KR102021787B1 - Highly heat-resistant polyketone composition with improved color - Google Patents

Abstract

The present invention relates to a high heat-resistant polyketone composition having an improved color, and in particular, by including linear alternating polyketone, a polymer having an amide group, rubber, silicone oil, and zinc oxide, thereby improving long-term heat resistance and improved color. It relates to a polyketone composition having a.

Description

HIGH HEAT-RESISTANT POLYKETONE COMPOSITION WITH IMPROVED COLOR}

The present invention relates to a high heat-resistant polyketone composition having an improved color, more specifically, polyketone, a polymer having an amide (amide) group, rubber, and zinc oxide (ZnO) to include excellent impact resistance and long-term heat resistance And high heat resistant polyketone compositions having improved color and automotive connector parts 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.

As a countermeasure, it is possible to improve long-term heat resistance by mixing an additive such as a heat stabilizer with polyketone, but when using a conventional heat stabilizer, the color of the resin becomes dark due to the additive mixing, and thus, various fields are required. There is a problem in that the application is limited.

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 mixing the polymer, rubber, silicone oil, and zinc oxide (ZnO) having an amide (amide) group in the polyketone, excellent long-term heat resistance and improved color It is an object to provide a heat resistant polyketone composition and a vehicle connector made therefrom.

The highly heat-resistant polyketone composition having an improved color according to embodiments of the present invention is a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), wherein y / x is 0.03 to 0.3 Phosphorus alternating polyketones, polymers having amide groups, rubber, and zinc 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)

The polyketone composition may comprise 44 to 61% by weight of the polyketone, 26 to 43% by weight of the polymer having the amide group, 5 to 20% by weight of the rubber, and 0.05 to 2% by weight of zinc oxide.

When the whiteness of the polyketone composition is measured, the color difference (ΔE) of the polyketone composition without zinc oxide may be 5.0 or less.

In addition, the tensile strength of the polyketone composition measured after aging for 42 days in an oven maintained at 145 ℃ is maintained at 80% or more compared to the tensile strength measured before the aging progress, impact strength retention may be at least 20% have.

In addition, the present invention provides a vehicle connector made of the high heat resistance polyketone composition.

The highly heat-resistant polyketone composition having the improved color of the present invention has long-term mechanical stiffness retention in a high temperature use environment but is not dark in color, and thus can be applied to a field requiring high heat grade and various colors simultaneously. Therefore, not only automotive junction blocks, band cables, chain guides, radiator end tanks, engine covers, harness protectors for electric wires, air intake manifolds, fuel valves, but also various Automotive parts, such as automotive connectors, cable ties that require color, brackets in the electrical / electronic field, various frames and industrial materials for office equipment, have the advantage that they can be widely applied to various industries such as electrical / 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 provides a high heat-resistant polyketone composition having an improved color with excellent long-term heat resistance by including polyketone, a polymer having an amide group, rubber, and zinc oxide.

First, the polyketone resin used in the present invention is an engineering plastic and is a recently developed new resin, and is a thermoplastic synthetic resin which is usefully applied as a material for various molded products or parts due to its excellent mechanical properties and molding properties such as impact strength. 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. In addition, polyketone resin has lower moisture absorption than polyamide material, so it is possible to design various products with little change in dimensions and physical properties due to moisture absorption, and polyketone resin has a lower density than aluminum material, which is very suitable for product weight reduction. Do. 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, trifluoroacetate, 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 equivalent to 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, known to exhibit the highest activity in the polymerization catalyst The structure is simpler and has a lower molecular weight. As a result, the present invention is able to provide a novel polyketone polymerization catalyst, while maintaining the highest activity as a polyketone polymerization catalyst in the art while further reducing the production cost and cost. The method for preparing 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 method for preparing a ligand for a 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 mass synthesized.

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. As follows.

The (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine ligand can be synthesized through four steps as follows: First, diethylmalonate and 1, 5-Dibromopentane is boiled under sodium ethoxide and ethanol, and then reduced under lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexanedimethanol, followed by reaction under tosyl chloride and pyridine. This ligand can be obtained by reacting 2-methoxyphenylphosphine with sodium hydride under dimethyl sulfoxide, each step being subjected to purification steps such as column chromatography and recrystallization. Purity can be confirmed through nuclear magnetic resonance analysis.

On the other hand, the ligand is preferably used alone as a single site, it is also preferable to have a multi-site (multi-site).

[Formula 2]

Formula 2 is a model of a multi-site polymerization catalyst, and preferably used ligands include 1,3-bis [bi (2-methoxyphenyl) phosphino] propane, (2,2-dimethyl-1,3- Polyketone polymerization comprising a ligand having a multi-site of one or two structures selected from the group consisting of dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine It is preferable to use a catalyst, and in case of using a ligand having a multi-site rather than using a single-site ligand, the effect of reducing fouling that grows after attaching to the reactor inner wall during polyketone polymerization is reduced. There is.

[constitutional formula]

In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst of the present invention is (a) adding bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) to a reaction vessel under a nitrogen atmosphere and hydrogenated at room temperature. Adding sodium 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, washing the oil layer with water after separating the layers, 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 performed through;

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. 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 can be 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 per molecule of unsaturated hydrocarbons. 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 (3) as a repeating unit.

[Formula 3]

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

In the formula (3), G is an ethylenically unsaturated hydrocarbon, in particular, a part 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 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 inherent viscosity number (IV) of the polymer measured at 60 ° C. using a standard tubular viscosity measuring device and HFIP (Hexafluoroisopropanol) is preferably 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, even more preferably 1.0dl / g ~ 1.4dl / g. At this time, when the intrinsic viscosity number is less than 0.5dl / g, the mechanical properties are inferior, and when the intrinsic viscosity exceeds 10dl / g, there is a problem inferior in workability.

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. The molecular weight distribution can be adjusted in proportion to the amount of 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 highly heat-resistant polyketone composition having an improved color according to embodiments of the present invention includes a polyketone, a polymer having an amide group, a rubber, and zinc oxide, wherein the polyketone component is 44 To 61% by weight.

The high heat resistance polyketone composition may include 26 to 43% by weight of the polymer having an amide group in the total composition. If the content of the polymer having an amide group is less than 26% by weight, the effect of improving tensile strength retention cannot be sufficiently obtained. If the content of the polymer having an amide group is more than 43% 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 heat resistant polyketone composition of the present invention comprises rubber, the content of which may be 5 to 20% by weight of the total composition, preferably 10 to 13% by weight. If the rubber content is less than 5% by weight, the impact resistance may not be sufficiently improved. If the rubber content exceeds 20% by weight, the mechanical properties may be reduced. Impact resistance may be improved by including rubber as a component of the composition. 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 heat-resistant polyketone composition of the present invention includes zinc oxide, and by including zinc oxide, heat resistance is improved while maintaining the brightness of the composition, and thus long-term tensile strength and impact strength retention can be improved without darkening of color. . Through this, the high heat-resistant polyketone composition of the present invention can be easily applied to the field produced in a variety of colors while requiring long-term heat resistance. Zinc oxide may be included in 0.05 to 2% by weight of the total composition, less than 0.05% by weight it is difficult to obtain a sufficient thermal stability effect, more than 2% by weight may reduce the workability and retention stability.

When the high heat resistance polyketone composition of the present invention is measured for whiteness, the color difference (ΔE) value may be 5.0 or less in contrast to the dyeability of the polyketone composition that does not include zinc oxide (when zinc oxide is not applied). When a heat stabilizer, for example, copper oxide is added to improve the heat stability of the polyketone composition, the effect of improving heat stability is excellent, but the L, a, and b values, which become white due to darkening of color, are greatly changed and oxidized. Compared with before applying copper, the color difference (ΔE) value is larger than 40. However, in the present invention, by applying zinc oxide instead of copper oxide, it exhibits excellent heat resistance and at the same time, the color difference (ΔE) value is 5.0 or less, and whiteness can be greatly improved as compared with before applying zinc oxide.

The high heat resistant polyketone composition of the present invention may further comprise components other than those described above. Preferred examples include silicone oil, and the impact resistance of the composition may be improved by including silicone oil. When the silicone oil is included, the silicone oil may be included in 0.1 to 1.0% by weight of the total composition, preferably 0.3 to 0.6% by weight. When the content of the silicone oil is less than 0.1% by weight, the effect of improving the wear resistance may be insignificant, and when the content of the silicone oil is more than 1.0% by weight, impact resistance and molding processability of the composition may be deteriorated.

Hereinafter, a manufacturing method for preparing (blending) a high heat-resistant polyketone composition having the improved color is as follows.

The polyketone resin obtained through the above-described method is mixed with a polymer having an amide group, rubber and zinc oxide 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 related to 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 part using a high heat-resistant polyketone composition having an improved color can be produced.

Tensile strength measured after aging for 42 days (1008 hours) at a temperature of 145 ℃ through the composition and manufacturing method as described above for the high heat-resistant polyketone composition having an improved color of the present invention The retention rate of the tensile strength is 80% or more and the impact strength retention is 20% or more, which may exhibit excellent long-term heat resistance.

Thus, the highly heat-resistant polyketone compositions having the improved color of the present invention are suitable for applications requiring long-term heat resistance and various colors, in particular for automotive parts, and in particular for automotive connectors, cable ties and the like.

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., the inherent viscosity measured at 60 ° C. with hexafluoroisopropanol (HFIP) was 1.4 dl / g, and the MWD was 2.0.

A polyketone composition was prepared by blending 60.45 wt% of the prepared polyketone terpolymer, 26 wt% of polyamide (PA6), 13 wt% of EOR rubber, 0.05 wt% of zinc oxide, and 0.50 wt% of silicone oil, to prepare a polyketone composition. Was prepared as pellets on an extruder using a biaxial screw with a diameter of 40 cm operating at 250 rpm and L / D = 32.

Example 2

The same procedure as in Example 1 was carried out except that 60.4 wt% polyketone terpolymer, 26 wt% polyamide (PA6), and 13 wt% EOR rubber were mixed with 0.10 wt% zinc oxide and 0.50 wt% silicone oil.

Example 3

The same procedure as in Example 1 was carried out except that 60.35 wt% polyketone terpolymer, 26 wt% polyamide (PA6), 13 wt% EOR rubber, 0.15 wt% zinc oxide, and 0.50 wt% silicone oil were blended.

Comparative Example 1

The same procedure as in Example 1 was conducted except that 60.5 wt% of polyketone terpolymer, 26 wt% of polyamide (PA6), 13 wt% of EOR rubber, and 0.50 wt% of silicone oil were not applied.

Comparative Example 2

Copper oxide (CuO) was applied in 0.10% by weight instead of 0.10% by weight of zinc oxide.

Property evaluation

The pellets prepared in Examples 1 to 3 and Comparative Examples 1 and 2, respectively, were prepared as specimens and evaluated for physical properties in the following manner, and the results of the evaluation of the respective contents and the physical properties are shown in Tables 1 to 4 below.

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

2. Impact strength: It carried out under the conditions of normal temperature [24 degreeC] based on ISO 179 / 1eA. Initial impact strength and impact strength after leaving at 145 ° C. for 42 days were measured.

3. Melt Index: measured according to ASTM D1238 at a load of 2.16 kg at 240 ° C. and expressed as the weight (g) of the composition melted for 10 minutes.

4. Whiteness: Measured under the following conditions.

Condition: 23 ℃, RH (relative humidity) 50%

Whiteness Measurement Method: CIE / E313

Devices Used: Gardner Spectrophotometer 9000

division Content (% by weight) MI
(g / 10min)
@ 240 ℃ Polyketone PA6 EOR CuO ZnO Silicone oil Comparative Example 1 60.5 26 13 - - 0.5 7.0 Comparative Example 2 60.4 26 13 0.1 - 0.5 4.8 Example 1 60.45 26 13 - 0.05 0.5 6.8 Example 2 60.4 26 13 - 0.10 0.5 6.3 Example 3 60.35 26 13 - 0.15 0.5 6.0

division Tensile Strength (Mpa) % Elongation 0 days
10 days
20 days
30 days
42 days
Retention rate
(%) 0 days 10 days 20 days 30 days 42 days Comparative Example 1 44 45 37 30 32 72 128 6 3 4 3 Comparative Example 2 45 42 44 44 43 95 207 11 13 12 10 Example 1 44 42 44 43 44 99 169 13 11 11 5 Example 2 44 42 43 44 45 101 169 13 11 11 5 Example 3 44 43 43 42 44 99 169 13 11 11 5

division Impact strength (kJ / m ² ) 0 days 10 days 20 days 30 days 42 days Retention rate
(%) Comparative Example 1 76 24 14 13 13 17 Comparative Example 2 79 39 37 36 31 39 Example 1 89 41 38 13 19 21 Example 2 89 42 40 12 20 23 Example 3 89 43 43 16 21 24

division L a b △ E Comparative Example 1 68.7 9.5 45.9 - Comparative Example 2 35.8 4.4 14.6 45.8 Example 1 70.2 7.7 42.3 4.6 Example 2 70.7 7.7 41.8 4.9 Example 3 70.9 7.6 41.2 4.8

In Table 4, ΔE is measured according to the color difference meter and is defined according to the change amount (ΔL, Δa, Δb) of coordinates L, a, and b in the color display system, and means a color difference between two color stimuli. ΔE values in Table 4 were calculated based on L, a, and b values of Comparative Example 1 without applying zinc oxide or copper oxide, and ΔE was calculated by the following Equation 1.

[Equation 1]

△ E = [(△ L) 2+ (△ a) 2+ (△ b) 2] 1/2

As shown in Tables 1 to 3, in Examples 1 to 3 there is no significant change in the melt index compared to Comparative Example 1 without using zinc oxide, it can be seen that both tensile strength and impact strength improved. Compared with Comparative Example 2 in which copper oxide was used instead of zinc oxide, although the retention of impact strength decreased slightly, the retention of tensile strength was found to be similar. In addition, referring to Table 4, the amount of change of the L value, the a value, and the b value, that is, the color difference (ΔE) value calculated based on Comparative Example 1 without applying zinc oxide or copper oxide, In this case, ΔE was decreased to 45.8 by applying copper oxide, but in the case of Examples 1 to 3, ΔE was found to be 4.9 or less, and even when zinc oxide was applied, the whiteness did not show a big difference. . That is, the polyketone composition according to the embodiments of the present invention has almost no difference in brightness as compared with the case of applying copper oxide, and it is possible to apply various colors.

Accordingly, the polyketone composition according to the embodiments of the present invention uses zinc oxide together with a polymer, a rubber, and a silicone oil having an amide group, thereby providing excellent long-term heat resistance, improving color, and requiring high heat resistance, but applying various colors. It has been shown to be suitable for manufacturing such necessary automotive connectors and cable ties. Therefore, a vehicle connector and a cable tie made of a high heat-resistant polyketone composition according to the embodiments of the present invention exhibit excellent mechanical properties for a long time and may be manufactured in various colors.

Claims (5)

As a polyketone copolymer which consists of repeating units represented by following General formula (1) and (2), 44-61 weight% of linear alternating polyketone whose y / x is 0.03-0.3;
26 to 43% by weight of a polymer having an amide group;
5 to 20% rubber; And
A high heat resistant polyketone composition having an improved color, characterized in that it comprises 0.05 to 2% by weight of zinc 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)
delete The method of claim 1,
A high heat-resistant polyketone composition having an improved color, characterized in that the color difference (ΔE) of the polyketone composition not containing zinc oxide is 5.0 or less.
The method of claim 1,
Tensile strength of the polyketone composition measured after aging for 42 days in an oven maintained at 145 ℃ has a retention of 80% or more compared to the tensile strength measured before the aging progress,
The impact strength of the polyketone composition measured after aging for 42 days in an oven maintained at 145 ° C is a high heat-resistant poly with improved color, characterized in that the retention ratio is 20% or more compared to the impact strength measured before the aging process Ketone composition.
A vehicle connector made of the polyketone composition according to any one of claims 1, 3 and 4.