KR102021793B1 - Composition of polyketone resin having flame retardant, and preparation method thereof - Google Patents

Abstract

The present invention is a polyketone resin; And a flame retardant polyketone resin composition comprising a flame retardant comprising a aluminum salt and a flame retardant comprising a zinc salt, and a method of manufacturing the same, and more particularly, a flame retardant poly with increased environmental friendliness and process stability. It relates to a ketone resin composition.

Description

Composition of polyketone resin having flame retardant, and preparation method

The present invention relates to a flame retardant composition comprising a polyketone resin and a non-halogen phosphorus-based flame retardant, and to a method of manufacturing the same, and more particularly, to a flame retardant polyketone resin composition having increased environmental friendliness and processing stability.

Polyketone (PK) or polyketone resin is a material that has lower raw materials and polymerization process costs than general engineering plastic materials such as polyamide, polyester, and polycarbonate, and has properties such as heat resistance, chemical resistance, fuel permeability, and wear resistance. It is excellent and widely applied to various industries. Therefore, there is a growing interest in linear alternating polyketone polymers composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon. U.S. Patent No. 4,880,903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide and ethylene and other olefinically unsaturated hydrocarbons such as propylene.

The method for preparing polyketone resin is usually a compound of Group VIII metal selected from palladium, cobalt or nickel, anion of a non-hydro halogen strong-hydrohalogentic acid. Catalyst compositions produced from bidentate ligands of phosphorus, arsenic or antimones are used. U.S. Patent No. 4,843,144 discloses a process for preparing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of nonhydrohalogenic acid having a pK of less than 6, and a catalyst that is a bidentate ligand of phosphorus. Presenting.

On the other hand, the composition comprising the polyketone resin, that is, the polyketone resin composition may include a variety of additives, and may include a flame retardant for the stability of the polymer during processing in the melt state.

For example, Japanese Patent Laid-Open No. 11-71513 discloses a polyketone resin composition that is useful as a housing part and has improved flowability, heat resistance, organic solvent resistance, and moldability. The said patent discloses the polyketone resin composition which contained 0.01-60 weight part of flame retardants with respect to 100 weight part of polyketone resin which mix | blended 50-99.00 weight% of polyketone resins and 0.01-50 weight% of liquid crystalline resins, As the flame retardant, an organic bromide, an organophosphorus compound, or the like is used. However, since halogen-containing flame retardants cause environmental problems, their use is limited, and many problems of odor and coloring occur.

In addition to the organic flame retardant has been proposed to solve the above problems by using an inorganic flame retardant, inorganic flame retardant compared to the organic flame retardant significantly increased the amount of use for expressing similar flame retardant, reducing the mechanical properties of the resin composition and stability of product processing stability There is a decreasing problem.

In addition, there is an example of using a melamine phosphate-based flame retardant to improve the environmental problems, odors and coloring problems of such flame retardants, but the problem of reducing the processing stability of the product is vulnerable to overheating exposure conditions during injection processing.

United States Patent No. 4,880,903 United States Patent No. 4,843,144 Japanese Patent Laid-Open No. 11-71513

The present invention uses a non-halogen phosphorus-based flame retardant containing a metal salt to improve the environmental problems caused by the flame retardant, to reduce the smell and free coloring, flame retardant polyketone resin composition with increased processing stability in the production of the product and its production To provide a method.

In order to solve the above problems, an embodiment of the present invention includes a polyketone resin, and a flame retardant comprising a phosphorus flame retardant comprising an aluminum salt and a zinc salt, the polyketone resin is the following general Provided is a flame retardant polyketone resin composition comprising a polyketone copolymer comprising repeating units represented by formulas (1) and (2), wherein y / x is a linear alternating polyketone having 0.1 to 0.3.

-[-CH ₂ CH ₂ -CO] x- (1)

-[-CH ₂ -CH (CH ₃ ) -CO] y- (2)

(x, y represents each mol% of General Formula (1) and (2) in a polyketone resin.)

Another embodiment of the present invention provides a flame retardant polyketone resin composition, wherein the phosphorus flame retardant is phosphinate.

Yet another embodiment of the present invention provides a flame retardant polyketone resin wherein the phosphorus flame retardant comprising aluminum salt comprises aluminum diethyl phosphinate or the phosphorus flame retardant comprising zinc salt comprises zinc diethyl phosphinate. To provide a composition.

Yet another embodiment of the present invention provides a flame retardant polyketone resin composition having a weight ratio of phosphorus flame retardant including aluminum salt and phosphorus flame retardant including zinc salt in a range of 3: 7 to 7: 3.

Yet another embodiment of the present invention provides a flame retardant polyketone resin composition, wherein the flame retardant is greater than 3 to less than 15 wt% based on 100 wt% of the total composition.

Another embodiment of the present invention, preparing a polyketone resin; And it provides a method for producing a flame retardant polyketone resin composition comprising the step of mixing the polyketone resin with a flame retardant.

The present invention provides a flame retardant polyketone resin composition which improves environmental problems caused by flame retardants, reduces odor and frees coloring, and increases processing stability during product manufacturing, and provides a variety of environments than conventional flame retardant polyketone resins. Better flame retardancy and processing stability.

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

The present invention is a polyketone resin; And it relates to a flame retardant polyketone resin composition comprising a flame retardant comprising a phosphorus flame retardant comprising an aluminum salt and a phosphorus flame retardant comprising a zinc salt.

The polyketone resin of the present invention is a linear alternating structure, and substantially contains carbon monoxide for each molecule of unsaturated hydrocarbon. Suitable ethylenically unsaturated hydrocarbons for use as precursors of polyketone resins have up to 20, preferably up to 10 carbon atoms. In addition, ethylenically unsaturated hydrocarbons are ethene and α-olefins such as propene, 1-butene, isobutene, 1-hexene, 1-octene Aryl aliphatic groups containing aryl substituents on aliphatic or other aliphatic molecules, such as aryl substituents on ethylenically unsaturated carbon atoms. Examples of the aryl aliphatic hydrocarbons in the ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene, and m-isopropyl styrene. Polyketone resins preferably used in the present invention are copolymers of carbon monoxide and ethene or second ethylenically unsaturated hydrocarbons having at least three carbon atoms with carbon monoxide and ethene, in particular α-olefins such as propene. Terpolymers.

When the polyketone terpolymer is used as the main polymer component of the composition of the present invention, for each unit containing the second hydrocarbon moiety in the terpolymer, there are at least two units containing the ethylene moiety. It is preferable that there are 10-100 units containing a 2nd hydrocarbon part.

In one embodiment, the preferable polyketone resin of this invention is a copolymer which consists of repeating units represented by following General formula (1) and (2), It is preferable that y / x is 0.1-0.3. If the value of the y / x value is less than 0.1, there is a problem of poor meltability and workability, and if it exceeds 0.3, the mechanical properties may be inferior.

-[-CH ₂ CH ₂ -CO] x- (1)

-[-CH ₂ -CH (CH ₃ ) -CO] y- (2)

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

The polyketone resin preferably has a number average molecular weight of 100 to 200,000, or 20,000 to 90,000, measured by gel permeation chromatography. The physical properties of the polyketone resin depend on the molecular weight, the polymer being the copolymer or the terpolymer, and in the case of the terpolymer the properties of the second hydrocarbon moiety present. The melting point of the total polyketone resin used in the present invention is 175 ° C to 300 ° C, or generally 210 ° C to 270 ° C.

The ultimate viscosity number (LVN) of polyketone resin measured at 60 ° C. using a standard tubular viscosity measuring device and HFIP (Hexafluoroisopropylalcohol) is 0.5dl / g to 10dl / g, more preferably 0.8dl / g to 4dl / g More preferably, they are 1.0 dl / g-2.0 dl / g. At this time, if the intrinsic viscosity number is less than 0.5dl / g, the mechanical properties are inferior, and if it exceeds 10dl / g, there is a problem of poor workability.

In addition, the molecular weight distribution of the polyketone resin may be 1.5 to 2.5, more preferably 1.8 to 2.2. If the molecular weight distribution is less than 1.5, the polymerization yield is inferior, and if it is 2.5 or more, there is a problem in inferior moldability. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of palladium catalyst and polymerization temperature. That is, when the amount of the palladium catalyst increases or the polymerization temperature is 100 ° C. or more, the molecular weight distribution is increased.

The content of the polyketone resin is 80 to 98% by weight based on 100% by weight of the total composition. If the content is less than 80% by weight, the impact strength and heat resistance are lowered, so that cracks are easily generated due to external impact when used as an exterior material. In addition, since the flame retardant content is increased, the flame retardant is precipitated on the surface of the product during molding, resulting in surface defects, and the price competitiveness is lowered due to the cost increase during the manufacture of the product, which is not preferable. And, if the content exceeds 98% by weight, the impact strength and heat resistance is excellent, but the flame retardancy is reduced, when used as an exterior material can not minimize the damage in case of fire.

As a method for producing a polyketone resin, a liquid phase polymerization may be employed in which an alcohol solvent is carried out under an alcohol solvent through a catalyst composition consisting of a carbon monoxide and an olefin with a palladium compound, an acid having a pKa of 6 or less, and a diligand compound of phosphorus. The polymerization reaction temperature is preferably 50 to 100 ° C. and the reaction pressure is 40 to 60 bar. The polyketone resin is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

As the palladium compound, palladium acetate is preferable, and the amount of use thereof 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 one embodiment, trifluoroacetic acid is used and the amount used may be 6-20 equivalents to palladium. In addition, 1,3-bis [di (2-methoxy phenylphosphino)] propane is preferable as a bidentate coordination compound of phosphorus, and the use amount is preferably 1 to 1.2 equivalents relative to palladium.

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

Carbon monoxide, ethylenically unsaturated compounds and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, in particular repeating units derived from carbon monoxide and repeating units derived from ethylenically unsaturated compounds and repeating units derived from propylene unsaturated compounds Polyketones of alternating interconnection are excellent in mechanical and thermal properties, have excellent processability, high wear resistance, chemical resistance and gas barrier properties, and are useful materials for various applications. High molecular weight copolymers of two- or three-copolymer polyketones are considered to be useful as engineering plastic materials having higher processability and thermal properties and excellent economic efficiency. In particular, the wear resistance is high, and parts such as gears of automobiles and chemical resistance are high, and the gas barrier properties, such as lining material of chemical transport pipe, are high, so that it can be used for light gasoline tanks and the like.

In addition, when the ultra high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fibers, the fibers can be stretched at a high magnification and have a high strength and a high modulus of elasticity oriented in the stretching direction. It is very suitable for building materials and industrial materials.

The process for producing polyketones is characterized by the presence of an organometallic complex catalyst consisting of a ligand having an element of (a) Group 9, Group 10 or Group 11, and (b) Group 15. In the method for producing polyketone by terpolymerization 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 form a linear terpolymer, the mixture 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 the water in the mixed solvent is less than 2 parts by weight of ketal may form a thermal stability during the process, if more than 10 parts by weight may lower the mechanical properties of the product.

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

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

Examples of the Group 10 transition metal compound include a complex of nickel or palladium, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, and 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, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include copper acetate, trifluoroacetate, copper acetylacetate, silver acetate, Silver trifluoroacetic acid, silver acetyl acetate, silver trifluoromethane sulfonic acid, etc. are mentioned.

Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and preferred transition metal compounds (a) in terms of yield and molecular weight of polyketones are palladium compounds, and in terms of improving catalytic activity and intrinsic viscosity. Most preferably, palladium acetate is used in the process.

Examples of the ligand (b) having a group 15 atom include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picolin , Nitrogen ligands such as 2,2'-bikinolin, 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 ) Pinospino] propane, 1,3-bis [di (2-methoxy-4-sulfonic acid-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-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) Spinosyns; there may be mentioned a ligand, such as propane.

Among these, the ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and in particular, a phosphorus ligand having a yield of polyketone is preferably 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 molecular weight of the polyketone. Di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) phosphino] propane, and do not require an organic solvent in terms of safety Water-soluble 1,3-bis [di (2-methoxy-4-sulfonate-phenyl) phosphino] propane, 1,2-bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino ] Methyl] benzene, the synthesis | combination is easy, it is available in large quantities, and economically preferable is 1, 3-bis (diphenyl phosphino) propane and 1, 4-bis (diphenyl phosphino) butane. 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).

((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) of Formula 1 is a polyketone introduced to date Activity equivalent to 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, known to exhibit the highest activity in the polymerization catalyst The structure is simpler and has a lower molecular weight. As a result, the present invention is able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst in the art while further reducing the production cost and cost. The method for preparing a ligand for a 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 Provided is a method for producing a ligand for a polyketone polymerization catalyst, characterized by obtaining -1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine). . 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 synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in bulk.

In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst of the present invention is (a) adding bis (2-methoxyphenyl) phosphine and dimethyl sulfoxide (DMSO) to a reaction vessel under 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 mixture, followed by stirring to react; (c) adding and stirring methanol after completion of the reaction; (d) adding toluene and water, washing the oil layer with water after separating the layers, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue is recrystallized under methanol ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) It can be performed through;

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

In addition, the addition of benzophenone during the polymerization of polyketones is another feature. In the present invention, it is possible to achieve the effect of improving the intrinsic viscosity of the polyketone by adding benzophenone during the 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 the transition metal and benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory. If the molar ratio of the transition metal and benzophenone is greater than 1: 100, the polyketone catalytic activity produced 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 esters, such as ethyl acrylate and methyl acrylate, etc. are mentioned. Among these, preferable ethylenically unsaturated compounds are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, most preferably ethylene, and 1 to 20 mol% propylene is added in the production of terpolymer copolyketones.

Ternary copolymerization of carbon monoxide with the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex comprising a Group 9, Group 10 or Group 11 transition metal compound (a) and a ligand (b) having an element of Group 15 As a result of the catalyst, the catalyst is produced by contacting the two components. Arbitrary methods can be employ | adopted as a method of making it contact. That is, you may make and use the solution which mixed two components previously in a suitable solvent, and may respectively supply two components separately to a polymerization system, and may contact them in a polymerization system.

The present invention may further include conventionally known additives such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials to improve processability and physical properties of the polymer.

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 are used. The polymerization may be either batchwise or continuous. The reactor used for superposition | polymerization can use a well-known thing as it is or processing it. There is no restriction | limiting in particular about polymerization temperature, Generally 40-180 degreeC, Preferably 50-120 degreeC is employ | adopted. Although there is no restriction | limiting also in the pressure at the time of superposition | polymerization, Usually, they are normal pressure-20 MPa, Preferably they are 4-15 MPa.

Linear alternating polyketones are formed by the polymerization method as described above.

On the other hand, the flame-retardant resin polyketone resin composition of the present invention contains a non-halogen phosphorus-based flame retardant. The flame retardant preferably comprises a phosphorus flame retardant comprising an aluminum salt and a phosphorus flame retardant comprising a zinc salt. Specifically, the type of phosphorus-based flame retardant used may include phosphate, phosphonate, phosphinate, phosphine oxide, phosphazene, and the like. Phosphorus-based flame retardants containing aluminum salts include aluminum diethyl phosphinate, and phosphorus-based flame retardants containing zinc salts include zinc diethyl phosphinate.

In one embodiment, the phosphorus flame retardant comprising aluminum and the phosphorus flame retardant comprising zinc salt may be used together, in which case the weight ratio is preferably 3: 7 to 7: 3. If the weight ratio is less than 3: 7, there is a problem (disadvantage) that the flame retardant performance is poor, and if the weight ratio exceeds 7: 3, there is a problem (disadvantage) that the processing stability is poor.

The flame retardant is more than 3 to less than 15% by weight, preferably 6 to 12% by weight, based on 100% by weight of the total flame retardant polyketone resin composition. If the content of the flame retardant is 3 wt% or less, the flame retardancy is lowered, and if the content of the flame retardant is 15 wt% or more, the flame retardancy is excellent but the price may increase and mechanical properties may be reduced.

Hereinafter, the manufacturing method for producing the flame retardant polyketone resin composition of the present invention is as follows.

Method for producing a flame retardant polyketone composition according to the present invention comprises the steps of preparing a polyketone resin; And mixing and extruding the polyketone resin with a flame retardant to prepare a composition. In one embodiment, preparing the polyketone resin comprises preparing a catalyst composition comprising an acid and a ligand compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; And removing the catalyst composition remaining in the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin, but is not limited thereto.

At this time, the extrusion temperature is 230 ~ 260 ℃, screw rotation speed is preferably in the range of 100 ~ 300rpm. If the extrusion temperature is less than 230 ℃ kneading may not occur properly, if it exceeds 260 ℃ may cause problems with the heat resistance of the resin. In addition, if the screw rotational speed is less than 100rpm may not occur smooth kneading, if it exceeds 300rpm plasticizer is volatilized may require a decrease in flexibility.

Hereinafter, specific examples will be presented to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the examples.

<Example 1>

In the presence of a catalyst composition consisting of palladium acetate, anion of trifluoroacetic acid and 1,3-bis [diphenylphosphino] propane, a linear terpolymer of carbon monoxide, ethylene and propylene was added to 100 parts by weight of methanol. It polymerized in the solvent of 70-90 degreeC to which the negative water was added. Melting point of the prepared terpolymer was 210 ℃, intrinsic viscosity (LVN) measured in 1,1,1,3,3,3-HFIP was 2.1 dl / g.

Using a 90 wt% of the prepared terpolymer (polyketone resin), 6 wt% of aluminum phosphinate flame retardant, 4 wt% of zinc phosphinate flame retardant, pellets with a coaxial twin screw extruder having a diameter of 40 mm and L / D = 32 (pellet) and dried in an 80 ° C. oven for 12 hours, and then injected into an injection machine under a cylinder portion of 220 to 240 ° C., a mold temperature of 80 ° C., and a pressure of 60 kg / cm 2 to evaluate mechanical properties, flame retardancy test specimens, and injection processing stability. A test specimen was prepared.

<Example 2>

An evaluation specimen was prepared in the same manner as in Example 1 except that 4 wt% of aluminum phosphinate flame retardant and 6 wt% of zinc phosphinate flame retardant were used.

Comparative Example 1

An evaluation specimen was prepared in the same manner as in Example 1 except that 90 wt% of the terpolymer and 10 wt% of the aluminum phosphinate flame retardant were used.

Comparative Example 2

Evaluation specimens were prepared in the same manner as in Example 1, except that 90 wt% of the terpolymer of Example 1 and 10 wt% of the melamine phosphate flame retardant were used.

Experimental Example 1

Tensile Strength Test

Tensile strength tests were conducted according to ISO 527.

<Flammability UL-94V test>

The test piece of 127 mm in length, 12.7 mm in width, and 1.6 mm in thickness was held vertically, and after the flame of the burner was flamed for 10 seconds at the lower end, the burner was removed, and the time that the fire ignited on the test piece was measured. Next, the second infection was performed for 10 seconds at the same time as the fire was turned off, and the time when the ignited fire was turned off was measured in the same manner as the first.

Moreover, it evaluated simultaneously whether the surface under a test piece was ignited by falling embers. From the first and second combustion times and the presence of ignition, the combustion was ranked according to the UL-94V specification. As for the combustion rank, V-O is the best and flame retardance falls as it becomes V-1 and V-2.

Injection retention stability test

The mold used in this test uses a cochlear mold having a length of 500 mm, a width of 10 mm, and a thickness of 1.5 mm. When the specimen is ejected several times by the normal injection method and the specimen of a certain length comes out, the length of the specimen is measured (L1). After weighing until just before the injection step, the injection molding machine is stopped for 30 minutes in the state before injection into the mold and waits. After molten resin stays in the injection machine for 30 minutes, it is injected into a mold 2-3 times to measure the length of the produced specimen (L2). L2 / L1x100% and the viscosity rise degree of the resin which stayed are confirmed. The closer to 100%, the better the heat-resistant processing stability of the resin, and the closer to 0%, the higher the viscosity increase and the higher carbonization.

The results of the experiments are shown in Table 1 below.

As a result, in comparison with the resin of Comparative Example 2 using 10% by weight of the existing flame retardant, Examples 1 and 2 using the phosphorus-based flame retardant containing the metal salt (aluminum salt and zinc salt) of the present invention increased the tensile strength , Flame retardant grades of Example 1 and 2 both show a V-0 having a high flame retardance at the same content. In addition, when the molten resin stayed in the injection machine at 240 ℃, the length of the injected specimen was increased compared to the resin of Comparative Example 2 using a conventional flame retardant, it was found that the heat resistance stability value of the prepared resin significantly increased Can be. Furthermore, in the case of Comparative Example 1 using only a phosphorus-based flame retardant containing aluminum salt, the flame retardancy grade was V-O, but the tensile strength was low, and the heat resistance was particularly low.

Experimental Example 2

Specimens were prepared according to Example 1, except that 91 wt% of terpolymer (polyketone resin) and 8 wt% of each of the materials described in Table 2 were used as the phosphorus flame retardant. The physical properties of the prepared specimens were examined and shown in Table 2 below. Flexural modulus was performed according to ISO 178.

Phosphorus Flame Retardant Content (wt.%) Tensile Strength (MPa) Flexural modulus (MPa) Flame retardant
(Based on 0.8mm thickness specimen) 240 ℃
Heat stability Aluminum
diethyl phosphinate 8 53 1780 V0 33% Triphenyl phosphineoxide 8 51 950 V2 15% Triphenyl phosphate 8 52 1110 V0 47%

As a result, when triphenyl phosphine oxide was used as the phosphorus-based flame retardant, mechanical properties such as low flexural modulus were lowered, flame retardancy was also low as V2, and heat stability was insufficient. In addition, when triphenyl phosphate was used, the flame retardancy was excellent, but the mechanical properties decreased. Furthermore, when aluminum diethyl phosphinate, which is a case where only a phosphorus-based flame retardant containing aluminum was used, a low heat stability was shown.

Experimental Example 3

Specimens were prepared according to Example 1, except that 10 wt% of the combination of each of the materials described in Table 3 was used as the phosphorus flame retardant. The physical properties of the prepared specimens were examined and shown in Table 3 below. For example, (Al 8% + Zn 2%) is a combination of 8% by weight aluminum phosphinate flame retardant and 2% by weight zinc phosphinate flame retardant.

Main additives Al 10% Al 8% + Zn 2% Al 6% + Zn 4% Al 5% + Zn 5% Al 4% + Zn 6% Al 2% + Zn 8% Zn 10% The tensile strength ISO 527 MPa 48 51 52 48 50 51 53 Flexural modulus ISO 178 MPa 1708 1684 1670 1611 1590 1570 1524 Flame retardant UL-94 class V0 V0 V0 V0 V0 V2 No flame retardancy Injection processing stability 0min mm 328 361 347 355 351 378 473 30min mm 108 181 289 317 302 325 389 Heat stability % 32.9 50.1 83.3 89.3 86.0 86.0 82.2

As a result of the experiment, when 10% by weight of aluminum phosphinate flame retardant was used, and when 8% by weight of aluminum phosphinate flame retardant and 2% by weight of zinc phosphinate flame retardant were used, the value of heat stability was very low. In addition, the use of 2% by weight of aluminum phosphinate flame retardant and 8% by weight of zinc phosphinate flame retardant was found to be very poor in flame retardancy as V2. On the other hand, the tensile strength of the remaining three cases (Al 6% + Zn 4%, Al 5% + Zn 5%, Al 4% + Zn 6%) with an appropriate ratio of aluminum phosphinate flame retardant and zinc phosphinate flame retardant And mechanical properties such as flexural modulus, flame retardancy and heat stability were excellent.

Experimental Example 4

Specimens were prepared according to Example 1, except that aluminum phosphinate flame retardants were used in the respective amounts set forth in Table 4 below as phosphorus flame retardants. For reference, the content of the terpolymer (polyketone resin) was adjusted according to the content of the flame retardant used. The physical properties of the prepared specimens were examined and shown in Table 4 below.

Main additives Al 3% Al 6% Al 10% Al 13% Al 15% The tensile strength ISO 527 MPa 55 54 53 49 45 Flexural modulus ISO 178 MPa 1642 1684 1708 1845 2010 Flame retardant UL-94 class V2 V0 V0 V0 V0 Manufacturing cost small Small medium company versus

Experimental results showed that the flame retardant grade was V2 when the phosphorus flame retardant was used at 3% by weight, and that the flame retardancy was very poor.

Claims (6)

Polyketone resins; And
A flame retardant comprising aluminum diethyl phosphinate and zinc diethyl phosphinate in a weight ratio of 3: 7 to 7: 3,
The content of the flame retardant is more than 3 to less than 15% by weight based on 100% by weight of the total composition,
The polyketone resin is a flame-retardant polyketone resin composition of the polyketone copolymer consisting of repeating units represented by the following general formula (1) and (2) y / x of 0.1 to 0.3 linear alternating polyketone.
-[-CH ₂ CH ₂ -CO] x- (1)
-[-CH ₂ -CH (CH ₃ ) -CO] y- (2)
(x, y represents each mol% of General Formula (1) and (2) in a polyketone resin.) delete delete delete delete Preparing a polyketone resin; And
Method of producing a flame retardant polyketone resin composition according to claim 1, comprising the step of mixing the polyketone resin with a flame retardant.