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    • 专利摘要:
    composite material, structural adhesive composition, and, method for making a composite laminate composite materials and structural adhesives containing functionalized polymer particles as a toughening agent. the particles are composed of functionalized polyaryletherketone polymer (paek) or copolymer thereof that contain chemical functional groups capable of reacting with a thermosetting resin component to form covalent bonds.
    公开号:BR112016027027B1
    申请号:R112016027027-4
    申请日:2015-05-21
    公开日:2021-06-15
    发明作者:James Francis Pratte；Robin K. Maskell；James Martin Griffin；Judith Anne Elder
    申请人:Cytec Industries Inc.；
    IPC主号:
    专利说明:

    FUNDAMENTALS
    [001] Fiber reinforced polymer composites (FRP) have been used as high strength, low weight engineered materials to replace metals in aerospace structures such as aircraft primary structures. Important properties of such composite materials are high strength, rigidity, and light weight.
    [002] Multiple layers of prepreg ply are commonly used to form structural composite parts that have a laminated structure. Delamination of such composite parts is an important failure mode. Delamination occurs when two layers detach from each other. Important factors limiting the design include both the energy required to initiate a delamination and the energy required to propagate the same.
    [003] A cured composite (eg, prepreg arrangement) with improved resistance to delamination is one with improved compressive strength after impact (CAI) and fracture toughness (GIC and GIIC).
    [004] CAI measures the ability of a composite material to withstand damage. In the test to measure CAI, the composite material is subjected to an impact of a given energy and then loaded in compression. The damaged and deep dent area is measured following impact and before the compression test. During this test, the composite material is compressed to ensure that no elastic instability occurs and the strength of the composite material is recorded.
    [005] Fracture toughness is a property that describes the ability of a material containing a crack to resist fracture, and is one of the most important properties of a material for aerospace applications. Fracture toughness is a quantitative means of expressing a material's resistance to brittle fracture when a crack is present.
    [006] Fracture toughness can be quantified as strain energy release rate (Gc), which is the energy dissipated during fracture per unit of newly created fracture surface area. Gc includes GIC (Mode 1 - open mode) or Gnc (Mode II - in flat shear). The subscript "IC" denotes Mode I crack opening, which is formed under a normal tensile strength perpendicular to the crack, the subscript "IIC" denotes Mode II crack produced by a shear stress action parallel to the plane of the crack and perpendicular ahead of the crack. The onset and development of a delamination is often determined by examining fracture toughness in Mode I and Mode II.
    [007] The CAI performance of fiber reinforced polymer composites can be improved through two main technologies. The first technology involves the use of high strength reinforcing fibers that have relatively high deformation to failure. These fibers appear to absorb a high amount of energy without fracturing, thus redistributing the energy over a larger area of the composite laminate.
    [008] The CAI performance of fiber reinforced polymer composites can be improved by incorporating certain particles with tenacity within interlaminar regions of a multilayer composite laminate. The "interlaminar region" refers to a region between two adjacent structural layers of reinforcing fibers in the composite laminate.
    [009] The presence of particles with toughness in the composite laminate creates a resin-rich interlayer that helps to contain crack propagation in this region of the interlayer. It can be hypothesized that the particles create a spacing between the structural fiber layers as well as interact with the propagating crack to dissipate the energy absorbed from the impact event. Conventionally used toughness particles include crosslinked polyamide particles (Nylon 6, 6), which can impart good toughness, adequate fluid resistance when they are incorporated into carbon fiber reinforced prepregs, but being made of polyamide, they absorb water, and consequently cause a significant reduction in hot/wet compressive properties. Amorphous thermoplastic particles such as polyphenylene oxide (PPO) may provide good toughness but have poor fluid resistance which could result in solvent stress cracking of the particles. Polyphthalamide (PPA) particles, which is a semi-aromatic polyamide with high heat resistance, can give good GIIC performance but also absorb water. Polyimide particles (eg P84™ from HP Polimer Inc.) have been used to improve carving properties, but they also absorb water.
    [0010] In some cases, the combination of three different particle types may be necessary to achieve the desired CAI and fracture toughness properties for aerospace applications. Multiple particle types that interact differently with the resin matrix in the composite have been shown to mitigate the limitations of one particle type. However, the use of multiple types of particles in a resin formulation increases the problem of non-uniform dispersion and mixing as well as increasing the cost of manufacturing.
    [0011] Particles with toughness have also been incorporated into structural adhesives that are used in bonding composite parts. These particles are typically rubbers (CTBN, core-shell) polyamides, and polyethersulfones to name a few that interact with an initiating crack to absorb the fracture energy thus stiffening the bond line.
    [0012] Taking into account the state of the art, there remains a need for particles with toughness that can overcome the above mentioned disadvantages of particles with conventional toughness. In particular, it would be advantageous to obviate the need to use a mixture of different types of particles to achieve desirable CAI and fracture toughness performance in advanced composites such as those for aerospace applications. SUMMARY
    [0013] The present description pertains to the use of functionalized polymer particles as a toughening agent to increase damage tolerance and fracture toughness of fiber reinforced polymer composites. More specifically, the particles are composed of polyaryletherketone (PAEK) polymers or copolymers thereof that contain chemical functional groups that can react with thermosetting resins such as epoxides, bismaleimides, benzoxazines, and mixtures thereof to form a covalent bond. In a preferred embodiment, the particles are functionalized with amine groups.
    [0014] Another aspect of the present description is related to the incorporation of the functionalized particles mentioned above in structural adhesives that are suitable for bonding composite parts. BRIEF DESCRIPTION OF THE DRAWINGS
    [0015] FIG. 1 illustrates an impact event on a particle-stiffened carbon fiber/epoxy composite.
    [0016] FIG. 2 provides scanning electron microscopy (SEM) images of reactive terminated PEKK polymer particles with different T:I ratios.
    [0017] FIG. 3 provides SEM images of PEKK imide of amino-chain terminated copolymer backbone and crosslinked versions at different magnifications, showing size, shape and surface characteristics.
    [0018] FIG. 4 is SEM image with 500X magnification of amine reactive terminated PEKK polymer particles with a T:I ratio of 80/20.
    [0019] FIG. 5 is a 2000X SEM image of an amine reactive terminated PEKK polymer particle with a T:I ratio of 80/20 showing particle surface characteristics.
    [0020] FIG. 6 is a diagram showing a fracture toughness sample and SEM scan site of the fractured surface.
    [0021] FIG. 7 is 1000X SEM image of the fracture surface of the GIIC specimen of a fiber/carbon particle stiffened epoxy composite using amine-terminated PEKK particle with T:I = 80/20 ratio. DETAILED DESCRIPTION
    [0022] The functionalized polymer particles described herein are particularly suitable as interlaminar particles in fiber reinforced polymer composites. The incorporation of such particles imparts high toughness and high damage tolerance (ie, CAI) properties to the cured composites while maintaining high hot/wet and shear compressive properties. FIG. 1 illustrates an impact event on a particle-stiffened carbon fiber/epoxy composite. As can be seen from the force diagram, the inner bends are loaded primarily into shear like those in a GIIC test. High GIIC performance has been correlated with reduced impact damage area and, in turn, improved CAI performance. Thus, it is desirable to have high GIIC performance along with low moisture take on particles with toughness which would lead to superior hot/wet notch properties.
    [0023] Recent attempts to use finely ground polyetherketone ketone (PEKK) particles have given superior notch properties, but no improvement has been seen in fracture toughness and CAI performance. Notch properties that can be measured as full hole stress and full hole compression (FHT, FHC), and open hole stress and open hole compression (OHT, OHC), refer to the ability of a given composite material to transport charge once a hole is drilled in the region containing charge of the composite material itself. Without wishing to be bound by any theory, it is believed that the shape and chemical functional groups on the particle contribute to the improvements discussed above. Furthermore, functionalized thermoplastic particles are also suitable as toughness particles in structural adhesives that are used for bonding composite parts.
    [0024] Functionalized particles contain chemical functional groups that can react with thermosetting resins such as epoxides, bismaleimides (BMI), benzoxazines, and mixtures thereof to form covalent bonds. The term "functionalized" as used in this context means chemical groups on the particles, and at least some of which have a potential for binding with some or all of the monomers in the thermosetting formulation (eg, epoxy, BMI, benzoxazine).
    [0025] Preferably, the functionalized particles are particles of an amine functionalized polyaryletherketone polymer or copolymer thereof. In one embodiment, the amine-functionalized polyaryletherketone polymer or copolymer thereof has a weight average molecular weight (Mw) of at least 8,000, preferably greater than 10,000, an inherent viscosity of at least 0.28 dl/g, and a glass transition temperature of at least 140°C as measured by differential scanning calorimetry (DSC). The term "amine functionalized" is intended to enclose polymers with one or more amine functional groups as end groups. It also encloses polymers where the amine groups are substituents on the polymer chain, ie, pendant to the backbone. Preferably the polymers/copolymers are functionalized at the end groups.
    [0026] The functionalized polyaryletherketones of the present description are polymers containing the unit -Ar-O-Ar-C(=O)-, where Ar is an aromatic moiety. They are characterized by aryl groups that are linked by ether, carbonyl (ketone), sulfone or imide groups and include, but are not limited to the following: Poly (ether ketone), i.e., PEK, a polymer consisting essentially of the repeating unit : -Ar-O-Ar-C(=O)-; Poly (ether ketone ketone), i.e. PEKK, a polymer consisting essentially of the repeating unit: - Ar-O-Ar-C(=O)-Ar-C(=O)-; Poly (ether ether ketone), i.e. PEEK, a polymer consisting essentially of the repeating unit: -Ar-O-Ar-O-Ar-C(=O)-; Poly (ether ether ketone ketone), i.e. PEEKK, a polymer consisting essentially of the repeating unit: -Ar-O-Ar-O-Ar-C(=O)-Ar-C(=O)-; Poly (ether ketone ether ketone ketone), i.e. PEKEKK, a polymer consisting essentially of the repeating unit: -Ar-O-Ar-C(=O)-Ar-O-Ar-C(=O)-Ar- C(=O)-; Poly (ether ketone ketone), i.e., PEKK; and combinations thereof; where each Ar in the repeating units above is independently an aromatic moiety.
    [0027] Each aromatic moiety (Ar) in the polymer repeating unit can be independently selected from substituted and unsubstituted mononuclear aromatic moieties (eg, phenylene) and substituted and unsubstituted polynuclear aromatic moieties. The term "polynuclear" is considered to encompass fused aromatic rings such as naphthalene and unfused aromatic rings such as biphenyl, etc. In some embodiments, Ar is phenylene (Ph), for example, unsubstituted phenylene.
    The phenylene and polynuclear aromatic (i.e., "Ar") moieties may contain substituents on the aromatic rings. Such substituents will be readily understood by those skilled in the art and should not inhibit or otherwise interfere with the polymerization reaction to any significant extent. Typical substituents may include, for example, phenyl, halogen (for example, F, Cl, Br, I), ester, nitro, cyano and the like.
    [0029] In cases where Ar is substituted, the substituents are preferably pendant to the chains rather than to the backbone, i.e. not attached to a carbonyl carbon atom of a ketone bond nor an oxygen atom of a bond. ether. Thus, in a particularly preferred aspect, the ketone bonds (i.e., the carbon atoms of the carbonyl group) are attached directly to the carbon atoms, especially to the carbon atoms of adjacent aromatics (i.e., to aromatic carbons). Similarly, the oxygen atoms of the ether bonds are preferably attached to carbon atoms, especially to aromatic carbon atoms from adjacent aromatic groups.
    [0030] Homopolymers of the above repeating units or copolymers of the above repeating units with one another (eg PEKK-PEKEKK-PEKK) and with imide or sulfone units are enclosed. Copolymers include alternating, periodic, statistical, random and block copolymers.
    [0031] The copolymer may have an aryl etherketone repeating unit and one or more of the following repeating units:

    [0032] The particulate polymers described herein are "functionalized" as they contain one or more amine groups as end groups (i.e., at one or more ends of the polymer chain) and/or as pendant groups (i.e., at one or more positions along the polymer backbone).
    [0033] The functional groups for the polymers are amines represented by the following formulas: -NR2, -NRH or -NH2, preferably -NRH or -NH2, more preferably -NH2, and derivatives thereof, where "R" is or a group aliphatic or aromatic. Where R is an aromatic group it can be "Ar" as described here (eg phenyl). Where R of -NR2 or -NRH is an aliphatic group, it is preferably selected from alkyl groups, for example C1-C6 aliphatic groups, especially methyl or ethyl groups.
    [0034] Preferably, the particulate polymers are terminated with an amine group, i.e. an amine group is found at at least one end of the polymer chain. Typically at least 50% of the end groups, i.e. the ends of the polymer chains are amine functionalised, preferably at least 70%, especially preferably at least 85%, for example at least 95%. In certain embodiments, substantially all of the chain ends comprise an amine group.
    [0035] In a further aspect, as an alternative to, or in addition to, at the amine termination of the chain, the amine groups may be pendant to the polymer chain, i.e. they are substituents of the aromatic polymer moieties. For example, 25% to 75%, or about 50% of Ar groups are replaced with an amine group.
    [0036] In some embodiments, the particulate polymers of this description are linear and terminated with a functional group. Particularly preferred compounds are those according to the following formulas (as well as imide or sulfone copolymers thereof):
    where n is an integer from 1 to 200, for example 15 to 200 or 20 to 200, or 30 to 150, preferably 30 to 60, for example around 40 or 50, and E is an amine functional group like described here, for example, NH2.
    [0037] In a preferred embodiment, functionalized particles are particles of a polymer or copolymer represented by the following structure:
    where E is an amine functional group (eg NH2) or protected amine, and n is an integer from 15 to 200.
    [0038] In the above structure, the end groups of the polymer chain (E) can be comprised either completely or partially of an aromatic amine such as phenoxy aniline. Other end groups that may be present along with the amine-functionalized end groups could be non-reactive or reactive to the thermosetting resin matrix with which the particles could be combined with.
    [0039] In one modality, at least one of R1 and R3 in the above structure is the branching unit:
    and the branching unit(s) is/are present in a molar percentage of 0.5% to 25%.
    [0040] PAEK polymers can have different ether/ketone ratios in order to adapt the properties of the resulting materials. In any of the embodiments described herein, R1 can be a terephthaloyl (T) group and R2 can be either a terephthaloyl (T) or isophthaloyl (I) group and the T:I ratio in the PAEK polymer backbone can be in the range from 0:100 to 100:0. In any of the embodiments described herein, R1 may contain the branching agents 1,3,5-triphenoxybenzene and/or 1,3,5-benzenetricarboxylic acid chloride at a level of 1% by weight - 10% by weight by weight of the polymer, where "% by weight" refers to percentage by weight.
    [0041] In one embodiment, the functionalized particles are polyetherketone (PEKK), polyetherketone (PEK), polyetherketonepolyetherketone (PEKPEKK), polyetheretherketone (PEEK) particles, or mixtures thereof, and contain aromatic amine functional groups such as phenoxyaniline .
    [0042] In a preferred embodiment, the amine functionalized polyaryletherketone polymer or copolymer thereof has a weight average molecular weight (Mw) of at least 8,000, preferably 26,000 - 162,000. The Mw as described herein can be determined by gel permeation chromatography (GPC).
    [0043] The particulate amine functionalized PAEK polymer or copolymer of the present description has an inherent viscosity (IV) of at least 0.28 dl/g, particularly in the range of 0.4 - 1.7 dl/g, and in In some modalities, IV is in the range of 0.6 - 1.5 dl/g. IV as discussed here can be measured using a conventional viscometer.
    [0044] Preferably, the particulate amine functionalized PAEK polymer or copolymer of the present description has a glass transition temperature (Tg) of at least 140°C as measured by differential scanning calorimetry (DSC), more specifically, in the range of 140 -190°C, and in some embodiments, 158 -178°C.
    [0045] The functional groups of the functionalized particles are present on the outer surface and inside the particles and are capable of forming covalent bonds with the components of the curable thermosetting resin system in which they are placed. The curable thermosetting resin system into which the functionalized particles are added can include one or more of epoxides, bismaleimides, and benzoxazines that are capable of forming covalent bonds with the functionalized particles. Other components within the curable thermosetting resin system that can form covalent bonds with the functionalized PAEK particles include amine curing agents if the functional groups are of the carboxylic acid type.
    [0046] The PAEK polymers/copolymers described here are semi-crystalline thermoplastics that have low moisture take up, high shear modulus, good solvent resistance, high glass transition temperature, good oxidation stability, and low dielectric constants. These polymers also substantially retain these mechanical properties at elevated temperatures.
    [0047] The functionalized polymer particles of the present description can be produced through polymerization using a chain termination which can be subsequently converted to a reactive end group.
    [0048] Generally, functionalized polymer particles can be made by polymerization using the following reagents: (a) at least one monomer; (b) a polymerizing agent; (c) a chain terminating agent; and (d) other reagents. Monomer
    [0049] According to a modality, the monomer is represented by the following structure:
    where X can be -C(O)-, -S(O2)-, terephthaloyl group, isophthaloyl group, or an imide group of the following structure.
    where R can be -C(O)-, -S(O2)-, -O-, or simply a bond to produce a biphenyl dianhydride group which reacts with phenoxyaniline groups.
    [0050] Also contemplated are non-symmetrical monomers and self-polymerizing monomers. polymerization agent
    [0051] According to an embodiment the polymerization agent is at least one of terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC). This will be optional if a self-curing monomer is used. Another embodiment can include at least one of TPC and IPC together with 1 wt%-10 wt% benzenetricarboxylic acid chloride to make a branched and/or lightly crosslinked polymer particle. chain termination agent
    [0052] According to an embodiment the chain terminating agent has the general formula Z-Ar-O-Ph, where Z is a protected nucleophilic group, Ar is an aryl group, and Ph is phenyl.
    [0053] As an example, Z may include -YHn-R, where Y is nitrogen, oxygen or sulfur, n is the integer 0 or 1 and R is a leaving group such as an acetyl, haloacetyl (eg. trifluoroacetyl), and carbonate (for example, t-Boc).
    [0054] A preferred chain terminating agent is:

    [0055] The trifluoroacetyl group is removed during acid/base working conditions after polymerization to result in an amine end group that can react with the monomer components of a thermosetting matrix. Other reagents
    [0056] Other reagents may include one or more solvents (eg dichloromethane), Lewis acids (eg AlCl3), and control agents (eg benzoic acid).
    [0057] In one embodiment, functionalized particles are obtained by the method that includes the steps of: (i) polymerizing a monomer system in a reaction medium containing: (a) a chain terminating agent containing -NR2, -NRH or a protected amine group, where R is either an aliphatic or aromatic group, (b) a Lewis acid, and (c) a control agent selected from an aromatic carboxylic acid, an aromatic sulfonic acid, and a derivative thereof; and (ii) adjust the ratio of controlling agent to monomers in the monomer system in order to control the particle size distribution.
    [0058] Functionalized polymer particles to be used as the polymer particles with toughness in a thermosetting matrix resin may have a dimension (larger or smaller dimension) being 75 microns or less. Such a dimension could be achieved either directly from the synthesis of the functionalized particles or through a subsequent crushing operation. Particle size can be measured by laser diffraction, for example, using a Malvern Mastersizer particle size analyzer.
    [0059] In some embodiments, the functionalized polymer particles are substantially spherical in shape with an aspect ratio (R) of about 1 to 1.5 or in stick shape with an aspect ratio of 1.5 to 10, where R = a/b, “a” is the largest dimension, and “b” is the smallest dimension). Composite materials and manufacturing methods
    [0060] The composite material described here is composed of reinforcing fibers impregnated with a matrix resin. matrix resin
    [0061] The curable matrix resin (or resin composition) for impregnating/infusing the reinforcing fibers is preferably a hardenable or thermosetting resin containing one or more uncured thermosetting resins, including, but not limited to, epoxy resins, imides (such as polyimide or bismaleimide), vinyl ester resins, cyanate ester resins, isocyanate modified epoxy resins, phenolic resins, furan resins, benzoxazines, formaldehyde condensate resins (such as urea, melamine or phenol), polyesters, acrylics, hybrids, mixtures and combinations thereof.
    [0062] Suitable epoxy resins include aromatic diamine polyglycidyl derivatives, monoaromatic primary amines, aminophenols, polyhydric phenols, polyhydric alcohols, polycarboxylic acids. Examples of suitable epoxy resins include polyglycidyl ethers of biphenols such as bisphenol A, bisphenol F, bisphenol S and bisphenol K; and cresol and phenol based polyglycidyl ethers of novolacs.
    [0063] Specific examples are tetraglycidyl derivatives of 4,4'-diaminodiphenylmethane (TGDDM), resorcinol diglycidyl ether, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, bromobisphenol F diglycidyl ether, tetraglycidyl derivatives of diaminodiphenylmethane, trihydroxyphenyl methane triglycidyl ether, novolac phenol-formaldehyde polyglycidyl ether, o-cresol novolac polyglycidyl ether or tetraphenylethane tetraglycidyl ether.
    Suitable commercially available epoxy resins for use in the host matrix resin include N,N,N',N'-tetraglycidyl diamino diphenylmethane (e.g. MY 9663, MY 720, and MY 721 by Huntsman); N,N,N',N'-tetraglycidyl-bis(4-aminophenyl)-1,4-di-iso-propylbenzene (e.g. EPON 1071 from Momentive); N,N,N',N'-tetracyclidyl-bis(4-amino-3,5-dimethylphenyl)-1,4-diisopropylbenzene, (for example EPON 1072 from Momentive); p-aminophenol triglycidyl ethers (eg MY 0510 from Hunstman); m-aminophenol triglycidyl ethers (eg MY 0610 from Hunstman); diglycidyl ethers of bisphenol A-based materials such as 2,2-bis(4,4'-dihydroxy phenyl) propane (eg, DER 661 from Dow, or EPON 828 from Momentive, and novolac resins preferably of 8-20 viscosity At 25°C; glycidyl ethers of phenol novolac resins (eg, DEN 431 or DEN 438 from Dow); phenolic novolac based on dicyclopentadiene (eg, Tactix 556 from Huntsman); diglycidyl 1,2-phthalate (by example, GLY CEL A-100); diglycidyl derivative of dihydroxy diphenyl methane (Bisphenol F) (eg PY 306 from Huntsman) Other epoxy resins include cycloaliphatics such as 3',4'-epoxycyclohexyl-3,4 carboxylate - epoxycyclohexane (eg CY 179 from Huntsman).
    [0065] Generally, the curable matrix resin contains one or more thermosetting resins in combination with other additives such as curing agents, curing catalysts, comonomers, rheology control agents, tackifiers, inorganic or organic fillers, thermoplastic polymers and/or elastomeric such as toughening agents, stabilizers, inhibitors, pigments, dyes, flame retardants, reactive diluents, and other additives well known to those skilled in the art to modify the properties of the matrix resin before or after curing.
    [0066] Apart from the functionalized PAEK particles, other toughening agents can be added in the curable resin composition. Other toughening agents include, but are not limited to, homopolymers or copolymers either alone or in combination of polyamides, copolyamides, polyimides, aramids, polyketones, polyether ketones (PEK), polyetherimides (PEI), polyether ketones (PEEK), polyether ketones (PEKK) , polyethersulfones (PES), polyetherethersulfones (PEES), polyesters, polyurethanes, polysulfones, polysulfides, polyphenylene oxide (PPO) and modified PPO, poly(ethylene oxide) (PEO) and polypropylene oxide, polystyrenes, polybutadienes, polyacrylates, polymethacrylates , polyacrylics, polyphenylsulfone, high performance hydrocarbon polymers, liquid crystal polymers, elastomers and segmented elastomers.
    [0067] The curing agent is appropriately selected from known curing agents, for example, aromatic or aliphatic amines, or guanidine derivatives. An aromatic amine curing agent is preferred, preferably an aromatic amine having at least two amino groups per molecule, and particularly preferred are diaminodiphenyl sulfones, for example, where the amino groups are at the meta- or para-positions with respect to the group. sulfone. Particular examples are 3,3'- and 4-,4'-diaminodiphenylsulfone (DDS); methylenedianiline; bis(4-amino-3,5-dimethylphenyl)-1,4-diisopropylbenzene; bis(4-aminophenyl)-1,4-diisopropylbenzene; 4,4'methylenebis(2,6-diethyl)-aniline (MDEA from Lonza); 4,4'methylenebis-(3-chloro, 2,6-diethyl)-aniline (MCDEA from Lonza); 4,4'methylenebis-(2,6-diisopropyl)-aniline (M-DIPA from Lonza); 3,5-diethyl toluene-2,4/2,6-diamine (D-ETDA 80 from Lonza); 4,4'methylenebis-(2-isopropyl-6-methyl)-aniline (M-MIPA from Lonza); 4-chlorophenyl-N,N-dimethyl-urea (for example Monuron); 3,4-dichlorophenyl-N,N-dimethyl-urea (for example DIURON TM) and dicyandiamide (for example AMICURE TM CG 1200 from Pacific Anchor Chemical).
    Suitable curing agents also include anhydrides, particularly polycarboxylic anhydrides, such as nadic anhydride, methylnadic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and metal anhydride. The addition of catalyst(s) to the curable matrix resin is optional, but its use can increase the cure rate and/or reduce the cure temperatures if desired.
    [0069] The curable matrix resin in the interlaminar region is also a hardenable or thermosetting resin containing one or more uncured thermosetting resins of the type discussed above. In certain embodiments, the curable matrix resin in the interlaminar region is the same as the matrix resin in the region containing the reinforcing fibers. In other embodiments, the resin in the interlaminar region is different from the matrix resin in the region containing the reinforcing fibers. Reinforcement fibers
    [0070] For making high performance composite and prepreg materials, suitable reinforcing fibers are, but not limited to, fibers having a high tensile strength, preferably greater than 500 ksi (or 3447 MPa). Fibers that are usable for this purpose include carbon or graphite fibers, glass fibers and fibers formed from silicon carbide, alumina, boron, quartz, and the like, as well as fibers formed from organic polymers such as, for example, polyolefins, poly(benzothiazole), poly(benzimidazole), polyacrylates, poly(benzoxazole), aromatic polyamides, polyaryl ethers and the like, and can include blends having two or more such fibers. Preferably, the fibers are selected from glass fibers, carbon fibers and aromatic polyamide fibers, such as fibers sold by the DuPont Company under the trade name KEVLAR. The reinforcing fibers can be used in the form of discontinuous or continuous tows made from multiple filaments, as continuous unidirectional or multidirectional tapes, or as woven, non-pleated, or non-woven fabrics. The woven shape can be selected from plain, satin or twill weave style. The woven shape can be selected from plain, satin or twill weave style. Non-pleated fabric can have multiple pleats and fiber orientations.
    [0071] Fibers can be sized or unsized. Fibers may be present at an amount of 5% to 35% by weight, preferably at least 20%, based on the total weight of the composite material. For structural applications, the use of continuous fibers, for example glass or carbon, is preferred, especially at 30% to 70% by volume, more especially 50% to 70% by volume. Manufacture of laminates and composite parts
    [0072] To form a composite part, a plurality of flexible, curable prepreg plies can be arranged on a tool in a stacking sequence to form a prepreg arrangement. The prepreg folds within the layout can be positioned in a selected orientation relative to one another, eg 0°, ± 45°, 90°, etc. Prepreg arrays can be fabricated by techniques that may include, but are not limited to, manual disposition, automated tape disposition (ATL), advanced fiber placement (AFP), and filament winding.
    [0073] Each prepreg is composed of a sheet or layer of reinforcing fibers that have been impregnated with a matrix material in at least a portion of its volume. In one embodiment, the prepreg has a fiber volume fraction between about 0.50 to 0.60 based on the total volume of the prepreg.
    [0074] The prepreg used to manufacture aerospace structures is usually a resin impregnated sheet of unidirectional reinforcing fibers, typically carbon fibers, which is often referred to as "tape" or "unidirectional tape" or "uni-tape ”. Prepregs can be fully impregnated prepregs or partially impregnated prepregs. The matrix resin impregnating the reinforcing fibers can be in a partially cured or uncured state.
    [0075] Typically, the prepreg is in a bendable or flexible form that is ready for laying and molding into a three-dimensional configuration, followed by curing into a final composite part. This type of prepreg is particularly suitable for manufacturing load-bearing structural parts such as aircraft wings, fuselages, bulkheads and control surfaces. Important properties of cured prepregs are high strength and stiffness with reduced weight.
    [0076] According to an embodiment, a specific amount of particles with functionalized PAEK toughness is mixed with a curable resin composition prior to impregnation of the reinforcing fibers (i.e., prior to fabrication of the prepreg). In this embodiment, a resin film is manufactured by first coating the particle-containing resin composition onto a release paper. Next, one or two such resin films are/are laminated onto one or both sides of a layer of reinforcing fibers (eg unidirectional fiber mesh) with the aid of heat and pressure to impregnate the fibers, forming thus a fiber reinforced polymer layer (or pre-impregnated ply) with a specific weight per fiber area and resin content. During the lamination process, particles with tenacity are filtered out and remain outside the fiber layer due to the fact that the particle size is larger than the spacing between the fiber filaments. The resulting prepreg ply contains a structural fiber reinforced layer adjacent to one or two layers of matrix resin in which the toughened particles are embedded. Subsequently, when two or more plies of prepreg containing particles having tenacity therein are laminated on top of one another by a disposition process, the particles having tenacity are positioned in the interlaminar region between two adjacent fiber layers. In this embodiment, the matrix resin in the interlaminar region (no particles with polymeric toughness) is the same as the matrix resin contained in the structural fiber reinforced layer and contains uniformly dispersed carbon nanomaterials.
    [0077] In a second embodiment, a curable matrix resin containing particles with tenacity is coated onto a release paper to form a resin film. This resin film is then placed in contact with one side of a fiber layer (eg unidirectional fiber mesh). When pressure is applied, the resin film impregnates the fibers and leaves little or no resin on the outer surfaces of the fiber layer. Subsequently, a curable resin film containing particles with tenacity is laminated to an exposed outer surface of the resin-impregnated fiber layer. The curable resin carrying the particles with tenacity can be the same as or different from the matrix resin impregnating the reinforcing fibers. As a result, a particle-containing resin layer remains outside the impregnated fiber layer and does not further impregnate the fibers. A plurality of such structures are laminated together to form a composite structure with particles having toughness in the interlaminar regions.
    [0078] In another embodiment, two particulate-free curable matrix resin films with toughness are laminated onto two opposing surfaces of a fiber layer. Resin films impregnate the fibers and leave little or no resin on the outer surfaces of the fiber layer, resulting in a resin impregnated fiber layer. Subsequently, two curable resin films containing toughened particles are contacted with opposing surfaces of the resin-impregnated fiber layer to form a sandwich-like structure. Such an approach tends to produce a well-defined and regular interlaminar region in the cured laminate.
    [0079] The curing of the composite material or prepreg arrangement described here is generally carried out at elevated temperature up to 200°C, preferably in the range of 170°C - 190°C, and using high pressure to restrict effects of exhaust gas deformation, or to restrict void formation, suitably at pressure up to 10 bar (1 MPa), preferably in the range of 3 bar (0.3 MPa) to 7 bar (0.7 MPa). Preferably, the curing temperature is reached by heating to up to 5°C/min, for example 2°C/min to 3°C/min and is maintained for the required period of up to 9 h, preferably up to 6 h, for example 2 h to 4 h. The use of a catalyst in the matrix resin can still allow for lower curing temperatures. Pressure is completely released, and the temperature is reduced by cooling down to 5°C/min, eg up to 3°C/min. Post-curing at temperatures in the range of 190°C to 350°C and atmospheric pressure can be carried out by employing appropriate heating rates to improve the glass transition temperature of the matrix resin.
    [0080] The terms "cure" and "cured" as used herein may include polymerization and/or crosslinking processes. Curing can be accomplished by processes that include, but are not limited to, heating, exposure to ultraviolet light, and exposure to radiation. applications
    [0081] The composite materials described here are applicable to the fabrication of structural components for aerospace applications, including aircraft, and automotive applications, including automotive vehicles and railroad. For example, composite materials can be used to fabricate primary and secondary aircraft structures, space and ballistic structures. Such structural components include composite wing structures. The composite materials described herein also find use in building and construction applications, as well as commercial applications. Notably, composite materials are particularly suitable for the fabrication of load-bearing or impact-resistant structures. structural adhesives
    [0082] Structural adhesives have been conventionally used for structural bonding in the manufacture of structural parts that demand severe mechanical requirements such as automobile parts and aircraft bodies. Structural adhesives for aerospace application must have the durability to withstand harsh environmental conditions. Generally, heat-curable epoxy adhesives are used as structural adhesives.
    [0083] The functionalized PAEK particles discussed above can be incorporated into curable adhesive compositions that are based on thermosetting resins, eg epoxy, which are usable for bonding various composites or metal substrates. Furthermore, functionalized particles in combination with other components in the adhesive composition could provide improved resistance to superimposed shear under hot/wet conditions.
    [0084] The preferred adhesive composition is based on epoxy resins, which can be selected from those discussed above for composite matrix resin. Furthermore, it is preferred that the epoxy resin has a plurality of epoxy groups per molecule, i.e. multifunctional epoxies. In one embodiment, a plurality of different multifunctional epoxies are present in the adhesive composition. Epoxy resins are not used alone, but are combined with suitable curing agents, catalysts, rheology control agents, tackifiers, particulate fillers (eg fumigated silica), elastomeric toughening agents, soluble thermoplastics, reactive diluents, and other additives well known to those skilled in the art. EXAMPLES Synthesis of functionalized PEKK polymer particles Example 1: Production method of 1,4-(100:0) PEKK with terminal NH2 functionality, 5% unbalance
    [0085] The reaction vessel was a five liter jacketed, round-bottomed glass reaction vessel with a bottom outlet and four bulkheads. Dichloromethane (2500 ml) was placed in the reaction vessel which was fitted with an overhead stirrer with an anchor head plus two intermediate blades set at 90°, a solids inlet, a nitrogen inlet and a thermocouple. The vessel temperature was controlled by an external Julabo cooler/heater unit and was recorded using the Julabo EasyTemp software.
    [0086] The vessel was purged with nitrogen and the dichloromethane cooled to -20°C with stirring at 200 rpm, this stirring rate was used from the beginning to the end of the addition of all reagents. Nitrogen purge was removed during solids additions but reconnected during longer cooling periods. Aluminum chloride (AlCl3) (764.8g; 5.74M) was added to the cooled dichloromethane resulting in a small increase in temperature. On cooling again to -20°C, benzoic acid (292.96 g; 2.399 M) was added slowly into the AlCl3 slurry so as to maintain the slurry temperature below -10°C. The dichloromethane slurry developed a yellow color due to aluminum chloride; most of it remained at the bottom of the vase. The reaction mixture was then allowed to cool again to -20°C.
    [0087] Keeping the reaction mixture below -5oC 1,4-bis(4-phenoxybenzoyl)benzene (EKKE) 265.99 g; 0.5653 M) was carefully added in portions. At this point the mixture turned to a bright opaque orange. The remaining monomer was transferred by washing with approximately 4x50ml (200ml) portions of dichloromethane. Terephthaloyl chloride (TPC) (120.81 g; 0.5951 M) was carefully added at a rate so as not to allow the mixture to rise above -10°C. The terephthaloyl chloride residues were transferred into the vessel by washing with approximately 200 ml of dichloromethane in three portions.
    [0088] Lastly the chain terminator ("CF3-EC"), 2,2,2-Trifluoro-N-(4-phenoxyphenyl) acetamide (16.69 g; 0.0596 M) obtainable from Chem Bridge Corporation, SanDiego, USA and purified prior to use was added with its washings, along with the remaining 100 ml of dichloromethane. The stirrer speed was increased to 500 rpm and maintained throughout the reaction time. The reaction mixture was heated slowly to 5°C then after 10 minutes to 20°C, where it was kept constant throughout the reaction time. After approximately 30 minutes all solids had dissolved forming an orange-red solution. After this point, dispersed polymer particles began to form. The reaction mixture was stirred rapidly for five hours. Sometimes it is necessary to add an additional 500 ml of dichloromethane to replace material that evaporates during the reaction. If the reaction is carried out in a pressurized vessel this will not be necessary. During this phase the nitrogen purge was replaced with a collector to collect and neutralize the hydrogen chloride evolved during the reaction.
    [0089] The reaction mixture was removed from the reaction vessel and isolated by vacuum filtration through a sinter. The orange solid was transferred to and decomplexed into approximately three liters of ice-cold deionized water with stirring to produce a white particulate product. During decomplexation, the mixture should not reach more than 5°C. The filtrate is also poured into ice water for decomplexation and disposal. The polymer remains in deionized water until work starts. Before work, the polymer particles must be completely white, with no orange residue.
    [0090] Working procedures are typically performed using a hot plate with stirrer. Constant agitation is achieved with a large magnetic stirrer bar. A representative working procedure for a PEKK polymerization performed in a one liter reactor is as follows: • Stand/stir in deionized water overnight at room temperature. • Filter and slowly add to 1.5 liters of hot deionized water, stirred to remove residual dichloromethane. • 100 ml of concentrated hydrochloric acid added, boiled for 1 hour, filtered, washed with 500 ml of filtered deionized water. • Fluid paste in 2 liters of deionized water, boiled for 1 hour, filtered, washed with 500 ml of deionized, filtered water. Repeat the above • Slurry in 2 liters of deionized water made to pH 13 with ammonia solution (~30 ml), boiled for 1 hour, filtered, washed with 500 ml of deionized water, filtered. • Slurry in 2 liters of deionized water, boiled for 1 hour, filtered, washed with 500 ml of deionized water, filtered • Isolated pale cream PEKK powder.
    [0091] During this process the trifluoroacetyl protecting groups are removed from the chain terminator leaving the terminal amine functionality free.
    [0092] The powder was first dried at 120°C overnight, or even dried, in an air oven. The powder was then dried again at 200°C overnight in a vacuum oven where the oven was continuously evacuated.
    [0093] Dry yield ~ 270g: 80% yield. The process produces a fair amount of very fine particles and many of these are lost during the filtration steps.
    [0094] The inherent viscosity (IV) of the resulting polymer was 0.85 dl/g. Tg was 182°C; Tm (melting temperature) was 396°C. Example 2: Production method of 1.4:1.3 - (80:20) PEKK with terminal NH2 functionality, 5% imbalance
    [0095] This was carried out in exactly the same way as in example 1, but where the amounts of terephthaloyl chloride (TPC) and isophthaloyl (IPC) were 73.69 g, 0.3630 M and 47.12 g 0.2321 M respectively.
    [0096] The IV of the resulting polymer was 0.81 dl/g; Tg was 165°C; Tm was 355°C. Example 3: Production method of 1.4; 1.3 - (60:40) PEKK with terminal NH2 functionality, 5% imbalance
    [0097] This was carried out in exactly the same way as in example 1, but where the amounts of TPC and IPC chlorides were 26.58 g, 0.1309 M and 94.23 g 0.4642 M respectively.
    [0098] The IV of the resulting polymer was 0.83 dl/g; Tg was 158°C. Example 4: Production method of 1.4; 1.3 - (80:20) PEKK with terminal NH2 functionality, 5% crosslinked, 5% imbalance
    [0099] This was performed using the same procedure as described in example 1, but using the following reagents:


    [00100] Note: This is based on end group concentration. The total acid chloride end-group concentration was (0.3369 + 0.2249)x2 + 0.025x3 = 1.1986. 5% imbalance was 0.95x1.1986 = 1.1387 or 0.5693M EKKE = 267.88g. CF3-EC required was 1.1986-1.1387 = 0.0599 M = 16.85g.
    The IV of the resulting polymer was 1.5 dl/g; Tg was 166°C; Tm was 352°C. Example 5 - Method for the production of 10% random copolymer PEKK-EIEIE (100:0) chain terminated with NH2
    [00102] Dichloromethane was placed in a reaction vessel fitted with an overhead stirrer. The vessel temperature was controlled by an external cooler/heater unit.
    [00103] The vessel was purged with nitrogen and the dichloromethane allowed to cool to -20°C with stirring at 200 rpm. The mixture in the reaction vessel was constantly agitated at an average rate of approximately 200 rpm during the following additions. Nitrogen purge was removed during additions but reconnected during longer cooling periods. Aluminum chloride (609.64 g) was added, followed by benzoic acid (218.24 g), not allowing the mixture to rise above -10°C due to the exotherms. The dichloromethane developed a yellow color due to the aluminum chloride, most of which remained at the bottom of the vessel. The reaction mixture was then allowed to cool again to -20°C.
    [00104] Terephthaloyl chloride (90.60 g) was added carefully at a rate so as not to allow the mixture to rise above -10°C. The remaining acid chloride was transferred by washing with approximately 100 ml of dichloromethane in three portions. 5,5'-Oxibis(2-(4-phenoxyphenyl)isoindoline-1,3-dione) (EIEIE) (82.20 g) was added carefully at a rate so as not to allow the mixture to rise above -10 °C, causing the mixture to become a bright opaque orange. The remaining monomer was transferred by washing with approximately 50 ml of dichloromethane in three portions. EKKE (1,4-bis(4-phenoxybenzoylbenzene) (140.00 g) was added carefully at a rate so as not to allow the mixture to rise above -5°C. The remaining monomer was washed away with approximately 50 ml of dichloromethane in three portions.
    [00105] Lastly, 2,2,2-trifluoro-N-(4-phenoxyphenyl) acetamide (11.96 g) was added with its washings, along with the remaining dichloromethane. The stirrer speed was increased to 500 rpm and maintained throughout the reaction time. The nitrogen purge was removed and replaced with a water pump fitted with an air port so as not to place the reaction system under vacuum. This was to trap and remove the hydrogen chloride evolved from polymerization. The reaction mixture was slowly heated to 5°C, then after 10 minutes to 20°C, where it was held constant throughout the reaction time. After approximately 30 minutes all solids had dissolved forming an orange-red solution. After this point, dispersed polymer particles began to form. The reaction mixture was stirred rapidly for five hours. The reaction mixture was removed from the vessel through a bottom outlet.
    [00106] The reaction mixture was removed from the reaction vessel and isolated by vacuum filtration through a sinter. The orange solid was decomplexed in approximately three liters of ice-cold deionized water with stirring to produce a white particulate product.
    [00107] The working procedure for PEKK polymerization was carried out in a one liter reactor as follows: • Stand in deionized water overnight • Filtered and slowly added into 1.5 liters of hot deionized water, stirred to remove the residual dichloromethane • Make up to 5 L with hot deionized water, 100 ml of concentrated hydrochloric acid added, boiled for 1 hour, filtered, washed with 1 L deionized water, filtered 5 liters of deionized water made to pH 13 with sodium hydroxide globules , boiled for 1 hour, filtered, washed with 1 L of deionized water, filtered • 5 liters of deionized water, boiled for 1 hour, filtered, washed with 1 L of deionized water, filtered • 5 liters of deionized water, boiled for 1 hour , filtered, washed with 1 L of deionized water, filtered • 5 liters of deionized water, boiled for 1 hour, filtered, washed with 1 L of deionized water, filtered • PEKK powder without white isolated
    [00108] The IV of the resulting polymer was 0.75 dl/g.
    [00109] FIG. 2 shows functionalized PEKK particles produced with different tere:iso (T:I) ratios produced according to examples 1 (100:0), 2 (80:20) and 3 (60:40). FIG. 3 shows the back structure of the PEKK imide copolymer and crosslinked versions according to examples 4 and 5 at different magnifications showing size, shape and surface characteristics.
    [00110] FIGS. 4 and 5 are Scanning Electron Micrograph (SEM) images of amine reactive chain terminated PEKK polymer particles produced according to Example 2 at a T:I ratio of 80:20 at 500X and 2000X magnification, respectively. These images show spherical particles that are on average 50-60 µm in diameter (as measured by laser diffraction) with some agglomeration of the particles as shown in FIG. 4. Surface aspects of the spherical particle as shown in FIG. 5 have similar characteristics to a “dried grape” so that cracks and wrinkles have been formed possibly due to particle contraction upon precipitation from the solution. Fabrication of particle-stiffened composite panels Example 6
    [00111] A composite test panel was made by arranging 13 plies of epoxy/carbon fiber prepreg (weight per fiber area (FAW) =190 grams per square meter) without any particle stiffener in it to form a half of a disposition. The epoxy/carbon fiber prepreg contained unidirectional intermediate modulus (IM) carbon fibers impregnated with an epoxy-based resin containing a dissolved thermoplastic toughening agent as described in table 1. % by weight refers to percentage by weight. TABLE 1

    [00112] A crack initiator was inserted into the top of the highest bend and functionalized PEKK particles prepared according to example 2 were screen printed over the rest of the highest bend. 13 additional prepreg plies were placed on top of the existing layout. The final disposition was enclosed in a vacuum bag, consolidated under pressure, and then cured. For comparison, a second composite panel was prepared in a similar manner except that non-functionalized PEKK particles were used. Non-functionalized PEKK particles were formed by polymer jet milling (Cypek®FC available from Cytec Industries Inc.) to a particle size with a D50 between 15 and 20 microns.
    [00113] FIG. 6 is a diagram showing a specimen with fracture toughness that was tested for GIIC fracture toughness and SEM scan site of fractured surface. GIIC fracture toughness (end notch bending) was measured by a modified version of the ASTM D7905 in which the two inner bends near the crack initiator are oriented +/-2 degrees to avoid fiber nesting.
    [00114] Table 2 shows the GIIC (fracture toughness) results of testing cured composite test panels containing the unfunctionalized and functionalized PEKK particles using the GIIC fracture toughness test method described above. Table 3 shows that the GIIC (crack 1) value for the functionalized PEKK particles was almost twice that of the non-functionalized PEKK particles. TABLE 2

    [00115] FIG. 7 is a 1000X SEM image of the fracture surface of the GIIC test specimen derived from epoxy fiber/carbon particle composite, which contained amine-terminated PEKK particles with T:I = 80/20 (prepared according to the example 2). The highlighted areas (C & D) show the “drag” of the particle and “fracture through” the particle as the crack propagates. The “fracture through” of the particles is evidence that reactive end groups have reacted with the epoxy matrix. "Drag" of particles refers to an area of the fracture surface where every particle with tenacity has been dragged leaving a crater; and “fracture through” the particle refers to an area on the fracture surface where the perimeter of the toughened particle can be seen clearly, but the fracture has entered through the particle leaving a fragment in the crater. Example 7
    [00116] Functionalized PEKK polymer with T:I ratios of 80/20 and 100/0 with an imbalance (OOB) of 5% was made with the dispersion polymerization process described in examples 1 and 2 having phenoxyaniline as the chain termination after the trifluoroacetic acid group has been removed by the working/deprotection procedure. The particle size range for PEKK T:I =80/20 was 30 to 180 microns and for PEKK T:I = 100/0 was 15 to 800 microns. The particles were sieved through a 75 micron mesh size to remove particles larger than 75 microns. The average particle size was 60 and 45 microns respectively for PEKK T:I = 80/20 and PEKK T:I = 100/0. Non-functionalized PEKK polymer (Cypek® FC available from Cytec Industries Inc.) was finely ground to a particle size range in diameter from 5 to 50 microns with an average value between 15 - 20 microns to be used as the prepreg control to compare with functionalized PEKK particles. The particle size range (or distribution) was determined by the Malvern Mastersizer (laser diffraction) particle size analyzer. Functionalized and unfunctionalized PEKK particles were mixed separately into an epoxy resin blend using the formulation in Table 3. % by weight refers to percentage by weight. TABLE 3

    [00117] The resin mixtures were then cast into films on a release paper. These cast films were then combined with carbon fiber from the IM7 intermediate module (12K filaments) in a single-tape prepreg process with the resin content being 35% and weight per fiber area (FAW) being 190 grams per meter square. The uni-tape prepreg was then cut to size and orientation to form individual plies, which were subsequently laid out and cured to make the mechanical test panels. The test panels produced were then subjected to the fracture toughness test described in example 6, post impact compressive strength test (CAI) (ASTM test method D7137), and full bore (OHC) compression test (test method). test ASTM D6484). OHC test samples were moisture conditioned by immersing the samples in a water bath set at 71°C for 2 weeks and then testing at 82°C. The other tests were carried out at room temperature under ambient conditions. Table 4 summarizes the test results for the IM7 carbon fiber reinforced particle stiffened composites using unfunctionalized and functionalized PEKK particles. The functionalized particles showed a 24% - 29% improvement in CAI, a 74% to 250% improvement in the GIIC fracture toughness values (critical strain energy release rate), and a 70% to 236% improvement in the values of GIIP fracture toughness (deformation energy release rate propagation) while maintaining excellent hot/wet filled hole compression strength due to the low moisture take up of PEKK polymer. TABLE 4 - CAI, Fracture Toughness, and OHC Performance of Carbon Fiber Reinforced Particle Stiffened Epoxy Prepregs
    Example 8
    [00118] Functionalized PEKK polymer with a T:I ratio of 60/40 with an imbalance (OOB) of 5% was made with a dispersion polymerization process described in example 3 having phenoxyaniline as the chain termination after the trifluoroacetic acid group has been removed by the work/deprotection procedure. Functionalized PEKK polymer with a T:I ratio of 80/20 which was 5% crosslinked with an OOB of 5% was made by the dispersion polymerization procedure in example 4 while PEKK-EIEIE T:I = 100/0 amine chain terminated with 10% random copolymer was made by the procedure described in example 5. The particle size range for PEKK T:I =60/40 was 3 to 1905 microns; for PEKK T:I =80/20 with 5% crosslinking was 2 to 240 microns; and for PEKK-EIEIE T:I = 100/0 PEKK-EIEIE with 10% random copolymer was 5 to 832 microns. The particles were sieved through a 75 micron mesh size to remove particles larger than 75 microns. Non-functionalized PEKK polymer (Cypek® FC) was finely ground to a particle size range in diameter from 5 to 50 with an average value between 15 - 20 was used as non-functionalized PEKK particles. The particle size range (or distribution) was determined using a Malvern Mastersizer (laser diffraction) particle size analyzer. Functionalized and unfunctionalized PEKK particles were separately blended into an epoxy resin blend using the formulation shown in table 5. % by weight refers to percentage by weight. TABLE 5

    [00119] The resin mixtures were then cast into films on a release paper. These cast films were then combined with carbon fiber from the IM7 intermediate module (12K filaments) in a single-tape prepreg hot melt process with the resin content being 35% and weight per fiber area (FAW) being 190 grams per square meter. The prepreg uni-tape was then cut to size and orientation to form individual plies, which were subsequently arranged and cured to make the mechanical test panels. The produced test panels were then subjected to the fracture toughness, impact compressive strength (CAI), and full bore compression (OHC) tests described in example 7. Table 6 summarizes the test results for the composites hardened with particle using unfunctionalized and functionalized PEKK particles, crosslinked PEKK particles, and PEKK-EIEIE particles. Composites with functionalized particles showed an improvement over composite with non-functionalized particle control of 5 to 19% in CAI, 4% to 32% improvement in fracture toughness values GIIC (critical strain energy release rate) ), and 18 to 44% improvement in GIIP (spreading strain energy release rate) while maintaining excellent hot/wet hole compressive strength due to the low moisture take up of PEKK polymer. TABLE 6 - Performance of CAI, Fracture Toughness, and OHC pre-impregnated epoxy pre-impregnated with carbon fiber reinforced particle with PEKK, cross-linked PEKK, and PEKK-EIEIE particles
    权利要求:
    Claims (10)
    [0001]
    1. Composite material, characterized in that it comprises: a curable thermosetting matrix resin comprising at least one thermosetting resin; reinforcement fibers impregnated with matrix resin; particles of an amine-functionalized polyaryletherketone polymer or copolymer thereof, wherein the functionalized PAEK particles comprise amine functional groups capable of forming covalent bonds with the thermosetting resin, and wherein the polymer or copolymer has the following structure:
    [0002]
    2. Composite material according to claim 1, characterized in that E is phenoxyaniline.
    [0003]
    3. Composite material according to any one of claims 1 or 2, characterized in that said particles are substantially spherical in shape with an aspect ratio (R) from 1 to 1.5.
    [0004]
    4. Composite material according to any one of claims 1 to 3, characterized in that the particles are substantially spherical particles having a diameter of less than 75 µm.
    [0005]
    5. Composite material according to claim 1, characterized in that at least one of R1 and R3 is the branching unit:
    [0006]
    6. Composite material according to any one of claims 1 to 5, characterized in that the at least one thermosetting resin is selected from the group consisting of: epoxides, bismaleimide and benzoxazine.
    [0007]
    7. Composite material according to any one of claims 1 to 6, characterized in that the reinforcing fibers are arranged as a plurality of fibrous layers, and at least one interlaminar region is created between two adjacent fibrous layers, and wherein the particles are positioned in the interlaminar region.
    [0008]
    8. Composite material according to claim 7, characterized in that the reinforcing fibers in each fibrous layer are unidirectional fibers, or woven.
    [0009]
    9. Method for making a composite laminate, said method characterized in that it comprises: forming a plurality of prepregs, each prepreg comprising a layer of reinforcing fibers impregnated with the curable matrix resin and functionalized polymer particles of amine-functionalized polyaryletherketone (PAEK) positioned adjacent the layer of reinforcing fibers; and arranging the prepregs in a stacking arrangement such that an interlaminar region is defined between adjacent layers of reinforcing fibers, and functionalized PAEK particles are positioned within said interlaminar region, wherein the curable matrix resin comprises at least at least one thermosetting resin, and wherein the functionalized polymer particles are particles of an amine-functionalized polyaryletherketone polymer or copolymer thereof which comprise amine functional groups capable of forming covalent bonds with the at least one thermosetting resin, and wherein the polymer or copolymer has the following structure:
    [0010]
    10. Method according to claim 9, characterized in that said particles are substantially spherical in shape with an aspect ratio (R) of 1 to 1.5.
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    同族专利:
    公开号 | 公开日
    CA2949691A1|2015-11-26|
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    JP2021101014A|2021-07-08|
    TWI685536B|2020-02-21|
    CA2949691C|2021-12-14|
    WO2015179618A1|2015-11-26|
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    法律状态:
    2020-03-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-15| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/05/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201462001829P| true| 2014-05-22|2014-05-22|
    US62/001,829|2014-05-22|
    PCT/US2015/031937|WO2015179618A1|2014-05-22|2015-05-21|Functionalized polymer particles for use as toughening agent|
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