Films 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 application claims priority to U.S. Provisional Patent Application No. 63 / 151820, filed February 22, 2021, and European Patent Application Publication No. 21181637.6, filed June 25, 2021, the entire contents of which are incorporated herein by reference for all purposes. In the event of any discrepancy affecting the clarity of terminology or wording between this application and this PCT application, only this application shall be referenced.

[0002] 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, the film being such that the film comprises at least one poly(ether ketone ketone) (PEKK) polymer and at least one nucleating agent, the assembly can be used to prepare parts and articles for the aerospace and automotive industries, among others. [Background technology]

[0003] Within many industries, particularly the aerospace industry, laminates, composites, and other assemblies that include multiple layers of different materials are heavily used, with each material contributing specific properties to the final assembly. Achieving satisfactory direct adhesion or bonding between the different layers that may be required to utilize a composite or laminate often proves difficult. Poor compatibility between the composite layers can limit the properties offered by such assemblies. In particular, certain thermoplastic polymers (especially crystalline and / or high temperature thermoplastics) have been shown to have poor adhesion to other materials, resulting in problems with delamination and loss of structural integrity when the assembly is subjected to extreme environmental conditions.

[0004] Numerous techniques have been proposed for fastening and / or joining thermoplastic components together. In particular, many different welding processes have been proposed for fastening a first and a second thermoplastic component together, such as ultrasonic welding, induction welding and hot plate welding. However, local melting of the first and second parts in the weld area can affect the integrity and / or shape of the parts. Also, residual stresses can build up in the parts during melting and / or cooling of the thermoplastic in the weld area, causing deformation.

[0005] To address some of the problems associated with the welding process, it has been proposed to provide films and / or adhesives between the components and / or layers to bond them together.

[0006] WO 2011 / 001103 A2 describes the use of amorphous poly(ether ketone ketone) (PEKK) films as tie layers 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. In general terms, the use of amorphous materials as a bonding layer in a composite can result in the weakest part of the structure, with relatively poor properties such as solvent resistance. Thus, the joints can be susceptible to corrosion by liquids, leading to premature failure of the structure.

[0007] WO 2015 / 198063 A1 describes a polyaryletherketone polymer, in particular a PEEK, as an adhesive between a first part and a second part, the first part comprising the polyaryletherketone polymer, in particular a PEEK-PEDEK polymer, i.e. a polymer of the formula -O-Ph-O-Ph-CO-Ph-I and a repeating unit of the formula -O-Ph-Ph-O-Ph-CO-Ph-II Repeating units of (wherein Ph represents a phenylene moiety) The use of polymeric materials has been disclosed, including polymers having the formula: However, the mechanical properties of PEEK-PEDEK polymers are not as good as other polyaryletherketone polymers.

[0008] WO 2021 / 085797, WO 2019 / 243433 and WO 2018 / 115233 are other technical applications, but do not disclose the subject matter of claim 1. Summary of the Invention [Problem to be solved by the invention]

[0009] There is a need for a film capable of strongly bonding together two components (or parts) made of polymers so as to prepare assemblies that exhibit improved chemical resistance and improved mechanical properties. The film should be processed at a temperature below the melting temperature of the two components to be bonded, advantageously below 310°C.

[0010] The present invention aims to solve this technical problem. [Means for solving the problem]

[0011] The invention is defined in the appended claims. An object of the invention is therefore an assembly as defined in claims 1 to 33.

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

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

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

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

[0016] More precise and detailed information regarding these purposes is provided below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention is in the field of laminates, composites, and other assemblies that include multiple layers of different materials, each material providing specific properties to the assembly. These assemblies include at least two components, which may be the same or different, and at least one film, sometimes referred to herein as a "bonding film."

[0018] The films used in the present disclosure exhibit a set of properties suitable for joining polymeric components in assembly structures, especially those 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 is such that its T / I ratio is 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 makes it well suited for assembly 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 polymeric components to which they are bonded.

[0020] In this application: - any description, even if made in relation to a particular embodiment, is applicable and interchangeable with other embodiments of the present disclosure; - when an element or component is said to be included in and / or selected from a list of enumerated elements or components, it is to be understood that in the relevant embodiments expressly contemplated herein, the element or component may be any one of the individually enumerated elements or components, or may be selected from a group consisting of any two or more of the explicitly enumerated elements or components, and that any element or component enumerated in a list of elements or components may be omitted from such list; - Any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited range, as well as the endpoints of the range, and equivalents thereof.

[0021] The first object of the present invention is to a first component comprising a polymer (P1), a second component comprising a polymer (P2), a film disposed between the first component and the second component and bonded to the first component and the second component; An assembly comprising: The film is an assembly that includes at least one poly(ether ketone ketone) (PEKK) polymer exhibiting a particular T / I ratio and at least one nucleating agent.

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

[0023] The films of the assembly may further include scrims and / or nonwoven reinforcements and / or lightweight fabrics, which may help regulate the melt flow and / or provide a uniform surface to bond to and may also affect the local morphology at the bond line.

[0024] The assembly of the present invention may comprise further components (third, fourth, fifth, ...) and films depending on the composite part to be constructed. For example, the assembly of the present invention may comprise a third component comprising a polymer (P3) and a film between the second and third components, this additional film joining the second and third components.

[0025] PEKK Polymer The poly(ether ketone ketone) (PEKK) polymers described herein are those that contain at least 50 mole % of repeat units of the formulae (M) and (P) (mol % based on the total number of moles in the polymer): [ka] (In the formula, - R 1 and R 2 is independently selected at each occurrence 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, at each occurrence, are independently selected integers ranging from 0 to 4; The molar ratio of the repeating unit (P) to the repeating unit (M) (herein, referred to as "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 is independently selected from the group consisting of C1-C12 moieties optionally containing one or more heteroatoms, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amines and quaternary ammonium groups, at each position of formulas (P) and (M) above.

[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 repeat units in the PEKK are repeat units of formula (M) and (P).

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

[0029] The molar ratio of repeat units (P) to repeat units (M), also referred to as the "T / I ratio", of the PEKK utilized as the polymeric component of the film ranges from 50:50 to 56:44, preferably from 51:49 to 55:45. The 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 According to this embodiment, the PEKK polymer comprises at least 50 mole % of repeat units of the formulae (M') and (P') (mol % 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 repeat units in the PEKK are repeat units of formulas (M') and (P').

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

[0033] The molar ratio of repeat units (P') to repeat units (M'), also referred to as the "T / I ratio", of the PEKK utilized as the polymeric component of the film ranges from 50:50 to 56:44, preferably from 51:49 to 55:45. The PEKK preferably has a T / I ratio of 54:46 or 53:47.

[0034] As noted above, the molar ratio of repeat units (P) / (P') to repeat units (M) / (M'), also referred to as the "T / I ratio," of the PEKK utilized as the polymeric component of the film ranges from 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 polymers described herein have a Tm in the range of 270-310°C, preferably 280-305°C, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.

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

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

[0038] Such a formula is an empirical formula that, for the purposes of this invention, distinguishes PEKK of acceptable crystallinity for a given melting temperature (Tm) from PEKK of unacceptable crystallinity at the same Tm.

[0039] According to one embodiment of the present disclosure, the PEKK polymers described herein are such that they have a heat of fusion ΔHf of 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, the heat of fusion measured by DSC in the second heat scan using a heating and cooling rate of 10° C. / min according to ASTM D3418. The following cycle can be followed: - 1st heating cycle: 30.00°C to 400.00°C at 10.00°C / min, isothermal at 400.00°C for 1 min; - 1st cooling cycle: 400.00℃~30.00℃ at 10.00℃ / min, isothermal for 1 min; - Second heating cycle: 30.00°C to 400.00°C at 10.00°C / min, isothermal at 400.00°C for 1 min.

[0041] Synthesis of PEKK polymer The synthesis of PEKK polymers typically involves the steps of polycondensing monomers in a solvent to yield the PEKK polymer and extracting the solvent and salts.

[0042] In a preferred embodiment of the invention, the polycondensation of the monomers occurs 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, more preferably less than 0.5% by weight, based on the total weight of the monomers.

[0043] In the context of the present invention, Lewis acids may be defined as selected from the group consisting of BF3, AlCl3, FeCl3, CF3SO3H and CH3SO3H.

[0044] In a preferred embodiment, the synthesis of the PEKK polymer is Step a) reacting the following monomers (P-OH), (M-OH), (PF) and / or (MF) 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: [ka] (In the formula, - R 3 , R 4 , R 5 and R 6 is independently selected at each occurrence 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, at each occurrence, are independently selected integers ranging from 0 to 4. A step of polycondensing 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 process produces specific PEKK powders with particularly low volatile content, which in turn have specific properties, in particular a specific high enthalpy of fusion ΔH f 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, as measured by thermogravimetric analysis according to ASTM D3850, heating from 30°C to 800°C under nitrogen using a heating rate of 10°C / min. Td(1%) indicates the temperature at which a given amount of volatile material (=1.0 wt%) has escaped from the sample.

[0047] In one embodiment, R 3 , R 4 , R 5 and R 6 is independently selected from the group consisting of C1-C12 moieties optionally containing 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 of 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 of Na2CO3, K2CO3 or a combination thereof. The temperature in step a) is usually 250°C to 350°C, more particularly 300°C to 350°C.

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

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

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

[0054] In step b), the polymer obtained in step a) is treated to remove the solvent and salts. For example, step b) can be carried out by contacting the polymer with a liquid selected from the group of water, alcohols, ethers, ketones and combinations thereof. The liquid can conveniently be a mixture of water and a liquid selected from the group of water, alcohols, ethers, ketones and combinations thereof. The liquid can also include an acid or a base.

[0055] The synthetic approach may involve contacting PEKK 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 mixtures thereof, preferably with the additional step of washing the PEKK therewith. For example, the PEKK may be contacted with (e.g., washed with) a solution, such as an aqueous solution containing both NaH2PO4 and Na2HPO4. The phosphate salts used in the solutions used herein may be, for example, anhydrous, monohydrate, dihydrate, or heptahydrate.

[0056] In addition to 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 mixtures thereof, the synthesis approach may also involve at least one step of contacting, and preferably washing, the 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 a solubility of at least 0.1% by weight in organic solvents such as alcohols, ketones, amides, aromatic hydrocarbons, or in water at a temperature below the boiling point of the solvent. Preferably, the solvent has a boiling point of at most 250° C., more preferably at most 150° C., and most preferably at most 100° C. Preferably, the acid has a pK in the range of 3.0 to 7.5. a and preferably the base has a pK in the range of -1.0 to 8.0. b has.

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

[0059] In some embodiments, the base is selected from an organic amine, a tetraalkylammonium hydroxide, a tetraalkylammonium acetate, a tetraalkylphosphonium hydroxide, a tetraalkylphosphonium acetate, an alkali metal or alkaline earth metal hydroxide, an alkali metal or alkaline earth metal monohydrogen phosphate, an alkali metal or alkaline earth metal phosphate, and combinations thereof.

[0060] Preferred solvents are water, alcohols, ethers, or ketones with a boiling point of at most 150° C., but any solvent capable of dissolving at least 0.1% by weight of an acid or base and that does not adversely react with the PEKK polymer can be used. Preferably, the solvent is water, methanol, ethanol, propanol, or isopropanol. More preferably, the solvent is water, methanol, or ethanol. In some embodiments, more than one solvent can be used.

[0061] The PEKK polymer may more particularly be prepared according to the processes disclosed in Examples 1-3, and in particular according to Example 3, where the T / I ratio is altered by varying the amounts of monomers (see Tables 1 and 2).

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

[0063] The Al and F contents are conveniently measured by elemental analysis, such as ICP-OES analysis for Al and combustion-ion chromatography for fluorine.

[0064] Nucleating 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 oxide, aluminum oxide, magnesium oxide, zinc oxide, antimony trioxide, etc.), silicates (e.g., talc, sodium aluminum silicate, calcium silicate, magnesium silicate, etc.), salts of alkaline earth metals (e.g., calcium carbonate, calcium sulfate, etc.), nitrides, etc. 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 as well as other forms of carbon.

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

[0066] The proportion of nucleating agent is generally less than 2.0% by weight, or even less than 1.5% by weight, based on the weight of the PEKK polymer. This proportion is usually greater than 0.1% by weight, or even greater than 0.5% by weight. This proportion can usually 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 comprises at least one additive as a further component other than the PEKK polymer and the 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 control agents, (xv) weighting agents, (xvi) metal deactivators, and (xvii) flow aids such as silica. The film may contain one additive, two, three or several additives, such as a heat stabilizer and a pigment, from the same or different categories of additives as listed above.

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

[0069] In another embodiment, the film does not contain any fillers or contains less than 0.5% by weight, preferably less than 0.1% by weight, of any fillers.

[0070] In another embodiment, the film does not contain a filler, but does contain "reinforcing fibrous fibers" as described below, such as a scrim, nonwoven, or lightweight fabric. The term "reinforcing fibrous fibers" may include one or more fibrous materials employed for the reinforcement of 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.

[0071] As described herein, the film includes a polymeric component that is at least one PEKK polymer, as well as at least one nucleating agent. As used herein, the term "polymeric component" means a compound having repeating units and having a molecular weight of at least 2,000 g / mole.

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

[0073] In some other embodiments, the polymer component of the film comprises a blend of two or more polymers, for example, a blend of several PEKK polymers or separate polymers.

[0074] For example, the polymer component of the film may consist of a blend of PEKK and one further separate polymer, where at least 60% by weight of the polymer component consists of the PEKK described above and less than 40% by weight of at least one polymer different from the PEKK polymer described above. As another example, the polymer component of the film consists of at least 70% by weight of the PEKK described above and less than 30% by weight of at least one polymer different from the PEKK polymer described above. As yet another example, the polymer component of the film consists of at least 80% by weight of the PEKK described above and less than 20% by weight of at least one polymer different from the PEKK polymer described above. As another example, the polymer component of the film consists of at least 90% by weight of the PEKK described above and less than 10% by weight of at least one polymer different from the PEKK polymer described above.

[0075] In some embodiments, the polymer component of the film consists of less than 3% by weight, less than 2% by weight, less than 1% by weight, or less than 0.5% by weight of a polymer different from the above PEKK polymers.

[0076] Such separate polymers may be selected from the group consisting of poly(arylethersulfone) (PAES) polymers and poly(aryletherketone) (PAEK) polymers. If the additional polymer component is a PAES polymer, it may be selected from the group consisting of polysulfone (PSU), polyphenylsulfone (PPSU), and poly(ethersulfone) (PES). If the additional polymer component is a PAEK polymer, it may advantageously be selected from the group consisting of poly(etheretherketone) (PEEK) polymers, poly(etherketoneketone) (PEKK) polymers, poly(etherketone) (PEK), poly(etherketoneetherketoneketone) (PEKEKK), and PEEK-PEDEK copolymers. The additional polymer component may be a polyimide, such as polyetherimide (PEI) or poly(amideimide) (PAI).

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

[0078] Scrims, nonwovens and lightweight reinforcements The films of the assembly may further include scrims and / or nonwoven reinforcements and / or lightweight fabrics, which may help regulate the melt flow and / or provide a uniform surface to bond to and may also affect the local morphology of the bond line.

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

[0080] The films described herein may also advantageously comprise nonwoven fabrics, also referred to as nonwoven fabrics or fibrous webs.

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

[0082] Film Preparation Process The films described herein may have 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.

[0083] The described films may be prepared by any conventional method known in the art of polymer processing, for example, the film components may be processed in the form of a film by cast extrusion, optionally with uniaxial or biaxial orientation.

[0084] In some embodiments, the method of making the film comprises melt-kneading the physical mixture of the components of the film.Conventional melt-kneading equipment can be used, such as co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disk pack processors and various other types of extrusion equipment.Preferably, extruders can be used, more preferably twin screw extruders.

[0085] According to one embodiment, the components of the film are contacted in a solvent for PEKK, such as DPS, and the mixture is stirred at a temperature at which the polymer dissolves in whole or in part in the solvent. The solvent is then extracted, for example by the methods already disclosed above. Example 4 illustrates this embodiment.

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

[0087] Alternatively, the physical mixture can be compounded in an extruder and then formed directly into a film.

[0088] A technique particularly suitable for the production of films involves extruding the molten composition through an elongated die to obtain an extruded tape, which is then cast / rolled to obtain a film. The tape can be rolled into a film by passing it through suitable rolls, which can be maintained at a suitable temperature and whose speed can be adjusted to achieve the required thickness. The thickness of the film is adjusted at the die. Depending on the cooling temperature used to solidify the film, the film in its finished (extruded) form can be amorphous or semi-crystalline.

[0089] In an advantageous embodiment, the film is a monolayer film, ie, it consists of only one layer comprising the PEKK copolymer.

[0090] If the film comprises a scrim, nonwoven or lightweight fabric, these reinforcing layers or woven reinforcements can be impregnated with the PEKK polymer by a variety of methods, such as the APC process, a slurry impregnation process or film lamination. For example, this process includes: - impregnating the fabric in a liquid medium comprising a PEKK component in the form of polymer powder particles, at least an aqueous solvent and at least one surfactant; - heating the impregnated fabric to a temperature above the melting temperature of PEKK; and - shaping the fabric, for example with at least one die of a particular 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 in contact with the bonding film comprising polymer (P1). The first component may be composed of said polymer (P1). Alternatively, the first component comprises one surface comprising polymer (P1). The surface comprising polymer (P1) typically has a thickness suitable for forming a bond with the bonding film. Said thickness may conveniently 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 in contact with the bonding film comprising polymer (P2). The second component may be composed of said 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. Said thickness may conveniently be 5 μm or more.

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

[0094] Polymer (P1) and polymer (P2) may 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, the polymer (P1) and the polymer (P2) are independently selected from the group consisting of PAEK and blends of PAEK. The PAEK can be, for example, selected from the group consisting of poly(ether ether ketone) (PEEK) polymers, PEEK copolymers, poly(ether ketone ketone) (PEKK) polymers, poly(ether ketone) (PEK) and poly(ether ketone ether ketone ketone) (PEKEKK). The PEEK copolymer can be, for example, a PEEK-PEDEK copolymer.

[0096] Poly(aryl ether ketone) (PAEK) As used herein, poly(aryl ether ketone) (PAEK) refers to a repeat unit (R PAEK ), where mole % is based on the total moles of repeat units in the polymer. PAEK ) is selected from the group consisting of units of formula (JA) to formula (JD): [ka] (In the formula, R' is independently selected at each occurrence from the group consisting of halogen, 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; j' is independently zero or an integer ranging from 1 to 4.

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

[0098] Repeating unit (R PAEK ), j' is preferably zero at each position, so that the phenylene moiety has no other substituents other than those connecting the main chain of the polymer.

[0099] According to one embodiment, the PAEK is poly(ether ether ketone) (PEEK).

[0100] As used herein, poly(ether ether ketone) (PEEK) is a polymer that is made up of repeating units (R PEEK ) any polymer containing: [ka] (In the formula, R' is independently selected at each occurrence from the group consisting of halogen, 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; j' is independently for each R' zero or an integer ranging from 1 to 4 (e.g., 1, 2, 3, or 4).

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

[0102] Repeating unit (R PEEK Each phenylene moiety of R 2 may, independently of the others, 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 1 has, independently of the other, 1,3 or 1,4 bonds to the other phenylene moieties. PEEK Each phenylene moiety of has a 1,4 bond to the other phenylene moiety.

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

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

[0105] According to another embodiment of the present disclosure, poly(ether ether ketone) (PEEK) has at least 10 mol % of repeat units represented by the formula (J-A″): [ka] Repeating units (R PEEK ) (mol % is based on the total moles of repeat units in the polymer).

[0106] According to one embodiment of the present disclosure, at least 10 mol % (based on the total moles of repeat 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 repeat units in the PEEK are repeat units (R PEEK ).

[0107] The PEEK polymer may therefore be a homopolymer or a copolymer. When the PEEK polymer is a copolymer, it may be a random, alternating or block copolymer.

[0108] When PEEK is a copolymer, it has the formula (JD) [ka] (In the formula, R' is independently selected at each occurrence from the group consisting of halogen, 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; j' is independently, for each R', zero or an integer ranging from 1 to 4. Repeating units (R PEEK ), and in addition to this repeating unit, the repeating unit (R* PEEK ) can be constructed.

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

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

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

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

[0113] According to one embodiment of the present disclosure, less than 90 mol% (based on the total moles of repeat 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 repeat units in the PEEK are repeat units (R*) of formula (JD), (J'-D), and / or (J''-D). PEEK ).

[0114] According to one embodiment, the PEEK polymer is a PEEK-PEDEK copolymer. As used herein, a PEEK-PEDEK copolymer is Recurring units (R PEEK )and, The repeating unit (R*) of the formula (JD), (J'-D) or (J''-D) PEEK ) (repeating unit (R PEDEK) ) (also written as PEEK-PEDEK copolymers refer to polymers containing the repeat units in relative molar ratios (R PEEK / R PEDEK ) may be included. PEEK ) and (R PEDEK ) may represent, for example, at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, 99 mol% of the repeat units in the PEEK copolymer. PEEK ) and (R PEDEK ) may also represent the repeat units in 100 mole % of the PEEK copolymer.

[0115] PEEK is commercially available as KetaSpire® PEEK from Solvay Specialty Polymers USA, LLC.

[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, e.g., 65,000 to 85,000 g / mol (measured by gel permeation chromatography (GPC) using phenol and trichlorobenzene (1:1) at 160° C. with polystyrene standards).

[0117] In another embodiment, the PAEK is poly(ether ketone ketone) (PEKK). The PEKK described in connection with polymers (P1) and (P2) may be different from that used to prepare the film that joins the two components of the assembly. In particular, this PEKK polymer may have a different T / I ratio. 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(ether ketone ketone) (PEKK) that may be used as the polymer of the first and second components of the assembly actually denotes a polymer that contains more than 50 mol % of repeat units of the formulae (J-B1) and (J-B2) (mol % based on the total number of moles of repeat units in the polymer): [ka] (In the formula, R 1 and R 2 is independently selected in each occurrence 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; and i and j, in each occurrence, are independently selected integers ranging from 0 to 4.

[0119] According to one embodiment, R 1 and R 2is 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, optionally containing one or more heteroatoms at each position in formulas (J-B2) and (J-B1) above.

[0120] According to another embodiment, i and j are each R 1 and R 2 According to this embodiment, the PEKK polymer comprises at least 50 mole % of repeat units of formulas (J'-B1) and (J'-B2), where the mole % is based on the total moles of repeat 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 repeat units in the PEKK are repeat units of formula (J-B1) and (J-B2).

[0122] In a particular embodiment, polymer (P1) and polymer (P2) are independently selected from PEKK polymers as defined above, having a molar ratio of repeating units (J-B1) / (J'-B1) to repeating units (J-B2) / (J'-B2), also described as T / I ratio, ranging from 55 / 45 to 85 / 15, preferably from 57 / 43 to 80 / 20, more preferably from 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) to isophthaloyl (I) moieties present in the polymer.

[0124] In other embodiments, polymer (P1) and polymer (P2) may be independently selected from compositions comprising a first and a second PEKK polymer, each PEKK polymer being characterized by a T / I ratio, the T / I ratio of the first PEKK polymer being different from the T / I ratio of the second PEKK polymer, particularly those compositions having a melting temperature of 330° C. or less. In one aspect of this embodiment, the first PEKK polymer preferably has a) 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 b) a T / I ratio of at most 64 / 36, preferably at most 63 / 37, more preferably at most 62 / 38. The second PEKK polymer preferably has a) a T / I ratio of at least 65 / 35, preferably at least 66 / 34, more preferably at least 67 / 33, and / or b) a T / I of at most 85 / 15, preferably at most 83 / 17, more preferably at most 82 / 18.

[0125] PEKK is commercially available, inter alia, from Solvay Specialty Polymers USA, LLC as NovaSpire® PEKK, or as Cypek® FC and Cypek® DS.

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

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

[0128] In another embodiment, the PAEK is a poly(ether ketone) (PEK). As used herein, the terms "poly(ether ketone)" and "polymer (PEK)" refer to a polymer having a repeating unit (R PEK) is represented by the formula (K'-C): [ka] Repeat units (mol % is based on the total moles of repeat units in PEK) The present invention relates to any polymer in which

[0129] According to this embodiment, the PEK polymer comprises 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 of the repeat units (R PEK ) may be such that the repeating units are (K'-C). Preferred PEK polymers are those in which substantially all of the repeating units are units of the formula (K'-C), it being understood that end groups, defects and small amounts of impurities may be present.

[0130] In some embodiments, the polymer (PAEK) is poly(ether diphenyl ether ketone) (PEDEK). As used herein, the terms "poly(ether diphenyl ether ketone)" or "polymer (PEDEK)" refer to a repeating unit (R K ) has the formula (K'-D): [ka] repeat unit (mol % is based on the total moles of repeat 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 of the repeat units (R K ) is the repeat unit (K'-D) detailed above. Preferred PEDEK polymers are polymers in which substantially all of the repeat units are units of the formula (K'-D), it being 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 fibrous and non-fibrous fillers.

[0133] Additionally or alternatively, the second component of the assembly may include a polymer (P2) as well as a filler. The filler may include a fibrous filler or a non-fibrous filler. The filler may include both fibrous and non-fibrous fillers.

[0134] According to a preferred embodiment, both the first and second components of the assembly contain at least one filler, which may be the same or different. According to this embodiment, the film disposed between the first and second components may itself contain a filler, which may be the same or different from the filler used in the first or second components of the assembly. Alternatively, the film disposed between the first and second components is preferably filler-free (or contains less than 1 wt. %, less than 0.5 wt. %, or even less than 0.1 wt. %, 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, aligned or randomly oriented.

[0136] In some embodiments, the fibers comprise at least one carbon fiber. The term "carbon fiber" as used herein is intended to include graphitized, partially graphitized, and non-graphitized carbon reinforcing fibers, as well as mixtures thereof. Carbon fibers can be obtained by heat treatment and pyrolysis of different polymer precursors, such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamides, or phenolic resins, and carbon fibers may also be obtained from pitch-based materials. The term "graphitic fiber" is intended to mean carbon fibers obtained by pyrolysis of carbon fibers at high temperatures (above 2000°C), in which the carbon atoms are arranged similarly to the graphite structure. The carbon fibers are preferably selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, graphitic fibers, and mixtures thereof.

[0137] In some embodiments, the fibers comprise at least one glass fiber. The glass fibers may have a circular cross section or a non-circular cross section, such as an oval or rectangular cross section. If the glass fibers used have a circular cross section, it is preferred that they have an average glass fiber diameter of 3 to 30 μm, particularly preferably an average glass fiber diameter of 5 to 12 μm. Different types of glass fibers with a circular cross section are available on the market depending on the type of glass from which they are produced. In particular, glass fibers made from E-glass or S-glass may be mentioned. In some embodiments, the glass fibers are standard E-glass materials with a non-circular cross section. In some embodiments, the first and second components of the assembly comprise S-glass fibers with a circular cross section.

[0138] In one embodiment, the first and second components of the assembly of the invention comprise continuous fibers. "Continuous fibers" as referred to herein refers to fibers having a length of 3 mm or greater, more typically 10 mm or greater, and an aspect ratio of 500 or greater, more typically 5000 or greater.

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

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

[0141] A second object of the present invention is a method for producing an assembly using the above film, the method comprising the steps of: a) placing a film between a first component comprising a polymer (P1) and a second component comprising a polymer (P2); b) The film is heated to a temperature (T m x ) and where T m x ≧T m (1) or T m x >T m (2) or T m x >T m +5 (3), or T m x >T m +10 (4), Here, T m is the melting temperature of the film (°C).

[0142] That is, temperature (T m x ) is the processing temperature suitable for melting the film. m x ) is the melting temperature of the film (T m ) and preferably greater.

[0143] Temperature (T m x ) may be less than 330°C, preferably less than 320°C, and more preferably less than 310°C. m x ) may be greater than 270° C., for example greater than 275° C. 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 the melting temperature (T m1 ) and / or the melting temperature (T m2 ) lower than: T m x <T m1 (5) and / or T m x <T m2 (6) Here, T m1 and T m2 are the melting temperatures of polymer (P1) and polymer (P2), respectively.

[0145] Advantageously, the temperature (T m x ) is preferably a polymer (P1) (T m1 ) and polymer (P2) (T m2 ) lower than the melting temperatures of both

[0146] According to some embodiments, T m x <T m1 -5 (7), T m x <T m2 -5 (8), T m x <T m1-10 (9), and / or T m x <T m2 -10 (10).

[0147] In some preferred embodiments, the film and the first and second components of the assembly are heated to a temperature (T m x During exposure to the temperature (T m x ) while simultaneously applying pressure to the first and second components.

[0148] The method of the 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%, in particular at least 20% after cooling, the crystallinity being measured as described in the examples below.

[0149] A third aspect of the invention relates to the use of the assemblies described herein to prepare parts or articles for use in various end uses. Reference may be made to applications in the aerospace and automotive industries. For example, parts or articles that include or are constructed from the assemblies of the invention may include, but are not limited to, brackets, clips, stiffeners, and other similar types of parts.

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

[0151] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements in this application to the extent that a term may be unclear, the statements herein shall control. EXAMPLES

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

[0153] 1,4-Bis(4-phenoxybenzoyl)benzene was prepared according to Indian Patent No. 193687, filed on Jun. 21, 1999, and incorporated herein by reference.

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

[0155] Sodium carbonate, light soda ash, was procured from Solvay SA, France and dried before use. Its particle size is d 90 was 130 μm.

[0156] d 90 Potassium carbonate <45 μm was 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 to Gilb et al., filed November 25, 1992, which is 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 the 1,4-DFDK in a polymerization reaction to produce the PEKK described below, while 1,4-DFDK recrystallized in chlorobenzene was used as the precursor to 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 to Hackenbruch et al., filed Feb. 24, 1992, which is 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 f) is determined according to ASTM D3418 using a differential scanning calorimeter (DSC) at a heating rate of 10° C. / min.

[0163] T g (midpoint, using half-height method), heat of fusion ΔH f , and T m (peak temperature of melting endotherm) was determined in the second heating scan. c was determined as the peak temperature of the crystallization exotherm in the first cooling scan.

[0164] The melting of the composition was taken as the area across a linear baseline drawn from 220° C. to the temperature beyond the last endotherm. When assessing the crystallinity of films in bonded structures (parts), the heat of fusion was measured on the first heating scan.

[0165] The details of the procedure are as follows: A TA Instruments DSC Q20 was used with nitrogen as the carrier gas (99.998% purity, 50 mL / min). Temperature and heat flow calibration was performed using indium. Sample sizes were 5-7 mg. Weights were recorded to ±0.01 mg. The heating cycle was - 1st heating cycle: 30.00°C to 400.00°C at 10.00°C / min, isothermal at 400.00°C for 1 min; - 1st cooling cycle: 400.00℃~30.00℃ at 10.00℃ / min, isothermal for 1 min; - Second heating cycle: 30.00°C to 400.00°C at 10.00°C / min, then isothermal at 400.00°C for 1 min.

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

[0167] Synthesis Examples PEKK#1 with T / I=71 / 29 Into a 500 mL 4-neck reaction flask equipped with a stirrer, N2 inlet tube, Claisen adapter with thermocouple plunged into the reaction medium, and Dean-Stark trap with condenser and dry ice trap, 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. The contents of the flask were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O2). The reaction mixture was then placed under a continuous nitrogen purge (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 min. At the end of the addition, the reaction mixture was heated to 310°C at 1°C / min. After 2 minutes at 310°C, 1.107g of 1,4-DFDK was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 0.741g of lithium chloride was added to the reaction mixture. After 10 minutes, another 0.402g of 1,4-DFDK was added to the reactor and the reaction mixture was held at temperature for 15 minutes. Another charge of 15g of diphenylsulfone was added to the reaction mixture, which was held under stirring for 15 minutes.

[0168] The reactor contents were then poured out of the reactor into a stainless steel tray to cool. The solids were divided and ground in an attrition mill through a 2 mm sieve. Diphenylsulfone and salts were extracted from the mixture with acetone and water at pH 1-12. For the 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 at 120 °C under vacuum for 12 h to obtain 72 g of a yellow powder.

[0169] PEKK#2 and PEKK#3: PEKK polymers with various T / I and different melt viscosities (MV). The same procedure as in Example 1 was carried out 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 Into a 500 mL 4-neck reaction flask equipped with a stirrer, N2 inlet, Claisen adapter for inserting a thermocouple into the reaction medium, and a condenser, 235.00 g of diphenylsulfone (DPS) and boron nitride as a nucleating agent were introduced (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 into the molten DPS via a flex tube. At the end of the addition, the stirring speed was increased to mix well, and the mixture was held at 330°C for an additional hour.

[0173] The reactor contents were then poured out of the reactor into a stainless steel tray to cool. The solids were divided and ground in an attrition mill through a 2 mm sieve. Diphenylsulfone was extracted from the mixture using acetone and water. For the 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 h to obtain 90–95 g of a yellow powder.

[0174] [Table 3]

[0175] [Table 4]

[0176] As demonstrated by the data collected above, the PEKK composition of Example 4 (in accordance with 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 fusion ΔHf of the PEKK composition of Example 4 is higher than the minimum ΔHf calculated by Equation 1 below, which means that the PEKK composition of Example 4 satisfies the following equation: ΔH f >1.69×T m -480 (Formula 1) During the ceremony, - T m is the melting point in °C, - ΔH f is in units of J / g.

[0178] Thus, the PEKK composition of Example 4 according to the present invention: · Melting point T m ≦310℃; Heat of fusion ΔH f >5 J / g; and ΔH that satisfies Equation 1 f The polymer exhibits a set of properties that are suitable for processing into films for use in laminate structures.

[0179] For comparative examples, - PEEK#1 with T / I ratio equal to 71 / 29 has too high Tm, higher than 310°C, and does not satisfy Eq. 1; - PEKK#2 with a T / I ratio equal to 58 / 42 has a measured heat of fusion ΔH f The minimum heat of fusion ΔH calculated by Eq. f does not satisfy Equation 1 because it is equal to; and - PEKK#3 with a T / I ratio within the range of the present invention (50:50 to 56:44) is amorphous (no Tm) and therefore is susceptible to attack by fluids, leading to premature failure of the structure, and therefore is not suitable for use in structural applications.

Claims

1. a first component comprising a polymer (P1), a second component comprising a polymer (P2), a film disposed between the first component and the second component and bonded to the first component and to the second component; An assembly comprising: The film, a) at least one poly(ether ketone ketone) (PEKK) polymer The PEKK polymer comprises at least 50 mole % of formula (M) and (P), based on the total moles in the polymer: 【Chemistry 1】 (In the formula, - R １ and R ２ is independently selected at each occurrence 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, at each occurrence, are independently selected integers ranging from 0 to 4; the molar ratio of repeating units (P) to repeating units (M) is 50:50 to 56:44; b) at least one nucleating agent; 1. An assembly comprising or consisting of:

2. i and j are each R １ and R ２ The assembly of claim 1 , wherein the R is 0 for the group.

3. The PEKK polymer at least 95 mol % of repeat units of the formulae (M) and (P); or at least 99 mol % of repeat units of the formulae (M) and (P) 3. The assembly of claim 1 or 2, comprising:

4. 4. The assembly according to claim 1, wherein the molar ratio of repeating units (P) to repeating units (M) is from 51:49 to 55:45 or from 54:46 to 53:

47.

5. 5. An 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, as measured by DSC according to ASTM D3418.

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

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 (Formula 1) (In the formula, Tm is the melting temperature of PEKK (° C.); and ・ ΔH ｆ is in J / g) An assembly according to any one of claims 1 to 6, in accordance with

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

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

10. 10. The assembly of any one of claims 1 to 9, wherein the PEKK polymer is such that it 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 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, based on the total weight of the monomers.

11. 11. An assembly according to any one of claims 1 to 10, wherein the PEKK polymer comprises polymer-bound fluorine in an amount greater than 100 ppm, preferably greater than 200 ppm, even more preferably greater than 300 ppm.

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

13. 13. The assembly of 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, as measured by thermogravimetric analysis according to ASTM D3850, heating from 30°C to 800°C under nitrogen using a heating rate of 10°C / min.

14. 14. An assembly according to any one of the preceding claims, 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. 15. The assembly according to any one of claims 1 to 14, wherein the polymer (P1) and the polymer (P2) are independently selected from the group consisting of poly(aryl ether ketone)s (PAEK), poly(etherimide)s (PEI), poly(amide imide)s (PAI), poly(aryl ether sulfone)s (PAES), poly(arylene sulfide)s (PAS), poly(phthalamide)s (PPA), polyamide (PA), polycarbonate (PC), liquid crystal polymers (LCP), poly(aromatic ester)s (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 that contains at least 10 mol % repeat units of the formula (J″-A): 【Chemistry 2】 Repeating units (R ＰＥＥＫ ) (mol % is based on the total moles of repeat units in the polymer); and PEEK is a polymer in which any polymer has at least 50 mol % of the formula (J'-B １ ) and (J'-B ２ ): 【Chemistry 3】 The assembly of any one of claims 1 to 14, characterized in that it comprises repeat units of the formula: (mol % is based on the total moles of repeat units in the polymer).

17. 17. The assembly according to any one of the preceding claims, wherein the polymer (P1) and the polymer (P2) are independently selected from PEKK polymers and mixtures thereof having a T / I ratio in the range of from 55 / 45 to 85 / 15, preferably from 57 / 43 to 80 / 20, more preferably from 58 / 42 to 75 / 25.

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

19. 19. An assembly according to any one of the preceding claims, wherein the proportion of nucleating agent is less than 2.0% by weight, or even less than 1.5% by weight, relative to the weight of the PEKK polymer.

20. - placing a film between a first component comprising a polymer (P1) and a second component comprising a polymer (P2); - a temperature (T) suitable for melting the film without melting the polymers (P1) and (P2) ｍ ｘ exposing the film to A method for manufacturing an assembly according to any one of claims 1 to 19, comprising:

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