KR101545286B1 - Polyketone nanofiber non woven fabric - Google Patents

Abstract

The purpose of the present invention is to provide a polyketone nanofiber nonwoven fabric comprising carbon monoxide and at least one olefin copolymer, and an industrial product manufactured with a polyketone nanofiber nonwoven fabric.

Description

Polyketone nanofiber non woven fabric < RTI ID = 0.0 >

The present invention relates to a polyketone nanofiber nonwoven fabric, and more particularly, to a polyketone nanofiber nonwoven fabric produced by meltblown or spunbond spinning of 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.

In addition, PVDF, nylon, or polyurethane is used as a material of the nanofiber nonwoven fabric used as a general industrial product. However, there has been no attempt to produce a nanofiber nonwoven fabric by using a polyketone having excellent mechanical properties and chemical properties as described above, and the inventors of the present invention have developed nanofiber nonwoven fabrics using polyketone.

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 an industrial product comprising 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), wherein y / x is 0.03 to 0.3, intrinsic viscosity is 0.5 to 4.0 dl / g, To 2.5, by melt-blown spinning or spunbond spinning. The polyketone nanofiber nonwoven fabric of the present invention is produced by melt-blown spinning or spunbond spinning.

- [- 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 diameter of the polyketone nanofiber nonwoven fabric is 500 to 5,000 nm.

In the present invention, the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is a ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) 2-methoxyphenyl) phosphine). ≪ / RTI >

In addition, the present invention provides a separation membrane made of the polyketone nanofiber nonwoven fabric.

The present invention provides a polyketone nanofiber nonwoven fabric having excellent mechanical and chemical properties and a fiber diameter of 500 to 5,000 nm by using a polyketone nanofiber nonwoven fabric as a polyketone nanofiber material.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is not limited to the scope of the present invention, but is merely an example, and various modifications can be made without departing from the technical spirit of the present invention.

As used herein, the term "nanofiber" refers to a microfine fiber having a diameter of about 50 to about 500 nm, and the term "nonwoven fabric" means that fibers are arranged in a parallel or non- Means a fabric made by mechanical treatment so that the fibers are entangled with each other.

In the present invention, "polyketone" means carbon monoxide and at least one olefinically unsaturated hydrocarbon, more preferably a spinning solution and a spinning fiber characterized in that the molar ratio of ethylene to propylene is 99: 1 or more .

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 activity is less affected by the catalytic activity, but when the concentration 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.

[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 y / x is preferably 0.03 to 0.3. When the value of the y / x value is less than 0.03, the workability is poor. When the value of y / x is more than 0.3, the mechanical properties are poor.

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

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

On the other hand, the polyketone resin preferably has an intrinsic viscosity (LVN) of 0.5 to 4.0 dl / g. If the intrinsic viscosity of the polyketone resin is less than 0.5 dl / g, the mechanical properties may be deteriorated. If the intrinsic viscosity exceeds 4.0 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. The reactor used in the polymerization can be used as it is or in a known manner. 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, a method for producing a nanofiber nonwoven fabric using the polyketone will be described.

Melt blowing is an extrusion technique for producing fine fiber webs directly from the polymer. In meltblowing, the thermoplastic polymer stream is extruded through a die comprising a compact outlet and is attenuated by two converging streams of high velocity hot air into the microfibers. These fine fibers can be used to form meltblown webs, often referred to as blown micro-fiber webs. Blown microfiber-fibrous webs are used in a variety of applications, among other things, including sound insulation and insulation, filtration, barrier webs and wipes.

Especially, the spunbonded nonwoven fabric refers to a nonwoven fabric produced by spinning chemical fibers, and is a kind of nonwoven fabric formed by forming a long fiber layer on a conveyor by blowing on a conveyor running on a fiber coming from a nozzle. .

The meltblown nonwoven fabric refers to a nonwoven fabric manufactured by a meltblown process. Since the used web is a superfine fiber, it has a softness, a warmth and a high filtration performance, There is a drawback.

In the present invention, the diameter of the polyketone nanofiber is preferably from 500 to 5,000 nm, more preferably from 800 to 1,000 nm, and the preferred production method is melt blown or spunbond spinning, A method for producing a polyketone nanofiber nonwoven fabric using blowing.

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 present invention will now be described in more detail with reference to the following non-limiting examples of the present invention. 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 46 to 4. The polyketone terpolymer had an LVN of 1.4 dl / g, a melt index (MI) of 60 g / 10 min, and an MWD of 2.0 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.

The polyketone pellets were melted at 265 占 폚 and melt-spun by melt blowing so as to have a fiber diameter of 2000 nm and a fiber thickness of 3 占 퐉 by high-pressure hot air to prepare a polyketone nano fiber nonwoven fabric.

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.

The polyketone pellets were melted at 265 占 폚 and melt-spun by melt blowing so as to have a fiber diameter of 1000 nm and a fiber thickness of 3 占 퐉 by high-pressure hot air to prepare a polyketone nano fiber nonwoven fabric.

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 46 to 4. The polyketone terpolymer had an LVN of 1.1 dl / g, a melt index (MI) of 60 g / 10 min, and an MWD of 2.0 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.

The polyketone pellets were melted at 265 캜 and melted and spin-spun by high-pressure hot air to a fiber diameter of 2500 nm and a fiber thickness of 3 탆 to prepare a polyketone nano fiber nonwoven fabric.

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 46 to 4. The polyketone terpolymer had an LVN of 2.0 dl / g, a melt index (MI) of 60 g / 10 min, and an MWD of 2.0 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.

The polyketone pellets were melted at 265 占 폚 and melt-spun by melt blowing so as to have a fiber diameter of 3,000 nm and a fiber thickness of 3 占 퐉 by high-pressure hot air to prepare a polyketone nano fiber nonwoven fabric.

Example 5

A polyketone nanofiber nonwoven fabric having a thickness of 3 탆 and a fiber diameter of 600 nm was prepared by the method of Example 2 by using a polyketone whose intrinsic viscosity was adjusted to 1.1 dl / g when polymerizing the polyketone.

Example 6

A polyketone nanofiber nonwoven fabric having a thickness of 3 탆 and a fiber diameter of 1500 nm was prepared by the method of Example 2 by using a polyketone having an intrinsic viscosity adjusted to 2.0 dl / g in polymerization of polyketone.

Claims (4)

1. A polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), having a y / x of 0.03 to 0.3, an intrinsic viscosity of 0.5 to 4.0 dl / g and a molecular weight distribution of 1.5 to 2.5 Characterized in that the polyketone nanofiber nonwoven fabric is produced by meltblown spinning or spunbond spinning of a polyketone 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)
The method according to claim 1,
Wherein the polyketone nanofiber nonwoven fabric has a diameter of 500 to 5,000 nm.
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 made from the polyketone nanofiber nonwoven fabric of any one of claims 1 to 3.