KR930000245B1 - Manufacturing process of aromatic polyamide fiber and pulp-type shape fiber - Google Patents

Abstract

Preparing method of title fibers of homopolymer or copolymer having repet unit (I) or (II) [R1=R2=R3= (a), (b), (c) or (d); X=H, Cl, Br, I or C1-4 alkyl or alkoxy; Y=-CH2-, -C(O)- or -O- comprises; adding lewis acid compds, e.g. BF3, AlCl3, FeCl2, FeCl3, ZnCl2, SbCl2 or HgCl2, alone with the amt. of 0.1-0.5 wt.% against pure polymerization solvent (a) or its mixed compds. with inorganic salts or content against (a) 0.1-20 wt.% into (a) of amide or urea solvent alone or their mixture to make first polymerization solvent (b), adding aromatic diamine and aromatic diacidchloride into (b), reacting at -20 - 50 deg.C to make polymer solution (c), the polymer content in (c) against (a) 4-35 wt.%, spinning simultaneously with polymn. accelerating precipitant of tert- amine solvent alone or its compds, containing (b) 0.1-30 wt.%, extruding.

Description

Method for producing aromatic polyamide fibers and pulp-like short fibers

The present invention relates to a method for producing aromatic polyamide fibers and pulp-like short fibers, and more particularly, after dissolving an inorganic salt Lewis acid compound in an amide solvent or a urea pure polymerization solvent, aromatic diamine and aromatic dieside chloride are prepared. The present invention relates to a method for producing a polymer solution by directly reacting the polymer solution with a polymerization accelerator precipitant, which is a mixed solvent with a tertiary amine containing a polymerization solvent, to produce aromatic polyamide fibers or pulp short fibers.

Conventionally, in US Pat. No. 4,500,623 as a technique for producing aromatic polyamide, it is described in the method of polymerization by adding tertiary amine to the amide polymerization solvent, but in the above method, the rapid polymerization rate is caused by the excessive addition of tertiary amine. Due to the gelation within a few seconds, the actual process control is impossible and even if the gelation occurs, the molecular chains show an isotropic orientation without orientation, and has to be left for more than 5 hours to produce a polymer having a property, Korean Patent No. 257542 According to the present invention, an aromatic diamine and an aromatic dieside chloride were added in an amide-based solvent to which an inorganic salt was added, and then a liquid crystal prepolymer was prepared, and then spun, extruded and sprayed simultaneously with a polymerization accelerator precipitant containing a tertiary amine prior to gelation. It is described to produce pulsed short fibers or films. However, even in the above method, the gelling time is not long, and thus there is a problem in stabilizing the process.

Accordingly, an object of the present invention is to provide a method for producing aromatic polyamide and pulsed upper fiber having excellent physical properties by eliminating these problems.

Hereinafter, the present invention will be described in detail.

In the present invention, a primary polymerization solvent is prepared by adding a Lewis acid compound alone or an inorganic salt together with an amide solvent or a urea solvent alone or a mixed solvent thereof, and then adding an aromatic diamine and an aromatic dieside chloride. After the reaction at -20 to 50 ℃ to prepare a polymer solution, the polymer solution is transferred to a detention or pulping apparatus and the polymerization accelerator precipitant containing 0.1 to 30% by weight of tertiary amine solvent alone or primary polymerization solvent At the same time, it is characterized in that the method for producing aromatic polyamide fibers and pulsed top fibers that are spun, extruded, and sprayed.

Hereinafter, the present invention will be described in more detail as follows.

In the present invention, the primary polymerization solvent is an amide solvent or a urea solvent (eg, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMA _C ), hexamethylphospho). Pure polymerized solvent, amide (HMPA), N, N, N ', N'-tetramethylurea (TMU), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO, etc.) alone or a mixed solvent thereof It was made by adding Lewis acid compound alone or an inorganic salt together.

The Lewis acid-based compound (ie, a transition metal compound bound to a halogen element or a compound of group IIIA, IVA, VA or VIA with a halogen element of the periodic table), for example, BF ₃ , BCl ₃ , AlCl ₃ , FeCl ₂ , FeCl ₃ , ZnCl ₂ , SbCl ₂ or HgCl ₂ and the like, the amount of the Lewis acid-based compound is preferably 0.1 to 50% by weight with respect to the pure polymerization solvent, if less than 0.1% by weight solubility increases If the effect is weak and exceeds 50% by weight, there is no further effect of increasing solubility, which is disadvantageous in terms of cost.

In addition, examples of the inorganic salts include CaCl ₂ , LiCl, NaCl, KCl, LiBr or KBr. In this case, it is preferable to use 0 to 20% by weight of the inorganic salt with respect to the pure polymerization solvent.

Basically, when the amount of Lewis acid is low, the amount of inorganic salt must be increased. When the amount of Lewis acid is high, the amount of inorganic salt that needs to be reduced is complementary, but the ability to increase solubility is different depending on the Lewis acid compound. The input method is not necessarily established.

For example, AlCl ₃ is more effective than HgCl ₂ , so even if a small amount is added, it is not necessary to add a large amount of inorganic salt.

Subsequently, an aromatic diamine and an aromatic dieside chloride are added to the primary polymerization solvent to react at low temperature, in particular, -20 to 50 ° C. to prepare a polymer solution. The polymer concentration in the polymer solution is 4 relative to the pure polymerization solvent. It is preferable to make it to 35% by weight. If it is less than 4% by weight, it is possible to obtain a polymer having a high intrinsic viscosity (I.V), but it is disadvantageous in terms of cost, and when it exceeds 35% by weight. Since the solubility of the polymer is reduced, the intrinsic viscosity is lowered.

The polymer solution thus prepared is transferred to a detention or pulping apparatus to obtain a tertiary amine solvent (e.g. pyridine, triethylamine, quinoline, t-butylamine, picoline, pyrimidine, pyrazine, quinoxaline, quittu). Glycine, diethylmethylamine, and the like, and the amount of use is preferably 0 to 30% by weight based on the pure polymer solvent) alone or simultaneously with the polymerization accelerator precipitant containing 0.1 to 30% by weight of the primary polymerization solvent. Alternatively, when extruded or sprayed, aromatic polyamide fibers and pulp-like short fibers in the form of homopolymers or copolymers having repeating units represented by the following structural formulas (I) or (II) are produced directly.

Wherein R ₁ R ₂ R ₃ is

Is selected from the above, X is H, C1, Br, I is an alkyl or alkoxy group having 1 to 4 carbon atoms,

I.V of the polymer of the polymer solution prepared in the present invention was 4.0 ml / g or more, and the degree of crystallinity was 45% or more and the aromatic polyamide having an orientation of 25 ° or less.

The intrinsic viscosity of the polymer produced in the present invention is obtained from the following relationship.

Where C is the concentration of the polymer solution (the solution of 0.125 g of the polymer dissolved in 25 ml of 95-98% sulfuric acid), and the relative viscosity η rel is the flow time ratio between the solvent and the solution measured with a capillary viscometer at a temperature of 30 ° C. Solvent is 95-98% concentrated sulfuric acid.

The great effect of the present invention is that if the polymerization is performed by using a transition metal compound combined with an inorganic salt and a halogen element or a compound of group IIIA, group IVA, group VA or group VIA with a halogen element and tertiary amine simultaneously, In comparison, the gelation time can be increased by at least 1.5 times to stabilize the process, and the solubility of the polymer in the polymerization solvent can be increased by about 2 times, which can stabilize the process and reduce manufacturing costs. In the manufacture of fiber or film, even if the shear rate is 5sec ^-1 , the orientation of polymer molecules is less than 25 °, and the development of fibril is easy due to the increase in the orientation of molecules due to slight shear rate or elongation force. This has the advantage of easy pulping.

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

Example 1

After fully purifying the 2 liter reactor with nitrogen to completely remove moisture, 10.0 g of calcium chloride and 20 g of BF ₃ were added to NMP 400ml to prepare a primary polymerization solvent, and the temperature was raised to 70 ° C to completely dissolve 1,4-phenyl. Add 24.5 g of lendiamine and dissolve it. After dissolving the solution for 10 minutes and lowering it to 5 ° C. with water and ice, 45.95 g of terephthaloyl chloride was added and polymerized to prepare a polymer solution, which was then transferred to a spinning apparatus, where pyridine containing 5% by weight of the primary polymerization solvent was used. The fiber was spun to a polymerization accelerator precipitant, which is a mixed solvent, washed with water and dried to prepare a fiber directly.

In this case, the polymer IV of the polymer solution was 2.3 ml / g, the fiber IV of the prepared fiber was 6.7 ml / g, the crystallinity was 64%, and the orientation was 17.

Example 2

Except that the composition of the primary polymerization solvent and the preparation of the precipitant were changed as in Table 1, it was carried out as in Example 1, and the results are shown in Table 1 below.

TABLE 3

Example 3

After sufficiently purifying the 2 liter reactor with nitrogen to completely remove the water, add 20 g of calcium chloride and 40 g of BF ₃ to NMP 300ml, and completely dissolve by raising the temperature to 70 ° C. Then, add 25.4 g of 1,4-phenylene diamine and dissolve for 10 minutes. Let's do it. The solution was lowered to 5 ° C. with water and ice, and then 45.95 g of terephthaloyl chloride was added to polymerize to prepare a polymer solution, which was transferred to a spinning device and spun to 100% pyridine to prepare fibers.

At this time, I.V of the polymer of the polymer solution was 3.2ml / g, I.V of the prepared fiber was 6.4ml / g, the crystallinity was 60% and the degree of orientation was 20 °.

Example 4

After sufficiently purifying the 2 liter reactor with nitrogen to completely remove the water, add 20 g of calcium chloride and 40 g of FeCl ₃ to 200 ml of NMP, and completely dissolve the temperature by raising the temperature to 70 ° C. Then, add 25.4 g of 1,4-petylene diamine and add 10 minutes. Dissolve. The solution was lowered to 5 ° C. with water and ice, and then polymerized by adding 45.95 g of terephthaloyl chloride. The polymer solution was washed and transferred to a spinning apparatus. The fiber was spun onto triethylamine containing 10% by weight of the primary polymerization solvent. Was prepared.

At this time, I.V of the polymer of the polymer solution was 2.5ml / g, I.V. of the prepared fiber was 5.7ml / g, the crystallinity was 58% and the orientation was 21 °.

Example 5

After fully purifying the 2 liter reactor with nitrogen to completely remove moisture, add 30 g of calcium chloride and 40 g of AlCl ₃ to 600 ml of NMP, and completely dissolve by raising the temperature to 70 ° C. Then, add 25.4 g of 1,4-petylene diamine and dissolve for 10 minutes. Let's do it. After the solution was lowered to 5 with water and ice, 45.95 g of tefephthaloyl chloride was added thereto to polymerize to prepare a polymer solution, which was then transferred to a spinning device, whereupon the fiber was spun onto pyridine containing 5% by weight of the primary polymerization solvent. Prepared.

At this time, I.V of the polymer of the polymer solution was 3.7ml / g, I.V of the prepared fiber was 6.5ml / g, the crystallinity was 65% and the orientation was 19 °.

As a result of measuring the physical properties of the fiber, D / E / T / Mi was 1.5 / 3.0 / 23/540. (However, D: denier, E: elongation, T: strength, Mi: modulus)

Example 6

After fully purifying the 2 liter reactor with nitrogen to completely remove water, add 10 g of calcium chloride and 40 g of ZnCl ₂ to NMP 150ml, completely dissolve it by raising the temperature to 70 ° C, add 25.4 g of 1,4-petylene diamine and dissolve for 10 minutes. Let's do it. The solution was lowered to 5 ° C. with water and ice, and then polymerized by adding 45.95 g of terephthaloyl chloride to prepare a polymer solution. The polymer solution was transferred to a spinning device and spun in pyridine containing 20% of the primary polymerization solvent to prepare fibers. .

At this time, I.V. of the polymer of the polymer solution was 1.7ml / g, I.V. of the prepared fiber was 5.2ml / g, the crystallinity was 45% and the orientation was 25 °.

As a result of measuring the physical properties of the fiber, D / E / T / Mi was 1.5 / 3.5 / 21/530. (However, D: denier, E: elongation, T: strength, Mi: modulus)

After completely purifying the 2 liter reactor with nitrogen to completely remove the water, add 70 g of ZnCl ₂ to NMP 150ml, completely dissolve by raising the temperature to 70 ° C, and then dissolve 10 minutes with 25.4 g of 1,4-phenylene diamine. After the solution was cooled to 5 ° C. with water and ice, 45.95 g of terephthaloyl chloride was added thereto to polymerize to prepare a polymer solution, which was then transferred to a spinning device to spun into pyridine containing 20% of the primary polymerization solvent to prepare fibers. .

At this time, I.V. of the polymer of the polymer solution was 2.5ml / g, I.V. of the prepared fiber was 5.8ml / g, the crystallinity was 55% and the orientation was 21 °.

Comparative Example 1

The 2 liter reactor was thoroughly purged with nitrogen to completely remove water, and then 10.0 g of calcium chloride was added to 150 ml of NMP, and the temperature was raised to 70 ° C. to completely dissolve. Then, 24.5 g of 1, 4-phenylene diamine was added and dissolved. After dissolving the solution for 10 minutes and lowering to 5 ° C. with water and ice, 45.95 g of terephthaloyl chloride was added and polymerized. As a result, gelation occurred with precipitation formation within 1 minute, and I.V was 2.3 ml / g. I.V was 3.1 ml / g even when the polymer was precipitated in pyridine to complete the reaction.

Comparative Example 2

After fully purifying the 2 liter reactor with nitrogen to completely remove water, add 30 g of calcium chloride and 50 g of AlCl ₃ to 700 ml of NMP, raise the temperature to 70 ° C, completely dissolve, and then add 25.4 g of 1,4-phenylene diamine for 10 minutes. Dissolve. After the polymer solution was lowered to 0 ° C. with water and ice, 45.95 g of terephthaloyl chloride was added to the polymer solution to prepare a polymer solution, and the reaction was continued. At this time, the time required for the gelation to occur was more than 20 hours, the gelation occurred after 2 hours in the conventional method without adding 50g AlCl ₃ in the experimental conditions.

Comparative Example 3

After fully purifying the 2 liter reactor with nitrogen to completely remove the water, add 30 g of calcium chloride and 50 g of AlCl ₃ to NMP400ml, dissolve it completely by raising the temperature to 70 ° C, add 25.4 g of 1,4-phenylene diamine and dissolve for 10 minutes. . The solution was lowered to 5 ° C. with water and ice, and then 45.95 g of terephthaloyl chloride was added to polymerize to prepare a polymer solution. In this case, the gelation time was 15 hours or more, and the gelation occurred after 1.5 hours by the conventional method in which 50 g of AlCl ₃ was not added under the experimental conditions.

Example 7

After completely purifying the 2 liter reactor with nitrogen to completely remove the water, 30 g of calcium chloride and 30 g of AlCl ₃ were added to 400 ml of NMP, and the temperature was raised to 70 ° C. to completely dissolve. Then, 24.5 g of 1,4-phenylene diamine was added and dissolved. After dissolving the solution for 10 minutes, the mixture was lowered to 5 ° C. with water and ice, and then polymerized by adding 45.95 g of terephthaloyl chloride to a polymerizing solution. Pulp-like short fibers were prepared by extrusion and spraying simultaneously with Dean.

At this time, I.V. of the polymer of the polymer solution was 2.5ml / g, I.V. of the prepared pulsed short fibers was 6.1ml / g, the crystallinity was 58%, and the degree of orientation was 21 °.

Example 8

2 liters of semi-silver is completely purged with nitrogen to completely remove moisture. Then, 15 g of calcium deterioration and 30 g of AlCl ₃ are added to 400 ml of NMP, and the temperature is raised to 70 ° C. to completely dissolve the 24.5 g of 1,4-petylene diamine. Add and dissolve. After dissolving the solution for 10 minutes, the mixture was lowered to 5 ° C. with water and ice, and then polymerized by placing 45.95 g of terephthaloyl chloride. The polymer solution was transferred to a pulping apparatus and pyridine containing 10% by weight of a primary polymerization solvent. Simultaneously extruded and sprayed to prepare pulsed short fibers.

At this time, I.V. of the polymer of the polymer solution was 2.3 ml / g, I.V. of the prepared pulsed short fibers was 5.9 ml / g, the crystallinity was 53%, and the degree of orientation was 23 °.

Example 9

After completely purifying the 2 liter reactor with nitrogen to completely remove the water, add 5 g of CaCl ₂ and 40 g of ZnCl ₂ to NMP 400 ml, and completely dissolve by heating the temperature to 70 ° C. Then, add 24.5 g of 1,4-phenylene diamine. . After dissolving the solution for 10 minutes and lowering the temperature to 5 ° C. with water and ice, 45.95 g of terephthaloyl chloride was added and polymerized to prepare a polymer solution, which was then transferred to a pulping apparatus and pyridine containing 15% of a primary polymerization solvent. At the same time, the pulp-like short fibers were produced by extrusion and spraying.

At this time, I.V. of the polymer of the polymer solution was 1.9 ml / g, I.V. of the prepared pulp-like short fibers was 5.9 ml / g, the crystallinity was 48%, and the degree of orientation was 25 °.

Example 10

After completely purifying the 2 liter reactor with nitrogen to completely remove water, 40 g of AlCl ₃ was added to 400 ml of NMP, and the temperature was raised to 70 ° C. to completely dissolve. Then, 24.5 g of 1,4-phenylene diamine was added and dissolved. After dissolving the solution for 10 minutes, the mixture was lowered to 5 ° C. with water and ice, and then polymerized by adding 45.95 g of terephthaloyl chloride to prepare a polymer solution, which was then transferred to a pulping apparatus and extruded and sprayed simultaneously with 100% pyridine to give a pulp phase. Short fibers were prepared.

At this time, I.V. of the polymer of the polymer solution was 2.1ml / g, I.V. of the prepared pulsed short fibers was 6.2ml / g, the crystallinity was 50% and the orientation was 24 °.

Claims (6)

Into the pure polymerization solvent which is an amide solvent or urea solvent alone or a mixed solvent thereof, a Lewis acid compound alone or an inorganic salt is added to make a primary polymerization solvent, and then aromatic diamine and aromatic dieside chloride are added. After preparing a polymer solution by reacting at ℃, the polymer solution is transferred to a detention or pulping apparatus, spinning, extrusion, and simultaneously with a tertiary amine solvent alone or a polymerization accelerator precipitant containing 0.1 to 30% by weight of the primary polymerization solvent. A process for producing aromatic polyamide fibers and pulp-like short fibers in the form of homopolymers or copolymers having a repeating unit represented by the following structural formula (I) or (II), characterized by spraying. Wherein R ₁ , R ₂ , and R ₃ are Is selected from the above, X is H, Cl, Br, I, alkyl or alkoxy group having 1 to 4 carbon atoms, The method according to claim 1, wherein the Lewis acid-based compound is composed of a halogen element and a transition metal compound or a halogen element and a compound combined with a group IIIA, group IVA, group VA or group VIA of the periodic table. The method of claim 2, wherein the Lewis acid-based compound is characterized in that the BF ₃ , BCl ₃ , AlCl ₃ , FeCl ₂ , Fecl ₃ , ZnCl ₂ , SbCl ₂ or HgCl _{2 It} contains 0.1 to 0.5% by weight of the hand-polymerized solvent Manufacturing method. The method according to claim 1, wherein the content of the polymer in the polymer solution is 4 to 35% by weight relative to the pure polymer solvent. The pyridine of claim 1, wherein the tertiary solvent is pyridine. A process according to claim 1, which is selected from quinoline, triethylamine, t-butylamine, picoline, pyrimidine, pyrazine, quinoxaline, quituclidine, and dimethylamine. The method according to claim 1, wherein when the inorganic salt is added, the content rate is 0.1 to 20% by weight based on the pure polymer solvent.