KR20180085413A - Manufacturing method of polyketone fibers - Google Patents

Abstract

The present invention relates to a method for manufacturing polyketone fibers, capable of effectively removing the residual metal salt of the polyketone fibers by an ultrasonic treatment in a washing step and improving a ratio of yarns generated in the washing step in manufacturing the polyketone fibers. According to the present invention, the concentration of ions which exist in water attached to the polyketone fibers in which the ultrasonic treatment is performed in the washing step is reduced, thereby manufacturing a fiber which is effective in removing fine foreign materials.

Description

Technical Field [0001] The present invention relates to a manufacturing method of polyketone fibers,

The present invention relates to a method for producing polyketone fibers. More particularly, the present invention relates to a method for producing polyketone fibers, which comprises an ultrasonic device for washing polyketone fibers, And a method for producing the fiber.

It is a known fact that olefins such as carbon monoxide and ethylene and propylene are polymerized by using a transition metal complex such as palladium or nickel as a catalyst to obtain a polyketone in which carbon monoxide and olefin alternate.

Polyketone is preferably thermally crosslinked when it melts, so it is preferable to use wet spinning in the case of fiberization. Particularly, polyketone (poly (1-oxotrimethylene)) fibers having substantially excellent physical properties and substantially containing only carbon monoxide and ethylene are apt to undergo thermal crosslinking. Thus, the fibers are very difficult to produce by melt spinning and can only be obtained substantially by wet spinning.

When the polyketone is wet-spun, examples of the solvent to be used include hexafluoroisopropanol and an organic solvent such as m-cresol, phenolic solvent such as resorcinol / water, and resorcinol / carbonate 2-112413, 4-228613, and 7-508317). However, the fibers obtained by wet spinning using such a solvent tend to be easily dispersed, and fatigue resistance and workability are insufficient for use as an industrial material. In addition, such a solvent has high toxicity and flammability, and there is a problem that a large measure against the toxicity and flammability of a solvent is required to make a spinning facility of an industrial scale.

Further, a method of radiating using a polyketone solution prepared by dissolving a polyketone in an aqueous solution containing zinc chloride at a specific concentration, zinc halide such as zinc bromide, or lithium salt such as lithium chloride, lithium iodide and lithium thiocyanate (WO99 / 18143, USP5955019). These aqueous solutions are relatively inexpensive, have low toxicity and are non-flammable and are excellent as polyketone solvents.

On the other hand, in order to remove the metal salt derived from the solvent remaining in the polyketone fibers before hot-drawing, it is preferable to clean with a cleaning liquid. The cleaning liquid is not particularly limited as long as it can be cleaned by washing the metal salt from the fiber. For example, washing with a combination of an aqueous solution containing acid, sulfuric acid, phosphoric acid and the like and an aqueous solution having a pH of 4 or less is preferable in that it is possible to reduce the amount of metal salts remaining in the fibers, rather than using only water. As the cleaning method, there are a method of immersing a thread in a bath containing a cleaning liquid, a method of spraying a cleaning liquid from above or below the thread, and the like, or both of these methods may be combined.

Korean Patent No. 10-1205940 Korean Patent No. 10-0607086

Disclosed is a method for effectively removing metal salts in washing polyketone fibers. The method comprises the steps of: providing an ultrasonic generator in a water tank to remove residual metal salts in the polyketone fibers by ultrasonic treatment in a washing step; Ketone fibers and a process for producing the same.

In order to attain the above object, the present invention provides a poly (methyl methacrylate) having a y / x of 0 to 0.1 and an intrinsic viscosity of 5 to 7 dl / g, which is composed of the repeating units represented by the following general formulas (1) and Spinning the ketone copolymer; Washing the irradiated polyketone fibers with water; Drying the washed polyketone fibers; And stretching the dried unoriented polyketone fibers, wherein in the washing step, the polyketone fibers are washed with ultrasonic waves by providing an ultrasonic wave generator in a water bath, and ultrasound generated from the ultrasonic wave generator Is in the range of 40 to 200 KHz, and the temperature of the water bath is 40 to 65 占 폚.

- [- CH2CH2-CO-] x- (1)

- [- CH2 --CH (CH3) - CO--] y- (2)

(x and y are mole% of each of the general formulas (1) and (2) in the polymer)

Specifically, the ultrasound range is 40 to 200 KHz, specifically, 40 to 60 KHz in the case of single stage washing

In the case of the second stage to the sixth stage cleaning, 100 to 200 KHz is used. The water bath temperature at this time is 40 to 65 degrees, and more specifically, it is kept at 65 degrees in the 5th and 6th stages.

Here, the catalyst composition used in the polymerization of the polyketone copolymer comprises (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine, Wherein the concentration of the lithium ion is less than 2 ppm, the concentration of the calcium ion is less than 7 ppm, and the concentration of the zinc ion is less than 7 ppm in analyzing the adhesion number of the polyketone fibers.

According to another preferred embodiment of the present invention, there is provided a polyketone fiber produced by the above production method.

The polyketone fibers according to the present invention have the effect that the concentration of the residual metal salt ion is lowered as a result of analysis of the number of fibers attached, and the ratio of the yarn is reduced accordingly.

1 is a view showing that an ultrasonic wave generator is provided in a polyketone water tank according to the present invention.

Hereinafter, the present invention will be described.

The present invention provides a method for producing a polyketone copolymer, comprising the steps of: spinning a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), having y / x of 0 to 0.1 and an intrinsic viscosity of 5 to 7 dl / g; Washing the irradiated polyketone fibers with water; Drying the washed polyketone fibers; And stretching the dried unoriented polyketone fibers, wherein in the washing step, the polyketone fibers are washed with ultrasonic waves by providing an ultrasonic wave generator in a water bath, and ultrasound generated from the ultrasonic wave generator Is in the range of 40 to 200 KHz, and the temperature of the water bath is 40 to 65 占 폚.

- [- CH2CH2-CO-] x- (1)

- [- CH2 --CH (CH3) - CO--] y- (2)

(x and y are mole% of each of the general formulas (1) and (2) in the polymer)

Specifically, the ultrasound range is 40 to 200 KHz, specifically, 40 to 60 KHz in the case of single stage washing

In the case of the second stage to the sixth stage cleaning, 100 to 200 KHz is used. The water bath temperature at this time is 40 to 65 degrees, and more specifically, it is kept at 65 degrees in the 5th and 6th stages.

Here, the catalyst composition used in the polymerization of the polyketone copolymer comprises (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine, Wherein the concentration of the lithium ion is less than 2 ppm, the concentration of the calcium ion is less than 7 ppm, and the concentration of the zinc ion is less than 7 ppm in analyzing the adhesion number of the polyketone fibers.

According to another preferred embodiment of the present invention, there is provided a polyketone fiber produced by the above production method.

Hereinafter, the polymerization method of the polyketone used in the present invention will be described in detail.

One or more olefinically unsaturated compounds (simply referred to as " A "), wherein the monomer units are alternating, and thus the polymer is composed of units of the formula - (CO) -A'- wherein A 'represents the monomer units derived from the applied monomer A ) And a high molecular weight linear polymer of carbon monoxide can be prepared by contacting monomers with a solution of a palladium-containing catalyst composition in a dilute solution in which the polymer does not dissolve or actually dissolve. During the polymerization process, the polymer is obtained in the form of a suspension in a diluent. The polymer preparation is carried out primarily batchwise.

The batchwise preparation of the polymer is typically carried out by introducing the catalyst into a reactor containing the diluent and the monomer and having the desired temperature and pressure. As the polymerization proceeds, the pressure drops, the concentration of the polymer in the diluent increases, and the viscosity of the suspension increases. The polymerization is continued until the viscosity of the suspension reaches a high value, for example, to the point where difficulties associated with heat removal occur. During batch polymer preparation, monomers can be added to the reactor during polymerization, if desired, to maintain the temperature as well as the pressure constant.

In the present invention, not only methanol, dichloromethane or nitromethane, which has been conventionally used for producing polyketones, but also mixed solvents comprising acetic acid and water, ethanol, propanol, and isopropanol can be used as the liquid medium. Particularly, when a mixed solvent of acetic acid and water is used as a liquid medium in the production of polyketone, the catalyst activity can be improved while reducing the production cost of polyketone. Further, since the use of methanol or a dichloromethane solvent forms a mechanism for causing a stopping reaction during the polymerization step, the use of acetic acid or water other than methanol or dichloromethane in the solvent does not have an effect of stopping the catalytic activity stochastically, It plays a big role in improvement.

When a mixed solvent of acetic acid and water is used as a liquid medium, when the concentration of water is less than 10% by volume, the effect of the catalyst is less affected. When the concentration of water is 10% by volume or more, the catalytic activity increases sharply. On the other hand, when the concentration of water exceeds 30% by volume, the catalytic activity tends to decrease. In the present invention, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 30 to 10% by volume of water as the liquid medium.

In the present invention, the organometallic complex catalyst comprises (a) a Group 9, Group 10 or Group 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989), (b) And (c) an anion of an acid having a pKa of 4 or less.

Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, and sulfonates. Specific examples thereof include nickel acetate, nickel acetyl acetate, palladium acetate, palladium trifluoroacetate , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium and palladium sulfate.

Examples of the Group 11 transition metal compound include a complex of copper and silver, a carbonate, a phosphate, a carbamate, and a sulfonate, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the trifluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

Of these, transition metal compounds (a), which are inexpensive and economically preferable, are nickel and copper compounds, and preferable transition metal compounds (a) in terms of yield and molecular weight of polyketones are palladium compounds, It is most preferable to use palladium acetate.

Examples of ligands (b) having a Group 15 atom include 2,2-bipyridyl, 4,4-dimethyl-2,2-bipyridyl, 2,2- (Diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,3-bis (diphenylphosphino) Bis [di (2-methylphenyl) phosphino] propane, 1,3-bis [di (2-isopropyl) Bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) phosphine, ) Benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) Bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) ) Phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) Phosphino] propane, and the like.

Among these ligands, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of yield of polyketone are 1,3-bis [di (2- Methoxyphenyl) phosphino] propane and 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, Di (2-methoxyphenyl) phosphino] propane, and it is safe in that it does not require an organic solvent. Soluble sodium salts such as 1,3-bis [di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] propane, 1,2- ] Methyl] benzene, and 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred for ease of synthesis and availability in large quantities and economically.

The ligand (b) having a group 15 atom preferred in the present invention, which focuses on the intrinsic viscosity and catalytic activity of the polyketone, is 1,3-bis- [di (2-methoxyphenyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and more preferably 1,3-bis Bis (methylene)) bis (bis (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- ) Phosphine) is better.

Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Activity equivalent to that of 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, which is known to exhibit the highest activity among polymerization catalysts The structure is simpler and has a lower molecular weight. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst of the present invention, while further reducing its manufacturing cost and cost. A method for producing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) -2,3-dioxolane was obtained by using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) is obtained by reacting a bis (methylene) . The process for preparing a ligand for a polyketone polymerization catalyst according to the present invention is a process for producing a ligand for a polyketone polymerization catalyst which comprises reacting 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in a large amount.

It is also preferable to use bis (bis (2-methoxyphenyl) phosphine as the ligand (cyclohexane-1,1-diylbis (methylene)) bis Respectively.

In a preferred embodiment, the process for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under nitrogen atmosphere, Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the resulting mixture, followed by stirring and reacting; (c) adding methanol and stirring after completion of the reaction, (d) adding toluene and water, separating the layer, washing the oil layer with water, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And then performing a step of acquiring

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) varies depending on the kind of the ethylenically unsaturated compound to be selected and other polymerization conditions. But is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol, per liter of the reaction volume of the reaction zone. The capacity of the reaction zone means the liquid phase capacity of the reactor.

Examples of the anion (c) of the acid having a pKa of 4 or less include an anion of an organic acid having a pKa of 4 or less, such as trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, or m-toluenesulfonic acid; Anions of inorganic acids having a pKa of 4 or less such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, tetrafluoroboric acid, hexafluorophosphoric acid, and fluorosilicic acid; And anions of boron compounds such as trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylarinium tetrakis (pentafluorophenyl) borate.

In particular, the anion (c) of the acid having a pKa of 4 or less, which is preferred in the present invention, is p-toluenesulfonic acid. When used together with a mixed solvent of acetic acid and water as a liquid medium, It is possible to prepare a polyketone having a functional group

The molar ratio of (a) the ninth, tenth or eleventh group transition metal compound and (b) the ligand having an element of Group 15 element is 0.1 to 20 moles of the Group 15 element of the ligand per 1 mole of the palladium element, Is preferably added in a proportion of 0.1 to 10 moles, more preferably 0.1 to 5 moles. When the ligand is added in an amount of less than 0.1 mole based on the palladium element, the binding force between the ligand and the transition metal decreases, accelerating the desorption of the palladium during the reaction, and causing the reaction to terminate quickly. When the ligand exceeds 20 moles When added, the ligand is shielded from the polymerization reaction by the organometallic complex catalyst, so that the reaction rate is remarkably lowered.

The molar ratio of (a) the anion of the ninth, tenth or eleventh group transition metal compound and (c) the anion of the acid having a pKa of 4 or less is 0.1 to 20 mol, preferably 0.1 to 10 mol, Mol, and more preferably 0.1 to 5 mol. When the acid is added in an amount of less than 0.1 mol based on the palladium element, the effect of improving the intrinsic viscosity of the polyketone is unsatisfactory. If the acid is added in an amount exceeding 20 mol based on the palladium element, the catalytic activity for producing the polyketone tends to be rather reduced. not.

In the present invention, the reaction gas to be reacted with the catalyst for producing polyketone is preferably a mixture of carbon monoxide and an ethylenically unsaturated compound.

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide in the present invention include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, - C2 to C20 alpha-olefins including tetradecene, 1-hexadecene, vinylcyclohexane; Styrene, C2-C20 alkenyl aromatic compounds including? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclo undecene, pentacyclopentadecene, pentacyclohexadecene, C4 to C40 cyclic olefins including cyclododecene; C2 to C10 halogenated vinyls containing vinyl chloride; Ethyl acrylate, methyl acrylate, and mixtures of two or more selected from among C3 to C30 acrylic esters. These ethylenically unsaturated compounds are used singly or as a mixture of plural kinds. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.

In the production of polyketones, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is generally 1: 1. In the present invention, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is adjusted to a molar ratio of 1:10 to 10: 1 . As in the present invention, when an ethylenically unsaturated compound and carbon monoxide are mixed in an appropriate ratio, they are effective also in terms of catalytic activity, and the intrinsic viscosity improvement effect of the produced polyketone can be simultaneously achieved. When carbon monoxide or ethylene is added in an amount of less than 5 mol% or more than 95 mol%, the reactivity is poor and the physical properties of the produced polyketone may be deteriorated.

On the other hand, the polyketone copolymer used as the fiber may be composed of ethylene, propylene, and carbon monoxide, but it is unsuitable as the molar ratio of propylene becomes larger, and the molar ratio of ethylene to propylene is preferably 100: 0 to 90:10.

That is, y / x of the polyketone copolymer represented by the following general formulas (1) and (2) is preferably 0 to 0.1.

- [- CH2CH2-CO-] x- (1)

- [- CH2 --CH (CH3) - CO--] y- (2)

(x and y are mole% of each of the general formulas (1) and (2) in the polymer)

Here, when y / x is more than 0.1, it is difficult to use as a fiber and the workability also deteriorates.

On the other hand, the molecular weight distribution of the polyketone is preferably in the range of 1.5 to 4.0, and if it is less than 1.5, the polymerization yield is lowered. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 or more, the molecular weight distribution becomes large. The molecular weight distribution of the most preferred polyketones is 2.5 to 3.5.

Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 to 300 占 폚, and is generally 210 to 270 占 폚. The intrinsic viscosity (LVN) of the polymer measured by HFIP (Hexafluoroisopropylalcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, and preferably 5.0 dl / g to 7.0 dl / g . At this time, when the intrinsic viscosity of the polyketone polymer is less than 5.0, the mechanical strength is lowered in production of the fiber, and when it exceeds 7.0, the workability is lowered.

The production method of the polyketone fiber of the present invention will be described.

First, the solution extruded from the spinning nozzle passes through an air gap in a vertical direction and solidifies in a coagulating bath. At this time, the air gap is radiated within a range of about 1 to 300 mm in order to obtain a dense and uniform fiber and to provide a smooth cooling effect.

Thereafter, the filament passing through the coagulation bath passes through the water bath. At this time, the temperature of the coagulation bath and the water bath is maintained at about 0 to 80 ° C to prevent the deterioration of the physical properties due to the formation of pores in the fiber structure due to the rapid desolvation

In the present invention, an ultrasonic wave generator is provided in a water bath. Specifically, when the polyketone fibers that have undergone the precoagulation process in the drying step pass through the water-treating tank provided with the ultrasonic generator, the cohesive force acting between the fibers by the ultrasonic waves is weakened. The yarn with weak cohesion between fibers has a weak effect of holding micro-particles, so it is effective to remove micro-debris, and the amount of metal salt ions remaining in the fibers is also very small.

In one embodiment of the present invention, the water for washing is contained in the water bath at a pH of 3 to 4, and the ultrasonic wave generator is immersed in the water bath. According to another embodiment of the present invention, it is also possible that the ultrasonic generator is not provided in the water tank but is provided outside the water tank.

Also, a guide bar is provided in the water tank to fix the polyketone fibers when the polyketone fibers pass through the water tank, and to prevent the fibers from cracking when the polyketone fibers pass through the water tank.

As shown in Fig. 1, an ultrasonic wave generator is provided in a water tank, and ultrasonic waves are generated in the water washing step to ultrasonically process the polyketone fibers.

Specifically, the ultrasound range is from 40 to 200 KHz, more specifically from 40 to 60 KHz for one-stage cleaning and from 100 to 200 KHz for cleaning from two to six stages. The water bath temperature at this time is 40 to 65 degrees, and more specifically, it is kept at 65 degrees in the 5th and 6th stages.

In the present invention, the range of the ultrasonic waves is 40 to 200 KHz. If the range of the ultrasonic waves is less than 40 KHz, it is difficult to remove the residual metal salts, and when the frequency exceeds 200 KHz, the properties of the fibers are deteriorated.

The temperature of the water bath is 40 to 65 degrees. If the temperature of the water bath is less than 40 degrees, it is difficult to remove the residual metal salt. If the temperature is more than 65 degrees, the economical efficiency is lowered due to an increase in cost .

Thereafter, the fibers having passed through the water bath are subjected to acid washing in an aqueous solution containing the acid, then passed through a second water bath for removal of the acid, passed through a dryer, and then emulsified .

In addition, in order to improve the flatness and improve the property of the housing, it passed the interlace nozzle. At this time, the air pressure was supplied at 0.5 to 4.0 kg / cm 2, and the number of entanglement per filament was 2 to 40.

Thereafter, the filament yarn passed through the interlace nozzle is dried while passing through the drying device. In this case, the drying temperature and the drying method have a great influence on the post-processing and physical properties of the filament.

The filament that has passed through the drying device is finally wound in a winder through a secondary emulsion treatment device.

Further, the stretching process in the polyketone fibers of the present invention is very important for improvement of high strength and water resistance. In the drawing method, hot air heating method and roller heating method are used, but since the filament is in contact with the roller surface in the roller heating method, the fiber surface is likely to be damaged, so that hot air heating method is more effective in manufacturing high strength polyketone fiber. However, the inventors of the present invention have found that applying a heat-resistant stabilizer while applying a roller heating method, especially a hot-roll drying method, and a stretching step of 1.0 to 2.0 times, preferably 1.2 to 1.6 times, High strength multifilament could be obtained. At this time, the strength of the fiber at drawing of less than 1.0 times is lowered, and the workability at the time of drawing of more than 2.0 times is lowered.

That is, the present invention is characterized in that the stretching process is performed by using a method of passing through a heating chamber at 230 ° C to 300 ° C.

On the other hand, as the solvent for dissolving the polyketone, it is preferable to use an aqueous solution containing at least one metal salt selected from the group consisting of zinc salts, calcium salts, lithium salts, thiocyanates and iron salts. Specific examples of the zinc salt include zinc bromide, zinc chloride and zinc iodide. Examples of the calcium salt include calcium bromide, calcium chloride and calcium iodide. Examples of the lithium salt include lithium bromide, lithium chloride, lithium iodide . Examples of the iron salts include iron bromide and iron iodide. Among these metal salts, it is particularly preferable to use at least one selected from the group consisting of zinc bromide, calcium bromide, lithium bromide and iron bromide in terms of the solubility of the raw material polyketone and the homogeneity of the polyketone solution.

The concentration of the metal salt in the metal salt aqueous solution of the present invention is preferably 30 to 80% by weight. If the concentration of the metal salt is less than 30% by weight, the solubility decreases. If the concentration of the metal salt is more than 80% by weight, the cost for concentration increases, which is disadvantageous in terms of economy. As the solvent for dissolving the metal salt, water, methanol, ethanol and the like can be used. In particular, water is used in the present invention because it is economical and advantageous in solvent recovery.

In order to obtain polyketone fibers in the present invention, an aqueous solution containing zinc bromide is preferable, and the composition ratio of zinc bromide in the metal salt is an important factor. For example, in an aqueous solution containing only zinc bromide and calcium bromide, the weight ratio of zinc bromide to calcium bromide is 80/20 to 50/50, more preferably 80/20 to 60/40. Further, in the aqueous solution containing zinc bromide, calcium bromide and lithium bromide, the total weight ratio of zinc bromide, calcium bromide and lithium bromide is 80/20 to 50/50, more preferably 80/20 to 60/40, , The weight ratio of calcium bromide to lithium bromide is 40/60 to 90/10, preferably 60/40 to 85/15.

The production method of the polyketone solution is not particularly limited, but an example of a preferable production method will be described below.

The metal salt aqueous solution maintained at 20 to 40 캜 is defoamed at a pressure of 200 torr or less, the polyketone polymer is heated to 60 to 100 캜 under a vacuum of 200 torr or less, and stirred for 0.5 to 10 hours to prepare a sufficiently dissolved homogeneous dope .

In the present invention, the polyketone polymer may be mixed with other polymer materials or additives. Examples of the polymer material include polyvinyl alcohol, carboxymethyl polyketone, and polyethylene glycol. Examples of additives include viscosity improvers, titanium dioxide, silica dioxide, carbon, and ammonium chloride.

Hereinafter, a method of producing a polyketone fiber including spinning, washing, drying and stretching the homogeneous polyketone solution of the present invention will be described in more detail. However, the polyketone fibers claimed in the present invention are not limited by the following process.

The spinning process of the method according to the present invention will be described in more detail. An orifice having a diameter of 100 to 500 μm and a length of 100 to 1500 μm, wherein the ratio of the diameter to the length (L / D) is 1 to 3 to 8 times, The spinning stock solution is extruded and spun through a spinning nozzle containing a plurality of orifices having an interval of 1.0 to 5.0 mm to allow the fiber spinning solution to pass through the air layer to reach the coagulation bath and then solidify to obtain multifilaments .

The shape of the spinning nozzle used is usually circular, and the nozzle diameter is 50 to 200 mm, more preferably 80 to 130 mm. When the nozzle diameter is less than 50 mm, the distance between the orifices is too short, so that the adhesion may occur before the discharged solution solidifies. If the nozzle diameter is too large, peripheral devices such as spinning packs and nozzles become large, If the diameter of the nozzle orifice is less than 100 탆, a large number of yarn breaks occur at the time of spinning, which adversely affects radioactivity. If the diameter exceeds 500 탆, the coagulation speed of the solution in the spinning coagulation bath is slow, And water washing becomes difficult.

The number of orifices is set to 100 to 2,200, more preferably 300 to 1,400 in consideration of the orifice spacing for uniform cooling of the solution, taking into account the industrial application, especially for polyketone fiber composite materials.

If the number of orifices is less than 100, the fineness of each filament becomes thick and the solvent can not sufficiently escape within a short time, so that the coagulation and flushing can not be completely performed. When the number of the orifices is more than 2,200, adjacent filaments are easily formed in the air layer section, and the stability of each filament after spinning is lowered. In addition to the deterioration of physical properties, the yarn is subjected to a twisting process and a heat treatment process Can lead to problems.

When the fiber stock solution passing through the spinning nozzle coagulates in the upper coagulating solution, the larger the diameter of the fluid becomes, the larger the difference in the coagulation speed between the surface and the inside becomes, and it becomes difficult to obtain a dense and uniform tissue fiber. Therefore, when the polyketone solution is spun, even if the same discharge amount is maintained, the spun fibers having a smaller diameter can be obtained in the coagulating solution while maintaining an appropriate air layer.

The air layer is preferably 5 to 50 mm, more preferably 10 to 20 mm. It is difficult to increase the spinning speed because the too short air layer distance increases the micropore generation rate due to the rapid surface layer coagulation and desolvation process, and it is difficult to increase the spinning speed. On the other hand, the too long air layer distance is affected by the adhesion of the filament, It is difficult to maintain process stability.

The composition of the coagulating bath used in the present invention is such that the concentration of the metal salt aqueous solution is 1 to 20% by weight. The coagulating bath temperature is maintained at -10 to 60 ° C, more preferably -5 to 20 ° C. In the coagulation bath, when the filament passes through the coagulation bath of the multifilament, when the spinning speed is increased by 500 m / min or more, the coagulation of the coagulating solution becomes severe due to the friction between the filament and coagulating liquid. In order to improve the productivity by increasing the excellent physical properties and the spinning speed through the stretching orientation, such a phenomenon is a factor that hinders the process stability, so that it is necessary to minimize such a phenomenon.

In the present invention, the coagulating bath is characterized by a temperature of -10 to 40 ° C and a metal salt concentration of 1 to 30% by weight, and the water bath is preferably at a temperature of 0 to 40 ° C and a metal salt concentration of 1 to 30% The acid washing bath preferably has a temperature of 0 to 40 캜 and an acid concentration of 0.5 to 2% by weight, and the secondary washing bath for acid removal is maintained at a temperature of 30 to 70 캜.

In the present invention, an ultrasonic wave generator is provided in a water bath. Specifically, when the polyketone fibers that have undergone the precoagulation process in the drying step pass through the water-treating tank provided with the ultrasonic generator, the cohesive force acting between the fibers by the ultrasonic waves is weakened. The yarn with weak cohesion between fibers has a weak effect of holding micro-particles, so it is effective to remove micro-debris, and the amount of metal salt ions remaining in the fibers is also very small.

In one embodiment of the present invention, the water for washing is contained in the water bath at a pH of 3 to 4, and the ultrasonic wave generator is immersed in the water bath. According to another embodiment of the present invention, it is also possible that the ultrasonic generator is not provided in the water tank but is provided outside the water tank.

Also, a guide bar is provided in the water tank to fix the polyketone fibers when the polyketone fibers pass through the water tank, and to prevent the fibers from cracking when the polyketone fibers pass through the water tank.

As shown in Fig. 1, an ultrasonic wave generator is provided in a water tank, and ultrasonic waves are generated in the water washing step to ultrasonically process the polyketone fibers.

Specifically, the range of the ultrasonic wave during the ultrasonic treatment is 40 to 200 KHz, specifically, 40 to 60 KHz in the case of one stage washing, and 100 to 200 KHz in the case of 2 to 6 stages washing. The water bath temperature at this time is 40 to 65 degrees, and more specifically, it is kept at 65 degrees in the 5th and 6th stages.

In the present invention, the range of the ultrasonic waves is 40 to 200 KHz. If the range of the ultrasonic waves is less than 40 KHz, it is difficult to remove the residual metal salts, and when the frequency exceeds 200 KHz, the properties of the fibers are deteriorated.

The temperature of the water bath is 40 to 65 degrees. If the temperature of the water bath is less than 40 degrees, the residual metal salt is difficult to remove, In the case of 65 degrees or more, there is a problem in that the economical efficiency is lowered due to an increase in cost.

In the present invention, a multifilament of high strength can be obtained through a stretching process of 1.0 to 2.0 times, preferably 1.2 to 1.6 times, more preferably 1.4 times in the course of washing the fibers. At this time, the strength of the fiber at drawing of less than 1.0 times is lowered, and the workability at the time of drawing of more than 2.0 times is lowered.

Also, in the present invention, the temperature of the dryer is 100 ° C or higher, preferably 200 ° C or higher, and the emulsion, heat-resistant agent, antioxidant or stabilizer is added to the fiber passed through the dryer.

Hereinafter, the drawing process and the drying process will be described.

The present invention provides a high-strength fiber by securing the heat stability of the polyketone during wet spinning and by directly drying the fiber. In the conventional spinning process, the maximum strength is 13 g / d even at the time of germination drying and optimization of the stretching temperature. However, the present invention optimizes the heating method and the temperature profile of the drying method to form a dense structure by fusion- As a result, the draw ratio and the strength are improved. Further, in order to prevent thermal deterioration of the polyketone at the time of heating, the stretching magnification and strength are improved by a process including a heat stabilizer during drying and stretching.

Polyketone fibers have oxidation or degradation mechanisms at high temperatures. As a radical oxidation mechanism, polyketone releases carbon dioxide and oxidative degradation occurs when exposed to oxygen at temperatures above 90 ° C. In addition, due to the radical deterioration mechanism, when the polyketone is exposed to a high temperature of 200 ° C or more, carbon monoxide and ethylene are released and thermal degradation occurs. A heat-resistant stabilizer is used to prevent oxidation and deterioration of the polyketone at such a high temperature. As the heat-resistant stabilizer, both of antioxidants capable of preventing radical oxidation and deterioration can be used.

Preferably, phenolic heat stabilizers are used, and one or more heat stabilizers may be used alone or in combination. Oxidation and deterioration prevention mechanisms prevent radicals by radicals by holding radicals with heat stabilizers and alkyl radicals generated by heat or ultraviolet rays. The heat stabilizer may be used before drying or before stretching, and the immersion or application method may be used alone or in combination. Specifically, in an embodiment of the present invention, 0.1% of a solution of a phenolic heat stabilizer obtained by mixing a phenolic heat stabilizer with a methanol solvent in a pre-drying step and a stretching step is applied in a pre-drying step and a drawing step, Of the heat stabilizer was 250 ppm, but after the drying and the stretching step, 25 ppm remained. The heat stabilizer should be used in an appropriate amount depending on the process. If the heat stabilizer is large, the workability is poor. If the heat stabilizer is small, the heat stabilization effect is not sufficient. The heat stabilizer may be used in one-pot or two-pot or more.

Meanwhile, in order to increase the strength of the fiber, the present invention uses a direct drying method of a hot roller drying method, rather than an indirect drying method of a hot air drying method. In the conventional hot air drying method, a hot air drying method was used at a temperature of 180 ° C. for a residence time of about 3 minutes and 30 seconds. This has the effect of achieving uniform drying and improving the adhesion, but it is difficult to generate fusion, loops, and static electricity, and it is difficult to generate a fusion structure. The present invention uses a hot roll drying method at a temperature of 220 to 230 DEG C for a residence time of about 1 minute and 30 seconds. When such a drying method is used, there is no entanglement, less static electricity is generated, and a fine structure is formed due to the formation of a fusion structure, which is easy to apply for commercialization.

In the drying process, the multi-filament of high strength can be obtained through the drawing step of 1.0 to 2.0 times, preferably 1.2 to 1.6 times, more preferably 1.4 times. At this time, the strength of the fiber at drawing of less than 1.0 times is lowered, and the workability at the time of drawing of more than 2.0 times is lowered.

In addition, the present invention is subjected to a stretching process in which the fibers are stretched 15 to 18 times. For stretching the polyketone fibers, stretching is carried out in one or more stages. In the case of multi-stage stretching, it is preferable to perform the temperature-raising stretching in which the stretching temperature gradually increases with an increase in the stretching magnification. Specifically, the stretching process is performed at a temperature of 240 to 270 ° C, and the residence time is within about 1 minute and 30 seconds, and the first and second stages are performed. Stretching is carried out from step 1 to step 7, second step to step 2.5, and step 2 is stepwise stretching in a 3 step form. After the first stage, the elongation of the polyketone fibers is 10% and the strength is 8 g / d. After the second stage, the elongation is about 5.2%, and the strength of the polyketone fibers is 20 g / d.

In addition, since the polyketone is thermally deteriorated at a high temperature due to the drying and stretching process as described above, a heat stabilizer is added. It is applied before drying or before stretching. In the present invention, both raw or dip can be used. In general, when the two-dip or more is performed, the elongation of the fiber is decreased independently of the increase in the strength, but in the case of the hot-roll drying method according to the present invention, there is little decrease in elongation.

The multifilament produced by the method according to the present invention is a polyketone multifilament with a total denier range of 500 to 3,500 and a breaking load of 6.0 to 40.0 kg. The multifilament is composed of 100 to 2,200 individual filaments with a fineness of 0.5 to 8.0 denier.

The fiber density of the monofilament is 1.295 to 1.310 g / cm < 3 > by the hot-roll drying method of the present invention and the step of adding the heat stabilizer, and the structure thereof is as shown in Fig. As a result, the initial modulus value of the polyketone monofilament prepared by the above process is 200 g / d or more, elongation is 2.5 to 3.5% at 10.0 g / d, and elongation is at least 0.5% or more at 19.0 g / d or more.

In the present invention, the polyketone weave structure comprising the polyketone fibers produced by the spinning process preferably has a density of 15 to 25 ea / inch, and is preferably a peel test measured by Peel Test (ASTM D1876) Strength) is 0.2 to 0.5 kgf / cm.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to specific examples and comparative examples. However, these examples are merely intended to clarify the present invention and are not intended to limit the scope of the present invention.

Preparation Example: Preparation of polyketone polymer

Linear alternating polyketone copolymers composed of carbon monoxide and ethylene are prepared by reacting palladium acetate, trifluoroacetic acid and a catalyst (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) The polyketone copolymer had a melting point of 240 DEG C, an intrinsic viscosity of 6.0 dl / g measured by HFIP (hexafluoroisopropanol) at 25 DEG C, a MI index of 10 g / 10 min and a molecular weight distribution (MWD) was 3.0.

Example 1

A zinc bromide aqueous solution having a concentration of 60% by weight was injected into an extruder maintained at an internal temperature of 30 ° C at an injection temperature of 25 ° C with a gear pump at a rate of 13,000 g / hour to obtain a product having a molecular weight distribution of 3.0 and an intrinsic viscosity of 6.0 dl / The obtained polyketone powder was extruded by a screw feeder at 1160 g / hour to give a retention time of 0.8 minutes in a swelling zone of the extruder and the temperature was raised to 40 DEG C to sufficiently dissolve the polyketone powder in the metal salt solution. Polyketone fibers were prepared by dry-wet spinning by maintaining each block temperature at 55-60 < 0 > C in a dissolution zone and operating the screw at 110 rpm.

At this time, a circular nozzle having an odd number of nozzles of 667 and a diameter of 0.18 mm and an L / D of 1 was used, and an air gap was 10 mm. The concentration of the polyketone in the discharged solution was 8.2 wt%, and it was in a homogeneous state in which the undissolved polyketone particles were not contained.

In the step of washing the obtained fibers, an ultrasonic wave generating device is provided in a water bath, and ultrasonic treatment is performed at the time of washing with water. 50 kHz for single stage cleaning and 150 kHz for double stage to 6 stage cleaning. The temperature of the water bath in this case was 50 degrees in the first stage to the fourth stage, and 65 degrees in the fifth stage and the sixth stage.

1.2 times stretching is carried out in the washing process, and the heat stabilizer is dipped in a 0.1% solution of a mixed solution of AO80 and methanol of Adeka as a phenolic heat stabilizer before drying. In the drying process, 1.2-fold stretching was performed by a hot-roll drying method, and then fibers were produced in a heating chamber method at a total stretching magnification of 16.8 times, stretched at a stretch ratio of 7 times at the first stretch, 2.4 times at the second stretch, 1.5, 1.3, and 1.23 times of 3 step stretching, and each step was performed at temperatures of 240, 255, 265, and 268 DEG C to produce polyketone fibers.

Comparative Example 1

Polyketone fibers were prepared in the same manner as in Example 1, except that ultrasonic treatment was carried out in the washing step.

The adhesion number IC (Ion chromatography) of the polyketone fibers obtained in Example 1 and Comparative Example 1 was analyzed and described in Table 1.

Property evaluation

(1) The number of fibers attached IC analysis

The wet cleaning cleanser (POK fiber) was sampled at 6 rinsing stages, dewatered at 5000 rpm, diluted 10 times with the dehydrated solution, and subjected to IC analysis.

Fiber adhesion number IC analysis Residual ion concentration (ppm) Li Ca Zn Example 1 One 5 5 Comparative Example 1 One 10 10

As shown in Table 1, it was confirmed that the residual ion concentration of the polyketone fibers produced by the example of the present invention was lower than that of the comparative example.

Claims (4)

Radiating a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), having y / x of 0 to 0.1 and an intrinsic viscosity of 5 to 7 dl / g;
Washing the irradiated polyketone fibers with water;
Drying the washed polyketone fibers; And
Stretching the dried non-drawn polyketone fibers,
The ultrasonic wave generator is provided in the water tank in the washing step, and the polyketone fibers are washed with ultrasonic waves,
Wherein the range of ultrasonic waves generated in the ultrasonic wave generator is 40 to 200 KHz, and the temperature of the water bath is 40 to 65 占 폚.
- [- CH2CH2-CO-] x- (1)
- [- CH2 --CH (CH3) - CO--] y- (2)
(x and y are mole% of each of the general formulas (1) and (2) in the polymer)
The method according to claim 1,
The catalyst composition used in the polymerization of the polyketone copolymer includes (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine and the polyketone copolymer Wherein the molecular weight distribution is 2.5 to 4.0.
The method according to claim 1,
The concentration of residual lithium ions is less than 2 ppm, the concentration of residual calcium ions is less than 7 ppm, and the concentration of residual zinc ions is less than 7 ppm in the analysis of the polyketone fibers by adhering water ion chromatography (IC, Ion Chromatography) A method for producing polyketone fibers.
A polyketone fiber produced by the method of any one of claims 1 to 3.

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