WO2013182023A1 - Modificateur de surface pour fibre de carbone, fibre de carbone modifiée, matériau composite et procédés de préparation associés - Google Patents

Modificateur de surface pour fibre de carbone, fibre de carbone modifiée, matériau composite et procédés de préparation associés Download PDF

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WO2013182023A1
WO2013182023A1 PCT/CN2013/076655 CN2013076655W WO2013182023A1 WO 2013182023 A1 WO2013182023 A1 WO 2013182023A1 CN 2013076655 W CN2013076655 W CN 2013076655W WO 2013182023 A1 WO2013182023 A1 WO 2013182023A1
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carbon fiber
group
surface modifier
fiber surface
hydrogen
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PCT/CN2013/076655
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English (en)
Chinese (zh)
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谢怀玉
黄险波
蔡彤旻
曾祥斌
宋威
辛伟
马雷
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金发科技股份有限公司
上海金发科技发展有限公司
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Publication of WO2013182023A1 publication Critical patent/WO2013182023A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
    • C07C215/50—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
    • C07C215/80—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring containing at least two amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
    • C07C217/58—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/20—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated
    • C07C219/22—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/34—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/325—Amines
    • D06M13/332—Di- or polyamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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

Definitions

  • Carbon fiber surface modifier modified carbon fiber, composite material and preparation method thereof
  • the invention relates to a modifier, in particular to a carbon fiber surface modifier and a preparation method thereof, a modified carbon fiber prepared by a carbon fiber surface modifier and a preparation method of the modified carbon fiber, and a modified carbon fiber and a resin system.
  • Carbon fiber has outstanding mechanical properties, and carbon fiber is widely used in composite materials for reinforcement. In recent years, improving the interface properties between carbon fiber and matrix resin has become a research hotspot.
  • the surface active carbon fiber of the carbon fiber is small, and the effective chemical bond formed when the composite is combined with the matrix resin is small, and the compatibility is poor, which results in the formation of a brittle interface layer structure in the carbon fiber composite material.
  • the surface of the carbon fiber is usually oxidized in the industry to impart active oxygen-containing functional groups such as hydroxyl groups and carbonyl groups on the surface of the carbon fiber. Anodizing, nitric acid oxidation, and potassium permanganate oxidation are common. Etc.
  • the technical solution adopted by the present invention is a carbon fiber surface modifier whose structural formula is as shown in formula (I):
  • R 2 and R 2 ' each independently represent a hydrogen group, a hydroxyl group, or a fluorenyl group.
  • the alkyl group of C r C 3 means a linear or branched fluorenyl group having 1 to 3 carbon atoms.
  • R 2 , R, ' represents methyl, ethyl, propyl and hydrogen, particularly preferably methyl, ethyl and hydrogen, most preferably methyl and in formula (I),
  • R 3 and R 4 are each independently of one another Represents C r C 18 fluorenyl, ⁇ alkoxy, hydroxy, amino, halogen, hydrogen, amide, ester, or siloxy, with the proviso that R 3 and R 4 are not hydrogen at the same time.
  • Preferred are a hydroxyl group, an amino group, and a decyloxy group, a siloxy group, an ester group, and an amide group of dC ls .
  • the alkyl group of dC 18 means a linear or branched fluorenyl group having 1 to 18 carbon atoms.
  • the mercapto group and the stearyl group and the like are preferably 12 to 18, particularly preferably 14 to 18 carbon atoms. Most preferred are myristyl, octadecyl, which include both linear and branched isomers.
  • the decyloxy group of C r C 18 means a linear or branched alkoxy group having 1 to 18 carbon atoms.
  • the dodecyloxy group or the like is preferably 1 to 12, particularly preferably 3 to 12 carbon atoms. Most preferred are propoxy, (2-ethyl)-hexyloxy, decyloxy, which include both straight and branched isomers.
  • the amino group includes -NH 2 , -NHRj, -NR X R 2 , wherein R 2 each independently represents each other
  • the halogen means a fluorine, chlorine, bromine or iodine atom.
  • a fluorine atom is preferred.
  • the amide group has the formula -(CH 2 ) n CONH-R, and n includes an integer of from 1 to 15.
  • n is taken A linear or branched chain of 1-10, and n is most preferably 2 and 3.
  • R is a linear or branched fluorenyl group of C1-C18, hydrogen, preferably a linear or branched fluorenyl group having 1 to 6 carbon atoms, hydrogen, and R is most preferably a methyl group, an ethyl group or a hydrogen.
  • the amide group is most preferably an acetamide group or a propionamide group.
  • the ester group has the formula -(CH 2 ) n CO 2 -R, and n includes an integer of from 1 to 15. Preferably, n takes from 1 to 10 linear or branched, and n is most preferably 2.
  • a linear or branched fluorenyl group wherein R is 18 preferably a linear or branched fluorenyl group having 1 to 6 carbon atoms, most preferably a methyl group and an ethyl group.
  • the ester group is most preferably an ethyl acetate methyl ester or an ethyl alcohol ethyl ester.
  • the siloxy group includes a siloxane derivative, and examples thereof are trimethylsiloxy, tert-butyldimethylsilyloxy, -(CH 2 ) 3 Si (OCH 3 ) 3 , - (CH 2 ) 2 OSi (CH 3 ) 2 (CH2 ) 3 CH 3 , -(CH 2 ) 6 Si (C3 ⁇ 4) 2 0-CH 3 .
  • Most preferred is -(CH 2 ) 3 Si (OCH3 ) 3 , - CCH 2 ) 2 OSi[CH 3 ) 2 C(CH 3 ) 3 , -(CH 2 ) 6 Si (CH 3 ) 2 0-CH 3 .
  • the formula (I) includes hydrogen, a hydroxyl group, an amino group, a halogen, and a decyloxy group. Preferred are a hydroxyl group, a hydrogen group, and most preferably a hydroxyl group.
  • R 2 , RA R 2 ' represents hydrogen and methyl; and represents tetradecyl, octadecyl, acetamido, propionamido, methyl acetate, ethanol Ethyl ester, selected propoxy, (2-ethyl)-hexyloxy, decyloxy, N,N-di-2-methoxy-ethylamino, N,N-diethylhydroxyamino, - ⁇ 2 , hydroxyl, hydrogen, fluorine, trimethylsilyloxy, tert-butyldimethylsilyloxy, -(CH 2 ) 3 Si (OCH3 ) 3, - (CH 2 ) 2 OSi (CH 3 ) 2 C (CH 3 ) 3 , -(CH 2 ) 6 Si (CH 3 ) 2 0-CH 3 ; R 5 represents a hydroxyl group.
  • the carbon fiber surface modifier of the present invention comprises a large cavity composed of 12 atoms of carbon, nitrogen, hydrogen and/or oxygen, and a plurality of amino functional groups in the cavity, including hydrogen, hydroxyl and amino groups. , halogen or decyloxy group, these functional groups and amino groups can chemically react with or form hydrogen bonds with functional groups such as oxygen-containing carboxyl groups, aldehyde groups, ketone groups, and hydroxyl groups inherent on the surface of carbon fibers, which are adsorbed on the surface of carbon fibers by chemical bonds;
  • the R 3 and R 4 functional substituent groups of the modifier have good compatibility with the resin, and the resin matrix undergoes chemical reaction and physical crosslinking with the molecular chain of the resin to form a network structure under melt processing conditions.
  • the appropriate modifier of the invention can increase the interlaminar shear strength of the carbon fiber reinforced resin material by 9-30%, and the invention can effectively improve the interface between the carbon fiber and the resin.
  • the above R5 and the functional groups of the amino functional group and the carbon fiber surface may have various reaction mechanisms, such as mechanism 1: the surface modifier amino group is polycondensed with the ketone group on the surface of the carbon fiber to produce an enamine, so that the modifier is firmly adsorbed on the surface of the carbon fiber. .
  • Mechanism 2 Surface modification agent hydroxyl group and carbon fiber surface carboxyl group undergo esterification reaction during heating and drying process, acid dehydroxy alcohol dehydrogenation, ROHOH remove -OH, ROH remove hydrogen, then RCO- and -OR are connected together to generate RCOOR allows the modifier to adhere firmly to the surface of the carbon fiber.
  • Mechanism 3 The ammonia of the surface modifier undergoes a ring-opening substitution reaction with the epoxy group on the surface of the carbon fiber to form an amino alcohol. The surface modifier is firmly adsorbed on the surface of the carbon fiber.
  • the surface modifier is firmly adsorbed on the surface of the carbon fiber.
  • the surface modifier can chemically react with the oxygen-containing functional groups on the surface of the carbon fiber through mechanisms 1-3, and a chemical bond is formed between them to allow the surface modifier to be attached to the surface of the carbon fiber.
  • a chelating base Sali-cylaldehydoethylenediamine
  • Salen 0 and Salen a chelating base formed by condensation of two identical aldehyde molecules and one diamine molecule
  • the imine becomes saturated.
  • amino groups such compounds are referred to as Salan.
  • the central position of Salen and Salan is 0, N, N, 0 4 atoms, and the large cavity is composed of 12 atoms of carbon, nitrogen, hydrogen and oxygen.
  • the invention necessitates a method for preparing a carbon fiber surface modifier, comprising the following steps:
  • the component A is an ethylenediamine derivative such as ethylenediamine, 1,1-dimethylethylenediamine, 1,2-dimethylethylenediamine, hydroxyethylenediamine, tetramethyl Ethylenediamine, tetraethylethylenediamine; can be obtained by known conventional experimental methods and commercially available.
  • the carbon fiber surface modifier C is prepared by the component A and the component B, and the reaction process is as follows:
  • Condensation reaction Component A and component B are dissolved in an ethanol solution at a molar ratio of 1:2-1:4, the temperature is 0-70 ° C, and the reaction time is l-8 h ;
  • Reduction reaction After the condensation reaction is completed, an excess of Na 2 BH 4 and dimethyl sulfoxide (DMSO) are added to continue the reaction, the reaction temperature is 0-10 ° C, the reaction time is l-6 h, and the product is further extracted and dried. The solution was rotary evaporated to obtain a carbon fiber surface modifier C.
  • DMSO dimethyl sulfoxide
  • the present invention necessites a method for preparing a modified carbon fiber by using the carbon fiber surface modifier, which comprises the following steps:
  • the carbon fiber surface modifier is dissolved in an organic solvent or water to form a modifier solution having a concentration of 1.2-2.4 wt%.
  • the carbon fiber is placed in the modifier solution for infiltration, and the carbon fiber is reacted with the modifier;
  • the resulting surface-modified carbon fibers are well suited for reinforcing polymers, particularly thermoplastics, and resins for preparing modified carbon fiber/resin composites. It is therefore necessary in the present invention to provide a method of preparing a composite material from the modified carbon fiber and resin.
  • the preparation method is as follows: The following weight percentage components are provided,
  • thermoplastic or thermosetting resin as a matrix component B, B: 60-95%;
  • the components A, B, and C were extruded into a water-cooled strand in a twin-screw extruder (ZSK 25, Wemer & Pfleiderer) for granulation.
  • Extruder heating zone 1-6 zone temperature control range 180-420 ⁇
  • resin and additive mixed main feed carbon fiber side feed
  • speed 100-200rpm capacity 4-20kg / hour.
  • the modified carbon fiber comprises: the carbon fiber in the national standard GB T26752-2011 is modified by the modifier of the invention.
  • the lipids include: PC, POM; PE, PP, ABS, SAN, PS PA, PBT, PET, PPO, LCP, TPU; PPSU, PPA, PEEK, PEI, PPS, PSU, PI; Thermosettingplastics-Epoxy .
  • the auxiliary agent comprises: a flame retardant, a toughening agent, a conductive agent, an antioxidant, a light stabilizer, a lubricant, a coloring agent, a nucleating agent, an antistatic agent, and a filler.
  • Aerospace industry used as missile heat protection and structural materials such as rocket nozzles, nose cones, large-area heat protection layers; satellite structures, antennas, solar fin base plates, satellite-rocket combined components; space shuttle noses, machines Parts such as the leading edge of the wing and the hatch; the measuring frame of the Hubble Space Telescope, solar panels and radio antennas.
  • the aviation industry is used as the main bearing structural material, such as the main wing, the empennage and the body; the secondary bearing members, such as the rudder, the landing gear, the aileron, the spoiler, the engine compartment, the fairing and the seat plate, etc.
  • the secondary bearing members such as the rudder, the landing gear, the aileron, the spoiler, the engine compartment, the fairing and the seat plate, etc.
  • Transportation is used as parts for automobile drive shafts, leaf springs, frames and brake pads; ships and marine engineering are used to manufacture fishing boats, torpedo boats, speedboats and patrol boats, as well as masts, navigation rods and casings for racing boats. And water-jetting; submarine cables, submarines, radomes, lifts and pipelines in deep-sea oil fields.
  • Biomedical and medical equipment such as artificial bones, teeth, ligaments, X-ray machine bed plates and film boxes.
  • Other materials such as electromagnetic shielding, electrode degree, acoustics, anti-wear, energy storage and anti-static have also been widely used.
  • the interlaminar shear strength of the material can be used to determine the interfacial bonding properties of carbon fiber with the resin matrix. It is verified that the functional groups in the macrocavity can chemically react with or form chemical bonds with functional groups such as oxygen-containing carboxyl groups, aldehyde groups, ketone groups and hydroxyl groups inherent on the carbon fiber surface. Adsorption on the surface of carbon fibers; also verified that the R3, R4 functional substituents of the species of the invention have good compatibility with a certain resin.
  • the carbon fiber is modified by a carbon fiber surface modifier to greatly improve the bonding force between the carbon fiber and the resin.
  • the activity of the surface of the carbon fiber is improved, and the interface property between the carbon fiber and the resin matrix is remarkably improved.
  • Example 1 is a comparison diagram of shear strength of a test composite material before and after modification in Example 1;
  • Example 2 is a comparison diagram of shear strength of a test composite material before and after modification in Example 2;
  • Fig. 3 is a graph showing the comparison of the shear strength of the test composite material before and after the modification in Example 3. Detailed ways
  • the invention discloses a carbon fiber surface modifier and a preparation method thereof, a modified carbon fiber prepared by a carbon fiber surface modifier, a modified carbon fiber preparation method, a composite material prepared by modifying a carbon fiber and a resin, and a preparation method of the composite material, and a preparation method thereof The application of composite materials.
  • a surface modification of carbon fiber the structural formula of which is as shown in formula (I):
  • R 2, R 2 ' include hydrogen, hydroxy, or C r C 3 alkyl;
  • R 3, R4 comprises a C r C ls ⁇ alkyl, C r C 18 embankment group, a hydroxyl group , amino, halogen, hydrogen, amide, ester, or siloxy, including hydrogen, hydroxy, amino, halogen, decyloxy.
  • the hydroxyl group, the modified carbon fiber improver has the structural formula:
  • the preparation method of the carbon fiber surface modifier is as follows.
  • reaction temperature is 0-70 ° C
  • reaction time is l-8h ;
  • the product obtained after the reduction reaction is further subjected to extraction, dried, and the solution is rotary-screwed to obtain a carbon fiber surface modifier C.
  • the carbon fiber surface modifier is used to prepare the modified carbon fiber as follows:
  • the carbon fiber surface modifier is dissolved in an organic solvent or water to form a modifier solution having a concentration of 1.2-2.4 wt%.
  • the carbon fiber is placed in the modifier solution for infiltration, and the carbon fiber is reacted with the modifier;
  • the fibers are unidirectionally arranged in the matrix of the composite; 3.
  • the carbon reference resin is formulated according to the ISO reference standard. Manufacturing conditions, sample specifications for composite samples. 4.
  • the carbon fiber defined in the composite material cannot be sheared, so the test composite material cannot be prepared using a twin-screw extruder.
  • Component 1 Modified carbon fiber;
  • Component 2 PA6 resin;
  • the modified carbon fiber has good interfacial properties in combination with a certain resin, and the R 3 and R 4 functional substituent pairs of the species of the present invention are also verified.
  • a certain resin has the characteristics of good compatibility.
  • the method for preparing a modified carbon fiber/resin composite material using modified carbon fiber and resin is as follows:
  • thermoplastic or thermosetting resin as a matrix component B, B: 60-95 wt% ;
  • the processing conditions can be arbitrary, the fiber is cut by a twin-screw extruder, the fibers are arranged disorderly in the resin, and an auxiliary agent (flame retardant, toughening agent, pigment) can be added.
  • auxiliary agent flame retardant, toughening agent, pigment
  • the temperature is controlled by extrusion in the extruder, and the strands are cut into small particles.
  • the particles are produced modified carbon fiber composite materials, namely: modified T700 PA6 composite material.
  • the composite materials obtained can be widely used in the production of aerospace equipment, transportation equipment, sports equipment, civil construction materials, daily necessities and medical equipment.
  • the carbon fiber surface modifier of the present invention comprises a large cavity, and the large cavity is composed of carbon, nitrogen, hydrogen and/or oxygen.
  • the 12-atom open-loop structure has a plurality of amino functional groups in the cavity, which can chemically react with or form hydrogen bonds with functional groups such as oxygen-containing carboxyl groups, aldehyde groups, ketone groups, and hydroxyl groups inherent on the surface of carbon fibers.
  • the R5 and the amino group chemically react with the oxygen-containing carboxyl group, the aldehyde group, the ketone group, and the hydroxyl group on the surface of the carbon fiber, and form a chemical bond therebetween, whereby the surfactant is firmly adsorbed on the surface of the carbon fiber through a chemical bond; or R5 and The amino group forms hydrogen bonds with the oxygen-containing carboxyl group, aldehyde group, ketone group, and hydroxyl group on the surface of the carbon fiber, and they are firmly bonded by van der Waals force.
  • the R3 and R4 functional substituent groups of the carbon fiber surface modifier have good compatibility with the resin selection, and they undergo chemical reaction and physical crosslinking with the molecular chain of the resin matrix in the hot working molten state.
  • the selection of a suitable modifier of the present invention can increase the interlaminar shear strength of the carbon fiber reinforced resin material by 9-30%, and the present invention can effectively improve the interfacial properties of the carbon fiber and the resin.
  • the carbon fiber surface modifier of the present invention the preparation method of the carbon fiber surface modifier, the modified carbon fiber prepared by the carbon fiber surface modifier, the preparation method of the modified carbon fiber, the modified carbon fiber and the resin are prepared in combination with the examples and the comparative examples.
  • the composite material, the method of preparing the composite material, and the application of the composite material are described in detail, but the embodiment of the invention is not limited thereto.
  • Preparation of carbon fiber surface modifier Add 1.5 mol of 1-dimethyl-1,2-diamine (A1) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 3, 5- Dihydroxysalicylaldehyde (0.2mol) in 300 mL ethanol solution (Bl), control the polymerization temperature of 55 °C, reflux for 6h, add 300 mL of DMSO solution, control the polymerization temperature 0 °C, then add 4 equivalents of Na 2 BH 4 , Stir, until the reaction solution is colorless, the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated.
  • A1 1-dimethyl-1,2-diamine
  • Carbon fiber surface modifier for preparing modified carbon fiber Dissolving carbon fiber surface modifier Cl with dimethyl sulfoxide (DMSO) and water, carbon fiber surface modifier C1 concentration is 1.2 wt%, for model T700 carbon fiber surface The infiltration modification is carried out, and the surface-modified carbon fiber is obtained after drying.
  • DMSO dimethyl sulfoxide
  • the composite material is prepared by using modified T700 carbon fiber and PA6, and the preparation method is as follows: carbon fiber modified by modifier II is used as reinforcing component A: 10wt% ; PA6 resin as matrix component B: 85wt%; processing aid as component C: 5wt% (N, bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)) Propionyl) hexamethylenediamine: lwt%, 2-(2H-benzotriazol-2)-4,6-bis(1-methylbenzophenethyl)phenol: lwt%, Licomont® CaV 102: lwt% , erucamide: 2wt%);
  • the components A, B and C were extruded in a twin-screw extruder (ZSK 25, Werner & Pfleiderer) by water-cooled granulation: resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1 Zone 6 (230 ⁇ 280.C), with a speed of 150 rpm and a capacity of 6kg/hour.
  • the composite materials of T700 carbon fiber and PA6 can be applied in the fields of automotive, medical, food processing, and chemical industry.
  • the specific components include: the motive part includes the air intake system and the fuel system, such as the engine cylinder cover and section. Valves, air filter housings, automotive air horns, automotive air conditioning hoses, cooling fans and their enclosures, inlet pipes, brake oil tanks and gluing, etc.
  • Body part zero The components are: car fenders, rear view frames, bumpers, dashboards, luggage racks, door handles, wiper brackets, seat belt buckles, various decorative parts in the car, and more.
  • In-car electrical appliances such as electronically controlled doors and windows, connectors, crisper boxes, cable ties, etc.
  • Preparation of carbon fiber surface modifier Add 1.5 mol of 1-dimethyl-1,2-diamine (A2) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 4,6- Dipropoxy salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B2), control the polymerization kettle temperature 55 ° C, reflux 6 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ⁇ , then add 4 equivalents of Na 2 BH 4 , Stir, until the reaction solution is colorless, the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated.
  • A2 1-dimethyl-1,2-diamine
  • the aqueous layer was extracted with CH 2 C1 2 , and the organic layer was combined, dried over anhydrous Na 2 SO 4 , allowed to stand, filtered, and evaporated to give a carbon fiber surface modifier C2.
  • the carbon fiber surface modifier C2 was white solid.
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C2 is dissolved in DMSO and water at a concentration of 1.2 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
  • the composite material is prepared by using modified T700 carbon fiber and PEEK, and the preparation method is as follows: providing modified carbon fiber as modified by formula (III) Component A: 10wt%; PEEK resin as matrix component B: 85wt% ; processing aid is component C: 5wt% (bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite: lwt %, 2-(2H-benzotriazol-2)-4,6-bis(1-methyl-1-phenylethyl)phenol: lwt%, Licomont NaV101: lwt%. erucamide: 2wt%) ;
  • the components A, B, and C were extruded in a twin-screw extruder (ZSK25, Werner & Pfleiderer) by water-cooled granulation: resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1-6 ( 330 ⁇ 420 °C), the speed is 200rpm, and the capacity is 8kg/hour.
  • ZSK25 Werner & Pfleiderer
  • water-cooled granulation resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1-6 ( 330 ⁇ 420 °C)
  • the speed is 200rpm
  • the capacity is 8kg/hour.
  • PEEK in the aerospace, medical, pharmaceutical and food processing industries, chemical industry, for the fabrication of gas analyzer structural components such as satellites, heat exchanger blades; chemical industry such as sleeve bearings, Sliding bearings, valve seats, seals, pump wear rings, solenoid valves, precision gears, pipes, etc.
  • a carbon fiber surface modifier and a preparation method thereof, the steps are as follows:
  • Preparation of carbon fiber surface modifier Add 1.5 mol of 1,1,2-tetramethyl-1,2-diamine (A3) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then drip Add 4-(dibutylamino)salicylaldehyde (0.2mol) in 300 mL ethanol solution (B3), control the polymerization temperature of 55 °C, reflux for 6 h, add 300 mL DMSO solution, control the polymerization temperature 0 °C Further, 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated.
  • A3 1,1,2-tetramethyl-1,2-diamine
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C3 is dissolved in DMSO and water at a concentration of 1.2 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
  • modified carbon fiber/resin composite material by modified carbon fiber and resin The composite material is prepared by using modified T700 carbon fiber and ABS, and the preparation method is as follows: providing modified carbon fiber modified by formula (IV) As reinforcing component A: 10wt%; ABS resin as matrix component B: 85wt%; processing aid as component C: 5wt% (Igganox® 245: 1 wt%, 2- (2H-benzotriazole-2) -4,6-bis(1-methyl-1-phenylethyl)phenol: lwt%, Licomont
  • the components A, B and C were extruded in a twin-screw extruder (ZSK25, Werner & Pfleiderer) by water-cooled granulation: resin and auxiliary mixed main feed, carbon fiber side feed, extruder heating zone 1-6 (180 ⁇ 220 °C), the speed is lOOrpm, the capacity is 4kg/hour.
  • Applications for this composite include: commercial machinery, electronic components, communication facilities, personal computers, electrical appliances, automotive parts, showers, luggage, faucets and other household items. Such as large appliances, cars, computer casings and accessories.
  • the composite material obtained by modifying the carbon fiber and the resin, and the composite material prepared by the unmodified carbon fiber and the resin are compared with each other, and it is known that the carbon fiber surface modifier is passed.
  • Modification of carbon fiber greatly enhances the bonding force between carbon fiber and resin.
  • the modified carbon fiber can be widely used as a thermoplastic resin such as PA, PU, PEEK, or polyolefin to prepare a carbon fiber reinforced composite material having excellent mechanical properties.
  • the following Examples 4-17 focus on the preparation of the carbon fiber surface modifier, and the method for preparing the modified carbon fiber by using the prepared carbon fiber modifier to fully support the general structure of the carbon fiber surface modifier in the present invention;
  • the method for preparing composite materials of carbon fiber and resin and the verification and verification are not described in detail.
  • the carbon fiber surface modifier and the modified carbon fiber prepared by the modifier can be selected according to the need to prepare a composite material between the resin and the modified carbon fiber.
  • the modified carbon fiber and composite material obtained can measure the interlaminar shear strength (ILSS) of the composite before and after carbon fiber modification at 20 °C according to the national building materials industry standard: JC T 773-2010/ISO 14130: 1997. It is known that the shear strength of the modified carbon fiber is greatly improved compared to the shear strength of the unmodified carbon fiber.
  • ILSS interlaminar shear strength
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-dimethyl-1,2-diamine (A4) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 4 - octadecyl salicylaldehyde (0.2mol) in 300 mL ethanol solution (B4), control the polymerization temperature of 55 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization temperature of 0 ° C, then add 4 equivalents of Na 2 BH 4 , stir until anti The reaction is completed until the liquid is colorless. 500 mL of water was added to the reaction system, and the mixture was separated.
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C4 is dissolved in DMSO and water at a concentration of 1.3 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-molar, 2-diamine (A5) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then add 4-pentyl-2-hydroxy- Salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B5), control the polymerization temperature of the reactor at 65 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 ° C, then add 4 equivalents of Na 2 BH4, stir, The reaction was completed until the reaction solution was colorless. 500 mL of water was added to the reaction system, and the mixture was separated.
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier using a DMSO and water to dissolve a carbon fiber surface modifier C5 at a concentration of 1.6 wt%, infiltrating the surface of the T700 carbon fiber, and drying the surface-modified carbon fiber.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 1,1,2-tetramethyl-1,2-diamine (A6) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then drip Add 1-formyl-2-hydroxy-4-phenylethylethyl ester (0.2 mol) in 300 mL ethanol solution (B6), control the polymerization kettle temperature 60 ° C, reflux for 8 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ° C, another 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the liquid was separated.
  • A6 1,1,2-tetramethyl-1,2-diamine
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C6 is dissolved in DMSO and water at a concentration of 1.5 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-dimethyl-1,2-diamine (A7) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 5 -formyl-6-hydroxy-phenylacetic acid methyl ester (0.2mol) in 300 mL ethanol solution (B7), control the polymerization kettle temperature 55 ° C, reflux for 6 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ° C, another 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated.
  • Formula (VIII) Method for preparing modified carbon fiber by carbon fiber surface modifier: The carbon fiber surface modifier C7 is dissolved in DMSO and water at a concentration of 1.3 wt%, and the surface of T700 carbon fiber is immersed and modified, and the surface modified carbon fiber is obtained after drying.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-dimethyl-1,2-diamine (A8) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 3 - Jiuhexylbenzaldehyde (0.2mol) in 300 mL ethanol solution (B8), control the polymerization temperature of 55 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization temperature of 0 ° C, then add 4 equivalents Na 2 BH 4 was stirred until the reaction mixture was colorless and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated.
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C8 is dissolved in DMSO and water at a concentration of 1.2 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-dimethyl-1,2-diamine (A9) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 3 -formyl-4-hydroxy-phenylpropanamide (0.2mol) 300mL ethanol solution (B9), control the polymerization temperature of the reactor at 60 °C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 V, then add 4 equivalents of Na 2 BH 4 , stir , until the reaction solution is colorless, the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated.
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C9 is dissolved in DMSO and water at a concentration of 1.7 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier using a DMSO and water to dissolve a carbon fiber surface modifier C10 at a concentration of 1.9 wt%>, infiltrating the surface of the T700 carbon fiber, and drying the surface-modified carbon fiber.
  • the carbon fiber surface modifier is used for preparing the modified carbon fiber: the carbon fiber surface modifier C11 is dissolved in DMSO and water at a concentration of 2.4 wt%, and the surface of the T700 carbon fiber is infiltrated and modified, and the surface modified carbon fiber is obtained after drying.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 2-dimethyl-1,2-diamine (A12) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add B12 dropwise. (0.2mol) 300mL ethanol solution, control the polymerization temperature of 55 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 V, then add 4 equivalents of Na 2 B, stir until the reaction solution The color is complete and the reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated.
  • A12 2-dimethyl-1,2-diamine
  • Method for preparing modified carbon fiber by carbon fiber surface modifier The carbon fiber surface modifier C12 is dissolved in DMSO and water at a concentration of 2.2 wt%, and the surface of T700 carbon fiber is immersed and modified, and the surface modified carbon fiber is obtained after drying.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 1-methyl-1,2-diamine (A13) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add B13 (0.2 mol). 300 mL ethanol solution, control the polymerization kettle temperature 55 ° C, reflux for 6 h, add 300 mL DMSO solution, control the polymerization kettle temperature 0 ° C, then add 4 equivalents of Na 2 BH 4 , stir until the reaction liquid is colorless The reaction is completed. 500 mL of water was added to the reaction system, and the mixture was separated.
  • A13 1-methyl-1,2-diamine
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier using a DMSO and water to dissolve a carbon fiber surface modifier C13 at a concentration of 2.2 wt%, infiltrating the surface of the T700 carbon fiber, and drying the surface-modified carbon fiber.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 1-ethyl-1,2-diamine (A14) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then add 4-(N) , N-diethylhydroxyamino)-salicylaldehyde (0.2mol) in 300 mL ethanol solution (B14), control the polymerization temperature of 70 ° C, reflux for 6 h, add 300 mL of DMSO solution, control the polymerization kettle temperature 0 V Further, 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated.
  • A14 1-ethyl-1,2-diamine
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C14 is dissolved in DMSO and water at a concentration of 2.3 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 0.1-dimethyl-1,2-diamine (A15) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and add 4 - (N, N-di-2-methoxy-ethylamino)-salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B15), control the temperature of the polymerization vessel at 65 ° C, reflux for 6 h, add 300 mL The DMSO solution controls the temperature of the polymerization vessel to 0. C, another 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed.
  • A15 0.1-dimethyl-1,2-diamine
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C15 is dissolved in DMSO and water at a concentration of 2.1 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 1-methyl-1,2-diamine (A16) to a 1.5 L polymerization vessel, dissolve it by adding 300 mL of ethanol, and then add 4- (2) -ethyl)-hexaneoxy-3-hydroxy salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B16), control the temperature of the polymerization vessel at 67 ° C, reflux for 6 h, then add 300 mL of DMSO solution to control the polymerization. The temperature of the kettle was 0 ° C, and 4 equivalents of Na 2 BH 4 was added thereto, and the mixture was stirred until the reaction mixture was colorless, and the reaction was completed.
  • A16 1-methyl-1,2-diamine
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C16 is dissolved in DMSO and water at a concentration of 2.1 wt%, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.
  • Preparation of a carbon fiber surface modifier Add 1.5 mol of 1,1,2,2-tetramethyl-1,2-diamine (A17) to a 1.5 L polymerization vessel, and dissolve it by adding 300 mL of ethanol. Then add 3, 4-dimethoxy salicylaldehyde (0.2 mol) in 300 mL ethanol solution (B17), control the temperature of the polymerization vessel at 70 ° C, reflux for 6 h, then add 300 mL of DMSO solution to control the polymerization kettle. At a temperature of 0 ° C, 4 equivalents of Na 2 BH 4 was added and stirred until the reaction mixture was colorless, and the reaction was completed. 500 mL of water was added to the reaction system, and the mixture was separated.
  • a method for preparing a modified carbon fiber by using a carbon fiber surface modifier a carbon fiber surface modifier C17 is dissolved in DMSO and water at a concentration of 1.5 wt%>, and the surface of the T700 carbon fiber is infiltrated and modified to obtain a surface-modified carbon fiber.

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Abstract

La présente invention concerne un modificateur de surface pour fibre de carbone, une fibre de carbone modifiée, des composites, et des procédés de préparation correspondants. La formule développée générale du modificateur de surface pour fibre de carbone est telle que représentée par la formule (I): dans la formule (I), R1, R2, R1' et R2' représentent respectivement et indépendamment hydrogène, hydroxyle ou l'alkyle C1-C3; R3 et R4 représentent respectivement et indépendamment alkyle C1-C18, alcoxyle C1-C18, hydroxyle, amino, halogène, hydrogène, amide, ester, ou siloxyle, R3, R4 ne représentant pas simultanément hydrogène; et R5 représente hydrogène, hydroxyle, amino, halo ou alkoxyle. Le modificateur de surface pour fibre de carbone selon la présente invention étend le champ d'application des fibres de carbone. La fibre de carbone modifiée peut être largement utilisée dans des résines thermoplastiques telles que PA, ABS, PEEK, la polyoléfine, et pour la préparation de matériau composite de résine de fibres de carbone présentant d'excellentes propriétés mécaniques.
PCT/CN2013/076655 2012-06-04 2013-06-03 Modificateur de surface pour fibre de carbone, fibre de carbone modifiée, matériau composite et procédés de préparation associés WO2013182023A1 (fr)

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CN115092927B (zh) * 2022-07-15 2023-06-20 安徽工程大学 碳纤维复材树脂基活性炭及其制备方法
CN117304687B (zh) * 2023-11-29 2024-02-23 江苏巨力特塑业科技股份有限公司 一种改性碳纤维复合材料及其制备方法

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