High-performance fiber as well as preparation method and application thereof

Abstract

The invention discloses a high-performance fiber, a preparation method and application thereof, and a composition for preparing the fiber. The composition comprises polyether-ether-ketone, a siloxane compound Si (A) a (R1) b (R2) c (R3) d (R4) e, and a metal compound and / or metalloid compound gel precursor. The components are mixed to prepare a spinning solution, and the spinning solution is subjected to wet spinning and multi-stage drafting to obtain the finished fiber. Through the bridging effect of the siloxane compound, the inorganic phase is uniformly dispersed in a PEEK matrix in a nanoscale to form an organic-inorganic hybrid structure, so that the mechanical property, flame retardance and surface characteristics of the fiber are synergistically improved. The tensile strength of the obtained fiber is larger than or equal to 600 MPa, the friction coefficient is smaller than or equal to 0.15, the limit oxygen index is high, and the fiber is suitable for manufacturing high-grade bulletproof protective fabrics, aerospace composite materials and biomedical materials.

Description

Technical Field

[0001] This invention relates to the field of polymer materials and fiber manufacturing technology, specifically to a high-performance fiber composed of polyether ether ketone (PEEK) and organic-inorganic hybrid materials, its preparation method, and its application in aerospace, medical, and protective fields. Background Technology

[0002] Polyetheretherketone (PEEK) is a semi-crystalline thermoplastic high-temperature resistant specialty engineering plastic. PEEK's molecular structure contains p-methacrylate and terephthalic anhydride side chains, exhibiting a wide molecular weight distribution, high reactivity of the side chain groups, and strong conjugation effect. It is renowned for its excellent high-temperature resistance, superior mechanical properties, chemical corrosion resistance, good biocompatibility, and self-lubricating properties. Therefore, PEEK fibers are considered one of the ideal candidate materials for manufacturing high-performance composite materials, medical implants, and advanced protective equipment. It has wide applications in aerospace, automotive manufacturing, electronics, and medical implants, including dental instruments, endoscopes, dialyzers, autoclaves, and other healthcare products, as well as lightweight components in automotive fuel management systems and 3D printing technology.

[0003] Since its introduction, polyetheretherketone (PEEK) resin has been listed as a strategic material and subject to export restrictions by many countries due to its important applications in the defense and military industries. In my country, the research and development of this material has been included in several major national science and technology projects, such as the Seventh Five-Year Plan to the Tenth Five-Year Plan and the "863" Program, demonstrating the high importance and continuous investment the country attaches to its development.

[0004] However, pure PEEK fibers still have limitations in certain extreme applications: First, their mechanical properties—especially tensile strength and modulus—are still inferior to top-performing fibers such as para-aramid (e.g., Kevlar®) or ultra-high molecular weight polyethylene (e.g., Dyneema®); second, the smooth surface of PEEK fibers results in weak interfacial bonding with the resin matrix, limiting their reinforcing effect in composite materials; furthermore, although the limiting oxygen index (LOI) of pure PEEK can reach 35%, its flame retardant properties still need further improvement given the increasingly stringent requirements for halogen-free flame retardancy.

[0005] In existing technologies, the performance of PEEK fibers is typically improved through blending modification or surface treatment. For example, CN11209597A discloses a PEEK composite material containing nano-silica, but its inorganic and organic phases have poor compatibility, which easily leads to stress concentration and affects the mechanical properties of the fibers. US2018 / 0155341A1 describes a method for improving adhesion by treating the surface of PEEK fibers with plasma, but this process is complex, costly, and the effect is not lasting.

[0006] Therefore, developing a PEEK-based high-performance fiber that can simultaneously achieve high strength, high modulus, low coefficient of friction, and excellent flame retardancy through molecular-level design and simple processes has significant industrial value. Summary of the Invention

[0007] This invention provides a high-performance fiber, a method for preparing the same, and a composition for preparing the fiber.

[0008] The first aspect of this invention is to provide a composition for preparing high-performance fibers, comprising polyetheretherketone (PEEK) and a siloxane compound Si(A). a (R1) b (R2) c (R3) d (R4) e A metal compound and / or metalloid compound gel precursor, wherein a, b, c, d, and e are each independent numbers ≥ 0, and a + b + c + d + e = 4, and b + c + d + e is not 0; wherein R1, R2, R3, and R4 are each independently selected from the groups shown in R5-D, where R5 is a hydrocarbon group or R6 is a substituted hydrocarbon group, D is a single bond, O atom, S atom, or Si atom, and R6 is a substituent; A is H, hydroxyl, mercapto, or halogen atom (such as F, Cl, Br, I).

[0009] It should be understood that a gel precursor is a substance that can undergo a sol-gel reaction with siloxanes.

[0010] It should be understood that an R6-substituted hydrocarbon group may contain one R6; or an R6-substituted hydrocarbon group may contain more than one R6, and the R6s may be the same or different.

[0011] In a preferred embodiment, in the R6-substituted hydrocarbon group, R6 can be a side group located on the hydrocarbon group, such as a hydrocarbon group, a heterocyclic group, a halohydrocarbon group, -OH, -COOH, -F, -Cl, -Br, -CN, -NH2, -CHO, -CONH2, -SH, -SO3H, -NO2, or a combination of one or more of these.

[0012] In a preferred embodiment, R6 may be located on a segment of the hydrocarbon group, i.e., R6 may replace a carbon atom of the hydrocarbon group. For example, R6 may be one or more combinations selected from divalent hydrocarbon groups, divalent heterocyclic groups, divalent halohydrocarbon groups, -O-, -S-, -SO2-, -NH2-, -CO-, -COO-, -CONH-, and -C=N-.

[0013] In a preferred embodiment, the hydrocarbon group is selected from one or more combinations of aliphatic hydrocarbon groups and aromatic hydrocarbon groups, such as alkyl, olefinic, aliphatic ring group, and aromatic ring group, such as alkyl-substituted aliphatic ring group, aliphatic ring group-substituted alkyl, alkyl-substituted aromatic ring group, aromatic ring group-substituted alkyl, (alkyl-substituted aromatic ring group)-substituted alkyl, (aromatic ring group-substituted alkyl)-substituted aromatic ring group, etc.

[0014] It should be understood that the heterocyclic group is a group formed by replacing the C atom in an aliphatic or aromatic ring group with a heteroatom, and the heteroatom can be one or more combinations of N, S, O, Si, and P.

[0015] It should be understood that the haloalkyl group refers to a group formed by replacing the H atom in the hydrocarbon group with a halogen atom (such as F, Cl, Br, I), and the divalent haloalkyl group is a group formed after the haloalkyl group loses one H atom, or a group formed by replacing the H atom in the divalent hydrocarbon group with a halogen atom (such as F, Cl, Br, I).

[0016] It should be understood that the divalent hydrocarbon group is a group formed by losing one hydrogen atom from the hydrocarbon group; the divalent heterocyclic group is a group formed by losing one hydrogen atom from the heterocyclic group; and the divalent halohydrocarbon group is a group formed by losing one hydrogen atom from the halohydrocarbon group. For example, if the hydrocarbon group is methyl, then the divalent hydrocarbon group is methylene.

[0017] In a preferred embodiment, the alkyl group is selected from C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, and C18 alkyl groups, specifically such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, -CH(CH3)-CH2-CH2-CH3, and -CH2-CH(CH3)-CH2. -CH3, -CH2-CH2-CH(CH3)2, -CH(CH3)-CH(CH3)2, -C(CH3)2-CH2-CH3, -CH2-C(CH3)3, -CH(CH2CH3)2, -CH(CH3) -(CH2)3-CH3, -CH2-CH(CH3)-(CH2)2-CH3, -(CH2)2-CH(CH3)-CH2-CH3, -(CH2)3-CH(CH3)2, -CH(CH3)-CH(CH3) -CH2-CH3, -CH(CH3)-CH2-CH(CH3)2, -CH(CH3)2-(CH2)2-CH3, -CH2-CH(CH3)2-CH2-CH3, -CH2-CH2-C(CH3)3, - CH2-CH(CH2CH3)2, -CH(CH2CH3)-CH2(CH2CH3), -C(CH2CH3)2-CH3, -CH(CH2CH3)-(CH2)2-CH3, -(CH2)4-CH(CH3 )2, -(CH2)3-C(CH3)3, -(CH2)5-CH(CH3)2, -(CH2)4-C(CH3)3, -(CH2)6-CH(CH3)2, -(CH2)5-C(CH3)3, -(CH2)7 -CH(CH3)2, -(CH2)6-C(CH3)3, -(CH2)8-CH(CH3)2, -(CH2)7-C(CH3)3, -(CH2)9-CH(CH3)2, -(CH2)8-C(CH3)3, etc.

[0018] In a preferred embodiment, the hydrocarbon group is selected from hydrocarbon groups of C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, and C18. Preferably, the C=C in the hydrocarbon group can be located at the end or not at the end of the hydrocarbon group, such as CH2=CH-CH2-, CH2=CH-(CH2)2-, CH3-CH=CH-CH2-, CH2=C(CH3)-CH2-, CH2=CH-C(CH3)2-, CH2=CH-CH(CH3)-, CH2=CH-CH=CH-, CH2=CH-(CH2)5-, etc.

[0019] In a preferred embodiment, the alicyclic group may be an alicyclic structure selected from C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, and C18. Preferably, the alicyclic structure may be selected from: , , , , , , , , , , , , , , , , , , , , wait.

[0020] In a preferred embodiment, the aromatic ring group may be an aromatic ring structure selected from C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, and C20. Preferably, the aromatic ring structure may be selected from: , , , , , , , , , , , , , , , , , , , wait.

[0021] In a preferred embodiment, the heterocyclic group may be a heterocyclic structure selected from C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, and C20. For example, the heterocyclic structure may be selected from: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , wait.

[0022] In a preferred embodiment, the siloxane compound Si(H) a (R1) b (R2) c (R3) d (R4) e It can be selected from: CH3-(CH2) 17 -O-SiH3, CH3CH2-O-SiH-O-CH2CH3, , , , , , , , , , , , , , ... , , , , , , , , , , , , , , , , , , , , , , , , , , wait.

[0023] In a preferred embodiment, the metal compound and / or metal-like compound gel precursor may be one or more of the following: metal oxide, metal hydroxide, metal sulfide, metal chloride, metal fluoride, metal bromide, metal iodide, metal carbide, metal sulfate, metal nitrate, metal silicate, metal carbonate, metal alkoxide, molybdic acid, molybdate, metal borate, and organometallic acid salt.

[0024] In a preferred embodiment, the metal compound and / or metalloid compound gel precursor may contain one or more metalloids selected from boron, silicon, germanium, arsenic, antimony, tellurium, polonium, and arsenic.

[0025] In a preferred embodiment, the metal-like compound may be one or more of the following: metal oxide, metal chloride, metal sulfide, metal selenide, metal telluride, organometallic compound, metal alkoxide, organic acid salt, boric acid, borate, silicate, silicic acid, arsenic acid, arsenate, germanic acid, germanate, antimony acid, antimonate, metal antimony compound, and boride.

[0026] In a preferred embodiment, the metal compound and / or metalloid compound gel precursor may be SiO2, SiN, Si3N4, SiF4, SiCl4, MgSi, Si(OH)4, H2SiO3, B2H6, B2O3, BCl3, BBr3, Na2B4O7, NaB(OH)4, NaBH4, B4C, H3BO3, BN, TiB2, CrB2, ZrB2, HfB2, CaB6, As2O3, As2O5, AsCl3, AsF5, H3AsO4, H3AsO3, Sb2S3, Sb2S5, SbO, SbO2, Sb2O, Sb2O3, Sb2O4, Sb2O5, Sb6O 13 , SbF5, SbCl5, SbF3, SbBr3, SbCl3, HSb(OH)6, InSb, NiSb, Pd5Sb2, Ag3Sb, Sb(C6H5)3, Sb(C6H5)4, Sb(C6H5)5, Ge2Cl6, Ge O2, GeS2, GeO, GeS, Na2GeO3, H2GeO3, GeSe2, GeSe, GeTe, Ge(SO4)2, GeI4, GeF4, GeCI4, Ge(C2H5)4, Ge(CH3)4, GeH4, GeH3 [CH2CH2(CH3)2], Al2O3, Al(NO3)3, Al2(SO4)3, AlCl3, Al(OH)3, Al(OCH2CH3)3, MgO, MgCl2, Mg(NO3)2, MgSO4, Mg(OH)2, Mg(OCH3)2, Mg(OCH2CH3)2, CaCO3, CaS, CaO, Fe2O3, FeCl3, Fe(NO3)3, Fe(SO4)3, CuO, CuCl2, Cu(NO3)2, CuSO4, Cu(OH)2, etc.

[0027] In a preferred embodiment, the weight content of PEEK in the composition is 10-60%, such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%.

[0028] In a preferred embodiment, the composition contains 10-20% by weight of a siloxane compound, such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%.

[0029] In a preferred embodiment, the metal compound / metal-like compound gel precursor in the composition has a weight content of 0.5-10%, such as 0.6%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%.

[0030] In a preferred embodiment, the weight ratio of PEEK, siloxane compound, and metal compound / metal-like compound gel precursor in the composition is preferably (10-60):(1-20):(0.5-10).

[0031] In a preferred embodiment, the composition further includes a solvent, which may be one or more of alcohols, ethers, phenols, aldehydes, ketones, carboxylic acids, amines, amides, esters, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, heterocyclic compounds, sulfoxides, nitriles, and carbon disulfide. For example, it may be methanol, ethanol, propanol, isopropanol, glycerol, diethyl ether, dimethyl ether, petroleum ether, dimethoxyethane, acetone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, benzophenone, ethylenediamine, ethyl acetate, methyl acetate, propyl acetate, and butyl acetate. Esters, hexane, pentane, octane, benzene, toluene, xylene, benzyl chloride, carbon dichloride, carbon trichloride, carbon tetrachloride, dioxane, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, N-methylpyrrolidone, cyclopentane, cyclohexane, triethanolamine, chlorobenzene, dichlorobenzene, propylene oxide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, pyridine, phenol, carbon disulfide, trichloropropane, dichloroethane, amyl formate, amyl acetate, butanol, turpentine, kerosene, cumene, tetrachloroethane, etc.

[0032] In a preferred embodiment, the composition may further include a hydroxyl-modified polymer (i.e., hydroxyl groups are added to the polymer molecular chain), which may be one or more of hydroxyl-modified polyester, hydroxyl-modified polyamide, and hydroxyl-modified polyimide.

[0033] In a preferred embodiment, the weight content of the hydroxyl-modified polymer in the composition is preferably 0.1%-5%, such as 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%.

[0034] In a preferred embodiment, the composition may further include functional additives, which may be one or more of antioxidants, lubricants, flame retardants, reinforcing agents, plasticizers, ultraviolet absorbers, mildew inhibitors, antibacterial agents, defoamers, toughening agents, colorants, antistatic agents, deodorizers, heat stabilizers, and antifreeze agents.

[0035] In a preferred embodiment, the functional additive in the composition is preferably 0.1%-5% by weight, such as 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%.

[0036] A second aspect of the present invention is to provide a method for preparing the composition, comprising: PEEK is dissolved in a solvent to form a homogeneous solution; Add the siloxane compound Si(A) to the solution. a (R1) b (R2) c (R3) d (R4) e The composition is obtained by stirring and mixing a metal compound / metal-like compound gel precursor (preferably, a functional additive is also added).

[0037] In a preferred embodiment, the dissolution temperature of PEEK in the solvent is 50-150°C, more preferably 60-120°C, and even more preferably 80-100°C.

[0038] In a preferred embodiment, the dissolution time of PEEK in the solvent is 1-10h, more preferably 2-8h, and even more preferably 3-7h, such as 4h, 5h, or 6h.

[0039] A third aspect of the present invention is to provide a method for preparing high-performance fibers, comprising: The composition described in the first aspect of the present invention is provided, or the composition is obtained using the second aspect of the present invention, as a spinning solution; The spinning solution is extruded through a spinneret into a coagulation bath to obtain nascent fibers; The high-performance fiber is obtained by stretching and drying the nascent fiber.

[0040] In a preferred embodiment, the pH value of the coagulation bath is 3-9, such as 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, or 9.

[0041] In a preferred embodiment, the coagulation bath is one or more of water, alcohol, ether, phenol, aldehyde, ketone, carboxylic acid, amine, amide, ester, aliphatic hydrocarbon, aromatic hydrocarbon, halogenated hydrocarbon, heterocyclic compound, sulfoxide, nitrile, and carbon disulfide. For example, it may be water, methanol, ethanol, propanol, isopropanol, glycerol, diethyl ether, dimethyl ether, petroleum ether, dimethoxyethane, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, benzophenone, ethylenediamine, ethyl acetate, methyl acetate, propyl acetate, butyl acetate, hexane, pentane, etc. Alkane, octane, benzene, toluene, xylene, benzyl chloride, carbon dichloride, carbon trichloride, carbon tetrachloride, dioxane, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, N-methylpyrrolidone, cyclopentane, cyclohexane, triethanolamine, chlorobenzene, dichlorobenzene, propylene oxide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, pyridine, phenol, carbon disulfide, trichloropropane, dichloroethane, amyl formate, amyl acetate, butanol, turpentine, kerosene, cumene, tetrachloroethane, etc.

[0042] In a preferred embodiment, the coagulation bath temperature is preferably 10-50℃, such as 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, or 50℃.

[0043] In a preferred embodiment, the draw ratio is 2-10 times, more preferably 3-9 times, more preferably 4-8 times, such as 5 times, 6 times, or 7 times.

[0044] In a preferred embodiment, the stretching temperature is preferably 50-250℃, more preferably 60-240℃, even more preferably 80-220℃, and even more preferably 100-200℃, such as 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, and 190℃.

[0045] In a preferred embodiment, the stretching is a two-stage stretching, with the first-stage stretching having a stretching ratio of 2-5 times (e.g., 2 times, 3 times, 4 times, 5 times) and the second-stage stretching having a stretching ratio of 1.5-3 times (e.g., 1.8 times, 2 times, 2.5 times, 2.8 times).

[0046] In a preferred embodiment, the temperature of the first stage of stretching is preferably 50-150°C, more preferably 60-150°C, even more preferably 70-140°C, and even more preferably 80-130°C, such as 90°C, 100°C, 110°C, and 120°C.

[0047] In a preferred embodiment, the temperature of the second-stage stretching is preferably 180-250°C, more preferably 190-240°C, and even more preferably 200-230°C, such as 210°C, 220°C, and 230°C.

[0048] A fourth aspect of the present invention is to provide a high-performance fiber prepared from the composition or by the method for preparing the high-performance fiber.

[0049] In a preferred embodiment, the tensile strength of the high-performance fiber is ≥600 MPa.

[0050] In a preferred embodiment, the breaking elongation of the high-performance fiber is ≤8%.

[0051] In a preferred embodiment, the surface friction coefficient of the high-performance fiber is ≤0.15.

[0052] A fifth aspect of the present invention is to provide an application of the composition for preparing aerospace composite materials, medical implant materials, or protective fabrics (such as high-strength protective fabrics, preferably with a strength ≥ 500 MPa).

[0053] In a preferred embodiment, the areal density of the aerospace composite material, medical implant material, or protective fabric is ≤200 g / m². 2 .

[0054] In a preferred embodiment, the protective fabric may be a bulletproof protective fabric.

[0055] In a preferred embodiment, the protective fabric has a ballistic protection level of NIJ IIIA.

[0056] Compared with the prior art, the technical solution of the present invention has the following beneficial effects: 1) The specific siloxane compound of this invention not only acts as a compatibilizer to improve the interfacial compatibility between PEEK and the inorganic phase, but also undergoes a sol-gel reaction with the metal / metal-like compound gel precursor during spinning and post-treatment, forming a nanoscale organic-inorganic hybrid network inside the fiber, which further significantly improves the tensile strength and modulus of the fiber.

[0057] 2) The introduction of inorganic phase and optimization of the drafting process in this invention result in a dense and smooth structure on the fiber surface, which has an extremely low coefficient of friction (≤0.15). This can effectively reduce yarn wear and improve processing efficiency during weaving.

[0058] 3) The formed inorganic network structure, such as silicon-oxygen or boron-oxygen, can form a strong ceramic protective layer at high temperatures, which greatly improves the flame retardant properties and thermal stability of the fiber.

[0059] 4) The composition of the present invention can be produced using a mature wet spinning process. By precisely controlling the coagulation bath conditions and multi-stage drawing parameters, the stable preparation of high-content inorganic impurity phase PEEK fibers has been successfully achieved, resulting in dense fiber structure and uniform properties. Detailed Implementation

[0060] To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the following examples further illustrate the invention in detail. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of the invention.

[0061] It should be noted that the terms "first," "second," etc., used in the specification and claims of this invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be used interchangeably where appropriate. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or apparatus that includes a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to these processes, methods, products, or apparatuses.

[0062] Example 1: Preparation of spinning solution: 40% of PEEK resin (Victrex 450G) by weight of the total composition was dissolved in 50% NMP and stirred at 100°C for 4 hours until completely dissolved. Then, 5% of bis(triethoxysilyl)benzene, 3% of silica sol (by weight of silica), and 0.5% of antioxidant Irganox 1010 by weight of the total composition were added, and the mixture was stirred and mixed at 80°C for 2 hours. After vacuum degassing, a uniform spinning solution was obtained.

[0063] Wet spinning: The spinning solution is passed through a spinneret with a diameter of 0.08 mm and extruded into a water / N-methylpyrrolidone (volume ratio 7:3) coagulation bath at a temperature of 25℃ and a pH of 7 to form nascent fibers.

[0064] Drafting and post-treatment: The nascent fibers are first-stage drafted in a hot water bath at 100°C with a draft ratio of 3. Then, a second-stage drafting is performed in hot air at 220°C with a draft ratio of 2. Finally, after drying, the fibers are wound to obtain high-performance fiber F1.

[0065] Example 2: Preparation of spinning solution: 40% of PEEK resin (Victrex 450G) by weight of the composition was dissolved in 50% NMP and stirred at 100°C for 4 hours until completely dissolved. Then, 5% of KH-550 (γ-aminopropyltriethoxysilane) by weight of the composition, 3% of alumina sol (obtained by hydrolysis of aluminum nitrate solution), and 0.5% of antioxidant Irganox 1010 by weight of the composition were added. The mixture was stirred and mixed at 80°C for 2 hours, and then degassed under vacuum to obtain a uniform spinning solution.

[0066] Wet spinning: The spinning solution is passed through a spinneret with a diameter of 0.08 mm and extruded into a water / N-methylpyrrolidone (volume ratio 7:3) coagulation bath at a temperature of 25℃ and a pH of 7 to form nascent fibers.

[0067] Drafting and post-treatment: The nascent fibers are first-stage drafted in a hot water bath at 100°C with a draft ratio of 3. Then, a second-stage drafting is performed in hot air at 220°C with a draft ratio of 2. Finally, after drying, the fibers are wound to obtain high-performance fiber F2.

[0068] Comparative Example 1: Preparation of spinning solution: 40% of the total weight of PEEK resin (Victrex 450G) was dissolved in 50% NMP and stirred at 100°C for 4 hours until completely dissolved. Then, 0.5% of the total weight of antioxidant Irganox 1010 was added, and the mixture was stirred and mixed at 80°C for 2 hours. The solution was then degassed under vacuum to obtain a homogeneous spinning solution.

[0069] Wet spinning: The spinning solution is passed through a spinneret with a diameter of 0.08 mm and extruded into a water / N-methylpyrrolidone (volume ratio 7:3) coagulation bath at a temperature of 25℃ and a pH of 7 to form nascent fibers.

[0070] Drafting and post-treatment: The nascent fibers are first-stage drafted in a hot water bath at 100°C with a draft ratio of 3. Then, a second-stage drafting is performed in hot air at 220°C with a draft ratio of 2. Finally, after drying, the fibers are wound to obtain high-performance fiber C1.

[0071] Comparative Example 2: Preparation of spinning solution: 40% of PEEK resin (Victrex 450G) by weight of the total composition was dissolved in 50% NMP and stirred at 100°C for 4 hours until completely dissolved. Then, 3% of silica sol (by weight of silica) and 0.5% of antioxidant Irganox 1010 by weight of the total composition were added, and the mixture was stirred and mixed at 80°C for 2 hours. After vacuum degassing, a uniform spinning solution was obtained.

[0072] Wet spinning: The spinning solution is passed through a spinneret with a diameter of 0.08 mm and extruded into a water / N-methylpyrrolidone (volume ratio 7:3) coagulation bath at a temperature of 25℃ and a pH of 7 to form nascent fibers.

[0073] Drafting and post-treatment: The nascent fibers are first-stage drafted in a hot water bath at 100°C with a draft ratio of 3. Then, a second-stage drafting is performed in hot air at 220°C with a draft ratio of 2. Finally, after drying, the fibers are wound to obtain high-performance fiber C2.

[0074] Performance Tests and Results The fibers obtained in the above embodiments and comparative examples were subjected to performance tests, and the results are shown in Table 1 below: Table 1. Fiber performance test results of embodiments and comparative examples of the present invention. Results analysis: Mechanical properties: The tensile strength of the fibers in Examples 1 and 2 both exceeded 600 MPa, significantly higher than that of the pure PEEK fiber in Comparative Example 1 (520 MPa). This indicates that the present invention achieves effective reinforcement through the synergistic effect of siloxane compounds and inorganic precursors. Comparative Example 2, due to the lack of a compatibilizer, experienced inorganic phase agglomeration, resulting in brittle fibers, low strength, and difficulty in spinning.

[0075] Surface properties: The fiber surface friction coefficient of the present invention is extremely low (F1 is 0.12, F2 is 0.14), and is much lower than that of pure PEEK fiber. This is due to the smooth and dense surface structure, which is beneficial to the subsequent weaving and processing of the fabric.

[0076] Flame retardant properties: The LOI of Example 1 of this invention is as high as 42%, reaching the level of flame-retardant materials, which is far superior to pure PEEK. This is attributed to the fact that the formed B or Si can form BO networks or Si-O networks, which promote the formation of dense C layers during combustion.

[0077] Processability: The spinning process of Examples 1 and 2 of the present invention is stable and comparable to that of pure PEEK fiber, proving that the composition has good spinnability.

[0078] Example 3: Preparation of spinning solution: 38% PEEK resin (Victrex 450G) by weight of the composition was dissolved in 52% NMP and stirred at 105°C for 4.5 hours until completely dissolved. Zirconium oxychloride (ZrOCl2·8H2O) was pre-hydrolyzed under dilute hydrochloric acid catalysis, and after aging and dialysis, a stable zirconia sol was obtained. 6% of this zirconia sol (equivalent to approximately 2.4% ZrO2 by weight of the composition), 4% of the silane coupling agent KH-560 by weight of the composition, and 0.6% of the antioxidant 1076 by weight of the composition were stirred and mixed at 80°C for 2.5 hours to obtain a homogeneous spinning solution.

[0079] Wet spinning: The spinning solution is extruded through a spinneret with an aperture of 0.07 mm into a coagulation bath of water / NMP / ethanol (volume ratio 6:3:1) at a temperature of 20°C and a pH of 4. The acidic environment facilitates the hydrolysis and condensation of the coupling agent, promoting interfacial bonding.

[0080] Drafting and post-treatment: The nascent fibers were first-stage drafted in a 95°C hot water bath with a draft ratio of 3.2. A second-stage drafting was then performed in a hot nitrogen atmosphere at 235°C with a draft ratio of 2.2, and the fibers were held at this temperature for tension heat setting for 30 seconds. Finally, after cooling, oiling, and winding, high-hardness and excellent abrasion resistance PEEK / ZrO2 composite fiber F3 was obtained.

[0081] Example 4: Preparation of spinning solution: 41% PEEK resin (by weight of the total composition) was dissolved in 51% NMP and stirred at 100°C for 4 hours until completely dissolved. While maintaining the temperature at 80°C, the following were added sequentially: 1) 2% tetrabutyl titanate (as a TiO2 precursor); 2) 5% composite coupling agent (of which KH-550 reacts with the hydroxyl groups on the surface of the titanate hydrolysis product, and a small amount of titanate coupling agent NDZ-201 was added); 3) 0.8% antioxidant Irganox 1010. The mixture was stirred at this temperature for 3 hours to allow complete hydrolysis of the tetrabutyl titanate and grafting of the coupling agent. This mixture was then mixed with and modified with nano-powder TiO2 to obtain the spinning solution.

[0082] Wet spinning: The spinning solution is passed through a spinneret with a diameter of 0.09 mm and extruded into a coagulation bath with a temperature of 30°C and a pH of about 6.5, consisting of water / NMP (volume ratio 8:2), to form nascent fibers.

[0083] Drawing and post-treatment: The nascent fibers were first drawn in saturated steam at 105℃ with a draw ratio of 2.8 times. This was followed by two stages of hot drawing: first, a 2.0-fold draw in hot air at 200℃, and then a 1.5-fold draw and heat-set in a heat pipe at 250℃ (nitrogen protection). The final product was a composite fiber F4 with strong interfacial bonding and excellent overall mechanical properties and abrasion resistance.

[0084] Example 5: Preparation of spinning solution: 39% PEEK resin (by weight of the total composition) was dissolved in 50% NMP at 100°C. Hydroxyapatite (HA) nanocrystals (approximately 20 aspect ratio, pretreated with stearic acid to improve dispersibility in the organic phase) (7% by weight of the total composition), silane coupling agent KH-570 (3% by weight of the total composition), and calcium stearate lubricant (1% by weight of the total composition) were added. The mixture was stirred at high speed at 85°C for 3.5 hours to ensure thorough dispersion of the whiskers, yielding the spinning solution.

[0085] Wet spinning: The spinning solution is extruded through a spinneret with an aperture of 0.1 mm into a coagulation bath at 15°C with an NMP concentration as high as 40% (volume ratio of water:NMP = 6:4). Milder coagulation conditions are used to slow down phase separation, reduce internal fiber defects, and improve density.

[0086] Drafting and post-processing: The nascent fibers are first-stage drawn in 90°C hot water (draw ratio 2.5 times). Then, a second-stage drawn (draw ratio 2.5 times) is performed in 210°C hot air. Finally, a third-stage drawn (draw ratio 1.3 times) is performed under tension through heated rollers at 250°C, simultaneously completing heat setting. This yields F5, a composite fiber that combines high strength and abrasion resistance.

[0087] Application Example: Ballistic Performance Testing The fiber F1 obtained in Example 1 is used to weave a fabric with an areal density of 180 g / m². 2 The fabric is a plain weave material. It underwent Level IIIA (fire of .44 Magnum semi-jacketed pistol ammunition) protection testing according to the U.S. Department of Justice NIJ Standard-0101.06. Test results showed that the fabric successfully withstood the impact of the bullet, with a clay indentation depth of 22 mm, far below the standard requirement of 44 mm, achieving a ballistic protection level of NIJ IIIA.

[0088] The specific embodiments of the present invention have been described in detail above, but they are merely examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and substitutions to the present invention are also within the scope of the present invention. Therefore, all equivalent transformations and modifications made without departing from the spirit and scope of the present invention should be covered within the scope of the present invention.

Claims

1. A composition for preparing high-performance fibers, characterized in that, Including polyetheretherketone (PEEK) and siloxane compounds Si(A). a (R1) b (R2) c (R3) d (R4) e A metal compound and / or metalloid compound gel precursor, wherein a, b, c, d, and e are each an independent number ≥ 0, and a + b + c + d + e = 4, and b + c + d + e is not 0; wherein R1, R2, R3, and R4 are each independently selected from the groups shown in R5-D, where R5 is a hydrocarbon group or R6 is a substituted hydrocarbon group, D is a single bond, an O atom, an S atom, or a Si atom, and R6 is a substituent; A is a H, hydroxyl, mercapto, or halogen atom.

2. The composition according to claim 1, characterized in that, In the R6-substituted hydrocarbon group, R6 is located as a side group of the hydrocarbon group and is selected from one or more combinations of hydrocarbon group, heterocyclic group, haloalkyl group, -OH, -COOH, -F, -Cl, -Br, -CN, -NH2, -CHO, -CONH2, -SH, -SO3H, and -NO2; or In the R6-substituted hydrocarbon group, R6 is located on the hydrocarbon group chain segment, and R6 is selected from one or more combinations of divalent hydrocarbon group, divalent heterocyclic group, divalent halohydrocarbon group, -O-, -S-, -SO2-, -NH2-, -CO-, -COO-, -CONH-, -C=N-.

3. The composition according to claim 1 or 2, characterized in that, The hydrocarbon group is selected from one or more combinations of alkyl, olefin, aliphatic ring, and aromatic ring groups.

4. The composition according to claim 3, characterized in that, The alkyl group is selected from alkyl groups of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, and C18; and / or The hydrocarbon group is selected from hydrocarbon groups of C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, and C18; and / or The alicyclic group is selected from alicyclic structures of C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, and C18; and / or The aromatic ring group is selected from aromatic ring structures of C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, and C20; and / or The heterocyclic group can be a heterocyclic structure selected from C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, and C20.

5. The composition according to claim 4, characterized in that, The alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, -CH(CH3)-CH2-CH2-CH3, -CH2-CH(CH3)-CH2-CH3, -CH2-CH2-CH(CH3)2, -CH(CH3)-CH(CH3)2, -C(CH3)2-CH2-CH3, -C H2-C(CH3)3, -CH(CH2CH3)2, -CH(CH3)-(CH2)3-CH3, -CH2-CH(CH3)-(CH2)2-CH3, -(CH2)2-CH(CH3) -CH2-CH3, -(CH2)3-CH(CH3)2, -CH(CH3)-CH(CH3)-CH2-CH3, -CH(CH3)-CH2-CH(CH3)2, -CH(CH3)2- (CH2)2-CH3, -CH2-CH(CH3)2-CH2-CH3, -CH2-CH2-C(CH3)3, -CH2-CH(CH2CH3)2, -CH(CH2CH3)-CH2 (CH2CH3), -C(CH2CH3)2-CH3, -CH(CH2CH3)-(CH2)2-CH3, -(CH2)4-CH(CH3)2, -(CH2)3-C(CH3)3, -( CH2)5-CH(CH3)2, -(CH2)4-C(CH3)3, -(CH2)6-CH(CH3)2, -(CH2)5-C(CH3)3, -(CH2)7-CH(CH3)2, -( CH2)6-C(CH3)3, -(CH2)8-CH(CH3)2, -(CH2)7-C(CH3)3, -(CH2)9-CH(CH3)2, -(CH2)8-C(CH3)3; and / or The hydrocarbon group is selected from CH2=CH-CH2-, CH2=CH-(CH2)2-, CH3-CH=CH-CH2-, CH2=C(CH3)-CH2-, CH2=CH-C(CH3)2-, CH2=CH-CH(CH3)-, CH2=CH-CH=CH-, CH2=CH-(CH2)5-; and / or The fatty ring structure is selected from: , , , , , , , , , , , , , , , , , , , , ; and / or The aromatic ring structure is selected from: , , , , , , , , , , , , , , , , , , , ; and / or The heterocyclic structure is selected from: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

6. The composition according to claim 1, characterized in that, The siloxane compound Si(H) a (R1) b (R2) c (R3) d (R4) e Selected from: CH3-(CH2) 17 -O-SiH3、CH3CH2-O-SiH-O-CH2CH3、 、 、 、 、 、 、 、 、 、 、 、 、 、 、、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 7. The composition according to claim 1, characterized in that, In the metal compound and / or metal-like compound gel precursor, the metal compound is selected from one or more of the following: metal oxides, metal hydroxides, metal sulfides, metal chlorides, metal fluorides, metal bromides, metal iodides, metal carbides, metal sulfates, metal nitrates, metal silicates, metal carbonates, metal alkoxides, molybdic acid, molybdates, metal borates, and organometallic acid salts; and / or The metalloids are selected from one or more of boron, silicon, germanium, arsenic, antimony, tellurium, polonium, and arsenic; and / or The metalloid compound is selected from one or more of the following: metalloid oxides, metalloid chlorides, metalloid sulfides, metalloid selenides, metalloid tellurides, organometalloid compounds, metalloid alkoxides, organic acid salts, boric acid, borates, silicates, silicic acid, arsenic acid, arsenates, germanic acid, germanates, antimony acid, antimonates, metal antimony compounds, and borides.

8. The composition according to claim 1, characterized in that, The preferred weight ratio of PEEK, siloxane compounds, and metal / metal-like compound gel precursors is (10-60):(1-20):(0.5-10).

9. A method for preparing high-performance fibers, comprising: Provide the composition according to claim 1, or obtain the composition by the following method: PEEK is dissolved in a solvent to form a homogeneous solution; Add the siloxane compound Si(A) to the solution. a (R1) b (R2) c (R3) d (R4) e The composition is obtained by stirring and mixing a metal compound / metal-like compound gel precursor (preferably, a functional additive is also added); The composition was used as a spinning solution; The spinning solution is extruded through a spinneret into a coagulation bath to obtain nascent fibers; The high-performance fiber is obtained by stretching and drying the nascent fiber.

10. The method for preparing high-performance fibers according to claim 9, characterized in that, The drawing process is a two-stage drawing process. The first stage of drawing has a draw ratio of 2-5 times and a temperature of 50-150℃. The second stage of drawing has a draw ratio of 1.5-3 times and a temperature of 180-250℃.

11. A high-performance fiber prepared by the method of claim 9.

12. An application of the composition of claim 1 or the high-performance fiber of claim 9, characterized in that, The composition or the fiber is used to prepare aerospace composite materials, medical implant materials, or protective fabrics.

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