KR900008721B1 - Manufacturing process of aromatic polyamide fibre - Google Patents

Abstract

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Description

Method for producing aromatic polyamide fibers

The present invention relates to a method for producing an aromatic polyamide fiber, in particular an aromatic having at least 3.0 or more intrinsic viscosity having a repeating unit of any one or two or more monomers selected from the following structural formulas (I), (II) and (III) A method for producing a polyamide fiber.

In the above formula, R, R ', R "is an aromatic reactor which may be the same or different from each other, M is a transition metal element, L is a ligand (Ligand), n is an integer of 0 to 3.

Aromatic polyamide fibers are lightweight, have high strength and elasticity, and have good abrasion resistance. They are not only widely used in building materials, tire cords of automobiles or special industries in aerospace industries, but also in recent years due to their excellent heat resistance and insulation resistance. It is also attracting attention as a substitute for asbestos, which causes cancer or pollution in the human body.

Looking at the conventional technology for such an aromatic polyamide fiber, US Patent Nos. 3,869,429 and 3,869,430 first mix an aromatic diamine, an inorganic salt, and an aromatic dieside chloride in an amide solvent, and polymerize it to acid crumb (acid) crumb), washed with water and dried, dissolved in 89% or more sulfuric acid solvent to prepare a dope, and then spun into water through water, washed and dried to prepare aromatic polyamide fiber. Although disclosed, these methods require complex separation of the polymer, washing with water and drying to produce sulphate dope, and then spinning it. the risk that the following processes such as CaSO ₄ produced as a by-product is difficult, such as there are a number of problems The.

In addition, U.S. Patent No. 3,673,143 dissolves an aromatic diamine and benzoyl chloride in an amide solvent or a mixed solvent thereof, and then adds an aromatic dieside chloride to polymerize it, and spins the polymer directly into water through a single cell. There is disclosed a method of preparing aromatic polyamide fibers by drying, but in such a method, when the polymerization time is delayed when spinning the polymer, the polymer is gelled and it is difficult to spin. If the polymer is spun before it has a problem that the intrinsic viscosity and physical properties of the molded product falls.

That is, the conventional method for producing aromatic polyamide fibers is uneconomical because the manufacturing process is complicated or the manufacturing cost is high, there is a risk of corrosion of the device by sulfuric acid, risk of degradation of the polymer due to decomposition reaction of the polymer. In addition, there was a problem in that the by-products produced during the manufacturing process is difficult, or the physical properties of the degree of polymerization is reduced. In particular, the fiber produced by the method using a sulfuric acid solvent has a fear of color change due to residual sulfuric acid.

Accordingly, in the present invention, a polycomplex prepared by aromatic diamine and a transition metal is formed to prepare an aromatic polyamide fiber, thereby increasing the solubility of the polymer in a solvent, and thus having a high intrinsic viscosity (IV) even in a simple manufacturing process and having excellent physical properties. It is an object to provide a method for producing an amide fiber.

Hereinafter, the present invention will be described in detail.

The present invention polymerizes a precomplex and an aromatic dieside chloride obtained by dissolving an aromatic diamine and a transition metal compound in an aprotic solvent in an amide solvent alone or a mixed solvent thereof. Of aromatic polyamide fibers having an intrinsic viscosity of 3.0 or more having a repeating unit of one or two or more monomers selected from structural formulas (I), (II) and (III) by spinning in acetone or a protic solvent It is a manufacturing method.

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

The aromatic polyamide fiber of the present invention is based on any one or two or more monomers selected from structural formulas (I), (II), and (III) as basic repeating units, wherein R, R ', R " Examples of the most suitable aromatic reactor that can be used as follows.

, -OCH₃, -NO₂-, -CN등으로서 오르토나 메타위치에 치환될 수 있고, Y는

, -O-, -CH₂,-S- ,

또는

이다.In the above formula, X is H, CI, Br,

, -OCH ₃ , -NO _2- , -CN and the like can be substituted in the ortona meta position, Y is

, -O-, -CH ₂ , -S-,

or

to be.

Examples of the transition metals represented by M in the structural formulas (I), (II), and (III) include Cr, Mo, W, Ni, and Co. Examples of ligands (L) for these transition metals include CO and pyridine. , NH ₃ , PCI ₃ , I, CN, THF, etc.

On the other hand, the method for producing such aromatic polyamide fibers is as follows.

In order to prepare the aromatic polyamide fiber of the present invention, first, the aromatic diamine and the transition metal compound are dissolved in an aprotic solvent, and then heated appropriately, and then the solvent is removed and dried to prepare a precomposite. Examples of the solvent include ethyl ether, n-propyl ether, n-butyl ether, ethyl methyl ether, butyl ethyl ether, butyl propyl ether, THF (1,2,3,4-Tetrahydro-9-fluorenone), acetone, dioxane, pi Ferridine, piperazine and the like can be exemplified, and these solvents alone or mixtures thereof can be used.

Subsequently, the precomplex is reacted with an aromatic dieside chloride, and the polymer is gradually polymerized from a low temperature in an amide solvent. As the amide solvent used, N-methylpyrrolidone (NMP) and hexamethylphosphoamide (HMPA) are used. ), N, N-dimethylacetamide (DNAc), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) N, N, N ', N'-tetramethylurea (TMU) or mixtures thereof This can be used.

In this case, in order to obtain a high molecular weight polymer, the monomer and the solvent should contain only the minimum impurities, and the water content in the entire reaction mixture may be 0.03% or less by weight. The content of the polymer in the solvent is 5.0 to 50.0. % (W / V) and the intrinsic viscosity (IV) of the final product should be at least 3.0. The precomplex is preferably used in an amount of 1 to 100 mol% based on the aromatic dieside chloride.

When the polymer produced in this way is spun into acetone or a protic solvent, ie, water, methanol, ethanol, or the like, the polyamide fiber represented by the following structural formula (IV) is produced.

In the above formula, n '/ m should be 1% or more and the unexplained symbols (R, R', M, L, n) are as described above.

On the other hand, the present invention includes in addition to the aromatic polyamide fibers prepared as described above, including the film produced through the pulp and film die prepared by chopping and pulverizing the polymer using a pulp and a device and all the above process Is carried out in a cancerous reaction.

Hereinafter, an embodiment of the present invention is as follows.

Example 1

10.81 g of PPD and 22.1 g of Cr (CO) _{6 were} added to 400 ml n-butyl ether and 25 ml of THF mixed solvent, refluxed for about 20 hours, and then the solvent was removed and dried to prepare a precomposite.

24.17 g of the precomplex is dissolved in 400 ml of DMAc, cooled, and then polymerized sufficiently by adding 21.10 g of TPC with vigorous stirring, which is spun onto water to prepare aromatic polyamide fibers. The I.V of the fiber produced was 4.8.

[Examples 2 to 9]

In the same manner as in Example 1, but when preparing a pre-composite, the mixed solvent shown in Table 1 is used. I.V of the prepared fiber is shown in Table 1 below.

TABLE 1

[Examples 10 to 18]

The same method as in Example 1 was carried out, except that the solvent shown in Table 2 was used to polymerize the precomposite and TPC. I.V of the prepared fiber is shown in Table 2 below.

TABLE 2

Example 19

12.09 g of PPD monomer and Cr (CO) ₆ were dissolved in 400 ml of NMP and 5.14 g of PPD, and 21.10 g of TPC was added at low temperature, and then sufficiently polymerized with vigorous stirring with high stirring. Manufacture. IV was 5.0.

Example 20

19.34 g of PPD monomer and Cr (CO) ₆ precomposite and 2.16 g of PPD were dissolved in 200 ml of DMAc, 21.10 g of TPC was added at low temperature, and then sufficiently polymerized with vigorous stirring. Prepare pulp. IV was 5.7.

Example 21

10.81 g of PPD and 37.32 g of Cr (CO) ₃ (Py) ₃ were dissolved in a mixed solvent of 400 ml of n-butyl ether and 25 ml of THF, refluxed, and then the solvent was removed and dried to prepare a precomposite. 29.52 g of the precomplex is dissolved in 400 ml of DMAc, and 20.31 g of TPC is added at low temperature to sufficiently polymerize with vigorous stirring. The polymer is spun into water to produce fibers and pulp. IV was 6.1.

In the above embodiment, the intrinsic viscosity (I.V) is a value measured after drying for 15 hours or more in a vacuum at a temperature of 25 ℃ is expressed by the following equation.

Where C is the concentration of the polymer solution (the solution of 0.125 g of polymer dissolved in 25 ml of 95-98% sulfuric acid solution), and rel is a relative viscosity, and the flow time between the solution and the solvent was measured by a capillary viscosity meter at a temperature of 30 ° C. Ratio.

Claims (3)

In the method for producing an aromatic polyamide fiber, a precomplex and an aromatic dieside chloride obtained by dissolving an aromatic diamine and a transition metal compound in an aprotic solvent are polymerized in an amide solvent or a mixed solvent thereof, and the double polymer is before gelation. Aromatic polyamide fibers having an intrinsic viscosity of 3.0 or more having a repeating unit having a monomer composed of one or two or more selected from the following structural formulas (I), (II) and (III) by spinning in water, methanol or ethanol Manufacturing method.

Wherein R, R 'and R "are aromatic reactors which may be the same or different from each other, M is a transition gold element, Cr, Mo, Ni, Co or W, L is a ligand CO, pyridine, NH ₃ , PCI ₃ , I, CN or THF, n is an integer from 0 to 3. The method of producing an aromatic polyamide fiber according to claim 1, wherein the precomposite is used in an amount of 1 to 100 mol% based on the aromatic dieshad chloride. The method of claim 1, wherein the amide solvent is N-methylpyrrolidone (NMP), hexamethylphosphoramide (HMPA), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF) And dimethyl sulfoxide (DMSO), N, N, N ', N'-tetramethylurea (TMU) or a mixture thereof.