WO2018124576A1 - Robinet à boisseau sphérique et bouchon de conduite de distribution d'eau comprenant une composition de polycétone - Google Patents

Robinet à boisseau sphérique et bouchon de conduite de distribution d'eau comprenant une composition de polycétone Download PDF

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WO2018124576A1
WO2018124576A1 PCT/KR2017/014942 KR2017014942W WO2018124576A1 WO 2018124576 A1 WO2018124576 A1 WO 2018124576A1 KR 2017014942 W KR2017014942 W KR 2017014942W WO 2018124576 A1 WO2018124576 A1 WO 2018124576A1
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weight
polyketone
composition
water
bis
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PCT/KR2017/014942
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English (en)
Korean (ko)
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이명녕
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(주)효성
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Priority claimed from KR1020160184110A external-priority patent/KR101867937B1/ko
Priority claimed from KR1020160183628A external-priority patent/KR101867936B1/ko
Application filed by (주)효성 filed Critical (주)효성
Publication of WO2018124576A1 publication Critical patent/WO2018124576A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D59/00—Plugs, sleeves, caps, or like rigid or semi-rigid elements for protecting parts of articles or for bundling articles, e.g. protectors for screw-threads, end caps for tubes or for bundling rod-shaped articles
    • B65D59/06—Caps
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • 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
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K5/00—Plug valves; Taps or cocks comprising only cut-off apparatus having at least one of the sealing faces shaped as a more or less complete surface of a solid of revolution, the opening and closing movement being predominantly rotary
    • F16K5/06—Plug valves; Taps or cocks comprising only cut-off apparatus having at least one of the sealing faces shaped as a more or less complete surface of a solid of revolution, the opening and closing movement being predominantly rotary with plugs having spherical surfaces; Packings therefor
    • 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
    • F16L55/00—Devices or appurtenances for use in, or in connection with, pipes or pipe systems
    • F16L55/10—Means for stopping flow from or in pipes or hoses
    • F16L55/115—Caps

Definitions

  • the present invention relates to a polyketone composition
  • a polyketone composition comprising linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon, talc, glass fibers, etc., and is suitable for application to water ball valves and water pipe caps.
  • a water ball valve and a water pipe cap comprising a ketone composition.
  • the process for preparing polyketone polymers is usually a compound of Group VIII metal selected from palladium, cobalt or nickel, and anions of non-hydro halogen strong-hydrohalogentic acid.
  • Catalyst compositions produced from bidentate ligands of phosphorus, arsenic or antimones are used.
  • U.S. Patent No. 4,843,144 describes a process for preparing polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of nonhydrohalogenic acid with a pKa of less than 6, and a catalyst that is a bidentate ligand of phosphorus. It is starting.
  • the ball valve (water valve) for water is mostly used as brass and polybutylene (polybutylene).
  • This is a water-related part, so it must have excellent water resistance and no thermal discoloration.
  • Brass and polybutylene have been used in water ball valves because of these advantages, but brass has a disadvantage of low productivity due to castings and higher cost than plastic.
  • Polybutylene is difficult to mold and requires one week of aging. Has the disadvantage.
  • polyamide materials have been used as alternative materials, polyketone materials having water resistance with excellent physical property retention under a water atmosphere have been considered for related applications.
  • nylon 6 is used as a water pipe cap.
  • Nylon 6 was used because of its excellent heat resistance, elastic modulus and strength, but had high water absorption and had disadvantages of physical property change and dimensional change. In order to compensate for this, the disadvantage of the dimensional change is improved but the initial property retention is not improved. Therefore, there is an increasing demand for a material having excellent dimensional stability and property retention suitable for water pipe cap application. .
  • the present invention provides a polyketone composition having excellent water resistance, dimensional stability, and mold release property, including talc, glass fiber, polyethylene wax, antioxidant, and the like in a polyketone having water resistance, and including a water ball valve and a water cap pipe including the same.
  • the purpose is to develop a.
  • the polyketone composition further comprises 0.1 to 1.0 parts by weight of antioxidant relative to the composition weight; And 0.1 to 1.0 parts by weight of polyethylene wax (PE Wax).
  • antioxidant relative to the composition weight
  • PE Wax polyethylene wax
  • the intrinsic viscosity (IV) of the polyketone is 1.0 to 2.0dl / g
  • the molecular weight distribution is 1.5 to 2.5, it is composed of repeating units represented by the following general formula (1) and (2), y / x value may be 0.03 to 0.3.
  • the linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; And 25 to 45% by weight of a filler; wherein the flexural strength and flexural modulus under water immersion conditions measured at 23 ° C. for 500 hours are characterized in that they maintain 80 to 95% of the initial property value.
  • a pipe pipe cap comprising a polyketone composition.
  • the filler is 17 to 27% by weight talc relative to the total polyketone composition; And 8 to 18% by weight of glass fibers; wherein the polyketone composition further comprises 0.1 to 1.0 parts by weight of an antioxidant based on the weight of the composition; And 0.1 to 1.0 parts by weight of polyethylene wax (PE Wax), wherein the polyketone has an intrinsic viscosity (IV) of 1.0 to 2.0 dl / g, a molecular weight distribution of 1.5 to 2.5, and the following general formula (1) and It consists of a repeating unit represented by (2), y / x value may be 0.03 to 0.3.
  • PE Wax polyethylene wax
  • the polyketone composition of the present invention has an excellent mechanical strength under water immersion conditions and hardly exhibits thermal discoloration, compared to a polyamide material used in conventional water ball valves, and thus is excellent for use in ball valves requiring water resistance and heat resistance. It works.
  • the polyketone composition of the present invention has an excellent mechanical strength in the water immersion conditions compared to the polyamide material used in the conventional water cap pipe, there is an excellent effect for use as a water cap pipe for water resistance and dimensional stability is required.
  • Figure 1 is a photograph showing the results after the thermochromic evaluation of the composition specimen prepared by the present invention.
  • the present invention provides polyketone compositions comprising polyketones, fillers or talc, glass fibers, polyethylene waxes and antioxidants.
  • the polyketone is a linear alternating structure and contains substantially 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 examples 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 polyketone polymer preferred in the present invention can be represented by the following formula.
  • G is an ethylenically unsaturated hydrocarbon, in particular, a part obtained from ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is preferably at least 1: 0.01.
  • 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.
  • 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.
  • the palladium compound palladium acetate is preferable, and the amount of use is preferably 10-3 to 10-1 mole.
  • the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, sulfonic acid, and the like. 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.
  • 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 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, such as belts, rubber hose reinforcements, tire cords, and concrete reinforcements. It is very suitable for building materials and industrial materials.
  • 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 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 acetyl acetate, 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 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 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 the transition metal and benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory. If the molar ratio of the transition metal and benzophenone is greater than 1: 100, the polyketone catalytic activity produced is rather It is not desirable because it tends to decrease
  • Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 ⁇ -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
  • the catalyst is produced by contacting the two components.
  • Arbitrary methods can be employ
  • 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.
  • the polyketone of this invention is 50 ppm or less in content of Pd element.
  • the content of the Pd element exceeds 50 ppm, thermal denaturation and chemical modification due to the remaining Pd element are likely to occur, and during melt molding, a phenomenon such as an increase in melt viscosity and an increase in dopant viscosity when dissolved in a solvent occurs. , Workability becomes poor.
  • a large amount of Pd elements remain in the polyketone molded body obtained after molding, the heat resistance of the molded body is also deteriorated.
  • the smaller the content of the Pd element in the polyketone from the viewpoint of process passability and the heat resistance of the molded body the more preferable.
  • the content is more preferably 10 ppm or less, still more preferably 5 ppm or less, and most preferably 0 ppm.
  • Linear alternating polyketones are formed by the polymerization method as described above.
  • the water ball valve composition of the present invention comprises the polyketone as a first component, the second component is talc, in the present invention is characterized in that talc is 23 to 33% by weight relative to the total composition.
  • talc is 23 to 33% by weight relative to the total composition.
  • Glass fiber is used as another component of the composition for water ball valves of this invention.
  • the content of the glass fiber is characterized in that 12 to 22% by weight, when the content of the glass fiber is less than 12% by weight of the total composition, the effect of preventing the bending property of the product is insufficient, and when the content of more than 22% by weight may be poor workability. .
  • the talc and glass fibers serve to prevent warpage characteristics of the final product.
  • the water ball valve composition may further include polyethylene wax and antioxidant to improve processability or physical properties.
  • the polyethylene wax is characterized in that 0.1 to 1.0 parts by weight relative to the total polyketone composition, respectively, less than 0.1 parts by weight is inferior in moldability, when more than 1.0 parts by weight has a disadvantage of lowering the impact strength.
  • Polyethylene wax used in the present invention is a non-polar series, and serves to improve the releasability and fastening property by applying to the polar polyketone.
  • the polyethylene wax used in the present invention has a melting point of 135 ° C., a density of 0.96 g / cm 3, and has a white form. In the present invention, 0.5 parts by weight is preferably used.
  • antioxidant used in the present invention CaO / P 2 O 5 may be used, wherein CaO is 53 to 55%, P 2 O 5 is 40 to 42%, and the medium particle size (d 50) is 2.9 to 3.4 ⁇ m.
  • Such an antioxidant has the deactivation effect of the metal catalyst used in the polymerization. It is preferable that antioxidant is contained 0.1-1.0 weight part with respect to 100 weight part of polyketone compositions. If the amount of the antioxidant is less than 0.1 part by weight, the deactivation function of the metal catalyst may be lowered. If the content of the antioxidant is greater than 1.0 part by weight, the physical properties of the product may be reduced.
  • the manufacturing method for producing the polyketone composition for water ball valve of the present invention is as follows.
  • 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 polyketone terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and a mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone; 45 to 65% by weight of polyketone, 23 to 33% by weight of talc, and 12 to 22% by weight of glass fibers are compounded together by employing two side feeders at 240 ° C.
  • a solvent eg, alcohol and acetone
  • composition to prepare a composition and additionally add 0.1 antioxidant to the composition.
  • 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 mol, 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 polyketone obtained is a talc and glass fibers are compounded together by employing two side feeders at 240 ° C. to prepare a composition, and additionally 0.1 to 1.0 parts by weight of antioxidant and 0.1 to 1.0 parts by weight of polyethylene wax.
  • the polyketone composition for water valves of the present invention can be produced by mixing, extruding and injection molding.
  • 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 occur smooth kneading, if the screw speed exceeds 300rpm mechanical properties may be reduced.
  • composition for water pipe caps of this invention contains the said polyketone as a 1st component, and a filler is used for a 2nd component.
  • the filler includes talc and glass fibers.
  • talc of the filler is characterized in that 17 to 27% by weight relative to the total composition.
  • the content of talc is less than 17% by weight of the total composition, the effect of preventing warpage characteristics of the product is inadequate, and when it exceeds 27% by weight, workability may be reduced.
  • Glass fiber is used as another component of the filler.
  • the content of the glass fiber is characterized in that from 8 to 18% by weight, when the content of glass fiber is less than 8% by weight of the total composition, the effect of preventing warpage properties of the product is insufficient, when the content of more than 18% by weight may be poor workability have.
  • the filler serves to prevent the bending characteristics of the final product.
  • composition ratio of the polyketone composition for a water pipe cap of the present invention is preferably 59.5% by weight, 25% by weight of talc, 15% by weight of glass fiber, and 0.5% by weight of polyethylene wax.
  • the polyketone has a MFI of 40 to 80, a melting temperature of 219 to 225 ° C, a yellowness of 22 or less, a volatile of 0.13 or less, and a special gravity of 1.21 to 1.27.
  • talc has a specificity of 96.0%, median particle size of 5.5 ⁇ 0.5 ⁇ m, and bulk density loose of 0.50 ⁇ 0.05 gr / ⁇ l.
  • the maximum moisture content of the glass fiber used in the present invention is 0.06%, the organic content is 0.2 to 0.5%, more preferably 0.35%, the normal diameter is 10 ⁇ m, Chop Length is 4.0mm. .
  • it in order to improve processability or physical properties, it may further include polyethylene wax and antioxidant.
  • the polyethylene wax is characterized in that 0.1 to 1.0 parts by weight relative to the total polyketone composition, respectively, less than 0.1 parts by weight is inferior in moldability, when more than 1.0 parts by weight has a disadvantage of lowering the impact strength.
  • Polyethylene wax used in the present invention is a non-polar series, and serves to improve the releasability and fastening property by applying to the polar polyketone.
  • the polyethylene wax used in the present invention has a melting point of 135 ° C., a density of 0.96 g / cm 3, and has a white form. In the present invention, 0.5 parts by weight is preferably used.
  • antioxidant used in the present invention CaO / P 2 O 5 may be used, wherein CaO is 53 to 55%, P 2 O 5 is 40 to 42%, and the medium particle size (d 50) is 2.9 to 3.4 ⁇ m.
  • Such an antioxidant has the deactivation effect of the metal catalyst used in the polymerization. It is preferable that antioxidant is contained 0.1-1.0 weight part with respect to 100 weight part of polyketone compositions. If the amount of the antioxidant is less than 0.1 part by weight, the deactivation function of the metal catalyst may be lowered. If the content of the antioxidant is greater than 1.0 part by weight, the physical properties of the product may be reduced.
  • a method of producing a polyketone composition for producing a water pipe of the present invention is as follows.
  • 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 polyketone terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and a mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone; 45 to 65% by weight of polyketone, 23 to 33% by weight of talc, and 12 to 22% by weight of glass fibers are compounded together by employing two side feeders at 240 ° C.
  • a solvent eg, alcohol and acetone
  • composition to prepare a composition and additionally add 0.1 antioxidant to the composition.
  • 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 mol, 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 polyketone obtained is a talc and glass fibers are compounded together by employing two side feeders at 240 ° C. to prepare a composition, and additionally 0.1 to 1.0 parts by weight of antioxidant and 0.1 to 1.0 parts by weight of polyethylene wax.
  • the polyketone composition for a water valve of the present invention and a water pipe cap including the same can be produced.
  • 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 occur smooth kneading, if the screw speed exceeds 300rpm mechanical properties may be reduced.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene are obtained from palladium acetate, trifluoroacetic acid and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine
  • the polyketone terpolymer prepared above had a melting point of 220 ° C., a viscosity IV of 1.3 dl / g measured at 25 ° C. with hexa-fluoroisopropano (HFIP), and a melt index (MI).
  • the blend was prepared by adding talc and glass fibers to the polyketone terpolymer prepared above using two side feeders and compounding the blend.
  • Example 1 was repeated two more times under the same conditions, and this was indicated as Example 2 and Example 3, respectively.
  • the prepared test piece was injection molded on a molding machine having a clamping force of 80 tons.
  • Examples 1 to 3 and Comparative Example 1 were subjected to water immersion and seawater immersion for 0 hours, 100 hours and 500 hours under 23 ° C., and then measured the impact strength, tensile strength, flexural strength and flexural modulus, respectively. It is described in 1 and 2.
  • Example 1 was subjected to thermochromic evaluation under the following conditions.
  • Thermochromic evaluation was performed for 290 hours at 90 ° C., 100 ° C. and 125 ° C., and the results are shown in FIG. 1.
  • Example 1 the thermal discoloration was evaluated for 0 hours and 290 hours. As shown in FIG.
  • Example 1 it can be seen from Example 1 that the polyketone composition of the present invention is excellent in heat resistance because it is almost no initial discoloration.
  • the polyketone composition prepared according to the present invention is excellent in water resistance and heat resistance and suitable for application as a water ball valve.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene are obtained from palladium acetate, trifluoroacetic acid and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine
  • the polyketone terpolymer prepared above had a melting point of 220 ° C., a viscosity IV of 1.3 dl / g measured at 25 ° C. with hexa-fluoroisopropano (HFIP), and a melt index (MI).
  • the blend was prepared by adding talc and glass fibers to the polyketone terpolymer prepared above using two side feeders and compounding the blend.
  • Example 4 was reproduced twice under the same conditions, and these were designated as Example 5 and Example 6, respectively.
  • the composition was prepared by mixing 60% by weight of nylon 6, 25% by weight of talc, and 15% by weight of fiberglass, and then pelleted on an extruder using a biaxial screw having a diameter of 2.5 cm and operating at 250 rpm. pellet).
  • the prepared test piece was injection molded on a molding machine having a clamping force of 80 tons.
  • Examples 4 to 6 and Comparative Examples 2 to 4 were subjected to water immersion for 0 hours, 100 hours, and 500 hours under 23 ° C., and then the flexural strength and flexural modulus were measured and described in Table 3.
  • Examples 4 to 6 show that flexural strength and flexural modulus are maintained at 80% or more under water immersion conditions compared to Comparative Examples 2 to 4. Can be.
  • the polyketone composition prepared according to the present invention is excellent under water immersion conditions and suitable for application as a water pipe cap.

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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)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne une composition comprenant : une polycétone linéaire alternée comprenant du monoxyde de carbone et au moins un hydrocarbure à insaturation oléfinique ; du talc ; une fibre de verre ; et équivalent, et une composition de polycétone présentant une excellente résistance à l'eau et de remarquables taux de rétention de ses propriétés mécaniques par rapport aux matériaux de type laiton et plomb utilisés dans les robinets à boisseau sphérique de distribution d'eau. Ladite composition peut être développée et utilisée de manière appropriée pour la fabrication d'un robinet à boisseau sphérique. De plus, une composition de polycétone présentant une excellente résistance à l'eau et de remarquables taux de rétention de ses propriétés mécaniques, par rapport à un matériau de type polyamide classiquement utilisé pour les bouchons de conduite de distribution d'eau, peut être développée et utilisée de manière appropriée pour la fabrication d'un bouchon de conduite de distribution d'eau.
PCT/KR2017/014942 2016-12-30 2017-12-18 Robinet à boisseau sphérique et bouchon de conduite de distribution d'eau comprenant une composition de polycétone WO2018124576A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020160184110A KR101867937B1 (ko) 2016-12-30 2016-12-30 내수성 및 내열성이 뛰어난 폴리케톤 조성물을 포함하는 수도용 볼 밸브
KR10-2016-0184110 2016-12-30
KR1020160183628A KR101867936B1 (ko) 2016-12-30 2016-12-30 치수안정성이 높은 폴리케톤 조성물을 포함하는 수도 파이프 캡
KR10-2016-0183628 2016-12-30

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11126643A (ja) * 1997-10-24 1999-05-11 Toray Ind Inc ポリケトン樹脂製コネクター
JPH11181081A (ja) * 1997-12-24 1999-07-06 Toray Ind Inc ポリケトン樹脂からなる摺動部品
JP2001172496A (ja) * 1999-12-20 2001-06-26 Toray Ind Inc 気体および／または液体バリア用樹脂組成物および成形品
JP2008007582A (ja) * 2006-06-28 2008-01-17 Asahi Kasei Chemicals Corp 耐衝撃性、高剛性ポリケトン樹脂組成物およびその成形体
KR20160139363A (ko) * 2015-05-27 2016-12-07 주식회사 효성 폴리케톤 블렌드를 포함하는 자동차용 아웃사이드 도어 핸들
KR101684890B1 (ko) * 2014-11-19 2016-12-12 주식회사 효성 폴리케톤 파이프 홀더 및 이의 제조방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11126643A (ja) * 1997-10-24 1999-05-11 Toray Ind Inc ポリケトン樹脂製コネクター
JPH11181081A (ja) * 1997-12-24 1999-07-06 Toray Ind Inc ポリケトン樹脂からなる摺動部品
JP2001172496A (ja) * 1999-12-20 2001-06-26 Toray Ind Inc 気体および／または液体バリア用樹脂組成物および成形品
JP2008007582A (ja) * 2006-06-28 2008-01-17 Asahi Kasei Chemicals Corp 耐衝撃性、高剛性ポリケトン樹脂組成物およびその成形体
KR101684890B1 (ko) * 2014-11-19 2016-12-12 주식회사 효성 폴리케톤 파이프 홀더 및 이의 제조방법
KR20160139363A (ko) * 2015-05-27 2016-12-07 주식회사 효성 폴리케톤 블렌드를 포함하는 자동차용 아웃사이드 도어 핸들

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