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JP-7856658-B2 - Adhesive film

JP7856658B2JP 7856658 B2JP7856658 B2JP 7856658B2JP-7856658-B2

Inventors

  • ルイス， シャンタル
  • プラット， ジェームズ フランシス
  • エル－ヒブリ， モハマド ジャマル

Assignees

  • サイエンスコ スペシャルティ ポリマーズ ユーエスエー， エルエルシー
  • サイテック インダストリーズ インコーポレイテッド

Dates

Publication Date
20260511
Application Date
20220110
Priority Date
20210423

Claims (15)

  1. An assembly comprising a first component comprising polymer (P1), a second component comprising polymer (P2), and a film comprising at least one type of PEEK-PEoEK copolymer, wherein the PEEK-PEoEK copolymer comprises at least 50 mol% in total of repeating units (R PEEK ) and repeating units (R PEoEK ) relative to the total number of moles of repeating units of the PEEK-PEoEK copolymer, - The repeating unit (R PEEK ) is given by the formula: It is a repeating unit, - The repeating unit (R PEoEK ) is given by the formula: It is a repeating unit, In the formula, each R1 and R2 is either the same as or different from each other, and at each occurrence, is independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali metal or alkaline earth metal sulfonates, alkyl sulfonates, alkali metal or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. Each of a and b is independently selected from the group of integers in the range of 0 to 4. The PEEK-PEoEK copolymer comprises the repeating units (R PEEK ) and (R PEoEK ) in a molar ratio (R PEEK )/(R PEoEK ) in the range of 95/5 to 5/95. The film is placed and bonded between the first and second components . An assembly in which the melting temperatures of polymer (P1) and polymer (P2) are higher than the melting temperature of the film containing the PEEK-PEoEK copolymer .
  2. The aforementioned repeating unit (R PEEK ) is given by the formula: The repeating unit is and/or the repeating unit (R PEoEK ) is of the formula: The assembly according to claim 1, which is a repeating unit.
  3. The assembly according to claim 1 or 2, wherein the PEEK-PEoEK copolymer has a molar ratio (R PEEK )/(R PEOEK ) in the range of 90/10 to 55/45, preferably 85/15 to 60/40, and more preferably 80/20 to 65/35.
  4. The assembly according to any one of claims 1 to 3, wherein the PEEK-PEoEK copolymer has a melting temperature (T m ) of 320°C or less, preferably 315°C or less, when measured according to the method of this specification.
  5. The assembly according to any one of claims 1 to 4, wherein the PEEK-PEoEK copolymer has a solubility of less than 0.2% by weight in N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF) when measured at a temperature of 150°C or lower.
  6. The assembly according to any one of claims 1 to 5, wherein the film has a thickness of 15 to 800 μm.
  7. The assembly according to any one of claims 1 to 6, wherein polymer (P1) and polymer (P2) are independently selected from the group consisting of polyarylether ketones, polyamides, polyetherimides, polyamideimides, polysulfones, polyethersulfones, polyarylethers, polycarbonates, liquid crystal polymers, polyphenylene sulfide, polyarylene (polyphenylene), polyphthalamides, polycyclic aromatic esters, and blends thereof.
  8. The assembly according to claim 7, wherein polymer (P1) and polymer (P2) are independently selected from the group consisting of polyaryletherketone, polyetherimide, polyamideimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyphthalamide, and blends thereof.
  9. The assembly according to claim 7 or 8, wherein polymer (P1) and polymer (P2) are independently selected from PEKK polymers and mixtures thereof having a T/I ratio in the range of 55/45 to 85/15, preferably 57/43 to 80/20, and more preferably 58/42 to 75/25.
  10. The assembly according to any one of claims 7 to 9, wherein the first component is a composite material comprising one or more layers containing fibers and polymer (P1), and/or the second component is a composite material comprising one or more layers containing fibers and polymer (P2).
  11. The assembly according to claim 10, wherein the aforementioned fibers are carbon fibers or glass fibers, preferably continuous carbon fibers or continuous glass fibers.
  12. A method for producing an assembly according to any one of claims 1 to 11, comprising the steps of: placing a film between a first component containing polymer (P1) and a second component containing polymer (P2); and exposing the film to a temperature (T m x ) that is suitable for melting the film but does not melt the polymer (P1) and polymer (P2).
  13. The method according to claim 12, wherein the temperature (T m x ) is higher than the melting temperature of the film, and preferably lower than the melting temperatures of polymer (P1) and polymer (P2).
  14. The method according to claim 12 or 13, comprising the steps of: placing the film between a first component comprising a polymer (P1) and a second component comprising a polymer (P2); and exposing the film to a temperature (T m x ) in the range of 280°C to 315°C.
  15. The method according to any one of claims 12 to 14, wherein pressure is applied to the film while it is exposed to the temperature (T m x ) to solidify the components.

Description

Related Applications This application claims priority to U.S. Provisional Patent Application No. 63/136,227, filed in the United States on 12 January 2021, and to European Patent Application Publication No. 21170100.8, filed in Europe on 23 April 2021, the entire contents of each of these applications are incorporated herein by reference for all purposes. This invention relates to the use of PEEK-PEoEK copolymers for manufacturing adhesive films, and to their use in assemblies such as composites or laminates. In many industries, particularly within the aerospace industry, laminates, composites, and other assemblies composed of different materials in multiple layers are widely used, with each material contributing specific properties to the final assembly. Achieving satisfactory direct adhesion or bonding between the different layers that may be required to utilize a composite or laminate has often proven difficult. Poor fit between composite layers can limit the properties presented in such assemblies. In particular, certain thermoplastic polymers (especially crystalline and/or high-temperature thermoplastics) have been shown to have poor adhesion to other materials, leading to problems of delamination and loss of structural integrity when assemblies are subjected to extremely harsh environments. Numerous techniques have been proposed for fixing and/or bonding thermoplastic components together. In particular, many different welding processes, such as ultrasonic welding, induction welding, and hot plate welding, have been proposed for fixing the first and second thermoplastic components together. However, localized melting of the first and second components in the welding area can affect the integrity and/or shape of the components. Furthermore, deformation can occur due to the accumulation of residual stress in the components during the melting and/or cooling of the thermoplastic material in the welding area. To address some of the problems associated with the welding process, it has been proposed to place a film and/or adhesive between the parts and/or layers and bond them together. International Publication No. 11/001103A2 describes the use of amorphous polyetherketone (PEKK) films as a bonding layer in assemblies such as composites and laminates. However, when the film is amorphous, it is not considered suitable for structural applications in the aerospace industry. Generally speaking, using amorphous materials as bonding layers in composites can result in the weakest part of the structure, with relatively low solvent resistance and other properties. Consequently, the joints become more susceptible to liquid corrosion, potentially leading to premature failure of the structure. International Publication No. 2015/198063A1 describes polyaryl ether ketone polymers, particularly PEEK-PEDEK polymers, as adhesives between a first part and a second part, i.e., PEEK-PEDEK polymers, i.e., formula -O-Ph-O-Ph-CO-Ph-I The use of polymer materials is disclosed, which include polymers having repeating units of the formula -O-Ph-Ph-O-Ph-CO-Ph- II [wherein Ph represents the phenylene moiety]. However, the mechanical properties of PEEK-PEDEK polymers are not as good as those of other polyaryl ether ketone polymers. Therefore, there remains a need to provide films and/or layers that can bond together parts made from polyaryletherketone polymers with good chemical resistance and mechanical properties. To fabricate composite components at lower processing temperatures, it is advantageous to use polyaryletherketone polymers with a melting temperature lower than that of conventionally used polyaryletherketone polymers. Therefore, an adhesive film containing a semi-crystalline polymer with a melting temperature of less than 310°C is required to properly bond components based on low-melting-point polyaryletherketone polymers. Here, it was found that films containing PEEK-PEoEK copolymers, particularly those having a molar ratio (R PEEK )/(R PEoEK ) in the range of 90/10 to 55/45, preferably 85/15 to 60/40, are compatible with the chemical properties of polyaryletherketones, thereby providing bonded polyaryletherketone polymer components with high fracture toughness, and having a minimum crystallinity level of 4 J/g when measured by DSC (cooling rate of 10°C/min), thereby providing composite materials with outstanding mechanical properties. Therefore, the first object of the present invention is a film comprising a PEEK-PEoEK copolymer. This film is suitable for use as an adhesive film, and the terms "film" and "adhesive film" can be used interchangeably throughout this specification. For the purpose of explaining the present invention, - The use of parentheses around symbols or numbers that identify compounds, chemical formulas, or parts of formulas is solely for the purpose of better distinguishing those symbols or numbers from the rest of the text; therefore, such parentheses may be omitted. - If a numerical range is given, in