WO2020190018A1 - Tube multicouche comprenant une polycétone et une polyoléfine - Google Patents

Tube multicouche comprenant une polycétone et une polyoléfine Download PDF

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Publication number
WO2020190018A1
WO2020190018A1 PCT/KR2020/003681 KR2020003681W WO2020190018A1 WO 2020190018 A1 WO2020190018 A1 WO 2020190018A1 KR 2020003681 W KR2020003681 W KR 2020003681W WO 2020190018 A1 WO2020190018 A1 WO 2020190018A1
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Prior art keywords
polyketone
ethylene
bis
formula
polyolefin
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PCT/KR2020/003681
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English (en)
Korean (ko)
Inventor
조동현
김중인
오영일
윤성균
Original Assignee
효성화학 주식회사
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Priority claimed from KR1020200032597A external-priority patent/KR102291059B1/ko
Application filed by 효성화학 주식회사 filed Critical 효성화학 주식회사
Publication of WO2020190018A1 publication Critical patent/WO2020190018A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to a multi-layered tube comprising an inner layer comprising a polyketone, an outer layer comprising a polyolefin, and an adhesive layer disposed between the inner layer and the outer layer.
  • Polyketone (PK) is a copolymer of carbon monoxide, ethylene, and propylene, and has high crystallinity because it is close to linear in structure. Due to these characteristics, oxygen barrier properties are superior to other polymers in general, and chemical resistance is excellent, so that it can be applied to special applications such as food packaging films, pesticide bottles, and geometric liners.
  • polyketones have insufficient moisture barrier properties compared to oxygen barrier properties, so when a certain level of moisture barrier properties are required, it is inevitable that a product should be designed in a multilayer structure with polyolefins such as polyethylene or polypropylene.
  • polyolefins such as polyethylene or polypropylene.
  • polyketone and polyolefin are completely insoluble, in the case of manufacturing a product using the coextrusion method with such a multilayer structure, there is no adhesion between each polymer, so that delamination or beak occurs, so that the durability and performance of the product are not properly expressed. do.
  • An object of the present invention is to provide a multi-layered tube comprising an inner layer comprising a polyketone, an outer layer comprising a polyolefin, and an adhesive layer disposed between the inner layer and the outer layer.
  • the multi-layered tube according to an embodiment of the present invention includes an inner layer comprising polyketone; An outer layer comprising a polyolefin; And an adhesive layer disposed between the inner layer and the outer layer and comprising an ethylene-propylene-dimer grafted with maleic anhydride represented by Formula 1 and an ethylene butyl acrylate-carbon monooxide copolymer represented by Formula 2 below. can do.
  • x and y are each independently an integer of 40 to 60, and z and w are each independently an integer of 1 to 10.
  • x, y, and z are each independently an integer of 1 to 10.
  • the adhesive layer may include 20 to 80% by weight of the grafted ethylene-propylene-dimer and 20 to 80% by weight of the ethylene-butyl acrylate-carbon monooxide copolymer.
  • the adhesive layer may have an adhesive strength with the inner layer of 3.0 to 5.0N/15mm, and an adhesive strength with the outer layer of 7.0 to 9.0N/15mm.
  • the multilayered tube may have an outer diameter of 4mm to 2m.
  • the adhesive layer has excellent adhesion between polyketone and polyolefin, and is positioned between two polymers and completely adheres to both sides when manufacturing a multilayered product using polyketone and polyolefin, thereby improving the peeling phenomenon.
  • the adhesive layer according to the present invention can be applied to a multilayered product that requires both moisture barrier properties and oxygen barrier properties.
  • FIG. 1 schematically shows a multi-layered tube according to an embodiment of the present invention.
  • first and second may be used to describe various components, but the components should not be limited by the terms. These terms are used only for the purpose of distinguishing one component from another component.
  • a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.
  • Singular expressions include plural expressions unless the context clearly indicates otherwise.
  • the multi-layered tube comprising a polyketone; An outer layer comprising a polyolefin; And an adhesive layer disposed between the inner layer and the outer layer and comprising an ethylene-propylene-dimer grafted with maleic anhydride represented by Formula 1 and an ethylene butyl acrylate-carbon monooxide copolymer represented by Formula 2 below.
  • the inner layer comprising a polyketone;
  • An outer layer comprising a polyolefin;
  • an adhesive layer disposed between the inner layer and the outer layer and comprising an ethylene-propylene-dimer grafted with maleic anhydride represented by Formula 1 and an ethylene butyl acrylate-carbon monooxide copolymer represented by Formula 2 below.
  • x and y are each independently an integer of 40 to 60, and z and w are each independently an integer of 1 to 10.
  • x, y, and z are each independently an integer of 1 to 10.
  • x and y are each independently an integer of 40 to 60, and z and w may each independently be 1.
  • x may be 6
  • y may be 3
  • z may be 1.
  • the adhesive layer of the present invention may be made of an adhesive resin composition containing an ethylene-propylene-dimer grafted with maleic anhydride represented by Formula 1 and an ethylene butyl acrylate-carbon monooxide copolymer represented by Formula 2.
  • Maleic anhydride grafted ethylene-propylene-dimer is a compound in which polar maleic anhydride is introduced into a non-polar linear ethylene-propylene main chain, and maleic anhydride is grafted as shown in Formula 1 above. It is a polymer that forms a branched chain. Specifically, maleic anhydride can be easily grafted into ethylene by a radical initiator. The radical initiator attacks the carbon of one of the ethylene-propylene chains to bring a hydrogen atom, and when maleic anhydride is added thereto, a double bond of maleic anhydride is opened and bonded with ethylene-propylene to form a branch. At this time, the ratio of such parts tends to be proportional to the reaction time, and increases in proportion to the concentration of maleic anhydride. On the other hand, the rate of grafting under a nitrogen atmosphere may rather decrease.
  • the ethylene-propylene-dimer grafted with maleic anhydride may contain 0.5 to 2.0% by weight of maleic anhydride. If maleic anhydride is contained in an amount of less than 0.5% by weight, the grafting ratio is too small to reduce adhesion, and if it exceeds 2.0% by weight, a problem of deteriorating workability occurs.
  • the ethylene-propylene-dimer grafted with maleic anhydride may increase compatibility with the ethylene-butyl acrylate-carbon monooxide copolymer described later, and the adhesive resin composition may have a homogeneous composition and distribution.
  • the ethylene-propylene-dimer grafted with maleic anhydride may serve to improve the adhesion of the adhesive resin composition for a multilayer film.
  • the ethylene-propylene-dimer grafted with maleic anhydride has a small difference between the melt index of the polyketone and the polyolefin when the melt index measured at 220°C is 10 to 30 g/10 min. Can be improved.
  • the content of the ethylene-propylene-dimer grafted with maleic anhydride based on the total weight of the adhesive layer may be 20 to 80% by weight, preferably 30 to 70% by weight, more preferably 40 to 60 It may be% by weight, more preferably 50% by weight.
  • the adhesive performance with the polyolefin is 1N/15mm or less, so that sufficient adhesive performance is not expressed, and when it exceeds 80% by weight, the adhesive performance with the polyketone is 1N/15mm or less. The adhesion performance will not be expressed.
  • the adhesive layer of the present invention may include an ethylene butylacrylate-carbon monoxide (EBA-CO) copolymer.
  • EBA-CO ethylene butylacrylate-carbon monoxide
  • ethylene-butyl acrylate-carbon monooxide can improve the appearance quality of the manufactured multilayer film because the difference between the melting index of polyketone and polyolefin is small when the melt index measured at 220°C is 10 to 30 g/10min. I can.
  • the content of the ethylene-butyl acrylate-carbon monooxide copolymer may be 20 to 80% by weight, preferably 30 to 70% by weight, and more preferably 40 to 60% by weight based on the total weight of the adhesive layer. %, more preferably 50% by weight.
  • the adhesive performance with the polyolefin is 1N/15mm or less, so that sufficient adhesive performance is not expressed, and when it exceeds 80% by weight, the adhesive performance with the polyketone is 1N/15mm or less. The adhesion performance will not be expressed.
  • the adhesive resin composition as described above preferably has a melt index measured at 220° C. of 5 to 9 g/10 min. If the melt index is within the above range, it is easy to apply for adhesion at the interface between the polyketone and the polyolefin. If the melt index is less than 5g/10min, it is not preferable because processability deteriorates, and if the melt index exceeds 9g/10min, the adhesiveness decreases, which is not preferable.
  • the adhesive resin composition according to the present invention may be pelletized in a twin-screw extruder, and the prepared pellets may be manufactured into an adhesive sheet (adhesive layer) using a hot press.
  • the temperature of the extruder is preferably 150 to 200°C. If it is less than 150°C, it is not suitable for extrusion, and if it exceeds 200°C, it will exceed the molding temperature, which is not preferable.
  • the prepared adhesive sheet may be put between the polyketone sheet and the polyethylene sheet and hot pressed again to manufacture a laminated sheet, but is not limited thereto.
  • polyketone pellets, pellets containing the adhesive resin composition, and polyolefin pellets may be added to each extruder, and then co-extruded.
  • the thickness of the adhesive sheet is preferably 100 ⁇ 300 ⁇ m, but is not limited thereto.
  • the inner layer (polyketone sheet) comprising the polyketone according to the present invention has an advantage of excellent fuel barrier properties and chemical resistance.
  • the inner layer (polyketone sheet) containing polyketone can be prepared in the following manner.
  • the polyketone of the present invention is a linear alternating structure, and substantially contains carbon monoxide per molecule of unsaturated hydrocarbon.
  • Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers have up to 20 carbon atoms, preferably up to 10 carbon atoms.
  • ethylenically unsaturated hydrocarbons include ethene and ⁇ -olefins, such as propene, 1-butene, iso-butene, 1-hexene, and 1-octene. ), or an aryl aliphatic containing an aryl substituent on another aliphatic molecule, and particularly an aryl substituent on an ethylenically unsaturated carbon atom.
  • aryl aliphatic hydrocarbons among ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene, and m-isopropyl styrene.
  • the polyketone polymer preferably used in the present invention is a copolymer of carbon monoxide and ethene, or a second ethylenically unsaturated hydrocarbon having at least 3 carbon atoms with carbon monoxide and ethene, especially ⁇ -olefins such as propene. It is a terpolymer of the family.
  • each unit containing the second hydrocarbon moiety in the terpolymer there are at least two units containing an ethylene moiety. It is preferable that there are 10 to 100 units containing the second hydrocarbon moiety.
  • the polymer ring of the preferred polyketone polymer in the present invention can be represented by the following structural formula 1.
  • G is an ethylenically unsaturated hydrocarbon, particularly a moiety obtained from an ethylenically unsaturated hydrocarbon having at least 3 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 y/x is preferably 0.03 to 0.3.
  • y/x is more preferably 0.03 to 0.1.
  • the melting point of the polymer can be controlled by adjusting the ratio of ethylene and propylene in the polyketone polymer. For example, when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46:4:50, the melting point is about 220°C, but when the molar ratio is adjusted to 47.3:2.7:50, the melting point is adjusted to 235°C.
  • the physical properties of the polymer are determined according to the molecular weight, depending on the polymer being a copolymer or terpolymer, and in the case of a terpolymer, depending on the properties of the second hydrocarbon moiety present.
  • the melting point of the polymer used in the present invention is 175°C to 300°C, and generally 210°C to 270°C.
  • the intrinsic viscosity (IV) of the polymer measured at 60°C with HFIP (Hexafluoroisopropylalcohol) using a standard customs viscosity measuring device is 0.5dl/g to 10dl/g, preferably 0.8dl/g to 4dl/g, and more Preferably, it is 1.0dl/g-1.4dl/g. At this time, if the number of intrinsic viscosity is less than 1.0 dl/g, mechanical properties deteriorate, and if it exceeds 1.4 dl/g, processability deteriorates.
  • the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. If it is less than 1.5, the polymerization yield is lowered, and if it is more than 2.5, there is a problem that the moldability is lowered.
  • it can be adjusted in proportion to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst increases or the polymerization temperature is 100°C or higher, the molecular weight distribution increases.
  • a liquid phase polymerization carried out in an alcohol solvent through a catalyst composition consisting of a palladium compound, an acid having a PKa of 6 or less, and a di-di ligand compound of phosphorus may be employed.
  • the polymerization reaction temperature is preferably 50 to 100 °C and the reaction pressure is 40 to 60 bar.
  • the polymer is recovered through filtration and purification after polymerization, 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.
  • trifluoroacetic acid was used, and the amount used is preferably 6 to 20 equivalents compared to palladium.
  • 1,3-bis[di(2-methoxyphenylphosphino)]propane is preferable as the compound of phosphorus bidentate coordination, and the amount is preferably 1 to 1.2 equivalents compared to palladium.
  • the polyketone production method includes carbon monoxide and carbon monoxide in a liquid medium in the presence of an organometallic complex catalyst consisting of (a) a group 9, group 10 or group 11 transition metal compound, and (b) a ligand having an element of group 15.
  • an organometallic complex catalyst consisting of (a) a group 9, group 10 or group 11 transition metal compound, and (b) a ligand having an element of group 15.
  • the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer
  • a mixed solvent eg, methanol
  • the catalyst is composed of (a) a Group 9, Group 10, or Group 11 transition metal compound of the Periodic Table (IUPAC Nomenclature Revised Edition, 1989), and (b) a ligand having an element of Group 15.
  • Examples of the Group 9 transition metal compound among the Group 9, 10 or 11 transition metal compounds (a) include cobalt or ruthenium complexes, carbohydrates, phosphates, carbamates, sulfonates, and the like, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, ruthenium trifluoromethane sulfonate, and the like.
  • Examples of the Group 10 transition metal compound include a complex of nickel or palladium, a carbonate, a phosphate, a carbamate, a sulfonate, etc., and specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, palladium trifluoroacetate. , Palladium acetylacetate, palladium chloride, bis(N,N-diethylcarbamate)bis(diethylamine)palladium, palladium sulfate, and the like.
  • Examples of the Group 11 transition metal compound include a complex of copper or silver, a carbonate, a phosphate, a carbamate, a sulfonate, and the like, and specific examples thereof include copper acetate, trifluoro copper acetate, copper acetylacetate, silver acetate, tri Silver fluoroacetic acid, silver acetylacetate, silver trifluoromethane sulfonic acid, etc. are mentioned.
  • transition metal compounds (a) are nickel and copper compounds
  • preferable transition metal compounds (a) in terms of the yield and molecular weight of polyketones are palladium compounds, and improvement in catalytic activity and intrinsic viscosity It is most preferable to use palladium acetate.
  • Examples of the ligand (b) having an atom of Group 15 include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picoline , Nitrogen ligands such as 2,2'-bikinoline, 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) )Phosphino]propane, 1,3-bis[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]propane, 1,2-bis(diphenylphosphino)
  • the preferred ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly preferred in terms of the yield of polyketone is 1,3-bis[di(2- Methoxyphenyl)phosphino]propane, 1,2-bis[[di(2-methoxyphenyl)phosphino]methyl]benzene, and in terms of the molecular weight of the polyketone, 2-hydroxy-1,3-bis[ It is di(2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, and it does not require an organic solvent and is safe.
  • the 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, ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2 -Methoxyphenyl)phosphine) or (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine.
  • the preparation method of the ligand for 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 -1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) is obtained.
  • a method for preparing a ligand for a polyketone polymerization catalyst is provided. .
  • the method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventional 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-) through an easy process in a safe environment where lithium is not used, Methoxyphenyl)phosphine) can be commercially synthesized in large quantities.
  • the (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine ligand can be synthesized through the following four steps: First, diethylmalonate and 1, 5-dibromopentane is boiled under sodium ethoxide and ethanol, then reduced under lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexanedimethanol, and reacted under tosyl chloride and pyridine to obtain release By reacting this ligand with 2-methoxyphenylphosphine, sodium hydride and dimethyl sulfoxide, the ligand can be obtained, and each step undergoes purification steps such as column chromatography and recrystallization. The purity can be confirmed through nuclear magnetic resonance analysis.
  • the method for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises (a) adding bis(2-methoxyphenyl)phosphine and dimethyl sulfoxide (DMSO) to a reaction vessel under nitrogen atmosphere and hydrogenating at room temperature.
  • DMSO dimethyl sulfoxide
  • the amount of the transition metal compound (a) used in the Group 9, 10 or 11 transition metal compound (a) varies according to the selected ethylenic and propylene unsaturated compounds or other polymerization conditions. Although it cannot be limited, it is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol per 1 liter of the capacity of the reaction band.
  • the capacity of the reaction zone refers to 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 moles, preferably 1 to 3 moles, per 1 mole of the transition metal compound (a).
  • the intrinsic viscosity of the polyketone can be improved by adding benzophenone during polymerization of the polyketone.
  • 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 prepared polyketone is not satisfactory, and if the molar ratio of the transition metal and benzophenone exceeds 1:100, the catalytic activity of the polyketone 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
  • the three-way copolymerization of carbon monoxide with the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex consisting of the group 9, 10 or 11 transition metal compound (a), and a ligand (b) having an element of group 15 It is caused by a catalyst, and the catalyst is produced by contacting the two components. Any method can be adopted as a method of contacting. That is, in a suitable solvent, the two components may be premixed and used, or the two components may be separately supplied to the polymerization system and brought into contact within the polymerization system.
  • additives such as antioxidants, stabilizers, fillers, refractory materials, release agents, colorants, and other materials may additionally be included in order to improve the processability or physical properties of the polymer.
  • the polymerization method a solution polymerization method using a liquid medium, a suspension polymerization method, and a gas phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution are used.
  • the polymerization may be a batch type or a continuous type.
  • the reactor used for polymerization a known reactor can be used as it is or processed.
  • the polymerization temperature is not particularly limited, and is generally 40 to 180°C, preferably 50 to 120°C. There is also no restriction on the pressure during polymerization, but it is generally normal pressure to 20 MPa, preferably 4 to 15 MPa.
  • Alternating linear polyketones are formed by the polymerization method as described above.
  • a manufacturing method for manufacturing the polyketone sheet of the present invention is as follows.
  • the obtained polyketone is mixed with a compatibilizer and then extruded with an extruder to finally obtain a blend composition.
  • the blend is put into a twin-screw extruder, melt-kneaded, and extruded to form a pellet.
  • the extrusion temperature is 200 ⁇ 240 °C
  • the screw rotation speed is preferably in the range of 100 ⁇ 300rpm. If the extrusion temperature is less than 200°C, kneading may not occur properly, and if it exceeds 240°C, problems related to heat resistance of the resin may occur. In addition, if the screw rotation speed is less than 100 rpm, smooth kneading may not occur, and if it exceeds 300 rpm, mechanical properties may deteriorate.
  • the outer layer (polyolefin sheet) comprising the polyolefin according to the present invention has the advantages of excellent moisture barrier properties, flexibility and impact resistance.
  • the polyolefin may be a maleic anhydride grafted, but is not limited thereto.
  • the polyolefin may be composed of polyethylene showing excellent transparency, flexibility and heat adhesion, or polypropylene having a low adhesive strength, adhesion temperature and melting point.
  • additives such as antioxidants, stabilizers, fillers, refractory materials, release agents, colorants and other materials may additionally be included.
  • polyolefin is mixed with a compatibilizer and then extruded with an extruder to finally obtain a blend composition.
  • the blend may be prepared in a pellet form by melt-kneading and extruding into a twin screw extruder.
  • the sheet of the present invention can be obtained by first manufacturing a pellet in the form of a pellet as described above, and then melt-processing it or directly melting a mixed composition, and the film is a casting film or a film by a Slit T-die melt molding. It can be extruded into a blown film.
  • the multi-layered tube may have an outer diameter of 4 mm to 2 m.
  • Such multi-layered pipes may be tubes or pipes.
  • the tube may be flexible and have a small diameter, and the pipe may be rigid and have a large diameter.
  • the multi-layered pipe according to the present invention contains a polyketone having excellent oxygen barrier properties, fuel barrier properties and chemical resistance on the innermost side, and a polyolefin having excellent moisture barrier properties, flexibility and impact resistance on the outermost side, such as an oil pipeline. It can be easily applied to tubes for transporting fuel of In addition, by disposing an adhesive layer having excellent adhesion between polyketone and polyolefin between the inner layer and the outer layer, interlayer adhesion is improved to improve the peeling phenomenon, and products with robust durability and excellent quality can be manufactured. .
  • the obtained adhesive resin pellets were put into one extruder (B) of a multi-tube extruder consisting of three extruders, and polyketone (A) and polyethylene (C) were respectively added to the other extruder, and A (inner layer)-B (intermediate layer)- A three-layer tube composed of a C (outer layer) structure was obtained.
  • the extrusion conditions were set equally at 30 rpm for each extruder screw speed A, B, and C, and the temperature was set from 150°C in the input unit to 220°C in the T-Die unit where the film is generated.
  • the resulting tube was cut into a specimen having a width of 15 mm and a length of 125 mm, and the adhesive strength of the polyketone and polyethylene was measured by the method of ASTM D1876, and the location of the peeled surface was confirmed, and the results are shown in Table 1 below.
  • the tube When preparing the adhesive resin pellet, the tube through the same procedure as in Example 1, except that the maleic anhydride grafted EPDM (Dupont Fusabond N416) 50% by weight and EBA-CO (Dupont Elvaloy HP441) 50% by weight. After manufacturing, the adhesive strength was measured and the position of the peeled surface was confirmed.
  • the tube When preparing the adhesive resin pellet, the tube through the same procedure as in Example 1, except that the maleic anhydride grafted EPDM (Dupont Fusabond N416) 30% by weight and EBA-CO (Dupont Elvaloy HP441) 70% by weight were adjusted. After manufacturing, the adhesive strength was measured and the position of the peeled surface was confirmed.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Adhesive strength 8.8N/15mm 4.1N/15mm 3.5N/15mm 1.1N/15mm 0.3N/15mm 0.2N/15mm Peeling side Polyethylene-adhesive resin Polyketone-adhesive resin Polyketone-adhesive resin Polyketone-adhesive resin Polyketone-adhesive resin Polyketone-adhesive resin
  • the peeling surface was a polyethylene-adhesive resin, and the adhesive strength was 8.8N/15mm, indicating that the adhesive resin had excellent adhesion to polyethylene.
  • the peeling surface was polyketone-adhesive resin, and the adhesion strength was improved compared to the comparative example, indicating that the adhesive resin had excellent adhesion to the polyketone.
  • the adhesive strength of the adhesive resin to the polyketone is very low as 1.1N/15mm or less. Appeared.
  • the adhesive strength of the adhesive resin to the polyketone was very low.
  • the adhesive strength with the polyketone sheet is 3.0 to 5.0N/15mm, and the polyethylene sheet and The adhesive strength of is 7.0 to 9.0N/15mm, and the interlayer adhesion is improved so that peeling does not occur, and thus, a product having strong durability and excellent quality can be manufactured.
  • outer layer (polyolefin)

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polyethers (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un tube multicouche comprenant: une couche interne comprenant une polycétone; une couche externe comprenant une polyoléfine; et une couche adhésive disposée entre la couche interne et la couche externe et comprenant un dimère éthylène-propylène greffé avec un anhydride maléique, et un copolymère éthylène-acrylate de butyle-monoxyde de carbone.
PCT/KR2020/003681 2019-03-18 2020-03-18 Tube multicouche comprenant une polycétone et une polyoléfine WO2020190018A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20190030353 2019-03-18
KR10-2019-0030353 2019-03-18
KR10-2020-0032597 2020-03-17
KR1020200032597A KR102291059B1 (ko) 2019-03-18 2020-03-17 폴리케톤 및 폴리올레핀을 포함하는 다층구조의 관

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WO2020190018A1 true WO2020190018A1 (fr) 2020-09-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023218483A1 (fr) * 2022-05-09 2023-11-16 Ashirvad Pipes Pvt. Ltd Tuyaux de pression flexibles multicouches

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0886387A (ja) * 1994-05-31 1996-04-02 Hutchinson Sa 燃料輸送用パイプ
KR0155962B1 (ko) * 1990-06-25 1998-11-16 미리암 디. 메코너헤이 압출 가능하며 프라이머가 없는 개선된 접착제 및 그로부터 얻은 제품
WO1999042286A1 (fr) * 1998-02-18 1999-08-26 Bp Chemicals Limited Structure a couches multiples
JP2009522413A (ja) * 2005-12-30 2009-06-11 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ホットメルト接着剤組成物
KR20180072791A (ko) * 2015-12-15 2018-06-29 미쓰이 가가쿠 가부시키가이샤 적층체 및 그의 제조 방법, 및 접착용 조성물

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0155962B1 (ko) * 1990-06-25 1998-11-16 미리암 디. 메코너헤이 압출 가능하며 프라이머가 없는 개선된 접착제 및 그로부터 얻은 제품
JPH0886387A (ja) * 1994-05-31 1996-04-02 Hutchinson Sa 燃料輸送用パイプ
WO1999042286A1 (fr) * 1998-02-18 1999-08-26 Bp Chemicals Limited Structure a couches multiples
JP2009522413A (ja) * 2005-12-30 2009-06-11 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ホットメルト接着剤組成物
KR20180072791A (ko) * 2015-12-15 2018-06-29 미쓰이 가가쿠 가부시키가이샤 적층체 및 그의 제조 방법, 및 접착용 조성물

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023218483A1 (fr) * 2022-05-09 2023-11-16 Ashirvad Pipes Pvt. Ltd Tuyaux de pression flexibles multicouches

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