CN106811823B - Modified phenolic resin fiber and preparation method and application thereof - Google Patents
Modified phenolic resin fiber and preparation method and application thereof Download PDFInfo
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- CN106811823B CN106811823B CN201611179317.1A CN201611179317A CN106811823B CN 106811823 B CN106811823 B CN 106811823B CN 201611179317 A CN201611179317 A CN 201611179317A CN 106811823 B CN106811823 B CN 106811823B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
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Abstract
The invention relates to a preparation method of modified phenolic resin fibers, which comprises the following steps: (1) mixing graphene substances and polymers, and stirring to obtain a mixed solution; (2) compounding the graphene substance with phenolic resin in the form of the mixed solution in the step (1) to obtain modified thermoplastic phenolic resin; (3) and (3) purifying the modified thermoplastic phenolic resin obtained in the step (2), carrying out melt spinning to obtain phenolic fiber precursor, and curing and crosslinking to obtain the modified phenolic resin fiber. According to the invention, graphene and phenolic resin are compounded to obtain modified phenolic resin, and the modified phenolic fiber is obtained after spinning. According to the invention, the problem that the graphene is easy to agglomerate and has poor dispersibility when being added singly is solved by innovatively adding the phenolic resin in a form of mixing the graphene and the polymer, and the strength, toughness, electrical property and the like of the phenolic fiber are improved.
Description
Technical Field
The invention belongs to the field of phenolic resin modification, and relates to a modified phenolic resin fiber and a preparation method thereof.
Background
The phenolic fiber is a fiber with a three-dimensional reticular structure obtained by spinning and curing phenolic resin, and is firstly developed and succeeded by American carborundum company in 1968 [ J.Economy, R.A.Clark.fibers from Nocolacs [ P ]. USPat.3650102,1968 ]. The phenolic fiber has the characteristics of outstanding high temperature resistance, flame resistance, corrosion resistance, melting resistance and the like, has high extreme oxygen index and has self-extinguishing property; the shrinkage rate is small during combustion, and the smoke is less; based on the excellent performances, the research on the phenolic fibers is highly concerned, and the further research and development of the phenolic fibers are driven; the phenolic fiber spinning process generally takes thermoplastic phenolic resin as a raw material, obtains protofilaments through melt spinning, and is formed by cross-linking and curing through formaldehyde, hydrochloric acid and other solutions; meanwhile, because the residual carbon content of the phenolic fiber is high, the escape of harmful gas is less, the phenolic fiber can be further activated into carbon fiber, and the phenolic fiber can be widely applied to various fields of heat resistance, adsorption and the like. With the development of industries such as aerospace, national defense and the like, the application field of the phenolic fiber is continuously expanded, and the pure phenolic fiber cannot meet the increasingly expanded market demand. The preparation performance is excellent, the application field is wide, and especially the high-performance phenolic fiber with more excellent heat resistance, strength and toughness becomes the key point of the field.
The structure of the phenolic fiber can be exemplarily expressed as:
as can be seen from the above formula, because the benzene ring density is high, and only methylene is connected between two adjacent benzene rings, the phenolic fiber is very brittle, so that the phenolic fiber has low toughness and small elongation at break, phenolic hydroxyl is easy to oxidize, the heat resistance, oxidation resistance and alkali resistance of the phenolic fiber are influenced to a certain extent, and the performance of the product is reduced due to the defects, and the use is limited to a certain extent. Therefore, the modification of the phenolic fiber is carried out, the structural defects of the phenolic fiber are reduced, and the method is a fundamental method for improving the high strength, the toughness and the heat resistance of the phenolic fiber.
There is a need in the art to develop a phenolic fiber having excellent heat resistance, high strength and high toughness.
Disclosure of Invention
Aiming at the defects of poor mechanical property, low mechanical strength, poor heat resistance and the like of the phenolic fiber in the prior art, the invention aims to provide a preparation method of a modified phenolic resin fiber, which comprises the following steps:
(1) mixing graphene substances and polymers, and stirring to obtain a mixed solution;
(2) compounding the graphene substance with phenolic resin in the form of the mixed solution in the step (1) to obtain modified thermoplastic phenolic resin;
(3) and (3) purifying the modified thermoplastic phenolic resin obtained in the step (2), carrying out melt spinning to obtain phenolic fiber precursor, and curing and crosslinking to obtain the modified phenolic resin fiber.
The graphene oxide is used as a precursor or a derivative of graphene, the performance of the graphene oxide is not inferior to that of graphene, and the surface of the graphene oxide contains rich oxygen-containing functional groups, so that the active sites can be improved for the further chemical reaction of the graphene oxide; the graphene oxide can be subjected to co-curing reaction with resin or form a partial interpenetrating network structure embedded polymer intermediate group, has good compatibility, does not have the condition of phase separation, increases the spinnability and mechanical property of the phenolic fiber, and improves the electrical property of the phenolic fiber.
The graphene substance is doped into the phenolic resin in a form of mixing the graphene substance and the polymer, and weak bonds and actions (such as Van der Waals force and the like) exist between the graphene substance and the polymer, so that the agglomeration of the graphene substance is effectively prevented, and the uniform dispersion of the graphene substance in the phenolic resin is realized.
In addition, the addition of the polymer during the preparation of the phenolic resin can also omit the addition of the polymer in the subsequent spinning step for improving spinnability.
The polymer of the present invention is not particularly limited, and any polymer capable of increasing spinnability may be used herein.
Preferably, in the process of compounding the graphene-like substance with the phenolic resin, the mass of the graphene-like substance is 0.01 to 15wt% of the phenolic resin, such as 0.05 wt%, 0.1 wt%, 0.6 wt%, 0.9 wt%, 2wt%, 3.5 wt%, 4.2 wt%, 4.6 wt%, 5.8 wt%, 7 wt%, 8 wt%, 9 wt%, 10wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, etc., preferably 0.01 to 10wt%, more preferably 0.01 to 5wt%, particularly preferably 0.01 to 2wt%, most preferably 0.1 to 1 wt%.
Preferably, the method of compounding the graphene-based material with the phenolic resin in the form of the mixed solution in the step (1) includes the following steps:
the first method is as follows: and (2) adding the mixed solution obtained in the step (1) into a synthetic monomer of the phenolic resin, and carrying out polymerization reaction of the phenolic resin together with the synthetic monomer.
In the second mode, the mixed solution in the step (1) is added in the polymerization reaction of the phenolic resin.
In the third embodiment, the polymerization monomer of the phenol resin is subjected to a polymerization reaction of the phenol resin, and the mixed solution in the step (1) is added to the obtained phenol resin.
In other words, the graphene-based material of the present invention may be added before (during monomer synthesis), during (after partial prepolymerization) or after (after phenolic resin is obtained) phenolic resin synthesis in the form of the mixed solution of step (1).
Of course, the graphene-like substance according to the present invention may be added in any 1 or at least 2 combinations of the first, second or third modes, for example, both at the time of monomer synthesis and at the time of prepolymerization, or both at the time of monomer synthesis and in the phenolic resin obtained after the synthesis, and the like.
Preferably, the mixed solution is added dropwise at a rate of 0.5-2mL/min, such as 0.6mL/min, 0.9mL/min, 1.3mL/min, 1.6mL/min, 1.9mL/min, and the like.
Preferably, the mixed solution of step (1) includes a liquid polymer in which a graphene-based substance is dispersed;
alternatively, the mixed solution includes a solvent in which a polymer and a graphene-based substance are dispersed.
Preferably, in the solvent in which the polymer and the graphene-based material are dispersed, the polymer and the graphene-based material undergo partial or complete grafting reaction.
Preferably, the polymer comprises any 1 or combination of at least 2 of rubber, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol, preferably polyvinyl alcohol.
Illustratively, the combination of polymers includes a combination of polyacrylamide and polyacrylic acid, a combination of polyvinylpyrrolidone and polyethylene glycol, a combination of polyvinyl alcohol and polyacrylic acid, and the like.
The rubber is one or more of nitrile rubber, styrene butadiene rubber and natural rubber.
Preferably, the solvent comprises a combination of any 1 or at least 2 of ethanol, water, ethylene glycol, DMF, NMP or acetone; ethanol or water is preferred.
The solvent of the graphene-based material solution may be selected from various solvents as long as the graphene-based material has high solubility and does not have an excessive adverse effect on the polymerization reaction, and for example, the solvent is one or more selected from water, ethanol, ethylene glycol, DMF, NMP and acetone, and ethanol or water is preferred.
Preferably, when the mixed solution is a liquid polymer in which a graphite-based substance is dispersed, the mass ratio of the graphene-based substance to the polymer is 1:0.01 to 10, for example, 1:0.1, 1:0.3, 1:0.6, 1:0.9, 1:1.3, 1:3, 1:5, 1:6, 1:7, 1:8, 1:9, and the like.
Preferably, when the mixed solution is a solvent in which a polymer and a graphene-based material are dispersed, the concentration of the polymer is 10 to 20 wt%, such as 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, etc., and the concentration of the graphene-based material is 15mg/g or less, preferably 1 to 10mg/g, preferably 3 to 5 mg/g;
preferably, the stirring time in step (1) is 1min to 2h, such as 5min, 20min, 36min, 50min, 65min, 80min, 90min, 110min and the like.
Preferably, the graphene-based material comprises any 1 or a mixture of at least 2 of graphene, biomass graphene, graphene oxide, and graphene derivatives including element-doped graphene.
Preferably, the graphene derivative comprises any 1 or combination of at least 2 of element-doped graphene or functionalized graphene species.
Preferably, the element-doped graphene includes any 1 or a combination of at least 2 of metal-doped graphene or non-metal element-doped graphene.
The metal-doped metal element comprises any 1 or at least 2 of potassium, sodium, gold, silver, iron, copper, nickel, chromium, titanium, vanadium or cobalt.
The nonmetal elements of the nonmetal element doped graphene comprise any 1 or at least 2 of nitrogen, phosphorus, silicon, boron or oxygen.
Preferably, the non-metal element doped graphene includes any 1 or a combination of at least 2 of nitrogen-doped graphene, phosphorus-doped graphene, or sulfur-doped graphene.
Preferably, the functionalized graphene comprises graphene grafted with a functional group.
Preferably, the functionalized graphene comprises graphene grafted with any 1 or a combination of at least 2 of hydroxyl, carboxyl or amino groups.
Preferably, the hydroxy group comprises-R1-OH, said R1Including hydrocarbyl groups, preferably including any 1 or combination of at least 2 of methyl, ethyl, propyl, butyl, pentyl, hexyl, ethenyl, propenyl groups.
Preferably, the carboxyl group comprises-R2-COOH, said R2Including hydrocarbyl groups, preferably including any 1 or combination of at least 2 of methyl, ethyl, propyl, butyl, pentyl, hexyl groups.
Preferably, the amino group comprises R3-NH3Said R is3Including an alkane group, preferably including any 1 or a combination of at least 2 of methyl, ethyl, propyl, butyl, pentyl, hexyl.
Preferably, the polymerization reaction of the phenolic resin comprises a prepolymerization reaction and a polycondensation reaction which are sequentially carried out.
Preferably, the temperature of the prepolymerization reaction is 60-80 ℃, such as 62 ℃, 68 ℃, 73 ℃, 78 ℃ and the like, and the reaction time is 0.5-5 h, such as 0.6h, 0.8h, 1h, 2h, 3h, 4h and the like.
Preferably, the temperature of the polycondensation reaction is 80-90 ℃, such as 82 ℃, 83 ℃, 85 ℃, 88 ℃ and the like, and the reaction time is 0.5-5 h, such as 0.6h, 0.8h, 1h, 2h, 3h, 4h and the like.
In the polymerization reaction of the phenolic resin, the molar ratio of the phenol monomer in terms of hydroxyl group, the aldehyde monomer in terms of aldehyde group and the catalyst is preferably 1 (0.7-1) to (0.005-0.05), such as 1:0.8:0.008, 1:0.9:0.01, 1:0.8:0.02, 1:0.9:0.03, 1:0.8:0.04, and the like.
Preferably, the acidic catalyst preferably comprises any 1 or a combination of at least 2 of hydrochloric acid, oxalic acid, acetic acid or sulfuric acid.
Preferably, the phenolic compound comprises phenol and derivatives thereof, preferably any 1 or a combination of at least 2 of phenol, cresol, xylenol, naphthol, alkyl substituted phenol, alkyl substituted naphthol, bisphenol a or bisphenol F;
preferably, the aldehyde compound comprises formaldehyde and derivatives thereof, preferably a combination of any 1 or at least 2 of formaldehyde, acetaldehyde or furfural.
As one of the preferable technical proposal, the preparation method of the modified phenolic resin fiber comprises the following steps:
(a 1') dispersing a graphene-based material in a solvent to obtain a graphene-based material dispersion liquid; dispersing a polymer in a solvent to obtain a polymer dispersion;
(a1) mixing the graphene substance dispersion liquid obtained in the step (a 1') with the polymer dispersion liquid, and stirring to obtain a mixed liquid of the graphene substance and the polymer;
(a2) adding the mixed solution obtained in the step (a1) into a polymerization monomer of phenolic resin in a dropwise manner, carrying out polymerization reaction on the thermoplastic phenolic resin to obtain a reaction solution, and purifying to obtain modified phenolic resin;
(a3) and carrying out melt spinning on the phenolic resin to obtain phenolic fiber precursor, and curing and crosslinking to obtain the modified phenolic resin fiber.
As a second preferred technical solution, the method for preparing the modified phenolic resin fiber of the present invention comprises the following steps:
(b 1') dispersing a graphene-based material in a solvent to obtain a graphene-based material dispersion liquid; dispersing a polymer in a solvent to obtain a polymer dispersion;
(b1) mixing the graphene substance dispersion liquid obtained in the step (b 1') with the polymer dispersion liquid, and stirring to obtain a mixed liquid of the graphene substance and the polymer;
(b2) reacting a phenolic compound with an aldehyde compound for a period of time, adding the mixed solution obtained in the step (b1) into the reaction solution, reacting to obtain a reaction solution, and purifying to obtain a modified phenolic resin;
(b3) carrying out melt spinning on the phenolic resin to obtain phenolic fiber protofilaments, and then curing and crosslinking to obtain modified phenolic resin fibers;
as a third preferred technical solution, the preparation method of the modified phenolic resin fiber of the present invention comprises the following steps:
(c 1') dispersing the graphene-based material in a solvent to obtain a graphene-based material dispersion liquid; dispersing a polymer in a solvent to obtain a polymer dispersion;
(c1) mixing the graphene substance dispersion liquid obtained in the step (c 1') with the polymer dispersion liquid, and stirring to obtain a mixed liquid of the graphene substance and the polymer;
(c2) adding the mixed solution obtained in the step (c1) into phenolic resin to obtain modified phenolic resin;
(c3) and carrying out melt spinning on the phenolic resin to obtain phenolic fiber protofilaments, and then curing and crosslinking to obtain the modified phenolic resin fibers.
The phenolic resin of the present invention is not particularly limited, and may include a reaction solution obtained by completely reacting ① phenolic compounds with aldehyde compounds, and ② finished phenolic resin.
The second object of the present invention is to provide a modified phenolic resin fiber obtained by the method for producing a modified phenolic resin fiber according to the first object.
The third object of the present invention is to provide a use of the modified phenolic resin fiber described in the second object as any 1 or a combination of at least 2 of a reinforcing material, a flame-retardant and heat-insulating material, a thermal insulating material, a cushioning material, a phenolic-based carbon fiber, and an electrode material.
The invention also provides an electrode composite material which is characterized in that the prepared phenolic resin fiber is obtained by carbonization.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, graphene and phenolic resin are compounded to obtain modified phenolic resin, and the modified phenolic fiber is obtained after spinning. According to the invention, the problem that the graphene is easy to agglomerate and has poor dispersibility when being added singly is solved by innovatively adding the phenolic resin in a form of mixing the graphene and the polymer, and the strength, toughness and electrical properties of the phenolic fiber are improved.
Particularly, when the graphene substance is graphene oxide and the polymer is polyvinylpyrrolidone PVA, the graphene oxide can be co-cured with the phenolic resin in a uniformly dispersed state or form an inter-transmission network in the synthesis process of the phenolic resin, so that the effects of improving the toughness of the phenolic resin, the tensile strength of 159-330 MPa, the elongation of 6.7-20%, and the strength and heat resistance are realized.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the following examples, the ratio of phenol, aldehyde and catalyst is the molar ratio of the phenol monomer in terms of hydroxyl group, the aldehyde monomer in terms of aldehyde group and the catalyst.
The graphene used in all of the following examples and comparative examples was commercially available HX-G graphene;
the graphene oxide is obtained by ultrasonically dispersing commercially available SE2430 graphite oxide.
The carboxylated graphene oxide, the biomass graphene and the oxidized biomass graphene can be prepared by the following methods, but are not limited to the following methods, and can also be prepared by the methods of graphene and graphene oxide in the prior art, or can also be directly prepared by the commercially available graphene and graphene oxide.
The commercially available biomass graphene is prepared from biomass graphene produced by the Jinan Shengquan group or prepared by the preparation example 2.
Preparation example 1: carboxylated graphene oxide
Ultrasonically dispersing 100mg of graphite oxide in 100ml of water to obtain a 1mg/ml graphene oxide aqueous solution, then adding 6g of sodium hydroxide and 5g of chloroacetic acid, ultrasonically treating for 3h to convert epoxy groups and hydroxyl groups on the surface of the graphene oxide into carboxyl groups, filtering while hot to remove impurities, and then carrying out vacuum drying at 65 ℃ to obtain the carboxylated graphene oxide.
Preparation example 2: biomass graphene
Firstly, preparing cellulose:
(1) crushing wheat straws, pretreating, cooking the treated wheat straws by using organic acid liquor of formic acid and acetic acid with total acid concentration of 80 wt%, wherein the mass ratio of acetic acid to formic acid in the organic acid liquor is 1:12, adding hydrogen peroxide (H2O2) accounting for 1wt% of the raw materials of the wheat straws as a catalyst before adding the raw materials, controlling the reaction temperature at 120 ℃, reacting for 30min, and carrying out first solid-liquid separation on the obtained reaction liquid, wherein the solid-liquid mass ratio is 1: 10;
(2) adding organic acid liquor of formic acid and acetic acid with the total acid concentration of 75 wt% into the solid obtained by the first solid-liquid separation for acid washing, wherein hydrogen peroxide (H2O2) accounting for 8 wt% of the wheat straw raw material is added into the organic acid liquor with the total acid concentration of 75 wt% as a catalyst, the mass ratio of the acetic acid to the formic acid is 1:12, the temperature is controlled at 90 ℃, the washing time is 1H, the solid-liquid mass ratio is 1:9, and performing second solid-liquid separation on the reaction liquid;
(3) collecting the liquid obtained by the first solid-liquid separation and the second solid-liquid separation, evaporating at 120 ℃ and 301kPa until the liquid is evaporated to dryness, condensing and refluxing the obtained formic acid and acetic acid vapor to the reaction kettle in the step (1) to be used as cooking liquid for the cooking in the step (1);
(4) collecting the solid obtained by the second solid-liquid separation, washing with water, controlling the washing temperature to be 80 ℃, and the concentration of the washed pulp to be 6 wt%, and carrying out the third solid-liquid separation on the obtained washed pulp;
(5) collecting liquid obtained by the third solid-liquid separation, and performing water-acid rectification to obtain mixed acid liquid which is reused in the reaction kettle in the step (1) and used as cooking liquid for cooking in the step (1), and reusing the obtained water as washing water in the step (5);
(6) and collecting the solid obtained by the third solid-liquid separation and screening to obtain the required fine pulp cellulose.
Step two, preparing graphene by taking the cellulose prepared above as a raw material:
(1) mixing cellulose and ferrous chloride according to the mass ratio of 1:1, stirring at 150 ℃ for catalytic treatment for 4 hours, and drying until the moisture content of a precursor is 10wt% to obtain the precursor;
(2)N2in the atmosphere, heating the precursor to 170 ℃ at the speed of 3 ℃/min, preserving heat for 2h, then, programming to 400 ℃, preserving heat for 3h, then, heating to 1200 ℃, and preserving heat for 3h to obtain a crude product; the temperature rising rate of the temperature programming is 15 ℃/min;
(3) and (3) washing the crude product with 10% sodium hydroxide solution and 4 wt% hydrochloric acid at 55-65 ℃, and washing with water to obtain the biomass graphene.
Preparation example 3: oxidized biomass graphene
Due to the existence of a porous structure, the sheet layer of the biomass graphene is in an open state relative to graphite, so that the oxidation condition is weaker than that of graphite. The specific implementation process is as follows:
mixing 2g of biomass graphene and 30mL of concentrated sulfuric acid in a reactor, stirring for 10min under the ice-water bath condition, gradually adding 7g of potassium permanganate, controlling the temperature to be not higher than 35 ℃, continuing stirring for 2h under the normal temperature condition after the potassium permanganate is added, heating to 40 ℃, reacting for 30min, adding 30 wt% hydrogen peroxide of about 5mL in volume, changing the color of the solution into golden yellow, adding 150mL of distilled water for diluting, filtering the reaction solution while hot, respectively washing with 4mL of dilute hydrochloric acid with the mass fraction of 10% and 100mL of deionized water for 2-3 times, centrifuging, and spray-drying slurry to obtain oxidized biomass graphene.
Example 1
A preparation method of modified phenolic fiber comprises the following steps:
(1) adding the graphene oxide dispersion liquid into a polyvinyl alcohol aqueous solution (the concentration of the polyvinyl alcohol aqueous solution is 15 wt%), and stirring to obtain a mixed solution, wherein the concentration of graphene oxide in the mixed solution is 10 mg/g;
wherein the molar ratio of the prepolymer of the phenolic resin to the polymer PVA is 1:0.05 in terms of aldehydes;
(2) adding phenol, formaldehyde and oxalic acid into a four-neck flask according to the molar ratio of 1:0.8:0.05, heating at 70 ℃, stirring, refluxing for 2 hours, adding the mixed solution obtained in the step (1), heating to 85 ℃, continuing to react for 3 hours, and stopping heating and stirring;
(3) adding ethanol, distilling by using steam, removing free phenol, purifying, carrying out melt spinning on the obtained high-purity resin at 130 ℃ and 0.2MPa, drafting to obtain nascent phenolic fiber, putting the nascent phenolic fiber into a coagulating bath for solidification, wherein the content of formaldehyde, the content of hydrochloric acid and the content of water in the coagulating bath are respectively 10%, 15% and 75%, the temperature is 80-100 ℃, the heating rate is 10-20 ℃/h, then keeping the temperature constant, solidifying for 1-2 h, washing with water, and drying to obtain the graphene modified phenolic fiber.
Wherein the addition amount of the graphene oxide is 0.5 percent of that of the phenolic resin product.
Example 2
The graphene-modified phenolic fiber is prepared by replacing graphene oxide with carboxylated graphene oxide and using the same amount and conditions as those in example 1.
Example 3
The difference from example 1 is only that graphene oxide is replaced by graphene, and other amounts and conditions are the same, so that the graphene modified phenolic fiber is prepared.
Example 4
The difference from the embodiment 1 is only that graphene oxide is replaced by biomass graphene, and other using amounts and conditions are the same, so that the graphene modified phenolic fiber is prepared.
Example 5
The difference from the example 1 is only that graphene oxide is replaced by oxidized biomass graphene, and other using amounts and conditions are the same, so that the graphene modified phenolic fiber is prepared.
Examples 6 to 9
Compared with the example 1, the difference is only that the amount of the graphene oxide is different, and the addition amount of the graphene oxide is 0.01%, 1%, 10% and 15% of the phenolic resin product.
Examples 10 to 12
The difference from example 1 is only that the concentrations of graphene oxide in the mixed solution were 1mg/g, 5mg/g, and 15mg/g, respectively.
Examples 14 to 16
Examples 14 to 16 differ from example 1 only in the solvents used for the ultrasonic dispersion of graphene oxide, which are ethanol, DMF, and acetone.
Examples 17 to 22
The difference between examples 17 to 22 and example 15 (the solvent is DMF) is that polyvinyl alcohol is replaced by polyvinylpyrrolidone, polyethylene glycol, nitrile rubber, styrene butadiene rubber, polyurethane, and natural rubber, and the other amounts and conditions are the same, so as to obtain the graphene modified phenolic fiber. The polyvinyl alcohol has good effect, the rubber is relatively poor, and the others are similar to the polyvinyl alcohol.
Example 23
The difference from example 1 is that the kinds of phenol and aldehyde are different, that is, step (2) is different,
(2) adding phenol, furfural and oxalic acid into a four-neck flask according to the molar ratio of 1:0.8:0.05, heating, stirring and refluxing for 2h at 70 ℃, adding the mixed solution obtained in the step (1), heating to 85 ℃, continuing to react for 3h, and stopping heating and stirring.
The other steps are the same as in example 1.
Example 24
Compared with the example 1, the proportion of the phenolic resin and the PVA is different,
in the step (1), PVA (based on aldehyde substances, the molar ratio of the prepolymer of the phenolic resin to the polymer PVA is 1:0.01) is added into the phenolic resin prepolymer.
Example 25
Compared with the example 1, the proportion of the phenolic resin and the PVA is different,
in the step (1), PVA (based on aldehyde substances, the molar ratio of the prepolymer of the phenolic resin to the polymer PVA is 1:0.1) is added into the phenolic resin prepolymer.
Comparative example 1
The only difference from example 1 is that step (1) is not performed, and a mixed solution of graphene oxide and an aqueous polyvinyl alcohol solution is not added in step (2).
Comparative example 2
The only difference from example 1 is that step (1) is not performed, and the addition of the mixed solution of graphene oxide and the polyvinyl alcohol aqueous solution in step (2) is replaced by the addition of only the graphene oxide aqueous solution.
Comparative example 3
The only difference from example 1 is that step (1) is not performed, and the mixed solution of graphene oxide and the aqueous solution of polyvinyl alcohol added in step (2) is replaced by adding only the aqueous solution of polyvinyl alcohol.
Comparative example 4
The difference from example 1 is that graphene and polyvinyl alcohol are added to the phenolic resin in one pot at the start of the reaction.
The method specifically comprises the following steps:
mixing phenol: formaldehyde: adding oxalic acid into a four-neck round-bottom flask provided with a stirrer, a thermometer and a condenser according to a molar ratio of 1:0.8:0.05, uniformly stirring, then adding polyvinyl alcohol and a graphene oxide solution, heating and stirring at 70 ℃ for 2h, heating to 85 ℃, continuing heating and stirring for 3h, stopping stirring, adding ethanol, removing free phenol through steam distillation, and purifying to obtain phenolic resin;
carrying out melt spinning on the phenolic resin at 130 ℃ and 0.2MPa, drafting to obtain nascent phenolic fibers, putting the nascent phenolic fibers into a solidification bath for solidification, wherein the content of formaldehyde in the solidification bath is 10%, the content of hydrochloric acid is 15%, the content of water is 75%, the temperature is 80-100 ℃, the heating rate is 10-20 ℃/h, then keeping the temperature constant, solidifying for 1-2 h, washing with water, and drying to obtain the graphene modified phenolic fibers.
Wherein the concentration of the graphene oxide is 10 mg/g;
the addition of the graphene oxide is 0.5 percent of the phenolic resin product.
The experimental data of all the graphene modified phenolic fibers are shown in table 1 below.
TABLE 1 Experimental data for composites of the examples and comparative examples
In table 1, the content of the polymer is the molar ratio of the polymer to the phenolic resin.
The mechanical property data of the fibers prepared in the above examples 1 to 24 and comparative examples 1 to 3 were determined according to GB/T14344-.
TABLE 2
As can be seen from the test results of example 1 and comparative example 4 in table 2, the problem of easy agglomeration and poor dispersibility of the graphene added alone is solved by adding the phenolic resin in a form of mixing the graphene with the polymer, and the strength, toughness and the like of the phenolic fiber are improved. From the results of example 1 and comparative example 2, it can be seen that the addition of PVA enables graphene oxide to be better dispersed in resin without agglomeration, thereby further improving the strength of the fiber; from the results of the example 1 and the comparative example 1, the strength and the toughness of the fiber can be improved by adding the graphene, and the application field of the phenolic fiber is expanded; from the results of example 1 and comparative example 3, it can be seen that the modification of the phenolic resin by polyvinyl alcohol as a modifier also improves the toughness and strength of the resin, but not so much. From the results of examples 1, 17, 18, 19, 20, 21, 22 and 23, it can be seen that polyvinyl alcohol is effective, the rubber is relatively poor, and the other is almost as good as polyvinyl alcohol.
The phenolic resin fibers obtained in the examples 1-25 and the comparative examples 1-3 are placed in a tubular resistance furnace, heated to 800 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, and kept at the constant temperature for 3 hours to obtain an electrode material, and the electrode material is applied to the preparation of electrodes.
Preparing an electrode: mixing the electrode material, the conductive carbon black and the binder according to a mass ratio of 85:10:5, then carrying out ultra-high speed shearing mixing at a speed of 5000rpm, then forming a film with uniform thickness by vertically rolling and horizontally rolling at 80MPa, and placing the film at 100 ℃ for 24 hours. And cutting the dried film into electrode slices of 1 multiplied by 1cm, weighing, placing between two pieces of foamed nickel, leading out by nickel slices, and compacting by using a tablet press under 8MPa to obtain the electrode to be measured.
And (3) electrochemical performance testing:
and (3) placing the electrode to be tested in 6M KOH solution, soaking for 24h, then accessing to an electrochemical workstation, and testing by adopting a three-electrode system. The specific capacitance at 0.1A/g is shown in Table 3 below.
TABLE 3
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (36)
1. A method for preparing modified phenolic resin fibers, which is characterized by comprising the following steps:
(1) mixing graphene substances and polymers, and stirring to obtain a mixed solution;
(2) compounding the graphene substance with phenolic resin in the form of the mixed solution in the step (1) to obtain modified thermoplastic phenolic resin;
(3) purifying the modified thermoplastic phenolic resin obtained in the step (2), carrying out melt spinning to obtain phenolic fiber protofilaments, and carrying out curing and crosslinking to obtain modified phenolic resin fibers;
the mixed solution in the step (1) comprises a liquid polymer dispersed with graphene substances;
or the mixed solution comprises a solvent in which a polymer and a graphene substance are dispersed;
the solvent comprises any 1 of ethanol, water or DMF;
when the mixed solution is a solvent in which a polymer and a graphene substance are dispersed, the concentration of the graphene substance is 10-15 mg/g.
2. The method according to claim 1, wherein in the process of compounding the graphene-based material with the phenolic resin, the mass of the graphene-based material is 0.01 to 15wt% of the phenolic resin.
3. The method according to claim 2, wherein the graphene-based material is 0.01 to 10wt% of the phenolic resin.
4. The method according to claim 3, wherein the graphene-based material is 0.01 to 5wt% of the phenolic resin.
5. The method according to claim 4, wherein the graphene-based material is 0.01 to 2wt% of the phenolic resin.
6. The method according to claim 5, wherein the graphene-based material is 0.1 to 1wt% of the phenolic resin.
7. The method according to claim 1, wherein the step of compounding the graphene-based material with a phenol resin in the form of the mixed solution of step (1) comprises: adding the mixed solution obtained in the step (1) into a synthetic monomer of phenolic resin, and carrying out polymerization reaction of the phenolic resin together with the synthetic monomer;
or, adding the mixed solution in the step (1) into the polymerization reaction of the phenolic resin;
or, polymerizing the polymerization monomer of the phenolic resin with the phenolic resin, and adding the mixed solution in the step (1) into the obtained phenolic resin.
8. The method of claim 1, wherein the mixture is added dropwise at a rate of 0.5 to 2 mL/min.
9. The method according to claim 1, wherein the polymer and the graphene-based material are partially or completely grafted in the solvent in which the polymer and the graphene-based material are dispersed.
10. The method of claim 1, wherein the polymer comprises any 1 or a combination of at least 2 of rubber, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, or polyethylene glycol;
the rubber is one or more of nitrile rubber, styrene butadiene rubber and natural rubber.
11. The method of claim 10, wherein the polymer is polyvinyl alcohol.
12. The method of claim 1, wherein the solvent comprises ethanol or water.
13. The method according to claim 1, wherein when the mixed solution is a liquid polymer in which a graphite-based substance is dispersed, the mass ratio of the graphene-based substance to the polymer is 1:0.01 to 10.
14. The method according to claim 1, wherein the stirring time in step (1) is 1min to 2 hours.
15. The method of claim 1, wherein the graphene-based material comprises any 1 or a mixture of at least 2 of graphene, biomass graphene, graphene oxide, and graphene derivatives including element-doped graphene.
16. The method of claim 15, wherein the graphene derivative comprises any 1 or a combination of at least 2 of element-doped graphene or functionalized graphene.
17. The method of claim 16, wherein the element-doped graphene comprises any 1 or a combination of at least 2 of metal-doped graphene or non-metal element-doped graphene;
the metal-doped metal element comprises any 1 or at least 2 of potassium, sodium, gold, silver, iron, copper, nickel, chromium, titanium, vanadium or cobalt;
the nonmetal elements of the nonmetal element doped graphene comprise any 1 or at least 2 of nitrogen, phosphorus, silicon, boron or oxygen.
18. The method of claim 17, wherein the non-metallic element doped graphene comprises any 1 or a combination of at least 2 of nitrogen doped graphene, phosphorus doped graphene, or sulfur doped graphene.
19. The method of claim 16, wherein the functionalized graphene is graphene grafted with any 1 or a combination of at least 2 of hydroxyl, carboxyl, or amino groups.
20. The method of claim 19, wherein the hydroxy group is-R1-OH, said R1Selected from hydrocarbyl groups.
21. The method of claim 19, wherein the carboxyl group is-R2-COOH, said R2Selected from hydrocarbyl groups.
22. The method of claim 19, wherein the amino group is-R3-NH2Said R is3Selected from alkyl groups.
23. The method according to claim 1, wherein the polymerization reaction of the phenolic resin comprises a prepolymerization reaction and a polycondensation reaction carried out in this order.
24. The method according to claim 23, wherein the prepolymerization temperature is 60-80 ℃ and the reaction time is 0.5-5 h.
25. The method according to claim 23, wherein the polycondensation reaction is carried out at a temperature of 80 to 90 ℃ for 0.5 to 5 hours.
26. The method according to claim 1, wherein the phenolic resin is polymerized in a molar ratio of 1 (0.7-1) to 0.005-0.05) of the phenolic monomer in terms of hydroxyl group, the aldehyde monomer in terms of aldehyde group, and the catalyst.
27. The method of claim 26, wherein the catalyst comprises any 1 or a combination of at least 2 of hydrochloric acid, oxalic acid, acetic acid, or sulfuric acid.
28. The method of claim 26, wherein the phenolic monomer comprises phenol and derivatives thereof.
29. The method of claim 26, wherein the phenolic monomer comprises any 1 or a combination of at least 2 of phenol, naphthol, alkyl substituted phenol, alkyl substituted naphthol, bisphenol a, or bisphenol F.
30. The method of claim 26, wherein the phenolic monomer comprises cresol and/or xylenol.
31. The method of claim 26, wherein the aldehyde monomer comprises formaldehyde and derivatives thereof.
32. The method of claim 26, wherein the aldehyde monomer comprises any 1 or a combination of at least 2 of formaldehyde, acetaldehyde, or furfural.
33. The method of any one of claims 1 to 32, comprising the steps of:
(a 1') dispersing a graphene-based material in a solvent to obtain a graphene-based material dispersion liquid; dispersing a polymer in a solvent to obtain a polymer dispersion;
(a1) mixing the graphene substance dispersion liquid obtained in the step (a 1') with the polymer dispersion liquid, and stirring to obtain a mixed liquid of the graphene substance and the polymer;
(a2) adding the mixed solution obtained in the step (a1) into a polymerization monomer of phenolic resin in a dropwise manner, carrying out polymerization reaction on the thermoplastic phenolic resin to obtain a reaction solution, and purifying to obtain modified phenolic resin;
(a3) carrying out melt spinning on the phenolic resin to obtain phenolic fiber protofilaments, and then curing and crosslinking to obtain modified phenolic resin fibers; alternatively, the method comprises the steps of:
(b 1') dispersing a graphene-based material in a solvent to obtain a graphene-based material dispersion liquid; dispersing a polymer in a solvent to obtain a polymer dispersion;
(b1) mixing the graphene substance dispersion liquid obtained in the step (b 1') with the polymer dispersion liquid, and stirring to obtain a mixed liquid of the graphene substance and the polymer;
(b2) reacting a phenolic compound with an aldehyde compound for a period of time, adding the mixed solution obtained in the step (b1) into the reaction solution, reacting to obtain a reaction solution, and purifying to obtain a modified phenolic resin;
(b3) carrying out melt spinning on the phenolic resin to obtain phenolic fiber protofilaments, and then curing and crosslinking to obtain modified phenolic resin fibers;
alternatively, the method comprises the steps of:
(c 1') dispersing the graphene-based material in a solvent to obtain a graphene-based material dispersion liquid; dispersing a polymer in a solvent to obtain a polymer dispersion;
(c1) mixing the graphene substance dispersion liquid obtained in the step (c 1') with the polymer dispersion liquid, and stirring to obtain a mixed liquid of the graphene substance and the polymer;
(c2) adding the mixed solution obtained in the step (c1) into phenolic resin to obtain modified phenolic resin;
(c3) and carrying out melt spinning on the phenolic resin to obtain phenolic fiber protofilaments, and then curing and crosslinking to obtain the modified phenolic resin fibers.
34. A modified phenolic resin fiber obtained by the method for producing a modified phenolic resin fiber according to any one of claims 1 to 33.
35. Use of the modified phenolic resin fiber of claim 34 as any 1 or combination of at least 2 of reinforcement, flame retardant and thermal insulation, cushioning, phenolic based carbon fiber, electrode material.
36. An electrode composite material, characterized in that it is obtained by carbonizing the phenolic resin fiber obtained in any one of claims 1 to 33.
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| CN104627994A (en) * | 2015-02-06 | 2015-05-20 | 中国科学院山西煤炭化学研究所 | Preparation method of reduced graphene oxide/phenol formaldehyde resin-base activated carbon in-situ composite material |
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