KR20120073959A - Process for preparing aromatic polyamide filament - Google Patents

Process for preparing aromatic polyamide filament Download PDF

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Publication number
KR20120073959A
KR20120073959A KR1020100135892A KR20100135892A KR20120073959A KR 20120073959 A KR20120073959 A KR 20120073959A KR 1020100135892 A KR1020100135892 A KR 1020100135892A KR 20100135892 A KR20100135892 A KR 20100135892A KR 20120073959 A KR20120073959 A KR 20120073959A
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KR
South Korea
Prior art keywords
aromatic polyamide
sulfuric acid
solution
spinning
producing
Prior art date
Application number
KR1020100135892A
Other languages
Korean (ko)
Inventor
김창우
이기환
Original Assignee
주식회사 효성
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Filing date
Publication date
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Priority to KR1020100135892A priority Critical patent/KR20120073959A/en
Publication of KR20120073959A publication Critical patent/KR20120073959A/en

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/04—Dry spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs
    • D10B2505/022—Reinforcing materials; Prepregs for tyres

Abstract

The present invention provides a method for producing an aromatic polyamide filament, wherein p-phenylenediamine and terephthaloyl chloride are polymerized with intrinsic viscosity (IV) 5.5 to 7.0 by polycondensation, and dissolved in sulfuric acid at a concentration of 99.0 to 101.1%. Preparing dope,
After spinning through the spin dope through the spinneret, and passing through the air layer and the coagulation solution continuously, the coagulation solution is characterized in that the aqueous solution of sulfuric acid and ethylen diaminetetra acetic acid of the formula (1) A method for producing an aromatic polyamide filament is provided.

Description

Process for preparing aromatic polyamide filament

The present invention is a method for producing an aromatic polyamide filament, specifically, by using EDTA-2Na 0.5 to 5% by weight compared to the resin content in the coagulation liquid used in the aromatic polyamide wet-dry spinning has improved color and physical properties A method for producing aromatic polyamide fibers.

The wholly aromatic polyamide filaments are prepared by polymerizing aromatic diamine and aromatic dieside chloride in a polymerization solvent containing N-methyl-2-pyrrolidone, as disclosed in US Pat. Nos. 3,869,492 and 3,869,430. Preparing an aromatic polyamide polymer; dissolving the polymer in a concentrated sulfuric acid solvent to produce a spinning stock solution; spinning the spinning stock solution from a spinneret and spinning the spinning material into a coagulant bath through a non-coagulating fluid layer. It is manufactured through a process of forming a filament by passing through, and a process of washing, drying and heat treating the filament.

The prior art related to the coagulation solution is disclosed in Korean Patent Laid-Open No. 2008-22832 to maintain the temperature of the coagulation solution below -5 ° C to rapidly cool the radiated spinning material so that the skin layer is formed thick. In addition, Japanese Patent Laid-Open No. 11-189916 discloses a method for producing a high strength, high elastic aramid fiber by adjusting the ratio of the amount of coagulated liquid to the mass of the filament passed. U.S. Patent No. 4,965,033 and Japanese Patent Application Laid-Open No. 11-189916, Patents on Coagulation Fluid Mass / Speed, disclose the ratio of coagulation liquid mass and filament mass, the ratio of filament speed and coagulation liquid velocity in the spinning tube, orifice. The diameter and the like. U.S. Patent No. 5,330,698 proposes a method for obtaining high elongation by maintaining the coagulating solution temperature at 40 ~ 80 ℃.

In the wet-and-dry spinning method in which a dope dissolved in sulfuric acid passes through a coagulating solution through an air layer through a spinning nozzle, sulfuric acid, which is a solvent, is removed, and sulfuric acid is dissolved in a coagulant used for smooth elution of sulfuric acid present in the filament. It consists of an aqueous solution.

However, in terms of achieving a smooth sulfuric acid leaching due to the osmotic effect is good, the aqueous solution containing sulfuric acid has a strong corrosiveness is adversely affecting the color and physical properties of the aramid fibers due to the corrosion of the equipment and the resulting corrosive.

The present invention is an aromatic polyamide filament manufacturing method, using an aqueous solution of sulfuric acid and ethylen diamine tetraacetic acid in the coagulation solution to prevent the corrosion of the equipment and to remove impurities of the resin, the aromatic poly with improved color and physical properties It is aimed at providing amide filaments.

In order to solve the above problems, according to a preferred embodiment of the present invention, in the method for producing an aromatic polyamide filament, intrinsic viscosity (IV) 5.5 to 7.0 prepared by polycondensation of p-phenylenediamine and terephthaloyl chloride Preparing a spinning dope by dissolving the polymer in sulfuric acid, and spinning the spinning dope through a spinneret, and then continuously passing the air layer and the coagulating solution, wherein the coagulating solution is a sulfuric acid aqueous solution and the following structural formula ( Provided is a method for producing an aromatic polyamide filament, which is an ethylen diaminetetra acetic acid of 1).

C 10 H 14 N 2 O 8 Na 2 2H 2 0 ----- (1)

According to another suitable embodiment of the present invention, it is preferred that the aqueous sulfuric acid solution in the coagulating solution is at a concentration of 3 to 10%.

According to another suitable embodiment of the present invention, the ethylen diaminetetra acetic acid is preferably 0.5 to 5% by weight relative to the total weight of the aromatic polyamide in the coagulation liquid.

In the present invention, to prevent problems caused by using the sulfuric acid aqueous solution as a coagulant solution and to inject the EDTA-2Na, a metal ion collecting agent into the coagulation solution for the purpose of effective removal of impurities contained in the resin to prevent corrosion of the equipment and the remaining of the resin The removal of impurities leads to excellent color and improved fiber properties.

The present invention relates to a method for producing para-aramid fibers having improved color and physical properties by preparing EDTA-2Na in an amount of 0.5 to 5% by weight relative to the resin content in a coagulant used in para-aramid wet and dry spinning.

The present invention is a dry-wet spinning method in which a dope dissolved in sulfuric acid passes through a coagulating solution with an air gap of about 3-20 mm through a spinning nozzle to remove sulfuric acid as a solvent, for smooth elution of sulfuric acid present in the filament. The coagulant used is an aqueous sulfuric acid solution for smooth sulfuric acid elution due to the osmotic effect, specifically, it is preferably a sulfuric acid solution of 3 to 10% concentration. At this time, if the concentration of the sulfuric acid solution is less than 3%, the sulfuric acid dissolution rate in the dope is lowered, and if it exceeds 10%, the equipment corrosion and aramid color and physical properties are inferior.

In order to solve the problems caused when the sulfuric acid aqueous solution is used as a coagulant solution, by adding EDTA-2Na, a metal ion collector, to the coagulant solution to prevent corrosion of the equipment and to remove residual impurities in the resin, excellent color And improved aromatic polyamide filaments. The ethylene diamine tetra acetic acid is preferably 0.5 to 5% by weight based on the weight of the total aromatic polyamide in the coagulation liquid. At this time, if less than 0.5% by weight impurity removal effect is lowered, if it exceeds 5% is economical.

Hereinafter, the configuration and operation of the embodiment according to the present invention will be described in detail.

According to the present invention, in order to increase the solubility of the polyamide polymer, calcium chloride is added to N-methyl-2-pyrrolidone (NMP) to make a polymerization solvent, and aromatic diamine and aromatic dicarboxylic acid halide is added to the polymerization solvent. A para polyamide polymer having improved physical properties such as intrinsic viscosity can be prepared by adding a polymer in a molar ratio of 1: 1.

Aromatic diamines that can be used in the present invention are paraphenylene diamine, 4,4'-diaminobiphenyl, 2-methyl-paraphenylenediamine, 2-chloro-paraphenylenediamine, 2,6-naphthalenediamine, 1 , 5-naphthalenediamine, 4,4'-diaminobenzanilide, and the like can be used.

Aromatic dicarboxylic acid halides that can be used in the present invention include terephthaloyl chloride (TPC), 4,4'-benzoyl chloride, 2-chloroterephthaloyl chloride, 2,5-dichloroterephthaloyl chloride, 2-methyl Terephthaloyl chloride, 2,6-naphthalenecarboxylic acid chloride, 1,5-naphthalenedicarboxylic acid chloride, etc. are mentioned.

In the present invention, para-phenylenediamine is added to the mixed solvent of NMP and calcium chloride, and then terephthaloyl chloride (TPC) is added to polymerize to obtain a para-polyamide polymerization solution. Intrinsic viscosity of the polyamide in the present invention is preferably 5.5 to 7.0. At this time, when the strength is less than 5.5, the strength of the fiber is decreased.

Spinning may be wet, dry, or wet, but in particular, the wet and dry spinning method enables the production of an aromatic polyamide fiber having a uniform structure, thereby making it possible to manufacture fibers having excellent fatigue resistance.

Specifically describing the wet-and-dry spinning process according to the present invention, when the aromatic polyamide solution is quantitatively supplied from the gear pump, the spinning solution discharged through the spinning nozzle passes through the air layer in the vertical direction to reach the interface of the coagulating solution. . The spinning nozzle used is usually circular in shape. Considering the tire cord and the industrial in terms of use, in consideration of the nozzle interval for uniform cooling of the solution, the number of nozzles is preferably 200 to 1,500.

When the fibrous spinning stock solution passing through the spinning nozzle is solidified in the coagulating solution, the larger the diameter of the fluid, the greater the difference in the coagulation rate between the surface and the inside, making it difficult to obtain a dense and uniform fiber. Therefore, even when the aromatic polyamide solution is spun, even the same discharge amount can be obtained into the coagulating solution with a thinner diameter by maintaining an appropriate air layer. Too short air gap distances increase the rate of micropores generated during rapid surface layer solidification and desolvation, which hinders the increase in elongation ratio, while too long air gap distances are associated with filament adhesion, atmospheric temperature, and humidity. It is difficult to maintain process stability by receiving a lot. The air layer is preferably 3 to 20 mm.

Inside the coagulation bath is installed a roller to switch in the horizontal direction. The rollers are rotated to reduce the frictional resistance.

The physical property evaluation of an Example and a comparative example was measured or evaluated as follows.

1) Measuring method of modulus and elongation of multifilament

After leaving the yarn in a standard condition, that is, a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 55 RH% for 24 hours, the sample is measured by a tensile tester using the ASTM 2255 method.

<Comparative Example 1, Examples 1 to 4>

In a polymerization batch reactor equipped with a cooling jacket, 1500 kg of an N-methyl-2-pyrrolidone mixed solution containing 8.2% by weight of calcium chloride was added and maintained at 80 ° C., followed by 90 kg of para-phenylenediamine. It was. The prepared paraphenylenediamine mixture was cooled to 15 ° C., and then molten terephthaloyl chloride was added to the reactor in two equal amounts, followed by polymerization, followed by neutralization, washing, and drying to obtain poly (paraphenyl) having an intrinsic viscosity of 6.3. Lenterephthalamide) polymerization resins were prepared.

Next, the prepared resin was dissolved in 99.9% concentrated sulfuric acid to prepare an optically anisotropic spinning dope having a polymer content of 19.3% by weight. The spinning dope was spun through a 1000-hole spinneret with a hole diameter of 64 microns, passed through a 6 mm air bed, and then passed through a coagulating solution at 5 ° C with a sulfuric acid concentration of 8%. Neutralization was achieved by cleaning the sulfuric acid by spraying water in the configured device and then spraying with dilute caustic soda.

At this time, the coagulation solution containing 8% sulfuric acid used contained EDTA-2Na, and was continuously added in the weight% of Table 1 relative to the resin content.

Yarn tension during washing and neutralization was 0.5 g / d, and the yarn tension was 1 g / d in a drying apparatus consisting of a pair of rollers having a surface temperature of 155 ° C., and the emulsion was applied and then wound on a winder.

Comparative Example 1 Example 1 Example 2 Example 3 Example 4 EDTA-2Na
(Wt% / resin) 0 0.5 One 3 5 Yarn
color L * 76 77 81 83 83 a * -2.9 -3.6 -6.7 -6.8 -6.1 b * 38 40 41 44 41 strong (kg) 34.7 35.4 37.2 37.1 35.4 burglar (g / d) 22.6 22.9 23.9 23.9 22.9 Body (%) 3.64 3.72 3.67 3.60 4.11 Modulus (g / d) 661 622 682 717 622

The yarn colors of Table 1 were measured by L, a, b value of the yarn using a color difference meter manufactured by BYK Gardner.

Although the present invention has been described with reference to the above embodiments, the present invention is not limited thereto. The above embodiments may be modified or changed without departing from the spirit and scope of the present invention, and those skilled in the art will recognize that such modifications and changes also belong to the present invention.

Claims (3)

In the method for producing an aromatic polyamide filament,
preparing a spinning dope by dissolving a polymer of intrinsic viscosity (IV) 5.5 to 7.0 prepared by condensation polymerization of p-phenylenediamine and terephthaloyl chloride in sulfuric acid, and
After spinning the spinning dope through a spinneret, continuously passing through the air layer and the coagulating liquid,
The coagulation solution is an aqueous sulfuric acid solution and a method for producing an aromatic polyamide filament, characterized in that the ethylen diamine tetra acetic acid of the formula (1).
C 10 H 14 N 2 O 8 Na 2 2H 2 0 ----- (1) The method according to claim 1,
The aqueous sulfuric acid solution is a method for producing an aromatic polyamide filament, characterized in that the concentration of 3 to 10%. The method according to claim 1,
The ethylen diamine tetra acetic acid is a method for producing an aromatic polyamide filament, characterized in that 0.5 to 5% by weight relative to the total weight of the aromatic polyamide in the coagulation liquid.
KR1020100135892A 2010-12-27 2010-12-27 Process for preparing aromatic polyamide filament KR20120073959A (en)

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Publications (1)

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