Films for multilayer assemblies

Abstract

The present invention relates to an assembly comprising a first component, a second component, and a film, each component comprising a polymer, the film being disposed between and bonded to the first and second components. The film comprises a blend of at least two poly(ether ketone ketone) (PEKK) polymers and optionally at least one nucleating agent. The assembly has improved fracture toughness and excellent overall mechanical properties.

Description

[Technical field]

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 151822, filed February 22, 2021, and European Patent Application No. 21181639.2, filed June 25, 2021, the contents of which are incorporated herein by reference in their entirety for all purposes. In the event of any discrepancy affecting the clarity of terminology or wording between this application and this PCT application, reference shall be made solely to this application.

[0002] The field of the invention is that of polymer composites. The invention relates to an assembly comprising a first component, a second component and a film, each component comprising a polymer, the film being disposed between the first and second components and bonded to the first and second components. The film comprises a blend of at least two poly(etherketoneketone) (PEKK) polymers having different T / I ratios. The assembly can be used to manufacture parts and articles, particularly for the aerospace and automotive industries. [Background technology]

[0003] In many industries, particularly within the aerospace industry, laminates, composites, and other assemblies made of multiple layers of different materials are used extensively, 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 of 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 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. In general terms, when amorphous materials are used as a bonding layer in composites, they can be 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 The use of polymeric materials has been disclosed, including polymers having the formula: where Ph represents a phenylene moiety. However, the mechanical properties of PEEK-PEDEK polymers are not as good as other polyaryletherketone polymers.

[0008] US 2021 / 039369 discloses a structure comprising polyetheretherketone (PEEK) and carbon fibers, but not PEKK polymers. WO 2018 / 115033 does not disclose the assembly of claim 1 or the PEKK blends of the present invention. Summary of the Invention [Problem to be solved by the invention]

[0009] There is a need for a film capable of firmly bonding two polymeric components (or parts) together to produce assemblies that exhibit improved chemical resistance and improved mechanical properties. The film needs to be processed at a temperature below the melting temperature of the two components to be bonded, preferably below 340° 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. The object of the invention is therefore an assembly as defined in claims 1 to 40.

[0012] Another object of the invention is a method for manufacturing an assembly according to any one of claims 41 to 47.

[0013] Another object of the invention is a component or article according to claim 48.

[0014] Another object of the invention is the use according to claim 49 or claim 50.

[0015] Another object is a composition comprising a blend of PEKK1, PEKK2, and optionally at least one nucleating agent.

[0016] More precise details regarding these objectives are 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 imparting 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 this disclosure exhibit a set of properties that make them well suited for joining polymeric components in assembly structures, especially those made from poly(aryl ether ketone) (PAEK) polymers. These films comprise blends of at least two poly(ether ketone ketone) (PEKK) polymers (PEKK1, PEKK2), where PEKK1 and PEKK2 differ from each other in that they have different molar T / I ratios (also interchangeably referred to herein as the molar ratio of repeat units (P) and repeat units (M)). The PEKK blends exhibit crystallinity that makes them well suited for assembly structures where chemical resistance and mechanical properties are required, such as in composite structures in the aerospace industry.

[0019] 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.

[0020] The films described herein are advantageously compatible with the polymer-based components to which they are bonded.

[0021] 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 also 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.

[0022] 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 and bonded to a first component and a second component, The film comprises a blend of at least two poly(ether ketone ketone) (PEKK) polymers (PEKK1, PEKK2), wherein the PEKK polymers are at least 50 mole % of the formulas (M) and (P), based on the total moles of polymer: [ka] The repeat unit In these formulas: - 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; PEKK1 and PEKK2 differ from each other in that they have different molar ratios of repeat units (P) to repeat units (M), also called the T / I ratio; It is an assembly.

[0023] The two PEKKs are prepared by specific methods that provide specific features, detailed below, that allow the technical problem to be solved.

[0024] In the context of the present invention, the term "joined" means that components are attached, preferably permanently, one to the other or to each other.

[0025] The films of the assembly may further include at least one nucleating agent.

[0026] The film may contain scrims and / or nonwoven reinforcements and / or lightweight fabrics, which may help regulate melt flow and / or provide a uniform surface to bond to as well as affect the local morphology of the bond line.

[0027] The assembly of the present invention may also include additional components (third, fourth, fifth, ...) and films depending on the composite part to be 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, this additional film binding the second and third components together.

[0028] PEKK polymers (PEKK1, PEKK2) Poly(ether ketone ketone) (PEKK) polymers described herein are those that contain at least 50 mole % of repeat units of the formulas (M) and (P), where mole % is based on the total number of moles in the polymer: [ka] (In these formulas, - 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.

[0029] 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 formula (P) and (M) above.

[0030] 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 at least one of the PEKK polymers (PEKK1, PEKK2), preferably both PEKK1 and PEKK2, in the film are repeat units of formula (M) and formula (P).

[0031] In one embodiment, substantially all of the repeat units of at least one of the PEKK polymers (PEKK1, PEKK2), preferably both PEKK1 and PEKK2, are repeat units of formula (M) and formula (P). In one embodiment, the repeat units of at least one of the PEKK polymers (PEKK1, PEKK2), preferably both PEKK1 and PEKK2, consist of repeat units of formula (M) and formula (P).

[0032] According to another preferred embodiment, i and j are each R 1 and R2 According to this embodiment, at least one of the PEKK polymers (PEKK1, PEKK2) in the film, preferably both PEKK1 and PEKK2, comprises at least 50 mole % of repeat units of formula (M') and formula (P'), where mole % is based on the total number of moles in the polymer: [ka]

[0033] 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 at least one of the PEKK polymers (PEKK1, PEKK2), preferably both PEKK1 and PEKK2, in the film are repeat units of formula (M') and formula (P').

[0034] In one embodiment, substantially all of the repeat units of at least one of the PEKK polymers (PEKK1, PEKK2), preferably both PEKK1 and PEKK2, are repeat units of formula (M') and formula (P'). In one embodiment, the repeat units of at least one of the PEKK polymers (PEKK1, PEKK2), preferably both PEKK1 and PEKK2, consist of repeat units of formula (M') and formula (P').

[0035] According to the present invention, the molar ratio of repeat units (P) to repeat units (M) of PEKK1 (also referred to herein as the "PEKK1 T / I ratio") is different from the molar ratio of repeat units (P) to repeat units (M) of PEKK2 (the PEKK2 T / I ratio).

[0036] In some embodiments, the T / I molar ratio of PEKK1 is: at least 50 / 50, preferably at least 54 / 46, more preferably at least 56 / 44, most preferably at least 57 / 43, and / or - up to 64 / 36, preferably up to 63 / 37, more preferably up to 62 / 38 The T / I molar ratio of PEKK1 is suitably 50 / 50 to 64 / 36.

[0037] In some embodiments, the T / I molar ratio of PEKK2 is: at least 65 / 35, preferably at least 66 / 34, more preferably at least 67 / 33, and / or - maximum 85 / 15, preferably maximum 83 / 17, more preferably maximum 82 / 18 The T / I molar ratio of PEKK2 is suitably 65 / 35 to 85 / 15.

[0038] In some embodiments, the assembly film has a weight ratio of PEKK1 to PEKK2 in the film of at least 65 / 35, more preferably at least 70 / 30, even more preferably at least 75 / 25, and / or at most 99 / 1, preferably at most 97 / 3, even more preferably at most 96 / 4.

[0039] The weight ratio of PEKK1 / PEKK2 is preferably 65 / 35 to 99 / 1. The weight ratio may be preferably 80 / 20 to 99 / 1, or 90 / 10 to 99 / 1.

[0040] In some embodiments, the assembly film has PEKK1 comprising 50-95% by weight of the PEKK blend, such as 60-90% by weight, or 70-85% by weight.

[0041] According to one embodiment of the present disclosure, at least one PEKK polymer (PEKK1, PEKK2) or preferably a PEKK blend in the film described herein has a melting temperature Tm in the range of 270-340°C, preferably 280-330°C, as measured by Differential Scanning Calorimetry (DSC) according to ASTM D3418. More preferably, Tm is 280-320°C, most preferably 280-310°C.

[0042] More specifically, Tm is measured by DSC using heating and cooling rates of 10° C. / min according to ASTM D3418. Tm is determined in the second heating 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℃~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.

[0043] According to one embodiment of the present disclosure, the PEKK polymer blends used in the films described herein have 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 of PEKK (°C), - ΔH f is in J / g).

[0044] Such a formula, in the context of the present invention, is an empirical formula that distinguishes blends of acceptable crystallinity at a given melting temperature (Tm) from blends of unacceptable crystallinity at the same Tm.

[0045] According to one embodiment of the present disclosure, the PEKK polymer blends used in the films described herein have a heat of fusion ΔHf of at least 5.0 J / g, at least 6.0 J / g, or at least 7.0 J / g.

[0046] More specifically, the heat of fusion was measured by DSC in the second heating 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.

[0047] Synthesis of PEKK polymer The synthesis of PEKK polymers has been described in the literature and typically involves the steps of polycondensing monomers in a solvent to yield the PEKK polymer and extracting the solvent and salts.

[0048] 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.

[0049] 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.

[0050] In a preferred embodiment, the synthesis of the PEKK polymer comprises: Step a) reacting 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, more preferably less than 0.5% by weight based on the total weight of the monomers, of the following monomers (P-OH), (M-OH), (PF) and / or (MF): [ka] (In these formulas, - R 3 , R 4 , R 5 and R 6is 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 from 0 to 4. A step of polycondensing The molar ratio of moles of (P-OH) and (M-OH) to moles of (PF) and (MF) is

number

[0051] Preferably, p=q=r=s=0.

[0052] The above process produces a PEKK powder with low volatile content. According to one embodiment, the PEKK polymer has a Td(1%) of at least 500°C, preferably 505°C, more preferably 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%) represents the temperature at which a determined amount of volatile material (=1.0% by weight) leaves the sample.

[0053] In one embodiment, R 3 , R 4 , R 5 , and R 6are 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 (P-OH), (PF), (M-OH), and (MF) above.

[0054] The T / I ratio is controlled by the amounts of (PF)+(P-OH) and (MF)+(M-OH).

[0055] According to a preferred embodiment, the polycondensation resulting in the PEKK polymer involves only the following monomers: (P-OH), (M-OH), and (PF).

[0056] 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 of a base selected from the group of Na2CO3, K2CO3, or a combination thereof. The temperature of step a) is usually 250°C to 350°C, more specifically 300°C to 350°C.

[0057] The amount of base should preferably be sufficient to activate all OH groups of the monomer. The amount of base is usually slightly more than the amount of OH groups. A molar excess of 1.0 to 5.0% may be used.

[0058] According to one embodiment, the base is added to a mixture comprising the solvent and the monomer, the mixture being preferably at a temperature higher than 250° C., in particular 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.

[0059] 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 fluorine end groups are included in the PEKK polymer.

[0060] 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 may conveniently be a mixture of water and a liquid selected from the group of water, alcohols, ethers, ketones, and combinations thereof. The liquid may also contain an acid or a base.

[0061] The synthetic approach may involve contacting PEKK with, and preferably washing the 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. For example, 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.

[0062] 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.

[0063] 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. aand preferably the base has a pK in the range of -1.0 to 8.0. b has.

[0064] In some embodiments, the acid is selected from acetic acid, monoalkali metal citrates, and combinations thereof.

[0065] 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.

[0066] Preferred solvents are water, alcohols, ethers, or ketones with a boiling point of up to 150° C., but any solvent that can dissolve at least 0.1% by weight of an acid or base and 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.

[0067] The PEKK polymer can be more specifically prepared according to the recipes disclosed in Examples 1-2, with the T / I ratio being modified and adjusted by varying the amount of monomers used in the polycondensation (see Tables 1 and 1').

[0068] The preparation methods disclosed herein make it possible to obtain specific PEKK1 and PEKK2, either generally or according to the specific embodiments disclosed, that have one or more of the following characteristics: - PEKK polymers usually contain more than 100 ppm of fluorine, preferably more than 200 ppm, and more preferably more than 300 ppm of fluorine. Such polymer-bound fluorine is an unavoidable fingerprint of the use of fluorine-containing monomers; - the PEKK polymer is substantially free of aluminium. The amount of Al in the PEKK polymer is usually 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.

[0069] The Al and F contents are conveniently measured by elemental analysis, such as ICP-OES analysis for Al and combustion-ion chromatography for fluorine.

[0070] Nucleating Agent According to the present invention, the film may further comprise 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. Carbon black may also be other forms of carbon.

[0071] Particularly good results were obtained when the nucleating agent was boron nitride.

[0072] The proportion of nucleating agent is usually less than 2.0% by weight, or even less than 1.5% by weight, based on the weight of the PEKK polymer. The proportion is usually greater than 0.1% by weight, or even greater than 0.5% by weight. The proportion is usually between 0.5 and 2.0% by weight, or between 0.5 and 1.5% by weight.

[0073] Other Additives In some embodiments, the film comprises at least one additive as an additional component other than the PEKK polymer and optional 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 more additives from the same or different categories listed above, for example, a heat stabilizer and a pigment.

[0074] According to these embodiments, the amount of such additives is less than 20 wt. % based on the total weight of the film, preferably less than 10 wt. %, more preferably less than 5 wt. %, even more preferably less than 2 wt. % additive, and most preferably less than 1 wt. %.

[0075] In another embodiment, the film contains no fillers or less than 0.5% by weight, preferably less than 0.1% by weight, of any fillers.

[0076] In another embodiment, the film does not contain any fillers, but does contain "reinforcing fibrous fibers" such as scrims, nonwovens, or lightweight fabrics, as described below. The term "reinforcing fibrous fibers" may include one or more fibrous materials suitable for reinforcing composite structures, i.e., "reinforcing fibers." The term "fiber" is used herein to refer to organic and / or inorganic fibers having a length of at least 0.5 mm.

[0077] The films described herein comprise a polymeric component that is a blend of at least two PEKK polymers and, optionally, 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.

[0078] In some embodiments, the PEKK polymer detailed above is the only polymer component in the film.

[0079] In some other embodiments, the polymer component of the film comprises a blend of more than two PEKK polymers as described herein, for example a blend of different polymers.

[0080] For example, the polymer component of the film may be a blend of PEKK1, PEKK2, and one additional separate polymer, where at least 60% by weight of the polymer component is the PEKK blend and less than 40% by weight of at least one polymer different from the PEKK blend. As another example, the polymer component of the film may be at least 70% by weight of the PEKK blend and less than 30% by weight of at least one polymer different from the PEKK blend. As yet another example, the polymer component of the film may be at least 80% by weight of the PEKK blend and less than 20% by weight of at least one polymer different from the PEKK blend. As another example, the polymer component of the film may be at least 90% by weight of the PEKK blend and less than 10% by weight of at least one polymer different from the PEKK blend.

[0081] In some embodiments, the polymer component of the film contains less than 3 wt.%, less than 2 wt.%, less than 1 wt.%, or less than 0.5 wt.% of a polymer different from the PEKK blend.

[0082] Such separate polymers may be selected from the group consisting of poly(arylethersulfone) (PAES) polymers and poly(aryletherketone) (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(ethersulfone) (PES). When 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, polyetherketone (PEK), polyetherketoneetherketoneketone (PEKEKK), and PEEK-PEDEK copolymers. The additional polymer component may be a polyimide, such as polyetherimide (PEI) or poly(amideimide) (PAI).

[0083] In certain embodiments, the film comprises at least 90% by weight of the PEKK blend and at least one additive. Most preferably, the film comprises at least 95% by weight, and preferably at least 98% by weight, of the PEKK blend and at least one additive, based on the total weight of the film.

[0084] Scrims, nonwovens, and lightweight reinforcements The films of the assembly may additionally include scrims and / or nonwoven reinforcements and / or lightweight fabrics that help regulate melt flow and / or provide a uniform surface to bond to, as well as potentially affecting the local morphology of the bond line.

[0085] The films described herein may advantageously include a scrim or scrim layer. The scrim may be made from a natural woven fabric, a synthetic woven fabric, a nonwoven fabric, a knit fabric (such as, but not limited to, a weft-insertion knit fabric), or a plastic.

[0086] The films described herein may also advantageously comprise a nonwoven fabric, also referred to as a nonwoven fabric or fibrous web.

[0087] Such scrims, nonwovens, or lightweight fabrics are advantageous because they help maintain a uniform bond line thickness.

[0088] Film manufacturing method 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.

[0089] The films of the present description can be manufactured by any conventional method known in the art of polymer processing, for example, the film components can be processed into the film form by cast extrusion, optionally with uniaxial or biaxial orientation.

[0090] In some embodiments, the method of making the film includes 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, an extruder can be used, more preferably a twin screw extruder.

[0091] In some embodiments, the physical mixture is compounded in an extruder and then chopped into pellets or granules, which can then be further processed to produce a film.

[0092] Alternatively, the physical mixture is kneaded in an extruder and then directly formed into a film. A particularly suitable technique for the production of films involves extruding the molten composition through an elongated die to obtain an extruded tape, which is then cast / calendared 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.

[0093] According to one embodiment, the components of the film are contacted with a solvent for PEKK, such as DPS, and the mixture is stirred at a temperature at which the polymer dissolves completely or partially in the solvent. The solvent is then extracted, for example using the methods already disclosed above. The solution blends disclosed in the examples illustrate this embodiment.

[0094] In an advantageous embodiment, the film is a monolayer film, i.e., it is composed of only one layer containing the PEKK blend.

[0095] If the film comprises a scrim, nonwoven, or lightweight fabric, these reinforcing layers or fabric-based reinforcements can be impregnated with the PEKK polymer blend by a variety of methods, such as the APC process, a slurry impregnation process, or film lamination. For example, the method may include: - impregnating the textile in a liquid medium comprising the PEKK blend components in the form of polymer powder particles, at least an aqueous solvent and at least one surfactant; - heating the impregnated fabric above the melting temperature of PEKK; and - shaping the dough using at least one die, e.g. of a particular shape; may include.

[0096] 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 consist 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.

[0097] 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.

[0098] Polymer (P1) and polymer (P2) may be the same or different.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] Repeating unit (R PAEK ), each phenylene moiety is independently a repeat unit (R PAEK) to other moieties different from R'. Preferably, the phenylene moieties have 1,3- or 1,4-bonds, more preferably they have 1,4-bonds.

[0103] 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.

[0104] According to one embodiment, the PAEK is poly(ether ether ketone) (PEEK).

[0105] 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).

[0106] 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′.

[0107] Repeating unit (R PEEKEach 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.

[0108] 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.

[0109] According to one embodiment, j' is zero for each R'. In other words, according to this embodiment, the repeating unit (R PEEK ) is represented by the formula (J'-A): [ka] This is in accordance with the following.

[0110] 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).

[0111] 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 ).

[0112] 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.

[0113] When PEEK is a copolymer, 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 produced.

[0114] 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′.

[0115] According to one embodiment, R' at each position in formula (JD) above 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.

[0116] According to one embodiment, j' is zero for each R'. In other words, according to this embodiment, the repeating unit (R* PEEK ) is represented by the formula (J'-D): [ka] Follow.

[0117] According to another embodiment of the present disclosure, the repeating unit (R* PEEK ) is represented by the formula (J''-D): [ka] Follow.

[0118] 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 ).

[0119] According to one embodiment, the PEEK polymer is a PEEK-PEDEK copolymer. As used herein, a PEEK-PEDEK copolymer is a polymer having repeat units (R PEEK ) and a repeating unit (R*) of the formula (JD), (J'-D) or (J''-D) PEEK ) (repeating unit (R PEDEK)PEEK-PEDEK copolymers refer to polymers containing repeat units with 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.

[0120] PEEK is commercially available as KetaSpire® PEEK from Solvay Specialty Polymers USA, LLC.

[0121] 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 (determined by gel permeation chromatography (GPC), using phenol and trichlorobenzene (1:1), 160° C., polystyrene standard).

[0122] In another embodiment, the PAEK is poly(ether ketone ketone) (PEKK). The PEKK described in relation to polymers (P1) and (P2) may be different from the PEKK1 and PEKK2 used to manufacture the film joining the two components of the assembly. In particular, the PEKK polymers may have different T / I ratios. The polymers (P1) and (P2) may themselves be the same or different PEKKs, for example PEKKs with different T / I ratios.

[0123] More precisely, poly(ether ketone ketone) (PEKK) that may be used as the polymer of the first and second components of the assembly actually means a polymer containing more than 50 mol % of repeat units of the formulae (J-B1) and (J-B2), the mol % being based on the total number of moles of repeat units in the polymer: [ka] (In these formulas, 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 or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; i and j, in each occurrence, are independently selected integers ranging from 0 to 4.

[0124] According to one embodiment, R 1 and R 2 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, optionally containing one or more heteroatoms, at each position in formulas (J-B2) and (J-B1) above.

[0125] 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]

[0126] 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).

[0127] In a particular embodiment, polymer (P1) and polymer (P2) are independently selected from PEKK polymers as defined above (PEKK1, PEKK2) having a molar ratio of repeat units (J-B1) / (J'-B1) to repeat units (J-B2) / (J'-B2), also called the 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.

[0128] 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 characterized by a T / I ratio, which is different from the T / I ratio of the first PEKK polymer from that of the second PEKK polymer, particularly those compositions having a melting temperature below 330° C. 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 ratio of at most 85 / 15, preferably at most 83 / 17, more preferably at most 82 / 18.

[0129] PEKK is commercially available, inter alia, from Solvay Specialty Polymers USA, LLC as NovaSpire® PEKK, or as Cypek® FC and Cypek® DS.

[0130] In one embodiment, the polymers (P1) and / or (P2) are nucleophilic PEKK, i.e. PEKK formed by polycondensation in the absence of a Lewis acid of monomers, where the monomers are di-hydroxy and di-fluorobenzoyl-containing aromatic compounds, and / or hydroxyl-fluorobenzoyl-containing aromatic compounds.

[0131] In an alternative embodiment, the polymeric PEKK is an electrophilic PEKK.

[0132] In another embodiment, the PAEK is a poly(ether ketone) (PEK). As used herein, the terms "poly(ether ketone)" and "polymer (PEK)" refer to the repeating unit (R PEK ) are more than 50 mol % of the formula (K'-C): [ka] where mole % is based on the total moles of repeat units in PEK.

[0133] According to this embodiment, the PEK polymer is comprised of at least 60 mol%, at least 70 mol%, at least 80 mol%, at least mol%, at least 95 mol%, at least 99 mol%, or even substantially all of the repeat units (R PEK ) may be a repeat unit (K'-C). Preferred PEK polymers are those in which substantially all of the repeat units are units of the formula (K'-C), it being understood that end groups, defects, and small amounts of impurities may be present.

[0134] 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 repeat unit (R K ) are more than 50 mol % of the formula (K'-D): [ka] where mole % is based on the total moles of repeat units in PEDEK.

[0135] 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 even 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.

[0136] 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.

[0137] Additionally or alternatively, the second component of the assembly may comprise a polymer (P2) and a filler. The filler may comprise a fibrous or non-fibrous filler. The filler may comprise both fibrous and non-fibrous fillers.

[0138] 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 placed 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 placed 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).

[0139] 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.

[0140] 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.

[0141] 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.

[0142] 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 more, more typically 10 mm or more, and an aspect ratio of 500 or more, more typically 5000 or more.

[0143] In one embodiment of the invention, the first component is a composite material, also called a laminate, comprising one or more layers, these layers comprising, for example, a polymer (P1) and fibers. The polymer (P1) can, for example, be impregnated, coated or laminated onto the fibers.

[0144] 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 can for example be impregnated, coated or laminated onto the fibers.

[0145] A second object of the present invention is a method for manufacturing an assembly using the film described above, 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), T m x ≧T m (1) T m x >T m (2) T m x >T m +5 (3), or T m x >T m +10 (4), (T m is the melting temperature of the film (°C); Includes.

[0146] In other words, temperature (T m x ) is a suitable processing temperature for melting the film. m x ) is the melting temperature of the film (T m ) and preferably higher.

[0147] Temperature (T m x ) may be less than 360°C, preferably less than 350°C, and more preferably less than 340°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.

[0148] 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 mx <T m2 (6) (In the formula, T m1 and T m2 are the melting temperatures of polymer (P1) and polymer (P2), respectively).

[0149] Advantageously, the temperature (T m x ) is the melting temperature (T m1 ) and the melting temperature (T m2 ) is lower than both.

[0150] 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) It is.

[0151] In some preferred embodiments, the film and the first and second components of the assembly are heated to a temperature (T m x ), the method further comprises the step of applying pressure to the assembly to consolidate the assembly. In other words, the method preferably comprises, simultaneously with step b), applying pressure to the first and second components and subjecting the film to a temperature (T m x )

[0152] The method of the invention preferably further comprises step c) consisting of controlled cooling of the assembly. This additional step is advantageous for building crystallinity into the film. The film in the assembly preferably exhibits a crystallinity of at least 3% after cooling, preferably at least 5%, more preferably at least 15%, in particular at least 20%, the crystallinity being measured as described in the examples below.

[0153] A third aspect of the invention relates to the use of the assemblies described herein to manufacture parts or articles for use in a variety of end uses, including in the aerospace and automotive industries. For example, parts and articles that include or are constructed from the assemblies of the invention can include, but are not limited to, brackets, clips, stiffeners, and other similar types of parts.

[0154] The present invention will now be described in more detail in the following sections by way of non-limiting examples.

[0155] 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 certain terms may be unclear, the statements herein shall control. EXAMPLES

[0156] raw materials 1,2-Dichlorobenzene, terephthaloyl chloride, isophthaloyl chloride, 3,5-dichlorobenzoyl chloride, aluminum chloride (AlCl3), and methanol were purchased from Sigma Aldrich.

[0157] 1,4-Bis(4-phenoxybenzoyl)benzene was prepared according to Indian Patent No. 193687, filed on Jun. 21, 1999, and incorporated herein by reference.

[0158] Diphenylsulfone (polymer grade) was sourced from Proviron (99.8% purity).

[0159] Sodium carbonate, light soda ash, was procured from Solvay SA, France and dried before use. Its particle size is d 90 was 130 μm.

[0160] d 90 Potassium carbonate <45 μm was sourced from Armand products and dried before use.

[0161] Lithium chloride (anhydrous powder) was sourced from Acros.

[0162] NaH2PO4·2H2O and Na2HPO4 were purchased from Sigma-Aldrich.

[0163] 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. A portion of the 1,4-DFDK was purified by recrystallization in chlorobenzene as described in U.S. Patent No. 5,300,693, and a portion 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).

[0164] 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.

[0165] Boron nitride: Boronid® S1-SF, a hexagonal boron nitride grade commercially available from 3M Corporation.

[0166] Glass transition temperature (Tg), melting temperature (T m ), crystallization temperature (Tc), and heat of fusion (ΔH f ) Determination Glass transition temperature (Tg), melting temperature (T m ), crystallization temperature (Tc), and heat of fusion (ΔH f ) was determined by differential scanning calorimetry (DSC) according to ASTM D3418 using heating and cooling rates of 10° C. / min.

[0167] T g (midpoint using half-value 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.

[0168] 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 determined in the first heating scan.

[0169] 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, isothermal at 400.00°C for 1 min; It was.

[0170] Determination of Melt Flow Index 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.

[0171] 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 placed in 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 flask contents 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 over 60 minutes by a powder dispenser. 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.

[0172] 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.

[0173] PEKK#2 with T / I=58 / 42 The same procedure as in Example 1 was followed using the amounts of reagents shown in Table 1 below.

[0174] [Table 1]

[0175] [Table 2]

[0176] Solution Blending Procedure for the PEKK Composition of Example 3 A 500 mL 4-neck reaction flask equipped with stirrer, N2 inlet tube, Claisen adapter with thermocouple placed in the reaction medium, and condenser was charged with 235.00 g of diphenylsulfone (DPS) and boron nitride nucleating agent (Table 2). The contents of the flask were slowly heated to 330°C. At 330°C, PEKK polymer powders #1 (5 g) and #2 (95 g) were slowly added into the molten DPS via the 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.

[0177] 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.

[0178] [Table 3]

[0179] Thermal properties

[0180] [Table 4]

[0181] As shown by the data collected above (Table 3), the PEKK composition of Example 3 (invention) exhibits improved crystallization and degree of crystallinity compared to the PEKK compositions of Examples 1-2.

[0182] The measured fusion enthalpy ΔHf of the PEKK composition of Example 3 is higher than the minimum ΔHf calculated according to Equation 1 below, which means that the PEKK composition of Example 3 satisfies the following equation: ΔH f >1.69×T m -480 (Formula 1) (In the formula, - T m is the melting point in °C, - ΔH f is in J / g).

[0183] Thus, the PEKK composition of Example 3 according to the present invention has the following set of properties: · Melting point T m ≦310℃; Heat of fusion ΔH f >5 J / g; and ΔH that satisfies Equation 1 f ; and therefore suitable for processing into films for use in laminate structures.

[0184] As far as comparative examples go: - PEKK#1 with a T / I ratio of 71 / 29 exhibits a too high Tm of over 340°C and does not satisfy formula 1; and - PEKK#2, with a T / I ratio of 58 / 42, had a measured heat of fusion ΔH f is the minimum heat of fusion ΔH calculated by Eq. f Therefore, equation 1 is not satisfied.

[0185] Preparation of the Blend Composition of Example 4 The polymer blend composition of this example consisted of 93.8 wt% n-PEKK#2, 5.0 wt% n-PEKK#1, and 1.2 wt% boron nitride. It was prepared by melt compounding using a 26 mm Coperion® (Model ZSK-26) co-rotating partially intermeshing twin screw extruder with a L / D ratio of 48:1. The two PEKK resins in coarse powder form and the boron nitride nucleating agent in fine powder form were first tumble blended for 20 minutes to form a physical preblend. The preblend was then gravimetrically fed into the feed hopper of barrel section 1 of the extruder at a rate of 35 lbs / hr (15.9 kg / hr). The extruder had 12 barrel sections, and barrel sections 2-12, as well as the die, were heated with a temperature profile setting of 350° C. throughout. The melt temperature of the extrudate was measured with a handheld pyrometer as it exited the die. The melt temperature of the extrudate was about 385° C. throughout the entire compounding run. The screw speed was set at 200 rpm and the resulting extruder torque reading was about 55% throughout the entire production run. A vacuum vent at a vacuum level of 26 Hg was applied at barrel section 10 during compounding to remove moisture and any possible residual volatiles from the compound. The extrudate from the run was stranded and cooled in a water bath and then pelletized into pellets about 2.7 mm in diameter and 3.0 mm in length.

[0186] PEKK#3 with a T / I ratio of 60 / 40 (comparison) Into a 2000 mL 4-necked reaction flask equipped with an agitator, dry N2 inlet tube, a thermocouple placed in the reaction medium, and a condenser, 1000 g of 1,2-dichlorobenzene and 65 g of 1,4-bis(4-phenoxybenzoyl)benzene were introduced. Then, under a dry nitrogen sweep, 5.4 g of terephthaloyl chloride, 22.2 g of isophthaloyl chloride, and 0.2 g of benzoyl chloride were added to the reaction mixture. The reactor was then cooled to -5°C, and 115 g of aluminum chloride (AlCl3) was added slowly while keeping the temperature below 5°C. The reaction was held at 5°C for 10 minutes, and then the temperature of the mixture was increased to 90°C at 5°C / min. The reaction mixture was held at 90°C for 30 minutes, and then cooled to 30°C. At 30°C, 250 g of methanol was added slowly to keep the temperature below 60°C. After the addition was complete, the reaction mixture was kept under stirring for 2 hours and then cooled to 30°C. The solids were then removed by filtration on a Buchner. The wet cake was rinsed on the filter with an additional 188 g of methanol. The wet cake was then reslurried in a beaker with 440 g of methanol for 2 hours. The polymer solids were filtered again on a Buchner funnel and the wet cake was rinsed on the filter with 188 g of methanol. The solids were slurried in 470 g of aqueous hydrochloric acid (3.5 wt%) for 2 hours. The solids were then removed by filtration on a Buchner. The wet cake was rinsed on the filter with an additional 280 g of water. The wet cake was then reslurried in a beaker with 250 g of 0.5N aqueous sodium hydroxide for 2 hours. The wet cake was then reslurried in a beaker with 475 g of water and filtered on a Buchner funnel. The final water washing step was repeated three more times. The polymer was then slurried with 0.75 g of an aqueous solution containing 6.6 wt. % NaH2PO4·2H2O and 3.3 wt. % Na2HPO4, then dried in a vacuum oven at 180° C. for 12 h. The melt flow index (360° C., 8.4 kg) was 82.g / 10 min. The PEKK had the following characteristics: · MFI:33g / 10min · MFI temperature: 360℃ · Al content:>10ppm(25ppm) · F content:<100ppm.

[0187] [Table 5]

[0188] Extrusion of binder films from the compositions of Examples 4 and 5c The compounded pellets were processed into films with a nominal thickness of 140 μm and a width of 8.5-9 cm using melt extrusion in a single screw extruder. For this purpose, an OCS (Optical Control Systems, GmbH) extruder was used. The extruder had a single stage non-vented screw with a diameter of 20 mm and an L / D ratio of 30. The extruder was equipped with a 125 mm wide film die with a gap thickness of 0.5 mm. The extruder barrel had four heating sections, which operated from rear to front at set temperatures of approximately 335°C, 345°C, 345°C, and 350°C, respectively. The film die was set at a temperature of 360°C. Before extrusion into a film, the pellets were dried overnight (approximately 16 hours) in a dry air convection oven set at 150°C. The blends were extruded using a screw speed of 36 rpm and an output of approximately 5 lbs / h (2.3 kg / h). A film was cast and drawn down onto two chill rolls, the first (upper) roll and the second (lower) roll, which were set at 155° C. and 160° C., respectively.

[0189] Assembly fabrication and fracture toughness testing material APC(PEKK-FC) / AS4D available from Solvay Fiberglass fabric style 108 available from BGF Kapton® film (51 mm) available from Solvay.

[0190] procedure An assembly (also called a laminate) measuring 305 mm x 305 mm, in which the crack face layer was a PEKK film, was prepared as follows: - APC(PEKK FC) / AS4D uni-tape with nominal fiber weight=145gsm and resin content of 34wt% was cut and stacked to produce 16 plies of quasi-isotropic orientation (layup of +45° / 90° / -45° / 0°02s). - Place one ply of Style 108 Fiberglass Fabric over the layup stack to cover the entire surface. - On top of the fiberglass fabric, a 280mm x 305mm x 0.125mm PEKK film (Example 4 or 5c) was placed with three edges aligned with the edges of the layup. On the other edge was a 305mm x 25mm x 0.05mm thick release coated Kapton® film which acted as a crack starter once the panel was consolidated. - The remainder of the layup begins with a style 108 fiberglass fabric, followed by 16 plies of quasi-isotropic, reversing the order of materials.

[0191] The layup should be symmetrical in the mid-plane. The layup was then placed on a flat steel tool, vacuum bagged (710-730mmHg vacuum) and processed in a high temperature autoclave. The autoclave cycle was a linear temperature ramp up to 375°C, at which point a pressure of 6.7 bar was applied and held for 15 minutes, after which the layup was cooled under 6.7 bar pressure and 711mmHg. The pressure was released at 93°C and the panels were cooled to room temperature before being removed from the autoclave. The resulting panels were measured for thickness and then machined into 1'' x 12'' test coupons for G1c fracture toughness measurements.

[0192] [Table 6]

[0193] The data shows that using a film according to the invention (Example 4) results in similar levels of bonding as a film made from PEKK 60 / 40 (Table 5). In addition, the PEKK blend according to the invention shows higher crystallinity at the same Tm (Table 3), which is important for chemical resistance and high temperature performance.

Claims

1. a first component comprising a polymer (P1), a second component comprising a polymer (P2), a film disposed between and bonded to said first component and said second component, The film comprises a blend of at least two poly(ether ketone ketone) (PEKK) polymers (PEKK1, PEKK2), wherein the PEKK polymers have at least 50 mole % of the formulas (M) and (P), based on the total moles of the polymer: 【Chemistry 1】 In these formulae, - Each 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; Said PEKK1 and PEKK2 differ from each other in that they have different molar ratios T / I of repeating units (P) to repeating units (M); assembly.

2. Each R １ and R ２ 2. The assembly of claim 1, wherein for the group:

3. At least one of the PEKK polymers (PEKK1, PEKK2), preferably both PEKK1 and PEKK2 at least 95 mol %; or at least 99 mol %; 3. The assembly according to claim 1 or 2, wherein:

4. - the T / I molar ratio of PEKK1 is 50 / 50 to 64 / 36; and / or - the T / I molar ratio of PEKK2 is between 65 / 35 and 85 / 15; Assembly according to any one of claims 1 to 3.

5. 5. The assembly according to claim 1, wherein the weight ratio PEKK1 / PEKK2 is between 65 / 35 and 99 / 1.

6. 6. The assembly according to any one of claims 1 to 5, wherein the PEKK blend has a melting temperature Tm in the range of 270 to 340°C, preferably 280 to 330°C, measured by Differential Scanning Calorimetry (DSC) according to ASTM D3418.

7. The assembly of any one of claims 1 to 6, wherein the PEKK polymer blend 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 of the blend (° C.); ΔH ｆ is in J / g).

8. 8. The assembly of claim 1, wherein the blend has a heat of fusion ΔHf of at least 5.0 J / g.

9. 9. The assembly of claim 1, wherein the film further 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 at least one of the PEKK polymers of the film is produced in a solvent in the absence of a Lewis acid or in the presence of a Lewis acid in an amount that is less than 2 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, based on the total weight of monomers.

11. 11. An assembly according to any one of claims 1 to 10, wherein PEKK1 and PEKK2 each contain more than 100 ppm, preferably more than 200 ppm, more preferably more than 300 ppm of polymer-bound fluorine.

12. Assembly according to any one of the preceding claims, wherein the amount of Al in PEKK1 and PEKK2 is less than 50 ppm, preferably less than 25 ppm, more preferably less than 10 ppm.

13. 13. An assembly according to any one of the preceding claims, wherein PEKK1 and PEKK2 exhibit 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, heating from 30°C to 800°C under nitrogen using a heating rate of 10°C / min.

14. 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, 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; At least 10 mol % of the repeating units of the PEEK are of the formula (J″-A): 【Chemistry 3】 Repeating units (R ＰＥＥＫ wherein said mole percent is based on the total moles of repeat units in said polymer; and At least 50 mol % of the PEEK is of the formula (J′-B １ ) and (J'-B ２ ): 【Chemistry 4】 16. The assembly of claim 1, wherein the mol % refers to any polymer comprising repeat units of the formula:

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 - said film comprises at least one scrim, nonwoven or lightweight fabric; Assembly according to any one of the preceding claims.

19. A method for manufacturing an assembly according to any one of claims 1 to 18, comprising the steps of: - placing said film between a first component comprising a polymer (P1) and a second component comprising a polymer (P2); and a temperature (T) suitable for melting the film but not melting the polymers (P1) and (P2) ｍ ｘ exposing the film to A method comprising:

20. The film is heated to the temperature (T ｍ ｘ 20. The method of claim 19, wherein pressure is applied to consolidate the component while exposed to the

Images