KR20140090463A - Polyketone resin composition and method for preparing the same - Google Patents

Abstract

The present invention relates to a polyketone resin composition and a method for preparing the same, and more particularly, to a polyketone resin composition, a molded product thereof and a method of forming the composition and the molded product. By manufacturing a radiator end tank of a car using a composition including a polyketone resin and a glass fiber, chemical resistance such as calcium chloride resistance and the like, antifreeze resistance, absorption resistance, and durability may be largely improved.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyketone resin composition,

More particularly, the present invention relates to a polyketone resin composition and a method for producing the same, and more particularly, to a polyketone resin composition and a method for producing the same, A polyketone resin composition, a molded article thereof, and a method for producing the same.

The present invention is derived from the research carried out as part of the WPM project of the Ministry of Knowledge Economy.

National R & D project supporting the present invention

Assignment number: 10037857

Department name: Ministry of Knowledge Economy

Research Project: WPM Business

Research title: Development of polyketone material

Organizer: Hyosung Corporation

Research period: Sep. 1, 2010 ~ Mar. 2017

The radiator end tank for an automobile distributes a high temperature antifreeze received from an automobile engine to a radiator core for heat exchange and collects an antifreeze solution so that the heat exchanged antifreeze flows into the automobile engine again. At this time, the radiator end tank is in constant contact with the antifreeze in the temperature range of about 100 ° C with a pressure of about 1 kg / cm ² . It also requires a high mechanical strength to provide a shape for mounting peripheral components and is complicated in shape.

Typical materials used in conventional automotive radiator end tanks include polyamide 66 (PA66) and glass fiber blends, and polyamide 6,12 / 66 blends (PA6, 12/66) and glass fiber blends.

However, PA66, PA6, 12/66 and the like have a problem that their physical properties and dimensions change after water absorption, and because of their low chemical resistance, they cause cracks in the radiator end tank due to the contact of calcium chloride (CaCl ₂ ) There is a case where the antifreeze is leaked to reach a state where the vehicle can not be operated.

Accordingly, there is a demand for development of new materials suitable for various materials, particularly automobile radiator end tanks, because of excellent chemical resistance, antifreeze resistance, durability and resistance to water absorption such as calcium chloride resistance as well as mechanical properties .

U.S. Patent No. 4,843,144 U.S. Patent No. 4,880,903

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide an automobile radiator end tank having excellent mechanical properties such as calcium chloride resistance as well as mechanical properties, The present invention provides a polyketone resin composition which can be suitably applied to a polyketone resin composition.

In order to accomplish the above object, the present invention provides a polyketone resin composition comprising: a polyketone resin; And a glass fiber coated with a silane coupling agent and a urethane-based film-forming agent, and a molded article thereof (particularly, an automobile radiator end tank).

According to another aspect of the present invention, there is also 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 comprising an alcohol 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 mixing and extruding the polyketone resin with a silane coupling agent and a glass fiber coated with a urethane-based film-forming agent, and then extruding the polyketone resin composition.

According to still another aspect of the present invention, there is provided a method of manufacturing an automobile radiator end tank by injecting a polyketone resin composition produced according to the above-described method.

By using the polyketone resin and the glass fiber, the composition of the present invention can provide various mechanical properties such as calcium chloride resistance, anti-antifreeze property, durability and resistance to water absorption, Particularly, a material for an automobile radiator end tank).

Further, according to the manufacturing method of the present invention, the injection molding cycle time is shortened by 20%, and the productivity is significantly improved as compared with the existing material.

Hereinafter, the present invention will be described in detail.

Polyketone  Resin composition and molded article thereof

The polyketone resin composition of the present invention comprises a polyketone resin; And glass fiber coated with a silane-based coupling agent and a urethane-based film-forming agent, and more particularly, a resin composition comprising 100 parts by weight of a polyketone resin; 0.1 to 0.4 part by weight of a silane coupling agent and 0.1 to 0.4 part by weight of a urethane-based film forming agent, and 30 to 35 parts by weight of a glass fiber having a particle size of 10 to 13 μm.

The polyketone resin, which is the subject of the composition of the present invention, is a newly developed thermoplastic resin which is excellent in mechanical properties such as impact strength and molding properties and is thus useful as a molded article such as a food container or a material for various parts. The mechanical properties of the polyketone resin belong to the category of high performance plastics. Polyketone resins having other desirable properties such as conductivity while retaining inherent physical properties such as mechanical properties and molding properties are widely used for various purposes. In addition, polyketone resin is a polymer material synthesized from carbon monoxide as a raw material, and has attracted great attention as an environmentally friendly material.

Generally, the polyketone resin is synthesized from carbon monoxide and olefins. For example, U.S. Patent No. 4,843,144 discloses line alternating polymers synthesized from olefins such as ethylene and propylene and carbon monoxide. The polyketone resin produced in this patent has been shown to have excellent impact resistance, high rebound resilience at room temperature and low temperature, and excellent creep properties.

In recent years, among polyketones, there is a growing interest in a series of alternating polyketones in which ketone groups and at least one ethylenically unsaturated hydrocarbon are alternately polymerized and improved in mechanical properties and molding characteristics. For example, U.S. Patent No. 4,880,903 discloses a polyketone terpolymer in which ketone groups, ethylene, and other olefinically unsaturated hydrocarbons (such as propylene) are alternately polymerized and formed.

The contents of the aforementioned U.S. Patent Nos. 4,843,144 and 4,880,903 are incorporated herein by reference.

Specifically, the linear alternating polyketone as a main component of the polyketone resin composition of the present invention is a linear alternating structure composed of a ketone group and at least one ethylenically unsaturated hydrocarbon, and substantially one carbon monoxide (or ketone group ), And is excellent in physical properties, appearance characteristics and molding properties.

The polyketone resin may contain a repeating unit represented by the following formula (1).

[Chemical Formula 1]

- {- CO - (- CH 2 -CH 2 -) -} x - {CO- (G) -} y -

Wherein G is derived from monomers of at least three ethylenically unsaturated hydrocarbons polymerized through ethylenic unsaturation and x: y is at least 2: 1.

Ethylenically unsaturated hydrocarbons suitable for use as the precursor of the polyketone resin include ethyne having 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 in which aryl substituents are formed on aliphatic molecules, in particular ethylenically unsaturated carbon Is an aryl aliphatic hydrocarbon having an aryl substituent on the atom. Examples of the aryl aliphatic hydrocarbon in the ethylenic unsaturated hydrocarbon include styrene, p-methylstyrene, p-ethylstyrene, and m-isopropyl styrene.

Such ethylenically unsaturated hydrocarbons and ketone compounds are copolymerized to form a linear alternating polyketone. Among them, a linear alternating polyketone formed by copolymerization of ethene and a ketone compound, or a mixture of at least three Linear alternating polyketone formed by copolymerization of an ethylenically unsaturated hydrocarbon having a carbon atom is preferable in view of the fact that the copolymerization reaction is easy and the molecular weight of the copolymerized linear alternating polyketone is relatively uniform. In short, the preferred polyketone resin is a copolymer of carbon monoxide and ethene, more preferably a second ethylenically unsaturated hydrocarbon having carbon monoxide, ethene and at least three carbon atoms (especially propene) is a linear terpolymer with an a-olefin.

The polyketone resin preferably has an intrinsic viscosity (LVN) of 0.5 to 10 dl / g, more preferably 0.8 to 4 dl / g, and most preferably 1 to 1.5 dl / g. If the intrinsic viscosity of the polyketone resin is less than 0.5 dl / g, the mechanical properties may be deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability may be deteriorated.

The polyketone resin has a number-average molecular weight, as measured by gel permeation chromatography, of preferably 100 to 200,000, more preferably 20,000 to 90,000. The physical properties of the polymer depend on the molecular weight, whether the polymer is a copolymer or a terpolymer, and in the case of a terpolymer, the physical properties of the second hydrocarbon moiety are determined.

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

The glass fibers are preferably coated with a silane-based coupling agent and a urethane-based film-forming agent and have a particle diameter of 10 to 13 탆. If the particle size of the glass fiber is less than 10 탆, the shape of the glass fiber may change and the mechanical properties may deteriorate. If the particle size exceeds 13 탆, the glass fiber may protrude from the product surface.

As the silane-based coupling agent, aminosilane can be used, and it is coated on the glass fiber to give compatibility of the glass fiber and the polyketone. The silane-based coupling agent is preferably used in an amount of 0.1 to 0.4 parts by weight based on 100 parts by weight of the polyketone resin. If the coating amount of the silane coupling agent is less than 0.1 parts by weight, the compatibility of the glass fiber and the polyketone may be poor, which may result in difficulty in kneading. If the amount exceeds 0.4 parts by weight, the relative content of the polyketone resin or glass fiber decreases, The physical properties such as chemical properties may be deteriorated.

As the urethane-based film-forming agent, polyurethane or epoxy / polyurethane may be used, and the film may be formed by coating it on glass fiber. The urethane-based film forming agent is preferably used in an amount of 0.1 to 0.4 parts by weight based on 100 parts by weight of the polyketone resin. If the coating amount of the urethane-based film-forming agent is less than 0.1 part by weight, it may be difficult to smoothly form the film. If the amount is more than 0.4 part by weight, the relative content of the polyketone resin or glass fiber is decreased to deteriorate durability and chemical resistance .

The glass fiber is preferably contained in an amount of 30 to 35 parts by weight based on 100 parts by weight of the polyketone resin. When the content of the glass fiber is less than 30 parts by weight, the mechanical rigidity may be deteriorated, and when it exceeds 35 parts by weight, the viscosity may be excessively increased, resulting in poor extrusion and injection workability and deterioration in appearance quality.

The polyketone resin composition of the present invention may additionally contain additives commonly used in the art within the scope not deviating from the object.

In one preferred embodiment, antioxidants, heat stabilizers, lubricants, processing aids and weathering stabilizers may be added to the polyketone resin composition of the present invention, alone or in combination.

As the antioxidant, a phenolic oxamide antioxidant may be used, which has a deactivation effect of the metal catalyst used in the polymerization. The antioxidant is preferably contained in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the polyketone resin. If the content of the antioxidant is less than 0.1 parts by weight, the deactivation function of the metal catalyst may be deteriorated. If the amount is more than 0.5 parts by weight, the physical properties of the product may be deteriorated.

Examples of the heat stabilizer include phosphorus thermal stabilizers, particularly hydroxy apatite represented by M ₁₀ (PO ₄ ) ₆ (OH) ₂ (wherein M is barium, strontium or calcium), preferably calcium hydroxyapatite Can be used, which suppresses the problem of an increase in viscosity during processing. The heat-resistant stabilizer is preferably contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polyketone resin. If the content of the heat-resistant stabilizer is less than 0.1 parts by weight, the viscosity-restraining function may be deteriorated. If the content is more than 2 parts by weight, the physical properties of the product may be deteriorated.

As the activator, an ethylene-methacrylic acid ester and / or a polyethylene-based synthetic lubricant such as ethylene bisstearamide, which is an acrylic lubricant, may be used. These lubricants are preferably contained in an amount of 0.1 to 1 part by weight per 100 parts by weight of the polyketone resin. If the content of the lubricant is less than 0.1 part by weight, the appearance quality may be deteriorated, and if it exceeds 1 part by weight, the mechanical properties may be deteriorated.

As the processing aid, ethylene methacrylic acid may be used. As the weather stabilizer, a benzotriazole-based material, a triazine-based material, a hindered amine-based material, and the like may be used, but the present invention is not limited thereto.

As described above, the polyketone resin composition of the present invention can be molded into a variety of products by extrusion, injection molding, or the like.

Specifically, the polyketone resin composition of the present invention is injection-molded or extruded to produce polyketone sheets, films, plates, OA appliances, electric / electronic parts, housing parts, automobile parts, Various industrial materials can be produced, and these industrial materials have excellent mechanical properties and molding properties.

Particularly, the polyketone resin composition of the present invention is excellent in mechanical strength and durability as well as excellent in calcium chloride resistance, anti-freeze property, and water absorption property, and is very suitable as a material for an automobile radiator end tank.

Polyketone  Resin composition and automobile radiator using same End  Manufacturing method of tank

According to another aspect of the present invention, there is provided a method of manufacturing the polyketone resin composition of the present invention and a method of manufacturing an automobile radiator end tank using the same.

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

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

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

Examples of the bidentate ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (for example, 1,3-bis [di (2-methoxyphenylphosphino)] propane and 1,3- Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane, the amount of which is 1 to 1.2 ) Equivalent.

The carbon monoxide, ethylene and propylene are liquid phase polymerized in a mixed solvent of alcohol (e.g. methanol) and water to produce a linear terpolymer. As the mixed solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of water in the mixed solvent is less than 2 parts by weight, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated.

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

In the present invention, the obtained polyketone resin is mixed with a silane-based coupling agent and glass fiber coated with a urethane-based film-forming agent and then extruded by an extruder to finally obtain a polyketone resin composition.

In one specific example, 100 parts by weight of the polyketone resin, 30 to 35 parts by weight of glass fibers coated with 0.1 to 0.4 parts by weight of a silane coupling agent and 0.1 to 0.4 parts by weight of a urethane-based film forming agent, 0.1 to 0.5 parts by weight of a ric oxamide-based antioxidant, 0.1 to 2 parts by weight of a phosphorus-based heat stabilizer, 0.1 to 1 part by weight of an acrylic lubricant and / or a polyethylene- And melt-kneaded and extruded to prepare the polyketone resin composition of the present invention.

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.

By manufacturing the glass fiber-reinforced polyketone resin by the above-mentioned method and injecting it, an automobile radiator end tank can be manufactured.

The automobile radiator end tank manufactured using the polyketone resin composition according to the present invention is excellent in all of the required physical properties, particularly, the chemical resistance against calcium chloride used as a winter seasoning agent. As a result, it is possible to minimize the problems such as cracking of the radiator end tank and leakage of the antifreeze, and it has been confirmed that the objective evaluation criteria for calcium chloride resistance is also satisfied.

Hereinafter, the present invention will be described more specifically 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  One

A linear terpolymer of carbon monoxide, ethylene and propylene was added to 100 parts by weight of methanol in the presence of a catalyst composition consisting of palladium acetate, anion of trifluoroacetic acid and 1,3-bis [diphenylphosphino] The polymerization was carried out in a solvent of 70 to 90 DEG C in which water was added. The melting point of the prepared terpolymer was 220 DEG C and the intrinsic viscosity (LVN) measured on 1,1,1,3,3,3-HFIP was 1.5 dl / g.

0.2 part by weight of Irganox 1010 (manufactured by Ciba-Geigey), 0.3 part by weight of calcium hydroxyapatite (manufactured by Budenheim), and 0.3 part by weight of a copolymer made of ethene and methacrylic acid Nucrel 1183C) was put into a pellet on an extruder at a temperature of 240 DEG C using a 40 mm twin screw operated at 200 rpm.

100 parts by weight of the polyketone resin prepared above, 30 parts by weight of a glass fiber coated with 0.1 to 0.4 part by weight of a silane coupling agent and 0.1 to 0.4 part by weight of a urethane-based film forming agent, 0.5 part by weight of a polyethylene- Were fed into a twin-screw extruder of L / D 32 and D 40 and extruded at a temperature of 240 캜 at a screw rotation speed of 250 rpm through melt-kneading.

The physical properties of the final polyketone resin were as shown in Table 1 below.

[Table 1]

Example  2

In the presence of a catalyst composition composed of palladium acetate, anion of trifluoroacetic acid and 1,3-bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane, A linear terpolymer of ethylene and propylene was polymerized in 100 parts by weight of methanol in a solvent at 70 to 90 DEG C added with 2 parts by weight of water. The melting point of the prepared terpolymer was 200 DEG C and the intrinsic viscosity (LVN) measured in 1,1,1,3,3,3-HFIP was 1.0 dl / g.

0.2 part by weight of Irganox 1010 (manufactured by Ciba-Geigey), 0.3 part by weight of calcium hydroxyapatite (manufactured by Budenheim), and 0.3 part by weight of a copolymer made of ethene and methacrylic acid Nucrel 1183C) was put into a pellet on an extruder at a temperature of 240 DEG C using a 40 mm twin screw operated at 200 rpm.

100 parts by weight of the polyketone resin prepared above, 30 parts by weight of a glass fiber coated with 0.1 to 0.4 part by weight of a silane coupling agent and 0.1 to 0.4 part by weight of a urethane-based film forming agent, 0.5 part by weight of a polyethylene- Were fed into a twin-screw extruder of L / D 32 and D 40 and extruded at a temperature of 240 캜 at a screw rotation speed of 250 rpm through melt-kneading.

The physical properties of the final polyketone resin were as shown in Table 2 below.

[Table 2]

Example  3

A linear terpolymer of carbon monoxide, ethylene and propylene was added to 100 parts by weight of methanol in the presence of a catalyst composition consisting of palladium acetate, anion of trifluoroacetic acid and 1,3-bis [diphenylphosphino] The polymerization was carried out in a solvent of 70 to 90 DEG C in which water was added. The melting point of the prepared terpolymer was 220 DEG C and the intrinsic viscosity (LVN) measured at 1,1,1,3,3,3-HFIP was 2.0 dl / g.

0.2 part by weight of Irganox 1010 (manufactured by Ciba-Geigey), 0.3 part by weight of calcium hydroxyapatite (manufactured by Budenheim), and 0.3 part by weight of a copolymer made of ethene and methacrylic acid Nucrel 1183C) was put into a pellet on an extruder at a temperature of 240 DEG C using a 40 mm twin screw operated at 200 rpm.

100 parts by weight of the polyketone resin prepared above, 30 parts by weight of a glass fiber coated with 0.1 to 0.4 part by weight of a silane coupling agent and 0.1 to 0.4 part by weight of a urethane-based film forming agent, 0.5 part by weight of a polyethylene- Were fed into a twin-screw extruder of L / D 32 and D 40 and extruded at a temperature of 240 캜 at a screw rotation speed of 250 rpm through melt-kneading.

The physical properties of the final polyketone resin were as shown in Table 3 below.

[Table 3]

Comparative Example  One

KOPLA PA6, 12/66 Glass Fiber 33% and KDG1133CR were used.

Comparative Example  2

Rhoda PA66 Glass Fiber 33%, A218V30 product was used.

Property evaluation

The polyketone resin composition pellets of the above examples were (injection molded) molded to prepare automotive radiator end tank specimens. The properties of the automotive radiator end tanks were evaluated by the following methods in comparison with the products of the comparative examples, and the results are shown in Table 4 below.

1. Tensile strength: ASTM D638.

2. Flexural strength: ASTM D790.

3. Flexural modulus: It was conducted according to ASTM D790.

4. Izod Impact Strength: Performed according to ASTM D256.

5. Heat distortion temperature: ASTM D648.

6. Calcium chloride bending strength, flexural elasticity, tensile strength and Izod impact strength retention rate: The specimens prepared according to ASTM D790, D638 and D256 were immersed in water at 100 ° C for 2 hours, removed from the surface water, After immersing in a 5% aqueous solution of calcium chloride and 35% aqueous solution for 2 hours, it is left at room temperature for 1 hour and then the surface water is removed. Total 5.5 hours is taken as one cycle to obtain flexural strength, flexural elasticity and tensile strength And retention of Izod impact strength were evaluated. The maintenance rate evaluation was carried out for a total of 20 cycles.

7. Antifreeze Flexural Strength, Flexural Elasticity, Tensile Strength and Izod Impact Strength Retention: Specimens prepared in accordance with ASTM D790, D638 and D256 were placed in an aqueous solution consisting of 3.7 bar, 146 ° C, 50 parts by weight of ethylene glycol and 50 parts by weight of water After 144 hours of immersion, flexural strength, flexural elasticity, tensile strength and retention of Izod impact strength were evaluated.

8. Reliability Evaluation of Calcium Chloride: A radiator end tank was prepared from the polyketone resin compositions of Examples and Comparative Examples, and 35% aqueous calcium chloride solution was sprayed from the calcium chloride-resistant calcium chloride test chamber at room temperature (25 캜) (1 kg / cm ² ) and deteriorated in an oven at 120 ° C. A total of 3 hours was carried out in one cycle, and it was judged to be suitable for passing more than 40 cycles when leakage or leakage of pressure due to cracking occurred.

[Table 4]

As shown in Table 4, it was evaluated that the durability such as stability of calcium chloride and stability of the anti-freeze solution was excellent in the Examples, while exhibiting substantially equivalent mechanical rigidity to the Comparative Example.

Comparative Examples 1 and 2 are currently used as radiator end tanks. In the case of Comparative Example 1, although the physical properties that can be used for the radiator end tanks were the lowest, the overall physical properties were very poor compared with the Examples. It was remarkably inadequate to be applied to the radiator end tank because the calcium chloride and the anti-freeze property were remarkably reduced.

Claims (11)

Polyketone resin; And a glass fiber coated with a silane coupling agent and a urethane-based film-forming agent.
The method according to claim 1,
100 parts by weight of a polyketone resin; And 0.1 to 0.4 part by weight of a silane coupling agent and 0.1 to 0.4 part by weight of a urethane-based film forming agent, and 30 to 35 parts by weight of a glass fiber having a particle size of 10 to 13 μm.
The method according to claim 1,
The polyketone resin is a linear terpolymer of carbon monoxide, ethylene and propylene,
Wherein said silane-based coupling agent is aminosilane,
Wherein the urethane-based film-forming agent is a polyurethane or epoxy / polyurethane film-forming agent.
The method according to claim 1,
An antioxidant, a heat-resistant stabilizer and a lubricant.
5. The method of claim 4,
The antioxidant is a phenolic oxamide antioxidant, which is contained in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the polyketone resin,
The heat-resistant stabilizer is a hydroxyapatite, which is contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polyketone resin,
Wherein the lubricant is an ethylene-methacrylic acid ester as an acrylic lubricant and an ethylene bisstearamide as a polyethylene-based synthetic lubricant, each of which is contained in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the polyketone resin.
A molded article of the polyketone resin composition according to any one of claims 1 to 5.
The method according to claim 6,
Characterized in that it is for an automobile radiator end tank.
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 comprising an alcohol 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
Mixing the polyketone resin with a glass fiber coated with a silane coupling agent and a urethane-based film-forming agent, and extruding the polyketone resin composition.
9. The method of claim 8,
As the palladium compound is palladium acetate, and the amount of use thereof is 10 ^-3 to 10 ^-1 molar,
The acid having a pKa value of 6 or less is at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, the amount of which is 6 to 20 equivalents relative to the palladium compound,
The phosphorus bidentate compound may be prepared by reacting 1,3-bis [diphenylphosphino] propane and 1,3-bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] Wherein the amount of the palladium compound to be used is 1 to 1.2 equivalents based on the palladium compound.
9. The method of claim 8,
Wherein the mixed solvent comprises 100 parts by weight of methanol and 2 to 10 parts by weight of water.
A method for manufacturing an automobile radiator end tank by injecting a polyketone resin composition produced according to any one of claims 8 to 10.