KR102562351B1 - Method for preparing polyamide and polyamide prepared by using the same - Google Patents

Abstract

The present invention relates to a method for producing polyamide and a polyamide produced using the same, wherein the method for producing polyamide includes a first nylon salt as a first reactant and a second nylon salt or lactam as a second reactant. and reacting a lactam compound and a third reactant.
According to the method for producing polyamide, it is possible to manufacture polyamide having excellent water absorption rate, easy fiber formation, and excellent spin elongation property.

Description

Polyamide manufacturing method and polyamide manufactured using the same {METHOD FOR PREPARING POLYAMIDE AND POLYAMIDE PREPARED BY USING THE SAME}

The present invention relates to a method for producing polyamide capable of producing a polyamide having excellent water absorption rate, easy fiber formation, and excellent spinning stretchability, and a polyamide manufactured using the same.

Nylon 6 fiber has advantages such as excellent stiffness, elastic recovery rate, dyeability, etc., but most synthetic fibers including nylon 6 fiber have the disadvantage of low absorbency, and cotton, a natural fiber, has excellent absorbency compared to conventional synthetic fibers. It has a good touch, but has the disadvantage of very slow moisture drying speed, extremely poor UV blocking properties, and high price.

In general, the absorbability of crystalline polymers is influenced by various factors such as the type of hydrophilic functional group, crystal structure, and degree of crystallinity. In the case of nylon, which is one of the crystalline polymers, when the hydrocarbon group having a hydrophilic property is reduced compared to the amide group having a hydrophilic property in the repeating unit of the polymer, the hydrophilic property will increase and the absorbency will increase. Compared to nylon 6 fibers, In-depth research has been conducted on nylon 3 fibers or nylon 4 fibers with a low carbon number.

In particular, nylon 4 fiber has an excellent water absorption (moisture content) similar to that of natural fiber cotton due to an increase in hydrophilicity due to a smaller number of carbon atoms than nylon 6 in the repeating unit, and its strength is similar to that of conventional nylon 6.

However, it was thought that nylon 4 fibers could be synthesized by condensation polymerization of GABA (gamma amino butyric acid), a raw material monomer, by heating and dehydration like other nylons. A linear polymer could not be obtained. Moreover, since 2-pyrrolidone is a 5-membered ring lactam, it is thermally stable and ring-opening polymerization is not easy.

However, in 1953, Ney et al. dehydrated by heating under reduced pressure at 90 ° C to 120 ° C using potassium hydroxide, and heated at 160 ° C under a nitrogen stream to conduct ring-opening polymerization of 2-pyrrolidone, thereby successfully synthesizing nylon 4 fibers for the first time. did Based on the method, from the 1950s to the 1990s, technologies such as new catalyst materials and polymerization methods were developed for the purpose of high molecular weight, polydispersity control, and simplification of the manufacturing process.

Polymerization of the nylon 4 resin and fabrication using it were actively conducted at Chevron Research from the 1970s to the 1980s, and mainly catalyst research, polymerization process research, heat stabilization research, processing technology and fiber manufacturing technology research were conducted on a pilot scale However, commercialization was not successful.

In addition, nylon 4 (Poly(2-pyrrolidone)) resin, synthesized in 1953, has a low number of lipophilic carbons per repeating unit in its structure, so it has excellent water absorption and excellent rigidity. It entered history as a synthetic fiber.

However, nylon 4 has a melting point of 265 °C, which is higher than that of nylon 6, while its thermal decomposition temperature is 260 °C. As a result, in the case of using a spinning process that requires melt spinning at a temperature higher than the melting point when manufacturing fibers using nylon 4, nylon 4 is thermally decomposed before reaching the melting point, making it impossible to form fibers by continuous spinning.

In order to solve this problem, a technique of synthesizing a copolymer to lower the melting point has been developed, but this has problems in that the excellent water absorption rate of nylon 4 cannot be maintained or it is difficult to form fibers.

Accordingly, there is a demand for a new method for producing nylon that can easily form fibers while having excellent water absorption.

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

An object of the present invention is to provide a method for producing polyamide, which can easily form fibers while having excellent water absorption, and has excellent spinning stretchability, and a polyamide manufactured using the same.

According to one embodiment of the present invention, as a first reactant, a first nylon salt represented by Formula 1; As the second reactant, a second nylon salt or lactam compound represented by the following formula (2); and reacting diamine represented by Chemical Formula 4a and dimethyl-5-sulfoisophthalate sodium (DMIS) represented by Chemical Formula 4b as a third reactant. provides a way

[Formula 1]

[Formula 2]

[Formula 4a]

[Formula 4b]

In Formula 1, Formula 2, Formula 4a, and Formula 4b, X ¹ and Y ¹ are each independently an alkylene group having 4 carbon atoms, and X ² and Y ² are each independently an alkylene group having 3 to 6 carbon atoms, The X is an alkylene group having 3 to 6 carbon atoms.

According to another embodiment of the present invention, as a first reactant, a first nylon salt represented by Formula 1 below; As the second reactant, a second nylon salt or lactam compound represented by the following formula (2); and reacting, as a third reactant, a fourth nylon salt prepared by reacting a polyether diamine represented by the following Chemical Formula 5a with a dicarboxylic acid represented by the following Chemical Formula 5b.

[Formula 1]

[Formula 2]

[Formula 5a]

[Formula 5b]

In Formula 1, Formula 2, Formula 5a, and Formula 5b, X ¹ and Y ¹ are each independently an alkylene group having 4 carbon atoms, and X ² and Y ² are each independently an alkylene group having 3 to 6 carbon atoms, Y is an alkylene group having 3 to 6 carbon atoms, R ₁ , R ₂ and R ₃ are each independently an alkylene group having 3 to 6 carbon atoms, x+z is an integer of 0 to 10, and y is 1 is an integer from 50 to 50.

The first nylon salt or the second nylon salt may be prepared by reacting a diamine represented by Chemical Formula 1a with a dicarboxylic acid represented by Chemical Formula 1b.

[Formula 1a]

[Formula 1b]

In Chemical Formulas 1a to 1b, X and Y are each independently an alkylene group having 3 to 6 carbon atoms.

The lactam-based compound may be any one selected from the group consisting of 2-Pyrrolidone, 2-Piperidone, and ε-Caprolactam.

The reaction may be performed by heat treatment at 200 °C to 260 °C.

According to another embodiment of the present invention, as the first repeating unit, a repeating unit derived from a first nylon salt represented by Formula 1; As the second repeating unit, a repeating unit derived from a second nylon salt or lactam compound represented by Formula 2 below; and a polyamide comprising a repeating unit derived from diamine represented by Formula 4a and dimethyl-5-sulfoisophthalate sodium (DMIS) represented by Formula 4b as a third repeating unit. provides

[Formula 1]

[Formula 2]

[Formula 4a]

[Formula 4b]

In Formula 1, Formula 2, Formula 4a, and Formula 4b, X ¹ and Y ¹ are each independently an alkylene group having 4 carbon atoms, and X ² and Y ² are each independently an alkylene group having 3 to 6 carbon atoms, The X is an alkylene group having 3 to 6 carbon atoms.

According to another embodiment of the present invention, as the first repeating unit, a repeating unit derived from a first nylon salt represented by Formula 1; As the second repeating unit, a repeating unit derived from a second nylon salt or lactam compound represented by Formula 2 below; and a repeating unit derived from a fourth nylon salt prepared by reacting a polyether diamine represented by the following Chemical Formula 5a with a dicarboxylic acid represented by the following Chemical Formula 5b as a third repeating unit.

[Formula 1]

[Formula 2]

[Formula 5a]

[Formula 5b]

In Formula 1, Formula 2, Formula 5a, and Formula 5b, X ¹ and Y ¹ are each independently an alkylene group having 4 carbon atoms, and X ² and Y ² are each independently an alkylene group having 3 to 6 carbon atoms, Y is an alkylene group having 3 to 6 carbon atoms, R ₁ , R ₂ and R ₃ are each independently an alkylene group having 3 to 6 carbon atoms, x+z is an integer of 0 to 10, and y is 1 is an integer from 50 to 50.

The polyamide may include 50 mol% to 90 mol% of the first repeating unit, 2 mol% to 15 mol% of the third repeating unit, and the rest of the second repeating unit, based on the total amount of the polyamide. can

According to the manufacturing method according to the present invention, it is possible to easily form fibers while having excellent water absorption of polyamide, and it is possible to manufacture polyamide having excellent spinning stretchability.

Since the present invention can apply various transformations and have various embodiments, specific embodiments will be exemplified and described in detail in the detailed description. However, it should be understood that this is not intended to limit the present invention to specific embodiments, and includes all transformations, equivalents, and substitutes included in the spirit and scope of the present invention.

A method for producing polyamide according to an embodiment of the present invention includes, as a first reactant, a first nylon salt represented by Formula 1 below; As the second reactant, a second nylon salt or lactam compound represented by the following formula (2); and reacting diamine represented by Chemical Formula 4a and dimethyl-5-sulfoisophthalate sodium (DMIS) represented by Chemical Formula 4b as a third reactant.

[Formula 1]

[Formula 2]

[Formula 4a]

[Formula 4b]

A method for producing polyamide according to another embodiment of the present invention includes, as a first reactant, a first nylon salt represented by Formula 1 below; As the second reactant, a second nylon salt or lactam compound represented by the following formula (2); and reacting, as a third reactant, a fourth nylon salt prepared by reacting a polyether diamine represented by the following Chemical Formula 5a with a dicarboxylic acid represented by the following Chemical Formula 5b.

[Formula 1]

[Formula 2]

[Formula 5a]

[Formula 5b]

In Formula 1, Formula 2, Formula 4a, Formula 4b, Formula 5a, and Formula 5b, X ¹ and Y ¹ are each independently an alkylene group having 4 carbon atoms, and X ² and Y ² each independently have 3 to 5 carbon atoms. 6 alkylene group, X is an alkylene group having 3 to 6 carbon atoms, Y is an alkylene group having 3 to 6 carbon atoms, and R ₁ , R ₂ and R ₃ are each independently an alkylene group having 3 to 6 carbon atoms And, the x + z is an integer from 0 to 10, and the y is an integer from 1 to 50.

In the polyamide production method, the first nylon salt represented by Chemical Formula 1 as the first reactant may be prepared by reacting a diamine represented by Chemical Formula 1a with a dicarboxylic acid represented by Chemical Formula 1b.

[Formula 1a]

[Formula 1b]

In Formula 1a and Formula 1b, X and Y are each independently an alkylene group having 4 carbon atoms.

More specifically, the diamine may be 1,4-diaminobutane, and the dicarboxylic acid may be adipic acid.

The second nylon salt represented by Chemical Formula 2 as the second reactant may also be prepared by reacting the diamine represented by Chemical Formula 1a with the dicarboxylic acid represented by Chemical Formula 1b.

However, in Formulas 1a and 1b, X and Y are each independently an alkylene group having 3 to 6 carbon atoms.

More specifically, the diamine is 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane ) and 1,6-diaminohexane (1,6-diaminohexane) may be any one selected from the group consisting of.

The dicarboxylic acid may be any one selected from the group consisting of adipic acid, glutaric acid, pimelic acid, and suberic acid.

Preparation of the first nylon salt or the second nylon salt may be made at 20 ℃ to 80 ℃ under a nitrogen atmosphere. If the production temperature of the first nylon salt or the second nylon salt is less than 20 ° C, the nylon salt may not be well formed, and if it exceeds 80 ° C, polymerization control may be difficult.

In addition, it may be preferable that the reaction for preparing the first nylon salt or the second nylon salt is carried out under moisture conditions. Specifically, the water content may be preferably 30% to 80% by weight based on the total weight of raw materials input to prepare the first nylon salt or the second nylon salt. If the water content is less than 30% by weight, there is a concern that the salt may not be uniformly produced, and the conductivity of the salt solution or salt dispersion may increase, making handling difficult. On the other hand, when the water content exceeds 80% by weight, the process time is prolonged and the yield of polyamide may be lowered, which is undesirable.

Meanwhile, the lactam-based compound as the second reactant is any one selected from the group consisting of 2-Pyrrolidone, 2-Piperidone, and ε-Caprolactam. lactam-based compounds having 3 to 6 carbon atoms, etc., among which, 2-pyrrolidone and ε-caprolactam are preferable considering physical properties such as yield and melting point and heat resistance of the finally produced polyamide. can

Diamine represented by Chemical Formula 4a and dimethyl-5-sulfoisophthalate sodium represented by Chemical Formula 4b as the third reactant use the diamine represented by Chemical Formula 4a as a melt phase, and the dimethyl-5-sulfoisophthalate represented by Chemical Formula 4a It can be reacted by introducing sodium phthalate into a solid phase into a reaction tube.

[Formula 4a]

[Formula 4b]

In Chemical Formula 4a, X may be an alkylene group having 3 to 6 carbon atoms, and more specifically, X may be an alkylene group having 4 to 6 carbon atoms. The diamine represented by Formula 4a is specifically any one selected from the group consisting of 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane. can

In addition, the fourth nylon salt as the third reactant may be prepared by reacting a polyether diamine represented by the following Chemical Formula 5a with a dicarboxylic acid represented by the following Chemical Formula 5b.

[Formula 5a]

[Formula 5b]

In Formulas 5a and 5b, Y may be an alkylene group having 3 to 6 carbon atoms, and more specifically, Y may be an alkylene group having 4 to 6 carbon atoms.

The R ₁ , R ₂ and R ₃ are each independently an alkylene group having 3 to 6 carbon atoms, and may specifically be an alkylene group having 3 or 4 carbon atoms. The alkylene group is an atomic group having two bonding groups, and for example, R may be a propylene group, an isopropylene group, a butylene group, an isobutylene group, or a 2,3-butylene group.

In addition, x is an integer from 0 to 10, y is an integer from 1 to 50, z is an integer from 0 to 10, more specifically, x + z is an integer from 0 to 10, and y is It may be an integer from 4 to 39.

In addition, the polyether diamine represented by Chemical Formula 5a may have a weight average molecular weight of 1000 to 3000 g/mol, more specifically 1500 to 2500 g/mol.

The dicarboxylic acid represented by Chemical Formula 5b may be any one selected from the group consisting of adipic acid, glutaric acid, pimelic acid, and suberic acid.

Since the method for preparing the fourth nylon salt is the same as the method for preparing the first nylon salt or the second nylon salt except for using the compounds represented by Formula 5a and Formula 5b, repeated description is omitted.

The reaction of the first reactant, the second reactant, and the third reactant may be performed by heat treatment at 200 °C to 260 °C. At this time, the heat treatment process may be performed as a continuous multi-step heat treatment at various temperatures within the above range. When the reaction temperature is less than 200 ° C., the polymerization reaction is insufficient, and it may not be possible to prepare a polymer of sufficient size. When the reaction temperature exceeds 260 ° C., polymerization and decomposition occur simultaneously, accompanied by a rapid increase in viscosity, resulting in uneven molecular weight distribution. and obtain polymers of sufficient size.

The polyamide manufacturing method according to the present invention as described above has excellent water absorption rate by including a material derived from dimethyl-5-sulfoisophthalate sodium or polyether diamine as a reactant used in the production of polyamide. However, fiber formation can be facilitated, and polyamide having excellent spinning stretchability can be produced.

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

Specifically, the polyamide according to one example includes, as a first repeating unit, a repeating unit derived from a first nylon salt represented by Formula 1 below; As the second repeating unit, a repeating unit derived from a second nylon salt or lactam compound represented by Formula 2 below; and a repeating unit derived from diamine represented by Chemical Formula 4a and dimethyl-5-sulfoisophthalate sodium (DMIS) represented by Chemical Formula 4b as a third repeating unit.

[Formula 1]

[Formula 2]

[Formula 4a]

[Formula 4b]

The polyamide according to another example includes, as a first repeating unit, a repeating unit derived from a first nylon salt represented by Formula 1 below; As the second repeating unit, a repeating unit derived from a second nylon salt or lactam compound represented by Formula 2 below; and a repeating unit derived from a fourth nylon salt prepared by reacting a polyether diamine represented by the following Chemical Formula 5a with a dicarboxylic acid represented by the following Chemical Formula 5b as a third repeating unit.

[Formula 1]

[Formula 2]

[Formula 5a]

[Formula 5b]

In Formula 1, Formula 2, Formula 4a, Formula 4b, Formula 5a, and Formula 5b, X ¹ and Y ¹ are each independently an alkylene group having 4 carbon atoms, and X ² and Y ² each independently have 3 to 5 carbon atoms. 6 alkylene group, X is an alkylene group having 3 to 6 carbon atoms, Y is an alkylene group having 3 to 6 carbon atoms, and R ₁ , R ₂ and R ₃ are each independently an alkylene group having 3 to 6 carbon atoms And, the x + z is an integer from 0 to 10, and the y is an integer from 1 to 50.

For example, the repeating unit derived from the first nylon salt represented by Formula 1 may have a structure of -[-NH-(CH ₂ ) ₄ -NH-CO-(CH ₂ ) ₄ -CO-]- there is.

The polyamide may include 50 to 90 mol% of the first repeating unit, 2 to 15 mol% of the third repeating unit, and the remaining content of the second repeating unit, based on the total amount of the polyamide. It may contain 60 mol% to 75 mol% of the first repeating unit, 5 mol% to 10 mol% of the third repeating unit, and the remaining content of the second repeating unit.

As the polyamide includes the first repeating unit, the second repeating unit, and the third repeating unit within the above range, the water absorption rate is excellent, the fiber formation can be facilitated, and the spinning stretchability is excellent. Specifically, when the content of the first repeating unit is less than 50 mol%, the regularity of the basic structure of polyamide is insufficient, resulting in irregular crystallization, resulting in insufficient fiber formation, and when it exceeds 90 mol%, polyamide If the crystallization rate is too fast and the stretching properties are poor during the manufacturing process, fiber formation may be insufficient, and if the content of the third repeating unit is less than 2 mol%, a sufficient moisture content may not be obtained, and if it exceeds 15 mol%, poly Due to the lack of regularity of the amide basic structure, crystallization formation may be irregular, resulting in poor fiber formation.

The polyamide may have an intrinsic viscosity (η) of 0.4 dl/g to 2.2 dl/g measured at 30 °C and m-cresol, a melting point of 150 °C to 280 °C, and a water absorption rate under process conditions after fiberization. It may be 5% by weight to 15% by weight, and the strength of the fiber may be 1.5 g / d to 6.0 g / d.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

[ manufacturing example One: of nylon salts manufacturing]

( manufacturing example One)

An ethanol solution of 1,4-diaminobutane prepared by dissolving 42 g of 1,4-diaminobutane in 535 ml of ethanol, and an ethanol solution of adipic acid prepared by dissolving 50 g of adipic acid in 633 ml of ethanol and reacted at 25 ° C. under a nitrogen atmosphere to prepare a nylon 46 salt.

( manufacturing example 2)

A 1,6-diaminohexane methanol solution prepared by dissolving 38 g of 1,6-diaminohexane in 457 ml of methanol was mixed with a methanol solution of adipic acid prepared by dissolving 50 g of adipic acid in 367 ml of methanol. and reacted at 25° C. under a nitrogen atmosphere to prepare a nylon 66 salt.

( manufacturing example 3)

An ethanol solution of 1,4-diaminobutane prepared by dissolving 42 g of 1,4-diaminobutane in 535 ml of ethanol was added to an ethanol solution of DMIS prepared by dissolving 101 g of DMIS in 1260 ml of ethanol and nitrogen It was reacted at 25 °C under an atmosphere.

( manufacturing example 4)

A compound composed of PEG (polyethylene glycol) having a weight average molecular weight of 950 g / mol as a main chain and a diamine terminal (in Formula 5a, the R ₁ , R ₂ and R ₃ are each independently an isopropylene group having 3 carbon atoms, , x + z = 6, y = 39, MW = 2000 g / mol) ethanol solution prepared by dissolving 410 g of ethanol in 5,300 ml of ethanol, adipic acid prepared by dissolving 50 g of adipic acid in 633 ml of ethanol was added to an ethanol solution and reacted at 25 ° C. under a nitrogen atmosphere to prepare a nylon salt.

[ Example : of polyamide manufacturing]

( Example One)

Nylon 46 salt prepared in Preparation Example 1 was used as a first reactant, caprolactam was used as a second reactant, and diamine prepared in Preparation 3 and DMIS (dimethylene isophthalixodium sulfonate) were used as a second reactant. A reactant was used as a third reactant and reacted at a molar ratio of 2:1:0.2 to prepare polyamide (1).

( Example 2)

The nylon 46 salt prepared in Preparation Example 1 was used as a first reactant, the nylon 66 salt prepared in Preparation Example 2 was used as a second reactant, and the diamine prepared in Preparation 3 and DMIS (dimethylene Sophthalixodium sulfonate) was used as a third reactant and reacted at a molar ratio of 2:1:0.2 to prepare polyamide (2).

( Example 3)

Nylon 46 salt prepared in Preparation Example 1 was used as a first reactant, caprolactam was used as a second reactant, and PEG (polyethylene glycol) prepared in Preparation 4 was used as a main chain and the terminal was composed of diamine. A salt of adipic acid was used as a third reactant and reacted at a molar ratio of 2: 1: 0.2 to prepare polyamide (3)

( Example 4)

The nylon 46 salt prepared in Preparation Example 1 was used as a first reactant, the nylon 66 salt prepared in Preparation Example 2 was used as a second reactant, and PEG (polyethylene glycol) prepared in Preparation Example 4 was used as a main chain and polyamide (4) was prepared by reacting a compound having a terminal with diamine and a salt of adipic acid as a third reactant at a molar ratio of 2:1:0.2.

( Example 5 to Example 8)

Polyamide was prepared in the same manner as in Examples 1 to 4, except that the reaction was performed at a molar ratio of 3:1:0.5 in Examples 1 to 4.

( reference example 1 to reference example 4)

Polyamide was prepared in the same manner as in Examples 1 to 4, except that the molar ratio in Examples 1 to 4 was 1:1:0.5.

( reference example 5 to reference example 8)

Polyamide was prepared in the same manner as in Examples 1 to 4, except that the molar ratio in Examples 1 to 4 was 2:1:0.05.

( comparative example 1 and comparative example 2)

Polyamide was prepared in the same manner as in Examples 1 and 2, except that the molar ratio in Examples 1 and 2 was 2:1:0.

[ test example : of polyamide performance measurement]

Spin elongation, tensile strength, and moisture content were measured for the polyamides prepared in Examples, Reference Examples, and Comparative Examples, and the results are shown in Table 1 below.

The spinning stretchability, tensile strength and moisture content were measured in the following manner.

1) Stretchability: Measured by spinning equipment GR1~3 Speed (In Line sensor).

2) Tensile strength: Tensile elongation was measured when a filament (Fiber) in a standard state was stretched at a gripping distance of 30 cm and a tensile speed of 30 ± 2 cm/min and cut (KS K 0412).

3) Moisture content (%): After measuring the mass by treating the sample in the standard or presented state at 105 ± 2 ℃ until it reaches a constant weight, it is calculated by the following Equation 1 (KS K 0221).

[Equation 1]

Moisture content = (O - D) / D × 100

O: mass of standard or presented test piece

D: mass of test piece in dry state

first reactant second reactant third reactant mole ratio radiation
extensibility Seal
robbery Moisture rate
(%) Example 1 nylon 46 caprolactam DA+DMIS 2:1:0.2 Good 2.5 7.5 Example 2 nylon 46 nylon 66 DA+DMIS 2:1:0.2 Good 2.8 6.8 Example 3 nylon 46 caprolactam PEGDA+AA 2:1:0.2 Good 3.1 10.8 Example 4 nylon 46 nylon 66 PEGDA+AA 2:1:0.2 Good 3.3 8.1 Example 5 nylon 46 caprolactam DA+DMIS 3:1:0.5 Good 3.1 9.0 Example 6 nylon 46 nylon 66 DA+DMIS 3:1:0.5 Good 3.5 8.0 Example 7 nylon 46 caprolactam PEGDA+AA 3:1:0.5 Good 3.4 14.0 Example 8 nylon 46 nylon 66 PEGDA+AA 3:1:0.5 Good 3.7 12.0 Reference example 1 nylon 46 caprolactam DA+DMIS 1:1:0.5 error - - Reference example 2 nylon 46 nylon 66 DA+DMIS 1:1:0.5 error - - Reference example 3 nylon 46 caprolactam PEGDA+AA 1:1:0.5 error - - Reference example 4 nylon 46 nylon 66 PEGDA+AA 1:1:0.5 error - - Reference Example 5 nylon 46 caprolactam DA+DMIS 2:1:0.5 error - - Reference example 6 nylon 46 nylon 66 DA+DMIS 2:1:0.5 error - - Reference example 7 nylon 46 caprolactam PEGDA+AA 2:1:0.5 error - - Reference example 8 nylon 46 nylon 66 PEGDA+AA 2:1:0.5 error - - Comparative Example 1 nylon 46 caprolactam - 2:1:0 Good 2.7 5.0 Comparative Example 2 nylon 46 nylon 66 - 2:1:0 Good 3.0 4.8

Referring to Table 1, it can be seen that the polyamide prepared in Example has excellent spinning stretchability, tensile strength, and moisture content.

In the above, one embodiment of the present invention has been described, but those skilled in the art can add, change, delete, or add components within the scope not departing from the spirit of the present invention described in the claims. The present invention can be variously modified and changed by the like, and this will also be said to be included within the scope of the present invention.

Claims (8)

As the first reactant, a first nylon salt represented by Formula 1 below;
As the second reactant, a second nylon salt or lactam compound represented by the following formula (2); and
As a third reactant, preparing polyamide by reacting diamine represented by the following formula 4a and dimethyl-5-sulfoisophthalate sodium (DMIS) represented by the following formula 4b; and
50 to 90 mol% of the first repeating unit derived from the first reactant, 2 to 15 mol% of the third repeating unit derived from the third reactant, and 50 to 90 mol% of the first repeating unit derived from the third reactant, and A method for producing polyamide comprising the second repeating unit as the remaining content.
[Formula 1]

[Formula 2]

[Formula 4a]

[Formula 4b]

(In Formula 1, Formula 2, Formula 4a and Formula 4b,
Wherein X ¹ and Y ¹ are each independently an alkylene group having 4 carbon atoms,
Wherein X ² and Y ² are each independently an alkylene group having 3 to 6 carbon atoms;
The X is an alkylene group having 3 to 6 carbon atoms) As the first reactant, a first nylon salt represented by Formula 1 below;
As the second reactant, a second nylon salt or lactam compound represented by the following formula (2); and
As a third reactant, preparing a polyamide by reacting a fourth nylon salt prepared by reacting a polyether diamine represented by the following Chemical Formula 5a with a dicarboxylic acid represented by the following Chemical Formula 5b,
50 to 90 mol% of the first repeating unit derived from the first reactant, 2 to 15 mol% of the third repeating unit derived from the third reactant, and 50 to 90 mol% of the first repeating unit derived from the third reactant, and A method for producing polyamide comprising the second repeating unit as the remaining content.
[Formula 1]

[Formula 2]

[Formula 5a]

[Formula 5b]

(In Formula 1, Formula 2, Formula 5a and Formula 5b,
Wherein X ¹ and Y ¹ are each independently an alkylene group having 4 carbon atoms,
Wherein X ² and Y ² are each independently an alkylene group having 3 to 6 carbon atoms;
Y is an alkylene group having 3 to 6 carbon atoms,
Wherein R ₁ , R ₂ and R ₃ are each independently an alkylene group having 3 to 6 carbon atoms, x+z is an integer of 0 to 10, and y is an integer of 1 to 50) According to claim 1 or 2,
The first nylon salt or the second nylon salt is prepared by reacting a diamine represented by the following Chemical Formula 1a with a dicarboxylic acid represented by the following Chemical Formula 1b.
[Formula 1a]

[Formula 1b]

(In Formulas 1a and 1b,
In the case of the first nylon salt, X and Y are each independently an alkylene group having 4 carbon atoms,
In the case of the second nylon salt, X and Y are each independently an alkylene group having 3 to 6 carbon atoms) According to claim 1 or 2,
The lactam-based compound is any one selected from the group consisting of 2-Pyrrolidone, 2-Piperidone and ε-Caprolactam Preparation of polyamide method. According to claim 1 or 2,
The reaction is a method for producing a polyamide that is carried out by heat treatment at 200 ℃ to 260 ℃. As the first repeating unit, a repeating unit derived from a first nylon salt represented by Formula 1 below;
As the second repeating unit, a repeating unit derived from a second nylon salt or lactam compound represented by Formula 2 below; and
As a third repeating unit, a repeating unit derived from diamine represented by the following Chemical Formula 4a and dimethyl-5-sulfoisophthalate sodium (DMIS) represented by the following Chemical Formula 4b; polyamide containing is,
Polyamide comprising 50 mol% to 90 mol% of the first repeating unit, 2 mol% to 15 mol% of the third repeating unit, and the rest of the second repeating unit, based on the total amount of the polyamide.
[Formula 1]

[Formula 2]

[Formula 4a]

[Formula 4b]

(In Formula 1, Formula 2, Formula 4a and Formula 4b,
Wherein X ¹ and Y ¹ are each independently an alkylene group having 4 carbon atoms,
Wherein X ² and Y ² are each independently an alkylene group having 3 to 6 carbon atoms;
The X is an alkylene group having 3 to 6 carbon atoms) As the first repeating unit, a repeating unit derived from a first nylon salt represented by Formula 1 below;
As the second repeating unit, a repeating unit derived from a second nylon salt or lactam compound represented by Formula 2 below; and
As a third repeating unit, a repeating unit derived from a fourth nylon salt prepared by reacting a polyether diamine represented by the following Chemical Formula 5a and a dicarboxylic acid represented by the following Chemical Formula 5b;
Polyamide comprising 50 mol% to 90 mol% of the first repeating unit, 2 mol% to 15 mol% of the third repeating unit, and the rest of the second repeating unit, based on the total amount of the polyamide.
[Formula 1]

[Formula 2]

[Formula 5a]

[Formula 5b]

(In Formula 1, Formula 2, Formula 5a and Formula 5b,
Wherein X ¹ and Y ¹ are each independently an alkylene group having 4 carbon atoms,
Wherein X ² and Y ² are each independently an alkylene group having 3 to 6 carbon atoms;
Y is an alkylene group having 3 to 6 carbon atoms,
Wherein R ₁ , R ₂ and R ₃ are each independently an alkylene group having 3 to 6 carbon atoms, x+z is an integer of 0 to 10, and y is an integer of 1 to 50) delete