KR101705622B1 - Vehicle ash tray comprising polyketone blend - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ashtray for a vehicle produced by injection molding a polyketone blend, and more particularly, to an ashtray for a vehicle having excellent flame retardancy and impact strength by producing a polyketone blend containing polyketone polymer and glass fiber by injection molding will be.

Description

A vehicle ash tray comprising a polyketone blend and a polyketone blend,

TECHNICAL FIELD The present invention relates to a vehicle ashtray produced by injection molding a polyketone blend, and more particularly to a vehicle ashtray exhibiting excellent flame retardancy and impact strength.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyketone composition, and polyketone (PK) is a material which is low in raw material and polymerization process ratio compared to general engineering plastic materials such as polyamide, polyester and polycarbonate. And abrasion resistance and is useful as a vehicle component compared to conventional materials.

Polyketone resins are new resins that have been developed recently, and are synthesized from carbon monoxide and olefins. Mechanical properties fall into the category of high performance plastics. U.S. Patent No. 4,843,144 discloses line alternating polymers synthesized from olefins such as ethylene and propylene and carbon monoxide.

Conventionally, inorganic filler-reinforced polyamide resins have been widely used for various molded articles since long ago due to the advantage of being improved in flexural modulus and heat resistance due to the addition of glass fibers or minerals used as inorganic materials, Has been used. In addition, in addition to the other polymers, there are mainly general plastics, alloys with thermoplastic elastomers, and alloys with other encapsulants. Examples of the elastomer include polypropylene, polystyrene, and olefin elastomers, The compatibility with amides is so low that the technology for producing functional polyamides through commercialization techniques has been applied to various industrial fields. However, since such an alloy composition can not attain the desired object, there has been proposed a technique for improving the heat resistance and dimensional stability by strengthening the inorganic material after freezing.

Thus, the prior art has proposed a technique of manufacturing glass fiber reinforced by using a thermosetting resin. However, in the case of a thermosetting resin, it is a composition excellent in rigidity and strength and weather resistance which is an important requirement characteristic of outdoor parts. However, it is expensive and difficult to mold, and since it is not an environmentally friendly material as a thermosetting resin, It is hard to say that it is more advantageous than the rigid metal material which is widely used now because of its weak characteristic. In addition, due to structural limitations in molding, odors such as sewage and dirt are exposed after installation.

In order to solve the above problems, the present invention aims to provide a vehicle ashtray which exhibits sufficient flame retardancy and impact strength by using a polyketone in which a wear-resistant agent is not blended by injection molding using a polyketone blend.

In order to accomplish the above object, the present invention provides a process for producing a polyphenylene sulfide polymer comprising 60 to 90 weight percent of a linear alternating polyketone polymer consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon and having a residual amount of palladium catalyst of 5 to 50 ppm and a molecular weight distribution of 1.5 to 3.0 And 10 to 40% by weight of a glass fiber is injection-molded into an ashtray for a vehicle.

The linear alternating polyketone preferably has a molar ratio of ethylene to propylene in the range of 99: 1 to 85:15.

The intrinsic viscosity of the linear alternating polyketone polymer is preferably 1.2 to 2.0 dl / g.

The vehicle ashtray has an impact strength of 8 kJ / m ² or more and an impact strength measured at 50 캜 and 90% RH at 25 캜 and a relative humidity of 65% RH of 90% or more .

The ashtray for a vehicle according to the present invention is produced by injection molding a polyketone blend containing a polyketone polymer and glass fibers, so that sufficient flame retardancy and impact strength can be obtained despite the use of polyketone.

Hereinafter, the present invention will be described in detail.

The present invention relates to a composition comprising 60 to 90% by weight of a linear alternating polyketone polymer composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon and having a residual amount of palladium catalyst of 5 to 50 ppm and a molecular weight distribution of 1.5 to 3.0, % Of the blend is injection-molded into an ashtray for a vehicle.

At this time, it is preferable that the glass fibers have a particle diameter of 10 to 15 탆, but the present invention is not limited thereto. If the particle diameter of the glass fiber is less than 10 mu m, the shape of the glass fiber may be changed and the mechanical properties may be deteriorated.

In addition, it is preferable that the composition ratio of the glass fiber to the total composition is 10 to 40% by weight. If the composition ratio of the glass fiber is less than 10% by weight, the mechanical stiffness may be lowered, and if it exceeds 40% by weight, the extrusion and injection workability may be deteriorated.

Hereinafter, the polyketone polymer will be described as follows.

The polyketone polymer of the present invention is a linear 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.

Preferred polymeric rings of the polyketone polymers in the present invention can be represented by the following formula (1).

In the above formula (1), 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 at least 2: 1.

In the above, when y is 0, it may be represented by the following general formula (2), and it becomes a copolymer and does not contain the second ethylenic unsaturated hydrocarbon.

And

The units of formula (2) are randomly applied throughout the polymer chain. The preferred y: x ratio is from 0.01 to 0.5. The terminal root, or "cap ", of the polymeric ring is determined depending on what material is present during the preparation of the polymer and how the polymer will be purified or the polymer will be purified.

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 (Hexafluoroisopropylalcohol) at 60 DEG C using a standard tubular viscosity measuring device is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g, Preferably 1.2 dl / g to 2.0 dl / g.

As a method of producing the polyketone polymer, liquid phase polymerization in which carbon monoxide and olefin are carried out in an alcohol solvent through a catalyst composition composed of a palladium compound, an acid having 6 or less of PKa, and a ligand compound of phosphorus can be employed. The polymerization temperature is preferably from 50 to 100 ° C. and the reaction pressure is from 40 to 60 bar. The 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.

This is preferred as palladium acetate and a palladium compound in the amount of 10 ^-3 to ^10-2 1mole preferred. Specific examples of the acid having a pKa value of 6 or less include trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid, and sulfonic acid. In the present invention, trifluoroacetic acid is used and its amount is preferably 6 to 20 equivalents based on palladium. Also, 1,3-bis [di (2-methoxyphenylphosphino)] propane is preferably used as the left-handed compound of phosphorus, and the amount to be used is preferably 1 to 1.2 equivalents based on palladium.

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

The repeating unit derived from carbon monoxide, an ethylenically unsaturated compound and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, especially repeating units derived from carbon monoxide, and ethylenically unsaturated compounds and repeating units derived from propylenically unsaturated compounds are substantially Are excellent in mechanical properties and thermal properties, excellent in processability, high in abrasion resistance, chemical resistance and gas barrier property, and are useful materials for various applications. It is considered that the high molecular weight product of the copolymerized polyketone having three or more members is more useful as an engineering plastic material having higher workability and thermal properties and having excellent economy. Particularly, it has high abrasion resistance and can be used in light gasoline tanks because of high gas barrier properties such as parts of gears of automobiles, high chemical resistance, and lining materials of chemical transport pipes. In the case of using an ultrahigh molecular weight polyketone having an intrinsic viscosity of 2 or more as the fiber, it is possible to conduct stretching at a high magnification and to have a high strength and a high modulus of elasticity oriented in the stretching direction as belts, reinforcements of rubber hoses, tire cords, And is suitable for use in building materials and industrial materials.

The production method 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 elements, A process for producing a polyketone by terephthalic copolymerization of an ethylenic and a propylenically unsaturated compound is characterized in that a mixed solvent of 70 to 90% by volume of acetic acid and 10 to 30% by volume of water is used as a liquid medium and benzophenone .

Here, the liquid medium is characterized in that a mixed solvent of acetic acid and water is used without using methanol, dichloromethane, or nitromethane, which has conventionally been used for producing polyketones. This is because the use of a mixed solvent of acetic acid and water as a liquid medium for the production of polyketone can improve the catalytic activity while reducing the manufacturing cost of the polyketone.

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 effect of the catalyst is less affected. When the concentration of water 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 the 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).

(3)

Bis (bis (2-methoxyphenyl) phosphine) bis (methylene) bis (bis (2-methoxyphenyl) 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 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).

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 1 to 20 mol% of 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 mixing ratio of carbon monoxide and ethylenic unsaturated compound to 1: 1. However, in the present invention in which a mixed solvent of acetic acid and water is used as a liquid medium and benzophenone is added during polymerization, It has been found that when the feed ratio of the 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 but also the catalyst activity and the intrinsic viscosity can be simultaneously achieved. 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 polymerization step, 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, But it is also possible to prepare a terpolymerized polyketone having a high intrinsic viscosity only in a polymerization time of about 1 to 2 hours, unlike the prior art which requires a polymerization time of at least 10 hours to improve the intrinsic viscosity Do.

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 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.

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

Hereinafter, a manufacturing method for manufacturing the ashtray for a vehicle of the present invention is as follows.

A method for manufacturing an ashtray for a vehicle according to 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 polymer; And mixing and extruding 60 to 90% by weight of the polyketone polymer and 10 to 40% by weight of glass fiber to produce a blend; And injection molding the blend. However, the present invention is not limited thereto.

As the palladium compound constituting the catalyst composition, palladium acetate can be used. The amount of the palladium compound to be used is preferably 10 ^-3 to 10 ^-1 mole, but is not limited thereto.

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

Examples of the bidentate ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (for example, 1,3-bis [di (2-methoxyphenylphosphino)] propane, , 3-bis [bis [anilyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane and ((2,2-dimethyl-1,3-dioxane- ) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and the amount thereof is suitably 1 to 20 (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 polymer is mixed with glass fibers and then extruded by an extruder to finally obtain a blend 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 rotational speed is less than 100 rpm, smooth kneading may not occur. If the screw rotation speed is more than 300 rpm, the glass fiber may be broken and the mechanical properties may be deteriorated.

A blend is manufactured in the same manner as described above, and the ashtray for a vehicle can be manufactured by extrusion molding or injection molding.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to specific embodiments. However, these embodiments are merely intended to clarify the present invention and are not intended to limit the scope of the present invention. The present invention will be described in detail with reference to the following non-limiting examples.

Example  One

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. In the polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. 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, and the MWD was 2.0.

90% by weight of the polyketone terpolymer prepared above and 10% by weight of glass fiber were added to prepare a composition. The composition thus prepared was extruded by using a twin screw having a diameter of 40 cm and operating at 250 rpm and having L / D = 32 , And then injection molded into a specimen of a vehicle ashtray.

Example  2

Example 1 was the same as Example 1 except that the content of the polyketone was set at 80 wt% and the content of the glass fiber was set at 20 wt%.

Example  3

The same as Example 1 except that the content of the polyketone in Example 1 was set at 70% by weight and the content of the glass fiber was set at 30% by weight.

Example  4

The same as Example 1 except that the content of the polyketone in Example 1 was set at 60% by weight and the content of the glass fiber was set at 40% by weight.

Comparative Example  One

A nylon 66 resin and 30 wt% glass fiber were added to prepare a composition. The composition thus prepared was pelletized on an extruder using a twin screw having a diameter of 40 cm and operating at 250 rpm and having an L / D of 32 After that, the ashtray specimens were manufactured by injection molding.

Property evaluation

The properties of the specimens prepared in Examples 1 to 4 and Comparative Example 1 were evaluated by the following methods. The results are shown in Table 1 below.

1. Evaluation of Impact Strength: ISO 179.

2. Evaluation of physical property retention: ASTM D648 and ISO 179 were used.

(The impact strength retention ratio measured at 25 DEG C and relative humidity of 65% relative to the impact strength measured at 50 DEG C and 90% relative humidity)

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

Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Impact strength
(kJ / m2) 8 10 13 15 7 Property retention
(%) 90 93 95 100 75 Flammability evaluation
(UL94, 1/16 '') V-0 V-0 V-0 V-0 V-0

As can be seen from Table 1, the impact strength of the examples was improved compared to the comparative example, and the impact strength retention was 90% or more, indicating that the retention of the physical properties was excellent. Further, in the case of the examples, the flame retardancy characteristics were found to be equal to or higher than those of the comparative examples.

Therefore, the vehicle ashtray according to the present invention has excellent impact resistance and physical property retention, exhibits excellent flame retardancy, and is more suitable for use as a vehicle ashtray.

Claims (4)

60 to 90% by weight of a linear alternating polyketone polymer having 10 to 40% by weight of glass fibers and 5 to 50 ppm of a palladium catalyst residual amount having a molecular weight distribution of 1.5 to 3.0, which is composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon In an ashtray for a vehicle manufactured by injection molding,
The ligand of the catalyst composition used in the polymerization of the linear alternating polyketone polymer is preferably a bis (methylene) Phenyl) phosphine)
The vehicle ashtray has an impact strength of 8 to 15 kJ / m ² and an impact strength measured at 50 캜 and a relative humidity of 90% RH of 90 to 100% relative to an impact strength measured at 25 캜 and a relative humidity of 65% Wherein the ashtray is an ashtray for a vehicle. The method according to claim 1,
Wherein the linear alternating polyketone has an ethylene / propylene molar ratio of 99: 1 to 85:15. The method according to claim 1,
Wherein said linear alternating polyketone polymer has an intrinsic viscosity of 1.2 to 2.0 dl / g. delete