KR102011917B1 - High impact polyketone composition with excellent heat stability for long period - Google Patents

Abstract

The present invention relates to a high-impact polyketone composition having excellent long-term heat resistance, and in particular, polyketone, a polymer having an amide (amide) group, rubber, and copper oxide (II), thereby providing excellent impact resistance and long-term heat resistance It relates to an excellent polyketone composition.

Description

High impact polyketone composition with excellent heat stability for long period}

The present invention relates to a high impact polyketone composition having excellent long-term heat resistance, and more particularly, to impact resistance prepared using a composition containing polyketone, a polymer having an amide group, rubber, and copper oxide (II). The present invention relates to a high impact polyketone composition having excellent excellent long-term heat resistance and a vehicle intake manifold made therefrom.

Polyketone (PK) has a lower raw material and polymerization process cost than general engineering plastic materials such as polyamide, polyester, and polycarbonate, and has excellent properties such as heat resistance, chemical resistance, fuel permeability, and abrasion resistance. It is widely applied. However, despite the superiority of polyketone materials, along with stricter environmental regulations, various applications are required for improved physical properties, especially for automobile junction blocks, engine covers, and other electrical and electronic components. Heat stability and strong impact resistance that can withstand heat are required.

On the other hand, there is a growing interest in a group of linear alternating polymers consisting 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 and ethylene and other olefinically unsaturated hydrocarbons, such as propylene.

The process for preparing polyketone polymers is usually a compound of a Group VIII metal selected from palladium, cobalt or nickel, and anions of non-hydro halogen strong-hydrohalogentic acid. Catalyst compositions produced from bidentate ligands of phosphorus, arsenic or antimones are used. U.S. Patent No. 4,843,144 describes a process for preparing polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of nonhydrohalogenic acid with a pKa of less than 6, and a catalyst that is a bidentate ligand of phosphorus. It is starting.

In order to be applicable to a variety of applications, there is a need for a study on a polyketone composition resistant to impact and long-term heat resistance.

The present invention is to solve the above problems by adding a thermoplastic polyurethane (TPU; Themoplastic Polyurethane) excellent in fluidity and flexibility to the polyketone to improve the flexibility that was lacking while maintaining the advantages of the existing high-impact heat-resistant polyketone resin It is an object to provide a polyketone composition.

In order to achieve the above technical problem, the present invention is a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), having a linear alternating polyketone and an amide group of y / x of 0.03 ~ 0.3 Provided is a polyketone composition excellent in long-term heat resistance, comprising a polymer, rubber, and copper (II) oxide.

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

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

(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer)

According to a preferred embodiment of the present invention, the composition ratio of the total resin component in the composition is 44 to 61 parts by weight of polyketone, 26 to 43 parts by weight of polymer having an amide group, 5 to 20 parts by weight of rubber The copper (II) oxide may be included in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the total resin component.

In addition, the retention rate of the tensile strength of the polyketone composition is 80% or more, characterized in that the retention of impact strength is 40% or more.

In addition, the present invention provides a vehicle intake manifold made of the high-impact polyketone composition.

The high impact polyketone composition having excellent long-term heat resistance of the present invention has a long-term mechanical stiffness retention rate in a high temperature use environment, thereby meeting a high heat resistance grade (Grade). Therefore, automotive junction blocks, band cables, chain guides, radiator end tanks, engine covers, harness protectors for electric wires, air intake manifolds, fuel valves, etc. Brackets in the field of components and battery transfer, various frames of office equipment, and industrial materials have advantages that can be widely applied to various industries such as electrical and electronic components.

EMBODIMENT OF THE INVENTION Hereinafter, although the best form for implementing this invention is demonstrated in detail, this invention is not limited to these.

The present invention is characterized by providing a high impact polyketone composition having excellent long-term heat resistance by including polyketone, a polymer having an amide group, rubber, and copper oxide.

First, the poly ketone resin used in the present invention is an engineering plastic and a recently developed new resin, which has excellent mechanical properties and molding properties such as impact strength, and is usefully applied as a material for various molded products or parts. It is a synthetic resin. Mechanical properties of the polyketone resin belongs to the category of high performance plastics, and is a polymer material that synthesizes carbon monoxide as a raw material.

Polyketone resin has a low moisture hygroscopicity compared to polyamide material, so it is a material capable of designing various products with little change in dimensions and physical properties due to moisture absorption. In particular, polyketone is a material having a stronger molecular bond than polyethylene, and the melting temperature is about 100 ° C. higher than that of polyethylene, and is a material having superior strength and heat resistance stability to polyethylene.

Hereinafter, the manufacturing process of the said polyketone is demonstrated.

The process for preparing polyketones is characterized by the presence of carbon monoxide in a liquid medium in the presence of an organometallic complex catalyst comprising a ligand having an element of group (a) Group 9, Group 10 or Group 11, and group (b) Group 15. In the method for preparing polyketone by terpolymerization of ethylenic and propylene unsaturated compounds, the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer. As an example of the solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product. As a preferable example of the mixed solvent, a mixed solvent consisting of 70 to 90% by volume acetic acid and 10 to 30% by volume of water can be used as a liquid medium, and can be prepared by adding benzophenone during polymerization. In the case where a mixed solvent consisting of acetic acid and water is used without using methanol, dichloromethane, or nitromethane, which have been used mainly for the production of polyketone as a liquid medium, it is possible to improve the catalytic activity while reducing the production cost of polyketone. It has an excellent effect. When a mixed solvent of acetic acid and water is used as the liquid medium, when the concentration of water is less than 10% by volume, the catalyst activity is less affected. However, when the concentration is more than 10% by volume, the catalytic activity increases rapidly. 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 the mixed solvent which consists of 70-90 volume% acetic acid and 10-30 volume% water as a liquid medium.

The catalyst is composed of a ligand having an element of (a) Group 9, Group 10 or Group 11 transition metal compound (b) Group 15 of the Periodic Table (IUPAC Inorganic Chemistry Nomenclature, 1989).

Examples of the Group 9 transition metal compound in the Group 9, 10 or 11 transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamate salts, sulfonates, and the like. Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, trifluoro ruthenium acetate, ruthenium acetylacetate, and trifluoromethane sulfonate ruthenium.

Examples of the Group 10 transition metal compound include a complex of nickel or palladium, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include nickel acetate, nickel acetyl acetate, palladium acetate, and palladium trifluoroacetate. And palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium, palladium sulfate and the like.

Examples of the Group 11 transition metal compound include copper or silver complexes, carbonates, phosphates, carbamates, sulfonates, and the like, and specific examples thereof include copper acetate, trifluoro copper acetate, copper acetylacetate, silver acetate, tri Silver fluoroacetic acid, silver acetyl acetate, silver trifluoromethane sulfonic acid, etc. are mentioned.

Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and preferred transition metal compounds (a) in terms of yield and molecular weight of polyketone are palladium compounds, and in terms of catalytic activity and intrinsic viscosity improvement. Most preferably, palladium acetate is used in the process.

Examples of the ligand (b) having a group 15 atom include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picolin , Nitrogen ligands such as 2,2'-bikinolin, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Butane, 1,3-bis [di (2-methyl) phosphino] propane, 1,3-bis [di (2-isopropyl) phosphino] propane, 1,3-bis [di (2-methoxyphenyl ) Pinospino] propane, 1,3-bis [di (2-methoxy-4-sulfonic acid-phenyl) phosphino] propane, 1,2-bis (diphenylphosphino) cyclohexane, 1,2-bis (Diphenylphosphino) benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, 1,2- Bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino] methyl] benzene, 1,1'-bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) Spinosyns; there may be mentioned a ligand, such as propane.

Among them, the ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly, in view of the yield of polyketone, a phosphorus ligand is preferably 1,3-bis [di (2- Methoxyphenyl) phosphino] propane, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, and 2-hydroxy-1,3-bis [in terms of molecular weight of the polyketone. Di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) phosphino] propane, and do not require an organic solvent in terms of safety Water-soluble 1,3-bis [di (2-methoxy-4-sulfonate-phenyl) phosphino] propane, 1,2-bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino ] Methyl] benzene, the synthesis | combination is easy, it is available in large quantities, and economically preferable is 1, 3-bis (diphenyl phosphino) propane and 1, 4-bis (diphenyl phosphino) butane. Preferred ligand (b) having an atom of group 15 is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) propane, most preferably 1,3-bis [di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2 Methoxyphenyl) phosphine).

[Formula 1]

((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) of Formula 1 is a polyketone introduced to date Activity expression equivalent to 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, known to have the highest activity in the polymerization catalyst The structure is simpler and has a lower molecular weight. As a result, the present invention can provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst in the art while further reducing the production cost and cost thereof. The method for producing a ligand for a polyketone polymerization catalyst is as follows. Using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) ((2,2-dimethyl Provided is a method for producing a ligand for a polyketone polymerization catalyst, characterized by obtaining -1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine). . The ligand preparation method for the polyketone polymerization catalyst of the present invention is conventionally 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane Unlike the synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in bulk.

In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst is (a) adding bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) to a reaction vessel under a nitrogen atmosphere and sodium hydride at room temperature. Adding and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the obtained mixture, followed by stirring to react; (c) adding and stirring methanol 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 is recrystallized under methanol ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) It can be carried out by obtaining a step.

On the other hand, it is also preferable to use (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine as the ligand used in the polymerization catalyst. The (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine ligand can be synthesized through the following four steps. Nate and 1,5-dibromopentane are boiled under sodium ethoxide and ethanol, and then reduced under lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexanedimethanol, and tosyl chloride and pyridine. It can be reacted under to give a leaving group, which is reacted under 2-methoxyphenylphosphine, sodium hydride and dimethyl sulfoxide to obtain the ligand. Purification steps such as graphy and recrystallization, and purity of each step can be confirmed by nuclear magnetic resonance analysis.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) used is generally in the range thereof because the appropriate value varies depending on the type of the ethylenic and propylene unsaturated compounds selected or other polymerization conditions. Although not limited, it is usually from 0.01 to 100 mmol, preferably from 0.01 to 10 mmol, per liter of capacity of the reaction zone. The capacity of the reaction zone means the capacity of the liquid phase 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 mol of the transition metal compound (a).

It is also possible to add benzophenones during the polymerization of polyketones. By adding benzophenone during the polymerization of the polyketone, the effect of improving the intrinsic viscosity of the polyketone can be achieved. The molar ratio of the (a) Group 9, Group 10 or Group 11 transition metal compound and benzophenone is 1: 5 to 100, preferably 1:40 to 60. If the molar ratio of the transition metal and benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory. If the molar ratio of the transition metal and benzophenone is greater than 1: 100, the polyketone catalytic activity produced is rather It is not desirable because it tends to decrease.

Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 Α-olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and α-methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Acrylic esters, such as ethyl acrylate and methyl acrylate, etc. are mentioned. Among these, preferred ethylenically unsaturated compounds are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, most preferably ethylene, and 120 mol% propylene is added in the production of terpolymer copolyketones.

Here, it is preferable to adjust the input ratio of carbon monoxide and ethylenically unsaturated compound to 1 to 2 (molar ratio) and to adjust the propylene to 1 to 20 mol% relative to the total mixed gas. In the production of polyketone, the ratio of carbon monoxide and ethylenically unsaturated compound is generally 1: 1. However, when a mixed solvent of acetic acid and water is used as a liquid medium and benzophenone is added during polymerization, carbon monoxide and ethylenically unsaturated compound are used. When the ratio of 1 to 1 to 2 and propylene is adjusted to 1 to 20 mol% relative to the total mixed gas, not only the workability is improved but also the catalytic activity and the intrinsic viscosity can be simultaneously achieved. If the amount of propylene is less than 1 mol%, the effect of terpolymerization to lower the melting temperature cannot be obtained. If it exceeds 20 mol%, there is a problem of inhibiting the intrinsic viscosity and the improvement of catalyst activity. It is desirable to.

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 olefinically unsaturated compounds are added to increase the catalytic activity and intrinsic viscosity of the polyketone. In addition to being improved, in the prior art, the polymerization time should be at least 10 hours to improve the intrinsic viscosity, but it is possible to prepare a terpolymer copolymer polyketone having a high intrinsic viscosity even if the polymerization time is about 12 hours.

Ternary copolymerization of carbon monoxide, the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex comprising a Group 9, Group 10 or Group 11 transition metal compound (a) and a ligand (b) having an element of Group 15 As a result of the catalyst, the catalyst is produced by contacting the two components. Arbitrary methods can be employ | adopted as a method of making it contact. That is, you may make and use the solution which mixed two components previously in a suitable solvent, and may respectively supply two components separately to a polymerization system, and may contact them in a polymerization system.

The present invention may further include conventionally known additives such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials to improve processability and physical properties of the polymer.

As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a gas phase polymerization method in which a small amount of a polymer is impregnated with a high concentration of a catalyst solution are used. The polymerization may be either batchwise or continuous. The reactor used for superposition | polymerization can use a well-known thing as it is or processing it. There is no restriction | limiting in particular about polymerization temperature, Generally 40-180 degreeC, Preferably 50-120 degreeC is employ | adopted. There is no restriction | limiting also about the pressure at the time of superposition | polymerization, Usually, it is normal pressure-20 MPa, Preferably it is 4-15 MPa.

As mentioned above, polyketone is manufactured according to the above manufacturing process.

On the other hand, the polyketone polymer of the present invention is a linear alternating structure, and substantially contains carbon monoxide for each molecule of unsaturated hydrocarbon. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers are ethene, α-olefins (e.g. propene, 1-butene) having up to 20 carbon atoms, preferably up to 10 carbon atoms. ), Aliphatic hydrocarbons such as isobutene, 1-hexene and 1-octene), or arylaliphatic hydrocarbons having aryl substituents on aliphatic molecules, in particular ethylenically unsaturated carbon atoms Arylaliphatic hydrocarbon with an aryl substituent on the phase. Examples of the arylaliphatic hydrocarbons among the ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene, m-isopropyl styrene, and the like. Polymers preferably used in the present invention are linear terpolymers of carbon monoxide with ethene and α-olefins such as second ethylenically unsaturated hydrocarbons having at least three carbon atoms (especially propene).

When the polyketone terpolymer is used as the main polymer component of the composition of the present invention, for each unit containing the second hydrocarbon moiety in the terpolymer, there are at least two or more units containing the ethylene moiety, and It is preferable that there are 10-100 units containing the hydrocarbon part of 2.

In one embodiment, the polyketone polymer may include a unit represented by the following formula (2) as a repeating unit.

[Formula 2]

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

In the formula (2), G is an ethylenically unsaturated hydrocarbon, in particular, a part obtained from 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 composed of repeating units represented by the following General Formulas (1) and (2), and it is preferable that y / x is 0.03 to 0.3. When the value of the y / x value is less than 0.03, there is a limit inferior in meltability and workability, and when it exceeds 0.3, mechanical properties are inferior. And 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 may be controlled by controlling the ratio of ethylene and propylene of the polyketone polymer. In one example, the melting point is about 220 ° C. when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46: 4: 50, but 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 100 to 200,000, particularly 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer depend on the molecular weight, whether the polymer is copolymer or terpolymer, and in the case of the terpolymer, the properties of the second hydrocarbon moiety present. Melting | fusing point of the conversion of the polymer used by this invention is 175-300 degreeC, and is 210-270 degreeC generally. The ultimate viscosity number (LVN) of the polymer measured at 25 ° C. using a standard tubular viscosity measuring device and HFIP (Hexafluoroisopropanol) is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g. Preferably it may be 1.0dl / g ~ 2.0dl / g. At this time, when the limiting viscosity number is less than 0.5dl / g, the mechanical properties are inferior, when it exceeds 10dl / g, there is a problem that the workability is inferior. In the present invention, polyketone having an intrinsic viscosity number of 1.0 dl / g to 2.0 dl / g is most preferable in terms of mechanical properties and processability.

Meanwhile, the molecular weight distribution of the polyketone may be 1.5 to 2.5, more preferably 1.8 to 2.2. If the molecular weight distribution is less than 1.5, the polymerization yield falls, and if it exceeds 2.5, there is a problem in inferior moldability. In order to control the molecular weight distribution, it is possible to adjust according to the amount of the palladium catalyst and / or polymerization temperature. That is, when the amount of the palladium catalyst increases or the polymerization temperature is 100 ° C. or more, the molecular weight distribution is increased.

The polyketone of the present invention preferably has a content of palladium element of 50 ppm or less. When the content of the palladium element exceeds 50 ppm, thermal denaturation and chemical denaturation due to the remaining palladium element are likely to occur, and during melt molding, a phenomenon such as an increase in melt viscosity and an increase in dopant viscosity when dissolved in a solvent occurs. , Workability becomes poor. In addition, since a large amount of palladium elements remain in the polyketone molded body obtained after molding, the heat resistance of the molded body is deteriorated. The smaller the content of the palladium element in the polyketone from the viewpoint of process passability and the heat resistance of the molded product, the more preferable. The content is more preferably 10 ppm or less, still more preferably 5 ppm or less, and most preferably 0 ppm.

Specifically, the high impact polyketone composition having excellent long-term heat resistance according to embodiments of the present invention includes a resin component and copper oxide (II), and the polyketone component described above is based on 100 parts by weight of the total resin component. To 61 parts by weight.

The high impact polyketone composition of the present invention is a second component, 26 to 43 parts by weight of a polymer having an amide group based on 100 parts by weight of the total resin component It may include. If the content of the polymer having an amide group is less than 26 parts by weight, the effect of improving the tensile strength retention cannot be sufficiently obtained. If the content of the polymer having an amide group is more than 43 parts by weight, workability may decrease due to factors such as viscosity increase. Tensile strength retention can be improved by including a polymer having an amide group as a component constituting the composition. Polymers having an amide group that can be used in the present invention include, but are not limited to, polyamide, polyurethane, and the like.

The high impact polyketone composition of the present invention comprises a rubber, it may be included 5 to 20 parts by weight, preferably 10 to 13 parts by weight based on 100 parts by weight of the total resin component. If the rubber content is less than 5 parts by weight, the impact resistance may not be sufficiently improved. If the content of the rubber is more than 20 parts by weight, the mechanical properties may be lowered and the physical properties retention may be lowered. By including rubber as a component of the composition, impact resistance can be improved. Rubbers that may be used in the present invention include, for example, ethylene octene rubber (EOR) such as maleic anhydride grafted ethylene-octene rubber (EOR-MAH), but are not limited thereto.

The high-impact polyketone composition includes copper oxide (II) in addition to the above resin components, thereby improving heat resistance stability and improving long-term tensile strength and impact strength retention. Copper oxide (II) may be included in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the total resin component. If it is less than 0.05 parts by weight, sufficient thermal stability effect may not be obtained. .

Hereinafter, the production method for producing a high impact polyketone composition excellent in the long-term heat resistance is as follows.

Method for producing a polyketone composition 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 double ligand compound of phosphorus; Preparing a mixed solvent (polymerization solvent); Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and a mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin; And mixing and extruding the polyketone resin with a polymer having an amide group, rubber, and copper oxide (II) to prepare a composition. And extruding / injecting the composition to prepare pellets, but is not limited thereto.

Palladium acetate may be used as the palladium compound constituting the catalyst composition, and the amount of palladium acetate is preferably 10 ⁻³ to 10 ⁻¹ moles, but is not limited thereto.

As the acid having a pKa value of 6 or less constituting the catalyst composition, one or more selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid, and sulfonic acid may be used, and preferably trifluoroacetic acid is used. 6-20 (mole) equivalent weight of the compound is appropriate.

Examples of the ligand ligands constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (e.g., 1,3-bis [di (2-methoxyphenylphosphino) propane), 1,3- Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane, ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis ( 1 selected from the group consisting of methylene)) bis (bis (2-methoxyphenyl) phosphine) and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine It is possible to use more than one species, and the amount of use thereof is 1 to 1.2 (mole) equivalents relative to the palladium compound.

The carbon monoxide, ethylene and propylene are liquid-phase polymerized in a mixed solvent to produce a linear terpolymer. As one embodiment of 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 the water in the mixed solvent is less than 2 parts by weight of the ketal may be formed to reduce the heat resistance during the process, if more than 10 parts by weight may lower the mechanical properties of the product.

In addition, the reaction temperature is 50 ~ 100 ℃ during the polymerization, the reaction pressure is in the range of 40 ~ 60bar is appropriate. The resulting polymer is recovered through polymerization and filtration and purification, 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 polymer having an amide group, rubber, and copper oxide (II), and then extruded with an extruder to finally obtain a composition. The blend may be prepared by melt kneading and extrusion into a twin screw extruder. At this time, the extrusion temperature is 230 ~ 260 ℃, screw rotation speed is preferably in the range of 100 ~ 300rpm. If the extrusion temperature is less than 230 ℃ kneading may not occur properly, if it exceeds 260 ℃ may cause problems with the heat resistance of the resin. In addition, if the screw rotational speed is less than 100rpm it may not occur smooth kneading.

By preparing a composition in the same manner as described above and extruding or injection molding it, a high heat-resistant component using a high impact polyketone composition having excellent long-term heat resistance can be prepared.

In the high-impact polyketone composition having excellent long-term heat resistance of the present invention, the retention rate of the tensile strength measured before and after 1008 hours at a temperature of 145 ° C relative to the initial tensile strength is 80% or more through the composition and preparation method as described above. And, the retention of impact strength is 40% or more can exhibit an excellent long-term heat resistance.

Hereinafter, the present invention will be described in detail through examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention in any sense is not limited to these examples.

Example 1

Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene are obtained from palladium acetate, trifluoroacetic acid and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine In the presence of the resulting catalyst composition, the content of trifluoroacetic acid relative to palladium is 10-fold molar ratio, and goes through 1 step of polymerization temperature of 78 ° C. and 2 steps of 84 ° C. Polyketone terpolymer prepared above The molar ratio of ethylene and propene at was 85 to 15. The melting point of the polyketone terpolymer was 220 ° C., LVN measured at 25 ° C. with hexafluoroisopropanol (HFIP) was 1.4 dl / g, and MWD was 2.0.

After forming a resin mixture of 61% by weight of the prepared polyketone terpolymer, 26% by weight of polyamide, and 13% by weight of ABS rubber, 0.1 parts by weight of copper (II) was blended with respect to 100 parts by weight of the resin mixture to Ketone compositions were prepared and prepared compositions were pelleted onto an extruder using a biaxial screw with a diameter of 40 cm operating at 250 rpm and L / D = 32.

Example 2

After forming a resin mixture of 57% by weight of the prepared polyketone terpolymer, 30% by weight of polyamide, and 13% by weight of EOR rubber, 0.1 parts by weight of copper (II) was blended with respect to 100 parts by weight of the resin mixture. It is the same as Example 1 except for it.

Example 3

After forming a resin mixture of 53% by weight of the prepared polyketone terpolymer, 34% by weight of polyamide, and 13% by weight of EOR rubber, 0.1 parts by weight of copper (II) was blended with respect to 100 parts by weight of the resin mixture. It is the same as Example 1 except for it.

Example 4

After forming a resin mixture of 44% by weight of the prepared polyketone terpolymer, 43% by weight of polyamide, and 13% by weight of EOR rubber, 0.1 parts by weight of copper (II) was blended with respect to 100 parts by weight of the resin mixture. It is the same as Example 1 except for doing.

Comparative Example 1

Using only the polyketone resin prepared in Example 1 was prepared in pellet form on the extruder using a biaxial screw having a diameter of 40 cm operating at 250 rpm, L / D = 32.

Comparative Example 2

It is the same as Comparative Example 1 except that mPPO (Modified Polyphenylene Oxide) was used instead of the polyketone resin.

Comparative Example 3

It is the same as Comparative Example 1 except that high impact PA66 (Nylon 66) was used instead of the polyketone resin.

Property evaluation

The pellets prepared in Examples 1 to 4 and Comparative Examples 1 to 3, respectively, were prepared as specimens and evaluated for physical properties in the following manner, and the results are shown in Table 1 below.

1. Tensile strength: It was conducted according to ISO 527. Initial tensile strength and tensile strength after standing at 145 ° C. for 1008 hours (42 days) were measured.

2. Impact strength: According to ISO 179 / 1eA, it was carried out under the condition of room temperature [24 ° C]. Initial impact strength and impact strength after standing at 145 ° C. for 1008 hours were measured.

division Tensile Strength (MPa) Impact strength (kJ / m ² ) Early 145 ° C,
After 1008 hours Retention rate
(%) Early 145 ° C,
After 1008 hours Retention rate
(%) Comparative Example 1 62 18 29 8 One 13 Comparative Example 2 63 53 85 237 30 13 Comparative Example 3 62 67 108 533 30 6 Example 1 47 48 102 88 41 47 Example 2 48 49 102 89 41 46 Example 3 59 51 85 88 52 59 Example 4 61 54 89 89 54 61

As shown in Table 1, in the case of Examples 1 to 4, the retention of tensile strength and impact strength values was excellent after 1008 hours at 145 ° C compared to Comparative Examples 1 and 2, and in the case of Comparative Example 3 Although the strength retention is excellent, the impact strength retention is very low, and it can be seen that the long-term heat resistance of Examples 1 to 4 is superior to Comparative Examples 1 to 3.

Therefore, the high-impact polyketone composition according to the embodiments of the present invention shows excellent long-term heat resistance compared to the conventional polyketone material by using a polymer, rubber, and copper oxide (II) having an amide group together with the polyketone. It was found to be suitable for use in parts of the entire industry, such as automobiles and electrical and electronics. Therefore, the intake manifold for vehicles manufactured from the high-impact polyketone composition according to the embodiments of the present invention may also maintain excellent mechanical properties for a long time even in an actual use environment and thus exhibit excellent quality.

Claims (4)

A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), 44 to 61 parts by weight of linear alternating polyketones having y / x of 0.03 to 0.3; 26 to 43 parts by weight of polyamide; And a resin composed of 5 to 20 parts by weight of ABS rubber or ethylene octene rubber,
Copper oxide (II) is contained from 0.05 to 2 parts by weight based on 100 parts by weight of the total resin component,
High strength polyketone composition having excellent long-term heat resistance, characterized in that the retention of tensile strength is 85 ~ 102%, the impact strength retention is 46 ~ 61%.
-[-CH2CH2-CO] x- (1)
-[-CH2-CH (CH3) -CO] y- (2)
(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer)
delete delete A vehicle intake manifold made of the polyketone composition of claim 1.