CN113089320A - Surface appearance controllable high-adhesion modified fiber and preparation method and application thereof - Google Patents

Surface appearance controllable high-adhesion modified fiber and preparation method and application thereof Download PDF

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CN113089320A
CN113089320A CN202110552983.XA CN202110552983A CN113089320A CN 113089320 A CN113089320 A CN 113089320A CN 202110552983 A CN202110552983 A CN 202110552983A CN 113089320 A CN113089320 A CN 113089320A
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CN113089320B (en
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沈璐
谢卫萍
陈希跑
苗利静
文能博
李波
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Yancheng Institute of Technology
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    • D—TEXTILES; PAPER
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06M2101/40—Fibres of carbon

Abstract

The invention discloses a high-adhesion modified fiber with a controllable surface appearance, and a preparation method and application thereof. The modified fiber comprises a fiber matrix and a coating covering the fiber matrix; the coating has a micro-nano structure formed by nano particles, wherein the size of the nano particles is 1-500nm, and the shape of the nano particles comprises at least any one of sphere, sheet and column; and the thickness of the coating is 2-500nm, the content of Si in the coating is 2-15%, the content of N is 1-8 wt%, and in the Si characteristic fine spectrum of the modified fiber, the ratio of the characteristic peak area with the peak value of 101.1eV to the characteristic peak area with the peak value of 103.2eV is 5:1-50: 1. The surface appearance of the high-adhesion modified fiber with the controllable surface appearance can be accurately controlled, the adhesion between the high-adhesion modified fiber and matrix resin is strong, the mechanical property is excellent, the preparation process is simple, convenient and feasible, and the cost is controllable.

Description

Surface appearance controllable high-adhesion modified fiber and preparation method and application thereof
Technical Field
The invention relates to a modified fiber and a preparation method thereof, in particular to a modified fiber with controllable surface appearance, high adhesiveness and excellent mechanical property, a preparation method and application thereof, belonging to the technical field of material science.
Background
In a large family of composite materials, fiber reinforced materials are always the focus of attention, and the fiber reinforced composite materials have the advantages of high specific strength, large specific modulus, designability, corrosion resistance, good durability and the like. These characteristics make fiber reinforced materials widely used in various civil and aerospace fields. However, the traditional reinforced fibers, such as glass fibers, ultra-high molecular weight polyethylene (UHMWPE) fibers, carbon fibers and other materials, have smooth surfaces and low polar group content, which results in weak interfacial bonding strength between the fibers and matrix resin, and the fibers are easily pulled out of the matrix under stress, which severely restricts the application of the fibers in the field of composite materials. Therefore, the preparation of the fiber with controllable high surface appearance, the improvement of the bonding property of the fiber and the resin matrix and the maintenance of the excellent mechanical property of the fiber are always hot points of research in recent years.
At present, the modification of the fiber is mainly carried out by two methods, one is a composite spinning method, and the other component containing polar groups is added during spinning and is spun; one is a surface modification method, which mainly introduces polar groups on the fiber surface by surface treatment methods such as oxidation treatment, plasma treatment, irradiation, coating and the like. The Chinese patent with publication number CN112030563A discloses a preparation method of a profiled fiber non-woven fabric with a one-way moisture-conducting function, a rough structure is formed on the surface of the fiber based on green dopamine chemistry, and dopamine is a natural mucin substance and is more environment-friendly than the traditional chemical reagent. Chinese patent publication No. CN112010572A discloses a conductive glass fiber and a preparation method thereof, wherein tannic acid is oxidized by itself to deposit on the surface of the glass fiber to form a poly-tannic acid functional coating. The invention discloses a coating method for improving wear resistance of polyester harness cords, which takes aqueous polyurethane slurry as coating slurry, and immerses pretreated polyester in the coating slurry for padding, and obtains the coating polyester harness cords after drying and heat setting treatment. Chinese patent publication No. CN103993479A discloses a method for preparing silane crosslinked modified ultra-high molecular weight polyethylene fibers, which comprises placing non-dried ultra-high molecular weight polyethylene UHMWPE gel fibers in a modifying solution, performing ultrasonic treatment, and performing multistage thermal stretching to obtain UHMWPE fibers with high surface bonding property and substantially maintained mechanical properties. Although the above methods all produce fibers with improved adhesion, they still suffer from several disadvantages: 1. the preparation process is complicated, the modification in the spinning process needs to modify the existing spinning process, and the production cost is increased; 2. oxidation or radiation modification can be at the expense of reduced mechanical properties of the fiber and require additional processing equipment; 3. when the surface of a compound with a polyphenol bionic structure (such as dopamine, tannic acid and the like) is coated, the purpose of improving the adhesion can be realized on the premise of keeping the mechanical property of the fiber, but the fiber obtained by the method has a smooth surface and an uncontrollable shape, and the adhesion improvement is mainly obtained by the key bond or non-covalent bond between a surface polar group and matrix resin.
In addition, the traditional surface coating method of the polyphenols at present realizes the effective coating of the surface of the matrix by means of non-covalent bonds such as hydrogen bonds, van der waals force and the like of phenolic hydroxyl groups and the surface of the matrix, and the coating condition is mild, so that the excellent mechanical properties of the fibers are effectively maintained. However, this method still has some problems: 1. the coatings formed by the polyphenols exist in the form of films on the fiber surface, and although the surfaces become rough compared with the unmodified fiber surface, the surface morphology cannot be effectively controlled; 2. the acting force of the coating and the matrix resin mainly depends on the covalent bond or the non-covalent bond formed between the polyphenol substances and the matrix resin, and the mechanical interlocking action between the rough surface and the matrix resin cannot be regulated and controlled.
There is therefore a need for new adhesion promoting fibers and methods for making the same.
Disclosure of Invention
The invention mainly aims to provide a modified fiber with controllable surface appearance, high adhesiveness and excellent mechanical property, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a high-adhesion modified fiber with a controllable surface appearance, which comprises a fiber matrix and a coating covering the fiber matrix; the coating has a micro-nano structure formed by nano particles, wherein the size of the nano particles is 1-500nm, and the shape of the nano particles comprises at least any one of sphere, sheet and column; and the content of Si in the coating accounts for 2-15 wt% of the total mass of the coating, the content of N accounts for 1-8 wt% of the total mass of the coating, and in a Si characteristic fine spectrum of the modified fiber, the ratio of a characteristic peak area with a peak value of 101.1eV to a characteristic peak area with a peak value of 103.2eV is 5:1-50: 1.
Wherein the total mass of the fibers is the sum of the mass of the fiber matrix and the mass of the coating.
In some embodiments, the modified fiber has a contact angle with water of 50 to 95 °.
In some embodiments, the tensile strength of the modified fiber is 3-6GPa, the tensile strength retention rate of the modified fiber is 80-99%, the monofilament extraction force of the modified fiber in the epoxy resin embedding test is 10-50cN, and the interfacial shear strength of the modified fiber/epoxy resin composite material is 5-30 MPa.
In some embodiments, the fiber matrix comprises ultra-high molecular weight polyethylene fibers, carbon fibers, or aramid fibers, among others.
The embodiment of the invention also provides a preparation method of the high-adhesion modified fiber with the controllable surface appearance, which comprises the following steps:
(1) cleaning the fiber matrix;
(2) adding an amine compound into a silane coupling agent reaction solution, and reacting to obtain a siloxane modified amino compound with an amino group at the tail end;
(3) and (3) adding the siloxane modified amino compound obtained in the step (2) into a trihydroxymethyl aminomethane buffer solution with the pH value of 7-10 for reaction, then adding a polyphenol compound and metal ions, and then adding the fiber matrix cleaned in the step (1) for continuous reaction, thereby obtaining the high-adhesion modified fiber with controllable surface appearance.
In some embodiments, the amine compound includes any one or a combination of two or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and polyethyleneimine, and the like.
In some embodiments, the polyphenolic compound comprises any one or a combination of two or more of dopamine, catechol, pyrogallol, 5-hydroxy-1, 4-naphthoquinone, tannic acid, and the like.
In some embodiments, the metal ion comprises Fe3+、Al3+、Ag+、Cu2+、Zn2+、Fe2+And the like, or a combination of two or more thereof.
The embodiment of the invention also provides the high-adhesion modified fiber with the controllable surface appearance, which is prepared by the method.
The embodiment of the invention also provides application of the high-adhesion modified fiber with the controllable surface morphology in preparation of a polymer matrix composite material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the surface of the high-adhesion modified fiber with controllable surface morphology generates a large amount of polar groups, the surface morphology (spherical, flaky and columnar) of the fiber can be accurately controlled, covalent bonds, non-covalent bonds and mechanical interlocking between the fiber and matrix resin are facilitated to be generated, the adhesion is improved, and the mechanical property of the modified fiber is excellent;
(2) the preparation process of the modified fiber provided by the invention is simple, convenient and feasible, controllable in cost, not harsh in coating conditions and convenient for large-scale production.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1 a-1 e are schematic illustrations of the structures and reaction sites of various amine-based compounds employed in the preparation of surface modified fibers in accordance with an exemplary embodiment of the present invention;
FIG. 2 is a schematic diagram of a process for preparing a high-adhesion modified fiber with a controlled surface topography according to an exemplary embodiment of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, wherein an oxidation product benzoquinone group of a polyphenol compound and two terminal amino groups of a siloxane modified amino compound are subjected to Schiff base reaction to generate an organic cage compound, and the precise control of the coating surface morphology is realized by regulating and controlling the crystallization process and the form of the compound. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiment of the invention provides a modified fiber with controllable surface appearance, high adhesion and excellent mechanical property, wherein the fiber has controllable surface appearance, excellent mechanical property and strong adhesion between the fiber and matrix resin.
Specifically, the modified fiber with controllable surface appearance, high adhesion and excellent mechanical property comprises a fiber matrix and a coating covering the fiber matrix; the coating has a micro-nano structure formed by nano particles, wherein the size (the diameter or the maximum value from one end to the other end) of the nano particles is 1-500nm, and the shape of the nano particles comprises at least any one of sphere, sheet and column; and the content of Si in the coating accounts for 2-15 wt% of the total mass of the coating, the content of N accounts for 1-8 wt% of the total mass of the coating, and XPS tests show that in an Si characteristic fine spectrum of the modified fiber, two peaks are present, which are near 101.1eV and 103.2eV and respectively correspond to Si-O-C characteristic peaks and Si-O-Si characteristic peaks, and the ratio of the characteristic peak area at the peak of 101.1eV to the characteristic peak area at 103.2eV is 5:1-50: 1.
Furthermore, the modified fiber with controllable surface morphology, high adhesion and excellent mechanical property is divided into a coating layer and a fiber matrix, wherein the coating layer is formed by coating a coating layer with controllable micro-nano morphology on the surface of the fiber matrix.
Further, the mass of the coating is 1-10 wt% of the mass of the fiber matrix.
Further, the thickness of the coating is 2-500 nm.
Further, the contact angle of the modified fiber and water is 50-95 degrees.
Further, the tensile strength of the modified fiber is 3-6 GPa.
Further, the tensile strength retention rate (ratio of modified fiber to unmodified fiber) of the modified fiber is 80-99%.
Furthermore, the monofilament extraction force of the modified fiber in the epoxy resin embedding test is 10-50 cN.
Furthermore, the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber is 5-30 Mpa.
Further, the fiber matrix includes, but is not limited to, any one of ultra-high molecular weight polyethylene (UHMWPE) fibers, carbon fibers, or aramid fibers.
Another aspect of the embodiments of the present invention provides a method for preparing a modified fiber with controllable surface morphology, high adhesion, and excellent mechanical properties, including:
(1) cleaning the fiber matrix;
(2) adding an amine compound into a silane coupling agent reaction solution, and reacting to obtain a siloxane modified amino compound with an amino group at the tail end;
(3) and (3) adding the siloxane modified amino compound obtained in the step (2) into a trihydroxymethyl aminomethane buffer solution with the pH value of 7-10 for reaction, then adding a polyphenol compound and metal ions, and then adding the fiber matrix cleaned in the step (1) for continuous reaction, thereby obtaining the high-adhesion modified fiber with controllable surface appearance.
Further, the step (1) comprises the following steps: carrying out ultrasonic treatment on a fiber matrix in a solvent, and then taking out and drying; the solvent includes, but is not limited to, any one or combination of ethanol, acetone, propylene glycol, glycerol, n-hexane, ethylene glycol, and the like.
Further, the fiber matrix includes, but is not limited to, any one of ultra-high molecular weight polyethylene (UHMWPE) fibers, carbon fibers, or aramid fibers, etc.
In some embodiments, step (2) comprises: adding an amine compound into a silane coupling agent reaction solution at a temperature of 10-80 ℃ (preferably 50-80 ℃), stirring for 5-120min, and then freeze-drying to obtain the siloxane modified amino compound.
Further, the weight average molecular weight of the siloxane-modified amino compound was 100-2000.
Further, the amine compound includes, but is not limited to, any one or a combination of two or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, and the like; referring to fig. 1a to 1e, schematic views of reaction sites in compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and polyethyleneimine are shown, wherein n of the polyethyleneimine is 5 to 200.
Further, the silane coupling agent reaction solution comprises a mixture of any one or a combination of two of water and alcohol and KH560, and can be also called as a KH560 reaction solution.
Further, the KH560 reaction solution is one or a mixture of water, ethanol, glycol and glycerol.
Further, the alcohol includes any one or a combination of two or more of ethanol, ethylene glycol, glycerin, and the like (in any ratio), but is not limited thereto.
Furthermore, the mass of KH560 in the mixture accounts for 1-20% of the total mass, the mass of water accounts for 0.1-10% of the total mass, and the mass of alcohol accounts for 98.9-70% of the total mass.
Further, the molar ratio of the amino group in the amine compound to the epoxy group in KH560 is 0.8:1-2: 1.
Furthermore, the siloxane modified amino compound is a compound with an amino group at the terminal obtained by the ring-opening reaction of an epoxy group of a silane coupling agent and an amino group (or imino group) of an amino compound, and taking a reaction product of the reaction site No. i of ethylenediamine and diethylenetriamine as an example (see the following structure), different reaction sites of different amine compounds can participate in the reaction to obtain the siloxane modified amino compound with the amino group at the terminal.
Figure BDA0003075990380000061
Further, the structure of the siloxane-modified amino compound may be represented as:
Figure BDA0003075990380000062
further, in the Si characteristic fine spectrum of the siloxane-modified amino compound, there are two peaks in the vicinity of 101.1eV and 103.2eV corresponding to the area ratio of Si-O-C and Si-O-Si characteristic peaks, respectively, of more than 500:1, that is, the ratio of the characteristic peak area at a peak of 101.1eV to the characteristic peak area at 103.2eV is more than 500: 1.
In some embodiments, step (3) comprises: adding the siloxane modified amino compound obtained in the step (2) into a trihydroxymethyl aminomethane buffer solution (also called Tris buffer solution) with the pH value of 7-10 to form a first reaction system, carrying out hydrolysis crosslinking reaction for 0.1-1 hour, then adding a polyphenol compound and metal ions to form a second reaction system, carrying out Schiff base reaction to generate an organic cage compound, then rapidly adding the fiber matrix cleaned in the step (1) to continue reacting for 1-48 hours, and washing and drying the obtained fibers, thereby obtaining the modified fibers with controllable surface appearance, high adhesion and excellent mechanical property.
In some embodiments, the polyphenolic compound includes, but is not limited to, any one or a combination of two or more of dopamine, catechol, pyrogallol, 5-hydroxy-1, 4-naphthoquinone, tannic acid, and the like.
In some embodiments, the metal ion includes, but is not limited to, Fe3+、Al3+、Ag+、Cu2+、Zn2+、Fe2+And the like, or a combination of two or more thereof.
Further, the concentration of the metal ions in the second reaction system is 0.1-10 mg/ml.
Further, the concentration of the polyphenol compound in the second reaction system is 0.5-5 mg/ml.
Further, the concentration of the silicone-modified amino compound in the first reaction system is 0.1 to 4 mg/ml.
Further, the temperature of the hydrolytic crosslinking reaction is 20-60 ℃, preferably, the temperature of the hydrolytic crosslinking reaction is 20-50 ℃, and more preferably, the temperature of the hydrolytic crosslinking reaction is 30-50 ℃.
Further, the temperature of the Schiff base reaction is 20-60 ℃, and preferably 30-50 ℃.
Further, in the step (3), the Tris buffer solution (i.e., Tris buffer solution) contains Tris at a concentration of 0.05 to 0.2mol/L, water and an alcohol compound, that is, the amount of Tris in the Tris buffer solution is 0.05 to 0.2mol/L, and the buffer solution is a mixture of water and an alcohol compound.
Further, the alcohol compound includes, but is not limited to, any one or a combination of two or more of ethanol, ethylene glycol, glycerol, and the like.
Furthermore, the mass of water in the tris buffer solution accounts for 5% -30% of the total mass of the water and the alcohol, and the mass of the alcohol compound accounts for 70% -95% of the total mass of the water and the alcohol.
Another aspect of the embodiments of the present invention provides a high-adhesion modified fiber having a controlled surface morphology, prepared by the foregoing method.
Another aspect of the embodiments of the present invention provides a use of the high-adhesion modified fiber with controllable surface morphology for preparing a polymer matrix composite.
Further, the polymer matrix composite is a fiber reinforced resin composite.
Referring to fig. 1, in the embodiment of the present invention, polyphenols can be oxidized into quinones under the action of air, and carbon-oxygen double bonds (C ═ O) of the quinones can undergo schiff base reaction with amino groups of siloxane-modified amino compounds to form organic cage compounds (see fig. 2). The different morphologies of the organic cage compound can be accurately regulated and controlled by controlling the reaction conditions and the crystallization process of the organic cage compound.
In some more specific embodiments, the preparation method of the modified fiber with controllable surface morphology, high adhesion and excellent mechanical properties of the invention comprises the following specific steps:
step 1, fiber cleaning:
the fiber surface cleaning process is that the fiber matrix is treated by ultrasonic in a solvent, and then taken out and dried; the solvent includes, but is not limited to, any one or combination of more of ethanol, acetone, and the like.
The fiber refers to any one of UHMWPE fiber, carbon fiber or aramid fiber.
Step 2, preparation of a siloxane modified amino compound: adding the amine compound into the KH560 reaction solution at the temperature of 10-80 ℃ (preferably 50-80 ℃), stirring for 5-120min, and freeze-drying to obtain the siloxane modified amino compound.
Step 3, preparing the modified fiber with controllable surface morphology: firstly, adding the siloxane modified amino compound prepared in the step 2 into a Tris buffer solution with the pH value of 7-10, reacting for 0.1-1 hour, then adding a polyphenol compound and metal ions, then soaking the cleaned fiber obtained in the step 1 into the mixed solution, continuously reacting for 1-48 hours, and then washing and drying the fiber to obtain the modified fiber with controllable surface appearance, high adhesion and excellent mechanical property.
The structure of the siloxane modified amino compound is influenced by preparation conditions, when the water content in the KH560 reaction solution is too low, the ring-opening reaction of an epoxy group and an amino group is difficult to occur, and when the water content is too high, the siloxane group can undergo a hydrolytic crosslinking reaction, so that a target product cannot be obtained. In addition, the molecular weight of the siloxane modified amino compound can be controlled within a certain range (the weight average molecular weight is 100-2000), because when the molecular weight is too high, the molecular chain containing amino can wrap siloxane groups, and the occurrence of hydrolytic crosslinking reaction is hindered.
In the above embodiment of the present invention, the structure of the siloxane modified amino compound hydrolysis cross-linked product affects the morphology and structure of the product, on one hand, the hydrolysis cross-linked product is a compound with amino groups at both ends, which facilitates the subsequent schiff base reaction to obtain a ring-forming organic cage compound; on the other hand, the structure of the hydrolysis crosslinking product can be regulated and controlled by changing the hydrolysis crosslinking condition to obtain the hydrolysis crosslinking product with different molecular chain structures (net or linear) and large molecular weight, so that the aim of controlling the crystal morphology and the crystal size of the organic cage compound is fulfilled.
In the above embodiment of the present invention, the pre-reaction time of the siloxane modified amino compound in the Tris buffer solution affects the generation of the organic cage compound, the pre-reaction is mainly aimed at the hydrolytic crosslinking of siloxane, a compound having amino groups at both ends of a molecular chain cannot be obtained if the hydrolytic crosslinking time is too short, and a large amount of self-polymerization occurs on the siloxane modified amino compound if the time is too long, so that the next schiff base reaction cannot be performed. The ratio of the alcohol compound to the aqueous solution in the Tris buffer solution can also influence the generation of the organic cage compound, the alcohol substance is too high, the siloxane can not be subjected to hydrolytic crosslinking, the alcohol substance is too low, the hydrolytic crosslinking process of the siloxane can be quickly completed, the structure of a hydrolytic crosslinking product can not be regulated, and the organic cage compound with controllable structure morphology can not be formed. The concentrations of the polyphenol compound and the siloxane modified amino compound also influence the appearance of the product, the concentration is too high, the generated crystals are too fast, and the accurate regulation and control of the appearance are difficult to realize; the concentration is too low, the probability of reaction is low, the distribution of surface nano particles is too little, and the adhesion promotion of the fiber is weak. In addition, the metal ions can be added to play roles in inducing crystallization and controlling crystallization morphology, which is obtained through a large number of experiments, and the type and concentration of the metal ions can also influence the surface morphology and the adhesion of the modified fiber.
In summary, the surface of the high-adhesion modified fiber with controllable surface morphology provided by the invention generates a large amount of polar groups, the surface morphology (spherical, flaky and columnar) of the fiber can be accurately controlled, covalent bonds, non-covalent bonds and mechanical interlocking between the fiber and matrix resin are facilitated to improve the adhesion, and the mechanical property of the modified fiber is excellent; meanwhile, the preparation process of the modified fiber is simple, convenient and feasible, the cost is controllable, the coating condition is not harsh, and the large-scale production is facilitated.
The technical solution of the present invention will be described in more detail with reference to several embodiments as follows. The fibers and other materials used in the following comparative examples and examples are commercially available and the various types of reaction equipment, test methods, etc. used therein are known to those skilled in the art unless otherwise specified.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
(1) Fiber cleaning and preparation of siloxane modified amino compound: immersing UHMWPE fibers into acetone for ultrasonic treatment for 1h, and drying at room temperature after washing; adding ethylenediamine into a KH560 reaction solution (mixed solution of ethanol and water) at 10 ℃, wherein the mass of water accounts for 0.1% of the total mass of KH560, ethanol and water, the mass of KH560 accounts for 1% of the total mass, the mass of ethanol accounts for 98.9% of the total mass, the molar ratio of amino groups in ethylenediamine to epoxy groups in KH560 is 0.8:1, stirring for 5min, and freeze-drying to obtain a siloxane modified amino compound with the weight-average molecular weight of 100, wherein in an Si characteristic fine spectrum of the compound, the area ratio of Si-O-C characteristic peaks to Si-O-Si characteristic peaks is 501: 1.
(2) Preparing modified fibers with controllable surface morphologies: firstly, adding the siloxane modified amino compound prepared in the step 2 into a Tris buffer solution (a mixture of water and ethanol, wherein the mass of the water accounts for 5% of the total mass of the ethanol and the water, and the mass of the ethanol accounts for 95% of the total mass of the ethanol and the water) with the pH value of 7 and the concentration of 0.05mol/L to obtain a mixed solution with the concentration of the siloxane modified amino compound of 0.1mg/ml, reacting at the temperature of 20 ℃ for 0.1 hour, and then adding dopamine (the concentration is 0.5mg/ml) and metal ion Fe3+(the concentration is 0.1mg/ml), then soaking the cleaned fiber obtained in the step 1 into the mixed solution, continuing to react for 1 hour at 20 ℃, and then washing and drying the fiber to obtain the UHMWPE fiber with controllable surface appearance, high adhesion and excellent mechanical property.
The nano particles on the surface of the modified UHMWPE fiber are spherical, the size is 1nm, the mass of the coating is 1 wt% of the mass of the fiber substrate, the thickness is 2nm, the surface Si content accounts for 2 wt% of the total mass of the coating, the N content accounts for 1 wt% of the total mass of the coating, XPS tests show that in a characteristic fine spectrum of Si, two peaks exist near 101.1eV and 103.2eV, and the area ratio of the characteristic peaks corresponding to Si-O-C and Si-O-Si is 50:1 respectively. The contact angle between the modified fiber and water is 95 degrees, the tensile strength of the modified fiber is 3GPa, the retention rate of the tensile strength after modification (the ratio of the modified fiber to the unmodified fiber) is 80 percent, the monofilament extraction force is 10cN in a matrix resin embedding test, and the interfacial shear strength of the matrix resin/modified fiber composite material is 5 Mpa.
Example 2
(1) Fiber cleaning and preparation of siloxane modified amino compound: soaking carbon fibers in ethanol for ultrasonic treatment for 1h, washing and drying at room temperature; adding diethylenetriamine into a KH560 reaction solution (a mixed solution of ethanol and water) at 80 ℃, wherein the mass of water accounts for 10% of the total mass of KH560, ethanol and water, the mass of KH560 accounts for 20% of the total mass, the mass of ethanol accounts for 70% of the total mass, the molar ratio of amino groups in the ethylenediamine to epoxy groups in KH560 is 2:1, stirring for 120min, and freeze-drying to obtain a siloxane modified amino compound with the weight-average molecular weight of 2000, wherein in an Si characteristic fine spectrum of the compound, the area ratio of Si-O-C and Si-O-Si characteristic peaks is 600: 1.
(2) Preparing modified fibers with controllable surface morphologies: firstly, adding the siloxane modified amino compound prepared in the step 2 into a Tris buffer solution (a mixture of water and ethylene glycol, wherein the mass of the water accounts for 30% of the total mass of the ethylene glycol and the water, and the mass of the ethanol accounts for 70% of the total mass of the buffer solution) with the pH value of 10 and the concentration of 0.2mol/L to obtain a mixed solution with the concentration of the siloxane modified amino compound of 4mg/ml, reacting at 60 ℃ for 0.5 hour, and then adding pyrocatechol (the concentration is 5mg/ml) and metal ion Al3+(the concentration is 10mg/ml), then soaking the cleaned carbon fiber obtained in the step 1 into the mixed solution, continuing to react for 48 hours at 60 ℃, and then washing and drying the fiber to obtain the carbon fiber with controllable surface appearance, high adhesion and excellent mechanical property.
The nano particles on the surface of the modified carbon fiber are flaky, the size of the nano particles is 500nm, the mass of the coating is 10 wt% of the mass of the fiber substrate, the thickness of the nano particles is 500nm, the Si content of the surface accounts for 15 wt% of the total mass of the coating, the N content accounts for 8 wt% of the total mass of the coating, XPS tests show that two peaks exist in a characteristic fine spectrum of Si, the two peaks are near 101.1eV and 103.2eV, and the area ratio of the two peaks respectively corresponding to Si-O-C characteristic peaks and Si-O-Si characteristic peaks is 5: 1. The contact angle between the modified fiber and water is 50 degrees, the tensile strength of the modified fiber is 6GPa, the retention rate of the modified tensile strength (the ratio of the modified fiber to the unmodified fiber) is 99 percent, the monofilament extraction force is 50cN in a matrix resin embedding test, and the interfacial shear strength of the matrix resin/modified fiber composite material is 30 Mpa.
Example 3
(1) Fiber cleaning and preparation of siloxane modified amino compound: immersing carbon fibers in propylene glycol for ultrasonic treatment for 1h, and drying at room temperature after washing; adding triethylenetetramine into a KH560 reaction solution (a mixed solution of ethylene glycol and water) at 45 ℃, wherein the mass of water accounts for 5% of the total mass of KH560, ethylene glycol and water, the mass of KH560 accounts for 10% of the total mass, the mass of ethylene glycol accounts for 85% of the total mass, the molar ratio of amino groups in triethylenetetramine to epoxy groups in KH560 is 1.4:1, stirring for 60min, and freeze-drying to obtain a siloxane modified amino compound with the weight-average molecular weight of 1000, wherein in an Si characteristic fine spectrum of the compound, the area ratio of Si-O-C characteristic peaks to Si-O-Si characteristic peaks is 510: 1.
(2) Preparing modified fibers with controllable surface morphologies: firstly, adding the siloxane modified amino compound prepared in the step 2 into a Tris buffer solution (a mixture of water and glycerol, wherein the mass of the water accounts for 18% of the total mass of the glycerol and the water, and the mass of the glycerol accounts for 82% of the total mass of the buffer solution) with the pH value of 8 and the concentration of 0.12mol/L to obtain a mixed solution with the concentration of the siloxane modified amino compound of 2mg/ml, reacting for 1 hour at 50 ℃, and then adding pyrocatechol (the concentration is 5mg/ml) and metal ion Ag+(the concentration is 5mg/ml), then soaking the cleaned carbon fiber obtained in the step 1 into the mixed solution, continuing to react for 24 hours at 40 ℃, and then washing and drying the fiber to obtain the carbon fiber with controllable surface appearance, high adhesion and excellent mechanical property.
The nano particles on the surface of the modified carbon fiber are columnar, the size of the nano particles is 250nm, the mass of the coating is 5 wt% of the mass of the fiber substrate, the thickness of the nano particles is 280nm, the Si content of the surface accounts for 8 wt% of the total mass of the coating, the N content accounts for 4 wt% of the total mass of the coating, XPS tests show that two peaks exist in a characteristic fine spectrum of Si, the two peaks are near 101.1eV and 103.2eV, and the area ratio of the two peaks respectively corresponding to Si-O-C characteristic peaks and Si-O-Si characteristic peaks is 28: 1. The contact angle between the modified fiber and water is 72 degrees, the tensile strength of the modified fiber is 4.5GPa, the retention rate of the modified tensile strength (the ratio of the modified fiber to the unmodified fiber) is 90 percent, the monofilament extraction force is 30cN in a matrix resin embedding test, and the interfacial shear strength of the matrix resin/modified fiber composite material is 18 Mpa.
Example 4
(1) Fiber cleaning and preparation of siloxane modified amino compound: soaking aramid fiber in glycerol for ultrasonic treatment for 1h, washing and drying at room temperature; adding tetraethylenepentamine into a KH560 reaction solution (a mixed solution of glycerol and water) at 50 ℃, wherein the mass of water accounts for 8% of the total mass of KH560, glycerol and water, the mass of KH560 accounts for 15% of the total mass, the mass of glycerol accounts for 77% of the total mass, the molar ratio of amino groups in the tetraethylenepentamine to epoxy groups in KH560 is 1.5:1, stirring for 100min, and freeze-drying to obtain a siloxane modified amino compound with the weight-average molecular weight of 1200, wherein in an Si characteristic fine spectrum of the compound, the area ratio of Si-O-C and Si-O-Si characteristic peaks is 700: 1.
(2) Preparing modified fibers with controllable surface morphologies: firstly, adding the siloxane modified amino compound prepared in the step 2 into a Tris buffer solution (a mixture of water, glycol and glycerol, wherein the mass of the water accounts for 25% of the total mass of the glycol, the glycerol and the water, and the mass of the glycol and the glycerol accounts for 75% of the total mass of the buffer solution) with the pH value of 9 and the concentration of 0.12mol/L to obtain a mixed solution with the concentration of the siloxane modified amino compound of 2mg/ml, reacting for 1 hour at 30 ℃, adding pyrogallol (the concentration is 4mg/ml) and metal ions are Cu2+(the concentration is 4mg/ml), then the cleaned aramid fiber obtained in the step (1) is immersed into the mixed solution, the reaction is continued for 44 hours at the temperature of 30 ℃, and then the fiber is washed and dried, so that the aramid fiber with controllable surface appearance, high adhesion and excellent mechanical property is obtained.
The nano particles on the surface of the modified carbon fiber are flaky, the size of the nano particles is 400nm, the mass of the coating is 8 wt% of the mass of the fiber substrate, the thickness of the nano particles is 300nm, the Si content of the surface accounts for 10 wt% of the total mass of the coating, the N content accounts for 4 wt% of the total mass of the coating, XPS tests show that two peaks exist in a characteristic fine spectrum of Si, the two peaks are near 101.1eV and 103.2eV, and the area ratio of the two peaks respectively corresponding to Si-O-C characteristic peaks and Si-O-Si characteristic peaks is 40: 1. The contact angle between the modified fiber and water is 80 degrees, the tensile strength of the modified fiber is 4.6GPa, the retention rate of the modified tensile strength (the ratio of the modified fiber to the unmodified fiber) is 90 percent, the monofilament extraction force is 38cN in a matrix resin embedding test, and the interfacial shear strength of the matrix resin/modified fiber composite material is 25 Mpa.
Example 5
(1) Fiber cleaning and preparation of siloxane modified amino compound: immersing UHMWPE fibers into n-hexane for ultrasonic treatment for 1h, washing and drying at room temperature; adding polyethyleneimine (n is 5) into a KH560 reaction solution (a mixed solution of ethanol, ethylene glycol, glycerol and water) at 65 ℃, wherein the mass of water accounts for 8% of the total mass of KH560, ethanol, ethylene glycol, glycerol and water, the mass of KH560 accounts for 8% of the total mass, the mass of alcohols (miscible in any ratio of ethanol, ethylene glycol and glycerol) accounts for 84% of the total mass, the molar ratio of amino groups in the polyethyleneimine to epoxy groups in KH560 is 1.2:1, stirring for 80min, and freeze-drying to obtain a siloxane-modified amino compound with the weight-average molecular weight of 1900, wherein in an Si characteristic fine spectrum of the compound, the area ratio of Si-O-C and Si-O-Si characteristic peaks is 650: 1.
(2) Preparing modified fibers with controllable surface morphologies: firstly, adding the siloxane modified amino compound prepared in the step 2 into a Tris buffer solution (a mixture of water, ethanol and glycol, wherein the mass of the water accounts for 15% of the total mass of the ethanol, the glycol and the water, and the mass of the ethanol and the glycol accounts for 85% of the total mass of the buffer solution) with the pH value of 9 and the concentration of 0.16mol/L to obtain a mixed solution with the concentration of the siloxane modified amino compound of 2.4mg/ml, reacting at 40 ℃ for 0.5 hour, adding 5-hydroxy-1, 4-naphthoquinone (the concentration is 3mg/ml) and Zn as metal ions2+(the concentration is 3mg/ml), then soaking the cleaned fiber obtained in the step 1 into the mixed solution, continuing to react for 40 hours at 50 ℃, and then washing and drying the fiber to obtain the UHMWPE fiber with controllable surface appearance, high adhesion and excellent mechanical property.
The nano particles on the surface of the modified UHMWPE fiber are spherical, the size is 200nm, the mass of the coating is 3 wt% of the mass of the fiber substrate, the thickness is 210nm, the surface Si content accounts for 10 wt% of the total mass of the coating, the N content accounts for 6 wt% of the total mass of the coating, XPS tests show that in a characteristic fine spectrum of Si, two peaks exist near 101.1eV and 103.2eV, and the area ratio of the characteristic peaks corresponding to Si-O-C and Si-O-Si is 33:1 respectively. The contact angle of the modified fiber and water is 80 degrees, the tensile strength of the modified fiber is 5GPa, the retention rate of the modified tensile strength (the ratio of the modified fiber to the unmodified fiber) is 89 percent, the monofilament extraction force is 32cN in a matrix resin embedding test, and the interfacial shear strength of the matrix resin/modified fiber composite material is 20 Mpa.
Example 6
(1) Fiber cleaning and preparation of siloxane modified amino compound: soaking aramid fiber in glycol for ultrasonic treatment for 1h, and drying at room temperature after washing; adding polyethyleneimine (n value is 200) into a KH560 reaction solution (a mixed solution of glycerol and water) at 40 ℃, wherein the mass of water accounts for 18% of the total mass of KH560, glycerol and water, the mass of KH560 accounts for 6% of the total mass, the mass of glycerol accounts for 76% of the total mass, and the molar ratio of amino groups in ethylenediamine to epoxy groups in KH560 is 1.8:1, stirring for 90min, and freeze-drying to obtain a siloxane modified amino compound with the weight-average molecular weight of 800, wherein in an Si characteristic fine spectrum of the compound, the area ratio of Si-O-C characteristic peaks to Si-O-Si characteristic peaks is 800: 1.
(2) Preparing modified fibers with controllable surface morphologies: firstly, adding the siloxane modified amino compound prepared in the step 2 into a Tris buffer solution (a mixture of water and ethylene glycol, wherein the mass of the water accounts for 30% of the total mass of the ethylene glycol and the water, and the mass of the ethanol accounts for 70% of the total mass of the buffer solution) with the pH value of 9 and the concentration of 0.16mol/L to obtain a mixed solution with the concentration of the siloxane modified amino compound of 4mg/ml, reacting at 60 ℃ for 1 hour, and then adding tannic acid (the concentration of 4mg/ml) and metal ions Fe2+(the concentration is 9mg/ml), then the cleaned aramid fiber obtained in the step (1) is immersed into the mixed solution, the reaction is continued for 40 hours at the temperature of 60 ℃, and then the fiber is washed and dried, so that the aramid fiber with controllable surface appearance, high adhesion and excellent mechanical property is obtained.
The nano particles on the surface of the modified aramid fiber are columnar, the size of the nano particles is 200nm, the mass of the coating is 6 wt% of the mass of the fiber substrate, the thickness of the nano particles is 300nm, the Si content of the surface accounts for 11 wt% of the total mass of the coating, the N content accounts for 6 wt% of the total mass of the coating, XPS tests show that two peaks exist in a characteristic fine spectrum of Si, the two peaks are near 101.1eV and 103.2eV, and the area ratio of the two peaks respectively corresponding to Si-O-C characteristic peaks and Si-O-Si characteristic peaks is 35: 1. The contact angle between the modified fiber and water is 58 degrees, the tensile strength of the modified fiber is 5.6GPa, the retention rate of the modified tensile strength (the ratio of the modified fiber to the unmodified fiber) is 87 percent, the monofilament extraction force is 39cN in a matrix resin embedding test, and the interfacial shear strength of the matrix resin/modified fiber composite material is 25 Mpa.
Comparative example 1 (unmodified UHMWPE fiber)
Cleaning unmodified fibers: and immersing the UHMWPE fibers in acetone for ultrasonic treatment for 1h, and drying at room temperature after washing.
The UHMWPE fiber is not treated, the surface of the UHMWPE fiber is not coated, the pore diameter of the surface of the UHMWPE fiber is 900nm, and the BET specific surface area of the UHMWPE fiber is 20m2(ii) in terms of/g. It was found using XPS test that in the characteristic fine spectrum of Si, characteristic peaks of Si-O-C and Si-O-Si were not observed in the vicinity of 101.1eV and 103.2 eV.
The contact angle of the UHMWPE fiber and water is 120 degrees, the tensile strength is 3.5GPa, the tensile stress is 118cN, the monofilament extraction force in the epoxy resin embedding test is 4cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 3 Mpa.
Comparative example 2
This comparative example differs from example 1 in that: in the step (1), ethylenediamine is not added.
No nanoparticles with regular shapes are observed on the surface of the modified UHMWPE fiber, the mass of the coating is 0.8 wt% of the mass of the fiber substrate, the thickness is 3nm, the surface Si content accounts for 16 wt% of the total mass of the coating, the N content accounts for 10 wt% of the total mass of the coating, and XPS tests show that in a characteristic fine spectrum of Si, two peaks exist near 101.1eV and 103.2eV, and the area ratio of the characteristic peaks corresponding to Si-O-C and Si-O-Si is 60: 1.
the contact angle of the obtained modified UHMWPE fiber and water is 100 degrees, the tensile strength is 5GPa, the retention rate of the modified tensile strength (the ratio of the modified fiber to the unmodified fiber) is 79 percent, the monofilament extraction force is 8cN in a matrix resin embedding test, and the interfacial shear strength of the matrix resin/modified fiber composite material is 4 Mpa.
Comparative example 3
This comparative example differs from example 1 in that: in the step (2), the catalyst is not addedMetallic ion Fe3+。
No nanoparticles with regular shapes are observed on the surface of the modified UHMWPE fiber, the mass of the coating is 12 wt% of the mass of the fiber substrate, the thickness is 600nm, the surface Si content accounts for 19 wt% of the total mass of the coating, the N content accounts for 12 wt% of the total mass of the coating, and XPS tests show that in a characteristic fine spectrum of Si, two peaks exist near 101.1eV and 103.2eV, and the area ratio of the characteristic peaks corresponding to Si-O-C and Si-O-Si is 4: 1.
the contact angle of the obtained modified UHMWPE fiber and water is 101 degrees, the tensile strength is 3.5GPa, the retention rate of the modified tensile strength (the ratio of the modified fiber to the unmodified fiber) is 76 percent, the monofilament extraction force is 4cN in a matrix resin embedding test, and the interfacial shear strength of the matrix resin/modified fiber composite material is 2 Mpa.
Comparative example 4
This comparative example differs from example 1 in that: dopamine is not added in the step (2).
No nanoparticles with regular shapes are observed on the surface of the modified UHMWPE fiber, the mass of the coating is 0.3 wt% of the mass of the fiber substrate, the thickness is 1nm, the surface Si content accounts for 1 wt% of the total mass of the coating, the N content accounts for 0.8 wt% of the total mass of the coating, and the XPS test shows that two Si-O-C and Si-O-Si characteristic peaks with peaks near 101.1eV and 103.2eV cannot be observed in a characteristic fine spectrum of Si.
The contact angle of the obtained modified UHMWPE fiber and water is 110 degrees, the tensile strength is 5.4GPa, the retention rate of the modified tensile strength (the ratio of the modified fiber to the unmodified fiber) is 60 percent, the monofilament extraction force is 4cN in a matrix resin embedding test, and the interfacial shear strength of the matrix resin/modified fiber composite material is 2 Mpa.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (10)

1. A high-adhesion modified fiber with controllable surface appearance comprises a fiber matrix and a coating covering the fiber matrix; the method is characterized in that: the coating has a micro-nano structure formed by nano particles, wherein the size of the nano particles is 1-500nm, and the shape of the nano particles comprises at least any one of sphere, sheet and column; and the content of Si in the coating accounts for 2-15 wt% of the total mass of the coating, the content of N accounts for 1-8 wt% of the total mass of the coating, and in a Si characteristic fine spectrum of the modified fiber, the ratio of a characteristic peak area with a peak value of 101.1eV to a characteristic peak area with a peak value of 103.2eV is 5:1-50: 1.
2. The surface-topography-controllable high-adhesion modified fiber according to claim 1, wherein: the thickness of the coating is 2-500 nm; and/or the mass of the coating is 1-10 wt% of the mass of the fiber matrix; and/or the modified fiber has a contact angle with water of 50-95 degrees; and/or the tensile strength of the modified fiber is 3-6 GPa; and/or the tensile strength retention rate of the modified fiber is 80-99%; and/or the monofilament extraction force of the modified fiber in the epoxy resin embedding test is 10-50 cN; and/or the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber is 5-30 Mpa.
3. The surface-topography-controllable high-adhesion modified fiber according to claim 1, wherein: the fiber matrix comprises any one of ultra-high molecular weight polyethylene fiber, carbon fiber or aramid fiber.
4. A preparation method of a high-adhesion modified fiber with a controllable surface topography is characterized by comprising the following steps:
(1) cleaning the fiber matrix;
(2) adding an amine compound into a silane coupling agent reaction solution, and reacting to obtain a siloxane modified amino compound with an amino group at the tail end;
(3) and (3) adding the siloxane modified amino compound obtained in the step (2) into a trihydroxymethyl aminomethane buffer solution with the pH value of 7-10 for reaction, then adding a polyphenol compound and metal ions, and then adding the fiber matrix cleaned in the step (1) for continuous reaction, thereby obtaining the high-adhesion modified fiber with controllable surface appearance.
5. The method according to claim 4, wherein the step (1) comprises: carrying out ultrasonic treatment on a fiber matrix in a solvent, and then taking out and drying; the solvent comprises any one or combination of more of ethanol, acetone, propylene glycol, glycerol, n-hexane and ethylene glycol; and/or the fiber matrix comprises any one of ultra-high molecular weight polyethylene fiber, carbon fiber or aramid fiber.
6. The method according to claim 4, wherein the step (2) comprises: adding an amine compound into a silane coupling agent reaction solution at the temperature of 10-80 ℃, preferably 50-80 ℃, stirring for 5-120min, and then freeze-drying to obtain the siloxane modified amino compound, wherein the weight average molecular weight of the siloxane modified amino compound is 100-2000;
and/or the amine compound comprises any one or a combination of more than two of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine; wherein the value of n of the polyethyleneimine is 5-200;
and/or the silane coupling agent reaction solution comprises a mixture of KH560 and any one or two of water and alcohol, preferably the alcohol comprises any one or two of ethanol, glycol and glycerol; preferably, the mass of KH560 in the mixture accounts for 1-20% of the total mass, the mass of water accounts for 0.1-10% of the total mass, and the mass of alcohol accounts for 98.9-70% of the total mass;
and/or the molar ratio of amino groups in the amine compound to epoxy groups in KH560 is 0.8:1-2: 1;
and/or, in the Si characteristic fine spectrum of the siloxane modified amino compound, the ratio of the characteristic peak area with a peak value of 101.1eV to the characteristic peak area with a peak value of 103.2eV is more than 500: 1.
7. The method according to claim 4, wherein the step (3) comprises: adding the siloxane modified amino compound obtained in the step (2) into a trihydroxymethyl aminomethane buffer solution with the pH value of 7-10 to form a first reaction system, carrying out hydrolysis crosslinking reaction for 0.1-1 hour, then adding a polyphenol compound and metal ions to form a second reaction system, carrying out Schiff base reaction to generate an organic cage compound, then rapidly adding the fiber matrix cleaned in the step (1) to continue reacting for 1-48 hours, and washing and drying the obtained fiber, thereby obtaining the high-adhesion modified fiber with controllable surface appearance;
and/or the polyphenol compound comprises any one or the combination of more than two of dopamine, catechol, pyrogallol, 5-hydroxy-1, 4-naphthoquinone and tannic acid;
and/or, the metal ions comprise Fe3+、Al3+、Ag+、Cu2+、Zn2+、Fe2+Any one or a combination of two or more of them; preferably, the concentration of the metal ions in the second reaction system is 0.1-10 mg/ml; preferably, the concentration of the polyphenol compound in the second reaction system is 0.5-5 mg/ml;
preferably, the concentration of the silicone-modified amino compound in the first reaction system is 0.1 to 4 mg/ml;
preferably, the temperature of the hydrolytic crosslinking reaction is 20-60 ℃, preferably 20-50 ℃, and more preferably 30-50 ℃;
preferably, the temperature of the Schiff base reaction is 20-60 ℃, preferably 30-50 ℃.
8. The production method according to claim 4 or 7, characterized in that: in the step (3), the tris buffer solution contains tris at a concentration of 0.05 to 0.2mol/L, water and an alcohol compound; preferably, the alcohol compound comprises any one or a combination of more than two of ethanol, ethylene glycol and glycerol; preferably, the mass of water in the tris buffer solution accounts for 5% -30% of the total mass of the water and the alcohol, and the mass of the alcohol compound accounts for 70% -95% of the total mass of the water and the alcohol.
9. A high-adhesion modified fiber having a controlled surface morphology, produced by the method of any one of claims 4 to 8.
10. Use of the high-adhesion modified fiber with controllable surface morphology according to any one of claims 1 to 3 and 9 for preparing a polymer matrix composite; preferably, the polymer matrix composite is a fiber reinforced resin composite.
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