JP6772649B2 - Polyamide compound - Google Patents

Description

The present invention relates to polyamide compounds. In particular, it relates to a polyamide compound having elastomeric properties.

From the viewpoint of preventing global warming and reducing resource risk, polymers using plant-derived compounds as starting materials are attracting attention instead of petroleum-based polymers (see, for example, Non-Patent Documents 1 to 3).
However, although polylactic acid, which is a typical example thereof, is a plant-derived compound, it has problems in heat resistance and hydrolysis resistance. Therefore, the applicable range is limited only by polylactic acid.
Under these circumstances, the development of plant-derived high-performance polymers other than polylactic acid is desired.

Conventionally, as polyamide compounds, PA6 polymerized with ε-caprolactam, PA66, PA610, PA1010 polymerized with dicarboxylic acid and diamine, and the like are known. Further, PA11, which is a plant-derived polyamide compound, is obtained by polymerization of 11-aminoundecanoic acid.

However, conventional polyamide compounds obtained by polymerization of ε-caprolactam, dicarboxylic acid and diamine, and 11-aminoundecane may not have sufficient properties.

S. Chatti, M. Bortolussi, A. Loupy, J. C. Blais, D. Bogdal, M. Majdoub. Eur. Polym. J. 38, 1851 (2002). S. Chatti, H. R. Kricheldorf. G. Schwarz. J. Polym. Sci. Part A: Polym. Chem. 44, 3616 (2006). C. -H. Lee, H. Takagi, H. Okamoto, M. Kato. J. Appl. Polym. Sci. 127, 530 (2013).

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyamide compound having better properties than conventional polyamide compounds.

The present inventors have developed a novel polyamide compound as a result of intensive research in view of the above-mentioned prior art.
And we have found the unexpected fact that this novel polyamide compound has excellent properties not found in conventional polyamide compounds. The present invention has been made based on this finding.

（ｘは６〜１２の整数を示し、ｙは８〜１８の整数を示す。）

（Ｂは、上記置換基の群から選ばれるいずれかを表す。） That is, the invention according to claim 1 is
It contains a dicarboxylic acid unit represented by the following general formula (1), a diamine unit represented by the following general formula (2), and a diamine unit represented by the following general formula (3) .
A polyamide compound having an elastomeric property, characterized in that the molar ratio of the diamine unit represented by the general formula (2): the diamine unit represented by the general formula (3) is 90:10 to 10:90. The gist is that there is.

(X indicates an integer of 6 to 12, and y indicates an integer of 8 to 18.)

(B represents any of the above groups of substituents.)

The invention according to claim 2
In the notched Charpy test, which is performed by adding a notch to a JIS K7110 type 1 test piece in accordance with JIS K7111.
The Charpy impact strength is 80 kJ / m ² or more, or
The polyamide compound according to claim 1, wherein the polyamide compound is not destroyed.

The invention according to claim 3
The polyamide compound according to claim 1 or 2, wherein the tensile fracture strain measured under the condition of a tensile speed of 1 mm / min with a 5A type test piece prepared according to JIS K7162 is 100 to 300%.

The polyamide compound of the present invention has elastomeric properties.

The matters shown here are for exemplifying and exemplifying embodiments of the present invention, and are considered to be the most effective and effortless explanations for understanding the principles and conceptual features of the present invention. It is stated for the purpose of providing what seems to be. In this regard, it is not intended to show structural details of the invention beyond a certain degree necessary for a fundamental understanding of the invention, and some embodiments of the invention are provided by description in conjunction with the drawings. It is intended to clarify to those skilled in the art how it is actually realized.

（ｘは６〜１２の整数を示し、ｙは８〜１８の整数を示す。
ｘは８〜１０の整数であることが好ましい。
ｙは９〜１３の整数であることが好ましい。）

（Ｂは、上記置換基の群から選ばれるいずれかを表す。） Hereinafter, the present invention will be described in detail.
[1] Polyamide compound The polyamide compound of the present invention is represented by a dicarboxylic acid unit represented by the following general formula (1), a diamine unit represented by the following general formula (2), and the following general formula (3). Diamine unit and.

(X indicates an integer of 6 to 12, and y indicates an integer of 8 to 18.
x is preferably an integer of 8-10.
y is preferably an integer of 9 to 13. )

(B represents any of the above groups of substituents.)

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

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

（ｘは６〜１２の整数を示し、ｙは８〜１８の整数を示す。） [1-1] Dicarboxylic acid unit The polyamide compound of the present invention contains a dicarboxylic acid unit represented by the following general formula (1) as described above.

(X indicates an integer of 6 to 12, and y indicates an integer of 8 to 18.)

As the dicarboxylic acid unit, the unit represented by the following formula (4) is particularly preferable. The unit represented by the formula (4) is derived from a plant, which is preferable from the viewpoint of preventing global warming and reducing resource risk.

When the total amount of dicarboxylic acid units in the polyamide compound of the present invention is 100 mol%, the content of the dicarboxylic acid units represented by the above general formula (1) is not particularly limited. The dicarboxylic acid unit represented by the general formula (1) is preferably contained in an amount of 30 to 100 mol%, more preferably 50 to 100 mol%, and particularly preferably 70 to 100 mol%. This is because the elastomeric properties are good when the content of the dicarboxylic acid unit represented by the general formula (1) is within this range.

The compound that can constitute a dicarboxylic acid unit other than the dicarboxylic acid unit represented by the general formula (1) is not particularly limited.
For example, specific examples of the dicarboxylic acid compound include carbons such as oxalic acid, malonic acid, fumaric acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. A dimeric acid dicarboxylic acid (dimeric acid) having 14 to 48 carbon atoms, which is a dimerization of an unsaturated fatty acid obtained by distilling a linear aliphatic dicarboxylic acid having a number of 2 to 25 or a triglyceride, and hydrogenated products thereof. An aliphatic dicarboxylic acid such as (hydrogenated dimeric acid), an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, and terephthalic acid, isophthalic acid, 1,3-benzenediacetic acid, 1,4-benzenedi. Examples thereof include aromatic dicarboxylic acids such as acetic acid. Moreover, you may use the derivative of these dicarboxylic acid compounds. Examples of the derivative include a carboxylic acid halide and the like. These can be used alone or in combination of two or more.
When the total amount of dicarboxylic acid units in the polyamide compound of the present invention is 100 mol%, the content of dicarboxylic acid units other than the dicarboxylic acid represented by the above general formula (1) is not particularly limited. The content of the dicarboxylic acid unit other than the dicarboxylic acid represented by the general formula (1) is preferably less than 50 mol%, more preferably less than 20 mol%, and more preferably less than 10 mol%. Especially preferable. This is because the elastomer properties are good when the content of the dicarboxylic acid unit other than the dicarboxylic acid unit represented by the general formula (1) is within this range.

（Ｂは、上記置換基の群から選ばれるいずれかを表す。） [1-2] Diamine Unit The diamine unit in the polyamide compound of the present invention includes at least a diamine unit represented by the general formula (2) and a diamine unit represented by the general formula (3).

(B represents any of the above groups of substituents.)

（Ｍ−１）

（Ｍ−２）

（Ｍ−３）

（Ｍ−４） Preferable combinations of the compound that can form the diamine unit represented by the general formula (2) and the compound that can form the diamine unit represented by the general formula (3) include, for example, the following combinations.

(M-1)

(M-2)

(M-3)

(M-4)

In the present invention, in addition to the diamine unit represented by the general formula (2), the diamine unit represented by the general formula (3) is included. It is preferable that the total of 100 mol% of the diamine units in the polyamide compound contains 50 to 100 mol% of the total of the diamine units represented by the general formula (2) and the diamine units represented by the general formula (3). , 60 to 100 mol% is more preferable, and 70 to 100 mol% is particularly preferable. This is because the elastomer properties are good when it is within this range.
The molar ratio of the diamine unit represented by the general formula (2): the diamine unit represented by the general formula (3) is not particularly limited. Diamine units represented by the general formula (2): the molar ratio of the diamine unit represented by the general formula (3) is 90: 10 to 10: 90 der is, 80: 20 to 20: it is 80 preferable.

A repeating unit consisting of a dicarboxylic acid unit represented by the general formula (1) and a diamine unit represented by the general formula (2), and a dicarboxylic acid unit represented by the general formula (1) and a general formula (3). The repeating unit consisting of the diamine unit to be formed may be randomly present in the polyamide compound.
Further, a repeating unit composed of a dicarboxylic acid unit represented by the general formula (1) and a diamine unit represented by the general formula (2), and a dicarboxylic acid unit represented by the general formula (1) and the general formula (3). The repeating unit composed of the diamine unit represented by is may be present in the polyamide compound in the form of blocks. That is, in the case of this block shape, a block in which only repeating units consisting of a dicarboxylic acid unit represented by the general formula (1) and a diamine unit represented by the general formula (2) are gathered, and a general formula (1). ), And the diamine unit represented by the general formula (3), and only the repeating unit is gathered. Then, in the polyamide compound having these blocks, the property of the polyamide compound consisting only of the repeating unit consisting of the dicarboxylic acid unit represented by the general formula (1) and the diamine unit represented by the general formula (2), and the general formula. It has the properties of a polyamide compound consisting only of a repeating unit consisting of a dicarboxylic acid unit represented by (1) and a diamine unit represented by the general formula (3).

The compound that can constitute a diamine unit other than the diamine unit represented by the general formulas (2) and (3) is not particularly limited.
For example, examples of diamines other than the diamine units represented by the general formulas (2) and (3) include known aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes.

Examples of the aliphatic diamine that can constitute a diamine unit other than the diamine unit represented by the general formulas (2) and (3) include 1,1-methoxylylenediamine, 1,3-propanediamine, and pentamethylenediamine. be able to.
Examples of the alicyclic diamine include 4,4'-methylenebis (cyclohexylamine) and 1,3-bis (aminomethyl) cyclohexane.
As aromatic diamines, for example, 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-phenylenediisopropyridene) 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) -benzene, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4 -Bis- (4-aminophenyl) -piperazin, 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, cholestanoloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4 -Diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholesterol, 3,6-bis (4-Amino Phenoxy) cholesterol, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 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) piperazin-4-carboxylic acid, 4- (morpholin-4-yl) benzene-1,3 -Diamine, 1,3-bis (N- (4-aminophenyl) piperidinyl) propane, α-amino-ω-aminophenylalkylene and the like can be mentioned.
These can be used alone or in combination of two or more.

When the total amount of diamine units in the polyamide compound of the present invention is 100 mol%, the content of diamine units other than the diamines represented by the above general formulas (2) and (3) is not particularly limited. The content of the diamine unit other than the diamine represented by the general formulas (2) and (3) is preferably less than 50 mol%, more preferably less than 30 mol%, and less than 10 mol%. Is particularly preferable. This is because the elastomer properties are good when the content of diamine units other than the diamine units represented by the general formulas (2) and (3) is within this range.

[1-3] Degree of Polymerization of Polyamide Compound The degree of polymerization of the polyamide compound of the present invention is not particularly limited. Relative viscosities measured at 25 ° C. in a 1% concentrated sulfuric acid solution in the range 1.01 to 5.0, further in the range 1.01 to 5.0, especially in the range 2.0 to 4.0. Is preferable.
Regarding the relative viscosity, 1 g of the polyamide compound was dissolved in 100 mL of 96% sulfuric acid, and the drop time (t) measured at 25 ° C. with a Canon Fenceke type viscometer and the drop time of 96% sulfuric acid itself measured in the same manner ( It is a ratio of t ₀ ) and is expressed by the following equation.
Relative viscosity = t / t ₀

[1-4] Characteristics of Polyamide Compound The characteristic of the polyamide compound of the present invention is that it has high impact resistance. Another feature is high flexibility. Another feature is non-crystalline (transparency).
These features are not found in conventional polyamides obtained by polymerization of ε-caprolactam, dicarboxylic acid and diamine, and 11-aminoundecane.
The polyamide compound of the present invention uses a compound having a long chain (a dicarboxylic acid component that can constitute a dicarboxylic acid unit). Therefore, the polyamide compound has excellent water absorption resistance because the content of hydrogen bonds in the molecule is reduced.
Further, if the diamine unit has an aromatic ring, this portion functions as a hard segment. On the other hand, the − (CH ₂ ) _y − portion of the dicarboxylic acid unit functions as a soft segment that imparts soft properties. Therefore, in the polyamide compound having an aromatic ring in the diamine unit, the soft segment and the hard segment are linked by an amide bond. Therefore, this polyamide compound becomes a resin having a hydrophobic structure, excellent elongation characteristics due to the flexible alkyl chain of the soft segment, and having a rigid portion due to the aromatic ring of the hard segment.

（ｘは６〜１２の整数を示し、ｙは８〜１８の整数を示す。） [2] Method for Producing Polyamide Compound The method for producing the polyamide compound of the present invention is not particularly limited. Examples of the production method include a method of reacting a dicarboxylic acid compound having a structure represented by the following general formula with a diamine compound.

(X indicates an integer of 6 to 12, and y indicates an integer of 8 to 18.)

Here, 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 replaced with another heteroatom (an atom other than carbon, hydrogen, or metal) can also be used. Examples of the carboxylic acid derivative include an acyl halide (acid halide) in which the hydroxyl group replaces the halogen.

The polyamide compound of the present invention can be produced by polycondensing a diamine component capable of constituting a diamine unit and a dicarboxylic acid component capable of constituting a dicarboxylic acid unit. The degree of polymerization can be controlled by adjusting the polycondensation conditions and the like.
The method for producing the polyamide compound is not particularly limited as described above. Specific examples of the method for producing a polyamide compound include (1) a method using an acid or a base catalyst, (2) a method of activating a carboxylic acid, (3) a method using transesterification, and (4). A method using a condensing agent or the like is preferably used. Here, as a suitable production method, a method for producing a polyamide compound using an acid chloride in which a carboxylic acid is activated is illustrated.

For example, the polyamide compound can be produced according to the following production scheme. In this method, a dicarboxylic acid is activated to form an acid chloride, and the acid chloride and a diamine are reacted to form a polyamide compound. In addition, since the polyamide compound of the present invention may use a plant-derived raw material, it may also be referred to as a biopolymer or a biopolyamide in the present specification.

When a dicarboxylic acid is activated to form an acid chloride and then reacted with a diamine, a polyamide compound can be efficiently produced.

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

When polymerizing by a dehydrohalogenation reaction by the reaction of 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 in the range of −10 ° C. to 100 ° C.
The reaction solvent is not particularly limited, and a known solvent can be widely applied. For example, examples of the organic polar solvent as the reaction solvent 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 kinds. Further, if necessary, hydrogen chloride and metal halides, for example, lithium chloride, calcium chloride, potassium chloride and the like may be used in combination to improve the solubility.

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

Further, in the case of the polyamide compound of the present invention, in order to improve the properties, an addition method intended to block the polymer is also adopted, in which a part of diamine or acid chloride is reacted and then the remaining raw material is added. You can do it.

The polymerization reaction product (polyamide compound) thus obtained is accompanied by hydrogen halide, which is a by-product, and therefore requires neutralization. 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 and the like are preferably used. be able to. Further, such a neutralizing agent may be added alone as a powder, but it is preferable to use a neutralizing agent that has been pulverized and dispersed as a slurry in an organic solvent 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 the polyamide compound of the present invention is not particularly limited, and a known method is widely used. For example, a pressurized salt method, a normal pressure dropping method, a pressure dropping method, a reaction extrusion method and the like can be mentioned. Further, when the reaction temperature is as low as possible, yellowing and gelation of the polyamide compound can be suppressed, and a polyamide compound having stable properties can be obtained.

The pressurized salt method is a method of performing melt polycondensation under pressure using a nylon salt as a raw material. Specifically, a nylon salt aqueous solution containing a diamine component, a dicarboxylic acid component, and other components if necessary is prepared, the aqueous solution is concentrated, and then the temperature is raised under pressure to prepare condensed water. Polycondensate while removing. While gradually returning the inside of the can to normal pressure, the temperature of the polyamide compound was raised to about + 10 ° C. and held, and then the pressure was gradually reduced to 0.02 MPaG and held at the same temperature to continue polycondensation. To do. When a certain stirring torque is reached, the inside of the can is pressurized with nitrogen to about 0.3 MPaG to recover the polyamide compound.

In the normal pressure dropping method, the diamine component is continuously dropped into a mixture of the dicarboxylic acid component and, if necessary, other components heated and melted under normal pressure, and polycondensed while removing the condensed 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 produced polyamide compound.

In the pressurized dropping method, first, a dicarboxylic acid component and, if necessary, other components are charged into a polycondensation can, and each component is stirred and melt-mixed to prepare a mixture. Next, the diamine component is continuously added dropwise to the mixture while pressurizing the inside of the can to preferably about 0.3 to 0.4 MPaG, and polycondensation is carried out while removing the condensed 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 produced polyamide compound. When the set molar ratio is reached, the dropping of the diamine component is completed, the temperature inside the can is gradually returned to normal pressure, the temperature is raised to about + 10 ° C. While maintaining the temperature as it is, polycondensation is continued. When a certain stirring torque is reached, the inside of the can is pressurized with nitrogen to about 0.3 MPaG to recover the polyamide compound.
The reaction extrusion method is a method of incorporating into the skeleton of polyamide by an amide exchange reaction.

[3] Polyamide Composition Using Polyamide Compound The polyamide compound of the present invention contains a lubricant, a crystallization nucleating agent, an anti-whitening agent, a matting agent, a heat-resistant stabilizer, a weather-resistant stabilizer, and an ultraviolet absorber, depending on the application and performance. The polyamide composition may be prepared by adding additives such as an agent, a plasticizer, a flame retardant, an antistatic agent, an antioxidant, an antioxidant, and an impact resistance improving material. These additives can be added as needed as long as the effects of the present invention are not impaired. Further, the polyamide compound of the present invention may be mixed with various resins to obtain a polyamide composition, depending on the required use and performance.

[4] Applications of Polyamide Compound The polyamide compound of the present invention can be used for all applications requiring elastomeric properties.

Hereinafter, the present invention will be described in more detail with reference to Examples.

1. 1. Synthesis of polyamide compound <Example 1> (Synthesis of synthesis of PA ₁₀₀ BPE ₈₀ DPE ₂₀ )
The polyamide compound (PA ₁₀₀ BPE ₈₀ DPE ₂₀ ) was synthesized according to the following scheme (Note that Examples 2 to 6 were also synthesized according to the same scheme).

Specifically, in a separable flask (500 mL) under a nitrogen atmosphere, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BPE) (19.8 g, 47.4 mmol), 4, Add 4'-diaminodiphenyl ether (DPE) (2.37 g, 11.8 mmol) and DMAc (170 mL), stir at room temperature for a while using a mechanical stirrer, add triethylamine (18.6 mL, 133.2 mmol), and then at room temperature for 5 minutes. Stirred. Then, acid chloride (40.0 g, 59.2 mmol) was dissolved in DMAc (50 mL), added dropwise, and reacted at room temperature for 4 hours. After completion of the reaction, the product was reprecipitated with water, purified, and washed with water and methanol. The product was vacuum dried (95 ° C., 8 hours). White fibrous, yield: 60.0 g. FT-IR (ATR, cm ^-1 ): 3277.4 (NH, amide), 2922.6, 2850.3, 1653.7 (C = O, carbonyl), 1601.6, 1533.1, 1493.6, 1461.8, 1405.9, 1226.5, 1170.6, 827.3, 719.3, 503.3 ..

The chemical formula of the diamine used in this example is shown below.

<Example 2> (Synthesis of PA ₁₀₀ BPE ₈₀ NB ₂₀ )
2,2-bis [4- (4-aminophenoxy) phenyl] propane (BPE) (24.2g, 57.8 mmol ), bis amino methyl norbornene (NB) (2.23 g, 14.45 mmol) and DMAc (170 mL), triethylamine ( The synthesis was carried out in the same manner as for PA ₁₀₀ BPE ₈₀ DPE ₂₀ except for 22.8 mL, 162.5 mmol), acid chloride (48.8 g, 72.24 mmol) and DMAc (50 mL). White fibrous, yield: 72.0 g. FT-IR (ATR, cm ^-1 ): 3281.4 (NH, amide), 2918.7, 2850.3, 1653.7 (C = O, carbonyl), 1601.6, 1538.0, 1497.5, 1461.8, 1409.7, 1226.5, 1170.6, 827.3, 719.3, 508.2 ..

The chemical formula of the diamine used in this example is shown below.

<Example 3> (Synthesis of PA ₁₀₀ BPE ₆₀ NB ₄₀ )
2,2-bis [4- (4-aminophenoxy) phenyl] propane (BPE) (15.73g, 37.57 mmol ), bis amino methyl norbornene (NB) (3.86 g, 25.05 mmol) and DMAc (170 mL), triethylamine ( The same procedure as for the synthesis of PA ₁₀₀ BPE ₈₀ DPE ₂₀ was carried out except for 19.7 mL, 140.9 mmol), acid chloride (42.3 g, 62.62 mmol) and DMAc (50 mL). White fibrous, yield: 58.0g. FT-IR (ATR, cm ^-1 ): 3277.4 (NH, amide), 2918.7, 2850.3, 1653.7 (C = O, carbonyl), 1538.0, 1497.5, 1461.8, 1230.4, 1170.6, 827.3, 719.3, 512.0.

The chemical formula of the diamine used in this example is shown below.

<Example 4> (Synthesis of PA ₁₀₀ BPE ₇₅ DPM ₂₅ )
2,2-Bis [4- (4-aminophenoxy) phenyl] Propane (BPE) (18.83 g, 44.97 mmol), 4,4'-Diaminodiphenyl methane, DPM) (3.03 g, The synthesis was carried out in the same manner as for PA ₁₀₀ BPE ₈₀ DPE ₂₀ except for 14.99 mmol), DMAc (170 mL), triethylamine (16.8 mL, 119.9 mmol), acid chloride (40.5 g, 59.96 mmol) and DMAc (50 mL). White fibrous, yield: 68.0g. FT-IR (ATR, cm ^-1 ): 3285.1 (NH, amide), 2922.6, 2850.3, 1657.5 (C = O, carbonyl), 1601.6, 1493.6, 1461.8, 1413.6, 1226.5, 1174.4, 831.2, 719.3, 508.2.

The chemical formula of the diamine used in this example is shown below.

<Example 5> (Synthesis of PA ₁₀₀ BPE ₈₀ PD ₂₀ )
2,2-bis [4- (4-aminophenoxy) phenyl] propane (BPE) (21.52 g, 51.4 mmol), p-phenylenediamine (PD) (1.4 g, 12.85 mmol) and DMAc (170 mL), triethylamine The same procedure as for the synthesis of PA ₁₀₀ BPE ₈₀ DPE ₂₀ was carried out except for (20.2 mL, 144.6 mmol), acid chloride (43.4 g, 64.25 mmol) and DMAc (50 mL). White fibrous, yield: 68.0g. FT-IR (ATR, cm ^-1 ): 3285.1 (NH, amide), 2922.6, 2850.3, 1657.5 (C = O, carbonyl), 1605.4, 1497.5, 1461.8, 1402.0, 1226.5, 1174.4, 1010.5, 835.0, 719.3, 512.0 ..

The chemical formula of the diamine used in this example is shown below.

<Example 6> (Synthesis of PA ₁₀₀ BPE ₇₀ DPM ₃₀ )
2,2-Bis [4- (4-aminophenoxy) phenyl] Propane (BPE) (17.24g, 42.0 mmol), 4,4'-Diaminodiphenyl methane, DPM) (3.57g, The synthesis was carried out in the same manner as for PA ₁₀₀ BPE ₈₀ DPE ₂₀ except for 18.08 mmol), DMAc (170 mL), triethylamine (18.9 mL, 135.0 mmol), acid chloride (40.53 g, 60.0 mmol) and DMAc (60 mL). White fibrous, yield: 60.0 g. FT-IR (ATR, cm ^-1 ): 3290.0 (NH, amide), 2918.7, 2850.3, 1653.7 (C = O, carbonyl), 1601.6, 1493.6, 1457.9, 1409.7, 1226.5, 1170.6, 831.2, 719.3, 512.0.

The chemical formula of the diamine used in this example is shown below.

2. Mechanical property evaluation 2-1. Preparation of test pieces For the preparation of test pieces by injection molding, each polyamide compound was scaled up (scale-up) and collected samples (about 500 g) were used. Using Mini Test Press-10 manufactured by Toyoseiki Co., Ltd., it was formed into a flat plate and cut into pellets. Using pellets, test pieces were prepared by an injection molding machine (small electric injection molding machine SE18DUZ, manufactured by Sumitomo Heavy Industries, Ltd.). The molding conditions were a resin temperature of 140 to 200 ° C. and a mold temperature of 14 to 18 ° C. As a test piece, a JIS K 7162 (t 2 mm) multipurpose test piece 5A type (dumbbell shape), width 10 mm x length 80 mm x thickness 4 mm test piece (strip shape) was molded. The dumbbell-shaped test piece was used for the tensile test. The strip-shaped test piece was processed into a K7110 type 1 test piece and used for the Charpy impact test and the bending test.

2-2. Tensile test
Tensile properties were subjected to a tensile test to evaluate yield stress (tensile strength), tensile modulus, and elongation at break. As the test piece, JIS K 7162 multipurpose test piece 5A type (dumbbell-shaped) was used. In the measurement, the width and thickness of the test piece were measured and used. An AGI-50kN type testing machine manufactured by Shimadzu Corporation was used for the measurement. The measurement conditions were a tensile speed of 1 mm / min, a tensile load of 50 kN, and a measurement temperature of 23 ° C.

2-3. Bending test For bending characteristics, a bending test was performed to evaluate the flexural modulus and flexural strength. The test piece is 2-1. The type 1 test piece of K7110 produced in the above was evaluated in accordance with K7171. In the test, the width and thickness of the test piece were measured. An AGS-X 10kNX 5 tester manufactured by Shimadzu Corporation was used for the measurement. The measurement conditions were a test speed of 2 mm / min, a maximum load of 10 kN, and a measurement temperature of 23 ° C.

2-4. Charpy impact test The impact characteristics were evaluated by performing a notched Charpy test and determining the Charpy impact value. The test piece is 2-1. The type 1 test piece of K7110 produced in the above was produced with a notch in accordance with K7111. In the test, the width and thickness of the test piece were measured. A Charpy impact tester and DG-UB manufactured by Toyo Seiki Seisakusho Co., Ltd. were used for the measurement.

2-5. Results of Mechanical Property Evaluation Table 1 shows the results of mechanical property evaluation of the polyamide compound of the example.

It was confirmed that the polyamide compound of the example was a resin having elongation, very high impact resistance, and flexibility.
Further, it was confirmed that the polyamide compound of the example had the characteristics of an elastomer and was a soft and tenacious resin.
It was found that the polyamide compound of the example had a higher tensile strength than the conventional olefin-based thermoplastic elastomer (TPO).

3. 3. Dynamic viscoelasticity test 3-1. Measurement method The storage elastic modulus of the polyamide compound and the temperature dependence of tan δ were determined by dynamic viscoelasticity measurement. The width and thickness of the sample were measured and used for the measurement. The dynamic viscoelasticity measuring device Rheogel-E4000 manufactured by UBM Co., Ltd. was used for the measurement, and the measurement conditions were as follows.
Measurement temperature range: -100 to 100 ° C., heating rate: 4 ° C. / min, measurement frequency: 5 Hz, strain (epsilon) :( storage ^{modulus)> 10 8 Pa: 0.05%} . The test piece was formed by preliminarily vacuum-drying a polyamide compound using a hot press. A test piece having a width of 5 mm, a thickness of 2.0 mm, and a length of 30 mm was prepared, and this was used for dynamic viscoelasticity measurement.

3-2. Measurement results Table 2 shows the storage elastic modulus and tan δ of the polyamide compound determined by dynamic viscoelasticity measurement.

Table 2 shows the storage elastic modulus at −50 ° C. and the glass transition temperature obtained from the peak of tan δ determined by dynamic viscoelasticity measurement.
When stress is applied to a viscoelastic body to deform it, most of the applied force is stored as energy for internal deformation and becomes the driving force for restoration when stress is removed, but part of it is the friction of internal molecular movement due to strain. Is consumed for and eventually turns into heat. The value indicating the magnitude of the internal friction is tan δ. If this tan δ is large, the transfer coefficient is small and the energy absorption rate is large.
In Examples 2, 3, 4, 5, and 6, it was confirmed that tan δ was relatively large and the energy absorption rate was high. In Examples 2, 3, 4, 5, and 6, it was confirmed that the glass transition temperature was relatively large and the heat resistance was excellent.
The shock absorption rate (energy absorption rate) can be estimated by dynamic viscoelasticity evaluation. Generally, the higher the tan δ, the higher the energy absorption rate. Impact absorption rate of natural rubber (25%, tan δ = 0.1), impact absorption rate of silicon rubber (28%, tan δ = 0.5), impact absorption rate of butyl rubber (41%, tan δ = 1.0), The impact absorption rate of the flexible polyurethane (58%, tan δ = 1.4), and referring to these values, it is presumed that the polyamide of the example has a high impact absorption rate.

The test piece obtained by molding was transparent, and it was confirmed that the polyamide compound of the present invention was a non-crystalline resin.

<Effect of Examples>
The polyamide compound of the example of the present invention has a low content of hydrogen bonds in the molecule. A polyamide compound is a resin in which a soft segment and a hard segment are connected by an amide bond and have a hydrophobic structure, a flexible alkyl chain, elongation characteristics, and an tonic moiety. Polyamide compounds are characterized by [1] high impact resistance, [2] high flexibility, and [3] non-crystalline (transparency).

The above examples are for illustration purposes only and are not to be construed as limiting the invention. Although the present invention has been described with reference to typical embodiments, the language used in the description and illustration of the invention is understood to be descriptive and exemplary rather than restrictive. As detailed herein, modifications can be made within the scope of the appended claims without departing from the scope or nature of the invention in that form. Although specific structures, materials and examples have been referred to herein in detail of the invention, it is not intended to limit the invention to the disclosures herein, rather the invention is claimed in the accompanying 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 or modifications can be made within the scope of the claims of the present invention.

The polyamide compound of the present invention can be used in any application that requires elastomeric properties. For example, tires, footwear, hoses, belts, air springs, rubberized cloth, exercise equipment, floor tiles, battery cases, belts, anti-vibration rubber, plastic modifiers, wire coverings, conveyor belts, window gaskets, adhesives. , Paints, inner tubes of tires, curing bags, oil seals, gaskets, printing rolls, packings, seals, diaphragms, pump parts, sealants, coking agents, adhesives and the like.

Claims (3)

It contains a dicarboxylic acid unit represented by the following general formula (1), a diamine unit represented by the following general formula (2), and a diamine unit represented by the following general formula (3) .
A polyamide compound having an elastomeric property, wherein the molar ratio of the diamine unit represented by the general formula (2) to the diamine unit represented by the general formula (3) is 90:10 to 10:90 .

(X indicates an integer of 6 to 12, and y indicates an integer of 8 to 18.)

(B represents any of the above groups of substituents.) In the notched Charpy test, which is performed by adding a notch to a JIS K7110 type 1 test piece in accordance with JIS K7111.
The Charpy impact strength is 80 kJ / m ² or more, or
The polyamide compound according to claim 1, wherein the polyamide compound is not destroyed. The polyamide compound according to claim 1 or 2, wherein the tensile fracture strain measured under the condition of a tensile speed of 1 mm / min with a 5A type test piece prepared according to JIS K7162 is 100 to 300%.