KR20160139327A - Polyketone vehicle carrier in front end module and method for manufacturing of the same - Google Patents

Abstract

The present invention relates to a carrier for polyketone automobile front end modules and a production method thereof. More specifically, the present invention relates to a carrier for automobile front end modules, which exhibits outstanding impact resistance and tensile strength maintaining rate, by producing a carrier for polyketone automobile front end modules after injection-molding a polyketone blend including a linearly alternating polyketone terpolymer and a glass fiber. The present invention further relates to a production method thereof.

Description

TECHNICAL FIELD [0001] The present invention relates to a carrier of a polyketone automobile front end module and a manufacturing method thereof,

The present invention relates to a carrier of a polyketone automobile front end module and a method of manufacturing the same, and more particularly, to a carrier of a polyketone automobile front end module which is made of an engineering plastic polyketone as a molded product and has excellent impact resistance and tensile strength retention And a method for producing the same.

The present invention relates to a polyketone automotive front end module carrier.

In order to improve the productivity and economy of automobile manufacturers, research and development of various components such as front end module, front chassis module, end chassis module, door module, loop module and power train module are actively being studied and developed. The front-end module consists of a carrier, a cooling module, a head lamp, and a bumper. The cooling module is a sub-module of a front-end module including a radiator, a condenser, a fan and a shroud.

Traditionally, the carrier of a front end module for a vehicle is manufactured by pressing a metal sheet to ensure sufficient rigidity and strength against physical load. However, the metal carrier is expensive, and it is very difficult to process, and the weight of the automobile is heavy, which causes various problems such as lowering fuel efficiency. Therefore, automobile parts such as the carrier of the front end module are manufactured with materials that can be recycled in connection with environmental problems, and can be easily processed and exhibit high performance.

However, currently, materials used for the carrier of the automotive front-end module include materials blended with nylon 6 glass fiber. The material properties such as rigidity, long-term heat resistance, processability and dimensional stability are used as carriers of the front- It was not enough to be used.

On the other hand, Polyketone (PK) is a material that is low in raw material and polymerization process ratio compared to 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 method for producing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of a nonhydrohalogenic acid having a pKa of less than 6, and a catalyst that is a bidentate ligand Lt; / RTI >

An object of the present invention is to provide a carrier of a polyketone automobile front end module having excellent impact resistance and tensile strength retention using polyketone and glass fiber, and a method for producing the same.

In order to achieve the above object, according to a preferred embodiment of the present invention, a blend comprising 60 to 90% by weight of a linear alternating polyketone consisting of carbon monoxide and at least one olefinic hydrocarbon and 10 to 40% The present invention provides a carrier of a vehicle front end module manufactured by molding.

According to another preferred embodiment of the present invention, the linear alternating polyketone has a molar ratio of ethylene to propylene in the range of 99: 1 to 85:15.

According to another preferred embodiment of the present invention, the linear alternating polyketone polymer has an intrinsic viscosity of 1.2 to 2.0 dl / g, and the carrier of the polyketone automobile front end module is provided.

The carrier of the polyketone automobile front end module has an impact strength of 8 kJ / m 2 or more and a tensile strength retention ratio of 100% or more after being treated at 120 캜 for 300 hours.

According to another preferred embodiment of the present invention, there is provided a process for preparing a catalyst composition, comprising: 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 to obtain a polyketone resin; And 100 wt% of a blend of 60 to 90 wt% of the polyketone resin and 10 to 40 wt% of glass fiber to produce a carrier of the polyketone automobile front end module A method of manufacturing a carrier of a module is provided.

The polyketone molded article of the present invention is excellent in impact resistance and tensile strength retention ratio as compared with the nylon 6 material used in the past and is suitable for use as a carrier of an automobile front end module.

The polyketone to be used in the present invention is a copolymer of repeating units derived from carbon monoxide, an ethylenically unsaturated compound and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, particularly carbon monoxide-derived repeating units, and ethylenically unsaturated compounds, Is a structure in which repeating units derived from an unsaturated compound are substantially alternately linked and has excellent mechanical and thermal properties, excellent processability, high abrasion resistance, chemical resistance, and gas barrier properties. 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 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.

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 process, a mixed solvent of acetic acid and water is used as a liquid medium, benzophenone is added during polymerization, and carbon monoxide, an ethylenically unsaturated compound and one or more olefinic unsaturated compounds are added to improve the catalytic activity and intrinsic viscosity of the polyketone In addition, in the prior art, it is possible to produce a terpolymer having a high intrinsic viscosity at a polymerization time of about 1 to 2 hours, unlike the case where the polymerization time has to be at least 10 hours or more for the purpose of improving the 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.

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 prepared by the polymerization method as described above.

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.

The polymer ring of the polyketone polymer preferred in the present invention can be represented by the following formula (2).

(2)

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

In the general formula (2), 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.

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 apparatus is 0.5 dl / g to 10 dl / g, and preferably 0.8 dl / g to 4 dl / g.

The melting point of the polyketone resin is usually in the range of 175 ° C to 300 ° C, specifically 210 ° C to 270 ° C.

On the other hand, the polyketone molded product of the present invention is composed of a blend composed of a combination of polyketone and glass fiber, and is characterized in that the rigidity, workability and dimensional stability are improved as compared with a conventional material.

The glass fiber preferably has a particle diameter of 10 to 13 mu m. 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.

The composition ratio of the polyketone to the glass fiber is preferably 60 to 90% by weight of the polyketone polymer and 10 to 40% by weight of the glass fiber. When the content of the glass fiber is less than 15% by weight, the mechanical stiffness may be deteriorated. When the content of the glass fiber exceeds 40% by weight, the viscosity may be excessively increased and the extrusion and injection workability may be deteriorated.

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 included in order to improve processability and physical properties of the polymer. The molded article can be produced by extrusion molding or injection molding of the polyketone as described above.

On the other hand, the blend composition of the polyketone and the glass fiber of the present invention is formed by a method such as extrusion and injection, and is made of a polyketone molded product, which is characterized by excellent rigidity, processability and dimensional stability. At this time, the polyketone molded product has a product moisture absorption rate of 2.0% or less and a property retention ratio of 70% or more upon water absorption. The impact strength is 10 kJ / m 2 or more, preferably 15 kJ / m 2 or more.

Hereinafter, a manufacturing method for manufacturing a carrier of the front-trend module for an automobile according to the present invention will be described.

A method of manufacturing a carrier of a front end module 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.

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 extruded by an extruder to finally obtain a polyketone resin. The polyketone resin 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 rotational speed is less than 100 rpm, smooth kneading may not occur. If the screw rotational speed is more than 300 rpm, dispersion of glass fiber and destruction of fiber structure may occur, and mechanical properties may be deteriorated.

A carrier of the front end module for an automobile can be manufactured by preparing a blend as described above and extruding or injection molding the blend.

Hereinafter, the constitution and effects of the present invention will be described in detail with reference to specific examples and comparative examples. However, these examples are merely intended to clearly understand 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. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 85 to 15. 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.

85% by weight of the polyketone terpolymer prepared above and 15% by weight of glass fiber were molded into a pellet on an extruder using a twin screw having a diameter of 40 mm and L / D = 32 operated at 250 rpm, Carrier specimens of automotive front end modules were prepared.

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 6 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 L / D = 32 Then, the carrier specimen of the automobile front end module was 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. Tensile strength evaluation: ASTM D638.

2. Evaluation of flexural strength: ASTM D790.

3. Evaluation of Impact Strength: ISO 179.

4. Evaluation of tensile strength retention: ASTM D648.

importance The tensile strength
(MPa) Flexural strength
(MPa) Flexural modulus (MPa) Charpy notched
(KJ / m2) 120 占 폚, 300 hours Tensile strength retention (%) Example 1 1.30 113 161 4400 8.0 110 Example 2 1.37 129 178 5000 9.7 113 Example 3 1.44 156 213 6900 12.4 115 Example 4 1.52 173 237 9300 14.9 116 Comparative Example 1 1.38 160 230 9000 6 80

As can be seen from the above Table 1, the impact strength and the tensile strength retention ratio of Examples were superior to Comparative Example 1. Therefore, the carrier of the automobile front-end module manufactured through the embodiment of the present invention shows superior impact strength and short-time strength maintenance ratio as compared with the comparative example used as the carrier material of the existing automobile front-end module, It is more suitable for application as a carrier.

Claims (5)

Characterized in that a carrier of an automotive front end module is manufactured by injection molding a blend of 60 to 90% by weight of a linear alternating polyketone consisting of carbon monoxide and at least one olefinic hydrocarbon and 10 to 40% Carriers in ketone automotive front end modules. The method according to claim 1,
Wherein the linear alternating polyketone has a molar ratio of ethylene to propylene in the range 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. The method according to claim 1,
Wherein the carrier of the polyketone automobile front end module has an impact strength of 8 kJ / m < 2 > or more and a tensile strength retention ratio of 100% or more after treatment at 120 DEG C for 300 hours. 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 to obtain a polyketone resin; And
Preparing a carrier of a polyketone automobile front end module by injection molding 100 wt% of a blend comprising 60 to 90 wt% of the polyketone resin and 10 to 40 wt% of glass fiber;
Gt; a < / RTI > polyketone automotive front end module.