KR101695732B1

KR101695732B1 - Polyketone industrial hoses including polyketone fiber

Info

Publication number: KR101695732B1
Application number: KR1020150074070A
Authority: KR
Inventors: 황순동; 이득진
Original assignee: 주식회사 효성
Priority date: 2015-05-27
Filing date: 2015-05-27
Publication date: 2017-01-12
Also published as: KR20160139383A

Abstract

Carbon ketone, carbon monoxide, ethylene and propylene copolymer, and to provide polyketone fibers having excellent strength and heat resistance from the polyketone solution and an aircraft or automobile hose comprising the same. The polyketone industrial hose produced according to the present invention is excellent in strength and heat resistance and is suitable for use as an aircraft or automobile hose.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyketone industrial hose including a polyketone fiber,

The present invention relates to a high strength polyketone yarn for a hose used in automobiles, aircrafts, and the like, and more particularly to a hose reinforced polyketone yarn for an aircraft or an automobile hose including polyketone fibers having remarkably improved impact absorption performance and excellent mechanical properties and work performance .

Currently, various materials such as polyester, nylon, aramid, polyvinyl alcohol (PVA) and rayon are used as reinforcing fibers for rubber hose. However, each material has various functions Therefore, it is used according to the inherent properties of each reinforcing material. In order to complement each other, we have overcome the weakness of each material by using different fibers in different layers. The basic performance required for these rubber hose reinforcing fibers is high strength, initial modulus, heat resistance, no deterioration in dry heat, flexural strength, shape stability and adhesion to rubber. .

For example, in the case of an oil or coolant transfer hose of an air or various engines in which initial modulus (elastic modulus) and heat resistance and shape stability are particularly required among the performances, it is preferable to use nylon having low flexural strength but low shape stability alone The use of reinforcing fibers can have properties of low shrinkage and excellent shape stability. In the case of reinforcing nylon or polyester on the inside and forming aramid or polyvinyl alcohol fibers having a high elastic modulus on the outer side in a multi-layered structure, A method of satisfying the requirements of the fiber for use is also used. Also, in the case of high-temperature solution transfer hoses, there is no change in physical properties due to a rise in temperature, so rayon or aramid is mainly used. Aramid fiber has a very low shrinkage ratio, high shape stability and elasticity, and does not deteriorate up to 400. However, a variety of alternative fibers have been developed because of high price.

In addition, in the case of rayon reinforcing fiber, decomposition does not occur up to about 300 ° C., adhesion with rubber is very good, but the strength is somewhat low and the elastic modulus due to moisture absorption is low. There is a disadvantage in that hose performance is lowered due to strength and modulus deterioration when moisture penetrates due to damage of the surface even after the hose is made. Therefore, it is required not only to have excellent strength, but also to maintain strength and elastic modulus when moisture absorption occurs in the production process.

On the other hand, 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 are alternated.

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.

In order to solve the above problems, the present invention provides a polyketone copolymer comprising carbon monoxide and a polyketone copolymer composed of at least one olefinically unsaturated hydrocarbon. In the process of producing the multifilament, the pre- To provide a hose comprising polyketone fibers which can be used for aircraft or automobiles with improved heat resistance.

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 A polyketone industrial hose characterized by containing a polyketone fiber produced by a spinning process, a washing process, a drying process and a stretching process of a ketone copolymer.

- [- 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)

In this case, the polyketone industrial hose is manufactured by using a dip cord manufactured by twisting the polyketone fibers using a direct twist, dipping them in a dipping solution, and subjecting them to heat treatment.

The monofilament of the polyketone fiber has an initial modulus value of 200 g / d or more, an elongation of 2.5 to 3.5% at 10.0 g / d, and elongation of at least 0.5% at 19.0 g / d or more.

Here, the monofilament of the polyketone fiber preferably has a fineness of 0.5 to 8.0 denier.

Further, the present invention is characterized in that it is 1.0 to 2.0 times in the washing step, and the drying step is hot-roll drying at 100 to 230 ° C, and preferably 1.0 to 2.0 times.

In addition, it is preferable that the stretching process is a method of passing through a heating chamber at 230 to 300 ° C.

Further, there is provided a polyketone industrial hose characterized by treating the heat stabilizer before drying and before stretching.

Also, the present invention provides a polyketone industrial hose having a strength of 15 g / d or more and a residual strength of 90% or more after applying heat in a dry state for 7 days in a dryer set at 150 캜 for 7 days.

In addition, the industrial hose is selected from hoses for aircraft or hoses for automobiles.

An object of the present invention is to provide a polyketone solution from carbon monoxide, ethylene and propylene copolymer, and to provide an aircraft or an automobile hose comprising polyketone fibers having excellent strength and heat resistance from the polyketone solution.

1 is a view schematically showing the role of a heat-resistant stabilizer according to the prior art.
2 is a schematic view of a conventional hot air drying type dryer.
3 is a schematic view of a hot roll drying method according to the present invention.
Fig. 4 is a cross-sectional view of the dry irradiation according to the conventional hot air drying method.
Fig. 5 is a cross-section view of a dry-type drying method according to the present invention.

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, The present invention provides a polyketone industrial hose comprising a polyketone fiber produced through a 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)

Further, it is characterized in that it is stretched 1.0 to 2.0 times in the washing step and 1.0 to 2.0 times in the drying step.

In addition, the drying step may be hot-rolled at 100 to 230 ° C, and the stretching step may be a heating chamber stretching method at 230 to 300 ° C.

In addition, it is preferable to treat the heat stabilizer before the drying step and the stretching step.

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.

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.

Particularly, 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 has high catalytic activity when used in combination with a mixed solvent of acetic acid and water as a liquid medium, It becomes possible to manufacture a polyketone having a high intrinsic viscosity suitable as a hose for use.

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-C20-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, tricyclodecene, 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, the 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 a hose for an aircraft or an automobile. The ratio of the ethylene to the propylene is 100: 0 to 90:10 .

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.

Further, the strength of the polyketone aircraft or the hose for automobiles made of the polyketone is preferably 10 to 20 g / d.

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. However, the inventors of the present invention have found that by applying a heat-resistant stabilizer while applying a roller heating method, especially a hot-roll drying method, and performing a stretching process 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, in the present invention, the stretching process is performed using a method of passing through a heating chamber at 230 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 a polyketone fiber having high strength and high fatigue resistance and dimensional stability 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 , And the spinning stock solution is extruded and spun through a spinning nozzle containing a plurality of orifices having an orifice spacing of 1.0 to 5.0 mm so that the fiber spinning solution passes through the air layer to reach the coagulation bath, .

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 the spinnability. If the diameter exceeds 500 탆, the coagulation speed of the solution in the spinning coagulating bath is slow, Solvent removal and washing become 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, taking into account the hose for aircraft or automobile in terms of usage.

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 form close-contact with each other in the air layer section, resulting in deterioration of the stability of each filament after spinning, resulting in deterioration of physical properties. .

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 캜, more preferably -5 to 20 캜. 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 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 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 capturing radicals with heat stabilizers (alkyl radicals) generated by heat or ultraviolet rays (see FIG. 1). 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 prepared 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 as shown in FIG. 2 was used at a temperature of 180 ° C. for a retention time of about 3 minutes and 30 seconds. This has the effect of achieving uniform drying and improving the affixation, but it is difficult to generate fusion, loops, static electricity, and fusion structure, so that the structure is not as dense (see FIG. 4). The present invention uses a hot-roll drying method as shown in Fig. 3 for a retention time of about 1 minute and 30 seconds at a temperature of 220 to 230 ° C. 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 (see FIG. 5).

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 processes 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 at 2.5 g / d at 2.5 g / d and elongation at least 0.5% at 19.0 g / d or more.

The polyketone fibers produced by the present invention can be made into hoses for aircraft or automobiles.

In the present invention, the wound yarn is twisted by a twisted yarn to produce a raw cord, which is then woven and immersed in a dipping solution to provide an aircraft or an automobile hose.

The polyketone multifilament produced by the above method is obtained by twisting the wound two yarns into a direct yarn twisted yarn at the same time, . The raw cord is manufactured by applying a ply twist to a polyketone yarn for a hose and then applying and twisting the cable twist. Generally, the upper and lower rim are subjected to the same training or different training as required.

An important result of the present invention is that the physical properties such as the strength of the cord, the tensile strength and the fatigue resistance of the cord are changed according to the degree of twisting (number of years) given to the polyketone multifilament. Generally, when the twist is high, the strength decreases, and the midline and the twist tend to increase. My fatigue shows a tendency to improve with increasing kinks. The softening point of the polyketone hose prepared in the present invention was 200/200 TPM to 500/500 TPM at the same time, but the upper and lower halves were given the same numerical values. This indicates that the manufactured hose does not show any rotation or twist, So that the phase can be easily maintained and the physical properties can be maximized. In this case, when the pressure is less than 200/200 TPM, the loss of the cord is decreased and the fatigue tends to decrease. When the pressure is higher than 500/500 TPM, the strength is lowered, which is not suitable for the hose.

The produced 'Raw Cord' is woven using a weaving machine, and the obtained fabric is immersed in the dipping solution and then cured to form a 'Raw Cord' Dip cord ".

The dipping process of the present invention will be described in more detail. Dipping is achieved by impregnating the surface of the fiber with a resin layer called RFL (Resorcinol-Formaline-Latex) . In the case of using PET fiber, since the reactor on the surface of the PET fiber is smaller than that of the rayon fiber or the nylon fiber, the surface of the PET is first activated before the bonding treatment is performed (2 bath dipping). The polyketone multifilament according to the present invention uses a 1-bath dipping. Dip splitting uses a known dip bath for hose cords.

The dip cord manufactured according to the above-described method can be advantageously used as an aircraft or automobile hose cord having a total denier of 1000 to 6000 dia. And a cutting load in the range of 14.0 to 35.0 kg.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

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 13,000 g / hour to obtain a polyketone powder having a molecular weight distribution of 3.0 and an intrinsic viscosity of 6.0 dl / The extruder was injected at 1160 g / hour into a screw type feeder, the residence time in the extruder swelling zone was set to 0.8 minutes, the temperature was raised to 40 DEG C, the polyketone powder was sufficiently dissolved in the metal salt solution, Polyketone fibers were prepared by dry-wet spinning by maintaining the temperature at 55-60 < 0 > C 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% by weight, and it was in a homogeneous state free of undissolved polyketone particles.

The fiber thus obtained is subjected to stretching at 1.2 times in the course of washing, 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, and each step is performed at temperatures of 240, 255, 265, and 268 ° C.

Industrial hoses were prepared using polyketone fibers obtained from the above process. At this time, the polyketone fibers were twisted 30 times / 10 cm using a direct twisted yarn, immersed in a normal RFL solution, and heat-treated to prepare dip cords.

Example 2

except that the temperature of each step of the first and second steps in the heating chamber type stretching was adjusted to 240, 250, 260 and 268 캜.

Example 3

except that the temperature of each step of the first and second stages in the heating chamber type stretching was adjusted to 240, 255, 265, and 272 캜, respectively.

Example 4

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 13,000 g / hour to obtain a polyketone powder having a molecular weight distribution of 3.0 and an intrinsic viscosity of 5.7 dl / The extruder was injected at 1160 g / hour into a screw type feeder, the residence time in the extruder swelling zone was set to 0.8 minutes, the temperature was raised to 40 DEG C, the polyketone powder was sufficiently dissolved in the metal salt solution, Polyketone fibers were prepared by dry-wet spinning by maintaining the temperature at 55-60 < 0 > C and operating the screw at 110 rpm.

Example 5

The same as Example 4 except that the intrinsic viscosity of the polyketone polymer was adjusted to 6.1 / g.

Example 6

And the intrinsic viscosity of the polyketone polymer was adjusted to 6.3 / g.

Example 7

A polyketone powder having a molecular weight distribution of 2.5 and an intrinsic viscosity of 6.0 dl / g was injected into an extruder maintained at 30 DEG C at an injection temperature of 25 with a gear pump at a rate of 13000 g / The extruder was injected at a rate of 1160 g / hour by means of a screw feeder. The residence time in the swelling zone of the extruder was set to 0.8 minutes and the temperature was raised to 40 ° C to sufficiently dissolve the polyketone powder in the metal salt solution. Was maintained at 55 to 60 DEG C, and the screw was operated at 110 rpm to produce polyketone fibers by dry-wet spinning.

Example 8

The same as Example 7 except that the molecular weight distribution of the polyketone polymer was adjusted to 2.8.

Example 9

And the molecular weight distribution of the polyketone polymer was adjusted to 3.5.

Example 10

The procedure of Example 1 was repeated except that a 0.1% solution of a mixed solution of AO80 and methanol of Adeka as a phenolic heat stabilizer was subjected to 1 dip before drying.

Example 11

Example 1 was the same as Example 1 except that a 0.1% solution of AO80 and methanol of Adeka Co. as a phenolic heat stabilizer was subjected to two dipping before drying and before drawing.

Comparative Examples 1 to 3

The same procedure as in Example 1 was conducted except that polyester fiber was used in the production of industrial hoses and the stretching ratio in the washing step was 1.0 times and the hot-air drying method was used instead of the hot-roll drying method. .

Comparative Example 1 Comparative Example 2 Comparative Example 3 Hot air dryer temperature (캜) 240 260 280 The stretching ratio (times) 1.0 times 1.0 times 1.0 times

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 solvent The RV value and the IV value were calculated by the following equation obtained by the same method as described above

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) 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 wt% 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) Method of measuring modulus and strength of filament

The yarn is left in a standard temperature condition, that is, in a constant temperature and humidity room at a temperature of 25 ° C and a relative humidity of 65% for 24 hours, and then the sample is measured by a tensile tester by ASTM 2256 method. The physical properties of the samples were measured by the average values of the remaining eight, excluding the maximum value and the minimum value, respectively, of the ten values measured from ten samples. The initial modulus represents the slope of the graph before the yield point.

(4) Heat resistance (%)

After the initial fabrication, the strength of the fiber was measured by the physical property measurement method described above, and heat was applied in a dryer set at 150 ° C for 7 days in an unloaded state, and the residual ratio of the strength was evaluated. The ratio of the original strength to the strength after application of heat was determined as a measure of heat resistance.

(5) The strength (g / d), elongation (%) and modulus (g / d)

24 monofilaments were extracted from the yarn (multifilament) which was allowed to stand for 24 hours at a temperature of 25 ° C. and a relative humidity of 55 RH%. The monofilament tensile tester Vibrojet 2000 manufactured by Lenzing Corporation was used to measure the dewar load in the Vibrojet (Mono-denier x50 (mg)) is added, and 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.

Multi-filament properties Monofilament properties Strength (g / d) Shinto (%) Heat resistance
(%) Initial modulus (g / d) 10.0g / d Elongation (%) when stressed 19.0g / d ~ Elongation (%) when stressed to cut Example 1 20.75 5.9 94.3 220 2.4 1.8 Example 2 21.00 5.6 93.1 280 2.5 2.1 Example 3 20.84 5.7 92.3 205 2.3 1.7 Example 4 19.95 6.3 94.0 250 2.9 2.0 Example 5 20.55 6.0 92.4 290 3.1 1.0 Example 6 20.13 6.1 92.3 212 2.8 1.4 Example 7 19.74 6.3 91.1 210 2.7 1.2 Example 8 20.87 5.7 90.7 230 3.2 1.3 Example 9 20.14 6.1 93.1 220 3.1 1.3 Example 10 20.20 6.0 91.5 260 3.4 1.4 Example 11 21.04 5.6 91.3 230 2.8 1.2 Comparative Example 1 7.5 4.9 35 210 3.1 0 Comparative Example 2 7.7 4.7 34.7 200 3.2 0 Comparative Example 3 7.3 5.0 34.7 215 3.0 0

As shown in Table 2, the industrial hose made of the polyketone fibers manufactured according to the embodiment of the present invention has excellent elongation and strength, and is excellent in heat resistance and is suitable for use as an hose for an aircraft or an automobile.

Claims

A polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2) and having an y / x of more than 0 and not more than 0.1 and an intrinsic viscosity of 5 to 7 dl / g is subjected to a spinning process, Wherein the monofilament has an initial modulus value of at least 200 g / d, an elongation at 2.5 to 3.5% at 10.0 g / d and a polyketone length of at least 0.5% at 19.0 g / d or more, Polyketone industrial hose characterized by containing fibers.
- [- 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,
Wherein the polyketone industrial hose is manufactured by using a dip cord manufactured by twisting the polyketone fibers using a direct twisted yarn, dipping them in a dipping solution, and then subjecting them to heat treatment.

The method according to claim 1,
Wherein the polyketone fiber has a strength of 15 g / d or more and a residual strength of 90% or more after applying heat in an unloaded state in a dryer set at 150 캜 for 7 days.

delete

The method according to claim 1,
Wherein the polyketone fiber monofilament has a fineness of 0.5 to 8.0 denier.

The method according to claim 1,
Characterized in that the polyketone is stretched 1.0 to 2.0 times in the washing step and 1.0 to 2.0 times in the drying step.

The method according to claim 1,
Characterized in that the drying step is a hot-roll drying at 100 to 230 ° C, and the stretching step is a heating chamber stretching at 230 to 300 ° C.

The method according to claim 1,
Characterized in that the heat-resistant stabilizer is treated before the drying step and the stretching step.

The method according to claim 1,
Wherein the industrial hose is selected from an aircraft hose or an automobile hose.