WO2017026745A1

WO2017026745A1 - Highly elastic copolymerized aramid fibers

Info

Publication number: WO2017026745A1
Application number: PCT/KR2016/008641
Authority: WO
Inventors: 이재영; 박영철; 구남대
Original assignee: 코오롱인더스트리(주)
Priority date: 2015-08-07
Filing date: 2016-08-05
Publication date: 2017-02-16
Also published as: JP6482724B2; CN107923073A; KR20170017828A; KR102400545B1; US20180223452A1; JP2018529031A; KR102400545B9

Abstract

Highly elastic aramid fibers, according to the present invention, comprise an aramid copolymer, comprising an aromatic group which substitutes for a cyano group (-CN), and have an elastic modulus of 1,100-1,300g/d, strength of 17-30g/d and elongation of 1-4%. According to the present invention, a solvent content remaining in the fibers is less than 100ppm, which is low, and the crystallinity, crystal size and degree of orientation of the fibers are appropriately controlled by means of heat treating. Therefore, the elastic modulus is greatly enhanced compared to existing aramid fibers even without decrease in strength. The present invention can be utilized as a material for various products which require high elasticity as well as high strength of aramid fibers.

Description

High Elastic Copolymer Aramid Fiber

The present invention relates to high-elastic copolymer aramid fibers, specifically composed of an aramid copolymer containing a cyano group (-CN) substituted aromatic group, the degree of crystallinity, crystal size and orientation of the fiber is properly controlled by heat treatment The present invention relates to a copolymerized aramid fiber having high elasticity without deterioration in strength.

Aramid fibers include para-aramid fibers and meta-aramid fibers. Among them, para-aramid fiber has excellent properties such as high strength, high elasticity, and low shrinkage. Especially, it has a strong strength enough to lift a 2 ton car with a thin thread of about 5mm thick, and is not only used for bulletproof applications. It is used for various purposes in high-tech industries such as aerospace.

Aramid fibers are typically (i) spinning the aramid spinning dope (Dope) through the spinneret 20, as shown in Figure 1, and (ii) coagulating the spun aramid fibers with the coagulation bath (30) Solidification while passing through the solidification tube 40 is injected into the solidification step, and (iii) passing the solidified aramid fibers over the at least one flushing roller 50 as shown in Figure 4, the outside of the top of the flushing roller (50) The washing process by spraying the washing liquid to the aramid fibers passing through the washing roller (50) through the washing liquid injection nozzle (90), and (iv) drying the washed aramid fibers with a drying apparatus (70) and then wound up It is manufactured through a series of winding process in the roller (80).

In this case, as an example of a method for producing the aramid spinning dope (Dope) as described in Korean Patent No. 10-0910537 aromatic diamine such as paraphenylenediamine dissolved in an organic solvent to which inorganic salts are added and mixed Prepare a solution, and add aromatic diacid halides such as terephthaloyl dichloride to the mixed solution. After reacting to prepare an aramid polymer, the prepared aramid polymer was dissolved in sulfuric acid to prepare a spinning dope.

The organic solvent may be N-methyl-2-pyrrolidone (NMP), N, N'-dimethylacetamide (DMAc), hexamethylphosphoamide (HMPA), N, N, N ', N'-tetra Methyl urea (TMU), N, N-dimethylformamide (DMF) or mixtures thereof may be used. As the inorganic salt, CaCl ₂ , LiCl, NaCl, KCl, LiBr, KBr, or a mixture thereof may be used.

The aromatic diamine may be para-phenylenediamine, 4,4'-diaminobiphenyl, 2,6-naphthalenediamine, 1,5-naphthalenediamine, or 4,4'-diaminobenzanilide.

The aromatic dieside halide may be terephthaloyl dichloride, 4,4'-benzoyl dichloride, 2,6-naphthalenedicarboxylic acid dichloride, or 1,5-naphthalenedicarboxylic acid dichloride.

The aramid polymer may be polyparaphenylene terephthalamide, poly (4,4'-benzanilide terephthalamide), poly (paraphenylene-4,4'-ratio depending on the type of aromatic diamine and aromatic dieside halide used. Phenylene-dicarboxylic acid amide), or poly (paraphenylene-2,6-naphthalenedicarboxylic acid amide).

As another example of preparing the aramid spinning dope (Dope) as described in Korean Patent No. 10-171994, paraphenylenediamine and cyano-para-phenylene diamine is dissolved in an organic solvent Terephthaloyldichloride was added and reacted to prepare a spinning dope comprising a copolymer aramid polymer containing an aromatic group substituted with a cyano group (-CN). In this case, there is an advantage that the copolymer aramid polymer can be produced by spinning dope (Dope) without the process of dissolving in sulfuric acid.

Conventional aramid fibers prepared as described above has an organic solvent remaining in the fiber exceeds 100ppm, or the crystallinity, crystal size and orientation of the fiber is not properly controlled by the heat treatment, the aramid fiber elastic modulus is less than 1,100g / d Low, there was a problem that the strength and elongation greatly decrease during the heat treatment.

An object of the present invention is composed of an aramid copolymer containing a cyano group (-CN) substituted aromatic group while maintaining the strength of 17 ~ 30g / d, excellent elastic modulus of 1,100 ~ 1,300g / d and elongation 1 ~ 4% It is to provide a high elastic aramid copolymer aramid fibers.

In order to achieve the above object, in the present invention, the aramid fibers are washed more uniformly and efficiently so that the content of the organic solvent remaining in the aramid fibers is less than 100 ppm, and the degree of crystallinity, crystal size and While properly adjusting the degree of orientation, the elastic modulus of the aramid fibers can be improved without reducing the strength.

In the present invention, the solvent content remaining in the fiber is less than 100ppm and the crystallinity, crystal size and orientation of the fiber are properly controlled by heat treatment, so that the modulus of elasticity is significantly improved than that of the conventional aramid fiber without a decrease in strength.

The present invention is useful as a material for various products in which high elasticity and high elasticity of aramid fibers are required.

1 is a process schematic diagram of making aramid fibers.

2 is a cross-sectional view of a flush roller used in an embodiment of the present invention.

Figure 3 is a schematic view of the process of washing the aramid fibers using the flushing roller of Figure 2 in the present invention.

Figure 4 is a schematic view of the process of washing the aramid fibers by the conventional method.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The high-elastic copolymer aramid fibers according to the present invention is composed of an aramid copolymer containing an aromatic group substituted with a cyano group (-CN) has an elastic modulus of 1,100 ~ 1,300g / d, strength of 17 ~ 30g / d, elongation 1 ~ It is characterized by 4%.

The present invention consists of an aramid copolymer containing an aromatic group substituted with a cyano group (-CN) is 1,100 ~ 1,300g / d, elasticity is 17 ~ 30g / d, crystallinity is 60 ~ 80%, crystal size It is 100-200 kPa (200 faces) and 100-170 kPa (110 faces), and the high elastic copolymerization aramid fiber whose orientation degree (200 faces) is 2-9 degrees.

The aramid copolymer including the aromatic group substituted with the cyano group (-CN) has a repeating unit of the following general formula (I).

[In Formula (I), Ar is an aromatic group of the following general formula (II), and A is an aromatic group of the following general formula (III) or an aromatic group of the general formula (II) Is an aromatic group having a ratio of 1: 9-9: 1]

Various physical properties of the high elastic copolymer aramid fibers according to the present invention was evaluated by the following method.

Crystallinity (%)

The diffraction pattern obtained through X-ray analysis was used to determine the ratio between the peak peak and the amorphous peak.

Crystal size (Å)

The full width at half maximum (FWHM) was obtained using the diffraction pattern obtained through the X-ray analysis and calculated using the Scherrer equation.

Strength (g / d), elongation (%) and modulus (g / d)

Tensile properties of aramid fibers were measured according to the ASTM D885 test method. Specifically, the physical properties of the fiber were obtained by pulling until the copolymer aramid fiber having a length of 25 cm was broken in an Instron Engineering Corp. (Cantion, Mass).

At this time, the tensile speed was 300 mm / min, the ultra-load was fineness × 1 / 30g. The number of samples was calculated | required as the average value after testing five. The modulus of elasticity was obtained from the slope on the S-S curve, the strength was the maximum load at break, and the elongation was calculated from the length at break.

Orientation

After the Azimutal scan (azimuth scan) at the position of each side of the diffraction pattern obtained through X-ray analysis, the orientation angle was obtained by obtaining the full width at half maximum (FWHM) of each peak.

Next, an example of the manufacturing method of the high elastic copolymer aramid fiber of this invention is examined.

The following preparation method is merely an example of the preparation of the high elastic copolymer aramid fibers of the present invention and should not be construed as limiting the protection scope of the present invention.

First, the present invention performs the step of preparing a spinning dope for producing aramid fibers. Specifically, an inorganic salt is added to the organic solvent to prepare a polymerization solvent, and then paraphenylenediamine and cyano-para-phenylenediamine are dissolved together in the organic solvent or cyano-para-phenylenediamine alone. After dissolving the mixture, a mixed solution was prepared, followed by primary polymerization by adding a small amount of terephthaloyldichloride to the mixed solution while stirring the mixed solution to form a prepolymer in the polymerization solvent.

Thereafter, terephthaloyldichloride was further added to the polymerization solvent to carry out the second polymerization to obtain a spinning dope for preparing aramid, in which a copolymerized aramid copolymer containing an aromatic group substituted with a cyano group (-CN) was dissolved in an organic solvent. Manufacture.

At this time, the organic solvent is N-methyl-2-pyrrolidone (NMP), N, N'- dimethylacetamide (DMAc), hexamethylphosphoramide (HMPA), N, N, N ', N' -Tetramethyl urea (TMU), N, N-dimethylformamide (DMF) or mixtures thereof can be used. As the inorganic salt, CaCl ₂ , LiCl, NaCl, KCl, LiBr, KBr, or a mixture thereof may be used.

Next, after spinning the spinning dope (Dope) prepared as described above as shown in Figure 1 through the spinneret 20, the coagulated bath 30 and the coagulating liquid is injected to the spun aramid fibers After passing through the coagulation tube 40 in turn, the coagulated aramid fiber is passed through the water washing rollers 50 and 60 in turn and washed with water, followed by heat treatment in the heat treatment apparatus 70 to obtain crystallinity, crystal size and orientation of the aramid fiber. After being controlled appropriately, the winding roller 80 is wound to produce high-elastic copolymer aramid fibers.

At this time, in the embodiment of the present invention, as shown in FIG. 2, the surface of the washing liquid injection port 51 for injecting the washing liquid with the centrifugal force generated by the rotation of the washing roller 50, the washing roller 50 ) Is formed inside the outer circumferential circle of the water washing roller (50) concentric with the hollow washing liquid supply pipe 52, the washing liquid injection port 51 is in communication with the washing liquid supply pipe (52) The aramid fibers (Y) are washed with a water washing roller 50 so that the content of the organic solvent remaining in the aramid fibers (Y) is less than 100 ppm.

Specifically, when the aramid fiber (Y) passes over the flushing roller 50, the flushing liquid contained in the flushing liquid supply pipe 52 formed in the flushing roller 50, as shown in Figure 3 the flushing roller The centrifugal force generated by the rotation of (50) is injected in the aramid fiber (Y) direction through the washing liquid injection port 51 formed on the surface of the washing roller (50).

Therefore, the jetted washing solution can be penetrated smoothly into the inside of the aramid yarn Y passing through the washing roller 50, so that the content of the organic solvent remaining in the aramid fiber Y can be lowered to less than 100 ppm. do.

In addition, in the embodiment of the present invention, the water-treated aramid fibers are heat treated for 0.5 to 20 seconds at a tension of 250 to 500 ° C. under tension or 0.01 to 5 g / d, and the water content during the heat treatment is adjusted to 5 to 100%. Do it.

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

However, the following examples are only examples of preferred embodiments of the present invention and should not be construed as limiting the protection scope of the present invention.

Example 1

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 p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.

Subsequently, 100 mol% of terephthaloyl dichloride was added to the reactor containing the mixed solution to prepare a spinning dope including a copolymerized aramid polymer.

Subsequently, as shown in FIG. 1, after the spinning dope is spun through the spinneret 20, the spun copolymerized aramid fibers are spun with a coagulation bath 30 and 40 ° C. containing 40 ° C. water (coagulant). After coagulation while passing through the coagulation tube 40 to which water (coagulation liquid) is injected, the coagulated aramid fiber passed through the coagulation tube 40 is continuously flushed to the surface of the water washing roller 50 as shown in FIGS. 2 and 3. Washing liquid injection holes 51 are formed to inject the washing liquid with the centrifugal force generated by the rotation, and the washing liquid which is hollow while forming a concentric circle with the outer circumference of the washing roller 50 inside the washing roller 50. A supply pipe 52 is formed, and the injection holes 51 pass through the flushing roller 50, which is in communication with the flushing liquid supply pipe 52, to the flushing liquid supply pipe 52 formed inside the flushing roller 50. Washing liquid with 50 degreeC water The process of spraying water by spraying toward the copolymerized aramid fibers passing through the washing roller 50 through the washing liquid injection port 51 formed on the surface of the washing roller 50 by the centrifugal force generated by the rotation of the roller 50 is performed. After the heat treatment, the heat treatment apparatus 70 was heat-treated at a temperature of 400 ° C. for 10 seconds under a moisture content of 10% and no tension, followed by winding up to a winding roller 80 to produce copolymerized aramid fibers. The results of evaluating various physical properties of the prepared copolymer aramid fibers were as shown in Table 1.

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 was added. Into the reactor was dissolved to prepare a mixed solution.

Subsequently, as shown in FIG. 1, after the spinning dope is spun through the spinneret 20, the spun copolymerized aramid fibers are spun with a

coagulation bath

30 and 50 ° C. containing 50 ° C. water (coagulant). After coagulation while passing through the coagulation tube 40 to which water (coagulation liquid) is injected, the coagulated aramid fiber passed through the coagulation tube 40 is continuously flushed to the surface of the water washing roller 50 as shown in FIGS. 2 and 3. Washing liquid injection holes 51 are formed to inject the washing liquid with the centrifugal force generated by the rotation, and the washing liquid which is hollow while forming a concentric circle with the outer circumference of the washing roller 50 inside the washing roller 50. A supply pipe 52 is formed, and the injection holes 51 pass through the flushing roller 50, which is in communication with the flushing liquid supply pipe 52, to the flushing liquid supply pipe 52 formed inside the flushing roller 50. Washing liquid with 60 degrees Celsius of water The process of spraying water by spraying toward the copolymerized aramid fibers passing through the washing roller 50 through the washing liquid injection port 51 formed on the surface of the washing roller 50 by the centrifugal force generated by the rotation of the roller 50 is performed. After the heat treatment, the heat treatment apparatus 70 was subjected to heat treatment at a temperature of 400 ° C. for 10 seconds under a moisture content of 10% and 0.5 g / d, and then wound in a winding roller 80 to prepare copolymerized aramid fibers. The results of evaluating various physical properties of the prepared copolymer aramid fibers were as shown in Table 1.

Example 3

Subsequently, as shown in FIG. 1, after the spinning dope is spun through the spinneret 20, the spun copolymerized aramid fibers are spun with a coagulation bath 30 and 40 ° C. containing 40 ° C. water (coagulant). After coagulation while passing through the coagulation tube 40 to which water (coagulation liquid) is injected, the coagulated aramid fiber passed through the coagulation tube 40 is continuously flushed to the surface of the water washing roller 50 as shown in FIGS. 2 and 3. Washing liquid injection holes 51 are formed to inject the washing liquid with the centrifugal force generated by the rotation, and the washing liquid which is hollow while forming a concentric circle with the outer circumference of the washing roller 50 inside the washing roller 50. A supply pipe 52 is formed, and the injection holes 51 pass through the flushing roller 50, which is in communication with the flushing liquid supply pipe 52, to the flushing liquid supply pipe 52 formed inside the flushing roller 50. Washing liquid with 50 degreeC water The process of spraying water by spraying toward the copolymerized aramid fibers passing through the washing roller 50 through the washing liquid injection port 51 formed on the surface of the washing roller 50 by the centrifugal force generated by the rotation of the roller 50 is performed. After the aging process, the heat treatment apparatus 70 heat-treated at a temperature of 450 ° C. for 15 seconds under 20% moisture content and no tension condition, and then wound the winding roller 80 to prepare copolymerized aramid fibers. The results of evaluating various physical properties of the prepared copolymer aramid fibers were as shown in Table 1.

Example 4

Comparative Example 1

Subsequently, as shown in FIG. 1, the spinning dope was spun through the spinneret 20, and then the spun copolymerized aramid fiber was n-methyl-2-pyrrolidone (NMP) 10% aqueous solution (coagulant). The coagulation bath 30 contained therein and N-methyl-2-pyrrolidone (NMP) 10% aqueous solution (coagulation liquid) are coagulated while passing through the coagulation tube 40 to be injected, and then coagulation tube 40 is continued. Passing the copolymer aramid fibers passed through the washing roller 50 as shown in Figure 4 through the washing liquid jet nozzle 90 outside the top of the washing roller 50, the washing liquid of 15 ℃ water washing roller (50) 2) After washing twice by spraying toward the copolymer aramid fibers passing through the above, and then heat treatment at a temperature of 300 ℃ under a 50% moisture content and 10g / d tension for 30 seconds with a heat treatment apparatus 70, then wound It was wound up to roller 80 to produce copolymerized aramid fibers. The results of evaluating various physical properties of the prepared copolymer aramid fibers were as shown in Table 1.

Comparative Example 2

Subsequently, as shown in FIG. 1, the spinning dope was spun through the spinneret 20, and then the spun copolymerized aramid fiber was n-methyl-2-pyrrolidone (NMP) 10% aqueous solution (coagulant). The coagulation bath 30 contained therein and N-methyl-2-pyrrolidone (NMP) 10% aqueous solution (coagulation liquid) are coagulated while passing through the coagulation tube 40 to be injected, and then coagulation tube 40 is continued. Passing the copolymer aramid fibers passed through the washing roller 50 as shown in Figure 4 through the washing liquid jet nozzle 90 outside the top of the washing roller 50, the washing liquid of 15 ℃ water washing roller (50) 2) After washing twice by spraying toward the copolymer aramid fibers passing through the water, and then heat-treated at a temperature of 500 ° C. under a 50% moisture content and 10 g / d tension for 30 seconds using a heat treatment apparatus 70, and then wound up. It was wound up to roller 80 to produce copolymerized aramid fibers. The results of evaluating various physical properties of the prepared copolymer aramid fibers were as shown in Table 1.

구분division		실시예 1Example 1	실시예 2Example 2	실시예 3Example 3	실시예 4Example 4	비교실시예 1Comparative Example 1	비교실시예 2Comparative Example 2
탄성율Modulus		1,2001,200	1,2501,250	1,1101,110	1,3001,300	900900	1,2501,250
강도(g/d)Strength (g / d)		2424	2222	1818	3030	2020	1515
신도(%)Elongation (%)		2.22.2	3.43.4	1.21.2	3.93.9	4.84.8	4.54.5
배향도(200면)Orientation degree (200 planes)		4°4 °	6°6 °	2°2 °	9°9 °	10°10 °	5°5 °
결정화도(%)Crystallinity (%)		6565	7878	6868	7575	5757	7575
결정크기 (Å)Crystal size (Å)	(200면)(P. 200)	130130	190190	110110	160160	9090	180180
결정크기 (Å)Crystal size (Å)	(110면)(P. 110)	125125	165165	100100	155155	8282	160160

* Description of the sign

10: Extruder 20: spinneret

30: coagulation tank 40: coagulation tube

41: coagulation liquid injection port Y: aramid fiber

50: Suse Roller

70: heat treatment apparatus 80: winding roller 90: washing liquid jet nozzle

J: flushing solution sprayed on aramid fibers

51: washing liquid injection port 52: washing liquid supply pipe

The present invention is useful as a material for various products that require high elasticity together with the high strength properties of aramid fibers, such as a bulletproof material.

Claims

High-elastic copolymer, characterized in that composed of aramid copolymer containing a cyano group (-CN) substituted aromatic group, elastic modulus is 1,100 ~ 1,300g / d, strength is 17 ~ 30g / d, elongation 1 ~ 4% Aramid Fiber.
The crystallinity of the highly elastic copolymerized aramid fibers is 60 to 80%, the crystal size is 100 ~ 200Å (200 faces) and 100 ~ 170Å (110 faces), the degree of orientation (200 faces) is 2 ~ 9 ° Highly elastic copolymerized aramid fiber, characterized in that.
The aramid copolymer according to claim 1, wherein the aramid copolymer comprising an aromatic group substituted with a cyano group (-CN) has a repeating unit of the following general formula (I).

[In Formula (I), Ar is an aromatic group of the following general formula (II), and A is an aromatic group of the following general formula (III) or an aromatic group of the general formula (II) Is an aromatic group having a ratio of 1: 9-9: 1]