KR20190088229A - Highly heat-resistant polyketone composition with improved color - Google Patents

Abstract

The present invention relates to a high heat-resistant polyketone composition having an improved color. Specifically, the present invention relates to a polyketone composition having excellent long term heat resistance and the improved color by comprising linear alternating polyketone, a polymer having an amide group, rubber, a silicone oil, and zinc oxide.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a high heat resistant polyketone composition having improved color,

The present invention relates to a high heat resistant polyketone composition having improved color, and more particularly, to a high heat resistant polyketone composition having improved impact resistance and long term heat resistance by including a polyketone, a polymer having an amide group, a rubber, and zinc oxide (ZnO) Heat-resistant polyketone compositions having improved color and automobile connector parts made therefrom.

Polyketone (PK) is superior to general engineering plastic materials such as polyamide, polyester, and polycarbonate because it has excellent properties such as heat resistance, chemical resistance, fuel permeability and abrasion resistance, Have been widely applied. However, in spite of the superiority of the polyketone material, it is required to have improved physical properties in accordance with the application as it is diversified in use with strict environmental regulation, and in particular, Heat-resistant stability that can withstand heat and strong impact resistance are required.

As a countermeasure thereto, it is possible to improve the long-term heat resistance by adding additives such as a heat-resistant stabilizer to polyketone. However, when a conventional heat-resistant stabilizer is used, the color of the resin becomes dark due to the addition of additives, There is a problem that application is restricted.

On the other hand, there is a growing interest in line-by-line alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon known as polyketone 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, there is a demand for research on a polyketone composition which is resistant to impact and has long-term heat resistance so that it can be applied to various applications.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a polyketone which is excellent in long-term heat resistance and improved in color by mixing a polymer having an amide group, a rubber, a silicone oil, and zinc oxide Heat-resistant polyketone composition, and a vehicle connector made of the same.

The high heat resistant polyketone composition having improved color according to embodiments of the present invention is a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), wherein y / x is 0.03 to 0.3 An alternating polyketone, an amide group-containing polymer, rubber, and zinc oxide.

- [- 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 polyketone composition may include 44 to 61% by weight of the polyketone, 26 to 43% by weight of the amide group-containing polymer, 5 to 20% by weight of the rubber, and 0.05 to 2% by weight of the zinc oxide.

When the degree of whiteness of the polyketone composition is measured, the color difference (? E) of the polyketone composition containing no zinc oxide may be 5.0 or less.

The tensile strength of the polyketone composition measured after aging for 42 days in an oven maintained at 145 캜 was 80% or more as compared with the tensile strength measured before the aging, and the impact strength retention ratio was 20% or more have.

In addition, the present invention provides a vehicle connector made of the high heat resistant polyketone composition

The high heat resistant polyketone composition having improved color of the present invention can be applied to a field requiring high heat resistance grades and various colors at the same time while maintaining long-term mechanical stiffness retention in a high temperature use environment. Therefore, it can be applied to a variety of applications such as automobile junction block, band cable, chain guide, radiator end tank, engine cover, harness protector for electric wire, air intake manifold, There is an advantage that it can be widely applied to various industries such as automobile connector such as vehicle connector which requires color, cable tie, electric / electronic field bracket, various frames of office equipment, and industrial material such as electric / electronic parts.

Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited to these.

The present invention provides a high heat-resistant polyketone composition having improved long term heat resistance and improved color by containing polyketone, a polymer having amide group, rubber, and zinc oxide.

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 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. In addition, polyketone resin has lower moisture absorption than polyamide material, so it is possible to design various products with less changes in dimensions and physical properties due to moisture absorption. Polyketone resin is very suitable for weight reduction because it has lower density than aluminum material. Do. Particularly, polyketone is a material having strong molecular bonding as compared with polyethylene and has a melting point higher than that of polyethylene by about 100 ° C, which is superior in strength to polyethylene and excellent in heat stability.

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 an example of 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. Preferable examples of the mixed solvent may be prepared by using a mixed solvent comprising 70 to 90% by volume of acetic acid and 10 to 30% by volume of water as a liquid medium and adding benzophenone during polymerization. When a mixed solvent composed of acetic acid and water is used as the liquid medium without using methanol, dichloromethane or nitromethane, which has been conventionally used for producing polyketones, the production cost of polyketones can be reduced and the catalytic activity can be improved Can have excellent effect. When a mixed solvent of acetic acid and water is used as a liquid medium, when the concentration of water is less than 10% by volume, the activity is less affected by the catalytic activity, but when the concentration is 10% by volume or more, the catalytic activity increases sharply. On the other hand, when the concentration of water exceeds 30% by volume, the catalytic activity tends to decrease. Therefore, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 10 to 30% by volume of water as a liquid medium.

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.

Meanwhile, it is also preferable to use bis (bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diylbis (methylene)) bis as the ligand used in the polymerization catalyst. As follows.

The above (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine ligand can be synthesized through the following four steps. First, diethyl malonate, After 5-dibromopentane was boiled with sodium ethoxide and ethanol, 1,1-cyclohexane dimethanol was synthesized by reduction under lithium aluminum hydride and tetrahydrofuran, and then reacted with tosyl chloride in pyridine to yield The ligand can be obtained by reacting it with 2-methoxyphenylphosphine and sodium hydride under dimethylsulfoxide. Each step is subjected to purification steps such as column chromatography and recrystallization, Purity can be confirmed by nuclear magnetic resonance analysis.

On the other hand, it is preferable that the ligand is used singly as a single site, but it is also preferable that the ligand has a multi-site.

(2)

As the model of the multi-site polymerization catalyst, the ligand preferably used is 1,3-bis [non-2- (methoxyphenyl) phosphino] propane, (2,2- Polyketone polymerization comprising a ligand having a multi-site structure of one or two kinds selected from the group consisting of bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) The use of a ligand having a multi-site as compared with the use of a single-site ligand reduces the occurrence of fouling that grows on the inner wall of the reactor during polyketone polymerization .

[constitutional formula]

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 from 0.01 to 100 mmol, preferably from 0.01 to 10 mmol, per 1 liter 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 0.1 to 3 mol, preferably 1 to 3 mol, per 1 mol of the transition metal compound (a).

In addition, benzophenone can be added during the polymerization of the polyketone. The addition of benzophenone to the polymerization of the polyketone can achieve an effect of improving the intrinsic viscosity 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 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.

Here, it is preferable to adjust the charging ratio of the carbon monoxide and the ethylenic unsaturated compound to 1: 1 to 2 (molar ratio) and to adjust the propylene to 1 to 20 mol% based on the total mixed gas. In the production of polyketones, it is general to set the ratio of the carbon monoxide and the ethylenic unsaturated compound to be 1: 1. However, when a mixed solvent of acetic acid and water is used as the liquid medium and benzophenone is added during polymerization, carbon monoxide and an ethylenic unsaturated compound Is adjusted to 1: 1 to 2 and the propylene is adjusted to 1 to 20 mol% based on the total mixed gas, not only the processability is improved but also the catalytic activity and the intrinsic viscosity are simultaneously improved. When the amount of propylene is less than 1 mol%, the effect of the ternary copolymerization to lower the melting temperature can not be obtained. When the amount exceeds 20 mol%, the intrinsic viscosity and the improvement of the catalytic activity are inhibited, so that the addition ratio is adjusted to 1 to 20 mol% .

In addition, in the process, a mixed solvent of acetic acid and water is used as a liquid medium, benzophenone is added during polymerization, and carbon monoxide, an ethylenic unsaturated compound and one or more olefinic unsaturated compounds are introduced, whereby the catalytic activity and intrinsic viscosity But it is possible to manufacture a terpolymer of polyketone having a high intrinsic viscosity only in a polymerization time of about 12 hours, as opposed to a polymerization time of at least 10 hours in order to improve intrinsic viscosity.

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.

In the present invention, conventionally known additives such as an antioxidant, a stabilizer, a filler, a refractory material, a releasing agent, a coloring agent, and other materials may be further added to improve the processability and physical properties of the polymer.

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 can be 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 according to the above-described production process.

On the other hand, the polyketone polymer of the present invention is a linear alternating structure and substantially contains carbon monoxide for each unsaturated hydrocarbon molecule. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers include ethynes with up to 20 carbon atoms, preferably up to 10 carbon atoms, alpha -olefins (e.g., propene, 1-butene, ), Aliphatic hydrocarbons such as isobutene, 1-hexene and 1-octene, or aryl aliphatic hydrocarbons having an aryl substituent on the aliphatic molecule, in particular ethylenically unsaturated carbon atoms Lt; / RTI > is an aryl aliphatic hydrocarbon in which an aryl substituent is formed. Examples of the aryl aliphatic hydrocarbon in the ethylenic unsaturated hydrocarbon include styrene, p-methylstyrene, p-ethylstyrene, and m-isopropyl styrene. The polymer preferably used in the present invention is a linear terpolymer of alpha-olefins such as carbon monoxide, ethene and a second ethylenically unsaturated hydrocarbon having at least three carbon atoms (especially propene).

When the polyketone terpolymer is used as the main polymer component of the composition of the present invention, it is preferable that at least two units containing an ethylene moiety are contained in each unit containing the second hydrocarbon moiety in the terpolymer, 2 < / RTI > of hydrocarbon units.

In one embodiment, the polyketone polymer may include a unit represented by the following formula (3) as a repeating unit.

(3)

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

In the above formula (3), G is an ethylenically unsaturated hydrocarbon, particularly a portion obtained from an ethylenically unsaturated hydrocarbon having at least three 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 the following 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.

A polyketone polymer having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000, as measured by gel permeation chromatography is particularly preferred. 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 nature of the second hydrocarbon moiety. The melting point of the total of the polymers used in the present invention is 175 to 300 占 폚, and is generally 210 to 270 占 폚. The intrinsic viscosity (IV) of the polymer measured by HFIP (Hexafluoroisopropanol) 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, Preferably 1.0 dl / g to 2.0 dl / g, and still more preferably 1.0 dl / g to 1.4 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 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 decreases. If the molecular weight distribution exceeds 2.5, moldability is deteriorated. The molecular weight distribution can be adjusted in proportion to the amount of the palladium catalyst and / or 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 palladium element in the polyketone of the present invention is preferably 50 ppm or less. When the content of the palladium element exceeds 50 ppm, thermal denaturation and chemical denaturation due to the residual palladium element are liable to occur. In the melt-forming, a phenomenon such as an increase in the melt viscosity and an increase in the viscosity of the dopant when dissolved in a solvent , The workability is poor. Further, since a large amount of palladium element remains in the polyketone molded body obtained after molding, the heat resistance of the molded body is deteriorated. The content of the palladium element in the polyketone is preferably as small as possible from the viewpoint of processability and heat resistance of the molded article, more preferably 10 ppm or less, still more preferably 5 ppm or less, and most preferably 0 ppm.

Specifically, the high heat-resistant polyketone composition having improved color according to the embodiments of the present invention includes a polyketone, a polymer having an amide group, a rubber, and zinc oxide. To 61% by weight.

The high heat-resistant polyketone composition may contain 26 to 43% by weight of a polymer having an amide group in the whole composition. If the content of the amide group-containing polymer is less than 26% by weight, the effect of improving the tensile strength retention can not be sufficiently obtained. If the content is more than 43% by weight, the workability may decrease due to factors such as viscosity increase. By including a polymer having an amide group as a component constituting the composition, the tensile strength retention ratio can be improved. Examples of the amide group-containing polymer that can be used in the present invention include, but are not limited to, polyamide, polyurethane, and the like.

The high heat-resistant polyketone composition of the present invention comprises rubber, and the content thereof may be 5 to 20 wt%, preferably 10 to 13 wt%, of the total composition. When the content of the rubber is less than 5% by weight, the improvement of the impact resistance is not sufficient, and when it exceeds 20% by weight, the mechanical properties may be deteriorated. The impact resistance can be improved by including a rubber as a component constituting the composition. Examples of the rubber that can be used in the present invention include, but are not limited to, ethylene-octene rubber (EOR) such as maleic anhydride grafted ethylene-octene rubber (EOR-MAH).

The high heat-resistant polyketone composition of the present invention contains zinc oxide, and by including zinc oxide, the heat stability is improved while maintaining the brightness of the composition, and the long-term tensile strength and impact strength retention ratio can be improved without hue . Accordingly, the high heat-resistant polyketone composition of the present invention can be easily applied to a field of various colors while demanding long-term heat resistance. Zinc oxide may be contained in an amount of 0.05 to 2% by weight in the total composition. If it is less than 0.05% by weight, it is difficult to obtain a sufficient heat stabilizing effect, and if it exceeds 2% by weight, workability and retention stability may be deteriorated.

The high heat-resistant polyketone composition of the present invention may have a color difference (ΔE) value of 5.0 or lower in comparison with the dyeability of a polyketone composition (when zinc oxide is not applied) which does not contain zinc oxide, when the whiteness degree is measured. When a heat-resistant stabilizer such as copper oxide is added to improve the heat-resistant stability of the polyketone composition, the effect of improving the heat stability is excellent, but the L, a, and b values indicating the whiteness value are greatly changed The color difference (ΔE) value is larger than 40 before copper is applied. However, in the present invention, by applying zinc oxide instead of copper oxide, whiteness can be greatly improved with a color difference (ΔE) value of 5.0 or less as compared with before zinc oxide is applied, while exhibiting excellent heat resistance stability.

The high heat-resistant polyketone composition of the present invention may further contain components other than the above-mentioned components. A preferred example is a silicone oil, and by including a silicone oil, the impact resistance of the composition can be improved. When a silicone oil is included, the silicone oil may be contained in an amount of 0.1 to 1.0% by weight, preferably 0.3 to 0.6% by weight, of the total composition. If the content of the silicone oil is less than 0.1% by weight, the synergistic effect of increasing the wear resistance may be insufficient. If the content of the silicone oil is more than 1.0% by weight, the impact resistance and molding processability of the composition may be deteriorated.

Hereinafter, a method for producing (blending) the high heat resistant polyketone composition having the improved color is as follows.

The polyketone resin obtained by the above method is mixed with a polymer having an amide group, rubber and zinc oxide, and then extruded by an extruder to finally obtain a composition. The blend may be prepared by charging it into a twin-screw extruder and melt-kneading and extruding it. 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.

When the composition is prepared by the above-mentioned method and extrusion molding or injection molding is performed, a high heat-resistant part using the high heat resistant polyketone composition having improved color can be produced.

The high heat resistant polyketone composition having improved color of the present invention has been aged at a temperature of 145 캜 for 42 days (1008 hours) through the composition and the manufacturing method as described above, and then the tensile strength measured before the aging It is possible to exhibit an excellent long term heat resistance with a retention ratio of 80% or more as compared with one tensile strength and a retention ratio of impact strength of 20% or more.

Therefore, the high heat-resistant polyketone composition having improved color of the present invention is suitable for manufacturing in a field requiring long-term heat resistance and various colors, in particular, for automobile parts, and in particular, for manufacturing a connector for vehicle, cable tie and the like.

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]

Linear alternating polyketone terpolymers of carbon monoxide and ethylene and propene are prepared from palladium acetate, trifluoroacetic acid, and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2- methoxyphenyl) The content of trifluoroacetic acid with respect to palladium is 10 times the molar ratio and is subjected to two steps of a first stage at a polymerization temperature of 78 ° C and a second stage at 84 ° C. The polyketone terpolymer The molar ratio of ethylene to propene was 85 to 15. The melting point of the polyketone terpolymer was 220 DEG C and the intrinsic viscosity measured by HFIP (hexafluoroisopropanol) at 60 DEG C was 1.4 dl / g, and the MWD was 2.0.

A polyketone composition was prepared by blending 60.45% by weight of the polyketone terpolymer, 26% by weight of polyamide (PA6), 0.05% by weight of zinc oxide and 0.50% by weight of silicone oil in 13% by weight of EOR rubber, Was made into a pellet on an extruder using a twin screw having a diameter of 40 cm and operating at 250 rpm and L / D = 32.

[Example 2]

Except that 60.4% by weight of polyketone terpolymer, 26% by weight of polyamide (PA6), 0.10% by weight of zinc oxide and 0.50% by weight of silicone oil were blended in 13% by weight of EOR rubber.

[Example 3]

Except that 60.35 wt% of polyketone terpolymer, 26 wt% of polyamide (PA6), 13 wt% of EOR rubber, 0.15 wt% of zinc oxide, and 0.50 wt% of silicone oil were blended.

[Comparative Example 1]

The procedure of Example 1 was repeated except that zinc oxide was not applied and 60.5 wt% of polyketone terpolymer, 26 wt% of polyamide (PA6), 13 wt% of EOR rubber and 0.50 wt% of silicone oil were applied.

[Comparative Example 2]

Except that 0.10 wt% of copper oxide (CuO) was used instead of 0.10 wt% of zinc oxide.

Property evaluation

The pellets prepared in each of Examples 1 to 3 and Comparative Examples 1 and 2 were prepared as test pieces, and physical properties were evaluated by the following methods. The contents and physical properties of the pellets were shown in Tables 1 to 4 below.

1. Tensile strength: Performed according to ISO 527. Initial tensile strength and tensile strength after standing at 145 占 폚 for 42 days were measured.

2. Impact strength: It was carried out under the conditions of room temperature [24 占 폚] according to ISO 179 / 1eA. Initial impact strength and impact strength after standing at 145 占 폚 for 42 days were measured.

3. Melt Index: Measured in accordance with ASTM D1238 at a temperature of 240 DEG C under a load of 2.16 kg, expressed as weight (g) of the composition melted for 10 minutes.

4. Whiteness: It was measured under the following conditions.

Condition: 23 ° C, RH (relative humidity) 50%

Whiteness measurement: CIE / E313

Equipment used: Gardner Spectrophotometer 9000

division Content (% by weight) MI
(g / 10 min)
@ 240 ℃ Polyketone PA6 EOR CuO ZnO Silicone oil Comparative Example 1 60.5 26 13 - - 0.5 7.0 Comparative Example 2 60.4 26 13 0.1 - 0.5 4.8 Example 1 60.45 26 13 - 0.05 0.5 6.8 Example 2 60.4 26 13 - 0.10 0.5 6.3 Example 3 60.35 26 13 - 0.15 0.5 6.0

division Tensile Strength (Mpa) Elongation (%) 0 days
10 days
20 days
30 days
42 days
Retention rate
(%) 0 days 10 days 20 days 30 days 42 days Comparative Example 1 44 45 37 30 32 72 128 6 3 4 3 Comparative Example 2 45 42 44 44 43 95 207 11 13 12 10 Example 1 44 42 44 43 44 99 169 13 11 11 5 Example 2 44 42 43 44 45 101 169 13 11 11 5 Example 3 44 43 43 42 44 99 169 13 11 11 5

division Impact strength (kJ / m ² ) 0 days 10 days 20 days 30 days 42 days Retention rate
(%) Comparative Example 1 76 24 14 13 13 17 Comparative Example 2 79 39 37 36 31 39 Example 1 89 41 38 13 19 21 Example 2 89 42 40 12 20 23 Example 3 89 43 43 16 21 24

division L a b ΔE Comparative Example 1 68.7 9.5 45.9 - Comparative Example 2 35.8 4.4 14.6 45.8 Example 1 70.2 7.7 42.3 4.6 Example 2 70.7 7.7 41.8 4.9 Example 3 70.9 7.6 41.2 4.8

In Table 4, ΔE is a color difference between two color stimuli, which is defined according to the amounts of change (ΔL, Δa, Δb) of the coordinates L, a, and b in the colorimeter by measuring the color by the color difference meter. The values of DELTA E in Table 4 were calculated on the basis of the values of L, a, and b of Comparative Example 1 in which zinc oxide or copper oxide was not applied, and DELTA E was calculated by the following equation (1).

[Equation 1]

△ E = [(△ L) 2+ (△ a) 2+ (△ b) 2] 1/2

As shown in Tables 1 to 3, in Examples 1 to 3, there was no significant change in melt index, and both tensile strength and impact strength were improved compared to Comparative Example 1 in which zinc oxide was not used. Compared with Comparative Example 2 in which copper oxide was used in place of zinc oxide, although the retention ratio of the impact strength slightly decreased, the tensile strength retention ratios were similar. Further, referring to Table 4, the amount of change in L value, a value, and b value, that is, the color difference (? E) value calculated on the basis of Comparative Example 1 in which zinc oxide or copper oxide was not applied, It was found that ΔE was 45.8 and whiteness was greatly decreased by applying copper oxide. However, in Examples 1 to 3, ΔE value was 4.9 or less, and it was found that whiteness was not significantly different even when zinc oxide was applied . That is, the polyketone composition according to the embodiments of the present invention can apply various colors because there is little difference in brightness compared to the case where copper oxide is applied.

Therefore, the polyketone composition according to the embodiments of the present invention is excellent in long-term heat resistance, has improved color and high heat resistance, and can be applied in various colors by using zinc oxide together with a polymer having an amide group, rubber, Which is required to be manufactured by a vehicle connector and a cable tie. Therefore, vehicle connectors and cable ties made of the high heat-resistant polyketone composition according to the embodiments of the present invention exhibit excellent mechanical properties for a long period of time and can be manufactured in various colors.

Claims (5)

A polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), which is a linear alternating polyketone having y / x of 0.03 to 0.3;
A polymer having an amide group;
Rubber; And
Wherein the polyketone composition comprises zinc oxide.
- [- 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 polyketone composition comprises 44 to 61% by weight of the polyketone, 26 to 43% by weight of the amide group-containing polymer, 5 to 20% by weight of the rubber, and 0.05 to 2% by weight of the zinc oxide, Resistant polyketone composition having improved color.
The method according to claim 1,
Wherein the polyketone composition containing no zinc oxide has a color difference (DELTA E) of not more than 5.0 in dyeability of the high heat resistant polyketone composition.
The method according to claim 1,
The tensile strength of the polyketone composition measured after aging for 42 days in an oven maintained at 145 캜 was 80% or more as compared with the tensile strength measured before the aging,
Wherein the polyketone composition has an impact strength as measured after aging for 42 days in an oven maintained at 145 캜, wherein the retention ratio of the polyketone composition to the impact strength measured before the aging is 20% or more. Ketone composition.
A vehicle connector manufactured by the polyketone composition according to any one of claims 1 to 4.