Polyamide polymer

Abstract

Provided are: a carboxypyrrolidone compound represented by formula (I) (wherein R1 represents an alkenyl group that may have a substituent, and R2 represents a group -NH2, a group -OH, or a group represented by formula (Ia)); a polyamide polymer obtained using the carboxypyrrolidone compound as a raw material; and a method for producing the polyamide polymer.

Description

Polyamide polymers

[0001] The present invention relates to a polyamide-based polymer. More specifically, the present invention relates to a carboxypyrrolidone compound that can be prepared using bio-derived itaconic acid as a raw material, a polyamide-based polymer that can be prepared using the carboxypyrrolidone compound as a raw material, and a method for producing the polyamide-based polymer. The polyamide-based polymer of the present invention is expected to be used as a replacement for conventional polyamides such as nylon.

[0002] Polyamides synthesized from itaconic acid and diamines include those of the formula:

[0003]

[0004] (wherein R represents a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group), and the remaining repeating units are based on a copolymer of a dibasic acid or a lactam with a primary diamine (see, for example, Patent Document 1). This polyamide is said to be useful for molded articles, fibers, laminates, and coating agents.

[0005] Furthermore, a method for producing polyamide has been proposed in which bio-derived itaconic acid is mixed with a dicarboxypyrrolidone compound selected from the group consisting of dimethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine in a polar solvent, and the resulting crystalline powder is thermally polymerized at a temperature equal to or higher than the melting point of the crystalline powder (see, for example, Patent Document 2). The polyamide obtained by this method is thought to have a high glass transition temperature and therefore can be used as an engineering plastic.

[0006] However, since all of the above polyamides are random copolymers having multiple types of repeating units, not only are the thermal and mechanical properties of the polyamides difficult to stabilize, but the density between polymer molecules is not high, and therefore the decomposition onset temperature of the polyamides cannot be increased.

[0007] U.S. Patent No. 4,420,608, U.S. Patent No. 5,777,134

[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 polyamide-based polymer which has stable thermal and mechanical properties and a higher decomposition onset temperature than conventional polyamide-based copolymers obtained by reacting itaconic acid with a dicarboxypyrrolidone compound, a method for producing the same, and a carboxypyrrolidone compound which is useful as a raw material for the polyamide-based polymer.

[0009] The present invention provides: (1) a compound of formula (I):

[0010]

[0011] (In the formula, R 1 is an alkylene group which may have a substituent, R 2 is an —NH group, an —OH group or a group of formula (Ia):

[0012]

[0013] (2) a carboxypyrrolidone compound represented by itaconic acid or a salt thereof and a compound represented by the formula (II): HN-R 1 -NH2 (II) (wherein, R 1 represents an alkylene group which may have a substituent) in an aqueous solvent, and the resulting aqueous solvent solution is heated to produce a diamine represented by formula (III):

[0014]

[0015] (In the formula, R 1 (3) a method for producing a carboxypyrrolidone compound represented by the formula (II): H2N-R 1 -NH2 (II) (wherein, R 1 represents an alkylene group which may have a substituent), and the resulting mixture is heated to melt the resulting mixture,

[0016]

[0017] (In the formula, R 1 (4) a method for producing a dicarboxypyrrolidone compound represented by formula (III):

[0018]

[0019] (In the formula, R 1 represents an alkylene group which may have a substituent),

[0020]

[0021] (In the formula, R 1 (5) A method for producing a polyamide polymer having a repeating unit represented by formula (V):

[0022]

[0023] (In the formula, R 1 (6) a polyamide-based polymer having a repeating unit represented by formula (IV):

[0024]

[0025] (In the formula, R 1 represents an alkylene group which may have a substituent) and a dicarboxypyrrolidone compound represented by formula (VI): HN-R 3 -NH2 (VI) (wherein, R 3 represents an alkylene group which may have a substituent),

[0026]

[0027] (In the formula, R 1 and R 3 (7) a method for producing a polyamide polymer having a repeating unit represented by formula (VII):

[0028]

[0029] (In the formula, R 1 and R 3 and each independently represents an alkylene group which may have a substituent.

[0030] According to the present invention, there are provided a polyamide-based polymer which has stable thermal and mechanical properties and a higher decomposition onset temperature than conventional polyamide-based copolymers obtained by reacting itaconic acid with a dicarboxypyrrolidone compound, a method for producing the same, and a carboxypyrrolidone compound which is useful as a raw material for the polyamide-based polymer.

[0031] Carboxypyrrolidone Compound A obtained in Example 1 1 1 is a graph showing the H-NMR spectrum of carboxypyrrolidone compound B obtained in Example 2. 1 1 is a graph showing the H-NMR spectrum of carboxypyrrolidone compound C obtained in Example 3. 1 1 is a graph showing the H-NMR spectrum of dicarboxypyrrolidone compound D obtained in Example 4. 1 1 is a graph showing the H-NMR spectrum of carboxypyrrolidone compound E obtained in Example 5. 1 1 is a graph showing the H-NMR spectrum of dicarboxypyrrolidone compound F obtained in Example 6. 1 1 is a graph showing the H-NMR spectrum of polyamide polymer A obtained in Example 7. 1 1 is a graph showing the H-NMR spectrum of polyamide polymer B obtained in Example 8. 1 1 is a graph showing the H-NMR spectrum of polyamide polymer C obtained in Example 9. 1 1 is a graph showing the H-NMR spectrum of polyamide polymer D obtained in Example 10. 1 1 is a graph showing the H-NMR spectrum of polyamide polymer E obtained in Example 11. 1 1 is a graph showing the H-NMR spectrum of polyamide polymer F obtained in Example 12. 11 is a graph showing H-NMR spectra. 2 is a graph showing FT-IR spectra of carboxypyrrolidone compound A and the corresponding polyamide-based polymer A, and FT-IR spectra of carboxypyrrolidone compound B and the corresponding polyamide-based polymer B. 3 is a graph showing FT-IR spectra of carboxypyrrolidone compound C and the corresponding polyamide-based polymer C, and FT-IR spectra of carboxypyrrolidone compound D and the corresponding polyamide-based polymer D. 4 is a graph showing IR spectra of carboxypyrrolidone compound E, carboxypyrrolidone compound F, and polyamide-based polymer E. 5 is a graph showing FT-IR spectra of the dicarboxypyrrolidone compound obtained in Example 13. 1 1 is a graph showing the H-NMR spectrum of the carboxypyrrolidone compound obtained in Example 15. 1 1 is a graph showing the H-NMR spectrum of the polyol obtained in Example 16. 1 1 is a graph showing the H-NMR spectrum of the polyurethane obtained in Example 17. 1 1 is a graph showing a H-NMR spectrum.

[0032] (1) Carboxypyrrolidone Compound As described above, the carboxypyrrolidone compound of the present invention is represented by the formula (I):

[0033]

[0034] (In the formula, R 1 is an alkylene group which may have a substituent, R 2 is an —NH group, an —OH group or a group of formula (Ia):

[0035]

[0036] The carboxypyrrolidone compound is a useful compound as a raw material for the polyamide polymer of the present invention.

[0037] In formula (I), R 1is an alkylene group which may have a substituent. Examples of the alkylene group include alkylene groups having 2 to 12 carbon atoms, such as an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a decylene group, and a dodecylene group, but the present invention is not limited to these examples.

[0038] Examples of the substituent include alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy groups, hydroxyl groups, halogen atoms such as fluorine, chlorine, bromine, and iodine atoms, cyano groups, and nitrile groups, but the present invention is not limited to these examples. Among the substituents, alkoxy groups having 1 to 4 carbon atoms, hydroxyl groups, and halogen atoms are preferred.

[0039] In formula (I), R 2 As described above, represents an —NH group, an —OH group, or a group of formula (Ia):

[0040]

[0041] It is a group represented by:

[0042] (2) In formula (I), R 2 Carboxypyrrolidone compounds and polymers thereof in which the group is an -NH group [Carboxypyrrolidone compounds]

[0043] In formula (I), R 2 The carboxypyrrolidone compound in which is an -NH group has the formula (III):

[0044]

[0045] (In the formula, R 1 is the same as above).

[0046] The carboxypyrrolidone compound represented by formula (III) can be prepared, for example, by reacting itaconic acid or a salt thereof with a compound represented by formula (II): H2N-R 1 -NH2 (II) (wherein, R 1is the same as above) in an aqueous solvent, and heating the resulting aqueous solvent solution.

[0047] Itaconic acid can be readily obtained commercially from, for example, Fuso Chemical Co., Ltd., Iwata Chemical Co., Ltd., Cargill, etc. Itaconic acid may be produced using fungi such as Aspergillus terreus, or may be synthesized using petroleum as a raw material. Among these, itaconic acid produced using fungi such as Aspergillus terreus has the advantage of being more environmentally friendly than itaconic acid synthesized using petroleum as a raw material.

[0048] Examples of the itaconate include alkali metal itaconates such as sodium itaconate and potassium itaconate, and ammonium itaconate, but the present invention is not limited to these examples. Among the itaconates, alkali metal itaconates are preferred, and sodium itaconate is more preferred.

[0049] Itaconic acid and itaconate may be used alone, or itaconic acid and itaconate may be used in combination.

[0050] Examples of diamines represented by formula (II) include 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 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 Examples of alkylene diamines having 2 to 12 carbon atoms include alkylene diamines having 2 to 12 carbon atoms, such as 2-1,8-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-1,9-nonanediamine, 3-propyl-1,9-nonanediamine, and 4-propyl-1,9-nonanediamine, but the present invention is not limited to these examples. These diamines may be used alone or in combination of two or more. From the viewpoint of obtaining a polyamide polymer having appropriate water resistance, as well as decomposability in water and durability, the diamine is preferably an alkylene diamine having 2 to 12 carbon atoms, and more preferably at least one diamine selected from the group consisting of 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptadiamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine.

[0051] Since itaconic acid or its salt (hereinafter referred to as itaconic acid (salt)) and diamine react in stoichiometric amounts, the amount of diamine per mole of itaconic acid (salt) is theoretically 1 mole. However, the amount of itaconic acid (salt) may be in excess of the amount of diamine, or the amount of diamine may be in excess of the amount of itaconic acid (salt), within a range that does not impair the object of the present invention. The amount of diamine per mole of itaconic acid (salt) is usually preferably 0.9 to 1.1 moles.

[0052] To react itaconic acid (salt) with a diamine, first, itaconic acid (salt) and diamine are dissolved in an aqueous solvent.

[0053] The aqueous solvent is usually water. The water may be any of city water, purified water, distilled water, and pure water, but purified water, distilled water, and pure water are preferred, and distilled water and pure water are more preferred. The aqueous solvent may contain a hydrophilic organic solvent within a range that does not impair the object of the present invention.

[0054] Examples of the hydrophilic organic solvent include monohydric alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and allyl alcohol; polyhydric alcohols such as ethylene glycol, propylene glycol, butane polyol, pentane polyol, hexane polyol, heptane polyol, and dipropylene glycol; ketones such as acetone, methyl ethyl ketone, and methyl propyl ketone; aliphatic organic acid alkyl esters such as methyl formate, ethyl formate, methyl acetate, and methyl acetoacetate; and alkyl ethers of polyhydric alcohols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and dipropylene glycol monomethyl ether. However, the present invention is not limited to these examples. These hydrophilic organic solvents may be used alone or in combination of two or more.

[0055] The temperature of the aqueous solvent when itaconic acid (salt) and diamine are dissolved in the aqueous solvent is not particularly limited. The temperature of the aqueous solvent is usually room temperature.

[0056] The amount of water per 100 parts by mass of the total amount of itaconic acid (salt) and diamine is preferably about 10 to 25 parts by mass from the viewpoint of promoting the reaction between itaconic acid (salt) and diamine.

[0057] Next, an itaconic acid (salt)-diamine solution obtained by dissolving itaconic acid (salt) and diamine in an aqueous solvent is heated.

[0058] The heating temperature of the itaconic acid (salt)-diamine solution is not particularly limited, but is preferably about 80 to 120°C from the viewpoint of efficiently preparing the carboxypyrrolidone compound. The heating time of the itaconic acid (salt)-diamine solution is the time required to produce the carboxypyrrolidone compound represented by formula (III). The heating time of the itaconic acid (salt)-diamine solution cannot be determined in general because it varies depending on the heating temperature of the itaconic acid (salt)-diamine solution, but is typically about 15 to 30 hours. The atmosphere in which the itaconic acid (salt)-diamine solution is heated is not particularly limited, and may be air or an inert gas such as nitrogen gas or argon gas. However, an inert gas is preferred from the viewpoint of avoiding the influence of oxygen gas contained in air.

[0059] By heating the itaconic acid (salt)-diamine solution in the above manner, the itaconic acid (salt) and the diamine react with each other to produce the carboxypyrrolidone compound represented by formula (III). After the reaction of the itaconic acid (salt) and the diamine is complete, the resulting carboxypyrrolidone compound is usually allowed to cool to room temperature.

[0060] The carboxypyrrolidone compound obtained as described above may be used as it is, or, if necessary, may be purified by a method such as reprecipitation using a solvent such as a mixed solvent of methanol and ethyl acetate. The carboxypyrrolidone compound is suitable for use as a raw material for polyamide polymers.

[0061] [Polyamide-based polymer] The polyamide-based polymer can be obtained by polycondensing a carboxypyrrolidone compound represented by formula (III). The polyamide-based polymer is a compound represented by formula (V):

[0062]

[0063] (In the formula, R 1 is the same as above).

[0064] Examples of methods for polycondensing the carboxypyrrolidone compound represented by formula (III) include bulk polymerization and solution polymerization, but the present invention is not limited to these examples. Among these polymerization methods, bulk polymerization is preferred from the viewpoint of efficiently preparing a polyamide polymer with a small amount of impurities.

[0065] The heating temperature of the carboxypyrrolidone compound when polycondensing the carboxypyrrolidone compound is preferably about 150 to 250° C. from the viewpoint of efficiently obtaining a polyamide polymer having a repeating unit represented by formula (V). The heating temperature may be constant or may be increased stepwise.

[0066] The polycondensation of the carboxypyrrolidone compound is preferably carried out under stirring to avoid uneven polymerization. The heating time of the carboxypyrrolidone compound is the time required to produce a polyamide-based polymer. The heating time of the carboxypyrrolidone compound cannot be determined in general because it varies depending on the heating temperature, but is usually about 3 to 10 hours. The atmosphere during the polycondensation of the carboxypyrrolidone compound is not particularly limited and may be air or an inert gas such as nitrogen gas or argon gas. However, an inert gas is preferred to avoid the influence of oxygen contained in air.

[0067] When polycondensing a carboxypyrrolidone compound, it is preferable to add an appropriate amount of a catalyst to the carboxypyrrolidone compound from the viewpoint of efficiently preparing a polyamide polymer. Examples of the catalyst include 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. Among these catalysts, sodium dihydrogen phosphate is preferred.

[0068] By polycondensing the carboxypyrrolidone compound represented by formula (III) in the above manner, a polyamide polymer having a repeating unit represented by formula (V) can be obtained. The polyamide polymer obtained above is usually allowed to cool to room temperature.

[0069] The polyamide-based polymer is obtained by homopolymerizing the carboxypyrrolidone compound represented by formula (III), and is therefore usually a homopolymer of the carboxypyrrolidone compound represented by formula (III). The polyamide-based polymer may be composed of a repeating unit represented by formula (V), and may also contain repeating units other than the repeating unit represented by formula (V) within the scope of the present invention.

[0070] The polyamide-based polymer obtained above may be used as it is, or may be purified by washing with a poor solvent such as methanol, if necessary. The polyamide-based polymer obtained above may also be dried, for example, by drying under reduced pressure.

[0071] (3) In formula (I), R 2 is a group represented by formula (Ia) [Carboxypyrrolidone compound] Carboxypyrrolidone compound and polymer thereof, 2 The carboxypyrrolidone compound in which is a group represented by formula (Ia) is a group represented by formula (IV):

[0072]

[0073] (In the formula, R 1 The dicarboxypyrrolidone compound is a compound useful as a raw material for the polyamide polymer of the present invention.

[0074] The dicarboxypyrrolidone compound represented by formula (IV) can be obtained, for example, by mixing itaconic acid (salt) and the diamine represented by formula (II) and heating the resulting mixture to melt it.

[0075] The itaconic acid (salt) and diamine are preferably the same as the itaconic acid (salt) and diamine used in preparing the carboxypyrrolidone compound represented by formula (III).

[0076] Since itaconic acid (salt) reacts with diamine stoichiometrically in a ratio of 1 mole per mole of diamine, the amount of itaconic acid (salt) per mole of diamine is theoretically 1 mole. However, the amount of itaconic acid (salt) may be in excess of the amount of diamine, or the amount of diamine may be in excess of the amount of itaconic acid (salt). The amount of itaconic acid (salt) per mole of diamine is usually preferably 0.9 to 1.1 moles.

[0077] The heating temperature when itaconic acid (salt) and diamine are mixed and the resulting mixture is heated to melt is not particularly limited, but from the viewpoint of efficiently preparing the dicarboxypyrrolidone compound represented by formula (IV), it is a temperature equal to or higher than the melting temperature of itaconic acid (salt) and diamine, and from the viewpoint of avoiding thermal decomposition of itaconic acid (salt) and diamine, it is preferably 200° C. or lower, more preferably 180° C. or lower. The heating temperature may be constant, or may be increased or decreased stepwise.

[0078] The atmosphere in which itaconic acid (salt) and diamine are reacted is not particularly limited, and may be air or an inert gas such as nitrogen gas or argon gas. However, an inert gas is preferable from the viewpoint of avoiding the influence of oxygen gas contained in air.

[0079] After the mixture is heated to a temperature equal to or higher than the melting temperature of itaconic acid (salt) and diamine, the resulting melt is preferably heated at a temperature of 120 to 140°C for 3 to 5 hours, from the viewpoint of promoting the reaction between itaconic acid (salt) and diamine.

[0080] The dicarboxypyrrolidone compound represented by formula (IV) obtained as described above is usually allowed to cool to room temperature.

[0081] The dicarboxypyrrolidone compound obtained above may be used as it is, or may be purified by a method such as reprecipitation with a solvent such as a methanol-ethyl acetate mixed solvent, and then dried, if necessary.

[0082] [Polyamide-based polymer] The polyamide-based polymer is a polymer obtained by mixing a dicarboxypyrrolidone compound represented by formula (IV) and a compound represented by formula (VI): H2N-R 3 -NH2 (VI) (wherein, R 3 The polyamide-based polymer can be obtained by reacting a diamine represented by formula (VII):

[0083]

[0084] (In the formula, R 1 and R 3 is the same as above).

[0085] In the diamine represented by formula (VI), R 3 is an alkylene group which may have a substituent. Examples of the alkylene group include alkylene groups having 2 to 12 carbon atoms, such as an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a decylene group, and a dodecylene group.

[0086] Examples of the substituent include alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy groups, hydroxyl groups, halogen atoms such as fluorine, chlorine, bromine, and iodine atoms, cyano groups, and nitrile groups, but the present invention is not limited to these examples. Among the substituents, alkoxy groups having 1 to 4 carbon atoms, hydroxyl groups, and halogen atoms are preferred.

[0087] Examples of diamines represented by formula (VI) include 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 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 Examples of alkylene diamines having 2 to 12 carbon atoms include alkylene diamines having 2 to 12 carbon atoms, such as 2-1,8-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-1,9-nonanediamine, 3-propyl-1,9-nonanediamine, and 4-propyl-1,9-nonanediamine, but the present invention is not limited to these examples. These diamines may be used alone or in combination of two or more. From the viewpoint of obtaining a polyamide polymer having appropriate water resistance, as well as decomposability in water and durability, the diamine is preferably an alkylene diamine having 2 to 12 carbon atoms, and more preferably at least one diamine selected from the group consisting of 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptadiamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine.

[0088] The dicarboxypyrrolidone compound represented by formula (IV) and the diamine represented by formula (VI) react in stoichiometric amounts, so that the amount of diamine per mole of the dicarboxypyrrolidone compound is theoretically 1 mole. The amount of the dicarboxypyrrolidone compound may be in excess of the amount of the diamine, or the amount of the diamine may be in excess of the amount of the dicarboxypyrrolidone compound.

[0089] A method for polycondensing the dicarboxypyrrolidone compound represented by formula (IV) and the diamine represented by formula (VI) includes bulk polymerization. The polycondensation of the dicarboxypyrrolidone compound represented by formula (IV) and the diamine represented by formula (VI) is preferably carried out while stirring the dicarboxypyrrolidone compound represented by formula (IV) and the diamine represented by formula (VI) to avoid uneven polymerization. The polymerization temperature during polycondensation of the dicarboxypyrrolidone compound represented by formula (IV) and the diamine represented by formula (VI) is approximately 150 to 250°C. The polymerization temperature may be constant, may be increased stepwise, or may be decreased during the polymerization reaction as necessary. The atmosphere in which the dicarboxypyrrolidone compound represented by formula (IV) and the diamine represented by formula (VI) are polycondensed is not particularly limited, and may be air or an inert gas such as nitrogen gas or argon gas. However, from the viewpoint of avoiding the influence of oxygen contained in air, an inert gas is preferred.

[0090] When polycondensing a dicarboxypyrrolidone compound represented by formula (IV) with a diamine represented by formula (VI), it is preferable to add an appropriate amount of a catalyst to the reaction system of the dicarboxypyrrolidone compound and the diamine represented by formula (VI) from the viewpoint of efficiently preparing a polyamide polymer. Examples of catalysts include 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. Among these catalysts, sodium dihydrogen phosphate is preferred.

[0091] By polycondensing the dicarboxypyrrolidone compound represented by formula (IV) and the diamine represented by formula (VI) as described above, a polyamide polymer having a repeating unit represented by formula (VII) can be obtained. The polyamide polymer obtained as described above is usually allowed to cool to room temperature.

[0092] The polyamide polymer is obtained by polycondensing a dicarboxypyrrolidone compound represented by formula (IV) with a diamine represented by formula (VI), and therefore has a repeating unit represented by formula (VII). The polyamide polymer may be composed of the repeating unit represented by formula (VII), or may contain repeating units other than the repeating unit represented by formula (VII) within the scope of the present invention.

[0093] The polyamide-based polymer obtained above may be used as is, or may be purified by washing with an organic solvent if necessary. The polyamide-based polymer obtained above may also be dried, for example, by drying under reduced pressure. (4) Properties and Uses of Polyamide-Based Polymers The number-average molecular weight of the polyamide-based polymer of the present invention is not particularly limited, but is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000, from the viewpoint of imparting appropriate water resistance to the polyamide-based polymer and increasing the thermal decomposition temperature of the polyamide-based polymer. The number-average molecular weight of the polyamide-based polymer is a value measured according to the method described in the following examples.

[0094] Since the polyamide polymer of the present invention is soluble in an organic solvent, a spinning dope can be prepared by dissolving the polyamide polymer in an organic solvent. The amount of organic solvent relative to the polyamide polymer of the present invention cannot be determined in general because it varies depending on the type of organic solvent, etc. Usually, it is preferable to add an organic solvent to the polyamide polymer so that the spinning dope has a desired viscosity. Polyamide fibers can be produced by extruding the spinning dope obtained above through the pores of a spinneret and volatilizing and removing the organic solvent.

[0095] Furthermore, since the polyamide-based polymer of the present invention has thermoplastic properties, the polyamide-based polymer can be heated and melted, and then spun using a melt spinning apparatus by injecting the melted polymer through fine holes in a spinneret, thereby producing a polyamide-based fiber.

[0096] The spinneret is generally made of an alloy 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.

[0097] The polyamide fiber may be a single fiber (filament), or may be a fiber (strand, etc.) formed by converging a plurality of single fibers extruded from a plurality of holes into a single bundle.

[0098] The polyamide fibers obtained as described above may be subjected to further treatments such as washing, drying, crimping, etc., if necessary.

[0099] 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, and therefore 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.

[0100] 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 uniaxial stretching, but may also be multiaxial stretching such as biaxial stretching.

[0101] The polyamide fibers may be used in the form of long fibers or may be cut to a desired length and used as short fibers. The fiber length of the 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.

[0102] The polyamide fibers may be used for fishing lines, and may also be used for knitted fabrics such as woven fabrics, nonwoven fabrics, and fishing nets.

[0103] The knitted fabric can be produced using the polyamide-based fibers and a knitting machine or the like. When producing a knitted fabric, the polyamide-based fibers may be used as they are, or, for example, a blend of the polyamide-based fibers with synthetic fibers such as polyester fibers and acrylic fibers, or fibers such as cotton yarn, wool yarn, or 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.

[0104] 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.

[0105] Nonwoven fabrics can be produced by dry or wet processes 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 processes include, for example, mechanical bonding methods such as the chemical pond method, thermal pond method, needle punch method, and airlaid method, but the present invention is not limited to these examples. Wet processes include, for example, hydroentanglement method, but the present invention is not limited to these examples.

[0106] The polyamide fiber, which uses the polyamide polymer of the present invention, has moderate water resistance, biodegradability, and excellent mechanical strength. Therefore, it can be used not only for fishing equipment such as fishing nets and fishing lines in the fishing industry, agricultural equipment, etc., but also for various other applications such as clothing such as gloves, underwear, socks, shirts, and western clothes, as well as face masks, materials for disposable diapers, and cosmetic sheets such as lotion wipes.

[0107] Furthermore, since the polyamide-based polymer of the present invention is soluble in organic solvents, it can be used as an organic solvent solution, and since it has thermoplastic properties, it can be used as a melt by heating. Therefore, the polyamide-based polymer of the present invention can be suitably used as a molding material such as an injection molding material.

[0108] 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.

[0109] The polyamide-based polymer of the present invention has a thermal decomposition onset temperature of 350°C or higher, whereas polymers generally referred to as super engineering plastics have a heat resistance temperature of 150°C or higher. Furthermore, bio-derived itaconic acid can be used as a raw material for the polyamide-based polymer of the present invention. Therefore, the polyamide-based polymer of the present invention is expected to be used as an industrial bioplastic for automobile engine parts such as intake manifolds and rocker covers, and automobile parts such as door covers.

[0110] Furthermore, since the amide bond in the polyamide-based polymer of the present invention is hydrolyzable, the polyamide-based polymer of the present invention is returned to a bio-derived substance by hydrolysis, and is therefore expected to be used as an environmentally friendly polymer.

[0111] (5) In formula (I), R 2 Carboxypyrrolidone compounds and polymers thereof in which R 2 Carboxypyrrolidone compounds in which is an —OH group can be prepared using itaconic acid (salt) and an amino alcohol.

[0112] The itaconic acid (salt) is preferably the same as the itaconic acid (salt) used in preparing the carboxypyrrolidone compound represented by formula (III).

[0113] The amino alcohol can be obtained by reacting an alkylamine with an alkylene oxide. Among the amino alcohols, an amino alcohol having an amino group and a hydroxyl group at the molecular terminal is preferred. Examples of the amino alcohol having an amino group and a hydroxyl group at the molecular terminal include those represented by the formula: HO-R 4 -NH2 (wherein, R 4 represents an alkylene group which may have a substituent). Examples of the alkylene group which may have a substituent include amino alcohols represented by the following formula: 1 Examples of the alkylene groups include those shown below, which may have a substituent. 4 Among these, alkylene groups having 1 to 8 carbon atoms are preferred. Suitable amino alcohols include, for example, alkanolamines having 1 to 8 carbon atoms, such as methanolamine, ethanolamine, propanolamine, butanolamine, heptanolamine, and hexanolamine, but the present invention is not limited to these examples.

[0114] Since itaconic acid (salt) and amino alcohol react in stoichiometric amounts, the amount of amino alcohol per mole of itaconic acid (salt) is theoretically 1 mole. However, the amount of itaconic acid (salt) may be in excess of the amount of diamine, or the amount of amino alcohol may be in excess of the amount of itaconic acid (salt). The amount of amino alcohol per mole of itaconic acid (salt) is usually preferably 0.9 to 1.1 moles.

[0115] The reaction temperature when reacting the itaconic acid (salt) with the amino alcohol is preferably about 80 to 120°C from the viewpoint of efficiently reacting the itaconic acid (salt) with the amino alcohol. The atmosphere when efficiently reacting the itaconic acid (salt) with the amino alcohol may be air or an inert gas such as nitrogen gas or argon gas. The reaction time between the itaconic acid (salt) and the amino alcohol varies depending on the reaction temperature and cannot be determined in general, so it is usually the time required for sufficient production of a carboxypyrrolidone compound.

[0116] By reacting the itaconic acid (salt) with the amino alcohol in the above manner, the compound represented by the formula (I) 1 is the same as above, and R 2 is an OH group.

[0117] [Polyurethane] [Polyurethane A] The dicarboxypyrrolidone compound of the present invention represented by formula (IV) is a dicarboxylic acid compound, and therefore can be used as a raw material for polyurethane.

[0118] A method for preparing a polyurethane using the dicarboxypyrrolidone compound represented by formula (IV) will be described below.

[0119] First, a polyol, which is a raw material for polyurethane, is prepared using the dicarboxypyrrolidone compound represented by formula (IV).

[0120] The polyol can be obtained by reacting the dicarboxypyrrolidone compound represented by formula (IV) with an amino alcohol.

[0121] The amino alcohol is represented by the formula (I): 2 is preferably the same as the amino alcohol used in preparing the carboxypyrrolidone compound in which is an —OH group.

[0122] The amount of the amino alcohol per mole of the dicarboxypyrrolidone compound is stoichiometrically 1 mole. However, the amount of the dicarboxypyrrolidone compound may be in excess of the amount of the amino alcohol, or the amount of the amino alcohol may be in excess of the amount of the dicarboxypyrrolidone compound. From the viewpoint of efficiently preparing a polyol, it is preferable that the amount of the amino alcohol is in excess of the amount of the dicarboxypyrrolidone compound. The amount of the amino alcohol per mole of the dicarboxypyrrolidone compound is usually about 0.8 to 2.6 moles, but preferably 1.0 to 2.0 moles.

[0123] The dicarboxypyrrolidone compound and the amino alcohol can be reacted in the presence of a condensing agent and an organic solvent.

[0124] Examples of the condensing agent include 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM), dicyclohexylcarbodiimide (DCC), O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU), 2-chloro-1-methylpyridinium iodide (CMPI), diethylphosphoric acid cyanide (DEPC), and (7-azabenzotriazol-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate, but the present invention is not limited to these examples. These condensing agents may be used alone, or two or more types may be used in combination. The amount of condensing agent per mole of amino alcohol is usually preferably 0.8 to 1.5 moles.

[0125] Examples of the organic solvent include aliphatic alcohols having 1 to 3 carbon atoms, such as methanol, ethanol, and propanol; ketone compounds, such as acetone and methyl ethyl ketone; ethyl acetate, tetrahydrofuran, dioxane, chloroform, dichloromethane, chlorobenzene, phenol, and cresol; 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 allows the dicarboxypyrrolidone compound and the amino alcohol to react efficiently. However, it is generally preferably about 3 to 20 times, and more preferably about 5 to 15 times, the total amount (mass) of the dicarboxypyrrolidone compound and the amino alcohol.

[0126] The reaction temperature during the reaction of the dicarboxypyrrolidone compound with the amino alcohol is preferably about 5 to 40°C from the viewpoint of efficiently reacting the dicarboxypyrrolidone compound with the amino alcohol. The atmosphere during the efficient reaction of the dicarboxypyrrolidone compound with the amino alcohol may be air or an inert gas such as nitrogen gas or argon gas. The reaction time between the dicarboxypyrrolidone compound and the amino alcohol varies depending on the reaction temperature and cannot be determined in general; therefore, the reaction time is usually the time required for sufficient production of polyol.

[0127] By reacting the dicarboxypyrrolidone compound with the amino alcohol in the above manner, a compound of the formula (VIII):

[0128] (In the formula, R 1 and R 4 The polyol represented by formula (VIII) is useful as a raw material for urethane.

[0129] Next, the polyol is reacted with a polyisocyanate compound to obtain a polyurethane.

[0130] The polyisocyanate compound refers to an isocyanate compound having at least two isocyanate groups. The polyisocyanate compound may be any of an aromatic polyisocyanate compound, an alicyclic polyisocyanate compound, and an aliphatic polyisocyanate compound, or may be a mixture of these polyisocyanate compounds.

[0131] Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, methylene diphenyl diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, and polymethylene polyphenylene polyisocyanate; alicyclic polyisocyanates such as hydrogenated methylene diphenyl diisocyanate, hydrogenated tolylene diisocyanate, and isophorone diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; mixtures thereof; and modified products thereof. Examples of the modified products include prepolymer-type modified products, which are reaction products with polyols, isocyanurate-modified products, urea-modified products, carbodiimide-modified products, allophanate-modified products, and biuret-modified products. Among these, aromatic polyisocyanates and modified products thereof are preferred.

[0132] When the polyol and the polyisocyanate compound are reacted, it is desirable to adjust the ratio of the polyol to the polyisocyanate compound so that the isocyanate index is preferably 80 to 110, more preferably 90 to 105.

[0133] The method for producing polyurethane is not particularly limited, and a commonly used method can be used. Examples of the method for producing polyurethane include a method of mixing a polyol, and components containing a catalyst, a chain extender, water, a silicone-based antifoaming agent, a silicon-containing inorganic powder, additives, etc., which are used as needed, with the polyisocyanate compound, and reacting the polyol with the polyisocyanate compound to prepare polyurethane, but the present invention is not limited to such a method.

[0134] By reacting the polyol with the polyisocyanate compound in the manner described above, polyurethane can be obtained.

[0135] [Polyurethane B] Polyurethane B is a polyurethane represented by the formula (I) 2 It can be prepared using a carboxypyrrolidone compound in which is an —OH group and a diamine.

[0136] First, R 2 A polyol can be obtained by reacting a carboxypyrrolidone compound having an —OH group with a diamine. The diamine can be, for example, a compound represented by the formula: HN—R 4 -NH2 (wherein, R 4 is the same as above. The diamine is preferably the same as the diamine represented by formula (II).

[0137] R 2 Since the carboxypyrrolidone compound in which the —OH group is an —OH group reacts with the diamine in stoichiometric amounts, the amount of the carboxypyrrolidone compound per mole of the diamine is theoretically 1 mole. However, the amount of the carboxypyrrolidone compound may be in excess of the amount of the diamine, or the amount of the diamine may be in excess of the amount of the carboxypyrrolidone compound. The amount of the carboxypyrrolidone compound per mole of the diamine is usually preferably 0.8 to 1.2 moles.

[0138] The reaction temperature during the reaction of the carboxypyrrolidone compound with the diamine is preferably about 100 to 150°C from the viewpoint of efficiently reacting the carboxypyrrolidone compound with the diamine. The atmosphere during the efficient reaction of the carboxypyrrolidone compound with the diamine may be air or an inert gas such as nitrogen gas or argon gas. The reaction time between the itaconic acid (salt) and the amino alcohol varies depending on the reaction temperature and cannot be determined in general; therefore, the reaction time is usually the time required for sufficient production of polyol.

[0139] By reacting the carboxypyrrolidone compound with the diamine in the above manner, a compound of the formula (IX):

[0140]

[0141] (In the formula, R 1 and R 4 The polyol represented by formula (IX) is useful as a raw material for urethane.

[0142] Next, the polyol is reacted with a polyisocyanate compound to obtain a polyurethane.

[0143] The polyisocyanate compound is preferably the same as the polyisocyanate compound used in producing the polyurethane A.

[0144] When the polyol and the polyisocyanate compound are reacted, it is desirable to adjust the ratio of the polyol to the polyisocyanate compound so that the isocyanate index is preferably 80 to 110, more preferably 90 to 105.

[0145] The method for producing the polyurethane is preferably the same as the method for producing the polyurethane A.

[0146] By reacting the polyol with the polyisocyanate compound in the manner described above, polyurethane B can be obtained.

[0147] The polyurethane of the present invention can be used in the same applications as conventional ether-based polyurethanes, such as seats, artificial leather materials, and cushioning materials.

[0148] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. The physical properties of the compounds obtained in each of the following examples were examined according to the following methods.

[0149] [Compound structure] The compound structure can be determined by nuclear magnetic resonance ( 1The solubility of the hydroxyl group was determined by 1 H-NMR and Fourier transform infrared spectroscopy (FT-IR).

[0150] (1) Nuclear magnetic resonance ( 1 H-NMR) Nuclear magnetic resonance ( 1 H-NMR was performed using a nuclear magnetic resonance spectrometer (manufactured by BRUKER, trade name: AVANCE III HD NMR Spectrometer, 400 MHz) by dissolving 5 mg of a sample in 0.5 mL of DO, placing the resulting solution in a glass sample tube, and measuring at a temperature of 25°C with 16 accumulations.

[0151] (2) Fourier transform infrared spectroscopy (FT-IR) Fourier transform infrared spectroscopy (FT-IR) was performed using a Fourier transform infrared spectrometer (Perkin Elmer, trade name: Spectrum 100, ATR method) in a measurement wavenumber range of 400 to 4000 cm -1 The measurement was carried out four times.

[0152] [Molecular Weight] (1) Molecular Weight of Compound (Monomer) The molecular weight of the compound (monomer) was measured by mass spectrometry using an electrospray ionization mass spectrometer (ESI-MS) [manufactured by Shimadzu Corporation, product number: LCMS2010EV].

[0153] (2) Average Molecular Weight of Polymer The average molecular weight of the polymer (weight average molecular weight and number average molecular weight) was measured by gel permeation chromatography (GPC). More specifically, the GPC measurement device was equipped with a liquid pump unit (manufactured by JASCO Corporation, product number: PU-2080), a column oven (manufactured by GL Sciences, 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), and two columns (manufactured by Showa Denko K.K., product name: Shodex SB-806M HQ). Polymethyl methacrylate standards [molecular weight (Mp): 3070, 7360, 18500, 68800, 211000, 569000, or 1050000] were used as standard samples, and an N,N-dimethylformamide solution of lithium bromide with a lithium bromide concentration of 0.01 mol / L was used as the mobile phase, with the flow rate of the solution being 1.0 mL / min.

[0154] [Thermal properties of polymers]

[0155] The thermal properties of the polymers were determined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).

[0156] (1) Thermogravimetric analysis (TGA) Thermogravimetric analysis was carried out using a differential thermobalance (manufactured by Rigaku Corporation, product number: TG 8121) with a sample amount of 4 to 8 mg, a platinum pan, and a reference blank (no sample) in a nitrogen gas atmosphere (nitrogen gas flow rate: 250 mL / min) by heating the sample in the temperature range from 25°C to 800°C at a heating rate of 10°C / min, and the decomposition onset temperature (T d0 The temperatures at which the mass of the sample decreased by 5% and 10% were determined as the 5% weight loss temperatures (T d5 ) or 10% weight loss temperature (T d10 )

[0157] (2) Differential Scanning Calorimetry (DSC) Differential scanning calorimetry was performed using a differential scanning calorimeter (Hitachi High-Tech Science Corporation, model number: X-DSC 7000T) with a sample of 3 to 5 mg. The sample was placed in an aluminum pan and heated in a nitrogen gas atmosphere (nitrogen gas flow rate: 40 mL / min) at a heating rate of 10°C / min over a temperature range from -20°C to 280°C, and then held at the maximum temperature for 5 minutes. The temperature was then lowered from the maximum temperature to -20°C at a cooling rate of -10°C / min, and the sample was held at -20°C for 5 minutes. This series of heating and cooling operations was repeated three times, and data from two or three times of the operation was used.

[0158] Example 1 (Preparation of Carboxypyrrolidone Compound A) [Synthetic Route]

[0159]

[0160] Based on the formula shown in the synthetic route above, carboxypyrrolidone compound A shown to the right of the formula was prepared. More specifically, 3.25 g (2.50 × 10) of itaconic acid was added. -2 mol) and 2.56 g (2.50 × 10) of 1,5-pentanediamine -2 1.50 mL of distilled water was added to the solution (1.00 mol) to dissolve itaconic acid and 1,5-pentanediamine in the distilled water, and the resulting solution was heated at 110°C for 24 hours to obtain carboxypyrrolidone compound A [1-(5-aminopentyl)-5-oxopyrrolidine-3-carboxylic acid].

[0161] The carboxypyrrolidone compound A obtained above was reprecipitated in a mixed solvent of methanol and ethyl acetate and dried under reduced pressure at 80° C. for 48 hours. The yield of the obtained carboxypyrrolidone compound A was 3.67 g, or 69%. Mass spectrometry analysis revealed that the m / z was 213.1, confirming that carboxypyrrolidone compound A was produced.

[0162] of the carboxypyrrolidone compound A obtained above 1 The H-NMR spectrum is shown in Figure 1. 1A peak (2.6-3.8 ppm) derived from the pyrrolidone ring and a peak (1.2-1.8 ppm) derived from the aliphatic diamine were observed in the H-NMR spectrum, confirming that carboxypyrrolidone compound A was obtained.

[0163] Example 2 (Preparation of Carboxypyrrolidone Compound B) [Synthetic Route]

[0164]

[0165] Based on the formula shown in the synthetic route above, the carboxypyrrolidone compound B shown to the right of the formula was prepared. More specifically, 7.16 g (5.50 × 10) of itaconic acid was added. -2 mol) and 2.56 g (2.50 × 10) of 1,5-pentanediamine -2 mol) was heated to 170°C to melt it, and then heated at 130°C for 4 hours to obtain carboxypyrrolidone compound B [1,1'-(pentane-1,5-diyl)bis(5-oxopyrrolidine-3-carboxylic acid)]. Mass spectrometry revealed that the m / z was 325.1, confirming that carboxypyrrolidone compound B was produced.

[0166] The carboxypyrrolidone compound B obtained above was reprecipitated in a mixed solvent of methanol and ethyl acetate and dried under reduced pressure for 48 hours at 80° C. The amount of the obtained carboxypyrrolidone compound B was 3.20 g, and the yield was 39%.

[0167] of the carboxypyrrolidone compound B obtained above 1 The H-NMR spectrum is shown in Figure 2. 1 A peak (2.6-3.8 ppm) derived from the pyrrolidone ring and a peak (1.2-1.7 ppm) derived from the aliphatic diamine were observed in the H-NMR spectrum, confirming that carboxypyrrolidone compound B was obtained.

[0168] Example 3 (Preparation of Carboxypyrrolidone Compound C) [Synthetic Route]

[0169]

[0170] Based on the formula shown in the synthetic route above, the carboxypyrrolidone compound C shown to the right of the formula was prepared. More specifically, 3.285 g (2.50 × 10) of itaconic acid was added. -2 mol) and 2.935 g (2.50 × 10 -2 To the 1,6-hexanediamine-3-carboxylic acid (1.50 mL) was added 1.50 mL of distilled water to dissolve itaconic acid and 1,6-hexanediamine in the distilled water, and the resulting solution was heated at 110°C for 4.5 hours to obtain carboxypyrrolidone compound C [1-(6-aminohexyl)-5-oxopyrrolidine-3-carboxylic acid]. The resulting carboxypyrrolidone compound C was used as is without purification. Mass spectrometry analysis revealed that the m / z was 227.1, confirming that carboxypyrrolidone compound C had been produced.

[0171] of the carboxypyrrolidone compound C obtained above. 1 The H-NMR spectrum is shown in Figure 3. 1 A peak (2.6-3.8 ppm) derived from the pyrrolidone ring and a peak (1.2-1.8 ppm) derived from the aliphatic diamine were observed in the H-NMR spectrum, confirming that carboxypyrrolidone compound C was obtained.

[0172] Example 4 (Preparation of dicarboxypyrrolidone compound D) [Synthetic route]

[0173]

[0174] Based on the formula shown in the synthetic route above, dicarboxypyrrolidone compound D shown to the right of the formula was prepared. More specifically, 16.2 g (0.123 mol) of itaconic acid and 4.81 g (4.10 × 10 -2 mol) was heated to 170°C to melt it, and then heated at 130°C for 4 hours to obtain dicarboxypyrrolidone compound D [1,1'-(hexane-1,6-diyl)bis(5-oxopyrrolidine-3-carboxylic acid].

[0175] The dicarboxypyrrolidone compound D obtained above was reprecipitated in a mixed solvent of methanol and ethyl acetate and dried under reduced pressure at 80° C. for 48 hours. The amount of the obtained dicarboxypyrrolidone compound D was 2.86 g, and the yield was 21%. Furthermore, as a result of mass spectrometry, the m / z was 339.2, confirming that dicarboxypyrrolidone compound D was produced.

[0176] of the dicarboxypyrrolidone compound D obtained above 1 The H-NMR spectrum is shown in Figure 4. 1 A peak (2.6-3.8 ppm) derived from the pyrrolidone ring and a peak (1.2-1.6 ppm) derived from the aliphatic diamine were observed in the H-NMR spectrum, confirming that dicarboxypyrrolidone compound D was obtained.

[0177] Example 5 (Preparation of Carboxypyrrolidone Compound E) [Synthetic Route]

[0178]

[0179] Based on the formula shown in the synthetic route above, the carboxypyrrolidone compound E shown to the right of the formula was prepared. More specifically, 0.651 g (5.00 × 10) of itaconic acid was added. -3 mol) and 0.862 g (5.00 × 10 -3 300 μL of distilled water was added to the 1,10-diamine (1,10-diamine tetracarboxylic acid) to dissolve itaconic acid and 1,10-decanediamine in the distilled water, and the resulting solution was heated at 110°C for 9 hours to obtain carboxypyrrolidone compound E [1-(10-aminodecyl)-5-oxopyrrolidine-3-carboxylic acid]. The resulting carboxypyrrolidone compound E was used as is without purification. Mass spectrometry revealed an m / z of 283.2, confirming that carboxypyrrolidone compound E had been produced.

[0180] Carboxypyrrolidone Compound E obtained above 1 The H-NMR spectrum is shown in Figure 5. 1A peak (2.6-3.7 ppm) derived from the pyrrolidone ring and a peak (1.1-1.7 ppm) derived from the aliphatic diamine were observed in the H-NMR spectrum, confirming that carboxypyrrolidone compound E was obtained.

[0181] Example 6 (Preparation of dicarboxypyrrolidone compound F) [Synthetic route]

[0182]

[0183] Based on the formula shown in the synthetic route above, dicarboxypyrrolidone compound E shown to the right of the formula was prepared. More specifically, 16.0 g (0.123 mol) of itaconic acid and 7.07 g (4.10 × 10 -2 mol) was heated to 170°C to melt it, and then heated at 130°C for 3 hours to obtain dicarboxypyrrolidone compound F [1,1'-(decane-1,10-diyl)bis(5-oxopyrrolidine-3-carboxylic acid].

[0184] The dicarboxypyrrolidone compound F obtained above was reprecipitated in a mixed solvent of methanol and ethyl acetate and dried under reduced pressure at 80° C. for 48 hours. The amount of dicarboxypyrrolidone compound F obtained above was 8.97 g, and the yield was 83%. Mass spectrometry analysis revealed that the m / z was 395.2, confirming that dicarboxypyrrolidone compound F was produced.

[0185] of the dicarboxypyrrolidone compound F obtained above 1 The H-NMR spectrum is shown in FIG.

[0186] In the figures, DMSO represents dimethyl sulfoxide, water represents water, and EtOAc represents ethyl acetate.

[0187] As shown in FIG. 1The H-NMR spectrum showed the disappearance of the C═C bond and peaks attributable to the pyrrolidone ring (2.5-3.8 ppm), peaks attributable to the alkyl group (1.2-1.5 ppm), and peaks attributable to the carboxyl group, confirming that dicarboxypyrrolidone compound F was obtained.

[0188] Example 7 (Preparation of Polyamide Polymer A) [Synthetic Route]

[0189]

[0190] Based on the formula shown in the synthetic route above, polyamide polymer A shown to the right of the formula was prepared. More specifically, 4.30 g (20.1 mmol) of carboxypyrrolidone compound A and 43.5 mg of disodium hydrogen phosphate were added to a flask, and the mixture was heated at 170°C for 2 hours with stirring while introducing nitrogen gas into the flask, and then heated at 210°C for 2 hours, thereby obtaining polyamide polymer A.

[0191] Next, the polyamide-based polymer A obtained above was dissolved in methanol, filtered, and then dried under reduced pressure at 70° C. for 48 hours. The yield of polyamide-based polymer A was 3.01 g. The number-average molecular weight of polyamide-based polymer A was 7,200 g / mol, the weight-average molecular weight was 15,300 g / mol, and the molecular weight distribution (Mw / Mn) was 2.13.

[0192] The polyamide polymer A obtained above 1 The H-NMR spectrum is shown in Figure 7. 1 The H-NMR spectrum showed a peak (1.2-1.6 ppm) derived from an aliphatic diamine and a peak (2.5-3.7 ppm) derived from a pyrrolidone ring, confirming that polyamide polymer A was obtained.

[0193] Example 8 (Preparation of Polyamide Polymer B) [Synthetic Route]

[0194]

[0195] Based on the formula shown in the synthetic route above, polyamide polymer B shown to the right of the formula was prepared. More specifically, 1.30 g (12.7 mmol) of 1,5-pentanediamine, 4.15 g (12.7 mmol) of carboxypyrrolidone compound B, and 55.1 mg of disodium hydrogen phosphate were added to a flask, and the mixture was heated at 170°C for 2 hours with stirring while introducing nitrogen gas into the flask, and then heated at 210°C for 2 hours, thereby obtaining polyamide polymer B.

[0196] Next, the polyamide-based polymer B obtained above was dissolved in methanol, filtered, and then dried under reduced pressure at 70° C. for 48 hours. The yield of polyamide-based polymer B was 4.04 g. The number-average molecular weight of polyamide-based polymer B was 6,600 g / mol, the weight-average molecular weight was 14,400 g / mol, and the molecular weight distribution (Mw / Mn) was 2.21.

[0197] The polyamide polymer B obtained above 1 The H-NMR spectrum is shown in Figure 8. 1 A peak (2.5-3.7 ppm) derived from a pyrrolidone ring and a peak (1.2-1.6 ppm) derived from an aliphatic diamine were observed in the H-NMR spectrum, confirming that polyamide polymer B was obtained.

[0198] Example 9 (Preparation of Polyamide-Based Polymer C) [Synthetic Route]

[0199]

[0200] Based on the formula shown in the synthetic route above, polyamide polymer C shown to the right of the formula was prepared. More specifically, 5.46 g (23.9 mmol) of carboxypyrrolidone compound C and 55.2 mg of disodium hydrogen phosphate were added to a flask, and the mixture was heated at 170°C for 2 hours with stirring while introducing nitrogen gas into the flask, and then heated at 210°C for 2 hours, thereby obtaining polyamide polymer C.

[0201] Next, the polyamide-based polymer C obtained above was dissolved in methanol, filtered, and then dried under reduced pressure at 70° C. for 48 hours. The yield of polyamide-based polymer C was 3.96 g. The number-average molecular weight of polyamide-based polymer C was 4600 g / mol, the weight-average molecular weight was 8600 g / mol, and the molecular weight distribution (Mw / Mn) was 1.87.

[0202] The polyamide polymer C obtained above 1 The H-NMR spectrum is shown in Figure 9. 1 A peak (2.5-3.7 ppm) derived from a pyrrolidone ring and a peak (1.2-1.6 ppm) derived from an aliphatic diamine were observed in the H-NMR spectrum, confirming that polyamide polymer C was obtained.

[0203] Example 10 (Preparation of Polyamide-Based Polymer D) [Synthetic Route]

[0204]

[0205] Based on the formula shown in the synthetic route above, polyamide polymer D shown to the right of the formula was prepared. More specifically, 0.98 g (8.47 mmol) of 1,6-hexanediamine, 2.88 g (8.47 mmol) of carboxypyrrolidone compound D, and 39.2 mg of disodium hydrogen phosphate were added to a flask, and the mixture was heated at 170°C for 2 hours with stirring while introducing nitrogen gas into the flask, and then heated at 210°C for 2 hours, thereby obtaining polyamide polymer D.

[0206] Next, the polyamide-based polymer D obtained above was dissolved in dimethylformamide, and the polyamide-based polymer D was precipitated from the obtained solution using ethanol, thereby recovering the polyamide-based polymer D. The yield of the polyamide-based polymer D was 0.327 g. The number-average molecular weight of the polyamide-based polymer D was 6,000 g / mol, the weight-average molecular weight was 14,400 g / mol, and the molecular weight distribution (Mw / Mn) was 2.38.

[0207] The polyamide polymer D obtained above 1The H-NMR spectrum is shown in Figure 10. 1 A peak (2.4-3.5 ppm) derived from a pyrrolidone ring and a peak (1.1-1.5 ppm) derived from an aliphatic diamine were observed in the H-NMR spectrum, confirming that polyamide polymer D was obtained.

[0208] Example 11 (Preparation of Polyamide Polymer E) [Synthetic Route]

[0209]

[0210] Based on the formula shown in the synthetic route above, polyamide polymer E shown to the right of the formula was prepared. More specifically, 5.46 g (23.9 mmol) of carboxypyrrolidone compound E and 40.0 mg of disodium hydrogen phosphate were added to a flask, and the mixture was heated at 170°C for 2 hours with stirring while introducing nitrogen gas into the flask, and then heated at 210°C for 2 hours, thereby obtaining polyamide polymer E.

[0211] Next, the polyamide polymer E obtained above was dissolved in dimethylformamide, filtered, and then dried under reduced pressure at 100° C. for 48 hours. The yield of polyamide polymer E was 2.52 g. The number-average molecular weight of polyamide polymer E was 12,900 g / mol, the weight-average molecular weight was 42,400 g / mol, and the molecular weight distribution (Mw / Mn) was 3.28.

[0212] The polyamide polymer E obtained above 1 The H-NMR spectrum is shown in Figure 11. 1 A peak (8.0 ppm) derived from an amide bond, a peak (2.3-3.5 ppm) derived from a pyrrolidone ring, and a peak (1.2-1.6 ppm) derived from an aliphatic diamine were observed in the H-NMR spectrum, confirming that polyamide polymer E was obtained.

[0213] Example 12 (Preparation of Polyamide Polymer F) [Synthetic Route]

[0214]

[0215] Based on the formula shown in the synthetic route above, polyamide polymer F shown to the right of the formula was prepared. More specifically, 3.00 g (7.57 mmol) of dicarboxypyrrolidone compound F, 1.30 g (7.57 mmol) of 1,10-diaminododecane, and 43.4 mg of disodium hydrogen phosphate were added to a flask, and the mixture was heated at 170°C for 2 hours with stirring while introducing nitrogen gas into the flask, and then heated at 210°C for 2 hours, thereby obtaining polyamide polymer F.

[0216] Next, the polyamide-based polymer F obtained above was dissolved in dimethylformamide, reprecipitated with a mixed solvent of ethanol and acetone, filtered, and then dried under reduced pressure at 70° C. for 48 hours. The yield of polyamide-based polymer F was 2.42 g. The number-average molecular weight of polyamide-based polymer F was 19,100 g / mol, the weight-average molecular weight was 24,200 g / mol, and the molecular weight distribution (Mw / Mn) was 1.27.

[0217] The polyamide polymer F obtained above 1 The H-NMR spectrum is shown in Figure 12. 1 A peak (8.0 ppm) derived from an amide bond, a peak (2.3-3.5 ppm) derived from a pyrrolidone ring, and a peak (1.1-1.4 ppm) derived from an aliphatic diamine were observed in the H-NMR spectrum, confirming that polyamide polymer F was obtained.

[0218] Comparative Example 1 (Preparation of Polyamide-Based Polymer X) [Synthetic Route]

[0219]

[0220] Based on the formula shown in the synthetic route above, polyamide-based polymer X shown to the right of the formula was prepared. More specifically, itaconic acid and 1,5-pentanediamine were mixed in ethanol to obtain a white crystalline powder. The obtained crystalline powder was heated and polymerized at 175°C in the presence of sodium dihydrogen phosphate to obtain polyamide-based polymer X (copolymer).

[0221] The polyamide-based polymer X obtained above was dissolved in N-methyl-2-pyrrolidine and reprecipitated with acetone to recover the polyamide-based polymer X, which was then washed with acetone and dried.

[0222] Comparative Example 2 (Preparation of Polyamide-Based Polymer Y) [Synthetic Route]

[0223]

[0224] Based on the formula shown in the synthetic route above, polyamide polymer Y shown to the right of the formula was prepared. More specifically, 4.00 g (15.2 mmol) of 1,6-hexadiamine itaconic acid salt and 40.3 mg of disodium hydrogen phosphate were added to a flask, and the mixture was heated at 170°C for 2 hours with stirring while introducing nitrogen gas into the flask, and then heated at 210°C for 2 hours, thereby obtaining polyamide polymer Y (copolymer).

[0225] Next, the polyamide-based polymer Y obtained above was dissolved in a mixed solvent of methanol and dimethylformamide, filtered, and then dried under reduced pressure at 100° C. for 48 hours. The yield of polyamide-based polymer Y was 1.54 g. The number-average molecular weight of polyamide-based polymer Y was 235,000 g / mol, the weight-average molecular weight was 348,000 g / mol, and the molecular weight distribution (Mw / Mn) was 2.42.

[0226] The polyamide polymer Y obtained above 1 The H-NMR spectrum was examined. 1 A peak (2.3-3.5 ppm) derived from a pyrrolidone ring and a peak (1.1-1.5 ppm) derived from an aliphatic diamine were observed in the H-NMR spectrum, confirming that polyamide polymer Y was obtained.

[0227] Comparative Example 3 (Preparation of Polyamide Polymer Z) [Synthetic Route]

[0228]

[0229] Based on the formula shown in the synthetic route above, polyamide polymer Z shown on the right side of the formula was prepared. More specifically, 0.710 g (2.50 × 10) of 1,10-decanediamine itaconic acid salt was used. -3 mol) and 55.2 mg of disodium hydrogen phosphate were added to the flask, and the mixture was heated at 170°C for 2 hours with stirring while introducing nitrogen gas into the flask, and then heated at 210°C for 2 hours, thereby obtaining a polyamide polymer Z.

[0230] Next, the polyamide polymer Z obtained above was reprecipitated in a mixed solvent of dimethylformamide and distilled water [dimethylformamide / distilled water (mass ratio): 1 / 7], filtered, and then dried under reduced pressure at 50° C. for 48 hours. The yield of polyamide polymer Z was 0.241 g. The number average molecular weight of polyamide polymer Z was 9,000 g / mol, the weight average molecular weight was 25,200 g / mol, and the molecular weight distribution (Mw / Mn) was 2.79.

[0231] [FT-IR Spectra (1)] FIG. 13 shows the FT-IR spectra of carboxypyrrolidone compound A and the corresponding polyamide polymer A, as well as the FT-IR spectra of carboxypyrrolidone compound B and the corresponding polyamide polymer B.

[0232] In FIG. 13, (a) is the FT-IR spectrum of carboxypyrrolidone compound A, (b) is the FT-IR spectrum of polyamide-based polymer A, (c) is the FT-IR spectrum of carboxypyrrolidone compound B, and (d) is the FT-IR spectrum of polyamide-based polymer B.

[0233] From the results shown in FIG. 13, the peak in the FT-IR spectrum of carboxypyrrolidone compound A is the CH antisymmetric stretching vibration (2929 cm -1 ), CH symmetric stretching vibration (2861 cm -1 ), C=O stretching vibration (1650cm -1 ), N-H bending vibration (1557cm -1 ), C-CO-C stretching vibration (1215-1336cm -1In contrast, the peak in the FT-IR spectrum of polyamide polymer A is attributable to the N-H stretching vibration (3284 cm -1 ), CH2 antisymmetric stretching vibration (2928 cm -1 ), CH symmetric stretching vibration (2861 cm -1 ), C=O stretching vibration (1644cm -1 ), N-H bending vibration (1543cm -1 )

[0234] In addition, the peak in the FT-IR spectrum of carboxypyrrolidone compound B is the CH antisymmetric stretching vibration (2932 cm -1 ), CH symmetric stretching vibration (2865 cm -1 ), C=O stretching vibration (1722cm -1 , 1628 cm -1 ), C-CO-C stretching vibration (1100-1320cm -1 ) is found to be attributable to the N-H stretching vibration (3289 cm). -1 ), CH2 antisymmetric stretching vibration (2928 cm -1 ), CH symmetric stretching vibration (2862 cm -1 ), C=O stretching vibration (1648cm -1 ), N-H bending vibration (1548cm -1 )

[0235] [FT-IR Spectra (2)] FIG. 14 shows the FT-IR spectra of carboxypyrrolidone compound C and the corresponding polyamide polymer C, as well as the FT-IR spectra of carboxypyrrolidone compound D and the corresponding polyamide polymer D.

[0236] In Figure 14, (a) is the FT-IR spectrum of carboxypyrrolidone compound C, (b) is the FT-IR spectrum of polyamide-based polymer C, (c) is the FT-IR spectrum of carboxypyrrolidone compound D, and (d) is the FT-IR spectrum of polyamide-based polymer D.

[0237] From the results shown in FIG. 14, the peak in the FT-IR spectrum of carboxypyrrolidone compound C is the antisymmetric stretching vibration (2927 cm -1 ), CH symmetric stretching vibration (2858 cm -1 ), C=O stretching vibration (1650cm -1 ), N-H bending vibration (1561cm -1 ), C-CO-C stretching vibration (1252-1291cm -1 ) In contrast, the peak in the FT-IR spectrum of polyamide-based polymer C is attributed to the N-H stretching vibration (3288 cm -1 ), CH2 antisymmetric stretching vibration (2929 cm -1 ), CH symmetric stretching vibration (2859 cm -1 ), C=O stretching vibration (1646cm -1 ), N-H bending vibration (1548cm -1 ), C-CO-C stretching vibration (1236-1296cm -1 )

[0238] The peak in the FT-IR spectrum of polyamide-based polymer C is the CH antisymmetric stretching vibration (2932 cm -1 ), CH symmetric stretching vibration (2864 cm -1 ), C=O stretching vibration (1717cm -1 , 1625 cm -1 ), C-CO-C stretching vibration (1195-1244cm -1 In contrast, the peak in the FT-IR spectrum of polyamide-based polymer D is attributable to the N-H stretching vibration (3294 cm -1 ), CH2 antisymmetric stretching vibration (2931 cm -1 ), CH symmetric stretching vibration (2860 cm -1 ), C=O stretching vibration (1647cm -1 ), N-H bending vibration (1549cm -1 ), C-CO-C stretching vibration (1098-1277cm -1 )

[0239] [IR Spectra] The IR spectra of the carboxypyrrolidone compound E, the dicarboxypyrrolidone compound F and the polyamide polymer E are shown in FIG.

[0240] 15, (a) is the IR spectrum of the carboxypyrrolidone compound E, (b) is the IR spectrum of the dicarboxypyrrolidone compound F, and (c) is the IR spectrum of the polyamide polymer E.

[0241] From the results shown in FIG. 15, the peak in the IR spectrum of carboxypyrrolidone compound E is the CH antisymmetric stretching vibration (2918 cm -1 ), CH symmetric stretching vibration (2848 cm -1 ), C=O stretching vibration (1654cm -1 ), N-H bending vibration (1530cm -1 ), C-CO-C stretching vibration (1144-1332cm -1 The peak in the IR spectrum of dicarboxypyrrolidone compound F is the CH antisymmetric stretching vibration (2926 cm -1 ), CH symmetric stretching vibration (2848 cm -1 ), C=O stretching vibration (1715cm -1 , 1620 cm -1 ), C-CO-C stretching vibration (1127-1305cm -1 ). In addition, the peak in the IR spectrum of polyamide polymer E is attributed to the N-H stretching vibration (3298 cm -1 ), CH2 antisymmetric stretching vibration (2922 cm -1 ), CH symmetric stretching vibration (2850 cm -1 ), C=O stretching vibration (1645cm -1 ), N-H bending vibration (1543cm -1 ), C-CO-C stretching vibration (1236-1297cm -1 ) can be seen to belong to

[0242] [Thermal Analysis] The results of analysis of the thermal properties of each polyamide polymer are shown in Tables 1 to 3.

[0243]

[0244] The results shown in Table 1 show that the decomposition onset temperatures of polyamide polymer A and polyamide polymer B are higher by about 20°C or more than that of polyamide polymer X. This is thought to be because polyamide polymer A and polyamide polymer B have a regular pyrrolidone ring bonding structure, and therefore polymer molecules are densely packed together.

[0245]

[0246] The results shown in Table 2 show that polyamide polymer C and polyamide polymer D have higher decomposition onset temperatures than polyamide polymer Y. This is thought to be because polyamide polymer C and polyamide polymer D have a regular pyrrolidone ring bonding structure, and therefore polymer molecules are densely packed together.

[0247]

[0248] The results shown in Table 3 show that the decomposition onset temperature and weight loss temperature of polyamide-based polymer E and polyamide-based polymer F are higher than those of polyamide-based polymer Z. This is thought to be because polyamide-based polymer E and polyamide-based polymer F have a regular pyrrolidone ring bonding structure, and therefore the polymer molecules are densely packed together.

[0249] [Solubility] The samples used were carboxypyrrolidone compound E, carboxypyrrolidone compound F, polyamide polymer E, or polyamide polymer F. The solvent used was water, methanol, formic acid, N,N-dimethylformamide, or dimethyl sulfoxide.

[0250] 2 mg of each sample was added to 1 mL of each solvent, and the mixture was left standing at room temperature (approximately 20°C) under atmospheric pressure to check whether the sample would dissolve in the solvent. If the sample did not dissolve in the solvent even after 1 hour from the start of sample addition, the sample was checked for solubility in the solvent at 60°C.

[0251] As a result, it was confirmed that carboxypyrrolidone compound E was soluble in water, methanol, and formic acid, and that carboxypyrrolidone compound F was soluble in methanol, N,N-dimethylformamide, dimethyl sulfoxide, and formic acid.

[0252] It was also confirmed that polyamide polymer E was soluble in methanol, N,N-dimethylformamide, dimethyl sulfoxide, and formic acid, and polyamide polymer F was soluble in N,N-dimethylformamide at 60°C and dimethyl sulfoxide at 60°C, and in formic acid at room temperature (approximately 20°C).

[0253] Therefore, since the polyamide-based polymer dissolves in an organic solvent, it can be formed into a film by casting a solution dissolved in an organic solvent, and the solution can also be used as a molding material.

[0254] [Film Formability] At room temperature (approximately 20°C), 0.3 g of polyamide polymer E was dissolved in 400 μL of N,N-dimethylformamide to prepare solution A, and 0.6 g of polyamide polymer F was dissolved in 900 μL of N,N-dimethylformamide to prepare solution B. Solutions A and B were each dropped onto a glass plate to investigate whether they could form a film. As a result, it was confirmed that when solution A was used, a film having a thickness of approximately 200 μm could be formed, and when solution B was used, a film having a thickness of approximately 600 μm could be formed.

[0255] Therefore, it is understood that the polyamide polymer can be used to form a film.

[0256] [Tensile Strength, Young's Modulus, and Elongation at Break] Test specimens measuring 20 mm in length, 5 mm in width, and approximately 400 μm in thickness were prepared using Solution A. 5 mm long sections at both ends of the lateral direction of the obtained test specimen were gripped with the chucks of a tensile testing machine (Shimadzu Corporation, Autograph, product number: AGS-X), and a tensile test was performed at room temperature (approximately 20° C.) at a tension rate of 5 mm / min to measure the tensile strength and Young's modulus of the test specimen, and the elongation at break was calculated based on the formula: [Elongation at Break (%)] = {[Test specimen length at break - original test specimen length] ÷ [original test specimen length]} × 100.

[0257] As a result, the test piece had a tensile strength of 3.3 MPa, a Young's modulus of 32 MPa, and an elongation at break of 25%.

[0258] Therefore, it can be seen that the polyamide-based polymer has good mechanical properties and can be used as a molding material.

[0259] Example 13 (Preparation of dicarboxypyrrolidone compound) [Synthetic route]

[0260]

[0261] Based on the formula shown in the synthetic route above, the dicarboxypyrrolidone compound shown on the right side of the formula was prepared. More specifically, 17.0 g (130.1 mmol) of itaconic acid and 7.42 g (43.37 mmol) of diaminodecane were added to a flask purged with nitrogen gas, and the contents of the flask were heated to 170°C with stirring to dissolve, and then further heated at 130°C for 3 hours to obtain the dicarboxypyrrolidone compound represented by R 1 A dicarboxypyrrolidone compound was obtained in which the alkylene group having 10 carbon atoms was used.

[0262] The dicarboxypyrrolidone compound obtained above was dissolved in methanol, and the dicarboxypyrrolidone compound was reprecipitated from the obtained solution with ethyl acetate and hexane, and then recovered by filtration and dried under reduced pressure. The amount of the recovered dicarboxypyrrolidone compound was 8.055 g (20.31 mmol), and the yield was 46.8 mass%. 1The H-NMR spectrum is shown in FIG.

[0263] Example 14 (Preparation of Polyol) [Synthetic Route]

[0264]

[0265] The polyol shown to the right of the formula was prepared based on the formula described in the synthetic route above. More specifically, 0.50 g (1.27 mmol) of the dicarboxypyrrolidone compound obtained in Example 13, 0.24 g (3.26 mmol) of 3-amino-1-propanol, and 1.01 g (3.62 mmol) of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) as a condensing agent were added to 50 mL of methanol, and the mixture was left to stand at room temperature (about 20°C) with stirring for one day, thereby obtaining a reaction product.

[0266] A part of the reaction product obtained above is extracted with ethyl acetate and water, and after removing the ethyl acetate, the reaction product is dissolved in methanol. The reaction product is recovered from the obtained solution by precipitating again with ethyl acetate and dried to obtain a compound of the formula:

[0267]

[0268] Thus, a polyol represented by the formula:

[0269] Example 15 (Preparation of Carboxypyrrolidone Compound) [Synthetic Route]

[0270]

[0271] Based on the formula shown in the synthetic route above, the carboxypyrrolidone compound shown to the right of the formula was prepared. More specifically, 3.24 g (24.9 mmol) of itaconic acid and 2.06 g (27.5 mmol) of 3-amino-1-propanol were mixed, methanol was added to the resulting mixture, and the mixture was heated in air at 110°C for 18 hours to obtain the carboxypyrrolidone compound. 1 The H-NMR spectrum is shown in Figure 17. The carboxypyrrolidone compound obtained above has the formula:

[0272]

[0273] It was confirmed that the compound was represented by the formula:

[0274] Example 16 (Preparation of Polyol) [Synthetic Route]

[0275]

[0276] Based on the formula shown in the synthetic route above, a polyol shown to the right of the formula was prepared. More specifically, 4.26 g (22.8 mmol) of the carboxypyrrolidone compound obtained in Example 15 and 1.31 g (7.59 mmol) of diaminodecane were mixed, and the resulting mixture was reacted for 2 hours at 140° C. under stirring in a nitrogen gas atmosphere to obtain a polyol of the formula:

[0277]

[0278] The polyol was recovered by reprecipitation with methanol and ethyl acetate. 1 The H-NMR spectrum is shown in FIG.

[0279] Example 17 (Preparation of Polyurethane) [Synthetic Route]

[0280]

[0281] Based on the formula shown in the synthetic route above, a polyurethane shown to the right of the formula was prepared. More specifically, 2.02 g (3.96 mmol) of the polyol obtained in Example 16 was dissolved in 4 mL of dimethyl sulfoxide, and 0.68 g (4.02 mmol) of hexamethylene diisocyanate (HDI) was added to the resulting solution in a nitrogen gas atmosphere. The mixture was stirred at room temperature (about 20° C.), whereby the polyol and hexamethylene diisocyanate reacted to produce a polyurethane of the formula:

[0282]

[0283] A polyurethane having a repeating unit represented by the formula: was obtained. 1 The H-NMR spectrum is shown in FIG.

[0284] The solubility of the polyurethane obtained above in solvents was examined, using dimethyl sulfoxide, N,N-dimethylformamide, dimethyl acetate, n-methylpyrrolidone, acetic acid, methanol, purified water, tetrahydrofuran, or dichloromethane as the solvent.

[0285] 10 mg of polyurethane was added to 5 mL of each solvent and allowed to stand at room temperature (approximately 20°C) for 24 hours. As a result, it was confirmed that the polyurethane was slightly soluble in N,N-dimethylformamide, dimethyl acetate, n-methylpyrrolidone, acetic acid, and methanol. When 10 mg of polyurethane was added to 5 mL of each solvent, the mixture was heated to 80°C, stirred, and then allowed to stand for 24 hours. As a result, it was confirmed that the polyurethane was soluble only in dimethyl sulfoxide.

[0286] The polyurethane obtained above was subjected to thermogravimetric analysis. As a result, the 5% weight loss temperature (T d5 ) is 67°C, and the 10% weight loss temperature (T d10 The glass transition temperature of the polyurethane obtained above was 129°C. The differential scanning calorimetry of the polyurethane obtained above was also measured. As a result, the glass transition temperature of the polyurethane was confirmed to be 26.1°C.

[0287] The polyamide-based polymer of the present invention is expected to be degradable in water because the amide bonds in the polyamide-based polymer are hydrolyzable, and because it has extensibility and toughness, it is expected to be used as a bio-nylon (nylon made from bio-derived materials) that can replace conventional nylon, for fishing equipment such as fishing nets and fishing lines in the fishing industry, agricultural tools, etc., as well as for high-performance polyamide-based polymers (industrial plastics) for automobile parts such as intake manifolds (engine parts), rocker covers (engine parts), and door covers, and as environmentally friendly plastic reinforcing materials.

Claims

1. (1) Formula (I): (In the formula, R 1 is an alkylene group which may have a substituent, R 2 is an -NH group, an -OH group or a group of formula (Ia): (representing a group represented by the following formula:) 2. Itaconic acid or a salt thereof and a compound of formula (II): H2N-R 1 -NH2 (II) (wherein, R 1 represents an alkylene group which may have a substituent) in an aqueous solvent, and the aqueous solvent solution thus obtained is heated to produce a diamine represented by formula (III): (In the formula, R 1 wherein the formula (I) is the same as above.

3. Itaconic acid or a salt thereof and a compound of formula (II): H2N-R 1 -NH2 (II) (wherein, R 1 represents an alkylene group which may have a substituent), and the resulting mixture is heated to melt, thereby producing a diamine represented by formula (IV): (In the formula, R 1 wherein the compound is the same as defined above.

4. Formula (III): (In the formula, R 1 represents an alkylene group which may have a substituent), (In the formula, R 1 wherein the repeating unit is the same as defined above.

5. Formula (V): (In the formula, R 1 (wherein represents an alkylene group which may have a substituent) 6. Formula (IV): (In the formula, R 1 represents an alkylene group which may have a substituent) and a dicarboxypyrrolidone compound represented by formula (VI): HN-R 3 -NH2 (VI) (wherein, R 3 represents an alkylene group which may have a substituent), (In the formula, R 1 and R 3 wherein the repeating unit is the same as defined above.

7. Formula (VII): (In the formula, R 1 and R 3 each independently represents an alkylene group which may have a substituent.

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