KR102144886B1 - Flame retardant polyketone composition - Google Patents

Abstract

The present invention relates to a flame-retardant polyketone composition, and more particularly, by containing an inorganic flame retardant as a flame retardant in a polyketone resin, it is equivalent to or higher flame retardant as a small amount of flame retardant compared to a thermoplastic plastic in which an inorganic flame retardant is added to the existing polyamide. It is a flame-retardant polyketone composition that does not show deterioration in properties of the resin due to the addition of a flame retardant, and has excellent mechanical properties and thermal deformation temperature properties, and thus can be used as an exterior material such as housing of home appliances and automobile interior decoration.

Description

Flame retardant polyketone composition {Flame retardant polyketone composition}

The present invention relates to a flame-retardant polyketone composition, and more particularly, to a flame-retardant polyketone composition that is manufactured by using a blend containing a polyketone resin and a flame retardant and can be applied as an industrial component.

Thermoplastic polymers are mainly processed in the molten state. No polymer resists changes related to structure and state without any change in its chemical structure. Crosslinking, oxidation, molecular weight changes, and resulting changes in physical and industrial properties can also be the result. In order to reduce the stress on the polymers during processing, different additives are added depending on the polymer.

Different additives are often used simultaneously, each of which has a specific task. For example, antioxidants and stabilizers to ensure that the polymer withstands processing without chemical damage, and then has stability against external influences such as heat, UV light, weathering and oxygen (air) for a sufficient period of time. Used. In addition to the improved flow properties, the lubricant prevents excessive adhesion of the polymer melt to hot machine parts and acts as a dispersant for pigments, fillers and reinforcing agents.

Materials used in everyday life can be classified into metallic materials, inorganic materials and organic materials. Among them, plastics belonging to organic materials have the advantage of having a lower specific gravity and easy processing compared to metals and inorganic materials, but they are weak in terms of thermal and internal combustion. There is a side. In particular, plastic products are not only a factor that increases human life and property damage in emergencies such as fires due to their combustion characteristics, but also become a source of fire. Due to these shortcomings, the use of flame-retardant plastics is mandatory for products that may cause fire in countries around the world, especially home appliances and OA devices, and products with excellent flame retardancy are used for large parts with a large weight.

The use of flame retardants can affect the stability of the polymer during processing in the melt state. Flame retardants often have to be added in high dosages to ensure sufficient flame retardancy of the polymer according to international standards. Because of their chemical reactivity required for flame retardancy at high temperatures, flame retardants can impair the processing stability of the polymer. This can lead to, for example, increased polymer degradation, crosslinking reactions, outgassing or discoloration. Polyamides are stabilized with, for example, small amounts of copper halides and aromatic amines, and hindered phenols, with an emphasis on achieving long-term stability at high sustained use temperatures [H. Zweifel (ed.): "Plastic Additives handbook", 5th Edition, Carl Hanser Verlag, Munich, 2000, pages 80 to 84).

However, the flame retardant should contain more than a certain weight ratio in order to exhibit flame retardant properties in the thermoplastic polymer, but the cost of the flame retardant is expensive, so there is a problem in that the economy is poor.

In addition, there is a suspicion that halogen-based flame retardants may generate corrosive hydrogen halides during combustion or may emit toxic substances, and due to environmental problems, there is a move to regulate the use of plastic products containing halogen-based flame retardants. have. In this respect, instead of halogen-based flame retardants, inorganic flame retardants are attracting attention.

In addition, polyketone (PK) is a material with low raw material and polymerization process cost compared to general engineering plastic materials such as polyamide, polyester, and polycarbonate, and has excellent physical properties such as heat resistance, chemical resistance, fuel permeability and abrasion resistance. It is widely applied in industry. Therefore, there is increasing interest in a group of linear alternating polymers comprising carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as a polyketone or polyketone polymer. U.S. Patent No. 4,880,903 discloses a linearly alternating polyketone terpolymer composed of carbon monoxide, ethylene and other olefinically unsaturated hydrocarbons, such as propylene.

The method for preparing a polyketone polymer is usually a compound of a Group VIII metal selected from palladium, cobalt, or nickel, and an anion of a strongon-hydrohalogentic acid. , Phosphorus, arsenic or antimony (Antimon) using a catalyst composition produced from the bidentate ligand. U.S. Patent No. 4,843,144 discloses a method for preparing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of a non-hydrohalogen acid having a pKa of less than 6, and a catalyst serving as the bidentate ligand of phosphorus Are doing.

Accordingly, a flame-retardant polyketone composition that provides a thermoplastic polymer having flame-retardant properties by adding the inorganic flame retardant to a polyketone polymer and secures sufficient flame retardancy of the polymer according to international standards while adding a small amount of inorganic flame retardant than the existing amount of the inorganic flame retardant. Research is being demanded.

In order to solve the above problems, an object of the present invention is to provide a flame-retardant polyketone composition that is cheaper than current materials and has flame retardancy that meets international standards.

The present invention is a polyketone copolymer consisting of repeating units represented by the following general formulas (1) and (2), characterized in that it comprises a linearly alternating polyketone having a y/x of 0.03 to 0.3 and an inorganic flame retardant. Provides a polyketone composition.

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

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

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

In addition, the present invention provides a flame-retardant polyketone composition and an industrial component comprising the flame-retardant polyketone composition, characterized in that the inorganic flame retardant is 2 to 40% by weight based on the total 100% by weight of the flame-retardant polyketone composition. .

The flame-retardant polyketone composition of the present invention exhibits an effect equal to or higher than that of the nylon 66 material used for conventional flame-retardant grade thermoplastics while adding a small amount of flame retardant.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by providing a flame-retardant polyketone composition having excellent flame retardancy, heat resistance and impact resistance by including an inorganic flame retardant in a polyketone.

First, the poly ketone resin used in the present invention is an engineering plastic and is a new resin developed in recent years. It has excellent mechanical properties such as impact strength and molding properties, so it is usefully applied as a material for various molded products or parts. It is a synthetic resin. The mechanical properties of polyketone resins belong to the category of high-performance plastics, and are high-molecular materials synthesized from carbon monoxide as a raw material, and thus are attracting great attention as eco-friendly materials.

Polyketone resin is a material that has less moisture absorption than nylon material, so it has less change in dimensions and properties due to moisture absorption, and various product designs are possible. In particular, polyketone resins have a lower density than aluminum materials, making them very suitable for product weight reduction.

Hereinafter, the manufacturing process of the polyketone will be described.

The polyketone production process is performed with carbon monoxide in a liquid medium in the presence of (a) an organometallic complex catalyst composed of a group 9, group 10 or group 11 transition metal compound, and (b) a ligand having an element of group 15. In the method for producing polyketone by ternary copolymerization of ethylenic and propylene unsaturated compounds, the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer, the mixing As a 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, the ketal is formed, and the heat resistance may decrease during the process, and if it exceeds 10 parts by weight, the mechanical properties of the product may decrease.

Here, the catalyst is composed of (a) a Group 9, Group 10, or Group 11 transition metal compound of the Periodic Table (IUPAC Nomenclature Revised Edition, 1989), and (b) a ligand having an element of Group 15.

Examples of the Group 9 transition metal compound among the Group 9, 10, or 11 transition metal compounds (a) include cobalt or ruthenium complexes, carbohydrates, phosphates, carbamates, sulfonates, and the like, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, ruthenium trifluoromethane sulfonate, and the like.

Examples of the Group 10 transition metal compound include a complex of nickel or palladium, a carbonate, a phosphate, a carbamate, a sulfonate, and the like, and specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, palladium trifluoroacetate. , Palladium acetylacetate, palladium chloride, bis(N,N-diethylcarbamate)bis(diethylamine)palladium, palladium sulfate, and the like.

Examples of the Group 11 transition metal compound include a complex of copper or silver, a carbonate, a phosphate, a carbamate, a sulfonic acid salt, and the like, and specific examples thereof include copper acetate, trifluoro copper acetate, copper acetylacetate, silver acetate, tri Silver fluoroacetic acid, silver acetylacetate, silver trifluoromethane sulfonic acid, etc. are mentioned.

Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and preferable transition metal compounds (a) in terms of the yield and molecular weight of polyketones are palladium compounds, and improvement in catalytic activity and intrinsic viscosity It is most preferred to use palladium acetate.

Examples of the ligand (b) having an atom of Group 15 include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picoline , Nitrogen ligands such as 2,2'-bikinoline, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino) Butane, 1,3-bis[di(2-methyl)phosphino]propane, 1,3-bis[di(2-isopropyl)phosphino]propane, 1,3-bis[di(2-methoxyphenyl) )Phosphino]propane, 1,3-bis[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]propane, 1,2-bis(diphenylphosphino)cyclohexane, 1,2-bis (Diphenylphosphino)benzene, 1,2-bis[(diphenylphosphino)methyl]benzene, 1,2-bis[[di(2-methoxyphenyl)phosphino]methyl]benzene, 1,2- Bis[[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]methyl]benzene, 1,1'-bis(diphenylphosphino)ferrocene, 2-hydroxy-1,3-bis[di And phosphorus ligands such as (2-methoxyphenyl)phosphino]propane and 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane.

Among these, the preferred ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly preferred in terms of the yield of polyketones is 1,3-bis[di(2- Methoxyphenyl)phosphino]propane, 1,2-bis[[di(2-methoxyphenyl)phosphino]methyl]benzene, and in terms of the molecular weight of the polyketone, 2-hydroxy-1,3-bis[ Di(2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, and in terms of safety without needing an organic solvent Water-soluble 1,3-bis[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]propane, 1,2-bis[[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino] ]Methyl]benzene, which is easy to synthesize, can be obtained in large quantities, and is preferably 1,3-bis(diphenylphosphino)propane and 1,4-bis(diphenylphosphino)butane in terms of economy. The preferred ligand (b) having an atom of Group 15 is 1,3-bis[di(2-methoxyphenyl)phosphino]propane or 1,3-bis(diphenylphosphino)propane, most preferably 1,3-bis[di(2-methoxyphenyl)phosphino]propane or ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2 -Methoxyphenyl)phosphine).

[Formula 1]

((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) of Formula 1 is a polyketone introduced so far. Expression equivalent to 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane, which is known to have the highest activity among polymerization catalysts It is a material with a simpler structure and 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 in the art and further reducing its manufacturing cost and cost. The preparation method of the ligand for polyketone polymerization catalyst is as follows. Using bis(2-methoxyphenyl)phosphine, 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) ((2,2-dimethyl -1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) is obtained. A method for preparing a ligand for a polyketone polymerization catalyst is provided. . The method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventional 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane Unlike the synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl)phosphine) can be commercially synthesized in large quantities.

In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises (a) adding bis(2-methoxyphenyl)phosphine and dimethyl sulfoxide (DMSO) to a reaction vessel under nitrogen atmosphere and hydrogenating at room temperature. Stirring after adding sodium; (b) adding 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and dimethyl sulfoxide to the obtained mixture, followed by stirring to react; (c) adding methanol and stirring after completion of the reaction; (d) adding toluene and water, washing the oil layer with water after layer separation, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) recrystallization of the residue under methanol ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) It can be carried out through the step of obtaining.

The amount of the transition metal compound (a) of the Group 9, 10 or 11 transition metal compound (a) varies according to the selected ethylenic and propylene unsaturated compounds or other polymerization conditions. Although it cannot be limited, it is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol per 1 liter of the capacity of the reaction band. The capacity of the reaction zone refers to the capacity of the liquid phase of the reactor. The amount of the ligand (b) used is also not particularly limited, but it is usually 0.1 to 3 moles, preferably 1 to 3 moles, per 1 mole of the transition metal compound (a).

In addition, it is another feature that benzophenone is added during polymerization of the polyketone. In the present invention, the intrinsic viscosity of the polyketone can be improved by adding benzophenone during polymerization of the polyketone. The molar ratio of the (a) Group 9, Group 10, or Group 11 transition metal compound and benzophenone is 1:5 to 100, preferably 1:40 to 60. If the molar ratio of transition metal and benzophenone is less than 1:5, the effect of improving the intrinsic viscosity of the prepared polyketone is not satisfactory. If the molar ratio of the transition metal and benzophenone exceeds 1:100, the resulting polyketone catalytic activity is rather It is not desirable because it tends to decrease

Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Α-olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and α-methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins, such as cyclododecene; Vinyl halides such as vinyl chloride; Acrylic acid esters, such as ethyl acrylate and methyl acrylate, etc. are mentioned. Among these, preferred ethylenically unsaturated compounds are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, most preferably ethylene, and 120 mol% propylene is added in the production of ternary copolymerized polyketones.

The three-way copolymerization of carbon monoxide with the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex consisting of the transition metal compound (a) of the Group 9, 10 or 11, and a ligand (b) having an element of Group 15 It is caused by a catalyst, and the catalyst is produced by contacting the two components. Any method can be adopted as a method of contacting. That is, the two components may be mixed in advance in a suitable solvent and used, or the two components may be separately supplied to the polymerization system and brought into contact within the polymerization system.

As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, and a gas phase polymerization method in which a small amount of polymer is impregnated with a high concentration catalyst solution are used. The polymerization may be a batch type or a continuous type. As the reactor used for polymerization, a known reactor can be used as it is or processed. The polymerization temperature is not particularly limited, and is generally 40 to 180°C, preferably 50 to 120°C. There is also no restriction on the pressure during polymerization, but it is generally normal pressure to 20 MPa, preferably 4 to 15 MPa.

As described above, polyketone is manufactured through a polymerization process according to the above manufacturing process.

On the other hand, the polyketone polymer of the present invention is a linear alternating structure, and substantially contains carbon monoxide per molecule of unsaturated hydrocarbon. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers have up to 20 carbon atoms, preferably up to 10 carbon atoms. In addition, ethylenically unsaturated hydrocarbons include ethene and α-olefins, such as propene, 1-butene, iso-butene, 1-hexene, and 1-octene. Or an aryl aliphatic containing an aryl substituent on another aliphatic molecule, and particularly an aryl substituent on an ethylenically unsaturated carbon atom. Examples of aryl aliphatic hydrocarbons among ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene, and m-isopropyl styrene. The polyketone polymer preferably used in the present invention is a copolymer of carbon monoxide and ethene, or a second ethylenically unsaturated hydrocarbon having at least 3 carbon atoms with carbon monoxide and ethene, in particular α-olefins such as propene. It is a terpolymer of the family.

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 for each unit containing the second hydrocarbon moiety in the terpolymer. It is preferable that there are 10 to 100 units containing the second hydrocarbon moiety.

In one embodiment, the polyketone polymer may include a unit represented by Formula 2 below as a repeating unit.

[Formula 2]

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

In Formula 2, G is an ethylenically unsaturated hydrocarbon, particularly, a moiety obtained from an ethylenically unsaturated hydrocarbon having at least 3 carbon atoms, and x:y is at least 1:0.01.

In another embodiment, the polyketone polymer is a copolymer composed of repeating units represented by 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 to inferior meltability and workability, and when it exceeds 0.3, mechanical properties are inferior. 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 adjusting the ratio of ethylene and 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℃, but when the molar ratio is adjusted to 47.3:2.7:50, the melting point is adjusted to 235℃.

Polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000 as measured by gel permeation chromatography, are particularly preferred. The physical properties of the polymer are determined according to the molecular weight, according to the polymer being a copolymer or terpolymer, and in the case of a terpolymer according to the properties of the second hydrocarbon moiety present. The melting point of the polymer used in the present invention is generally 175°C to 300°C, and generally 210°C to 270°C. The intrinsic viscosity number (LVN) of the polymer measured at 60°C with HFIP (Hexafluoroisopropylalcohol) using a standard customs viscosity measuring device is 0.5dl/g~10dl/g, and preferably 0.8dl/g~4dl/g, More preferably, it is 1.0dl/g-2.0dl/g. At this time, when the number of intrinsic viscosity is less than 0.5dl/g, mechanical properties are deteriorated, and when it exceeds 10dl/g, processability is deteriorated.

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. If it is less than 1.5, the polymerization yield is lowered, and if it is more than 2.5, there is a problem that the moldability is lowered. In order to control the molecular weight distribution, it can be adjusted in proportion to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst increases or the polymerization temperature is 100°C or higher, the molecular weight distribution increases.

The content of the polyketone resin is 60 to 98% by weight based on the total composition, and if the content is less than 60%, the impact strength and heat resistance are deteriorated, and when used as an exterior material, cracks due to external impacts easily appear. In addition, since the content of the flame retardant increases, the flame retardant is precipitated on the product surface during molding, resulting in surface defects, and price competitiveness is lowered due to an increase in cost during product manufacturing, which is undesirable. In addition, when the polyketone content exceeds 98%, the impact strength and heat resistance are excellent, but the flame retardancy decreases, so when used as an exterior material, damage in case of fire cannot be minimized.

In particular, the flame retardant of the present invention should impart flame retardancy to the polyketone resin, should have good blendability with the resin, and should not affect the mechanical properties of the product after molding. In addition, the selection should be made after sufficient environmental considerations, such as that there should be less generation of smoke and toxic gases during combustion.

Specifically, the flame-retardant polyketone composition of the present invention is composed of a blend consisting of a combination of a polyketone and an inorganic flame retardant, and is characterized by improving impact resistance, reducing moisture absorption, and improving physical property retention while having flame retardancy. .

The present invention is characterized in that an inorganic flame retardant is added to the polyketone to improve flame retardancy. The inorganic flame retardant of the present invention is characterized in that 2 to 40% by weight of the total blend. Here, if the flame retardant is less than 2% by weight, the flame retardancy is lowered, and if it exceeds 40% by weight, the flame retardancy is excellent, but the price increases and the mechanical properties may decrease.

Inorganic flame retardants include compounds containing aluminum hydroxide, antimony oxide, magnesium hydroxide and boron. Unlike organic flame retardants, inorganic flame retardants do not volatilize by heat and are decomposed to release gases such as water, carbon dioxide, dioxide, hydrochloric acid, etc., and are mostly endothermic reactions. In the gaseous phase, the combustible gas is diluted and a plastic surface is applied to prevent oxygen access. At the same time, there is an effect of reducing plastic cooling and generation of pyrolysis products through endothermic reactions on the solid surface. Also, in the case of boron compounds, there is an effect of blocking oxygen and heat by forming a glass-like protective layer on a solid surface. Aluminum hydroxide is most often used because it is inexpensive and can be easily added to plastics among inorganic flame retardants, but it can only be used in plastics with a low processing temperature of about 200℃. On the other hand, magnesium hydroxide decomposes above 300℃ and can be used for plastics with high processing temperatures.

In addition, mechanical properties may be reinforced by adding glass fibers (glass fibers), carbon fibers, mica and talc, etc. as reinforcing materials to the composition. In addition, antioxidants, pigments, and the like can be added as desired. These additives can be appropriately used by those of ordinary skill in the art. The content may be adjusted to 0 to 30% by weight, 0 to 40% by weight, or 0 to 50% by weight based on the total flame-retardant polyketone composition, but is not limited thereto.

Hereinafter, a manufacturing method for preparing the flame-retardant polyketone composition as described above is as follows.

The method of preparing a flame-retardant polyketone composition of the present invention comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a diligence compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing alcohol (eg, methanol) and water; Conducting polymerization in the presence of the catalyst composition and a mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene; Removing the catalyst composition remaining from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin; And mixing the polyketone resin with a flame retardant.

As the palladium compound constituting the catalyst composition, palladium acetate may be used, and the amount thereof is preferably 10 ^-3 to 10 ^-1 mol.

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

Examples of the phosphorus 2 ligand compound constituting the catalyst composition include 1,3-bis[diphenylphosphino]propane (eg, 1,3-bis[di(2-methoxyphenylphosphino)]propane, 1,3- Bis[bis[anisyl]phosphinomethyl]-1,5-dioxaspiro[5,5]undecane and ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis( One or more selected from the group consisting of methylene)) bis (bis (2-methoxyphenyl) phosphine) can be used, and the amount used is 1 to 1.2 (mol) equivalent compared to the palladium compound.

The carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer, and a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used as the mixed solvent. If the content of water in the mixed solvent is less than 2 parts by weight, the ketal is formed, and the heat resistance may decrease during the process, and if it exceeds 10 parts by weight, the mechanical properties of the product may decrease.

In addition, the polymerization temperature is 50 ~ 100 ℃, the reaction pressure is suitable in the range of 40 ~ 60 bar. The resulting polymer is recovered through filtration and purification after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

In the present invention, the obtained polyketone resin is mixed with an inorganic flame retardant and then extruded with an extruder to finally obtain a blend composition. The blend is prepared by melt-kneading and extruding in a twin screw extruder.

At this time, the extrusion temperature is 230 ~ 260 ℃, the screw rotation speed is preferably in the range of 100 ~ 300rpm. If the extrusion temperature is less than 230°C, kneading may not occur properly, and if it exceeds 260°C, problems related to heat resistance of the resin may occur. Also, if the screw rotation speed is less than 100 rpm, smooth kneading may not occur.

The polyketone composition prepared through the above process can be used as an exterior material such as housing of home appliances and interior decoration of automobiles, but is not limited thereto.

Hereinafter, the present invention will be described in detail through examples. However, these examples are only intended to aid 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 consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis( It was prepared in the presence of a catalyst composition produced from bis(2-methoxyphenyl)phosphine). In the above, the content of trifluoroacetic acid relative to palladium is a molar ratio of 10 times, and the first step of the polymerization temperature of 78°C and the second step of 84°C are performed. In the polyketone terpolymer prepared above, the molar ratio of ethylene and propene was 46 to 4. In addition, the melting point of the polyketone terpolymer was 220°C, LVN measured at 25°C with HFIP (hexa-fluoroisopropano) was 1.4 dl/g, MI (Melt index) was 60 g/10 min, and MWD was 2.0.

Magnesium hydroxide was used as the inorganic flame retardant.

A flame-retardant polyketone composition was prepared by blending 70% by weight of the prepared polyketone terpolymer and 30% by weight of an inorganic flame retardant.

Example 2

It is the same as in Example 1, except that 90% by weight of the polyketone terpolymer and 10% by weight of magnesium hydroxide were used.

Example 3

It is the same as Example 1, except that 60% by weight of the polyketone terpolymer and 40% by weight of magnesium hydroxide were used.

Examples 4 to 5

The same as in Example 1, except that the intrinsic viscosity of the polyketone terpolymer was adjusted to 1.2 (Example 4) or 2.0 (Example 5).

Comparative Example 1

60% by weight of Rhodda's PA66 (manufactured by A218V30) and 40% by weight of magnesium hydroxide were used.

Property evaluation

The prepared flame-retardant polyketone composition of Example 1 was prepared as a specimen, and then the physical properties were evaluated in the following manner compared to the specimen of Comparative Example 1, and the results are shown in Table 1 below.

It is shown in Table 1.

1. Impact strength (NOTCHED IZOD, KJ/m2): Conducted in accordance with ASTM D-256.

2. Heat deflection temperature (℃): It was carried out in accordance with ASTM D-648.

3. Flame retardancy evaluation: It was carried out in accordance with UL94.

Item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Izod impact strength
(KJ/m2) 4.5 5.1 4.1 4.3 4.7 3.0 Heat deflection temperature
(℃) 105 101 108 103 102 65 Flame retardancy evaluation
(UL94,1/16") V-0 V-0 V-0 V-0 V-0 V-0

As shown in Table 1, in the case of the Example, it was found that the flame retardant property was equal to or higher than that of Comparative Example 1.

Therefore, it was found that the flame-retardant thermoplastic plastic composition prepared through the examples rather than the comparative examples exhibits excellent flame-retardant properties while using a small amount of inorganic flame retardant, and thus, it was found to be more suitable for use as a flame-retardant thermoplastic plastic composition.

Claims (7)

A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), comprising: 60 to 90% by weight of linearly alternating polyketones having y/x of 0.03 to 0.3; And 10 to 40% by weight of magnesium hydroxide, which is an inorganic flame retardant,
The polyketone has an intrinsic viscosity of 1.0 to 2.0, a molecular weight distribution of 1.5 to 2.5, and the ligand of the catalyst composition during polymerization of the polyketone is ((2,2-dimethyl-1,3-dioxane-5,5- Diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine),
Flame-retardant polyketone composition, characterized in that the Izod impact strength is 4.1 to 5.1kJ/m ² , the heat deflection temperature is 101 to 108°C, and the flame retardancy evaluation grade according to UL94 is V-0.
-[-CH2CH2-CO]x- (1)
-[-CH2-CH(CH3)-CO]y- (2)
(x and y represent each mol% of the general formulas (1) and (2) in the polymer.)
delete delete The method of claim 1,
The flame-retardant polyketone composition includes glass fibers, and the content of the glass fibers is 0 to 50% by weight based on the total weight of the composition.
The method of claim 1,
The flame-retardant polyketone composition includes carbon fiber, and the content of the carbon fiber is 0 to 30% by weight based on the total weight of the composition.
The method of claim 1,
The flame-retardant polyketone composition comprises mica or talc, and the content of mica or talc is 0 to 40% by weight based on the total weight of the composition.
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