KR101766401B1 - Method for preparing polyamide and polyamide prepared by using the same - Google Patents

Abstract

상기 화학식 1에 있어서, A^-, X 및 Y는 명세서 중에서 정의한 바와 같다.In the present invention, a compound represented by the following general formula (1): Diamines and diacids, or nylon salts; And an amino acid or a lactam to produce a polyamide having a high moisture content due to a high amorphous property, and a polyamide prepared by using the same.
[Chemical Formula 1]

In Formula 1, A ^- , X and Y are as defined in the specification.

Description

METHOD FOR PREPARING POLYAMIDE AND POLYAMIDE PREPARED BY USING THE SAME [0002]

The present invention relates to a process for the preparation of polyamides having a high moisture content due to their high amorphous nature and to the polyamides produced by using them.

Nylon 6 fiber has advantages such as excellent stiffness, elastic recovery rate and dyeability, but most of the synthetic fibers including nylon 6 fibers have a low water absorption property. The cotton, which is a natural fiber, It has a good touch, but it has a drawback that it is very slow in moisture drying rate, extremely low in UV blocking property, and expensive in price.

Nylon 4 fiber developed to replace it has excellent water absorption (moisture content) similar to that of natural fiber cotton due to increased hydrophilicity due to a large number of carbon atoms in nylon 6 in the repeating unit, Similar level. However, nylon 4 has a melting point of 265 캜, higher than nylon 6, and a pyrolysis temperature of 260 캜. As a result, when a spinning process in which fibers are melt-spun at a temperature higher than the melting point in the production of fibers using nylon 4 is used, nylon 4 is thermally decomposed before reaching the melting point, so that fiber formation by continuous spinning is impossible.

Accordingly, it is urgently required to develop a polyamide having high water absorbability and excellent radiation-processability and heat resistance.

Japanese Patent Laid-Open No. 2001-348427 (published Dec. 18, 2001) Japanese Patent Application Laid-Open No. 2009-256610 (published on November 5, 2009)

It is an object of the present invention to provide a method for producing a polyamide having a high moisture content due to high amorphousness and a polyamide produced using the method.

It is a further object of the present invention to provide novel intermediates useful in the preparation of said polyamides.

According to an embodiment of the present invention, there is provided a compound represented by Formula 1 below: Diamines and diacids, or nylon salts; And reacting an amino acid or a lactam, comprising the steps of:

[Chemical Formula 1]

In the above Formula 1, A ^- is ^{F -, Cl -, Br -} , I -, CH 3 COO -, SO 4 H - , and SO ₃ H ^- is an anion selected from the group consisting of and X, and Y are Each independently represents an alkylene group having 1 to 6 carbon atoms.

The method may further include a step of reacting a diamine of Formula 2 with a diacid of Formula 3 to prepare the compound of Formula 1.

(2)

(3)

In the above Formula 2 and 3, A ^- it is ^{F -, Cl -, Br -} , I -, CH 3 COO -, SO 4 H - , and SO ₃ H ^- is an anion selected from the group consisting of and X and Y Are each independently an alkylene group having 1 to 6 carbon atoms.

The diacid of Formula 3 may be prepared by acid treatment of glutamic acid.

The diacid of Formula 3 may be a halide, an acetate salt, or a sulfonate of glutamic acid.

Further, in the above production method, the nylon salt may be a compound having a structure represented by the following formula (5)

[Chemical Formula 5]

In Formula 5, Z and W each independently represent an alkylene group having 1 to 6 carbon atoms.

The nylon salt may be a compound of the following formula (5a).

[Chemical Formula 5a]

In the above production method, the amino acid may be a compound of the following formula (8-1) and the lactam may be a compound of the following formula (8-2).

[Formula 8-1]

[Formula 8-2]

In Formulas (8-1) and (8-2), V and W each independently represent an alkylene group having 2 to 5 carbon atoms.

And the amino acid is 6-aminocaproic acid, and the lactam may be? -Caprolactam.

Also, the compound of formula (1) above; Diamines and diacids, or nylon salts; And the reaction of an amino acid or a lactam can be carried out by heat treatment at 200 to 295 ° C.

According to another embodiment of the present invention, there is provided a compound represented by the following general formula (2) and (3): Diamines and diacids, or nylon salts; And reacting the polyamide with an amino acid or a lactam.

(2)

(3)

In the above Formula 2 and 3, A ^- it is ^{F -, Cl -, Br -} , I -, CH 3 COO -, SO 4 H - , and SO ₃ H ^- is an anion selected from the group consisting of and X and Y Are each independently an alkylene group having 1 to 6 carbon atoms.

According to another embodiment of the present invention, there is provided a polyamide produced by the above production method.

The polyamide may have a structure represented by the following formula (9).

[Chemical Formula 9]

In Formula 9, A ^- is ^{F -, Cl -, Br -} , I -, CH 3 COO -, SO 4 H - , and SO ₃ H ^- is an anion selected from the group consisting of, X, Y, Z and W M and n are numbers representing the mole ratios of the respective repeating units and satisfy the condition of 1 + m + n = 1, where m is an integer of 1 to 6, 0 < l < 1, 0 < m <

The polyamide may have an average number of carbon atoms per amide group contained in the polyamide of 2 to 5.63, a melting point of 160 to 209.2 占 폚, and a heat of fusion (-? H) of 10 to 44.15 J / g.

According to another embodiment of the present invention, an alkali metal salt or an organic cation salt of an amino acid; Diamines and diacids, or nylon salts; And reacting the polyamide with an amino acid or a lactam.

The alkali metal salt of the amino acid may be a compound having any one structure selected from the group consisting of the following formulas (21-1) to (21-3).

[Formula 21-1]

[Formula 21-2]

[Formula 21-3]

In Formulas (21-1) to (21-3), A is an alkali metal ion or an organic cation. The alkali metal ions are Li ^+, Na ⁺ or K ⁺ and the like, wherein the organic cation is a quaternary ammonium (NR ₄ ^+), imidazolium ^{_{(C 3 H 5 N 2 +}} ) or pyridinium nium (C ₅ H ₆ N ₁ ⁺ ), and the like. Here, R is hydrogen or an alkyl group having 1 to 4 carbon atoms.

And X is an alkylene group having 1 to 6 carbon atoms.

Specifically, the alkali metal salt of the amino acid may be monosodium glutamic acid or L-glutamic acid monopotassium salt.

The nylon salt may be a compound of the following formula (22).

[Chemical Formula 22]

In Formula 22, Y and Z are each independently an alkylene group having 1 to 6 carbon atoms.

The nylon salt may be a compound of the following formula (22a).

[Chemical Formula 22a]

Wherein the amino acid is a compound of the following formula 25-1 and the lactam is a compound of the following formula 25-2.

[Formula 25-1]

[Formula 25-2]

In Formulas (25-1) and (25-2), V and W are each independently an alkylene group having 2 to 5 carbon atoms.

The amino acid may be 6-aminocaproic acid, and the lactam may be? -Caprolactam.

The reaction of an alkali metal salt or an organic cation salt of the amino acid, a diamine with a diacid or a nylon salt, and an amino acid or a lactam is carried out at a temperature of 200 to 260 ° C . &Lt; / RTI &gt;

According to another embodiment of the present invention, there is provided a polyamide produced by the above production method.

The polyamide may have a structure represented by the following formula (26).

(26)

In the above formula (26), A is an alkali metal ion or an organic cation, X, Y and Z are each independently an alkylene group having 1 to 6 carbon atoms, W is an alkylene group having 2 to 5 carbon atoms, n is a number representing the molar ratio of each repeating unit, and 0 <1 <1, 0 <m <1 and 0 <n <1 under the condition of 1 + m + n = 1.

The polyamide may have an average number of carbon atoms per amide group contained in the polyamide of 2 to 5.63, a melting point of 160 to 209.2 占 폚, and a heat of fusion (-? H) of 10 to 44.15 J / g.

Other details of the embodiments of the present invention are included in the following detailed description.

According to the process for producing a polyamide according to the present invention, a polyamide having a high moisture content due to high amorphous property and having excellent spinning processability and heat resistance can be produced.

Figures 1 to 12 show the differential scanning calorimetry (DSC) values for the polyamides prepared in Examples 1-1 to 1-4, Examples 2-1 to 2-4, and Examples 3-1 to 3-4, Fig.

The present invention is capable of various modifications and various embodiments and is intended to illustrate and describe the specific embodiments in detail. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

The present invention is characterized by improving the amorphousness and water content of polyamide by using an ionic monomer having enhanced hydrophilicity in the production of polyamide.

That is, the process for preparing polyamide according to one embodiment of the present invention comprises: Diamines and diacids, or nylon salts; And reacting an amino acid or a lactam.

[Chemical Formula 1]

In the above Formula 1, A ^- is ^{F -, Cl -, Br -} , I -, CH 3 COO -, SO 4 H - , and SO ₃ H ^- is an anion selected from the group consisting of and X and Y are each And is independently an alkylene group having 1 to 6 carbon atoms.

In the above process, the compound of Formula 1 may be prepared by reacting a diamine of Formula 2 with a diacid of Formula 3 below.

(2)

(3)

The polyamide may be prepared by directly reacting the compound of Formula 2 and Formula 3 with a diamine, a diacid, or a nylon salt; And may be reacted with an amino acid or lactam.

In the above Formula 2 and 3, A ^- it is ^{F -, Cl -, Br -} , I -, CH 3 COO -, SO 4 H - , and SO ₃ H ^- is an anion selected from the group consisting of and X and Y Are each independently an alkylene group having 1 to 6 carbon atoms.

The diamine compounds of formula (2) that can be used to prepare the compounds of formula (1) include 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane or 1,6-diaminohexane. Of these, 1,4-diaminobutane may be preferable.

The diacid of Formula 3, which is capable of reacting with the diamine of Formula 2, is prepared by acid treatment of amino acids. Specifically, the amino acid of Formula 4 is reacted with hydrogen chloride (HCl), hydrogen fluoride (HF), hydrogen bromide HBr) or hydrogen iodide (HI), or by treatment with an acid such as sulfuric acid.

[Chemical Formula 4]

In Formula 4, Y is an alkylene group having 1 to 6 carbon atoms.

More specifically, the diacid of Formula 3 may be prepared by various acid treatments of glutamic acid (4a) as an amino acid of Formula (4) as shown in Reaction Scheme 1 below. Reaction Scheme 1 is an example for illustrating the present invention, but the present invention is not limited thereto.

[Reaction Scheme 1]

The following Scheme 2 shows a process for preparing a compound of Formula 1 by reacting the diacid of Formula 3 with the diacid compound of Formula 2 and 1,4-diaminobutane 2a. Reaction Scheme 2 is an example for illustrating the present invention, but the present invention is not limited thereto.

[Reaction Scheme 2]

As shown in Reaction Scheme 2, the compound of Chemical Formula 1 may be prepared by reacting a compound of Chemical Formula 3 containing an intramolecular ionic bond with a diamine compound. The reaction may be carried out in an organic solvent such as ethanol.

Meanwhile, in the process for producing polyamide according to the present invention, the nylon salt is prepared by a reaction between a diamine and a carboxylic acid, specifically, a compound represented by the following formula (5)

[Chemical Formula 5]

In Formula 5, Z and W are each independently an alkylene group having 1 to 6 carbon atoms.

The nylon salt of formula (5) may be prepared by reacting a diamine of formula (6) with a dicarboxylic acid of formula (7).

[Chemical Formula 6]

(7)

In the above formulas (6) and (7), Z and W are the same as defined above.

More specifically, the diamine of formula (6) may be a 1,3-diaminopropane, 1,4-diaminobutane, 1,5- 1,5-diaminopentane, 1,6-diaminohexane, and the like. When considering the melt polymerization with a dicarboxylic acid, the 1,4-diaminopentane or 1,6- -Diaminobutane may be preferred.

The dicarboxylic acid of the above formula (7) may be adipic acid, glutaric acid, or succinic acid. Among them, adipic acid which does not cause decomposition at high temperatures or the generation of side reactants is preferable can do.

The reaction for preparing the nylon salt may be preferably carried out under a moisture condition. Specifically, it is preferable that the water content is in the range of 30 to 80% by weight. If the amount of water is less than 30% by weight, salt may not be uniformly produced, and the conductivity of the salt solution or salt dispersion may be high, which may be difficult to handle. On the other hand, when the amount of water exceeds 80% by weight, the process time is prolonged and the yield of polyamide is lowered.

More specifically, the nylon salt of Formula 5 may be a nylon 4,6 salt of Formula 5a.

[Chemical Formula 5a]

The polyamide may be prepared by directly adding a diamine of the formula (6) and a dicarboxylic acid of the formula (7) as a direct monomer instead of the nylon salt of the formula (5).

In addition, the amino acid usable for preparing polyamide may be a compound of the following formula (8-1).

[Formula 8-1]

In Formula (8-1), V is an alkylene group having 2 to 5 carbon atoms.

More specifically, the amino acid may be 3-aminoproanoic acid, 4-aminobutanoic acid or 6-aminocaproic acid, among which 6-amino Caproic acid may be preferred.

The lactam usable in the production of the polyamide may be a compound represented by the following formula (8-2).

[Formula 8-2]

In Formula (8-2), W is an alkylene group having 2 to 5 carbon atoms.

Specifically, the lactam may be 2-pyrrolidone,? -Caprolactam, or undecanolactam, laurolactam, or the like.

The smaller the carbon number in the polyamide, the higher the moisture content. Also, as the density of the amide groups in the polyamide increases, the melting point and moisture content increase, while the crystallinity increases, the moisture content decreases. Accordingly, it is preferable that the polyamide produced by the production method according to the present invention has an average number of carbon atoms of 2 to 5.63 per amide group contained in the polyamide to have high moisture content and amorphousness. In order to satisfy the above-mentioned conditions, the compound of formula (1), diamine and diacid or nylon salt, and amino acid or lactam lactam) is preferably selected.

Also, the compound of Formula 1 above; Diamines and diacids, or nylon salts; The reaction of an amino acid or a lactam may be preferably carried out by heat treatment at 200 to 295 ° C in consideration of improvement of reaction efficiency and shortening of reaction time. At this time, the heat treatment process may be performed by continuous multistage heat treatment at various temperatures within the above range.

Scheme 3 schematically illustrates the preparation of polyamides according to the process for preparing polyamides according to the invention. The following Reaction Scheme 3 is only an example for illustrating the present invention, but the present invention is not limited thereto.

[Reaction Scheme 3]

As shown in Reaction Scheme 3, the polyamide according to the present invention can be produced by reacting a compound (1a, 1b, 1c) of the formula (1) prepared by the reaction of a diacid and a diamine ₃ ⁺ Cl &lt; ^- &gt; and the like. The ionic bonds contained within the polyamide molecule can increase the amorphicity of the polyamide and improve the moisture content of the polyamide. As a result, the polyamide produced by the above production method can exhibit excellent spinnability and heat resistance.

Accordingly, according to another embodiment of the present invention, there is provided a polyamide produced by the above production method.

Specifically, the polyamide may include a repeating unit represented by the following formula (9).

[Chemical Formula 9]

In the above formula (9), the repeating unit l is a repeating unit derived from a compound of formula (I) produced by the die Acid and diamine reaction, repeating unit l in the A ^- is F ^-, Cl ^-, Br ^-, I ^{-, _{CH 3 COO -, SO 4 H}} - , and SO ₃ H ^-, and anions selected from the group consisting of, X and Y are each independently an alkylene group having 1 to 6 carbon atoms.

In the above formula (9), the repeating unit m is a repeating unit derived from the nylon salt of the above formula (2) which is a reactant prepared by the reaction of a diamine compound and a dicarboxylic acid. Z and W in the repeating unit m are each independently An alkylene group having 1 to 6 carbon atoms.

In the above formula (9), the repeating unit n is a repeating unit derived from an amino acid, and V in the repeating unit n is an alkylene group having 2 to 5 carbon atoms.

1, 0 < m < 1 and 0 < n < 1 at a condition of 1 + m + n = 1, . If the content of the repeating unit I in the polyamide is less than 0.01, the amorphous increasing effect is insignificant, and as a result, the moisture content in the polyamide may decrease. Therefore, it is more preferable that the repeating unit 1 is contained in a molar ratio of 0.01? L? 0.5 in consideration of the amorphous property and the water content improving effect of the polyamide.

In addition, the polyamide may have an average number of carbon atoms per amide group contained in the polyamide of 2 to 5.63, a melting point of 160 to 209.2 ° C, and a heat of fusion (-ΔH) of 10 to 44.15 J / g.

The polyamide may have a moisture content of 7% or more, or 7 to 11%.

A method for producing a polyamide according to another embodiment of the present invention comprises: reacting an alkali metal salt or an organic cation salt of an amino acid; Diamines and diacids, or nylon salts; And reacting an amino acid or a lactam.

In the above production method, the alkali metal salt of the amino acid may be a compound having any one structure selected from the group consisting of the following formulas (21-1) to (21-3):

[Formula 21-1]

[Formula 21-2]

[Formula 21-3]

In the general formula 21-1 to 21-3, A is an alkali metal ion or a quaternary ammonium, such as lithium, sodium, potassium (NR ₄ ^+), imidazolium ^{_{(C 3 H 5 N 2 +}} ), pyridinium nium (C ₅ H ₆ N ₁ ⁺ ), and X is an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, or a propylene group. Here, R is hydrogen or an alkyl group having 1 to 4 carbon atoms.

More specifically, the alkali metal salt of the amino acid may be monosodium glutamic acid of the following formula (21a) or L-glutamic acid monopotassium salt of the formula (21b).

[Chemical Formula 21a]

[Formula 21b]

The diamine, diacid, nylon salt, amino acid and lactam are the same as those described above, and thus a repetitive description thereof will be omitted.

An alkali metal salt or an organic cation salt of said amino acid; Diamines and diacids, or nylon salts; The reaction of an amino acid or a lactam may be preferably carried out by heat treatment at 200 to 295 ° C in consideration of improvement of reaction efficiency and shortening of reaction time. At this time, the heat treatment process may be performed by continuous multistage heat treatment at various temperatures within the above range.

As described above, according to another embodiment of the present invention, an alkali metal salt or an organic cation salt monomer to which an alkali metal ion or an organic cation is bound is used, wherein the alkali metal ion and the organic cation- Amide does not participate in the polymerization reaction and plays a role of increasing amorphousness and water content of the polyamide due to its specific structure. As a result, the polyamide produced by the above production method can exhibit excellent spinnability and heat resistance.

Accordingly, according to another embodiment of the present invention, a polyamide produced by the above production method is provided.

Specifically, the polyamide may include a repeating unit represented by the following formula (26).

(26)

In Formula 26, the repeating unit l is a repeated unit derived from an alkali metal salt or organic cation salt of the acid, the repeating unit l in the A is an alkali metal ion such as lithium, sodium, potassium, or quaternary ammonium (NR ₄ ⁺ ), Imidazolium (C ₃ H ₅ N ₂ ⁺ ), and pyridinium (C ₅ H ₆ N ₁ ⁺ ), and X is an alkylene group having 1 to 6 carbon atoms. Here, R is hydrogen or an alkyl group having 1 to 4 carbon atoms.

The repeating unit m in the formula (26) is a repeating unit derived from the nylon salt of the formula (22), which is a reactant prepared by the reaction of a diamine compound and a dicarboxylic acid. Y and Z in the repeating unit m are each independently An alkylene group having 1 to 6 carbon atoms.

In the above formula (26), the repeating unit n is a repeating unit derived from an amino acid, and W in the repeating unit n is an alkylene group having 2 to 5 carbon atoms.

1, 0 < m < 1 and 0 < n < 1 at a condition of 1 + m + n = 1, wherein l, m and n are numbers representing the molar ratio of each repeating unit. . If the content of the repeating unit I in the polyamide is less than 0.01, the amorphous increasing effect is insignificant, and as a result, the moisture content in the polyamide may decrease. Therefore, it is more preferable that the repeating unit 1 is contained in a molar ratio of 0.01? L? 0.5 in consideration of the amorphous property and the water content improving effect of the polyamide.

In addition, the polyamide may have an average number of carbon atoms per amide group contained in the polyamide of 2 to 5.63, a melting point of 160 to 209.2 ° C, and a heat of fusion (-ΔH) of 10 to 44.15 J / g.

The polyamide may have a moisture content of 7% or more, or 7 to 11%.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[ Manufacturing example : Preparation of compound of formula (1)

( Manufacturing example  One)

As shown in Reaction Scheme 4 below, 20 g of glutamic acid (i) was mixed with an aqueous hydrochloric acid solution having a concentration of 36% and reacted to prepare glutamic acid chloride (ii). The prepared glutamic acid chloride (ii) was reacted with 12 g of 1,4-diaminobutane (iii) in 800 ml of ethanol (EtOH) to prepare the compound (1a).

[Reaction Scheme 4]

( Manufacturing example  2)

As shown in Reaction Scheme 5 below, 20 g of glutamic acid (i) was mixed with a 48% aqueous solution of hydrogen bromide and reacted to prepare glutamic acid bromide (iv). The prepared glutamic acid bromide (iv) was reacted with 12 g of 1,4-diaminobutane (iii) and 800 ml of ethanol (EtOH) to prepare compound (1b).

[Reaction Scheme 5]

( Manufacturing example  3)

20 g of glutamic acid (i) was mixed with a 95% strength aqueous sulfuric acid solution and reacted as shown in Reaction Scheme 6 below to prepare glutamic acid sulfate (v). The prepared glutamic acid sulfate (v) was reacted with 12 g of 1,4-diaminobutane (iii) in 800 ml of ethanol (EtOH) to prepare a compound (1c) of the formula (1).

[Reaction Scheme 6]

( Manufacturing example  4)

A solution of 1,4-diaminobutane in which 42 g of 1,4-diaminobutane was dissolved in 535 ml of ethanol was added to an ethanolic solution of adipic acid prepared by dissolving 50 g of adipic acid in 633 ml of ethanol, To give a nylon 4,6-salt (5a).

[Chemical Formula 5a]

[ Example  One: Polyamide  Preparation of resin]

( Comparative Example  One)

The nylon 4,6 salt (5a) and 6-aminocaproic acid (vi) prepared in Preparation Example 4 were mixed at the ratios shown in Table 1, and then the mixture was heated at room temperature (25 ° C) And reacted in a nitrogen atmosphere to prepare a polyamide (nylon 46/6).

( Example  1-1)

The compound (1a) prepared in Preparation Example 1, the nylon 4,6 salt (5a) prepared in Preparation Example 4, and the 6-aminocaproic acid (vi) prepared in Preparation Example 4 were mixed at the ratios shown in Table 1 Then, the temperature was elevated at room temperature (25 ° C) and the reaction was carried out at 240 ° C for 2 hours under a nitrogen atmosphere to prepare polyamide (9a).

[Reaction Scheme 7]

( Example  1-2 to 1-4)

The compound (1a) prepared in Preparation Example 1, the nylon 4,6 salt (5a) prepared in Preparation Example 4, and the 6-aminocaproic acid (vi) prepared in Preparation Example 4 were used as ratios shown in Table 1 , The polyamide was produced in the same manner as in Example 1-1.

The compound (1a) of the formula (1)
(confiscation) Nylon 4,6 salt
(confiscation) 6-aminocaproic acid
(confiscation) The compound (1a) of the formula (1)
Molar ratio (mol%) Average carbon number
(dog) Comparative Example 1 0g 0.25 g
(0.001067) 0.25 g
(0.001906) 0 5.64 Example 1-1 0.02 g
(0.000109) 0.25 g
(0.001067) 0.25 g
(0.001906) 2.41 5.62 Examples 1-2 0.03 g
(0.000163) 0.25 g
(0.001067) 0.25 g
(0.001906) 3.58 5.61 Example 1-3 0.04 g
(0.000218) 0.25 g
(0.001067) 0.25 g
(0.001906) 4.72 5.6 Examples 1-4 0.05 g
(0.000272) 0.25 g
(0.001067) 0.25 g
(0.001906) 5.83 5.59

[ Test Example  One]

The polyamides prepared in Examples 1-1 to 1-4 and Comparative Example 1 were subjected to differential scanning calorimetry (DSC). The results are shown in Table 2 and Figs. 1-4.

The compound (1a) of the formula (1) The mole ratio (mol%) of the compound (1a) T _onset (占 폚) H (J / g) T _m (° C) Comparative Example 1 0g 0 167.7 -44.63 210.7 Example 1-1 0.02 g 2.41 149.5 -39.08 191.8 Examples 1-2 0.03 g 3.58 175.3 -44.15 209.2 Example 1-3 0.04 g 4.72 152.9 -41.01 198.1 Examples 1-4 0.05 g 5.83 155.3 -32.29 199.2

[ Example  2: Polyamide  Preparation of resin]

( Example  2-1)

Compound (1b) of Formula 1 prepared in Preparation Example 2, nylon 4,6 salt (5a) and 6-aminocaproic acid (vi) prepared in Preparation Example 4 were mixed in the ratios shown in Table 3 , Heated at room temperature (25 ° C), and reacted at 240 ° C for 2 hours under a nitrogen atmosphere to prepare polyamide (9b).

[Reaction Scheme 8]

( Example  2-2 to 2-4)

Except that the compound (1b) of the formula (1) prepared in Preparation Example 2, the nylon 4,6 salt (5a) prepared in Preparation Example 4 and the 6-aminocaproic acid (vi) Was used in the same manner as in Example 2-1 to prepare a polyamide.

The compound (1b) of the formula (1)
(confiscation) Nylon 4,6 salt
(confiscation) 6-aminocaproic acid
(confiscation) (1b) (mol%) of the formula (1) Average carbon number
(dog) Comparative Example 1 0g 0.25 g
(0.001067) 0.25
(0.001906) 0 5.64 Example 2-1 0.02 g
(6.32531E-05) 0.25 g
(0.001067) 0.25
(0.001906) 2.08 5.63 Example 2-2 0.03 g
(9.48797E-05) 0.25 g
(0.001067) 0.25
(0.001906) 3.09 5.62 Example 2-3 0.04 g
(0.000126506) 0.25 g
(0.001067) 0.25
(0.001906) 4.08 5.61 Examples 2-4 0.05 g
(0.000158133) 0.25 g
(0.001067) 0.25
(0.001906) 5.05 5.61

[ Test Example  2]

Differential scanning calorimetry (DSC) was performed on the polyamides prepared in Examples 2-1 to 2-4. The results are shown in Table 4 and Figs. 5 to 8.

The compound (1b) of the formula (1) The molar ratio (mol%) of the compound (1b) T _onset (占 폚) H (J / g) T _m (° C) Comparative Example 1 0g 0 167.7 -44.63 210.7 Example 2-1 0.02 g 2.08 166.7 -46.89 205.8 Example 2-2 0.03 g 3.09 153.4 -39.88 198.9 Example 2-3 0.04 g 4.08 161.5 -37.83 201.6 Examples 2-4 0.05 g 5.05 149.3 -25.14 194

[ Example  3: Polyamide  Preparation of resin]

( Example  3-1)

The compound (1c) of the formula (1) prepared in Preparation Example 3, the nylon 4,6 salt (5a) and the 6-aminocaproic acid (vi) prepared in Preparation Example 4 were mixed in the proportions shown in Table 3 , The temperature was raised at room temperature (25 ° C), and the reaction was carried out at 240 ° C for 2 hours under a nitrogen atmosphere to prepare polyamide (9c).

[Reaction Scheme 9]

( Example  3-2 to 3-4)

Except that the compound (1c) of the formula (1) prepared in Preparation Example 3, the nylon 4,6 salt (5a) prepared in Preparation Example 4 and the 6-aminocaproic acid (vi) Was used in the same manner as in Example 3-1 to prepare a polyamide.

The compound (1c) of the formula (1)
(confiscation) Nylon 4,6 salt
(confiscation) 6-aminocaproic acid
(confiscation) The molar ratio (mol%) of the compound (1c) Average carbon number
(dog) Comparative Example 1 0g 0.25 g
(0.001067) 0.25
(0.001906) 0 5.64 Example 3-1 0.02 g
(6.0361E-05) 0.25 g
(0.001067) 0.25
(0.001906) 1.99 5.63 Example 3-2 0.03 g
(9.0541E-05) 0.25 g
(0.001067) 0.25
(0.001906) 2.96 5.62 Example 3-3 0.04 g
(0.00012072) 0.25 g
(0.001067) 0.25
(0.001906) 3.90 5.62 Example 3-4 0.05 g
(0.0001509) 0.25 g
(0.001067) 0.25
(0.001906) 4.83 5.61

[ Test Example  3]

Differential scanning calorimetry (DSC) was performed on the polyamides prepared in Examples 3-1 to 3-4. The results are shown in Table 6 and Figs. 9 to 12.

The compound (1c) of the formula (1) The molar ratio (mol%) of the compound (1c) T _onset (占 폚) H (J / g) T _m (° C) Comparative Example 1 0 0 167.7 -44.63 210.7 Example 3-1 0.02 1.99 162.8 -40.88 205.6 Example 3-2 0.03 2.96 151.8 -35.99 194.9 Example 3-3 0.04 3.9 162.3 -29.16 204.8 Example 3-4 0.05 4.83 160.2 -32.37 197.2

As shown in Tables 2, 4 and 6, and Figs. 1 to 12, it was confirmed that in Examples 1-1 to 1-4, 2-1 to 2-1 and 2-5, which were prepared by using the compound of Chemical Formula 1 as a monomer for producing polyamide -4, and 3-1 to 3-4, the average number of carbon atoms, the melting point of the polymer, and the value of -ΔH were all lowered compared to the polyamide of Comparative Example 1 (nylon 46/6). Specifically, the average carbon number of the polyamide prepared according to the content of the compound of Chemical Formula 1 was lowered to 5.55 to 5.63, and the melting point was lowered to 4.9 to 22.2 占 폚. In addition, -ΔH was lowered to -12.3 J / g at the maximum compared to the polyamide of Comparative Example 1, and it was confirmed that the amorphousness was remarkably increased.

The moisture content of the polymer is due to the amorphous region in the polymer. From the above experimental results, it can be seen that the amorphous region of the polymer can be increased by using the hydrophilic salt type monomer. It is also expected that the polyamide produced has a melting point of 194.9 to 207.8 캜 and a heat of fusion of 27.32? -? H? 38.87 J / g, which is higher than that of the polyamide of the comparative example.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit of the invention as set forth in the appended claims. The present invention can be variously modified and changed by those skilled in the art, and it is also within the scope of the present invention.

Claims (24)

A compound of the formula 1 below;
Diamines and diacids, or nylon salts; And
Comprising reacting an amino acid or a lactam,
Wherein the nylon salt is represented by the following formula (5): &lt; EMI ID =
[Chemical Formula 1]

(In the formula 1,
A ^- is F ^- is an anion selected from the group consisting of and ^{-, Cl -, Br -,} I -, CH 3 COO -, SO 4 H - , and SO ₃ H
And X and Y each independently represent an alkylene group having 1 to 6 carbon atoms.
[Chemical Formula 5]

(5)
And Z and W are each independently an alkylene group having 1 to 6 carbon atoms. The method according to claim 1,
The compound of Formula 1; Diamines and diacids, or nylon salts; And a step of reacting a diamine of the following formula (2) with a diacid of the following formula (3) to prepare a compound of the above formula (1) before the step of reacting an amino acid or a lactam Process for preparing polyamides comprising:
(2)

(3)

In the general formulas (2) and (3)
A ^- is F ^- is an anion selected from the group consisting of and ^{-, Cl -, Br -,} I -, CH 3 COO -, SO 4 H - , and SO ₃ H
X and Y each independently represent an alkylene group having 1 to 6 carbon atoms. 3. The method of claim 2,
Wherein the diacid of Formula 3 is prepared by acid treatment of glutamic acid. 3. The method of claim 2,
Wherein the diacid of Formula 3 is a halide or acetate salt or sulfonate of glutamic acid. delete The method according to claim 1,
Wherein the nylon salt is a compound of the following formula (5a).
[Chemical Formula 5a]

The method according to claim 1,
Wherein the amino acid is a compound represented by the following formula (8-1)
Wherein the lactam is a compound of the following formula 8-2:
[Formula 8-1]

[Formula 8-2]

In Formulas (8-1) and (8-2)
V and W are each independently an alkylene group having 2 to 5 carbon atoms. The method according to claim 1,
Wherein the amino acid is 6-aminocaproic acid and the lactam is? -Caprolactam. The method according to claim 1,
The compound of Formula 1; Diamines and diacids, or nylon salts; And the reaction of an amino acid or a lactam is carried out by heat treatment at 200 to 295 占 폚. (2) and (3);
Diamines and diacids, or nylon salts; And
Comprising reacting an amino acid or a lactam,
Wherein the diamine is a compound represented by the following formula (6), and the diacid is a compound represented by the following formula (7): &lt; EMI ID =
(2)

(3)

(In the formulas (2) and (3)
A ^- is F ^- is an anion selected from the group consisting of and ^{-, Cl -, Br -,} I -, CH 3 COO -, SO 4 H - , and SO ₃ H
And X and Y each independently represent an alkylene group having 1 to 6 carbon atoms.
[Chemical Formula 6]

(7)

(In formulas (6) and (7)
And Z and W are each independently an alkylene group having 1 to 6 carbon atoms. 10. Polyamide prepared by the process according to claims 1 or 10. 12. The method of claim 11,
&Lt; RTI ID = 0.0 &gt; (9) < / RTI &gt;
[Chemical Formula 9]

In the above formula (9)
A ^- is F ^- is an anion selected from the group consisting ^{of, -, Cl -, Br -} , I -, CH 3 COO -, SO 4 H - , and SO ₃ H
X, Y, Z and W are each independently an alkylene group having 1 to 6 carbon atoms,
V is an alkylene group having 2 to 6 carbon atoms,
1, m and n are numbers representing the molar ratios of the respective repeating units, and 0 <1 <1, 0 <m <1 and 0 <n <1 under the condition of 1 + m + n = 1. 12. The method of claim 11,
Wherein the average number of carbon atoms per amide group contained in the polyamide is 2 to 5.63, the melting point is 160 to 209.2 占 폚, and the heat of fusion (-? H) is 10 to 44.15 J / g. Alkali metal or organic cation salts of amino acids;
Diamines and diacids, or nylon salts; And
A method for producing a polyamide comprising reacting an amino acid or a lactam. 15. The method of claim 14,
Wherein the alkali metal salt or the organic cation salt of the amino acid is a compound having any one structure selected from the group consisting of structures represented by the following formulas (21-1) to (21-3):
[Formula 21-1]

[Formula 21-2]

[Formula 21-3]

In Formulas (21-1) to (21-3)
A ⁺ is an alkali metal ion or an organic cation, and
X is an alkylene group having 1 to 6 carbon atoms. 15. The method of claim 14,
Wherein the alkali metal salt of the amino acid is monosodium glutamic acid or L-glutamic acid monopotassium salt. 15. The method of claim 14,
Wherein the nylon salt is a compound represented by the following formula (22).
[Chemical Formula 22]

In Formula 22,
Y and Z are each independently an alkylene group having 1 to 6 carbon atoms. 15. The method of claim 14,
Wherein the nylon salt is a compound of the following formula (22a).
[Chemical Formula 22a]

15. The method of claim 14,
Wherein the amino acid is a compound represented by the following formula (25-1)
Wherein the lactam is a compound represented by the following Formula 25-2:
[Formula 25-1]

[Formula 25-2]

In Formulas (25-1) and (25-2)
V and W are each independently an alkylene group having 2 to 5 carbon atoms. 15. The method of claim 14,
Wherein the amino acid is 6-aminocaproic acid and the lactam is? -Caprolactam. 15. The method of claim 14,
The reaction of an alkali metal salt or an organic cation salt of the amino acid, a diamine with a diacid or a nylon salt, and an amino acid or a lactam is carried out by heat treatment at 200 to 260 ° C Lt; RTI ID = 0.0 &gt; polyamide. &Lt; / RTI &gt; A polyamide produced by the process according to claim 14. 23. The method of claim 22,
A polyamide comprising the structure:
(26)

In Formula 26,
A ⁺ is an alkali metal ion or an organic cation,
X, Y and Z are each independently an alkylene group having 1 to 6 carbon atoms,
W is an alkylene group having 2 to 5 carbon atoms,
1, m and n are numbers representing the molar ratios of the respective repeating units, and 0 <1 <1, 0 <m <1 and 0 <n <1 under the condition of 1 + m + n = 1. 24. The method of claim 23,
Wherein the average number of carbon atoms per amide group contained in the polyamide is 2 to 5.63, the melting point is 160 to 209.2 占 폚, and the heat of fusion (-? H) is 10 to 44.15 J / g.

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