Adhesive film

Abstract

Adhesive films including PEEK-PEoEK copolymers match the chemical properties of polyaryletherketones, thereby providing bonded polyaryletherketone polymer parts with high fracture toughness and good overall mechanical properties.

Description

[Technical Field]

[0001] 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 being incorporated herein by reference for all purposes.

[0002] The present invention relates to the use of PEEK-PEoEK copolymers for manufacturing adhesive films, and to their use in assemblies such as composites or laminates. [Background technology]

[0003] In many industries, particularly within the aerospace industry, laminates, composites, and other assemblies consisting of different multilayer materials are widely used, with each material contributing specific properties to the final assembly. Achieving satisfactory direct adhesion or bonding between different layers that may be required to utilize composites or laminates 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.

[0004] 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 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.

[0005] 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.

[0006] 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 use in structural applications in the aerospace industry. From a general standpoint, 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.

[0007] 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., formula -O-Ph-O-Ph-CO-Ph- I The repeating unit and the formula -O-Ph-Ph-O-Ph-CO-Ph- II repeating unit The use of polymer materials is disclosed, including a polymer having [wherein Ph represents the phenylene moiety]. However, the mechanical properties of the PEEK-PEDEK polymer are not as good as those of other polyaryletherketone polymers.

[0008] Therefore, there remains a need to provide films and / or layers that can bond together parts made from polyaryletherketone polymers that are endowed with good chemical resistance and mechanical properties.

[0009] To fabricate composite parts 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 parts based on low-melting-point polyaryletherketone polymers. [Modes for carrying out the invention]

[0010] Here, a film containing PEEK-PEoEK copolymer, particularly with a molar ratio (R) in the range of 90 / 10 to 55 / 45, preferably 85 / 15 to 60 / 40. PEEK ) / (R PEoEK The film having ) was found to be compatible with the chemical properties of polyaryletherketone, 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 a composite material with outstanding mechanical properties.

[0011] Accordingly, 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 for the remainder of this specification.

[0012] 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, include the endpoints of the range. - The phrase "containing PEEK-PEoEK copolymer" means that the composition contains one or more PEEK-PEoEK copolymers.

[0013] PEEK-PEoEK copolymer As used herein, the expression "PEEK-PEoEK copolymer" refers to a polymer containing, in total, at least 50 mol% of repeating units (R PEEK ) and repeating units (R PEoEK ) in a molar ratio (R PEEK ) / (R PEoEK ) within the range of 95 / 5 to 5 / 95. In some embodiments, the PEEK-PEoEK copolymer contains at least 6 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, and most preferably at least 99 mol% of repeating units (R PEEK ) and (R PEoEK ).

[0014] The repeating units (R PEEK ) and (R PEoEK ) are present in the PEEK-PEoEK copolymer in a molar ratio (R PEEK ) / (R PEoEK ) within the range of 90 / 10 to 55 / 45. It is generally understood that a preferred PEEK-PEoEK copolymer suitable for the film of the present invention has a molar ratio (R PEEK ) / (R PEoEK ) preferably within the range of 85 / 15 to more than 55 / 45, more preferably 85 / 15 to 60 / 40, and still more preferably 80 / 20 to 65 / 35.

[0015] The repeating unit (R PEEK ) is represented by the formula:

Chemical formula

Chemical formula

[0016] In some preferred embodiments, in equation (A), each a is zero, and therefore the repeating unit (R PEEK ) is the formula: [ka] It is a repeating unit.

[0017] In some preferred embodiments, in equation (B), each b is zero, and therefore the repeating unit (R PEoEK ) is the formula: [ka] It is a repeating unit.

[0018] Preferably, a repeating unit (R PEEK ) is the repeating unit of formula (A-1), and the repeating unit (R PEoEK ) is the repeating unit of equation (B-1).

[0019] The PEEK-PEoEK copolymer of the present invention has repeating units (R) as detailed above. PEEK ) and (R PEoEK ) is a different repeating unit (R PAEK ) may further include. In such cases, the repeating unit (R PAEK The amount of ) may be 0.1 to less than 50 mol%, preferably less than 10 mol%, more preferably less than 5 mol%, and most preferably less than 2 mol%, relative to the total number of moles of repeating units of the PEEK-PEoEK copolymer.

[0020] Repeating unit (R PEEK ) and (R PEoEK ) is a different repeating unit (R PAEK If ) is present in the PEEK-PEoEK copolymer of the present invention, then the units (R) described above may be present. PEEK ) and (R PEoEK These repeating units (R) are different from the others. PAEK ) is generally expressed by the following formulas (KA)~(KM) in this specification: [ka] [ka] [ka] It conforms to any of the following conditions: In the formulas (KA) to (KM) above, each of the R' that are equal to or different from each other is, at each occurrence, independently selected from C1-C12 alkyl, alkenyl, alkynyl, or aryl groups containing one or more heteroatoms at any choice; sulfonic acids and sulfonic acid groups; phosphonic acids and phosphonic acid groups; amines and quaternary ammonium groups; and each of the j' that are equal to or different from each other is independently selected from 0 and integers from 1 to 4 at each occurrence, preferably j' is equal to zero. Repeating unit (R PAEK In this configuration, each phenylene portion may independently have 1,2, 1,4, or 1,3 bonds in a portion other than R' within the repeating unit.

[0021] Preferably, the PEEK-PEoEK copolymer used in the film of the present invention has repeating units (R) as detailed above. PEEK ) and (R PEoEK It is essentially composed of ). Therefore, in some preferred embodiments, the PEEK-PEoEK copolymer is composed of repeating units (R PEEK ) and (R PEoEK Essentially composed of ). The term "repeating unit (R)" used herein refers to the repeating unit (R).PEEK ) and (R PEoEK The expression "essentially composed of" refers to the repeating units (R) described in detail above. PEEK ) and (R PEoEK This means that any additional repeating units different from those specified above may be present in the PEEK-PEoEK copolymer in amounts of up to 2 mol%, up to 1 mol%, or up to 0.5 mol%, relative to the total number of moles of repeating units of the PEEK-PEoEK copolymer, and in such a manner that they do not substantially alter the favorable properties of the PEEK-PEoEK copolymer.

[0022] Preferred PEEK-PEoEK copolymers generally have 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 temperatures below 150°C. In some embodiments, PEEK-PEoEK copolymers used in connection with adhesive films are advantageously substantially insoluble in the solvents listed above, making them particularly suitable for use in applications where improved chemical resistance and / or, in some cases, liquid resistance are required.

[0023] In some embodiments, the PEEK-PEoEK copolymer has a melting temperature (T) of 320°C or lower, preferably 315°C or lower, as measured by differential scanning calorimetry (DSC) according to ASTM D3418-03, E1356-03, and E794-06. m ) has.

[0024] Melting temperature T m The glass transition temperature (Tg) and heat of fusion (ΔH) are determined by differential scanning calorimetry (DSC) according to ASTM D3418-03, E1356-03, E793-06, and E794-06 standards, with a sweep from 30°C to 400°C and applying heating and cooling rates of 10°C / min.

[0025] An advantageous adhesive film has a melting temperature of 320°C or lower, preferably 310°C or lower and / or at least 270°C (T mIt was made using a PEEK-PEoEK copolymer having ).

[0026] In some embodiments, the PEEK-PEoEK copolymer has a heat of fusion (ΔH) of at least 4 J / g, preferably at least 5 J / g, or at least 10 J / g, more preferably at least 15 J / g. In some embodiments, the PEEK-PEoEK copolymer may have a heat of fusion (ΔH) of up to 75 J / g, preferably up to 65 J / g.

[0027] In some embodiments, the PEEK-PEoEK copolymer has a glass transition temperature (T) of 165°C or lower, preferably 160°C or lower, 155°C or lower, or 150°C or lower, as measured by differential scanning calorimeter (DSC) according to ASTM D3418-03 and E1356-03. g ) has. In some embodiments, the PEEK-PEoEK copolymer has a glass transition temperature (Tg) of 130°C or higher, preferably 135°C or higher, as measured by differential scanning calorimeter (DSC) according to ASTM D3418-03 and E1356-03.

[0028] If necessary, the PEEK-PEoEK copolymer may be manufactured with a higher or lower molecular weight to adjust the viscosity of the molten copolymer over a very wide range. In some embodiments, the PEEK-PEoEK copolymer is prepared at 410°C, 46.3s. -1 When measured according to ASTM D3835, it is at least 0.10 kN / m 2 , more preferably at least 0.20 kN / m 2 , and most preferably at least 0.25 kN / m 2 It may have a melt viscosity (MV). In some embodiments, the PEEK-PEoEK copolymer is 410°C, 46.3s. -1 When measured according to ASTM D3835, the maximum is 1.50 kN / m 2 , more preferably at least 1.30 kN / m 2 , and most preferably at least 1.10 kN / m 2 It may have a melting viscosity (MV).

[0029] The stability of the PEEK-PEoEK copolymer in the molten phase is 46.3 s. -1 Melt viscosity can be measured as the ratio between the melt viscosity measured after a residence time of 40 minutes at 410°C under a shear rate and the melt viscosity measured after a residence time of 10 minutes at the same temperature and shear rate, and the melt viscosity is measured using a capillary rheometer according to the ASTM D3835 standard using a conical die (diameter = 1.016 mm, length = 20.32 mm, cone angle = 120°). The melt stability of the PEEK-PEoEK copolymer is preferably less than 1.23, preferably less than 1.22, and more preferably less than 1.21. Preferably, the melt stability is higher than 0.60, more preferably higher than 0.65, and most preferably higher than 0.70.

[0030] FT-IR analysis of PEEK-PEoEK copolymers can provide useful information regarding the copolymer's microstructure, including the linkage of various monomers, the characteristics of end groups, and the presence or absence of defects. According to certain preferred embodiments, the PEEK-PEoEK copolymer is subjected to FT-IR analysis on polymer powder in ATR mode at 600-1,000 cm⁻¹. -1 The FT-IR spectrum recorded by the device has a fine structure that satisfies the following inequality: (i)

number

number

number

number

number

number

number

number

number

number

number

number

[0031] PEEK-PEoEK copolymers having a specific microstructure (including monomer linkages, end groups, and defects) characterized by the spectroscopic features described above can provide improved chemical and mechanical properties.

[0032] The PEEK-PEoEK copolymer may have a calcium content of less than 5 ppm, as measured by inductively coupled plasma atomic emission spectroscopy (ICP-OES) calibrated to a known calcium content standard. According to these preferred embodiments, the PEEK-PEoEK copolymer may have a calcium content of less than 4 ppm, less than 3 ppm, or more preferably less than 2.5 ppm.

[0033] In these preferred embodiments, the PEEK-PEoEK copolymer may have a sodium content of less than 1,000 ppm as measured by inductively coupled plasma atomic emission spectroscopy (ICP-OES) calibrated to a known sodium content standard. Preferably, the PEEK-PEoEK copolymer may have a sodium content of less than 900 ppm, less than 800 ppm, or more preferably less than 500 ppm.

[0034] In some embodiments, the PEEK-PEoEK copolymer may have a phosphorus content of at least 6 ppm, as measured by inductively coupled plasma atomic emission spectroscopy (ICP-OES) calibrated to a known phosphorus content standard. Preferably, the PEEK-PEoEK copolymer has a phosphorus content of at least 10 ppm, at least 15 ppm, or more preferably at least 20 ppm.

[0035] In the adhesive film of the present invention, it may be advantageous to select a PEEK-PEoEK copolymer with improved thermal stability, which may be particularly beneficial when the components to be bonded by the adhesive film are polymers with high melting temperatures, and / or when the final component must withstand high operating temperatures. Accordingly, in some embodiments, the PEEK-PEoEK copolymer has a peak decomposition temperature of at least 550°C, more preferably at least 551°C, and even more preferably at least 552°C, as measured as TGA according to ASTM D3850.

[0036] Suitable methods for preparing PEEK-PEoEK copolymers are generally known in the art. Generally, the PEEK-PEoEK copolymer used herein is of formula (C): [ka] At least one difluoro compound of formulas (D) and (E): [ka] A mixture of di-hydroxy compounds [wherein R 3 , R 4 , and R 5 [where c, d, and e have the meanings defined above, and each c, d, and e are independently selected from the group consisting of integers in the range of 0 to 4] are prepared by a method comprising reacting them in a polar organic solvent in the presence of a base such as Na2CO3, K2CO3, or a combination thereof, in a molar ratio (D) / (E) in the range of 90 / 10 to 55 / 45. Preferably, each of c, d, and e is zero.

[0037] In one embodiment, the PEEK-PEoEK copolymer used in the film of the present invention is prepared as described in International Publication No. 2020 / 254097A1, the entire contents thereof, which are incorporated herein by reference.

[0038] Film composition and method for producing film In some embodiments, the film of the present invention comprises at least one additive other than the PEEK-PEoEK copolymer. Suitable additives include, but are not limited to, (i) colorants such as dyes, (ii) pigments such as titanium dioxide, zinc sulfide and zinc oxide, (iii) light stabilizers, e.g., UV stabilizers, (iv) heat stabilizers, (v) antioxidants such as organic phosphites and phosphonites, (vi) acid scavengers, (vii) processing aids, (viii) nucleating agents, (ix) internal lubricants and / or external lubricants, (x) flame retardants, (xi) smoke suppressants, (x) antistatic agents, (xi) antiblocking agents, (xii) conductive additives such as carbon black and carbon nanofibrils, (xiii) plasticizers, (xiv) flow regulators, (xv) bulking agents, (xvi) metal deactivators and (xvii) flow aids such as silica.

[0039] According to certain embodiments, the film of the present invention further comprises at least one nucleating agent. The nucleating agent may be selected from the group consisting of boron-containing compounds (e.g., boron nitride, sodium tetraborate, potassium tetraborate, calcium tetraborate, etc.), alkaline earth metal carbonates (e.g., calcium magnesium carbonate), oxides (e.g., titanium dioxide, aluminum oxide, magnesium oxide, zinc oxide, antimony trioxide, etc.), silicates (e.g., talc, sodium aluminum silicate, calcium silicate, magnesium silicate, etc.), alkaline earth metal salts (e.g., calcium carbonate, calcium sulfate, etc.), nitrides, and the like. The nucleating agent may also be carbon-based. Nucleating agents in this category include graphite, graphene, graphite nanoplatelets, and graphene oxide. Carbon black and other forms of carbon may also be used. Particularly good results were obtained when the nucleating agent was boron nitride.

[0040] Typically, the film contains less than 20% by weight of additives, preferably less than 10% by weight, more preferably less than 5% by weight, and even more preferably less than 2% by weight, and most preferably less than 1% by weight of additives.

[0041] In preferred embodiments, the film contains no reinforcing fibers, i.e., less than 0.5% by weight, preferably less than 0.1% by weight, of any reinforcing fibers. The term “fiber” has its usual meaning as known to those skilled in the art and may include one or more fibrous materials suitable for reinforcing composite structures, i.e., “reinforcing fibers”. The term “fiber” is used herein to refer to organic and / or inorganic fibers having a length of at least 0.5 mm.

[0042] In some embodiments, the film may contain a blend of two or more polymers, one of which is a PEEK-PEoEK copolymer. According to these embodiments, the adhesive film may contain at least one additional polymer component, different from the PEEK-PEoEK copolymer, in an amount of 40% by weight or less (based on the total weight of the polymer matrix). Such additional polymer components are advantageously selected from the group consisting of poly(aryl ether sulfone) (PAES) polymers and poly(aryl ether ketone) (PAEK) polymers. If the additional polymer component is a PAES polymer, it may advantageously be selected from the group consisting of polysulfone (PSU), polyphenylsulfone (PPSU), and poly(ether sulfone) (PES). If the additional polymer component is a PAEK polymer, it may advantageously be selected from the group consisting of poly(ether ether ketone) (PEEK) polymer, poly(ether ketone ketone) (PEKK) polymer, polyether ketone (PEK), polyether ketone ether ketone ketone (PEKEKK), and PEEK-PEDEK copolymer. Additional polymer components may include polyimides such as polyetherimide (PEI) or polyamideimide.

[0043] In alternative embodiments, the PEEK-PEoEK copolymer, as detailed above, is the sole polymer component in the adhesive film. As used herein, the term "polymer component" means a compound having repeating units and a molecular weight of at least 2,000 g / mol. In some embodiments, the adhesive film contains polymer components other than the PEEK-PEoEK copolymer in amounts of less than 3% by weight, less than 2% by weight, less than 1% by weight, or less than 0.5% by weight.

[0044] In certain embodiments, the adhesive film comprises at least 90% by weight of a PEEK-PEoEK copolymer and at least one additive and / or at least one additional polymer component different from the PEEK-PEoEK copolymer. Most preferably, the adhesive film comprises at least 95% by weight, preferably at least 98% by weight of a PEEK-PEoEK copolymer and at least one additive.

[0045] The film of the present invention may have a thickness of 15 to 800 μm, more preferably 25 to 600 μm, more preferably 30 to 500 μm, more preferably 40 to 300 μm, and most preferably 50 to 250 μm.

[0046] The film of the present invention may be prepared by any conventional method known in the art in polymer processing.

[0047] The components of the adhesive film are typically processed into film form by cast extrusion, with optional uniaxial or biaxial stretching. As used herein, the term “components of the film” includes the PEEK-PEoEK copolymer and optionally at least one additive, at least one additional polymer component different from the PEEK-PEoEK copolymer, or a combination thereof.

[0048] In some embodiments, the method for producing a film includes melting and kneading a physical mixture of the film components. Conventional melting and kneading equipment such as co-rotating and counter-rotating extruders, single-screw extruders, cone kneaders, disc pack processors, and various other types of extruders can be used. Preferably, an extruder, more preferably a twin-screw extruder, can be used.

[0049] In some embodiments, the physical mixture is kneaded in an extruder and then cut into pellets or granules. The granules or pellets can then be further processed to produce the film of the present invention.

[0050] Alternatively, the physical mixture is kneaded in an extruder and then directly formed into a film. A technique particularly suitable for producing the adhesive film of the present invention involves extruding a molten composition through an elongated die to obtain an extruded tape, and then casting / rolling the extruded tape to obtain a film. The tape can be rolled into a film by passing it through a suitable roll, the roll can be maintained at a suitable temperature, and its speed can be adjusted to achieve the required thickness. The thickness of the film is adjusted by the die. Depending on the cooling temperature used to solidify the film, the finished (extruded) film can be amorphous or semi-crystalline.

[0051] In an advantageous embodiment, the film is a single-layer film, i.e., it consists of only one layer containing the PEEK-PEoEK copolymer.

[0052] Method for manufacturing an assembly A second object of the present invention is a method for producing an assembly using a film according to the first object of the present invention. This method comprises the steps of placing a film according to the first object of the present invention between a first component containing polymer (P1) and a second component containing polymer (P2), and setting a temperature (T) that is suitable for melting the film but does not melt polymer (P1) and polymer (P2). m x This includes the step of exposing the film to the following:

[0053] Temperature (T m x ) is typically higher than the melting temperature of the adhesive film. m x The temperature may be less than 330°C, preferably less than 320°C, and more preferably less than 310°C. The temperature may be higher than 270°C. The temperature may be in the range of 270°C to 330°C, preferably in the range of 280°C to 315°C.

[0054] Temperature (T m x Preferably, the temperature is lower than the melting temperatures of polymer (P1) and polymer (P2).

[0055] This method comprises the steps of placing a film between a first component containing polymer (P1) and a second component containing polymer (P2), and using a temperature in the range of 280°C to 315°C (T), which is suitable for melting the film but does not melt polymer (P1) and polymer (P2). m x Preferably, the process includes the step of exposing the film to ).

[0056] Preferably, this method involves heating the film and the polymers (P1) and (P2) at the temperature (T m x The method includes solidifying the components by applying pressure while exposing the film to a temperature (T) to manufacture the assembly. m x The method further includes applying pressure to the first and second components while exposing them to the sun.

[0057] In this method, the cooling of the adhesive film after melting is preferably controlled so that the PEEK-PEoEK copolymer in the adhesive film undergoes crystallization (i.e., does not become amorphous). After cooling, the film preferably has a degree of crystallinity of at least 5%, preferably at least 15%, more preferably at least 20%, and particularly at least 23%, as measured as described herein.

[0058] The expression "first component comprising polymer (P1)" is used herein to refer to a component having at least one surface, in particular a surface that contacts the adhesive film comprising polymer (P1). The first component may consist of the polymer (P1). Alternatively, the first component may comprise one surface comprising polymer (P1). The surface comprising polymer (P1) typically has a thickness suitable for forming adhesion with the adhesive film. The thickness may, for convenience, be 5 μm or more.

[0059] The expression "second component comprising polymer (P2)" is used herein to refer to a component having at least one surface, in particular a surface that is in contact with the adhesive film comprising polymer (P2).

[0060] The second component may consist of the polymer (P2). Alternatively, the second component may include a surface containing the polymer (P2). The surface containing the polymer (P2) typically has a thickness suitable for forming adhesion with the adhesive film. The thickness may be 5 μm or more for convenience.

[0061] Polymer (P1) and polymer (P2) may be the same or different.

[0062] Polymers (P1) and (P2) may be independently selected from the group consisting of crystalline and / or high-temperature thermoplastic polymers. Notable non-limiting examples include, but are not limited to, poly(aryl ether ketones), polyetherimides, polyamideimides, polysulfones, polyethersulfones, polyaryl ethers, polycarbonates, liquid crystal polymers, polyphenylene sulfides, polyarylenes (polyphenylenes), polyamides, polyphthalamides, polycyclic aromatic esters, and blends thereof.

[0063] In preferred embodiments, polymer (P1) and polymer (P2) are independently selected from the group consisting of polyaryl ether ketones (hereinafter referred to as "PAEK") and blends of polyaryl ether ketones.

[0064] A suitable PAEK is a repeating unit (R) represented by a formula selected from the group consisting of formulas (A) and (KA) to (KM) as defined above. PAEK The polymer contains at least 50% by weight of ). In some embodiments, the PAEK contains at least 60% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, or at least 98% by weight of repeating units (R PAEK ) has.

[0065] The PAEK polymer may be a homopolymer, random, alternating, or block copolymer. If the PAEK polymer is a copolymer, (i) at least two different repeating units of formulas selected from formulas (A) and (KA) to (KM) (R PAEK ) may include.

[0066] According to some embodiments, the repeating unit (R PAEK ) is the unit of equation (J'-A)~(J'-D): [ka] It is selected from the group consisting of the following.

[0067] The PAEK polymer may be a polyether ether ketone ("PEEK") polymer. As used herein, the term "PEEK polymer" means that at least 50% by weight of repeating units are the repeating units (R) of formula J'-A. PAEK ), especially the repeating unit of formula (A-1) as defined above (R PAEKRefers to any polymer that is. In some embodiments, at least 75 wt%, at least 85 wt%, at least 95 wt%, or at least 99 wt% of the repeating units of the PEEK polymer are repeating units of formula J'-A. In some embodiments, 99.99 wt% of the PEEK polymer is a repeating unit of formula J'-A, particularly a repeating unit of formula (A-1) (R PAEK ).

[0068] The PAEK polymer may be a polyetherketoneketone ("PEKK") polymer.

[0069] As used herein, the term "PEKK polymer" refers to any polymer containing the repeating unit (R T ) and the repeating unit (R I ) in a total amount of at least 50 mol% based on the total number of moles of the PEKK polymer. The repeating unit (R T ) has the formula (T):

Chemical formula

Chemical formula

[0070] To avoid misunderstanding, the repeating unit (RT )'s molar content is [Number] defined as The molar content of the repeating unit (R I ) is [Number] defined as Therefore, the T / I ratio is [Number] defined as

[0071] According to one embodiment, i and j of each R 1 and R 2 groups are zero. In other words, the repeating units (R T ) and (R I ) are both unsubstituted. According to this embodiment, the repeating units (R T ) and (R I ) are represented by the formulas (T') and (I'): [Chemical formula] respectively. [[ID=5​​​​​In other embodiments, polymer (P1) and polymer (P2) may be independently selected from compositions comprising first and second PEKK polymers, each PEKK polymer characterized by a T / I ratio, wherein the T / I ratio of the first PEKK polymer is different from that of the second PEKK polymer, particularly those compositions having a melting temperature of 330°C or less. In one aspect of the embodiments, the first PEKK polymer preferably has a (T / I) ratio of at least 50 / 50, preferably at least 54 / 46, more preferably at least 56 / 44; most preferably at least 57 / 43, and / or a (T / I) low of up to 64 / 36, preferably up to 63 / 37, more preferably up to 62 / 38. The second PEKK polymer preferably has a (T / I) ratio of at least 65 / 35, preferably at least 66 / 34, more preferably at least 67 / 33, and / or a (T / I) height of up to 85 / 15, preferably up to 83 / 17, more preferably up to 82 / 18.

[0074] In a further embodiment of the above embodiment, the following inequality is satisfied: (the repeating unit of the second PEKK polymer (R T (molar content of the first PEKK polymer (R)) - (repeat unit of the first PEKK polymer) T (molar content of ) ≤ 20 mol%, preferably ≤ 17 mol%, more preferably ≤ 15 mol%. Typically, the following inequality also holds: (the repeating unit of the second PEKK polymer (R T (molar content of the first PEKK polymer (R)) - (repeat unit of the first PEKK polymer) T ) molar content) ≥ 3 mol%, preferably ≥ 4 mol%, more preferably ≥ 5 mol%.

[0075] In one embodiment of the present invention, polymer PEKK is nucleophilic PEKK, meaning that polymer PEKK is produced by polycondensation of dihydroxy and difluorobenzoyl-containing aromatic compounds and / or hydroxyl-fluorobenzoyl-containing aromatic compounds.

[0076] In an alternative embodiment, the polymer PEKK is electrophilic PEKK.

[0077] In other embodiments, the polymer (PAEK) is poly(etherketone)[polymer(PEK)]. The terms "poly(etherketone)" and "polymer(PEK)" used herein refer to the repeating unit (R PAEK ) exceeding 50 mol%, is given by equation (K'-C): [ka] It means any polymer that is a repeating unit of Mole percent is based on the total number of moles of repeating units of the polymer (PEK).

[0078] According to these embodiments, the repeating unit (R PAEK At least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or even substantially all of the polymer consists of repeating units (K'-C). A preferred polymer (PEK) is a polymer in which substantially all of the repeating units are units of formula (K'-C), and it is understood that end groups, defects, and small amounts of impurities may be present.

[0079] In some embodiments, the polymer (PAEK) is poly(etherdiphenyletherketone)[polymer(PEDEK)]. The terms "poly(etherdiphenyletherketone)" or "polymer(PEDEK)" as used herein refer to the repeating unit (R K ) exceeding 50 mol%, is given by equation (K'-D): [ka] It means any polymer that is a repeating unit of Mole percent is based on the total number of moles of repeating units of the polymer (PEDEK).

[0080] According to these embodiments, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or even substantially all repeating units (R K ) is the repeating unit (K'-D) as detailed above. A preferred polymer (PEDEK) is a polymer in which substantially all repeating units are units of formula (K'-D), and it is understood that end groups, defects, and small amounts of impurities may be present.

[0081] In some other embodiments, polymer (PAEK) is poly(etherdiphenyletherketone)-poly(etheretherketone) copolymer [polymer(PEEK-PEDEK)]. The expressions "poly(etherdiphenyletherketone)-poly(etheretherketone) copolymer" or "polymer(PEEK-PEDEK)" as used herein refer to the repeating unit (R K This means any polymer in which more than 50 mol% is a mixture of repeating units of formula (K'-A) and (K'-D) in a relative molar ratio of 95:5 to 5:95, preferably 80:20 to 20:80.

[0082] In some embodiments, the polymer (P1) may be part of a first composition, which may comprise the polymer (P1) and a filler. The filler may comprise a fibrous filler or a non-fibrous filler. The filler may comprise both a fibrous filler and a non-fibrous filler.

[0083] Furthermore, or alternatively, the polymer (P2) may be part of a second composition, the second composition may comprise the polymer (P2) and a filler. The filler may comprise a fibrous filler or a non-fibrous filler. The filler may comprise both a fibrous filler and a non-fibrous filler.

[0084] Suitable fibrous fillers include, for example, carbon fibers, graphite fibers, glass fibers such as E-glass fibers, ceramic fibers such as silicon carbide fibers, aromatic polyamide fibers, polyimide fibers, high modulus polyethylene (PE) fibers, polyester fibers, and polybenzoxazole fibers such as poly-p-phenylene-benzobisoxazole (PBO) fibers, synthetic polymer fibers such as aramid fibers, boron fibers, basalt fibers, quartz fibers, alumina fibers, zirconia fibers, and mixtures thereof. The fibers may be continuous or discontinuous, and may be aligned or randomly oriented.

[0085] In some embodiments, the fibers comprise at least one type of carbon fiber. As used herein, the term “carbon fiber” is intended to include graphitized, partially graphitized, and non-graphitized carbon-reinforced fibers, as well as mixtures thereof. Carbon fibers can be obtained, for example, by heat treatment and thermal decomposition of different polymer precursors such as rayon, polyacrylonitrile (PAN), aromatic polyamide, or phenolic resin, and carbon fibers may also be obtained from pitch-based materials. The term “graphite fiber” is intended to mean a carbon fiber obtained by thermal decomposition of a carbon fiber at a high temperature (above 2000°C), in which carbon atoms are arranged similarly to a graphite structure. The carbon fibers are preferably selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, graphite fibers, and mixtures thereof.

[0086] In some embodiments, the fibers comprise at least one type of glass fiber. The glass fibers may have a circular or non-circular cross-section (such as an oval or rectangular cross-section). If the glass fibers used have a circular cross-section, it is preferable that they have an average glass fiber diameter of 3 to 30 μm, particularly preferably 5 to 12 μm. Different types of glass fibers having a circular cross-section are available on the market depending on the type of glass from which they are manufactured. In particular, glass fibers made from E-glass or S-glass may be mentioned. In some embodiments, the glass fibers are standard E-glass material having a non-circular cross-section. In some embodiments, the polymer composition comprises S-glass fibers having a circular cross-section.

[0087] In one embodiment, the composite material of the present invention includes continuous fibers. As used herein, “continuous fibers” refers to fibers having a length of 3 mm or more, more typically 10 mm or more, and an aspect ratio of 500 or more, more typically 5000 or more.

[0088] In one embodiment of the present invention, the first component is a composite material comprising one or more layers containing fibers and a polymer (P1). The polymer (P1) is impregnated, coated, or laminated onto the fibers.

[0089] In a further embodiment of the present invention, the second component is a composite material comprising one or more layers containing fibers and a polymer (P2). The polymer (P2) is impregnated, coated, or laminated onto the fibers.

[0090] A further object of the present invention is an assembly comprising a first component comprising a polymer (P1), a second component comprising a polymer (P2), and a film of the present invention disposed between the first and second components and bonded to the first and second components.

[0091] In this specification, the term “bonded” means that the materials are preferably permanently bonded to one another.

[0092] The assembly may be a component or part of a component for use in the aerospace and automotive industries. For example, components that include or are composed of the assembly of the present invention include, but are not limited to, brackets, clips, stiffeners, and other similar types of parts.

[0093] Even if described in relation to a particular embodiment, it will be understood that all descriptions are applicable to and interchangeable with other embodiments of this disclosure.

[0094] The present invention will be described in more detail in the following sections by non-limiting embodiments.

[0095] If any disclosure of a patent, patent application, or publication incorporated herein by reference contradicts the description of this application to such an extent that certain terms become unclear, the description herein shall prevail. [Examples]

[0096] raw materials I purchased 1,2-dichlorobenzene, terephthaloyl chloride, isophthaloyl chloride, 3,5-dichlorobenzoyl chloride, aluminum chloride (AlCl3), and methanol from Sigma Aldrich.

[0097] 1,4-bis(4-phenoxybenzoyl)benzene was prepared in accordance with Indian Patent No. 193687 (filed on 21 June 1999 and incorporated herein by reference).

[0098] Photo-grade hydroquinone was sourced from Eastman, USA. This hydroquinone contains 0.38% by weight of water, which was used to adjust the load capacity. All weights shown include water.

[0099] We procured ACS reagent-grade resorcinol from Aldrich, USA.

[0100] Polymer-grade 4,4'-biphenol was sourced from SI, USA.

[0101] Flake-type pyrocatechol was sourced from Solvay USA. Its purity was 99.85% according to GC (German chemical). This pyrocatechol contained 680 ppm of moisture, which was used to determine the appropriate load. All weights shown include moisture.

[0102] Polymer-grade (99.8%+) 4,4'-difluorobenzophenone was sourced from Malwa, India.

[0103] Diphenyl sulfone (polymer grade) was sourced from Proviron (99.8% purity).

[0104] We sourced the light soda ash, sodium carbonate, from Solvay SA, France.

[0105] d 90 We sourced potassium carbonate with a particle size of <45μm from Armand Products.

[0106] We sourced lithium chloride (anhydrous grade) from Acros.

[0107] 1,4-bis(4'-fluorobenzoyl)benzene (1,4-DFDK) and 1,3-bis(4'-fluorobenzoyl)benzene (1,3-DFDK) were prepared by Friedel-Crafts acylation of fluorobenzene according to Example 1 of U.S. Patent No. 5,300,693 by Gilb et al. (which is incorporated herein by reference in its entirety). As described in U.S. Patent No. 5,300,693, a portion of 1,4-DFDK was purified by recrystallization in chlorobenzene, and a portion of 1,4-DFDK was purified by recrystallization in DMSO / ethanol. The 1,4-DFDK purified by recrystallization in DMSO / ethanol was used as 1,4-DFDK in a polymerization reaction to produce PEKK as described below, while the 1,4-DFDK recrystallized in chlorobenzene was used as a precursor for 1,4-bis(4'-hydroxybenzoyl)benzene (1,4-BHBB).

[0108] 1,4-BHBB and 1,3-bis(4'-hydroxybenzoyl)benzene (1,3-BHBB) were produced by hydrolysis of 1,4-DFDK and 1,3-DFDK, respectively, according to the procedure described in Example 1 of U.S. Patent No. 5,250,738 by Hackenbruch et al. (which is incorporated herein by reference in its entirety). They were purified by recrystallization in DMF / ethanol.

[0109] Melting temperature (T m ), measurement of crystallization temperature (Tc) and heat of fusion Melting temperature T m This was measured as the peak temperature of fusion endothermic reaction during the second heating scan of a differential scanning calorimeter (DSC) according to ASTM D3418-03, E1356-03, E793-06, and E794-06. The details of the procedure used in this invention are as follows: A TA Instruments DSC Q20 was used with nitrogen (99.998% purity, 50 mL / min) as the carrier gas. Temperature and heat flow calibration was performed using indium. The sample size was 5-7 mg. The weight was recorded as ±0.01 mg. The heating cycle was: - First heating cycle: 30.00°C to 400.00°C at 10.00°C / min, then isothermal at 400.00°C for 1 minute; - First cooling cycle: 400.00°C to 30.00°C at 10.00°C / min, isothermal for 1 minute; - Second heating cycle: 30.00°C to 400.00°C at 10.00°C / min, and isothermal at 400.00°C for 1 minute.

[0110] Melting temperature T m The heat of fusion was measured as the peak temperature of endothermic melting during the second heating scan. The enthalpy of fusion was measured during the second heating scan. Melting of the composition was defined as the area over the baseline of a straight line drawn from 220°C to a temperature exceeding the last endothermic melt. When evaluating the crystallinity of the film in the bonded structure (part), the heat of fusion during the first heating scan was measured.

[0111] Crystallization temperature T c This was measured as the peak temperature of crystallization exothermic reaction during the first cooling scan.

[0112] Measurement of melting viscosity The melt viscosity was measured using a capillary rheometer according to ASTM D3835. The following characteristics were observed: a die with a diameter of 1.016 mm, a length of 20.32 mm, and a cone angle of 120° was used, at 380°C or 410°C (as indicated) and 46.3 s. -1 Readings were taken at residence times of 10 minutes (reported in Table 2) and 40 minutes at the specified shear rate. The melt stability, VR40, was measured by the ratio of the viscosity at 40 minutes to the viscosity at 10 minutes.

[0113] Measurement of tensile properties Plaques measuring 762mm × 762mm × 3.2mm were fabricated from polymer by compression molding 30g of polymer under the following conditions: Preheat T1. T1 / 20min, 2000kg-f T1 / 2 min, 2700kg-f Cooling to 30°C over 40 minutes, 2000 kg-f.

[0114] The T1 values ​​used for the polymers are shown in the results table. The plaques were then annealed at 200°C for 3 hours.

[0115] Compression-molded plaques measuring 762 mm × 762 mm × 3.2 mm were machined into V-type ASTM tensile test specimens. These specimens, representing various polymer compositions, were subjected to tensile testing according to ASTM method D638 at room temperature (i.e., 23°C) at 0.05 inches / min (0.127 cm / min) for three specimens. The average values ​​for the three specimens are shown with the standard deviation in parentheses.

[0116] Synthesis Examples Comparative Example 1: PEKK with a T / I ratio of 60 / 40 112.50 g of diphenylsulfone, 33.390 g of 1,3-BHBB, 6.372 g of 1,4-BHBB, and 41.051 g of 1,4-DFDK were introduced into a 500 mL four-neck reaction flask equipped with a stirrer, an N2 injection tube, a Claisen-type connector with a thermocouple pushed into the reaction medium, and a Dean-Stark trap including a condenser and a dry eye trap. The contents of the flask were evacuated under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to continuous nitrogen purging (60 mL / min).

[0117] The reaction mixture was slowly heated to 270°C. At 270°C, 13.725 g of Na2CO3 and 0.086 g of K2CO3 were added to the reaction mixture over 60 minutes using a powder dispenser. After the addition was complete, the reaction mixture was heated to 320°C at a rate of 1°C / min. After 2 minutes at 320°C, 1.207 g of 1,4-DFDK was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 0.529 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 0.503 g of 1,4-DFDK was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes. 25 g of diphenyl sulfone was separately added to the reaction mixture and kept in place for 15 minutes with stirring. The contents of the reactor were then poured from the reactor into a stainless steel receiving dish and cooled. The solids were divided and ground in an attrition mill through a 2 mm sieve. Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH 1–12. For final washing, 0.67 g of NaH₂PO₄·2H₂O and 0.62 g of Na₂HPO₄ were dissolved in 1200 mL of deionized water. The powder was then removed from the reactor and dried under vacuum at 120°C for 12 hours to obtain 72 g of yellow powder. The properties of the final polymer are detailed in Table 2.

[0118] Comparative Example 2: Preparation of PEEK-PEDEK 72 / 25 copolymer 128.21 g of diphenylsulfone, 20.297 g of hydroquinone, 11.411 g of 4,4'-biphenol, and 54.377 g of 4,4'-difluorobenzophenone were introduced into a 500 mL four-neck reaction flask equipped with a stirrer, an N2 injection tube, a Claisen-type connector with a thermocouple pushed into the reaction medium, and a Dean-Stark trap including a condenser and a dry eye trap. The contents of the flask were evacuated under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to continuous nitrogen purging (60 mL / min).

[0119] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 26.955 g of Na2CO3 and 0.169 g of K2CO3 was added to the reaction mixture over 30 minutes using a powder dispenser. After the addition was complete, the reaction mixture was heated to 320°C at a rate of 1°C / min. After 13 minutes at 320°C, 3.742 g of 4,4'-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 1.039 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 2.138 g of 4,4'-difluorobenzophenone was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes.

[0120] Subsequently, the contents of the reactor were poured from the reactor into an SS receiving dish and cooled. The solid material was divided and ground in an attrition mill through a 2 mm sieve. Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH 1-12. The powder was then removed from the reactor and dried under vacuum at 120°C for 12 hours to obtain 74 g of white powder.

[0121] 410℃, 46s -1 The melting viscosity, measured by capillary rheology, was 0.28 kN-s / m 2 That was the case.

[0122] The final polymer properties are detailed in Table 2.

[0123] Comparative Example 3: Preparation of PEEK-PEmEK 70 / 30 copolymer 330.00 g of diphenylsulfone, 37.949 g of hydroquinone, 16.234 g of resorcinol, and 109.875 g of 4,4'-difluorobenzophenone were introduced into a 1000 mL four-neck reaction flask fitted with a stirrer, an N2 injection tube, a Claisen-type connector with a thermocouple pushed into the reaction medium, and a Dean-Stark trap including a condenser and a dry eye trap. The contents of the flask were evacuated under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to continuous nitrogen purging (60 mL / min).

[0124] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 54.099 g of Na2CO3 and 0.170 g of K2CO3 was added to the reaction mixture over 30 minutes using a powder dispenser. Upon completion of the addition, the reaction mixture was heated to 300°C at a rate of 1°C / min. After 57 minutes at 300°C, 17.135 g of 4,4'-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 2.081 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 4.284 g of 4,4'-difluorobenzophenone was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes.

[0125] Subsequently, the contents of the reactor were poured from the reactor into an SS receiving dish and cooled. The solid material was divided and ground in an attrition mill through a 2 mm sieve. Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH 1-12. The powder was then removed from the reactor and dried under vacuum at 100°C for 12 hours to obtain 125 g of light brown powder.

[0126] 410℃, 46s -1 The melting viscosity, measured by capillary rheology, was 0.70 kN-s / m 2 The final polymer properties are detailed in Table 2.

[0127] Example 4: Preparation of PEEK-PEoEK 80 / 20 copolymer 343.63 g of diphenylsulfone, 61.852 g of hydroquinone, 15.426 g of pyrocatechol, and 154.573 g of 4,4'-difluorobenzophenone were introduced into a 1000 mL four-neck reaction flask fitted with a stirrer, an N2 injection tube, a Claisen-type connector with a thermocouple pushed into the reaction medium, and a Dean-Stark trap including a condenser and a dry eye trap. The contents of the flask were evacuated under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to continuous nitrogen purging (60 mL / min).

[0128] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 76.938 g of Na2CO3 and 0.484 g of K2CO3 was added to the reaction mixture over 30 minutes using a powder dispenser. Upon completion of the addition, the reaction mixture was heated to 320°C at a rate of 1°C / min. After 1 minute at 320°C, the reaction was terminated in the following three steps: While maintaining a nitrogen purge in the reactor, 18.329 g of 4,4'-difluorobenzophenone was added to the reaction mixture. After 5 minutes, 2.338 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 6.110 g of 4,4'-difluorobenzophenone was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes.

[0129] Subsequently, the contents of the reactor were poured from the reactor into an SS receiving dish and cooled. The solid material was divided and pulverized in an attrition mill through a 2 mm sieve. Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH 1-12. The powder was then dried under vacuum at 120°C for 12 hours to obtain 174 g of white powder.

[0130] 410℃, 46s -1 The melting viscosity, measured by capillary rheology, was 1.50 kN-s / m 2 The polymer properties are disclosed in Table 2 below.

[0131] Examples 5-7: Preparation of PEEK-PEoEK 75 / 25 copolymer and 70 / 30 copolymer The same procedure as in Example 4 was followed, but the amounts of reagents shown in Table 1 below were used. The properties of the obtained polymer are shown in Table 2.

[0132] [Table 1]

[0133] Table 2 shows the characteristics of the samples prepared according to Examples 1 to 7.

[0134] [Table 2]

[0135] The data presented in Table 2 shows that PEEK-PEoEK copolymers are generally T m Characterized by its low performance, it has shown the following advantages over known PAEKs. - As shown by the values ​​of the heat of fusion (CE1 vs E4), the same T m However, the degree of crystallinity is higher than that of PEKK; - It has a higher Tg than PEEK-PEmEK, and therefore a higher continuous operating temperature; - Same T m However, its mechanical properties are improved compared to PEEK-PEDEK (CE2 vs. E4). - PEEK-PEDEK(T m T (<295℃) lower than T m It may reach this point.

[0136] Examples 10-11 - General procedure for preparing adhesive films from polymers of Example 5 and CE3 The polymer in coarse powder form was converted into pellets by melt-kneading using a 26 mm Coperion® (model ZSK-26) co-rotating partial-meshing twin-screw extruder with an L / D ratio of 48:1. The powder was gravimetrically fed into the feed hopper of barrel section 1 of the extruder at a rate of 37 pounds / hour (16.8 kg / hour). The extruder had 12 barrel sections, and barrel sections 2-12, as well as the die, were heated throughout at a temperature characteristic setting of 350°C. The melting temperature of the extruded material was measured with a portable pyrometer each time it exited the die.

[0137] The melting temperature of the extruded material was approximately 380°C throughout the entire mixing operation. With the screw speed set to 200 rpm, the resulting extruder torque reading was approximately 50% throughout the entire production operation. To remove moisture and any potentially present residual volatile substances from the compound, a vacuum vent at a vacuum level of 26 Hg was applied to barrel section 10 during mixing. The extruded material from the operation was formed into strands and cooled in a water bath, after which it was pelletized into pellets with a diameter of approximately 2.7 mm and a length of 3.0 mm.

[0138] The kneaded pellets were processed into a film with a nominal thickness of 140 microns and a width of 8.5-9 cm by melt-extrusion using a single-screw extruder. For this purpose, an OCS (Optical Control Systems, GmbH) extruder was used. This extruder had a single-stage non-vented screw with a diameter of 20 mm and an L / D ratio of 30. The extruder was equipped with a 125 mm wide film die with a gap thickness of 0.5 mm. The extruder barrel had four heating sections, operated from rear to front at set temperatures of approximately 335°C, 360°C, 360°C, and 370°C, respectively. The film die was set to a temperature of 390°C. Before extruding into film, the pellets were dried overnight (approximately 16 hours) in a dry air convection oven set to 150°C. The blend was extruded at a screw speed of 28 rpm and an extrusion rate of approximately 4 pounds / hour (1.8 kg / hour). The film was formed and stretched on two cooling rolls, a first (upper) roll and a second (lower) roll, set to 140°C and 145°C, respectively.

[0139] Example 11: Fabrication of an assembly and fracture toughness test A fracture-toughness (G1c) laminate (305mm x 305mm size), which is a fused adhesive film in which a crack plane layer is fused to the surface of a fiber-reinforced composite substrate, was fabricated as follows: Nominal fiber basis weight = 145 gsm, and AP with a resin content of 34% by weight. C / AS4D UniTape was cut and stacked to create a 16-ply pseudo-isotropic (+45° / 0° / -45° / 90°02s) layup. A single-ply style 108 glass fabric was placed on top of this layup stack to cover the entire surface, and then the 280mm × 305mm × 0.125mm film from Example 10 was placed with three sides aligned with the edges of the layup. On the other side was a 305mm × 25mm × 0.05mm thick Kapton film coated with a release agent, which acted as a crack starter once the panel solidified. The rest of the layup was done in reverse order of materials, starting with style 108 glass fiber cloth and then placing the 16-ply pseudo-isotropic glass fiber cloth.

[0140] The layup was then placed on a flat steel tool, placed in a vacuum bag (710-730 mm Hg vacuum), and processed in a high-temperature autoclave. The autoclave cycle was a linear temperature gradient up to 375°C, at which point a pressure of 6.7 bar was applied and held for 15 minutes, after which the layup was cooled under a pressure of 6.7 bar (670 kPa) and 711 mm Hg. The pressure was released at 93°C, and after cooling to room temperature, it was removed from the autoclave. The thickness of the obtained panel was measured, and then it was machined into a 1" × 12" (2.5 cm × 30.5 cm) test coupon for G1c fracture toughness measurement.

[0141] [Table 3]

[0142] The data demonstrates that using the adhesive film according to the present invention (Example 5) resulted in improved adhesion of the laminate, as evidenced by the high fracture toughness.

Claims

1. An assembly comprising a first component containing polymer (P1), a second component containing polymer (P2), and a film containing at least one type of PEEK-PEoEK copolymer, wherein the PEEK-PEoEK copolymer contains at least 50 mol% of repeating units (R) in total, relative to the total number of moles of repeating units of the PEEK-PEoEK copolymer. ＰＥＥＫ ) and repeating units (R ＰＥｏＥＫ ) including, - Repeating unit (R ＰＥＥＫ ) is the formula: 【Chemistry 1】 It is a repeating unit, - Repeating unit (R ＰＥｏＥＫ ) is the formula: 【Chemistry 2】 It is a repeating unit, In the formula, each R １ and R ２ These are either the same as or different from each other, and at each occurrence, are 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 contains the repeating units (R ＰＥＥＫ ), and (R ＰＥｏＥＫ ) in a molar ratio (R ＰＥＥＫ ) / (R ＰＥｏＥＫ ) within 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 repeating unit (R ＰＥＥＫ ) is the formula: 【Transformation 3】 It is a repeating unit of and / or The repeating unit (R ＰＥｏＥＫ ) is the formula: 【Chemistry 4】 The assembly according to claim 1, which is a repeating unit.

3. The PEEK-PEoEK copolymer has a molar ratio (R) in the range of 90 / 10 to 55 / 45, preferably 85 / 15 to 60 / 40, and more preferably 80 / 20 to 65 / 35. ＰＥＥＫ ) / (R ＰＥｏＥＫ The assembly according to claim 1 or 2, having )

4. The PEEK-PEoEK copolymer has a melting temperature (T) of 320°C or lower, preferably 315°C or lower, when measured according to the method specified herein. ｍ The assembly according to any one of claims 1 to 3, having )

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 ketone, polyamide, polyetherimide, polyamideimide, polysulfone, polyethersulfone, polyarylether, polycarbonate, liquid crystal polymer, polyphenylene sulfide, polyarylene (polyphenylene), polyphthalamide, polycyclic aromatic ester, 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 comprising fibers and polymer (P1), and / or the second component is a composite material comprising one or more layers comprising fibers and polymer (P2).

11. The assembly according to claim 10, wherein the fiber is a carbon fiber or a glass fiber, preferably a continuous carbon fiber or a continuous glass fiber.

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 a temperature (T) suitable for melting the film but not for melting polymer (P1) and polymer (P2). ｍ ｘ A method comprising the step of exposing the film to the following.

13. Temperature (T ｍ ｘ The method according to claim 12, wherein the melting temperature of the film is higher than the melting temperature of the film, and preferably lower than the melting temperatures of polymer (P1) and polymer (P2).

14. A step of placing the film between a first component containing polymer (P1) and a second component containing polymer (P2), and a temperature in the range of 280°C to 315°C (T ｍ ｘ The method according to claim 12 or 13, further comprising the step of exposing the film to the following:

15. The film is at the temperature (T ｍ ｘ The method according to any one of claims 12 to 14, wherein pressure is applied while the components are exposed to the heat, thereby solidifying them.

Images