Composite composition comprising aramid copolymer particles and thermoplastic engineered polymer and article comprising composition

Abstract

Disclosed are a composite composition, and a method for manufacturing the composite composition and an article comprising the composite composition, the composition comprising 3 to 30 parts by weight of particles comprising an aramid copolymer comprising imidazole groups, and up to 97 parts by weight of a thermoplastic engineering polymer; wherein the particles are homogeneously dispersed in the thermoplastic engineered polymer and reduce the wear rate of the thermoplastic engineered polymer by at least 25%.

Description

Background of the Invention

[0002] Field of the Invention. The present invention is a composite composition comprising solid polymer particles dispersed in an engineering polymer, wherein the combination of the dispersed solid material and the engineering polymer has unexpected mechanical properties. The solid polymer particles can be, for example, polymer chips or powder-like particles, or flocs.

[0003] Description of the Related Art. Articles made from engineering polymers in a molten state are highly regarded for their ease and flexibility of manufacture. Such articles can be in the form of injection molded parts or parts made by 3-D printing or additive manufacturing (such as by fused deposition modeling (FDM), stereolithography (SLA), or selective laser sintering (SLS)). Such parts can be, for example, thin-walled parts or industrial large parts for the automotive and / or aerospace industries. Any improvement in a composition containing such an engineering polymer that adds additional product features or improved performance is desirable. Summary of the Invention

[0004] The present invention relates to a composite composition comprising:

[0005] a) 3 to 30 parts by weight of particles comprising an aromatic polyamide copolymer containing an imidazole group, and

[0006] b) up to 97 parts by weight of a thermoplastic engineering polymer;

[0007] wherein the particles are uniformly dispersed in the thermoplastic engineering polymer and reduce the wear rate of the thermoplastic engineering polymer by at least 25 percent. The present invention further relates to an article comprising the composite composition.

[0008] The present invention also relates to a method for manufacturing a composite composition, the method comprising the steps

[0009] a) polymerizing monomers to form an aromatic polyamide copolymer containing an imidazole group, the monomers comprising at least one aromatic diacid and at least one aromatic diamine and an imidazole diamine;

[0010] b) crushing and separating the aromatic polyamide copolymer containing an imidazole group in the form of polymer chips of a desired particle size;

[0011] c) optionally, further grinding or milling the polymer chips to form particles of a desired particle size comprising an aromatic polyamide copolymer containing an imidazole group; and

[0012] d) combining and mixing 3 to 30 parts by weight of the particles with up to 97 parts by weight of a thermoplastic engineering polymer to form the composite composition. Description of the Drawings

[0013] Figure 1 is a photograph at 30X magnification of raw polymer particles having an overall size of 1 mm or greater and containing an aromatic polyamide copolymer containing an imidazole group, the particles being dried and coarsely ground polymer fragments obtained and separated from a polymerization step.

[0014] Figure 2 is a photograph at 30X magnification of milled particles (referred to herein as "dry extruder" particles) having an overall size of less than 1 mm and containing an aromatic polyamide copolymer containing an imidazole group, the particles being made by further reducing the size of the raw polymer particles in the dry state using a twin-screw extruder; that is, the particles have less than 10 weight percent moisture.

[0015] Figure 3 and Figure 4 are photographs at 30X and 100X magnification levels, respectively, of the same milled particles (referred to herein as "wet extruder" particles) having an overall size of less than 1 mm and containing an aromatic polyamide copolymer containing an imidazole group, the particles being made by reducing the size of water-wet fragments from polymerization in a twin-screw extruder only once to achieve a desired particle size. Detailed Description

[0016] The present invention relates to a composite composition and articles made therefrom, which contain a blend of a thermoplastic engineering polymer and aromatic polyamide copolymer particles, wherein the aromatic polyamide copolymer contains an imidazole group in the copolymer chain. Preferably, the particles are uniformly dispersed in the thermoplastic engineering polymer. Uniformly dispersed means that the particles are preferably uniformly distributed in a random manner in the thermoplastic engineering polymer, which can preferably provide uniform mechanical properties for any article made from the composite composition.

[0017] Composite composition

[0018] Specifically, the composite composition comprises 3 to 30 parts by weight of particles comprising an aromatic polyamide copolymer containing an imidazole group. These solid materials are uniformly dispersed in up to 97 parts by weight of a thermoplastic engineering polymer in the composition. If only the particles and the thermoplastic engineering polymer are present, the thermoplastic engineering polymer is used in an amount of 3 to 97 parts by weight in the composition. The resulting composition reduces the wear rate of the thermoplastic engineering polymer by at least 25 percent (when compared to the wear rate of the thermoplastic engineering polymer alone), thereby improving the wear resistance of the thermoplastic engineering polymer. In some embodiments, the composite composition comprises 5 to 25 parts by weight of particles comprising an aromatic polyamide copolymer containing an imidazole group and 75 to 95 parts by weight of a thermoplastic engineering polymer. In some embodiments, when compared to the wear rate of the thermoplastic engineering polymer alone, the addition of particles comprising an aromatic polyamide copolymer containing an imidazole group reduces the wear rate of the thermoplastic engineering copolymer by at least 45 percent. In some embodiments, when compared to the wear rate of the thermoplastic engineering polymer alone, the addition of particles comprising an aromatic polyamide copolymer containing an imidazole group reduces the wear rate of the thermoplastic engineering copolymer by at least 80 percent.

[0019] It is believed that the wear rate of articles comprising the composite composition is most improved in applications simulating high pressure - velocity wear, such as shown by the thrust washer (TW) test presented herein. In those applications, when compared to the wear rate of the thermoplastic engineering polymer alone, the addition of particles comprising an aromatic polyamide copolymer containing an imidazole group can reduce the wear rate of the thermoplastic engineering copolymer by up to at least 75 percent, preferably at least 80 percent, and most preferably at least 85 percent or higher.

[0020] However, the wear rate of articles comprising the composite composition also shows improvement in applications simulating low pressure - velocity wear, such as shown by the three - pad washer (3PW) test presented herein. In those applications, when compared to the wear rate of the thermoplastic engineering polymer alone, the addition of particles comprising an aromatic polyamide copolymer containing an imidazole group can reduce the wear rate of the thermoplastic engineering copolymer by up to at least 45 percent, preferably at least 60 percent, even more preferably at least 80 percent or higher, and most preferably at least 85 percent or higher.

[0021] Adhesion property

[0022] In addition to the improved wear characteristics, it has been found that aromatic polyamide copolymers containing imidazole groups have unexpectedly excellent adhesion to thermoplastic engineering polymers such as PEEK, relative to para-aramid homopolymers such as poly(p-phenyleneterephthalamide). It is believed that this excellent adhesion is provided by the aromatic polyamide copolymer containing imidazole groups in addition to the unexpectedly improved wear and other properties for the article.

[0023] A method for characterizing the improved adhesion properties between materials has been found using DIN SPEC 19289:2022-08 “Fibre-reinforced composites - Measurement of Interfacial Shear Strength by means of a Micromechanical Single-Fibre Pull-Out Test [Fibre-reinforced composites - Measurement of Interfacial Shear Strength by means of a Micromechanical Single-Fibre Pull-Out Test]”, in which fibres of one material are embedded in the matrix of another material and then the force required to pull the fibres out of the matrix is measured. (As used herein, the words “fibre” and “filament” are used interchangeably.) This European standard defines the “apparent interfacial shear strength” (τ app ) in MPa as the maximum force normalized with respect to the contact area between the fibre and the cured matrix, where the maximum force is the highest force value that occurs just before the fibre is completely debonded from the matrix during the pull-out. In addition, the “local interfacial shear strength” (τ d ) in MPa is defined as the debonding force related to the contact area of the interface between the fibre and the cured matrix in the absence of the influence of friction between the fibre and the matrix, where the debonding force is the force at which the fibre begins to debond from the cured matrix. Additionally, the “critical interfacial energy release rate” (G ic ) in joules per square metre is defined as the interfacial toughness, which takes into account the deformation of the fibre and the matrix during the pull-out. For the purpose of determining the adhesion properties herein, the fibre material is an aromatic polyamide copolymer containing imidazole groups and the matrix material is a thermoplastic engineering polymer.

[0024] It is believed that in many cases, the “local interfacial shear strength” (τ d ) can be the best measure of the adhesion between the polymer of the fibre material and the polymer of the cured matrix material, as this is the debonding force in the absence of the influence of friction between the fibre and the matrix material; however, all of these specified properties describe the adhesion between the fibre and the matrix material.

[0025] When the particles of the aromatic polyamide copolymer containing an imidazole group are in the form of flocks, the adhesion using DIN SPEC 19289:2022-08 between the fibrous material of the aromatic polyamide copolymer containing an imidazole group and the engineering polymer matrix material is directly applicable. Additionally, the particles of the aromatic polyamide copolymer containing an imidazole group in the form of flocks can contain a surface or spinning "finish". It is well known that such finishes are oils, waxes, or other materials used as fiber processing aids to reduce damage to the fibers. It has been found that the fibers of the aromatic polyamide copolymer containing an imidazole group further having a surface finish have an improved τ d when compared to the "local interfacial shear strength" (τ d ) of the same fibrous material without the finish (i.e., the fibers from which any surface finish has been removed). It is believed that the finish can help the matrix polymer better wet the surface of the fibers for better contact.

[0026] Additionally, it is believed that when the particles of the aromatic polyamide copolymer containing an imidazole group are in the form of a crude or ground polymer, the adhesion using DIN SPEC 19289:2022-08 between the fibrous material without the finish (i.e., the aromatic polyamide copolymer containing an imidazole group) and the engineering polymer matrix material is directly applicable. Thus, it then follows that even though the polymeric material may be in various forms, the adhesion characteristics of the polymer particles to various thermoplastic engineering polymers can be determined by first making filaments of the polymeric material (ensuring the absence of a finish), and then embedding the filaments without the finish into the matrix of the thermoplastic engineering polymer, and subsequently pulling out the filaments, all in accordance with the standard DIN SPEC 19289:2022-08.

[0027] In some embodiments, the "local interfacial shear strength" (τ d ) between the particles of the aromatic polyamide copolymer containing an imidazole group and the engineering polymer is greater than the "local interfacial shear strength" (τ d ) between the particles of a para - aromatic polyamide homopolymer (such as PPD - T) and the same engineering polymer. In some embodiments, the "local interfacial shear strength" (τ d ) between the particles of the aromatic polyamide copolymer containing an imidazole group and the engineering polymer is at least 9 percent or more greater than the "local interfacial shear strength" (τ d ) between the particles of a para - aromatic polyamide homopolymer (such as PPD - T) and the same engineering polymer. In some preferred embodiments, the "local interfacial shear strength" (τ d) The "local interfacial shear strength" (τ) between the particles of para - aromatic polyamide homopolymers (such as PPD - T) and the same engineering polymer d ) is at least 35 percent or more greater. In some embodiments, the particles of aromatic polyamide copolymers containing imidazole groups provide a 25 - percent to 125 - percent increase in local interfacial shear strength relative to PPD - T.

[0028] In some embodiments, the local interfacial shear strength (τ) between the particles of aromatic polyamide copolymers containing imidazole groups and the engineering polymer d ) is 72 MPa or greater, and can range up to 100 MPa or higher.

[0029] Thermoplastic engineering polymer

[0030] "Thermoplastic engineering polymer" means a polymer that can be used as the sole, primary, or main polymeric material for fabricating polymeric parts or components of a device. Additionally, as used herein, "thermoplastic" has its conventional definition, i.e., an engineering polymer in solid form can be heated to a liquid state and then cooled back to a solid state, and this cycle can be repeated with little change in the melting point of the copolymer. In many cases, thermoplastic engineering polymers contain aromatic rings as substituents or as part of the polymer backbone, and these aromatic rings can be readily substituted or modified to provide additional functionality for specific applications.

[0031] Generally, engineering polymers are desirable in articles that may be used at elevated temperatures, and one measure is, for example, the deflection temperature under load as measured according to ASTM D648 - 07 "Standard Test Method for Deflection Temperature of Plastics Under Flexural Load In the Edgewise Position" (which is equivalent to ISO 75). This test determines the temperature at which deformation occurs under a specific load, which is referred to as the heat deflection temperature (HDT). Typically, the HDT can be measured with a load value of 1820 kPa, which is commonly referred to as 1.8 MPa (264 psi). In some preferred embodiments, the preferred thermoplastic engineering polymer for use in this composite composition has an unfilled or "pure" HDT of 100 °C or higher at 1.8 MPa. Representative heat deflection temperatures of certain example thermoplastic engineering polymers are shown in Table 1.

[0032] Table 1

[0033]

[0034] In some embodiments, the thermoplastic engineering polymer of the composite composition preferably comprises polyaryletherketone (PAEK), and in some embodiments, the PAEK is poly(ether ketone) (PEK), poly(ether ether ketone) (PEEK), poly(ether ketone ketone) (PEKK), or a mixture thereof. In some preferred embodiments, the thermoplastic engineering polymer is poly(ether ether ketone) (PEEK) or comprises poly(ether ether ketone) (PEEK).

[0035] In some embodiments, the thermoplastic engineering polymer of the composite composition comprises polyamide (PA), polyamide-imide (PAI), polyethersulfone (PES), polyether-imide (PEI), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polyoxymethylene (POM), acetal copolymer (AC), polycarbonate (PC), or a mixture thereof. As used herein, "liquid crystal polyester" (LCP) means a polyester polymer that is anisotropic when tested using the TOT test or any reasonable variant thereof, as described in U.S. Patent 4,118,372. A preferred form of LCP is "wholly aromatic", i.e., all groups in the polymer backbone are aromatic (except for linking groups such as ester groups), but there may be side groups that are not aromatic. The LCPs that can be used as thermoplastics in the present invention have a melting point of up to 350 °C. The melting point is measured according to test method ASTM D3418. The melting point is taken as the maximum of the melting endotherm and is measured at a heating rate of 10 °C / min during the second heating. If there are more than one melting point, the melting point of the polymer is taken as the highest of these melting points.

[0036] Aromatic polyamide copolymer containing imidazole groups

[0037] As used herein, the term "polymer" means a material prepared by polymerizing monomers, end-functionalized oligomers, and / or end-functionalized polymers, whether of the same type or different types. As used herein, the term aromatic polyamide means an aromatic polyamide in which at least 85% of the amide (-CONH-) bonds are directly attached to two aromatic rings.

[0038] As used herein, the term "aromatic polyamide copolymer containing imidazole groups" refers to a copolymer prepared from aromatic diacids and diamines, in which there are at least two different diamines, namely aromatic diamines and imidazole diamines. The two different diamines can be polymerized with stoichiometric amounts of one or more aromatic diacids.

[0039] Among the aromatic diacids, para-oriented aromatic diacids are preferred, and the most preferred para-oriented aromatic diacid is terephthaloyl chloride. Similarly, among the aromatic diamines, para-oriented aromatic diamines are preferred, and the preferred para-oriented aromatic diamine is p-phenylenediamine.

[0040] "Imidazole diamine" means a diamine having at least one imidazole group. Preferably, the imidazole diamine is benzimidazole. In some preferred embodiments, the imidazole diamine is 5(6)-amino-2-(p-aminophenyl) benzimidazole (DAPBI). In some preferred embodiments, the aromatic polyamide copolymer is made by polymerizing the monomers 5(6)-amino-2-(p-aminophenyl) benzimidazole, one or more aromatic diamines, and one or more aromatic diacyl chlorides. In some most preferred embodiments, the aromatic polyamide copolymer is made by polymerizing the monomers 5(6)-amino-2-(p-aminophenyl) benzimidazole, p-phenylenediamine, and terephthaloyl chloride.

[0041] In some embodiments, the molar ratio of the imidazole diamine (such as 5(6)-amino-2-(p-aminophenyl) benzimidazole) to the aromatic diamine is from 50 / 50 to 80 / 20. In some specific embodiments, the aromatic polyamide copolymer containing an imidazole group contains residues of 5(6)-amino-2-(p-aminophenyl) benzimidazole and residues of p-phenylenediamine, wherein the molar ratio of the residues of 5(6)-amino-2-(p-aminophenyl) benzimidazole to the residues of p-phenylenediamine is from 50 / 50 to 80 / 20. In some specific embodiments, the aromatic polyamide copolymer containing an imidazole group contains residues of 5(6)-amino-2-(p-aminophenyl) benzimidazole and residues of p-phenylenediamine, wherein the molar ratio of the residues of 5(6)-amino-2-(p-aminophenyl) benzimidazole to the residues of p-phenylenediamine is from 50 / 50 to 70 / 30.

[0042] In still other embodiments, the imidazole diamine (such as 5(6)-amino-2-(p-aminophenyl) benzimidazole) is 50 mole percent or more of the total moles of imidazole diamine and aromatic diamine present.

[0043] As used herein, "stoichiometric amount" means the amount of a component that is theoretically required to react with all of the reactive groups of a second component. For example, "stoichiometric amount" refers to the number of moles of terephthaloyl chloride required to react with substantially all of the amine groups of an amine component. One of ordinary skill in the art will understand that the term "stoichiometric amount" refers to a range of amounts that are typically within 10% of the theoretical amount. For example, the stoichiometric amount of terephthaloyl chloride used in a polymerization reaction can be 90%-110% of the amount of terephthaloyl chloride theoretically required to react with all of the amine groups.

[0044] In some embodiments, all monomers can be combined and reacted to form a polymer. In some embodiments, monomers or different amounts of monomers can be reacted sequentially to form oligomers, which can further react with one or more additional monomers or one or more oligomers to form a polymer. "Oligomer" means a polymer or substance eluted at <3000 MW on a column calibrated with poly(p-phenylenediamine terephthalamide) homopolymer.

[0045] As used herein, the term "residue" of a chemical substance refers to the portion of the resulting product of the chemical substance in a particular reaction scheme or subsequent formulation or chemical product, regardless of whether the portion is actually obtained from the chemical substance. Thus, a copolymer containing a residue of p-phenylenediamine refers to a copolymer having one or more units of the formula:

[0046]

[0047] And a copolymer containing a residue of terephthaloyl chloride contains one or more units of the formula:

[0048]

[0049] Similarly, a copolymer containing a residue of an imidazole group (such as a benzimidazole group) contains one or more units of the formula:

[0050]

[0051] And in particular, a copolymer containing a residue of DAPBI contains one or more units of the formula:

[0052]

[0053] Thus, in some embodiments, the aromatic polyamide copolymer contains a residue of benzimidazole, and in some embodiments, the aromatic polyamide copolymer contains a residue of 5(6)-amino-2-(p-aminophenyl).

[0054] Crude polymer particles

[0055] The composite composition can contain particles of an aromatic polyamide copolymer comprising imidazole groups, which are made by comminuting the copolymer to a desired size. For example, the aromatic polyamide polymer made according to the teachings of U.S. Patent Publication 20130018138 is ultimately in the form of an aqueous wet acidic granulate and is coarsely ground while in the wet state using various types of size reduction equipment (including, for example, hammer mills, disk mills, roller mills, etc.). The acidic granulate is then preferably neutralized by washing with an alkali, and the neutralized granulate is then separated. The neutralized granulate can then be dried to form polymer particles that have irregular sizes and most of which will pass through a sieve having an opening of 1.4 mm. Figure 1 is a photograph representative of these particles, which are referred to herein as "crude polymer" particles. The specific crude polymer particles are made by polymerizing monomer 5(6)-amino-2-(p-aminophenyl) benzimidazole, p-phenylenediamine, and terephthaloyl chloride.

[0056] The size of the aromatic polyamide copolymer particles described herein can preferably be determined by using any industrial method of screening particles, preferably by sizing using a sieve. An alternative method (which is typically used for very small particles) uses laser diffraction according to DIN ISO 13320-2020, which can also determine the fine particle diameter and its distribution.

[0057] A typical method of screening particles uses a column of sieve trays with graded sieve mesh sizes. The material to be classified is poured onto the top sieve tray having the largest sieve opening. Each lower sieve tray in the column has a smaller opening than the sieve tray above. Typically, the column of sieve trays is placed in a mechanical shaker that vibrates all the sieve trays in the column to facilitate the movement of the particles on the surface of each sieve in each tray so that particles small enough to fit through the sieve opening can fall by gravity to the next sieve tray. After the vibration is complete, the particles remaining on each sieve of each sieve tray have a particle size that is too large to pass through the opening in that sieve.

[0058] Although there are various systems for identifying sieve mesh sizes, such as U.S. Standard or Tyler mesh, any sieve size herein is identified by its opening in millimeters to avoid confusion. Additionally, as used herein, it is assumed that the opening in the sieve is a square opening; for example, a sieve having an opening of 0.150 mm has a square opening, and each side of the square opening is nominally 0.150 mm.

[0059] In some embodiments, the crude polymer particles comprising an aromatic polyamide copolymer containing an imidazole group have a size distribution such that at least 90 weight percent of the particles pass through a sieve having an opening of 1.4 mm, but 85 weight percent or more of those particles will not pass through a sieve having an opening of 0.212 mm. In other words, it can be considered that at least 75 weight percent of the crude polymer particles have a size range of about 0.212 to 1.4 mm.

[0060] Ground particles

[0061] In addition, although the composite composition may contain crude polymer particles, in some embodiments, the crude polymer particles comprising an aromatic polyamide copolymer containing an imidazole group are further pulverized to further reduce their particle size and then used in the composite composition. Such size reduction methods may include variants of the previously mentioned hammer mills, disk mills, roller mills, etc., as well as other methods that can be used to reduce the particle size to less than 1 mm, preferably less than 0.5 mm, such as jet mills and twin-screw extruders. In some preferred embodiments, a twin-screw extruder can be used as a mill to reduce the size of the aromatic polyamide copolymer particles comprising an aromatic polyamide copolymer containing an imidazole group to particles having a desired size distribution.

[0062] In some embodiments, the particles comprising an aromatic polyamide copolymer containing an imidazole group have a size distribution such that these particles will pass through a sieve having an opening of 0.425 mm, but about 50 weight percent will not pass through a sieve having an opening of 0.150 mm. As used herein, such particles of an aromatic polyamide copolymer containing an imidazole group that have been reduced in size to this range are herein considered to be "ground particles". In other words, the ground particles can be considered to be less than about 0.425 mm, where about half of those particles are greater than 0.150 mm, which means that the particles have a median particle size or diameter or D50 of about 0.150 mm.

[0063] One embodiment of manufacturing "ground particles" of an aromatic polyamide copolymer containing an imidazole group using a twin-screw extruder is herein referred to as the "dry extruder" method. In this type of method, the crude polymer as described above is further reduced in size through the extruder in a dry state; that is, the reduced-size polymer has less than 10 weight percent moisture. Figure 2 is a photograph representative of these dry extruder particles. And Figure 1 Similarly, these ground particles are made by polymerizing monomer 5(6)-amino-2-(p-aminophenyl) benzimidazole, p-phenylenediamine, and terephthaloyl chloride.

[0064] Another embodiment of making aromatic polyamide copolymer particles having a size of less than 1 mm using a twin-screw extruder is herein referred to as the "wet extruder" method. In this type of method, the neutralized chips from polymerization are passed through a twin-screw extruder only once for size reduction to achieve the desired size; there is no intermediate step of making crude polymer particles. Figure 3 and Figure 4 are representative photos of these wet extruder particles after air drying in shallow trays. These ground particles are also made by polymerizing monomer 5(6)-amino-2-(p-aminophenyl)benzimidazole, p-phenylenediamine, and terephthaloyl chloride.

[0065] Both the particles containing an aromatic polyamide copolymer containing an imidazole group made using the dry extruder method and the particles containing an aromatic polyamide copolymer containing an imidazole group made using the wet extruder method are considered "ground particles" because both meet the definition of ground particles herein. It is believed that any minor differences in the particle size distribution of the particles do not affect the performance of these particles in the composite composition.

[0066] Flocculent particles

[0067] In some embodiments, the particles containing an aromatic polyamide copolymer containing an imidazole group are in the form of flocks in the composite composition. As used herein, the term flock means short fibers typically produced by cutting continuous fibers into the desired length using methods well known in the art. In some preferred embodiments, the flocks have a length of about 0.5 to about 15 millimeters. The preferred length of the flocks is about 1 to about 12 millimeters, and the most preferred length of the flocks is about 1 to 6 millimeters. In some embodiments, the flocks can have a linear density of 0.5 to 3 denier / filament, and in some embodiments, the flocks can have a linear density of 0.75 to 2.25 denier / filament.

[0068] Representative methods of making flocks include, for example, the methods described in U.S. Patent Nos. 8,501,071; 9,988,514; 9,994,974; 10,400,082; 10,400,357; and 11,279,800. Such methods can utilize a spinning solvent (such as sulfuric acid) and the polymer chips or crude polymer particles mentioned previously herein to form a suitable polymer spinning solution. Such methods preferably provide continuous filaments that are further cut into short lengths for use as flocks.

[0069] If desired, the composite composition can contain a mixture of crude polymer particles or ground particles of an aromatic polyamide copolymer containing an imidazole group and a floc of an aromatic polyamide copolymer containing an imidazole group. The weight ratio range of the particles to the floc can be from 1:4 to 4:1. In some embodiments, the composite composition can contain a mixture of crude polymer particles or ground particles of an aromatic polyamide copolymer containing an imidazole group and different types of reinforcing flocs (such as carbon fiber flocs or glass flocs); likewise, the weight ratio range of the particles to the floc can be from 1:4 to 4:1. Alternatively, in some embodiments, the composite composition can contain a mixture of a floc of an aromatic polyamide copolymer containing an imidazole group and crude polymer particles or ground particles of different polymer or copolymer types; likewise, the weight ratio range of the particles to the floc can be from 1:4 to 4:1.

[0070] Pellets of composite composition

[0071] The particles of the aromatic polyamide copolymer containing an imidazole group can be combined with a thermoplastic engineering polymer in any suitable container or device that can mix the materials and disperse the particles evenly in the engineering polymer. Such devices can include, for example, a batch mixer, a LIST kneader-reactor type mixer, or a single-screw or twin-screw extruder. Once the particles of the aromatic polyamide copolymer containing an imidazole group are combined with the thermoplastic engineering polymer to form the composite composition, the composite composition can be further shaped as needed; for example, pellets can be made from the composite composition for further use in various methods of manufacturing articles. For example, a molten composite composition can be made in a twin-screw extruder, which further extrudes the molten composite composition through a die at the extruder outlet to form a molten strand of the heat-quenched composite composition; then the solid or partially solid strand of the composite composition can be directed to a pelletizer to make pellets. In some embodiments, the pellets are made to be sized such that there are 25 to 45 pellets per gram. In some embodiments, the pellets have an average diameter of 1 to 3 mm.

[0072] Additionally, it is believed that if desired, these pellets can be further ground to make a finer powder of the composite composition for use in special applications such as 3-D printing or additive manufacturing processes. The fine particles are typically characterized by having a certain D50, which is the median particle size or particle size of the distribution. For example, for a powder sample with a D50 of 5 microns, it means that 50% of the particles are larger than 5 microns and 50% of the particles are smaller than 5 microns. The D50 of the fine particles is preferably determined by laser diffraction DIN ISO 13320-2020.

[0073] Fine powders of the composite composition having a D50 of from 1 to 150 microns are considered useful. In some embodiments, these fine powders of the composite composition have a D50 of from 30 to 150 microns. In some embodiments, the fine powders of the composite composition have a D50 of from 45 to 120 microns, and in still other embodiments, the fine powders of the composite composition have a D50 of from 48 to 100 microns.

[0074] Article comprising composite composition

[0075] Articles comprising the composite composition can be manufactured. In some embodiments, the articles include those in which the aromatic polyamide copolymer particles are the only microparticles other than optional pigments incorporated into the engineering polymer. In some other embodiments, the articles include those comprising aromatic polyamide copolymer particles, optional pigments, and one or more fillers; wherein the fillers are herein considered to be particles that do not affect the wear characteristics or wear performance (such as noise) of the article. In some other embodiments, the articles include those in which the aromatic polyamide copolymer particles are the major microparticle additive (not a pigment or filler) by weight in the composite composition. In still some other embodiments, the articles include those in which the aromatic polyamide copolymer particles are the major microparticle additive by weight in the composite composition.

[0076] In many embodiments, preferred articles are parts made from the composite composition when in a molten state, such as extruded parts and injection molded parts; or parts made by 3-D printing or additive manufacturing, such as by fused deposition modeling (FDM), stereolithography (SLA), or selective laser sintering (SLS). Such parts can be, for example, thin-walled parts or industrial large parts for the automotive and / or aerospace industries.

[0077] Wear resistance

[0078] In many embodiments, the composite composition and articles made therefrom have improved wear resistance. Based on comparing the wear rate of a part made of only a thermoplastic engineering polymer with the wear rate of a part made of a composite composition comprising a thermoplastic engineering polymer and particles of an aromatic polyamide copolymer containing an imidazole group dispersed therein, adding particles of the aromatic polyamide copolymer containing an imidazole group reduces the wear rate of the thermoplastic engineering polymer by at least 25 percent.

[0079] In some embodiments, adding particles comprising an aromatic polyamide copolymer containing an imidazole group reduces the wear rate of the thermoplastic engineering polymer by at least 45 percent. Unexpectedly, the composite composition and articles made therefrom have an average dynamic coefficient of friction equal to or less than that of articles consisting solely of the thermoplastic engineering copolymer. In other words, unexpectedly, adding these particles improves the wear properties of the material without increasing its coefficient of friction.

[0080] Method for manufacturing composite composition

[0081] In some embodiments, the present invention relates to a method for manufacturing a composite composition, the method comprising the following steps:

[0082] a) polymerizing monomers to form an aromatic polyamide copolymer containing an imidazole group, the monomers comprising at least one aromatic diacid and at least one aromatic diamine and an imidazole diamine;

[0083] b) comminuting and separating the aromatic polyamide copolymer containing an imidazole group in the form of polymer chips of a desired particle size;

[0084] c) optionally, further grinding or milling the polymer chips to form particles of a desired particle size comprising the aromatic polyamide copolymer containing an imidazole group; and

[0085] d) combining and mixing 3 to 30 parts by weight of the said particles with up to 97 parts by weight of a thermoplastic engineering polymer to form the composite composition.

[0086] It should be understood that all of the various elements, features, definitions, and other explanations provided previously herein for the composite composition apply equally to the method for manufacturing the composite composition, but are not repeated herein to avoid redundancy.

[0087] In step a) of the method, the step of polymerizing monomers to form an aromatic polyamide copolymer containing an imidazole group is preferably accomplished using the general disclosure of solution polymerization as disclosed in U.S. Patent Publication 20130018138A1. This method produces wet polymer chips containing a polymerization solvent and acidic by-products (usually hydrochloric acid, which is generated during polymerization) similar to wet sand.

[0088] In step b) of the method, the wet polymer chips are comminuted and separated by grinding or milling (e.g., using a hammer mill or a disk mill), while washing the chips with water or an aqueous solution to remove the polymerization solvent from the chips. Optionally, the chips can be additionally washed with an alkali to remove acidic by-products from the polymerization. The separated polymer can then be optionally dried.

[0089] Then, optionally in step c), the separated chips are further comminuted to further reduce their size by grinding or milling the polymer chips to a desired particle size. For example, as previously disclosed herein, the chips can be comminuted to produce crude polymer particles, or the chips can be comminuted to produce milled particles as previously described. Additionally, although for clarity, the comminution of the chips to milled particles has been discussed herein in two steps, such as first reducing the size of the chips in step b) to obtain crude polymer particles and then further reducing the size of those crude polymer particles in optional step c) to obtain milled particles, it should be understood that the polymer chips can be directly comminuted to "milled particles" in one step (i.e., step b)). In some preferred embodiments, step c) is carried out in a twin-screw extruder that reduces the size of the material to the desired size.

[0090] Then in step d), the particles comprising the aromatic polyamide copolymer containing imidazole groups are combined and mixed with a thermoplastic engineering polymer in a ratio of 3 to 30 parts by weight of the particles to up to 97 parts by weight of the thermoplastic engineering polymer to form a composite composition. In some embodiments, 3 to 30 parts by weight of the particles and 70 to 97 parts by weight of the thermoplastic engineering polymer are used in step d) to form the composite material. In some embodiments, 5 to 25 parts by weight of the particles and 75 to 95 parts by weight of the thermoplastic engineering polymer are used in step d) to form the composite material.

[0091] Preferably, step d) is carried out in a twin-screw extruder. Typically, the thermoplastic engineering polymer is provided to the extruder in the form of solid pellets, and these pellets can be conveniently metered into the twin-screw extruder together with the particles comprising the aromatic polyamide copolymer containing imidazole groups, where they are combined and mixed to uniformly disperse the particles comprising the aromatic polyamide copolymer containing imidazole groups in the thermoplastic engineering polymer. Alternatively, any number of batch, semi-continuous, or continuous methods using the thermoplastic engineering polymer in solid and molten forms can be used to combine and mix the thermoplastic engineering polymer with the particles comprising the aromatic polyamide copolymer containing imidazole groups.

[0092] In some embodiments, the method for manufacturing the composite composition includes forming pellets of the composite composition during or after step d). For example, a pelletizing device can be connected to the outlet of the extruder, or the extruded composite composition can be pelletized in a separate step.

[0093] For example, a melt compounded composition made in a twin screw extruder can be extruded through a die at the extruder exit and then thermally quenched to make strands of the compounded composition, which can then be directed to a pelletizer to make pellets. Preferably, the pellets are made such that there are 25 to 45 pellets per gram.

[0094] As previously discussed herein, in some embodiments, the thermoplastic engineering polymer used in the method for making the compounded composition comprises poly(ether ketone) (PEK), poly(ether ether ketone) (PEEK), poly(ether ketone ketone) (PEKK), or mixtures thereof. In some preferred embodiments, the thermoplastic engineering polymer used in the method for making the compounded composition comprises poly(ether ether ketone) (PEEK). In some embodiments, the thermoplastic engineering polymer used in the method for making the compounded composition comprises polyamide (PA), polyamide-imide (PAI), polyethersulfone (PES), polyether-imide (PEI), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polyoxymethylene (POM), acetal copolymer (AC), polycarbonate (PC), or mixtures thereof.

[0095] The monomers used in polymerization step a) of the method for making the compounded composition can include any of the monomers previously described herein. In some embodiments, the monomers include the aromatic diacid terephthaloyl chloride. In some embodiments, the monomers include the aromatic diamine p-phenylenediamine. In some embodiments, the monomers include imidodiamine in the form of benzimidazole, preferably benzimidazole 5(6)-amino-2-(p-aminophenyl)benzimidazole. In some embodiments, the monomers include 5(6)-amino-2-(p-aminophenyl)benzimidazole, p-phenylenediamine, and terephthaloyl chloride.

[0096] As previously discussed herein, the method can be used to make a compounded composition having an average dynamic coefficient of friction equal to or less than that of the thermoplastic engineering copolymer.

[0097] Test Method

[0098] According to test method ASTM D3702-94, a friction and wear tester is used to determine the wear rate reduction and coefficient of friction for each sample.

[0099] For the three-piece washer (3PW) test, a diameter of 1.3125 inches is used. For the test conditions, the linear velocity is 0.18 m / min; the pressure applied to each specimen is 0.55 MPa; the atmospheric temperature is 21 °C; the test period is nominally 100 hours. The resulting PV is 0.1 MPa*m / s. Each specimen is subjected to sliding contact with 4140 steel as the mating member. No lubricant is used in the test.

[0100] For the thrust washer (TW) test, a diameter of 1.125 inches was used. For the test conditions, the machine speed was 500 RPM, corresponding to a linear speed of 0.7 m / min; the pressure applied to each specimen was 1.75 MPa; the atmospheric temperature was 21°C; the test period was nominally 100 hours. The resulting PV was 1.2 MPa*m / s. Each specimen was subjected to sliding contact with 4140 steel as the mating member. No lubricant was used in the test.

[0101] The adhesion properties were determined in accordance with DIN SPEC 19289:2022-08 “Fibre-reinforced composites-Measurement of Interfacial Shear Strength by means of a Micromechanical Single-Fibre Pull-Out Test”.

[0102] Example 1

[0103] An aromatic polyamide copolymer containing an imidazole group was manufactured as follows. The monomers 5(6)-amino-2-(p-aminophenyl) benzimidazole (DAPBI) and p-phenylenediamine (PPD) in amounts suitable for forming a copolymer with a DABPI / PPD monomer ratio of 70 / 30 were combined with a stoichiometric amount of terephthaloyl chloride (TCl) in a solvent system comprising an N-methyl-2-pyrrolidone (NMP) solvent and 4.5 weight percent calcium chloride (CaCl2) as a solubility enhancer. These monomers were polymerized to form a copolymer.

[0104] After polymerization was completed, the copolymer chips were recovered, ground (by a hammer mill or a disk mill) and washed with sodium hydroxide to neutralize the by-product hydrochloric acid to form crude polymer particles of approximately 3 mm pellets in the form of undried neutral pellets. The copolymer had an intrinsic viscosity of approximately 6.4 dl / g. This procedure was repeated to manufacture another aromatic polyamide copolymer containing an imidazole group with a DABPI / PPD monomer ratio of 50 / 50. This aromatic polyamide copolymer also had an intrinsic viscosity of approximately 6.4 dl / g.

[0105] The crude polymer particles in the form of undried neutral crumbs are then used directly in the wet extruder process or dried to form particles with a size of approximately 1 mm. The dried crude polymer is further processed into "dry extruder" ground particles by grinding the approximately 1 mm crude polymer particles in a dry state with less than 10% moisture in a twin-screw extruder using solid-state grinding. "Wet extruder" ground particles are made by grinding a sample of undried neutral crumbs in a twin-screw extruder. As shown in Table 2, samples of dried 1 mm crude polymer particles are also used.

[0106] A portion of the 70 / 30 DABPI / PPD copolymer was converted into fibers, and then these fibers were chopped into fluffs with a cut length of 3 mm. In addition, samples of glass fiber fluffs, carbon fiber fluffs, and polytetrafluoroethylene (PTFE) powder were also obtained for comparative samples. The sample items are summarized in Table 2.

[0107] Table 2

[0108]

[0109]

[0110] After obtaining various particles, fluffs, and powders, they are combined and blended with a thermoplastic engineering resin using a twin-screw extruder. Items 1-10 from Table 1 are blended with a polyetheretherketone polymer (PEEK 150G TM , purchased from Victrex). The extrusion temperature is maintained between 350°C - 400°C. The blend is granulated and separated into pellets. The pellets are used in an injection molding machine that operates at a melt temperature of 400°C and a mold temperature of 175°C to manufacture test items, which are three-pad washers (3PW) for low-pressure-velocity testing and thrust washers (TW) for high-pressure-velocity testing, as shown in Table 3.

[0111] Table 3

[0112]

[0113]

[0114] Using a rotational wear test according to Test Method ASTM D3702-94, three-piece washers were tested for 70 - 96 hours against a 4140 steel counter surface. The pressure-velocity for the three-piece washer test was 0.1 (MPa-m / s). Using the same test method, thrust washers were tested for 24 hours against a 4140 steel counter surface and a pressure-velocity of 1.2 (MPa-m / s). The low pressure-velocity wear rate data obtained from the three-piece washer test are shown in Table 4. Blends of PEEK with aromatic polyamide copolymers having imidazole groups showed a reduction in wear rate relative to the control. For this test, the dynamic coefficient of friction of the blend samples was essentially unchanged compared to that of the control samples.

[0115] Table 4

[0116]

[0117]

[0118] * Standard deviation = 0.2

[0119] The high pressure-velocity wear rate data obtained from the thrust washer test are shown in Table 5. Blends of PEEK with aromatic polyamide copolymers having imidazole groups showed a reduction in wear rate relative to the control. For this test, blends of PEEK with aromatic polyamide copolymers having imidazole groups had a lower dynamic coefficient of friction than the control samples, approaching the very low dynamic coefficient of friction of PTFE blends.

[0120] Table 5

[0121]

[0122] ** Standard deviation = 0.05

[0123] Example 2

[0124] A portion of the fibers made from the 70 / 30 DABPI / PPD aromatic polyamide copolymer manufactured in Example 1 was not cut into fluffs but was used to determine the adhesion characteristics between this aromatic polyamide copolymer and certain thermoplastic engineering polymers, and further to compare the adhesion characteristics of those thermoplastic engineering polymers to the aromatic polyamide copolymer with their adhesion characteristics to a comparative para-aramid terephthaloyl terephthalamide (PPD-T) homopolymer.

[0125] The adhesion characteristics between materials were determined according to DIN SPEC 19289:2022-08 using a fiber matrix adhesion tester (FIMATEST) from Textechno. This is a micromechanical method which involves embedding a single filament of an aromatic polyamide copolymer (or a comparative material) into a matrix of a thermoplastic engineering polymer and then pulling the fiber out of the matrix at a constant extension rate (CRE) while recording the force-displacement curve, from which the apparent interfacial shear strength, local interfacial shear strength and critical interfacial energy release rate can be determined. Specifically, each filament to be tested as follows was embedded into a matrix of a thermoplastic engineering polymer (TEP). The TEP was held in a crucible at room temperature and flushed with nitrogen for 5 minutes. The temperature of the TEP was raised to above the melting temperature and held at this temperature for 10 minutes to completely melt the TEP. The filament was positioned at the center of the polymer matrix and then embedded at a rate of 300 μm / min to an embedding depth of 90 μm. The filament was held in position at 400 °C for 30 seconds and then the matrix was cooled to 300 °C by nitrogen over a period of 3 minutes, held at 300 °C for 1 second and then cooled to 50 °C over a period of 5 minutes. Then the sample was held at ambient temperature overnight and then pulled. Filaments without sizing were used in the tests.

[0126] Tables 6 and 7 summarize the adhesion data generated using DIN SPEC 19289:2022-08. The data in these tables compare aromatic polyamide copolymer filaments with PPD-T filaments in various engineering polymers including poly(ether ether ketone) (PEEK), polycarbonate (PC), and polyamide (PA) in the form of nylon-6 (PA-6). Specifically, Tables 6 and 7 summarize the apparent interfacial shear strength (τ app ), local interfacial shear strength (τ d ), and critical interfacial energy release rate (G ic ) of the fiber material polymer with the engineering polymer, where Table 6 provides data for "unsized" fiber materials and Table 7 provides data for fiber materials with a spinning finish. This data illustrates the percentage increase (Δ) in the adhesion of the aromatic polyamide copolymer to the engineering polymer relative to the PPD-T para-aramid homopolymer based on these adhesion characteristics. Additionally, it was found that the presence of the spinning finish does not detract from the adhesion performance but rather enhances the adhesion performance of the aromatic polyamide copolymer particles to the engineering polymer, which would be an unexpected advantage for using floc particles in thermoplastic engineering polymer articles. A fiber finish is typically desired in fiber cutting operations to more easily short cut continuous filaments into flocs, and it would be advantageous not to have to remove the finish from the short cut flocs before using them as particles in a composite composition.

[0127] Table 6

[0128]

[0129] Table 7

[0130]

Claims

1. A composite composition comprising: a) 3 to 30 parts by weight of particles comprising an aromatic polyamide copolymer containing an imidazole group, and b) up to 97 parts by weight of a thermoplastic engineering polymer; wherein the particles are uniformly dispersed in the thermoplastic engineering polymer and reduce the wear rate of the thermoplastic engineering polymer by at least 25 percent.

2. The composite composition according to claim 1, comprising: a) 5 to 25 parts by weight of the particles comprising an aromatic polyamide copolymer containing an imidazole group, and b) 75 to 95 parts by weight of a thermoplastic engineering polymer.

3. The composite composition according to claim 1 or 2, wherein The particles comprising an aromatic polyamide copolymer containing an imidazole group reduce the wear rate of the thermoplastic engineering copolymer by at least 45 percent.

4. The composite composition according to claim 3, wherein, The particles comprising an aromatic polyamide copolymer containing an imidazole group reduce the wear rate of the thermoplastic engineering copolymer by at least 80 percent.

5. The composite composition according to any one of claims 1 to 4, wherein, The thermoplastic engineering polymer is poly(ether ketone) (PEK), poly(ether ether ketone) (PEEK), poly(ether ketone ketone) (PEKK), or a mixture thereof.

6. The composite composition according to claim 5, wherein, The thermoplastic engineering polymer is poly(ether ether ketone) (PEEK).

7. The composite composition according to any one of claims 1 to 6, wherein The thermoplastic engineering polymer comprises polyamide (PA), polyamide-imide (PAI), polyethersulfone (PES), polyether-imide (PEI), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polyoxymethylene (POM), acetal copolymer (AC), polycarbonate (PC), or a mixture thereof.

8. The composite composition according to any one of claims 1 to 7, wherein, The local interfacial shear strength (τ d ) between the particles of the aromatic polyamide copolymer containing imidazole groups and the engineering polymer is greater than the local interfacial shear strength (τ d ) between the particles of a para-aromatic polyamide homopolymer such as PPD-T and the same engineering polymer.

9. The composite composition according to claim 8, wherein, The local interfacial shear strength (τ d ) between the particles of the aromatic polyamide copolymer containing an imidazole group and the engineering polymer is at least 9 percent or more greater than the local interfacial shear strength (τ d ) between the particles of a para - aromatic polyamide homopolymer such as PPD - T and the same engineering polymer.

10. The composite composition according to claim 9, wherein, The local interfacial shear strength (τ d ) between the particles of the aromatic polyamide copolymer containing an imidazole group and the engineering polymer is at least 35 percent or more greater than the local interfacial shear strength (τ d ) between the particles of a para-aromatic polyamide homopolymer such as PPD-T and the same engineering polymer.

11. The composite composition according to any one of claims 1 to 10, wherein, The local interfacial shear strength (τ d ) between the particles of the aromatic polyamide copolymer containing an imidazole group and the engineering polymer is 72 MPa or greater.

12. The composite composition according to any one of claims 1 to 11, wherein, The aromatic polyamide copolymer containing an imidazole group comprises residues of p-phenylenediamine.

13. The composite composition according to claim 12, wherein, The aromatic polyamide copolymer containing an imidazole group further comprises residues of 5(6)-amino-2-(p-aminophenyl)benzimidazole, and wherein the molar ratio of the residues of 5(6)-amino-2-(p-aminophenyl)benzimidazole to the residues of p-phenylenediamine is 50 / 50 to 80 / 20.

14. The composite composition according to claim 13, wherein, The aromatic polyamide copolymer containing an imidazole group further comprises residues of 5(6)-amino-2-(p-aminophenyl)benzimidazole, and wherein the molar ratio of the residues of 5(6)-amino-2-(p-aminophenyl)benzimidazole to the residues of p-phenylenediamine is 50 / 50 to 70 / 30.

15. The composite composition according to any one of claims 1 to 14, wherein, The aromatic polyamide copolymer containing an imidazole group comprises residues of 5(6)-amino-2-(p-aminophenyl)benzimidazole.

16. The composite composition according to any one of claims 1 to 15, wherein, The particles comprising an aromatic polyamide copolymer containing an imidazole group are in the form of ground or milled polymer fragments.

17. The composite composition according to any one of claims 1 to 16, wherein, The particles comprising an aromatic polyamide copolymer containing an imidazole group have a size distribution such that 90 weight percent of the particles will pass through a sieve having an opening of 1.4 mm, and 85 weight percent or more of those particles will not pass through a sieve having an opening of 0.212 mm.

18. The composite composition according to any one of claims 1 to 16, wherein, The particles comprising an aromatic polyamide copolymer containing an imidazole group have a size distribution such that the particles will pass through a sieve having an opening of 0.425 mm, and 50 weight percent will not pass through a sieve having an opening of 0.150 mm.

19. The composite composition according to any one of claims 1 to 15, wherein, The particles comprising an aromatic polyamide copolymer containing an imidazole group are in the form of flocs.

20. The composite composition according to claim 19, wherein, The floc has a cutting length of 0.5 to 15 mm.

21. The composite composition according to claim 20, wherein, The floc has a cutting length of 1 to 6 mm.

22. An article comprising the composite composition according to any one of claims 1 to 21.

23. The article according to claim 22, having an average dynamic coefficient of friction equal to or less than that of an article consisting only of the thermoplastic engineering copolymer.

24. The article according to claim 22, the article being in the form of extruded pellets having a size such that there are 25 to 45 pellets per gram.

25. The article according to claim 22 or claim 24, the article being in the form of extruded pellets having an average diameter of 1 to 3 mm.

26. A method for manufacturing a composite composition, the method comprising the following steps a) polymerizing monomers to form an aromatic polyamide copolymer containing imidazole groups, the monomers including at least one aromatic diacid and at least one aromatic diamine and an imidazole diamine; b) crushing and separating the aromatic polyamide copolymer containing imidazole groups in the form of polymer fragments having a desired particle size; c) optionally, further grinding or milling the polymer fragments to form particles of the aromatic polyamide copolymer containing imidazole groups having a desired particle size; and d) combining and mixing 3 to 30 parts by weight of the particles with up to 97 parts by weight of a thermoplastic engineering polymer to form the composite composition.

27. The method for manufacturing a composite composition according to claim 26, wherein, The thermoplastic engineering polymer is poly(ether ketone) (PEK), poly(ether ether ketone) (PEEK), poly(ether ketone ketone) (PEKK), or a mixture thereof.

28. The method for manufacturing a composite composition according to claim 27, wherein, The thermoplastic engineering polymer is poly(ether ether ketone) (PEEK).

29. The method for manufacturing a composite composition according to any one of claims 26 to 28, wherein, The thermoplastic engineering polymer comprises polyamide (PA), polyamide-imide (PAI), polyethersulfone (PES), polyether-imide (PEI), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polyoxymethylene (POM), acetal copolymer (AC), polycarbonate (PC), or a mixture thereof.

30. The method for manufacturing a composite composition according to any one of claims 26 to 29, wherein, The aromatic diacid is terephthaloyl chloride.

31. The method for manufacturing a composite composition according to any one of claims 26 to 30, wherein, The aromatic diamine is p-phenylenediamine.

32. The method for manufacturing a composite composition according to any one of claims 26 to 31, wherein, The imidazole diamine is 5(6)-amino-2-(p-aminophenyl)benzimidazole.

33. The method for manufacturing a composite composition according to any one of claims 26 to 32, wherein, Step c) is carried out in a twin-screw extruder.

34. The method for manufacturing a composite composition according to any one of claims 26 to 33, wherein, Step d) is carried out in a twin-screw extruder.

35. The method for manufacturing a composite composition according to any one of claims 26 to 34, wherein, Pellets of the composite composition are manufactured during or after step d).

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