Polymer compound

Abstract

Provided is a polymer compound capable of further imparting practically preferable various properties such as handleability improved by increasing the melting point thereof, while maintaining properties such as specific optical properties derived from an azulene skeleton, the polymer compound also being capable of imparting hydrophilicity (preferably, water solubility) by design. The problem addressed by the present invention is solved by a polymer compound that has a structure having a structural moiety (A) and a structural moiety (B), wherein: the structural moiety (A) has an azulene skeleton; the structural moiety (B) is selected from a structural moiety (B1) having a polyallylamine structure, a structural moiety (B2) having a polydiallylamine structure, and a structural moiety (B3) having a polyethyleneimine structure; and the structural moiety (A) and the structural moiety (B) are bonded via a carbonyl group.

Description

High molecular compound

[0001] The present invention relates to a high molecular compound, and more specifically, to a high molecular compound having a structural part with an azulene skeleton and a structural part selected from a structural part having a polyallylamine structure, a structural part having a polydiallylamine structure, and a structural part having a polyethyleneimine structure, which has both optical physical properties such as light absorption characteristics mainly due to the former and physical properties such as a high melting point mainly due to the latter.

[0002] Compounds having an azulene skeleton such as guaiazulene have specific molecular orbitals different from those of general aromatic hydrocarbons and the property of having polarized charges in the molecule, and have optical physical properties such as specific light absorption characteristics resulting therefrom (see, for example, Non-Patent Documents 1 and 2, etc.), and various applications in optoelectronics fields such as dyes, electro-optical materials, non-linear optical materials, electroluminescent materials, and organic solar cells have been proposed (see, for example, Patent Documents 1 and 2, and Non-Patent Document 3, etc.).

[0003] Since guaiazulene and the like are lipophilic and have limitations in handling, etc., it has been proposed to introduce a sulfonium salt for the purpose of imparting water solubility, etc. (see, for example, Patent Documents 3 and 4). Since guaiazulene and the like have a melting point near room temperature, the handling property is not necessarily good, and further improvements such as an improvement in handling property due to an increase in the melting point are required.

[0004] Japanese Patent Application Laid-Open No. 2024-519688 Japanese Patent Application Laid-Open No. 2004-020928 Japanese Patent Application Laid-Open No. 58-144365 Japanese Patent Application Laid-Open No. 2003-081822

[0005] Newsome et al., J. Agric. Food Chem., Vol. 62 (2014), pp 6498-6511 Zadeh et al., J. Mater. Chem. C, 2015, 3, pp 8495-8503 Dong et al., Chinese Chemical Letters, Vol. 27 (2016), pp 1097-1104

[0006] In view of the above-mentioned prior art, the object of the present invention is to provide a polymer compound that maintains unique optical properties and other characteristics originating from the azulene skeleton, while further possessing practically desirable properties such as improved handling due to a higher melting point, and which can also be given hydrophilicity (preferably water-soluble) through design.

[0007] As a result of diligent research, the present inventors have found that by combining a structural portion having an azulene skeleton with a structural portion selected from a structural portion having a polyallylamine structure, a structural portion having a polydiallylamine structure, and a structural portion having a polyethyleneimine structure, and by bonding the two via a specific structure, it is possible to achieve both the unique optical properties and other characteristics derived from the azulene skeleton and the high melting point derived from the polyallylamine structure, polydiallylamine structure, or polyethyleneimine structure, thus completing the present invention. That is, the present invention relates to [1] a polymer compound having a structural portion (A) having an azulene skeleton and a structural portion (B) selected from a structural portion having a polyallylamine structure (B1), a structural portion having a polydiallylamine structure (B2), and a structural portion having a polyethyleneimine structure (B3), wherein the structural portion (A) and the structural portion (B) are bonded via a carbonyl group.

[0008] Hereinafter, [2] to

[12] are all preferred embodiments or models of the present invention. [2] The polymer compound according to [1], wherein the azulene skeleton has a guaiazulene structure (7-isopropyl-1,4-dimethylazulene structure), a chamazulene structure, a guaiazulenone structure, or a lactazulene structure. [3] The polymer compound according to [1] or [2], wherein the carbonyl group is bonded to a structural part (A) at position 1 or 2 of the azulene skeleton. [4] The polymer compound according to any one of [1] to [3], wherein the melting point is 40 to 300°C. [5] The polymer compound according to any one of [1] to [4], wherein the structural portion (B) has a plurality of structural units b1 derived from allylamine, structural units b2 derived from diallylamine, and / or structural units b3 derived from ethyleneimine, and 0.1 to 70 mol% of the total of the structural units b1, b2, and / or b3 are bonded to the structural portion (A) via carbonyl groups. [6] The polymer compound according to any one of [1] to [5], wherein the weight-average molecular weight is in the range of 500 to 2,000,000. [7] The maximum absorption wavelength peak L is in the range of 200 to 1000 nm. Ａ１ A polymer compound according to any one of [1] to [6] having the following: [8] an azulene carboxylic acid compound (A) having a structure in which a carboxyl group is bonded to the structural portion (A) in place of the carbonyl group. ０ ) Maximum absorption wavelength peak L Ａ０ And the above maximum absorption wavelength peak L Ａ１ The difference between, L Ａ１ -L Ａ０ A polymer compound according to any one of [1] to [7], wherein the absolute value of is 10 nm or less. [9] A polymer compound according to any one of [1] to [8], which is water-soluble at pH 7 at at least a portion of the temperature range of 15 to 35°C.

[10] 1) Azulene carboxylic acid compound having an azulene skeleton and a carboxyl group (A １ ) a step of providing, and 2) an azulene carboxylic acid compound (A) obtained in step 1) above １ ) and a compound selected from polyallylamine, polydiallylamine, and polyethyleneimine (B１ A process of subjecting ( ) to a condensation reaction, and a method for producing a polymer compound.

[11] The method for producing a polymer compound according to

[10] , wherein the polymer compound according to any one of [1] to [9] is produced.

[12] A dye fixing agent, a color shampoo, a colored aqueous solution, a fluorescent probe, a material for forming an ion or metal complex, a solar cell, or a gas separation adsorbent using the polymer compound according to any one of [1] to [9].

[0009] According to the present invention, there is provided a polymer compound having high practical value, which has characteristics such as specific optical properties due to the azulene skeleton and a high melting point due to the polyallylamine structure, has specific optical properties, etc., while having a wide application range and being relatively easy to handle.

[0010] (a) The light absorption spectrum (solid line) of a polymer compound (Compound H) which is an example of the present invention is shown in comparison with the light absorption spectrum (broken line) of 1GA (7-isopropyl-4-methylazulene-1-carboxylic acid). (b) The fluorescence spectrum (solid line) of a polymer compound (Compound H) which is an example of the present invention is shown in comparison with the fluorescence spectrum (broken line) of 1GA (7-isopropyl-4-methylazulene-1-carboxylic acid). The vertical axis represents the normalized intensity of light absorption or fluorescence (arbitrary unit), and the horizontal axis represents wavelength (nm). The light absorption spectrum (solid line) of a polymer compound (Compound A) which is an example of the present invention is shown in comparison with the light absorption spectrum (broken line) of 2GA (7-isopropyl-1,4-dimethylazulene-2-carboxylic acid). The vertical axis represents the normalized intensity of light absorption (arbitrary unit), and the horizontal axis represents wavelength (nm).

[0011] The present invention relates to a polymer compound having a structural portion (A) having an azulene skeleton and a structural portion (B) selected from a structural portion (B1) having a polyallylamine structure, a structural portion (B2) having a polydiallylamine structure, and a structural portion (B3) having a polyethyleneimine structure, wherein structural portion (A) and structural portion (B) are bonded via a carbonyl group. In other words, the polymer compound of the present invention has three structural portions: a structural portion (A) having an azulene skeleton, a structural portion (B1) having a polyallylamine structure, a structural portion (B2) having a polydiallylamine structure, and a structural portion (B3) having a polyethyleneimine structure, and a carbonyl group. Each of these structural portions will be described below.

[0012] Structural portion (A) having an azulene skeleton The structural portion (A) having an azulene skeleton that constitutes a part of the polymer compound of the present invention has a structure represented by the following formula (A). In the following formula (A), R １ ~R ８ At least one of the groups is a carbonyl group, and is bonded to structural part (B) via the carbonyl group. The remaining R １ ~R ８ Each of these is a hydrogen atom, or a substituent selected from alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, alkoxy groups, acyl groups, acyloxy groups, amino groups, nitro groups, cyano groups, ester groups, amide groups, and halogen groups.

[0013] As described above, in equation (A), R １ ~R ８ At least one of these is a group containing a carbonyl group, and more preferably a carbonyl group. That is, the carbons constituting the azulene skeleton of structural part (A) are R １ ~R ８ It is preferable that at least one of the positions is directly bonded to the carbonyl group. In formula (A), R １ ~R ８ R １ , R ２ or R ４ It is preferable that the group contains a carbonyl group,１ or R ２ It is more preferable that the group contains a carbonyl group, that is, it is preferable that the carbonyl group is bonded to the 1st or 2nd position of the azulene skeleton of formula (A).

[0014] A preferred example of a structural portion (A) having an azulene skeleton is R １ and R ４ is a methyl group, R ７ A structure in which is an isopropyl group, namely a guaiazulene structure (7-isopropyl-1,4-dimethylazulene structure), can be cited. Another preferred example is R １ and R ４ is a methyl group, R ７ A structure in which is an ethyl group, i.e., a chamazulene structure, and R １ and R ４ is a methyl group, R ７ A structure in which is an isopropenyl group, i.e., a lactazulene structure, and R １ and R ４ is a methyl group, R ７ One example is a structure in which the group is an acetyl group, namely the guaiazurenone structure.

[0015] The polymer compound of the present invention may have at least one structural portion (A) having an azulene skeleton per molecule, but from the viewpoint of fully realizing optical properties such as light absorption characteristics due to the structural portion (A), and from the viewpoint of fully realizing coloring performance, it is preferable to have one or more structural portions (A) per molecule, more preferably 1 to 450 structural portions (A), and particularly preferable 2 to 85 structural portions (A).

[0016] Structural part (B) selected from a structural part having a polyallylamine structure (B1), a structural part having a polydiallylamine structure (B2), and a structural part having a polyethyleneimine structure (B3) The structural part (B) that constitutes a part of the polymer compound of the present invention is a structural part selected from a structural part having a polyallylamine structure (B1), a structural part having a polydiallylamine structure (B2), and a structural part having a polyethyleneimine structure (B3). Structural part (B) may have only one type of structural part selected from the polyallylamine structure (B1), the polydiallylamine structure (B2), and the polyethyleneimine structure (B3), or it may have two or more types. In the latter case, for example, it may have the structure of a copolymer having a polyallylamine structure (B1) and a polydiallylamine structure (B2).

[0017] Structural portion (B1) having a polyallylamine structure A preferred option of structural portion (B) that constitutes a part of the polymer compound of the present invention is a structural portion (B1) having a polyallylamine structure, which has a structural unit b1 having a structure represented by the following formula (b1), or a structure which is an acid addition salt thereof. In formula (b1), R ９ R is a group containing a carbonyl group, or a hydrogen atom, preferably a hydrogen atom. １０ R represents a group containing a carbonyl group, a hydrogen atom, a C1-C12 alkyl group which may have a hydroxyl group, a C7-C12 aralkyl group, or a C5-C6 cycloalkyl group. １０ The preferred alkyl or aralkyl group having 1 to 12 carbon atoms may be linear or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, and benzyl groups. ９ and R １０ Preferred cycloalkyl groups having 5 to 6 carbon atoms include, but are not limited to, cyclopentyl and cyclohexyl groups. １０It is preferably a hydrogen atom, a methyl group, an ethyl group, or a benzyl group, and is particularly preferably a hydrogen atom or a methyl group.

[0018] There are no particular restrictions on the type of addition salt when the constituent unit b1 is an acid addition salt of the structure represented by general formula (b1). However, from the viewpoint of availability and ease of reaction control, for example, hydrochloride, sulfate, phosphate, nitrate, sulfite, phosphate, nitrite, hydrobromide, acetate, amide sulfate, methanesulfonate, trifluoroacetate, p-toluenesulfonate, etc., can be used. Among these, hydrochloride, sulfate, phosphate, and amide sulfate are preferred, and hydrochloride, sulfate, phosphate, and amide sulfate with structures derived from monoallylamine are particularly preferred.

[0019] In at least one of the constituent units b1, R ９ This group contains a carbonyl group and is bonded to the structural portion (A) having an azulene skeleton via this group. As a result, the polymer compound of this embodiment has at least one structural portion (A) having an azulene skeleton.

[0020] There are no particular restrictions on the molecular weight of the structural portion (B1) having a polyallylamine structure. A polyallylamine having a suitable molecular weight can be obtained and polymerized as a raw material for the structural portion (B1) in relation to the physical properties and applications required for the polymer compound of the present invention, such as water solubility and melting point. From the viewpoint of water solubility and melting point, the weight-average molecular weight of the structural portion (B1) is preferably in the range of 500 to 500,000, more preferably in the range of 750 to 250,000, and particularly preferably in the range of 1,000 to 100,000.

[0021] The molecular weight of the structural portion (B1) having the polyallylamine structure described above can also be substantially determined by the number of repeating constituent units b1 having the structure represented by formula (b1), or the structure which is an acid addition salt thereof. The number of repeating constituent units b1 in the structural portion (B1) having the polyallylamine structure is preferably 8 to 9000, more preferably 13 to 4300, and particularly preferably 17 to 1800.

[0022] The structural portion (B1) having a polyallylamine structure may consist only of constituent units b1 having the structure represented by formula (b1), or the structure being an acid addition salt thereof, or it may have a structure equivalent to a so-called copolymer, having constituent units of other structures. When the structural portion (B1) has a structure equivalent to a so-called copolymer, the proportion of constituent units b1 in the structural portion (B1) is preferably 10 mol% or more, more preferably 30 mol% or more, and particularly preferably 50 mol% or more.

[0023] When the structural part (B1) has a structure equivalent to a so-called copolymer, there are no particular restrictions on structural units other than structural unit b1, and such structural units can be derived by copolymerizing with monomers copolymerizable with allylamine as appropriate. Preferred examples of copolymerizable monomers include diallylamines such as diallylamine and diallylmethylamine or their addition salts; diallyldialkylammonium salts such as diallyldimethylammonium chloride; acrylamides such as acrylamide, dimethylacrylamide, acryloylmorpholine, N-[3-(dimethylamino)propyl](meth)acrylamide, (3-acrylamidopropyl)trimethylammonium chloride, (3-methacrylamidopropyl)trimethylammonium chloride; allyl alcohols, ethylene glycol monoallyl ethers, etc. Examples of monomers that can be used to derive structural units other than structural unit b1 include, but are not limited to, telamines, unsaturated carboxylic acids such as (meth)acrylic acid (sodium) or their addition salts; unsaturated dicarboxylic acids such as maleic acid and fumaric acid or their addition salts; sulfur dioxide; allyl sulfonic acids such as (meth)allyl sulfonic acid (sodium) or their addition salts; vinyl sulfonic acids such as vinyl sulfonic acid (sodium) or their addition salts; sodium isoprene sulfonate, styrene monomers or their addition salts; vinyl benzoate, sodium p-styrene sulfonate, cyclic olefins or their addition salts; vinylpyridine, phenylmaleimide, etc. Only one monomer may be used to derive structural units other than structural unit b1, or two or more monomers may be used in combination.

[0024] Structural part (B2) having a polydiallylamine structure A preferred option of structural part (B) constituting a part of the polymer compound of the present invention, the structural part (B2) having a polydiallylamine structure has a constituent unit b2 derived from a diallylamine monomer. More specifically, the constituent unit b2 derived from a diallylamine monomer that constitutes the structural part (B2) having a polydiallylamine structure has a structure represented by the following structural formula (b2a) or (b2b), or a structure that is an inorganic salt or organic salt thereof. In the above formulas (b2a) and (b2b), R １１ This represents a group containing a carbonyl group or a hydrogen atom, preferably a hydrogen atom.

[0025] The structural portion (B2) having a polydiallylamine structure may have a structural unit b2 derived from a diallylamine monomer, which is a structural unit of the structure shown in the above structural formula (b2a) or (b2b), i.e., a free structural unit. However, it may also have a structure that is an inorganic or organic acid salt of the structure shown in the above structural formula (b2a) or (b2b), i.e., a structural unit of a structure having an addition salt. In the production of the structural portion (B2) having a polydiallylamine structure or its preferred precursor, polydiallylamine, it is preferable from the viewpoint of production cost, etc., to use a diallylamine monomer having an addition salt. The process of removing addition salts such as HCl from polymers is complicated and can increase costs. Therefore, using an addition salt type polydiallylamine structure that can be produced without such a process is a preferred embodiment from the viewpoint of cost, etc. From the viewpoint of ease of availability and controllability of the reaction, the inorganic or organic acid salt of the structure represented by the above structural formula (b2a) or (b2b) is preferably a hydrochloride salt, sulfate salt, phosphate salt, nitrate salt, carboxylate salt, sulfonate salt, amidosulfate salt, or alkyl sulfate salt, and is particularly preferably a hydrochloride salt, amidosulfate salt, or carboxylate salt.

[0026] In the structural portion (B2) having a polydiallylamine structure, a single constituent unit b2 derived from one type of diallylamine monomer may be used alone, or a combination of constituent units b2 derived from multiple types of diallylamine monomers with different structures may be used. When multiple types of constituent units b2 derived from diallylamine monomers with different structures are used, each constituent unit b2 derived from a diallylamine monomer may have different structures within the range represented by the same general structural formula (b2a) or (b2b), or it may have different structures represented by different general structural formulas. In the former case, for example, it is represented by the general structural formula (b2a), but R １１ Constituent units b2 derived from multiple types of diallylamine monomers, whose structures differ from each other, may be used. In the latter case, for example, one constituent unit b2 having the structure represented by structural formula (b2a) and another constituent unit b2 having the structure represented by structural formula (b2b) may be used.

[0027] In at least one of the constituent units b2, R １１ This group contains a carbonyl group and is bonded to the structural portion (A) having an azulene skeleton via this group. As a result, the polymer compound of this embodiment has at least one structural portion (A) having an azulene skeleton.

[0028] There are no particular restrictions on the molecular weight of the structural portion (B2) having a polydiallylamine structure. A polydiallylamine having a molecular weight that is appropriately suitable in relation to the physical properties and applications required for the polymer compound of the present invention, such as water solubility and melting point, can be obtained, polymerized, or otherwise used as a raw material for the structural portion (B2). From the viewpoint of water solubility and melting point, the weight-average molecular weight of the structural portion (B2) is preferably in the range of 500 to 500,000, more preferably in the range of 750 to 250,000, and particularly preferably in the range of 1,000 to 100,000.

[0029] The molecular weight of the structural portion (B2) having the polydiallylamine structure described above can also be substantially determined by the number of repeating constituent units b2. The number of repeating constituent units b2 in the structural portion (B2) having the polydiallylamine structure is preferably 5 to 5500, more preferably 7 to 2600, and particularly preferably 10 to 1050.

[0030] The structural portion (B2) having a polydiallylamine structure may consist only of constituent units b2, or it may have a structure equivalent to a so-called copolymer, having constituent units of other structures. When the structural portion (B2) has a structure equivalent to a so-called copolymer, the proportion of constituent units b2 in the structural portion (B2) is preferably 10 mol% or more, more preferably 30 mol% or more, and particularly preferably 50 mol% or more.

[0031] In the structural portion (B2) having a polydiallylamine structure, there are no particular restrictions on the structural units other than the structural unit b2 derived from the diallylamine monomer. Such structural units can be derived by copolymerizing monomers that are copolymerizable with diallylamine monomers as appropriate. Preferred copolymerizable monomers include, but are not limited to, monoallylamines or their addition salts; anionic monomers such as dicarboxylic acids; sulfur dioxide; acrylamides such as acrylamide, dimethylacrylamide, acryloylmorpholine, N-[3-(dimethylamino)propyl](meth)acrylamide, (3-acrylamidopropyl)trimethylammonium chloride, and (3-methacrylamidopropyl)trimethylammonium chloride; allyl alcohols; allyl ethers such as ethylene glycol monoallyl ether; allyl sulfonic acids such as (meth)allyl sulfonic acid (sodium) or their addition salts; vinyl sulfonic acids such as vinyl sulfonic acid (sodium) or their addition salts; sodium isoprene sulfonate; styrene monomers or their addition salts; vinyl benzoate; sodium p-styrene sulfonate; cyclic olefins or their addition salts; vinylpyridine, phenylmaleimide, etc.

[0032] Monomers other than diallylamine monomers can be used individually or in combination of two or more.

[0033] Structural portion having a polyethyleneimine structure (B3) A preferred option of structural portion (B) which constitutes a part of the polymer compound of the present invention, the structural portion having a polyethyleneimine structure (B3) has constituent units derived from ethyleneimine. More specifically, the structural portion having a polyethyleneimine structure (B3) has constituent units b3 of a structure represented by the following formula (b3).

[0034] The structural portion (B3) having a polyethyleneimine structure may consist only of structural unit b3 represented by the above formula (b3), or it may have structural unit b3 other than those shown. When it consists only of structural unit b3, the structural portion (B3) having a polyethyleneimine structure has a linear structure. The structural portion (B3) having a polyethyleneimine structure may have a branched structure by having a tertiary amino group, and may have a structure represented by, for example, the following formula (b3a).

[0035] In formulas (b3) and (b3a), the amino groups are both represented in a free state, but some or all of these amino groups may be addition salts. There are no particular restrictions on the type of addition salt; for example, the various organic and inorganic salts described above in relation to the polyallylamine structure (B1) and the polydiallylamine structure (B2) can be used as appropriate.

[0036] At least one of the constituent units b3 of the structural portion (B3) having a polyethyleneimine structure has a group containing a carbonyl group instead of H in the above formula (b3), and is bonded to the structural portion (A) having an azulene skeleton via this. Thus, the polymer compound of this embodiment has at least one structural portion (A) having an azulene skeleton.

[0037] The molecular weight of the structural portion (B3) having a polyethyleneimine structure is not particularly limited, but preferably its weight-average molecular weight is in the range of 100 to 2,000,000, more preferably 500 to 2,000,000, and particularly preferably 1,000 to 2,000,000. The structural portion (B3) having a polyethyleneimine structure can be introduced into the polymer compound of the present invention by synthesizing polyethyleneimine, for example, by ring-opening polymerization of ethyleneimine in the presence of an acid catalyst, and using this. Alternatively, commercially available polyethyleneimines, such as Lupasol (product names: Lupasol SK (average molecular weight approximately 2,000,000), Lupasol G20 (average molecular weight approximately 1,300), Lupasol G20 WF (average molecular weight approximately 1,300), Lupasol P (average molecular weight approximately 750,000), Lupasol PS (average molecular weight approximately 750,000), Lupasol PR 8515 (2,000), Lupasol PN 40, Lupasol WF (average molecular weight approximately 25,000), Lupasol SC-61B (average molecular weight 110,000) and Lupasol) from BASF. You may also use FG), Epomin (model numbers: SP-003 (average molecular weight approximately 300), SP-006 (average molecular weight approximately 600), SP-012 (average molecular weight approximately 1,200), SP-018 (average molecular weight approximately 1,800), SP-200 (average molecular weight approximately 10,000), and P-1000 (average molecular weight approximately 70,000)) commercially available from Nippon Shokubai Co., Ltd., or BPEI (distributor code 161-17831 (average molecular weight approximately 600), distributor code 167-17811 (average molecular weight approximately 1,800), and distributor code 164-17821 (average molecular weight approximately 10,000)) commercially available from Wako Pure Chemical Industries, Ltd.

[0038] Carbonyl Group The polymer compound of the present invention has a carbonyl group in addition to a structural part (A) having an azulene skeleton and a structural part (B) selected from a structural part (B1) having a polyallylamine structure, a structural part (B2) having a polydiallylamine structure, and a structural part (B3) having a polyethyleneimine structure, and structural part (A) and structural part (B) are bonded via the carbonyl group. The carbonyl group is a divalent group having a structure represented by -C(=O)-, to which the structural part (A) having an azulene skeleton is bonded, and to which the structural part (B) selected from a structural part (B1) having a polyallylamine structure, a structural part (B2) having a polydiallylamine structure, and a structural part (B3) having a polyethyleneimine structure is bonded. The carbonyl group may be directly bonded to structural part (A), or it may be bonded to structural part (A) via a divalent group or atom. The carbonyl group may be directly bonded to structural moiety (B), or it may be bonded to structural moiety (B) via a divalent group or atom.

[0039] Polymer Compound As described above, the polymer compound of the present invention has a structural portion (A) having an azulene skeleton and a structural portion (B) selected from a structural portion (B1) having a polyallylamine structure, a structural portion (B2) having a polydiallylamine structure, and a structural portion (B3) having a polyethyleneimine structure, and the structural portion (A) and structural portion (B) are bonded via a carbonyl group. The polymer compound of the present invention may consist only of a structural portion (A) having an azulene skeleton, a structural portion (B1) having a polyallylamine structure, a structural portion (B2) having a polydiallylamine structure, and a structural portion (B3) having a polyethyleneimine structure, and a carbonyl group, or it may contain other atoms, groups, structural portions, etc. Examples of other atoms, groups, structural portions, etc. include nitrogen atoms, sulfur atoms, alkyl groups, phenyl groups, etc., but are not limited to these.

[0040] There are no particular restrictions on the molecular weight of the polymer compound of the present invention, but from the viewpoint of water solubility, melting point, viscosity, etc., the weight-average molecular weight is preferably in the range of 600 to 2,000,000, more preferably in the range of 1,000 to 950,000, and particularly preferably in the range of 1,200 to 150,000.

[0041] The molecular weight of the polymer compound of the present invention can be measured by GPC if it is soluble in the polymer compound eluent. It can also be indirectly evaluated by measuring the intrinsic viscosity [η]. The molecular weight of the polymer compound of the present invention can be appropriately adjusted by adjusting the structure, molecular weight, introduction rate, etc. of structural part (A), the structure, molecular weight, etc. of structural part (B), the manufacturing conditions of the polymer compound, etc. In particular, the molecular weight of structural part (B), selected from structural part (B1) having a polyallylamine structure, structural part (B2) having a polydiallylamine structure, and structural part (B3) having a polyethyleneimine structure, has a significant influence. １ By using () to adjust the molecular weight of the structural part (B), the molecular weight of the polymer compound can be adjusted as appropriate.

[0042] As described above, the polymer compound of the present invention only needs to have at least one structural part (A) having an azulene skeleton per molecule, but as also described above, it is preferable to have one or more structural parts (A) per molecule from the viewpoint of sufficiently realizing optical properties such as light absorption characteristics caused by the structural part (A). Based on the constituent units b1, b2, and / or b3 that constitute the structural part (B), it is preferable that 0.1 to 70 mol% of all constituent units b1, b2, and / or b3 that constitute the structural part (B) are bonded to the structural part (A) via carbonyl groups. The proportion of constituent units (on a molar basis) of all constituent units b1, b2, and / or b3 that are bonded to the structural part (A) via carbonyl groups, that is, the proportion of constituent units that are actually bonded to the structural part (A) via carbonyl groups out of all constituent units b1, b2, and / or b3 that can be bonded to the structural part (A) via carbonyl groups, will be referred to below as the "introduction rate". The above introduction rate is more preferably 0.5 to 70 mol%, and particularly preferably 1 to 50 mol%. Furthermore, from the viewpoint of realizing a polymer compound having a high melting point, for example, a melting point of 200°C or higher, the above introduction rate is preferably 20 to 50 mol%. On the other hand, from the viewpoint of realizing a polymer compound with good water solubility, the above introduction rate is preferably 0.5 to 7.5 mol%, and more preferably 1 to 5.5 mol%.

[0043] The polymeric compounds of the present invention may be lipophilic or water-soluble, but from the viewpoint of convenience when used in applications such as dyes, they are preferably water-soluble or hydrophilic. Since the structural portion (B) selected from the structural portion having a polyallylamine structure (B1), the structural portion having a polydiallylamine structure (B2), and the structural portion having a polyethyleneimine structure (B3) has an amino group, the polymeric compounds of the present invention having structural portion (B) can control their polarity with a high degree of freedom, thereby achieving desired hydrophilicity or water solubility. While compounds having an azulene skeleton are generally lipophilic, the polymeric compounds of this embodiment having a structural portion (A) having an azulene skeleton and being water-soluble or hydrophilic achieve a highly practical technical effect by possessing hydrophilicity (preferably water-soluble), which was difficult to achieve in the prior art, while maintaining the unique photophysical properties and other characteristics caused by the azulene skeleton. The polymer compound of this embodiment is preferably water-soluble at at least a portion of the temperature range of 15 to 35°C, for example, at 25°C and pH 7. More specifically, it is preferable that no solid material is visible when dissolved in deionized water at 25°C and pH 7.

[0044] The polymer compound of the present invention can have a high melting point by having a structural portion (B) selected from a structural portion (B1) having a polyallylamine structure, a structural portion (B2) having a polydiallylamine structure, and a structural portion (B3) having a polyethyleneimine structure, which generally have high melting points. As a result, it is a compound with a high melting point while having a structural portion having an azulene skeleton, which generally has a low melting point, and has excellent handling properties. The melting point of the polymer compound of the present invention can be appropriately adjusted by adjusting the structure, molecular weight, etc., of the structural portion (B) having a polyallylamine structure. The melting point of the polymer compound of the present invention is preferably 40 to 300°C (or solid in the range of 30°C to a minimum of 40°C and a maximum of 300°C), more preferably 50 to 250°C, and particularly preferably 100 to 200°C.

[0045] The polymer compound of the present invention, by having a structural portion (A) having an azulene skeleton, can possess unique optical properties and other characteristics resulting from the azulene skeleton. For example, from the viewpoint of use in optoelectronic fields such as dyes, electro-optical materials, nonlinear optical materials, electroluminescent materials, and organic solar cells, the maximum absorption wavelength peak L of the polymer compound of the present invention Ａ１ The wavelength is preferably in the range of 200 to 1000 nm. The maximum absorption wavelength peak L of the polymer compound of the present invention. Ａ１ This can be appropriately adjusted by adjusting the maximum absorption wavelength peak of the structural portion (A) having an azulene skeleton. In addition, an azulene carboxylic acid compound (A) having an azulene skeleton and a carboxyl group １ When introducing a structural portion (A) having an azulene skeleton into the polymer compound of the present invention using the azulene skeleton and an azulene carboxylic acid compound (A) having a carboxyl group, １ By adjusting the maximum absorption wavelength peak of the polymer compound of the present invention, the maximum absorption wavelength peak L Ａ１ The maximum absorption wavelength peak L of the polymer compound of the present invention can be adjusted as appropriate. Ａ１ The wavelength is more preferably in the range of 250 to 850 nm, and particularly preferably in the range of 300 to 800 nm.

[0046] In the polymer compound of the present invention, the influence of the structural portion (B) selected from the structural portion having a polyallylamine structure (B1), the structural portion having a polydiallylamine structure (B2), and the structural portion having a polyethyleneimine structure (B3), and the carbonyl group on the electronic state of the structural portion having an azulene skeleton (A) is relatively small. Therefore, the optical properties such as the maximum absorption wavelength peak of the azulene compound alone can be maintained with a relatively low range of variation. For example, the maximum absorption wavelength peak L of the polymer compound of the present invention Ａ１ And, an azulene carboxylic acid compound (A) having a structure in which a carboxyl group is bonded to the structural part (A) in place of a carbonyl group. ０ ) Maximum absorption wavelength peak L Ａ０ The difference between, L Ａ１ -L Ａ０The absolute value of is preferably 10 nm or less, preferably 5 nm or less, and particularly preferably 3 nm or less.

[0047] Furthermore, from the viewpoint of applications in electro-optical materials and electroluminescent materials, the maximum fluorescence wavelength peak L of the polymer compound of the present invention is considered. Ｆ１ The wavelength is preferably in the range of 350 to 800 nm. The maximum fluorescence wavelength peak L of the polymer compound of the present invention. Ｆ１ This can be appropriately adjusted by adjusting the maximum fluorescence wavelength peak of the structural portion (A) having an azulene skeleton. In addition, azulene carboxylic acid compound (A) having an azulene skeleton and a carboxyl group １ When introducing a structural portion (A) having an azulene skeleton into the polymer compound of the present invention using the azulene skeleton and an azulene carboxylic acid compound (A) having a carboxyl group, １ By adjusting the maximum fluorescence wavelength peak of the polymer compound of the present invention, the maximum fluorescence wavelength peak L Ｆ１ The maximum fluorescence wavelength peak L of the polymer compound of the present invention can be adjusted as appropriate. Ｆ１ The wavelength is more preferably in the range of 350 to 700 nm, and particularly preferably in the range of 370 to 600 nm.

[0048] In the polymer compounds of the present invention, the influence of the structural portion (B) having a polyallylamine structure, a polydiallylamine structure, or a polyethyleneimine structure, and the carbonyl group on the electronic state of the structural portion (A) having an azulene skeleton is relatively small. Therefore, the maximum fluorescence wavelength peak of the azulene compound alone can be maintained with a relatively low range of fluctuation. For example, the maximum fluorescence wavelength peak L of the polymer compound of the present invention Ｆ１ And, an azulene carboxylic acid compound (A) having a structure in which a carboxyl group is bonded to the structural part (A) in place of a carbonyl group. ０ ) Maximum fluorescence wavelength peak L Ｆ０ The difference between, L Ｆ１ -L Ｆ０ The absolute value of is preferably 10 nm or less, preferably 5 nm or less, and particularly preferably 3 nm or less.

[0049] Method for producing polymer compounds There are no particular limitations on the method for producing polymer compounds of the present invention, but they can preferably be produced by the following method having steps 1) and 2). 1) Azulene carboxylic acid compound having an azulene skeleton and a carboxyl group (A １ ) Step 2) A step to provide the azulene carboxylic acid compound (A) obtained in step 1) above Step 1) １ ) and a compound selected from polyallylamine, polydiallylamine, and polyethyleneimine (B １ ) and a condensation reaction,

[0050] In step 1) above, an azulene carboxylic acid compound (A) having an azulene skeleton and a carboxyl group １ There are no particular restrictions on the method of providing (A), but for example, by introducing a carboxyl group to a compound having an azulene skeleton by reacting it with an oxidizing agent such as a transition metal or peroxide, or with carbon dioxide, an azulene carboxylic acid compound having an azulene skeleton and a carboxyl group (A １ It can be manufactured, more specifically, according to the method described in K. Maruoka et al., Bull. Chem. Soc. Jpn, 2022, Vol. 95, pp. 1169-1177.

[0051] In step 2) above, the azulene carboxylic acid compound (A １ ) and a compound selected from polyallylamine, polydiallylamine, and polyethyleneimine (B １ There are no particular restrictions on the method of condensing the azulene carboxylic acid compound (A) in a solvent, preferably an organic solvent, in the presence of a condensing agent such as an organic triazine derivative. １ ) and a compound selected from polyallylamine, polydiallylamine, and polyethyleneimine (B １) can be reacted with by condensation. More specifically, for example, the reaction can be carried out by the method described in each example of this application. There are no particular restrictions on the conditions of step 2) above, but it is preferable to react at a temperature of 15 to 70°C, more preferably 25 to 50°C, for 12 to 48 hours, more preferably 15 to 25 hours. There are no particular restrictions on the type of solvent, but water, DMF (dimethylformamide), alcohols; methanol, ethanol, polar ethers; THF (tetrahydrofuran), 1,4-dioxane, etc. can be preferably used. The azulene carboxylic acid compound (A) to be subjected to step 2) １ ) and a compound selected from polyallylamine, polydiallylamine, and polyethyleneimine (B １ By appropriately adjusting the ratio of ) to the compound of the present invention, the introduction rate (the proportion of structural units among all structural units b1, b2, and / or b3 that are bonded to the structural part (A) via a carbonyl group (on a molar basis)) can be appropriately adjusted.

[0052] Applications, etc. The polymer compound of the present invention combines unique optical properties and other characteristics derived from the azulene skeleton with a high melting point derived from the polyallylamine structure. It possesses unique optical properties and other characteristics while having a wide range of applications and being relatively easy to handle, thus achieving a high level of practical value in terms of technical effects that surpass the limitations of conventional technology. Utilizing these technical effects, the polymer compound of the present invention can be suitably used in various applications such as dye fixatives, color shampoos, colored aqueous solutions, fluorescent probes, materials for forming ions or metal complexes, solar cells, or gas separation adsorbents.

[0053] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0054] The physical properties and characteristics of the examples / comparative examples were evaluated by the following method. [Method for measuring introduction rate] NMR measurement The synthesized sample was mixed with methanol-d ４ , DMSO (dimethyl sulfoxide)-d ６ Dissolve in a deuterated solvent １¹H NMR measurements (magnetic field strength: 400 MHz) were performed. The introduction rate (mol%) of 1GA or 2GA was calculated from the signal intensity ratio from the main chain of PAA (polyallylamine) and the signal intensity ratio from 1GA (7-isopropyl-4-methylazulene-1-carboxylic acid) or 2GA (7-isopropyl-1,4-dimethylazulene-2-carboxylic acid) in the obtained spectrum.

[0055] [Melting Point Measurement Method] Using an AS ONE melting point analyzer (DTM-01), the melting point of compounds A-G was determined by visually confirming the melting point temperature in the temperature range of 25.0°C to 400°C at a heating rate of 10°C / min. A melting point higher than 35°C was judged as ○ (good), and a melting point below 35°C was judged as × (poor).

[0056] [Water solubility test] Each sample was dissolved in Eppendorf tubes containing 0.5 or 1 mL of deionized water at 25°C to a concentration of 0.008 M, 0.05 M, or 0.1 M. After shaking 20 times, the samples were visually inspected for solids, insoluble matter, and turbidity. Water solubility was evaluated according to the following criteria: ◎ (Excellent) if dissolved at 0.1 M; ○ (Good) if dissolved at 0.05 M; △ (Average) if dissolved at 0.008 M; × (Poor) if not dissolved at 0.008 M.

[0057] [Method for measuring optical absorption spectra] Measurements were taken using a Hitachi High-Tech Science Co., Ltd. spectrophotometer (double-beam spectrophotometer UH5300) in the wavelength range of 250-800 nm with a wavelength scanning speed of 200 nm / min and a data interval of 1 nm. The sample concentration was adjusted with methanol to 0.08 mM.

[0058] [Fluorescence Spectrum Measurement Method] Fluorescence spectra were measured using a Hitachi High-Tech Science Co., Ltd. spectrofluorometer (Spectrofluorometer F-7000) in the wavelength range of 350–600 nm, with an excitation wavelength of 324 nm and a wavelength scanning speed of 240 nm / min. The sample concentration was adjusted with methanol to 0.08 mM.

[0059] [Stability test in acidic range] 15 ml each of standard buffer solutions pH 4, pH 7, and pH 9 are placed in screw tubes, each containing 60 wt% ethanol and the compound to be evaluated, measured in terms of azulene units at 0.5 × 10⁻¹⁶. －６ Azulene solutions were prepared by adding mol. These azulene solutions were stored at 40°C for two weeks and one month, after which the ultraviolet-visible absorption spectra from 250 nm to 800 nm were measured. The remaining percentage of the target compound was calculated from the maximum absorption wavelength (λmax) and minimum absorption wavelength (λmin) in the visible light region (400-800 nm) of each sample before and after storage, according to the following formula: Formula: Remaining percentage = (λmax - λmin) of the sample after each test / (λ) of the sample before the test ０ max - λ ０ The remaining percentage was calculated as follows: min) × 100. A value of ○ (good) was assigned when the remaining percentage was 90% or higher, △ (average) when it was between 80% and 90%, and × (poor) when it was 80% or lower.

[0060] The details of the materials used in the following examples / comparative examples are as follows: [Reagents] Guaiazulene (GA), dimethylformamide (DMF), methanol, acetonitrile, and diethyl ether (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride (DMT-MM) (manufactured by Tokyo Chemical Industries, Ltd.) Standard buffer solutions pH 4, pH 7, and pH 9 (all manufactured by Nacalai Tesque Corporation) PAA-01 (Mw: 1,600), PAA-10L-10C (Mw: 100,000) (allylamine (free) polymers manufactured by Nitto Boseki Medical Co., Ltd.), PAS-21 (Mw: 5,000) (diallylamine (free) polymers manufactured by Nitto Boseki Medical Co., Ltd.) Azulene carboxylic acids (1GA (7-isopropyl-4-methylazulene-1-carboxylic acid) and 2GA (7-isopropyl-1,4-dimethylazulene-2-carboxylic acid)) were synthesized according to the method described in K. Maruoka et al., Bull. Chem. Soc. Jpn, 2022, Vol. 95, pp. 1169-1177.

[0061] [Comparative Example] The melting point and water solubility of guaiazulene (GA) were evaluated according to the method described above. The results are shown in Table 1. In addition, a stability test in the acidic range of guaiazulene (GA) was performed according to the method described above. The results are shown in Table 2.

[0062] [Example 1] Synthesis and evaluation of compound A (PAA-2GA, theoretical introduction rate 5%, measured introduction rate 3.2%) 12.1 mg [0.05 mmol] of azulene carboxylic acid (2GA) and 373.5 mg [1.0 mmol] of polyallylamine PAA-01 manufactured by Nitto Boseki Medical Co., Ltd. were added to 3.3 mL of methanol and stirred, after which 13.8 mg [0.05 mmol] of DMT-MM was added. The reaction was continued at 25°C for 24 hours. After the reaction, the entire sample was added dropwise to 75 mL of stirred diethyl ether, reprecipitation occurred, and after filtration and washing with acetonitrile, a blue solid compound A was obtained. The 2GA introduction rate, melting point, and water solubility of compound A were evaluated according to the above method. The results are shown in Table 1. Furthermore, the acidic stability test of compound A was performed according to the above method, and the results are shown in Table 2. In addition, the absorption spectra of azulene carboxylic acid (2GA) and compound A were measured according to the above method. The results are shown in Figure 2.

[0063] [Example 2] Synthesis and evaluation of compound B (PAA-2GA, theoretical introduction rate 7%, measured introduction rate 6.8%) was carried out in the same manner as in Example 1, except that the reaction conditions were changed to 17.0 mg [0.07 mmol] of azulene carboxylic acid (2GA) and 19.4 mg [0.07 mmol] of DMT-MM, and a blue solid compound B was obtained. The 2GA introduction rate, melting point, and water solubility of compound B were evaluated according to the above method. The results are shown in Table 1.

[0064] [Example 3] Synthesis and evaluation of compound C (PAA-2GA, theoretical introduction rate 10%, measured introduction rate 8.8%) was carried out in the same manner as in Example 1, except that the reaction conditions were changed to 24.2 mg [0.10 mmol] of azulene carboxylic acid (2GA) and 27.7 mg [0.10 mmol] of DMT-MM, and a blue solid compound C was obtained. The 2GA introduction rate, melting point, and water solubility of compound C were evaluated according to the above method. The results are shown in Table 1.

[0065] [Example 4] Synthesis and Evaluation of Compound D (PAA-2GA, Theoretical Intake Rate 30%, Measured Intake Rate 28%) 72.6 mg [0.30 mmol] of azulene carboxylic acid (2GA) and 373.5 mg [1.0 mmol] of polyallylamine PAA-01 manufactured by Nitto Boseki Medical Co., Ltd. were added to 6.7 mL of methanol and stirred, after which 107.9 mg [0.40 mmol] of DMT-MM was added. The reaction was continued at 50°C for 48 hours. After the reaction, the entire sample was added dropwise to 75 mL of stirred diethyl ether, reprecipitation occurred, and after filtration and washing with acetonitrile, a blue solid compound D was obtained. The 2GA intake rate, melting point, and water solubility of compound D were evaluated according to the above method. The results are shown in Table 1. Note that since decomposition occurred before it began to melt, the thermal decomposition temperature is recorded in the melting point column. Furthermore, a stability test in the acidic range of compound D was performed according to the above method, and the results are shown in Table 2.

[0066] [Example 5] Synthesis and Evaluation of Compound E (PAA-2GA, Theoretical Incorporation Rate 50%, Measured Incorporation Rate 41%) 96.9 mg [0.40 mmol] of azulene carboxylic acid (2GA) and 298.7 mg [0.8 mmol] of polyallylamine PAA-01 manufactured by Nitto Boseki Medical Co., Ltd. were added to 5.3 mL of methanol and stirred, after which 143.9 mg [0.52 mmol] of DMT-MM was added. The procedure was then carried out in the same manner as in Example 4 to obtain a blue solid compound E. The 2GA incorporation rate, melting point, and water solubility of compound E were evaluated according to the above method. The results are shown in Table 1. Note that since decomposition occurred before melting began, the thermal decomposition temperature is recorded in the melting point column.

[0067] [Example 6] Synthesis and evaluation of compound F (PAA-2GA, molecular weight modified, theoretical introduction rate 5%, measured introduction rate 3.2%) The procedure was the same as in Example 3, except that the polyallylamine PAA-01 manufactured by Nitto Boseki Medical Co., Ltd. was replaced with the same amount of polyallylamine PAA-10L-10C manufactured by Nitto Boseki Medical Co., Ltd. in the reaction conditions, and a blue solid compound F was obtained. The 2GA introduction rate, melting point, and water solubility of compound F were evaluated according to the above method. The results are shown in Table 1.

[0068] [Example 7] Synthesis and evaluation of compound G (PAS-2GA, polymer modification, theoretical introduction rate 5%, measured introduction rate 4.9%) 12.9 mg [0.05 mmol] of azulene carboxylic acid (2GA) and 68.6 mg [1.4 mmol] of polydiallylamine PAS-21 manufactured by Nitto Boseki Medical Co., Ltd. were added and stirred, and then 16.2 mg [0.06 mmol] of DMT-MM was added. The procedure was then carried out in the same manner as in Example 1 to obtain a blue solid compound G. The 2GA introduction rate, melting point, and water solubility of compound G were evaluated according to the above method. The results are shown in Table 1.

[0069] [Example 8] Synthesis and Evaluation of Compound H (PAA-1GA, Theoretical Incorporation Rate 10%, Measured Incorporation Rate 7.0%) 11.4 mg [0.05 mmol] of azulene carboxylic acid (1GA) and 190.5 mg [0.5 mmol] of polyallylamine PAA-01 manufactured by Nitto Boseki Medical Co., Ltd. were added to 2.5 mL of DMF and stirred, then 15.2 mg [0.06 mmol] of DMT-MM was added. The reaction was continued at 25°C for 24 hours. After the reaction, the entire sample was added dropwise to 200 mL of stirred diethyl ether, reprecipitation occurred, and after filtration and washing with acetonitrile, a red solid compound H was obtained. The 1GA incorporation rate and water solubility of compound H were evaluated according to the above method. The results are shown in Table 1. Furthermore, the absorption spectra and fluorescence spectra of azulene carboxylic acid (1GA) and compound H were measured according to the above method. The results are shown in Figure 1.

[0070] [Example 9] Synthesis and evaluation of compound I (PAA-1GA, theoretical introduction rate 100%, measured introduction rate 21%) Compound I was obtained by following the same procedure as in Example 8, except that the type and amount of azulene carboxylic acid in the reaction conditions were changed to 1GA, 114 mg [0.5 mmol] and the amount of DMT-MM was changed to 152.2 mg [0.55 mmol]. The 1GA introduction rate and water solubility of the red solid compound I were evaluated according to the above method. The results are shown in Table 1.

[0071]

[0072] As shown in Table 1, the melting points of compounds A to G, which are examples of the present invention, are all 35°C or higher and are solid at room temperature, thus offering excellent handling properties. On the other hand, the melting points of the comparative examples are low, below 35°C, and they dissolve from the moment the sample is taken out, raising concerns about poor handling. In other words, it has been demonstrated that one of the challenges of the present invention, improved handling through increased melting points (improvement of the melting point of azulene by bonding with polyallylamine, etc.), has been achieved. Furthermore, compounds A, B, F, G, and H in the examples were dissolved in water at a concentration of 0.008 to 0.1 M. By controlling the introduction rate of the azulenyl group, it is also possible to make them water-soluble or color them in aqueous systems.

[0073]

[0074] The results shown in Table 2 confirm that Examples 1 and 4 (compounds A and D) exhibited high stability at pH 4.0, 7.0, or 9.0, suggesting that the azlenyl group did not decompose under either acidic or basic conditions. It is thought that the protonation of the amino group of PAA in the acidic bath suppressed the decomposition of the azlenyl group. In the comparative example at pH 4.0, the solution changed from blue to blue-green after two weeks, indicating a decrease in the remaining percentage. At pH 7.0 or 9.0, there was no visible change in the solution color, but the remaining percentage decreased. After one month, the solution color changed at all pH levels, and the remaining percentage fell below 80%. In addition, blue color was present on the caps of all screw-cap tubes in the comparative example. It is thought that GA sublimated during the test, leading to a decrease in the remaining percentage. On the other hand, no sublimation was observed in compounds A and D (Examples 1 and 4) bound to polymers. These results confirm that introducing an azlenyl group into PAA, which has an amino group, ensures stability in the pH range of 4 to 9.

[0075] According to the present invention, the material combines unique optical properties and other characteristics derived from the azulene skeleton with a high melting point derived from the polyallylamine structure. While possessing unique optical properties and other characteristics, it has a wide range of applications, is relatively easy to handle, and can be given hydrophilicity through design. Thus, it can realize various technical effects that have high practical value and has high applicability in various fields of industry, such as dyeing, household products, analysis, life sciences, general chemistry, electrical and electronic industries, and energy industries.

Claims

1. A polymer compound having a structural portion (A) having an azulene skeleton and a structural portion (B) selected from a structural portion (B1) having a polyallylamine structure, a structural portion (B2) having a polydiallylamine structure, and a structural portion (B3) having a polyethyleneimine structure, wherein structural portion (A) and structural portion (B) are bonded via a carbonyl group.

2. The polymer compound according to claim 1, wherein the azulene skeleton has a guaiazulene structure (7-isopropyl-1,4-dimethylazulene structure), a chamazulene structure, a guaiazulenone structure, or a lactazulene structure.

3. The polymer compound according to claim 1 or 2, wherein the carbonyl group is bonded to the structural portion (A) at position 1 or 2 of the azulene skeleton.

4. The polymer compound according to claim 1 or 2, wherein the melting point is 40 to 300°C.

5. The polymer compound according to claim 1 or 2, wherein the structural portion (B) has a plurality of structural units b1 derived from allylamine, structural units b2 derived from diallylamine, and / or structural units b3 derived from ethyleneimine, and 0.1 to 70 mol% of the total of the structural units b1, b2, and / or b3 are bonded to the structural portion (A) via carbonyl groups.

6. The polymer compound according to claim 1 or 2, wherein the weight-average molecular weight is in the range of 500 to 2,000,000.

7. The maximum absorption wavelength peak L is within the wavelength range of 200 to 1000 nm. Ａ１ A polymer compound according to claim 1 or 2, having the following characteristics.

8. Azulene carboxylic acid compound (A) having a structure in which a carboxyl group is bonded to the structural portion (A) in place of the carbonyl group. ０ ) Maximum absorption wavelength peak L Ａ０ And the above maximum absorption wavelength peak L Ａ１ The difference between, L Ａ１ -L Ａ０ The polymer compound according to claim 1 or 2, wherein the absolute value of is 10 nm or less.

9. The polymer compound according to claim 1 or 2, which is water-soluble at pH 7 at at least a portion of the temperature range of 15 to 35°C.

10. 1) A step of providing an azulene carboxylic acid compound (A) having an azulene skeleton and a carboxyl group １ ), and 2) a step of subjecting the azulene carboxylic acid compound (A) obtained in the above step 1) １ ) to a condensation reaction with a compound (B) selected from polyallylamine, polydiallylamine, and polyethyleneimine １ ), which is a method for producing a polymer compound.

11. A method for producing a polymer compound according to claim 10, wherein the polymer compound according to claim 1 or 2 is produced.

12. A dye fixative, a color shampoo, a colored aqueous solution, a fluorescent probe, a material for forming ions or metal complexes, a solar cell, or a gas separation adsorbent, using the polymer compound described in claim 1 or 2.

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