WO2025082995A1 - Procédé de préparation d'une structure liée, structure liée et utilisation de ladite structure liée pour préparer une pièce d'automobile - Google Patents

Procédé de préparation d'une structure liée, structure liée et utilisation de ladite structure liée pour préparer une pièce d'automobile Download PDF

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Publication number
WO2025082995A1
WO2025082995A1 PCT/EP2024/079089 EP2024079089W WO2025082995A1 WO 2025082995 A1 WO2025082995 A1 WO 2025082995A1 EP 2024079089 W EP2024079089 W EP 2024079089W WO 2025082995 A1 WO2025082995 A1 WO 2025082995A1
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Prior art keywords
polyolefin
propane
adhesive
gas
flame
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PCT/EP2024/079089
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English (en)
Inventor
Jana HRACHOVÁ
Hans LEENDERS
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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Publication of WO2025082995A1 publication Critical patent/WO2025082995A1/fr
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    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/166—Metal in the pretreated surface to be joined
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/008—Presence of polyolefin in the pretreated surface to be joined
    • 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
    • C09J2463/00—Presence of epoxy resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Polymeric and metal materials can be bonded by means of a bonding agent that is applied to the bonding surfaces of the materials to be bonded. This requires deposition of the bonding agent onto the bonding surfaces of the polymeric and metal materials. Adhesion of the bonding agent to the bonding surfaces might be difficult to accomplish due to the inherent incompatible chemical nature of the materials.
  • a polyolefin e.g., a polypropylene
  • another surface e.g., a metal surface
  • low surface energy and low polarity of the polyolefin due to, for example, low surface energy and low polarity of the polyolefin.
  • a process for preparing of a bonded structure comprising treating a surface of a polyolefin part to provide an activated polyolefin surface; directly applying an adhesive to the activated polyolefin surface and a surface of a metal part; and curing the adhesive to form a bond between the polyolefin part and the metal part, wherein the adhesive comprises an epoxy structural adhesive comprising two components, wherein each of the components comprises an amine, has a density of less than 1 .38 grams per milliliter, or a combination thereof.
  • Each of the components can comprise the amine and have the density of less than 1 .38 grams per milliliter.
  • the polyolefin can comprise a polypropylene.
  • the polyolefin can comprise a polyethylene.
  • the polyolefin part can further comprise glass fiber.
  • the polyolefin part can further comprise a flame retardant additive.
  • the bond can have a lap shear strength of greater than 8.0 MPa after conditioning for 168 hours at 23 ⁇ 2°C and 50 ⁇ 6% relative humidity and being fully immersed in ethylene-glycol/water for 45 days at 65°C.
  • Treating the surface of the polyolefin part comprises treating with a flame of a propane-comprising gas, said propane-comprising gas being propane or a mixture comprising at least 50 weight percent (wt. %) of propane based on a weight of the propane-comprising gas with methane, ethane, butane, pentane, hexane, or a combination thereof, wherein, during treatment with the flame of the propane-comprising gas, a flame is produced by burning a mixture of air and the propane-comprising gas, wherein the gas-to-air ratio is chosen such that the propane gas to oxygen volume ratio is equal to or less than 1 :5.01 .
  • the adhesive can comprise two components.
  • a bonded structure prepared by the process a battery comprising the bonded structure, and an electric vehicle comprising the battery.
  • electric vehicle comprising the bonded structure.
  • Bonding agent means a material capable of fasten two surfaces together, usually producing a smooth bond.
  • a bonding agent is also known as an adhesive.
  • Gap between the burner nozzle(s) and the surface means the distance between the burner nozzles and the surface to be treated, for example, the surface of a polyolefin part.
  • Gas-to-air ratio means, the ratio of parts of gas to parts of air used in a flame, i.e., in the total gas and air flow. Unless otherwise specified, the ratio is a volume ratio. For example, 1 :17, means that for 1 liter (L) of gas fed to the flame 17 L of air is used as oxidiser.
  • Treatment speed means, the length of a surface that is exposed to the flame per unit time; for example, the length of the surface of a polyolefin part per unit time that is exposed to the flame.
  • a treatment speed of 300 millimeters per second (mm/s) means that 300 millimeters (mm) of the surface of, e.g., a polyolefin part, is exposed to the flame per second.
  • Total flow of gas and air mixture means the liters per unit time of the mixture gas and air that is fed to the burner in order to produce the flame.
  • a total flow of gas and air mixture of 300 liters per minute (L/min) means that 300 liters of gas and air mixture are fed to the burner in order to produce the flame.
  • Activation of the surface or surface activation means, modification of the surface chemistry of a solid, e.g., a polyolefin part, leading to an increase of its surface energy (also known as surface free energy), an increase of the polar part contributing to the surface energy, and/or a decrease of the contact angle of the surface with water.
  • “Surface energy”, as used in the present application, means the surface free energy calculated according to the Owens, Wendt, Rabel and Kaelble method, which is a standard method for calculating the surface free energy of a solid from the contact angle with two liquids water, diiodomethane. This allows for the determination of the surface energy, which is divided into a polar part and a disperse (or dispersive) part. Based on the theory by Owens, Wendt, Rabel and Kaelble, the surface tension (o) can be divided into a polar and disperse part as follows: with P for polar, D for disperse and s for solid and I for liquid.
  • o s p can be estimated by the square of the slope m and o s D can be estimated by the square of the ordinate intercept b.
  • water and diiodomethane are used due to their diverse c ⁇ / /cr ”-ratio.
  • the present application relates in a first aspect to a process for the preparation of a bonded structure comprising a polyolefin part having a polyolefin bonding surface, an adhesive and a metal part having a metal bonding surface, wherein said polyolefin bonding surface and metal bonding surface are in contact with said adhesive, said process preferably comprising the steps of: a) treating at least part of a polyolefin bonding surface of said polyolefin part with a flame of a propane-comprising gas, said propane-comprising gas being propane or a mixture comprising at least 50 wt.
  • % of propane based on the weight of the propane-comprising gas with one or more gases selected from the group consisting of methane, ethane, butane, pentane, and hexane to obtain a polyolefin part having a flame-treated polyolefin bonding surface; b) providing a metal part having a metal bonding surface; and c) bonding said polyolefin part and said metal part together by contacting at least part of the flame-treated polyolefin bonding surface and at least part of said metal bonding surface with said adhesive, wherein said adhesive comprises an epoxy structural adhesive comprising two components, wherein each of the components comprises an amine, has a density of less than 1.38 grams per milliliter, or a combination thereof.
  • the polyolefin bonding surface can be washed before performing step a) of the method according to the invention.
  • the metal bonding surface can also be washed before bonding this to the polyolefin part or before subjecting this to a treatment with a flame of propane-comprising gas.
  • the metal bonding surface may also be activated using a different activation method, by treating said surface with e.g., atmospheric plasma, low pressure plasma, with a corona-treatment or by fluorination.
  • the washing step can be performed by immersing the polyolefin part in a solution comprising a cleansing agent, such as a surfactant.
  • the washing step can also comprise immersing the polyolefin part in a solvent, such as an alcohol, preferably an alcohol chosen from the group of propanol, isopropyl alcohol (IPA), more preferably isopropyl alcohol with a purity higher than 96 wt. %.
  • a solvent such as an alcohol, preferably an alcohol chosen from the group of propanol, isopropyl alcohol (IPA), more preferably isopropyl alcohol with a purity higher than 96 wt. %.
  • the washing step can be substituted by a cleaning step, which comprises applying a solution comprising a cleansing agent or a solvent to the polyolefin bonding surface, optionally followed by rinsing said surface with water.
  • At least part of a polyolefin bonding surface is treated, or at least part of a metal bonding surface is treated is meant that preferably at least 80 %, more preferably at least 90 %, even more preferably at least 95 % or even at least 99 % or 100 % of the polyolefin bonding surface or the metal bonding surface is treated, respectively.
  • a polyolefin bonding surface can also be a polyolefin bonding surface that has been washed or cleaned.
  • a metal bonding surface can also be a metal bonding surface that has been washed or cleaned.
  • the polyolefin part may be prepared from a composition comprising polypropylene and long glass fibers, for example, from compositions as commercially available from SABIC under the trademark STAMAXTM polypropylene.
  • the polyolefin part may be prepared from a composition comprising polypropylene and a mineral filler.
  • the polyolefin part can comprise a polyolefin chosen from the group of propylene- based polymers (polypropylenes), elastomers of ethylene and a-olefin comonomer having 4 to 8 carbon atoms, and any mixtures thereof.
  • the polyolefin comprises a propylene-based polymer.
  • the thermoplastic polymer composition comprises at least 80 wt. % of the propylene-based polymer, for example, at least 90 wt. %, at least 93 wt. %, at least 95 wt. %, at least 97 wt. % at least 98 wt. % or at least 99 wt. % of the propylene-based polymer based on the thermoplastic polymer composition.
  • the thermoplastic polymer composition consists of the propylene-based polymer.
  • the propylene-based polymer can be at least one selected from the group consisting of a propylene homopolymer, a propylene random copolymer and a heterophasic propylene copolymer and mixtures thereof, preferably wherein the polyolefin comprises a propylene random copolymer; a propylene homopolymer and a heterophasic propylene copolymer; or a propylene homopolymer and a propylene random copolymer.
  • a propylene homopolymer can be obtained by polymerizing propylene under suitable polymerization conditions.
  • a propylene copolymer can be obtained by copolymerizing propylene and one or more other a-olefins, preferably ethylene, under suitable polymerization conditions.
  • the preparation of propylene homopolymers and copolymers is, for example, described in Moore, E. P. (1996) Polypropylene Handbook. Polymerization, Characterization, Properties, Processing, Applications, Hanser Publishers: New York.
  • the random propylene copolymer may comprise as the comonomer ethylene and/or an a-olefin chosen from the group of a-olefins having 4 to 10 C-atoms, preferably ethylene, 1-butene, 1-hexene or any mixtures thereof.
  • the amount of the comonomer is preferably at most 10 wt. % based on the random propylene copolymer, for example, in the range from 2 to 7 wt. % based on the random propylene copolymer.
  • Polypropylenes can be made by any known polymerization technique as well as with any known polymerization catalyst system. Regarding the techniques, reference can be given to slurry, solution or gas phase polymerizations; regarding the catalyst system reference can be given to Ziegler-Natta, metallocene or single-site catalyst systems. All are, in themselves, known in the art. Heterophasic propylene copolymers are generally prepared in one or more reactors, by polymerization of propylene in the presence of a catalyst and subsequent polymerization of an ethylene-a-olefin mixture. The resulting polymeric materials are heterophasic, but the specific morphology usually depends on the preparation method and monomer ratios used.
  • the heterophasic propylene copolymers can be produced using any conventional technique known to the skilled person, for example, multistage process polymerization, such as bulk polymerization, gas phase polymerization, slurry polymerization, solution polymerization or any combinations thereof.
  • Any conventional catalyst systems for example, Ziegler-Natta or metallocene may be used.
  • Such techniques and catalysts are described, for example, in W006/010414; Polypropylene and other Polyolefins, by Ser van der en, Studies in Polymer Science 7, Elsevier 1990; W006/010414, US4399054 and US4472524.
  • the polymers or thermoplastic materials may be linear polymers or branched polymers or combinations thereof.
  • the plastic can optionally be reinforced, e.g., with fibers, particles, flakes, as well as combinations comprising at least one of the foregoing, such as especially for example, long glass fibers, short glass fibers, glass beads, talc, mica, inorganic fillers, natural fibers, conductive fillers and/or carbon fibers.
  • the thermoplastic second component can be formed from STAMAX® materials, a long glass fiber reinforced polypropylene commercially available from SABIC.
  • the polymer can comprise an additive, such as stabilizers, antioxidants, pigments; wherein the polymer preferably comprises at most 5% of the additive.
  • the combination can be a blend or a copolymer.
  • the polymer can be filled with a mineral filler, e.g., talc, or glass fibers; for example, the polymer can comprise at most 45 wt. % of the filler, such as for example, at most 40 wt. % of the filler, based on the total weight of the polymer.
  • the polymer can comprise a flame retardant additive such as a nitrogen-phosphorus based flame retardant.
  • the polymer can comprise 20 to 40 wt. % or 25 to 30 wt. % of long glass fibers; 20 to 40 wt. % or 25 to 30 wt. % of short glass fibers; or 30 to 50 wt. % or 35 to 45 wt. % of long glass fibers.
  • the glass fibers used as filler in the polymer can be long and/or short glass fibers. Short glass fibers in the polymer may have an average length of up to 1 .0 mm. Long glass fibers in the polymer may have an average length of 1.0 to 4.5 mm, for example, 2.0 to 4.0 mm.
  • the diameter of the glass fibers can be 5.0 to 50.0 micrometers (pm), specifically, 8.0 to 30.0 pm, more specifically, 10.0 to 20.0 pm.
  • the lengths and the diameters of the glass fibers can be determined based on the photo images by an image analysis software.
  • the term “average” refers to an arithmetic average.
  • the polyolefin is polypropylene or a combination of polypropylene and polyethylene, wherein preferably the polyolefin comprises at least 45 wt. % of polypropylene based on the total weight of the polyolefin.
  • the polyolefin part can comprise a polyolefin filled with at most 40 wt. % of a filler based on the total weight of the polyolefin, wherein the polyolefin comprises a polypropylene or a combination of polypropylene and polyethylene, wherein preferably the polyolefin comprises at least 45 wt. % of polypropylene based on the total weight of the polyolefin.
  • a combination of polypropylene and polyethylene is meant a heterophasic propylene copolymer or polypropylene impact copolymer, which is a polypropylene blended with an elastomer impact modifier, such as polyethylene particles, C2-C8 (ethylene-octene copolymer) elastomer impact modifier or C2-C4 (ethylene-butene copolymer) impact modifier.
  • an elastomer impact modifier such as polyethylene particles, C2-C8 (ethylene-octene copolymer) elastomer impact modifier or C2-C4 (ethylene-butene copolymer) impact modifier.
  • the bonded structure can comprise a polyolefin comprising a polyolefin selected from the group consisting of: polypropylene, a combination of polypropylene and polyethylene, and combinations thereof.
  • the polymer can be filled with a mineral filler, e.g., talc, or glass fibers, wherein the polymer comprises at most 45 wt. % of the filler, such as for example, at most 40 wt. % of the filler, based on the total weight of the polymer.
  • the polyolefin part can comprise a polymer
  • the polyolefin part comprises at least 35 wt. %, for example, at least 50 wt. %, for example, at least 75 wt. %, or at least 83 wt. % or even 99 wt. % or 100 wt. % of one or more polymers based on the weight of the polyolefin part.
  • the polyolefin can be polypropylene or a combination of polypropylene and polyethylene, wherein preferably the polyolefin comprises at least 45 wt. % of polypropylene based on the total weight of the polyolefin.
  • a process for the preparation of a bonded structure comprising a polyolefin part having a polyolefin bonding surface can comprise the step of: a) treating at least part of a polyolefin bonding surface of said polyolefin part with a flame of a propane-comprising gas, said propane-comprising gas being propane or a mixture comprising at least 50 wt.
  • % of propane based on the weight of the propane-comprising gas with one or more gases selected from the group consisting of methane, ethane, butane, pentane, and hexane, wherein, during treatment with a flame of the propane-comprising gas, a flame is produced by burning a mixture of air and the propane-comprising gas, wherein the gas-to-air ratio is chosen such that the propane gas to oxygen volume ratio is equal to or less than 1 : 5.01 , for example, less than 1 :5.00 and preferably at least 3.50 to obtain a polyolefin part having a flame-treated polyolefin bonding surface.
  • the process further comprises the sequential steps of: b1) providing a metal part, wherein the metal part has a metal bonding surface and c1) contacting said polyolefin bonding surface and metal bonding surface with an adhesive (3) together by contacting at least part of the flame-treated polyolefin bonding surface and at least part of said metal bonding surface with said adhesive, wherein said adhesive comprises an epoxy structural adhesive comprising two components, wherein each of the components comprises an amine, has a density of less than 1.38 grams per milliliter, or a combination thereof.
  • step c1) at least part of a polyolefin bonding surface may be treated with a flame of a propane-comprising gas, said propane-comprising gas being propane or a mixture comprising at least 50 wt. % of propane with one or more gases selected from the group consisting of ethane, butane, and hexane to obtain a metal part having a flame-treated polyolefin bonding surface.
  • propane-comprising gas being propane or a mixture comprising at least 50 wt. % of propane with one or more gases selected from the group consisting of ethane, butane, and hexane
  • the propane-comprising gas can comprise at least 80 wt. % of propane, preferably at least 95 wt. % of propane, more preferably at least 99 wt. % of propane, or even 100 wt. % based on the weight of the propane-comprising gas.
  • a burner may be used for producing the flame, said burner comprising at least one nozzle for providing a mixture of air and the propane-comprising gas to be burned, wherein the gap between the at least one nozzle and said polyolefin bonding surface and/or said metal bonding surface is between 5 centimeters (cm) and 15 cm, preferably 8 cm.
  • the temperature reached on the said flame-treated polyolefin bonding surface during treatment with a flame of a propane-comprising gas may for example, be between 30°C and 90°C, preferably between 50 °C and 80 °C, more preferably between 60 °C and 65 °C.
  • the surface energy of the flame-treated polyolefin bonding surface is preferably higher than 30 millinewtons per meter (mN/m), and the polar part of the surface energy is preferably higher than 1.5 mN/m, preferably higher than 2 mN/m.
  • the flame treatment can be performed using a burner for producing the flame. The burner is fed with a defined mixture of a fuel (propane-comprising gas) and an oxidiser (air), thoroughly premixed before combustion.
  • a fuel propane-comprising gas
  • an oxidiser air
  • Variables affecting the flame treatment are for example, the gas-to-air ratio, the composition of the gas, the gap between the burner nozzles and the polyolefin bonding surface, the treatment speed, and the total flow of gas and air mixture. These variables affect the temperature reached on the flame treated bonding surface during the flame treatment.
  • the propane-comprising gas comprises at least 80 wt. % of propane, more preferably at least 95 wt. % of propane, such as for example, at least 99 wt. % of propane or even 100 wt. % of propane.
  • a flame is produced by burning a mixture of air and the propane-comprising gas, wherein the gas-to-air ratio is chosen such that the propane to oxygen ratio is equal to or less than 1 : 5.01 . This also contributes to a further activation of the polyolefin bonding surface.
  • a burner can be used for producing the flame, said burner comprising at least one nozzle for providing a mixture of air and the propane-comprising gas to be burned, wherein the gap between the at least one nozzle and the polyolefin bonding surface can easily be determined by the person skilled in the art.
  • the gap between the polyolefin bonding surface or metal bonding surface is, for example, between 5 cm and 15 cm, for examples cm. This gap influences the extent of activation accomplished by the flame treatment. A too large distance between the cone of the flame and bonding surface, causes the surface activation to decrease. A too low distance between the cone of the flame and the polyolefin bonding surface may damage the surface.
  • the temperature reached on the flame-treated polyolefin bonding surface, during treatment with a flame of a propane-comprising gas, can be between 30°C and 90°C, preferably between 50 °C and 80 °C, more preferably between 60 °C and 65 °C; for example, 60°C.
  • the desired increase in surface energy, increase of the polar part of the surface energy and increase wettability of the polyolefin bonding surface is not obtained, or the surface is overtreated.
  • the surface energy of said flame-treated polyolefin bonding surface is higher than 30 mN/m, and the polar part of the surface energy is higher than 1.5 mN/m, preferably higher than 2 mN/m.
  • Activation of a polyolefin surface can be characterized by quantifying the changes on surface free energy and wettability.
  • Surface free energy (SFE) quantifies the disruption of intermolecular bonds that occur when a surface is created. SFE is the energy required to increase the size of the surface of a phase. It can be considered as having a polar and a disperse (or dispersive) part. Wettability is the ability of a liquid (e.g., water) to maintain contact with a solid surface. Wettability is generally determined by measuring is given by the contact angle of water with a surface.
  • Activation of a polyolefin surface can then lead to an increase of its surface free energy, an increase of the polar part contributing to the surface free energy, and/or a decrease of the contact angle of the surface with water.
  • the treatment speed may, for example, be between 200 mm/s and 1 ,200 mm/s, preferably between 250 mm/s and 1 ,000 mm/s, more preferably between 250 mm/s and 700 mm/s, such as, for example, 300 mm/s.
  • the total flow of gas and air mixture can be between 200 L/min and 750 L/min, preferably 450 L/min.
  • the polyolefin may achieve a surface chemistry that is favorable for further secondary operations and does not have a detrimental effect on long-term adhesion or on the original properties of the polyolefin.
  • Creating a specific surface chemistry on the polyolefin can aid with achieving strong initial and long-term adhesion of adhesive systems, for long life expectancy and safety of automotive parts in real environment conditions.
  • a primer need not be applied on the flame-treated polyolefin bonding surface and/or the (flame-treated) metal bonding surface before performing step c1) to ensure suitable adhesion.
  • a primer which is also known as an adhesion promoter, need not be applied onto a polyolefin bonding surface before contacting the surface with the disclosed adhesive, in order to ensure suitable adhesion of the adhesive to the polyolefin bonding surface.
  • adhesive can be directly applied to an activated polyolefin surface and a surface of a metal part.
  • the adhesive may be a single-component adhesive.
  • This single component adhesive can be a high temperature curing type adhesive.
  • the adhesive may be a two-component adhesive.
  • the two component adhesive preferably comprises a first resin component and a second hardener component. Upon combination of the resin and the hardener a chemical reaction takes place to form an adhesive.
  • the adhesive may be applied to the first flame-treated bonding surface and/or to the metal bonding surface.
  • the epoxy adhesive e.g., epoxy structural adhesive
  • each of the components can comprise an amine, have a density of less than 1 .38 grams per milliliter (g/mL), or a combination thereof.
  • each of the components can comprise an amine, have a density of 0.5 to 1 .38 g/mL, or 0.9 to 1 .25 g/mL, or 1 .09 to 1 .15 g/mL, or a combination thereof.
  • the bond can have a lap shear strength of greater than 8.0 after conditioning for 168 hours at 23 ⁇ 2°C and 50 ⁇ 6% relative humidity and being fully immersed in ethylene- glycol/water for 45 days at 65°C; or a combination thereof.
  • the metal part can be an automotive part, for example, a part of a battery for a vehicle such as an electric vehicle.
  • the metal part is aluminum.
  • the present inventors surprisingly discovered that by using the disclosed epoxy structural adhesive, polyolefin and metal can be bonded without roughening the metal surface, such as by laser radiation into the metal surface. Prior to bonding, the metal surface can be cleaned, for example, with isopropyl alcohol.
  • a bonded structure can be obtained by the process according to the invention.
  • Such bonded structure can, for example, be used as an automotive part, such as a tailgate or a roof spoiler or a bumper.
  • the bonded structure can, for example, be used in a battery, for example, a battery of an electric vehicle.
  • the invention relates to a bonded structure obtainable or obtained by the process according to the invention.
  • the invention relates to a use of the bonded structure as an automotive part, for example, as a tailgate or roof spoiler or a bumper.
  • an electric vehicle comprises the bonded structure.
  • the term “comprising” does not exclude the presence of other elements.
  • a description on a product/composition comprising certain components also discloses a product/composition consisting of these components.
  • the product/composition consisting of these components may be advantageous in that it offers a simpler, more economical process for the preparation of the product/composition.
  • a description on a process comprising certain steps also discloses a process consisting of these steps.
  • the process consisting of these steps may be advantageous in that it offers a simpler, more economical process.
  • autonomous or “automobile(s)” or “vehicle(s)” or other similar term as used herein is inclusive of motor vehicles in general such as passenger automobiles including sports utility vehicles (SUV), buses, trucks, various commercial vehicles, watercraft including a variety of boats and ships, aircraft, and the like, and includes hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles and other alternative fuel vehicles (e.g., fuels derived from resources other than petroleum).
  • a hybrid vehicle is a vehicle that has two or more sources of power, for example, both gasoline-powered and electric-powered vehicles.
  • the present invention is related to a method for the preparation of a bonded structure.
  • the bonded structure is formed by bonding a polyolefin part and an aluminum part.
  • FIG. 1 illustrates a setup for lap sheer testing in accordance with the Examples.
  • Polyolefin lap shear specimens with dimensions 100 x 25 x 4 millimeters (mm) and metal lap shear specimens with dimensions 100 x 25 x 2 mm were used for lap shear test.
  • Bonded structures were subjected to different forms of conditioning. “Initial” conditioning involved conditioned for 168 hours at 23 ⁇ 2°C and 50 ⁇ 6% relative humidity. Samples subjected to “extended” conditioning (also referred to herein as “accelerated aging”) were first subjected to Initial conditioning followed by being subjected to heating and cooling cycles at various relative humidities. Samples subjected to “Ethylene-Glycol” or “E-G” conditioning were first subjected to Initial conditioning followed by being fully immersed in ethylene-glycol/water (50/50) for 45 days at 65°C.
  • FIG. 2 illustrates failure types of adhesive bonds (DIN EN ISO 10365).
  • substrate failure can include normal substrate failure (SF), cohesive substrate failure (CSF), or delamination failure (DF).
  • SF normal substrate failure
  • CSF cohesive substrate failure
  • DF delamination failure
  • “Substrate failure” or “SF”, as used herein, means fracture of the bonded material on one of the bonded parts in the zone adjacent to the adhesive and approximately along the centre of the plane of the adhesive locates perpendicular to the bonding surfaces, without internal breakdown of the adhesive.
  • Cohesive substrate failure” or “CSF”, as used herein means fracture of the bonded material. There is an internal breakdown on one of the bonded parts in the zone adjacent to the adhesive and approximately along the centre of the plane of the adhesive located parallel to both bonding surfaces, without internal breakdown of the adhesive.
  • Cohesive failure can be subdivided into normal cohesive failure (CF) and special cohesive failure (SCF).
  • CF normal cohesive failure
  • SCF special cohesive failure
  • SCF/CF means that the bonds between the adhesive and the bonded surfaces break exhibiting a combination of special cohesive failure and normal cohesive failure. More than 50% of the bonded area after de-bonding shows special cohesive failure.
  • Adhesive failure can be subdivided into normal adhesive failure (AF) and adhesive cohesive failure with peeling (ACFP).
  • AF adhesive failure
  • ACFP adhesive cohesive failure with peeling
  • CF/AF means that the bonds between the adhesive and the bonded surfaces break exhibiting a combination of cohesive failure and adhesive failure. There are areas of the bonded surfaces after de-bonding showing no residuals of the adhesive, and areas on the same bonded surface showing residuals of the adhesive. More than 50% of the bonded area after de-bonding shows a cohesive failure.
  • AF/CF means that the bonds between the adhesive and the bonded surfaces break exhibiting a combination of adhesive failure and cohesive failure. There are areas of the bonding surfaces after de-bonding showing no residuals of the adhesive, and areas on the same bonding surface showing residuals of the adhesive. More than 50% of the bonded area after de-bonding shows adhesive failure.
  • FIGS. 3-8 present results of adhesives that achieved bond lap shear strengths of greater than 8 MPa following ethylene-glycol conditioning.
  • FIGS. 3 and 4 present results of Epoxy- 1 ;
  • FIGS. 5 and 6 present results of Epoxy-2; and
  • FIGS. 7 and 8 present results of Epoxy- 3.
  • FIG. 3 shows that for Epoxy-1 , good adhesion after ethylene-glycol conditioning was achieved without aluminum laser treatment.
  • FIG. 4A shows further details for aluminum IPA treatment with no primer or aluminum laser treatment and initial conditioning
  • FIG. 4B shows further details for aluminum IPA treatment with no primer or aluminum laser treatment and extended conditioning
  • FIG. 4C shows further details for aluminum IPA treatment with no primer or aluminum laser treatment and ethylene-glycol conditioning.
  • Primerl was a black, pigmented, solvent-based polyurethane solution.
  • Reference in FIG. 4 to “primer” is Primerl .
  • FIGS. 5 shows results for Epoxy-2 with aluminum IPA treatment (no primer) or aluminum laser treatment (no primer).
  • FIG. 6A shows further details for Epoxy-2 with aluminum IPA treatment (no primer) or aluminum laser treatment (no primer) and initial conditioning
  • FIG. 6B shows further details for Epoxy-2 with aluminum IPA treatment (no primer) or aluminum laser treatment (no primer) and extended conditioning
  • FIG. 6C shows further details for Epoxy-2 with aluminum IPA treatment (no primer) or aluminum laser treatment (no primer) and ethylene-glycol conditioning. It is believed that missing laser treated samples would provide as good results as IPA treated samples.
  • FIGS. 7 shows results for Epoxy-3 with aluminum IPA treatment (no primer) or aluminum laser treatment (no primer).
  • FIG. 8A shows further details for Epoxy-3 with aluminum IPA treatment (no primer) or aluminum laser treatment (no primer) and initial conditioning
  • FIG. 8B shows further details for Epoxy-3 with aluminum IPA treatment (no primer) or aluminum laser treatment (no primer) and extended conditioning
  • FIG. 8C shows further details for Epoxy-3 with aluminum IPA treatment (no primer) or aluminum laser treatment (no primer) and ethylene-glycol conditioning. Good adhesion after ethyleneglycol conditioning was achieved without aluminum laser treatment, but overall better adhesion was achieved with aluminum laser treatment.
  • FIGS. 7 shows results for Epoxy-3 with aluminum IPA treatment (no primer) or aluminum laser treatment (no primer).
  • FIG. 8A shows further details for Epoxy-3 with aluminum IPA treatment (no primer) or aluminum laser treatment (no primer) and initial conditioning
  • FIG. 8B shows further details for Epoxy-3 with aluminum IPA
  • FIGS. 9 and 10 present results of Epoxy-4, which exhibited decreased bond lap shear strengths after ethylene-glycol conditioning, achieved bond lap shear strengths of equal to or less than 8 MPa following ethylene-glycol conditioning, or a combination thereof.
  • FIGS. 9 shows results for Epoxy-4.
  • FIG. 10A shows further details for Epoxy-4 with initial conditioning
  • FIG. 10B shows further details for Epoxy-4 with extended conditioning
  • FIG. 10C shows further details for Epoxy-4 with ethylene-glycol conditioning. Initial adhesion was less than 8 MPa and lap shear strength decreased after ethylene-glycol conditioning.

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Abstract

L'invention concerne un procédé de préparation d'une structure liée comprenant le traitement d'une surface d'une pièce en polyoléfine pour fournir une surface de polyoléfine activée ; l'application directe d'un adhésif sur la surface de polyoléfine activée et une surface d'une pièce métallique ; et le durcissement de l'adhésif pour former une liaison entre la partie polyoléfine et la partie métallique, l'adhésif comprenant un adhésif structural époxy comprenant deux constituants, chacun des constituants comprenant une amine, ayant une masse volumique inférieure à 1,38 gramme par millilitre, ou une combinaison de ceux-ci.
PCT/EP2024/079089 2023-10-19 2024-10-16 Procédé de préparation d'une structure liée, structure liée et utilisation de ladite structure liée pour préparer une pièce d'automobile Pending WO2025082995A1 (fr)

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US202363544880P 2023-10-19 2023-10-19
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US4472524A (en) 1982-02-12 1984-09-18 Montedison S.P.A. Components and catalysts for the polymerization of olefins
US5900321A (en) * 1994-06-17 1999-05-04 Pelindaba District Brits Atomic Energy Corp. Of South Africa Limited Method for the production of composites
JP2003027012A (ja) * 2001-07-23 2003-01-29 Hitachi Chem Co Ltd 繊維強化プラスチック成形品の接着方法及びその接着物
KR20040067620A (ko) * 2003-01-24 2004-07-30 한국화학연구원 금속과의 접착력이 우수한 폴리올레핀계 필름의 제조방법
WO2006010414A1 (fr) 2004-07-30 2006-02-02 Saudi Basic Industries Corporation Compositions copolymeres de propylene de transparence elevee
US20130273356A1 (en) * 2010-11-01 2013-10-17 Dow Brasil S.A. Polyolefins having one or more surfaces modified to improve adhesion of polyisocyanate functional adhesives thereto
US20210245489A1 (en) * 2018-06-14 2021-08-12 The Yokohama Rubber Co., Ltd. Method for manufacturing multilayer member
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US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
US4472524A (en) 1982-02-12 1984-09-18 Montedison S.P.A. Components and catalysts for the polymerization of olefins
US5900321A (en) * 1994-06-17 1999-05-04 Pelindaba District Brits Atomic Energy Corp. Of South Africa Limited Method for the production of composites
JP2003027012A (ja) * 2001-07-23 2003-01-29 Hitachi Chem Co Ltd 繊維強化プラスチック成形品の接着方法及びその接着物
KR20040067620A (ko) * 2003-01-24 2004-07-30 한국화학연구원 금속과의 접착력이 우수한 폴리올레핀계 필름의 제조방법
WO2006010414A1 (fr) 2004-07-30 2006-02-02 Saudi Basic Industries Corporation Compositions copolymeres de propylene de transparence elevee
US20130273356A1 (en) * 2010-11-01 2013-10-17 Dow Brasil S.A. Polyolefins having one or more surfaces modified to improve adhesion of polyisocyanate functional adhesives thereto
US20210245489A1 (en) * 2018-06-14 2021-08-12 The Yokohama Rubber Co., Ltd. Method for manufacturing multilayer member
US20230024134A1 (en) * 2019-12-20 2023-01-26 Sabic Global Technologies B.V. Process for the preparation of a bonded structure, a bonded structure and use of said bonded structure for preparing an automotive part

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MOORE, E. P.: "Polypropylene Handbook. Polymerization, Characterization, Properties, Processing, Applications", 1996, HANSER PUBLISHERS

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