Film for multilayer assemblies

Abstract

The present invention relates to an assembly comprising a first component and a second component, each comprising a polymer, and a film disposed between and bonded to the first and second components, such that the film comprises at least one poly(ether ketone ketone) (PEKK) polymer and at least one nucleating agent, the assembly having improved fracture toughness and good overall mechanical properties.

Description

[Technical Field]

[0001] This invention claims priority to U.S. Provisional Patent Application No. 63 / 151820 filed on 22 February 2021 and European Patent Application Publication No. 21181637.6 filed on 25 June 2021, the entire contents of those applications being incorporated herein by reference for any purpose. In the event of any inconsistency between this application and this PCT application affecting clarity of terminology or expression, this application alone shall be referenced.

[0002] The present invention relates to an assembly comprising a first component and a second component, each containing a polymer, and a film disposed between the first component and the second component and bonded to the first component and the second component. The film comprises at least one poly(etherketone)(PEKK) polymer and at least one nucleating agent. This assembly can be used, in particular, to prepare parts and articles for the aerospace and automotive industries. [Background technology]

[0003] In many industries, particularly within the aerospace industry, laminates, composites, and other assemblies containing 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 joining 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 join them together.

[0006] International Publication No. 2011 / 001103A2 describes the use of amorphous poly(etherketoneketone) (PEKK) film 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 properties such as solvent resistance. Consequently, the joints become more susceptible to corrosion by liquids, 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 (In the formula, Ph represents the phenylene part) The use of polymer materials containing polymers is disclosed. However, the mechanical properties of PEEK-PEDEK polymers are not as good as those of other polyaryletherketone polymers.

[0008] International Publication Nos. 2021 / 085797, 2019 / 243433, and 2018 / 115233 are other technical applications, but they do not disclose the subject matter of claim 1. [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] A film is needed that can strongly bond two polymer components (or parts) together to prepare assemblies exhibiting improved chemical resistance and improved mechanical properties. The film should be processed at a temperature lower than the melting temperatures of the two components being bonded, preferably below 310°C.

[0010] This invention aims to solve technical problems. [Means for solving the problem]

[0011] The present invention is described in the appended claims. Accordingly, the object of the present invention is the assembly defined in claims 1 to 33.

[0012] Another object of the present invention is a method for manufacturing an assembly as defined in any one of claims 34 to 40.

[0013] Another object of the present invention is a component or article as defined in claim 41.

[0014] Another object of the present invention is the use as defined in claim 42.

[0015] Another object of the present invention is a composition comprising the PEKK polymer as defined in claim 43.

[0016] More accurate and detailed information regarding these objectives is provided below. [Modes for carrying out the invention]

[0017] The present invention relates to laminates, composites, and other assemblies comprising multilayers of different materials, each material giving the assembly specific properties. These assemblies comprise at least two components, which may be identical or different, and at least one film, which may be referred to herein as a “bonding film.”

[0018] The films used as described in this disclosure exhibit a set of properties suitable for bonding polymer components in assembled structures, particularly assembled structures made from poly(aryl ether ketone) (PAEK) polymers. These films comprise at least one poly(ether ketone ketone) (PEKK) polymer and at least one nucleating agent. The PEKK polymer has a T / I ratio in the range of 50:50 to 56:44, preferably in the range of 51:49 to 55:45. The PEKK polymer further exhibits a degree of crystallinity that is well suited to assembled structures where chemical resistance and mechanical properties are required, such as in composite structures in the aerospace industry.

[0019] The films described herein are advantageously compatible with the polymer components to be bonded.

[0020] In this application, - Any description, even if it is described in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure. - Where it is said that an element or component is included in and / or selected from an enumerated list of elements or components, in the relevant embodiments expressly contemplated herein, the element or component may be any one of the individual enumerated elements or components, or may be selected from any group of two or more of the expressly enumerated elements or components, and any element or component enumerated in a list of elements or components may be omitted from such list. - Any enumeration of numerical ranges by endpoints in this specification includes all numbers, as well as the endpoints and equivalents of the ranges, that fall within the enumerated range.

[0021] The first object of the present invention is, - A first component comprising polymer (P1), - A second component comprising polymer (P2), - A film positioned between the first component and the second component, and bonded to the first component and the second component. An assembly including, The film is an assembly comprising at least one poly(etherketoneketone)(PEKK) polymer exhibiting a specific T / I ratio and at least one nucleating agent.

[0022] In relation to the present invention, the term "joining" means that components are preferably permanently attached to each other or to one another.

[0023] The assembly film may further include scrim and / or nonwoven fabric reinforcements and / or lightweight fabrics, which help to regulate the molten flow and / or provide a uniform surface for joining, and may further influence the local morphology at the joint line.

[0024] The assembly of the present invention may include further components (third, fourth, fifth, ...) and films, depending on the composite component being constructed. For example, the assembly of the present invention may include a third component comprising a polymer (P3), and a film between the second and third components, the additional film bonding the second and third components together.

[0025] PEKK Polymer The poly(etherketoneketone) (PEKK) polymers described herein contain at least 50 mol% of repeating units of formulas (M) and (P) (mol% is based on the total number of moles in the polymer): [ka] (In the formula, - R 1 and R 2 In each case, the following are independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium: - i and j are independently selected integers in the range of 0 to 4 in each case; The molar ratio of repeating unit (P) to repeating unit (M) (hereinafter referred to as the "T / I ratio") is 50:50 to 56:44, preferably 51:49 to 55:45.

[0026] According to one embodiment, R 1 and R 2 The C1-C12 moieties are independently selected from the group consisting of C1-C12 moieties that optionally contain one or more heteroatoms, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amines and quaternary ammonium groups at each position of the above formulas (P) and (M).

[0027] According to one embodiment of the present disclosure, at least 55 mol%, 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 all of the repeating units in PEKK are repeating units of formulas (M) and (P).

[0028] In one embodiment, substantially all of the repeating units of PEKK are repeating units of formulas (M) and (P). In one embodiment, the repeating units of PEKK consist of repeating units of formulas (M) and (P).

[0029] The molar ratio of repeating units (P) to repeating units (M), also referred to as the "T / I ratio," of PEKK used as a polymer component of films is in the range of 50:50 to 56:44, preferably 51:49 to 55:45. PEKK preferably has a T / I ratio of 54:46 or 53:47.

[0030] According to another embodiment, i and j are each R 1 and R 2 The base is zero. According to this embodiment, the PEKK polymer contains at least 50 mol% of repeating units of formulas (M') and (P') (mol% is based on the total number of moles in the polymer): [ka]

[0031] According to one embodiment of the present disclosure, at least 55 mol%, 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 all of the repeating units in PEKK are repeating units of formulas (M') and (P').

[0032] In one embodiment, substantially all of the repeating units of PEKK are repeating units of formulas (M') and (P'). In one embodiment, the repeating units of PEKK consist of repeating units of formulas (M') and (P').

[0033] The molar ratio of repeating units (P') to repeating units (M'), also referred to as the "T / I ratio," of PEKK used as a polymer component of films is in the range of 50:50 to 56:44, preferably 51:49 to 55:45. PEKK preferably has a T / I ratio of 54:46 or 53:47.

[0034] As described above, the molar ratio of repeating units (P) / (P') to repeating units (M) / (M'), also referred to as the "T / I ratio," of PEKK used as a polymer component of the film is in the range of 50:50 to 56:44, preferably 51:49 to 55:45. The component PEKK preferably has a T / I ratio of 54:46 or 53:47.

[0035] According to one embodiment of the present disclosure, the PEKK polymer described herein has a Tm in the range of 270 to 310°C, preferably 280 to 305°C, as measured by differential scanning calorimetry (DSC) in accordance with ASTM D3418.

[0036] More specifically, the melting temperature Tm is measured by DSC using a heating / cooling rate of 10°C / min according to ASTM D3418. Tm is determined by the second heat scan. The following cycle can be followed: - First heating cycle: Heat from 30.00°C to 400.00°C at 10.00°C / min, then isothermally at 400.00°C for 1 minute; - First cooling cycle: From 400.00°C to 30.00°C at 10.00°C / min, isothermal for 1 minute; - Second heating cycle: Heat from 30.00°C to 400.00°C at 10.00°C / min, then isothermally at 400.00°C for 1 minute.

[0037] According to one embodiment of the present disclosure, the PEKK polymer described herein has a heat of fusion ΔHf that satisfies the following formula: ΔH f >1.69×T m -480 (Formula 1) (In the formula, - T m is the melting temperature (°C) of PEKK and - ΔH f is in the unit of J / g).

[0038] Such an equation is an empirical equation for distinguishing, with respect to the present invention, PEKK with a crystallinity acceptable for a predetermined melting temperature (Tm) from PEKK with a crystallinity not acceptable at the same Tm.

[0039] According to one embodiment of the present disclosure, the PEKK polymer described herein is such that the heat of fusion ΔHf is at least 5 J / g, at least 6 J / g or at least 7 J / g. The heat of fusion may be as defined in one of claims 13 to 15.

[0040] More specifically, according to ASTM D3418, using a heating and cooling rate of 10 °C / min, the heat of fusion measured by DSC in the second heat scan. The following cycle can be followed: - First heating cycle: from 30.00 °C to 400.00 °C at 10.00 °C / min, isothermal at 400.00 °C for 1 minute; - First cooling cycle: from 400.00 °C to 30.00 °C at 10.00 °C / min, isothermal for 1 minute; - Second heating cycle: from 30.00 °C to 400.00 °C at 10.00 °C / min, isothermal at 400.00 °C for 1 minute.

[0041] Synthesis of PEKK polymer The synthesis of the PEKK polymer typically includes a step of polycondensing monomers in a solvent to obtain the PEKK polymer and a step of extracting the solvent and salts.

[0042] In a preferred embodiment of the present invention, the polycondensation of the monomers occurs in the absence of a Lewis acid or in the presence of an amount of Lewis acid less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, based on the total weight of the monomers.

[0043] In connection with the present invention, a Lewis acid may be defined as one selected from the group consisting of BF3, AlCl3, FeCl3, CF3SO3H, and CH3SO3H.

[0044] In a preferred embodiment, the synthesis of the PEKK polymer is carried out by Step a) In a solvent such as DPS, in the absence of Lewis acid or in the presence of Lewis acid in an amount of less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, based on the total weight of the monomers, the following monomers (P-OH), (M-OH), (PF), and / or (MF): [ka] (In the formula, - R 3 , R 4 , R 5 and R 6 In each case, the following are independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium: - p, q, r, and s are, in each case, independently selected integers in the range of 0 to 4. A process of polycondensation of The molar ratio of the number of moles of (P-OH) and (M-OH) to the number of moles of (PF) and (MF) is,

number

[0045] Preferably, p=q=r=s=0.

[0046] The above method produces a specific PEKK powder having particularly low volatile content, which has certain properties, especially a specific high enthalpy of fusion ΔH f This helps to obtain PEKK having the following characteristics. According to one embodiment, the PEKK polymer has a Td(1%) of at least 500°C, preferably at least 505°C, more preferably at least 510°C, when measured by thermogravimetric analysis according to ASTM D3850, which is heated from 30°C to 800°C under nitrogen at a heating rate of 10°C / min. Td(1%) indicates the temperature at which a given amount of volatile substance (=1.0 wt%) has been released from the sample.

[0047] In one embodiment, R 3 , R 4 , R 5 and R 6 The C1-C12 moieties are independently selected from the group consisting of C1-C12 moieties that optionally contain one or more heteroatoms, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amines and quaternary ammonium groups at each position of the above formulas (P-OH), (PF), (M-OH), and (MF).

[0048] The T / I ratio is controlled by the amounts of (PF)+(P-OH) and (MF)+(M-OH).

[0049] In a preferred embodiment, the polycondensation leading to the PEKK polymer comprises only the following monomers: (P-OH), (M-OH), and (PF).

[0050] Step a): The polycondensation in step a) is based on nucleophilic substitution. The polycondensation is carried out in a solvent such as DPS in the presence of at least one salt selected from the group consisting of Na2CO3, K2CO3, or combinations thereof. The temperature in step a) is typically 250°C to 350°C, more particularly 300°C to 350°C.

[0051] The amount of base should preferably be sufficient to activate all of the monomer's OH groups. The amount of base is usually slightly greater than the amount of OH groups. A molar excess of 1.0–5.0% may be used.

[0052] According to one embodiment, the base is added to a mixture containing a solvent and a monomer, preferably at a temperature higher than 250°C, particularly at a temperature of 250°C to 350°C. The introduction time of the base may be 10 to 120 minutes, preferably 30 to 90 minutes.

[0053] In another preferred embodiment, monomers (PF) and / or (MF), preferably (PF), are added to the mixture at the end of the polycondensation. This ensures that the PEKK polymer contains fluorine-terminated groups.

[0054] In step b), the polymer obtained in step a) is treated to remove the solvent and salt. For example, step b) may be carried out by contacting the polymer with a liquid selected from the group consisting of water, alcohol, ether, ketone, and combinations thereof. The liquid may, conveniently, be a mixture of water and a liquid selected from the group consisting of water, alcohol, ether, ketone, and combinations thereof. The liquid may also contain an acid or a base.

[0055] The synthetic approach may involve contacting PEKK with a solution of at least one of the following: sodium dihydrogen phosphate (NaH2PO4), disodium hydrogen phosphate (Na2HPO4), potassium dihydrogen phosphate (KH2PO4), and dipotassium hydrogen phosphate (K2HPO4), or a mixture thereof, preferably with an additional step of washing PEKK with them. For example, PEKK may be contacted with a solution, such as an aqueous solution containing both NaH2PO4 and Na2HPO4 (for example, it may be washed therein). The phosphates used in the solutions used herein may be, for example, anhydrous, monohydrate, dihydrate, or heptahydrate.

[0056] In addition to the step of contacting the PEKK polymer with a solution of at least one of sodium dihydrogen phosphate (NaH2PO4), disodium hydrogen phosphate (Na2HPO4), potassium dihydrogen phosphate (KH2PO4), and dipotassium hydrogen phosphate (K2HPO4), or a mixture thereof, the synthetic approach may also involve at least one step of contacting PEKK, preferably washing PEKK with a solution containing a sufficient amount of acid or base to neutralize the PEKK polymer.

[0057] Suitable acids and bases include any organic or inorganic acid or base that exhibits solubility of at least 0.1% by weight in organic solvents such as alcohols, ketones, amides, and aromatic hydrocarbons, or in water at a temperature lower than the boiling point of the solvent. Preferably, the solvent has a boiling point of up to 250°C, more preferably up to 150°C, and most preferably up to 100°C. Preferably, the acid has a pK in the range of 3.0 to 7.5. a Preferably, the base has a pK in the range of -1.0 to 8.0. b It holds.

[0058] In some embodiments, the acid is selected from acetic acid, monoalkali metal citric acid, and combinations thereof.

[0059] In some embodiments, the base is selected from organic amines, tetraalkylammonium hydroxides, tetraalkylammonium acetates, tetraalkylphosphonium hydroxides, tetraalkylphosphonium acetates, alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal monohydrogen phosphates, alkali metal or alkaline earth metal phosphates, and combinations thereof.

[0060] Preferred solvents are water, alcohol, ether, or ketone, with a boiling point of at most 150°C, but capable of dissolving at least 0.1% by weight of acid or base and not reacting unfavorably with the PEKK polymer. Preferably, the solvent is water, methanol, ethanol, propanol, or isopropanol. More preferably, the solvent is water, methanol, or ethanol. In some embodiments, two or more solvents can be used.

[0061] The PEKK polymer may be prepared more particularly according to the methods disclosed in Examples 1-3, and especially according to Example 3, where the T / I ratio is changed by varying the amount of monomer (see Tables 1 and 2).

[0062] The preparation methods disclosed herein generally, or according to specific embodiments disclosed, enable obtaining specific PEKK polymers having one or more of the following properties: - PEKK polymers generally contain fluorine in amounts higher than 100 ppm, preferably higher than 200 ppm, and more preferably higher than 300 ppm. Such polymer-bound fluorine is an inevitable feature of the use of fluorine-containing monomers; - PEKK polymers are substantially aluminum-free. The amount of Al in PEKK polymers is generally less than 50 ppm, preferably less than 25 ppm, and more preferably less than 10 ppm; - PEKK polymers have a Td (1%) of at least 500°C, preferably at least 505°C, and more preferably at least 510°C, as measured by thermogravimetric analysis according to ASTM D3850, which involves heating from 30°C to 800°C under nitrogen at a heating rate of 10°C / min.

[0063] Al and F content can be conveniently measured by elemental analysis, such as ICP-OES analysis for Al and combustion-ion chromatography for fluorine.

[0064] Nuclear agent According to the present invention, the film 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. It may also be carbon black and other forms of carbon.

[0065] Particularly favorable results were obtained when the nucleating agent was boron nitride.

[0066] The proportion of the nucleating agent is generally less than 2.0% by weight, and moreover less than 1.5% by weight, relative to the weight of the PEKK polymer. This proportion is usually higher than 0.1% by weight, and moreover higher than 0.5% by weight. This proportion can typically be between 0.5% and 2.0% by weight, or between 0.5% and 1.5% by weight.

[0067] Other additives In some embodiments, the film includes at least one additive as a further component other than the PEKK polymer and nucleating agent. 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, (ix) internal 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. The film may contain one, two, three, or more additives, such as one heat stabilizer and one pigment, which may be in the same or different categories as those listed above.

[0068] According to these embodiments, the amount of such additive is less than 20% by weight, preferably less than 10% by weight, more preferably less than 5% by weight, even more preferably less than 2% by weight, and most preferably less than 1% by weight, based on the total weight of the film.

[0069] In another embodiment, the film is free of any filler or contains less than 0.5% by weight, preferably less than 0.1% by weight, of any filler.

[0070] In another embodiment, the film is not filled with fillers but contains “reinforcement fibrous fibers” such as scrim, nonwoven fabric or lightweight cloth, as described below. The term “reinforcement fibrous fibers” may include one or more types of fibrous materials, i.e., “reinforcement fibers,” employed for the reinforcement of the composite structure. The term “fiber” is used herein to refer to organic and / or inorganic fibers having a length of at least 0.5 mm.

[0071] As described herein, the film comprises polymer components, which are at least one PEKK polymer, and at least one nucleating agent. As used herein, the term “polymer component” means a compound having repeating units and a molecular weight of at least 2,000 g / mol.

[0072] In some embodiments, the PEKK polymer detailed above is the only polymer component in the film.

[0073] In some other embodiments, the polymer components of the film include a blend of two or more polymers, for example, several PEKK polymers or a blend of distinct polymers.

[0074] For example, the polymer components of the film may consist of a blend of PEKK and one other distinct polymer, where at least 60% by weight of the polymer components is the aforementioned PEKK and less than 40% by weight is at least one polymer different from the aforementioned PEKK polymer. Another example is a polymer component of the film consisting of at least 70% by weight of the aforementioned PEKK and less than 30% by weight of at least one polymer different from the aforementioned PEKK polymer. Yet another example is a polymer component of the film consisting of at least 80% by weight of the aforementioned PEKK and less than 20% by weight of at least one polymer different from the aforementioned PEKK polymer. Yet another example is a polymer component of the film consisting of at least 90% by weight of the aforementioned PEKK and less than 10% by weight of at least one polymer different from the aforementioned PEKK polymer.

[0075] In some embodiments, the polymer components of the film consist of a polymer different from the PEKK polymer described above, 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.

[0076] Such distinct polymers may be selected from the group consisting of poly(aryl ether sulfone) (PAES) polymers and poly(aryl ether ketone) (PAEK) polymers. When the additional polymer component is a PAES polymer, it may be selected from the group consisting of polysulfone (PSU), polyphenylsulfone (PPSU), and poly(ether sulfone) (PES). When the additional polymer component is a PAEK polymer, it may be advantageously selected from the group consisting of poly(ether ether ketone) (PEEK) polymer, poly(ether ketone ketone) (PEKK) polymer, poly(ether ketone) (PEK), poly(ether ketone ether ketone ketone) (PEKEKK), and PEEK-PEDEK copolymer. The additional polymer component may be a polyimide such as polyetherimide (PEI) or poly(amide imide) (PAI).

[0077] In certain embodiments, the film comprises at least 90% by weight of PEKK polymer and at least one additive. Most preferably, the film comprises at least 95% by weight, preferably at least 98% by weight of PEKK polymer and at least one additive, based on the total weight of the film.

[0078] Scrim, nonwoven fabrics and lightweight reinforcing materials The assembly film may further contain scrim and / or nonwoven fabric reinforcements and / or lightweight fabrics, which may help to regulate the molten flow and / or provide a uniform surface for joining, and may also affect the local morphology of the joint lines.

[0079] The films described herein may, advantageously, include scrim or a scrim layer. The scrim may be made from natural woven fabrics, synthetic woven fabrics, nonwoven fabrics, knits (including, but not limited to, weft-inserted knits) or plastics.

[0080] The films described herein may also advantageously include nonwoven fabrics, also known as nonwoven textiles or fiber webs.

[0081] Such scrims, nonwovens, or lightweight fabrics are advantageous because they help maintain a uniform thickness at the joint.

[0082] Film preparation process The films described herein may have thicknesses ranging from 15 to 800 μm, 25 to 600 μm, preferably 30 to 500 μm, more preferably 40 to 300 μm, and most preferably 50 to 250 μm.

[0083] The described films may be prepared by any conventional method known in the art in polymer processing. For example, the components of the film can be processed into a film form by cast extrusion while optionally undergoing uniaxial or biaxial stretching.

[0084] In some embodiments, the method for producing a film includes melting and kneading a physical mixture of the film's constituent elements. 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.

[0085] According to one embodiment, the components of the film are brought into contact with a PEKK solvent such as DPS, and the mixture is stirred at a temperature at which the polymer is completely or partially dissolved in the solvent. The solvent is then extracted, for example, by the method already disclosed above. Example 4 illustrates this embodiment.

[0086] According to one embodiment, a physical mixture containing the components of a film is compounded in an extruder and then cut into pellets or granules. The granules or pellets can then be further processed to produce a film.

[0087] Alternatively, the physical mixture is kneaded in an extruder and then formed directly into a film.

[0088] A particularly suitable technique for film production 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, which can be maintained at a suitable temperature and its speed can be adjusted to achieve the required thickness. The thickness of the film is controlled by the die. Depending on the cooling temperature used to solidify the film, the finished (extruded) film can be amorphous or semi-crystalline.

[0089] In an advantageous embodiment, the film is a single-layer film, i.e., it consists of only one layer containing the PEKK copolymer.

[0090] If the film contains scrim, nonwoven fabric, or lightweight fabric, these reinforcing layers or woven reinforcing materials can be impregnated with PEKK polymer by various methods such as the APC process, slurry impregnation process, or film lamination. For example, this process is - Impregnating a cloth with PEKK components in the form of polymer powder particles, in a liquid medium containing at least an aqueous solvent and at least one surfactant, - Heating the impregnated cloth to a temperature higher than the melting point of PEKK, and - For example, shaping fabric using at least one die of a specific shape. Includes.

[0091] Polymers (P1) and (P2) 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 bonding 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 a bond with the bonding film. The thickness may, for convenience, be 5 μm or more.

[0092] 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 contacts the bonding film comprising polymer (P2). The second component may consist of the polymer (P2). Alternatively, the second component comprises one surface comprising polymer (P2). The surface comprising polymer (P2) typically has a thickness suitable for forming a bond with the bonding film. The thickness may, for convenience, be 5 μm or more.

[0093] Polymer (P1) and polymer (P2) may be the same or different.

[0094] Polymers (P1) and (P2) can be independently selected from the group consisting of crystalline and / or high-temperature thermoplastic polymers. Non-limiting examples include, but are not limited to, poly(aryl ether ketone) (PAEK), poly(etherimide) (PEI), poly(amide-imide) (PAI), poly(aryl ether sulfone) (PAES), poly(arylene sulfide) (PAS), poly(phthalamide) (PPA), polyamide (PA), polycarbonate (PC), liquid crystal polymer (LCP), poly(aromatic ester) (PAE), and blends thereof.

[0095] In a preferred embodiment, polymer (P1) and polymer (P2) are independently selected from the group consisting of PAEK and blends of PAEK. PAEK can be selected from the group consisting of, for example, poly(ether ether ketone) (PEEK) polymer, PEEK copolymer, poly(ether ketone ketone) (PEKK) polymer, poly(ether ketone) (PEK), and poly(ether ketone ether ketone ketone) (PEKEKK). PEEK copolymer can be, for example, PEEK-PEDEK copolymer.

[0096] Poly(aryl ether ketone) (PAEK) As used herein, poly(aryl ether ketone) (PAEK) is a repeating unit (R) containing an Ar'-C(=O)-Ar* group (wherein Ar' and Ar* are the same or different and are aromatic groups). PAEK This indicates any polymer containing the repeating unit (R), and the mol% is based on the total number of moles of repeating units in the polymer. PAEK ) is selected from the group consisting of the following equations (JA) to (JD): [ka] (In the formula, R' is independently selected at each position from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. j' is an independent integer, either zero or between 1 and 4.

[0097] Repeating unit (R PAEK In ), each phenylene portion is independently a repeating unit (R PAEK ) may have 1,2, 1,4, or 1,3 bonds to other sites different from R'. Preferably, the phenylene moiety has 1,3 or 1,4 bonds, and more preferably they have 1,4 bonds.

[0098] Repeating unit (R PAEK In this configuration, j' is preferably zero at each position, such that the phenylene portion does not have any substituents other than those that link the main chain of the polymer.

[0099] According to one embodiment, PAEK is poly(etheretherketone)(PEEK).

[0100] As used herein, poly(etheretherketone) (PEEK) is defined as the repeating unit (R) of formula (JA) based on the total number of moles of repeating units in the polymer. PEEK This indicates any polymer containing: [ka] (In the formula, R' is independently selected at each position from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. j' is, for each R', independently zero or an integer in the range of 1 to 4 (e.g., 1, 2, 3, or 4).

[0101] According to formula (JA), the repeating unit (R PEEK Each aromatic ring in ) may contain 1 to 4 radical groups R'. If j' is 0, the corresponding aromatic ring does not contain any radical groups R'.

[0102] Repeating unit (R PEEK Each phenylene moiety of (R) may independently have 1,2, 1,3 or 1,4 bonds to other phenylene moieties. According to one embodiment, the repeating unit (R PEEK Each phenylene moiety of (R) independently has 1,3 or 1,4 bonds to other phenylene moieties. In yet another embodiment, the repeating unit (R PEEK Each phenylene moiety in ) has 1,4 bonds to other phenylene moieties.

[0103] According to one embodiment, R' is independently selected from the group consisting of C1-C12 moieties, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amines, and quaternary ammonium groups, each of which optionally contains one or more heteroatoms at each position in the above formula (JA).

[0104] According to one embodiment, j' is zero for each R'. In other words, according to this embodiment, the repeating unit (R PEEK ) follows formula (J'-A). [ka]

[0105] According to another embodiment of the present disclosure, poly(etheretherketone) (PEEK) is a repeating unit of formula (J-A'') in which at least 10 mol% is present. [ka] Repeating unit (R PEEK This indicates any polymer (mol% is based on the total number of moles of repeating units in the polymer).

[0106] According to one embodiment of the present disclosure, at least 10 mol% (based on the total number of moles of repeating units in the polymer), at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, 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 all of the repeating units (R) of formula (JA), (J'-A) and / or (J''-A) are present in the PEEK. PEEK )

[0107] PEEK polymers can therefore be homopolymers or copolymers. If a PEEK polymer is a copolymer, it can be random, alternating, or block copolymer.

[0108] If PEEK is a copolymer, then this is formula (JD) [ka] (In the formula, R' is independently selected at each position from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. j' is an integer, either zero or between 1 and 4, independently for each R'. Repeating units such as (R PEEK Unlike this, and in addition to this repeating unit, the repeating unit (R* PEEK It can be composed of the following:

[0109] According to formula (JD), the repeating unit (R* PEEK Each aromatic ring in ) may contain 1 to 4 radical groups R'. If j' is 0, the corresponding aromatic ring does not contain any radical groups R'.

[0110] According to one embodiment, R' is independently selected from the group consisting of C1 to C12 moieties, each of which optionally contains one or more heteroatoms, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amines, and quaternary ammonium groups at each position in the above formula (JD).

[0111] According to one embodiment, j' is zero for each R'. In other words, according to this embodiment, the repeating unit (R* PEEK ) follows formula (J'-D). [ka]

[0112] According to another embodiment of this disclosure, the repeating unit (R* PEEK ) follows formula (J''-D). [ka]

[0113] According to one embodiment of the present disclosure, less than 90 mol% (based on the total number of moles of repeating units in the polymer), less than 80 mol%, less than 70 mol%, less than 60 mol%, less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, less than 10 mol%, less than 5 mol%, less than 1 mol%, or all of the repeating units of formula (JD), (J'-D), and / or (J''-D) (R* PEEK )

[0114] According to one embodiment, the PEEK polymer is a PEEK-PEDEK copolymer. When used herein, the PEEK-PEDEK copolymer is Repeating units of formulas (JA), (J'-A), and / or (J''-A) (R PEEK )and, Repeating units (R*) of formula (JD), (J'-D), or (J''-D) PEEK )(In this specification, the repeating unit (R PEDEK) ) is also written as This refers to a polymer containing PEEK-PEDEK copolymers with a relative molar ratio (R) of repeating units in the range of 95 / 5~5 / 95, 90 / 10~10 / 90, or 85 / 15~15 / 85. PEEK / R PEDEK ) may include repeating units (R PEEK ) and (R PEDEK The total of the repeating units (R) can, for example, represent at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, and 99 mol% of the repeating units in the PEEK copolymer. PEEK ) and (R PEDEK The sum of these can also represent the repeating units in 100 mol% of the PEEK copolymer.

[0115] PEEK is marketed by Solvay Specialty Polymers USA, LLC as KetaSpire® PEEK.

[0116] According to one embodiment of the present disclosure, the PEEK polymer has a weight-average molecular weight (Mw) in the range of 55,000 to 105,000 g / mol, for example, 65,000 to 85,000 g / mol, (measured by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1:1) at 160°C with a polystyrene standard).

[0117] In another embodiment, PAEK is poly(etherketoneketone) (PEKK). The PEKK described in relation to polymers (P1) and (P2) may be different from those used to prepare the film that joins two components of the assembly. In particular, this PEKK polymer may have different T / I ratios. Polymers (P1) and (P2) may be the same PEKK or different PEKKs themselves, for example, PEKKs with different T / I ratios.

[0118] More precisely, poly(etherketoneketone) (PEKK), which can be used as the first and second component polymers of the assembly, actually refers to polymers containing more than 50 mol% of repeating units of formulas (J-B1) and (J-B2) (mol% is based on the total number of moles of repeating units in the polymer): [ka] (In the formula, R 1 and R 2 In each case, the following are independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium: i and j are, in each case, independently selected integers in the range of 0 to 4.

[0119] According to one embodiment, R 1 and R 2In the above formulas (J-B2) and (J-B1), each position contains one or more heteroatoms, which are independently selected from the group consisting of C1-C12 moieties, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amines and quaternary ammonium groups.

[0120] According to another embodiment, i and j are each R 1 and R 2 The base is zero. According to this embodiment, the PEKK polymer contains at least 50 mol% of repeating units of formulas (J'-B1) and (J'-B2), where mol% is based on the total number of moles of repeating units in the polymer: [ka]

[0121] According to one embodiment of the present disclosure, at least 55 mol%, 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 all of the repeating units in the PEKK are repeating units of formulas (J-B1) and (J-B2).

[0122] In certain embodiments, polymer (P1) and polymer (P2) are independently selected from the PEKK polymers defined above, having a molar ratio of repeating units (J-B1) / (J'-B1) to repeating units (J-B2) / (J'-B2), also referred to as the 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.

[0123] PEKK polymers are known to be characterized by the T / I ratio, which is the molar ratio of terephthaloyl (T) moieties to isophthaloyl (I) moieties present in the polymer.

[0124] In other embodiments, polymer (P1) and polymer (P2) may be independently selected from compositions comprising first and second PEKK polymers, each 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 embodiment of this present invention, the first PEKK polymer preferably has a T / I ratio of a) at least 50 / 50, preferably at least 54 / 46, more preferably at least 56 / 44; most preferably at least 57 / 43, and / or b) a T / I ratio 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 a) at least 65 / 35, preferably at least 66 / 34, more preferably at least 67 / 33, and / or b) a T / I ratio of up to 85 / 15, preferably up to 83 / 17, more preferably up to 82 / 18.

[0125] PEKK is particularly marketed by Solvay Specialty Polymers USA, LLC as NovaSpire® PEKK, or as Cypek® FC and Cypek® DS.

[0126] In one embodiment, polymers (P1) and / or (P2) are nucleophilic PEKK, i.e., PEKK produced by polycondensation of monomers in the absence of a Lewis acid, where the monomers are dihydroxy and difluorobenzoyl-containing aromatic compounds and / or hydroxyl-fluorobenzoyl-containing aromatic compounds.

[0127] In an alternative embodiment, the polymer PEKK is electrophilic PEKK.

[0128] In another embodiment, PAEK is poly(etherketone)(PEK). As used herein, the terms "poly(etherketone)" and "polymer (PEK)" refer to the repeating unit (R PEKMore than 50 mol% of ) is given by formula (K'-C): [ka] Repeating units (mol% is based on the total number of moles of repeating units in PEK) This shows any polymer that is [this polymer].

[0129] According to this embodiment, the PEK polymer contains at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 10% mol%, at least 95 mol%, at least 99 mol%, or substantially all repeating units (R PEK ) may be such that the repeating unit is (K'-C). A preferred PEK polymer is a polymer in which substantially all repeating units are units of formula (K'-C), and it is understood that end groups, defects, and small amounts of impurities may be present.

[0130] In some embodiments, the polymer (PAEK) is poly(etherdiphenyletherketone) (PEDEK). As used herein, the expressions "poly(etherdiphenyletherketone)" or "polymer (PEDEK)" refer to the repeating unit (R K More than 50 mol% of ) is given by formula (K'-D): [ka] This indicates any polymer whose repeating units are (mol% is based on the total number of moles of repeating units in PEDEK).

[0131] According to this embodiment, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least mol%, at least 95 mol%, at least 99 mol%, or substantially all repeating units (R K ) is the repeating unit (K'-D) detailed above. A preferred PEDEK polymer 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.

[0132] In some embodiments, the first component of the assembly may include a polymer (P1) and a filler. The filler may include a fibrous filler or a non-fibrous filler. The filler may include both a fibrous filler and a non-fibrous filler.

[0133] In addition, or instead, the second component of the assembly may include a polymer (P2) and a filler. The filler may include a fibrous filler or a non-fibrous filler. The filler may include both a fibrous filler and a non-fibrous filler.

[0134] In a preferred embodiment, both the first and second components of the assembly contain at least one type of filler, which may be the same or different. In this embodiment, the film placed between the first and second components may contain a filler itself, which may be the same or different from the filler used in the first or second component of the assembly. Alternatively, the film placed between the first and second components may preferably contain no filler (or contain an amount of filler less than 1% by weight, less than 0.5% by weight, or even less than 0.1% by weight based on the total weight of the film).

[0135] 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.

[0136] 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 carbon fibers obtained by thermal decomposition of carbon fibers at high temperatures (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.

[0137] 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 first and second components of the assembly comprise S-glass fibers having a circular cross-section.

[0138] In one embodiment, the first and second components of the assembly of the present invention include 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.

[0139] In one embodiment of the present invention, the first component is a composite material, also called a laminate, comprising one or more layers, the layers comprising, for example, a polymer (P1) and fibers. The polymer (P1) may be impregnated, coated, or laminated onto the fibers, for example.

[0140] In a further embodiment of the present invention, the second component is a composite material, also called a laminate, comprising one or more layers, the layers comprising, for example, fibers and a polymer (P2). The polymer (P2) may be impregnated, coated, or laminated onto the fibers, for example.

[0141] A second object of the present invention is a method for manufacturing an assembly using the above-mentioned film. This method is a) Placing a film between a first component containing polymer (P1) and a second component containing polymer (P2); b) The film is heated to a temperature (T m x ) exposure to Including, here, T m x ≧T m (1) is, or T m x >T m (2) is, or T m x >T m +5 (3), or T m x >T m +10 (4), Here, T m This is the melting temperature (°C) of the film.

[0142] That is, temperature (T m x ) is the appropriate processing temperature for melting the film. m x ) is the melting temperature of the film (T m It is equal to, and preferably greater than, )

[0143] The temperature (T m x ) may be less than 330 °C, preferably less than 320 °C, more preferably less than 310 °C. The temperature (T m x ) may be higher than 270 °C, for example, higher than 275 °C. The temperature (T m x ) may be in the range of 274 °C to 328 °C, for example, in the range of 278 °C to 315 °C.

[0144] According to some embodiments, the temperature (T m x ) is lower than the melting temperature (T m1 ) of the polymer (P1) and / or lower than the melting temperature (T m2 ) of the polymer (P₂): T<000009A>[[ID=B]]<000009B><T<000009C>(5), and / or T<000009D><000009E><T<000009F>(6). Here, T<000009A>and T<000009B>are the melting temperatures of the polymer (P1) and the polymer (P2), respectively.

[0145] Advantageously, the temperature (T<000009C><000009D>) is preferably lower than the melting temperatures of both the polymer (P1)(T m1 ) and the polymer (P2)(T m2 ).

[0146] According to some embodiments, T m [[ID=B]] x <T m1 -5 (7), T m x <T m2 -5 (8), T m x <T m1 Please note that there seems to be a formatting issue with the original text, especially in the use of tags like m etc. which might be specific to a particular system or format. The translation attempts to maintain the integrity of those tags as much as possible while making the text legible in English. Also, the use of some non - standard or placeholder - like notations such as <T(5)> etc. is a bit unclear, but the translation follows the best understanding based on the given text. If there are any specific clarifications about these notations, it would help in providing a more accurate translation.-10 (9) and / or T m x <T m2 -10 (10).

[0147] In some preferred embodiments, the film of the assembly and the first and second components are at a temperature (T m x While exposed to the temperature (T), the method further includes applying pressure to the assembly to solidify it. In other words, the method preferably involves heating the film in step b) to a temperature (T m x The method further includes exposing the first and second components to the substance while simultaneously applying pressure to them.

[0148] The method of the present invention preferably further comprises step c) consisting of controlled cooling of the assembly. This additional step is advantageous for increasing the crystallinity of the film. The film of the assembly preferably exhibits a crystallinity of at least 3%, preferably at least 5%, more preferably at least 15%, and particularly at least 20% after cooling, and the crystallinity is measured as described in the following examples.

[0149] A third aspect of the present invention relates to the use of the assemblies described herein for preparing parts or articles used in various end uses. Applications in the aerospace and automotive industries may be mentioned. For example, parts or articles that include or are composed of the assemblies of the present invention include, but are not limited to, brackets, clips, stiffeners, and other similar types of parts.

[0150] The present invention will be described in more detail in the following sections by non-limiting embodiments.

[0151] If any disclosure of a patent, patent application, or publication incorporated herein by reference conflicts with any description of this application to such an extent that it could obscure certain terms, the description herein shall prevail. [Examples]

[0152] Raw materials used I purchased 1,2-dichlorobenzene, terephthaloyl chloride, isophthaloyl chloride, 3,5-dichlorobenzoyl chloride, aluminum chloride (AlCl3), and methanol from Sigma Aldrich.

[0153] 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).

[0154] Diphenyl sulfone (polymer grade) was sourced from Proviron (99.8% purity).

[0155] Sodium carbonate and light soda ash were sourced from Solvay SA, France, and dried before use. Their particle size was d 90 It was something like 130 μm.

[0156] d 90 Potassium carbonate particles <45μm were sourced from Armand Products and dried before use.

[0157] Lithium chloride (anhydrous powder) was sourced from Acros.

[0158] NaH2PO4·2H2O and Na2HPO4 were purchased from Sigma-Aldrich.

[0159] 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. (filed November 25, 1992, and incorporated herein by reference in its entirety). Some of the 1,4-DFDK was purified by recrystallization in chlorobenzene as described in U.S. Patent No. 5,300,693, and some of the 1,4-DFDK was purified by recrystallization in DMSO / ethanol. 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 1,4-DFDK recrystallized in chlorobenzene was used as a precursor of 1,4-bis(4'-hydroxybenzoyl)benzene (1,4-BHBB).

[0160] 1,4-BHBB and 1,3-bis(4'-hydroxybenzoyl)benzene (1,3-BHBB) were prepared 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. (filed February 24, 1992, and incorporated herein by reference in its entirety). They were purified by recrystallization in DMF / ethanol.

[0161] Boron Nitride: Boronid® S1-SF, a hexagonal boron nitride grade commercially available from 3M Corporation.

[0162] Glass transition temperature (Tg), melting temperature (T m ), crystallization temperature (Tc) and heat of fusion (ΔH f ) measurement Glass transition temperature (T g ), melting temperature (T m ), crystallization temperature (T c ) and heat of fusion (ΔH fThe temperature is determined according to ASTM D3418 using a differential scanning calorimeter (DSC) and a heating / cooling rate of 10°C / min.

[0163] T g (Using the midpoint and half-height method), heat of fusion ΔH f , and T m The peak temperature of the melting endothermic reaction was determined during the second heating scan. c This was determined as the peak temperature of crystallization exothermic reaction during the first cooling scan.

[0164] The melting of the composition was obtained as the area over a linear baseline drawn from 220°C to a temperature exceeding the last endothermic reaction. When evaluating the crystallinity of the film in the bonded structure (component), the heat of fusion during the first heating scan was measured.

[0165] The procedure details 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 were performed using indium. Sample size was 5–7 mg. Weight was recorded to ±0.01 mg. The heating cycle was as follows: - 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.

[0166] Measurement of Melt Flow Index The melt flow index was determined according to ASTM D1238 using a 3.8 kg load at the specified temperature (340–380°C depending on the melting point of the material). The final MFI with an 8.4 kg load was obtained by multiplying the obtained value by 2.35.

[0167] Synthesis Examples PEKK#1 with T / I=71 / 29 112.50 g of diphenylsulfone (DPS), 23.054 g of 1,3-BHBB, 16.695 g of 1,4-BHBB, and 41.292 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 adapter with a thermocouple immersed in the reaction medium, and a Dean-Stark trap with a condenser and 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). The reaction mixture was slowly heated to 270 °C. At 270 °C, 13.725 g of Na2CO3 and 0.078 g of K2CO3 were added to the reaction mixture from a powder dispenser over 60 minutes. At the end of the addition, the reaction mixture was heated to 310 °C / min. After 2 minutes at 310°C, 1.107 g of 1,4-DFDK was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 0.741 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 0.402 g of 1,4-DFDK was added to the reactor, and the reaction mixture was kept at the temperature for 15 minutes. Another charge of 15 g of diphenyl sulfone was added to the reaction mixture, and it was kept stirred for 15 minutes.

[0168] Subsequently, the contents of the reactor were 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 a final wash, 0.67 g of NaH2PO4·2H2O and 0.62 g of Na2HPO4 were dissolved in 1200 mL of DI 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.

[0169] PEKK#2 and PEKK#3: PEKK polymers with various T / I ratios and melt viscosities (MV). The same procedure as in Example 1 was followed using the amounts of reagents shown in Table 1 below.

[0170] [Table 1]

[0171] [Table 2]

[0172] General procedure for solution blending of the PEKK composition of Example 4 235.00 g of diphenylsulfone (DPS) and boron nitride as a nucleating agent were introduced into a 500 mL four-necked reaction flask equipped with a stirrer, an N2 inlet tube, a Claisen adapter for inserting a thermocouple into the reaction medium, and a condenser (Table 3). The contents of the flask were slowly heated to 330°C. At 330°C, 100 g of PEKK polymer powder #3 was slowly added to the molten DPS via a flexible tube. At the end of the addition, the stirring speed was increased to mix thoroughly, and the mixture was held at 330°C for a further 1 hour.

[0173] Subsequently, the contents of the reactor were 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 was extracted from the mixture using acetone and water. For final washing, 0.67 g of NaH2PO4·2H2O and 0.62 g of Na2HPO4 were dissolved in 1200 mL of DI water. The powder was then removed from the reactor and dried under vacuum at 120°C for 12 hours to obtain 90-95 g of yellow powder.

[0174] [Table 3]

[0175] [Table 4]

[0176] As shown by the data collected above, the PEKK composition of Example 4 (according to the present invention) exhibits improved crystallization and degree of crystallinity compared to the PEKK compositions of Examples 1-3 (without nucleating agent).

[0177] The measured enthalpy of melting ΔHf of the PEKK composition in Example 4 is higher than the minimum ΔHf calculated by the following formula 1, which means that the PEKK composition in Example 4 satisfies the following formula: ΔH f >1.69×T m -480 (Formula 1) During the ceremony, - T m This is the melting point in °C, - ΔH f This is a unit of J / g.

[0178] Therefore, the PEKK composition of Example 4 according to the present invention is · Melting point T m ≤310℃; • Heat of fusion ΔH f >5J / g; and · ΔH that satisfies Equation 1 f It exhibits a series of characteristics, making it suitable for processing into films used in laminated structures.

[0179] Regarding the comparative example, - PEEK#1 with a T / I ratio equal to 71 / 29 has a Tm that is too high, above 310°C, and does not satisfy Equation 1; - PEKK#2, with a T / I ratio equal to 58 / 42, has its measured heat of fusion ΔH f The minimum heat of fusion ΔH is calculated using Equation 1. f Since it is equal to, it does not satisfy equation 1; and - PEKK#3 with a T / I ratio within the range of the present invention (50:50 to 56:44) is amorphous (no Tm), making it susceptible to fluid attack and leading to premature failure of structures; therefore, it is not suitable for use in structural applications.

Claims

1. - A first component comprising polymer (P1), - A second component comprising polymer (P2), - A film that is positioned between the first component and the second component and bonded to the first component and the second component. An assembly including, The aforementioned film, a) At least one poly(etherketone) (PEKK) polymer [The PEKK polymer contains at least 50 mol% of formulas (M) and (P) based on the total number of moles in the polymer: 【Chemistry 1】 (In the formula, - R １ and R ２ In each case, the following are independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium: - Includes repeating units of (i and j are, in each case, independently selected integers in the range of 0 to 4); The molar ratio of repeating unit (P) to repeating unit (M) is 50:50 to 56:

44. b) At least one nuclear agent and An assembly that includes or is composed of.

2. i and j are each R １ and R ２ The assembly according to claim 1, wherein the base is 0.

3. SEPEKK polymer - At least 95 mol% of repeating units of formulas (M) and (P); or - At least 99 mol% of repeating units of formulas (M) and (P) The assembly according to claim 1 or 2, including the following:

4. The assembly according to any one of claims 1 to 3, wherein the molar ratio of repeating unit (P) to repeating unit (M) is 51:49 to 55:45 or 54:46 to 53:

47.

5. The assembly according to any one of claims 1 to 4, wherein the PEKK polymer exhibits a melting temperature Tm in the range of 270 to 310°C, preferably 280 to 305°C, when measured by DSC according to ASTM D3418.

6. The PEKK polymer has a heat of fusion ΔH ｆ However, the following equation: ΔH ｆ >1.69×T ｍ -480 (Equation 1) (In the formula, - Tm is the melting temperature (°C) of PEKK, and - ΔH ｆ (This is a unit of J / g) An assembly according to any one of claims 1 to 5, which satisfies the following conditions.

7. The PEKK polymer has the following set of properties: ・ Melting point T ｍ ≤ 310 °C; and • Heat of fusion ΔH ｆ > 5 J / g; and • ΔH ｆ >1.69×T ｍ -480 (Equation 1) (In the formula, • Tm is the melting temperature (°C) of PEKK, and ΔH ｆ (This is a unit of J / g) An assembly according to any one of claims 1 to 6.

8. The heat of fusion ΔH of the PEKK polymer ｆ The assembly according to any one of claims 1 to 7, wherein the ratio is at least 5.0 J / g.

9. The assembly according to any one of claims 1 to 8, wherein the film comprises at least one nucleating agent selected from the group consisting of boron-containing compounds, alkaline earth metal carbonates, oxides, silicates, alkaline earth metal salts, nitrides, and carbon-based compounds.

10. The assembly according to any one of claims 1 to 9, wherein the PEKK polymer is produced in a solvent in the absence of a Lewis acid, or in the presence of a Lewis acid in an amount of less than 2% by weight, preferably less than 1% by weight, and more preferably less than 0.5% by weight, based on the total weight of the monomer.

11. The assembly according to any one of claims 1 to 10, wherein the PEKK polymer contains more than 100 ppm, preferably more than 200 ppm, and more preferably more than 300 ppm of polymer-bound fluorine.

12. The assembly according to any one of claims 1 to 11, wherein the amount of Al in the PEKK polymer is less than 50 ppm, preferably less than 25 ppm, and more preferably less than 10 ppm.

13. The assembly according to any one of claims 1 to 12, wherein the PEKK polymer exhibits a Td (1%) of at least 500°C, preferably at least 505°C, more preferably at least 510°C, when measured by thermogravimetric analysis according to ASTM D3850, with the PEKK polymer heated from 30°C to 800°C under nitrogen at a heating rate of 10°C / min.

14. The assembly according to any one of claims 1 to 13, wherein the film has a thickness in the range of 15 to 800 μm, 25 to 600 μm, preferably 30 to 500 μm, more preferably 40 to 300 μm, and most preferably 50 to 250 μm.

15. The assembly according to any one of claims 1 to 14, wherein polymer (P1) and polymer (P2) are independently selected from the group consisting of poly(aryl ether ketone) (PAEK), poly(etherimide) (PEI), poly(amide imide) (PAI), poly(aryl ether sulfone) (PAES), poly(arylene sulfide) (PAS), poly(phthalamide) (PPA), polyamide (PA), polycarbonate (PC), liquid crystal polymer (LCP), poly(aromatic ester) (PAE), and blends thereof.

16. Polymer (P1) and / or polymer (P2) are independently selected from the group consisting of PEEK and PEKK. PEEK is any polymer containing at least 10 mol% repeating units, formula (J''-A): 【Chemistry 2】 Repeating unit (R ＰＥＥＫ ) (The mol% is based on the total number of moles of repeating units in the polymer) and PEKK is a polymer in which at least 50 mol% of formula (J'-B １ ) and (J'-B ２ ): 【Transformation 3】 The assembly according to any one of claims 1 to 14, wherein it contains repeating units (mol% is based on the total number of moles of repeating units in the polymer).

17. The assembly according to any one of claims 1 to 16, 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.

18. - The first component is a composite material comprising one or more layers including fibers and polymer (P1), - The second component is a composite material comprising one or more layers containing fibers and polymer (P2), and / or - The assembly according to any one of claims 1 to 17, wherein the film comprises scrim, nonwoven fabric, or lightweight fabric.

19. The assembly according to any one of claims 1 to 18, wherein the proportion of the nucleating agent is less than 2.0% by weight, and moreover less than 1.5% by weight, relative to the weight of the PEKK polymer.

20. - A step of placing a film between a first component containing polymer (P1) and a second component containing polymer (P2); - A suitable temperature (T) for melting the film without melting polymer (P1) and polymer (P2). ｍ ｘ The process of exposing the film to the environment A method for manufacturing an assembly according to any one of claims 1 to 19, including the method described in any one of claims 1 to 19.

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