KR102387201B1 - Polyketone composition improved flame retardant and economy - Google Patents

Abstract

The present invention is a polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon, 72.0-89.0% by weight; 5.0 to 11.0 wt% of a phosphorus-based flame retardant; 2.0 to 5.0% by weight of a melamine-based flame retardant; 0.1 to 15.0 wt% of a filler; And it relates to a polyketone composition with improved flame retardancy and economy, comprising 0.3 to 1.0 wt% of a fluorine-based anti-drip agent.

Description

Polyketone composition with improved flame retardancy and economy {POLYKETONE COMPOSITION IMPROVED FLAME RETARDANT AND ECONOMY}

The present invention relates to a polyketone composition having improved flame retardancy and economy.

Polyketone (PK) is a material that has a lower raw 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 resistance.

Polyketone having these properties is included in general-purpose high-performance plastics and has a strength comparable to that of conventional engineering plastics.

On the other hand, in order to apply a plastic material to parts in the electrical and electronic field, a flame retardant enhanced than the existing flame retardant is required (UL 94 test 0.8T V-0 grade). Therefore, in the case of the existing flame-retardant polyketone composition, it is essential to add 8 to 10% by weight of the phosphorus-based flame retardant alone in order to secure the UL 94 test 0.8T V-0 grade.

On the other hand, in the case of relatively inexpensive melamine flame retardants and inorganic flame retardants, when added alone, an excess of 15 to 30% by weight is required to secure UL 94 test 0.8T V-0 grade. In the case of phosphorus-based flame retardants, it is possible to secure V-0 by adding 8 to 10% by weight, but there is a problem in economic efficiency due to an increase in manufacturing cost due to the relatively high price of the flame retardant.

Accordingly, there is a demand for the development of a flame-retardant polyketone resin capable of improving economic efficiency by improving the manufacturing cost without deterioration of flame retardancy and physical properties.

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

The polyketone composition according to an embodiment of the present invention comprises 72.0-89.0 wt% of a polyketone composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon; 5.0 to 11.0 wt% of a phosphorus-based flame retardant; 2.0 to 5.0% by weight of a melamine-based flame retardant; 0.1 to 15.0 wt% of a filler; and 0.3 to 1.0 wt% of a fluorine-based anti-drip agent.

In this case, the sum of the phosphorus-based flame retardant and the melamine-based flame retardant content may be 10 to 13% by weight based on the total weight of the polyketone composition.

In addition, the polyketone composition may further include 0.1 to 2.0% by weight of tricalcium phosphate based on the total weight of the polyketone composition.

The filler may be at least one selected from the group consisting of glass fiber, carbon fiber, mica and talc.

The fluorine-based anti-drip agent may be polytetrafluoroethylene (PTFE).

In addition, the polyketone composition may have a grade of 0.8T V-0 or more in the UL94 flame retardancy evaluation, a tensile strength of 50 MPa or more, a flexural strength of 60 MPa or more, a flexural modulus of 1900 MPa or more, and an impact strength of 60 J/m or more.

According to an embodiment of the present invention, as the polyketone composition includes a phosphorus-based flame retardant and a melamine-based flame retardant as a flame retardant in combination, it is possible to minimize the content of a relatively expensive phosphorus-based flame retardant while maintaining the existing flame retardancy, so that economic efficiency can be improved. there is.

In addition, since the polyketone composition of the present invention includes a flame retardant and an anti-drip agent, it is possible to prevent deterioration of processability and mechanical properties that occur when only a flame retardant is included, so that it is rated V-0 in UL94 flame retardancy evaluation without deterioration of mechanical properties It is possible to secure a flame retardant grade or higher. In addition, the polyketone composition of the present invention may have improved processing stability by including tricalcium phosphate.

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

Since the present invention can have various changes and can have various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In describing each figure, like reference numerals have been used for like elements. In the accompanying drawings, the dimensions of the structures are enlarged than the actual size for clarity of the present invention. Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. The singular expression includes the plural expression unless the context clearly dictates otherwise.

In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, component, part, or a combination thereof described in the specification exists, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Also, when a part of a layer, film, region, plate, etc. is said to be “on” another part, it includes not only the case where the other part is “directly on” but also the case where there is another part in between. Conversely, when a part of a layer, film, region, plate, etc. is said to be “under” another part, it includes not only cases where it is “directly under” another part, but also cases where another part is in between. In addition, in the present application, “on” may include the case of being disposed not only on the upper part but also on the lower part.

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

A polyketone composition according to an embodiment includes a polyketone comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon; phosphorus-based flame retardants; melamine-based flame retardants; fillers; and a fluorine-based anti-drip agent.

First, the polyketone of the present invention is a linear alternating structure, and contains substantially carbon monoxide for each molecule of unsaturated hydrocarbons. Suitable ethylenically unsaturated hydrocarbons 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 aryl aliphatic containing an aryl substituent on another aliphatic molecule, in particular an aryl substituent on an ethylenically unsaturated carbon atom. Examples of the aryl aliphatic hydrocarbon among the 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, particularly an α-olefin such as propene. It is a terpolymer of the family.

When the polyketone terpolymer is used as the main polymer component of the composition according to 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 preferred that there are 10 to 100 units comprising a second hydrocarbon moiety.

The polymer ring of the polyketone polymer preferred in the present invention may 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 moiety 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 comprising repeating units represented by formulas (1) and (2), and y/x is preferably 0.03 to 0.3. When the numerical value of the y/x value is less than 0.03, there is a limitation in that meltability and processability are deteriorated, 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 adjusting 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 235 °C.

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 a polymer depend on its molecular weight, on whether the polymer is a copolymer or terpolymer, and in the case of a terpolymer, on the nature of the secondary hydrocarbon moieties present. The general melting point of the polymer used in the present invention is 175°C to 300°C, and generally 210°C to 270°C. The intrinsic viscosity (I.V) of the polymer measured at 60 ° C with HFIP (Hexafluoroisopropylalcohol) using a standard customs viscosity measuring device is 0.5 dl/g to 10 dl/g, and preferably 0.8 dl/g to 4 dl/g, and more Preferably, it is 1.0 dl/g - 1.4 dl/g. In this case, if the intrinsic viscosity number is less than 1.0 dl/g, mechanical properties are deteriorated, and if it exceeds 1.4 dl/g, the 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 deteriorated, and if it is 2.5 or more, there is a problem in that the moldability is poor. In order to control the molecular weight distribution, it is possible to control in proportion to the amount of the palladium catalyst and the polymerization temperature. That is, if the amount of the palladium catalyst increases or the polymerization temperature is 100° C. or higher, the molecular weight distribution increases.

Liquid polymerization carried out in an alcohol solvent through a catalyst composition comprising carbon monoxide and an olefin as a palladium compound, an acid having a PKa of 6 or less, and a diligand compound of phosphorus can be employed as a method for preparing the polyketone polymer. The polymerization reaction temperature is preferably 50 ~ 100 ℃ and the reaction pressure is 40 ~ 60 bar. After polymerization, the polymer is recovered through filtration and purification processes, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

Here, as the palladium compound, palladium acetate is preferable, and the amount used is preferably 10 ^{-3 to} 10 -1 mole. Specific examples of the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, and sulfonic acid. In the present invention, trifluoroacetic acid was used, and the amount used is preferably 6 to 20 equivalents compared to palladium. In addition, as the bidentate compound of phosphorus, 1,3-bis[di(2-methoxyphenylphosphino)]propane is preferable, and the amount used 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, an ethylenically unsaturated compound and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, in particular a repeating unit derived from carbon monoxide and a repeating unit derived from an ethylenically unsaturated compound, and a repeating unit derived from a propyleneically unsaturated compound are substantially Polyketones, which are alternately connected with each other, have excellent mechanical and thermal properties, excellent processability, and high abrasion resistance, chemical resistance, and gas barrier properties, making it a useful material for various purposes. The high molecular weight of this ternary or higher copolymerized polyketone has higher processability and thermal properties, and is considered to be useful as an engineering plastic material with excellent economic efficiency. In particular, it can be used in parts such as gears of automobiles because of its high wear resistance, as a lining material for chemical transport pipes because of its high chemical resistance, and in lightweight gasoline tanks because of its high gas barrier properties. In addition, when ultra-high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fiber, it is possible to draw at a high magnification, and as a fiber having high strength and high modulus of elasticity oriented in the stretching direction, it is a reinforcing material for belts and rubber hoses, tire cords, and concrete reinforcing materials. It is a very suitable material for building materials and industrial materials such as

The method for producing polyketones comprises carbon monoxide and carbon monoxide in a liquid medium in the presence of an organometallic complex catalyst comprising (a) a Group 9, Group 10 or Group 11 transition metal compound, and (b) a ligand having a Group 15 element. In the method for producing a polyketone by terpolymerizing an ethylenic and propylene unsaturated 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, the mixture As 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, ketal may be formed and heat resistance stability may decrease 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) a Group 9, Group 10, or Group 11 transition metal compound of the Periodic Table (IUPAC Nomenclature of Inorganic Chemistry Revision, 1989), and (b) a ligand having an element of Group 15.

Examples of the Group 9 transition metal compound among the Group 9, Group 10 or Group 11 transition metal compounds (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 compound include nickel or palladium complexes, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include nickel acetate, nickel acetyl acetate, palladium acetate, and palladium trifluoroacetate. , palladium acetyl acetate, 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 acetyl acetate, silver acetate, tri A silver fluoroacetic acid, silver acetyl acetate, trifluoromethane sulfonic acid silver, etc. are mentioned.

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

Examples of the ligand (b) having a group 15 atom include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picoline , nitrogen ligands such as 2,2'-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-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 (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 these, the ligand (b) having a group 15 element is preferred is a phosphorus ligand having a group 15 atom, and in particular, a preferred phosphorus ligand in view of the yield of polyketone is 1,3-bis[di(2-) Methoxyphenyl) phosphino] propane, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, in terms of the molecular weight of the polyketone, 2-hydroxy-1,3-bis [ They are di(2-methoxyphenyl)phosphino]propane and 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, and in terms of safety, they do not require 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 from the viewpoint of economy. A 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, ((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 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 show the highest activity among polymerization catalysts However, the structure is simpler and the molecular weight is also lower. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst with the highest activity as a polyketone polymerization catalyst in the art, while further reducing the manufacturing cost and cost. A 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 conventional method for preparing a ligand for a polyketone polymerization catalyst of the present invention is 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 synthesized in large quantities commercially.

On the other hand, it is also preferable to use (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine as the ligand used in the polymerization catalyst. The method for synthesizing the ligand is as follows. It is the same as the reaction formula.

[reaction formula]

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

In a preferred embodiment, in the method for preparing a ligand for a polyketone polymerization catalyst of the present invention, (a) bis(2-methoxyphenyl)phosphine and dimethylsulfoxide (DMSO) are added to a reaction vessel under a nitrogen atmosphere, and hydrogenated at room temperature Stirring after adding sodium; (b) adding 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the obtained mixture, followed by stirring to react; (c) after completion of the reaction, adding methanol and stirring; (d) adding toluene and water, and after layer separation, the oil layer was washed with water, dried over anhydrous sodium sulfate, filtered under reduced pressure, and concentrated under reduced pressure; and (e) recrystallizing the residue in methanol to obtain ((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 Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies according to the type of the selected ethylenically and propylene unsaturated compound or other polymerization conditions, so it is uniformly within the range Although not limited, it is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol, per 1 liter of capacity of the reaction zone. The capacity of the reaction zone refers to the capacity of the liquid phase of the reactor. The amount of the ligand (b) to be used is not particularly limited, either, 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 to add benzophenone during polymerization of polyketone. In the present invention, an effect of improving the intrinsic viscosity of polyketone can be achieved by adding benzophenone during polymerization of polyketone. The molar ratio of the (a) Group 9, Group 10 or Group 11 transition metal compound to benzophenone is 1:5-100, preferably 1:40-60. If the molar ratio of the transition metal to benzophenone is less than 1:5, the effect of improving the intrinsic viscosity of the produced polyketone is not satisfactory. It tends to decrease, so it is undesirable

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 - ?-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 ester, such as ethyl acrylate and methyl acrylate, etc. are mentioned. Among these, a preferable ethylenically unsaturated compound is an ?-olefin, more preferably an ?-olefin 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 comprising the Group 9, Group 10 or Group 11 transition metal compound (a) and the ligand (b) having a Group 15 element. It is caused by a catalyst, wherein the catalyst is produced by bringing the two components into contact. Arbitrary methods can be employ|adopted as a method of making contact. That is, the two components may be prepared as a solution in which the two components are 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, a gas phase polymerization method in which a small amount of polymer is impregnated with a high concentration of a catalyst solution, and the like are used. Polymerization may be either batch type or continuous type. As a reactor used for polymerization, a well-known thing can be used as it is, or it can process and use it. There is no restriction|limiting in particular about the polymerization temperature, Generally 40-180 degreeC, Preferably 50-120 degreeC is employ|adopted. Although there is no restriction|limiting also about the pressure at the time of polymerization, Usually, it is normal pressure - 20 MPa, Preferably it is 4-15 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, preferably 72 to 89% by weight. If the content of polyketone is less than 72% by weight, mechanical properties, thermal stability, fluidity, etc. may be reduced, and if it exceeds 89% by weight, the content of specific substances added to the composition is relatively small, so the flame retardancy improvement effect will be insignificant. can

In addition, a flame retardant may be added to the polyketone composition according to the present invention to improve flame retardancy, and it is preferable to use a phosphorus-based flame retardant and a melamine-based flame retardant. As the flame retardant includes the phosphorus-based flame retardant and the melamine-based flame retardant in combination, it is possible to minimize the content of the relatively expensive phosphorus-based flame retardant while maintaining the existing flame retardancy, thereby improving economic efficiency.

The phosphorus-based flame retardant of the present invention may be 5.0 to 11.0% by weight based on the total weight of the composition. Here, if the phosphorus-based flame retardant is less than 5.0% by weight, the flame retardancy is lowered, and if it exceeds 11.0% by weight, the flame retardancy is excellent, but the price may increase and mechanical properties may decrease.

Specific examples of the phosphorus-based flame retardant used include phosphonate, phosphinate, phosphine oxide, and phosphazene, and in this case, phosphate-based flame retardant. , in particular tricalcium phosphate (TCP) may be excluded. Meanwhile, in the present invention, it is preferable to use a phosphinate-based flame retardant as a phosphorus-based flame retardant. An example of the phosphinate-based flame retardant may include aluminum diethylphosphinate. The phosphinate-based phosphorus-based flame retardant imparts a flame retardant effect by reducing the concentration of O and OH, which are active radicals, in diethylphosphinic acid in the gas phase, and stopping the chain reaction. In addition, the phosphinate system forms a char by diethylphosphinic acid and aluminum phosphate in a solid phase, and blocks heat and oxygen.

The melamine-based flame retardant of the present invention may be 2.0 to 5.0% by weight based on the total weight of the composition, and when the above range is satisfied, the flame retardancy of the composition is secured, and the retention rate is increased during injection retention evaluation, thereby improving processing stability. On the other hand, if the phosphorus-based flame retardant is less than 2.0% by weight, the flame retardancy is lowered, and if it exceeds 5.0% by weight, the processing stability is improved but the flame retardancy is reduced, and if an excessive amount is added, the flame retardancy is not ensured. .

Specifically, as the type of the melamine-based flame retardant used, melamine cyanurate, melamine phosphate, melamine sulfate, etc. may be used, and it is preferable to use melamine cyanurate. Melamine-based flame retardant melamine cyanurate dilutes oxygen and combustion gas by discharging inert gas (NH ₃ , CO ₂ , HOCN) in the gas phase. In addition, melamine cyanurate undergoes an endothermic reaction according to melamine sublimation and decomposition of cyanuric acid in a solid phase, and cyanuric acid decomposes polymers and prevents the polymer from being used as a combustion raw material by melt dripping.

In addition, the polyketone composition according to the present invention may include one kind of filler selected from the group consisting of glass fiber, carbon fiber, mica and talc. The mechanical properties of the composition can be reinforced by adding such a filler, and it is preferable to use glass fiber as the filler.

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

In addition, 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 above-described flame retardant, 0.8T V-0 grade can be secured in the UL94 flame retardancy evaluation, but the processability and mechanical properties decrease, and the manufacturing cost increases due to the excessive addition of the flame retardant. will do Accordingly, the present invention optimizes the content of the flame retardant added to the above-mentioned range by applying the fluorine-based anti-drip agent to have economic feasibility compared to the composition including only the flame retardant, and it may be possible to secure a flame retardant grade without lowering the mechanical properties of the flame-retardant polyketone material. . That is, the anti-drip agent can enhance the flame retardancy of the composition without deterioration of physical properties such as tensile strength, flexural strength/elastic modulus, impact strength and elongation while an internal network is formed with the polyketone polymer in the composition.

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

In addition, the anti-drip agent may be 0.3 to 1.0% by weight, preferably 0.5 to 1.0% by weight, based on the total weight of the composition. At this time, when the anti-drip agent is less than 0.3% by weight, the effect of preventing deterioration of mechanical properties is not sufficient, and when it exceeds 1.0% by weight, the flowability is reduced and the manufacturing cost is increased.

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

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

In addition, tricalcium phosphate serves to maintain the viscosity of the polyketone. In detail, since polyketone has a disadvantage of increasing viscosity and gelling at high temperatures, tricalcium phosphate is added to maintain the viscosity of polyketone. Due to the addition of tricalcium phosphate, it is possible to obtain the effect of maintaining the viscosity of the polyketone uniformly, thereby minimizing damage to the molded part and maintaining low specific gravity.

Such tricalcium phosphate may include 0.1 to 2.0% by weight, preferably 0.1 to 1.0% by weight, based on the total weight of the composition. 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 the gelation of polyketone cannot be suppressed. There may be a problem of strength degradation.

On the other hand, the polyketone composition of the present invention may additionally contain additional additives conventionally known in order to improve the processability or physical properties of the polymer, for example, antioxidants, heat stabilizers, lubricants, fillers, fireproof materials, mold release agents, colorants and other materials. can 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 preparing the polyketone composition of the present invention is as follows.

The method for preparing a 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 double ligand compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing alcohol (eg, methanol) and water; preparing a linear terpolymer of carbon monoxide, ethylene and propylene by performing polymerization in the presence of the catalyst composition and a mixed solvent; 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, phosphorus-based flame retardant, melamine-based flame retardant, filler, fluorine-based anti-drip agent and/or tricalcium phosphate to injection molding.

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

In addition, during the polymerization, the reaction 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 processes after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

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

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 ℃, kneading may not occur properly, and if it exceeds 260 ℃, problems related to the heat resistance of the resin may occur. In addition, if the screw rotation speed is less than 100 rpm, smooth kneading may not occur, and if it exceeds 300 rpm, mechanical properties may be deteriorated.

The polyketone composition prepared as described above has excellent flame retardancy with a grade of V-0 or higher in the UL94 flame retardancy evaluation, and has mechanical properties such as tensile strength of 50 MPa or more, flexural strength of 60 MPa or more, flexural modulus of 1900 MPa or more, and impact strength of 60 J/m or more. can 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 in recent years, it is possible to secure the V-0 rating at a thinner thickness for application to electrical and electronic materials such as washing machine/refrigerator connectors. is essential. However, in the case of the conventional flame-retardant polyketone composition, when the flame retardancy is evaluated at a thickness thinner than 0.8 mm, drip occurs according to the melting of the resin, which causes a problem in that it is difficult to secure a V-0 flame retardant grade. Accordingly, flame retardancy can be secured by additionally adding a flame retardant, but since phosphorus-based flame retardants are expensive, price competitiveness is lost as the content of added flame retardants increases, and processing stability and mechanical properties are reduced. do.

On the other hand, the present invention can secure price competitiveness by minimizing the phosphorus-based flame retardant content through the composite application of the melamine-based flame retardant. Specifically, when only phosphorus-based flame retardants are added, the flame retardant price is 135 won/kg among 1 kg manufacturing cost, but when phosphorus-based flame retardants and melamine-based flame retardants are added in combination, the flame retardant price can be reduced to 87.5 won/kg.

In addition, by applying an anti-drip agent, it is possible to prevent dripping of the resin during combustion and minimize the content of the added flame retardant. In addition, after improving processability through addition of tricalcium phosphate while maintaining mechanical properties, it is possible to secure V-0 grade flame retardancy at a thinner thickness.

A sheet, a film, a plate, and a molded part can be manufactured by preparing the composition in the same manner as described above and extruding or injection molding the composition. As such an application example, it can be used for electrical and electronic materials such as a washing machine and a refrigerator connector.

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

[Examples 1 to 10]

Linear alternating polyketones composed of carbon monoxide, ethylene and propene are palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis( 2-methoxyphenyl)phosphine) prepared in the presence of a catalyst composition. In the above, the content of trifluoroacetic acid compared to palladium is 10 times the molar ratio, and the first step of polymerization temperature is 78°C and the second step is 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 using hexa-fluoroisopropano (HFIP) was 1.4 dl/g.

The prepared polyketone, phosphinate flame retardant (Clariant's OP1230), melamine cyanurate flame retardant, glass fiber, anti-drip agent (Hannanotek's FS200) and tricalcium phosphate (TCP) were each added in the amounts shown in Table 1 below. The composition was prepared by input, and the prepared composition was prepared as pellets on an extruder using a twin screw screw having a diameter of 40 cm and L/D = 32 operating at 250 rpm.

[Comparative Examples 1 to 6]

Pellets were each prepared in the same manner as in Example 1, except that the component content of the composition was adjusted as described in Table 1 below.

polyketone
(wt%) Phosphorus flame retardant
(wt%) Melamine-based flame retardant (wt%) fiberglass
(wt%) anti-drip agent
(wt%) TCP
(wt%) Comparative Example 1 90 10 - - - - Comparative Example 2 85 10 - 5 - - Comparative Example 3 90 7.5 2.5 - - - Example 1 84.5 7.5 2.5 5 0.5 - Example 2 84 7.5 2.5 5 0.5 0.5 Example 3 84.5 7 3 5 0.5 - Example 4 84 7 3 5 0.5 0.5 Example 5 84.5 6 4 5 0.5 - Example 6 84.5 5 5 5 0.5 - Comparative Example 4 85 5 5 5 - - Comparative Example 5 81 13 - 5 0.5 0.5 Example 7 81 11 2 5 0.5 0.5 Example 8 81 10 3 5 0.5 0.5 Example 9 81 9 4 5 0.5 0.5 Example 10 81 8 5 5 0.5 0.5 Comparative Example 6 81 7 6 5 0.5 0.5

[Experimental example]

The physical properties of the pellets prepared in Examples and Comparative Examples were evaluated using the following method, and the results are shown in Table 2 below.

(1) Flame retardant evaluation

The polyketone compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were prepared as specimens having a thickness of 0.8 mm, and then measured according to the flame retardancy test standard of UL94V. In addition, the polyketone compositions prepared in Examples 7 to 10 and Comparative Examples 5 to 6 were prepared as specimens having a thickness of 0.4 mm, and then measured according to the flame retardancy test standard of UL94V. The evaluation result is V-O, V-1, V-2, out of specification. V-0 indicates that it has a high degree of flame retardancy, V-1 and V-2 indicate that it has a relatively high flame retardancy, 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 carried out according to ASTM D638.

- Flexural strength, flexural modulus: It was carried out according to ASTM D256.

- Impact strength: It was carried out according to ASTM D256.

(3) Injection machine Spiral Flow Length and injection machine retention evaluation

Spiral Flow Length injection was performed in accordance with ASTM-D3123 on a clamping force 1.5T injection machine. Each composition was extruded and injected to proceed, and the working temperature was 240°C. In Table 2, the average value for the length of 10 shots of the Spiral Flow Length specimen was written. To evaluate the residence time of the injection machine, the injection machine was stopped while the heater of the injection machine was maintained at 240° C. for 30 minutes after measurement, and after reaching a certain injection residence time, injection was performed by 10 shots.

tensile properties flexural properties Shock
robbery
(J/m) Flame-retardant evaluation Flow length(m) Seal
robbery
(MPa) surrender
elongation
(%) break
elongation
(%) curve
robbery
(MPa) curve
modulus of elasticity
(MPa) Early
0 minutes 30 minutes
(Retention %) Comparative Example 1 52 18 30 59 1806 62 V-2 34 21.5 (63%) Comparative Example 2 57 12 17 77 2286 72 V-2 32.1 22
(69%) Comparative Example 3 53 17 29 56 1712 61 V-1 34.5 22.6 (66%) Example 1 59 12 17 78 2348 70 V-0 32.1 24.2
(75%) Example 2 59 12 17 78 2348 70 V-0 31.7 25.5
(80%) Example 3 59 11 16 77 2350 71 V-0 33.2 23.2
(70%) Example 4 59 11 16 77 2350 71 V-0 31.8 24.8
(78%) Example 5 59 11 15 77 2350 71 V-0 33 20
(61%) Example 6 60 11 17 77 2304 71 V-0 33.2 23.2
(70%) Comparative Example 4 60 11 17 77 2304 71 V-1 32.5 19.5
(60%) Comparative Example 5 59 12 17 77 2,287 71 V-0 35.1 16.2 (46.2%) Example 7 59 12 17 78 2,350 70 V-0 33.8 20.7
(61.2%) Example 8 59 11 15 77 2,345 69 V-0 33.6 20.6
(61.3%) Example 9 59 11 15 77 2,305 70 V-0 33.6 21.9
(65.2%) Example 10 59 11 15 78 2,331 70 V-0 33.8 20.9
(61.8%) Comparative Example 6 59 11 16 78 2315 70 V-2
(drip 2 times) 34 23.3
(68.5%)

Referring to Table 2, it can be seen that in Comparative Examples 1 and 2, since only the phosphorus-based flame retardant was included, the flame retardancy was lowered to V-2 and V-1 grades, respectively, in the UL94 flame retardancy evaluation, and it was prepared by adding an excessive amount of the phosphorus-based flame retardant. The problem of rising cost arises. In addition, in the case of Comparative Example 3, although the phosphorus-based flame retardant and the melamine-based flame retardant were added in combination, it was confirmed that the mechanical properties were lowered because glass fiber was not included. In the case of Comparative Example 4, mechanical properties were improved as the glass fiber was included, but it was found that the processing stability was reduced because the anti-drip agent and/or TCP were not included (low flow length retention rate).

In addition, in the case of Comparative Example 5, it can be seen that processing stability is lowered compared to Example 7 because the melamine-based flame retardant is not included. In the case of Comparative Example 6 containing more than 5% by weight of the melamine-based flame retardant, it was confirmed that the processing stability was improved, but the flame retardancy was lowered.

On the other hand, when a flame retardant compound includes a phosphorus-based flame retardant and a melamine-based flame retardant, and includes glass fiber, a fluorine-based anti-drip agent and/or TCP (Examples 1 to 10), while securing V-0 grade flame retardancy It can be seen that the mechanical properties are also improved. In addition, as the embodiment includes a combination of a phosphorus-based flame retardant and a melamine-based flame retardant as a flame retardant, price competitiveness can be secured by minimizing the content of the phosphorus-based flame retardant compared to the comparative example.

As a result, it was found that the polyketone composition prepared according to the example exhibited superior flame retardancy and processing stability than the case of the comparative example, and at the same time was also excellent in tensile strength, elongation, flexural strength, flexural modulus and impact strength. In addition, it is possible to secure price competitiveness by minimizing the phosphorus-based flame retardant content through the combined application of the phosphorus-based flame retardant and the melamine-based flame retardant as a flame retardant. Accordingly, the polyketone composition according to the present invention can be applied as a component in the electrical and electronic field requiring both flame retardancy and processing stability, in particular, as a connector for a refrigerator or washing machine.

Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art or those having ordinary skill in the art will not depart from the spirit and scope of the present invention described in the claims to be described later. It will be understood that various modifications and variations of the present invention can be made without departing from the scope of the present invention.

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

Claims (6)

81.0-84.0% by weight of a polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon;
5.0 to 11.0 wt% of a phosphinate flame retardant;
2.0-5.0 wt% of melamine cyanurate flame retardant;
Glass fiber 0.1 to 15.0% by weight;
0.3 to 1.0 wt% of polytetrafluoroethylene (PTFE) as a fluorine-based anti-drip agent and
As a polyketone composition comprising 0.1 to 2.0% by weight of tricalcium phosphate,
The sum of the contents of the phosphinate flame retardant and the melamine cyanurate flame retardant is 10 to 13% by weight based on the total weight of the polyketone composition. delete delete delete delete The method of claim 1,
A polyketone composition with improved flame retardancy and economic efficiency that is 0.8T V-0 grade or higher in the UL94 flame retardancy evaluation, tensile strength of 50 MPa or more, flexural strength of 60 MPa or more, flexural modulus of 1900 MPa or more, and impact strength of 60 J/m or more.