KR20160057686A - Polyketone nanonfiber non woven fabric - Google Patents

Abstract

The present invention relates to a polyketone nanofiber non-woven fabric and a production method thereof. More specifically, the present invention relates to a polyketone nanofiber non-woven fabric on which polyketone nanofiber non-woven fabrics are consecutively laminated by electrospinning a polyketone solution. According to the present invention, the polyketone nanofiber non-woven fabric can be applicable to various industrial fields.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyketone nanofiber nonwoven fabric,

TECHNICAL FIELD The present invention relates to a polyketone nanofiber nonwoven fabric, and more particularly, to a polyketone nanofiber nonwoven fabric by electrospinning a polyketone solution.

It is a known fact that olefins such as ethylene and propylene and carbon monoxide 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 interchanged. The aliphatic polyketone is a polymer compound containing olefin and carbon monoxide as raw materials, such as ethylene, which is suitable for general purpose high performance plastics and is excellent in impact resistance and chemical resistance at low temperature, and has high strength of para-aramid fiber In addition, it has an advantage of good affinity with rubber. Due to the characteristics of polyketone, it is expected that polyketone can be used for tire cords and rubber materials, which are currently used exclusively for para-aramid fibers.

When a high molecular weight polyketone is melted, heat-crosslinking reaction occurs and melt spinning is inadequate. In general, wet spinning is preferable when polyketone having a high molecular weight is made into a fiber. In wet spinning of polyketones, conventional organic solvents such as hexafluoroisopropanol and metacresol have problems of toxicity and flammability. Further, the fibers obtained by wet spinning using the above solvent tend to be fragile, There is a disadvantage that it is insufficient for use as industrial yarn because of fatigue resistance and workability.

In addition, when an aqueous solution of a metal salt such as zinc chloride, zinc bromide, lithium bromide, lithium iodide, lithium thiocyanate or the like is used as a solvent, the solubility is low and phase separation occurs, making it difficult to produce a uniform solution. In addition, the fiber prepared using such a solvent can remove the solvent contained in the fibrous phase by using water, alcohol, or acetone as a coagulating solution in the coagulation step. However, since the difference in solidification rate between the fiber surface portion and the center portion is large, -Core structure, which makes it difficult to produce polyketone fibers having a uniform and dense structure.

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

In order to solve the above problems, it is an object of the present invention to provide a polyketone nanofiber nonwoven fabric and a polyketone nanofiber nonwoven fabric which are made of a copolymer of carbon monoxide and at least one olefin.

The present invention relates to a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2) and having y / x of 0 to 0.1, a polyketone copolymer obtained by electrospinning or electrobath spinning And the fibers have a diameter of 50 to 500 nm. The present invention also provides polyketone nanofiber nonwoven fabric.

- [- 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)

Also, the present invention provides a polyketone nanofiber nonwoven fabric characterized in that the polyketone copolymer has an intrinsic viscosity of 4.0 to 7.0 dl / g.

The present invention also relates to a catalyst composition for use in the polymerization of a polyketone copolymer, wherein the ligand is selected from the group consisting of bis (2,2-dimethyl-1,3-dioxane-5,5-diyl) bis -Methoxyphenyl) phosphine). ≪ / RTI >

By using electrospinning in the production of polyketone nanofiber nonwoven fabric, it is possible to produce a nano-sized nonwoven fabric which has not been produced by conventional wet spinning and to produce a polyketone nanofiber nonwoven fabric applicable to various industrial fields .

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 the monomer with a solution of the 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, 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.

[Chemical Formula 1]

.

.

     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 preferable in the present invention, is p-toluenesulfonic acid, which has high catalytic activity when used 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 the polyolefin.

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 include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, C2-C20 alpha-olefins including 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.

The polyketone polymer preferably used in the present invention is a copolymer of carbon monoxide and ethene or a second ethylenically unsaturated hydrocarbon having carbon monoxide, ethene and at least three carbon atoms, in particular alpha-olefins such as propene Is a terpolymer.

When the polyketone terpolymer is used as the main polymer component of the blend of the present invention, there are at least two units containing an ethylene moiety in each unit containing the second hydrocarbon moiety in the terpolymer. It is preferable that the number of units containing the second hydrocarbon moiety is from 10 to 100.

In one embodiment, the polyketone polymer is a copolymer comprising repeating units represented by the general formulas (1) and (2), and it is preferable that y / x is 0.01 or less. When the value of the y / x value exceeds 0.01, the mechanical properties are deteriorated.

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

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

On the other hand, the polyketone resin preferably has an intrinsic viscosity (LVN) of 4.0 to 7.0 dl / g. When the intrinsic viscosity of the polyketone resin is less than 4.0 dl / g, the mechanical properties may be deteriorated. If the intrinsic viscosity exceeds 7.0 dl / g, the workability may be deteriorated.

A preferred process for producing a polyketone polymer is disclosed in U.S. Patent No. 4,843,144. In the present invention, a mixed solvent of acetic acid and water is used as a liquid medium, and the polymerization reaction is caused by a catalyst composition composed of (a) a palladium compound, (b) a bidentate ligand and (c) an anion of an acid having a pKa of 4 or less , The catalyst is produced by contacting the three components. Any method may be employed. A solution prepared by preliminarily mixing three components in a suitable solvent may be used, or the three components may be supplied to the polymerization system and contacted in the polymerization system.

On the other hand, it is preferable that the molecular weight distribution of the polyketone is 1.5 to 2.5, 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.

A preferred process for producing a polyketone polymer is disclosed in U.S. Patent No. 4,843,144. In the present invention, a mixed solvent of acetic acid and water is used as a liquid medium, and the polymerization reaction is caused by a catalyst composition composed of (a) a palladium compound, (b) a bidentate ligand and (c) an anion of an acid having a pKa of 4 or less , The catalyst is produced by contacting the three components. Any method may be employed. A solution prepared by preliminarily mixing three components in a suitable solvent may be used, or the three components may be supplied to the polymerization system and contacted in the polymerization system.

In carrying out the present invention, the polymerization method includes a solution polymerization method using a liquid medium, a suspension polymerization method, a vapor phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution, and the like. The polymerization may be either batchwise or continuous. As the reactor used for the polymerization, known ones can be used as they are or by processing. The polymerization temperature is not particularly limited and generally 40 to 250 占 폚, preferably 50 to 180 占 폚 is employed. If the reaction temperature is less than 40 ° C, the polymerization reaction is poor and the reaction does not proceed. If the reaction temperature exceeds 250 ° C, a side reaction such as oligomerization or monomer preparation and decomposition reaction is more active than polymerization reaction with a polymer, . The pressure at the time of polymerization is not particularly limited, but is generally from normal pressure to 20 MPa, preferably from 4 to 15 MPa. The polymerization reaction rate is very low at a pressure lower than the atmospheric pressure, and the side reaction speed is increased at a pressure of 20 MPa or higher.

Hereinafter, an electrospinning and electrospinning apparatus for producing the nanofiber nonwoven fabric of the present invention will be described.

Electrospinning is a technique for producing ultrafine fibers and porous webs, that is, nonwoven fabrics having a diameter of several nanometers to several micrometers, using an electrostatic spraying phenomenon of a high viscosity fluid such as a polymer, It is a device that emits ultra fine fibers by pulling.

The polymer solution at the tip of the capillary (nozzle) vertically positioned in the electrospinning device forms an equilibrium between gravity and surface tension and forms a hemispherical droplet which, when an electric field is applied, causes charge or dipole orientation on the hemispherical droplet surface So that a force opposite to the surface tension is generated due to charge or dipole repulsion. This force causes the hemispherical surface of the solution suspended at the tip of the capillary to expand into a conical shape known as the Taylor cone. At some critical electric field strength (Vc), this repulsive electrostatic force overcomes the surface tension, Jet is emitted from the tail cone tip. In the case of a solution with a low viscosity, the jet collapses into fine droplets, resulting in spraying. However, in the case of a solution having a high viscosity such as a polymer, the jet is not collapsed, the solvent is evaporated as it flows toward the collecting plate toward the air, and the charged continuous polymer fibers are accumulated on the collecting plate. This phenomenon is called electrospinning . The reason why very thin fibers are produced by electrospinning is because the jet is thinned by the elongation of the jet and the spraying phenomenon in the course of flying towards the collector plate. Because of this small diameter, the electrospun fiber will have a larger surface area and volume, and more moisture can be absorbed than other fibers of larger diameter. The ultrafine fiber web thus produced is ultra thin and light in weight and has a very high volume to surface ratio and a high porosity as compared with conventional fibers. Therefore, it is also possible to have a breathable and windproof structure capable of structurally discharging internal sweat, and to prevent liquid from entering the outside of the fiber web.

The electrospinning device includes a spinning liquid main tank for storing a spinning solution, a metering pump for supplying a spinning solution in a fixed amount, a nozzle block for combining a plurality of tubular nozzles composed of a plurality of pins in block form and discharging the spinning solution in a fiber form, A collector for accumulating short fibers emitted at a position corresponding to the nozzle block, a voltage generating device for generating a high voltage, and a spinning solution discharging device connected to the top of the nozzle block.

A method for producing a polyketone nonwoven fabric by electrospinning the polyketone of the present invention will be described.

First, a spinning solution is prepared by dissolving polyketone in an appropriate solvent. The polyketone spinning solution is stored in the spinning liquid main tank, metered by a separate metering pump, and supplied to the spinning solution dropping device in a fixed amount.

The intrinsic viscosity of the polyketone is preferably 4 to 7. When the intrinsic viscosity is less than 4, the physical properties for producing the nonwoven fabric can not be sufficiently obtained. When the intrinsic viscosity is more than 7, the solution handling is not easy and the processability is poor.

The solvent is not particularly limited as long as the solvent can sufficiently dissolve the polymer and is applicable to electrospinning. In addition, when the porous polymer membrane is prepared by the electrospinning method, ordinary solvents are almost removed, Can also be used. For example, propylene carbonate, butylene carbonate, 1,4-butyrolactone, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, polyethylene sulfolane, tetraethylene glycol dimethyl ether, acetone, alcohol or mixtures thereof May be selected and used, and it is more preferable to use acetone.

The spinning solution supplied into the spinning solution dropping device passes through the spinning solution dropping device and is transferred to the spinning solution supply plate of the nozzle block which has a discontinuous high voltage and is mounted on the stirrer. The spinning liquid drop device also blocks the flow of spinning liquid and prevents electricity from flowing into the spinning liquid main tank.

Subsequently, in the nozzle block, the spinning liquid is discharged through a multi-tubular nozzle to a collector at an upper portion where a high voltage is applied to produce a nonwoven web or filament.

The spinning solution transferred to the spinning solution supply pipe is discharged to the collector through the multi-tubular nozzle to form the fibers. At this time, the nanofibers electrospun from the tubular nozzle are widely spread by the air injected from the nozzle for supplying air, and are collected on the collector, thereby widening the collecting area and making the density uniform. The surplus spinning solution which can not be fiberized in the multi-tubular nozzle is collected from the nozzle for overflow removal and moved back to the spinning solution supply plate through the temporary storage plate of the overflow solution.

In the case of producing an electrospun nonwoven fabric, it is preferable that the speed of air in the air supply nozzle is 0.05 m to 50 m / sec, more preferably 1 to 30 m / sec. When the velocity of the air is less than 0.05 m / sec, the spreadability of the non-woven fabric collected in the collector is low and the collecting area is not greatly improved. When the air velocity exceeds 50 m / sec, And more seriously, the radiated nanoweb is adhered to the collector in the form of a coarse tortoise so that the nanofiber forming ability and the ability to form an electrospun nonwoven fabric are remarkably deteriorated.

In addition, the spinning solution which is excessively supplied to the top of the nozzle block is forcibly transferred to the spinning liquid main tank by the spinning solution discharging device.

In order to promote fiber formation by the electric force, a voltage of 1 kV or more, preferably 20 kV or more, generated by the voltage generator is applied to the conductive plate and the collector provided at the lower end of the nozzle block. It is more advantageous in terms of productivity to use an endless belt as the collector. It is preferable that the collector reciprocates a predetermined distance to the left and right to uniform the density of the nonwoven fabric.

When the nonwoven fabric formed on the collector is wound on the winding roller through the web supporting roller, the nonwoven fabric manufacturing process is completed.

The manufacturing apparatus can increase the collection area of the nonwoven fabric to uniform the density of the nonwoven fabric, effectively prevent the droplet phenomenon, improve the quality of the nonwoven fabric, increase the fiber forming effect by the electric force, The nonwoven fabric can be mass-produced. In addition, the width and thickness of the nonwoven fabric and the filament can be freely changed and adjusted by arranging the nozzles composed of a plurality of pins in block form.

The electrospinning method may be any one of a bottom-up type, a top-down type, and a combination type, but it is more preferable to deploy the bottom-up type.

The electrobull apparatus in the present invention can be used both as a thermoplastic resin and a thermosetting resin, and is a nanofiber manufacturing apparatus that does not require solution heating and is easy to implement an insulation method.

In the electroblue manufacturing method, a polymer solution dissolved in a predetermined solvent is transferred to a spinning nozzle, and the polymer solution is ejected through a spinning nozzle to which high voltage is applied while injecting compressed air to the lower end of the spinning nozzle, And radiating on the section collector.

The present invention relates to a method of manufacturing a polymer solution, and more particularly, to a method of manufacturing a polymer solution, which comprises a spinning nozzle for discharging a polymer solution transferred from a reservoir for producing a polymer solution, an air injection hole for injecting compressed air to a lower end of the spinning nozzle, a voltage applying means for applying a high voltage to the spinning nozzle, And a grounded collector for collecting the discharged fiber discharged from the discharge port in a web state.

It is possible to spray the compressed air at the lower end of the spinning nozzle to minimize nozzle contamination due to suction through the collector.

The nanofiber nonwoven fabric produced by the above process can be applied to various industrial products. Preferably, it may be used for a water treatment separation membrane, a separation membrane for a secondary battery, a filter for air filtration and the like, but the scope of the present invention is not limited thereto.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following non-woven fabrics and non-woven fabrics of the present invention will be described in more detail with reference to the following examples and drawings. It will be apparent, however, to those skilled in the art that the scope of the invention is not limited to the disclosed embodiments and modifications or improvements made therefrom.

Example 1

Polymerization of polyketone, which is used as a polymer of nanofiber, was prepared by the following procedure.

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid with respect to palladium is 10 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 78 占 폚 and 84 占 폚 are carried out. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 99: 1. The polyketone terpolymer had an LVN of 6.0 dl / g, a melt index (MI) of 60 g / 10 min, and an MWD of 2.3 as measured by HFIP (hexa-fluoroisopropano) at 25 ° C. The polyketone terpolymer prepared above was prepared in the form of pellets on an extruder using a twin-screw of 40 mm diameter and L / D = 32 operating at 250 rpm.

14.0% by weight of the polyketone polymer (PK) prepared above was added to an aqueous solution containing 75% by weight of resorcinol, and the mixture was reduced at 60 DEG C to 150 torr and mixed for 30 minutes to remove air bubbles.

After the bubbles in the aqueous solution were completely removed, the mixture was sealed in a reduced pressure state, then heated to 70 캜 and stirred for 2 hours to obtain a transparent polyketone spinning solution. The polyketone solution was charged into the spinning liquid main tank, and the applied voltage was applied to the nozzle block at 25 kV to be electrospun. A polyketone nanofiber nonwoven fabric having a thickness of 2.5 탆 and a fiber diameter of 350 nm was produced. At this time, electrospinning was performed under the conditions of a distance between the electrode and the collector of 40 cm, a spinning solution flow rate of 0.1 mL / h, a temperature of 22 ° C, and a humidity of 20 ° C.

Example 2

14.0% by weight of the polyketone polymer (PK) prepared in Example 1 was added to an aqueous solution containing 75% by weight of resorcinol, the pressure was reduced from 60 ° C to 150 torr, and the mixture was mixed for 30 minutes to remove air bubbles.

After the bubbles in the aqueous solution were completely removed, the mixture was sealed in a reduced pressure state, then heated to 70 캜 and stirred for 2 hours to obtain a transparent polyketone spinning solution. The polyketone solution was charged into the spinning liquid main tank, and the applied voltage was applied to the nozzle block at 30 kV to be electrospun. A polyketone nanofiber nonwoven fabric having a thickness of 2.5 mu m and a fiber diameter of 150 nm was laminated to produce a polyketone nanofiber nonwoven fabric. At this time, electrospinning was performed under the conditions of a distance between the electrode and the collector of 40 cm, a spinning solution flow rate of 0.1 mL / h, a temperature of 22 ° C, and a humidity of 20 ° C.

Example 3

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid with respect to palladium is 9 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 80 ° C and the second stage at 84 ° C are carried out. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 99: 1. The polyketone terpolymer had an LVN of 5.7 dl / g, an MI index of 60 g / 10 min, and an MWD of 2.3 as measured by HFIP (hexa-fluoroisopropano) at 25 ° C. The polyketone terpolymer prepared above was prepared in the form of pellets on an extruder using a twin screw having a diameter of 40 mm and operating at 250 rpm and L / D = 32.

A polyketone nanofiber nonwoven fabric having a thickness of 2.5 탆 and a fiber diameter of 280 nm was prepared by the method of Example 1 by the above-mentioned polyketone in which the intrinsic viscosity of the polyketone was adjusted to 5.7.

Example 4

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid with respect to palladium is 11 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 74 deg. C and the second stage at 84 deg. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 99: 1. The polyketone terpolymer had an LVN of 6.3 dl / g, an MI index of 60 g / 10 min, and an MWD of 2.3 as measured by HFIP (hexa-fluoroisopropano) at 25 ° C. The polyketone terpolymer prepared above was prepared in the form of pellets on an extruder using a twin-screw of 40 mm diameter and L / D = 32 operating at 250 rpm.

A polyketone nanofiber nonwoven fabric having a thickness of 2.5 탆 and a fiber diameter of 400 nm was prepared by the method of Example 1 by the above-mentioned polyketone in which the intrinsic viscosity of the polyketone was adjusted to 6.3.

Example 5

A polyketone nanofiber nonwoven fabric having a thickness of 2.5 탆 and a fiber diameter of 80 nm was prepared by the method of Example 2 by using a polyketone having an intrinsic viscosity adjusted to 5.7 when the polyketone was polymerized.

Example 6

A polyketone nanofiber nonwoven fabric having a thickness of 2.5 탆 and a fiber diameter of 200 nm was prepared by the method of Example 2 by using a polyketone whose intrinsic viscosity was adjusted to 6.3 when polymerizing the polyketone.

Example 7

A polyketone having an intrinsic viscosity of 6.0 dl / g and an MWD of 2.3 is dissolved in an acetone solvent to prepare a polyketone dope of 20 mass%. The above dope was subjected to bottom-up electrospinning on a polyolefin substrate (Celgard 2400) having a thickness of 10 탆 at a distance of 40 cm between the electrode and the collector, an applied voltage of 25 kV, a spinning solution flow rate of 0.1 mL / h, a temperature of 22 캜 and a humidity of 20% To form a polyketone nano-nonwoven fabric layer to prepare a porous separator for a secondary battery.

Claims (4)

A polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2) and having y / x of 0 to 0.1, a polyketone copolymer produced by electrospinning or electro- Wherein the fiber has a diameter of 50 to 500 nm.
- [- 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 copolymer has an intrinsic viscosity of 4.0 to 7.0 dl / g.
The method according to claim 1,
The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is preferably selected from the group consisting of bis (2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) ) Phosphine). ≪ / RTI >
An industrial article comprising the polyketone nanofiber nonwoven fabric of any one of claims 1 to 3.