KR20160059885A - Polyketone vehicle valve body - Google Patents

Abstract

The present invention relates to a polyketone molded product and a producing method thereof and, more specifically, to a polyketone molded product which can significantly improve impact resistance and oil resistance and can be produced as a vehicle valve body by producing the polyketone molded product through using a blend of a linear alternating polyketone terpolymer and glass fibers, and to a producing method thereof.

Description

 [0001] The present invention relates to a polyketone vehicle valve body,

The present invention relates to a polyketone molded article, a polyketone automobile valve body and a process for producing the same, and more particularly, to a polyketone molded article having excellent impact resistance and oil resistance by producing polyketone, which is an engineering plastic, will be.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a valve body belonging to a steering booster for a vehicle and relates to a valve body used in a brake system of a vehicle.

In general, the valve body is likely to be exposed to oil in that it is used for a mission oil storage tank, and is likely to be exposed to high heat. As a result, the material used for the valve body is required to have oil resistance, surface properties, heat resistance, dimensional stability and impact resistance.

However, currently used materials for automotive valve bodies are polyamide alone or blended glass fiber blends in polyamide. The material properties such as oil resistance, heat resistance and impact resistance of these materials are used as the valve body of automobile It was not enough to be.

On the other hand, Polyketone (PK) is an inexpensive material of raw material and polymerization process ratio compared with general engineering plastic materials such as polyamide, polyester and polycarbonate. It has excellent properties such as heat resistance, chemical resistance, fuel permeability and abrasion resistance It is widely applied to various industries.

For this reason, there is a growing interest in a family of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as polyketones or polyketone polymers. U.S. Patent No. 4,880,903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide, ethylene and terephthalic unsaturated hydrocarbons such as propylene. The process for preparing the polyketone polymer is generally carried out by reacting a compound of a Group VIII metal selected from among palladium, cobalt or nickel with an anion of a strong halogen-hydrohalogentic acid, , Phosphorus, arsenic, or antimony (Antimon). U.S. Patent No. 4,843,144 discloses a method for producing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of a nonhydrohalogen acid having a pKa of less than 6, and a catalyst that is a bidentate ligand Lt; / RTI >

Korean Patent No. 1004453540000 Korean Patent No. 1008108650000

Disclosed is a polyketone molded article excellent in oil resistance and impact resistance using polyketone and glass fiber, and a polyketone automobile valve body 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 50 to 90% by weight of a linear alternating polyketone consisting of carbon monoxide and at least one olefinic hydrocarbon and 10 to 50% And forming an automobile valve body by molding, and the oil absorption amount is 0.14% or less after being immersed in gasoline at 50 DEG C for 48 hours.

Also, the present invention provides a polyketone automobile valve body, wherein the polyketone automobile valve body has an impact strength of 15 kJ / m 2 or more and a flexural strength of 80 MPa or more.

In addition, the present invention provides a method 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 comprising 50 to 90 wt% of the polyketone resin and 10 to 50 wt% of glass fiber, to produce a polyketone automotive valve body; The present invention provides a method of manufacturing a polyketone automotive valve body.

The polyketone molded product of the present invention is superior in impact resistance to nylon 66 which has been used in the past, and is excellent in oil resistance and is suitable for use as an automobile valve body.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a valve body of an automatic transmission, and more particularly, to a valve body made of polyketone.

Generally, an automatic transmission has a torque converter and a multistage transmission mechanism connected to the torque converter. The automatic transmission includes a hydraulic operating friction element for selecting one of the gear positions of the transmission mechanism according to the running state of the vehicle . The hydraulic control system of such an automatic transmission for an automobile has a function of automatically selecting an appropriate shift according to the running state of the vehicle by selecting a friction element through a control valve and operating the hydraulic pressure generated from the oil pump. This hydraulic control system includes a pressure regulating means for regulating the hydraulic pressure generated from the oil pump, a manual and automatic transmission control means capable of forming a speed change mode, a hydraulic pressure control means A control means, a damper clutch control means for a damper clutch operation of the torque converter, and a hydraulic pressure distributing means for distributing an appropriate hydraulic pressure supply to each friction element. The automotive automatic transmission generally used includes a pump impeller connected to the output shaft of the engine and driven together, a turbine runner connected to the input shaft of the transmission and operating together, and a stator disposed between the impeller and the turbine runner It has a fluid torque converter.

With this arrangement, the fluid is circulated by the pump impeller driven by the engine with the auxiliary action of the stator that allows the fluid to flow in the direction that does not interfere with the rotation of the pump impeller when the fluid enters the impeller from the turbine runner. The automatic transmission is made by changing the transmission ratio in the planetary gear unit by the operation of a friction element such as a clutch or kick-down brake for each gear position. In addition, the friction element is selectively operated by changing the flow direction of the hydraulic pressure by a plurality of valves of the hydraulic control apparatus. The manual valve performs port conversion at the selected position of the driver's shift lever, And is connected to a conduit through which the fluid pressure can be supplied to the shift control valve.

Particularly, the hydraulic control means has a pressure control valve controlled by the transmission control unit so that the hydraulic pressure delivered to the hydraulic pressure distributing means has an appropriate pressure, and a pressure control solenoid valve for controlling the pressure control valve.

These pressure control solenoid valves are mainly used with 2-way valves, but they are replaced with 3-way valves due to poor control pressure ripple characteristics and control the pressure control valves. The valve body made of the above valves is highly likely to be exposed to oil and the like. The present invention uses a polyketone which is a material forming the valve body and excellent in oil resistance and impact resistance.

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

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

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

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

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

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

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

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

[Chemical Formula 1]

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

      In a preferred embodiment, the process for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under nitrogen atmosphere, Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the resulting mixture, followed by stirring and reacting; (c) adding methanol and stirring after completion of the reaction; (d) adding toluene and water, separating the layers, washing the oil layer with water, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And a step of acquiring the image data.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies depending on the kinds of the ethylenic and propylenically unsaturated compounds to be selected and other polymerization conditions. Therefore, But it is usually 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, and most preferably ethylene.

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.

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

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

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

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

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

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. When the ratio is less than 1.5, the polymerization yield decreases. When the ratio is 2.5 or more, the moldability is poor. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger.

On the other hand, the polyketone molded article of the present invention is composed of a blend composed of a combination of polyketone and glass fiber, and is characterized in that impact resistance and oil resistance are improved with respect to materials used in the past.

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 and the glass fiber is preferably 50 to 90% by weight of the polyketone and 10 to 50% by weight of the glass fiber. If the content of the glass fiber is less than 10% by weight, the mechanical stiffness may be deteriorated. If the content is more than 50% 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 oil resistance and impact resistance. At this time, the impact strength of the polyketone molded product is 10 kJ / m 2 or more, preferably 15 kJ / m 2 or more.

On the other hand, it is possible to manufacture the molded polyketone product by injection molding with an automobile exterior automobile valve body.

Hereinafter, a production method for producing the polyketone molded article as described above is as follows.

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

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 (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 polyketone molded product can be produced by preparing a resin by the above-mentioned method and injecting it. In addition, the injected polyketone molded product could be manufactured from an automotive valve body.

In addition, the polyketone molded product produced according to the present invention has an excellent impact resistance, an excellent oil resistance, and a low dimensional strain.

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 1

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid with respect to palladium is 10 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 78 占 폚 and 84 占 폚 are carried out. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 46 to 4. The melting point of the polyketone terpolymer was 220 占 폚, the LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, the MI index was 60 g / 10 min and the MWD was 2.0. 70% by weight of the polyketone terpolymer prepared above and 30% by weight of glass fiber were manufactured into pellets on an extruder using a twin screw having a diameter of 40 mm and L / D = 32 operating at 250 rpm, And specimens for automotive valve bodies were prepared and evaluated for physical properties.

Example 2

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.

Example 3

The same as Example 1 except that the content of the polyketone in Example 1 was set at 50% by weight and the content of the glass fiber was set at 50% by weight.

Comparative Examples 1 to 2

In the past, 50% by weight of polyamide 6 (PA 6), 50% by weight of glass fiber and 37% by weight of polyamide 66 (PA 66) and 63% by weight of glass fiber as materials of DuPont Impact strength and retention of physical properties after moisture absorption were measured.

Property evaluation

The prepared pellets of the above examples were injection-molded to prepare automotive valve body specimens. The specimens were evaluated in the following manner in comparison with the products of the comparative examples, and the results are shown in Table 1 below.

1. Evaluation of Izod impact strength: ASTM D256.

2. Oil resistance: Measurement of oil absorption after mission oil 50 ℃ immersion, 48 hours, 96 hours

3. Tensile strength: ASTM D638.

4. Flexural strength: The flexural strength was measured according to ASTM D790.

5. Evaluation of retention of calcium chloride property in product

The test specimens were repeatedly subjected to the following tests 20 times in 35% aqueous solution of calcium chloride, and tensile strength retention was measured

1) Removal of surface moisture after treatment at 100 ℃ for 2 hours

2) Leave at room temperature for 30 minutes, cool

3) Treatment in a 35% aqueous solution of calcium chloride at 100 ° C for 2 hours

4) Allow to stand for 60 minutes at room temperature,

5) Remove surface moisture after cleaning with water

The properties of Examples and Comparative Examples were as shown in Table 1 below.

division Mixing ratio Oil absorption
(After 48 hours) Oil absorption
(After 96 hours) The tensile strength Flexural strength Impact strength Calcium chloride resistance
(Physical property retention rate) % % MPa MPa KJ / m ² % Comparative Example 1 PA6 / GF50 0.15 0.18 39 43 30 60 Comparative Example 2 PA66 / GF63 0.16 0.20 36 46 25 65 Example 1 PK / GF30 0.10 0.13 90 85 50 90 Example 2 PK / GF40 0.11 0.14 77 88 52 92 Example 3 PK / GF50 0.11 0.16 73 87 59 88

As shown in Table 1, the examples prepared by blending polyketone and glass fiber have excellent oil resistance due to low oil absorption after 48 hours or 96 hours compared with the comparative example (oil absorption after immersing in gasoline at 50 DEG C for 48 hours) 0.14% or less), and it was evaluated that the impact resistance was high and the impact resistance was excellent. Therefore, the automobile valve body manufactured through the embodiment of the present invention is very suitable for application to an automobile valve body because of excellent impact resistance and oil resistance.

Claims (4)

50 to 90% by weight of a linear alternating polyketone composed of carbon monoxide and at least one olefinic hydrocarbon, and 10 to 50% by weight of glass fibers are injection molded to prepare an automobile valve body, And the oil absorption amount is 0.14% or less after immersion.
The method according to claim 1,
Wherein the polyketone automobile valve body has an impact strength of 15 kJ / m < 2 > or more.
The method according to claim 1,
Wherein the polyketone automotive valve body has a flexural strength of 80 MPa or more.
The method according to claim 1,
Wherein the polyketone has an intrinsic viscosity of 1.0 to 2.0 dl / g and a molecular weight distribution of 1.5 to 2.5.