WO2016072642A2 - Composition de résine de polycétone doté d'une excellente résistance au choc - Google Patents

Composition de résine de polycétone doté d'une excellente résistance au choc Download PDF

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Publication number
WO2016072642A2
WO2016072642A2 PCT/KR2015/011027 KR2015011027W WO2016072642A2 WO 2016072642 A2 WO2016072642 A2 WO 2016072642A2 KR 2015011027 W KR2015011027 W KR 2015011027W WO 2016072642 A2 WO2016072642 A2 WO 2016072642A2
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Prior art keywords
polyketone
bis
weight
composition
linear alternating
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PCT/KR2015/011027
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English (en)
Korean (ko)
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WO2016072642A3 (fr
Inventor
최종인
윤성균
김가영
김성환
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(주) 효성
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Priority claimed from KR1020140154624A external-priority patent/KR101646033B1/ko
Priority claimed from KR1020140154620A external-priority patent/KR101664219B1/ko
Priority claimed from KR1020140154626A external-priority patent/KR101664260B1/ko
Priority claimed from KR1020140154613A external-priority patent/KR101664264B1/ko
Priority claimed from KR1020140154617A external-priority patent/KR101611578B1/ko
Priority claimed from KR1020140161976A external-priority patent/KR101675828B1/ko
Priority claimed from KR1020140161988A external-priority patent/KR101664926B1/ko
Priority claimed from KR1020140162006A external-priority patent/KR101706052B1/ko
Priority claimed from KR1020140162004A external-priority patent/KR101706050B1/ko
Priority claimed from KR1020140161993A external-priority patent/KR101611580B1/ko
Priority claimed from KR1020140161994A external-priority patent/KR101664918B1/ko
Priority claimed from KR1020140161981A external-priority patent/KR101684890B1/ko
Priority claimed from KR1020140161978A external-priority patent/KR101655336B1/ko
Priority claimed from KR1020140162017A external-priority patent/KR101675286B1/ko
Priority claimed from KR1020140161977A external-priority patent/KR101655337B1/ko
Priority claimed from KR1020140161992A external-priority patent/KR101664919B1/ko
Priority claimed from KR1020140162011A external-priority patent/KR101684885B1/ko
Priority claimed from KR1020140161982A external-priority patent/KR101664929B1/ko
Priority claimed from KR1020150074020A external-priority patent/KR101716206B1/ko
Priority claimed from KR1020150073981A external-priority patent/KR101705619B1/ko
Priority claimed from KR1020150074035A external-priority patent/KR101716166B1/ko
Priority claimed from KR1020150073977A external-priority patent/KR101705633B1/ko
Priority claimed from KR1020150074032A external-priority patent/KR101734890B1/ko
Priority claimed from KR1020150074028A external-priority patent/KR101716164B1/ko
Priority claimed from KR1020150074024A external-priority patent/KR101716160B1/ko
Priority claimed from KR1020150073985A external-priority patent/KR101705622B1/ko
Priority claimed from KR1020150073984A external-priority patent/KR101705621B1/ko
Priority claimed from KR1020150073978A external-priority patent/KR101705634B1/ko
Priority claimed from KR1020150073975A external-priority patent/KR101705617B1/ko
Priority claimed from KR1020150074023A external-priority patent/KR101716159B1/ko
Priority claimed from KR1020150073989A external-priority patent/KR101807611B1/ko
Application filed by (주) 효성 filed Critical (주) 효성
Publication of WO2016072642A2 publication Critical patent/WO2016072642A2/fr
Publication of WO2016072642A3 publication Critical patent/WO2016072642A3/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
    • A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45C—PURSES; LUGGAGE; HAND CARRIED BAGS
    • A45C11/00—Receptacles for purposes not provided for in groups A45C1/00-A45C9/00
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J27/00—Cooking-vessels
    • A47J27/08—Pressure-cookers; Lids or locking devices specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L3/00—Supports for pipes, cables or protective tubing, e.g. hangers, holders, clamps, cleats, clips, brackets
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C5/00—Constructions of non-optical parts

Definitions

  • the present invention relates to a polyketone resin composition having excellent impact resistance, and more particularly, by blending a polyketone resin with glass fiber, an inorganic filler, a mineral reinforcing material, and the like, for a mask, a pipe holder, a transmission bracket, a bumper bracket, and an automobile.
  • junction box car wheel rim, bracket for power line, electronics cover, glasses frame, car air intake manifold, carrier of car front end module, car headlamp bezel, car ashtray, car multifunction switch, car speaker grill, car
  • the present invention relates to a polyketone resin composition applicable to various industrial parts such as a head restraint guide for a vehicle, a navigation base for an automobile, an automotive side molding, a hose connector, a stem bolt for an air conditioner, and the like.
  • the present invention relates to a polyketone composition having excellent mechanical properties, and more particularly, to a polyketone composition manufactured using a blend containing an amorphous semiaromatic polyamide or polyester in a polyketone resin and applicable to industrial parts. will be.
  • the present invention relates to a notebook lower housing manufactured by injection molding a polyketone resin composition, and more particularly to a notebook lower housing having excellent flexural modulus and low temperature impact strength by using a polyketone resin composition.
  • Polyketone (PK) is a material that has lower raw materials and polymerization process costs than general engineering plastic materials such as polyamide, polyester, and polycarbonate.
  • Polyketone (PK) has excellent properties such as heat resistance, chemical resistance, fuel permeability, and abrasion resistance. It is widely applied to.
  • polyketones or polyketone polymers 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. Pat.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.
  • the mechanical properties of the polyketone blends are diversified in application fields of thermoplastics, and due to industrial demands for more excellent properties, studies on polyketone resin compositions having excellent tensile strength and impact strength are required.
  • Japanese Patent Laid-Open No. 11-71513 discloses a polyketone resin composition which is useful as a housing part and improves fluidity, heat resistance, organic solvent resistance and moldability.
  • This patent discloses the polyketone resin composition which contains 0.01-60 weight part of flame retardants with respect to 100 weight part of polyketone resin which mix
  • an organic bromide, an organophosphorus compound, etc. are used as a flame retardant.
  • flame retardants containing organic halogen (Halogen) is limited because of the use of environmental problems, and a lot of problems of smell and coloring occurs.
  • nylon resins, non-reinforced flame retardant ABS resins and flame retardant PC / ABS resins have low rigidity and are not suitable for the recent thinning requirements. Due to the mobility of electric and electronic devices such as personal computers, telephones, notebooks, and the like, development of housings having lightweight and high strength mechanical properties is required. For example, in the case of a notebook housing, a material is developed to solve the problem that a part is bent and comes into contact with an internal component, and the internal component is broken or the housing itself is destroyed. Japanese Patent Laid-Open No.
  • 2008-34823 discloses a technique for producing an electronic device housing by injection molding a thermoplastic resin member containing glass fibers by interposing a thermosetting resin member containing carbon fibers with an adhesive layer made of a nonwoven fabric of a thermoplastic resin.
  • the conventional carbon fiber reinforced thermoplastic resin composition can achieve high rigidity and light weight, but has a problem of being soft and brittle as a material for a housing.
  • An object of the present invention to provide a polyketone resin composition excellent in tensile strength and impact strength compared to the existing polyketone polymer to solve the above problems.
  • an object of the present invention is to provide a polyketone composition that can improve the bending characteristics while maintaining a certain level of tensile strength, impact strength compared to the existing polyketone composition.
  • an object of the present invention is to obtain a notebook bottom housing characterized by sufficient flexural modulus and excellent low temperature impact resistance by injection molding a polyketone composition.
  • the present invention to solve the above problems
  • a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), the molecular weight distribution of 1.5 to 2.5, y / x of 0.03 to 0.3 linear alternating polyketone and glass fiber, inorganic filler, It provides a polyketone resin composition with improved impact resistance comprising a mineral reinforcing agent as a means for solving the problem.
  • the present invention may be prepared by further comprising a polyurethane resin, polycarbonate resin, polyamide 6 resin, rubber, ASA and sulfonamide plasticizer in order to solve the above problems more effectively.
  • the polyketone resin composition of the present invention is a glass fiber, inorganic filler, mineral reinforcing agent, polyurethane resin, polycarbonate resin, polyamide 6 resin, rubber, ASA and sulfonamide plasticizer relative to 100 parts by weight of the polyketone copolymer It is characterized in that it is added alone or mixed by 5 to 50 parts by weight.
  • the present invention consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon, 60 to 90% by weight of alternating polyketone and 10 to 40% by weight of linear fiber having a residual amount of palladium catalyst of 5 to 50 ppm and a molecular weight distribution of 1.5 to 3.0. It provides a polyketone composition, characterized in that the blend is prepared by injection molding.
  • Preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bipolar compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And preparing a polyketone automobile air intake manifold by injection molding 100 wt% of the blend containing 60 to 90 wt% of the polyketone resin and 10 to 40 wt% of the glass fiber; Characterized in that the manufacturing method of the polyketone composition comprising a.
  • a mixed solvent including an alcohol (eg, methanol) and water
  • Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymer
  • Intrinsic viscosity is 1.0 ⁇ 2.0dl / g, the impact strength is 10 ⁇ 12kJ / m 2, provides a molded article made of a polyketone-polyurethane resin composition, characterized in that the resilience is 35% to 45% do.
  • the weight ratio of polyketone and glass fiber is 50:50 to 95: 5, and the glass fiber has a diameter of 10 ⁇ m, a length of 4 mm, and is coated with polyurethane, and a ligand of a catalyst composition used in polyketone polymerization.
  • the hardness is 95 or more, and the composition ratio of polycarbonate is 1% by weight to 30% by weight based on the total weight of the polyketone composition, and the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1, 3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and has an inherent viscosity of 1.0 to 2.0 dl / g, as a polyketone composition. Provides manufactured industrial parts.
  • the polyketone spectacle frame has a bending angle of 2 ° or less, and the intrinsic viscosity of the polyketone copolymer provides a polyketone spectacle frame, characterized in that 1.0dl / g to 2.0dl / g.
  • Polyketone high impact mask characterized in that the impact resistance of the polyketone mask is 80kJ / m2 or more, the retention of physical properties after moisture absorption of the polyketone is 85% or more relative to the physical properties before the moisture absorption, the catalyst composition used for the polymerization of polyketone Ligand is a poly (ketone) high impact, characterized in that ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) Provide a mask.
  • 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 (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And injection molding 100% by weight of the blend of 50 to 90% by weight of the polyketone resin and 10 to 50% by weight of the mineral reinforcing material to manufacture a polyketone pipe holder. It provides a method for producing a polyketone pipe holder comprising a.
  • Linear alternating polyketone polymer, sulfonamide plasticizer, polyurethane, ASA Anarylic Styrene Acrylonitrile consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon and having a residual amount of palladium catalyst of 50 ppm or less and a molecular weight distribution of 1.5 to 2.5 It is prepared by injection molding the blend, wherein the sulfonamide-based plasticizer, polyurethane and ASA is a shoe material, characterized in that 10 to 20% by weight, 15 to 20% by weight and 1 to 10% by weight, respectively, relative to the total blend
  • the ligand of the catalyst composition is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl Phosphine)
  • the flexural modulus is 7000 to 8500MPa to provide a shoe material, characterized in that.
  • Polyketone molded product characterized in that the moisture absorption rate is less than 1.0% at 50 °C, 90% relative humidity conditions, the impact strength is 15kJ / m2 or more, the content of the polyketone terpolymer is 50 to 90% by weight, The content of the glass fiber is 10 to 50% by weight and provides a polyketone molded product, characterized in that the polyketone molded product is an accelerator pedal.
  • the impact strength is 17 kJ / m 2 or more, the molecular weight distribution of the polyketone copolymer is 1.5 to 2.5, the ligand of the catalyst composition used in the polyketone polymerization is ((2,2-dimethyl-1,3-dioxane-5,5 -Diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and provides a polyketone transmission bracket characterized in that the tensile strength retention after moisture absorption of the polyketone transmission bracket is 80% or more.
  • a polyketone bumper bracket produced by injection molding a blend of linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon, polyamide 6 and rubber, wherein the polyketone is 40% by weight of the total blend. To 90% by weight, 5 to 40% by weight of polyamide 6 and 5 to 20% by weight of rubber, 70% by weight of polyketone, 22% by weight of polyamide 6 and 8% by weight of rubber.
  • the impact strength is 75 kJ / m2
  • the polyketone bumper bracket provides a polyketone bumper bracket, characterized in that the tensile strength retention of 75% or more in a 10% calcium chloride solution, the rubber is ethylene propylene diene monomer rubber.
  • the ligand of the catalyst composition used in the polymerization of a polyketone copolymer is characterized in that the impact strength at room temperature is 12 kJ / m 2 or more and the tensile strength retention after moisture absorption is 85% or more relative to the property before absorption.
  • an automotive junction box which is, 2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).
  • the glass fiber and the inorganic filler are included in an amount of 20 to 50 parts by weight and 5.5 to 15.5 parts by weight, respectively, based on 100 parts by weight of the polyketone copolymer, and the inorganic filler is selected from calcium carbonate, magnesium sulfate, silicon carbide, and calcium oxide, and the catalyst composition.
  • Polyketone electronic device cover characterized in that the content of the glass fiber compared to the blend is 5 to 50% by weight, the product strain of the electronic device cover is less than 0.1%, the electronic device cover is a poly protective cover Provides ketone electronics cover.
  • the linear alternating polyketone is a lid for electrical and electronic products, characterized in that the molar ratio of ethylene and propylene is 9 to 24: 1, the lid for battery electronics has an impact strength of 15 kJ / m 2 or more, 50 °C, relative humidity The moisture absorption rate is less than 1.5% at 90% RH, and the tensile strength measured at 50 ° C and 90% RH is maintained at a level of 85% or higher than the tensile strength measured at 25 ° C and 65% RH.
  • a lid for electrical and electronic products characterized in that for the pressure cooker.
  • Polyketone automotive air intake manifold is a polyketone automotive air intake manifold, characterized in that the impact strength is 8kJ / m2 or more, the tensile strength retention is 100% or more after 300 hours treatment at 120 °C, palladium compound, pKa value
  • a catalyst composition comprising an acid that is less than or equal to 6 and a ligand compound of phosphorus
  • Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin
  • manufacturing a polyketone car air intake manifold by injection molding 100% by weight of the blend containing 60 to 90% by weight of the polyketone resin and 10 to 40% by weight of glass fiber to manufacture a polyketone car air intake manifold.
  • the carrier of the polyketone automotive front end module has an impact strength of 8 kJ / m 2 or more and a tensile strength retention of 100% or more after 300 hours of treatment at 120 ° C., a palladium compound, an acid having a pKa of 6 or less, and a double ligand of phosphorus.
  • Preparing a catalyst composition comprising a compound; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And manufacturing a carrier of the polyketone car front end module by injection molding 100 wt% of the blend containing 60 to 90% by weight of the polyketone resin and 10 to 40% by weight of glass fiber. It provides a method of manufacturing a carrier of a module.
  • Impact strength of automobile headlamp bezel is 20kJ / m 2 or more
  • mineral fillers are talc, kaolin, mica, wollastonite, TiO2-coated mica compact (TiO2- coated mica platelets), silica (silica), alumina (alumina), borosilicate (borosilicates) and oxides (oxides), characterized in that any one selected from the group consisting of, based on 100% by weight of the total blend, the mineral Filler provides an automotive headlamp bezel, characterized in that 5 to 50% by weight.
  • Linear alternating polyketone is a vehicle canister comprising a polyketone blend, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15, characterized in that the canister has an impact strength of 20 kJ / m 2 or more.
  • Consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon containing 5 to 50 ppm of palladium catalyst residue, 60 to 85 wt% of linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 3.0, and 15 to 40 wt% of glass fibers.
  • the interior lamp housing characterized in that the blend is manufactured by injection molding, characterized in that the impact strength is 20kJ / m 2 or more.
  • the ashtray for vehicles has an impact strength of 8 kJ / m 2 or more, and the impact strength measured at 50 ° C. and 90% RH is maintained at a level of 90% or more compared to the impact strength measured at 25 ° C. and 65% RH.
  • An ashtray for a vehicle is provided.
  • Automotive multi-function switch provides a multi-function switch for the automobile, characterized in that the impact strength is 8kJ / m 2 or more, and the property retention is 90% or more.
  • An automobile speaker grill which is produced by injection molding a linear alternating polyketone polymer comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon, having a residual amount of palladium catalyst of 5 to 50 ppm and a molecular weight distribution of 1.5 to 3.0. , Impact strength is characterized in that more than 15kJ / m 2 .
  • the headrest guide for automobiles provides a headrest guide for automobiles, characterized in that the impact strength is 20kJ / m 2 or more.
  • the car navigation support provides a car navigation support, characterized in that the impact strength is more than 15kJ / m 2 .
  • Automotive side moldings provide automotive side moldings characterized in that the impact strength is at least 15 kJ / m 2 .
  • Polyketone hose connector characterized in that the low temperature impact strength at minus 30 °C 4kJ / m2 or more, the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-di
  • the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-di)
  • a polyketone hose connector characterized in that it is oxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).
  • Stem bolt for polyketone air conditioner is a stem bolt for polyketone air conditioner characterized in that the elongation at break is more than 100%, the impact strength is 10kJ / m2 or more, the ligand of the catalyst composition used for the polymerization of the polyketone copolymer (( Provides a stem bolt for polyketone air conditioner, characterized in that 2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) do.
  • the present invention is a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), having a molecular weight of 20,000 to 200,000, a molecular weight distribution of 1.5 to 2.5, and y / x of 0.03 to 0.3
  • polyketone compositions comprising phosphorus alternating polyketones and amorphous semiaromatic polyamides, wherein the weight ratio of said polyketones to amorphous semiaromatic polyamides is from 60:40 to 95: 5.
  • the amorphous semiaromatic polyamide is preferably polyhexamethyleneisophthalamide.
  • the flexural strength of the polyketone composition is 65 to 90MPa, the flexural modulus is 1,700MPa or more, the impact strength is preferably 7kJ / m2 or more.
  • the present invention also provides a polyketone molded article made of the polyketone composition.
  • the present invention is a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), and includes a linear alternating polyketone and a polyester having y / x of 0.03 to 0.3, wherein the polyester Is a polyketone composition, characterized in that 10 to 90% by weight relative to the total weight of the composition.
  • the polyketone preferably has an intrinsic viscosity of 1.0 to 2.0 dl / g.
  • the polyketone composition was heat treated at 300 ° C. for 2 hours by ASTM D-638, and the width of the injection direction portion and the right angle direction of the polyketone composition specimens before and after the treatment were measured by a slide caliper, respectively, 2.0% or less. And 0.5% or less.
  • the present invention also provides a polyketone molded article for an automobile fuel container including the polyketone composition.
  • the present invention is composed of 53 to 71% by weight of a linear alternating polyketone polymer consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon in the polyketone composition, the residual amount of palladium catalyst is 50 ppm or less, molecular weight distribution of 1.5 to 2.5,
  • a polyketone notebook bottom housing which is manufactured by injection molding a blend comprising 25 to 35% by weight of glass fiber, 2 to 12% by weight of phosphorus flame retardant, and 2 to 8% by weight of nylon 6I.
  • the ligand of the catalyst composition during the polymerization of the linear alternating polyketone is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl Phosphine).
  • the intrinsic viscosity of the linear alternating polyketone polymer is preferably 1.0 to 2.0 dl / g.
  • the polyketone notebook lower housing is characterized in that the flexural modulus is 8,000MPa or more, low temperature impact strength is 11.0kJ / m 2 or more.
  • Polyketone resin composition of the present invention is excellent in flexural properties, tensile strength, impact strength, moisture resistance and dimensional stability mask, pipe holder, transmission bracket, bumper bracket, automotive junction box, automotive wheel rim, power line binding bracket, electronics There is an advantage that can be applied to various industrial parts, such as device covers, eyeglass frames.
  • the polyketone composition of the present invention is higher in strength than the nylon resin used as a conventional notebook bottom housing material can obtain a notebook bottom housing with improved impact resistance.
  • the poly ketone resin used in the present invention is an engineering plastic and is a recently developed new resin, and is a thermoplastic synthetic resin that is usefully applied as a material for various molded products or parts due to its excellent mechanical properties and molding properties such as bending characteristics. .
  • 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 lower moisture absorption than nylon material, so it is possible to design various products with little change in dimensions and physical properties due to moisture absorption.
  • polyketone resin has a lower density than aluminum, making it suitable for weight reduction.
  • the polyketones used in the present invention are carbon monoxide, ethylenically unsaturated compounds and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, in particular repeating units derived from carbon monoxide and repeating units derived from ethylenically unsaturated compounds and propylene-like. It is a structure in which repeating units derived from an unsaturated compound are alternately connected to each other, and have excellent mechanical and thermal properties, excellent workability, high wear resistance, chemical resistance and gas barrier properties, and are useful materials for various applications.
  • the high molecular weight of these ternary or higher copolymerized polyketones is considered to be useful as an engineering plastic material having higher processability and thermal properties and excellent economic efficiency.
  • the wear resistance is high, and parts such as automobile gears and chemical resistance are high, and the gas barrier property, such as lining material of chemical transport pipe, is high, so that it can be used for light gasoline tanks and the like.
  • the ultra high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fibers, the fibers can be stretched at a high magnification and have a high strength and a high modulus of elasticity oriented in the stretching direction. It is very suitable for building materials and industrial materials.
  • the polyketone polymer of the present invention is a linear alternating structure, and substantially contains carbon monoxide for each molecule of unsaturated hydrocarbon.
  • Suitable ethylenically unsaturated hydrocarbons for use as precursors of polyketone polymers have up to 20, preferably up to 10 carbon atoms.
  • ethylenically unsaturated hydrocarbons are ethene and ⁇ -olefins such as propene, 1-butene, isobutene, 1-hexene, 1-octene
  • aryl aliphatic hydrocarbons in the ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene and m-isopropyl styrene.
  • the polyketone polymers preferably used in the present invention are copolymers of carbon monoxide and ethene or second ethylenically unsaturated hydrocarbons having at least three carbon atoms with carbon monoxide and ethene, in particular ⁇ -olefins such as propene. Terpolymers.
  • each unit containing the second hydrocarbon moiety in the terpolymer there are at least two units containing the ethylene moiety. It is preferable that there are 10-100 units containing a 2nd hydrocarbon part.
  • Polyketone polymers are prepared by contacting carbon monoxide with hydrocarbon monomers under polymerization conditions in the presence of a palladium compound, a catalyst composition suitably produced from anionic and phosphorus bidentate ligands of less than pKa 6 or preferably less than pKa 2.
  • a liquid phase polymerization may be employed in which an alcohol solvent is carried out in an alcohol solvent through a catalyst composition composed of a carbon monoxide and an olefin with a palladium compound, an acid having a PKa of 6 or less, and a diligand compound of phosphorus.
  • the polymerization reaction temperature is preferably 50 ⁇ 100 °C and the reaction pressure is 40 ⁇ 60bar.
  • the polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.
  • the palladium compound palladium acetate is preferable, and the amount of use thereof is preferably 10 -3 to 10 -1 1 mole.
  • the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, sulfonic acid, and the like.
  • trifluoroacetic acid is used, and the amount is preferably 6 to 20 equivalents relative to palladium.
  • 1, 3-bis [di (2-methoxy phenylphosphino)] propane is preferable as a bidentate coordination compound of phosphorus, and 1-1.2 equivalents are preferable with respect to palladium.
  • the process for producing polyketones is characterized by the presence of an organometallic complex catalyst consisting of a ligand having an element of (a) Group 9, Group 10 or Group 11, and (b) Group 15.
  • an organometallic complex catalyst consisting of a ligand having an element of (a) Group 9, Group 10 or Group 11, and (b) Group 15.
  • the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg methanol) and water to form a linear terpolymer, the mixture
  • a mixed solvent eg methanol
  • 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.
  • a liquid medium a mixed solvent consisting of 7090 vol% acetic acid and 1030 vol% water is used, and benzophenone is added during polymerization.
  • a mixed solvent consisting of acetic acid and water is used as a liquid medium, without using methanol, dichloromethane, or nitromethane, which have been mainly used in the production of polyketone.
  • a mixed solvent of acetic acid and water is used as the liquid medium in the production of the polyketone it is possible to improve the catalytic activity while reducing the production cost of the polyketone.
  • 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, trifluoromethane sulfonate ruthenium and the like.
  • 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, acetylacetate, palladium acetate and trifluoroacetic acid.
  • Examples of the Group 11 transition metal compound include a complex of copper or silver, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include copper acetate, trifluoroacetate, copper acetylacetate, silver acetate, Silver trifluoroacetic acid, silver acetyl acetate, silver trifluoromethane sulfonic acid, etc. are mentioned.
  • transition metal compounds (a) are nickel and copper compounds
  • preferred transition metal compounds (a) are palladium compounds in terms of yield and molecular weight of polyketones, and in terms of improving catalytic activity and intrinsic viscosity.
  • 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 (
  • 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.
  • 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).
  • 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) ((2,2-dimethyl) ((2,2-dimethyl) ((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.
  • 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.
  • DMSO dimethylsulfoxide
  • the amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies uniformly since 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 0.01-100 mmol, preferably 0.01-10 mmol, per liter of the 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).
  • 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.
  • the molar ratio of genus 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 transition metal and benzophenone is greater than 1: 100, the polyketone catalytic activity is rather decreased. It is not preferable because it tends to.
  • 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 ⁇ -olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and ⁇ -methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl
  • preferred ethylenically unsaturated compounds are ⁇ -olefins, more preferably ⁇ -olefins having 2 to 4 carbon atoms, most preferably ethylene, and 120 mol% propylene is added in the production of terpolymer copolyketones.
  • the input ratio of carbon monoxide and ethylenically unsaturated compound is 1: 12 (molar ratio) and to adjust propylene to 120 mol% relative to the total mixed gas.
  • polyketone it is common to set the ratio of carbon monoxide and ethylenically unsaturated compound to 1: 1, but in the present invention using a mixed solvent of acetic acid and water as a liquid medium and adding benzophenone during polymerization, carbon monoxide and ethylenic
  • the ratio of the unsaturated compound to 1: 12 and propylene is adjusted to 120 mol% of the total mixed gas, it was found that not only the processability was improved but also the catalytic activity and the intrinsic viscosity were simultaneously improved.
  • the amount of propylene is less than 1 mol%, the effect of three-way copolymerization 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. desirable.
  • a mixed solvent of acetic acid and water is used as a liquid medium, benzophenone is added during polymerization, and carbon monoxide and ethylenically unsaturated compound and one or more olefinically unsaturated compounds are added to the catalytic activity and intrinsic viscosity of the polyketone.
  • 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.
  • the catalyst is produced by contacting the two components.
  • Arbitrary methods can be employ
  • the molar ratio of the ethylenically unsaturated compound and the propylene unsaturated compound is preferably 99: 1 to 85:15. If the molar ratio of propylene is less than 1%, it is difficult to process the molded part, and if it exceeds 15%, There is a problem that the mechanical properties fall.
  • 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.
  • additives such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials to improve processability and physical properties of the polymer.
  • 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.
  • polymerization can use a well-known thing as it is or processing it.
  • polymerization Usually, it is normal pressure-20 MPa, Preferably it is 4-15 MPa.
  • Linear alternating polyketones are formed by the polymerization method as described above.
  • the polymer ring of the polyketone polymer preferred in the present invention may be represented by the following formula (2).
  • 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.
  • the polyketone polymer is a copolymer composed of repeating units represented by General Formulas (1) and (2), and it is preferable that y / x is 0.03 to 0.3.
  • y / x is 0.03 to 0.3.
  • y / x is more preferably 0.03 to 0.1.
  • the melting point of the polymer may be controlled by controlling the ratio of ethylene and propylene of the polyketone polymer.
  • 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.
  • 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, on whether the polymer is a copolymer or terpolymer, and in the case of terpolymers, on the nature of the second hydrocarbon moiety present.
  • fusing point of the conversion of the polymer used by this invention is 175 degreeC-300 degreeC, and is 210 degreeC-270 degreeC generally.
  • the ultimate viscosity number (LVN) of the polymer measured at 60 ° C.
  • HFIP Hexafluoroisopropylalcohol
  • the polyketone molding of the present invention is composed of a blend consisting of a combination of polyketone and glass fiber, it is characterized in that the stiffness, processability and dimensional stability compared to the conventional materials used.
  • the glass fiber preferably has a particle diameter of 10 to 13 ⁇ m.
  • the particle diameter of the glass fiber is less than 10 ⁇ m, the shape of the glass fiber may change and mechanical properties may decrease.
  • the composition ratio of the polyketone and glass fiber is preferably comprised of 60 to 90% by weight of polyketone polymer and 10 to 40% by weight of glass fiber. If the glass fiber content is less than 15% by weight, the mechanical rigidity may be lowered. If the glass fiber content is more than 40% by weight, the viscosity may be excessively increased, thereby reducing extrusion and injection workability.
  • additives may include, for example, antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials.
  • the polyketone as described above may be produced by extrusion molding or injection molding.
  • the blend composition of the polyketone and glass fibers of the present invention as described above is molded by a method such as extrusion, injection, and the like is produced as a polyketone molding, which is characterized by excellent rigidity, processability and dimensional stability.
  • the polyketone molded article has a product moisture absorption rate of 2.0% or less and the moisture content retention rate of 70% or more.
  • the impact strength is 10 kJ / m 2 or more, preferably 15 kJ / m 2 or more.
  • a liquid phase polymerization may be employed in which an alcohol solvent is carried out in an alcohol solvent through a catalyst composition consisting of a carbon monoxide and an olefin with a palladium compound, an acid having a PKa of 6 or less, and a binary ligand compound of phosphorus.
  • the polymerization reaction temperature is preferably 50 ⁇ 100 °C and the reaction pressure is 40 ⁇ 60bar.
  • the polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.
  • palladium acetate and a palladium compound in the amount of 10 -3 to 10-2 1mole preferred.
  • the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, sulfonic acid, and the like. In the present invention, trifluoroacetic acid is used, and the amount is preferably 6 to 20 equivalents relative to palladium.
  • 1, 3-bis [di (2-methoxy phenylphosphino)] propane is preferable as a bidentate coordination compound of phosphorus, and 1-1.2 equivalents are preferable with respect to palladium.
  • the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. Less than 1.5 had a poor polymerization yield, and more than 2.5 had a problem of poor moldability.
  • the glass fiber which is a subcomponent of this invention is demonstrated. It is also called glass fiber or glass wool by melting and processing the glass containing silicate as a main component to make it into a fiber shape. Glass fiber is classified according to manufacturing method and divided into short fiber and long fiber. In addition, there are optical fibers for image transmission and glass fibers (optical fibers) for optical communication. Glass has been known for its craft use since ancient times because it stretches like snow at high temperatures. It was the first time that industrialized short fibers were manufactured in Germany as a substitute for natural asbestos during World War I. Long fibers were industrialized in the United States in the 1930s and optical fibers in the 60s. Short fibers are simple to manufacture and are made of felt and used for insulation.
  • Optical fibers are a regular bundle of thousands of hundreds to hundreds of thousands of specially structured fibers, and when an image is inserted at one end of the bundle, it is transmitted to the other end according to the bundle's refraction. It also has a wide range of uses besides fiber scopes.
  • glass fibers are thin, so the specific surface area is very large. For example, if a glass bead with a diameter of 1 cm is stretched into a fiber having a diameter of 1 ⁇ m, its length is about 4,000 m and its area is nearly 400 times larger, thus having a chemical composition (E glass) that is not easily eroded by moisture.
  • C-glass is acid-resistant, and alkali-resistant fibers, such as battery cells, have recently been put to practical use and are used for cement reinforcement.
  • Method for producing a polyketone resin composition excellent in impact resistance 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 (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the 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 glass fibers, inorganic fillers, mineral reinforcing materials, and the like into the polyketone resin.
  • a mixed solvent polymer solvent
  • a solvent eg, alcohol and acetone
  • polyurethane resin polycarbonate, polyamide 6 resin, rubber, ASA (Acrylic Styrene Acrylonitrile), etc. can be further mixed to further improve impact resistance and elasticity, and sulfonamide to improve processability and formability.
  • Systemic plasticizers can be added.
  • Palladium acetate may be used as the palladium compound constituting the catalyst composition, and the amount of the palladium compound is preferably 10 -3 to 10 -1 mole.
  • 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 (molar) equivalents to the compound are appropriate.
  • Examples of the phosphorus double ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (eg, 1,3-bis [di (2-methoxyphenylphosphino)] propane, 1,3- Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane and ((2,2-dimethyl-1,3-diox
  • One or more selected ones can be used, and the amount used is 1 to 1.2 (mol) compared to the palladium compound.
  • the carbon monoxide, ethylene, and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer.
  • the mixed solvent may be a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water. 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.
  • the polymerization temperature is 50 ⁇ 100 °C
  • the reaction pressure is suitable for the range of 40 ⁇ 60bar.
  • 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.
  • the obtained polyketone resin is mixed with glass fiber, inorganic filler, mineral reinforcing material, polyurethane resin, polycarbonate, polyamide 6 resin, rubber, Acrylic Styrene Acrylonitrile (ASA), sulfonamide plasticizer as necessary.
  • Extrusion with an extruder finally yields the blend composition.
  • the blend is prepared by melt kneading and extrusion into a twin screw extruder.
  • the extrusion temperature is 230 ⁇ 260 °C
  • screw rotation speed is preferably in the range of 100 ⁇ 300rpm. If the extrusion temperature is less than 230 °C kneading may not occur properly, if it exceeds 260 °C may cause problems with the heat resistance of the resin. In addition, if the screw rotational speed is less than 100rpm it may not be a smooth kneading, if it exceeds 300rpm conductive carbon black or elastic polyurethane or carbon fiber may be destroyed and mechanical properties may be reduced.
  • the glass fiber is added to improve the tensile strength and impact strength is 10 ⁇ m in diameter, 4mm in length, preferably coated with polyurethane.
  • the blending efficiency with the polyketone is excellent, and when the composition is manufactured as an industrial part, the mechanical properties are excellent.
  • the present invention is not limited thereto.
  • the inorganic filler is added to further improve the mechanical properties of the polyketone blend resin composition, but calcium carbonate, magnesium sulfate, silicon carbide, calcium oxide and the like are used, but are not necessarily limited thereto.
  • the mineral reinforcing material is to improve impact resistance and dimensional stability, such as talc, kaolin, mica, wollastonite, TiO2-coated mica platelets, It is preferably one of silica, alumina, borosilicates and oxides.
  • a blend of the linear alternating polyketone and the mineral filler is used, wherein the mineral filler is talc, kaolin, mica, wollastonite, TiO 2 -coated.
  • Mica plates TiO 2 -coated mica platelets
  • silica silica
  • alumina alumina
  • borosilicates and oxides a blend of the linear alternating polyketone and the mineral filler
  • the content of the mineral filler is 5 to 50% by weight. Preferably it is 30 to 40% by weight.
  • the mineral filler is added in less than 5% by weight, the dimensional stability is lowered, and when it exceeds 50% by weight, the injection moldability is lowered.
  • the polyurethane resin is added as necessary to improve the impact strength and resilience of the polyketone resin.
  • the polycarbonate is added as necessary to improve the hardness of the polyketone resin.
  • the polyamide 6 resin and rubber are intended to improve impact resistance, water resistance, and the like.
  • the melt index of the polyamide (240 ° C., 21.2 N) is preferably 5 to 70 g / 10 min. If it is less than 5 g / 10 min, the moldability of parts becomes weak, and if the flow index is more than 70 g / 10 min, physical properties such as impact strength are lowered.
  • EPDM ethylene propylene diene monomer
  • EPDM ethylene propylene diene monomer
  • the ASA (Acrylic Styrene Acrylonitrile) is about 90 kcal / mol of dissociation energy of hydrogen in the rubber main chain, and has a characteristic of dissociating in light having a high wavelength energy of 300 nm or less, and thus, it is difficult to basically cause weathering degradation. Therefore, it is possible to enhance the elasticity and weather resistance of the polyketone resin due to the addition of the ASA.
  • the glass fiber, inorganic filler, mineral reinforcing material, polyurethane resin, polycarbonate, polyamide 6 resin, rubber, ASA (Acrylic Styrene Acrylonitrile), sulfonamide-based plasticizer may be blended alone or mixed, the amount is added 5 to 50 parts by weight relative to 100 parts by weight of the polyketone terpolymer is good, preferably 10 to 20 parts by weight. If the added content is less than 5 parts by weight, it is not possible to give the desired tensile strength and impact strength, and if it exceeds 50 parts by weight, the mechanical strength, dimensional stability and molding characteristics of polyketones may be lowered and thus, may lack practicality.
  • Polyketone resin composition according to the production method of the present invention is excellent in tensile strength and impact strength mask, pipe holder, transmission bracket, bumper bracket, automotive junction box, automobile wheel rim, power line binding bracket, electronic device cover, eyeglass frame, etc. There is an advantage that can be applied to industrial parts of various fields.
  • the polyketone composition according to an embodiment of the present invention is characterized in that the bending properties are excellently improved by containing an amorphous semiaromatic polyamide in the polyketone.
  • Non-limiting examples of such amorphous semiaromatic polyamides include poly hexamethyleneisophthalamide (nylon 6I), hexamethyleneisophthalamide / hexamethylene terephthalamide copolymer (nylon 6I / 6T), poly (methazyl Yleneisophthalamide) (nylon MXDI), caprolactam / methaxylyleneisophthalamide copolymer (nylon 6 / MXDI), caprolactam / hexamethyleneisophthalamide copolymer (nylon 6 / 6I), and the like.
  • poly hexamethyleneisophthalamide (nylon 6I) can be particularly preferably used.
  • the polyketone composition of the present invention is composed of a blend made of a combination of polyketone and amorphous semiaromatic polyamide, and is characterized by improving bending characteristics.
  • the weight of the amorphous semiaromatic polyamide is 5 to 40% by weight relative to the total weight. Preferably it is 10-30 weight%, More preferably, it is 10-20 weight%. If the content of the polyketone resin is less than 60% by weight, the mechanical strength, dimensional stability, and molding properties of the polyketone resin are inferior, resulting in a lack of practicality and workability, and exceeding 95% of the amorphous semiaromatic polyamide. Relative content reduction can make it difficult to impart desired levels of flexural properties.
  • carbon fibers, mica and talc may be added to the composition to reinforce the mechanical properties.
  • antioxidants, pigments and the like can be added as desired. Such additives may be suitably used by those skilled in the art.
  • the polyketone composition according to another embodiment of the present invention is characterized by having excellent moisture resistance and dimensional stability by containing polyester in the polyketone.
  • polyester resin which is a subcomponent of the said polyketone composition is demonstrated.
  • the polyketone composition of the present invention is composed of a blend consisting of a polyketone and a polyester combination, characterized in that to improve moisture resistance.
  • the weight of the polyester is 10 to 90% by weight relative to the total weight. Preferably it is 10-60 weight%, More preferably, it is 20-60 weight%. If the content of the polyketone resin is less than 10% by weight, the mechanical strength, dimensional stability, and molding characteristics of the polyketone resin may be lowered, thereby causing a lack of practicality. It can be difficult to impart moisture resistance.
  • carbon fibers, mica and talc may be added to the composition to reinforce the mechanical properties.
  • antioxidants, pigments and the like can be added as desired. Such additives may be suitably used by those skilled in the art.
  • the polyketone notebook bottom housing is composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon in the polyketone composition, the residual amount of palladium catalyst is 50 ppm or less, and the molecular weight distribution is 1.5 to 2.5. It is prepared by injection molding a blend comprising 53 to 71% by weight of the linear alternating polyketone polymer, 25 to 35% by weight of glass fiber, 2 to 12% by weight of phosphorus flame retardant, and 2 to 8% by weight of nylon 6I. do. If the content of the polyketone, glass fiber, phosphorus-based flame retardant and nylon 6I is less than or above the above range, mechanical properties are poor for use in a notebook housing.
  • Glass fibers are mixed to enhance the mechanical strength of the polyketone resin composition.
  • the amount to be mixed is 20 to 40% by weight, preferably 25 to 35% by weight, more preferably 35% by weight relative to the total weight. If it is less than 20% by weight, the mechanical strength such as impact resistance is not excellent, and if it exceeds 40% by weight, there is a problem that the improvement effect of the mechanical strength is insignificant compared to the economic cost increase due to mixing.
  • the present invention further mixes a flame retardant and nylon 6I to enhance the heat and flame resistance of the final notebook product.
  • the mixing amount is 5 to 10% by weight of the flame retardant, 2 to 8% by weight of nylon 6I relative to the total weight%, preferably 7% by weight of flame retardant, 5% by weight of nylon.
  • the flame retardant used in the present invention is non-halogen-based, particularly preferably a phosphorus flame retardant.
  • Representative phosphorus flame retardants are Cyclic Phosphate Phosphonic, P- [3-[(hydroxymethyl) amino] -3-oxopropyl] -dimethyl ester, Dimethyl methyl phosphonate, Phosphonic, P-[[bis (2-hydroxyethyl) amino] methyl] -diethyl esters, Triethyl Phosphate, Isopropyl phenyl diphenyl phosphate, Tris (2-chloroethyl) phosphate, Tetrakis hydroxymethyl phosphonium sulfate, etc., but are not necessarily limited thereto.
  • a manufacturing method for manufacturing a notebook lower housing of the present invention is as follows.
  • a method of manufacturing a notebook lower housing 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 of methanol-water (polymerization solvent); Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone polymer; And mixing and extruding 52 wt% of the polyketone polymer, 30 wt% of glass fiber, 7 wt% of trimethyl phosphate, and 5 wt% of nylon 6I to prepare a blend; And injection molding the blend, but is not limited thereto.
  • a solvent eg, alcohol and acetone
  • the notebook lower housing made of the polyketone composition as described above is characterized in that the flexural modulus is 8000 MPa or more, and the impact strength is 11 kJ / m 2 or more. Accordingly, the polyketone composition may be usefully applied to a notebook lower housing having excellent flexural modulus and impact resistance.
  • Polyketone manufacturing method for industrial parts 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 (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone polymer; Preparing a blend by mixing and extruding 60 to 90 wt% of the polyketone polymer and 10 to 40 wt% of glass fibers; And injection molding the blend, but is not limited thereto.
  • a mixed solvent polymer solvent
  • a solvent eg, methanol
  • 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.
  • the acid having a pKa value of 6 or less constituting the catalyst composition may be at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, preferably trifluoroacetic acid.
  • the use amount is 6-20 (mole) equivalents with respect to a palladium compound.
  • 1,3-bis [diphenylphosphino] propane for example, 1,3-bis [di (2-methoxyphenylphosphino)] propane, 1 , 3-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 one or more selected from the group consisting of, the amount of 1 to 20 (mole) equivalent to the palladium compound is appropriate.
  • the carbon monoxide, ethylene, and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer.
  • the mixed solvent may be a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water. 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.
  • the polymerization temperature is 50 ⁇ 100 °C
  • the reaction pressure is suitable for the range of 40 ⁇ 60bar.
  • 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.
  • the obtained polyketone polymer is mixed with glass fibers and then extruded with an extruder to finally obtain a blend composition.
  • the blend may be prepared by melt kneading and extrusion into a twin screw extruder.
  • the extrusion temperature is 230 ⁇ 260 °C
  • screw rotation speed is preferably in the range of 100 ⁇ 300rpm. If the extrusion temperature is less than 230 °C kneading may not occur properly, if it exceeds 260 °C may cause problems with the heat resistance of the resin. In addition, if the screw rotational speed is less than 100rpm may not be smooth kneading, if the screw speed exceeds 300rpm glass fiber may be destroyed and mechanical properties may be reduced.
  • Industrial parts may be manufactured by preparing a blend in the same manner as described above and extruding or injection molding it.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C.
  • polyketone terpolymer prepared by Example 1 100 parts by weight of polyketone terpolymer prepared by Example 1 3 parts by weight of glass fiber, 3 parts by weight of calcium carbonate, 3 parts by weight of talc, 5 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate, polyamide 4 parts by weight of the resin were mixed and prepared into pellets on an extruder using a biaxial screw with a diameter of 2.5 cm and operating at 250 rpm.
  • PA66 70 parts by weight (A218V30) 3 parts by weight of glass fiber, 5 parts by weight of calcium carbonate, 5 parts by weight of talc, 5 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate to operate at 250rpm It was made into pellets on an extruder using a biaxial screw with a diameter of 2.5 cm and L / D 32.
  • PA66 A218V30 product
  • glass fiber 3 parts by weight of glass fiber
  • calcium carbonate 3 parts by weight of talc
  • polyurethane resin 2 parts by weight of polycarbonate
  • polyamide resin 4 parts by weight
  • PA66 70 parts by weight (A218V30) 2 parts by weight of glass fiber, 2 parts by weight of calcium carbonate, 3 parts by weight of talc, 3 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate, 2 parts by weight of polyamide resin Part, 2 parts by weight of rubber, 2 parts by weight of ASA and 2 parts by weight of sulfonamide-based plasticizer were mixed into pellets on an extruder by using a biaxial screw having a diameter of 2.5 cm and operating at 250 rpm. Prepared.
  • the prepared polyketone composition of the above Example was prepared as a specimen, and then compared with the product of the comparative example, the physical properties were evaluated in the following manner, and the results are shown in Table 1 below.
  • Example 1 Item Tensile Strength (MPa) Impact Strength (kJ / m 2 ) Flexural modulus Product Strain Rate (Vertical%) Product strain rate (horizontal%)
  • Example 1 148 18 7800 0.08 0.05
  • Example 2 155 17 7800 0.08 0.06
  • Example 3 156 16 8200 0.09 0.07
  • Example 4 158 16 8400 0.07 0.05
  • Example 5 158 15 8400 0.11 0.07 Comparative Example 1 120 5 6400 0.84 0.75 Comparative Example 2 125 4 6600 0.75 0.66 Comparative Example 3 130 4 7000 0.72 0.62 Comparative Example 4 134 5 7200 0.77 0.68 Comparative Example 5 136 4 7400 0.64 0.58
  • the polyketone resin composition of the present invention through Table 1 was confirmed that not only excellent impact resistance, such as tensile strength, impact strength, but also excellent retention of properties after elasticity and moisture absorption. Therefore, the polyketone resin composition of the present invention is expected to be applied to industrial parts in various fields such as masks, pipe holders, transmission brackets, bumper brackets, automotive junction boxes, automobile wheel rims, power line binding brackets, electronic device covers, eyeglass frames, and the like. .
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Example 6 Except for setting the content of the polyketone in Example 6 80% by weight, the glass fiber content 20% by weight is the same as in Example 6.
  • the glass fiber content 30% by weight is the same as in Example 6.
  • the glass fiber content 40% by weight is the same as in Example 6.
  • the air intake manifold manufactured through the embodiment of the present invention exhibits better impact resistance and long-term heat resistance than the comparative example used as a conventional air intake manifold material, and thus is more suitable for application as an air intake manifold. Do.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Example 10 Except for setting the content of the polyketone in Example 10 80% by weight, the content of the glass fiber 20% by weight is the same as in Example 10.
  • Example 10 Except for setting the content of the polyketone in Example 10 70% by weight, the glass fiber content of 30% by weight is the same as in Example 10.
  • Example 10 is the same as in Example 10 except that the content of the polyketone 60% by weight, the glass fiber content of 40% by weight.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 °C
  • LVN measured at 25 °C by hexa-fluoroisopropano (HFIP) was 1.4dl / g.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • Example 14 Example 15
  • Example 16 Izod impact strength (KJ / m 2 ) 6 23 24 22 Formability usually Great Great Great Great
  • Example was evaluated to be excellent in impact strength and injection properties compared to the comparative example.
  • the automobile headlamp bezel manufactured according to the embodiment of the present invention was excellent in impact resistance and injection resistance, it was very suitable for application as an automobile headlamp bezel.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • the canister manufactured through the embodiment of the present invention exhibits excellent dimensional stability than that of the comparative example used as a conventional canister material, and thus is more suitable for application as a canister.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • a screw was used to make pellets on an extruder, and then injection molded to prepare specimens of an indoor lamp housing.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • Example 21 Example 22
  • Example 23 Example 24 Comparative Example 10 Impact strength (kJ / m2) 25 23 28 27 18 Formability Great Great Great Great usually Dimensional rate of change (%) 1.3 1.1 1.2 1.5 5.2
  • the interior lamp housing manufactured through the embodiment of the present invention exhibits excellent moldability, impact resistance and dimensional stability than the case of the comparative example used as a conventional interior lamp housing material, it is more suitable for application to the interior lamp housing.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • Example 25 Except for setting the content of the polyketone in Example 25 80% by weight, the glass fiber content 20% by weight is the same as in Example 25.
  • Example 25 Except for setting the content of the polyketone in Example 25, 70% by weight, the glass fiber content of 30% by weight is the same as in Example 25.
  • Example 25 Except for setting the content of the polyketone in Example 25, 60% by weight, and the content of glass fiber 40% by weight is the same as in Example 25.
  • the impact strength was improved compared to the comparative example, and the impact strength retention was 90% or more.
  • the flame retardant properties were found to be equal or higher than those of the comparative examples.
  • the ashtray for vehicles according to the present invention has excellent impact resistance and physical property retention rate, and shows excellent flame retardant properties, and thus, has been shown to be more suitable for use as a vehicle ashtray.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • Example 29 Except for setting the content of the polyketone in Example 29 80% by weight, the glass fiber content 20% by weight is the same as in Example 29.
  • the glass fiber content 30% by weight is the same as in Example 29.
  • Example 29 Except for setting the content of the polyketone in Example 29 60% by weight, the content of the glass fiber 40% by weight is the same as in Example 29.
  • the impact strength was improved compared to the comparative example, the impact strength retention was found to be 90% or more.
  • the multifunction switch for automobiles according to the present invention has been found to be more suitable for being used as a multifunction switch for automobiles because of its excellent impact strength and physical property retention rate.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 °C and two stages of 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 °C and two stages of 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • the headrest guide manufactured through the embodiment of the present invention exhibits excellent moldability and dimensional stability than the comparative example used as a conventional headrest guide material, and thus is more suitable for application as a headrest guide for automobiles. .
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 °C and two stages of 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • Example 39 Example 40
  • Example 41 Comparative Example 14 Impact strength (kJ / m2) 18 20 22 7 Formability Great Great Great usually Dimensional rate of change (%) 1.3 1.1 1.2 5.2
  • the navigation pedestal produced through the embodiment of the present invention exhibits excellent moldability and dimensional stability than the case of the comparative example used as a conventional navigation pedestal material, it is more suitable for application as a navigation for automobiles.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 °C and two stages of 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • the side molding prepared through the embodiment of the present invention exhibits excellent moldability and dimensional stability than the case of the comparative example used as a conventional side molding, it is more suitable for application as an automotive side molding.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 235 ° C
  • LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 2.0 dl / g
  • MWD was 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 225 ° C
  • LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 2.0 dl / g
  • MWD was 2.0.
  • Example 46 Comparative Example 16 Low temperature elongation (%) 40 35 25 Low temperature impact strength (kJ / m2) 7.0 4.8 3.5 Freeze test Good Good Destruction
  • the polyketone hose connector manufactured through the embodiment of the present invention exhibits better low temperature tensile elongation and impact resistance than that of the comparative example, and thus is more suitable for application to the hose connector.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 235 ° C
  • LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 2.0 dl / g
  • MWD was 2.0.
  • the stem bolt for polyketone air conditioner manufactured through the embodiment of the present invention shows better elongation at break and impact resistance than the case of the comparative example, it is more suitable for applying to the air conditioner stem bolt.
  • a polyketone-polyurethane resin composition was prepared by blending 99% by weight of the prepared polyketone terpolymer and 1% by weight of thermoplastic polyurethane.
  • Polyketone-polyurethane resin composition was prepared by blending 90% by weight of polyketone terpolymer and 10% by weight of thermoplastic polyurethane prepared in the same manner as in Example 48.
  • Polyketone-polyurethane resin composition was prepared by blending 80% by weight of polyketone terpolymer and 20% by weight of thermoplastic polyurethane prepared in the same manner as in Example 48.
  • Polyketone-polyurethane resin compositions were prepared using 90% by weight of Rhodia PA66 (available from A218V30) and 10% of thermoplastic polyurethane instead of polyketone.
  • the prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 15 below.
  • Example 48 Example 49 Example 50 Comparative Example 18 Comparative Example 19 Resilience (%) 35 38 42 25 37 Impact Strength (KJ / m 2 ) 12 11.8 12.2 11.8 5.4
  • Polyketone-polyurethane resin composition of the present invention in Table 15 is excellent in resilience (35% to 45%) and impact strength (10 ⁇ 12kJ / m 2 ) compared to PA66 to be used as a thermoplastic plastic for industrial use Was evaluated as suitable for.
  • Example 54 It is the same as Example 54 except the intrinsic viscosity of polyketone is 1.0.
  • Specimens were prepared in the same manner as in Example 54 except for 70% by weight of Rhodia PA66 (manufactured by A218V30) instead of polyketone.
  • the prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 16 below.
  • Example 51 Example 52 Example 53 Example 54 Example 55 Example 56 Example 57 Comparative Example 20 Furtherance PK95% / GF5% PK90% / GF10% PK80% / GF20% PK70% / GF30% PK60% / GF40% PK50% / GF50% PK70% / GF30% PA70% / GF30% Tensile Strength Rating (MPa) 148 155 156 158 162 170 180 130 Impact Strength (KJ / m2) 18 20 21 18 20 17 23 12
  • Example 51 As shown in Table 16, in Example 51, the tensile strength and the impact strength were superior to those of Comparative Example 20.
  • Example 51 the polyketone composition prepared in Example 51 rather than Comparative Example 20 was evaluated to be suitable for use as a thermoplastic plastic used for industrial bar having excellent electrical properties.
  • Example 58 Same as Example 58 except for 90 weight percent polyketone terpolymer and 10 weight percent polycarbonate.
  • Example 58 Same as Example 58 except 80 wt% polyketone terpolymer and 20 wt% polycarbonate.
  • Example 58 Same as Example 58 except for 70 weight percent polyketone terpolymer and 30 weight percent polycarbonate.
  • a specimen was prepared in the same manner as in Example 58, except that 100 wt% polyketone was used.
  • the prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 17 below.
  • Hardness measurement Hardness was measured according to the following method in R scale of Rockwell hardness.
  • Example 58 Example 59 Example 60 Example 61 Comparative Example 21 Furtherance PK98% / PC2% PK90% / PC10% PK80% / PC20% PK70% / PC30% PA base Rockwell Hardness Measurement 99 103 110 108 90
  • the polyketone composition prepared according to the examples rather than the comparative example was evaluated to be suitable for use as a thermoplastic plastic used for industrial bar having excellent mechanical properties.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 80 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, a MI (Melt index) of 60 g / 10 min, and an MWD of 1.8.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.2.
  • PEI specimens which were conventionally used as materials for eyeglass frames, were used as comparative examples.
  • the bending angle of the final specimen was measured after 100 repeated measurements of flexural modulus in accordance with ASTM D790.
  • Example 62 Example 63 Example 64 Example 65 Example 66 Comparative Example 22 Properties IV: 1.2MWD: 2.0 IV: 1.4 MWD: 2.0 IV: 1.6MWD: 2.0 IV: 1.4 MWD: 1.8 IV: 1.4 MWD: 2.2 PEI Formability Good Good Good Good Good Medium (standard) Elastic restoring force (bending angle) 1.5 ° 1.3 ° 1.2 ° 1.5 ° 1.6 ° 2.5 °
  • the spectacle frame manufactured through the embodiment of the present invention has excellent elastic restoring power, and thus, was very suitable for application to the spectacle frame.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 80 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • the test specimen was injection molded on a molding machine having a clamping force of 80 tons to prepare a mask specimen. Notched Izod impact strength of the final mask specimen was measured by the test method of ASTM D256, and the tensile property retention after moisture absorption was measured.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • the test specimen was injection molded on a molding machine having a clamping force of 80 tons to prepare a mask specimen. Notched Izod impact strength of the final mask specimen was measured by the test method of ASTM D256, and the tensile property retention after moisture absorption was measured.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • HFIP hexa-fluoroisopropano
  • the test specimen was injection molded on a molding machine having a clamping force of 80 tons to prepare a mask specimen. Notched Izod impact strength of the final mask specimen was measured by the test method of ASTM D256, and the tensile property retention after moisture absorption was measured.
  • polyamide 66 (polyamide 66, PA66) were measured as a material of DuPont, which was previously used as a high-impact mask material.
  • Comparative Example is a product that is currently used in a high impact mask, the high impact mask produced through the embodiment of the present invention was very suitable for applying as a high impact mask having excellent impact resistance and physical properties.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the melting point of the polyketone terpolymer was 220 °C
  • LVN measured at 25 °C by hexa-fluoroisopropano (HFIP) was 1.4dl / g
  • MI (Melt index) was 60g / 10min.
  • 70% by weight of the polyketone terpolymer prepared above and 30% by weight of kaolin as a mineral reinforcing material at a diameter of 40 mm operating at 250 rpm, and prepared in pellet form on an extruder using a biaxial screw with L / D 32. Injection molding was performed to prepare specimens for pipe holders.
  • Example 70 Except that the content of the polyketone terpolymer and kaolin was adjusted as shown in Table 20, through the same procedure as in Example 70 were prepared for the pipe holder specimens, respectively.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • the examples prepared by blending polyketone and mineral reinforcement are excellent in impact resistance and impact stability at 10 KJ / m 2 or more and dimensional change rate of 0.1% or less compared to the comparative example. Was evaluated.
  • the pipe holder manufactured according to the embodiment of the present invention was very suitable for application as a pipe holder because it is very excellent in impact resistance and dimensional stability.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • the residual amount of palladium catalyst was 5 ppm.
  • 65% by weight of the polyketone terpolymer prepared in the same manner as in Example 73 and 16% by weight of sulfonamide-based plasticizer were prepared by adding 18% by weight of ASA and 1% by weight of ASA, and the prepared composition was operated at 250 rpm.
  • the diameter of 40cm, using a biaxial screw of L / D 32 to produce a pellet (pellet) on the extruder, and then injection molding to prepare a shoe material.
  • 65% by weight of the polyketone terpolymer prepared in the same manner as in Example 73 and 12% by weight of sulfonamide-based plasticizer were prepared by adding 20% by weight of polyurethane and 3% by weight of ASA, and the prepared composition was operated at 250 rpm.
  • the diameter of 40cm, using a biaxial screw of L / D 32 to produce a pellet (pellet) on the extruder, and then injection molding to prepare a shoe material.
  • Adhesiveness It hold
  • Examples 73 to 75 was found to be very suitable for use as a shoe material due to excellent flexural strength, elastic modulus and adhesiveness and deformation compared to the comparative example.
  • the shoe material including the polyketone blend of the present invention has excellent flexural modulus of 7000 to 8500 MPa.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 80 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • HFIP hexa-fluoroisopropano
  • a specimen was prepared in the same manner as in Example 77 except for 60 wt% of the polyketone terpolymer and 40 wt% of the glass fiber of Example 2.
  • a specimen was prepared in the same manner as in Example 77 except for 90 wt% of the polyketone terpolymer and 10 wt% of the glass fiber of Example 2.
  • Rhodia PA66 80% by weight Glass Fiber 20%, (A218V30) was prepared in the same manner as in Example 77.
  • Izod impact strength It was conducted according to ASTM D256.
  • Example 27 As shown in Table 22, in the case of Example compared to Comparative Example 27, the product moisture absorption was lower, the impact strength was found to be more excellent. Thus, the specimens prepared through the examples rather than the comparative examples were found to be more advantageous for use as an accelerator pedal.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 80 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • HFIP hexa-fluoroisopropano
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, a MI (Melt index) of 60 g / 10 min, and an MWD of 1.8.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.2.
  • the blend composition of 90% by weight of the polyketone terpolymer prepared in Example 82 and 10% by weight of glass fiber was introduced into a twin screw extruder of L / D32 and D 40 and extruded through melt kneading at a temperature of 240 ° C. at a 250 rpm screw rotation speed. After the pellet was prepared by injection molding to prepare a transmission bracket specimen.
  • the blend composition of 60% by weight of polyketone terpolymer and 40% by weight of glass fiber prepared in Example 82 was introduced into a twin screw extruder of L / D32 and D40, and extruded through melt kneading at a temperature of 240 ° C. at a 250 rpm screw rotation speed. After the pellet was prepared by injection molding to prepare a transmission bracket specimen.
  • Izod impact strength It was conducted according to ASTM D256.
  • Example 81 Example 82
  • Example 83 Example 84
  • Example 85 Example 86
  • the transmission bracket manufactured according to the embodiment rather than the comparative example has a high impact resistance (impact strength of 17kJ / m2 or more) and high water resistance property retention (tensile strength retention of 80% or more) is more suitable for use as a transmission bracket appear.
  • Example 88 Same as Example 88 except that the intrinsic viscosity of the polyketone was adjusted to 1.1.
  • Example 88 Same as Example 88 except that the intrinsic viscosity of the polyketone was adjusted to 2.0.
  • Rhodia's PA66 Glass Fiber 33% and A218V30 were used.
  • Izod impact strength It was conducted according to ASTM D256.
  • Example 88 Example 89 Example 90 Comparative Example 29 Izod impact strength (kJ / m2) 90 89 92 49 Tensile Strength (MPa) 55 56 57 58 Physical property retention rate (%) (90% relative humidity) 85 84 83 40 Physical property retention rate (%) (10% calcium chloride) 80 78 79 30
  • the tensile strength was similar to that of Comparative Example 29 in the case of Example 88, but the impact strength (75 kJ / m 2 or more) was significantly higher.
  • the physical property retention rate of high humidity and the chemical resistance test of calcium chloride showed that the property retention rate was higher than 75%.
  • the bumper brackets manufactured according to the examples rather than the comparative examples were found to be more suitable for use as bumper brackets because of high impact resistance and high physical property retention.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C.
  • Example 91 Same as Example 91 except that the molar ratio of ethylene and propene in the polyketone terpolymer was adjusted to 47 to 3.
  • Example 91 Same as Example 91 except that the intrinsic viscosity of the polyketone terpolymer was adjusted to 1.1 dl / g.
  • Example 91 Same as Example 91 except that the intrinsic viscosity of the polyketone terpolymer was adjusted to 2.0 dl / g.
  • Example 91 Except for using a polyamide instead of a polyketone terpolymer, a specimen for a car junction box was prepared in the same manner as in Example 91.
  • test piece for an automobile junction box was prepared in the same manner as in Example 91.
  • test box for automobile junction box prepared in Example 91 were evaluated by the following method in comparison with the products of Comparative Examples 30 and 31, and the results are shown in Table 25 below.
  • Example 91 Example 92
  • Example 93 Example 94 Comparative Example 30
  • Comparative Example 31 rescue - Polyketone Polyketone Polyketone Polyketone PA6 Noril
  • Tensile strength retention rate after moisture absorption (%) % 90 88 91 92 60 - Impact strength (room temperature) kJ / m 2 15 16 14 17 6 7 Impact Strength (-40 °C) kJ / m 2 6 7 5 8 3 4
  • the Example showed higher physical property retention after moisture absorption and better impact strength at room temperature and low temperature than the comparative example.
  • the impact strength at room temperature was excellent at 12 KJ / m 2 or more, and the tensile strength retention after moisture absorption was more than 85% compared to before the moisture absorption.
  • the specimen produced by the embodiments of the present invention is suitable for use as a junction box for automobiles.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • HFIP hexa-fluoroisopropano
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 1.8.
  • polyketone polymer 20 parts by weight of glass fiber, 10 parts by weight of calcium carbonate, and 3.5 parts by weight of polyvinyl acetate were mixed with 60 parts by weight of 60% by weight of carbon fiber and 100% by weight of the composite resin composition of polyester. It was put in a twin screw extruder and extruded through melt kneading at a 250 rpm screw rotational speed at a temperature of 240 °C.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 80 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, a MI (Melt index) of 60 g / 10 min, and an MWD of 1.8.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.2.
  • Example 99 Same as Example 99 except that high impact PBT is used instead of the polyketone of Example 99.
  • the polyketone resin composition pellets of the above examples were molded (injected) to prepare bracket specimens for power line binding, and then evaluated for physical properties in the following manner compared to the products of Comparative Examples, and the results are shown in Table 27 below.
  • Izod impact strength It was conducted according to ASTM D256.
  • Cycle time injection molding evaluation sec: The time until the pellets prepared in Examples or Comparative Examples before the crystallization after melting was measured in seconds.

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Abstract

La présente invention concerne une composition de résine de polycétone préparée par mélange d'une fibre de verre, d'une charge inorganique, d'un agent de renforcement minéral et de produits similaires avec un terpolymère de polycétone comprenant un motif répété représenté par les formules générales (1) et (2) ci-dessous, laquelle composition a une résistance au choc, un module d'élasticité et un maintien des propriétés après absorption d'eau qui sont excellents, et est donc applicable à des composants industriels comme des masques, des supports de tuyau, des supports de transmission, des supports de pare-chocs, des boîtiers de dérivation pour automobiles, des jantes de roue pour automobiles, des supports pour connecter les lignes de transport d'électricité, des couvertures d'équipement électronique, des montures de lunette, des collecteurs d'admission d'air pour automobiles, des supports de modules d'extrémité avant d'automobiles, des enjoliveurs de phares d'automobile, des boîtiers d'éclairages intérieurs, des cendriers pour automobiles, des commutateurs multifonctions pour automobiles, des grilles de haut-parleur pour automobiles, des guides d'appui-tête pour automobiles, des socles de navigation pour automobiles, des pièces moulées latérales pour automobiles, des raccords de tuyau, des boulons à tige pour climatiseurs, etc:- [-CH2CH2-CO] x- (1)- [-CH2-CH (CH3)-CO] y- (2) La présente invention concerne également une composition dans laquelle un polyamide semi-aromatique amorphe et un polyester sont mélangés en tant que polymère de polycétone, la composition de polycétone améliorant les propriétés de flexion, de résistance à l'humidité et la stabilité dimensionnelle pendant l'utilisation comme plastique industriel par rapport aux matériaux thermoplastiques antérieurs. En outre, la présente invention concerne un boîtier inférieur d'un ordinateur portable en polycétone préparés par moulage par injection de la composition de polycétone et, plus particulièrement, un boîtier inférieur d'un ordinateur portable ayant un module d'élasticité en flexion et une résistance aux chocs à basse température excellents, préparé par moulage par injection d'un mélange de polycétone comprenant un autre polymère de polycétone linéaire, une fibre de verre, un agent ignifugeant à base de phosphore, et du nylon 6I.
PCT/KR2015/011027 2014-11-07 2015-10-19 Composition de résine de polycétone doté d'une excellente résistance au choc WO2016072642A2 (fr)

Applications Claiming Priority (62)

Application Number Priority Date Filing Date Title
KR1020140154613A KR101664264B1 (ko) 2014-11-07 2014-11-07 폴리케톤 안경테
KR10-2014-0154620 2014-11-07
KR1020140154617A KR101611578B1 (ko) 2014-11-07 2014-11-07 폴리케톤 고충격 마스크
KR10-2014-0154617 2014-11-07
KR10-2014-0154626 2014-11-07
KR1020140154624A KR101646033B1 (ko) 2014-11-07 2014-11-07 폴리케톤 전력선 결속용 브라켓
KR10-2014-0154624 2014-11-07
KR10-2014-0154613 2014-11-07
KR1020140154626A KR101664260B1 (ko) 2014-11-07 2014-11-07 내충격성이 우수한 폴리케톤 성형제품
KR1020140154620A KR101664219B1 (ko) 2014-11-07 2014-11-07 폴리케톤 전자기기 커버
KR1020140162004A KR101706050B1 (ko) 2014-11-19 2014-11-19 유리섬유가 포함된 폴리케톤 조성물
KR1020140161993A KR101611580B1 (ko) 2014-11-19 2014-11-19 폴리케톤 블렌드를 포함하는 신발용 소재
KR1020140161994A KR101664918B1 (ko) 2014-11-19 2014-11-19 폴리케톤 자동차 휠 림
KR1020140161981A KR101684890B1 (ko) 2014-11-19 2014-11-19 폴리케톤 파이프 홀더 및 이의 제조방법
KR10-2014-0161981 2014-11-19
KR10-2014-0162011 2014-11-19
KR1020140161978A KR101655336B1 (ko) 2014-11-19 2014-11-19 폴리케톤 범퍼 브라켓
KR10-2014-0161982 2014-11-19
KR1020140162017A KR101675286B1 (ko) 2014-11-19 2014-11-19 폴리케톤 블렌드를 포함하는 전기전자제품용 뚜껑
KR10-2014-0162004 2014-11-19
KR1020140161977A KR101655337B1 (ko) 2014-11-19 2014-11-19 폴리케톤 변속기 브라켓
KR10-2014-0162017 2014-11-19
KR10-2014-0161976 2014-11-19
KR10-2014-0161977 2014-11-19
KR1020140161992A KR101664919B1 (ko) 2014-11-19 2014-11-19 열가소성 폴리우레탄 수지가 포함된 폴리케톤 조성물
KR1020140161976A KR101675828B1 (ko) 2014-11-19 2014-11-19 기계적 물성이 우수한 폴리케톤 조성물
KR10-2014-0162006 2014-11-19
KR1020140161982A KR101664929B1 (ko) 2014-11-19 2014-11-19 폴리케톤 자동차용 정션 박스
KR10-2014-0161993 2014-11-19
KR1020140162011A KR101684885B1 (ko) 2014-11-19 2014-11-19 노트북 하단 하우징으로 사용 가능한 폴리케톤 수지 조성물
KR1020140162006A KR101706052B1 (ko) 2014-11-19 2014-11-19 폴리카보네이트가 포함된 폴리케톤 조성물
KR1020140161988A KR101664926B1 (ko) 2014-11-19 2014-11-19 폴리에스테르가 포함된 폴리케톤 조성물
KR10-2014-0161992 2014-11-19
KR10-2014-0161978 2014-11-19
KR10-2014-0161994 2014-11-19
KR10-2014-0161988 2014-11-19
KR10-2015-0073978 2015-05-27
KR10-2015-0074028 2015-05-27
KR1020150073977A KR101705633B1 (ko) 2015-05-27 2015-05-27 폴리케톤 자동차 프론트 엔드 모듈의 캐리어 및 이의 제조방법
KR10-2015-0074032 2015-05-27
KR10-2015-0073975 2015-05-27
KR1020150073984A KR101705621B1 (ko) 2015-05-27 2015-05-27 폴리케톤 블렌드를 포함하는 실내등 하우징
KR10-2015-0073989 2015-05-27
KR10-2015-0074023 2015-05-27
KR10-2015-0073977 2015-05-27
KR1020150074028A KR101716164B1 (ko) 2015-05-27 2015-05-27 폴리케톤 폴리머를 포함하는 자동차용 사이드 몰딩
KR1020150073985A KR101705622B1 (ko) 2015-05-27 2015-05-27 폴리케톤 블렌드를 포함하는 차량용 재떨이
KR1020150073975A KR101705617B1 (ko) 2015-05-27 2015-05-27 폴리케톤 자동차 에어 인테이크 매니폴드 및 이의 제조방법
KR1020150074020A KR101716206B1 (ko) 2015-05-27 2015-05-27 폴리케톤 폴리머를 포함하는 자동차용 스피커 그릴
KR1020150073978A KR101705634B1 (ko) 2015-05-27 2015-05-27 폴리케톤 블렌드 자동차 헤드 램프 베젤
KR10-2015-0074035 2015-05-27
KR1020150073981A KR101705619B1 (ko) 2015-05-27 2015-05-27 폴리케톤 블렌드를 포함하는 차량용 캐니스터
KR10-2015-0074024 2015-05-27
KR1020150074023A KR101716159B1 (ko) 2015-05-27 2015-05-27 폴리케톤 폴리머를 포함하는 자동차용 헤드레스트 가이드
KR1020150073989A KR101807611B1 (ko) 2015-05-27 2015-05-27 폴리케톤 블렌드를 포함하는 자동차용 멀티펑션 스위치
KR1020150074024A KR101716160B1 (ko) 2015-05-27 2015-05-27 폴리케톤 폴리머를 포함하는 자동차용 내비게이션 받침대
KR10-2015-0074020 2015-05-27
KR1020150074032A KR101734890B1 (ko) 2015-05-27 2015-05-27 폴리케톤 호스 커넥터
KR10-2015-0073985 2015-05-27
KR10-2015-0073981 2015-05-27
KR10-2015-0073984 2015-05-27
KR1020150074035A KR101716166B1 (ko) 2015-05-27 2015-05-27 폴리케톤 에어컨용 스템 볼트

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Cited By (4)

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CN108977747A (zh) * 2017-06-01 2018-12-11 佛山市顺德区美的电热电器制造有限公司 不粘涂层及其制备方法以及锅具和煮食设备
CN110088197A (zh) * 2016-12-27 2019-08-02 Lg化学株式会社 基于聚碳酸亚烷基酯的树脂膜
US20200010676A1 (en) * 2016-12-27 2020-01-09 Lg Chem, Ltd. Polyketone resin composition and polyketone resin molded article
US10941291B2 (en) * 2016-12-27 2021-03-09 Lg Chem, Ltd. Polyalkylene carbonate resin composition and polyalkylene carbonate resin molded article

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4851482A (en) * 1988-04-28 1989-07-25 Shell Oil Company Blends and articles of linear alternating polyketone polymer with polyurethane polymer
CA2233165A1 (fr) * 1995-10-16 1997-04-24 Shell Internationale Research Maatschappij B.V. Melange polymere polycetonique ignifuge
JPH101590A (ja) * 1996-06-18 1998-01-06 Kuraray Co Ltd 熱可塑性樹脂組成物
JP4282131B2 (ja) * 1998-12-18 2009-06-17 横浜ゴム株式会社 タイヤ用熱可塑性エラストマー組成物
KR20140097719A (ko) * 2013-01-29 2014-08-07 현대자동차주식회사 내마모성이 우수한 폴리케톤 조성물

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110088197A (zh) * 2016-12-27 2019-08-02 Lg化学株式会社 基于聚碳酸亚烷基酯的树脂膜
US20200010676A1 (en) * 2016-12-27 2020-01-09 Lg Chem, Ltd. Polyketone resin composition and polyketone resin molded article
US10844220B2 (en) * 2016-12-27 2020-11-24 Lg Chem, Ltd. Polyketone resin composition and polyketone resin molded article
US10941261B2 (en) 2016-12-27 2021-03-09 Lg Chem, Ltd. Polyalkylene carbonate-based resin film
US10941291B2 (en) * 2016-12-27 2021-03-09 Lg Chem, Ltd. Polyalkylene carbonate resin composition and polyalkylene carbonate resin molded article
CN110088197B (zh) * 2016-12-27 2021-12-28 Lg化学株式会社 基于聚碳酸亚烷基酯的树脂膜
CN108977747A (zh) * 2017-06-01 2018-12-11 佛山市顺德区美的电热电器制造有限公司 不粘涂层及其制备方法以及锅具和煮食设备

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