WO2018026047A1 - Polycétone à couleur améliorée et son procédé de production - Google Patents

Polycétone à couleur améliorée et son procédé de production Download PDF

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WO2018026047A1
WO2018026047A1 PCT/KR2016/009367 KR2016009367W WO2018026047A1 WO 2018026047 A1 WO2018026047 A1 WO 2018026047A1 KR 2016009367 W KR2016009367 W KR 2016009367W WO 2018026047 A1 WO2018026047 A1 WO 2018026047A1
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polyketone
maleic anhydride
bis
composition
polyketone composition
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PCT/KR2016/009367
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English (en)
Korean (ko)
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정진주
김홍운
문혜경
박선근
김기수
최소정
김중인
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(주)효성
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polyketone with improved color.
  • a small amount of maleic anhydride is blended and extruded into a polyketone powder obtained during the initial polymerization process to improve discoloration stability of a basic resin without deteriorating mechanical properties and to reduce color change.
  • a method for producing a polyketone is described in detail below.
  • Polyketone (PK) is a raw material and polymerization process cost cheaper than general engineering plastic materials such as polyamide polyester and polycarbonate, and has excellent heat resistance chemical resistance, impact resistance and fuel permeability.
  • Polyketones having the above characteristics can be converted to olefins such as carbon monoxide (CO) and ethylene and propylene using transition metal complex catalysts such as palladium (Pd) and nickel (Ni). It is already known to be obtained by polymerisation (Industrial Materials. December, p. 5, 1997).
  • polyketone has excellent chemical resistance and chemical stability and is suitable to be applied to automobile fuel parts and molded articles.
  • polyketone has a disadvantage of discoloration during processing because polyketone itself is inferior to heat stability.
  • the present invention has been conceived to solve the above problems, and aims to improve the discoloration stability by lowering the yellowness index (YI) of the base resin without deteriorating mechanical properties, and to provide a polyketone having a low color change value. .
  • YI yellowness index
  • the present invention is a linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; And blending and extruding maleic anhydride or maleic anhydride copolymer to provide a polyketone composition, wherein the polyketone composition has a yellowness index of 15 or less.
  • the content of maleic anhydride is 100ppm to 15,000ppm
  • the maleic anhydride copolymer is styrene, polyolefin, ethylene propylene (EP) rubber, ethylene propylene diene monomer (EPDM) rubber, ethylene octene rubber (EOR), styrene
  • EP ethylene propylene
  • EPDM ethylene propylene diene monomer
  • EOR ethylene octene rubber
  • SEBS ethylene butylene styrene
  • the present invention provides a polyketone molded part manufactured using the polyketone composition.
  • the polyketone composition prepared according to the present invention may improve discoloration stability by improving the yellowness index (YI) of the base resin to 15 or less. Therefore, through such a polyketone composition it is possible to reduce the cost of the master batch (color batch) processing (pigment), such as titanium dioxide (TiO2).
  • YI yellowness index
  • 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.
  • the polymer ring of the preferred polyketone polymer in the present invention may be represented by the following formula (1).
  • G is an ethylenically unsaturated hydrocarbon, in particular, a part obtained from ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is preferably at least 1: 1.
  • 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 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.
  • Preferred methods of preparing polyketone polymers are disclosed in US Pat. No. 4,843,144.
  • Contact is made under conditions to produce a polyketone polymer.
  • Polyketones of alternating interconnection are excellent in mechanical and thermal properties, have excellent processability, 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 process for producing a polyketone is characterized by the presence of carbon monoxide in a liquid medium in 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.
  • 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 a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product.
  • the catalyst is composed of a ligand having an element of (a) Group 9, Group 10 or Group 11 transition metal compound (b) Group 15 of the Periodic Table (IUPAC Inorganic Chemistry Nomenclature, 1989).
  • Examples of the Group 9 transition metal compound in the Group 9, 10 or 11 transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamate salts, sulfonates, and the like. Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, trifluoro ruthenium acetate, ruthenium acetylacetate, and trifluoromethane sulfonate ruthenium.
  • Examples of the Group 10 transition metal compound include a complex of nickel or palladium, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, and palladium trifluoroacetate. , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium, palladium sulfate and the like.
  • Group 11 transition metal compound examples include copper or silver complexes, carbonates, phosphates, carbamates, sulfonates, and the like, and specific examples thereof include copper acetate, trifluoro copper acetate, copper acetylacetate, silver acetate, tri Silver fluoroacetic acid, silver acetyl acetate, silver trifluoromethane sulfonic acid, etc. are mentioned.
  • 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 2hydroxy-1,3-bis [di in terms of molecular weight of the polyketone (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) phosphino] propane, which is water-soluble in that it does not require an organic solvent and is safe.
  • 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) is not particularly limited, but is usually 0.1 to 3 moles, preferably 1 to 3 moles per one mole of the transition metal compound (a).
  • the addition of benzophenone during the polymerization of polyketones is another feature.
  • the molar ratio of the (a) Group 9, Group 10 or Group 11 transition metal compound and benzophenone is 1: 5 to 100, preferably 1:40 to 60. If the molar ratio of transition metal and benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory. If the molar ratio of transition metal and benzophenone is greater than 1: 100, the polyketone catalytic activity produced is rather It is not desirable because it tends to decrease.
  • Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 ⁇ -olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds, such as styrene and (alpha) -methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins such as cyclododecene; Vinyl hal
  • Ternary copolymerization of carbon monoxide with the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex consisting of the Group 9, Group 10 or Group 11 transition metal compound (a) and the ligand (b) having an element of Group 15
  • the catalyst is produced by contacting the two components.
  • 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 polyketone is formed by the polymerization method as described above.
  • Polyketone composition improved color according to the present invention polyketone excellent in heat resistance, chemical resistance, fuel permeability and impact resistance; And a maleic anhydride, which is a specific polymer of another kind, by blending and extruding a small amount of maleic anhydride into a polyketone powder obtained in the initial polymerization process of polyketone, without reducing the mechanical properties.
  • the discoloration stability of can be improved significantly.
  • the maleic anhydride copolymer another kind of polymer blended in small amounts to the polyketone powder obtained in the initial polymerization process of the present invention, should improve the color of the polyketone base resin, be mixed with the resin, and be extruded. It should not affect the mechanical properties of the product.
  • cost considerations such as the cost of master batch processing for color concentrate and the cost of pigments such as titanium dioxide (TiO2) should be reduced. do.
  • the polyketone composition having improved color according to the present invention is composed of a blend consisting of a combination of polyketone and maleic anhydride, and is characterized by improving discoloration stability without deteriorating mechanical properties such as tensile, bending and impact strength. .
  • the present invention is an additive blended to polyketone powder, using maleic anhydride alone, or styrene, polyolefin, ethylene propylene (EP) rubber, ethylene propylene diene monomer (EPDM) Rubber, ethylene octene rubber (EOR), styrene ethylene butylene styrene (SEBS) rubber, natural rubber, polyamides, polyesters, copolymers of at least one compound selected from the group consisting of polyethers with maleic anhydride It is preferable.
  • EP ethylene propylene
  • EPDM ethylene propylene diene monomer
  • EOR ethylene octene rubber
  • SEBS styrene ethylene butylene styrene
  • natural rubber polyamides
  • polyesters copolymers of at least one compound selected from the group consisting of polyethers with maleic anhydride It is preferable.
  • the maleic anhydride monomer of the present invention is characterized in that 100ppm to 15000ppm relative to the total blend.
  • the effect of the maleic anhydride monomer is less than 100ppm relative to the total blend weight, the effect is insignificant, and when the content of the maleic anhydride exceeds 15000ppm may be deteriorated processability and mechanical properties.
  • Method for producing a polyketone composition with improved color 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 extruding a small amount of maleic anhydride in the polyketone powder obtained in the initial polymerization process.
  • a mixed solvent polymer solvent
  • a solvent eg, alcohol and acetone
  • 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, sulfur phase and sulfonic acid may be used, and preferably trifluoroacetic acid is used. 6-20 (mole) equivalent weight of the compound is appropriate.
  • Examples of the phosphorus double ligand compounds constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (eg, 1,3-bis [di (2methoxyphenylphosphino)] 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 at least one member selected from the group consisting of, the amount of use is 1 ⁇ 1.2 (mole) equivalents relative to the palladium compound.
  • 1,3-bis [diphenylphosphino] propane eg, 1,3-bis [di (2methoxyphenylphosphino)] propane, 1,3-bis [Bis [anisyl] phosphinomethyl] -1
  • 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.
  • a small amount of maleic anhydride is blended into the polyketone powder obtained in the initial polymerization process and then extruded by an extruder to finally obtain a blend composition.
  • the blend is prepared by melt kneading and extruding by feeding into a twin screw.
  • the extrusion temperature is preferably in the range of 220 ⁇ 260 °C, screw rotational speed 100 ⁇ 300rpm. If the extrusion temperature is less than 220 °C kneading may not occur properly, if it exceeds 260 °C may cause problems related to the heat resistance of the resin. In addition, if the screw rotational speed is less than 100rpm it may not occur smooth kneading.
  • Blends of the present invention may include additives known in the art, such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials to improve processability of the polymer or physical properties of the blend.
  • additives may be added by known methods before, during or after mixing with the polyketone and the modifier.
  • the blend production method of the present invention is not particularly limited as long as the blend is produced uniformly without making the blend or blend components create excessive collapse.
  • the polymer component may be blended in a mixing device exhibiting high shear stress.
  • Blends may be molded by conventional methods such as extrusion or injection molding to produce sheets, films, plates and shaped articles. Such application examples may be used in electric electronics, automobiles, industrial parts, and the like.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propylene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) in the presence of a catalyst composition.
  • 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 hexafluoroisopropano (HFIP) was 1.4dl / g.
  • a polyketone composition with improved color having a concentration of 100 ppm was prepared.
  • Example 2 It is the same as Example 1 except the polyketone terpolymer and styrene maleic anhydride are blended to give a concentration of maleic anhydride of 625 ppm.
  • Example 2 It is the same as Example 1 except the polyketone terpolymer and styrene maleic anhydride are blended and the concentration of maleic anhydride is 1250 ppm.
  • Example 2 It is the same as Example 1 except the polyketone terpolymer and styrene maleic anhydride are blended and the concentration of maleic anhydride is 7500 ppm.
  • Example 2 It is the same as Example 1 except the polyketone terpolymer and styrene maleic anhydride are blended and the concentration of maleic anhydride is 15000 ppm.
  • Example 2 Same as Example 1 except that the polyketone terpolymer and polypropylene grafted maleic anhydride were blended to give a concentration of maleic anhydride of 625 ppm.
  • Example 2 Same as Example 1 except that the polyketone terpolymer and styrene ethylene butylene styrene (SEBS) grafted maleic anhydride were blended to give a concentration of maleic anhydride of 625 ppm.
  • SEBS styrene ethylene butylene styrene
  • Example 2 It is the same as Example 1 except 100weight% of a polyketone terpolymer.
  • Example 2 It is the same as Example 1 except the polyketone terpolymer and styrene maleic anhydride are blended and the concentration of maleic anhydride is 80 ppm.
  • Example 2 Same as Example 1 except that the polyketone terpolymer and styrene maleic anhydride were blended to give a concentration of 16250 ppm of maleic anhydride.
  • Example 1 MI [g / 10min] Tensile Strength [MPa] Impact Strength [kJ / m 2 ] Comparative Example 1 72 66 7 Comparative Example 2 72 66 7 Comparative Example 3 58 54 5 Example 1 71 65 7 Example 2 73 65 7 Example 3 70 65 7 Example 4 68 64 7 Example 5 65 62 6 Example 6 63 68 6 Example 7 51 60 10
  • SMA styrene maleic anhydride
  • Example 3 the mechanical properties such as tensile, bending, and impact strength are all 100% by weight of polyketone terpolymer. It remained at the same level as Example 1.
  • the polyketone composition (Examples 1 to 7) prepared by blending a small amount of styrene maleic anhydride, which is a specific polymer of another kind, with a polyketone powder and extruding with an extruder (Examples 1 to 7) has a conventional yellow index.
  • the color was remarkably improved under the same experimental conditions as compared with the polyketone composition (Comparative Example 1) which is 100% by weight of the polyketone terpolymer.
  • the yellow index was reduced by 18, so that only a small blend of maleic anhydride was used for the color concentrate through the polyketone composition with markedly improved discoloration stability. It has been shown to be suitable to reduce the processing cost of master batch and pigment such as titanium dioxide (TiO2).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne une composition de polycétone qui est préparée par mélange et extrusion d'une polycétone linéaire alternée constituée de monoxyde de carbone et d'au moins un hydrocarbure oléfiniquement insaturé, avec un anhydride maléique. Une résine de base formée de la polycétone produite présente un indice de jaunissement égal ou inférieur à 15. L'invention concerne plus précisément une composition de polycétone présentant une teneur en anhydride maléique de 100 ppm à 15 000 ppm par rapport au poids total de la composition de polycétone. L'invention concerne également une pièce moulée en polycétone produite à l'aide de la composition de polycétone. La composition de polycétone préparée selon la présente invention peut améliorer la stabilité à la décoloration en améliorant l'indice de jaunissement (YI) de la résine de base pour qu'il soit égal ou inférieur à 15. Ainsi, cette composition de polycétone permet de réduire le coût de traitement d'un mélange maître pour un concentré de matière colorante, et le coût d'un pigment tel que le dioxyde de titane (TiO2), et équivalent.
PCT/KR2016/009367 2016-08-02 2016-08-24 Polycétone à couleur améliorée et son procédé de production WO2018026047A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
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JPH101606A (ja) * 1996-06-18 1998-01-06 Kuraray Co Ltd 耐光性に優れた樹脂組成物
JPH1171513A (ja) * 1997-06-25 1999-03-16 Toray Ind Inc ポリケトン樹脂組成物
KR20120090112A (ko) * 2010-12-30 2012-08-17 주식회사 효성 폴리케톤 나노 복합체
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KR20130028560A (ko) * 2011-09-09 2013-03-19 현대자동차주식회사 내충격성 및 유연성이 향상된 폴리케톤 조성물

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Publication number Priority date Publication date Assignee Title
JPH101606A (ja) * 1996-06-18 1998-01-06 Kuraray Co Ltd 耐光性に優れた樹脂組成物
JPH1171513A (ja) * 1997-06-25 1999-03-16 Toray Ind Inc ポリケトン樹脂組成物
KR20120090112A (ko) * 2010-12-30 2012-08-17 주식회사 효성 폴리케톤 나노 복합체
KR20120118737A (ko) * 2011-04-19 2012-10-29 현대자동차주식회사 내충격성이 우수한 폴리케톤 조성물
KR20130028560A (ko) * 2011-09-09 2013-03-19 현대자동차주식회사 내충격성 및 유연성이 향상된 폴리케톤 조성물

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