KR101725812B1 - Flame retardant polyketone composition - Google Patents

Abstract

The present invention relates to a flame retardant polyketone composition, and more particularly, to a flame retardant polyketone composition which contains a phosphorus-based flame retardant as a flame retardant in a polyketone resin, The present invention relates to a flame retardant polyketone composition which is excellent in mechanical properties and thermal deformation temperature characteristics and does not deteriorate in physical properties of a resin due to the addition of a flame retardant agent and thus can be used as a casing for home appliances and as an exterior material for automobile interior decorations.

Description

FIELD OF THE INVENTION The present invention relates to flame retardant polyketone compositions,

FIELD OF THE INVENTION The present invention relates to a flame retardant polyketone composition, and more particularly, to a flame retardant polyketone composition prepared by using a blend including a polyketone resin and a flame retardant and applicable as an industrial component.

Thermoplastic polymers are predominantly processed in molten state. No polymer is resistant to changes associated with structure and state without any change in its chemical structure. Cross-linking, oxidation, molecular weight changes, and consequent changes in physical and industrial properties can also result. To reduce the stresses on the polymers during processing, different additives are added according to the polymer.

Different additives are often used at the same time, each of which takes on a particular task. For example, antioxidants and stabilizers can be used to allow the polymer to withstand processing without chemical damage and then to have stability for external effects such as heat, UV light, weathering, and oxygen (air) Is used. In addition to improved flow properties, the lubricant prevents the polymer melt from being excessively attached to high temperature mechanical components and acts as a dispersant for pigments, fillers and reinforcing agents

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

Especially for thermoplastic polymers, phosphinic acid salts (phosphinates) have been found to be effective flame retardant additives (DEA-2 252 258 and DE-A-2-447 727). Calcium phosphinates and aluminum phosphinates are described as being particularly effective in polyesters and impair the material properties of the polymer molding compositions to a lesser extent than, for example, alkali metal salts (EP-A-0 699 708). In addition, synergistic combinations of specific nitrogen-containing compounds and phosphinates have been found, which have been found to be more effective as flame retardants in all series of polymers than in the case of phosphinate alone (PCT / EP97 / 01664, and also DE -A-19 734 437 and DE-A-19-737-727).

Polymeric molding compositions comprising phosphorus-containing flame retardants can stabilize carbodiimides, isocyanates and isocyanurates (DE-A-19-920 276).

However, the above-mentioned phosphorus-containing flame retardant agent must contain a certain weight ratio or more in order to exhibit flame retardant properties to the thermoplastic polymer, and the cost of the phosphorus-containing flame retardant agent is high.

In addition, Polyketone (PK) is a material that is low in raw material and polymerization process ratio compared with general engineering plastic materials such as polyamide, polyester and polycarbonate. It has excellent properties such as heat resistance, chemical resistance, fuel permeability and abrasion resistance It is widely applied to various industries. For this reason, there is a growing interest in a family of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as polyketones or polyketone polymers. U.S. Patent No. 4,880,903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide, ethylene and terephthalic unsaturated hydrocarbons such as propylene.

The process for preparing the polyketone polymer is generally carried out by reacting a compound of a Group VIII metal selected from among palladium, cobalt or nickel with an anion of a strong halogen-hydrohalogentic acid, , Phosphorus, arsenic, or antimony (Antimon). U.S. Patent No. 4,843,144 discloses a process for producing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon by using a palladium compound, an anion of a nonhydrohalogenic acid having a pKa of less than 6, and a catalyst which is a bidentate ligand Lt; / RTI >

Accordingly, the above-mentioned phosphorus-containing flame retardant is added to the polyketone polymer to produce a thermoplastic polymer having flame retardant properties, and a phosphorus-containing flame retardant is added in a smaller amount than the amount of the phosphorus-containing flame retardant, There is a demand for research on a flame retardant polyketone composition.

The object of the present invention is to provide a flame retardant polyketone composition having flame retardancy that meets international standards while being less expensive than the current material.

The present invention relates to a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), wherein the flame retardant comprises a linear alternating polyketone with y / x of 0.03 to 0.3 and a phosphorus- A polyketone composition is provided.

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

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

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

Further, the phosphorus-based flame retardant of the present invention is a phosphorus-based flame retardant composed of a phosphorus compound selected from at least one group selected from the group consisting of phosphate, phosphonate, phosphinate, phosphine oxide and phosphazene .

In addition, the present invention provides a flame retardant polyketone composition, wherein the phosphorus-based flame retardant is based on 100 wt% of the flame retardant polyketone composition as a whole, and 2 to 20 wt% do.

The flame retardant polyketone composition of the present invention exhibits the same or better effects while adding a small amount of a flame retardant agent as compared with the nylon 66 material used in the past.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by providing a flame retardant polyketone composition improved in flame retardancy, heat resistance and impact resistance by containing a phosphorus flame retardant in polyketone.

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

The polyketone resin is less hygroscopic than nylon, and it is possible to design various products with less changes in dimensions and physical properties due to moisture absorption. Especially, polyketone resin is more suitable for weight reduction because it has lower density than aluminum material.

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

The production process of polyketone is carried out in the presence of an organometallic complex catalyst comprising (a) a Group 9, 10 or 11 transition metal compound, and (b) a ligand having an element of Group 15, Wherein the carbon monoxide, ethylene and propylene are subjected to liquid phase polymerization in a mixed solvent of an alcohol (e.g., methanol) and water to produce a linear terpolymer, As the solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of water in the mixed solvent is less than 2 parts by weight, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated.

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

Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, sulfonates and the like. Specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, palladium trifluoroacetate , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium and palladium sulfate.

Examples of the Group 11 transition metal compound include copper or silver complexes, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the fluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

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

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

Among these ligands, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of yield of polyketone are 1,3-bis [di (2- Methoxyphenyl) phosphino] propane and 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, Di (2-methoxyphenyl) phosphino] propane, and it is safe in that it does not require an organic solvent. Soluble sodium salts such as 1,3-bis [di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] propane, 1,2- ] Methyl] benzene, and 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred for ease of synthesis and availability in large quantities and economically. The preferred ligand (b) having a Group 15 atom is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) Bis (di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- -Methoxyphenyl) phosphine).

[Chemical Formula 1]

.

.

      Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Activity equivalent to that of 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, which is known to exhibit the highest activity among polymerization catalysts The structure is simpler and has a lower molecular weight. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst of the present invention, while further reducing its manufacturing cost and cost. A method for producing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) -2,3-dioxolane was obtained by using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) is obtained by reacting a bis (methylene) . The process for preparing a ligand for a polyketone polymerization catalyst according to the present invention is a process for producing a ligand for a polyketone polymerization catalyst which comprises reacting 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in a large amount.

      In a preferred embodiment, the process for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under nitrogen atmosphere, Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the resulting mixture, followed by stirring and reacting; (c) adding methanol and stirring 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) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And a step of acquiring the image data.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies depending on the kinds of the ethylenic and propylenically unsaturated compounds to be selected and other polymerization conditions. Therefore, But it is usually 0.01100 millimoles, preferably 0.0110 millimoles per liter of the capacity of the reaction zone. The capacity of the reaction zone means the liquid phase capacity of the reactor. The amount of the ligand (b) to be used is not particularly limited, but is usually 0.13 mol, preferably 13 mol, per 1 mol of the transition metal compound (a).

Further, the addition of benzophenone in the polymerization of the polyketone is another characteristic. In the present invention, an effect of improving the intrinsic viscosity of the polyketone can be achieved by adding benzophenone in the polymerization of the polyketone. The molar ratio of (a) the ninth, tenth, or eleventh transition metal compound to benzophenone is 1: 5-100, preferably 1:40-60. If the molar ratio of the transition metal to the benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the produced polyketone is unsatisfactory. If the molar ratio of the transition metal to the benzophenone exceeds 1: 100, It is not preferable 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, -Olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclodecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Ethyl acrylate, and acrylates such as methyl acrylate. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, most preferably ethylene, and 120 mol% propylene is added in the production of the terpolymerized polyketone.

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

As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a vapor phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution, and the like are used. The polymerization may be either batchwise or continuous. The reactor used in the polymerization can be used as it is or in a known manner. The polymerization temperature is not particularly limited, and is generally 40 to 180 占 폚, preferably 50 to 120 占 폚. The pressure at the time of polymerization is not particularly limited, but is generally from normal pressure to 20 MPa, preferably from 4 to 15 MPa.

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

On the other hand, the polyketone polymer of the present invention is a line-by-line alternating structure and substantially contains carbon monoxide per one molecule of unsaturated hydrocarbon. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers have up to 20 carbon atoms, preferably up to 10 carbon atoms. Ethylenically unsaturated hydrocarbons can also be selected from the group consisting of ethene and alpha-olefins such as propene, 1-butene, iso-butene, 1- hexene, 1- octene, , Or an aryl aliphatic group containing an aryl substituent on another aliphatic molecule, particularly containing an aryl substituent on an ethylenically unsaturated carbon atom. Examples of aryl aliphatic hydrocarbons in 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 carbon monoxide, ethene and at least three carbon atoms, in particular alpha-olefins such as propene Is a terpolymer.

When the polyketone terpolymer is used as the main polymer component of the blend of the present invention, there are at least two units containing an ethylene moiety in each unit containing the second hydrocarbon moiety in the terpolymer. It is preferable that the number of units containing the second hydrocarbon moiety is from 10 to 100.

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

(2)

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

In the above formula (2), G is an ethylenically unsaturated hydrocarbon, particularly an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is at least 1: 0.01.

In another embodiment, the polyketone polymer is a copolymer comprising repeating units represented by the general formulas (1) and (2), and y / x is preferably 0.03 to 0.3. When the value of the y / x value is less than 0.03, there is a limit in that the meltability and processability are inferior. When the value of y / x is more than 0.3, the mechanical properties are poor. Further, y / x is more preferably 0.03 to 0.1.

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

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

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

Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (hexafluoroisopropyl alcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g, And more preferably 1.0 dl / g to 2.0 dl / g. If the intrinsic viscosity is less than 0.5 dl / g, the mechanical properties are deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability is deteriorated.

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. When the ratio is less than 1.5, the polymerization yield decreases. When the ratio is 2.5 or more, the moldability is poor. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger.

The content of the polyketone resin is 80 to 98% by weight based on the total composition. If the content of the polyketone resin is less than 80% by weight, the impact strength and the heat resistance are lowered. Further, since the content of the flame retardant is increased, the flame retardant is precipitated on the surface of the product during molding, resulting in surface defects, and the price competitiveness due to an increase in the cost in manufacturing the product is lowered. When the content exceeds 98% by weight, the impact strength and heat resistance are excellent, but the flame retardancy is lowered, so that the damage can not be minimized when a fire is used.

In particular, the flame retardant of the present invention should impart flame retardancy to the polyketone resin, have good compatibility with the resin, and should not affect the mechanical properties of the molded product. In addition, it should be selected after sufficient environmental considerations such as low smoke generation and toxic gas generation during combustion

Specifically, the flame retardant polyketone composition of the present invention is composed of a blend composed of a combination of a polyketone and a phosphorus flame retardant, and is characterized by having flame retardancy, improving impact resistance, lowering the moisture absorption rate and improving the physical property retention rate .

The present invention is characterized by adding a phosphorus-based flame retardant to the polyketone to improve the flame retardancy. The phosphorus-based flame retardant of the present invention is characterized by being 2 to 20% by weight based on the total blend. As a preferred example, the phosphorus-based flame retardant is 2 to 15% by weight based on the total blend, and more preferably 5 to 10% by weight. If the content of the flame retardant is less than 2% by weight, the flame retardancy is lowered. If it exceeds 20% by weight, the flame retardancy is excellent, but the price may increase and the mechanical properties may be deteriorated.

Meanwhile, phosphate, phosphonate, phosphinate, phosphine oxide, and phosphazene may be used as the phosphorus flame retardant specifically used.

In addition, glass fiber (glass fiber), carbon fiber, mica and talc may be added as a reinforcing material to the composition to reinforce mechanical properties. Antioxidants and pigments may also be added as desired. These additives may be suitably used by those skilled in the art. The content may be adjusted to 0 to 30% by weight, 0 to 40% by weight or 0 to 50% by weight based on the whole flame retardant polyketone composition, but is not limited thereto.

Hereinafter, the production method for producing the flame retardant polyketone composition as described above is as follows.

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

As the palladium compound constituting the catalyst composition, palladium acetate can be used, and the amount of the palladium compound used is suitably 10 ^-3 to 10 ^-1 mole.

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

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

The carbon monoxide, ethylene and propylene are liquid phase polymerized in a mixed solvent of alcohol (e.g. methanol) and water to produce 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, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated.

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

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

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

The polyketone composition prepared through the above process can be applied to exterior materials such as housings of home appliances, automobile interior decorations, and industrial parts through bar injection molding and the like, which are excellent in flame retardancy, but are not limited thereto.

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

Example 1

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid with respect to palladium is 10 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 78 占 폚 and 84 占 폚 are carried out. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 46 to 4. The melting point of the polyketone terpolymer was 220 占 폚, the LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, the MI index was 60 g / 10 min and the MWD was 2.0.

The phosphorus flame retardant was OP-1314 manufactured by Clariant.

92% by weight of the polyketone terpolymer prepared above and 8% by weight of a phosphorus flame retardant were blended to prepare a flame retardant polyketone composition.

Example 2

Except that 95% by weight of a polyketone terpolymer and 5% by weight of a phosphorus-based flame retardant were used.

Example 3

70% by weight of a polyketone terpolymer and 20% by weight of a phosphorus-based flame retardant were used.

Examples 4 to 5

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

Comparative Example 1

82 weight% of Rhodda PA66 (product of A218V30) and 18 weight% of Clariant OP-1314 were used.

Property evaluation

The prepared flame retardant polyketone compositions of the above Examples were prepared as test pieces, and the properties were evaluated by the following methods in comparison with the products of Comparative Examples. The results are shown in Table 1 below.

Table 1 shows the results.

1. Impact strength (NOTCHED IZOD, KJ / m 2): ASTM D-256.

2. Heat distortion temperature (占 폚): ASTM D-648.

3. Evaluation of flame retardancy: The test was carried out in accordance with UL94.

Item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Izod impact strength
(KJ / m2) 10.00 11.00 9.00 0.95 10.30 5.00 Heat distortion temperature
(° C) 105 102 107 104.5 105.2 65 Flammability evaluation
(UL94, 1/16 ") V-0 V-0 V-0 V-0 V-0 V-0

As shown in Table 1, in the case of Examples, the impact strength was superior to that of Comparative Example 1, and the flame retardancy characteristics were equal to or higher than those of Comparative Example 1.

Therefore, the flame retardant thermoplastic plastic composition prepared through the examples was more suitable for use as a flame retardant thermoplastic plastic composition that exhibits excellent flame retardancy while using a small amount of phosphorus flame retardant.

Claims (5)

A flame retardant polyketone composition comprising a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), wherein the ratio y / x is 0.03 to 0.3,
Based flame retardant is 2 to 20% by weight based on 100% by weight of the flame-retardant polyketone composition as a whole,
The flame retardant polyketone composition does not contain glass fibers or contains glass fibers in an amount of more than 0 wt% to 50 wt%
The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is preferably selected from the group consisting of bis (2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) ) Phosphine). ≪ / RTI >
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
(x and y represent mol% of each of the general formulas (1) and (2) in the polymer).
The method according to claim 1,
Wherein the phosphorus flame retardant is a phosphorus-based flame retardant comprising at least one phosphorus compound selected from the group consisting of phosphate, phosphonate, phosphinate, phosphine oxide and phosphazene. .

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