JP7352171B2 - Polyamide compound and its manufacturing method - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to polyamide compounds and methods of manufacturing the same.

Polymers having self-repairing properties (self-healing properties) are known. The skeletons of conventional polymers having self-healing properties are urethane and urea (see, for example, Non-Patent Documents 1 and 2). These polymers have self-healing properties by increasing the number of hydrogen bonds between molecules.
At present, only a limited number of polymers such as the above-mentioned urethane-based polymers have been developed as polymers having self-healing properties. Therefore, the range of application is limited using only these limited polymers.
Moreover, conventional polymers having self-healing properties require a long time for self-healing.
Under these circumstances, the development of new polymers with self-healing properties is desired.

M. Hendrich, L. Lewerdomski, P. Vana. J. Polymer Science, Part A: Polymer Chemistry. 53, 2809-2819 (2015). E. D’Elia, S. Barg, N. Ni, V. G. Rocha, E. Saiz. Advanced Materials. 27, 4788-4794 (2015).

The present disclosure has been made in view of the above circumstances, and aims to provide a novel polymer having self-healing properties.
The present disclosure can be realized as the following forms.

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（ｎは６～１２の整数を示し、ｍは８～１８の整数を示す。） [1] Contains a dicarboxylic acid unit represented by the following general formula (1), a dicarboxylic acid unit represented by the following general formula (2), and a diamine unit represented by the following general formula (3) , polyamide compound.

(x represents an integer from 6 to 12, and y represents an integer from 8 to 18.)

(n represents an integer from 6 to 12, m represents an integer from 8 to 18.)

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（ｎは６～１２の整数を示し、ｍは８～１８の整数を示す。） [2] A dicarboxylic acid compound having a structure represented by the following general formula (4), a dicarboxylic acid compound having a structure represented by the following general formula (5), and a structure represented by the following general formula (6) The method for producing a polyamide compound according to claim 1, characterized in that the method comprises reacting a diamine compound having the following.

(x represents an integer from 6 to 12, and y represents an integer from 8 to 18.)

(n represents an integer from 6 to 12, m represents an integer from 8 to 18.)

The polyamide compound of the present disclosure has excellent self-healing properties (self-healing properties). Self-healing property here refers to the property that when a molded product made of a polyamide compound is cut and the cut surfaces are brought together, the cut surfaces are glued together, disappear or reduce, and return to their original state (restore). means.

Further, according to the method for producing a polyamide compound of the present disclosure, a polyamide compound with excellent self-healing properties can be produced.

The matter presented herein is exemplary and is intended to be an illustrative description of embodiments of the invention, and is intended to be a description that will most effectively and easily understand the principles and conceptual features of the invention. This is stated for the purpose of providing an idea. In this regard, it is not intended to present more structural details of the invention than are necessary for a fundamental understanding of the invention, and the description together with the drawings illustrates some aspects of the invention. It will be clear to those skilled in the art how to implement it in practice.

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（ｎは６～１２の整数を示し、ｍは８～１８の整数を示す。） [1] Polyamide Compound The polyamide compound of the present disclosure comprises a dicarboxylic acid unit represented by the following general formula (1), a dicarboxylic acid unit represented by the following general formula (2), and a dicarboxylic acid unit represented by the following general formula (3). diamine unit.

(x represents an integer from 6 to 12, and y represents an integer from 8 to 18.)

(n represents an integer from 6 to 12, m represents an integer from 8 to 18.)

x in general formula (1) is an integer of 6 to 12, preferably an integer of 7 to 11, more preferably an integer of 9 to 10.
In general formula (1), y is an integer of 8 to 18, preferably an integer of 9 to 15, more preferably an integer of 10 to 12.
In general formula (3), n is an integer of 6 to 12, preferably an integer of 7 to 11, more preferably an integer of 8 to 10.
m in the general formula (3) is an integer of 8 to 18, preferably an integer of 9 to 17, more preferably an integer of 10 to 16.

The polyamide compound may further contain structural units other than those mentioned above, as long as the effects of the polyamide compound are not impaired.

In the polyamide compound, the content of dicarboxylic acid units is not particularly limited. The content of dicarboxylic acid units is usually 5% to 50 mol%, preferably 20% to 50 mol%, and more preferably 30% to 50 mol%.
In the polyamide compound of the present invention, the content of diamine units is not particularly limited. The content of diamine units is usually 5% to 50 mol%, preferably 20% to 50 mol%, and more preferably 30% to 50 mol%.
The content ratio of dicarboxylic acid units and diamine units is preferably approximately the same amount from the viewpoint of polymerization reaction, and the content of dicarboxylic acid units is preferably ±1 mol% of the content of diamine units. More preferred.

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[1-1] Dicarboxylic acid unit As described above, the polyamide compound contains at least dicarboxylic acid units represented by the following general formulas (1) and (2).

(x represents an integer from 6 to 12, and y represents an integer from 8 to 18.)

As the dicarboxylic acid unit of general formula (1), the unit shown in the following formula (7) is particularly preferable. The unit shown in formula (7) is derived from plants and is preferable from the viewpoint of preventing global warming and reducing resource risks. By incorporating the unit shown in formula (7), a polyamide compound with extremely excellent self-healing properties can be obtained.

As mentioned above, the polyamide compound contains a dicarboxylic acid unit represented by the general formula (1) and a dicarboxylic acid unit represented by the general formula (2). The total of dicarboxylic acid units represented by general formula (1) and dicarboxylic acid units represented by general formula (2) is 50 mol% or more and 100 mol% in total of dicarboxylic acid units in the polyamide compound. % or less, more preferably 60 mol% or more and 100 mol% or less, particularly preferably 70 mol% or more and 100 mol% or less. This is because when it is within this range, self-repairing properties are excellent.
The molar ratio of dicarboxylic acid units represented by general formula (1) to dicarboxylic acid units represented by general formula (2) should be 99:1 to 1:99 from the viewpoint of particularly excellent self-healing properties. The ratio is preferably 95:5 to 25:75, and even more preferably 90:10 to 30:70.

A repeating unit consisting of a dicarboxylic acid unit represented by general formula (1) and a diamine unit represented by general formula (3), and a dicarboxylic acid unit represented by general formula (2) and a diamine unit represented by general formula (3). The repeating units consisting of diamine units may be randomly present in the polyamide compound.
Furthermore, a repeating unit consisting of a dicarboxylic acid unit represented by the general formula (1) and a diamine unit represented by the general formula (3), a dicarboxylic acid unit represented by the general formula (2), and a dicarboxylic acid unit represented by the general formula (3) Repeating units consisting of diamine units represented by may be present in the polyamide compound in the form of blocks. That is, in the case of this block shape, there is a block in which only repeating units consisting of dicarboxylic acid units represented by general formula (1) and diamine units represented by general formula (3) are assembled, and a block in which only repeating units consisting of dicarboxylic acid units represented by general formula (1) and diamine units represented by general formula ) There is a block in which only repeating units consisting of dicarboxylic acid units represented by the formula (3) and diamine units represented by the general formula (3) are assembled. Polyamide compounds having these blocks have the properties of polyamide compounds consisting only of repeating units consisting of dicarboxylic acid units represented by general formula (1) and diamine units represented by general formula (3). . Furthermore, this polyamide compound also has the properties of a polyamide compound consisting only of repeating units consisting of dicarboxylic acid units represented by general formula (2) and diamine units represented by general formula (3).

Compounds that can constitute dicarboxylic acid units other than the dicarboxylic acid units represented by general formulas (1) and (2) are not particularly limited.
For example, specific examples of dicarboxylic acid compounds include oxalic acid, malonic acid, fumaric acid, maleic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, etc. 25 linear aliphatic dicarboxylic acids or dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms (dimer acids) obtained by dimerizing unsaturated fatty acids obtained by fractional distillation of triglycerides, and their hydrogenated products (hydrogenated aliphatic dicarboxylic acids such as dimer acid), alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and terephthalic acid, isophthalic acid, 1,3-benzenediacetic acid, 1,4-benzenediacetic acid, etc. Examples include aromatic dicarboxylic acids. Further, derivatives of these dicarboxylic acid compounds may also be used. Examples of derivatives include carboxylic acid halides. These can be used alone or in combination of two or more.
When the total of dicarboxylic acid units in the polyamide compound is 100 mol%, the content of dicarboxylic acid units other than the dicarboxylic acids represented by the above-mentioned general formulas (1) and (2) is not particularly limited. The content of dicarboxylic acid units other than dicarboxylic acids represented by general formulas (1) and (2) is preferably less than 50 mol%, more preferably less than 20 mol%, and less than 10 mol%. It is particularly preferable that there be. This is because when the content of dicarboxylic acid units other than the dicarboxylic acid units represented by general formulas (1) and (2) is within this range, self-healing properties are improved.

（ｎは６～１２の整数を示し、ｍは８～１８の整数を示す。） [1-2] Diamine unit The diamine unit in the polyamide compound includes at least a diamine unit represented by general formula (3).

(n represents an integer from 6 to 12, m represents an integer from 8 to 18.)

When the total amount of diamine units in the polyamide compound is 100 mol%, the content of the diamine units represented by the above general formula (3) is not particularly limited. It is preferable that the diamine unit represented by the general formula (3) is contained in 5 mol% or more and 100 mol% or less, more preferably 20 mol% or more and 100 mol% or less, and 30 mol% or more and 100 mol% or less. Particularly preferred. This is because when the content of diamic acid units represented by general formula (3) is within this range, self-healing properties are excellent.

The polyamide compound may contain diamine units other than the diamine unit represented by general formula (3). Compounds that can constitute diamine units other than the diamine units represented by general formula (3) are not particularly limited.
For example, examples of diamines constituting diamine units other than the diamine unit represented by general formula (3) include known aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like.

Examples of aliphatic diamines that can constitute diamine units other than the diamine units represented by general formula (3) include 1,1-methaxylylene diamine, 1,3-propanediamine, and pentamethylene diamine. .
Examples of the alicyclic diamine include 4,4'-methylenebis(cyclohexylamine) and 1,3-bis(aminomethyl)cyclohexane.
Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diaminofluorene, 4,4'-diamino-2,2'-dimethylbiphenyl, 9,9-bis(4-aminophenyl)fluorene , 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediisopropylidene)bisaniline , 4,4'-(m-phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4 -bis-(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2 , 4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene , octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4 -Diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanil 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis (4-Aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzoyloxy)cyclohexyl-3,5-diamino Benzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1, 1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2 , 4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1-(2,4-diaminophenyl)piperazine-4-carboxylic acid, 4-(morpholin-4-yl)benzene Examples include -1,3-diamine, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, and α-amino-ω-aminophenylalkylene.
These can be used alone or in combination of two or more.

When the total amount of diamine units in the polyamide compound is 100 mol%, the content of diamine units other than the diamine units represented by the above-mentioned general formula (3) is not particularly limited. The content of diamine units other than the diamine units represented by general formula (3) is preferably less than 50 mol%, more preferably less than 30 mol%, particularly less than 10 mol%. preferable. When the content of diamine units other than the diamine units represented by general formula (3) is within this range, self-healing properties will be good.

[1-3] Molecular weight of polyamide compound The molecular weight of the polyamide compound of the present invention is not particularly limited. Generally, the number average molecular weight (Mn) is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 90,000 or less, particularly preferably 3,000 or more and 80,000 or less. Similarly, the weight average molecular weight (Mw) is preferably 3,000 or more and 400,000 or less, more preferably 6,000 or more and 300,000 or less, and particularly preferably 40,000 or more and 250,000 or less. All molecular weights herein mean values in terms of polystyrene.
The molecular weight of the polyamide compound can be determined by measurement using GPC (Gel Permeation Chromatography).

[1-4] Characteristics of the polyamide compound The polyamide compound contains a long chain dicarboxylic acid unit represented by the general formula (1), a long chain diamine unit represented by the general formula (3), and a long chain diamine unit represented by the general formula (2). ) is characterized by a combination of dicarboxylic acid units. It is presumed that this characteristic combination provides high self-healing properties.
Another feature of polyamide compounds is that they have high energy absorption. Another characteristic is that it is non-crystalline (transparent).
Note that these characteristics are not found in urethane-based polymers.

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（ｎは６～１２の整数を示し、ｍは８～１８の整数を示す。） [2] Method for producing a polyamide compound The method for producing a polyamide compound includes a dicarboxylic acid compound having a structure represented by the following general formula (4), a dicarboxylic acid compound having a structure represented by the following general formula (5), , and a diamine compound having a structure represented by the following general formula (6).

(x represents an integer from 6 to 12, and y represents an integer from 8 to 18.)

(n represents an integer from 6 to 12, m represents an integer from 8 to 18.)

Regarding "x" and "y" in the above general formula (4), the explanation of "x" and "y" in the above general formula (1) can be applied as is.
Regarding "n" and "m" in the above general formula (6), the explanation of "n" and "m" in the above general formula (3) can be applied as is.

As the dicarboxylic acid compound, in addition to the dicarboxylic acid, a carboxylic acid derivative in which the hydroxyl group of the carboxyl group of the dicarboxylic acid is substituted with another hetero atom (atom other than carbon, hydrogen, or metal) can also be used. Examples of carboxylic acid derivatives include acyl halides (acid halides) in which the hydroxyl group is replaced by a halogen.

A polyamide compound can be manufactured by polycondensing a diamine component that can constitute a diamine unit and a dicarboxylic acid component that can constitute a dicarboxylic acid unit. The degree of polymerization can be controlled by adjusting polycondensation conditions and the like.
It can also be manufactured by other methods. Examples of methods for producing polyamide compounds include (1) a method using an acid or base catalyst, (2) a method using carboxylic acid activation, (3) a method using transesterification, and (4) a method using a condensing agent. The method of doing so is preferably used. Here, as a suitable manufacturing method, a method for manufacturing a polyamide compound using an acid chloride obtained by activating a carboxylic acid will be exemplified.

For example, it can be manufactured according to the following manufacturing scheme. In this method, two types of dicarboxylic acids are activated to form acid chloride, and the acid chloride and diamine are reacted to form a polyamide compound.

Note that by activating the dicarboxylic acid to form an acid chloride and then reacting it with a diamine, a polyamide compound with excellent self-healing properties can be efficiently produced.

Moreover, a monoamine or monocarboxylic acid may be added as a molecular weight regulator during polycondensation. Further, in order to suppress the polycondensation reaction and obtain a desired degree of polymerization, the ratio (molar ratio) between the diamine component and the carboxylic acid component constituting the polyamide compound may be adjusted to be shifted from 1.

When polymerizing by dehydrohalogenation reaction by reacting a carboxylic acid dihalide such as the above-mentioned acid chloride with a diamine, the reaction proceeds rapidly, so it is preferable to carry out the reaction at a relatively low temperature in order to control the reaction rate.
For example, it is preferable to carry out the reaction at a temperature in the range of -40°C to 100°C.
The reaction solvent is not particularly limited, and a wide variety of known solvents can be used. For example, examples of organic polar solvents used as reaction solvents include dimethylacetamide, N-methylpyrrolidone, dimethylsulfone, dimethylformamide, N-methylcaprolactam, tetramethylurea, N,N'-dimethyl-2-imidazolidinone, and the like. . These may be used alone or as a mixed solvent of two or more. Further, if necessary, hydrogen chloride and a metal halide salt such as lithium chloride, calcium chloride, potassium chloride, etc. may be used in combination to improve solubility.

Further, the concentration of the polyamide compound (polymer concentration) is not particularly limited, although it varies depending on the solubility of the produced polyamide compound in the solvent and the viscosity of the solution. The concentration of the polyamide compound is preferably 0.1 to 40% by mass, for example, from the viewpoint of productivity and the like.
The concentration of the polyamide compound is determined comprehensively from the content and composition ratio of the polyamide compound composition, solubility, solution viscosity, handleability, and ease of defoaming.

The method of adding the raw materials is not particularly limited. For example, diamine is added to the reaction solvent and dissolved at low temperature, and then one of the raw materials, dicarboxylic acid halide such as acid chloride, is added. In this case, it is preferable to carry out the reaction under an inert atmosphere (for example, under a nitrogen atmosphere or an argon gas atmosphere) in order to prevent deterioration of the diamine. The molar ratio of diamine and acid halide should basically be equimolar, but in order to control the degree of polymerization, an excess of one of the raw materials, diamine or acid component, may be added, or a monofunctional An appropriate amount of an organic substance such as aniline, naphthylamine, acetic acid chloride, benzoyl chloride, etc. may be added.

In addition, in the case of the above-mentioned polyamide compounds, in order to improve their properties, we also adopt an addition method that aims to form polymer blocks, such as reacting a portion of the diamine or acid chloride and then adding the remaining raw materials. It's fine.

The polymerization reaction product (polyamide compound) thus obtained requires neutralization because it contains hydrogen halide as a by-product. The neutralizing agent is not particularly limited as long as it is a generally known basic compound.
As the neutralizing agent, triethylamine, tripropylamine, benzyldimethylamine, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, tetraethylammonium salt, etc. are preferably used. be able to. Further, although such a neutralizing agent may be added alone in the form of a powder, it is preferable to use one that has been pulverized and dispersed in an organic solvent as a slurry from the viewpoint of reactivity and operability. .

The polyamide compound solution obtained by the above method can be separated in a poor solvent such as water or methanol. Further, the solution after the neutralization reaction can also be used as it is as a molding solution.

Further, the industrial polycondensation method for polyamide compounds is not particularly limited, and known methods are widely used. Examples include a pressurized salt method, a normal pressure dropping method, a pressurized dropping method, and a reactive extrusion method. Moreover, the lower the reaction temperature is, the more yellowing and gelation of the polyamide compound can be suppressed, and a polyamide compound with stable properties can be obtained.

The pressurized salt method is a method in which melt polycondensation is performed under pressure using nylon salt as a raw material. Specifically, after preparing a nylon salt aqueous solution containing a diamine component, a dicarboxylic acid component, and other components as necessary, the aqueous solution is concentrated and then heated under pressure to remove condensed water. Polycondensate while While gradually returning the pressure inside the can to normal, the temperature was raised to about 10°C above the melting point of the polyamide compound and held there, and then the pressure was gradually reduced to 0.02 MPaG and kept at that temperature to continue polycondensation. do. When a certain stirring torque is reached, the inside of the can is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide compound.

In the normal pressure dropping method, the diamine component is continuously dropped under normal pressure into a heated and molten mixture of the dicarboxylic acid component and, if necessary, other components, and polycondensation is carried out while removing condensation water. The polycondensation reaction is carried out while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the polyamide compound to be produced.

In the pressure dropping method, first, a dicarboxylic acid component and, if necessary, other components are charged into a polycondensation vessel, and each component is stirred and melted and mixed to prepare a mixture. Next, the diamine component is continuously added dropwise to the mixture while pressurizing the inside of the can preferably to about 0.3 to 0.4 MPaG, and polycondensation is carried out while removing condensation water. At this time, the polycondensation reaction is carried out while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the polyamide compound to be produced. When the set molar ratio is reached, stop dropping the diamine component, and while gradually returning the pressure inside the can to normal pressure, raise the temperature to about 10°C above the melting point of the polyamide compound, maintain it, and then gradually reduce the pressure to 0.02 MPaG. While maintaining the same temperature, polycondensation is continued. When a certain stirring torque is reached, the inside of the can is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide compound.
The reactive extrusion method is a method of incorporating into the skeleton of polyamide by an amidation exchange reaction.

[3] Polyamide composition using a polyamide compound A polyamide compound may be added with a lubricant, a crystallization nucleating agent, an anti-whitening agent, a matting agent, a heat-resistant stabilizer, a weather-resistant stabilizer, an ultraviolet absorber, and a plasticizer, depending on the purpose and performance. A polyamide composition may be prepared by adding additives such as a flame retardant, an antistatic agent, a coloring inhibitor, an antioxidant, and an impact modifier. These additives can be added as necessary within a range that does not impair the effects of the present disclosure. Further, the polyamide compound of the present disclosure may be mixed with various resins to form a polyamide composition depending on the required use and performance.

[4] Applications of polyamide compounds Applications of polyamide compounds are not particularly limited. For example, it is used in clothing, paint, coatings, cosmetics, adhesives, electronic equipment materials, building materials, concrete reinforcing agents, printing inks, aircraft materials, spacecraft materials, etc.

Hereinafter, a more specific explanation will be given with reference to Examples.

1. Synthesis of polyamide compound <Example 1> (Synthesis of PA80TC20PAm)
The polyamide compound (PA80TC20PAm) was synthesized according to the scheme below. Note that "PA80TC20PAm" is an abbreviation indicating the polyamide compound of Example 1. TC is an abbreviation for "Terephthaloyl chloride."

Specifically, diamine (3') (42.9 g, 80.0 mmol) and THF (300 mL) were placed in a separable flask (1000 mL) under a nitrogen atmosphere, and after stirring at 0°C using a mechanical stirrer. , triethylamine (25.2 mL, 180.0 mmol) was added. Then, acid chloride (1') (45.8 g, 64.0 mmol) and Terephthaloyl chloride (2') (3.3 g, 16.0 mmol) were dissolved in THF (100 mL) and added dropwise, followed by reaction at room temperature for 2 hours. Ta. After the reaction was completed, the product was purified by reprecipitation using water and methanol, and washed with water. The product was vacuum dried (80°C, 8 hours). Yield: 85.0g. FT-IR (ATR, cm ^-1 ): 3296.7 (NH, amide), 2920.7, 2851.2, 1640.2 (C=O, carbonyl), 1549.5, 1459.8, 1460.8 , 1376.0, 1289.2, 721.2.

2. Evaluation of physical properties of polyamide compound (1) FT-IR measurement Measured by single reflection ATR method (ZnSe prism). The measurement range was 4000 cm ^-1 to 550 cm ^-1 , and FT-IR-4200+ATR410-S manufactured by JASCO Corporation was used. The measurement results are as described at the end of "1. Synthesis of polyamide compound".

(2) DSC (Differential Scanning Calorimeter) measurement DSC was measured under the conditions of sample weight: 5 mg, heating rate: 10°C/min, temperature range: -150°C to 300°C, and Tg ( glass transition temperature) was determined. EXSTAR DSC7020 manufactured by Hitachi High-Tech Science Co., Ltd. was used for the DSC measurement.

(3) TGA (Thermogravimetric Analysis) measurement Sample weight: 5 mg, heating rate: 10°C/min, temperature range: r. t. TG/DTA was measured under conditions of ~600°C, and the thermal decomposition temperature Td (5% weight loss temperature) and weight loss start temperature were determined. Thermoplus TG8120 manufactured by Rigaku Denki Co., Ltd. was used for TGA measurement.

(4) Water absorption measurement A polyamide compound that had been vacuum-dried in advance was molded using a hot press. A test piece with a length of 25 mm, a width of 6 mm, and a thickness of 2 mm was used. The measurement conditions were as follows.
Before measuring the water absorption rate, the weight of the test piece, which had been previously dried under reduced pressure (temperature: 30° C., 48 hours or more), was accurately measured. Thereafter, it was immersed in a beaker containing ion-exchanged water (100 mL) for 24 hours. After soaking, the test piece was taken out from the beaker and the water on the surface was wiped. The weight was accurately measured and the weight difference between the test pieces was determined. The water absorption rate was determined from the weight before and after soaking.

(5) Measurement results of DSC measurement, TGA measurement, and water absorption measurement Table 1 shows the measurement results of DSC measurement, TGA measurement, and water absorption measurement of the polyamide compound of the example.

(6) Tensile test (6.1) Test method For tensile properties, a tensile test was conducted to evaluate yield stress (tensile strength) and elongation at break. A strip-shaped test piece (40 mm x 9 mm x 4 mm) was prepared and used as the test piece. In the measurement, the width and thickness of the test piece were measured. A TECHNO GRAPH 5AG-X type testing machine (manufactured by Shimadzu Corporation) was used for the measurement. The measurement conditions were a tensile speed of 100 mm/min and a measurement temperature of 23°C.
The self-healing property test method is as follows. The test piece was cut across approximately the center in the longitudinal direction with scissors. For each test piece that was left for 0.5 hours (30 minutes), 6 hours, and 24 hours after cutting, the cut surfaces were pressed against each other for 5 seconds, and then the tensile properties were measured.

(6.2) Test results The test results are shown in Table 2. In either case, it was confirmed that when the cut surfaces were pressed together, they exhibited tensile strength and elongation at break equivalent to those of the uncut test piece (Pristine) in a short time of 5 seconds. Specifically, any test piece that was left for 0.5 to 24 hours after cutting had the same tensile strength and strength as an uncut test piece (Pristine) due to adhesion in just 5 seconds. It was confirmed that it exhibited elongation at break.

(7) Molecular weight evaluation of polyamide compound (7.1) Measuring method The molecular weight of the polyamide compound was determined by measurement using GPC (Gel Permeation Chromatography).
For the measurement, a measuring device (HLC-82220GPC) manufactured by Tosoh Corporation (using an RI detector) was used, and the column was Shodex GPC KF-806L x 3 manufactured by Showa Denko K.K. The measurement conditions were as follows. I got it right.
For GPC measurement, eluent: tetrahydrofuran (THF), standard substance: polystyrene (PS), sample concentration: 0.2 w/v%, injection volume: 100 μL, flow rate: 1.0 mL/min, column temperature: 40 °C. Measurements were taken.

(7.2) Measurement results Table 3 shows the measurement results.

3. Effects of Examples It was confirmed that the polyamide compounds of Examples had self-healing properties without introducing urethane or urea bonds into the polymer skeleton.
Furthermore, the polyamide compound specimens that were glued together after being cut repaired themselves in a short period of time.
Further, as a result of evaluating the test piece bonded after cutting by a tensile test, it was confirmed that the physical properties were equivalent to those of the test piece before cutting. Therefore, it was found that the polyamide compounds of Examples had very high self-healing properties.
The polyamide compound of this example is a resin that is connected by amide bonds and has elastomer properties and self-healing properties. The polyamide compound of this example is very useful as a resin that self-repairs in a short time. The polyamide compound of this example has the following characteristics: [1] it has self-healing properties, [2] it has elastomer properties, and [3] it has amorphousness (transparency). In particular, it has very excellent properties such as being able to self-repair after being cut (broken) by simply bringing the cut (broken) surface into contact again for a short period of time, and requiring no heat, pressure, or chemical reaction.
Furthermore, the polyamide compound of this example can use a plant-derived compound as a starting material for dicarboxylic acid units, which is advantageous from the viewpoint of preventing global warming and reducing resource risks.

The foregoing examples are for illustrative purposes only and are not to be construed as limiting the invention. Although the invention has been described in terms of exemplary embodiments, the language used in describing and illustrating the invention is to be understood to be in a descriptive and illustrative rather than a restrictive sense. Changes may be made in the form as detailed herein without departing from the scope or spirit of the invention and within the scope of the appended claims. Although reference has been made herein to specific structures, materials and embodiments in the detailed description of the invention, it is not intended to limit the invention to the disclosure herein; rather, the invention is defined by the appended claims. It shall cover all functionally equivalent structures, methods and uses within the scope.

The present invention is not limited to the embodiments detailed above, and various modifications and changes can be made within the scope of the claims of the present invention.

The polyamide compounds of the present disclosure are used in a wide variety of applications. It is particularly suitable for use in applications requiring self-repairing properties. Preferred applications include, for example, clothing, paints, coatings, cosmetics, adhesives, electronic devices, building materials, concrete reinforcing materials, printing applications, aircraft, and spacecraft.

Claims (2)

A polyamide compound containing a dicarboxylic acid unit represented by the following general formula (1), a dicarboxylic acid unit represented by the following general formula (2), and a diamine unit represented by the following general formula (3). .

(x represents an integer from 6 to 12, and y represents an integer from 8 to 18.)

(n represents an integer from 6 to 12, m represents an integer from 8 to 18.) A dicarboxylic acid compound having a structure represented by the following general formula (4), a dicarboxylic acid compound having a structure represented by the following general formula (5), and a diamine having a structure represented by the following general formula (6). 2. The method for producing a polyamide compound according to claim 1, which comprises reacting the compound with the polyamide compound.

(x represents an integer from 6 to 12, and y represents an integer from 8 to 18.)

(n represents an integer from 6 to 12, m represents an integer from 8 to 18.)