KR20190054718A - Polyketone industrial button component - Google Patents

Abstract

The present invention relates to a polyketone industrial button component including a composition comprising a linear alternating polyketone consisting of carbon monoxide and at least one olefin-based unsaturated hydrocarbon and a flame retardant agent. The polyketone industrial button component according to the present invention has an effect of exhibiting uniform flame retardancy and excellent fastening properties.

Description

Polyketone industrial button component [0001]

The present invention relates to a polyketone industrial button component made of a composition comprising a linear alternating polyketone composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon and a flame retardant and is excellent in flame retardancy and fastness, And an industrial button part with improved reliability of the product.

The fastening button of the wire finishing fabric used in ships and nuclear power plants is required to have flame retardancy and fastenability according to the ship and power station safety standards. In the case of polyethylene / flame retardant materials which are currently used as typical materials, the flame retardant quality is uneven and the fastening properties of the buttons are somewhat weak. Therefore, the flame retardancy may not be developed in actual use environment and the product may be damaged due to the lack of mechanical strength. There is a problem in securing the reliability in the apparatus.

On the other hand, there has recently been a growing interest in a group of linear alternating polymers known as polyketones, composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon. U.S. Patent No. 4,880,903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide, ethylene and terephthalic unsaturated hydrocarbons such as propylene.

The process for preparing the polyketone polymer is generally carried out by reacting a compound of a Group VIII metal selected from among palladium, cobalt or nickel with an anion of a strong halogen-hydrohalogentic acid, , Phosphorus, arsenic, or antimony (Antimon).

U.S. Patent No. 4,843,144 discloses a method for producing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of a nonhydrohalogen acid having a pKa of less than 6, and a catalyst that is a bidentate ligand Lt; / RTI >

Japanese Patent Laid-Open No. 1996-236500 Japanese Patent Laid-Open No. 2001-081306 Korean Patent Publication No. 1999-0064241 Korea Patent Publication No. 2011-0078120

An object of the present invention is to provide an industrial button component in which a polyketone / flame retardant material is used, which is not a polyethylene / flame retardant material, which has been used in the prior art, thereby improving flexural modulus and flame retardancy.

A polyketone industrial button component according to preferred embodiments of the present invention comprises 85 to 92 wt% of a linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; And 8 to 15% by weight of a flame retardant; and a flexural modulus of 1900 to 2200 MPa.

The polyketone has an intrinsic viscosity (IV) of 1.0 to 2.0 dl / g, a molecular weight distribution of 1.5 to 2.5, and a repeating unit represented by the following general formulas (1) and (2) 0.03 to 0.3.

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

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

(x and y represent mol% of each of the general formulas (1) and (2) in the polymer)

In addition, the ligand of the catalyst composition used in the polyketone polymerization is (cyclohexane-1,1-diylbis (methylene)) bis (bis (2- methoxyphenyl) phosphine and (cyclohexane- And bis (bis (2-methoxyphenyl) phosphine), and the flame retardant may be one selected from the group consisting of phosphorus-containing flame retardants including phosphorus Species or two or more species.

INDUSTRIAL APPLICABILITY The polyketone industrial button component of the present invention has high rigidity due to excellent rigidity and flowability of a polyketone material, and has an effect of improving safety of a product due to uniformity of flexural modulus and flame retardancy.

Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited to these.

The present invention provides a polyketone industrial button component comprising a polyketone composition comprising a polyketone and a flame retardant.

First, the polyketone resin used in the present invention is an engineering plastic and recently developed as a new resin, it is excellent in mechanical properties such as impact strength and molding characteristics, and is excellent in thermoplastic properties It is a synthetic resin. The mechanical properties of the polyketone resin belong to the category of high performance plastics, and they are attracting much attention as eco-friendly materials because they are polymeric materials synthesized from carbon monoxide as a raw material.

The polyketone resin has a lower moisture absorption than the polyamide material, so that it is possible to design various products with less change in dimensions and physical properties due to moisture absorption. The polyketone resin is more suitable for weight reduction because the density is lower than that of aluminum material. Particularly, polyketone is a material having strong molecular bonding as compared with polyethylene and has a melting point higher than that of polyethylene by about 100 ° C, which is superior in strength to polyethylene and excellent in heat stability.

Hereinafter, the process for producing the polyketone will be described.

The production process of polyketone is carried out in the presence of an organometallic complex catalyst comprising (a) a Group 9, 10 or 11 transition metal compound, and (b) a ligand having an element of Group 15, Wherein the carbon monoxide, ethylene and propylene are subjected to liquid phase polymerization in a mixed solvent of an alcohol (e.g., methanol) and water to produce a linear terpolymer, As an example of the solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of water in the mixed solvent is less than 2 parts by weight, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated. Preferable examples of the mixed solvent may be prepared by using a mixed solvent comprising 70 to 90% by volume of acetic acid and 10 to 30% by volume of water as a liquid medium and adding benzophenone during polymerization. When a mixed solvent composed of acetic acid and water is used as the liquid medium without using methanol, dichloromethane or nitromethane, which has been conventionally used for producing polyketones, the production cost of polyketones can be reduced and the catalytic activity can be improved Can have excellent effect. 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. Therefore, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 10 to 30% by volume of water as a liquid medium.

Wherein the catalyst comprises (a) a Group 9, 10 or 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature, 1989) and (b) a ligand having an element of Group 15 elements.

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, sulfonates and the like. Specific examples thereof include nickel acetate, nickel acetylacetate, 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 copper or silver complexes, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the fluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

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

Examples of the ligands (b) having an atom of Group XIII include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'- Bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) (2-methoxyphenyl) propane, 1,3-bis [di (2-isopropyl) Bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) phosphine] propane, (Diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) (Diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxy- (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2- Spinosyns; there may be mentioned a ligand, such as propane.

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 preferred ligand (b) having a Group 15 atom is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) Bis (di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- -Methoxyphenyl) phosphine).

[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 method for preparing a ligand for a polyketone polymerization catalyst comprises the steps of: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under a nitrogen atmosphere, Stirring the mixture; (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 after completion of the reaction and stirring the mixture; (d) adding toluene and water, separating the layers, washing the oil layer with water, drying with anhydrous sodium sulfate, filtration under reduced pressure, and concentration under reduced pressure; And (e) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And then performing a step of acquiring

Meanwhile, it is also preferable to use bis (bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diylbis (methylene)) bis as the ligand used in the polymerization catalyst. (Cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine ligand can be synthesized by the following four steps: First, Nate and 1,5-dibromopentane were boiled under sodium ethoxide and ethanol, and then reduced under lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexane dimethanol. To a mixture of tosyl chloride and pyridine The resulting ligand can be obtained by reacting 2-methoxyphenylphosphine with sodium hydride under dimethylsulfoxide. Each step is carried out using a column chromatography The purity of each step can be confirmed by nuclear magnetic resonance analysis through purification steps such as the grafting and recrystallization.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies depending on the kinds of the ethylenic and propylenically unsaturated compounds to be selected and other polymerization conditions. Therefore, But it is usually from 0.01 to 100 mmol, preferably from 0.01 to 10 mmol, per 1 liter of the reaction zone. The capacity of the reaction zone means the liquid phase capacity of the reactor. The amount of the ligand (b) to be used is not particularly limited, but is usually 0.1 to 3 mol, preferably 1 to 3 mol, per 1 mol of the transition metal compound (a).

In addition, benzophenone can be added during the polymerization of the polyketone. In the present invention, an effect of improving the intrinsic viscosity of the polyketone can be achieved by adding benzophenone in the polymerization of the polyketone. The molar ratio of (a) the ninth, tenth, or eleventh transition metal compound to benzophenone is 1: 5-100, preferably 1:40-60. If the molar ratio of the transition metal to the benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the produced polyketone is unsatisfactory. If the molar ratio of the transition metal to the benzophenone exceeds 1: 100, It tends to decrease.

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, -Olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclo undecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Ethyl acrylate, and acrylates such as methyl acrylate. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, most preferably ethylene, and 120 mol% propylene is added in the production of the terpolymerized polyketone.

Here, it is preferable to adjust the charging ratio of the carbon monoxide and the ethylenic unsaturated compound to 1: 1 to 2 (molar ratio) and to adjust the propylene to 1 to 20 mol% based on the total mixed gas. In the production of polyketones, it is general to set the ratio of the carbon monoxide and the ethylenic unsaturated compound to be 1: 1. However, when a mixed solvent of acetic acid and water is used as the liquid medium and benzophenone is added during polymerization, carbon monoxide and an ethylenic unsaturated compound Is adjusted to 1: 1 to 2 and the propylene is adjusted to 1 to 20 mol% based on the total mixed gas, not only the processability is improved but also the catalytic activity and the intrinsic viscosity are simultaneously improved. When the amount of propylene is less than 1 mol%, the effect of the ternary copolymerization to lower the melting temperature can not be obtained. When the amount exceeds 20 mol%, the intrinsic viscosity and the improvement of the catalytic activity are inhibited, so that the addition ratio is adjusted to 1 to 20 mol% .

In addition, in the process, a mixed solvent of acetic acid and water is used as a liquid medium, benzophenone is added during polymerization, and carbon monoxide, an ethylenic unsaturated compound and one or more olefinic unsaturated compounds are introduced, whereby the catalytic activity and intrinsic viscosity But it is possible to manufacture a terpolymer of polyketone having a high intrinsic viscosity only in a polymerization time of about 12 hours, as opposed to a polymerization time of at least 10 hours in order to improve intrinsic viscosity.

Wherein the carbon monoxide and the ethylenically unsaturated compound and the propylenically unsaturated compound are copolymerized with an organometallic complex comprising a ligand (b) having an element of group 9, group 10 or group 11 transition metal compound (a) or group 15 Catalyzed, the catalyst is produced by contacting the two components. Any method may be employed as the method of contacting. That is, the solution may be prepared as a solution in which two components are premixed in a suitable solvent, or the two components may be supplied separately to the polymerization system and contacted in the polymerization system.

In the present invention, conventionally known additives such as an antioxidant, a stabilizer, a filler, a refractory material, a releasing agent, a coloring agent, and other materials may be further added to improve the processability and physical properties of the polymer.

As the polymerization method, 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 are used. 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 is generally 40 to 180 占 폚, preferably 50 to 120 占 폚. 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.

As described above, the polyketone is produced according to the above-described production process.

On the other hand, the polyketone polymer of the present invention is a linear alternating structure and substantially contains carbon monoxide for each unsaturated hydrocarbon molecule. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers include ethynes with up to 20 carbon atoms, preferably up to 10 carbon atoms, alpha -olefins (e.g., propene, 1-butene, ), Aliphatic hydrocarbons such as isobutene, 1-hexene and 1-octene, or aryl aliphatic hydrocarbons having an aryl substituent on the aliphatic molecule, in particular ethylenically unsaturated carbon atoms Lt; / RTI > is an aryl aliphatic hydrocarbon in which an aryl substituent is formed. Examples of the aryl aliphatic hydrocarbon in the ethylenic unsaturated hydrocarbon include styrene, p-methylstyrene, p-ethylstyrene, and m-isopropyl styrene. The polymer preferably used in the present invention is a linear terpolymer of alpha-olefins such as carbon monoxide, ethene and a second ethylenically unsaturated hydrocarbon having at least three carbon atoms (especially propene).

When the polyketone terpolymer is used as the main polymer component of the composition of the present invention, it is preferable that at least two units containing an ethylene moiety are contained in each unit containing the second hydrocarbon moiety in the terpolymer, 2 < / RTI > of hydrocarbon units.

In one embodiment, the polyketone polymer may include a unit represented by the following formula (2) as a repeating unit.

(2)

- [CO- (-CH2-CH2-)] x- [CO- (G)] y-

In the general formula (2), G is an ethylenically unsaturated hydrocarbon, particularly a portion obtained from an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is preferably at least 1: 0.01.

In another embodiment, the polyketone polymer is a copolymer comprising repeating units represented by the following 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, there is a limit in that the meltability and processability are inferior. When the value of y / x is more than 0.3, the mechanical properties are poor. Further, y / x is more preferably 0.03 to 0.1.

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

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

In addition, the melting point of the polymer can be controlled by controlling the ratio of ethylene to propylene in the polyketone polymer. For example, when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46: 4: 50, the melting point is about 220 ° C, while the melting point is adjusted to 235 ° C when the molar ratio is adjusted to 47.3: 2.7: 50.

A polyketone polymer having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000, as measured by gel permeation chromatography is particularly preferred. 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 nature of the second hydrocarbon moiety. 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 (IV) of the polymer measured by HFIP (Hexafluoroisopropanol) at 25 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g, 0.0 > dl / g < / RTI > to 2.0 dl / g. If the intrinsic viscosity is less than 0.5 dl / g, the mechanical properties are deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability is deteriorated. In the present invention, it is most preferable to use a polyketone having an intrinsic viscosity of 1.0 dl / g to 2.0 dl / g from the viewpoints of mechanical properties and processability.

On the other hand, the molecular weight distribution of the polyketone may be 1.5 to 2.5, more preferably 1.8 to 2.2. If the molecular weight distribution is less than 1.5, the polymerization yield decreases. If the molecular weight distribution exceeds 2.5, moldability is deteriorated. In order to control the molecular weight distribution, it is possible to control the amount and / or the polymerization temperature of the palladium catalyst. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger.

The content of the palladium element in the polyketone of the present invention is preferably 50 ppm or less. When the content of the palladium element exceeds 50 ppm, thermal denaturation and chemical denaturation due to the residual palladium element are liable to occur. In the melt-forming, a phenomenon such as an increase in the melt viscosity and an increase in the viscosity of the dopant when dissolved in a solvent , The workability is poor. Further, since a large amount of palladium element remains in the polyketone molded body obtained after molding, the heat resistance of the molded body is deteriorated. The content of the palladium element in the polyketone is preferably as small as possible from the viewpoint of processability and heat resistance of the molded article, more preferably 10 ppm or less, still more preferably 5 ppm or less, and most preferably 0 ppm.

The polyketone polyketone industrial button component according to embodiments of the present invention comprises 85 to 92 wt% of the above-mentioned linear alternating polyketone.

The polyketone industrial button part also comprises 8 to 15% by weight of a flame retardant. In the present invention, a flame retardant may be added to the polyketone in order to improve the flame retardancy. Examples of the flame retardant include phosphorus flame retardants, halogen flame retardants, melamine flame retardants, and inorganic flame retardants. The flame retardant may be added singly or in combination of two or more. In the present invention, the flame retardant is 8 to 15% by weight based on the composition of the polyketone and the flame retardant. When the flame retardant is less than 8% by weight, the flame retardancy is not sufficiently obtained. When the flame retardant is more than 15% by weight, The manufacturing cost may increase and the mechanical properties may deteriorate.

The phosphorus flame retardant includes, for example, phosphate, phosphonate, phosphinate, phosphine oxide, and phosphazene. Examples of the halogen-based flame retardant include brominated flame retardants such as tribromophenoxyethane and tetrabromobisphenol. Examples of chlorine-based flame retardants include chlorinated paraffin, chlorinated polyethylene, and aliphatic chlorine-based flame retardants. Examples of the melamine-based flame retardant include melamine phosphate, melamine cialate, and melamine sulfate. Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, and boron-containing compounds. Unlike organic flame retardants, the inorganic flame retardants decompose without being volatilized by heat and release gases such as water, carbon dioxide, sulfur dioxide, hydrochloric acid, etc., which are mostly endothermic. In the gas phase, it dilutes the combustible gas and acts to cover the plastic surface, thus blocking oxygen. At the same time, the surface of the solid phase has an effect of cooling the plastic through the endothermic reaction and reducing the generation of pyrolysis products. In the case of the boron compound, on the other hand, a glass-like protective layer is formed on the solid surface to block oxygen and heat. Aluminum hydroxide is used as a flame retardant because it is low in price among inorganic flame retardants and can be easily injected into plastics. However, it can be used only for plastics having a low processing temperature of about 200 ° C. Magnesium hydroxide, on the other hand, is decomposed at temperatures above 300 ° C and can be used for plastics with high processing temperatures.

The polyketone industrial button part according to the embodiments of the present invention exhibits excellent flexural modulus of 1900 to 2200 MPa through the composition of the polyketone and the flame retardant as described above. Also, since the flame retardancy measured through UL94 according to the UL (Underwriters Laboratories) method is uniform to V-0 or V-1, excellent safety and reliability can be exhibited as an industrial button part.

Hereinafter, the production method for producing the polyketone composition is as follows.

The method for producing a polyketone composition of the present invention comprises: preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bidentate compound of phosphorus; Preparing a mixed solvent (polymerization solvent); Conducting the polymerization in the presence of the catalyst composition and the mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene; Removing the remaining catalyst composition from the linear terpolymer with a solvent (e.g., alcohol and acetone) to obtain a polyketone resin; And 85 to 92% by weight of the polyketone resin; And 8 to 15% by weight of a flame retardant to prepare a polyketone composition; And extruding / extruding the composition to produce pellets.

As the palladium compound constituting the catalyst composition, palladium acetate can be used. The amount of the palladium compound to be used is preferably 10 ^-3 to 10 ^-1 mole, but is not limited thereto.

As the acid having a pKa value of 6 or less constituting the catalyst composition, at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, preferably trifluoroacetic acid, may be used. 6 to 20 (mol) equivalents relative to the compound is appropriate.

Examples of the bidentate ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (e.g., 1,3-bis [di (2-methoxyphenylphosphino) propane) Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane, ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Methylene)) bis (bis (2-methoxyphenyl) phosphine) and (cyclohexane-1,1-diylbis (methylene)) bis Or more, and the amount thereof to be used is suitably 1 to 1.2 (molar) equivalent based on the palladium compound.

The carbon monoxide, ethylene, and propylene are liquid phase-polymerized in a mixed solvent to produce a linear terpolymer. As an example of the mixed solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of water in the mixed solvent is less than 2 parts by weight, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated.

The polymerization temperature is preferably in the range of 50 to 100 ° C and the reaction pressure in the range of 40 to 60 bar. The resulting polymer is recovered through filtration and purification processes after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

The obtained polyketone is blended with a flame retardant to prepare a composition. The composition ratio of the composition is 85 to 92% by weight of polyketone and 8 to 15% by weight of a flame retardant. The composition may be prepared by charging the mixture into a twin-screw extruder, and melt-kneading and extruding the mixture. In this case, the extrusion temperature is preferably 230 to 260 ° C, and the screw rotation speed is preferably in the range of 100 to 300 rpm. If the extrusion temperature is less than 230 캜, kneading may not occur properly, and if the extrusion temperature exceeds 260 캜, problems related to the heat resistance of the resin may occur.

Hereinafter, the present invention will be described in detail by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

[Example 1]

Linear alternating polyketone terpolymers of carbon monoxide and ethylene and propene are prepared from palladium acetate, trifluoroacetic acid, and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2- methoxyphenyl) The polyketone terpolymer prepared above had a melting point of 220 DEG C, a viscosity IV measured by HFIP (hexafluoroisopropanol) at 25 DEG C of 1.3 dl / g, and a melt index 60 g / 10 min. To 92 wt% of the polyketone terpolymer prepared above, phosphoric flame retardant OP1230 8% by weight of the composition was prepared and pelletized on an extruder using a twin screw having a diameter of 2.5 cm and operating at 250 rpm and L / D = 32. The produced pellets were injection-molded into button parts.

[Example 2]

The composition ratio was changed to 90 wt% of polyketone terpolymer with OP1230 To 10% by weight, the same procedure as in Example 1 was repeated.

[Example 3]

The composition ratio was changed to 85 wt% of polyketone terpolymer and added to OP1230 To 15% by weight of the component (A).

[Comparative Example 1]

Linear alternating polyketone terpolymers of carbon monoxide and ethylene and propene are prepared from palladium acetate, trifluoroacetic acid, and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2- methoxyphenyl) The polyketone terpolymer prepared above had a melting point of 220 占 폚, a viscosity IV of 1.3 dl / g as measured by HFIP at 25 占 폚, a melt index (MI) of 150 g / 10 min . The polyketone terpolymer prepared above was pelletized on an extruder using a twin screw having a diameter of 2.5 cm and operating at 250 rpm and L / D = 32. The pellets were injection molded into a button part Respectively.

Property evaluation

The tensile strength, flexural modulus, impact strength and flame retardancy of the buttons of Examples 1 to 3 and Comparative Example 1 were measured by the following methods, and the results are shown in Table 1 below.

1) Tensile Strength Evaluation: ASTM D638 was used.

2) Flexural modulus: It was conducted according to ASTM D790.

3) Evaluation of Impact Strength: ASTM D256.

4) Flame retardancy was measured by UL94.

Remarks The tensile strength
(MPa) Flexural modulus
(MPa) Impact strength
(kJ / m ² ) Flammability
0.8T Example 1 56 1953 4.0 V-1 Example 2 52 2042 3.9 V-0 Example 3 47 2143 3.7 V-0 Comparative Example 1 62 1500 4.0 HB

※ Flammability standard V-0: Within 10 seconds of digestion / V-2: Within 30 seconds of digestion / HB: Over 30 seconds of combustion

Referring to Table 1, Examples 1 to 3 of the present invention have a high flexural modulus as compared with Comparative Example 1, and in all the examples, they are extinguished within 30 seconds, and the flame retardancy is uniform and excellent. Accordingly, the polyketone industrial button component according to the present invention can provide an industrial button part having high flexural modulus, excellent fastening property, excellent flame retardancy, and improved reliability.

Claims (4)

From 85 to 92% by weight of a linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; And
8 to 15% by weight of a flame retardant;
And a flexural modulus of elasticity of 1900 to 2200 MPa.
The method according to claim 1,
The polyketone has an intrinsic viscosity (IV) of 1.0 to 2.0 dl / g, a molecular weight distribution of 1.5 to 2.5, and a repeating unit represented by the following general formulas (1) and (2) 0.03 to 0.3. ≪ / RTI >
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
(x and y represent mol% of each of the general formulas (1) and (2) in the polymer)
The method according to claim 1,
The ligand of the catalyst composition used in the polymerization of the polyketone is selected from the group consisting of bis (2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) ) And bis (bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diylbis (methylene)) bis (bisphenol A).
The method according to claim 1,
Wherein the flame retardant is one or more selected from the group consisting of a phosphorus-based flame retardant containing a phosphorus-based element (P).