KR860000729B1 - Process for preparing aromatic-aliphatic ordered copolyamide fibers - Google Patents

Abstract

Polyamide compd. (II) is prepared from N,N'-bis(4-amino phenyl) terephthalamide(I) by low temperature polymerization with aliphatic diacid chloride in the solution of alkali metal salt dissolved in tertiary amide solvent and added with aromatic tertiary amine as the reaction promoter; where X = 2 - 10. Aromatic or aliphatic copolymerized polyamide fiber having high strength and elasticity is manufactured from (II) by dissolving in high polar solvent, liquid crystal spinning, and thermal elongation.

Description

Method for producing aromatic-aliphatic copolymerized polyamide fibers in which structural units are regularly arranged

1 is a phase change curve of the relationship between concentration and temperature when poly-N, N'-bis (4-phenyl) terephthalamideadipamide polymer (inh = 2.34) is dissolved in 100% sulfuric acid. This curve shows the range of the temperature and concentration of anisotropic which is the preparation region of the liquid crystal spinning solution.

2 shows poly-N, N'-bis (4-phenyl) terephthalamideadipamide (PTAd), poly-N, N-bis (4-phenyl) terephthalamidesuberamide (PTSb), poly-N, The polymers of N'-bis (4-phenyl) terephthalamide sebakamide (PTSe) and poly-N, N'-bis (4-phenyl) terephthalamidedecanedicarboxamide (PTDe) were dissolved in 100% sulfuric acid. The viscosity at the time is a curve showing the relationship with the concentration (the measurement conditions of viscosity are a temperature of 25 ° C. and a shear rate of 7.5 sec ⁻¹ ). This curve shows that there is a sharp drop in viscosity above the critical temperature at which the poly-N, N'-bis (4-phenyl) terephthalamideadipamide solution forms a liquid crystal, whereas in other polymer solutions, this figure It can be seen that the liquid crystal is formed at a concentration higher than the concentration range shown in FIG.

The present invention relates to a process for the production of aromatic-aliphatic copolymerized polyamide polymers having a novel chemical structure and having a regular arrangement, and to a process for producing new synthetic fibers of high strength and high modulus by liquid crystal spinning from these polymers. Fibers so far known for their high strength and high elasticity as fibers and commercially available under the trade name "Kevlar" from DuPont are described in US Pat. Nos. 3,600,350 and 3,671,542. However, it should be noted that these "cablas" are fibers made by liquid crystal spinning from wholly aromatic pulloamide polymers. These wholly aromatic polyamides are very rigid throughout their molecular chains, so that their fibers have a low elongation of less than 5%, as well as a significant drawback of fibrillation and splitting of the fibers themselves. Due to this drawback, when these fibers are used in tire cords or other places of high friction, the durability is extremely weak. On the other hand, aliphatic polyamides, ie, general nylon fibers, which have a flexible molecular chain, have a high elongation and a small tendency to fibrillation, but their use is limited because their strength and elastic modulus are relatively low and heat resistance is insufficient.

Accordingly, an object of the present invention is to obtain a high strength, high modulus and high heat resistant fibers having improved physical properties by reducing the disadvantages of the conventional wholly aromatic polyamide fibers and aliphatic polyamide fibers. In other words, by preparing and obtaining a new polymer having regularly introduced flexible aliphatic units between rigid aromatic amide units, and liquid crystal spinning to produce aromatic-polyamide fibers, new high strength and high heat resistance without fibrillation tendency and excellent heat resistance The main object of the present invention is to prepare a fiber of elastic modulus.

As far as is known, in order to produce fibers of high strength and high modulus of elasticity, the polyamide-based polymer, which forms the fibers, must be able to form a lyotropic liquid crystal in a solution state. It has been found that the aromatic-aliphatic polyamides produced have the properties of forming such liquid crystals.

In the present invention, N, N'-bis (4-aminophenyl) terephthalamide represented by the following structural formula (1) is disclosed in the Republic of Korea Patent No. 11,475,

Was used as a polymerization starting material, and this was polycondensed with various kinds of aliphatic diacid chlorides to prepare polymers of aromatic-aliphatic ordered copolyamides, respectively. And high modulus fibers can be obtained. N, N'-bis (4-aminophenyl) terephthalamide is a diamine having the same aromatic amide units as the structural units of poly-p-phenyleneterephthalamide fibers, which are representative of high strength and high modulus fibers. The structure itself is shaped like a rigid rod. When an aliphatic dieside chloride is reacted with this diamine to prepare a polyamide-based polymer, these aromatic amide units act as mesogens in the molecular chain. In other words, the produced aromatic-aliphatic ordered copolyamides appear to form liquid crystals by the role of mesogens, and when dissolved in concentrated sulfuric acid, they form liquid crystals at relatively low critical concentrations. The chains can be easily oriented in the fiber axis direction to allow the production of fibers with high strength and high modulus.

A preparation example of an aromatic-aliphatic polyamide has been proposed by US Pat. No. 4,307,531, in which case 4, 4'-diaminoadipanilide,

Was prepared as a polymerization starting material, and this was subjected to polycondensation with an aromatic dieside chloride to prepare an aromatic-aliphatic polyamide. However, in this patent method, since only a polymer having a very low polymerization degree can be obtained, it is not possible to manufacture fibers having high strength and high modulus.

Accordingly, in order to achieve the above object of the present invention, the present invention firstly dissolves an alkali metal salt in a tertiary amide solvent, and adds N, N'- in a polymerization solvent in which an aromatic tertiary amine is added as a reaction accelerator. Polyamide of formula (2) is prepared by low temperature polycondensation of bis (4-aminophenyl) terephthalamide and aliphatic dieside chloride.

Here, x is an integer of 2-10.

Next, in the present invention, the polyamide of the structural formula (2) obtained above is dissolved in a high polar solvent and thermally stretched after liquid crystal spinning by a known method to obtain an aromatic-aliphatic ordered copolymerized polyamide fiber having high strength and high modulus.

According to the method of the present invention, each of the polymers prepared is N, N'-bis (4-aminophenyl) terephthalamide with succinyl chloride, glutaryl chloride, adipoyl chloride, pimeroyl chloride, It is produced by condensation polymerization with monochloride, azeolayl chloride, sebacoyl chloride, 1, 9-nonanedicarboxylic acid chloride or 1, 10-decanedicarboxylic acid chloride. Each of these polymers is as follows.

Poly-N, N'-bis (4-phenyl) terephthalamidesuccinamide, poly-N, N'-bis (4-phenyl) terephthalamideglutalamide, poly-N, N'-bis (4-phenyl) Terephthalamideadipamide, poly-N, N'-bis (4-phenyl) terephthalamidepimeramide, poly-N, N'-bis (4-phenyl) terephthalamidesuberamide, poly-N, N ' -Bis (4-phenyl) terephthalamideazeraamide, poly-N, N'-bis (4-phenyl) terephthalamide sebakamide, poly-N, N '-(4-bisphenyl) terephthalamidenonanedicarbox Amides, poly-N, N'-bis (4-pheny) terephthalamidedecanedicarboxamide.

Each of these polymers can form a liquid crystal in a solution state, and the production of fibers is also possible. However, in the case of poly-N, N 'bis (4-phenyl) terephthalamide adiamide, in which x = 4 among these nine polyamides, the critical temperature of liquid crystal formation is low, and a liquid crystal spinning solution can be easily produced. From which the best results are obtained. In the case of polymers other than poly-N, N'-bis (4-phenyl) terephthalamideadipamide, fibers having high strength and high modulus of elasticity because the critical temperature for forming the liquid crystal is too high or liquid crystal spinning is difficult. Could not be manufactured, but could be used as a film or heat resistant paint for a specific use.

N, N'-bis (4-aminophenyl) terephthalic acid amide is reacted with adipoyl chloride to give the poly-N, N'-bis (4-aminophenyl) terephthalamideadipamide polymer of the following formula (3),

To prepare them, solution low temperature polymerization should be carried out. N, N'-bis (4-aminophenyl) terephthalamide is a pale yellow solid amine, which is dissolved in a tertiary amide solvent and adipoyl chloride in liquid form at room temperature is added as chemical equivalent to HCl. During the production, polycondensation reactions occur rapidly at room temperature as in the following reaction formula.

At this time, as a polymerization solvent, N, N'- dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, N-methyl piperidone, N, N, N ', N'- tetramethylurea, N -Methyl caprolactam, N, N'-diethylacetamide, N-ethylpyrrolidone, N-acetylpyrrolidone alone or an appropriate mixture thereof are useful, and in order to increase the solubility of the reactants and the resulting polymer. It is effective to add alkali metal salts such as calcium chloride and lithium chloride in a weight ratio of 1-5% to these amide solvents. In order to further facilitate the reaction, it is advantageous to add an aromatic nitrogen hetoro cyclic compound such as pyridine, piclin, quinoline, etc. to the amide solvent in a weight ratio of 2-9% before the reaction to increase the degree of polymerization. Do. As the aliphatic dieside chloride, various kinds of the aforementioned compounds can be used. Among the patents, the fact that adifoyl chloride can be the most suitable for producing high strength and high modulus fibers has been mentioned above. When the polymerization reaction is completed in this way, excess water is added to the polymerized compound, pulverized with a mixer to precipitate the polymer, and then filtered to separate and recover the polymer. The recovered polymer can be washed several times with water and then dried in a vacuum dryer to be used for spinning the fibers.

In order to evaluate the molecular weight of the polymer of the present invention prepared above, the dried polymer was dissolved in 97% sulfuric acid at a concentration (c) of 0.5 g / dl, and the relative viscosity (η rel) was measured.

By the intrinsic viscosity (η inh), and then the molecular weight of the polymer is evaluated relative to this value.

The polymer produced in the present invention has an intrinsic viscosity value in the range of 1.0-3.5, but at least the intrinsic viscosity is preferably at least 2.0 for producing high strength fibers. In addition, the polymer is thermally very stable, and according to differential thermal analysis and gravimetric thermal analysis, it can be seen that decomposition occurs at 390 ° C. or higher. The heat resistance is slightly lower than that of the wholly aromatic polyamide. The heat resistance is higher than about 200 ℃ than ordinary nylon.

In order to produce high strength and high modulus fibers from the polymer of the present invention, first, the dried polymer is dissolved in concentrated sulfuric acid to prepare a liquid crystal spinning solution, and the liquid crystal spinning solution is spun by a known method to obtain desired fibers. have. The liquid crystal spinning solution uses 97-100% sulfuric acid as a solvent, to which a polymer is added at a weight ratio of 15-40% (the preferred concentration is around 20%), and the mixture is slowly heated to obtain a temperature of 50-%. Maintain at 120 ° C. and continue stirring until the polymer is completely dissolved. When the polymer is completely dissolved, it becomes a brown, highly viscous solution. The viscous solution exhibits a suspension-like phenomenon when stirred, and when observed under a polarized microscope, optical anisotropy, that is, a liquid crystal phenomenon. In particular, poly-N, N'-bis (4-phenyl) terephthalamideadipamide polymers, which are most suitable for the production of high strength and high modulus fibers, are dissolved in 100% sulfuric acid in a wide concentration range as shown in FIG. It forms liquid crystal paper, and the critical density is considerably low about 15% at normal temperature. That is, the concentration and temperature at which the region belonging to the anisotropy in the phase diagram of FIG. 1 can prepare a liquid crystal spinning solution from poly-N, N'-bis (4-phenyl) terephnalamide adiamide Range. These liquid crystal solutions show a sudden drop in viscosity due to the formation of liquid crystals as the concentration increases, as shown in FIG.

As a solvent for preparing a liquid crystal spinning solution from the polymer of the present invention, in addition to concentrated sulfuric acid, hydrogen fluoride, chlorosulfonic acid, methanesulfonic acid, or the aforementioned amides are added to the solvent and alkali metal salts such as calcium chloride and lithium chloride to the amide solvent One solvent and the like can be used. The liquid crystal spinning solution obtained by the use of these solvents can be used not only for the production of fibers by spinning, but also for the production of other moldings such as films.

Using the liquid crystal spinning solution, it becomes possible to produce fibers of high strength and high modulus by dry-jet spinning as described in US Pat. No. 3,671,542. In detail, the liquid crystal spinning solution is maintained at a temperature of 35-90 ° C. and injected through a spinning nozzle (eg, spinneret diameter 0.1 mm, spinneret number 12). The injected spinning solution saddles (stretches) while passing through the air gap (e.g. 1-2 cm) between the spinning nozzle and the coagulant, immediately enters into the coagulant and coagulates. Wind up in a winding roller. In the wet wet spinning method, unlike the conventional wet spinning method, an air gap is provided between the spinning nozzle and the coagulant liquid. The fiber is stretched by the difference between the linear velocity of the working liquid and the retraction velocity, that is, the linear velocity of the fiber wound on the winding roller. Since the polymer molecular chains in the solution state, in particular the liquid crystal solution state, are oriented in the fiber axis direction by the tension of the ejected spinning solution, the resulting fiber shows high orientation and also has high strength and high elastic modulus. In the characteristics of the fiber produced, in the case of the poly-N, N'-bis (4-phenyl) terephthalamide adipamide fiber which is easy to prepare a liquid crystal spinning solution, the strength is 10-22 g / den. And the elastic modulus is 250. -600 g / den. As excellent as it is. Other aromatic-aliphatic polyamides that are difficult to prepare liquid crystal spinning solutions, namely poly-N, N'-bis (4-phenyl) terephthalamidesveramide, poly-N, N'-bis (4-phenyl) terephthalamide In the case of sebacamide, poly-N, and N'-bis (4-phenyl) terephthalamide decancarboxamide fibers, the strength and elastic modulus range 4-10 g / den, respectively. And 70-200 g / den. to be. In particular, in the production of poly-N, N'-bis (4-phenyl) terephthalamideadipamide fibers, the equipment of the liquid crystal spinning solution, that is, the injected spinning solution is produced according to the magnification in the longitudinal direction in the air gap. The orientation of the fibers is markedly different, which results in different strengths and moduli. In other words, the fiber having a larger tensile capacity exhibits not only orientation but also excellent strength and elastic modulus.

The useful equipment for producing the high strength and high modulus fibers of the present invention is at least 2.0 times. In addition, for example, in the case of "cablas", the heat stretching after spinning is almost impossible in the case of the "aromatic" polyamide fibers, but the fibers of the present invention are surprisingly capable of heat stretching as much as 2.0 times, and the orientation of the fibers is determined by the heat stretching. The property is increased, and the strength and elastic modulus are also greatly improved. Heat-stretched fibers are a much improved fiber compared to wholly aromatic polyamide fibers, which are transparent and easily fibrillated. In particular, although the fiber of the present invention contains an aliphatic chain in the molecular chain of the polymer constituting the fiber, it has a significantly improved characteristic than the wholly aromatic polyamide fiber.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, it should be understood that these examples are merely illustrative of the present invention, and the present invention is not limited only to these examples.

Example 1

Preparation of Poly-N, N'-bis (4-phenyl) terephthalamideadifamide polymers

의 사구 구형 플라스크에 240ml(2.58몰)의 N, N'-디메틸아세트아미드, 7.2g(0.17몰)의 염화리튬 및 13.8g(0.04몰)의 N, N'-비스(4-아미노페닐)테레프탈아미드를 넣고 교반하여 용액을 만든다. 이 용액의 온도를 30℃로 유지시키고, 여기에 15.2ml(0.19몰)의 피리딘을 첨가한 다음, 7.32g(0.04몰)의 아디포일클로리드를 일시에 가하고 격력하게 교반한다. 이 때, 혼합물의 점도가 급격히 상승하면서 수분내에 고점성 용액이 된다. 이를 1시간 동안 계속 교반한 후 상온에서 1일 동안 방치해 둔다. 반응의 완료된 중합 혼합물에 과량의 물을 가하고 믹서로 분쇄하여 중합체를 분말상태로 침전시키고, 이를 여과하여 중합체를 회수한다. 회수된 중합체를 물로수회 세척하여 용매를 완전히 제거한 다음, 80℃의 진공 건조기에서 6시간 이상 건조시킨다. 얻어진 중합체는 연황색 분말이며, 그의 고유 점도는 2.92이다.Capacity with stirrer, thermometer and nitrogen inlet 1

240 mL (2.58 mol) of N, N'-dimethylacetamide, 7.2 g (0.17 mol) of lithium chloride and 13.8 g (0.04 mol) of N, N'-bis (4-aminophenyl) terephthal Add amide and stir to form a solution. The temperature of this solution is maintained at 30 ° C., and 15.2 ml (0.19 mol) of pyridine is added thereto, and then 7.32 g (0.04 mol) of adifoyl chloride are added temporarily and stirred vigorously. At this time, the viscosity of the mixture rises rapidly, resulting in a highly viscous solution in a few minutes. It is kept stirring for 1 hour and left to stand at room temperature for 1 day. Excess water is added to the completed polymerization mixture of the reaction and triturated with a mixer to precipitate the polymer into a powder, which is filtered to recover the polymer. The recovered polymer is washed several times with water to completely remove the solvent and then dried in a vacuum dryer at 80 ° C. for at least 6 hours. The polymer obtained is a pale yellow powder and has an inherent viscosity of 2.92.

Example 2

Preparation of Poly-N, N'-bis (4-phenyl) terephthalamideadifamide polymers

의 사구 구형 플라스크에 240ml(2.58몰)의 N, N'-디메틸아세트아미드, 6.2g(0.06몰)의 염화칼슘 및 13.84g(0.04몰)의 N, N'-비스(4-아미노페닐)테레프탈아미드를 넣고 교반하여 용액을 만든다. 이 용액의 온도를 30℃로 유지시키고 여기에 10.4ml(0.13몰)의 피리딘을 첨가한 다음 7.32g(0.04몰)의 아디포일클로리드를 일시에 가하고 격렬하게 교반한다. 이때, 혼합물의 점도가 급격히 상승하면서 수분내에 고점성 용액이 된다. 이를 1시간 동안 계속 교반한 후 상온에서 1일 동안 방치해 둔다. 반응이 완료된중합 반응 혼합물에 과량의 물을 가하고 믹서로 분쇄하여 중합체를 분말 상태로 침전시키며, 이를 여과하여 중합체를 회수한다. 회수된 중합체를 물로 수회 세척하여 용매를 완전히 제거한 다음, 80℃의 진공 건조기에서 6시간 이상 건조시킨다. 얻어진 중합체의 고유 점도는 2.62이다.This example is a case where calcium chloride is used as the alkali metal salt. Capacity with stirrer, thermometer and nitrogen inlet 1

240 mL (2.58 mol) of N, N'-dimethylacetamide, 6.2 g (0.06 mol) of calcium chloride and 13.84 g (0.04 mol) of N, N'-bis (4-aminophenyl) terephthalamide Add and stir to form a solution. The temperature of this solution is maintained at 30 ° C. and 10.4 ml (0.13 mole) of pyridine is added thereto, followed by 7.32 g (0.04 mole) of adifoyl chloride at once and vigorously stirred. At this time, while the viscosity of the mixture rises rapidly, it becomes a highly viscous solution in a few minutes. It is kept stirring for 1 hour and left to stand at room temperature for 1 day. Excess water is added to the completed polymerization reaction mixture and ground with a mixer to precipitate the polymer in powder form, which is filtered to recover the polymer. The recovered polymer is washed several times with water to completely remove the solvent and then dried in a vacuum dryer at 80 ° C. for at least 6 hours. The intrinsic viscosity of the obtained polymer is 2.62.

Example 3

Preparation of Poly-N, N'-bis (4-phenyl) terephthalamideadifamide polymers

This example is the case where N-methylpyrrolidone is used as a polymerization solvent.

의 사구 구형 플라스크에 240ml(2.49몰)의 N-메틸피롤리돈, 9.6g(0.23몰)의 염화리튬 및 13.84g(0.04몰)의 N, N'-비스(4-아미노페닐)테레프탈아미드를 넣고 교반하여 용액을 만든다. 이 용액의 온도를 25℃로 유지시키고, 여기에 13.7ml(0.17몰)의 피리딘을 첨가한 다음, 7.32g(0.04몰)의 아디포일클로리드르 일시에 가하고 격렬하게 교반한다. 이 때, 혼합물의 점도가 급격히 상승하면서 수분내에 고점성 용액이 된다. 이를 1시간 동안 계속 교반한 후 상온에서 1일 동안 방치해 둔다. 반응이 완료된 중합 혼합물에 과량의 물을 가하고, 믹서로 분쇄하여 중합체를 분말 상태로 침전시키고, 이를 여과하여 중합체를 회수한다. 회수된 중합체를 물로수회 세척하여 용매를 완전히 제거한 다음, 80℃의 진공 건조기에서 6시간 이상 건조시킨다. 얻어진 중합체의 고유 점도는 2.54이다.Capacity with stirrer, thermometer and nitrogen inlet 1

240 mL (2.49 moles) of N-methylpyrrolidone, 9.6 g (0.23 moles) of lithium chloride and 13.84 g (0.04 moles) of N, N'-bis (4-aminophenyl) terephthalamide Add and stir to form a solution. The temperature of this solution is maintained at 25 ° C., to which 13.7 ml (0.17 mole) of pyridine is added, then 7.32 g (0.04 mole) of adifoyl chloride are added and stirred vigorously. At this time, the viscosity of the mixture rises rapidly, resulting in a highly viscous solution in a few minutes. It is kept stirring for 1 hour and left to stand at room temperature for 1 day. Excess water is added to the completed polymerization mixture, triturated with a mixer to precipitate the polymer in powder form, and the polymer is recovered by filtration. The recovered polymer is washed several times with water to completely remove the solvent and then dried in a vacuum dryer at 80 ° C. for at least 6 hours. The intrinsic viscosity of the obtained polymer is 2.54.

Example 4

Preparation of Poly-N, N'-bis (4-phenyl) terephthalamideadifamide polymers

This example is a case where a 1: 1 (volume) mixture of hexamethylspsporamide and N-methylpyrrolidone is used as the polymerization solvent.

의 사구 구형 플라스크에 80ml(0.46몰의 헥사메틸포스포르아미드와 160ml(0.17몰)의 N-메틸필롤리돈 6.9g(0.14몰)의 염화리튬 및 13.84g(0.04몰)의 N, N'-비스(4-아미노페닐)테레프탈아미드를 넣고 교반하여 용액을 만든다. 이 용액의 온도를 20℃로 유지시키고, 여기에 22.8ml(0.28몰)의 피리딘을 첨가한 다음, 7.32g(0.04몰)의 아디포일클로리드를 일시에 가하고 격력하게 교반한다. 이때, 혼합물의 점도가 급격히 상승하면서 수분 내에 고점성 용액이 된다. 이를 1시간 동안 계속 교반한 후 상온에서 1일 동안 방치해 둔다. 반응이 완료된 중합 혼합물에 과량의 물을 가하고 믹서로 분쇄하여 중합체를 분말 상태로 침전시키고, 이를 여과하여 중합체를 회수한다. 회수된 중합체를 물로 수회 세척하여 용매를 완전히 제거한 다음, 80℃의 진공 건조기에서 6시간 이상 건조시킨다. 얻어진 중합체의 고유 점도는 2.48이다.Capacity with stirrer, thermometer and nitrogen inlet 1

80 mL (0.46 mol of hexamethylphosphoramide and 160 ml (0.17 mol) of 6.9 g (0.14 mol) of lithium chloride and 13.84 g (0.04 mol) of N, N'- Add bis (4-aminophenyl) terephthalamide and stir to form a solution, keep the temperature of this solution at 20 ° C, add 22.8 ml (0.28 mole) of pyridine, and then add 7.32 g (0.04 mole) Adipoyl chloride is added at a time and vigorously stirred, at which time the viscosity of the mixture rises rapidly to become a highly viscous solution within minutes, which is kept stirring for 1 hour and left at room temperature for 1 day. Excess water is added to the polymerization mixture and triturated with a mixer to precipitate the polymer into a powder, which is filtered to recover the polymer The washed polymer is washed several times with water to completely remove the solvent and then in a vacuum drier at 80 ° C. for 6 hours. Dry over. The intrinsic viscosity of the obtained polymer is 2.48.

Example 5

Preparation of Poly-N, N'-bis (4-phenyl) terephthalamideadifamide fibers

Into a 100 ml stainless steel vessel equipped with a kneading stirrer, a thermometer and a nitrogen inlet, 12 g of poly-N and N'-bis (4-terephthalamideadipamide polymer (ηinh = 2.72) and 54.6 g of 100% sulfuric acid were stirred. Mix uniformly, heat the mixture to vigorously stir for 20-60 minutes until the polymer is completely dissolved while maintaining the temperature at 60 ° C. This spinning solution exhibits typical liquid crystal phenomena and is highly viscous. The prepared spinning solution is transferred into a spinning machine and maintained at a temperature of 80 ° C., and then filtered through a filter (400 mesh) The filtered spinning solution is spinneret (0.1 mm in diameter, 12 balls of spinneret). The injection speed is 16.2 m / min., And the injected spinning solution is stretched 4.3 times as large as the equipment in the air space, and then solidified in the coagulation solution and wound into a winding roller. 69.6 m / min .. As a coagulating solution, 20-30% aqueous sulfuric acid solution is used, and the prepared fiber is dipped in an aqueous solution of sodium carbonate for 1 day to remove residual equivalents, and dried. Heat drawing is performed within 10 seconds at a draw ratio of 1.3 times at 200 ° C. The fiber produced is 3.2 denier, has an intensity of 18.4 g / den., An elongation of 6.4%, and an elastic modulus of 427 g / den.

Example 6

Preparation of polymers other than poly-N, N'-bis (4-phenyl) terephthalamideadipamide

As in Example 1, 240 ml (2.58 mol) of N, N'-dimethylacetamide as a polymerization solvent, 7.2 g (0.17 mol) of lithium chloride as an inorganic salt alkali metal salt, and 15.2 ml (0.19 mol) of pyridine as a reaction accelerator Polymers other than poly-N, N 'bis (4-phenyl) terephthalamideadipamide were prepared using N, N'-bis (4-aminophenyl) terephthalamide 13.84g (0.04 mol). How to do is shown in Table 1 below.

Table 1

Example 7

Manufacture of fibers other than poly-N, N'-bis (4-phenyl) terephthalamideadipamide

Poly-N, N'-bis (4-phenyl) terephthalamideadipamide, poly-N, N'-bis (4-phenyl) terephthalamide as in Example 5, using 100% sulfuric acid as the spinning solvent. Suberamide, and a method for preparing poly-N, N'-bis (4-phenyl) terephthalamide decane dicarboxamide fibers are shown in Table 2.

[Table 2]

T: strength (g / den.), E: elongation (%), M: elastic modulus (g / den.) D: denier.

Example 8

In the same manner as in Example 5, poly-N, N'-bis (4-phenyl) terephthalamide subberamide, poly-N, N'-bis (4-phenyl) terephthalamide sebakamide and poly-N, N The preparation method of the '-bis (4-phenyl) terephthalamide decanedicarboxamide fiber is shown in Table 3 below.

Table 3

Claims (11)

N, N'-bis (4-aminophenyl) terephthalamide of the following structural formula (1) in a polymerization solvent in which an alkali metal salt is dissolved in a tertiary amide solvent and an aromatic tertiary amine is added as a reaction accelerator. Low-temperature polycondensation of aliphatic dieside chloride leads to a polyamide polymer of the following formula (2), which is dissolved in a high polar solvent and thermally stretched after liquid crystal spinning. Process for producing copolymerized polyamide fiber.

Wherein x is an integer from 2 to 10. The tertiary amide solvent according to claim 1, wherein the tertiary amide solvent is N, N'-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, N, N, N ', N'-tetramethylurea, N , N'-diethylacetamide, N-ethylpyrrolidone, Nmethylpyrrolidone, N-methylcaprolactam and N-acetylpyrrolidone alone or a mixture of two or more thereof . The method of claim 1 wherein the alkali metal salt is selected from lithium chloride and calcium chloride. The method according to claim 1 or 3, wherein the weight ratio of the amount of alkali metal salt used is 1-5%. The method of claim 1 wherein the tertiary amine is selected from pyridine, picoline and quinoline. The method according to claim 1 or 5, wherein the amount of tertiary amine used is 1-50% by weight. The method of claim 1, wherein the aliphatic dieside chloride is succinyl chloride, glutaryl chloride, adipoyl chloride, pimeroyl chloride, submeroyl chloride, azeolayl chloride, sebacoyl chloride, 1, 9-nonanedicarboxylic acid chloride and 1, 10-decanedicarboxylic acid chloride. 8. The method of claim 1 or 7, wherein the aliphatic dieside chloride is adipoyl chloride. The process according to claim 1, wherein the high polar solvent is selected from 97% or more of concentrated sulfuric acid, hydrogen fluoride, chlorosulfonic acid, methanesulfonic acid and tertiary amide solvents. The method according to claim 9, wherein lithium chloride or calcium chloride is necessarily added to the tertiary amide solvent. The method of claim 1, wherein the stretching is performed at a temperature of 90-250 ° C. to a draw ratio of 1.1-2.0 times.

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