KR102123461B1 - Polyketone composition improved flame retardant and processability - Google Patents

Abstract

The present invention is a polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon 70.0 ~ 90.0% by weight; Phosphorus-based flame retardant 9.0-14.0 wt%; Fluorine-based anti-drip agent 0.3 to 8.0% by weight; And it relates to a polyketone composition having improved flame retardancy and processability, including 0.1 to 8.0% by weight of tricalcium phosphate.

Description

Polyketone composition with improved flame retardancy and processability{POLYKETONE COMPOSITION IMPROVED FLAME RETARDANT AND PROCESSABILITY}

The present invention relates to a polyketone composition with improved flame retardancy and processability.

Polyketone (polyketone, PK) is an inexpensive material and polymerization process cost compared to general engineering plastic materials such as polyamide, polyester, and polycarbonate, and has excellent heat resistance, chemical resistance, impact resistance, and fuel permeability.

Polyketones having these properties are included in general-purpose high-performance plastics and have comparable strength to conventional engineering plastics.

Meanwhile, in order to apply plastic materials to parts in the electric and electronic fields, reinforced flame retardancy is required rather than the existing flame retardancy. Accordingly, when a flame retardant is added in a certain amount or less in order to enhance flame retardancy in the existing flame retardant polyketone, flame retardancy does not appear due to dripping of a melt with a flame, and when added in excess, the physical properties of the resin and processing stability are reduced. A drop in may appear.

Accordingly, in order to apply polyketone to parts in the electric and electronic fields that require both flame retardancy and processing stability, there is a demand for technology development of polyketone having excellent flame retardancy and improved processing stability without deterioration and dropping of physical properties.

An object of the present invention is to provide a polyketone composition having improved flame retardancy and processability and a molded part comprising the same.

The polyketone composition according to an embodiment of the present invention comprises 70.0 to 90.0% by weight of a polyketone composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon; Phosphorus-based flame retardant 9.0-14.0 wt%; Fluorine-based anti-drip agent 0.3 to 8.0% by weight; And 0.1 to 8.0% by weight of tricalcium phosphate.

In addition, the polyketone composition may further include 0.1 to 15.0 wt% of one additive selected from the group consisting of glass fiber, carbon fiber, mica and talc based on the total weight of the polyketone composition.

In addition, the fluorine-based anti-drip agent may be polytetra fluoroethylene (PTFE).

In addition, the polyketone composition has a ULT flame retardancy rating of 0.4T V-0 or higher, tensile strength of 51 MPa or higher, flexural strength of 65 MPa or higher, flexural modulus of 2000 MPa or higher, and impact strength of 7.0 kJ/m ^{2 or} higher.

According to an embodiment of the present invention, as the polyketone composition includes a phosphorus-based flame retardant and an anti-drip agent, it is possible to prevent processability and mechanical property degradation that occur when only the phosphorus-based flame retardant is included, and thus evaluate UL94 flame retardancy without deteriorating mechanical properties. In the flame retardant grade of V-0 or higher can be secured. In addition, the polyketone composition of the present invention can improve processing stability by including tricalcium phosphate.

Accordingly, it can be widely applied as a material for parts requiring both flame retardancy and processability in various industries such as automobiles, electrical and electronic components.

The present invention can be applied to various changes and may have various forms, and specific embodiments will be illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to a specific disclosure form, and it should be understood that it includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In this application, the terms "include" or "have" are intended to indicate the presence of features, numbers, steps, actions, components, parts or combinations thereof described in the specification, one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, actions, components, parts or combinations thereof are not excluded in advance. In addition, when a part such as a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case of being "directly above" the other part but also another part in the middle. Conversely, when a portion of a layer, film, region, plate, etc. is said to be “under” another portion, this includes not only the case “underneath” another portion, but also another portion in the middle. In addition, in the present application, being referred to as being "on" may include the case of being disposed on the lower portion as well as the upper portion.

Hereinafter, embodiments of the present invention will be described in more detail.

The polyketone composition according to an embodiment includes a polyketone composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon; Phosphorus-based flame retardants; Fluorine-based anti-drip agents and tricalcium phosphate.

First, the polyketone of the present invention is a linear alternating structure, and substantially contains carbon monoxide for each molecule of unsaturated hydrocarbon. Suitable for use as a precursor for polyketone polymers are up to 20 ethylenically unsaturated hydrocarbons, preferably up to 10 carbon atoms. In addition, ethylenically unsaturated hydrocarbons include ethene and α-olefins, such as propene, 1-butene, isobutene, 1-hexene, 1-octene ) Or an aryl aliphatic group containing an aryl substituent on another aliphatic molecule, particularly an aryl substituent on an ethylenically unsaturated carbon atom. Examples of aryl aliphatic hydrocarbons among ethylenically unsaturated hydrocarbons include styrene, p-methylstyrene, p-ethylstyrene 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 three carbon atoms with carbon monoxide and ethene, in particular α-olefin such as propene. It is a terpolymer of a family.

When the polyketone terpolymer is used as the main polymer component of the composition according to the present invention, for each unit containing the second hydrocarbon portion in the terpolymer, there are at least two units containing the ethylene portion. It is preferred that there are 10 to 100 units containing the second hydrocarbon portion.

The polymer ring of the polyketone polymer preferred in the present invention can be represented by the following structural formula 1.

[Structural Formula 1]

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

In Structural Formula 1, G is an ethylenically unsaturated hydrocarbon, particularly a part obtained from an ethylenically unsaturated hydrocarbon having at least 3 carbon atoms, and x:y is preferably 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 it is preferable that y/x is 0.03 to 0.3. When the numerical value of the y/x value is less than 0.03, there is a limit of poor meltability and processability, and when it exceeds 0.3, mechanical properties are deteriorated. 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 and propylene of 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, but when the molar ratio is adjusted to 47.3:2.7:50, the melting point is adjusted to 235°C.

Polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000, measured by gel permeation chromatography (chromatography) are particularly preferred. The physical properties of the polymer depend on 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 present. The melting point of the polymer used in the present invention is 175°C to 300°C, and is generally 210°C to 270°C. The intrinsic viscosity (IV) of the polymer measured at 60°C using HFIP (Hexafluoroisopropylalcohol) using a standard customs viscosity measuring device is 0.5 dl/g to 10 dl/g, and also preferably 0.8 dl/g to 4 dl/g, more Preferably, it is 1.0 dl/g to 1.4 dl/g. At this time, if the number of intrinsic viscosities is less than 1.0 dl/g, mechanical properties are deteriorated, and if it exceeds 1.4 dl/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. Less than 1.5, the polymerization yield is poor, and 2.5 or more has a problem of poor moldability. In order to control the molecular weight distribution, it can be controlled 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.

As a method of preparing a polyketone polymer, liquid polymerization performed under an alcoholic solvent through a catalyst composition comprising a carbon monoxide and an olefin of a palladium compound, an acid having a PKa of 6 or less, and a phosphorus double ligand compound may be employed. The polymerization reaction temperature is preferably 50 to 100°C, and the reaction pressure is 40 to 60 bar. After polymerization, the polymer is recovered through a filtration and purification process, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

This is preferred as palladium acetate and a palladium compound in the amount of 10 ^-3 to ^10-2 1mole preferred. Specific examples of the acid having a pKa value of 6 or less include trifluoroacetic acid, p-toliensulfonic acid, sulfuric acid, and sulfonic acid. In the present invention, trifluoroacetic acid was used, and the use amount is preferably 6 to 20 equivalents compared to palladium. In addition, 1,3-bis[di(2-methoxy phenylphosphino)]propane is preferred as the phosphorus coordination compound, and the amount of phosphorus is preferably 1 to 1.2 equivalents compared to palladium.

Hereinafter, the polymerization process of the polyketone polymer will be described in detail.

Carbon monoxide, ethylenically unsaturated compounds and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, in particular repeat units derived from carbon monoxide and repeat units derived from ethylenically unsaturated compounds and repeat units derived from propylene unsaturated compounds Polyketones with alternating structures are excellent in mechanical and thermal properties, excellent in processability, high abrasion resistance, chemical resistance, and gas barrier properties, and are useful materials for various applications. This ternary or higher copolymerized polyketone high molecular weight is considered to be useful as an engineering plastic material having higher processability and thermal properties and excellent economical efficiency. In particular, it has high abrasion resistance, so it can be used for parts such as automobile gears, chemical resistance, and lining materials for chemical transport pipes, gas barrier properties, and thus can be used for lightweight gasoline tanks. In addition, when an ultra-high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for fibers, it is possible to stretch at a high magnification and as a fiber having high strength and high elasticity oriented in the stretching direction, a reinforcement material for a belt, rubber hose, tire cord, or concrete reinforcement material. It is a material suitable for building materials and industrial materials.

The method for producing polyketone comprises (a) a group 9, 10 or 11 transition metal compound, (b) an organometallic complex catalyst composed of a ligand having an element of group 15, and carbon monoxide in a liquid medium. In the method for producing polyketone by three-way copolymerization of ethylenic and propylene unsaturated compounds, the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (for example, methanol) and water to form a linear terpolymer. As a solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. When the content of water in the mixed solvent is less than 2 parts by weight, ketal is formed and heat stability may be deteriorated during the process, and if it exceeds 10 parts by weight, mechanical properties of the product may be deteriorated.

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

Examples of the Group 9 transition metal compound of the Group 9, 10, or 11 transition metal compound (a) include a complex of cobalt or ruthenium, a carboxylate, a phosphate, a carbamate, and a sulfonate. Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, trifluoro ruthenium acetate, ruthenium acetylacetate, and trifluoromethane sulfonate ruthenium.

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

Examples of the Group 11 transition metal compound include copper or silver complexes, carbonate salts, phosphate salts, carbamate salts, and sulfonate salts. Specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, silver acetate, and tri Silver fluoroacetate, silver acetylacetate, silver trifluoromethane sulfonate, etc. are mentioned.

Among them, the inexpensive and economically preferable transition metal compound (a) is a nickel and copper compound, and the preferred transition metal compound (a) is a palladium compound in terms of yield and molecular weight of polyketone, in terms of improving catalytic activity and intrinsic viscosity. It is most preferable to use palladium acetate.

Examples of the ligand (b) having an atom of group 15 are 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picoline , 2,2'- nitrogen ligands such as biquinoline, 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-sulfonic acid sodium-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-sulfonic acid sodium-phenyl)phosphino]methyl]benzene, 1,1'-bis(diphenylphosphino)ferrocene, 2-hydroxy-1,3-bis[di (2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, ((2,2-dimethyl-1,3-di Phosphorus ligands such as oxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine), (cyclohexane-1,1-diylbis(methylene))bis(bis( 2-methoxyphenyl)phosphine etc. are mentioned.

Among them, the ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and a phosphorus ligand particularly preferable in terms of yield of polyketone is 1,3-bis[di(2- Methoxyphenyl)phosphino]propane, 1,2-bis[[di(2-methoxyphenyl)phosphino]methyl]benzene, and 2-hydroxy-1,3-bis[ in terms of the molecular weight of the polyketone. It is di(2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, and does not require an organic solvent and is safe. Water-soluble 1,3-bis[di(2-methoxy-4-sulfonic acid sodium-phenyl)phosphino]propane, 1,2-bis[[di(2-methoxy-4-sulfonic acid sodium-phenyl)phosphino ]Methyl]benzene, easy to synthesize, available in large quantities, and preferred in terms of economy are 1,3-bis(diphenylphosphino)propane and 1,4-bis(diphenylphosphino)butane. The ligand (b) having a preferred group 15 atom 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, ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2 -Methoxyphenyl)phosphine) or (cyclohexane-1,1-diylbis(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 Chemical Formula 1 is a polyketone introduced to date. 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane, which is known to show the highest activity among polymerization catalysts However, the structure is simpler and has a lower molecular weight. As a result, the present invention has been able to provide a new polyketone polymerization catalyst that secures the highest activity as a polyketone polymerization catalyst in the art, while reducing its manufacturing cost and cost. The method for preparing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) using bis(2-methoxyphenyl)phosphine, 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and sodium hydride (NaH). Provided is a method for preparing a ligand for a polyketone polymerization catalyst, characterized in that -1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) is obtained. . The method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventionally 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane. Unlike the synthetic 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.

On the other hand, it is also preferable to use (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine) as a ligand used in the polymerization catalyst. It is the same as the scheme.

[Reaction formula]

The (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine ligand can be synthesized in four steps as follows: First, diethylmalonate and 1, 5-dibromopentane is boiled under sodium ethoxide and ethanol, and then reduced under lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexanediethanol, and reacted with tosyl chloride and pyridine to leave. The ligand can be obtained by reacting it with 2-methoxyphenylphosphine, sodium hydride and dimethyl sulfoxide.Each step undergoes purification steps such as column chromatography and recrystallization. Purity can be confirmed by nuclear magnetic resonance analysis.

In a preferred embodiment, the method for preparing a polyketone polymerization catalyst of the present invention comprises (a) bis(2-methoxyphenyl)phosphine and dimethylsulfoxide (DMSO) in a nitrogen atmosphere and hydrogenated at room temperature. Adding sodium and stirring; (b) adding 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the obtained mixed solution, followed by stirring to react; (c) adding and stirring methanol 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) 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 performed through the steps of obtaining.

The amount of the Group 9, 10, or 11 transition metal compound (a) used is uniform, since its suitable value varies depending on the type of ethylenic and propylene unsaturated compounds selected or other polymerization conditions. Although it is not possible to limit, it is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol, per liter of the reaction band. The capacity of the reaction band means the capacity of the liquid phase of the reactor. The use amount of the ligand (b) is also not particularly limited, but per 1 mol of the transition metal compound (a), it is usually 0.1 to 3 mol, preferably 1 to 3 mol.

In addition, it is another feature that benzophenone is added during polymerization of the polyketone. In the present invention, the effect of improving the intrinsic viscosity of the polyketone can be achieved by adding benzophenone during polymerization of the polyketone. The molar ratio of the (a) Group 9, 10 or 11 transition metal compound and benzophenone is 1:5 to 100, preferably 1:40 to 60. If the molar ratio of the transition metal and benzophenone is less than 1:5, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory, and when the molar ratio of the transition metal and benzophenone exceeds 1:100, the catalytic activity of the produced polyketone is rather It is not desirable because 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, 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 halide such as vinyl chloride; And acrylic acid esters such as ethyl acrylate and methyl acrylate. Preferred ethylenically unsaturated compounds among these are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, and most preferably ethylene.

The ternary copolymerization of carbon monoxide with the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex composed of the Group 9, 10, or 11 transition metal compound (a) and the ligand (b) having the elements of Group 15 Occurred by a catalyst, the catalyst is produced by contacting the two components. Any method can be adopted as the method of making contact. That is, two components may be used as a pre-mixed solution in a suitable solvent, or two components may be separately supplied to the polymerization system and contacted within the polymerization system.

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

A linear alternating polyketone is formed by the polymerization method as described above.

The content of the polyketone may be a residual amount such that the total weight of the polyketone composition is 100% by weight, and preferably 70 to 90% by weight. When the content of polyketone is less than 70% by weight, mechanical properties, thermal stability and fluidity may be reduced, and when it exceeds 90% by weight, the effect of improving flame retardancy is insignificant because the content of certain substances added to the composition is relatively small. Can be.

In addition, the polyketone composition according to the present invention may be added with a flame retardant in order to improve the flame retardancy. As the flame retardant, there are phosphorus-based flame retardants, halogen-based flame retardants, and inorganic flame retardants, but it is preferable to use phosphorus-based flame retardants.

The flame retardant of the present invention may be 9 to 14% by weight based on the total weight of the composition, preferably 10 to 13% by weight. Here, if the flame retardant is less than 9% by weight, the flame retardancy decreases, and if it exceeds 14% by weight, the flame retardancy is excellent, but the price increases and mechanical properties may deteriorate.

As the type of phosphorus-based flame retardant specifically used, phosphonate, phosphinate, phosphine oxide, and phosphazene may be used, and in this case, a phosphate-based flame retardant In particular, tricalcium phosphate (TCP) may be excluded. On the other hand, in the present invention, it is preferable to use a phosphinate-based flame retardant.

Further, the polyketone composition according to the present invention may include a fluorine-based anti-drip agent.

In the case of the polyketone composition containing only the phosphorus-based flame retardant, it is possible to secure a 0.4T V-0 rating when evaluating UL94 flame retardancy, but accompanied by a decrease in processability and mechanical properties, and an increase in manufacturing cost due to excessive addition of a flame retardant. Will occur. Accordingly, the present invention optimizes the added flame retardant content by applying a fluorine-based anti-drip agent to the above-described range, and thus has economical efficiency compared to a composition containing only a flame retardant, and can secure a flame retardant grade without deteriorating mechanical properties of the flame retardant polyketone material. . That is, the anti-drip agent can enhance the flame retardancy of the composition without deteriorating physical properties such as tensile strength, flexural strength/elasticity, impact strength, and elongation as the polyketone polymer and an internal network in the composition are formed.

The anti-drip agent may be polytetrafluoroethylene (PTFE), but is not limited thereto.

In addition, the anti-drip agent may be 0.3 to 8.0% by weight based on the total weight of the composition, preferably 0.3 to 3.0% by weight, and more preferably 0.3 to 1.0% by weight. At this time, if the anti-drip agent is less than 0.3% by weight, the effect of preventing mechanical properties from dropping is insufficient, and when it exceeds 8.0% by weight, flowability decreases and manufacturing cost increases.

Further, the polyketone composition according to the present invention may include tricalcium phosphate (TCP).

When a flame retardant is added to the polyketone, a problem may occur in which polymer properties are deteriorated and carbonization is accelerated during processing. To solve this problem, by adding tricalcium phosphate, processing stability can be improved.

In addition, tricalcium phosphate serves to maintain the viscosity of the polyketone. Specifically, polyketone has a disadvantage that the viscosity rises at high temperature and gels, and thus, tricalcium phosphate is added to maintain the viscosity of the polyketone. Due to the addition of tricalcium phosphate, it is possible to obtain an effect of uniformly maintaining the viscosity of the polyketone, thereby minimizing breakage of molded parts and maintaining low specific gravity.

The tricalcium phosphate may include 0.1 to 8.0% by weight based on the total weight of the composition, preferably 0.1 to 3.0% by weight, and more preferably 0.3 to 1.0% by weight. When the content of tricalcium phosphate is less than 0.1% by weight, it is difficult to obtain the effect of reducing the physical properties of the molded part and improving the processing stability because it cannot suppress the gelation of the polyketone, and when it exceeds 8.0% by weight, mechanical due to overdosing Strength degradation problems may occur.

In addition, the polyketone composition according to the present invention may further include one additive selected from the group consisting of glass fiber, carbon fiber, mica and talc. The mechanical properties of the composition may be reinforced by adding these additives, and it is preferable to use glass fibers as the additives.

The content of these additives may be 0.1 to 15.0% by weight based on the total weight of the composition, preferably 5.0 to 15.0% by weight. When the content of the additive is less than 0.1% by weight, it is difficult to obtain a mechanical property reinforcing effect, and when it exceeds 15.0% by weight, a problem occurs in that workability deteriorates.

Meanwhile, the polyketone composition of the present invention may additionally include additional additives conventionally known to improve the processability or physical properties of the polymer, for example, antioxidants, heat stabilizers, lubricants, fillers, refractory materials, mold release agents, colorants, and other materials. Can be. The content of these additional additives may be 0 to 2% by weight based on the total weight of the polyketone composition.

Meanwhile, the method for producing the polyketone composition of the present invention is as follows.

The method for preparing the 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 disaccharide compound of phosphorus; Preparing a mixed solvent (polymerized solvent) containing alcohol (eg, methanol) and water; Polymerizing 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 in the linear terpolymer with a solvent (for example, alcohol and acetone) to obtain a polyketone resin; And mixing the polyketone, a phosphorus-based flame retardant, a fluorine-based anti-drip agent, tricalcium phosphate and/or glass fiber, and injection molding the mixture.

The carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (for example, methanol) and water to form a linear terpolymer. As 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, ketal is formed, and heat stability may be deteriorated during the process, and if it exceeds 10 parts by weight, mechanical properties of the product may be deteriorated.

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

In the present invention, the obtained polyketone composition is extruded with an extruder to finally obtain a polyketone composition. The polyketone composition may be prepared by melt-kneading and extruding by putting it in a twin-screw extruder.

At this time, the extrusion temperature is preferably in the range of 230 ~ 260 ℃, screw rotation speed is 100 ~ 300rpm. When the extrusion temperature is less than 230°C, kneading may not occur properly, and when it exceeds 260°C, a problem 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, and if it exceeds 300 rpm, mechanical properties may deteriorate.

The polyketone composition prepared as described above has excellent flame retardancy with a V-0 rating or higher in UL94 flame retardancy evaluation, and has a tensile strength of 51 MPa or higher, a flexural strength of 65 MPa or higher, a flexural modulus of 2000 MPa or higher, and an impact strength of 7.0 kJ/m ² or higher. Physical properties can also be improved.

Specifically, the conventional flame-retardant polyketone composition can secure the UL 94 V-0 rating at a thickness of 0.8 mm, but the V-0 rating at a thinner thickness is secured for application to electrical/electronic materials such as washing machine/refrigerator connectors. Is essential. However, in the case of the conventional flame retardant polyketone composition, when evaluating flame retardancy at a thickness thinner than 0.8 mm, a drip occurs due to melting of the resin, and thus a problem of securing a V-0 flame retardant grade occurs. Accordingly, the flame retardant can be secured by additionally adding a flame retardant, but the cost of phosphorus-based flame retardant is high, so the price of the added flame retardant increases, resulting in a loss of price competitiveness, and a problem that is accompanied by a decrease in processing stability and mechanical properties. do. On the other hand, the present invention can prevent the drip of the resin during combustion through the application of an anti-drip agent, and minimize the added flame retardant content to secure price competitiveness. In addition, after maintaining the mechanical properties while improving the workability through the addition of tricalcium phosphate, it is possible to secure the flame retardancy of V-0 grade at a thinner thickness.

A sheet, a film, a plate, and a molded part may be manufactured by preparing a composition in the same manner as described above and extruding or injection molding the composition. As an example of such an application, it may be used in materials for electric and electronic devices such as washing machines and refrigerator connectors.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only to illustrate the present invention, the present invention is not limited by the following examples.

[Examples 1 to 5]

The linear alternating polyketone composed of carbon monoxide, ethylene and propene is palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis( 2-methoxyphenyl)phosphine). In the above, the content of trifluoroacetic acid compared to palladium is a molar ratio of 10 times, and undergoes one step at 78°C and two steps at 84°C. In the polyketone prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. In addition, the melting point of the polyketone was 220° C., and the viscosity (I.V) measured at 25° C. with HFIP (hexa-fluoroisopropano) was 1.4 dl/g.

The prepared polyketone and phosphinate flame retardant (Clariant OP1230), anti-drip agent (Hannanotech FS200), tricalcium phosphate, and glass fibers were added to each of the contents shown in Table 1 below to prepare a composition. The composition was prepared as pellets on a extruder using a twin-screw with a diameter of 40 cm and a L/D=32 operating at 250 rpm.

[Comparative Examples 1 to 4]

Each of the pellets was prepared through the same procedure as in Example 1, except that the component content of the composition was adjusted as described in Table 1 below.

[Experimental Example]

The physical properties of the pellets prepared in Examples and Comparative Examples were evaluated using the following methods, and the results are shown in Table 1 below.

(1) Flame retardancy evaluation

After the polyketone composition was prepared with a specimen having a thickness of 0.4 mm, it was measured according to the flame retardancy test standard of UL94V. The evaluation results are out of V-O, V-1, V-2, and standard. V-0 indicates that it is highly flame retardant, V-1 and V-2 indicate that it is relatively highly flame retardant, and failure to reach the V-2 level is recognized as having insufficient flame retardancy.

(2) Evaluation of mechanical properties

-Tensile strength, elongation: It was performed according to ISO 527-1.

-Flexural strength, flexural modulus: It was performed according to ISO 178.

-Impact strength: It was performed according to ISO 179.

(3) Evaluation of processing stability

After preparing the polyketone composition as a specimen, and injecting a COT specimen with a mini-injector, the cross-time (gel point) of COT was measured through a rheometer {Anton Paar's Physica MCR 301} to evaluate the processing stability. Table 1 shows the results. The gel point is determined by the time when G′=G″ (sol-gel transition time point).

Content (% by weight) Flame retardancy evaluation The tensile strength Elongation Flexural strength Flexural modulus Impact strength COT PK Flame retardant Anti-drip agent TCP glass fiber 0.4T MPa % MPa MPa kJ/m ² minute Example 1 86 13 0.5 0.5 - V-0 51 50 66 2202 7.3 7 Example 2 85 13 One One - V-0 52 48 70 2273 7.9 7 Example 3 87.2 12 0.3 0.5 - V-0 53 20 81 2665 7.1 8 Example 4 82.2 12 0.3 0.5 5 V-0 54 23 81 2675 7.0 7 Example 5 72.2. 12 0.3 0.5 15 V-0 75 7 135 3700 10.1 6 Comparative Example 1 90 10 - - - V-2 50 30 60 1890 6.6 - Comparative Example 2 87 13 - - - V-2 47 32 59 1954 5.4 - Comparative Example 3 85 15 - - - V-0 45 33 58 1976 5.3 5 Comparative Example 4 80 15 - - 5 V-0 48 12 75 2200 5.8 4

Referring to Table 1, in the case of Comparative Example 1 and Comparative Example 2, it can be seen that the flame retardancy is excellent as the flame retardant is included, but the mechanical properties are deteriorated. In addition, in the case of Comparative Examples 3 and 4, the flame retardancy is excellent, but as the content of the flame retardant increases, it can be seen that the price increases and the mechanical properties decrease, and the processing stability also decreases.

On the other hand, when the flame retardant content is in the range of 9 to 14% by weight and includes a fluorine-based anti-drip agent (Examples 1 to 5), it can be seen that mechanical properties are also improved as well as securing V-0 grade flame retardancy. In addition, the inclusion of TCP shows that the COT is increased compared to the comparative example, so it seems to have an effect of improving the processing stability (the correlation between the COT and the processing stability is not clear, but it is currently being used as an indicator of processing stability). In addition, it can be seen that Examples 4 and 5 significantly improved mechanical properties (tensile strength, flexural strength, flexural modulus, impact strength, etc.) by including glass fibers.

As a result, the polyketone composition prepared according to the Examples exhibits superior flame retardancy and processing stability, and also has excellent tensile strength, elongation, flexural strength, flexural modulus, and impact strength, as well as flame retardancy and processing stability. It can be applied as a required component in electric and electronic fields, especially as a connector for refrigerators or washing machines.

As a result, in the case of the embodiment, to solve the problems as described above, by controlling the content of each component in order to adjust the balance between flame retardancy and mechanical properties, excellent flame retardancy and mechanical properties, as well as excellent processing stability Able to know.

Although described above with reference to the preferred embodiment of the present invention, those skilled in the art or those skilled in the art will depart from the spirit and technical scope of the invention described in the claims below. It will be understood that various modifications and changes can be made to the present invention without departing from the scope.

Therefore, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.

Claims (4)

70.0 to 90.0% by weight of a polyketone composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon;
Phosphinate-based flame retardant 9.0-14.0 wt%;
0.3-8.0% by weight of polytetrafluoroethylene (PTFE), a fluorine-based anti-drip agent; And
Tricalcium phosphate 0.1 to 8.0% by weight,
A polyketone composition having an improved flame retardancy and workability of 0.4T V-0 or higher in UL94 flame retardancy evaluation, tensile strength of 51 MPa or higher, flexural strength of 65 MPa or higher, flexural modulus of 2000 MPa or higher, and impact strength of 7.0 kJ/m ² or higher. According to claim 1,
A polyketone composition having improved flame retardancy and processability, further comprising 0.1 to 15.0 wt% of one additive selected from the group consisting of glass fiber, carbon fiber, mica and talc based on the total weight of the polyketone composition. delete delete