KR101561545B1 - Method of manufacturing copolymerized aramid fiber and copolymerized aramid fiber manufactured thereby - Google Patents

Abstract

The present invention relates to a method for producing a copolymerized aramid fiber, which comprises polymerizing a polymerization solution containing a copolymerized aramid polymer by adding terephthaloyl dichloride to an organic solvent in which an aromatic diamine containing a cyano group is dissolved, Characterized in that 0.5 to 50 wt% of polyvinylpyridine is added to the copolymerized aramid polymer in the step of polymerizing the polymerization solution containing the copolymerized aramid polymer when the copolymerized aramid fiber is produced by spinning and coagulating the polymerization solution .
The copolymerized aramid fiber of the present invention is produced by the above method and has an intrinsic viscosity of 6.0 or more.
The present invention relates to a process for producing an aramid polymer by polymerizing an aramid polymer by adding polyvinylpyridine which has excellent bonding property with a dye and absorbs HCl generated during the polymerization to improve the degree of polymerization of the copolymerized aramid polymer and solubility in the polymerization solution The dyeability and intrinsic viscosity of the copolymerized aramid fiber are improved and the solubility of the copolymerized aramid polymer in the polymerization solvent is improved and the radioactivity is also improved.

Description

TECHNICAL FIELD The present invention relates to a method for producing a copolymerized aramid fiber and a copolymerized aramid fiber produced by the method.

The present invention relates to a method for producing a copolymerized aramid fiber and a copolymerized aramid fiber produced by the method. Specifically, when a polymerized solution containing a copolymerized aramid polymer is spun into a spinneret without using sulfuric acid, The present invention relates to a method for producing a copolymerized aramid fiber having improved durability and radioactivity and a high intrinsic viscosity by improving solubility and a copolymerized aramid fiber produced by the method.

Aromatic polyamides, commonly referred to as aramids, include para-aramids having a structure in which benzene rings are linearly connected through an amide group (CONH), and meta-based aramids that are not.

Para-aramid has excellent properties such as high strength, high elasticity and low shrinkage. The thin thread of 5 mm thickness produced from this has a strength enough to lift a 2-tonne automobile, so it is used not only for bulletproof but also for various applications in the aerospace industry.

In addition, since aramid is carbonized black at a temperature of 500 ° C or higher, it is also in the spotlight where high heat resistance is required.

A method of producing an aramid fiber is well described in Korean Patent Registration No. 10-0910537 of the present applicant. According to this patent, an aromatic diamine is dissolved in a polymerization solvent to prepare a mixed solution, and an aromatic diacid is added to this to prepare an aramid polymer. The aramid fiber is finally completed by dissolving the aramid polymer in a sulfuric acid solvent to prepare a spinning dope, spinning the spinning dope, followed by coagulation, washing, and drying.

However, when the aramid fiber is produced through such a process, since a solid state aramid polymer is prepared and then dissolved again in a sulfuric acid solvent to prepare a spinning dope, the spinning process is complicated and harmful to the human body, And the durability is degraded due to corrosion.

Furthermore, since the sulfuric acid solvent used to dissolve the aramid polymer having high chemical resistance and removed after the spinning causes environmental pollution, it has to be appropriately treated after use. The cost for treating such spent sulfuric acid is not only economical .

In order to solve the above problems, Korean Patent Registration No. 10-171994 discloses a method for producing an aramid fiber without using a sulfuric acid solvent by directly irradiating a copolymerized aramid polymerization solution.

Specifically, in the above prior art, terephthaloyl dichloride is added to an organic solvent in which paraphenylenediamine and cyano-para-phenylenediamine are dissolved and reacted to polymerize the polymerization solution containing the copolymerized aramid polymer, The solution was spun and coagulated to produce copolymerized aramid fibers.

However, although the prior art has the advantage of not using a sulfuric acid solvent, the produced copolymerized aramid fiber has a problem of low dyeability due to high crystallinity.

In order to solve such a problem, Korean Patent Registration No. 10-067338 discloses that terephthaloyl dichloride is added to an organic solvent in which paraphenylenediamine and cyano-para-phenylenediamine are dissolved and reacted to produce a copolymerized aramid polymer And then polymerizing the polymerized solution to prepare a copolymerized aramid fiber by spinning and solidifying the polymerized solution, and then adding polyvinylpyrrolidone, which is an amorphous polymer, to the polymerized solution. However, the above method can improve the dyeability of the produced copolymerized aramid fiber, but the copolymerized aramid polymer in the polymerization solvent is poor in solubility due to HCl generated during the polymerization, the radioactivity is lowered, the polymerization degree is lowered and the intrinsic viscosity of the fiber is low .

It is an object of the present invention to improve the radioactivity by improving the degree of polymerization and the solubility of the copolymerized aramid polymer in the polymerization solution when the copolymerized aramid polymerization solvent is used as it is without any use of sulfuric acid to produce the copolymerized aramid fiber, And to provide a method for producing a copolymerized aramid fiber which improves the viscosity.

In order to achieve the above object, in the present invention, terephthaloyl dichloride is added to an organic solvent in which an aromatic diamine containing a cyano group is dissolved and reacted to polymerize a polymerization solution containing the copolymerized aramid polymer, , 0.5 to 50 wt% of polyvinylpyridine is added to the copolymerized aramid polymer in the step of polymerizing the polymerization solution containing the copolymerized aramid polymer.

The present invention relates to a process for producing an aramid polymer by polymerizing an aramid polymer by adding polyvinylpyridine which has excellent bonding property with a dye and absorbs HCl generated during the polymerization to improve the degree of polymerization of the copolymerized aramid polymer and solubility in the polymerization solution The dyeability and intrinsic viscosity of the copolymerized aramid fiber are improved and the solubility of the copolymerized aramid polymer in the polymerization solvent is improved and the radioactivity is also improved.

Hereinafter, the present invention will be described in detail.

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 or scope of the invention. It will be apparent to those skilled in the art that variations are possible. Therefore, the present invention encompasses all changes and modifications that come within the scope of the invention as defined in the appended claims and equivalents thereof.

In the present invention, an inorganic salt is first dissolved in an organic solvent, and then an aromatic diamine containing a cyano group (CN-) is added and dissolved.

In this case, paraphenylenediamine and cyano-para-phenylenediamine may be dissolved in a molar ratio of 1: 9 to 9: 1 as an aromatic diamine containing a cyano group (CN-), or cyano-para-phenylenediamine May be dissolved alone.

Specific examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), hexamethylphosphoramide (HMPA) Tetramethylurea (TMU), N, N-dimethylformamide (DMF), or mixtures thereof.

The inorganic salt is added in order to increase the degree of polymerization of the aromatic polyamide. Specific examples thereof include alkali metal halides such as CaCl ₂ , LiCl, NaCl, KCl, LiBr and KBr, or alkaline earth metal halides. These inorganic salts may be added singly or in the form of a mixture of two or more.

The addition amount of the inorganic salt is preferably about 2 to 5% by weight based on the weight of the organic solvent.

Next, terephthaloyl dichloride is added to the organic solvent to which the aromatic diamine containing the cyano group is added and dissolved at the same molar amount as the aromatic diamine containing the cyano group, and the poly Vinyl pyridine is also added to the organic solvent to prepare a copolymerized aramid polymer.

The polyvinylpyridine absorbs HCl generated during the polymerization to increase the degree of polymerization of the copolymerized aramid polymer and to improve the radioactivity by allowing the copolymerized aramid polymer to dissolve in the polymerization solvent.

In addition, the polyvinylpyridine has excellent bonding properties to dyes and thus improves the dyeability of the produced copolymerized polyamide.

The content of the polyvinylpyridine is 0.5 to 50% by weight based on the weight of the copolymerized aramid polymer. If the amount of the polyvinylpyridine is less than 0.5% by weight, the effect of improving radioactivity, dyeability and degree of polymerization becomes insignificant. The physical properties are deteriorated.

Next, the polymerized solution prepared as described above is extruded through a spinneret using the spinning process as it is, and then the extruded polymer solution is solidified as a coagulating solution to produce copolymerized aramid fibers on the filament.

The copolymerized aramid fiber produced by the method according to the present invention contains graphene in the fiber and has a strength of 28 to 35 g / d.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.

Example  One

An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl ₂ was placed in a reactor under a nitrogen atmosphere, and 50 mol% of para-phenylenediamine and 40% 50 mol% of cyano-p-phenylenediamine was dissolved in the reactor to prepare a mixed solution.

Then, 100 mol% of terephthaloyl dichloride and 0.6 wt% of polyvinylpyridine (based on the weight of the copolymerized aramid polymer) were simultaneously added to the reactor containing the mixed solution to prepare a polymerization solution containing the copolymerized aramid polymer.

Subsequently, the polymer solution was extruded through a spinneret, and then passed through an air gap and a coagulating liquid sequentially to form a multifilament having a linear density of 3,000 denier. The pressure in the spinning pack was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).

Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched by a drying roller set at a temperature of 150 ° C. The drawn multifilament was heat-treated at 250 ° C and wound up to produce a copolymerized aramid fiber.

0.5 g of the copolymerized aramid fiber prepared as described above was added to 100 ml of distilled water and 0.2 g of the above dye (Blue GL 300%) and 1.2 ml of glacial acetic acid were added and the mixture was dyed at 100 ° C for 1 hour. , And dried.

Table 1 shows the results of evaluating the dyeability, intrinsic viscosity and radioactivity of the produced copolymerized aramid fibers.

Example 2

An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl ₂ was placed in a reactor under a nitrogen atmosphere, and 100 mol% of cyano-p-phenylenediamine The mixture was put into the reactor and dissolved to prepare a mixed solution.

Then, 100 mol% of terephthaloyl dichloride and 10 wt% of polyvinylpyridine (based on the weight of the copolymerized aramid polymer) were simultaneously added to the reactor containing the mixed solution to prepare a polymerization solution containing the copolymerized aramid polymer.

Subsequently, the polymer solution was extruded through a spinneret, and then passed through an air gap and a coagulating liquid sequentially to form a multifilament having a linear density of 3,000 denier. The pressure in the spinning pack was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).

Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched by a drying roller set at a temperature of 150 ° C. The drawn multifilament was heat-treated at 250 ° C and wound up to produce a copolymerized aramid fiber.

0.5 g of the copolymerized aramid fiber prepared as described above was added to 100 ml of distilled water and 0.2 g of the above dye (Blue GL 300%) and 1.2 ml of glacial acetic acid were added and the mixture was dyed at 100 ° C for 1 hour. , And dried.

Table 1 shows the results of evaluating the dyeability, intrinsic viscosity and radioactivity of the produced copolymerized aramid fibers.

Example  3

An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl ₂ was placed in a reactor under a nitrogen atmosphere, and 50 mol% of para-phenylenediamine and 40% 50 mol% of cyano-p-phenylenediamine was dissolved in the reactor to prepare a mixed solution.

Then, 100 mol% of terephthaloyl dichloride and 20 wt% of polyvinylpyridine (based on the weight of the copolymerized aramid polymer) were simultaneously added to the reactor containing the mixed solution to prepare a polymerization solution containing the copolymerized aramid polymer.

Subsequently, the polymer solution was extruded through a spinneret, and then passed through an air gap and a coagulating liquid sequentially to form a multifilament having a linear density of 3,000 denier. The pressure in the spinning pack was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).

Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched by a drying roller set at a temperature of 150 ° C. The drawn multifilament was heat-treated at 250 ° C and wound up to produce a copolymerized aramid fiber.

0.5 g of the copolymerized aramid fiber prepared as described above was added to 100 ml of distilled water and 0.2 g of the above dye (Blue GL 300%) and 1.2 ml of glacial acetic acid were added and the mixture was dyed at 100 ° C for 1 hour. , And dried.

Table 1 shows the results of evaluating the dyeability, intrinsic viscosity and radioactivity of the produced copolymerized aramid fibers.

Example  4

An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl ₂ was placed in a reactor under a nitrogen atmosphere, and 100 mol% of cyano-p-phenylenediamine The mixture was put into the reactor and dissolved to prepare a mixed solution.

Then, 100 mol% of terephthaloyl dichloride and 45 wt% of polyvinylpyridine (based on the weight of the copolymerized aramid polymer) were simultaneously added to the reactor containing the mixed solution to prepare a polymerization solution containing the copolymerized aramid polymer.

Subsequently, the polymer solution was extruded through a spinneret, and then passed through an air gap and a coagulating liquid sequentially to form a multifilament having a linear density of 3,000 denier. The pressure in the spinning pack was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).

Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched by a drying roller set at a temperature of 150 ° C. The drawn multifilament was heat-treated at 250 ° C and wound up to produce a copolymerized aramid fiber.

0.5 g of the copolymerized aramid fiber prepared as described above was added to 100 ml of distilled water and 0.2 g of the above dye (Blue GL 300%) and 1.2 ml of glacial acetic acid were added and the mixture was dyed at 100 ° C for 1 hour. , And dried.

Table 1 shows the results of evaluating the dyeability, intrinsic viscosity and radioactivity of the produced copolymerized aramid fibers.

Comparative Example  One

An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl ₂ was placed in a reactor under a nitrogen atmosphere, and 50 mol% of para-phenylenediamine and 40% 50 mol% of cyano-p-phenylenediamine was dissolved in the reactor to prepare a mixed solution.

Then, 100 mol% of terephthaloyl dichloride was added to the reactor containing the mixed solution to prepare a polymerization solution containing the copolymerized aramid polymer. (Polyvinylpyridine is not added)

Subsequently, the polymer solution was extruded through a spinneret, and then passed through an air gap and a coagulating liquid sequentially to form a multifilament having a linear density of 3,000 denier. The pressure in the spinning pack was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).

Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched by a drying roller set at a temperature of 150 ° C. The drawn multifilament was heat-treated at 250 ° C and wound up to produce a copolymerized aramid fiber.

0.5 g of the copolymerized aramid fiber prepared as described above was added to 100 ml of distilled water and 0.2 g of the above dye (Blue GL 300%) and 1.2 ml of glacial acetic acid were added and the mixture was dyed at 100 ° C for 1 hour. , And dried.

Table 1 shows the results of evaluating the dyeability, intrinsic viscosity and radioactivity of the produced copolymerized aramid fibers.

Comparative Example  2

An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl ₂ was placed in a reactor under a nitrogen atmosphere, and 100 mol% of cyano-p-phenylenediamine The mixture was put into the reactor and dissolved to prepare a mixed solution.

Then, 100 mol% of terephthaloyl dichloride and 57 wt% of polyvinylpyridine (based on the weight of the copolymerized aramid polymer) were simultaneously added to the reactor containing the mixed solution to prepare a polymerization solution containing the copolymerized aramid polymer.

Subsequently, the polymer solution was extruded through a spinneret, and then passed through an air gap and a coagulating liquid sequentially to form a multifilament having a linear density of 3,000 denier. The pressure in the spinning pack was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).

Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched by a drying roller set at a temperature of 150 ° C. The drawn multifilament was heat-treated at 250 ° C and wound up to produce a copolymerized aramid fiber.

0.5 g of the copolymerized aramid fiber prepared as described above was added to 100 ml of distilled water and 0.2 g of the above dye (Blue GL 300%) and 1.2 ml of glacial acetic acid were added and the mixture was dyed at 100 ° C for 1 hour. , And dried.

Table 1 shows the results of evaluating the dyeability, intrinsic viscosity and radioactivity of the produced copolymerized aramid fibers.

division Intrinsic viscosity Dyeability (K / S value) Radioactive Example 1 6.2 18.3 Great Example 2 6.3 18.9 Great Example 3 6.5 20.3 Great Example 4 6.6 20.7 Great Comparative Example 1 5.7 3.5 Bad Comparative Example 2 6.5 20.7 Bad

The strength and radioactivity of the above Table 1 were evaluated in the following manner.

Radioactive

The dewulling phenomenon immediately under the spinneret was visually observed, and when it occurred, it was judged to be defective, and when it did not occur, it was judged to be excellent.

Dyeability

The K / S value at the maximum absorption wavelength of the fiber sample dyed on the basis of the control board was measured at 6 points and the average value was obtained.

The higher the K / S value, the sharper and darker the color of the stained sample.

Copolymerization Aramid  Polymer Intrinsic viscosity ( Inherent Viscosity : I.V.) Measurement

The intrinsic viscosity (I.V.) is defined by the following equation.

I.V. = ln (? rel) / C

Where C is the concentration of the polymer solution (solution in which 0.5 g of the polymer is dissolved in 100 ml of concentrated sulfuric acid) and the relative viscosity? Rel is the flow time ratio between the polymer solution and the solvent measured by a capillary viscometer at 30 占 폚. Was measured using a concentrated sulfuric acid solvent of 95 to 98%.

Claims (5)

A copolymerized aramid fiber is prepared by polymerizing a polymerization solution containing a copolymerized aramid polymer by adding terephthaloyl dichloride to an organic solvent in which an aromatic diamine containing a cyano group is dissolved and then radiating and coagulating the polymerization solution As a result,
A process for producing a copolymerized aramid fiber characterized by adding 0.5 to 50% by weight of polyvinylpyridine to the copolymerized aramid polymer in the step of polymerizing the polymerization solution containing the copolymerized aramid polymer The organic electroluminescent device of claim 1, wherein the organic solvent is a diamine including an aromatic cyano group containing a cyano group and dissolves paraphenylenediamine and cyano-para-phenylenediamine in a molar ratio of 1: 9 to 9: 1 By weight based on the total weight of the aramid fibers. The method for producing a co-aramid fiber according to claim 1, wherein cyano-para-phenylenediamine is solely dissolved in the organic solvent as an aromatic diamine containing a cyano group. 2. The method according to claim 1, wherein terephthaloyl dichloride is added to the organic solvent in which the aromatic diamine containing cyano group is dissolved in the same molar amount as the aromatic diamine containing cyano group dissolved in the organic solvent By weight of the aramid fiber. delete