Method for producing triazole skeleton-containing polymer, triazole skeleton-containing polymer, and composition

Abstract

To provide a method for producing a triazole skeleton-containing polymer having a desired substituent, and to provide the triazole skeleton-containing polymer.SOLUTION: The present invention provides a method for producing a triazole-skeleton-containing polymer, the method including a step of reacting an acetylene group contained in a starting material polymer with an azide group-containing compound to obtain the triazole-skeleton-containing polymer, the starting material polymer being a polymer containing a first monomer unit 1A derived from a monomer having the acetylene group and a second monomer unit derived from a second monomer, the triazole-skeleton-containing polymer having a triazole-skeleton-containing monomer unit and the second monomer unit.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a triazole skeleton-containing polymer, a triazole skeleton-containing polymer, and a composition thereof. [Background technology]

[0002] In recent years, polymers having various functions have been in demand, and polymers having desired structures and substituents depending on the applications have been in demand. Summary of the Invention [Problem to be solved by the invention]

[0003] The present invention has been made in view of the above circumstances, and provides a method for producing a triazole skeleton-containing polymer having a desired substituent, and a triazole skeleton-containing polymer. [Means for solving the problem]

[0004] According to the present invention, there is provided a method for producing a triazole skeleton-containing polymer, the method comprising the step of reacting an acetylene group contained in a raw material polymer with an azide group-containing compound to obtain the triazole skeleton-containing polymer, the raw material polymer being a polymer containing first monomer units 1A derived from a monomer having the acetylene group and second monomer units derived from a second monomer, and the triazole skeleton-containing polymer having the triazole skeleton-containing monomer units and the second monomer units.

[0005] Various embodiments of the present invention will be described below as examples, and the embodiments shown below can be combined with each other. [1] A method for producing a triazole skeleton-containing polymer, the method comprising the step of reacting an acetylene group contained in a raw material polymer with an azide group-containing compound to obtain the triazole skeleton-containing polymer, the raw material polymer comprising first monomer units 1A derived from a first monomer having the acetylene group and second monomer units derived from a second monomer, and the triazole skeleton-containing polymer comprises the triazole skeleton-containing monomer units and the second monomer units. [2] The method according to [1], wherein the first monomer unit 1A is 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 production method according to [1] or [2], wherein the triazole skeleton-containing monomer unit is at least one of units represented by the following formula (2) and the following formula (3):

[0006] [ka] (In formula (2), R 15 is an organic group, and R 11is 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 12 , R 13 , R 14 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.

[0007] [ka] (In formula (3), R 25 is an organic group, and R 21 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 22 , R 23 , R 24 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. [4] The production method according to any one of [1] to [3], 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. [5] A triazole skeleton-containing polymer, comprising a triazole skeleton-containing monomer unit and a second monomer unit, wherein the triazole skeleton-containing monomer unit is a repeating unit represented by at least one of the following formulas (2) and (3):

[0008] [ka] (In formula (2), R 15 is an organic group, and R 11 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 12 , R 13 , R 14 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.

[0009] [ka] (In formula (3), R 25 is an organic group, and R 21is 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 22 , R 23 , R 24 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 triazole skeleton-containing polymer according to [5], further comprising a first monomer unit 1A derived from a first monomer having an acetylene group and 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. [7] The triazole skeleton-containing polymer according to [5] or [6], wherein the triazole skeleton-containing polymer has a molecular weight of 1000 or more, and the molecular weight of the triazole skeleton-containing polymer is measured in a deuterated chloroform solvent. 13 A triazole skeleton-containing polymer having at least one peak β observed in the range of 190 to 220 ppm in a C-NMR spectrum. [8] The triazole skeleton-containing polymer according to [7], wherein the triazole skeleton-containing polymer has an allene structure in at least one of the main chain and the side chain. [9] The triazole skeleton-containing polymer according to [8], further comprising at least one selected from a first monomer unit 1B and a first monomer unit 1C derived from the 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), R201 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 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.

[10] The triazole skeleton-containing polymer according to any one of [5] to [9], wherein the second monomer unit is a monomer unit derived from a second 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.

[11] In the triazole skeleton-containing polymer according to any one of [5] to

[10] , when the triazole skeleton-containing monomer unit is represented by formula (2), R 15 contains a polymer chain containing a third monomer unit derived from a third monomer, and when the triazole skeleton-containing monomer unit is represented by formula (3), R 25 a triazole skeleton-containing polymer comprising a polymer chain containing a third monomer unit derived from a third monomer, wherein the third monomer is a monomer having a radical polymerizable group and comprises 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.

[12] In the triazole skeleton-containing polymer according to any one of [5] to

[11] , when the triazole skeleton-containing monomer unit is represented by formula (2), R 15contains at least one selected from the group consisting of a carboxy group, an ester bond, an ether bond, an alkyl group, an alkenyl group, an allyl group, an aryl group, a mercapto group, a heterocyclyl group, a hydroxyl group, an amino group, and a silyl group, and when the triazole skeleton-containing monomer unit is represented by formula (3), R 25 is a triazole skeleton-containing polymer containing at least one selected from the group consisting of a carboxy group, an ester bond, an ether bond, an alkyl group, an alkenyl group, an allyl group, an aryl group, a mercapto group, a heterocyclyl group, a hydroxyl group, an amino group, and a silyl group.

[13] The triazole skeleton-containing polymer according to any one of [5] to

[12] , wherein the content of the triazole skeleton-containing monomer units is 1 to 99 mol % relative to a total of 100 mol % of the triazole skeleton-containing monomer units, the first monomer units derived from the first monomer, the second monomer units derived from the second monomer, and other monomer units contained in the triazole skeleton-containing polymer.

[14] The triazole skeleton-containing polymer according to any one of [5] to

[13] , A single glass transition point was observed in the differential scanning calorimetry curve. the glass transition temperature 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 triazole skeleton-containing polymer that satisfies the following formula (1), where T1 [K] is the glass transition temperature of a homopolymer made of the triazole skeleton-containing monomer, C1 is the mass fraction of the copolymerization amount of the triazole skeleton-containing 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

[15] A composition comprising the triazole skeleton-containing polymer according to any one of [5] to

[14] , wherein the content of a triazole skeleton-containing compound A in the composition is 5% by mass or less relative to 100% by mass of the triazole skeleton-containing polymer, and the triazole skeleton-containing compound A has a triazole skeleton and a polymerizable group bonded to the triazole skeleton. [Effects of the Invention]

[0010] According to the production method of the present invention, it is possible to provide a method for producing a triazole skeleton-containing polymer having a desired substituent, a triazole skeleton-containing polymer, and a composition containing the triazole skeleton-containing polymer. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 shows the 13C-NMR spectra of Copolymer 2 and the triazole skeleton-containing polymer according to Example 12. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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."

[0013] 1. Method for producing triazole skeleton-containing polymer A method for producing a triazole skeleton-containing polymer according to one embodiment of the present invention includes a step of reacting an acetylene group contained in a raw material polymer with an azide group-containing compound to obtain a triazole skeleton-containing polymer. Here, the raw material polymer is a polymer containing first monomer units 1A derived from a monomer having an acetylene group which may have a substituent and second monomer units derived from a second monomer, and the triazole skeleton-containing polymer has triazole skeleton-containing monomer units and second monomer units. According to the present invention, an acetylene group-containing polymer having a specific structure is used as a raw material polymer, and an azide group-containing compound having a specific substituent is reacted with the raw material polymer in accordance with the design of the target triazole skeleton-containing polymer, whereby the reaction can be carried out quickly and reliably to obtain the target triazole skeleton-containing polymer.

[0014] 1.1 Raw polymer The raw material polymer according to the present invention is a polymer containing first monomer units 1A derived from a monomer having an acetylene group and second monomer units derived from a second monomer.

[0015] 1.1.1 First monomer unit In the present invention, a monomer unit derived from a first monomer, which is a monomer having an acetylene group, 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 starting polymer of the present invention contains first monomer unit 1A.

[0016] 1.1.1.1 First Monomer Unit 1A The first monomer unit 1A is a monomer unit derived from a monomer having an acetylene group, and 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).

[0017] [ka]

[0018] In formula (1-A), R 1 R 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]

[0019] 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]

[0020] 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]

[0021] In formula (1-A), R 2 , R 3 , R 4 R 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:

[0022] 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).

[0023] 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.

[0024] A specific example of the first monomer unit 1A is R 1 , R 2 , R 3 , R 4 are each hydrogen. The raw polymer 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 raw polymer 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.

[0025] 1.1.1.2 First Monomer Unit 1B The raw polymer 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 starting polymer 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).

[0026] [ka]

[0027] 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:

[0028] In formula (1-B), R 102 , R 103 , R 104 is R 2 , R 3 , R4 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. 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:

[0029] 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).

[0030] 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.

[0031] A specific example of the first monomer unit 1B is R 101 , R 102 , R 103 , R 104 are each hydrogen.

[0032] 1.1.1.3 First monomer unit 1C The starting polymer 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).

[0033] [ka]

[0034] 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:

[0035] 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:

[0036] Whether the starting polymer 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. The starting polymer according to one embodiment of the present invention has 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. This allows, for example, first monomer unit 1A having an acetylene group to be used as a functionalization site for introducing a specific substituent, and first monomer unit 1B and / or first monomer unit 1C to be used as a functionalization site for introducing another substituent.

[0037] 1.1.2 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 raw polymer, and the ratio of the amounts when multiple types of second monomers are contained, can be appropriately set depending on the target polymer.

[0038] 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.

[0039] 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).

[0040] 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.

[0041] 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.

[0042] The unsaturated nitrile monomer unit is a unit derived from an unsaturated nitrile monomer such as acrylonitrile, methacrylonitrile, ethacrylonitrile, or phenylacrylonitrile.

[0043] 1.1.3 Amount of each monomer unit contained in the raw polymer The content of the first monomer unit in the raw polymer 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 raw polymer (100 mol% total of the first monomer unit, second monomer unit, and other monomer units). The content of the first monomer unit 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 mol%, and 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.

[0044] Similarly, the content of the second monomer unit in the raw polymer 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 raw polymer (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.

[0045] The raw polymer 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 raw polymer (100 mol% 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.

[0046] The content of the first monomer units 1A in the raw polymer 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 raw polymer (100 mol % total of the first monomer units, second monomer units, and other monomer units). The content of the first monomer units 1A 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 mol %, and may be within a range between any two of the values ​​exemplified here.

[0047] Similarly, the content of the first monomer units 1B in the raw polymer can be set appropriately 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 raw polymer (100 mol% total of the first monomer units, second monomer units, and other monomer units). The content of the first monomer units 1B is, 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 numerical values ​​exemplified here. For example, it may be 0, or within a range between any two of the numerical values ​​exemplified here.

[0048] The content of the first monomer unit 1C in the raw polymer 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 raw polymer (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.

[0049] The total content of first monomer units 1B and 1C (content of monomer units containing an allene structure) in the raw polymer 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 raw polymer (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 can be within a range between any two of the values ​​exemplified here.

[0050] 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 raw material polymer, 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, it can be calculated based on the presence or absence of peaks appearing at specific peak positions, peak intensity, peak area, amount charged, etc. It can also be confirmed by infrared spectroscopy (IR) based on the absorption associated with each functional group.

[0051] 1.1.4 Characteristics of raw polymer The raw polymer 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.

[0052] The raw material polymer according to one embodiment of the present invention can have a peak α in the range of 60 to 90 ppm in a 13C-NMR spectrum measured in deuterated chloroform solvent. 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.

[0053] In addition, in the 13C-NMR spectrum of the raw material polymer measured in deuterated chloroform solvent, 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.

[0054] The presence or absence of peaks in the 13C-NMR spectrum and their peak intensities (peak areas) can be confirmed by the methods described in the Examples or methods analogous thereto.

[0055] It is preferable that the starting polymer exhibits a single glass transition in a differential scanning calorimetry curve obtained by subjecting the starting polymer to differential scanning calorimetry (DSC).

[0056] 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.

[0057] The method for obtaining a differential scanning calorimetric 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.

[0058] 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 raw polymer is preferably Tp±10% [K] (ie, Tp±0.1×Tp [K]), where Tp [K] is the theoretical glass transition temperature of the raw polymer. Here, when the raw polymer 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 raw polymer, 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 raw polymer, 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 raw polymer.

number

[0059] The raw polymer may be a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, or the like. The raw polymer can 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 raw polymer in a differential scanning calorimetry curve. When the raw polymer 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.

[0060] The weight average molecular weight of the raw material polymer can be 1,000 to 2,000,000. The weight average molecular weight of the raw material polymer is, 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).

[0061] The raw polymer can serve as a stepping stone for producing polymers that may have various substituents. For example, a copolymer 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 raw polymer 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.

[0062] 1.1.5 Manufacturing method of raw polymer The method for producing a raw polymer according to an embodiment of the present invention is not particularly limited, but may include a polymerization step in which raw monomers including a first monomer and a second monomer are copolymerized to obtain a raw polymer. The first monomer unit 1A has an acetylene group in its side chain.

[0063] The first monomer can be represented by the following formula (4): [ka]

[0064] R in the above formula (4) 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 (4). 1 , R 3 and R 4 is R in formula (1-C) 201 , R 203 , R 204 It can be the same as:

[0065] 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.

[0066] 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.

[0067] 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).

[0068] 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.

[0069] 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.

[0070] The unsaturated nitrile monomer is an unsaturated nitrile monomer such as acrylonitrile, methacrylonitrile, ethacrylonitrile, or phenylacrylonitrile.

[0071] In the polymerization step of the raw material polymer 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 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 of the raw polymer 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 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 of the raw material polymer 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.

[0072] 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.

[0073] 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.

[0074] 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 0.05 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%.

[0075] 1.2 Azide group-containing compounds The azide group-containing compound is not particularly limited as long as it is a compound having an azide group, and can be selected according to the target triazole skeleton-containing polymer. In the reaction step, one or more azide group-containing compounds can be used, and the amount thereof and the quantitative ratio when multiple types of azide group-containing compounds are used can also be selected according to the target triazole skeleton-containing polymer.

[0076] The azide group-containing compound is R 5 -N3, and R 5 is any organic group. The molecular weight of the azide group-containing compound is not particularly limited, and it may be a low molecular weight compound or a polymer chain containing repeating units. When the azide group-containing compound is a low molecular weight compound, its molecular weight can be 67 to 1000. The molecular weight is, for example, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000, and may be within a range between any two of the numerical values ​​exemplified here. Furthermore, when the azide group-containing compound is a polymer chain, its weight average molecular weight can be 1,000 to 2,000,000. The weight average molecular weight of the azide group-containing compound is, 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.

[0077] The azide group-containing compound is (R 5 may contain at least one selected from the group consisting of a carboxy group, an ester bond, an ether bond, an alkyl group, an alkenyl group, an allyl group, an aryl group, a mercapto group, a heterocyclyl group, a hydroxyl group, an amino group, and a silyl group. As an example, the azide group-containing compound may be an alkyl group having 1 to 20 carbon atoms, which may have a substituent. Examples of the substituent include 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. Some of the carbon atoms of the alkyl group may be substituted with a heteroatom, and examples of the heteroatom include oxygen, sulfur, and nitrogen.

[0078] As another example, R 5 The polymer chain may include a polymer chain including a third monomer unit derived from a third monomer. The third monomer may be a monomer having a radical polymerizable group. The third monomer may include 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.

[0079] 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.

[0080] 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).

[0081] 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.

[0082] 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.

[0083] The unsaturated nitrile monomer is an unsaturated nitrile monomer such as acrylonitrile, methacrylonitrile, ethacrylonitrile, or phenylacrylonitrile.

[0084] 1.3 Reaction conditions In the reaction step according to one embodiment of the present invention, the acetylene group contained in the raw polymer is reacted with an azide group-containing compound to obtain a triazole skeleton-containing polymer by Huisgen reaction. The Huisgen reaction, known as click chemistry, involves the azide and acetylene groups reacting only with each other mildly and is stable against nucleophiles, electrophiles, and solvents commonly used in standard reaction conditions. Furthermore, the resulting triazole ring-containing polymer is also stable, allowing these groups to react quickly and reliably to yield the desired triazole skeleton-containing polymer.

[0085] In the reaction step, at least a portion of the acetylene groups contained in the raw material polymer may be reacted with an azide group-containing compound, and the resulting triazole skeleton-containing polymer may have the first monomer unit 1A. In the reaction step, of 100 mol % of first monomer units 1A contained in the raw polymer, acetylene groups contained in 1 to 100 mol % of the first monomer units 1A can be reacted with an azide group-containing compound to form a triazole skeleton. In the reaction step, of 100 mol % of first monomer units 1A contained in the raw polymer, the amount of first monomer units 1A reacted with the azide group-containing compound is 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or 100 mol %, and may be within a range between any two of the values ​​exemplified here. The reaction rate of the first monomer unit 1A can be controlled by adjusting the conditions of the Huisgen reaction, and the reaction can be carried out with high accuracy and high efficiency. The presence and amount of acetylene groups and first monomer units 1A in the triazole skeleton-containing polymer after the reaction can be confirmed by the same method as the above-mentioned method for confirming the presence and amount of acetylene groups and first monomer units 1A in the raw material polymer.

[0086] When the raw material polymer has an allene structure (when it has first monomer unit 1B and / or first monomer unit 1C), the resulting triazole skeleton-containing polymer may have an allene structure or may have first monomer unit 1B and / or first monomer unit 1C. In the reaction step, at least a portion of the allene structure contained in the raw polymer may be converted to another structure (e.g., introduction of a functional group). The allene structure contained in the raw polymer may also be reacted with any compound (e.g., a compound other than an azide group-containing compound) to use the allene structure as another functionalization site. The allene structure may be converted simultaneously with the Huisgen reaction, or may be converted and functionalized in a separate reaction step before or after the Huisgen reaction for synthesizing the triazole skeleton-containing polymer. It is preferable to convert and functionalize the allene structure simultaneously with the Huisgen reaction or before the Huisgen reaction. In the reaction step, of 100 mol % of the first monomer units 1B and 1C contained in the raw material polymer, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or 100 mol % may remain in the triazole skeleton-containing polymer, and may be within a range between any two of the numerical values ​​exemplified here. The residual ratio of the first monomer unit 1B and the first monomer unit 1C can be controlled by adjusting the reaction conditions, for example, by adjusting the type and amount of the reagent used in the Huisgen reaction. The presence and amount of the allene structure and the first monomer units 1B and 1C in the triazole skeleton-containing polymer after the reaction can be confirmed by the same method as the above-mentioned method for confirming the presence and amount of the allene structure and the first monomer units 1B and 1C in the raw material polymer.

[0087] The conditions for the Huisgen reaction are not particularly limited, but it is preferable to use a copper compound such as copper (II) acetate monohydrate as a catalyst. Examples of the solvent include linear alkanes such as 2-methylbutane, amylene, nitrooctane, pentane, hexane, heptane, octane, nonane, and decane; cyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, and ethylcyclohexane; branched alkanes such as 2-methylbutane, isopentane, 2,2,4-trimethylpentane, isohexane, isopentane, and isooctane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, trichlorobenzene, parachlorobenzotrifluoride, anisole, and nitrobenzene; alcohols including methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, tertiary butanol, 2-ethoxyethanol, 2-butoxyethanol, α-terpineol, pentanols, hexanols, benzyl alcohol, and furfuryl alcohol; Ethers such as ethyl ether, dipropyl ether, dibutyl ether, tertiary butyl methyl ether, cyclopentyl methyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,3-dioxolane, and morpholine; ketones such as acetone, ethyl methyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl normal amyl ketone, methyl isoamyl ketone, diethyl ketone, cyclohexanone, and isophorone; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isoamyl acetate, propyl propionate, butyl propionate, ethylene carbonate, dimethyl carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, propiolactone, and γ-butyrolactone; nitrile compounds including acetonitrile, propionitrile, butyronitrile, succinonitrile, capronitrile, adiponitrile, and benzonitrile; dichloromethane, chloroform, 1,Examples of suitable solvents include alkyl halides such as 2-dichloroethane, trichloroethane, tetrachloroethane, monochloropropane, dichloropropane, trichloropropane, and chlorobutane; vegetable oils such as pine oil, rapeseed oil, palm oil, soybean oil, castor oil, and linseed oil; DMSO, dimethylformamide, and dimethylacetamide; and also tetrahydrofuran, cyclopentyl methyl ether, diethyl ether, acetonitrile, dimethylformamide, and dimethyl sulfoxide. The reaction temperature can be set to 0 to 80°C. The reaction time can be 0.5 to 48 hours.

[0088] 2. Triazole skeleton-containing polymer A triazole skeleton-containing polymer according to one embodiment of the present invention comprises a triazole skeleton-containing monomer unit and a second monomer unit, and the triazole skeleton-containing monomer unit is at least one of repeating units represented by the following formula (2) and formula (3). The triazole skeleton-containing polymer according to one embodiment of the present invention may have a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3), or may have a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3). The triazole skeleton-containing polymer according to one embodiment of the present invention may comprise a polymer having a structural unit represented by formula (2) as the triazole skeleton-containing monomer unit, or a polymer having a structural unit represented by formula (3) as the triazole skeleton-containing monomer unit, or may comprise a polymer having a structural unit represented by formula (2) as the triazole skeleton-containing monomer unit and a polymer having a structural unit represented by formula (3) as the triazole skeleton-containing monomer unit. [ka] [ka]

[0089] In equation (2), R 15 can be an organic group.11 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 12 , R 13 , R 14 can each independently be 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.

[0090] R in Equation (2) 15 Regarding the azide group-containing compound, 5 It can be made in the same form as R 15 is R 5 can be considered identical to R 11 Regarding R in formula (1-A), 1 A specific example is R 11 can be hydrogen. R 11 is R in formula (1-A) 1 can be considered identical to Also, R 12 , R 13 , R 14 Regarding R in formula (1-A), 2 , R 3 , R 4 A specific example is R 12 , R 13 , R 14 R 12 , R 13 , R 14 is R in formula (1-A) 2 , R3 , R 4 can be considered identical to

[0091] R in Equation (3) 25 is R in Equation (2) 15 The same can be said about R in Equation (3). 22 , R 23 , R 24 is R in Equation (2) 12 , R 13 , R 14 The same can be said. R in Equation (3) 25 Regarding the azide group-containing compound, 5 It can be made in the same form as R 25 is R 5 can be considered identical to R 21 Regarding R in formula (1-A), 1 A specific example is R 21 can be hydrogen. R 21 is R in formula (1-A) 1 can be considered identical to Also, R 22 , R 23 , R 24 Regarding R in formula (1-A), 2 , R 3 , R 4 A specific example is R 22 , R 23 , R 24 R 22 , R 23 , R 24 is R in formula (1-A) 2 , R 3 , R 4 can be considered identical to

[0092] As described above, the triazole skeleton-containing polymer may contain the first monomer unit derived from the raw material polymer, or may contain the first monomer unit 1A. The first monomer unit 1A is as described above. The triazole skeleton-containing polymer may also contain the first monomer unit 1B and the first monomer unit 1C. The first monomer unit 1B and the first monomer unit 1C are as described above. The content of the triazole skeleton-containing monomer units relative to a total of 100 mol % of the triazole skeleton-containing monomer units, first monomer units (including all monomer units derived from the first monomer), second monomer units, and other monomer units contained in the triazole skeleton-containing polymer can be 1 to 99 mol %, 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 %, and may be within a range between any two of the numerical values ​​exemplified here. The content of the second monomer units relative to the total of 100 mol% of the triazole skeleton-containing monomer units, first monomer units (including all monomer units derived from the first monomer), second monomer units, and other monomer units contained in the triazole skeleton-containing polymer can be 1 to 99 mol%, 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%, and may be within a range between any two of the numerical values ​​exemplified here. The content of the first monomer units (including all monomer units derived from the first monomer) relative to the total of 100 mol% of the triazole skeleton-containing monomer units, first monomer units (including all monomer units derived from the first monomer), second monomer units and other monomer units contained in the triazole skeleton-containing polymer can be 0 to 99 mol%, for example, 0, 0.1, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 mol%, and may be within a range between any two of the numerical values ​​exemplified here. The content of the first monomer units 1A in the triazole skeleton-containing polymer may be appropriately set depending on the desired function of the polymer, but 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 % in total of the triazole skeleton-containing monomer units, first monomer units, second monomer units, and other monomer units). The content of the first monomer units 1A may be, for example, 0, 0.01, 0.1, 0.5, 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.

[0093] Similarly, the content of the first monomer units 1B 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 triazole skeleton-containing monomer units, first monomer units, second monomer units, and other monomer units). The content of the first monomer units 1B is, for example, 0, 0.01, 0.1, 1, 5, 10, 15, 20, 25, or 30 mol%, and may be within a range between any two of the numerical values ​​exemplified here. For example, it may be 0, or within a range between any two of the numerical values ​​exemplified here.

[0094] The content of the first monomer units 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 triazole skeleton-containing monomer units, first monomer units, second monomer units, and other monomer units). The content of the first monomer units 1C can be, for example, 0, 0.01, 0.1, 1, 5, 10, 15, 20, 25, or 30 mol %, or it can be within a range between any two of the values ​​exemplified here.

[0095] The other monomer units may not include the third monomer unit, and the polymer chain including the third monomer unit may be part of the second monomer unit and included in the second monomer unit. The content of the first monomer unit contained in the raw material polymer and the content of the triazole skeleton-containing monomer unit (azide bond amount) contained in the triazole skeleton-containing polymer can be determined by analysis using C-NMR, and specifically, can be determined by the method described in the Examples. The content of triazole skeleton-containing monomer units (azide bond content) can also be calculated from the nitrogen atom content determined by chemical analysis. For example, the nitrogen atom content in a polymer can be determined using an elemental analyzer (Sumigraph 220F, manufactured by Sumika Chemical Analysis Center, Ltd.) with a 100 mg dried sample. The electric furnace temperatures are set to 900°C for the reactor, 600°C for the reduction furnace, 70°C for the column, and 100°C for the detector. Oxygen is used as the combustion gas at a flow rate of 0.2 ml / min, and helium is used as the carrier gas at a flow rate of 80 ml / min. A calibration curve can be created using aspartic acid (10.52%), which has a known nitrogen content, as a standard substance.

[0096] 2.1 Characteristics of triazole-containing polymers The triazole skeleton-containing polymer according to one embodiment of the present invention is measured in a 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.

[0097] The triazole skeleton-containing polymer according to one embodiment of the present invention is measured in a 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 can be observed, for example, at 70, 72, 74, greater than 75, 76, 78, 80, 82, 84, 86, 88, 90 ppm, or within a range between any two of the values ​​exemplified herein. 13 The presence or absence of peaks in the C-NMR spectrum can be confirmed by the method described in the Examples or a method similar thereto. Peak α2 can be a peak based on a triple bond carbon bonded to carbon.

[0098] In the triazole skeleton-containing polymer according to one embodiment of the present invention, a plurality of glass transitions may be observed, but a single glass transition is preferably observed, in a differential scanning calorimetry curve obtained by subjecting the triazole skeleton-containing polymer to differential scanning calorimetry (DSC).

[0099] 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.

[0100] The method for obtaining a differential scanning calorimetric 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. The above glass transition temperature can be obtained by adjusting the method for producing the triazole skeleton-containing polymer, particularly the types and amounts of each raw material monomer and polymer, and the reaction conditions. The glass transition temperature of the triazole skeleton-containing polymer is preferably Tp±10% [K] (i.e., Tp±0.1×Tp [K]), where Tp [K] is the theoretical glass transition temperature of the triazole skeleton-containing polymer. Here, when the triazole skeleton-containing polymer is composed of monomer units derived from n types of monomers, Tp [K] can be determined to satisfy the following formula (1), where T1 [K] is the glass transition temperature of a homopolymer composed of the triazole skeleton-containing monomer (a homopolymer of a first monomer reacted with an azide group-containing compound), C1 is the mass fraction of the copolymerization amount of the triazole skeleton-containing monomer unit (the first monomer unit reacted with an azide group-containing compound) relative to 100 parts by mass of the triazole skeleton-containing polymer, 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 triazole skeleton-containing polymer, 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

[0101] The triazole skeleton-containing polymer 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 triazole skeleton-containing polymer according to one embodiment of the present invention can 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 homopolymers constituting the triazole skeleton-containing polymer in a differential scanning calorimetry curve. When the triazole skeleton-containing polymer is composed of a triazole skeleton-containing 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 point of the homopolymer of the triazole skeleton-containing monomer unit and the glass transition point of the homopolymer of the second monomer. The weight average molecular weight of the triazole skeleton-containing polymer according to one embodiment of the present invention can be 1,000 to 2,000,000. The weight average molecular weight is, 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.

[0102] 3. Composition A composition according to one embodiment of the present invention contains the triazole skeleton-containing polymer. The reaction liquid containing the triazole skeleton-containing polymer obtained by the above production method after the reaction step can be used as a composition according to one embodiment of the present invention. The composition according to one embodiment of the present invention is obtained through the above reaction steps, specifically the Huisgen reaction, and therefore can reduce unnecessary by-products.

[0103] A method for producing a polymer having a desired structure and functional groups includes, for example, preparing a triazole skeleton-containing compound A, which is a macromonomer having the desired structure and functional groups, a triazole ring, and a polymerizable group, and polymerizing the compound. However, when the triazole skeleton-containing polymer is prepared by such a method, the triazole skeleton-containing compound A may remain in the resulting reaction solution. In a composition according to one embodiment of the present invention, the content of the triazole skeleton-containing compound A relative to 100% by mass of the triazole skeleton-containing polymer can be 5% by mass or less. The content of the triazole skeleton-containing compound A relative to 100% by mass of the triazole skeleton-containing polymer is, for example, 0, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, or 5% by mass, and may be within a range between any two of the values ​​exemplified here. A composition according to one embodiment of the present invention may not contain any triazole skeleton-containing compound A relative to 100% by mass of the triazole skeleton-containing polymer. Here, the triazole skeleton-containing compound A can be a compound having a triazole skeleton and a polymerizable group bonded to the triazole skeleton. The triazole skeleton-containing compound A can be a compound having the R 5 (and R 15 or R 25 ) structure. According to the production method according to one embodiment of the present invention, it is possible to reduce unnecessary by-products, and since the triazole skeleton-containing polymer and composition according to one embodiment of the present invention have a low content of unnecessary by-products, it is possible to reduce the effort and cost of the purification step. [Example]

[0104] 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.

[0105] Example 1 <Preparation of raw polymer> A 1000 ml glass pressure vessel was charged with 400 ml of tetrahydrofuran, 208.3 g of styrene monomer, 0.1 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 Copolymer 1 (raw polymer).

[0106] <Production of Triazole Skeleton-Containing Polymer> 2.6 g of copolymer 1 was dissolved in 20 g of tetrahydrofuran, and 0.2 g of copper(II) acetate monohydrate and 0.7 g of ethyl azidoacetate were then dissolved therein. 0.2 g of sodium ascorbate was then added to generate catalytic copper(I) ions in the system, and the reaction proceeded to obtain a mixture of a triazole skeleton-containing polymer having a monomer unit represented by formula (5) and a triazole skeleton-containing polymer having a monomer unit represented by formula (6). The reaction temperature was 23°C, and the reaction time was 24 hours.

[0107] [ka]

[0108] [ka]

[0109] Examples 2 to 11 A mixture of triazole skeleton-containing polymers was obtained in the same manner as in Example 1, except that the types and amounts of raw material monomers and the type of azide were as shown in Table 1. The following azides were used: A: Ethyl azidoacetate B: Polystyrene azide (number average molecular weight Mn 3200) C: PMMA azide (number average molecular weight Mn 7900)

[0110] Polystyrene azide was synthesized based on the method described in Macromolecules, 2006, 39, 5286-5292. PMMA azide (polymethyl methacrylate azide) was synthesized based on the method described in J. Am. Chem. Soc. 2017, 139, 10551-10560. In all of the Examples, the triazole skeleton-containing compound A having a triazole skeleton and a polymerizable group bonded to the triazole skeleton was not detected in the resulting reaction solution.

[0111] The obtained raw material monomer and triazole skeleton-containing polymer were 13 The content of the first monomer unit 1A in the raw polymer and the amount of unreacted first monomer unit 1A remaining in the triazole skeleton-containing polymer were 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 raw polymer 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 %). The unreacted amount of the first monomer unit 1A indicates the remaining amount of the first monomer unit (first monomer unit 1A, 1B, and 1C) when the total of the triazole skeleton-containing monomer unit, the first monomer unit (first monomer unit 1A, 1B, and 1C), and the second monomer unit contained in one molecule of the triazole skeleton-containing polymer is taken as 100 mol %. These are 13 Measurement was performed using 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 In addition, the amount of azide bonds in the triazole skeleton-containing polymer was calculated from the amount of unreacted first monomer unit 1A using the following formula: Amount of azide bond (mol%) = "Content of first monomer unit 1A in raw polymer (mol%)" - "Unreacted amount of first monomer unit 1A in triazole skeleton-containing polymer (mol%)"

[0112] Differential scanning calorimetry (DSC) was performed on the mixtures of the copolymers (raw polymers) and the triazole skeleton-containing polymers according to Examples 1 to 11 to obtain differential scanning calorimetry curves, and the midpoint glass transition temperatures (Tmg) were calculated in accordance with JIS K 7121.

[0113] The measurement conditions for differential scanning calorimetry (DSC) 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

[0114] [Table 1]

[0115] Example 12 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 Copolymer 2 (raw polymer 2). The number average molecular weight Mn of the copolymer 2 was 8,500, and the polydispersity index PDI (Mw / Mn) was 2.28. The number average molecular weight Mn, weight average molecular weight Mw, and polydispersity index PDI (Mw / Mn) 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).

[0116] A mixture of triazole skeleton-containing polymers was obtained in the same manner as in Example 1, except that Copolymer 2 (raw polymer 2) was used. The obtained mixture of copolymer 2 and the triazole skeleton-containing polymer was subjected to the same procedure as in Example 1. 13 Analyzed by C-NMR method, 13 The C-NMR spectrum was obtained and the results are shown in Figure 1. Copolymer 2 13 In the C-NMR spectrum, a peak α derived from the acetylene group was confirmed at around 87 ppm. 13In the C-NMR spectrum, peak α derived from an acetylene group was not observed around 87 ppm, but a peak derived from a carbonyl group was observed around 166 ppm, confirming that the acetylene group contained in copolymer 2 had reacted to introduce a structure having a carbonyl group.

[0117] Differential scanning calorimetry (DSC) was performed on the mixture of copolymer 2 and the triazole skeleton-containing polymer in Example 12 to obtain a differential scanning calorimetry curve in the same manner as in Example 1. Furthermore, the midpoint glass transition temperatures (Tmg) were calculated in accordance with JIS K 7121, and the glass transition temperature of copolymer 2 was 58.81°C, and the glass transition temperature of the mixture of triazole skeleton-containing polymers was 95.74°C.

[0118] (Example 1-2) A 1000 ml glass pressure vessel was charged with cyclopentyl methyl ether (CPME), 176.4 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. 75.6 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 and methanol were mixed to obtain a copolymer. The obtained copolymer was used to obtain a triazole skeleton-containing copolymer mixture in the same manner as in Example 1.

[0119] (Examples 2-2 to 7-2, 11-2) A copolymer was obtained in the same manner as in Example 1-2, except that the types and amounts of the first monomer and the second monomer were as shown in Table 2. Using the obtained copolymer, a mixture of triazole skeleton-containing copolymers was obtained in the same manner as in Example 1.

[0120] (Example 8-2) A 1000 ml glass pressure vessel was charged with cyclopentyl methyl ether (CPME), 219.7 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. 32.3 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 and methanol were mixed to obtain a copolymer. The obtained copolymer was used to obtain a triazole skeleton-containing copolymer mixture in the same manner as in Example 1.

[0121] (Examples 9-2 and 10-2) A copolymer was obtained in the same manner as in Example 8-2, except that the types and amounts of the first monomer and the second monomer and the polymerization conditions were as shown in Table 2. Using the obtained copolymer, a mixture of triazole skeleton-containing copolymers was obtained in the same manner as in Example 1.

[0122] The copolymers according to Examples 1-2 to 11-2 were subjected to the same procedure as in Example 1. 13 The raw polymer was analyzed by C-NMR to determine the content of the first monomer units 1A in the raw polymer and the amount of unreacted first monomer units 1A remaining in the triazole skeleton-containing polymer, and the amount of azide bonds in the triazole skeleton-containing polymer was calculated in the same manner as in Example 1. 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 2.

[0123] [Table 2]

Claims

1. A method for producing a triazole skeleton-containing polymer, comprising: The production method includes a step of reacting an acetylene group contained in a raw material polymer with an azide group-containing compound to obtain the triazole skeleton-containing polymer, the raw material polymer is a polymer including first monomer units 1A derived from the first monomer having an acetylene group and second monomer units derived from a second monomer, The triazole skeleton-containing polymer has a triazole skeleton-containing monomer unit and the second monomer unit.

2. The method according to claim 1 , wherein the first monomer unit 1A is 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 manufacturing method according to claim 1 or claim 2, The triazole skeleton-containing monomer unit is at least one of units represented by the following formula (2) and the following formula (3): 【Chemistry 2】 (In formula (2), R １５ is an organic group, and R １１ 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 １２ , R １３ , R １４ 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. 【Transformation 3】 (In formula (3), R ２５ is an organic group, and R ２１ 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 ２２ , R ２３ , R ２４ 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.

4. The manufacturing method 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.

5. A triazole skeleton-containing polymer, The triazole skeleton-containing polymer includes a triazole skeleton-containing monomer unit and a second monomer unit, The triazole skeleton-containing polymer, wherein the triazole skeleton-containing monomer unit is a repeating unit represented by at least one of the following formulas (2) and (3): 【Chemistry 2】 (In formula (2), R １５ is an organic group, and R １１ 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 １２ , R １３ , R １４ 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. 【Transformation 3】 (In formula (3), R ２５ is an organic group, and R ２１ 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 ２２ , R ２３ , R ２４ 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 triazole skeleton-containing polymer according to claim 5, The triazole skeleton-containing polymer further comprises a first monomer unit 1A derived from a first monomer having an acetylene group and 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.

7. The triazole skeleton-containing polymer according to claim 5 or 6, The triazole skeleton-containing polymer is measured in a deuterated chloroform solvent. １３ A triazole skeleton-containing polymer having at least one peak β observed in the range of 190 to 220 ppm in a C-NMR spectrum.

8. 8. The triazole skeleton-containing polymer according to claim 7, wherein the triazole skeleton-containing polymer has an allene structure in at least one of a main chain and a side chain.

9. 9. The triazole skeleton-containing polymer according to claim 8, further comprising at least one selected from the group consisting of a first monomer unit 1B and a first monomer unit 1C derived from the first monomer, The first monomer unit 1B is represented by the following formula (1-B): The first monomer unit 1C is a triazole skeleton-containing polymer 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.

10. The triazole skeleton-containing polymer according to claim 5 or 6, The second monomer unit is a monomer unit derived from a second 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.

11. The triazole skeleton-containing polymer according to claim 5 or 6, When the triazole skeleton-containing monomer unit is represented by formula (2), R １５ comprises a polymer chain comprising a third monomer unit derived from a third monomer, When the triazole skeleton-containing monomer unit is represented by formula (3), R ２５ comprises a polymer chain comprising a third monomer unit derived from a third monomer, The third 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.

12. The triazole skeleton-containing polymer according to claim 5 or 6, When the triazole skeleton-containing monomer unit is represented by formula (2), R １５ contains at least one selected from the group consisting of a carboxy group, an ester bond, an ether bond, an alkyl group, an alkenyl group, an allyl group, an aryl group, a mercapto group, a heterocyclyl group, a hydroxyl group, an amino group, and a silyl group, When the triazole skeleton-containing monomer unit is represented by formula (3), R ２５ is a triazole skeleton-containing polymer containing at least one selected from the group consisting of a carboxy group, an ester bond, an ether bond, an alkyl group, an alkenyl group, an allyl group, an aryl group, a mercapto group, a heterocyclyl group, a hydroxyl group, an amino group, and a silyl group.

13. The triazole skeleton-containing polymer according to claim 5 or 6, a triazole skeleton-containing polymer, wherein a content of the triazole skeleton-containing monomer units is 1 to 99 mol % relative to a total of 100 mol % of the triazole skeleton-containing monomer units, first monomer units derived from a first monomer, second monomer units derived from a second monomer, and other monomer units contained in the triazole skeleton-containing polymer.

14. The triazole skeleton-containing polymer according to claim 5 or 6, A single glass transition point was observed in the differential scanning calorimetry curve. the glass transition temperature 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 triazole skeleton-containing polymer that satisfies the following formula (1), when T1 [K] is the glass transition temperature of a homopolymer made of the triazole skeleton-containing monomer, C1 is the mass fraction of the copolymerization amount of the triazole skeleton-containing 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]

15. A composition comprising the triazole skeleton-containing polymer according to claim 5 or 6, the composition contains the triazole skeleton-containing compound A in an amount of 5% by mass or less relative to 100% by mass of the triazole skeleton-containing polymer, The triazole skeleton-containing compound A is a composition having a triazole skeleton and a polymerizable group bonded to the triazole skeleton.

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