CN115369651A - Surface porous strong-adhesion modified fiber and preparation method and application thereof - Google Patents
Surface porous strong-adhesion modified fiber and preparation method and application thereof Download PDFInfo
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- CN115369651A CN115369651A CN202110556001.4A CN202110556001A CN115369651A CN 115369651 A CN115369651 A CN 115369651A CN 202110556001 A CN202110556001 A CN 202110556001A CN 115369651 A CN115369651 A CN 115369651A
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- fiber
- mixed solution
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- modified
- coating
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- 239000011159 matrix material Substances 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 26
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- 238000005406 washing Methods 0.000 claims description 60
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 58
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- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 24
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- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
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- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 6
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 6
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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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
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K7/06—Elements
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- 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
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
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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
- D06M2101/34—Polyamides
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- D06M2101/40—Fibres of carbon
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Abstract
The invention discloses a surface-porous strong-adhesion modified fiber 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 porous structure, wherein the pore diameter of pores contained in the coating is 2-300nm, and the specific surface area is 50-800m 2 (iv) g; and, siO contained in the coating 2 The mass of the modified fiber is 0.1-8% of the total mass of the modified fiber, and the infrared spectrum of the modified fiber is located in 1150-1000cm ‑1 The characteristic peak area of (A) is 2700-3000cm ‑1 The ratio of the characteristic peak area to the peak area is 1: 100-1: 10. The surface of the modified fiber with the strong adhesion and the porous surface provided by the invention is porous, the roughness is greatly improved, the durability is strong, the high-temperature resistance is excellent, the adhesion with matrix resin is strong, the mechanical property is excellent, the preparation process is simple, convenient and feasible, and the cost is controllable.
Description
Technical Field
The invention relates to a preparation method of modified fiber, in particular to surface-porous strong-adhesion modified fiber, a preparation method and application thereof, and belongs to the technical field of material science.
Background
The high-performance fibers such as the UHMWPE fibers, the carbon fibers and the like have the characteristics of high strength, high modulus, corrosion resistance and the like, and are widely applied to the fields of agriculture and forestry, marine aquatic products, sports equipment, war industry, aerospace, high-tech industry and the like. However, the UHMWPE fibers and carbon fibers have smooth surfaces and few polar groups, which results in weak interaction force (physical or chemical) between the fibers and the resin matrix when forming a composite material with the resin matrix, and further makes the fibers easily pulled out of the matrix resin, and thus is difficult to achieve the reinforcement and toughening effects. Therefore, it is very important to prepare a modified fiber with strong adhesion.
At present, the modified fiber is mainly prepared by a surface modification method, polar groups are introduced on the surface of the fiber by means of oxidation (acidification) treatment, plasma treatment, irradiation, surface polymerization, coating and the like, the fiber is roughened, and the aim of enhancing the interaction between the fiber and matrix resin is finally achieved. CN201510800212.2 discloses a method for surface treatment of ultra-high molecular weight polyethylene (UHMWPE) fibers, which sequentially adopts dopamine hydrochloride biomimetic modification and titanium dioxide coating methods to activate and modify the surface of the UHMWPE fibers, so that the roughness of the fiber surface is greatly increased, and finally the interface bonding strength between the fibers and matrix resin is enhanced. CN201410142484.3 discloses a preparation method of silane crosslinking modified ultra-high molecular weight polyethylene fiber. The method comprises the steps of placing UHMWPE gel fibers which are not dried into a modified solution, carrying out ultrasonic treatment, and then carrying out multistage hot stretching, wherein the fibers not only have excellent creep resistance, but also have high surface bonding performance, and the mechanical properties of the modified fibers are not reduced basically. CN201910721844.8 discloses a method for preparing a high-performance composite material by electrophoretic deposition of polymer micro-nano particles on a carbon fiber surface, which comprises the steps of treating Carbon Fiber (CF) with Dopamine (DA), and depositing polymer micro-nano particles with different morphologies, particle sizes, compositions and different functional groups on the CF surface by electrophoresis to obtain carbon fiber with significantly improved interface adhesion strength. CN201710548996.3 discloses a preparation method of a graphene nanosheet reinforced carbon fiber composite material, which comprises dispersing graphene nanosheets into an organic solvent containing a small amount of thermosetting resin and a curing agent to prepare a dip-coating solution, and then coating the dip-coating solution on the surface of carbon fibers, wherein the graphene nanosheets are uniformly adhered to the surface of the carbon fibers, so that the interlaminar shear strength of the fiber composite material is remarkably improved. CN201910158668.1 discloses a method for surface modification of ultra-high molecular weight polyethylene fiber, in which dopamine and silane coupling agent are coated on the surface of UHMWPE fiber to obtain UHMWPE fiber with improved adhesion.
In summary, although the prior art methods are capable of producing fibers with improved adhesion, they all suffer from disadvantages such as: 1. the process is complicated, the existing equipment needs to be transformed in a large scale, and the cost is high; 2. the interface action between the fiber and the matrix resin is mainly chemical action, and the adhesion is less enhanced due to the increase of roughness.
Disclosure of Invention
The invention mainly aims to provide a surface-porous strong-adhesion modified fiber, and a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the above object, the embodiment of the present invention adopts a technical solution comprising:
the embodiment of the invention provides a modified fiber with porous surface and strong adhesiveness, which comprises a fiber matrix and a coating covering the fiber matrix; the coating has a porous structure, wherein the pore diameter of pores contained in the coating is 2-300nm, and the specific surface area of the coating is 50-800m 2 (ii)/g; and, siO contained in the coating layer 2 Is 0.1 to 8 percent of the total mass of the modified fiber, and is located 1150 to 1000cm in an infrared test pattern of the modified fiber -1 The peak area of the peak is 2700-3000cm -1 The ratio of the characteristic peak area to the peak area is 1: 100-1: 10.
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 40 to 80 °.
In some embodiments, the modified fiber has a tensile strength of 3-6GPa, a tensile stress of 80-150cN, a tensile strength retention of greater than 85%, a tensile stress retention of greater than 90%, an epoxy embedding test monofilament pullout force of 20-60cN, an epoxy/modified fiber composite interfacial shear strength of 10-40mpa, a melting point of 145-160 ℃ as measured by dsc, a surface monofilament pullout force retention of greater than 96% after washing according to ISO 105-C03 standard (compared to before washing), and an epoxy/modified fiber composite interfacial shear strength retention of greater than 96% (compared to before washing).
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 surface porous strong-adhesion modified fiber, which comprises the following steps:
(1) Cleaning the fiber matrix;
(2) Adding a silane coupling agent into a mixture of water and alcohol to form a first mixed solution, and then carrying out prehydrolysis reaction to form a second mixed solution;
(3) Adding a pyrocatechol compound into a trihydroxymethyl aminomethane buffer solution with the pH value of 8-10 to form a third mixed solution, carrying out polymerization reaction, then adding the second mixed solution and nano silicon dioxide to carry out a first reaction, and then adding the fiber matrix cleaned in the step (1) to continue carrying out a second reaction, thereby obtaining the surface porous strong-adhesion modified fiber.
In some embodiments, the silane coupling agent has the structure shown below:
wherein X comprises methoxy or ethoxy, and n is 3-20.
The embodiment of the invention also provides application of the surface-porous strong-adhesion modified fiber in preparation of a polymer-based composite material.
Compared with the prior art, the invention has the following beneficial effects:
(1) The surface of the provided strong-adhesion modified fiber with porous surface is porous, the roughness is greatly improved, the adhesion between the fiber and matrix resin is strong, and the mechanical property is excellent;
(2) The provided modified fiber has excellent durability and high temperature resistance;
(3) The preparation process of the modified fiber is simple, convenient and feasible, and the cost is controllable.
Drawings
In order to more clearly illustrate the embodiments of the present application 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 description below are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of a process for preparing a highly adhesive surface-porous modified fiber according to an exemplary embodiment of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made long-term research and extensive practice to provide the technical scheme of the present invention, which mainly uses the oxidation product of the polyphenol compound, namely the benzoquinone group, and the amino group to perform michael addition and schiff base reaction, and then uses the hydrolytic crosslinking of the siloxane group to generate a product with a nano-pore structure, and the nano-silica is added in the reaction to improve the adhesion of the fiber surface coating and improve the mechanical properties of the modified fiber. As will be described in detail below.
An aspect of an embodiment of the present invention provides a surface-porous, strongly adherent, modified fiber comprising a fibrous substrate and a coating covering the fibrous substrate; the method is characterized in that: the coating has a porous structure, wherein the aperture of pores contained in the coating is 2-300nm, and the specific surface area is 50-800m 2 (iv) g; and, siO contained in the coating layer 2 Is 0.1 to 8 percent of the total mass of the modified fiber, and is located 1150 to 1000cm in an infrared test pattern of the modified fiber -1 (Si-O-Si, C-O-C and Si-O-C, etc.)) with a peak area of 2700-3000cm -1 The ratio of the characteristic peak area to the peak area of the (polyethylene) is 1: 100-1: 10.
Further, the mass of the coating is 0.1-20%, preferably 0.2-6% of the mass of the fiber matrix.
Furthermore, the aperture of the hole contained in the coating is 10-100nm, and the specific surface area is 500-800m 2 /g。
Further, the modified fiber is located 1150-1000cm in infrared test pattern -1 The characteristic peak area of (A) is 2700-3000cm -1 The ratio of the characteristic peak area to the peak area is 1: 100-1: 10 and 1: 80-1: 40.
Furthermore, the contact angle of the modified fiber and water is 40-80 degrees, and preferably 40-60 degrees.
Further, the tensile strength of the modified fiber is 3-6GPa, and preferably 4-6GPa.
Further, the modified fiber has a tensile stress of 80 to 150cN, preferably 100 to 150cN.
Further, the retention rate of the tensile strength of the modified fiber before and after modification is higher than 85% (the ratio of the modified fiber to the unmodified fiber), and preferably higher than 90%.
Further, the tensile stress retention of the modified fiber before and after modification is higher than 90% (ratio of modified fiber to unmodified fiber), preferably higher than 94%.
Further, the modified fiber has an epoxy resin embedded test monofilament extraction force of 20-60cN, preferably 40-60cN.
Furthermore, the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber is 10-40Mpa, preferably 25-40Mpa.
Further, the retention of surface monofilament pull-out force after washing treatment of said modified fiber according to ISO 105-C03 standard is higher than 96% (compared to before washing).
Further, after the modified fiber is washed according to ISO 105-C03 standard, the retention rate of the shear strength of the epoxy resin/modified fiber composite material interface is higher than 96% (compared with that before the modified fiber is washed).
Further, the modified fiber has a melting point of 145 to 160 ℃ (DSC test).
Further, the fiber matrix includes, but is not limited to, any one of ultra-high molecular weight polyethylene fiber, carbon fiber or aramid fiber, preferably any one of ultra-high molecular weight polyethylene fiber or carbon fiber.
Another aspect of an embodiment of the present invention provides a method for preparing a surface-porous strongly-adhesive modified fiber, including:
(1) Cleaning the fiber matrix;
(2) Adding a silane coupling agent into a mixture of water and alcohol to form a first mixed solution, and then carrying out a prehydrolysis reaction to form a second mixed solution;
(3) And (2) adding a catechol compound into a trihydroxymethyl aminomethane buffer solution with the pH value of 8-10 to form a third mixed solution, carrying out polymerization reaction, then adding the second mixed solution and nano silicon dioxide to carry out a first reaction, and then adding the fiber matrix cleaned in the step (1) to continue a second reaction, thereby obtaining the surface porous strong-adhesion modified fiber.
Further, the step (1) comprises the following steps: cleaning the fiber matrix in a solvent for 10-40 min, and then taking out and drying; the solvent includes, but is not limited to, any one or combination of more of ethanol, acetone, and tetrahydrofuran.
Further, the fiber matrix includes, but is not limited to, any one of ultra-high molecular weight polyethylene fibers, carbon fibers or aramid fibers, preferably ultra-high molecular weight polyethylene fibers or carbon fibers.
Further, the structure of the silane coupling agent in the step (2) is shown as the following formula:
wherein X comprises methoxy or ethoxy, and n is 3-20.
Further, the alcohol includes, but is not limited to, any one or combination of ethanol, propanol, butanol, ethylene glycol and glycerol.
Further, the silane coupling agent contained in the first mixed solution accounts for 1: 300-1: 50 of the total volume of the first mixed solution, and preferably 1: 200-1: 80.
Further, the first mixed solution contains water accounting for 1: 100-10: 100 of the total volume of the first mixed solution, preferably 2: 100-8: 100.
Further, the first mixed solution contains ethanol which accounts for 74: 75-66: 75 of the total volume of the first mixed solution, and preferably 39: 40-363: 400.
Further, the reaction time of the prehydrolysis reaction is 10-30 minutes.
Further, in the step (3), the reaction time of the polymerization reaction is 10 to 30 minutes.
Further, in the step (3), the reaction time of the first reaction is 20 to 60 minutes.
Further, in the step (3), the reaction time of the second reaction is 2 to 48 hours.
Further, in the step (3), the amount of the second mixed solution is 3-30% of the volume of the third mixed solution.
Further, in the step (3), the second mixed solution is added dropwise to the third mixed solution.
Further, the catechol compounds include, but are not limited to, catechol, pyrogallol, tannic acid, any one or more of the combination.
Further, the diameter of the nano silicon dioxide is 5-100nm, preferably 10-50nm.
Further, in the step (3), the buffer solution of tris comprises tris at a concentration of 0.05 to 0.5 mol/L. The solvent adopted in the trihydroxymethyl aminomethane buffer solution is water.
Further, the concentration of the catechol compound in the third mixed solution is 0.25-2g/L, preferably 0.5-1g/L.
Further, the mass of the nano silicon dioxide is 0.5-5%, preferably 1-3% of the total mass of the third mixed solution.
Further, the step (3) further comprises: and after the second reaction is finished, taking out the obtained modified fiber, cleaning and drying in vacuum.
Another aspect of an embodiment of the present invention provides a use of the surface-porous, strongly adherent, modified fiber for the preparation of a polymer-based composite. Preferably, the polymer matrix composite is a fiber reinforced resin composite.
Referring to fig. 1, in the embodiment of the present invention, an oxidation product of an ortho-dihydroxybenzene compound in air, i.e., a benzoquinone compound, is used to perform michael addition and schiff base reaction on the benzoquinone compound and a silane coupling agent under a certain condition, then a nanopore structure is generated by further hydrolytic crosslinking of the silane coupling agent, and nanosilicon dioxide is added during the reaction process, so as to further improve the adhesion of the modified fiber surface coating.
The structure of the silane coupling agent has a remarkable influence on the generation of a nanometer pore channel, amino groups can perform two chemical reactions of Michael addition and Schiff base reaction with a benzoquinone compound, and when the molecular chain length is too long (n is too long), the hydrolytic crosslinking of the silane coupling agent is not easy to occur.
In fact, the pore size of the nanopores is regulated by a number of factors, such as: (1) The prehydrolysis time of the silane coupling agent in the first mixed solution and the water content in the first mixed solution are too long (or the water content is too high), most of the silane coupling agent undergoes self-hydrolysis crosslinking, which is not beneficial to subsequent reaction with the benzoquinone compound and can cause the generated nanometer pore canal to be too large, and the prehydrolysis time is too short (or the water content is too low), so that the silane coupling agent is difficult to undergo hydrolysis crosslinking, and the nanometer pore canal generated after the silane coupling agent reacts with the benzoquinone compound is too small; (2) If the polymerization time of the catechol compound in the tris buffer solution is too short, the polymerization reaction cannot be carried out in time, and the nanopore is difficult to generate, and if the polymerization time is too long, the polymerization is too much, the nanopore is too large, and the target adhesion cannot be achieved.
And the reaction time after the second mixed solution and the nano-silica are added also influences the adhesion of the coating, the pre-hydrolyzed silane coupling agent can better react with the benzoquinone compound by selecting the appropriate reaction time to generate a part of porous compound, if the reaction time is too short, the porous compound is coated on the surface of the fiber without being generated in time, although the adhesion is improved, the nano-pore structure of the coating cannot be realized, and if the reaction time is too long, the generated porous compound mainly undergoes self-polymerization, so that the porous compound coated on the surface of the fiber is less and the sufficient adhesion cannot be obtained.
In the above embodiments of the present invention, the nanosilica mainly serves two functions: (1) Oxygen required for the oxidation of the catechol compound is provided, and (2) the adhesion of the coating is improved by the crosslinking agent in the coating. Furthermore, the nano silicon dioxide and the siloxane hydrolysis crosslinking product have similar chemical bonds, so that the silicon dioxide has better dispersibility and compatibility in the coating, and can be entangled with the molecular chain of the silane coupling agent to improve the adhesion of the coating. And by selecting the nano silicon dioxide with proper size (5-100 nm), the nano silicon dioxide can adsorb certain air, so that the continuous oxidation of the catechol compound into the benzoquinone substance is facilitated, if the nano silicon dioxide is too small in size, a large specific surface area of the nano silicon dioxide can adsorb a large amount of air, although the oxidation of the catechol substance is facilitated, the nano silicon dioxide is difficult to entangle in a coating, if the nano silicon dioxide is too large in size, the specific surface area is small, the adsorption amount of the air is not reduced, and the oxidation reaction of the catechol substance is facilitated. In addition, the mass ratio of the nano-silica to the third mixed solution also affects the adhesion and porous structure of the coating, if the mass ratio is too high, the nano-silica blocks the pore channels of the coating, and if the mass ratio is too low, it is difficult to provide enough entanglement points.
In addition, the applicant has discovered quite unexpectedly that the modified fiber of the present invention has excellent durability, which may be due to the silane coupling agent and the pyrocatechol compound adopted in the present invention, and the addition of the nano-silica, although the silane coupling agent and the pyrocatechol compound alone have adhesiveness, but the effects of the silane coupling agent and the pyrocatechol compound with the surface are single, the silane coupling agent is prehydrolyzed and added to the nano-silica, and then the pyrocatechol compound is added, so that the mixing effect of various acting forces is formed on the fiber surface, and in addition, the prehydrolyzed silane coupling agent, the nano-silica and the pyrocatechol compound are cross-linked in the coating, which greatly deepens the interaction with the fiber surface, thereby greatly improving the durability of the fiber surface. And, the applicant has also found, very surprisingly, that the modified fibres of the invention have excellent high temperature resistance, with a significantly improved melting point compared to unmodified fibres below 140 ℃, with a possible mechanism consisting in: the pyrocatechol type substance and the prehydrolyzed silane coupling agent form a cross-linked compound, and the existence of the nano silicon dioxide obviously reduces the heat conduction on the surface of the fiber, and finally improves the high-temperature resistance of the modified fiber.
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, unless otherwise specified, and the various types of reaction equipment, test methods, etc. used therein are known to those skilled in the art.
Comparative example 1 referring to CN110042665A, the process for making UHMWPE modified fibers comprises the following steps:
(1) Ultrasonically cleaning UHMWPE fiber in acetone for 20min, taking out and drying.
(2) Adding silane coupling agent S1 and dopamine in a molar ratio of 1: 300 into a Tris-HCl buffer solution with the pH value of 8.5, adding nano-silica with the diameter of 50nm, reacting for 10min under the condition that the stirring speed is 500rpm, adding UHMWPE fibers, and reacting for 3h.
(3) Adding a silane coupling agent S2 with the molar ratio of 10: 1 to the S1 in the step (2) into the mixed solution, adding nano silicon dioxide with the diameter of 50nm, stirring for reaction for 10 hours, taking out the prepared modified UHMWPE fiber, washing and drying.
The total mass of the nano silicon dioxide added in the step (2) and the step (3) is 4wt% of the total mass of the Tris-HCl buffer solution.
In the modified UHMWPE fiber, the mass of the coating accounts for 15wt% of the mass of the UHMWPE fiber before modification, the surface pore diameter is 900nm, the BET specific surface area is 6m 2 (ii) in terms of/g. SiO in the coating 2 Of the total mass of the modified UHMWPE fiber6wt%; is located at 1150-1000cm in infrared test -1 The peak area of the characteristic point (Si-O-Si, C-O-C, si-O-C, etc.) is 2700-3000cm -1 The ratio of the characteristic peak area to the peak area of the (polyethylene) is 1: 120.
The structures of S1 and S2 are as follows:
the contact angle of the modified UHMWPE fiber and water is 85 degrees, the tensile strength is 4GPa, the tensile stress is 120cN, the retention rate of the tensile strength (the ratio of the modified fiber to the unmodified fiber) is 83 percent, the retention rate of the tensile stress (the ratio of the modified fiber to the unmodified fiber) is 88 percent, the monofilament extraction force in an epoxy resin embedding test is 15cN, the interfacial shear strength of the epoxy resin/modified fiber composite material is 8Mpa, and the melting point of the epoxy resin/modified fiber composite material is 140 ℃ through DSC test. After washing treatment according to ISO 105-C03 standard, the retention rate of surface monofilament extraction force is 91% (compared with that before non-washing), and the retention rate of the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber after washing treatment is 90% (compared with that before non-washing).
Comparative example 2 this comparative example 2 provides a modified UHMWPE fiber that has been prepared in substantially the same way as in comparative example 1, with the difference that: dopamine was replaced by pyrogallol.
In the modified UHMWPE fiber, the mass of the coating accounts for 1wt% of the mass of the fiber before modification, the surface pore diameter is 1000nm, the BET specific surface area is 3m 2 (ii) in terms of/g. SiO in the coating 2 The mass of (a) is 0wt% of the total mass of the modified UHMWPE fiber; is located at 1150-1000cm in infrared test -1 In the formula (Si-O-Si, C-O-C and Si-O-C, etc.) with a peak area of 2700-3000cm -1 The ratio of the characteristic peak area to the peak area of the (polyethylene) is 1: 150.
The contact angle of the modified UHMWPE fiber and water is 90 degrees, the tensile strength is 4.5GPa, the tensile stress is 110cN, the retention rate of the tensile strength (the ratio of the modified fiber to the unmodified fiber) is 81 percent, the retention rate of the tensile stress (the ratio of the modified fiber to the unmodified fiber) is 84 percent, the monofilament extraction force in an epoxy resin embedding test is 18cN, the interfacial shear strength 9Mpa of the epoxy resin/modified fiber composite material is obtained, and the melting point is 135 ℃ in a DSC test. After washing treatment according to ISO 105-C03 standard, the retention rate of surface monofilament extraction force is 90% (compared with that before non-washing), and the retention rate of the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber after washing treatment is 89% (compared with that before non-washing).
Comparative example 3 a process for preparing a modified UHMWPE fiber comprises the steps of:
(1) Cleaning the fiber: the UHMWPE fibers were soaked in acetone for 1h and washed and dried at room temperature.
(2) Preparation of prehydrolysis silane coupling agent: adding a silane coupling agent into a water/ethanol mixture to obtain a first mixed solution, and performing prehydrolysis for 20 minutes to obtain a second mixed solution. Wherein the volume ratio of the silane coupling agent to the first mixed solution is 1: 200, the volume ratio of the water to the first mixed solution is 3: 100, and the volume ratio of the ethanol to the first mixed solution is 193: 200.
The structure of the silane coupling agent is as follows:
wherein X is methoxy and n is 5.
(3) Preparing modified fibers: preparing a trihydroxymethylaminomethane/water buffer solution with the pH value of 8.5 (the concentration of the trihydroxymethylaminomethane is 0.1 mol/L), firstly adding dopamine to obtain a third mixed solution (the concentration of the dopamine in the third mixed solution is 0.5 g/L), after carrying out polymerization reaction for 30 minutes, dropwise adding a certain amount of the second mixed solution prepared in the step 2 (the adding amount of the second mixed solution is 20vol% of the volume of the third mixed solution), nano-silica (the diameter is 20nm, and the adding mass accounts for 3wt% of the total mass of the third mixed solution), continuing to react for 50 minutes, adding the fibers cleaned in the step (1), and reacting for 8 hours. The obtained modified UHMWPE fibers were removed and washed and dried under vacuum.
In the modified UHMWPE fiber, the mass of the coating accounts for 3wt% of the mass of the fiber before modification, the surface pore diameter is 700nm, the BET specific surface area is larger than the total weight of the fiber before modificationIs 20m 2 (iv) g. SiO in the coating 2 The mass of (a) is 5wt% of the total mass of the modified UHMWPE fiber; is located at 1150-1000cm in infrared test -1 In the formula (Si-O-Si, C-O-C and Si-O-C, etc.) with a peak area of 2700-3000cm -1 The ratio of the characteristic peak area to the peak area of the (polyethylene) is 1: 60.
The contact angle of the modified UHMWPE fiber and water is 85 degrees, the tensile strength is 3.5GPa, the tensile stress is 108cN, the DSC test shows that the melting point is 138 ℃, the tensile strength retention rate (the ratio of the modified fiber to the unmodified fiber) is 83%, the tensile stress retention rate (the ratio of the modified fiber to the unmodified fiber) is 89%, the monofilament extraction force in the epoxy resin embedding test is 17cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 6Mpa. After washing treatment according to the ISO 105-C03 standard, the retention of the surface monofilament pullout force of the modified UHMWPE fibers was 88% (compared to before washing), and the retention of the interfacial shear strength of the epoxy resin/modified fiber composite of the modified fibers after washing treatment was 87% (compared to before washing).
Comparative example 4 a method for preparing a modified carbon fiber includes the steps of:
(1) Cleaning the fiber: and soaking the carbon fiber in acetone for ultrasonic treatment for 1h, washing and drying at room temperature.
(2) Preparation of prehydrolysis silane coupling agent: a silane coupling agent (same as in comparative example 3) was added to the water/ethanol-based mixture to obtain a first mixed solution, which was prehydrolyzed for 20 minutes. Wherein the volume ratio of the silane coupling agent to the first mixed solution is 1: 200, the volume ratio of the water to the first mixed solution is 3: 100, and the volume ratio of the ethanol to the first mixed solution is 193: 200.
(3) Preparing modified fibers: preparing a trihydroxymethylaminomethane/water buffer solution with a pH value of 8.5 (the concentration of the trihydroxymethylaminomethane is 0.1 mol/L), firstly adding pyrogallol to obtain a third mixed solution (the concentration of dopamine in the third mixed solution is 0.5 g/L), after 30 minutes of polymerization reaction, dropwise adding a certain amount of the second mixed solution prepared in the step 2 (the adding amount of the second mixed solution is 25vol% of the volume of the third mixed solution), and hydroxylated carbon nanotubes (the diameter is 30nm, and the adding amount of the hydroxylated carbon nanotubes accounts for 4wt% of the total mass of the third mixed solution), continuously reacting for 60 minutes, adding the fibers cleaned in the step (1), and reacting for 7 hours. And taking out the modified carbon fiber, cleaning and vacuum drying.
In the modified carbon fiber, the mass of the coating accounts for 3wt% of the mass of the fiber before modification, the surface pore diameter is 500nm, and the BET specific surface area is 950m 2 (ii) in terms of/g. SiO in the coating 2 The mass of (A) is 0wt% of the total mass of the modified fiber; is located at 1150-1000cm in infrared test -1 In the formula (Si-O-Si, C-O-C and Si-O-C, etc.) with a peak area of 2700-3000cm -1 The ratio of the characteristic peak-to-peak areas of the (polyethylene) is 1: 130.
The contact angle of the modified carbon fiber and water is 88 degrees, the tensile strength is 3.5GPa, the tensile stress is 118cN, the DSC test shows that the melting point is 139 ℃, the tensile strength retention rate (the ratio of the modified fiber to the unmodified fiber) is 79%, the tensile stress retention rate (the ratio of the modified fiber to the unmodified fiber) is 83%, the monofilament extraction force in the epoxy resin embedding test is 6cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 7Mpa. After washing treatment according to ISO 105-C03 standard, the retention rate of surface monofilament extraction force of the modified carbon fiber is 90% (compared with that before non-washing), and the retention rate of the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber after washing treatment is 87% (compared with that before non-washing).
Comparative example 5 (unmodified UHMWPE fibre)
Cleaning unmodified fibers: UHMWPE fibers (identical to comparative examples 1 to 3) were sonicated for 1h by immersing them in acetone, and dried at room temperature after washing.
The UHMWPE fiber is not treated, the surface of the UHMWPE fiber has no coating, the pore diameter of the surface of the UHMWPE fiber is 900nm, the BET specific surface area of the UHMWPE fiber is 20m 2 (ii) in terms of/g. Is located at 1150-1000cm in infrared test -1 In the formula (Si-O-Si, C-O-C and Si-O-C, etc.) with a peak area of 2700-3000cm -1 The ratio of the characteristic peak area to the peak area of the (polyethylene) is 1: 1000.
The contact angle of the UHMWPE fiber and water is 120 degrees, the tensile strength is 3.5GPa, the tensile stress is 118cN, the melting point is 137 ℃, the monofilament extraction force is 4cN in the epoxy resin embedding test, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 3Mpa. After washing treatment according to the ISO 105-C03 standard, the UHMWPE fibers have a retention of 85% of surface monofilament pullout force (compared to the fibers before washing) and 80% of retention of interfacial shear strength of the epoxy resin/modified fiber composite of the modified fibers after washing treatment (compared to the fibers before washing).
Example 1 a method of making a modified UHMWPE fiber comprises the steps of:
(1) Cleaning the fiber: and immersing the UHMWPE fibers into ethanol for ultrasonic treatment for 0.5h, and drying at room temperature after washing.
(2) Preparation of prehydrolysis silane coupling agent: the silane coupling agent was added to the water/ethanol mixture to obtain a first mixed solution, which was prehydrolyzed for 10 minutes. Wherein the volume ratio of the silane coupling agent to the first mixed solution is 1: 300, the volume ratio of the water to the first mixed solution is 1: 100, and the volume ratio of the ethanol to the first mixed solution is 74: 75.
The structure of the silane coupling agent is as follows:
wherein X is methoxy and n is 3.
(3) Preparing modified fibers: preparing a trihydroxymethylaminomethane/water buffer solution with the pH value of 8 (the concentration of the trihydroxymethylaminomethane is 0.05 mol/L), firstly adding pyrocatechol to obtain a third mixed solution (the concentration of the pyrocatechol in the third mixed solution is 0.25 g/L), after 10 minutes of polymerization reaction, dropwise adding a certain amount of the second mixed solution prepared in the step 2 (the adding amount of the second mixed solution is 3vol% of the volume of the third mixed solution), and nano-silica (the diameter is 5nm, and the adding mass accounts for 0.5wt% of the total mass of the third mixed solution), continuing to react for 20 minutes, adding the fibers cleaned in the step (1), and reacting for 2 hours. The modified UHMWPE fibers were removed and washed and dried under vacuum.
In the modified UHMWPE fiber, the mass of the coating accounts for 0.2wt% of the mass of the fiber before modification, the surface pore diameter is 300nm, the BET specific surface area is 50m 2 (ii) in terms of/g. SiO in the coating 2 The mass of (A) is 0.1wt% of the total mass of the modified fiber; is located at 1150-1000cm in infrared test -1 In the formula (Si-O-Si, C-O-C and Si-O-C, etc.) with a peak area of 2700-3000cm -1 The ratio of the characteristic peak area to the peak area of the (polyethylene) is 1: 100.
The contact angle of the modified UHMWPE fiber and water is 80 degrees, the tensile strength is 3GPa, the tensile stress is 80cN, the melting point is 145 ℃, the retention rate of the tensile strength (the ratio of the modified fiber to the unmodified fiber) is 85 percent, the retention rate of the tensile stress (the ratio of the modified fiber to the unmodified fiber) is 90 percent, the extraction force of the epoxy resin embedding test monofilament is 20cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 10Mpa. After washing treatment according to the ISO 105-C03 standard, the retention of the surface monofilament pullout force of the modified UHMWPE fibers was 96% (compared to before washing), and the retention of the interfacial shear strength of the epoxy resin/modified fiber composite of the modified fibers after washing treatment was 97% (compared to before washing).
Embodiment 2 a method for preparing a modified carbon fiber includes the steps of:
(1) Cleaning the fiber: and (3) immersing the carbon fiber in acetone for ultrasonic treatment for 1h, washing and drying at room temperature.
(2) Preparation of prehydrolysis silane coupling agent: the silane coupling agent was added to the water/propanol mixture to obtain a first mixed solution, which was prehydrolyzed for 30 minutes. Wherein the volume ratio of the silane coupling agent to the first mixed solution is 1: 50, the volume ratio of the water to the first mixed solution is 10: 100, and the volume ratio of the ethanol to the first mixed solution is 22: 25.
The structure of the silane coupling agent is as follows:
wherein X is ethoxy and n is 20.
(3) Preparing modified fibers: preparing a trihydroxymethylaminomethane/water buffer solution with the pH value of 10 (the concentration of the trihydroxymethylaminomethane is 0.5 mol/L), firstly adding pyrogallol to obtain a third mixed solution (the concentration of the pyrogallol in the third mixed solution is 2 g/L), after carrying out polymerization reaction for 30 minutes, dropwise adding a certain amount of the second mixed solution prepared in the step 2 (the adding amount of the second mixed solution is 30vol% of the volume of the third mixed solution), and nano silicon dioxide (the diameter is 100nm, and the adding mass accounts for 5wt% of the total mass of the third mixed solution), continuing to react for 60 minutes, adding the fibers cleaned in the step (1), and reacting for 48 hours. And taking out the modified carbon fiber, cleaning and vacuum drying.
In the modified carbon fiber, the mass of the coating accounts for 20wt% of the mass of the fiber before modification, the surface pore diameter is 2nm, the BET specific surface area is 800m 2 (ii) in terms of/g. SiO in the coating 2 The mass of (A) is 8wt% of the total mass of the modified carbon fiber; is located at 1150-1000cm in infrared test -1 The area of the characteristic peak of the (Si-O-Si, C-O-C, si-O-C, etc.) is 2700-3000cm -1 The ratio of the characteristic peak area to the peak area of the (polyethylene) is 1: 10.
The contact angle of the modified carbon fiber and water is 40 degrees, the tensile strength is 6GPa, the tensile stress is 150cN, the melting point is 146 ℃, the retention rate of the tensile strength (the ratio of the modified fiber to the unmodified fiber) is 98 percent, the retention rate of the tensile stress (the ratio of the modified fiber to the unmodified fiber) is 95 percent, the monofilament extraction force is 60cN in the embedding test of epoxy resin, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 40Mpa. After washing treatment according to ISO 105-C03 standard, the retention rate of surface monofilament extraction force of the modified carbon fiber is 98% (compared with that before washing), and the retention rate of the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber after washing treatment is 99% (compared with that before washing).
Embodiment 3 a method for preparing a modified aramid fiber comprises the steps of:
(1) Cleaning the fiber: soaking aramid fiber in ethanol for ultrasonic treatment for 0.4h, washing and drying at room temperature.
(2) Preparation of prehydrolysis silane coupling agent: the silane coupling agent was added to the water/butanol mixture to obtain a first mixed solution, which was prehydrolyzed for 20 minutes. Wherein the volume ratio of the silane coupling agent to the first mixed solution is 1: 170, the volume ratio of the water to the first mixed solution is 5: 100, and the volume ratio of the ethanol to the first mixed solution is 321: 340.
The structure of the silane coupling agent is as follows:
wherein X is methoxy and n is 11.
(3) Preparing modified fibers: preparing a trihydroxymethylaminomethane/water buffer solution with a pH value of 9 (the concentration of the trihydroxymethylaminomethane is 0.25 mol/L), firstly adding tannic acid to obtain a third mixed solution (the concentration of the tannic acid in the third mixed solution is 1.1 g/L), after 20 minutes of polymerization reaction, dropwise adding a certain amount of the second mixed solution prepared in the step 2 (the adding amount of the second mixed solution is 16vol% of the volume of the third mixed solution), and nano silicon dioxide (the diameter is 51nm, and the adding mass accounts for 2.7wt% of the total mass of the third mixed solution), continuing to react for 40 minutes, adding the fibers cleaned in the step (1), and reacting for 25 hours. And taking out the modified aramid fiber, cleaning and vacuum drying.
In the modified aramid fiber, the mass of the coating accounts for 10wt% of the mass of the fiber before modification, the surface pore diameter is 150nm, and the BET specific surface area is 400m 2 (iv) g. SiO in the coating 2 The mass of (A) is 4wt% of the total mass of the modified fiber; is located at 1150-1000cm in infrared test -1 The peak area of the characteristic point (Si-O-Si, C-O-C, si-O-C, etc.) is 2700-3000cm -1 The ratio of the characteristic peak to the peak area of the (polyethylene) is 1: 55.
The contact angle of the modified aramid fiber and water is 60 degrees, the tensile strength is 4.5GPa, the tensile stress is 115cN, the melting point is 150 ℃, the tensile strength retention rate (the ratio of the modified fiber to the unmodified fiber) is 92 percent, the tensile stress retention rate (the ratio of the modified fiber to the unmodified fiber) is 94 percent, the monofilament extraction force in the epoxy resin embedding test is 40cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 25Mpa. After washing treatment according to ISO 105-C03 standard, the retention rate of surface monofilament extraction force of the modified aramid fiber is 99% (compared with that before non-washing), and the retention rate of the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber after washing treatment is 99% (compared with that before non-washing).
Example 4 a method of making a modified UHMWPE fiber comprises the steps of:
(1) Cleaning the fiber: and immersing the UHMWPE fibers into ethanol for ultrasonic treatment for 0.5h, and drying at room temperature after washing.
(2) Preparation of prehydrolysis silane coupling agent: the silane coupling agent was added to the water/ethylene glycol mixture to obtain a first mixed solution, which was prehydrolyzed for 25 minutes. Wherein the volume ratio of the silane coupling agent to the first mixed solution is 1: 200, the volume ratio of the water to the first mixed solution is 8: 100, and the volume ratio of the ethanol to the first mixed solution is 183: 200.
The structure of the silane coupling agent is as follows:
wherein X is methoxy and n is 15.
(3) Preparing modified fibers: preparing a trihydroxymethylaminomethane/water buffer solution with the pH value of 9 (the concentration of the trihydroxymethylaminomethane is 0.4 mol/L), firstly adding catechol and pyrogallol to obtain a third mixed solution (the concentration of the catechol and the pyrogallol in the third mixed solution is 1.25 g/L), after carrying out polymerization reaction for 25 minutes, dropwise adding a certain amount of the second mixed solution prepared in the step 2 (the adding amount of the second mixed solution is 25vol% of the volume of the third mixed solution), nano silicon dioxide (the diameter is 80nm, and the adding mass accounts for 3.5wt% of the total mass of the third mixed solution), continuing to react for 50 minutes, then adding the fibers cleaned in the step (1), and reacting for 40 hours. The modified UHMWPE fibers are removed and washed and dried in vacuum.
In the modified UHMWPE fiber, the mass of the coating accounts for 3wt% of the mass of the fiber before modification, the surface aperture is 60nm, the BET specific surface area is 650m 2 (ii) in terms of/g. SiO in the coating 2 The mass of (A) accounts for 5wt% of the total mass of the modified fiber; is located at 1150-1000cm in infrared test -1 The peak area of the characteristic point (Si-O-Si, C-O-C, si-O-C, etc.) is 2700-3000cm -1 The ratio of the characteristic peak area to the peak area of the (polyethylene) is 1: 30.
The contact angle of the modified UHMWPE fiber and water is 55 degrees, the tensile strength is 4.3GPa, the tensile stress is 100cN, the melting point is 155 ℃, the retention rate of the tensile strength (the ratio of the modified fiber to the unmodified fiber) is 89%, the retention rate of the tensile stress (the ratio of the modified fiber to the unmodified fiber) is 93%, the monofilament extraction force in the embedding test of the epoxy resin is 55cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 38Mpa. After washing treatment according to the ISO 105-C03 standard, the retention of the surface monofilament pullout force of the modified UHMWPE fiber was 100% (compared to before washing), and the retention of the interfacial shear strength of the epoxy resin/modified fiber composite of the modified fiber after washing treatment was 99.5% (compared to before washing).
Embodiment 5a method for preparing a modified carbon fiber comprises the steps of:
(1) Cleaning the fiber: and soaking the carbon fiber in ethanol for ultrasonic treatment for 0.7h, washing and drying at room temperature.
(2) Preparation of prehydrolysis silane coupling agent: the silane coupling agent was added to the water/glycerol mixture to obtain a first mixed solution, which was prehydrolyzed for 25 minutes. Wherein the volume ratio of the silane coupling agent to the first mixed solution is 1: 160, the volume ratio of the water to the first mixed solution is 8: 100, and the volume ratio of the ethanol to the first mixed solution is 731: 800.
The structure of the silane coupling agent is as follows:
wherein X is methoxy and n is 13.
(3) Preparing modified fibers: preparing a trihydroxymethylaminomethane/water buffer solution with the pH value of 9.5 (the concentration of trihydroxymethylaminomethane is 4.25 mol/L), firstly adding pyrogallol and tannic acid to obtain a third mixed solution (the concentration of the pyrogallol and the tannic acid in the third mixed solution is 1.8 g/L), after carrying out polymerization reaction for 15 minutes, dropwise adding a certain amount of the second mixed solution prepared in the step 2 (the adding amount of the second mixed solution is 20vol% of the volume of the third mixed solution), nano silicon dioxide (the diameter is 30nm, and the adding mass accounts for 1.5wt% of the total mass of the third mixed solution), continuing to react for 55 minutes, then adding the fibers cleaned in the step (1), and reacting for 30 hours. And taking out the modified carbon fiber, cleaning and vacuum drying.
In the modified carbon fiber, the mass of the coating accounts for 18wt% of the mass of the fiber before modification, the surface pore diameter is 10nm, the BET specific surface area is 700m 2 (ii) in terms of/g. SiO in the coating 2 The mass of (A) accounts for 4wt% of the total mass of the modified fiber; is located at 1150-1000cm in infrared test -1 The area of the characteristic peak of the (Si-O-Si, C-O-C, si-O-C, etc.) is 2700-3000cm -1 The ratio of the characteristic peak area to the peak area of the (polyethylene) is 1: 40.
The contact angle of the modified carbon fiber and water is 44 degrees, the tensile strength is 4GPa, the tensile stress is 110cN, the melting point is 160 ℃, the retention rate of the tensile strength (the ratio of the modified fiber to the unmodified fiber) is 95 percent, the retention rate of the tensile stress (the ratio of the modified fiber to the unmodified fiber) is 93 percent, the monofilament extraction force is 52cN in the embedding test of epoxy resin, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 36Mpa. After washing treatment according to ISO 105-C03 standard, the retention rate of the surface monofilament extraction force of the modified carbon fiber is 99.8% (compared with that before non-washing), and the retention rate of the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber after washing treatment is 99.5% (compared with that before non-washing).
Embodiment 6 a method for preparing a modified aramid fiber comprises the steps of:
(1) Cleaning the fiber: soaking aramid fiber in ethanol for ultrasonic treatment for 0.5h, washing and drying at room temperature.
(2) Preparation of prehydrolysis silane coupling agent: adding a silane coupling agent with X being ethoxy and n being 16 into a water/glycerol mixture to obtain a first mixed solution, and pre-hydrolyzing for 20 minutes. Wherein the volume ratio of the silane coupling agent to the first mixed solution is 1: 260, the volume ratio of the water to the first mixed solution is 9: 100, and the volume ratio of the ethanol to the first mixed solution is 589: 650.
(3) Preparing modified fibers: preparing a trihydroxymethylaminomethane/water buffer solution with a pH value of 10 (the concentration of trihydroxymethylaminomethane is 0.47 mol/L), firstly adding pyrogallol to obtain a third mixed solution (the concentration of pyrogallol in the third mixed solution is 1.75 g/L), after 10 minutes of polymerization reaction, dropwise adding a certain amount of the second mixed solution prepared in the step 2 (the adding amount of the second mixed solution is 26vol% of the volume of the third mixed solution), nano silicon dioxide (the diameter is 40nm, and the adding amount of the nano silicon dioxide accounts for 1.45wt% of the total mass of the third mixed solution), continuously reacting for 28 minutes, adding the fibers cleaned in the step (1), and reacting for 42 hours. And taking out the modified aramid fiber, cleaning and vacuum-drying.
In the modified aramid fiber, the mass of the coating accounts for 16wt% of the mass of the fiber before modification, the surface pore diameter is 95nm, the BET specific surface area is 320m 2 (ii) in terms of/g. SiO in the coating 2 The mass of (A) is 6.1wt% of the total mass of the modified fiber; is located at 1150-1000cm in infrared test -1 The area of the characteristic peak of the (Si-O-Si, C-O-C, si-O-C, etc.) is 2700-3000cm -1 The ratio of the characteristic peak to the peak area of the (polyethylene) is 1: 60.
The contact angle of the modified aramid fiber and water is 77 degrees, the tensile strength is 5.3GPa, the tensile stress is 98cN, the melting point is 158 ℃, the tensile strength retention rate (the ratio of the modified fiber to the unmodified fiber) is 93 percent, the tensile stress retention rate (the ratio of the modified fiber to the unmodified fiber) is 96 percent, the monofilament extraction force in the epoxy resin embedding test is 48cN, and the interfacial shear strength of the epoxy resin/modified fiber composite material is 36Mpa. After washing treatment according to the ISO 105-C03 standard, the retention rate of the surface monofilament extraction force of the modified aramid fiber is 98 percent (compared with that before washing), and the retention rate of the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber after washing treatment is 99 percent (compared with that before washing).
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. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A surface-porous, strongly adherent, modified fiber comprising a fibrous substrate and a coating covering the fibrous substrate; the method is characterized in that: the coating has a porous structure, wherein the pore diameter of pores contained in the coating is 2-300nm, and the specific surface area of the coating is 50-800m 2 (iv) g; and, siO contained in the coating layer 2 Is 0.1 to 8 percent of the total mass of the modified fiber, and is located 1150 to 1000cm in an infrared test pattern of the modified fiber -1 The characteristic peak area of (A) is 2700-3000cm -1 The ratio of the characteristic peak area to the peak area is 1: 100-1: 10.
2. The surface-porous, strongly adherent modified fiber according to claim 1, wherein: the mass of the coating is 0.1-20%, preferably 0.2-6% of the mass of the fiber matrix; and/or the pore diameter of the pores contained in the coating is 10-100nm, and the specific surface area is 500-800m 2 (iv) g; and/or the modified fiber is located 1150-1000cm in infrared test pattern -1 The characteristic peak area of (A) is 2700-3000cm -1 The ratio of the characteristic peak area to the peak area is 1: 100-1: 10 and 1: 80-1: 40; and/or the contact angle of the modified fiber and water is 40-80 degrees, preferably 40-60 degrees; and/or the tensile strength of the modified fiber is 3-6GPa, preferably 4-6GPa; and/or the modified fiber has a tensile stress of 80 to 150cN, preferably 100 to 150cN; and/or the tensile strength retention of the modified fiber before and after modification is higher than 85%, preferably higher than 90%; and/or the tensile stress retention of the modified fiber before and after modification is higher than 90%, preferably higher than 94%; and/or the epoxy resin embedding test monofilament extraction force of the modified fiber is 20-60cN, preferably 40-60cN; and/orThe interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber is 10-40Mpa, preferably 25-40Mpa, and/or the retention rate of the surface monofilament extraction force of the modified fiber after washing treatment according to ISO 105-C03 standard is higher than 96%; and/or the retention rate of the interfacial shear strength of the epoxy resin/modified fiber composite material of the modified fiber before and after washing is higher than 96%; and/or the modified fiber has a melting point of 145-160 ℃ as measured by DSC.
3. The surface-porous, strongly adherent modified fiber according to claim 1, wherein: the fiber matrix comprises any one of ultra-high molecular weight polyethylene fibers, carbon fibers or aramid fibers, and preferably any one of the ultra-high molecular weight polyethylene fibers or the carbon fibers.
4. A method for preparing surface porous strong adhesive modified fiber is characterized by comprising the following steps:
(1) Cleaning the fiber matrix;
(2) Adding a silane coupling agent into a mixture of water and alcohol to form a first mixed solution, and then carrying out a prehydrolysis reaction to form a second mixed solution;
(3) Adding a pyrocatechol compound into a trihydroxymethyl aminomethane buffer solution with the pH value of 8-10 to form a third mixed solution, carrying out polymerization reaction, then adding the second mixed solution and nano silicon dioxide to carry out a first reaction, and then adding the fiber matrix cleaned in the step (1) to continue carrying out a second reaction, thereby obtaining the surface porous strong-adhesion modified fiber.
5. The method according to claim 4, wherein the step (1) comprises: cleaning the fiber matrix in a solvent for 10-40 min, and then taking out and drying; the solvent comprises any one or combination of ethanol, acetone and tetrahydrofuran; and/or the fiber matrix comprises any one of ultra-high molecular weight polyethylene fibers, carbon fibers or aramid fibers, and preferably the ultra-high molecular weight polyethylene fibers or the carbon fibers.
6. The production method according to claim 4, wherein the silane coupling agent in the step (2) has a structure represented by the following formula:
wherein X comprises methoxy or ethoxy, and n is 3-20;
and/or, the alcohol comprises any one or more of ethanol, propanol, butanol, glycol and glycerol;
and/or the silane coupling agent contained in the first mixed solution accounts for 1: 300-1: 50 of the total volume of the first mixed solution, preferably 1: 200-1: 80; and/or the first mixed solution contains water accounting for 1: 100-10: 100 of the total volume of the first mixed solution, preferably 2: 100-8: 100; and/or the ethanol contained in the first mixed solution accounts for 74: 75-66: 75 of the total volume of the first mixed solution, preferably 39: 40-363: 400.
And/or the reaction time of the prehydrolysis reaction is 10-30 minutes.
7. The method of manufacturing according to claim 4, characterized in that: in the step (3), the reaction time of the polymerization reaction is 10-30 minutes; and/or the reaction time of the first reaction is 20-60 minutes; and/or the reaction time of the second reaction is 2-48 hours; and/or the dosage of the second mixed solution is 3-30% of the volume of the third mixed solution.
8. The method of manufacturing according to claim 4, characterized in that: the catechol compound comprises any one or combination of more of catechol, pyrogallol and tannic acid; and/or the diameter of the nano silicon dioxide is 5-100nm, preferably 10-50nm.
9. The method of claim 4, wherein: in the step (3), the tris buffer solution contains tris at a concentration of 0.05 to 0.5 mol/L; and/or the concentration of the catechol compound in the third mixed solution is 0.25-2g/L, preferably 0.5-1g/L; and/or the mass of the nano silicon dioxide is 0.5-5%, preferably 1-3% of the total mass of the third mixed solution.
10. Use of the surface-porous, strongly adherent modified fiber according to any of claims 1 to 3 for the preparation of a polymer-based composite; preferably, the polymer matrix composite is a fiber reinforced resin composite.
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