to 0.050 MPaG. The pressure can be, for example, 0.005, 0.010, 0.015, 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, or 0.050 MPaG, and may be within a range between any two of the numerical values ​​exemplified here. The temperature can be, for example, 40 to 100° C. The temperature can be, for example, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100° C., and may be within a range between any two of the values ​​exemplified here. When the copolymer contains the first monomer units 1B and / or 1C, a preferred example of the production conditions is a polymerization temperature of 80° C. and a pressure of 0.15 MPaG or higher. In the polymerization step, polymerization can be carried out until the polymerization rate reaches 5 to 50%. [Example]

[0071] The present invention will be described in more detail below based on examples, but the present invention should not be construed as being limited to these examples.

[0072] Example 1 A 1000 ml glass pressure vessel was charged with 400 ml of tetrahydrofuran, 208.3 g of styrene monomer, 1.1 g of dodecyl mercaptan, and 1.6 g of 1,1,3,3-tetramethylbutoxyperoxy-2-ethylhexanoate (Perocta O, manufactured by NOF Corporation), and the gas phase was replaced with nitrogen. 43.7 g of monovinylacetylene (MVA) was pumped in using nitrogen, and the pressure was increased to 0.01 MPaG. The reaction solution was heated to 70°C and reacted until the polymerization rate reached 30%. After cooling, the reaction solution was mixed with methanol to obtain a copolymer. The polymerization rate indicates the mass % of the obtained copolymer when the charged first monomer and second monomer are taken as 100 mass %. The number average molecular weight Mn of the obtained copolymer was 6608, and the weight average molecular weight Mw was 11930. The number average molecular weight Mn and the weight average molecular weight Mw were analyzed by gel permeation chromatography (GPC) under the following measurement conditions. Device name: HLC-8320 (Tosoh Corporation) Column: Three TSKgel GMHHR-H columns in series Temperature: 40℃ Detection: Differential refractive index Solvent: tetrahydrofuran Calibration curve: Prepared using standard polystyrene (PS).

[0073] Examples 2 to 9 A copolymer was obtained in the same manner as in Example 1, except that the types and amounts of the first and second monomers and the polymerization conditions were as shown in Table 1.

[0074] The resulting copolymer 13 The content of the first monomer unit 1A was determined by C-NMR analysis. the content of the first monomer unit 1A indicates the content of the first monomer unit 1A when the total of all monomer units contained in the copolymer is taken as 100 mol % (i.e., when the total of the first monomer units 1A, 1B, and 1C and the second monomer unit is taken as 100 mol %), 13 Measurement was performed by C-NMR under the following conditions. Device name: FT-NMR AVANCE300 (BRUKER) Solvent: deuterated chloroform Concentration: 6.25% by mass Temperature: 27℃ Accumulation count: 8000 times

[0075] Further, the obtained copolymer was subjected to differential scanning calorimetry (DSC) to determine the midpoint glass transition temperature (Tmg) in accordance with JIS K 7121. The measurement conditions are shown below. Measuring equipment: Seiko Electronics EXSTAR6000 DSC-6200 Amount of sample to be measured: 10 mg Heating / cooling: Cool from 25°C to -80°C at 10°C / min, hold at -80°C for 10 minutes, heat from -80°C to 150°C at 10°C / min Measurement atmosphere: Nitrogen

[0076] [Table 1]

[0077] Example 10 A 1000 ml glass pressure vessel was charged with cyclopentyl methyl ether (CPME), 208.3 g of styrene monomer, and 1.6 g of 1,1,3,3-tetramethylbutoxyperoxy-2-ethylhexanoate (Perocta O, manufactured by NOF Corporation), and the gas phase was replaced with nitrogen. 43.7 g of monovinylacetylene (MVA) was pumped in using nitrogen, and the pressure was increased to 0.01 MPaG. The reaction solution was heated to 70°C and reacted until the polymerization rate reached 100%. After cooling, the reaction solution was mixed with methanol to obtain a copolymer. Furthermore, in the same manner as in Example 1, the number average molecular weight Mn and polydispersity index PDI (Mw / Mn) were determined by gel permeation chromatography (GPC). The results are shown in Table 2.

[0078] (Examples 11 and 12) A copolymer was obtained in the same manner as in Example 10, except that the types and amounts of the first and second monomers and the polymerization conditions were as shown in Table 2.

[0079] The copolymer of Example 10 was subjected to the same procedure as in Example 1. 13 The obtained product was analyzed by C-NMR. 13 The C-NMR spectrum is shown in Figure 1. As shown in Figure 1, two peaks were observed in the range of 190 to 220 ppm (near 205 ppm (intensity 0.0300) and near 192 ppm (intensity 0.0029)). In addition, peaks were observed near 88 ppm (intensity 0.4166) and near 70 ppm (intensity 0.4201).

[0080] Differential scanning calorimetry (DSC) was performed on the copolymers of Examples 10 to 12 in the same manner as in Example 1 to obtain differential scanning calorimetry curves. Furthermore, the midpoint glass transition temperature (Tmg, hereinafter also referred to as Tg) was calculated in accordance with JIS K 7121. The differential scanning calorimetry curves are shown in Figure 2 (Example 10), Figure 4 (Example 11), and Figure 5 (Example 12). In each differential scanning calorimetry curve, a single glass transition was observed between 40 and 60°C. It was also confirmed that the glass transition temperature could be controlled by changing the type and ratio of the components blended. Furthermore, assuming that the Tg of polystyrene is 100°C (373.15K), the Tg of polymonovinylacetylene was estimated to be -57.8°C (215.35K) using the Fox equation based on the Tg of the copolymer according to Example 10 (58.81°C (331.96K)). Furthermore, assuming that the Tg of polymethyl methacrylate is 105°C and the Tg of polymonovinylacetylene is -57.8°C, the Tp of Examples 11 and 12 was calculated. The Tg of the copolymers according to Examples 11 and 12 was within ±10% [K] of the Tp of the copolymers according to Examples 11 and 12.

[0081] The IR spectrum of the copolymer of Example 10 was obtained by infrared spectroscopy (IR). The results are shown in Figure 3. As shown in Figure 3, -1 An absorption peak thought to be derived from the acetylene group was confirmed in the vicinity. The measurement conditions are shown below. Measurement equipment: Perkin Elmer FT-IR Spectrometer Frontier Detector: ST Janan Durascope Focusing lens: KRS-5 Measurement method: Single reflection ATR method Measurement start: 4000cm -1 Measurement end: 400cm -1 Resolution: 4cm -1 Accumulation count: 16 times Spacing: 1.0cm -1

[0082] [Table 2]

[0083] (Example 1-2 (same conditions as Example 10)) A 1000 ml glass pressure vessel was charged with cyclopentyl methyl ether (CPME), 208.3 g of styrene monomer, and 1.6 g of 1,1,3,3-tetramethylbutoxyperoxy-2-ethylhexanoate (Perocta O, manufactured by NOF Corporation), and the gas phase was replaced with nitrogen. 43.7 g of monovinylacetylene (MVA) was pumped in using nitrogen, and the pressure was increased to 0.01 MPaG. The reaction solution was heated to 70°C and reacted until the polymerization rate reached 100%. After cooling, the reaction solution was mixed with methanol to obtain a copolymer.

[0084] (Examples 2-2 to 5-2, 9-2) A copolymer was obtained in the same manner as in Example 1-2, except that the types and amounts of the first and second monomers and the polymerization conditions were as shown in Table 3.

[0085] (Example 6-2) A 1000 ml glass pressure vessel was charged with cyclopentyl methyl ether (CPME), 208.3 g of chloroprene monomer, 1.1 g of dodecyl mercaptan, and 1.6 g of 1,1,3,3-tetramethylbutoxyperoxy-2-ethylhexanoate (Perocta O, manufactured by NOF Corporation), and the gas phase was replaced with nitrogen. 43.7 g of monovinyl acetylene (MVA) was pumped in using nitrogen, and the pressure was increased to 0.01 MPaG. The reaction solution was heated to 70°C and reacted until the polymerization rate reached 100%. After cooling, the reaction solution was mixed with methanol to obtain a copolymer.

[0086] (Examples 7-2 and 8-2) A copolymer was obtained in the same manner as in Example 6-2, except that the types and amounts of the first and second monomers and the polymerization conditions were as shown in Table 3.

[0087] The copolymers according to Examples 1-2 to 9-2 were subjected to the same procedure as in Example 1.13 The content of the first monomer unit 1A was determined by C-NMR analysis. Differential scanning calorimetry (DSC) was performed in the same manner as in Example 1 to obtain a differential scanning calorimetry curve, and the midpoint glass transition temperature (Tmg) was calculated in accordance with JIS K 7121. The results are shown in Table 3.

[0088] [Table 3]

Claims

1. A copolymer comprising a first monomer unit 1A derived from a first monomer and a second monomer unit 1B derived from a second monomer, A copolymer, wherein the first monomer unit 1A is a monomer unit having an acetylene group in a side chain.

2. The copolymer of claim 1 , A copolymer, wherein the first monomer unit 1A is a unit represented by the following formula (1-A): 【Chemistry 1-A】 (In formula (1-A), R １ is any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group; R ２ , R ３ , R ４ are each independently any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group.

3. The copolymer according to claim 1 or claim 2, The copolymer is measured in deuterated chloroform solvent. １３ A copolymer having at least one peak β observed in the range of 190 to 220 ppm in a C-NMR spectrum.

4. The copolymer according to claim 3 , wherein the copolymer has an allene structure in at least one of a main chain and a side chain.

5. The copolymer according to claim 4, further comprising at least one selected from a first monomer unit 1B derived from a first monomer and a first monomer unit 1C derived from a first monomer, The first monomer unit 1B is represented by the following formula (1-B): The first monomer unit 1C is a copolymer represented by the following formula (1-C): 【Chemistry 1-B】 (In formula (1-B), R １０１ is any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group; R １０２ , R １０３ , R １０４ are each independently any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group. 【Chemistry 1-C】 (In formula (1-C), R ２０１ is any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group; R ２０３ , R ２０４ are each independently any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group.

6. The copolymer of claim 2, R １ is hydrogen, copolymer.

7. The copolymer according to claim 1 or claim 2, The second monomer is a monomer having a radical polymerizable group, and includes at least one selected from the group consisting of a styrene-based monomer, a (meth)acrylic-based monomer, a diene-based monomer, a vinyl ether-based monomer, and an unsaturated nitrile-based monomer.

8. The copolymer according to claim 1 or claim 2, a content of the first monomer unit 1A relative to a total of 100 mol % of the first monomer unit derived from the first monomer contained in the copolymer, the second monomer unit, and other monomer units is 1 to 99 mol %; Copolymer.

9. 3. The copolymer according to claim 1 or 2, wherein a single glass transition is observed in a differential scanning calorimetric curve of the copolymer; The glass transition temperature of the copolymer is Tp±10% [K], where Tp [K] is the theoretical glass transition temperature of the copolymer; The copolymer is composed of monomer units derived from n types of monomers, Tp [K] is a copolymer that satisfies the following formula (1), when T1 [K] is the glass transition temperature of a homopolymer of a first monomer, C1 is the mass fraction of the copolymerization amount of the first monomer unit relative to 100 parts by mass of the copolymer, T2 [K] is the glass transition temperature of a homopolymer of a second monomer, C2 is the mass fraction of the copolymerization amount of the second monomer unit relative to 100 parts by mass of the copolymer, Tk [K] is the glass transition temperature of a homopolymer of a k-th monomer, and Ck is the mass fraction of the copolymerization amount of the k-th monomer unit relative to 100 parts by mass of the copolymer. [Equation 1]

10. The copolymer according to claim 1 or 2, which is used as a raw material for a Huisgen reaction with an azide compound.

11. A method for producing a copolymer, comprising a polymerization step: In the polymerization step, raw material monomers including a first monomer and a second monomer are copolymerized to obtain the copolymer including first monomer units 1A derived from the first monomer and second monomer units derived from the second monomer; The production method, wherein the first monomer unit 1A is a monomer unit having an acetylene group in a side chain.

12. A method for producing the copolymer according to claim 11, comprising: The method for producing the first monomer is represented by the following formula (2): 【Chemistry 2】 (In formula (2), R １ is any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group; R ２ , R ３ , R ４ are each independently any one selected from the group consisting of hydrogen, chlorine, bromine, iodine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted heterocyclyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group.

13. A method for producing the copolymer according to claim 11 or 12, comprising: the second monomer is a monomer having a radical polymerizable group and includes at least one selected from the group consisting of a styrene-based monomer, a (meth)acrylic-based monomer, a diene-based monomer, a vinyl ether-based monomer, and an unsaturated nitrile-based monomer.

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