CN110670352B - Method for reversibly modifying carbon fiber - Google Patents

Method for reversibly modifying carbon fiber Download PDF

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CN110670352B
CN110670352B CN201911018481.8A CN201911018481A CN110670352B CN 110670352 B CN110670352 B CN 110670352B CN 201911018481 A CN201911018481 A CN 201911018481A CN 110670352 B CN110670352 B CN 110670352B
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carbon fiber
ferrocene
carbon
drying
ferrocene derivative
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吴刚平
刘玉婷
张晓芳
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Shanxi Institute of Coal Chemistry of CAS
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    • 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
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    • D06M11/07—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/09—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with free halogens or interhalogen compounds
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    • D06M11/30—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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
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    • D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/34—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
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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
    • D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/50—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
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    • D06M11/51—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 sulfur, selenium, tellurium, polonium or compounds thereof
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

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Abstract

The invention relates to the field of carbon fiber surface modification, in particular to a method for reversibly modifying carbon fibers. The invention aims to solve the technical problems that the surface structure of carbon fibers is seriously damaged by the existing carbon fiber surface treatment method and the traditional surface modifier cannot be reversibly recycled. The ferrocene derivative is a switch type ferrocene derivative, has good reversible redox property, can respond to the change of external conditions, can control the reversible conversion of adsorption and desorption through redox reaction, and has good application prospect in surface modification and recycling of carbon fibers based on the reversible property. According to the invention, effective modification of the carbon fiber is realized by adsorbing the ferrocene derivatives on the carbon fiber, and the surface structure of the carbon fiber is hardly damaged.

Description

Method for reversibly modifying carbon fiber
Technical Field
The invention relates to the field of carbon fiber surface modification, in particular to a method for reversibly modifying carbon fibers.
Background
The carbon fiber has excellent properties of high strength, high modulus, high temperature resistance, light weight and the like, and the carbon fiber composite material is widely applied to the fields of new energy, materials and the like due to the excellent properties of the carbon fiber. However, the carbon fiber without surface treatment has a smooth surface, is chemically inert, has strong hydrophobicity, and has a particularly weak bonding force with a resin matrix. Surface modification of carbon fibers is an effective method for improving chemical inertness and hydrophilicity.
The traditional surface modification methods mainly include electrochemical oxidation, plasma, gas/liquid phase oxidation, chemical grafting and the like. Manabu et al introduced special functional groups on carbon fibers by electrochemical redox method, changed the surface structure of carbon fibers (see M.Ishifune, R.Suzuki, Y.Mima, K.Uchida, N.Yamashita, S.Kashimura.novel electrochemical surface modification method of carbon fiber and its utilization to the preparation of functional electrode.) electrochemical micro-Acta, 2005,51:14-22. Montes-Mor-n, etc. utilize plasma treatment to improve the interfacial properties between carbon fibers and epoxy resins (see m.a.montes-Mor n, a.mart i nez-Alonso, j.m.d.tasc. yan n, m.c.paiva, c.a.bernardo, r.j.young.effects of plasma oxidation on the surface and interfacial properties of ultra-high modulus carbon fibers, comp.part a-application.sci.man. 371, 2001: 371). Jingchangliang et al compared the mechanical properties of the thermoplastic polyimide composite material and the silane coupling agent modified carbon fiber under different conditions, and the introduced silane coupling agent chemically bonded with the fiber and could not be removed (Jingchangliang, Helichrysum. mechanical properties of surface-treated carbon fiber modified polyimide composite material. plastic. 2012,41: 4-6). However, the conventional surface treatment mainly has the following problems: firstly, the surface structure of the carbon fiber is damaged, defects are introduced, and secondly, a large amount of energy consumption is needed, so that pollution is possibly caused; and thirdly, the traditional modifier is difficult to remove.
In view of the above problems, there is a need for the development of a carbon fiber surface modifier that can modify the surface of carbon fibers without damage and can be removed easily when not needed. The switch type ferrocene derivative has a ferrocene group structure, so that the switch type ferrocene derivative can respond to the change of external conditions, such as light, temperature, redox conditions and the like, can perform reversible conversion between an active state and an inactive state under the control of the external conditions, and has good application prospect.
The invention aims to provide a method for modifying the surface of carbon fiber by a physical adsorption mode based on a switch type ferrocene derivative and reversibly removing a modifier, which can effectively improve the surface inertia of the carbon fiber and has important significance for recycling and reusing the carbon fiber.
Disclosure of Invention
The invention aims to provide a method for reversibly modifying carbon fibers, and aims to solve the technical problems that the surface structure of carbon fibers is seriously damaged by the conventional carbon fiber surface treatment method and the conventional surface modifier cannot be reversibly recycled.
In order to achieve the purpose, the invention provides the following technical scheme:
a method of reversibly modifying a carbon fiber comprising the steps of:
step 1, pretreatment of carbon fibers: desizing the carbon fiber to obtain the desized carbon fiber;
step 2, preparing ferrocene derivative solution: adding the ferrocene derivatives into a solvent according to a ratio, and uniformly dispersing and dissolving;
step 3, surface modification of carbon fibers: and (3) adding the desized carbon fiber obtained in the step (1) into the ferrocene derivative solution prepared in the step (2), modifying the surface of the carbon fiber, separating, removing supernatant, and drying the carbon fiber modified by the ferrocene derivative, thus finishing the surface modification of the carbon fiber.
And 4, reversible desorption of the ferrocene derivatives on the surface of the carbon fiber: and (3) oxidizing the surface-modified carbon fiber in the step (3) by an oxidant or electrochemistry to realize reversible desorption of the ferrocene derivatives on the surface of the carbon fiber.
Further, the carbon fiber used in the step 1 is continuous carbon fiber or chopped carbon fiber. The method is suitable for surface treatment of carbon fibers with different lengths.
Still further, the desizing treatment in the step 1 is a high-temperature desizing method or a Soxhlet extraction method; the high-temperature desizing method is to desize the carbon fiber in desizing air or inert atmosphere (nitrogen and argon) at the temperature of 300-800 ℃; the Soxhlet extraction method is to carry out heating reflux desizing on the carbon fiber by acetone or DMF organic solvent, and the desizing time is 5-300 min.
Furthermore, the concentration of the ferrocene derivative solution in the step 2 is 1.0-20mM, the modification effect is poor when the concentration is too low, and the treatment cost is increased when the concentration is too high.
Further, the ferrocene derivative in the ferrocene derivative solution in step 2 refers to a compound containing a ferrocene group, including ferrocenecarboxylic acid, (ferrocenylmethyl) dodecyldimethylammonium bromide, hydroxymethyl ferrocene, and butyl ferrocene. The purpose of modifying the surface of the carbon fiber by using different functional groups is realized, so that the further application of the carbon fiber is facilitated.
Furthermore, the solvent in the ferrocene derivative solution in the step 2 is one or a mixture of several of water, alcohol, acetone and tetrahydrofuran, and the alcohol includes ethanol, n-propanol or n-butanol. The problem of poor adsorption effect caused by different ferrocene derivatives with different solubilities is avoided.
Furthermore, the volume ratio of the carbon fiber desized in the step 3 to the ferrocene derivative solution is 1mg:0.1-100 ml. Too low concentration results in poor modification effect, and too high concentration increases modification cost.
Furthermore, in the step 3, the temperature of the reaction system in the surface modification of the carbon fiber is 15-100 ℃, the carbon fiber is surface modified by adopting a mode of oscillation, standing or combination of the oscillation and the standing, and the modification time is 1-1000 min. If the temperature is too high or too low, the ferrocene derivatives have poor adsorption activity, and if the time is too short, the adsorption is insufficient, and if the time is too long, the time cost is increased.
Furthermore, the separation process in the step 3 can adopt methods including centrifugation, filtration and sedimentation; separation time: 5-1500 min. Too short a time to separate completely, too long a time increases the time cost.
Furthermore, the drying of the carbon fiber modified by the ferrocene derivative in the step 3 can be normal pressure drying or vacuum oven drying, the drying temperature is 10-100 ℃, and the drying time is 1-48 h. The drying purpose can be achieved without damaging the fiber surface.
Further, the standard electrode potential E for oxidizing the oxidant in the step 4 is in the range of 0.8-2.2V; the oxidant is any one of concentrated sulfuric acid, hypochlorous acid, oxygen, ozone, permanganic acid, bromine, iodic acid, ferric acid or silver chloride; the electrochemical oxidation is a potentiostatic method, a cyclic voltammetry method and a galvanostatic method, and the oxidation voltage range is 0.6-5V. The oxidative desorption of the ferrocene derivatives cannot be realized when the potential or electrochemical oxidation voltage of the oxidant standard electrode is too low, and the fiber structure can be damaged when the potential or electrochemical oxidation voltage of the oxidant standard electrode is too high.
Compared with the prior art, the invention has the beneficial effects that:
1. the ferrocene derivative is a switch type ferrocene derivative, has good reversible redox property, can respond to the change of external conditions, can control the reversible conversion of adsorption and desorption through redox reaction, and has good application prospect in surface modification and recycling of carbon fibers based on the reversible property.
2. According to the invention, effective modification of the carbon fiber is realized by adsorbing the ferrocene derivatives on the carbon fiber, and the surface structure of the carbon fiber is hardly damaged.
3. The reversible modification method can realize the cyclic utilization of the ferrocene derivatives, and effectively reduces the material cost.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method of reversibly modifying a carbon fiber comprising the steps of:
step 1, pretreatment of carbon fibers: desizing a carbon fiber tow (PAN carbon fiber, HTS40) under the protection of nitrogen at 500 ℃ to obtain desized carbon fiber;
step 2, preparing ferrocene derivative solution: adding ferrocenecarboxylic acid (Aladdin) into deionized water according to a ratio, and uniformly dispersing and dissolving to obtain a ferrocene derivative solution with the concentration of 1.0 mM;
step 3, surface modification of carbon fibers: adding 1g of the continuous carbon fiber tows desized in the step 1 into 100ml of the ferrocene derivative solution prepared in the step 2, oscillating for 200min in a constant temperature oscillator at 15 ℃, separating by adopting a centrifugal mode for 5min, removing supernatant, drying the carbon fiber modified by the ferrocene derivative for 1h at normal pressure, wherein the drying temperature is 10 ℃, finishing surface modification of the continuous carbon fiber tows, and obtaining the content of Fe element on the surface of the carbon fiber subjected to surface modification through X-ray photoelectron spectroscopy (Table 2).
And 4, reversible desorption of the ferrocene derivatives on the surface of the carbon fiber: and (3) electrifying the continuous carbon fiber subjected to surface modification in the step (3) (0.6V) for oxidation, and realizing reversible desorption of the ferrocene derivatives on the surface of the carbon fiber. The surface-modified continuous carbon fiber is used for a reinforcement of an epoxy resin-based composite material, the infiltration of resin to the fiber can be improved, and then in order to realize the recycling of the ferrocene derivative, the ferrocene derivative is desorbed from the surface of the fiber. The content of Fe on the surface of the carbon fiber after desorption can be obtained by X-ray photoelectron spectroscopy (table 2).
Example 2
A method of reversibly modifying a carbon fiber comprising the steps of:
step 1, pretreatment of carbon fibers: carrying out air desizing treatment on a carbon fiber tow (PAN carbon fiber, HTS40) at 500 ℃ to obtain desized carbon fiber;
step 2, preparing ferrocene derivative solution: adding (ferrocenyl methyl) dodecyl dimethyl ammonium bromide (Tokyo Chemical Industry Co., Ltd., Japan) into deionized water according to a ratio, and uniformly dispersing and dissolving to obtain a 10mM ferrocene derivative solution;
step 3, surface modification of carbon fibers: and (2) adding 0.01g of carbon fiber desized in the step (1) into 100ml of the ferrocene derivative solution prepared in the step (2) in a short cut manner, standing for 1min in a constant-temperature water bath at 50 ℃, separating by adopting a filtering manner for 100min, removing supernatant, carrying out vacuum drying on the carbon fiber modified by the ferrocene derivative for 48h at the drying temperature of 100 ℃, finishing the surface modification of the short carbon fiber, and obtaining the content of the Fe element on the surface of the carbon fiber subjected to the surface modification by X-ray photoelectron spectroscopy (Table 2).
And 4, reversible desorption of the ferrocene derivatives on the surface of the carbon fiber: and (3) oxidizing the surface-modified chopped carbon fibers in the step (3) in an ozone (E-2.076V) atmosphere to realize reversible desorption of the ferrocene derivatives on the surfaces of the carbon fibers. The dispersion effect of the surface-modified chopped carbon fiber in the aqueous solution is obviously improved, and the controllable deposition of the carbon fiber can be realized after the ferrocene derivative is desorbed from the surface of the fiber, so that the carbon fiber can be used for preparing the carbon fiber felt. The content of the Fe element on the surface of the carbon fiber after desorption can be obtained by analyzing the carbon fiber by X-ray photoelectron spectroscopy (Table 2).
Examples 3 to 6
Examples 3-6 the basic operation procedures were the same as in examples 1 and 2, and one or more of the carbon fiber type, ferrocene derivative type and solution concentration, carbon fiber mass to solution volume ratio, reaction temperature, mixing method, separation time, drying method, temperature, time, desorption method and desorption conditions were changed, and the specific conditions for each example are shown in table 1.
The solvent in the ferrocene derivative solution may be replaced by acetone or tetrahydrofuran, in addition to those listed in examples 1 to 6; the oxidant in the oxidant oxidation can also be replaced by concentrated sulfuric acid, hypochlorous acid, oxygen, permanganic acid, bromine or iodine acid; the electrochemical oxidation may also be carried out by a galvanostatic method.
The content of the Fe element on the surface of the carbon fiber after surface modification and desorption can be obtained by X-ray photoelectron spectroscopy, the results are shown in table 2, and the adsorption and desorption conditions of the ferrocene derivatives on the surface of the carbon fiber can be seen through the change of the content of the Fe element.
TABLE 1
Figure BDA0002246444130000071
TABLE 2
Figure BDA0002246444130000081
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. A method of reversibly modifying carbon fibers, comprising: the method comprises the following steps:
step 1, pretreatment of carbon fibers: desizing the carbon fiber to obtain the desized carbon fiber;
step 2, preparing ferrocene derivative solution: adding the ferrocene derivatives into a solvent according to a ratio, and uniformly dispersing and dissolving;
step 3, surface modification of carbon fibers: adding the desized carbon fiber obtained in the step 1 into the ferrocene derivative solution prepared in the step 2, modifying the surface of the carbon fiber, separating, removing supernatant, and drying the carbon fiber modified by the ferrocene derivative, thus finishing the surface modification of the carbon fiber;
and 4, reversible desorption of the ferrocene derivatives on the surface of the carbon fiber: performing oxidant or electrochemical oxidation on the surface-modified carbon fiber in the step 3 to realize reversible desorption of the ferrocene derivatives on the surface of the carbon fiber;
the carbon fiber used in the step 1 is continuous carbon fiber or short carbon fiber;
the ferrocene derivatives comprise ferrocenecarboxylic acid, ferrocenyl methyl-dodecyl dimethyl ammonium bromide, hydroxymethyl ferrocene or butyl ferrocene;
in the step 3, the temperature of a reaction system in the surface modification of the carbon fiber is 15-100 ℃, the carbon fiber is surface modified in a mode of oscillation, standing or combination of the oscillation and the standing, and the modification time is 1-1000 min;
the separation process in the step 3 comprises centrifugation, filtration and sedimentation.
2. A method of reversibly modifying a carbon fiber according to claim 1, wherein: the concentration of the ferrocene derivative solution in the step 2 is 1.0-20 mM.
3. A method of reversibly modifying a carbon fiber according to claim 1, wherein: and the solvent in the ferrocene derivative solution in the step 2 is one or a mixture of water, alcohols, acetone and tetrahydrofuran.
4. A method of reversibly modifying a carbon fiber according to claim 1, wherein: the volume ratio of the desized carbon fiber to the ferrocene derivative solution in the step 3 is 1mg:0.1-100 ml.
5. A method of reversibly modifying a carbon fiber according to claim 1, wherein: the separation time in the step 3 is as follows: 5-1500 min.
6. A method of reversibly modifying a carbon fiber according to claim 1, wherein: the drying of the carbon fiber modified by the ferrocene derivatives in the step 3 can be normal pressure drying or vacuum oven drying, the drying temperature is 10-100 ℃, and the drying time is 1-48 h.
7. A method of reversibly modifying a carbon fiber according to claim 1, wherein: the standard electrode potential E for oxidizing the oxidant in the step 4 is in the range of 0.8-2.2V; the oxidant is any one of concentrated sulfuric acid, hypochlorous acid, oxygen, ozone, permanganic acid, bromine, iodic acid, ferric acid or silver chloride; the electrochemical oxidation is a potentiostatic method, a cyclic voltammetry method and a galvanostatic method, and the oxidation voltage range is 0.6-5V.
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