KR101857640B1

KR101857640B1 - Polyketone having high strength and its manufacturing method

Info

Publication number: KR101857640B1
Application number: KR1020160183745A
Authority: KR
Inventors: 김도회; 이득진
Original assignee: 주식회사 효성
Priority date: 2016-12-30
Filing date: 2016-12-30
Publication date: 2018-06-29

Abstract

The present invention relates to a high-strength polyketone fiber and a method for producing the same. More particularly, the present invention relates to a high-strength polyketone fiber, Bis-2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite is dispersed in acetone alone To a polyketone fiber capable of producing a high strength polyketone fiber and a method for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a high strength polyketone fiber,

Industrial fibers are used as structural members and composite materials in a wide range of fields such as tire cord, rope, cable, sling, and mesh. BACKGROUND ART For a long time, synthetic fibers such as PET fiber and nylon fiber have been used as industrial fibers. As the required performance of materials has been advanced, super fibers satisfying the properties that can not satisfy the performance of these materials have been developed and sold. In accordance with these market requirements, we have established the production technology of aliphatic polyketone fibers using carbon monoxide and ethylene as raw materials, and have obtained high strength and high elasticity comparable to super fibers. In addition to these properties, polyketone fibers have excellent properties such as dimensional stability at high temperatures, adhesiveness, and skid resistance, and are expected to be applied to industrial fibers in various fields.

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.

DISCLOSURE OF THE INVENTION In order to solve the problems described above, the present invention provides an antioxidant for use in hot rolling at a high temperature, which comprises a phosphorus compound such as bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol- (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite) alone in acetone to improve the thermal stability of the polyketone, will be.

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 Ketone copolymer is produced through a spinning process, a water washing process, a drying process and a stretching process,

(2,6-di-tert-butyl-diphenylphosphite) bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol as the antioxidant before the drying step and the drawing step. 4-methylphenyl) pentaerythritol-di-phosphite is dispersed in acetone alone to provide a polyketone fiber.

- [- 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, the bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite is contained in an amount of 0.01 to 10% by weight based on the total solution, A strength of 18.0 g / d or more, and a modulus of elasticity of 360 g / d or more.

According to another preferred embodiment of the present invention, the dried undrawn yarn made of a polyketone copolymer is treated with a phosphorus compound (bis (2,6-di-tert-butyl-4-methylphenyl) A polyketone fiber prepared by treating with a solution in which bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite alone is dispersed in acetone, Of the present invention.

The present invention relates to a process for producing polyketone fibers, which comprises reacting bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite (Bis 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite is dispersed in acetone alone to inhibit molecular weight decrease or thermal crosslinking during hot- A polyketone fiber having high strength properties can be produced.

Hereinafter, the present invention will be described.

The present invention relates to a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), having a y / x of 0 to 0.1 and an intrinsic viscosity of 5 to 7 dl / g, Process, a drying process, and a stretching process,

- [- 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)

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 phosphorus ligands such as (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine.

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 layers, 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 a step of acquiring the image data.

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, which, when used together with a mixed solvent of acetic acid and water as a liquid medium, It becomes possible to produce a polyketone having a high intrinsic viscosity suitable for a composite material.

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. The larger the molar ratio of propylene is, the more unsuitable as the polyketone fiber composite material. The molar ratio of ethylene and propylene is 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 ° C or higher, the molecular weight distribution becomes larger. 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 fibers made of the polyketone have a tensile strength of 18.0 g / d or more and a modulus of elasticity of 360 g / d or more.

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 water bath is maintained at about 0 to 80 ° C to prevent the deterioration of physical properties due to the formation of pores in the fiber structure due to rapid desolvation.

The fibers having passed through the water-washing tank were subjected to acid washing in an aqueous solution containing the acid, passed through a second water-washing bath to remove the acid, passed through a dryer, and then emulsified in an emulsion- do.

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. It is also possible to use roller heating, especially hot-roll drying. By using the hot-rolling method, an antioxidant is applied and the fiber is cleaned with 1.0 to 2.0 times, preferably 1.2 to 1.6 times, and more preferably 1.2 to 1.4 times, Fiber. 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.

The polyketone fibers undergo a stretching process at a high temperature in the range of 200 to 300 ° C. In this process, oxidation reaction of the fiber surface with oxygen causes browning and a large number of pin yarns. The polyketone fibers thus formed cause yarn splicing during the drawing process, resulting in deterioration of physical properties of the final drawn yarn. This problem can be solved by using an antioxidant during the stretching process.

The present invention is characterized in that an antioxidant is applied before the drying process and the stretching process. Concretely, it is firstly applied before the drying and single-stage drawing process, and applied secondarily before two-dimensional drawing.

In general, antioxidants act to block the chain reaction of oxygen by capturing radicals generated by light, heat, and initiators such as phenol, phosphorus, and sulfur.

In the present invention, instead of the phenolic antioxidant used in the prior art, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol- di (tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite) is dispersed and dissolved in acetone at a concentration of 0.01 to 10% by weight on the fiber surface before the drying process and the stretching process. More preferably 0.05 to 5% by weight.

The bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite was dissolved in a solution of 0.01 If it is used in an amount of less than 10% by weight, the effect of the antioxidant is deteriorated.

The bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite is a bis (2,6- -36 < / RTI > and has the structure of formula (2) as follows.

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite of bis (2,6- Is characterized by the appearance of white powder, Melting range 234 to 240 캜, Phosphorus content 9.3 to 9.9, and thermal decomposition at 1% TGA at 300 캜.

In the present invention, it is also possible to carry out the stretching process by passing through a heating chamber of 200 ° C to 300 ° C.

After the stretching step, the multifilament of high strength can be obtained through a stretching step of 1.0 to 2.0 times, preferably 1.2 to 1.6 times, more preferably 1.4 times in the cleaning process of the polyketone 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.

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 a polyketone fiber having high strength as a core technical matter 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 interval for uniform cooling of the solution.

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. If the number of orifices is more than 2,200, adjacent filaments are likely to be formed in close contact with each other in the air layer section, and the stability of each filament after spinning is lowered, resulting in deterioration of physical properties. 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.

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.

Further, the stretching process in the polyketone fibers of the present invention is very important for improvement of high strength and water resistance.

Hereinafter, the stretching process and drying method important in the present invention 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 heat deterioration of the polyketone at the time of heating, the stretching magnification and strength are improved by a process including an antioxidant 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. An antioxidant is used to prevent oxidation and deterioration of the polyketone at such a high temperature. As the antioxidant, any antioxidant capable of preventing radical oxidation and deterioration can be used.

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite) Have the same structure.

Oxidation and deterioration prevention mechanisms prevent radical reaction by blocking radicals with an antioxidant, which is an alkyl radical generated by heat or ultraviolet rays. The antioxidant of the present invention can be used before the drying process and the stretching process. The antioxidant may be used alone or in combination with the immersion method or the coating method. Specifically, in an embodiment of the present invention, before the drying step and the stretching step, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di- -butyl-4-methylphenyl) pentaerythritol-di-phosphite is dispersed and dissolved in acetone at a concentration of 0.01 to 10% by weight in a single step before and after the drying step, The inhibitor was 250 ppm, but after the drying and stretching steps, 25 ppm remained. The antioxidant should be used in an appropriate amount depending on the process. If it is large, the workability is poor. If the antioxidant is small, the effect of stabilizing heat stability is not sufficient.

In addition, since the polyketone is thermally deteriorated at a high temperature due to the drying and stretching process as described above, an antioxidant is added. It is applied before drying or before stretching. In the present invention, either raw or dip can be used.

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.

By the step of adding the antioxidant of the present invention, the polyketone fibers have a tensile strength of 18.0 g / d or more and a modulus of elasticity of 360 g / d or more.

The polyketone fibers produced by the present invention can be made into industrial products.

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 melting point of the polyketone copolymer was 240 占 폚, the LVN measured at 25 占 폚 by HFIP (hexafluoroisopropanol) was 6.0 dl / g, the MI index was 10 g / 10 min and the molecular weight distribution MWD) was 2.9.

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 캜 at an injection temperature of 25 캜 by a gear pump at a rate of 13000 g / hour to obtain a polyketone powder having a molecular weight distribution of 3.0 and an intrinsic viscosity of 6.0 dl / Was injected into the extruder at a rate of 1160 g / hr. The residence time in the swelling zone of the extruder was set to 0.8 minutes and the temperature was raised to 40 DEG C to sufficiently dissolve the polyketone polymer obtained in the production example 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.

The obtained fibers were subjected to 1.2-fold stretching in a washing process, and then bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite -tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, CAS No. 80693-00-1, ADEKA) dissolved in acetone in an amount of 0.05% by weight was dipped in an immersion method to prepare an antioxidant. Dried and stretched in one step.

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, which is a phosphorus compound, di-phosphite, CAS No. 80693-00-1, ADEKA) dissolved in acetone in an amount of 0.05 wt% was secondarily applied in the two-step stretching step.

The fiber was produced at a total drawing ratio of 16.8 times after the fiber was subjected to 1.2 times of drawing in the drying process, and the fiber was drawn at 7 times at the first step and 2.4 times at the second step. The second step was 3 steps of 1.5, 1.3 and 1.23 times And each step is performed at a temperature of 240, 265, 275 and 278 ° C.

Polyketone fibers were prepared through the above process.

Example 2

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, which is a phosphorus compound, CAS No. 80693-00-1, ADEKA) was dissolved in acetone in an amount of 1 wt%.

Example 3

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, which is a phosphorus compound, CAS No. 80693-00-1, ADEKA) was solely dissolved in acetone in an amount of 3% by weight.

Example 4

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, which is a phosphorus compound, CAS NO. 80693-00-1, ADEKA) was solely dissolved in acetone in an amount of 5% by weight.

Example 5

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, which is a phosphorus compound, CAS No. 80693-00-1, ADEKA) was solely dissolved in acetone in an amount of 7% by weight.

Example 6

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, which is a phosphorus compound, CAS NO. 80693-00-1, ADEKA) was solely dissolved in acetone in an amount of 10% by weight.

Comparative Example 1

The same experiment as in Example 1 was carried out except that 0.1% solution of AO80 of Adeka Co. in a methanol solution was used alone as a phenol antioxidant.

Property evaluation

(1) intrinsic viscosity

0.1 g of the sample was dissolved in a reagent (90 ° C) mixed with phenol and 1,1,2,2-tetrachloroethanol 6: 4 (weight ratio) for 90 minutes, transferred to a Ubbelohde viscometer, For 10 minutes, and use a viscometer and an aspirator to determine the number of drops of the solution. The number of drops of the solvent The RV value and I.V. The values were calculated

R.V. = Sample falling water / solvent falling water water

I.V. = 1/4 x [(R.V.- 1) / C] + 3/4 x (In R.V./C)

In the above equation, C represents the concentration (g / 100 ml) of the sample in the solution.

(2) Molecular weight distribution

A polyketone was dissolved in a hexafluoroisopropanol solution containing 0.01 N sodium trifluoroacetate so as to have a polyketone concentration of 0.01% by weight and measured under the following conditions.

Device: SHIMADZU LC-10Advp

Column: Use the following columns in the order of (a), (b) and (c).

(A): Shodex GPCHFIP-G

(B): Shodex HFIP-606M

(C): Shodex HFIP-606M

Column temperature: 40 ° C

Mobile phase: hexafluoroisopropanol solution containing 0.01 N sodium trifluoroacetate

Flow rate: 0.5 ml / min

Detector: differential refractometer

Injection volume: 30 μl

As a standard sample, polymethyl methacrylate (PMMA) having a monodispersed molecular weight distribution was used (concentration: 0.01% by weight), and the weight of the polyketone in terms of PMMA measured from the calibration curve of PMMA obtained under the same conditions as the above- The average molecular weight (Mw) and the number average molecular weight (Mn) were determined, and Mw / Mn was determined as a molecular weight distribution.

(3) Strength (g / d) and modulus of elasticity (modulus) (g / d)

24 monofilaments left for 24 hours at a temperature of 25 ° C and a relative humidity of 55% RH were extracted and then subjected to Vibrojet 2000 using a monofilament tensile tester Vibrojet 2000 manufactured by Lenzing Corporation to determine a denier load (about mono denier x50 mg) is added thereto, and then the sample is measured at a length of 20 mm and a tensile strength of 20 mm / min. The monofilament properties were measured by the average of the 22 values obtained by excluding the maximum value and the minimum value, respectively, out of the 24 values measured. The initial modulus represents the slope of the graph before the yield point.

Polyketone fiber Strength (g / d) Modulus of elasticity
(gf / d) Example 1 18.4 370 Example 2 18.8 377 Example 3 19.4 380 Example 4 18.9 376 Example 5 18.3 365 Example 6 18.0 360 Comparative Example 1 18.0 360

As shown in Table 1, the polyketone fibers produced by the examples of the present invention exhibited excellent improvement in strength and elastic modulus.

Claims

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A polyketone polymer comprising repeating units represented by the following general formulas (1) and (2) and having an y / x of 0 to 0.1 and an intrinsic viscosity of 5 to 7 dl / g is subjected to a spinning process, And a stretching process,
The dried undrawn fiber made of the above polyketone polymer is subjected to a drying process and a drawing process using bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite) alone in acetone,
The catalyst composition used in the polymerization of the polyketone polymer is a process for producing a polyketone fiber comprising (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine.
- [- 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)