Fiber-reinforced thermoplastic matrix composites

Abstract

Fiber-reinforced composites comprising a thermoplastic matrix containing a blend of poly(ether ketone ketone) (PEKK) polymers, methods for their manufacture and articles obtained therefrom.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 038,100, filed June 11, 2020, U.S. Provisional Patent Application No. 63 / 115,253, filed November 18, 2020, and to European Patent Application No. 20194026.9, filed September 2, 2020, the entire contents of each of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to fiber-reinforced composites comprising a thermoplastic matrix, and more particularly to fiber-reinforced composites wherein the thermoplastic matrix comprises a blend of poly(ether ketone ketone) (PEKK) polymers, particularly blends having a combination of melting temperature, crystallinity, and rate of crystallization tailored to the composite part manufacturing process and / or required performance. [Background technology]

[0003] Poly(ether ketone ketone) ("PEKK") polymers are established materials used in relatively extreme conditions. Due to their high crystallinity and high melting temperature, PEKK polymers have excellent thermal, physical, and mechanical properties. Such properties make PEKK polymers desirable in a wide range of demanding application settings, including, but not limited to, aerospace and oil and gas drilling, but also as thermoplastic matrices for composite structures.

[0004] PEEK, with a nominal terephthaloyl-to-isophthaloyl molar ratio (T / I) of approximately 70 / 30, is an established and proven matrix resin for thermoplastic continuous fiber composites. PEKK composites, such as APC (PEKK FC) / AS4D, a carbon fiber-reinforced PEKK unidirectional composite tape supplied by Solvay, are widely used to manufacture various aircraft parts using rapid manufacturing processes such as stamp molding and continuous compression molding. Their excellent mechanical and environmental performance, combined with cost-effective manufacturing processes, have made them relatively the industry standard for numerous composite parts, such as aircraft brackets, clips, stiffeners, and window frames, to name a few.

[0005] One limitation of using PEKK polymer as the polymer matrix in fiber-reinforced composites is the high melt processing temperatures (over 370°C) required to easily shape, mold, fuse, and reinforce this material. This limitation becomes more severe when the size of the part, especially on an area basis, increases substantially. An example of this would be manufacturing composite wings or fuselage skins for commercial jetliners. Today, these structures are manufactured with carbon fiber-reinforced epoxy composites using either automated tape laying (ATL) or automated fiber laying (AFP) machines. These machines deposit prepreg unidirectional composite tapes onto a tool using a designed layup, a process known as vacuum bag only (VBO), which is then bagged and cured in an autoclave or oven. The cure temperature for such materials is approximately 175°C, which is less than half the processing temperature of PEKK composites. The higher the processing temperature, the more likely there will be a temperature difference across the surface of the part. Such a difference can result in some areas being overheated and some areas not being reinforced. Additionally, the higher process temperatures of PEKK composites limit the deposition rate in AFP and ATL equipment. Adequate deposition rates are required to achieve economical rates and be cost-competitive with other materials such as carbon fiber epoxy and metal structures.

[0006] Other innovative part manufacturing approaches, such as in-situ consolidation, where thermoplastic composites are consolidated as they are fused to previous layers using specialized ATL or AFP machines, are too slow due to the large temperature gap between the fusion of the matrix while under pressure and its cooling, thus limiting the implementation of such innovative approaches, which have the potential to substantially reduce costs by eliminating the second consolidation step in an oven or autoclave. It is therefore desirable to have a lower processing temperature PEKK polymer that maintains the structural performance of PEKK composites, and which would allow more economical processing for larger composite structures.

[0007] More generally, it would be desirable to have a PEKK polymer composition that could be easily fine-tuned to provide optimization of melt temperature, crystallization level, and crystallization rate in relation to specific part manufacturing processes and / or performance requirements. Summary of the Invention

[0008] It has now been found that the thermal behavior and crystallization kinetics of PEKK polymers can be tailored by blending PEKK polymers having different T / I ratios, i.e., blending a first PEKK polymer having a first T / I ratio with a second PEKK polymer having a second T / I ratio that differs from the T / I ratio of the first PEKK polymer.

[0009] Advantageously, two PEKK polymers with different T / I ratios also have different melting temperatures and crystallization rates, which allows blends to be achieved in continuous fiber reinforced composites that have melting temperatures, crystallization levels, and crystallization rates intermediate between the two PEKK polymers. The composition of the blend can be adjusted to achieve a specific melting temperature, crystallization level, and rate to suit the application and manufacturing process.

[0010] In certain embodiments, the composite materials can be processed at lower temperatures than similar fiber-reinforced PEKK composites. The composite materials may also have high crystallization rates, allowing for rapid manufacturing processes with short cycle times. The composite materials exhibit composite mechanical performance similar to that of similar fiber-reinforced PEKK composites due to the high crystallinity level of the PEKK composition. The composite materials combine fast manufacturing cycle times with improved economics, accompanied by lower energy consumption. The high level of crystallinity in these compositions ensures robust chemical resistance in composite structures utilizing them. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention provides a composite material comprising: - Fibers and - a thermoplastic polymer matrix comprising a composition [composition (C)] comprising first and second PEKK polymers, each PEKK polymer being characterized by a T / I ratio, wherein the T / I ratio of the first PEKK polymer is different from the T / I ratio of the second PEKK polymer; The present invention provides a composite material comprising:

[0012] The present invention further provides a method for preparing the composite material of the present invention as well as moulded articles comprising it. Further objects of the present invention are the articles obtained therefrom.

[0013] Composition (C) The composite material of the present invention comprises a polymer matrix comprising a composition (C) comprising first and second PEKK polymers, each PEKK polymer characterized by a T / I ratio.

[0014] Each PEKK polymer is made up of repeating units (R T ) and repeating units (R I ) is included.

[0015] The expression "T / I ratio", (T / I) refers to the ratio of repeat units (R T ) and the molar content of repeating units (R I), where R T ) is the formula (T): [ka] and the repeating unit (R I ) is a compound of formula (I): [ka] is expressed as where: - In each formula (T) and formula (I), 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; each i and j, at each occurrence, is an integer independently selected from 0 to 4;

[0016] To avoid any misunderstanding, the repeating unit (R T ) is the molar content of

number

number

number

[0017] According to one embodiment, R 1 and R 2is a C1-C group optionally containing one or more heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups at each position in the above formulas (T) and (I). 12 The moieties are independently selected from the group consisting of:

[0018] According to another embodiment, i and j are each R 1 and R 2 In other words, the repeating unit (R T ) and (R I ) are both unsubstituted. According to this embodiment, the repeating units (R T ) and (R I ) are represented by the formulas (T') and (I'), respectively: [ka] It is expressed as:

[0019] According to another embodiment, the polymer (PEKK) comprises repeating units (R T ) and repeating units (R I ) in a total amount of at least 50 mole %, based on the total number of moles in the PEKK polymer.

[0020] Each PEKK polymer comprises a repeating unit (R T ) and repeating units (R I ), and a repeating unit (R ) containing an Ar-C(O)-Ar′ group, where Ar and Ar′ are aromatic groups, and are equal to or different from each other. PAEK The repeating unit (R PAEK ) are generally represented herein by the following formulae (JA) to (JO): [ka] [ka] [ka] (In the formula: each R', equal to or different from one another, is selected 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 zero or an integer from 0 to 4. may be selected from the group consisting of:

[0021] Repeating unit (R PAEK In the repeat unit, each phenylene moiety may independently have a 1,2-, 1,4-, or 1,3-bond to other moieties different from R'. Preferably, the phenylene moieties have a 1,3- or 1,4-bond, and more preferably, they have a 1,4-bond.

[0022] Furthermore, the repeating unit (R PAEK ), j' is zero at each occurrence, ie, the phenylene moiety does not have any substituents other than those that allow for attachment in the main chain of the polymer.

[0023] Preferred repeating units (R PAEK ) are therefore represented herein by the following formulae (J'-A) to (J'-O): [ka] [ka] The following are selected from:

[0024] The repeating units (R T ) and (R I ) and a repeating unit (R PAEK ), can be used, but generally, the preferred polymers (PEKK) are those containing the repeating units (R PAEK) is limited in amount, preferably at most 40 mol %, more preferably at most 30 mol %, more preferably at most 20 mol %, even more preferably at most 10 mol %, and even at most 5 mol %, it being understood that mol % is based on the total number of moles in the polymer.

[0025] Thus, according to some embodiments, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% or substantially all of the repeat units in the PEKK polymer are repeat units (R T ) and (R I ), where mole % is based on the total number of moles in the PEKK polymer. The phrase "substantially all," when used in reference to the constituent repeat units of a PEKK polymer, is intended to indicate that small amounts of incorrect / defective repeat units may be present, for example, in amounts less than 1 mole %, preferably less than 0.5 mole %, and more preferably less than 0.1 mole %. The repeat units (R T ) and (R I If no repeating units other than units (R ) are detected in the PEKK polymer, then the polymer is one in which all units are units (R T ) and (R I ), which is a preferred embodiment of the present invention.

[0026] Composition (C) therefore has a T / I ratio (T / I) 低 Polymer (PEKK) 低 a first PEKK polymer, hereinafter identified as (T / I) 低 <(T / I) 高 So, the T / I ratio (T / I) 高 Polymer (PEKK) 高 ) and a second PEKK polymer, identified herein below.

[0027] For the avoidance of doubt, (PEKK 低 ) and (PEKK 高) is a repeating unit (R T ) and (R I ) and optionally (R PAEK ) and (PEKK 低 )teeth,

number

number

number

[0028] Polymer (PEKK 高 )teeth,

number

number

number

[0029] Polymer (PEKK 低 ) is at least 50 / 50, preferably at least 54 / 46, more preferably at least 56 / 44; most preferably at least 57 / 43 (T / I) 低and / or (T / I) of at most 64 / 36, preferably at most 63 / 37, more preferably at most 62 / 38 低 Preferably, the (T / I) is included in 57 / 43 to 62 / 38. 低 Polymer (PEKK) 低 ) have been found to be particularly advantageous for use in the composite materials of the present invention.

[0030] Polymer (PEKK 高 ) is at least 65 / 35, preferably at least 66 / 34, more preferably at least 67 / 33 (T / I) 高 and / or (T / I) of at most 85 / 15, preferably at most 83 / 17, more preferably at most 82 / 18 高 Preferably, the (T / I) is between 67 / 33 and 72 / 28. 高 Polymer (PEKK) 高 ) have been found to be particularly advantageous for use in the composite materials of the present invention.

[0031] In one embodiment of the present invention, in composition (C), the following inequality is satisfied: T 高 -T 低 ≦20 mol% is satisfied. 低 A specific polymer (PEKK) having 低 Depending on the selection of the polymer (PEKK 高 )T 高 The choice of is consequently limited, and vice versa. Without being bound by this theory, the applicant is of the opinion that PEKK polymers, when differing in the fraction of T units by a moderate amount, are able to achieve the fundamental co-crystallization phenomenon that is ultimately responsible for the advantageous thermal properties of composition (C).

[0032] In a further embodiment, the polymer (PEKK 低 ) and polymer (PEKK 高 ) is preferably T 高 -T 低 ≦17 mol %, more preferably T 高 -T 低≦16 mol %, more preferably T 高 -T 低 ≦15 mol%. Polymer (PEKK 低 ) and polymer (PEKK 高 ) is generally expressed as T 高 -T 低 ≧3 mol %, more preferably T 高 -T 低 ≧4 mol%, and even more preferably T 高 -T 低 It is further understood that their T content may differ such that it is ≧5 mol %.

[0033] Compositions with advantageous properties include T 高 -T 低 A polymer (PEKK) having about 10 to about 13 mol % 低 ) and polymer (PEKK 高 ) is particularly well-obtained.

[0034] In one embodiment of the present invention, the polymer (PEKK 低 ) is a nucleophilic PEKK, which is a polymer (PEKK 低 ) is produced by polycondensation of di-hydroxy and di-fluorobenzoyl containing aromatic compounds and / or hydroxyl-fluorobenzoyl containing aromatic compounds.

[0035] Polymer (PEKK 高 ) is also preferably a nucleophilic PEKK, which is also a polymer (PEKK 高 ) is produced by polycondensation of di-hydroxy and di-fluorobenzoyl containing aromatic compounds and / or hydroxyl-fluorobenzoyl containing aromatic compounds.

[0036] Polymer (PEKK 低 ) and / or (PEKK 高The nucleophilicity of the polymer (PEKK) is evidenced, inter alia, by the presence of fluorine, generally in an amount greater than 100 ppm, preferably greater than 200 ppm, and even more preferably greater than 300 ppm. Such organically bound fluorine is an unavoidable fingerprint of the use of fluorine-containing monomers. 低 ) and / or (PEKK 高 Further evidence of the nucleophilicity of ) is provided by the substantial absence of Al residues, i.e., the Al content is generally less than 50 ppm, preferably less than 25 ppm, more preferably less than 10 ppm. The Al and F contents are conveniently measured by elemental analysis, such as ICP-OES analysis for Al and combustion-ion chromatography for fluorine.

[0037] If it is nucleophilic, the polymer (PEKK 低 ) and / or (PEKK 高 ) are also characterized by a low volatile matter content. The amount of volatile matter can be measured using thermogravimetric analysis (TGA) according to the ASTM D3850 method; the temperature, Td, at which a measured amount of volatile matter (e.g., 1% or 2% by weight) leaves the sample is measured by gradually heating the sample from 30°C to 800°C under nitrogen using a heating rate of 10°C / min. The thermal decomposition temperature at 1% by weight is referred to as Td(1%). In one embodiment of the present invention, the polymer (PEKK 低 ) and / or (PEKK 高 ) has a Td(1%) of at least 500°C, preferably at least 505°C, and more preferably at least 510°C, as measured by thermogravimetric analysis according to ASTM D3850, heating from 30°C to 800°C under nitrogen using a heating rate of 10°C / min.

[0038] The advantageous combination of low melting temperature, high crystallinity and low (fast) crystallization rate is achieved by at least one polymer (PEKK 低 ) is a nucleophilic PEKK, which has, inter alia, the above-mentioned advantageous characteristics (F content, Al content, Td (1%)). Preferably, both polymers (PEKK 低 ) and polymer (PEKK高 ) is a nucleophilic PEKK and therefore also polymer (PEKK 高 ) is a polymer (PEKK 低 ) and has the advantageous characteristics (F content, Al content, Td (1%)) described above in relation to

[0039] Without being bound by this theory, the applicant is of the opinion that the unique microstructure of PEKK polymers achieved by the nucleophilic synthetic route, including in particular the absence of "regioselectivity" errors and / or branching phenomena that, although rare, may nevertheless occur in the electrophilic synthetic route, is likely to enable the achievement of a unique and advantageous thermal behavior suitable for the manufacture of composite materials.

[0040] The composition (C) is (PEKK 低 ) and (PEKK 高 ) in any relative proportions.

[0041] Advantageously, composition (C) contains a large amount of polymer (PEKK 低 ) and a small amount of polymer (PEKK 高 The expressions "major amount" and "minor amount" have their commonly understood meaning, i.e., polymer (PEKK 低 The amount of polymer (PEKK 高 ) exceeds the amount of

[0042] Generally, the polymer (PEKK) in the composition (C) 低 ) and polymer (PEKK 高 ) is advantageously of at least 60 / 40, preferably of at least 65 / 35, more preferably of at least 70 / 30, even more preferably of at least 75 / 25, and / or it is of at most 99 / 1, preferably of at most 97 / 3, even more preferably of at most 96 / 4.

[0043] Composition (C) has the same melting temperature (T in °C) as measured in the second DSC heating scan. m) crystallization temperature (T in °C) measured in the second DSC heating scan that is higher than the crystallization temperature of the PEKK polymer c ) is advantageously characterized by T m and T c is measured by differential scanning calorimetry (DSC) as detailed herein below.

[0044] Additionally or alternatively, composition (C) may comprise - Melting temperature (T m ); - a heat of fusion (ΔHf) greater than 25 J / g; and - No crystallization peak ("cold crystallization peak") upon heating in the second DSC heating scan Shows.

[0045] Additionally or alternatively, composition (C) may be a compound having the following inequality: T c ≧1.3716×T m -190℃ The melting temperature (T in °C) measured in the second DSC heating scan satisfies m ) and the crystallization temperature (T in °C) measured in the first DSC cooling scan. c ) indicates the relationship between

[0046] T m , T c , ΔHf and the absence of a cold crystallization peak are measured by differential scanning calorimetry (DSC) according to ASTM D3418-03, E1356-03, E793-06, E794-06 standards, applying a heating and cooling rate of 20°C / min in a sweep from 300°C to 400°C.

[0047] As far as determining the presence / absence of a cold crystallization peak is concerned, if no exothermic peak above 0.5 J / g preceding the melting onset temperature is detected by DSC in the second heating scan, this is understood to represent the absence of a cold crystallization peak. Generally, for compositions of the present invention, substantially no exothermic peak is detected by DSC in the second heating scan, meaning that no detectable release of energy is observed within the sensitivity limits of the instrument.

[0048] Typically, the molecular weight of composition (C) is in the range of 60 to 120 g / 10 min. m at a temperature of +30 or +40° C. and under a piston load of 8.4 kg, as defined in the examples, will be suitable to obtain an MFI, measured according to ASTM D1238.

[0049] According to certain embodiments, the polymer (PEKK) based on the total weight of the composition (C) 低 ) and polymer (PEKK 高 ) is advantageously greater than or equal to 60% by weight, preferably greater than or equal to 70% by weight; more preferably greater than or equal to 80% by weight, more preferably greater than or equal to 85% by weight, most preferably greater than or equal to 90% by weight.

[0050] According to certain embodiments, composition (C) comprises a polymer (PEKK 低 ) and polymer (PEKK 高 ) and does not include any other polyaryletherketone polymers [polymer (PAEK)]. In other words, composition (C) according to these embodiments generally does not include repeating units (R*) of which more than 50 mol % contain Ar*C(O)Ar*' groups (equal or different, Ar* and Ar*' are aromatic groups). PAEK ), a polymer (PEKK) containing a repeating unit 低 ) or polymer (PEKK 高 The polymer (PAEK) is substantially free of any polymer that is not a repeating unit (R* PAEK ) is an optional repeating unit (R PAEK) has the same characteristics as those already described above in relation to

[0051] According to certain embodiments, composition (C) 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 and other forms of carbon.

[0052] In one advantageous embodiment, the nucleating agent is selected from the group of nitrides (NI) of elements having an electronegativity (ε) of 1.3 to 2.5, the electronegativity values ​​(ε) being listed, inter alia, in the "Handbook of Chemistry and Physics", CRC Press, 64th edition, pages B-65 to B-158.

[0053] In the context of the present invention, the expression "at least one nitride (NI)" is intended to mean one or more nitrides (NI). Mixtures of nitrides (NI) can be used advantageously for the purposes of the present invention.

[0054] Non-limiting examples of nitrides (NI) of elements having an electronegativity (ε) between 1.3 and 2.5 are listed, inter alia, in the "Handbook of Chemistry and Physics," CRC Press, 64th edition, pages B-65 to B-158. The code in brackets is the code ascribed to the nitride by the CRC Handbook, while ε refers to the electronegativity of the element from which the nitride is derived. Thus, nitrides of elements (NI) having an electronegativity (ε) of 1.3 to 2.5 suitable for the purposes of the present invention are, inter alia, aluminum nitride (AlN, a45, ε=1.5), antimony nitride (SbN, a271, ε=1.9), beryllium nitride (Be3N2, b123, ε=1.5), boron nitride (BN, b203, ε=2.0), chromium nitride (CrN, c406, ε=1.6), copper nitride (Cu3N, c615, ε=1.9), gallium nitride (GaN, g41, ε=1.6), trigermanium dinitride (Ge3N2, g82, ε=1.8), trigermanium tetranitride (Ge3N4, g83, ε=1.8), hafnium nitride. Iron nitrides such as ammonium nitride (HfN, h7, ε=1.3), iron nitrides such as FeN (i151, ε=1.8) and FeN or FeN2 (i152, ε=1.8), mercury nitride (Hg3N2, m221, ε=1.9), niobium nitride (n109, ε=1.6), silicon nitride (Si3N4, s109, ε=1.8), tantalum nitride (TaN, t7, ε=1.5), titanium nitride (Ti3N4, t249, ε=1.5), tungsten dinitride (WN2, t278, ε=1.7), vanadium nitride (VN, v15, ε=1.6), zinc nitride (Zn3N2, z50, ε=1.6), and zirconium nitride (ZrN, z105, ε=1.4).

[0055] Preferred nitrides (NI) for use in the compositions of the present invention are nitrides of elements having an electronegativity of preferably at least 1.6, more preferably at least 1.8 and / or preferably at most 2.2.

[0056] Moreover, the nitride (NI) is preferably selected from the nitrides of elements selected from groups IIIa, IVa, IVb, Va, Vb, VIa, VIb, VIIb and VIII of the periodic table of the elements, more preferably from the nitrides of elements of group IIIa of the periodic table of the elements.

[0057] Particularly good results have been obtained when the nitride (NI) is boron nitride, which is the preferred nitride (NI).

[0058] Of the different crystalline forms of boron nitride, hexagonal boron nitride is preferably used in the composition according to this embodiment.

[0059] Generally, the average particle size of the nucleating agent, in particular of the nitride (NI), is advantageously 30 μm or less, preferably 20 μm or less, more preferably 18 μm or less, more preferably 10 μm or less, and / or preferably 0.05 μm or more, 0.1 μm or more, more preferably 0.2 μm or more, 1 μm or more.

[0060] The average particle size of the nucleating agent, particularly the nitride (NI), is preferably 1 μm to 20 μm, more preferably 2 μm to 18 μm, and more preferably 2 μm to 10 μm.

[0061] An average particle size of the nucleating agent, especially of the nitride (NI), of about 2.5 μm has given particularly good results, and in particular boron nitride with such an average particle size has proven to be particularly effective.

[0062] The average particle size of the nucleating agent can be measured, for example, by light scattering techniques (dynamic or laser) using the respective equipment (Mastersizer Micro or 3000) from the company Malvern or by means of sieve analysis according to DIN 53196.

[0063] If used, the total weight of nucleating agents, in particular nitrides (NI), in composition (C) is advantageously at least about 0.1 wt.-%, generally at least about 0.2 wt.-%, preferably at least about 0.3 wt.-%, more preferably at least about 0.5 wt.-%, and / or at most about 10 wt.-%, preferably at most about 8 wt.-%, more preferably at most about 5 wt.-%, and even more preferably at most about 3 wt.-%, based on the total weight of composition (C).

[0064] In some embodiments, composition (C) comprises at least one additive other than a nucleating agent, including, but not limited to, (i) colorants such as dyes, (ii) pigments such as titanium dioxide, zinc sulfide, and zinc oxide, (iii) light stabilizers, e.g., UV stabilizers, (iv) heat stabilizers, (v) antioxidants such as organic phosphites and phosphonites, (vi) acid scavengers, (vii) processing aids, (viii) nucleating agents, (ix) internal 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) extenders, (xvi) metal deactivators, and (xvii) flow aids such as silica.

[0065] If additional optional ingredients are present in composition (C), the total weight of the optional ingredients, based on the total weight of composition (C), is advantageously at least 0.1 wt.%, preferably at least 0.5 wt.%, more preferably at least 1 wt.%, even more preferably at least 2 wt.%, and / or less than 30 wt.%, preferably less than 20 wt.%, more preferably less than 10 wt.%, even more preferably less than 5 wt.%, based on the total weight of composition (C).

[0066] According to certain embodiments, composition (C) comprises a polymer (PEKK), as described above. 低 ) and polymer (PEKK 高For the purposes of the present invention, the expression "consisting essentially of" should be understood to mean that any additional components other than those listed are present in an amount of at most 1% by weight, preferably at most 0.5% by weight, based on the total weight of composition (C), so as not to substantially alter the properties of the composition.

[0067] According to another embodiment, the composition (C) comprises a polymer (PEKK 低 ), polymer (PEKK 高 ), and nitride (NI), as described above.

[0068] According to yet another embodiment, the composition (C) comprises a polymer (PEKK 低 ), polymer (PEKK 高 ), and one or more additional ingredients other than nitrides (NI), as listed above. According to these embodiments, composition (C) may include nitrides (NI), as described above.

[0069] Method for producing a thermoplastic polymer matrix The thermoplastic polymer matrix comprises composition (C). The thermoplastic polymer matrix consists essentially of composition (C), preferably consists of composition (C).

[0070] The polymer matrix is ​​a polymer (PEKK 低 ), polymer (PEKK 高 The polymer matrix may be prepared by a variety of methods, including intimate mixing of a polymer (PEKK), optionally with a nucleating agent, such as, for example, nitride (NI), and / or any optional additional ingredients, as detailed above, as desired in the formulation. For example, dry (or powder) blending, suspension or slurry blending, solution blending, melt blending, or any combination thereof may be used. As used herein, "other components" of the polymer matrix may optionally include a polymer (PEKK), such as a nucleating agent or any of the additional optional ingredients listed above. 低) and polymer (PEKK 高 ) plus any other components desired in the polymer matrix.

[0071] The polymer matrix is ​​a polymer (PEKK) optionally in combination with other components in a medium that is liquid at the temperature of solubilization. 低 ) and polymer (PEKK 高 In practice, such solubilization can be achieved by dissolving a polymer (PEKK) in a liquid medium that may advantageously contain at least one of diphenylsulfone, benzophenone, 4-chlorophenol, 2-chlorophenol, and meta-cresol. 低 ) and polymer (PEKK 高 This can be achieved by heating the polymer (PEKK 低 ) and polymer (PEKK 高 A suitable liquid medium for effectively solubilizing the polymer (PEKK) is diphenyl sulfone (DPS), which is liquid above 123°C, or a blend of organic solvents containing a large amount of DPS. When DPS is used, mixing is achieved by heating to a temperature of at least 250°C, preferably at least 275°C, more preferably at least 300°C. Good results have been obtained with polymers (PEKK 低 ) and polymer (PEKK 高 ) was solubilized in DPS at a temperature of about 330°C.

[0072] The polymer matrix can be recovered from the liquid medium by standard techniques, such as liquid / solid separation, crystallization, extraction, and the like.

[0073] When DPS is used, the solubilized polymer (PEKK) in the liquid DPS 低 ) and polymer (PEKK 高 ) is cooled below the melting temperature of DPS to obtain a solid, which, optionally after grinding, is extracted with a mixture of acetone and water, optionally rinsed with an aqueous medium, and finally dried.

[0074] Alternatively, the polymer matrix can be produced by, for example, melt blending or a combination of powder blending and melt blending. Powder blending can be performed by blending polymers (PEKK, 低 ) and polymer (PEKK 高 ) and optionally other components are provided in powder form. Typically, the polymer (PEKK) as detailed above is used. 低 ) and polymer (PEKK 高 Powder blending of ) can be carried out by using high intensity mixers such as Henschel type mixers and ribbon mixers, among others.

[0075] Polymer (PEKK 低 ) and polymer (PEKK 高 The compositions of the present invention can also be prepared by melt compounding the powder mixture as described above with the hydroxypropyl methylcellulose copolymer (H2O3) and, optionally, other components, and / or by further melt compounding the powder mixture as described above. Conventional melt compounding devices 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, more preferably twin-screw extruders, can be used.

[0076] If necessary, the design of the compounding screw, such as flight pitch and width, clearance, length, and operating conditions, will be advantageously selected to provide sufficient thermal and mechanical energy to advantageously completely melt the powder mixture or raw materials as detailed above and advantageously obtain a homogeneous distribution of the different raw materials. Provided that optimal mixing is achieved between the bulk polymer and the filler content, it is advantageously possible to obtain strand extrudates of the polymer matrix. After some cooling time on a conveyor using a water spray, such strand extrudates can be chopped, for example, using a rotary cutting blade, to provide the polymer matrix in the form of pellets or beads. The polymer matrix pellets or beads can then be further used for the production of parts or composites, or can be ground to provide the polymer matrix in powder form for powder production techniques.

[0077] fiber As used herein, the term "fiber" has its ordinary meaning as known to those skilled in the art and may include one or more fibrous materials suitable for reinforcement of composite structures, i.e., "reinforcing fibers." The term "fiber" is used herein to refer to fibers having a length of at least 0.5 mm.

[0078] The fibers may be organic fibers, inorganic fibers, or mixtures thereof. Fibers suitable for use as the reinforcing fiber component 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, synthetic polymer fibers such as polyester fibers, polybenzoxazole fibers such as poly-p-phenylene-benzobisoxazole (PBO) fibers, 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.

[0079] In some embodiments, the composite materials of the present invention comprise continuous fibers. As referred to herein, "continuous fibers" refers to fibers having a length of 3 millimeters ("mm") or greater, more typically 10 mm or greater, and an aspect ratio of 500 or greater, more typically 5000 or greater. As referred to herein, "aligned fibers" means that the majority of the fibers are substantially aligned parallel to one another. For example, in some embodiments, fibers are aligned if, at any one location along at least about 75% of their length (preferably at least about 80% of their length, or even 85% of their length), the alignment of each fiber in a group does not deviate more than about 25 degrees from parallel to immediately adjacent fibers (preferably, not more than about 20 degrees, or even 15 degrees).

[0080] In one embodiment, the fibers include carbon fibers, glass fibers, or both carbon fibers and glass fibers.

[0081] In some embodiments, the fibers comprise at least one carbon fiber. As used herein, the term "carbon fiber" is intended to include graphitized, partially graphitized, and non-graphitized carbon reinforcement fibers, as well as mixtures thereof. Carbon fibers can be obtained by heat treatment and pyrolysis of different polymer precursors, such as rayon, polyacrylonitrile (PAN), aromatic polyamides, or phenolic resins; carbon fibers can also be obtained from pitch-based materials. The term "graphite fiber" is intended to mean carbon fibers obtained by high-temperature pyrolysis (above 2000°C) of carbon fibers, in which the carbon atoms are arranged similarly to the graphite structure. The carbon fiber is preferably selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, graphite fibers, and mixtures thereof.

[0082] End uses requiring high strength composite structures often dictate the use of fibers having a high tensile strength (e.g., ≥ 3500 megapascals or "MPa") and / or a high tensile modulus (e.g., ≥ 200 gigapascals or "GPa"). In one embodiment, therefore, the fibers comprise continuous carbon fibers, such as carbon fibers exhibiting a tensile strength of ≥ 3500 MPa and a tensile modulus of ≥ 200 GPa. In one embodiment, the reinforcing fibers comprise continuous carbon fibers having a tensile strength of ≥ 5000 MPa and a tensile modulus of ≥ 250 GPa. In such embodiments, the carbon fibers are preferably aligned, continuous carbon fibers exhibiting a tensile strength of ≥ 3500 MPa and a tensile modulus of ≥ 200 GPa.

[0083] The carbon fibers may be sized or unsized. In one embodiment, the carbon fibers are sized carbon fibers. Suitable sizes for the carbon fibers are those that are thermally compatible with the expected processing temperatures and may be selected, for example, from polyamideimide, polyetherimide, and polyimide polymers, each of which may optionally include additives, such as nucleating agents, to improve the interfacial properties of the fibers.

[0084] In some embodiments, the reinforcing fibers include at least one glass fiber. The glass fibers may have a circular or non-circular cross section (such as an elliptical or rectangular cross section). If the glass fibers used have a circular cross section, they preferably 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 made. Mention may be made, inter alia, of glass fibers made from E-glass or S-glass.

[0085] In some embodiments, the glass fibers are standard E-glass material with a non-circular cross section. In some embodiments, the polymer composition comprises S-glass fibers with a circular cross section.

[0086] Fibers suitable for producing the composite materials of the present invention can be included in the composite material in many different forms or configurations, depending on the target composite application. For example, reinforcing fibers can be provided in the form of continuous fibers, sheets, plies, and combinations thereof. Continuous fibers can also adopt any of the following configurations: unidirectional, multidimensional, nonwoven, woven, knitted, non-crimped, web, stitch, spiral, and braided configurations, as well as swirl mat, felt mat, and chopped mat structures. Fiber tows can be held in place in such configurations by a small amount of resin, such as a cross-tow stitch, a weft-insertion knit stitch, or sizing. Fibers can also be included as one or more plies throughout all or part of the composite material, or in the form of pad-ups or ply drops, with localized increases / decreases in thickness. The area weight of a single layer or cross section of such fibers can be, for example, from 50 to 600 g / m². 2 It can vary up to.

[0087] In some embodiments, continuous fibers suitable for use in connection with the composites of the present invention may be in the form of a roving or tow (e.g., individual tows or rovings, tow / roving bundles, or spread tows). A roving generally refers to a plurality of continuous, untwisted filaments of fiber, e.g., glass fiber, optionally reinforced with a chemical bonding material. Similarly, a tow generally refers to a plurality of continuous, individual filaments, e.g., carbon filaments, optionally with an organic coating. While the size of a roving or tow used herein is not particularly limited, exemplary tows can include, for example, aerospace-grade tow sizes, typically ranging from 1K to 24K, and commercial-grade tows, typically ranging from 48K to 320K. The tows can be bundled or spread (e.g., untwed) depending on the end-use requirements. For example, the use of spread tows can reduce the thickness of the tow as well as the occurrence of gaps between individual tows in the composite. This can result in a lighter weight composite laminate while potentially achieving the same or better performance.

[0088] In some embodiments, the fibers may be discontinuous, e.g., aligned discontinuous fibers. Such discontinuous tows may have random lengths (e.g., created by random breakage of individual filaments) or roughly uniform lengths (e.g., created by cutting or separation of individual filaments). The use of discontinuous fibers allows individual fibers to shift position relative to adjacent fibers, thus affecting the flexibility of the material and potentially aiding in the forming, draping, and stretching of the fiber.

[0089] In some embodiments, fibers suitable for use in connection with the composite materials of the present invention may be in the form of unidirectional tapes. As used herein, "tape" means a strip of material with longitudinally extending fibers aligned along a single axis of the strip material. Tapes are advantageous because they can be used in hand or automated layup processes to create composite materials with relatively complex shapes. In one embodiment, the composite material comprises unidirectional continuous fiber reinforcement tapes.

[0090] In some embodiments, fibers suitable for use in connection with the composite materials of the present invention may be in the form of a nonwoven fabric, such as a mat. A nonwoven fabric comprises fibers (continuous or discontinuous) in a randomly oriented arrangement. Because the fibers are randomly oriented, the nonwoven fabric is generally isotropic, having substantially equal strength in all directions.

[0091] In yet other embodiments, fibers suitable for use in connection with the composites of the present invention may be in the form of woven fabrics, typically woven on looms in various weights, weaves, and widths. Woven fabrics are generally bidirectional, providing good strength in the direction of the fiber axis orientation (0° / 90°). While woven fabrics can facilitate fast composite manufacturing, tensile strength may not be as high as, for example, nonwoven fabrics due to fiber crimping during the weaving process. In some embodiments, the woven fabric is in the form of a woven roving, in which continuous fiber rovings are woven into the fabric. Such woven rovings are thick and therefore can be used for powerful reinforcement in hand layup operations and tooling applications. Optionally, such woven rovings can contain fine fiberglass and therefore can be used for applications such as printed circuit board reinforcement. Hybrid fabrics can also be constructed using a variety of fiber types, strand compositions, and fabric types.

[0092] In some embodiments, fibers suitable for use in connection with the composites of the present invention may be in the form of a braided fabric. Braided fabrics are generally obtained by interweaving three or more fibers (e.g., in the form of tows or rovings) so that they cross each other and are laid together in a diagonal formation to form a narrow strip of flat or tubular fabric. Braided fabrics are generally woven continuously at an angle and have at least one axial yarn that is not crimped during the knitting process. Intertwining the fibers without twist typically results in a greater strength-to-weight ratio than found in woven fabrics. Braided fabrics, which can easily conform to various shapes, can be manufactured in a sleeve-type format or in flat fabric form. Flat braided fabrics can be manufactured in a triaxial architecture, in which the fibers are oriented at 0°, +60°, and -60° within a single layer, which can eliminate problems associated with the construction of multiple 0°, +45°, -45°, and 90° fabrics, including delamination. Because the fibers in a braided structure are interlocked and therefore participate in the loading event, the load is evenly distributed throughout the structure. Therefore, braided fabrics can absorb large amounts of energy and exhibit very good impact resistance, damage resistance, and fatigue performance.

[0093] In some embodiments, the composite materials of the present invention are provided in the form of substantially two-dimensional materials, e.g., materials having one dimension (thickness or height) significantly smaller than the other two dimensions (width and length), such as sheets and tapes. In certain preferred embodiments, the composite materials of the present invention are - plies of impregnated fabrics, including but not limited to nonwoven, multiaxial, woven or braided fabrics such as mats; and - unidirectional (continuous or discontinuous) fiber reinforced tapes or prepregs, preferably with aligned fibers is selected from the group consisting of:

[0094] According to certain embodiments, the fibers are provided as a preform. A preform is produced by stacking and shaping one or more layers of said form into a predetermined three-dimensional configuration. Preforms can be particularly desirable because complex part shapes can be closely approximated by careful selection of layers.

[0095] composite material As used herein, the term "composite material" generally refers to an assembly of fibers and a polymeric matrix material that is either impregnated, coated, or laminated onto the fibers as described above. The composite material of the present invention comprises a polymeric matrix that comprises composition (C).

[0096] In some aspects, the composite materials of the present invention exhibit a superior combination of thermal and crystallization properties, for example, compared to composites containing known PEKK polymers. In some embodiments, the composite materials of the present invention: - a composition (C) having a melting temperature of 330°C or less, preferably between 295°C and 328°C, and - exhibit at least one mechanical property (e.g. open pore compressive strength, in-plane shear modulus) with a value of at least 90%, or even at least 95%, of the corresponding mechanical property of a composite of the same morphology but comprising PEKK.

[0097] As used herein, "composite materials of the same form" refers to composite materials that have the same type of fibers (e.g., carbon fibers, glass fibers, etc.) in the same format (e.g., unidirectional, woven, nonwoven, etc.) and that differ only in their polymer matrices.

[0098] In some embodiments, the composite material of the present invention comprises a composition (C) having a melting temperature of 330°C or less, preferably 295°C to 328°C; an open-hole compressive strength of 320 MPa or more, even more preferably typically 322 MPa or more, as measured in accordance with ASTM D6484; - An in-plane shear modulus of greater than or equal to 4.7 GPa, more typically greater than or equal to 4.8 GPa, as measured in accordance with ASTM D3518 At least one of the following is shown.

[0099] In such an embodiment, the composite material may be, for example, a unidirectional tape comprising intermediate modulus carbon fibers and composition (C) as defined herein.

[0100] For example, in one embodiment, composition (C) has a melting temperature of 330°C or less, more typically 295°C to 328°C, and the composite exhibits an in-plane shear modulus of 4.7 GPa or more, more typically 4.8 GPa or more, as measured according to ASTM D3518. In such an embodiment, the composite can be, for example, a unidirectional tape comprising intermediate modulus carbon fiber and composition (C) as defined herein.

[0101] For example, in one embodiment, composition (C) has a melting temperature of 330°C or less, more typically 295°C to 328°C, and the composite exhibits an open-hole compressive strength of 320 MPa or more, even more typically 322 MPa or more, as measured according to ASTM D6484. In such an embodiment, the composite can be, for example, a unidirectional tape comprising intermediate modulus carbon fiber and composition (C) as defined herein.

[0102] The composite material of the present invention preferably contains 20 to 80% by weight of fibers and 80 to 20% by weight of a polymer matrix containing composition (C), based on the weight of the composite material.

[0103] In one embodiment, the composite material comprises 30 to 80, e.g., 50 to 80, more typically 55 to 75 wt. % continuous carbon fibers and 20 to 70, more typically 25 to 45 wt. % polymer matrix comprising composition (C). In one embodiment of the composite material, the fibers are continuous carbon fibers substantially aligned along a single axis, and the composite material is in the form of a unidirectional carbon fiber reinforced resin matrix tape comprising 50 to 80 wt. % carbon fibers and 20 to 50 wt. % polymer matrix comprising composition (C). In one embodiment of the composite material, the continuous carbon fibers are in the form of a woven or nonwoven fabric, and the composite material comprises 45 to 70 wt. % continuous carbon fibers and 30 to 55 wt. % polymer matrix comprising composition (C).

[0104] In one embodiment, the composite material comprises 30 to 80, more typically 50 to 75 wt. % continuous glass fibers and 20 to 70, more typically 25 to 45 wt. % composition (C). In one composite embodiment, the fibers are continuous glass fibers substantially aligned along a single axis, and the composite material is in the form of a unidirectional glass fiber reinforced resin matrix tape comprising 65 to 80 wt. % glass fibers and 20 to 35 wt. % polymer matrix comprising composition (C). In one composite embodiment, the continuous fibers are glass fibers in the form of a woven or non-woven glass cloth, and the composite material comprises 50 to 70 wt. % glass fibers and 30 to 50 wt. % polymer matrix comprising composition (C).

[0105] In one embodiment, the composite has a fiber areal weight of 50 to 400 grams per square meter. For unidirectional tapes, the composite has a typical fiber areal weight of 130 to 200 grams per square meter. For fabrics, the composite has a typical fiber areal weight of 170 to 400 grams per square meter.

[0106] The composite material of the present invention may be a single layer material consisting of fibers and a polymer matrix containing composition (C).

[0107] A composite material may alternatively include one or more layers.

[0108] A further object of the present invention is therefore a multilayer composite assembly comprising a first layer of composite material, the composite material consisting of fibers and a polymer matrix comprising composition (C), and at least one layer comprising a thermoplastic polymer composition [composition (TP)] in contact with at least one surface of the composite material.

[0109] Composition (TP) is generally selected to have a lower melting point and processing temperature than the polymer matrix comprising composition (C). In certain embodiments, the melting and / or processing temperature of composition (TP) is 10°C to 20°C lower than the melting and / or processing temperature of the high performance polymer. Composition (TP) does not include fibers.

[0110] Composition (TP) may suitably comprise a polymer chosen from polyaryletherketones (PAEKs), polyetherimides (PEIs), polyimides, PAEK copolymers with PEI and / or polyarylethersulfones (PAESs) and / or polyphenylene sulfide (PPS), and PAEK blends with one or more of PEI, PAES, PPS and / or polyimides.

[0111] Composite material manufacturing method To form plies, e.g., in the form of sheets or tapes, of fibers at least partially impregnated with a polymer matrix, various methods can be used to impregnate fibers with a polymer matrix comprising composition (C), where the matrix is ​​either in molten or particulate form, such as, for example, powder coating, film lamination, extrusion, pultrusion, aqueous slurry, and melt impregnation.

[0112] In one embodiment, the composite material comprises a unidirectional continuous fiber reinforcement tape produced by a melt impregnation process. Melt impregnation generally involves pulling a plurality of continuous filaments through a molten precursor composition comprising a polymer matrix. The precursor composition may further comprise specific components, such as plasticizers and processing aids, to facilitate impregnation. Melt impregnation processes include the direct melt process and the aromatic polymer composite ("APC") process, as described, for example, in EP 102158.

[0113] In one embodiment, the composite material includes unidirectional continuous fiber reinforcement tape produced by a slurry process. An exemplary slurry process can be found, for example, in U.S. Patent No. 4,792,481 (O'Connor et al.).

[0114] In one embodiment, the composite material comprises either a unidirectional continuous fiber reinforcement tape or a woven / nonwoven fiber reinforcement (e.g., fabric) produced by a film lamination process using either a series of heated and cooled rolls or a double belt press. Film lamination generally involves placing at least one layer of fibrous material on or between at least one layer of polymer matrix (e.g., a polymer matrix film) to form a layered structure, and passing the layered structure through a series of heated and cooled rolls or a double belt press.

[0115] In one embodiment, the composite material comprises either a unidirectional continuous fiber reinforcement tape or a woven / non-woven fiber reinforcement (e.g., fabric) produced by a dry powder coating / fusing process in which a dry powder is uniformly deposited onto fibers or a fiber web (e.g., fabric) and then heat is applied to fuse the powder to the fibers or fiber web (e.g., fabric).

[0116] The composite materials of the present invention may be in the form of plies of matrix-impregnated fibers. Multiple plies may be placed adjacent to one another to form an unreinforced composite laminate, such as a prepreg. The fiber-reinforced layers of the laminate may be arranged with their respective fiber reinforcements in a selected orientation relative to one another.

[0117] Composite materials may be manufactured by depositing or "laying up" layers of composite material onto a mold, mandrel, tool, or other surface, a process that is repeated several times to build up the layers of the final composite laminate.

[0118] The plies can be laid up manually or automatically, for example, by automated tape layup using "pick and place" robotics, or by advanced fiber placement, in which tows of pre-impregnated fibers are heated and compressed in a mold or on a mandrel, to form a composite laminate with the desired physical dimensions and fiber orientation.

[0119] The layers of an unreinforced laminate are typically not completely fused together, and an unreinforced composite laminate may exhibit a large void content, e.g., greater than 20% by volume, as measured by X-ray microtomography. For example, as an intermediate step to allow handling of the composite laminate prior to its consolidation, heat and / or pressure may be applied or sonic vibration welding may be used to stabilize the laminate and prevent the layers from moving relative to one another to form a composite "blank."

[0120] The composite laminate so formed is then consolidated, typically by subjecting the composite laminate to heat and pressure, for example, in a mold, to form a shaped fiber-reinforced thermoplastic matrix composite article. If desired, a tie layer made of composition (C) can be used for the adhesive layer of the untoughened laminate. Such a tie layer can be provided as a free-standing film made of composition (C) or can be provided in the form of a coating coated onto at least one surface of the layers of the untoughened composite laminate to be assembled and consolidated.

[0121] As used herein, "consolidation" refers to a process in which the matrix material is softened, the layers of the composite laminate are pressed together, air, moisture, solvents, and other volatile materials are forced out of the laminate, and adjacent plies of the composite laminate are fused together to form a solid, cohesive article. Ideally, reinforced composite articles exhibit minimal void content, e.g., less than 5% by volume, more typically less than 2% by volume, as measured by X-ray microtomography.

[0122] In one embodiment, the composite material is consolidated in a vacuum bag process in an autoclave or oven. In one embodiment, the composite material is consolidated in a vacuum bag process under a vacuum of greater than 600 mmHg by heating to a consolidation temperature of greater than 320°C, more typically 330-360°C, and once the consolidation temperature is reached, pressure, typically 0-20 bar, is applied for a time period typically between 1 minute and 240 minutes, followed by cooling. The total cycle time, including heating, compacting, and cooling, is typically within 8 hours or less, depending on the size of the part and the capacity of the autoclave.

[0123] In one embodiment, the composite is laid up by an automated lay-up machine (ATL, AFP, or filament wind) equipped with a heating device to simultaneously melt and fuse the layers to the pre-laid layers as they are laid and oriented to form a low-void, reinforced laminate (less than 2% voids by volume). This low-void, reinforced laminate can be used "as is" or can subsequently be annealed, typically in either a free-standing or vacuum-bagged run, at temperatures ranging from 170°C to 270°C for times ranging from 1 minute to 240 minutes.

[0124] In one embodiment, a ply of fully impregnated composite prepreg material is laid up by an automated lay-up machine equipped with a heating device to simultaneously melt and fuse the ply to the previous ply as it is laid and oriented onto the previous ply to form a preform with a void content of greater than 2%. The preform is then subsequently consolidated in either a "vacuum bag process," a compression mold, a stamp form, or a continuous compression molding process as previously described.

[0125] In one embodiment, the fully impregnated composite prepreg material plies are pre-oriented and consolidated in a heated and cooled press, a double belt press, or a continuous compression molding machine to produce a reinforced laminate that can be cut to size for use as a molded blank in a stamp molding process, where the tool temperature is between 10°C and 270°C and the molded blank is rapidly heated to a melt processing temperature of between 320°C and 360°C before shaping and consolidating the molten blank in the tool. The resulting part can be used "as is" or in a subsequent process where the molded part is placed in an injection molding tool to rapidly heat the laminate to an intermediate temperature and inject a higher melt processing temperature PEAK polymer, such as PEAK, either neat or filled, to produce a complex shaped hybrid part.

[0126] The composite materials of the present invention may be used in any end-use application in which composites are advantageously used or proposed to be used. Typical applications include composites and laminates (such as two-dimensional and three-dimensional panels and sheets) for aerospace / aircraft, automobiles and other vehicles, boats, machinery, heavy equipment, storage tanks, pipes, sporting goods, tools, biomedical devices (such as devices implanted in the human body), building components, wind turbine blades, etc.

[0127] If the disclosure of any patent, patent application, and publication incorporated herein by reference contradicts the statement of this application to the extent that it may render a term unclear, the statement shall control. [Example]

[0128] The present disclosure will now be described in more detail with reference to the following examples, the purpose of which is illustrative only and is not intended to limit the scope of the present disclosure.

[0129] Raw materials for polymer synthesis 1,2-Dichlorobenzene, terephthaloyl chloride, isophthaloyl chloride, 3,5-dichlorobenzoyl chloride, aluminum chloride (AlCl3), and methanol were purchased from Sigma Aldrich.

[0130] 1,4-Bis(4-phenoxybenzoyl)benzene was prepared according to Indian Patent No. 193687 (filed on June 21, 1999, incorporated herein by reference).

[0131] Diphenyl sulfone (polymer grade) was sourced from Proviron (99.8% purity).

[0132] Sodium carbonate, light soda ash, was procured from Solvay SA, France and dried before use. Its particle size is d 90 was 130 μm.

[0133] d 90 Potassium carbonate <45 μm was sourced from Armand products and dried before use.

[0134] Lithium chloride (anhydrous powder) was sourced from Acros.

[0135] NaH2PO4·2H2O and Na2HPO4 were purchased from Sigma-Aldrich.

[0136] 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. Pat. No. 5,300,693 to Gilb et al., filed Nov. 25, 1992, and incorporated herein by reference in its entirety. Some of the 1,4-DFDK was purified by recrystallization in chlorobenzene as described in U.S. Pat. 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 the polymerization reaction to produce 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).

[0137] 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 February 24, 1992, which is incorporated herein by reference in its entirety. They were purified by recrystallization in DMF / ethanol.

[0138] Melt Flow Index Measurement The melt flow index was measured according to ASTM D1238 at the indicated temperature (340-380 °C depending on the melting temperature of the material) for a 3.8 kg weight. The final MFI for an 8.4 kg weight was obtained by multiplying the obtained value by 2.35.

[0139] Determination of glass transition temperature, melting temperature and heat of fusion Glass transition temperature T g (using the midpoint, half-height method) and melting temperature T mwas determined in the second heating scan in a differential scanning calorimetry (DSC) in accordance with ASTM D3418-03, E1356-03, E793-06, E794-06, and the following details. The detailed procedure as used in this invention is as follows: A TA Instruments DSC Q20 was used with nitrogen (99.998% purity, 50 mL / min) as the carrier gas. Temperature and heat flow calibration was performed using indium. Sample size was 5-7 mg. Sealed pans were used. Weights were recorded to ±0.01 mg. The thermal cycle was 1 回目 Heating scan: 20.00°C / min from 30.00°C to 400.00°C, isothermal at 400.00°C for 1 min; 1 回目 Cooling scan: 400.00°C to 30.00°C at 20.00°C / min, isothermal for 1 min; 2 回目 Heating scan: 20.00°C / min from 30.00°C to 400.00°C, isothermal at 400.00°C for 1 minute It was.

[0140] Melting temperature T m was determined as the peak temperature of the melting endotherm in the second heating scan. The enthalpy of melting was determined in the second heating scan, T g The crystallization temperature, T, was taken as the area above the linear baseline drawn from the temperature above the end of the endothermic peak. c was determined as the peak temperature of the crystallization exotherm in the first cooling scan. The possible presence of cold crystallization was determined from the second heating scan: the presence of an exotherm before the onset of the endothermic melting peak was confirmed if an exothermic heat flow of more than 0.5 J / g was found.

[0141] Measurement of elemental impurities such as aluminum in polymer compositions by ICP-OES A clean, dry platinum crucible was placed on an analytical balance and the balance was zeroed. A 1 / 2-3 gram portion of the polymer sample was weighed into a boat and its weight recorded to the nearest 0.0001 g. The crucible with the sample was placed in a muffle furnace (Thermo Scientific Thermolyne F6000 Programmable Furnace). The furnace was gradually heated to 525°C and held at that temperature for 10 hours to dry ash the sample. After ashing, the furnace was cooled to room temperature, and the crucible was removed from the furnace and placed in a fume hood. The ash was dissolved in dilute hydrochloric acid. Using a polyethylene pipette, this solution was transferred to a 25 mL volumetric flask. The crucible was rinsed twice with approximately 5 mL of ultrapure water (R < 18 MΩ cm), and the rinses were added to the volumetric flask to achieve quantitative transfer. Ultrapure water was added to the flask to a total of 25 mL. The flask was stoppered and shaken thoroughly to mix the contents.

[0142] ICP-OES analysis was performed using a Perkin-Elmer Optima 8300 Dual View inductively coupled plasma optical emission spectrometer. The spectrometer was calibrated using a set of NIST-traceable multi-element mixed standards with analyte concentrations ranging from 0.0 to 10.0 mg / L. Linear calibration curves were obtained across the concentration range for each of the 48 analytes with correlation coefficients better than 0.9999. Standards were run before and after every 10 samples to ensure instrument stability. Results were reported as the average of three replicates. The concentrations of elemental impurities in the samples were calculated using the following equation: A = (B * C) / (D) (where: A = concentration of the element in the sample in mg / kg (= ppm by weight) B = element in solution analyzed by ICP-OES in mg / L C = volume of solution analyzed by ICP-OES in mL D = sample weight in grams used in this procedure) was calculated.

[0143] Determination of fluorine concentration in polymers by combustion ion chromatography For combustion ion chromatography (IC) analysis, a clean, pre-baked, dry ceramic sample boat was placed on an analytical balance and the balance was zeroed. Approximately 20 mg of polymer sample was weighed into the boat and the weight was recorded to the nearest 0.0001 g. The sample boat was placed in a combustion furnace set at an inlet temperature of 900°C and an outlet temperature of 1000°C. The combusted sample and argon carrier gas were passed through 18.2 MΩ ultrapure water and automatically injected into an IC system equipped with a conductivity detector.

[0144] Combustion IC analyses were performed using a Dionex ICS 2100 IC system equipped with a Dionex IonPac AS19 IC column and guard column (or equivalent), a Dionex CRD 200 4 mm suppressor set at 50 mA, and a GA-210 gas absorption unit, HF-210 furnace, and ABC-210 boat controller, all manufactured by Mitsubishi Analytech.

[0145] The elution gradient for this method is as follows: 0-10 minutes: 10mM KOH 10-15 min: Steady, constant increase to 20 mM KOH 15-30 minutes: 20mM KOH.

[0146] The equipment is F - The anion concentrations were calibrated using a three-point calibration from a NIST-traceable 7-anion mixture supplied by AllTech for analyte concentrations ranging from 0.1 to 3.0 mg / L. Linear calibration curves were obtained over the entire range of concentrations with correlation coefficients better than 0.9999 for each analyte. Control samples were run to verify that the machine was operating correctly before analyzing any samples. The concentration of an anion in a sample was calculated using the following equation: A=(B*C) / (D) (where, A = concentration of the element in the sample in mg / kg B = anion in solution analyzed by IC in mg / L C = volume of solution analyzed by IC in mL D = sample weight in mg used in this procedure) was calculated.

[0147] Preparation Example 1: Nucleophilic PEKK (PEKK) with T / I ratio = 71 / 29 高 ) synthesis A 500 mL four-neck reaction flask equipped with a stirrer, N2 inlet tube, a Claisen adapter with a thermocouple immersed in the reaction medium, and a Dean-Stark trap with a condenser and dry ice trap was charged with 112.50 g of diphenyl sulfone (DPS), 23.054 g of 1,3-BHBB, 16.695 g of 1,4-BHBB, and 41.292 g of 1,4-DFDK. 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 constant 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 using 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 diphenyl sulfone was added to the reaction mixture, which was held under stirring for 15 minutes.

[0148] The reactor contents were then poured from the reactor into a stainless steel pan and allowed to cool. The solids were crushed and ground in an attrition mill through a 2 mm screen. The diphenyl sulfone and salts were extracted with a mixture of 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 under vacuum at 120 °C for 12 hours, yielding 72 g of a yellow powder.

[0149] Preparation Example 2: Nucleophilic PEKK (PEKK) with T / I ratio = 58 / 42 低 ) synthesis The same procedure as in Example 1 was followed, but with the amounts of reagents shown in Table 1 below.

[0150] [Table 1]

[0151] Preparation Example 3: Preparation of electrophilic PEKK (e-PEKK) with T / I=72 / 28 A 2000 mL four-neck reaction flask equipped with a stirrer, a dry N2 inlet tube, a thermocouple immersed in the reaction medium, and a condenser was charged with 1000 g of 1,2-dichlorobenzene and 40.63 g of 1,4-bis(4-phenoxybenzoyl)benzene. Under a dry nitrogen sweep, 7.539 g of terephthaloyl chloride, 9.716 g of isophthaloyl chloride, and 0.238 g of benzoyl chloride were added to the reaction mixture. The reactor was then cooled to -5°C, and 71.88 g of aluminum chloride (AlCl3) was slowly added while maintaining 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, 250g of methanol was added slowly to maintain 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 funnel. The wet cake was rinsed on the filter with an additional 188g of methanol. The wet cake was then reslurried in a beaker with 440g 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 188g of methanol. The solids were slurried in 470g of aqueous hydrochloric acid (3.5 wt%) for 2 hours. The solids were then removed by filtration on a Buchner funnel. The wet cake was rinsed on the filter with an additional 280g of water. The wet cake was then reslurried in a beaker with 250g of 0.5N aqueous sodium hydroxide for 2 hours. The wet cake was then reslurried in 475 g of water in a beaker and filtered through a Buchner funnel. The final water wash 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 and then dried in a vacuum oven at 180 °C for 12 hours. The melt flow index (360 °C, 8.4 kg) was 82 g / 10 min.

[0152] Example 4: Preparation of compositions by melt blending The PEKK polymers of Examples 1 and 2 were extruded in a 15 / 85 wt / wt (PEKK) extruder using a Leistritz 18 mm twin-screw co-rotating intermeshing extruder with a length to diameter ratio (L / D) of 30. 高 / PEKK 低 The materials were melt-blended in a ratio of 1:1 (total 1:100). The raw materials, all in either powder or pellet form, were first tumble-blended in each case. Tumble blending was carried out for approximately 20 minutes, followed by melt compounding using the extruder described above. The extruder had six barrel sections, with barrel sections 2 to 6 being heated. A vacuum discharge of greater than 25 inches Hg was applied in barrel section 5 throughout compounding to strip moisture and any possible residual volatiles from the compound. The extrudate was stranded in each case on a conveyor belt, air-cooled, and fed to a pelletizer, which cut it into pellets approximately 3 mm in diameter and 3 mm in length. Other compounding conditions were as follows: barrel sections 2 to 6 as well as the die section were heated to 360°C. The extruder was operated at a screw speed of approximately 200 rpm, and the extrusion rate was approximately 2.7 g / h.

[0153] The thermal properties of the PEKK polymers of Examples 1-3 and of the inventive composition of Example 4 are reported in Table 2.

[0154] [Table 2]

[0155] The data in Table 2 demonstrate that the PEKK composition of Example 4 exhibits high T c and a heat of fusion ΔHf of more than 25 J / g, i.e., an acceptably high degree of crystallinity. As a result, the composition of Example 4 exhibits a balance of properties: a fast crystallization rate (high T c Good processing (T lower than 330°C) combined with a favorable final crystal fraction (as evidenced by ΔHf) m (as evidenced by to provide.

[0156] Example 5 and Comparative Example 1: Composite Material Hextow IM8 carbon fiber (12K filament, unsized; nominal fiber strength = 6067 MPa; nominal fiber modulus = 310 GPa) was impregnated by a melt impregnation method with the composition of Example 4 to yield a tape hereinafter identified as Example 5, and with the PEKK from Example 3 to yield a tape hereinafter identified as Comparative Example 1.

[0157] The resulting tape is 305mm wide and weighs 145±5g / m 2 and a resin weight percentage of 34±3 wt %. The tapes were then cut and laid up into the following test laminate layups:

[0158] [Table 3]

[0159] The layup was placed in a vacuum bag and then autoclaved using a continuous ramp heating and cooling cycle while applying a 635-735 mmHg vacuum. The heat-up ramp rate from 23°C to the maximum process temperature was 3-5°C / min, while the cooling rate was 5-7°C / min from the maximum temperature back down to room temperature (23°C). When the temperature reached the maximum, a pressure of 0.68 MPa was applied and held on the layup until the panel had consolidated, then cooled to below 100°C. The maximum temperatures for the two materials are shown in the following table:

[0160] [Table 4]

[0161] The test laminates were C-scanned to ensure low porosity and then machined into test coupons. The test laminates were tested at ambient conditions of 23° C. A summary of the tests is provided in Table 3.

[0162] [Table 5]

[0163] The data in Table 3 clearly show that the composite material of Example 5 is within experimental error for both the in-plane shear modulus and open pore compressive strength, which are the most important matrix properties, of the reference material of Comparative Example 1. Thus, the inventive composite material of Example 5 can achieve similar performance to the reference composite material, despite being molded at a temperature lower than 20°C.

Claims

1. - fibers, - T / I ratio [(T / I) 低 a first PEKK polymer [(PEKK 低 ) )] and T / I ratio [(T / I) 高 a second PEKK polymer [(PEKK 高 ) ], (T / I) 低 <(T / I) 高 a thermoplastic polymer matrix comprising a composition (C) wherein the T / I ratio of the first PEKK polymer is different from the T / I ratio of the second PEKK polymer such that Including, Each PEKK polymer has a repeating unit (R Ｔ ) and repeating units (R Ｉ ), wherein the repeating unit (R Ｔ ) is represented by the formula (T): 【number】 is expressed as Repeating unit (R Ｉ ) is represented by formula (I): 【number】 is expressed as During the ceremony: - 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; each i and j, at each occurrence, is an integer independently selected from 0 to 4; The T / I ratio is [Equation 1] where: [Equation 2] and (PEKK 高 ) is T 高 -T 低 ≦17 mol% of the unit (R Ｔ ) molecular content [(T 高 ) )], (PEKK 低 ) is the unit (R Ｔ ) molar content [(T 低 ) ], A composite material, wherein the weight ratio of polymer (PEKK low) / polymer (PEKK high) is at least 60 / 40 and at most 99 / 1.

2. (T / I) 低 10. The composite material of claim 1, wherein the % % % % % % is at least 50 / 50.

3. (T / I) 高 3. The composite material of claim 1, wherein the % % % % % % is at least 65 / 35.

4. Polymer (PEKK 低 ) / Polymer (PEKK 高 4. The composite material according to claim 1, wherein the weight ratio of α- and β-hydroxybenzoates is at least 65 / 45 and at most 97 / 3.

5. Polymer (PEKK 低 ) and / or polymer (PEKK 高 5. The composite material of claim 1, wherein the polymer is a nucleophilic PEKK polymer.

6. The composition (C) is - the same melting temperature (T in °C) determined in the second DSC heating scan ｍ a crystallization temperature (Tc in °C) determined in a second DSC heating scan that is higher than the crystallization temperature of a PEKK polymer having - Melting temperature (T) below 330 ° C ｍ ), a heat of fusion (ΔHf) of greater than 25 J / g; and no crystallization peak upon heating ("cold crystallization peak") in the second DSC heating scan; - Melting temperature (T in °C) determined during the second DSC heating scan ｍ ) and the crystallization temperature (T in °C) determined during the first DSC cooling scan. ｃ ) and the following inequality: T ｃ ≧1.3716×T ｍ Relationship that meets -190℃ characterized by one or more features selected from the group consisting of: Here, T ｍ , T ｃ , ΔHf, and the absence of a low-temperature crystallization peak are measured by differential scanning calorimetry (DSC) according to ASTM D3418-03, E1356-03, E793-06, E794-06 standards, applying a heating and cooling rate of 20°C / min, in a sweep from 300°C to 400°C; The composite material according to any one of claims 1 to 5.

7. The composite material according to any one of claims 1 to 6, wherein composition (C) further comprises at least one nucleating agent.

8. The composition (C) has a melting temperature (T ｍ 8. The composite material according to claim 1, wherein

9. 9. The composite material according to any one of claims 1 to 8, wherein the fibers are continuous fibers and / or selected from the group consisting of carbon fibers, graphite fibers, glass fibers, ceramic fibers, synthetic polymer fibers, boron fibers, basalt fibers, quartz fibers, alumina fibers, zirconia fibers and mixtures thereof.

10. an open-hole compressive strength of 320 MPa or greater, measured according to ASTM D6484; and - In-plane shear modulus of 4.7 GPa or greater, measured according to ASTM D3518 The composite material according to any one of claims 1 to 9, which exhibits at least one of the following:

11. A multilayer composite assembly comprising a first layer of a composite material according to any one of claims 1 to 10 and at least one layer comprising a thermoplastic polymer composition [composition (TP)] in contact with at least one surface of said composite material.

12. 11. A method for producing a composite material according to any one of claims 1 to 10, said method comprising the step of contacting the polymer matrix comprising composition (C) with at least a portion of the surface of the fibres.

13. 13. The method of claim 12, wherein the polymer matrix is ​​contacted with the fibers in a melt impregnation process, a slurry process, a film lamination process, or a dry powder coating / fusing process.

14. 1. A method for producing a low void, reinforced laminate, said method comprising: - processing layers of composite material according to any one of claims 1 to 10 in an automatic lay-up machine fitted with a heating device to simultaneously melt and fuse the layers to the previously laid layers so that said layers are laid and oriented on said previously laid layers to form a reinforced laminate with less than 2% by volume of voids; - optionally further annealing the reinforced laminate in either free-standing or vacuum-bag operation at a temperature range of 170°C to 270°C for a time typically between 1 minute and 240 minutes; A method comprising:

15. 1. A method of forming a composite part, said method comprising: - pre-orienting plies of composite material according to any one of claims 1 to 10, - consolidating the pre-oriented plies in a hot and cold press, a double belt press or a continuous compression moulding machine to produce a reinforced laminate; - optionally cutting the reinforced laminate to size to produce a shaped blank; - Rapidly heating the formed blank to a temperature of 320-360°C in a stamp forming process tool to produce a formed composite part. A method comprising:

16. A reinforced laminate, composite part or article comprising the composite material of any one of claims 1 to 10.

17. - fibers, - T / I ratio [(T / I) 低 a first PEKK polymer [(PEKK 低 ) )] and T / I ratio [(T / I) 高 a second PEKK polymer [(PEKK 高 ) ], (T / I) 低 <(T / I) 高 a thermoplastic polymer matrix comprising a composition (C) wherein the T / I ratio of the first PEKK polymer is different from the T / I ratio of the second PEKK polymer such that Including, Each PEKK polymer has a repeating unit (R Ｔ ) and repeating units (R Ｉ ), wherein the repeating unit (R Ｔ ) is represented by the formula (T): 【number】 is expressed as Repeating unit (R Ｉ ) is represented by formula (I): 【number】 is expressed as During the ceremony: - 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; each i and j, at each occurrence, is an integer independently selected from 0 to 4; The T / I ratio is [Equation 1] where: [Equation 2] and Polymer (PEKK 低 ) and / or polymer (PEKK 高 ) is a nucleophilic PEKK polymer; A composite material, wherein the weight ratio of polymer (PEKK low) / polymer (PEKK high) is at least 60 / 40 and at most 99 / 1.

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