Polyamide polymers

Abstract

To provide a polyamide-based polymer which has photo-functional properties and which can be prepared using bio-based itaconic acid and amino hydroxybenzoic acid as raw materials, and a method for producing the same, as well as a pyrrolidone ring-containing compound useful as a raw material of the polyamide-based polymer and a method for producing the same.SOLUTION: A polyamide-based polymer having a repeating unit represented by formula (IV) (where R1 represents an alkylene group or an arylene group, and q represents an integer of 1 or 2 indicating the number of -C(O)-NH-R1-NH- groups bonded to the benzene ring).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyamide-based polymer. More specifically, the present invention relates to a polyamide-based polymer and a method for producing the same, as well as a pyrrolidone ring-containing compound useful for the polyamide-based polymer and a method for producing the same. [Background technology]

[0002] Polyamides using itaconic acid as a raw material are polymers having a stimuli-responsive pyrrolidone ring in the main chain. When irradiated with ultraviolet light in the presence of an alkaline aqueous solution, the polyamides are converted into polymers of the formula:

[0003] [ka]

[0004] (wherein x, m, and n each represent a positive integer) As a result, polyamides have attracted attention as polymers that decompose in the natural environment (see, for example, Non-Patent Document 1).

[0005] However, since the polyamide is decomposed by irradiation with high-intensity ultraviolet light (wavelength: 250 to 450 nm) using a high-pressure mercury lamp or the like, studies are being conducted to develop polyamides that are easily decomposed by irradiation with sunlight by controlling the wavelength of light absorbed by the polyamide.

[0006] In recent years, phenol derivatives, which are used as raw materials for metal ion sensors, biomarkers, etc., have been attracting attention as polymers capable of controlling the wavelength of light they absorb. Because the fluorescent properties of phenol derivatives vary depending on the functional groups present in the benzene ring of the phenol derivative, studies have been conducted to control the decomposition wavelength of polyamides when irradiated with light by incorporating phenol derivatives having such functional groups into the polyamide molecule. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] Kaneko T. et al. Macromolecules Vol.46, No.10, pp.3719-3725 (2013) Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above-mentioned conventional techniques, and an object of the present invention is to provide a photoluminescent polyamide-based polymer that can be prepared using bio-derived itaconic acid and aminohydroxybenzoic acid as raw materials, a method for producing the same, and a pyrrolidone ring-containing compound that is useful as a raw material for the polyamide-based polymer, and a method for producing the same. [Means for solving the problem]

[0009] The present invention provides (1) Formula (I):

[0010] [ka]

[0011] (wherein p is the number of carboxyl groups bonded to the benzene ring and is an integer of 1 or 2). a pyrrolidone ring-containing compound represented by (2) Itaconic acid and a compound of formula (II):

[0012] [ka]

[0013] (wherein p is the number of carboxyl groups bonded to the benzene ring and is an integer of 1 or 2). and an amino acid compound represented by formula (I):

[0014] [ka]

[0015] (wherein p is the same as above) a method for producing a pyrrolidone ring-containing compound represented by the formula: (3) Formula (I):

[0016] [ka]

[0017] (wherein p is the number of carboxyl groups bonded to the benzene ring and is an integer of 1 or 2). and a pyrrolidone ring-containing compound represented by formula (III):

[0018] [ka]

[0019] (In the formula, R 1 represents an alkylene group or an arylene group) and a diamine represented by formula (IV):

[0020] [ka]

[0021] (In the formula, R 1 is the same as above, and q is —C(O)—NH—R bonded to the benzene ring 1 the number of -NH- groups is an integer of 1 or 2) A method for producing a polyamide polymer having a repeating unit represented by (4) Formula (IV):

[0022] [ka]

[0023] (In the formula, R 1 represents an alkylene group or an arylene group, and q is -C(O)-NH-R bonded to the benzene ring. 1 the number of -NH- groups is an integer of 1 or 2) A polyamide-based polymer having a repeating unit represented by (5) A film or molding material containing the polyamide polymer described in (4) above. Regarding. [Effects of the Invention]

[0024] According to the present invention, there are provided a photoluminescent polyamide-based polymer that can be prepared using bio-derived itaconic acid and aminohydroxybenzoic acid as raw materials, a method for producing the same, and a pyrrolidone ring-containing compound that is useful as a raw material for the polyamide-based polymer and a method for producing the same. [Brief explanation of the drawings]

[0025] [Figure 1] 1 is a graph showing the 1H-NMR spectrum of pyrrolidone ring-containing compound A obtained in Example 1. [Figure 2] 1 is a graph showing the 1H-NMR spectrum of pyrrolidone ring-containing compound B obtained in Example 2. [Figure 3] 1 is a photograph as a substitute for a drawing showing the appearance of a glass tube containing various pyrrolidone ring-containing compounds when the glass tube is irradiated with ultraviolet light. [Figure 4] 1 is a photograph, substituted for a drawing, showing the appearance of a glass tube containing water, hydrochloric acid or an aqueous solution of sodium hydroxide as a solvent and a pyrrolidone ring-containing compound when the glass tube is irradiated with ultraviolet light. [Figure 5] 1 is a graph showing the 1H-NMR spectrum of polyamide polymer A obtained in Example 3. [Figure 6]1 is a graph showing 1H-NMR of polyamide polymer B obtained in Example 4. [Figure 7] 1 is a graph showing 1H-NMR of polyamide polymer C obtained in Example 5. [Figure 8] 1 is a graph showing 1H-NMR of polyamide polymer D obtained in Example 6. [Figure 9] 1 is a drawing-substitute photograph of polyamide-based polymer A obtained in Example 3 before and during irradiation with ultraviolet light. DETAILED DESCRIPTION OF THE INVENTION

[0026] (1) Pyrrolidone ring-containing compounds The pyrrolidone ring-containing compound of the present invention has the formula (I):

[0027] [ka]

[0028] (wherein p is the number of carboxyl groups bonded to the benzene ring and is an integer of 1 or 2). It is a compound represented by the formula:

[0029] In formula (I), p is the number of carboxyl groups bonded to the benzene ring. p is an integer of 1 or 2, but is preferably 1 because amino acid compounds, which are raw materials for the pyrrolidone ring-containing compound, are easily available. The carboxyl group and hydroxyl group bonded to the benzene ring may each be located at the o-position, m-position, or p-position relative to the nitrogen atom bonded to the benzene ring.

[0030] The pyrrolidone ring-containing compound is, for example, a compound obtained by reacting itaconic acid with a compound of formula (II):

[0031] [ka]

[0032] (wherein p is the same as above) The compound can be prepared by reacting the compound with an amino acid compound represented by the formula:

[0033] The amino acid compound represented by formula (II) includes, for example, the amino acid compound represented by formula (IIa):

[0034] [ka]

[0035] 3-amino-4-hydroxybenzoic acid represented by formula (IIb):

[0036] [ka]

[0037] 4-amino-3-hydroxybenzoic acid represented by formula (IIc):

[0038] [ka]

[0039] 3-amino-salicylic acid represented by formula (IId):

[0040] [ka]

[0041] Examples of amino acid compounds include 3-hydroxyanthranilic acid represented by the formula (I), but the present invention is not limited to these examples. These amino acid compounds may be used alone or in combination of two or more. All of these amino acid compounds are readily commercially available and therefore can be suitably used in the present invention. Among these amino acid compounds, 3-amino-4-hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, and 3-hydroxyanthranilic acid are preferred because they can be produced by microorganisms, and 3-amino-4-hydroxybenzoic acid and 4-amino-3-hydroxybenzoic acid are more preferred. The amino acid compounds may also be in the form of salts within the scope of the present invention.

[0042] The reaction between itaconic acid and the amino acid compound can be carried out, for example, by mixing itaconic acid with the amino acid compound and heating the resulting mixture.

[0043] The heating temperature of the mixture is preferably about 180 to 240°C from the viewpoint of efficiently obtaining the pyrrolidone ring-containing compound. The heating time of the mixture varies depending on the heating temperature of the mixture and cannot be generally determined. Therefore, the heating time can be the time required for sufficient production of the pyrrolidone ring-containing compound. The heating time of the mixture is usually about 15 to 60 minutes. The atmosphere in which the mixture is heated may be either air or an inert gas. However, from the viewpoint of avoiding the influence of oxygen contained in air, an inert gas such as nitrogen gas or argon gas is preferred.

[0044] The reaction of itaconic acid with the amino acid compound can be carried out in the presence or absence of a solvent.

[0045] As described above, by reacting itaconic acid with the amino acid compound, the pyrrolidone ring-containing compound represented by formula (I) can be obtained. If necessary, the pyrrolidone ring-containing compound obtained above may be purified by a method such as reprecipitation using an organic solvent such as ethyl acetate.

[0046] The pyrrolidone ring-containing compound of the present invention is not only useful as a raw material compound for polyamide polymers, but also exhibits fluorescence upon irradiation with ultraviolet light (wavelength: 250 to 450 nm) under alkaline conditions, and is therefore expected to be used in applications such as optical functional materials.

[0047] (2) Polyamide polymers The polyamide-based polymer of the present invention comprises a pyrrolidone ring-containing compound represented by formula (I) and a compound represented by formula (III):

[0048] [ka]

[0049] (In the formula, R 1 represents an alkylene group or an arylene group) The compound can be obtained by polymerizing a diamine represented by the formula:

[0050] In the diamine represented by formula (III), R 1 is an alkylene group or an arylene group. 1 Among these, an alkylene group is preferred from the viewpoint of obtaining a polyamide-based polymer having luminescent properties and decomposability in water.

[0051] From the viewpoint of obtaining a polyamide-based polymer having luminescent properties and decomposability in water, the alkylene group is preferably an alkylene group having 2 to 18 carbon atoms, more preferably an alkylene group having 4 to 12 carbon atoms. The alkylene group may be linear or branched. The alkylene group may have a substituent within the scope of the present invention.

[0052] In formula (III), R 1 Examples of diamines in which is an alkylene group include 1,2-ethanediamine (1,2-ethylenediamine), 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine (1,6-hexamethylenediamine), 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, and the like. Diamine, 3-ethyl-1,5-pentanediamine, 2-methyl-1,6-hexanediamine, 2-ethyl-1,6-hexanediamine, 3-methyl-1,6-hexanediamine, 3-ethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 2-ethyl-1,8-octanediamine, 3-ethyl-1,8-octanediamine, 4-ethyl- 1,8-octanediamine, 3-propyl-1,8-octanediamine, 2-butyl-1,8-octanediamine, 3-butyl-1,8-octanediamine, 4-butyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, 3-methyl-1,9-nonanediamine, 4-methyl-1,9-nonanediamine, 2-ethyl-1,9-nonanediamine, 3-ethyl-1,9-nonanediamine, 4-ethyl-1,9-nonanediamine, 2-propyl Examples of diamines include propyl-1,9-nonanediamine, 3-propyl-1,9-nonanediamine, 4-propyl-1,9-nonanediamine, 2-methyl-1,10-decanediamine, 3-methyl-1,10-decanediamine, 4-methyl-1,10-decanediamine, 2-ethyl-1,10-decanediamine, 3-ethyl-1,10-decanediamine, and 4-ethyl-1,10-decanediamine, but the present invention is not limited to these examples. These diamines may be used alone or in combination of two or more.

[0053] Examples of the arylene group include a phenylene group, a tolylene group, a naphthalene group, an anthrylene group, and a phenanthrylene group, but the present invention is not limited to these examples. The arylene group may have a substituent within the scope of the present invention.

[0054] In formula (III), R 1 Examples of diamines in which R is an arylene group include, but are not limited to, phenylenediamine, xylylenediamine, naphthylenediamine, biphenylenediamine, etc. These diamines may be used alone or in combination of two or more.

[0055] When the pyrrolidone ring-containing compound has two carboxyl groups, the amount of diamine per mole of the pyrrolidone ring-containing compound is stoichiometrically 1 mole, but it is not necessarily 1 mole, and the amount of the pyrrolidone ring-containing compound may be in excess, or the amount of diamine acid may be in excess. The amount of diamine per mole of the pyrrolidone ring-containing compound is usually about 0.9 to 1.1 moles.

[0056] When the pyrrolidone ring-containing compound has three carboxyl groups, the amount of diamine per mole of the pyrrolidone ring-containing compound is stoichiometrically 1.5 moles, but it is not necessarily 1.5 moles, and the amount of the pyrrolidone ring-containing compound or the amount of diamine acid may be excessive. The amount of diamine per mole of the pyrrolidone ring-containing compound is usually about 1.2 to 1.8 moles.

[0057] Examples of methods for polymerizing the pyrrolidone ring-containing compound and the diamine include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., but the present invention is not limited to these examples. Among these polymerization methods, bulk polymerization and solution polymerization are preferred from the viewpoint of efficiently preparing a polyamide-based polymer with a small amount of impurities, and solution polymerization is more preferred from the viewpoint of improving the operability of the polymerization reaction.

[0058] When the pyrrolidone ring-containing compound and the diamine are polymerized by solution polymerization, the pyrrolidone ring-containing compound and the diamine are polymerized in the presence of an organic solvent.

[0059] Examples of the organic solvent include N,N-dimethylformamide, N-methylpyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, and trifluoroacetic acid, but the present invention is not limited to these examples. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent is not particularly limited as long as it is an amount that allows the pyrrolidone ring-containing compound and the diamine to undergo an efficient polymerization reaction. The amount of the organic solvent is usually preferably about 1.5 to 10 times (by mass) the total amount (by mass) of the pyrrolidone ring-containing compound and the diamine, and more preferably about 2 to 5 times (by mass).

[0060] In order to efficiently prepare a polyamide polymer, when polymerizing the pyrrolidone ring-containing compound with the diamine, it is preferable to add, as a condensing agent, triphenyl phosphite and pyridine to the reaction system of the pyrrolidone ring-containing compound with the diamine, or to add a complex of triphenyl phosphite and pyridine to the reaction system of the pyrrolidone ring-containing compound with the diamine. The amount of the condensing agent per mole of the total amount of the pyrrolidone ring-containing compound and the diamine is usually preferably about 0.5 to 3 moles.

[0061] From the viewpoint of efficient polymerization of the pyrrolidone ring-containing compound and the diamine, a catalyst may be used in an appropriate amount. Examples of the catalyst include lithium chloride, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, and trilithium phosphate, but the present invention is not limited to these examples.

[0062] When polymerizing the pyrrolidone ring-containing compound with the diamine, a suitable amount of a heat stabilizer can be used. Examples of the heat stabilizer include phenylphosphonic acid (PPA), dimethyl phenylphosphonate, diethyl phenylphosphonate, and diphenylphosphonic acid, but the present invention is not limited to these examples.

[0063] The polymerization reaction temperature between the pyrrolidone ring-containing compound and the diamine is not particularly limited, but from the viewpoint of increasing the reaction efficiency, it is preferably about 60 to 90° C. The polymerization reaction temperature may be constant or may be increased stepwise.

[0064] The polymerization reaction time between the pyrrolidone ring-containing compound and the diamine cannot be determined in general because it varies depending on the amount of organic solvent used, the polymerization reaction temperature, etc., so it can be the time required for a sufficient amount of polyamide polymer to be produced. The polymerization reaction time is usually about 10 to 30 hours.

[0065] The atmosphere in which the pyrrolidone ring-containing compound and the diamine are reacted is preferably an inert gas such as nitrogen gas or argon gas, from the viewpoint of avoiding the influence of oxygen contained in the air.

[0066] After polymerizing the pyrrolidone ring-containing compound and the diamine, a polyamide polymer is crystallized from the resulting reaction mixture. Examples of methods for precipitating the polyamide polymer from the reaction mixture include adding the reaction mixture to a poor solvent such as an aliphatic alcohol having 1 to 3 carbon atoms (e.g., methanol, ethanol, propanol), a ketone compound (e.g., acetone, methyl ethyl ketone), ethyl acetate, tetrahydrofuran, dioxane, chloroform, dichloromethane, chlorobenzene, phenol, or cresol, or gradually evaporating the solvent contained in the reaction mixture, but the present invention is not limited to these methods.

[0067] The precipitated polyamide-based polymer can be recovered by a method such as filtration, etc. If necessary, the recovered polyamide-based polymer may be washed with a poor solvent such as an aliphatic alcohol having 1 to 3 carbon atoms and having a temperature of about 0 to 25°C.

[0068] By polymerizing the pyrrolidone ring-containing compound and the diamine in the above manner, a compound of the formula (IV):

[0069] [ka]

[0070] (In the formula, R 1 is the same as above, and q is —C(O)—NH—R bonded to the benzene ring. 1 the number of -NH- groups is an integer of 1 or 2) Thus, a polyamide polymer having a repeating unit represented by the formula:

[0071] In formula (IV), q is —C(O)—NH—R bonded to the benzene ring. 1 It is the number of -NH- groups and represents an integer of 1 or 2. q corresponds to p in formula (I) and is the same integer as p.

[0072] The fact that the polyamide polymer represented by formula (IV) has been obtained can be confirmed, for example, by nuclear magnetic resonance spectroscopy, infrared spectroscopy, or the like.

[0073] The number average molecular weight of the polyamide polymer of the present invention is not particularly limited, but from the viewpoint of obtaining a polyamide polymer having luminescent properties and decomposability in water, it is preferably 10,000 to 200,000, and more preferably 12,000 to 100,000. The number average molecular weight of the polyamide polymer is a value measured based on the method described in the following examples.

[0074] The polyamide polymer of the present invention has a repeating unit represented by formula (IV), but may contain repeating units other than the repeating unit represented by formula (IV) within the scope of not impeding the object of the present invention.

[0075] The polyamide polymer of the present invention may contain an appropriate amount of additives depending on the intended use, as necessary. Examples of additives include colorants such as pigments and dyes, UV absorbers, UV stabilizers, antioxidants, rust inhibitors, antibacterial agents, plasticizers, algae inhibitors, mildew inhibitors, flame retardants, and foaming agents, but the present invention is not limited to these examples. These additives may be used alone or in combination of two or more. The amount of additive varies depending on the type of additive, so it cannot be determined in general. Therefore, it is preferable to determine the amount appropriately depending on the type of additive.

[0076] (3) Applications of polyamide polymers The polyamide polymer of the present invention has a repeating unit represented by formula (IV) containing an itaconic acid-derived group and an aromatic ring, and therefore has light-emitting properties, decomposability in water, heat resistance, and film-forming properties.

[0077] The polyamide-based polymer of the present invention is soluble in various organic solvents, and therefore a solution of the polyamide-based polymer dissolved in an organic solvent can be used to form a molded article, film, or the like having a desired shape, and therefore can be suitably used as a molding material, a raw material for a film, or the like.

[0078] The molded article can be obtained, for example, by molding a solution of a polyamide polymer dissolved in an organic solvent using a molding method such as injection molding, extrusion molding, or blow molding.

[0079] Examples of the organic solvent include, but are not limited to, N,N-dimethylformamide, N-methylpyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, trifluoroacetic acid, etc. These organic solvents may be used alone or in combination of two or more.

[0080] The amount of organic solvent relative to the polyamide-based polymer of the present invention cannot be determined in general because it varies depending on the type of organic solvent, the desired viscosity of the organic solvent solution of the polyamide-based polymer, etc. Usually, it is preferable to mix the polyamide-based polymer and the organic solvent in a desired ratio so that the organic solvent solution of the polyamide-based polymer has a desired viscosity at a predetermined temperature.

[0081] The polyamide-based polymer-containing film of the present invention can be obtained by forming an organic solvent solution of the polyamide-based polymer into a film by a method such as casting or flow-casting. After forming the film, the film may be dried to remove the organic solvent contained in the film. The thickness of the formed film cannot be determined in general because it varies depending on the application of the film, but is usually about 3 to 800 μm.

[0082] Since the polyamide-based polymer of the present invention melts when heated, a solution obtained by heating and melting the polyamide-based polymer can be used as a spinning dope. Also, a solution obtained by dissolving the polyamide-based polymer of the present invention in an organic solvent can be used as a spinning dope.

[0083] The spinning dope is extruded through the fine holes in the spinneret of a melt spinning device, and then, if a heated melt of a polyamide polymer is used as the spinning dope, the heated melt is cooled, or, if a solution of a polyamide polymer in an organic solvent is used, the organic solvent is volatilized off, thereby producing a polyamide fiber.

[0084] Spinnerets are generally made of alloys such as an alloy of gold and platinum, an alloy of platinum and iridium, or an alloy of platinum and palladium. The hole diameter of the spinneret is determined appropriately depending on the fineness of the target polyamide fiber, but is usually about 0.05 to 0.1 mm. The number of holes provided in the spinneret is not particularly limited, but is usually about 1 to 20,000.

[0085] The polyamide fiber may be a single fiber (filament), or may be a fiber (strand) formed by converging a plurality of single fibers extruded from a plurality of holes into a single bundle.

[0086] The polyamide fibers obtained as described above may be subjected to treatments such as washing, drying, crimping, etc., as required.

[0087] The fineness of the polyamide fiber obtained as described above varies depending on the application of the polyamide fiber and cannot be determined in general, so it is preferable to determine it appropriately depending on the application of the polyamide fiber. An example of the fineness of the polyamide fiber is 1 to 30 decitex, but the present invention is not limited to this fineness. The fineness of the polyamide fiber can be easily adjusted by adjusting the hole diameter of the spinneret or the draw ratio when drawing the polyamide fiber.

[0088] The polyamide fiber obtained as described above may be stretched as necessary to increase its mechanical strength. The stretching of the polyamide fiber is usually a single-stage stretching, but may also be a multi-stage stretching in which the fiber is further stretched under different temperature conditions or the like.

[0089] Polyamide fibers may be used in the form of continuous fibers or may be cut to a desired length and used as short fibers. The fiber length of polyamide fibers varies depending on the application of the polyamide fibers, and is therefore preferably determined appropriately depending on the application of the polyamide fibers. Polyamide fibers can be used, for example, in woven fabrics, nonwoven fabrics, knitted fabrics, etc.

[0090] Knitted fabrics can be produced using the polyamide fibers and a knitting machine or the like. When producing knitted fabrics, the polyamide fibers may be used as they are, or, for example, blended yarns of the polyamide fibers with synthetic fibers such as polyester fibers and acrylic fibers, or fibers such as cotton yarn, wool yarn, and raw silk may be used. Examples of knitted fabrics include plain knitting, rib knitting, and purl knitting, but the present invention is not limited to these examples.

[0091] The woven fabric can be produced using a loom or the like, using the polyamide fibers as the warp, weft, or both the warp and weft. The woven fabric may be a blended fabric using blended yarns containing polyamide fibers in some or all of the warp and weft, a union fabric in which the warp and weft have different compositions and polyamide fibers are used in the warp and / or weft, or a highly woven fabric using warp and weft yarns containing the polyamide fibers of the present invention and having different fiber diameters. Examples of weaves that the woven fabric may have include plain weave, twill weave, twill weave, satin weave, and modified weave, but the present invention is not limited to these examples.

[0092] Nonwoven fabrics can be produced by dry or wet methods using fibers containing the polyamide fibers. The fibers used in the nonwoven fabric may consist solely of the polyamide fibers, or may be blends of the polyamide fibers with synthetic fibers such as polyester fibers and acrylic fibers, or fibers such as cotton yarn, wool yarn, and raw silk. Dry methods include, for example, mechanical bonding methods such as chemical bonding, thermal bonding, needle punching, and airlaid, but the present invention is not limited to these examples. Wet methods include, for example, hydroentanglement, but the present invention is not limited to these examples.

[0093] The polyamide fibers are expected to be used in a variety of applications, including fishing equipment such as fishing nets and fishing lines in the fishing industry, agricultural tools, clothing such as gloves, underwear, socks, shirts and suits, face masks, materials for disposable diapers, and cosmetic sheets such as lotion wipes. [Example]

[0094] The present invention will now be described in more detail based on examples, but the present invention is not limited to these examples.

[0095] The physical properties of the pyrrolidone ring-containing compounds and polyamide polymers obtained in the following examples and comparative examples were determined based on the following methods.

[0096] (1) Nuclear magnetic resonance ( 13 C-NMR spectrum Nuclear magnetic resonance of pyrrolidone ring-containing compounds and polyamide polymers ( 13 C-NMR spectra were measured using a nuclear magnetic resonance spectrometer (Bruker Avance III, 500 MHz, product name: Bruker). 5 mg of a sample (pyrrolidone ring-containing compound or polyamide polymer) was dissolved in 0.5 mL of dimethyl sulfoxide-d6, and the resulting solution was transferred to a glass sample tube. Nuclear magnetic resonance was measured at 25°C with the number of accumulations set to 16.

[0097] (2) Average molecular weight of polyamide polymer The number average molecular weight and weight average molecular weight of the polyamide polymer were measured by gel permeation chromatography (GPC). More specifically, the equipment used was a liquid pump unit (manufactured by JASCO Corporation, product number: PU-2080), a column oven (manufactured by GL Sciences Inc., product number: CO631A, set temperature: 40°C), an ultraviolet-visible detector (manufactured by JASCO Corporation, product number: UV-2075), a differential refractometer (manufactured by JASCO Corporation, product number: RI-2031), two columns (manufactured by Showa Denko K.K., product name: Shodex SB-806M HQ), and a standard substance (polymethyl methacrylate standard, molecular weights: 3070, 7360, 18500, 68800, 211000, 569000, and 1050000). The mobile phase was an N,N-dimethylformamide solution containing 0.01 mol / L LiBr, and the flow rate of the solution was adjusted to 1.0 mL / min.

[0098] (3) Mass spectrometry of pyrrolidone ring-containing compounds The compound (monomer) was subjected to mass spectrometry using an electrospray ionization mass spectrometer (ESI-MS) [Shimadzu Corporation, product number: LCMS2010EV] to measure the molecular weight of the compound (monomer). (4) pKa of pyrrolidone ring-containing compounds The pKa of the pyrrolidone ring-containing compound was determined by titration. More specifically, 66.3 mg of the pyrrolidone ring-containing compound and 2.1 g of sodium chloride were dissolved in 250 mL of water. The temperature of the resulting solution was maintained at 25±0.1°C, and while nitrogen gas was being bubbled through the solution, 0.01 mol / L aqueous sodium hydroxide solution was added dropwise to the solution using a burette. The pH of the solution was measured, and the pKa was determined from the titration curve.

[0099] (5) Solubility of pyrrolidone ring-containing compounds and polyamide polymers Five mg of a sample (a pyrrolidone ring-containing compound or a polyamide polymer) was added to 2 mL of an organic solvent or 250 mL of water, and the mixture was left to stand at room temperature (approximately 20°C) under atmospheric pressure. One hour after the start of sample addition, the sample was checked for dissolution in the solvent. If the sample did not dissolve in the solvent even after one hour of sample addition, it was examined whether it had dissolved by irradiating it with ultrasound or by heating it to 60°C and then cooling it to room temperature.

[0100] The evaluation criteria for solubility are as follows: [Evaluation criteria] +: Sample is completely dissolved ±: Sample partially dissolved -: Sample is insoluble

[0101] (6) 5% weight loss temperature (T d5 ) and 10% weight loss temperature (T d10 ) The 5% weight loss temperature (T d5 ) and 10% weight loss temperature (T d10 ) was investigated by thermogravimetric analysis (TGA). Thermogravimetric analysis (TGA) was performed using a simultaneous differential thermal and thermogravimetric analyzer (Hitachi High-Tech Science Corporation, model number: STA7200) and a platinum pan. The sample (polyamide polymer) amounted to 10 mg, and the measurement was performed under a nitrogen gas atmosphere (nitrogen gas flow rate: 250 mL / min) with a reference blank (no sample). The measurement temperature was 0 to 800°C, and the heating rate was 10°C / min. The temperatures at which the sample weight decreased by 5% (5% weight loss temperature) and 10% (10% weight loss temperature) were defined as T d5 and T d10 It was decided.

[0102] Example 1 (Preparation of pyrrolidone ring-containing compound A) [Synthetic Route]

[0103] [ka]

[0104] Based on the synthetic route described in the above formula, pyrrolidone ring-containing compound A shown on the right of the formula was prepared. More specifically, 6.50 g of itaconic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product code: M0223, the same applies hereinafter) and 7.65 g of 3-amino-4-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product code: A0859, the same applies hereinafter) were mixed, and the resulting mixture was heated at 210°C for 30 minutes under stirring. Ethyl acetate was then added to the mixture, and pyrrolidone ring-containing compound A was recovered as a white solid. Subsequently, pyrrolidone ring-containing compound A was dissolved in ethyl acetate at 70°C, cooled, and filtered to recover pyrrolidone ring-containing compound A (yield: 10.2 g, yield: 77%). Mass spectrometry of the pyrrolidone ring-containing compound A obtained above revealed that the mass of pyrrolidone ring-containing compound A was 264. 1 The H-NMR spectra are shown in Figure 1. In each figure, DMSO indicates the peak of the solvent, dimethyl sulfoxide.

[0105] Example 2 (Preparation of pyrrolidone ring-containing compound B) [Synthetic Route]

[0106] [ka]

[0107] The pyrrolidone ring-containing compound B shown on the right side of the formula was prepared based on the synthetic route described above. More specifically, 4-amino-3-hydroxybenzoic acid sulfate (purity: 99.8%) prepared according to the method described in Microb Cell Fact. 2023 Aug 29; 22(1): 168. doi: 10.1186 / s12934-023-02179-y by Kao Corporation was neutralized to a pH of 6 to 7 with 0.1 M aqueous sodium hydroxide, and the precipitated 4-amino-3-hydroxybenzoic acid was collected, dried, and then used (same below). 6.50 g of itaconic acid and 7.65 g of 4-amino-3-hydroxybenzoic acid were mixed, and the resulting mixture was heated at 220 ° C. for 30 minutes with stirring. The mixture was then reprecipitated with ethyl acetate to obtain the pyrrolidone ring-containing compound B as a white solid. Subsequently, the pyrrolidone ring-containing compound B was dissolved in ethyl acetate at 70°C, cooled, and filtered to recover the pyrrolidone ring-containing compound B (yield: 10.9 g, yield: 78%). When the pyrrolidone ring-containing compound B obtained above was analyzed by mass spectrometry, the mass of the pyrrolidone ring-containing compound B was found to be 264. 1 The H-NMR spectrum is shown in Figure 2.

[0108] Comparative Example 1 For comparison with the pyrrolidone ring-containing compounds obtained in each example, compounds of formula (V):

[0109] [ka]

[0110] A pyrrolidone ring-containing compound X represented by the following formula was prepared and used: The pyrrolidone ring-containing compound X is a compound that does not have a hydroxyl group on the benzene ring.

[0111] [Fluorescence properties of pyrrolidone ring-containing compounds 1] 0.5 mL of dimethyl sulfoxide was placed in a glass tube (outer diameter: 8 mm), and 5 mg of each of pyrrolidone ring-containing compound A, pyrrolidone ring-containing compound B, or pyrrolidone ring-containing compound X was added to the glass tube. Then, ultraviolet light (wavelength: 365 nm, ultraviolet intensity: 100 mW / cm) was applied to the glass tube using a xenon lamp as the ultraviolet light source. 2 The results are shown in Figure 3.

[0112] In FIG. 3, symbol A indicates a glass tube in which pyrrolidone ring-containing compound B is used, symbol B indicates a glass tube in which pyrrolidone ring-containing compound A is used, and symbol C indicates a glass tube in which pyrrolidone ring-containing compound X is used.

[0113] As shown in Figure 3, when ultraviolet light was irradiated onto the glass tubes containing pyrrolidone ring-containing compound A and pyrrolidone ring-containing compound B, pyrrolidone ring-containing compound A and pyrrolidone ring-containing compound B exhibited yellow fluorescence, whereas when ultraviolet light was irradiated onto the glass tube containing pyrrolidone ring-containing compound X, pyrrolidone ring-containing compound X was transparent and no fluorescence was observed.

[0114] From this, it was confirmed that pyrrolidone ring-containing compound A and pyrrolidone ring-containing compound B, unlike pyrrolidone ring-containing compound X, exhibit fluorescent properties due to the presence of a hydroxyl group on the benzene ring.

[0115] [Fluorescence properties of pyrrolidone ring-containing compounds 2] Pyrrolidone ring-containing compound B was used as the pyrrolidone ring-containing compound. 0.5 mL of dimethyl sulfoxide was placed in a glass tube (outer diameter: 8 mm), and three test tubes were prepared, each containing 5 mg of pyrrolidone ring-containing compound B. 0.01 mL of water, 0.1 M hydrochloric acid, or 0.01 M sodium hydroxide aqueous solution was added to each test tube, and then ultraviolet light (wavelength: 365 nm, ultraviolet intensity: 100 mW / cm) was applied to each glass tube using a xenon lamp as an ultraviolet light source. 2 The results are shown in Figure 4.

[0116] In Figure 4, (A) shows the glass tube before UV irradiation, and (B) shows the glass tube after UV irradiation. Also in Figure 4, P is a glass tube with water added, Q is a glass tube with hydrochloric acid added, and R is a glass tube with sodium hydroxide aqueous solution added. Note that (B) is darker overall than (A) due to the shooting conditions.

[0117] From the results shown in FIG. 4, it can be seen that P, Q, and R all have different degrees of fluorescence, and therefore the fluorescence of the pyrrolidone ring-containing compound of the present invention (pyrrolidone ring-containing compound B) changes depending on the liquid property (pH) of the aqueous solution that comes into contact with it.

[0118] From this, it is believed that the pyrrolidone ring-containing compound of the present invention can be used as a pH-responsive material, since its fluorescence changes when the pH of the solution in contact with it is changed.

[0119] [pKa of pyrrolidone ring-containing compounds] The pKa of pyrrolidone ring-containing compound A and the pKa of pyrrolidone ring-containing compound B were investigated. As a result, the pKa of pyrrolidone ring-containing compound A was 3.7, and the pKa of pyrrolidone ring-containing compound B was 3.8.

[0120] This shows that the pyrrolidone ring-containing compound of the present invention is easily dissociated by an acid that comes into contact with it.

[0121] [Solubility of pyrrolidone ring-containing compounds] The solubility of pyrrolidone ring-containing compound A and pyrrolidone ring-containing compound B in various solvents was examined. The results are shown in Table 1.

[0122] The abbreviations in the following tables have the following meanings. DMF: N,N-dimethylformamide NMP: N-methylpyrrolidone DMAc: N,N-dimethylacetamide DMSO: dimethyl sulfoxide THF: tetrahydrofuran

[0123] [Table 1]

[0124] The results shown in Table 1 indicate that pyrrolidone ring-containing compounds are soluble in various organic solvents, and that by dissolving the pyrrolidone ring-containing compounds in an organic solvent, they can be used, for example, as pH-responsive materials.

[0125] [Weight loss temperature of pyrrolidone ring-containing compound] The weight loss temperature of each pyrrolidone ring-containing compound was investigated using pyrrolidone ring-containing compound A and pyrrolidone ring-containing compound B. The results are shown in Table 2.

[0126] [Table 2]

[0127] The results shown in Table 2 show that the pyrrolidone ring-containing compound has suitable heat resistance and can therefore be used in applications where it is used at high temperatures.

[0128] Example 3 (Preparation of Polyamide Polymer A) [Synthetic Route]

[0129] [ka]

[0130] Polyamide polymer A, shown to the right of the formula, was prepared based on the synthetic route described above. More specifically, 2.39 g of the pyrrolidone ring-containing compound A prepared in Example 1 was mixed with 1.05 g of hexamethylenediamine (hexanediamine) [Tokyo Chemical Industry Co., Ltd., product number: D0095, the same applies below]. To the resulting mixture was added a mixed solution of 10 mL of N-methylpyrrolidone, 3.6 mL of pyridine, and 7.1 mL of triphenyl phosphite in a nitrogen gas atmosphere. The resulting solution was heated and stirred at 80°C for 24 hours to polymerize the pyrrolidone ring-containing compound A and hexamethylenediamine, thereby obtaining polyamide polymer A. The resulting polyamide polymer A was added dropwise to acetone, and the precipitated polyamide polymer A was recovered by washing with methanol.

[0131] The number average molecular weight of the polyamide polymer A was 13,000, and the weight average molecular weight was 27,000. 1 The H-NMR spectrum is shown in Figure 5.

[0132] Example 4 (Preparation of Polyamide Polymer B) [Synthetic Route]

[0133] [ka]

[0134] Polyamide-based polymer B, shown to the right of the formula, was prepared based on the synthetic route described above. More specifically, 2.39 g of the pyrrolidone ring-containing compound B prepared in Example 2 was mixed with 1.05 g of hexamethylenediamine (hexanediamine). To the resulting mixture was added a mixed solution of 10 mL of N-methylpyrrolidone, 3.6 mL of pyridine, and 7.1 mL of triphenyl phosphite in a nitrogen gas atmosphere. The resulting solution was heated and stirred at 80°C for 24 hours to polymerize the pyrrolidone ring-containing compound B and hexamethylenediamine, thereby obtaining polyamide-based polymer B. The resulting polyamide-based polymer B was added dropwise to acetone, and the precipitated polyamide-based polymer B was recovered by washing with methanol.

[0135] The number average molecular weight of the polyamide polymer B was 13,000, and the weight average molecular weight was 22,000. 1 The H-NMR spectrum is shown in Figure 6.

[0136] Example 5 (Preparation of Polyamide Polymer C) [Synthetic Route]

[0137] [ka]

[0138] Polyamide-based polymer C, shown to the right of the formula, was prepared based on the synthetic route described above. More specifically, 2.65 g of pyrrolidone ring-containing compound A prepared in Example 1 and 1.72 g of 1,10-decanediamine were mixed, and a mixed solution of 10 mL of N-methylpyrrolidone, 4.0 mL of pyridine, and 7.8 mL of triphenyl phosphite was added to the resulting mixture in a nitrogen gas atmosphere. The resulting solution was heated and stirred at 80°C for 24 hours to polymerize pyrrolidone ring-containing compound A and 1,10-decanediamine, thereby obtaining polyamide-based polymer C. The resulting polyamide-based polymer C was added dropwise to acetone, and the precipitated polyamide-based polymer C was recovered by washing with methanol.

[0139] The number average molecular weight of the polyamide polymer C was 30,200, and the weight average molecular weight was 42,400. 1 The H-NMR spectrum is shown in Figure 7.

[0140] Example 6 (Preparation of Polyamide Polymer D) [Synthetic Route]

[0141] [ka]

[0142] Polyamide-based polymer D, shown to the right of the formula, was prepared based on the synthetic route described above. More specifically, 2.39 g of pyrrolidone ring-containing compound B prepared in Example 2 and 1.72 g of 1,10-decanediamine were mixed, and a mixed solution of 10 mL of N-methylpyrrolidone, 4.0 mL of pyridine, and 7.8 mL of triphenyl phosphite was added to the resulting mixture in a nitrogen gas atmosphere. The resulting solution was heated and stirred at 80°C for 24 hours to polymerize pyrrolidone ring-containing compound B and 1,10-decanediamine, thereby obtaining polyamide-based polymer D. The resulting polyamide-based polymer D was added dropwise to acetone, and the precipitated polyamide-based polymer D was recovered by washing with methanol.

[0143] The number average molecular weight of the polyamide polymer D was 26,100, and the weight average molecular weight was 30,300. 1 The H-NMR spectrum is shown in Figure 8.

[0144] [Fluorescence properties of polyamide polymers 1] Three test tubes were prepared, each containing 0.5 mL of dimethyl sulfoxide in a glass tube (outer diameter: 8 mm) and 5 mg of polyamide polymer A added to the tube. 0.01 mL of water, 0.1 M hydrochloric acid, or 0.01 M sodium hydroxide solution was added to each test tube, and then ultraviolet light (wavelength: 365 nm, ultraviolet intensity: 100 mW / cm) was applied to each tube using a xenon lamp as the ultraviolet light source. 2 As a result, it was found that when sodium hydroxide solution was added to the test tube, the fluorescence of polyamide polymer A changed as the pH increased.

[0145] From this, it is believed that the polyamide polymer A of the present invention can be used as a pH-responsive material, since its fluorescence changes when the pH of water that comes into contact with it is changed.

[0146] [Fluorescence properties of polyamide polymers 2] A block of polyamide polymer A (diameter: approximately 5 mm) was used as the polyamide polymer. The polyamide polymer A was directly irradiated with ultraviolet light (wavelength: 365 nm, ultraviolet intensity: 100 mW / cm) using a xenon lamp as the ultraviolet light source. 2 The results are shown in Figure 9. In Figure 9, (A) shows polyamide polymer A before irradiation with ultraviolet light, and (B) shows polyamide polymer A during irradiation with ultraviolet light.

[0147] 9, it can be seen that the polyamide-based polymer of the present invention emits fluorescence even when directly irradiated with ultraviolet light. Therefore, when a film is produced using the polyamide-based polymer of the present invention, the film can be used as an optical functional filter.

[0148] [Weight loss temperature of polyamide polymer] The weight loss temperatures of polyamide polymers A to D were investigated, and the results are shown in Table 1.

[0149] [Table 3]

[0150] From the results shown in Table 3, it can be seen that the polyamide polymers obtained in each example all have appropriate heat resistance and melt when heated, and therefore can be used as molding materials for injection molding, for example.

[0151] [Solubility of Polyamide-Based Polymers] The polyamide polymers A to D were used to examine their solubility in various solvents. The results are shown in Table 4.

[0152] [Table 4]

[0153] The results shown in Table 4 show that the polyamide polymers obtained in the examples are soluble in various organic solvents and can therefore be dissolved in organic solvents and used as molding materials.

[0154] [Film Preparation] 100 mg of the polyamide polymer obtained in each example was dissolved in 3 mL of dimethyl sulfoxide. The resulting solution was applied uniformly to a silicon plate using a dropper and dried at room temperature for 12 hours to evaporate the solvent, resulting in the formation of a transparent film. This confirmed that the polyamide polymer of the present invention can be used as a film. [Industrial Applicability]

[0155] The pyrrolidone ring-containing compound of the present invention is a compound that can be prepared using bio-derived compounds as raw materials, and is not only useful as a raw material for the polyamide-based polymer of the present invention, but also has luminescent properties, and is therefore expected to be used in applications such as optical functional materials.

[0156] The polyamide-based polymer of the present invention is a polymer that can be prepared using bio-derived compounds as raw materials, and emits fluorescence when irradiated with ultraviolet light. Therefore, it is expected to be used in applications such as optical functional filters and photo-degradable materials.

Claims

1. Formula (I): 【Chemistry 1】 (wherein p is the number of carboxyl groups bonded to the benzene ring and is an integer of 1 or 2). and a pyrrolidone ring-containing compound represented by formula (III): 【Chemistry 2】 (In the formula, R 1 represents an alkylene group or an arylene group) and a diamine represented by formula (IV): 【Transformation 3】 (In the formula, R 1 is the same as above, and q is —C(O)—NH—R bonded to the benzene ring. 1 the number of —NH— groups is an integer of 1 or 2) A method for producing a polyamide polymer having a repeating unit represented by the formula:

2. Formula (IV): 【Chemistry 4】 (In the formula, R 1 represents an alkylene group or an arylene group, and q represents —C(O)—NH—R 1 the number of —NH— groups is an integer of 1 or 2) A polyamide polymer having a repeating unit represented by the formula:

3. A film or molding material comprising the polyamide polymer according to claim 2.

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