Polyurea compound and method for producing polyurea compound

Abstract

To provide a polyurea compound having excellent heat resistance and a method for producing the polyurea compound.SOLUTION: The present invention provides a polyurea compound represented by one of general formulas (1)-(4); a method for producing a polyurea compound, comprising a step of reacting a polyurea compound represented by one of general formulas (5)-(8) with a polyamine compound (9) represented by a general formula (9); and a method for producing a polyurea compound, comprising a step of polymerizing a bis(phenylcarbamate) derived from an amino acid ester represented by a general formula (10) with a diamine represented by a general formula (11) to yield a polyurea compound represented by one of the general formulas (5)-(8).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Polyurea compounds are expected to be used in a wide range of applications, including automotive parts, electrical and electronic material parts, fibers, and films. In recent years, there has been a demand to reduce the use of fossil fuel-based materials such as petroleum, and therefore the demand for bio-based polyurea compounds has increased.

[0003] For example, US Pat. Nos. 5,991,333 and 5,943,633 disclose methods for producing polyureas from bio-based diamines. However, the diamines in Patent Documents 1 and 2 are produced from biomass through a multi-step process. On the other hand, lysine and ornithine, which are natural amino acids that are biomass, are themselves bio-based diamines and are useful in that they do not require the above-mentioned multi-step process. Non-Patent Document 1 discloses a method for producing a polyurea compound of lysine ester. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2012-107095 A [Patent Document 2] JP 2020-41025 A [Non-patent literature]

[0005] [Non-Patent Document 1] Daisuke Yakeya et al., “Phosgene-free and Chemoselective Synthesis of Novel Polyureas from Activated L-Lysine with Diphenyl Carbonate”, Macromolecules 2020,53,6809-6815 Summary of the Invention [Problem to be solved by the invention]

[0006] The polyurea compound disclosed in Non-Patent Document 1 has room for improvement in terms of improving heat resistance. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyurea compound having excellent heat resistance and a method for producing a polyurea compound. [Means for solving the problem]

[0007] That is, the present invention includes the following aspects. [1] A polyurea compound represented by any one of the following general formulas (1) to (4): [ka] (R 1 is as follows (R 1 )-1 or (R 1 )-2. R 2 is a divalent organic group. X is a hydrogen atom or a group represented by the following (X)-1 or (X)-2. n is 0 or more and 2000 or less. [ka] ((R 1 )-1 or (R 1 )-2 medium, R 3 and R 4 R is each independently a monovalent organic group or a hydrogen atom. 3 and R 4may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. a is 3 or 4. [ka] (R 5 and R 6 R is each independently a monovalent organic group or hydrogen. 5 and R 6 may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. [2] A method for producing the polyurea compound according to [1], comprising a step of reacting a polyurea compound represented by any one of the following general formulas (5) to (8) with a polyamine compound (9) represented by the following general formula (9): [ka] (R 11 is as follows (R 11 )-1 or (R 11 )-2. R 2 is a divalent organic group. X is a hydrogen atom or a group represented by the following (X)-1 or (X)-2. n is 0 or more and 2000 or less. [ka] (R 7 is a monovalent organic group. a is 3 or 4. [ka] (R 5 and 6 R is each independently a monovalent organic group or hydrogen. 5 and 6 may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. [ka] (R 3 and4 R is each independently a monovalent organic group or a hydrogen atom. 3 and 4 may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. [3] A method for producing the polyurea compound according to [2], comprising a step of polymerizing an amino acid ester-derived bis(phenylcarbamate) represented by the following general formula (10) with a diamine represented by the following general formula (11) to obtain a polyurea compound represented by any one of the general formulas (5) to (8). [ka] (R 7 is a monovalent organic group. a is 3 or 4. R 2 is a divalent organic group. [4] A method for producing the polyurea compound according to [3], comprising a step of esterifying an amino acid bis(phenylcarbamate) to obtain an amino acid ester-derived bis(phenylcarbamate) represented by the general formula (10). [5] A method for producing the polyurea compound according to [4], comprising a step of obtaining an amino acid-derived bis(phenylcarbamate) by reacting lysine or ornithine with diphenyl carbonate. [6] The method for producing a polyurea compound according to any one of [2] to [5], wherein a reaction temperature between the polyurea compound represented by any one of the general formulas (5) to (8) and the polyamine compound (9) represented by the general formula (9) is 50°C or higher and 100°C or lower. [7] The method for producing a polyurea compound according to any one of [2] to [6], wherein a reaction solvent for a polyurea compound represented by any one of the general formulas (5) to (8) and a polyamine compound (9) represented by the general formula (9) is an aprotic polar solvent. Effect of the Invention

[0008] According to the present invention, it is possible to provide a polyurea compound having excellent heat resistance and a method for producing a polyurea compound. [Brief description of the drawings]

[0009] [Figure 1] FIG. 2 is a diagram showing the results of 1H-NMR measurement of the polyurea compound produced in Example 1. [Diagram 2] FIG. 2 is a diagram showing the results of FT-IR measurement of the polyurea compound produced in Example 1. [Diagram 3] FIG. 2 is a diagram showing the results of FT-IR measurement of the polyurea compound produced in Example 2. [Figure 4] FIG. 1 is a diagram showing the results of FT-IR measurement of the polyurea compound produced in Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] <Polyurea compounds> The present invention is a polyurea compound represented by any one of the following general formulas (1) to (4).

[0011] [ka]

[0012] In general formulas (1) to (4), R 1 is as follows (R 1 )-1 or (R 1 )-2, where R 2 is a divalent organic group. [ka] ((R 1 )-1 or (R 1 )-2 medium, R 3 and R 4 R is each independently a monovalent organic group or a hydrogen atom. 3 and R 4 may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. a is 3 or 4.

[0013] (R1 )-1 or (R 1 The group represented by the formula (2)-2 is derived from the amino acids lysine and ornithine used as raw materials. (R 1 )-1 or (R 1 )-2 medium, R 3 and R 4 each independently represents a monovalent organic group or a hydrogen atom. R 3 and R 4 may each independently form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.

[0014] Among them, R 3 and R 4 are preferably each independently a monovalent aliphatic hydrocarbon group having 1 to 70 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms which may have a substituent.

[0015] R 3 and R 4 When an aliphatic hydrocarbon group is selected in at least one of the above, the number of carbon atoms is preferably 1 or more and 70 or less, more preferably 1 or more and 20 or less, even more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 10 or less. R 3 and R 4 Examples of the aliphatic hydrocarbon group in the formula (I) include linear alkyl groups, branched alkyl groups, and cycloalkyl groups, which may be unsubstituted or substituted. Examples of the substituents of these aliphatic hydrocarbon groups include hydroxyl groups, cyano groups, and halogen atoms. Examples of the halogen atoms of the substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0016] R 3 and R 4Specific examples of the aliphatic hydrocarbon group in include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl are preferred.

[0017] R 3 and R 4 When an aromatic hydrocarbon group is selected in at least one of the above, the number of carbon atoms is preferably 6 or more and 70 or less, more preferably 6 or more and 20 or less, even more preferably 6 or more and 12 or less, and particularly preferably 6 or more and 10 or less. R 3 and R 4 Examples of the aromatic hydrocarbon group in R include an aryl group, an aralkyl group, etc., which may be unsubstituted or substituted. Examples of the substituent of these aromatic hydrocarbon groups include an aliphatic hydrocarbon group, a hydroxyl group, a cyano group, a halogen atom, etc. 3 and R 4 The aliphatic hydrocarbon group selected as the substituent of the aromatic hydrocarbon group in R 3 and R 4 Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0018] R 3 and R 4 Specific examples of the aromatic hydrocarbon group in include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a benzyl group, and a phenethyl group.

[0019] R 3 and R 4 When they are bonded to each other to form a ring structure, R3 and 4 The group formed by bonding together is a divalent organic group. 3 and 4 The group in which the groups are bonded to each other is preferably a divalent aliphatic hydrocarbon group having 1 to 70 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 70 carbon atoms, which may have a substituted or unsubstituted ether group, a carbonyl group, an ester group, an imino group (-NH-), an amide group or an imide group.

[0020] One aspect of the present invention is R 3 is a hydrogen atom, and R 4 is a monovalent organic group. In this case, R 4 The monovalent organic group is preferably a linear alkyl group having 1 to 10 carbon atoms, and more preferably a linear alkyl group having 1 to 8 carbon atoms.

[0021] In the general formulas (1) to (4), X is a hydrogen atom or a group represented by the following (X)-1 or (X)-2. [ka] (R 5 and R 6 R is each independently a monovalent organic group or hydrogen. 5 and R 6 may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.

[0022] R 5 and R 6 The monovalent organic group of R 3 and R 4 Examples of the monovalent organic groups include those described above. One aspect of the present invention is R 5 is a hydrogen atom, and R 6 is a monovalent organic group. In this case, R 6 The monovalent organic group is preferably a linear alkyl group having 1 to 10 carbon atoms, and more preferably a linear alkyl group having 1 to 8 carbon atoms.

[0023] In the general formulas (1) to (4), n is 0 or more and 2,000 or less.

[0024] The polyurea compound represented by any one of the general formulas (1) to (4) has an ester moiety having an amide group, specifically, (R 1 )-1 or (R 1 By having a group represented by the formula (I)-2, heat resistance can be effectively improved.

[0025] <Method of producing polyurea compound> One aspect of the present invention is a method for producing the polyurea compound of the present invention. The method for producing a polyurea compound of the present embodiment includes a step of reacting a polyurea compound represented by any one of the following general formulas (5) to (8) with a polyamine compound (9) represented by the following general formula (9).

[0026] [ka]

[0027] In general formulas (5) to (8), R 11 is as follows (R 11 )-1 or (R 11 )-2. [ka]

[0028] (R 11 )-1 or (R 11 )-2 medium, R 7 R is a monovalent organic group. 7 The monovalent organic group of R 3 and R 4 The monovalent organic groups described in are examples of the monovalent organic groups. 7 is preferably an aliphatic group or aromatic group having 1 to 20 carbon atoms.

[0029] In general formulas (5) to (8), R 2is a divalent organic group. Examples of the divalent organic group include substituted or unsubstituted alkylene groups, cycloalkylene groups, arylene groups, arylene dialkylene groups, alkylenediarylene groups, and alkylenedicycloalkylene groups. The bifunctional primary amine compound may be a compound having an aminoalkyl group such as isophorone diamine, a compound having an aminocycloalkyl group such as dicyclohexylmethane 4,4'-diamine, a compound having an aminoaryl group such as diphenylmethane diamine, or a compound having a carbonyl group such as lysine alkyl ester.

[0030] In the general formulas (5) to (8), X is a hydrogen atom or a group represented by the above (X)-1 or (X)-2, and n is 0 or more and 2,000 or less.

[0031] The polyurea compound represented by the general formula (1) can be produced by reacting the polyurea compound represented by the general formula (5) with the polyamine compound represented by the general formula (9). The polyurea compound represented by the general formula (2) can be produced by reacting the polyurea compound represented by the general formula (6) with the polyamine compound represented by the general formula (9). The polyurea compound represented by the general formula (3) can be produced by reacting the polyurea compound represented by the general formula (7) with the polyamine compound represented by the general formula (9). The polyurea compound represented by the general formula (4) can be produced by reacting the polyurea compound represented by the general formula (8) with the polyamine compound represented by the general formula (9).

[0032] In one embodiment of the present invention, in the method for producing a polyurea compound, the reaction temperature between a polyurea compound represented by any one of general formulas (5) to (8) and a polyamine compound (9) represented by general formula (9) is preferably 20°C or higher and 150°C or lower, more preferably 40°C or higher and 120°C or lower, and even more preferably 60°C or higher and 100°C or lower.

[0033] It is preferable from the viewpoint of reactivity that the reaction temperature between the polyurea compound represented by any one of the general formulas (5) to (8) and the polyamine compound (9) represented by the general formula (9) is equal to or higher than the above lower limit. It is preferable that the reaction temperature of the polyurea compound represented by any one of the general formulas (5) to (8) and the polyamine compound (9) represented by the general formula (9) is equal to or lower than the above upper limit value, from the viewpoint of the reaction between the urea bond and the amine compound (9).

[0034] In one embodiment of the present invention, in the method for producing a polyurea compound, a reaction solvent for the polyurea compound represented by any one of general formulas (5) to (8) and the polyamine compound (9) represented by general formula (9) is preferably an aprotic polar solvent.

[0035] Examples of the aprotic polar solvent include ethyl acetate, dichloromethane, tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone. In the present embodiment, it is preferable to use N,N-dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone as the aprotic polar solvent.

[0036] It is preferable to use an aprotic polar solvent as a reaction solvent for the polyurea compound represented by any one of the general formulas (5) to (8) and the polyamine compound (9) represented by the general formula (9) from the viewpoints of solubility and suppression of side reactions due to the reaction between the solvent and the general formulas (5) to (8).

[0037] In one embodiment of the present invention, in the method for producing a polyurea compound, the ratio of the amounts of the polyurea compound represented by any one of general formulas (5) to (8) and the polyamine compound (9) represented by general formula (9) added can be selected arbitrarily. When expressed in terms of molar ratio, R of the polyurea compound represented by any one of the general formulas (5) to (8) is 2The ratio of the molar amount of (ester group) to the molar amount of amino group of the polyamine compound (9) represented by the general formula (9) is preferably 1:0.1 to 1:20.

[0038] The amine compound represented by the general formula (9) is as follows.

[0039] [ka] (R 3 and R 4 R is each independently a monovalent organic group or a hydrogen atom. 3 and R 4 may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.

[0040] R 3 and R 4 R is each independently a monovalent organic group or a hydrogen atom. 3 and R 4 may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. 3 and R 4 is preferably a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 70 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms, which may have an ether group, a carbonyl group, or an ester group.

[0041] R 3 and R 4 The aliphatic hydrocarbon group in has 1 or more and 70 or less carbon atoms, preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 10 or less. R 3 and R 4Specific examples of the aliphatic hydrocarbon group in the formula (I) include a methyl group, an ethyl group, a propyl group (each isomer), a butyl group (each isomer), a pentyl group (each isomer), a hexyl group (each isomer), a heptyl group (each isomer), an octyl group (each isomer), a nonyl group (each isomer), a decyl group (each isomer), an undecyl group (each isomer), a dodecyl group (each isomer), a tridecyl group (each isomer), a tetra ... Examples of alkyl groups include ladecyl groups (each isomer), pentadecyl groups (each isomer), hexadecyl groups (each isomer), heptadecyl groups (each isomer), octadecyl groups (each isomer), nonadecyl groups (each isomer), and eicosyl groups (each isomer); and cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cyclononyl groups, and cyclodecyl groups.

[0042] R 3 and R 4 The aromatic hydrocarbon group in has 6 or more and 70 or less carbon atoms, preferably 6 or more and 20 or less, more preferably 6 or more and 12 or less, and even more preferably 6 or more and 10 or less. R 3 and R 4 Specific examples of the aromatic hydrocarbon group in include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, and a phenanthryl group.

[0043] R 3 and R 4 Examples of the substituent on the aliphatic hydrocarbon group in the formula include an aromatic hydrocarbon group, a hydroxyl group, a cyano group, and a halogen atom. R 3 and R 4 Examples of the substituent on the aromatic hydrocarbon group in the formula (I) include an aliphatic hydrocarbon group, a hydroxyl group, a cyano group, and a halogen atom. The aromatic hydrocarbon group as the substituent of the aliphatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and specific examples thereof include those exemplified above. The aliphatic hydrocarbon group as the substituent of the aromatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof include those exemplified above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0044] In one embodiment of the present invention, the amine compound represented by the general formula (9) is R 3 is a hydrogen atom, and R 4 is a monovalent organic group. In this case, R 4 is preferably a linear alkyl group having 1 to 10 carbon atoms, and more preferably a linear alkyl group having 1 to 8 carbon atoms.

[0045] The amine compound represented by general formula (9) is not particularly limited, but from the viewpoint of easy availability, examples thereof include compounds represented by the following general formulas (I-1) to (I-3) (hereinafter, each of which may be referred to as "secondary amine compound (I-1)" etc.).

[0046] [ka]

[0047] (In general formula (I-1), R 111 is the above R 3 and R 4 is the same as R 112 represents a substituent of the benzene ring, and is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, which may have an ether group, a carbonyl group, or an ester group. n111 represents the number of substituents and is an integer of 0 to 5.

[0048] [ka]

[0049] (In general formula (I-2), R 121R is a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. 122 represents a substituent of the benzene ring, and is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, which may have an ether group, a carbonyl group, or an ester group. n121 represents the number of substituents and is an integer of 0 to 4.

[0050] [ka]

[0051] (In general formula (I-3), R 131 Z is a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. 131 is -O-, -NH-, or -C(=O)-. 132 represents a substituent of the benzene ring, and is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, which may have an ether group. n131 represents the number of substituents and is an integer of 0 to 4.

[0052] R 112 and R 122 are each a substituent on a benzene ring. R 112 and R 122 each independently represents a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, which may have an ether group, a carbonyl group, or an ester group. R 112 and R 122 The aliphatic hydrocarbon group and aromatic hydrocarbon group in R 3 and R 4 Among them, R 112 and R 122is preferably each independently an unsubstituted monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group (each isomer).

[0053] R 132 is a substituent on the benzene ring. R 132 represents a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have an ether group. R 132 The aliphatic hydrocarbon group and aromatic hydrocarbon group in R 3 and R 4 Among them, R 132 is preferably an unsubstituted monovalent aliphatic hydrocarbon group having from 1 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group (each isomer).

[0054] n111 represents the number of substituents and is an integer of 0 or more and 5 or less, preferably an integer of 0 or more and 3 or less, and more preferably 0 or 1. n121 and n131 each represent the number of substituents and are an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 3 or less, and more preferably 0 or 1.

[0055] R 121 and R 131 The divalent aliphatic hydrocarbon group in may be saturated or unsaturated. R 121 and R 131 Examples of the divalent saturated aliphatic hydrocarbon group in include an alkylene group having 1 to 12 carbon atoms and an alkylidene group having 2 to 12 carbon atoms.

[0056] Examples of the alkylene group having 1 to 12 carbon atoms include a chain alkylene group having 1 to 12 carbon atoms and a cyclic alkylene group having 3 to 12 carbon atoms.

[0057] Examples of the linear alkylene group having 1 to 12 carbon atoms include linear or branched linear alkylene groups having 1 to 12 carbon atoms. Specific examples of the linear or branched linear alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a pentylene group, a tetramethylene group, a propane-1,2-diyl group, an n-hexylene group, a pentamethylene group, a butane-1,3-diyl group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, and a dodecamethylene group.

[0058] Examples of cyclic alkylene groups having 3 to 12 carbon atoms include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cycloundecylene group, and a cyclocyclododecylene group.

[0059] Examples of the alkylidene group having 2 to 12 carbon atoms include a chain alkylidene group having 2 to 12 carbon atoms and a cyclic alkylidene group having 3 to 12 carbon atoms.

[0060] Examples of the linear alkylidene group having from 2 to 12 carbon atoms include linear or branched linear alkylidene groups having from 2 to 12 carbon atoms. Specific examples of the linear or branched linear alkylidene group having from 2 to 12 carbon atoms include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, a pentylidene group, a hexylidene group, a heptylidene group, an octylidene group, a nonylidene group, a decylidene group, an undecylidene group, and a dodecylidene group.

[0061] Examples of the cyclic alkylidene group having 3 to 12 carbon atoms include a cyclopropylidene group, a cyclobutylidene group, a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, a cycloheptylidene group, a cyclooctylidene group, a cyclononylidene group, a cyclodecylidene group, a cycloundecylidene group, and a cyclododecylidene group.

[0062] R 121 and R 131 Examples of the divalent unsaturated aliphatic hydrocarbon group in include alkenylene groups having 2 to 12 carbon atoms, alkadienylene groups having 2 to 12 carbon atoms, and alkynylene groups having 2 to 12 carbon atoms.

[0063] Examples of the alkenylene group having 2 to 12 carbon atoms include a chain alkenylene group having 2 to 12 carbon atoms and a cyclic alkenylene group having 3 to 12 carbon atoms.

[0064] Examples of the chain alkenylene group having from 2 to 12 carbon atoms include linear or branched chain alkenylene groups having from 2 to 12 carbon atoms. Specific examples of the linear or branched chain alkenylene group having from 2 to 12 carbon atoms include a vinylene group, a propenylene group, an isopropenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, a decenylene group, an undecenylene group, and a dodecenylene group.

[0065] Examples of cyclic alkenylene groups having 3 to 12 carbon atoms include a cyclopropenylene group, a cyclobutenylene group, a cyclopentenylene group, a cyclohexenylene group, a cycloheptenylene group, a cyclooctenylene group, a cyclononenylene group, a cyclodecenylene group, a cycloundecenylene group, and a cyclododecenylene group.

[0066] Examples of the alkadienylene group having 3 to 12 carbon atoms include a chain alkadienylene group having 3 to 12 carbon atoms and a cyclic alkadienylene group having 4 to 12 carbon atoms.

[0067] Examples of the chain alkadienylene group having 3 to 12 carbon atoms include linear or branched chain alkadienylene groups having 3 to 12 carbon atoms. Specific examples of the linear or branched chain alkadienylene group having 3 to 12 carbon atoms include a propadienylene group, a butadienylene group, a 2-ethylbutadienylene group, a pentadienylene group, a hexadienylene group, a heptadienylene group, an octadienylene group, a nonadienylene group, a decadienylene group, an undecadienylene group, and a dodecadienylene group.

[0068] Examples of cyclic alkadienylene groups having 4 to 12 carbon atoms include a cyclobutadienylene group, a cyclopentadienylene group, a cyclohexadienylene group, a cycloheptadienylene group, a cyclooctadienylene group, a cyclononadienylene group, a cyclodecadienylene group, a cycloundecadienylene group, and a cyclododecadienylene group.

[0069] Examples of the alkynylene group having 2 to 12 carbon atoms include a chain alkynylene group having 2 to 12 carbon atoms and a cyclic alkynylene group having 4 to 12 carbon atoms.

[0070] Examples of the chain alkynylene group having from 2 to 12 carbon atoms include linear or branched chain alkynylene groups having from 2 to 12 carbon atoms. Specific examples of the linear or branched chain alkynylene group having from 2 to 12 carbon atoms include an ethynylene group, a propynylene group, an isopropynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, and a dodecynylene group.

[0071] Examples of cyclic alkynylene groups having 4 to 12 carbon atoms include a cyclobutynylene group, a cyclopentynylene group, a cyclohexynylene group, a cycloheptynylene group, a cyclooctynylene group, a cyclononynylene group, a cyclodechynylene group, a cycloundecynylene group, and a cyclododecynylene group.

[0072] Among the above-mentioned secondary amine compounds (I-1) to (I-3), the compound in which the amino group bonded to the aromatic hydrocarbon is bonded to an aliphatic hydrocarbon is preferred as compared with a compound in which the amino group bonded to the aromatic hydrocarbon is directly bonded to the aromatic hydrocarbon or a compound in which the amino group bonded to the aromatic hydrocarbon is directly bonded to an unsaturated hydrocarbon. From the viewpoint of thermal stability, it is preferable that the structure be composed only of carbon atoms and hydrogen atoms, excluding the monovalent secondary amino group directly bonded to the aromatic hydrocarbon.

[0073] That is, preferred secondary amine compounds (I-1) include those represented by the formula: 111 is a monovalent aliphatic hydrocarbon group, and R 112 is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and n111 is preferably 0 or 1. More preferred secondary amine compounds (I-1) include those represented by the formula: 111 is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R 112 is preferably a methyl group or an ethyl group, and n111 is preferably 0 or 1.

[0074] Preferred secondary amine compounds (I-2) include those represented by the formula: 121 is a divalent aliphatic hydrocarbon group, R 122 is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and n121 is preferably 0 or 1. More preferred secondary amine compounds (I-2) include those represented by the formula: 121 is a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R 122 is preferably a methyl group or an ethyl group, and n121 is preferably 0 or 1.

[0075] Preferred secondary amine compounds (I-3) include those represented by the formula: 131 is a divalent aliphatic hydrocarbon group, R 132is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and n131 is preferably 0 or 1. More preferred secondary amine compounds (I-3) include those represented by the formula: 131 is a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R 132 is preferably a methyl group or an ethyl group, and n131 is preferably 0 or 1.

[0076] Specific examples of preferred secondary amine compounds (I-1) include N-methylaniline, N-ethylaniline, N-propylaniline (each isomer), N-butylaniline (each isomer), N-pentylaniline (each isomer), N-hexylaniline (each isomer), N-heptylaniline (each isomer), N-octylaniline (each isomer), and N-nonylaniline (each isomer). N-Decylaniline (each isomer), N-Methyltoluidine (each isomer), N-Ethyltoluidine (each isomer), N-Propyltoluidine (each isomer), N-Butyltoluidine (each isomer), N-Pentyltoluidine (each isomer), N-Hexyltoluidine (each isomer), N-Heptyltoluidine (each isomer), N-Octyltoluidine (each isomer), N-Aryl Toluidine (each isomer), N-arylaniline, 3-(phenylamino)propionitrile, 3-(O-toluylamino)propionitrile, 2-anilinoethanol, fluoro-N-methylaniline (each isomer), chloro-N-methylaniline (each isomer), bromo-N-methylaniline (each isomer), iodo-N-methylaniline (each isomer), fluoro-N-ethylaniline (each isomer), chloro-N-ethylaniline (each isomer), bromo-N-ethylaniline (each isomer), iodo-N-ethylaniline (each isomer), fluoro-N-propylaniline (each isomer), chloro-N-propylaniline (each isomer), bromo-N-propylaniline (each isomer), iodo-N-propylaniline (each isomer), and the like.

[0077] Specific examples of preferred secondary amine compounds (I-2) include 2,3-dihydro-4(1H)-quinolinone, diphenylamine, indoline, methylindoline (each isomer), 1,2,3,4-tetrahydroquinoline, and methyl-1,2,3,4-tetrahydroquinoline (each isomer).

[0078] A specific example of a preferred secondary amine compound (I-3) is 3,4-dihydro-2H-1,4-benzoxazine.

[0079] Among these, as the secondary amine compound (I), N-alkylaniline compounds such as N-methylaniline, N-ethylaniline, N-propylaniline (each isomer), N-butylaniline (each isomer), N-pentylaniline (each isomer), N-hexylaniline (each isomer), N-heptylaniline (each isomer), N-octylaniline (each isomer), N-nonylaniline (each isomer), and N-decylaniline (each isomer) are preferred, because they have high thermal stability as a compound and a higher coloration suppression effect. N-methyltoluidine (each isomer), N-ethyltoluidine ( N-alkyl toluidine compounds such as N-propyl toluidine (each isomer), N-butyl toluidine (each isomer), N-pentyl toluidine (each isomer), N-hexyl toluidine (each isomer), N-heptyl toluidine (each isomer), N-octyl toluidine (each isomer), N-nonyl toluidine (each isomer), and N-decyl toluidine (each isomer); or aromatic cyclic amine compounds such as indoline, methyl indoline (each isomer), 1,2,3,4-tetrahydroquinoline, and methyl 1,2,3,4-tetrahydroquinoline (each isomer) are preferred.

[0080] In one embodiment of the present invention, a method for producing a polyurea compound includes a step of polymerizing an amino acid ester-derived bis(phenylcarbamate) represented by the following general formula (10) with a diamine represented by the following general formula (11) to obtain a polyurea compound represented by any one of the general formulas (5) to (8). The step of polymerizing an amino acid ester-derived bis(phenylcarbamate) represented by the following general formula (10) with a diamine represented by the following general formula (11) to obtain a polyurea compound represented by any one of the general formulas (5) to (8) can be carried out by the method described in the above Non-Patent Document 1. In addition, the compound can be produced by the method of Reaction Scheme 2 described in the Examples below.

[0081] [ka]

[0082] In general formula (10), R 7 is a monovalent organic group, and is preferably an aliphatic or aromatic group having 1 to 20 carbon atoms.

[0083] In general formula (11), R 2 R is a divalent organic group. 2 The divalent organic group may be any of the above-mentioned divalent organic groups. 2 is preferably a linear alkylene group having 1 to 10 carbon atoms.

[0084] In one embodiment of the present invention, a method for producing a polyurea compound includes a step of esterifying an amino acid bis(phenylcarbamate) to obtain an amino acid ester-derived bis(phenylcarbamate) represented by the general formula (10).

[0085] In one embodiment of the present invention, a method for producing a polyurea compound includes a step of obtaining an amino acid-derived bis(phenylcarbamate) by reacting lysine or ornithine with diphenyl carbonate. EXAMPLES

[0086] (DSC measurement) The Tg of each compound was measured under the following conditions. Shimadzu DSC-60A plus Aluminum pan used Heating rate: 10℃ / min (25-200℃)

[0087] (TG-DTA measurement) Under the following conditions, the T d10 was measured. Seiko TG-DTA6200 Aluminum pan used Heating rate: 10℃ / min (30-550℃) Nitrogen atmosphere (200mL / min)

[0088] (GPC measurement) For Comparative Example 1, GPC was measured under the following conditions. Tosoh HLC-8320 (TSK-gels [bead size, exclusion limit molecular weight]; super-AW4000 [6 μm, >4 × 10 5 ], super-AW3000 [4μm,>6×10 4 ], super-AW2500 [4μm,>2×10 3 ]) ) Column oven temperature: 40°C Solvent: DMF (containing 10 mM LiBr) Flow rate: 0.6 mL / min, calibrated by polystyrene standards

[0089] (NMR measurement) NMR was measured for each compound under the following conditions. JEOL ECS-400 spectrometer 1H(400MHz), 13C{1H}(100MHz) Internal standard: TMS (tetramethylsilane)

[0090] (FT-IR measurement (ATR method)) For each compound, FT-IR was measured under the following conditions. Thermo Scientific Nicolet iS10 Measurement range: 600-4000cm -1

[0091] (HRMS: MALDI-TOF-MS) The compound obtained in Synthesis Example 1 was subjected to HRMS measurement under the following conditions. Shimadzu Biotech AXIMA Measurement solution preparation method: A mixed solution of solution A: solution B: solution C = 1:2:1 was prepared and used as the measurement solution for the measurement. Details of solutions A to C are shown below. Solution A: Measurement sample (compound represented by symbol 20 in reaction formula 1 below) / MeOH solution (10 mg / ml) Solution B: CHCA (α-cyano-4-hydroxycinnamic acid) / MeOH solution (5 mg / ml) Solution C: TFANa (Sodium trifluoroacetate) (1 mg / ml)

[0092] <Synthesis Example 1> N in a flame-dried two-neck flask α ,N γ To a chloroform solution (10 mL) of 1.00 g (2.68 mmol) of 1-bis(phenoxycarbonyl)-L-ornithine (the compound shown by symbol 1 in the following reaction formula 1), thionyl chloride (0.38 mL, 5.24 mmol) was added little by little. A catalytic amount of DMF (0.1 mL, 1.30 mmol) was added to the mixed solution, and then N 2 The mixture was stirred under atmospheric pressure at room temperature for 4 hours, and then MeOH (2 mL, 49.3 mmol) was added and the mixture was further stirred overnight.

[0093] After stirring, 5% sodium bicarbonate solution (15 mL) was added, and the mixture was washed three times with distilled water and saturated saline (20 mL each). 2 SO 4 After drying by 500° C., the solvent was removed by distillation to obtain the target compound N α ,N γ -Bis(phenoxycarbonyl)-L-ornithine methyl ester (compound represented by symbol 2 in the following reaction scheme 1) (0.93 g, 2.41 mmol, 90%) was obtained as a white solid, mp = 77-79°C.

[0094] 1H-NMR (400 MHz, CHLOROFORM-D) δ 7.37-7.33 (m, 4H), 7.22-7.16 (m, 2H), 7.13 (t, J = 6.9 Hz,4H), 5.82 (s, 1H), 5.28 (s, 1H), 4.46 (dd, J = 13C-NMR (101 MHz, CHLOROFORM-D) δ 172.5,154.7, 154.3, 150.9, 150.7, 129.3, 129.2, 125.5, 125.3, 121.6, 121.5, 77.3, 77.0, 76.7, 53.6, 52.6,40.6, 29.8, 25.7;IR (ATR, cm-1) : 3318.7, 2952.4, 2925.9, 2854.0, 1712.5, 1525.9, 1484.2,1197.37; HRMS(MALDI-TOF-MS) : m / z calcd for [M + Na]+, 409.39, found, 408.83.

[0095] [ka]

[0096] <Comparative Example 1> To a DMSO solution (3 mL) of the compound (0.5 mmol) represented by symbol 2 in the following reaction formula 2, diamine (compound represented by symbol a in the following reaction formula 2) (0.5 mmol) and triethylamine (1.5 mmol) were added, and then N 2 The mixture was stirred at 60° C. for 24 hours under atmospheric conditions. Then, the reaction solution was diluted with Et 2 The precipitate was collected by suction filtration and dried under vacuum at 80°C to obtain the target polyureas 2a-1 to 2a-4 (compounds shown by symbols 2a-1 to 2a-4 in the following reaction formula 2) in a yield of 76% as white solids. The molecular weights measured by GPC were Mn: 11000 and Mw / Mn: 2.63.

[0097] [ka]

[0098] <Example 1> Amine (0.64 mmol) was added to a DMSO solution (0.5 mL) of polyurea 2a-1 to 2a-4 (0.063 mmol), and the mixture was stirred at room temperature of 60°C for 30 hours under a N2 atmosphere. The reaction solution was then transferred to a sample tube and dried at 80°C under vacuum to obtain an amide-modified polyurea compound 2a-A. The polyurea compound 2a-A may contain multiple compounds with different terminal structures, and specifically, is one or more compounds selected from the group consisting of the compounds represented by symbols 2a-A-1 to 2a-A-4 in the following reaction formula 3.

[0099] The conversion of the ester to the amide was 1 This was confirmed by H-NMR and FT-IR measurements. 1 The results of H-NMR measurement are shown in Figure 1, and the results of FT-IR measurement are shown in Figure 2. 1 In the H NMR measurement, the signal (3.60 ppm) derived from the proton of the methoxycarbonyl group and the signal (7.77 ppm) derived from the proton of the urethane bond (NH) at the polymer end disappeared after the reaction. In the FT-IR measurement, the peak (v C=O =1726cm -1 ,v O-C =1206cm -1 ) disappeared after the reaction, and a new peak (v C=O =1701cm -1 ) appeared, confirming the progress of the reaction to convert to an amide.

[0100] [ka]

[0101] <Example 2> Amine B (0.020 mmol) was added to a DMSO solution (0.2 mL) of polyurea 2a-1 to 2a-4 (0.020 mmol), and the mixture was stirred at 100°C for 50 hours under a N2 atmosphere. The reaction solution was then transferred to a sample tube and dried at 90°C under vacuum to obtain a crosslinked polyurea compound 2a-B. The polyurea compound 2a-B may contain multiple compounds with different terminal structures, and specifically, is one or more compounds selected from the group consisting of the compounds represented by symbols 2a-B-1 to 2a-B-4 in the following reaction formula 4. In reaction scheme 4, Y is the terminus of amine B, and is -NH 2 or forms a urea bond with the carbamate group in 2a, or forms an amide bond with the ester group in 2a.

[0102] In this case, in the FT-IR measurement, a peak (v C=O =1726cm -1 ,v O-C =1206cm -1 ) disappeared after the reaction, and a new peak (v C=O =1701cm -1 ) appeared, which confirmed the conversion from ester to amide. The results of FT-IR measurement in Example 2 are shown in FIG. [ka]

[0103] <Example 3> Amine B (0.010 mmol) was added to a DMSO solution (0.2 mL) of polyurea 2a-1 to 2a-4 (0.020 mmol), and the mixture was stirred at 100°C for 114 hours under a N2 atmosphere. The reaction solution was then transferred to a sample tube and dried at 90°C under vacuum to obtain a crosslinked polyurea compound 2a-B. The polyurea compound 2a-B may contain multiple compounds with different terminal structures, and specifically, is one or more compounds selected from the group consisting of the compounds represented by symbols 2a-B-1 to 2a-B-4 in the following reaction formula 5. In reaction formula 5, Y is the terminal of amine B, and is -NH2 or forms a urea bond with the carbamate group in 2a, or forms an amide bond with the ester group in 2a. In this case, in the FT-IR measurement, a peak (v C=O =1726cm -1 ,v O-C =1206cm -1 ) disappeared after the reaction, and a new peak (v C=O =1703cm -1 ) appeared, which confirmed the conversion from ester to amide. The results of FT-IR measurement in Example 3 are shown in FIG.

[0104] [ka]

[0105] <Evaluation of thermal properties> TG-DTA and DSC measurements were carried out on the polyurea compounds obtained in Examples 1 to 3 and Comparative Example 1. The results are shown in Table 1.

[0106] [Table 1]

[0107] When Examples 1, 2, and 3 having amide groups in the side chains are compared with Comparative Example 1 having ester groups in the side chains, it was confirmed that Examples 1 to 3 had improved Tg compared to Comparative Example 1.

Claims

1. A polyurea compound represented by any one of the following general formulas (1) to (4): 【Chemistry 1】 (R １ is as follows (R １ )-1 or (R １ )-2. ２ is a divalent organic group. X is a hydrogen atom or a group represented by the following (X)-1 or (X)-2. n is 0 or more and 2000 or less. 【Chemistry 2】 ((R １ )-1 or (R １ )-2 medium, R ３ and R ４ R is each independently a monovalent organic group or a hydrogen atom. ３ and R ４ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. a is 3 or 4. 【Chemistry 3】 (R ５ and R ６ R is each independently a monovalent organic group or hydrogen. ５ and R ６ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.

2. A method for producing the polyurea compound according to claim 1, comprising a step of reacting a polyurea compound represented by any one of the following general formulas (5) to (8) with a polyamine compound (9) represented by the following general formula (9). 【Chemistry 4】 (R １１ is as follows (R １１ )-1 or (R １１ )-2. ２ is a divalent organic group. X is a hydrogen atom or a group represented by the following (X)-1 or (X)-2. n is 0 or more and 2000 or less. 【Chemistry 5】 (R ７ is a monovalent organic group. a is 3 or 4. 【Chemistry 6】 (R ５ and ６ R is each independently a monovalent organic group or hydrogen. ５ and ６ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. 【Chemistry 7】 (R ３ and ４ R is each independently a monovalent organic group or a hydrogen atom. ３ and ４ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.

3. The method for producing a polyurea compound according to claim 2, comprising the step of polymerizing an amino acid ester-derived bis(phenylcarbamate) represented by the following general formula (10) with a diamine represented by the following general formula (11) to obtain a polyurea compound represented by any one of the general formulas (5) to (8). 【Chemistry 8】 (R ７ is a monovalent organic group. a is 3 or 4. R ２ is a divalent organic group.

4. The method for producing a polyurea compound according to claim 3, comprising a step of esterifying an amino acid bis(phenylcarbamate) to obtain an amino acid ester-derived bis(phenylcarbamate) represented by the general formula (10).

5. The method for producing a polyurea compound according to claim 4, comprising a step of obtaining an amino acid-derived bis(phenylcarbamate) by reacting lysine or ornithine with diphenyl carbonate.

6. The reaction temperature of the polyurea compound represented by any one of the general formulas (5) to (8) and the polyamine compound represented by the general formula (9) is 50 ° C. or higher and 100 ° C. or lower. The method for producing a polyurea compound according to claim 2.

7. The method for producing a polyurea compound according to claim 2, wherein a reaction solvent for the polyurea compound represented by any one of the general formulas (5) to (8) and the polyamine compound represented by the general formula (9) is an aprotic polar solvent.

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