CN106811823A - A kind of phenol-formaldehyde resin modified fiber and its production and use - Google Patents
A kind of phenol-formaldehyde resin modified fiber and its production and use Download PDFInfo
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- CN106811823A CN106811823A CN201611179317.1A CN201611179317A CN106811823A CN 106811823 A CN106811823 A CN 106811823A CN 201611179317 A CN201611179317 A CN 201611179317A CN 106811823 A CN106811823 A CN 106811823A
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- D—TEXTILES; PAPER
- 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
- 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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- D—TEXTILES; PAPER
- 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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- D—TEXTILES; PAPER
- 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
- 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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- D—TEXTILES; PAPER
- 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
- 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
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The present invention relates to a kind of preparation method of modified phenolic fiber, methods described comprises the following steps:(1) admixed graphite alkenes material and polymer, stirring obtain mixed liquor;(2) the graphite alkenes material is combined in the form of step (1) described mixed liquor with phenolic resin, is obtained modified thermoplastic phenolic resin;(3) the modified thermoplastic phenolic resin for obtaining step (2) is purified, and after melt spinning obtains phenolic fibre precursor, solidification crosslinking obtains modified phenolic fiber.The present invention is combined by by Graphene with phenolic resin, modified phenolic resin is obtained, by obtaining modified phenolic fiber after spinning.Novelty of the present invention by by the form of Graphene and mixed with polymers add phenolic resin solve it is simple add Graphene easily to reunite, the problem of poor dispersion improves intensity, toughness and electric property of phenolic fibre etc..
Description
Technical field
The invention belongs to phenolic resin modified field, it is related to a kind of phenol-formaldehyde resin modified fiber and preparation method thereof.
Background technology
A kind of fiber of tridimensional network that phenolic fibre is phenolic resin to be obtained by spinning, solidification, nineteen sixty-eight, by
Carborundum Co. of the U.S. succeeds in developing [J.Economy, R.A.Clark.Fibers from Nocolacs [P] .US first
Pat.3650102,1968].Phenolic fibre has the characteristics, pole oxygen index (OI) such as prominent high temperature resistant, resistance to combustion, corrosion-resistant and resist melt
Height, and with self-extinguishment;Shrinkage factor is small during burning, and cigarette is few;Based on above excellent properties, the research of phenolic fibre is subject to height
Concern, and driven the further research and development of phenolic fibre;Phenolic fibre spinning technique is usually with thermoplastic phenolic
Resin is raw material, and precursor is obtained by melt spinning, carries out crosslinking curing by solution such as formaldehyde and hydrochloric acid and forms;Meanwhile,
Because phenolic fibre remaining carbon is high, pernicious gas effusion is few, can further activate into carbon fiber, is equally widely used in each
Plant the fields such as heat-resisting, absorption.With industrial expansions such as space flight and national defence, the application field of phenolic fibre is also constantly expanding
Exhibition, pure phenolic fibre can not meet the market demand for expanding day by day.Processability is excellent, and application field is wide, especially has
The high-performance pnenolic aldehyde fiber for having more excellent heat resistance, intensity and toughness has turned into the emphasis in the field.
The topology example of phenolic fibre can be expressed as:
As can be seen from the above equation, methylene is connected because its phenyl ring density is high, between two adjacent phenyl rings, thus it is very crisp,
The toughness that causes phenolic fibre is low, elongation at break is small, and phenolic hydroxyl group is oxidizable, is subject to its heat resistance, oxidative resistance, alkali resistance
A certain degree of influence, these shortcomings reduce the performance of product, using by a definite limitation.Therefore phenolic fibre is entered in itself
Row is modified, reduces the defect of its structure, is to improve phenolic fibre high intensity, toughness and heat-resist basic method.
This area phenolic fibre with excellent heat resistance, high intensity and high tenacity that has requirement developing a kind of.
The content of the invention
For in the prior art, phenolic fibre poor mechanical property, mechanical strength be not high, and heat resistance is bad to wait not enough, this
The first purpose of invention is to provide a kind of preparation method of modified phenolic fiber, and methods described comprises the following steps:
(1) admixed graphite alkenes material and polymer, stirring obtain mixed liquor;
(2) the graphite alkenes material is combined in the form of step (1) described mixed liquor with phenolic resin, is obtained
Modified thermoplastic phenolic resin;
(3) the modified thermoplastic phenolic resin for obtaining step (2) is purified, and melt spinning obtains phenolic fibre precursor
Afterwards, solidification crosslinking obtains modified phenolic fiber.
Graphene oxide as a kind of Graphene presoma or derivative, performance be no less than Graphene, moreover
Surface of graphene oxide contains abundant oxygen-containing functional group, is that graphene oxide can further occur chemical reaction and improve work
Property site;The introducing of graphene oxide can inlay and be polymerized with resin generation co-curing behavior or forming part inierpeneirating network structure
Thing intermediate radical, and with good compatibility, in the absence of situation about being separated, increased phenolic fibre spinnability and
Mechanical property, while improving its electric property.
The present invention is doped into graphite alkenes material in phenolic resin in the form of graphite alkenes material and mixed with polymers,
There is weaker key and effect (such as Van der Waals force) between graphite alkenes material and polymer, effectively prevent graphite alkenes thing
The reunion of matter, realizes graphite alkenes material dispersed in phenolic resin.
Additionally, in the preparation process of phenolic resin, the addition of polymer can also omit in follow-up spinning process in order to
Improve the polymer that spinnability is added.
Polymer of the present invention is not particularly limited, and any polymer that can increase spinnability is used equally to this Shen
Please.
Preferably, during the graphite alkenes material with phenolic resin be combined, the quality of graphite alkenes material
Be 0.01~15wt% of phenolic resin, such as 0.05wt%, 0.1wt%, 0.6wt%, 0.9wt%, 2wt%, 3.5wt%,
4.2wt%, 4.6wt%, 5.8wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%
Deng, preferably 0.01~10wt%, further preferred 0.01~5wt%, particularly preferred 0.01~2wt%, most preferably 0.1~
1wt%.
Preferably, the graphite alkenes material is combined in the form of step (1) described mixed liquor with phenolic resin
Mode include it is as follows:
Mode one:Step (1) described mixed liquor is added in the synthon of phenolic resin, is carried out together with synthon
The polymerisation of phenolic resin.
Mode two, adds step (1) described mixed liquor in the polymerisation of phenolic resin.
Mode three, the polymerized monomer of phenolic resin is carried out the polymerisation of phenolic resin, in the phenolic resin for obtaining
Add step (1) described mixed liquor.
In other words, graphite alkenes material of the present invention can be in the form of step (1) described mixed liquor in phenolic resin
Before synthesis (during synthon), among (after there is part prepolymerization reaction) or (obtain phenolic resin after) adds afterwards.
Certainly, graphite alkenes material of the present invention can also with any a kind of mode one, mode two or mode three or extremely
The form of few 2 kinds of combination is added, for example, can all be added when synthon and when pre-polymerization simultaneously, it is also possible to
Finish and add in the phenolic resin for obtaining etc. with synthesis when synthon.
Preferably, to be added dropwise, the drop rate is 0.5~2mL/min to the addition form of the mixed liquor, for example
0.6mL/min, 0.9mL/min, 1.3mL/min, 1.6mL/min, 1.9mL/min etc..
Preferably, step (1) described mixed liquor includes being dispersed with the liquid polymer of graphite alkenes material;
Or, the mixed liquor includes being dispersed with the solvent of polymer and graphite alkenes material.
Preferably, it is described to be dispersed with the solvent of polymer and graphite alkenes material, the polymer and graphite alkenes thing
There is all or part of graft reaction in matter.
Preferably, the polymer includes rubber, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol
Or any a kind or at least 2 kinds of combination in polyethylene glycol, preferred polyvinyl alcohol.
Exemplarily, the combination of the polymer includes combination, the polyvinylpyrrolidine of polyacrylamide and polyacrylic acid
Combination of combination, polyvinyl alcohol and polyacrylic acid of ketone and polyethylene glycol etc..
The rubber is one or more in nitrile rubber, butadiene-styrene rubber, natural rubber.
Preferably, the solvent includes any a kind or at least 2 kinds in ethanol, water, ethylene glycol, DMF, NMP or acetone
Combination;Preferred alcohol or water.
The solvent of the graphite alkenes substance solution has multiple choices, right as long as high to the solubility of graphite alkenes material
Polymerisation without excessive adverse effect, is selected from the one kind in water, ethanol, ethylene glycol, DMF, NMP, acetone again
Or various, preferred alcohol or water.
Preferably, when the mixed liquor is when being dispersed with the liquid polymer of graphite-like material, graphite alkenes material and poly-
The mass ratio of compound is 1:0.01~10, such as 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 etc..
Preferably, when the mixed liquor is when being dispersed with the solvent of polymer and graphite alkenes material, the polymer
Concentration be 10~20wt%, such as 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%,
19wt% etc., the concentration of the graphite alkenes material is below 15mg/g, preferably preferably 1~10mg/g, 3~5mg/g;
Preferably, the time of step (1) described stirring be 1min~2h, such as 5min, 20min, 36min, 50min,
65min, 80min, 90min, 110min etc..
Preferably, the graphite alkenes material includes that Graphene, biomass Graphene, graphene oxide, Graphene derive
Any a kind of thing or at least 2 kinds of mixing, the Graphene derivative include the Graphene of element doping.
Preferably, the Graphene derivative includes any 1 in element doping Graphene or functional group's graphite alkene thing
Kind or at least 2 kinds of combination.
Preferably, the element doping Graphene is including in metal-doped Graphene or nonmetal doping Graphene
Any a kind or at least 2 kinds of combination.
The metal-doped metallic element includes any 1 in potassium, sodium, gold, silver, iron, copper, nickel, chromium, titanium, vanadium or cobalt
Kind or at least 2 kinds of combination.
The nonmetalloid of the nonmetal doping Graphene include nitrogen, phosphorus, silicon, boron or oxygen in any a kind or
At least 2 kinds of combination.
Preferably, the nonmetal doping Graphene includes nitrogen-doped graphene, phosphorus doping Graphene or sulfur doping
Any a kind or at least 2 kinds of combination in Graphene.
Preferably, functional group's graphite alkene includes being grafted with the Graphene of functional group.
Preferably, functional group's graphite alkene includes any a kind or at least 2 be grafted with hydroxyl, carboxyl or amino
The Graphene of the combination planted.
Preferably, the hydroxyl includes-R1- OH, the R1Including alkyl, preferably include methyl, ethyl, propyl group, butyl,
Any a kind or at least 2 kinds of combination in amyl group, hexyl, vinyl, acrylic.
Preferably, the carboxyl includes-R2- COOH, the R2Including alkyl, methyl, ethyl, propyl group, fourth are preferably included
Any a kind or at least 2 kinds of combination in base, amyl group, hexyl.
Preferably, the amino includes R3-NH3, the R3Including alkyl, methyl, ethyl, propyl group, fourth are preferably included
Any a kind or at least 2 kinds of combination in base, amyl group, hexyl.
Preferably, the polymerisation of the phenolic resin includes the prepolymerization reaction and the polycondensation reaction that carry out successively.
Preferably, the temperature of the prepolymerization reaction be 60~80 DEG C, such as 62 DEG C, 68 DEG C, 73 DEG C, 78 DEG C etc., during reaction
Between be 0.5~5h, such as 0.6h, 0.8h, 1h, 2h, 3h, 4h etc..
Preferably, the temperature of the polycondensation reaction be 80~90 DEG C, such as 82 DEG C, 83 DEG C, 85 DEG C, 88 DEG C etc., during reaction
Between be 0.5~5h, such as 0.6h, 0.8h, 1h, 2h, 3h, 4h etc..
Preferably, in the polymerisation of the phenolic resin, the phenol monomer in terms of hydroxyl, the aldehyde monomer in terms of aldehyde radical and urge
The mol ratio of agent is 1:(0.7~1):(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 etc..
Preferably, the acidic catalyst preferably includes any a kind in hydrochloric acid, oxalic acid, acetic acid or sulfuric acid or at least 2 kinds
Combination.
Preferably, the phenolic compound includes phenol and its derivatives, preferably phenol, cresols, xylenol, naphthols, alkane
Any a kind or at least 2 kinds in phenol, alkyl-substituted naphthols, bisphenol-A or the Bisphenol F of base substitution of combination;
Preferably, the aldehyde compound includes formaldehyde and its derivative, any a kind preferably in formaldehyde, acetaldehyde or furfural
Or at least 2 kinds of combination.
Used as one of optimal technical scheme, the preparation method of phenol-formaldehyde resin modified fiber of the present invention includes following step
Suddenly:
(a1 ') dispersed graphite alkenes material obtains graphite alkenes material dispersion liquid in solvent;Dispersed polymeres are in solvent
In, obtain polymer dispersion liquid;
(a1) graphite alkenes material dispersion liquid and the polymer dispersion liquid mixing for obtaining step (a1 '), stirring obtain stone
The mixed liquor of black alkenes material and polymer;
(a2) to the mixed liquor for adding step (a1) to obtain in the polymerized monomer of phenolic resin in the way of being added dropwise, heat is carried out
The polymerisation of plastic phenolic resin obtains reaction solution, and modified phenolic resin is obtained after purification;
(a3) after the phenolic resin melt spinning being obtained into phenolic fibre precursor, solidification crosslinking obtains modified phenolic aldehyde tree
Fat fiber.
Used as the two of optimal technical scheme, the preparation method of phenol-formaldehyde resin modified fiber of the present invention includes following step
Suddenly:
(b1 ') dispersed graphite alkenes material obtains graphite alkenes material dispersion liquid in solvent;Dispersed polymeres are in solvent
In, obtain polymer dispersion liquid;
(b1) graphite alkenes material dispersion liquid and the polymer dispersion liquid mixing for obtaining step (b1 '), stirring obtain stone
The mixed liquor of black alkenes material and polymer;
(b2) by phenolic compound and after aldehyde compound reaction a period of time, to being added in reaction solution, step (b1) is described
Mixed liquor, reaction obtain reaction solution, modified phenolic resin is obtained after purification;
(b3) after the phenolic resin being obtained into phenolic fibre precursor through melt spinning, solidification crosslinking obtains modified phenolic aldehyde
Resin fibre;
Used as the three of optimal technical scheme, the preparation method of phenol-formaldehyde resin modified fiber of the present invention includes following step
Suddenly:
(c1 ') dispersed graphite alkenes material obtains graphite alkenes material dispersion liquid in solvent;Dispersed polymeres are in solvent
In, obtain polymer dispersion liquid;
(c1) graphite alkenes material dispersion liquid and the polymer dispersion liquid mixing for obtaining step (c1 '), stirring obtain stone
The mixed liquor of black alkenes material and polymer;
(c2) mixed liquor described in step (c1) is added in phenolic resin, modified phenolic resin is obtained;
(c3) after the phenolic resin being obtained into phenolic fibre precursor through melt spinning, solidification crosslinking obtains modified phenolic aldehyde
Resin fibre.
Phenolic resin of the present invention is not particularly limited, and can include the following two kinds 1. phenolic compound and aldehydes chemical combination
Thing reacts the completely rear reaction solution for being formed, 2. the phenolic resin of finished product.
The second object of the present invention is to provide a kind of modified phenolic fiber, and the modified phenolic fiber leads to
The preparation method for crossing the modified phenolic fiber described in the first purpose is obtained.
The third object of the present invention is to provide a kind of purposes of the modified phenolic fiber described in second purpose, described
Modified phenolic fiber is used as reinforcing material, flame resistant heat insulation material, insulation material, padded coaming, phenolic aldehyde base carbon fibre, electricity
Any a kind or at least 2 kinds of combination in the material of pole.
Present invention also offers a kind of electrode composite material, it is characterized in that, by phenolic fiber obtained above through charcoal
Change is obtained.
Compared with prior art, the invention has the advantages that:
The present invention is combined by by Graphene with phenolic resin, modified phenolic resin is obtained, by being obtained after spinning
Modified phenolic fiber.Novelty of the present invention by by the form of Graphene and mixed with polymers adds phenolic resin to solve list
Pure addition Graphene is easily reunited, and the problem of poor dispersion improves intensity, toughness and the electric property of phenolic fibre.
Especially when graphite alkenes material is graphene oxide, and polymer is polyvinylpyrrolidone PVA, in phenolic aldehyde tree
In the building-up process of fat, graphene oxide can occur co-curing or be formed mutually to pass net with dispersed state and phenolic resin
Network, realizes improving phenolic resin toughness, and, in 159~330Mpa, elongation is in 6.7~20%, intensity and heat resistance for tensile strength
Effect.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair
Bright concrete restriction.
In following examples, the ratio of phenol, aldehyde and catalyst is the phenol monomer in terms of hydroxyl, the aldehyde monomer in terms of aldehyde radical
With the mol ratio of catalyst.
Graphene used is commercially available HX-G Graphenes in all examples below and comparative example;
The graphene oxide is obtained for commercially available SE2430 graphite oxides through ultrasonic disperse.
Carboxylated graphene oxide, biomass Graphene, oxidizing biomass Graphene can be obtained by following methods, but not
It is limited to following methods, can be also obtained using the method for Graphene and graphene oxide in the prior art, also can directly using commercially available
Graphene and graphene oxide.
Commercially available biomass Graphene of the present invention is using the biomass Graphene of Jinan holy well group production or by system
Standby example 2 is prepared.
Preparation example 1:The graphene oxide of carboxylated
By 100mg graphite oxides ultrasonic disperse in 100ml water, the graphene oxide water solution of 1mg/ml is obtained, then
Add 6g NaOH and 5g monoxones ultrasound 3h so that the epoxy radicals and hydroxyl of surface of graphene oxide are converted into carboxyl, take advantage of
Heat filtering, goes the removal of impurity, and 65 DEG C of vacuum drying obtain carboxylated graphene oxide again afterwards.
Preparation example 2:Biomass Graphene
Step one, first prepare cellulose:
(1) after by wheat straw comminution pretreatment, dense using total acid is the formic acid and the organic acid solution pair of acetic acid of 80wt%
Wheat straw after treatment carries out boiling, and acetic acid and the mass ratio of formic acid are 1 in the organic acid solution of the present embodiment:12, and adding
Enter to add before raw material the hydrogen peroxide (H2O2) for accounting for wheat straw raw material 1wt% as catalyst, 120 DEG C of controlling reaction temperature,
Reaction 30min, solid-liquid mass ratio is 1:10, and the reaction solution that will be obtained carries out first time separation of solid and liquid;
(2) it is the formic acid and the organic acid solution of acetic acid of 75wt% that the solid for obtaining first time separation of solid and liquid adds total acid dense
Acid elution is carried out, wherein adding the peroxide for accounting for wheat straw raw material 8wt% in the above-mentioned dense organic acid solution for 75wt% of total acid
Change hydrogen (H2O2) as catalyst and acetic acid and the mass ratio of formic acid are 1:12, it is 90 DEG C, wash time 1h, solid-liquid to control temperature
Mass ratio is 1:9, and reaction solution is carried out into second separation of solid and liquid;
(3) collect for the first time and the liquid that obtains of second separation of solid and liquid, in 120 DEG C, HTHP is carried out under 301kPa
Evaporation, until being evaporated, as cooking liquor in the formic acid and acetic acid vapor condensing reflux to the reactor of step (1) that will obtain, uses
In the boiling of step (1);
(4) solid that second separation of solid and liquid of collection is obtained, water-filling of going forward side by side is washed, and it is 80 DEG C, washing slurry to control washing temperature
Dense is 6wt%, and the washing slurry that will be obtained carries out third time separation of solid and liquid;
(5) liquid that third time separation of solid and liquid is obtained is collected, enters water-filling, sour rectifying, the mix acid liquor for obtaining is back to step
Suddenly it is used for the boiling of step (1) in the reactor of (1) as cooking liquor, the Water circulation for obtaining washes water with water in step (5);
(6) collect the solid that obtains of third time separation of solid and liquid and screen and obtain required screened stock cellulose.
Step 2, with the cellulose that is prepared as above as raw material prepares Graphene:
(1) in mass ratio 1:1 cellulose mixture and frerrous chloride, stirring carries out catalytic treatment 4h at 150 DEG C, dries extremely
Presoma moisture 10wt%, obtains presoma;
(2)N2In atmosphere, presoma is warming up to 170 DEG C with 3 DEG C/min speed, is incubated 2h, temperature programming afterwards to 400
DEG C, 3h is incubated, 1200 DEG C are warming up to afterwards, obtain crude product after insulation 3h;The heating rate that described program heats up is 15 DEG C/min;
(3) at 55-65 DEG C, by crude product after sodium hydroxide solution, the chlorohydric acid pickling of 4wt% that over-richness is 10%, water
Wash and obtain biomass Graphene.
Preparation example 3:Oxidizing biomass Graphene
Biomass Graphene due to there is loose structure, while lamella for graphite in opened condition, therefore
Oxidizing condition is weak compared to graphite oxidation condition.Specific implementation process is as follows:
2g biomass Graphene is mixed with the 30mL concentrated sulfuric acids in reactor, 10min is stirred under the conditions of ice-water bath
Afterwards, 7g potassium permanganate is gradually added into, control temperature is not higher than 35 DEG C, stirring is continued under normal temperature condition after the completion of potassium permanganate sample-adding
2h, is warming up to 40 DEG C afterwards, adds the 30wt% hydrogen peroxide of about 5mL volumes, solution colour to be changed into golden yellow after reaction 30min,
150mL distilled water dilutings are added afterwards, while hot suction filtration reaction solution, respectively with the watery hydrochloric acid and 100mL that 4mL mass fractions are 10%
Deionized water is cleaned 2-3 times, and centrifugation disposed slurry spray drying can obtain oxidizing biomass Graphene.
Embodiment 1
A kind of preparation method of modified phenolic fiber, comprises the following steps:
(1) graphene oxide dispersion is added into polyvinyl alcohol water solution (concentration of polyvinyl alcohol water solution is 15wt%)
In, stirring obtains mixed liquor, and the concentration of graphene oxide is 10mg/g in the mixed liquor;
Wherein, in terms of aldehyde material, the prepolymer of the phenolic resin is 1 with the mol ratio of polymer P VA:0.05;
(2) by phenol, formaldehyde, oxalic acid according to 1:0.8:0.05 mol ratio is added in four-hole boiling flask, and 70 DEG C of heating are stirred
Mix after backflow 2h, add the mixed solution of step (1), be warming up to 85 DEG C and continue to react 3h, stop heating stirring;
(3) ethanol is added, by steam distillation, removal free phenol purification, gained pure resin high is in 130 DEG C, 0.2MPa
Melt spinning is carried out, drawing-off obtains nascent phenolic fibre, it is solidified into coagulating bath, and content of formaldehyde is in coagulating bath
10%, content of hydrochloric acid is 15%, and water content is 75%, and temperature is 80~100 DEG C, 10 DEG C of heating rate~20 DEG C/h, Zhi Houheng
Temperature, solidifies 1~2h, washing, dry Graphene modified phenolic fiber.
Wherein, the addition of graphene oxide is the 0.5% of phenolic resin product.
Embodiment 2
With the graphene oxide that graphene oxide is replaced with carboxylated of differing only in of embodiment 1, other consumptions and
Condition all same, is obtained Graphene modified phenolic fiber.
Embodiment 3
Graphene oxide is replaced with into Graphene with differing only in for embodiment 1, other consumptions and condition all same, system
Obtain Graphene modified phenolic fiber.
Embodiment 4
Graphene oxide is replaced with into biomass Graphene with differing only in for embodiment 1, other consumptions and condition are equal
It is identical, Graphene modified phenolic fiber is obtained.
Embodiment 5
Graphene oxide is replaced with into oxidizing biomass Graphene with differing only in for embodiment 1, other consumptions and bar
Part all same, is obtained Graphene modified phenolic fiber.
Embodiment 6~9
Compared with Example 1, the consumption for differing only in graphene oxide is different, and the addition of graphene oxide is phenolic aldehyde
0.01%, 1%, 10%, the 15% of naval stores.
Embodiment 10~12
Compared with Example 1, differ only in, the concentration of graphene oxide is different in mixed liquor, respectively 1mg/g,
5mg/g、15mg/g。
Embodiment 14~16
Embodiment 14~16 and embodiment 1 to differ only in solvent used during graphene oxide ultrasonic disperse different,
Respectively ethanol, DMF, acetone.
Embodiment 17~22
Polyvinyl alcohol is replaced with poly- second by embodiment 17~22 respectively with differing only in for embodiment 15 (solvent is DMF)
Alkene pyrrolidone, polyethylene glycol, nitrile rubber, butadiene-styrene rubber, polyurethane, natural rubber, other consumptions and condition all same, system
Obtain Graphene modified phenolic fiber.Preferably, rubber-like relative mistake, other and polyvinyl alcohol are similar for polyvinyl alcohol effect.
Embodiment 23
From the difference of embodiment 1 be phenol and aldehyde species it is different, that is, step (2) is different,
(2) by phenol, furfural, oxalic acid according to 1:0.8:0.05 mol ratio is added in four-hole boiling flask, and 70 DEG C of heating are stirred
Mix after backflow 2h, add the mixed solution of step (1), be warming up to 85 DEG C and continue to react 3h, stop heating stirring.
Other steps are with embodiment 1.
Embodiment 24
Compared with Example 1, phenolic resin is different with the ratio of PVA,
In step (1), in the phenolic resin prepolymer add PVA (in terms of aldehyde material, the phenolic resin it is pre-
Polymers is 1 with the mol ratio of polymer P VA:0.01).
Embodiment 25
Compared with Example 1, phenolic resin is different with the ratio of PVA,
In step (1), in the phenolic resin prepolymer add PVA (in terms of aldehyde material, the phenolic resin it is pre-
Polymers is 1 with the mol ratio of polymer P VA:0.1).
Comparative example 1
Do not carry out step (1) with differing only in for embodiment 1, step is added without graphene oxide and polyethylene in (2)
The mixed liquor of alcohol solution.
Comparative example 2
Do not carry out step (1) with differing only in for embodiment 1, graphene oxide and polyvinyl alcohol are added in step (2)
The mixed liquor of the aqueous solution is replaced with and only adds graphene oxide water solution.
Comparative example 3
Do not carry out step (1) with differing only in for embodiment 1, graphene oxide and polyvinyl alcohol are added in step (2)
The mixed liquor of the aqueous solution is replaced with and only adds polyvinyl alcohol water solution.
Comparative example 4
Difference with embodiment 1 is, when phenolic resin starts reaction, one pot of Graphene and polyvinyl alcohol to be added into it
In.
Specifically include following steps:
By phenol:Formaldehyde:Oxalic acid is according to 1:0.8:0.05 mol ratio is added to equipped with agitator, thermometer, condenser pipe
Four round flask in stir, be subsequently adding polyvinyl alcohol and graphene oxide solution, heating stirring 2h at 70 DEG C, rise
Temperature continues heating stirring 3h to 85 DEG C, stops stirring, adds ethanol, and by steam distillation, removal free phenol purification is obtained
Phenolic resin;
The phenolic resin is carried out into melt spinning in 130 DEG C, 0.2MPa, drawing-off obtains nascent phenolic fibre, entered
Enter coagulating bath to be solidified, content of formaldehyde is 10% in coagulating bath, and content of hydrochloric acid is 15%, and water content is 75%, and temperature is 80
~100 DEG C, 10 DEG C of heating rate~20 DEG C/h, constant temperature, solidifies 1~2h afterwards, and washing is dry that Graphene modified phenolic is fine
Dimension.
Wherein, the concentration of graphene oxide is 10mg/g;
The addition of graphene oxide is the 0.5% of phenolic resin product.
The experimental data of all of above Graphene modified phenolic fiber see the table below 1.
The experimental data of the composite of the embodiment of table 1 and comparative example
In table 1, the content of polymer is polymer and the mol ratio of phenolic resin.
The mechanical property number that above-described embodiment 1-24 and comparative example 1-3 is obtained fiber is determined according to GB/T 14344-2008
According to as a result such as table 2.
Table 2
The test result of embodiment 1 and comparative example 4 from table 2 can be seen that by by Graphene and mixed with polymers
Form addition phenolic resin solves simple addition Graphene and easily reunites, and the problem of poor dispersion improves phenolic fibre
Intensity and toughness etc..The addition that can be seen that PVA from the result of embodiment 1 and comparative example 2 enables to graphene oxide more
It is good to be dispersed in resin without reuniting, so further raising fiber intensity;From embodiment 1 and comparative example 1
Result can be seen that the intensity and toughness that fiber can be improved by the addition of Graphene, extend the application field of phenolic fibre;
Can be seen that it is also energy to be used as a kind of modifier modification phenolic resin by polyvinyl alcohol from the result of embodiment 1 and comparative example 3
The toughness and intensity of resin are enough improved, simply amplitude is little.Result from embodiment 1,17,18,19,20,21,22,23 can
To find out polyvinyl alcohol effect preferably, rubber-like relative mistake, other and polyvinyl alcohol are similar.
The phenolic fiber that embodiment 1-25 and comparative example 1-3 are obtained is placed in tube type resistance furnace, in nitrogen protection
Under rise to 800 DEG C with the heating rate of 3 DEG C/min, constant temperature 3h obtains electrode material, and be applied to the preparation of electrode.
The preparation of electrode:By above-mentioned electrode material, conductive black and binding agent according to 85:10:5 mass ratio mixing,
Then exceed the speed limit shear-mixed under the speed of 5000rpm again, then rolls to form thickness with level by vertical rolling under 80MPa
Homogeneous film, and film is placed at 100 DEG C places 24h.Dried film is cut into 1 × 1cm electrode slices, is weighed rearmounted
Between two panels nickel foam, and drawn with nickel sheet, be compacted under 8MPa using tablet press machine, obtain electrode to be measured.
Electrochemical property test:
Electrode to be measured is placed in after soaking 24h in the KOH solution of 6M, electrochemical workstation is accessed, using three-electrode system
Tested.Specific capacitance see the table below 3 under 0.1A/g.
Table 3
Applicant states that the present invention illustrates process of the invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of preparation method of modified phenolic fiber, it is characterised in that methods described comprises the following steps:
(1) admixed graphite alkenes material and polymer, stirring obtain mixed liquor;
(2) the graphite alkenes material is combined in the form of step (1) described mixed liquor with phenolic resin, is modified
Thermoplastic phenolic resin;
(3) the modified thermoplastic phenolic resin for obtaining step (2) is purified, after melt spinning obtains phenolic fibre precursor,
Solidification crosslinking obtains modified phenolic fiber.
2. preparation method as claimed in claim 1, it is characterised in that the graphite alkenes material is combined with phenolic resin
During, the quality of graphite alkenes material is 0.01~15wt%, the preferably 0.01~10wt% of phenolic resin, further excellent
Select 0.01~5wt%, most preferably particularly preferred 0.01~2wt%, 0.1~1wt%;
Preferably, the graphite alkenes material is carried out into compound side in the form of step (1) described mixed liquor with phenolic resin
Formula includes:Step (1) described mixed liquor is added in the synthon of phenolic resin, phenolic resin is carried out together with synthon
Polymerisation;
Or, step (1) described mixed liquor is added in the polymerisation of phenolic resin;
Or, the polymerized monomer of phenolic resin is carried out the polymerisation of phenolic resin, step is added in the phenolic resin for obtaining
Suddenly (1) mixed liquor;
Preferably, to be added dropwise, the drop rate is 0.5-2mL/min to the addition form of the mixed liquor.
3. preparation method as claimed in claim 1 or 2, it is characterised in that step (1) described mixed liquor includes being dispersed with graphite
The liquid polymer of alkenes material;
Or, the mixed liquor includes being dispersed with the solvent of polymer and graphite alkenes material;
Preferably, described to be dispersed with the solvent of polymer and graphite alkenes material, the polymer and graphite alkenes material are sent out
The graft reaction of first portion or whole;
Preferably, the polymer includes rubber, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol or poly-
Any a kind or at least 2 kinds of combination in ethylene glycol, preferably polyvinyl alcohol;
The rubber is one or more in nitrile rubber, butadiene-styrene rubber, natural rubber;
Preferably, group of the solvent including any a kind or at least 2 kinds in ethanol, water, ethylene glycol, DMF, NMP or acetone
Close;Preferred alcohol or water;
Preferably, when the mixed liquor is when being dispersed with the liquid polymer of graphite-like material, graphite alkenes material and polymer
Mass ratio be 1:0.01~10;
Preferably, when the mixed liquor is graphite alkenes material when being dispersed with the solvent of polymer and graphite alkenes material
Concentration be below 15mg/g, preferably preferably 1~10mg/g, 3~5mg/g;
Preferably, the time of step (1) described stirring is 1min-2h.
4. the preparation method as described in one of claims 1 to 3, it is characterised in that the graphite alkenes material include Graphene,
Biomass Graphene, graphene oxide, the mixing of any a kind of Graphene derivative or at least 2 kinds, the Graphene derivative
Graphene including element doping;
Preferably, the Graphene derivative include any a kind in element doping Graphene or functional group's graphite alkene thing or
At least 2 kinds of combination;
Preferably, it is any during the element doping Graphene is including metal-doped Graphene or nonmetal doping Graphene
1 kind or at least 2 kinds of combination;
The metal-doped metallic element include potassium, sodium, gold, silver, iron, copper, nickel, chromium, titanium, vanadium or cobalt in any a kind or
At least 2 kinds of combination;
The nonmetalloid of the nonmetal doping Graphene includes any a kind or at least 2 in nitrogen, phosphorus, silicon, boron or oxygen
The combination planted;
Preferably, the nonmetal doping Graphene includes nitrogen-doped graphene, phosphorus doping Graphene or sulfur doping graphite
Any a kind or at least 2 kinds of combination in alkene;
Preferably, functional group's graphite alkene includes being grafted with the Graphene of functional group;
Preferably, functional group's graphite alkene includes any a kind or at least 2 kinds be grafted with hydroxyl, carboxyl or amino
The Graphene of combination;
Preferably, the hydroxyl includes-R1- OH, the R1Including alkyl, preferably include methyl, ethyl, propyl group, butyl, amyl group,
Any a kind or at least 2 kinds of combination in hexyl, vinyl, acrylic;
Preferably, the carboxyl includes-R2- COOH, the R2Including alkyl, methyl, ethyl, propyl group, butyl, penta are preferably included
Any a kind or at least 2 kinds of combination in base, hexyl;
Preferably, the amino includes R3-NH3, the R3Including alkyl, methyl, ethyl, propyl group, butyl, penta are preferably included
Any a kind or at least 2 kinds of combination in base, hexyl.
5. according to any described preparation method of claim 2~4, it is characterised in that the polymerisation bag of the phenolic resin
Include the prepolymerization reaction and polycondensation reaction for carrying out successively;
Preferably, the temperature of the prepolymerization reaction is 60~80 DEG C, and the reaction time is 0.5~5h;
Preferably, the temperature of the polycondensation reaction is 80~90 DEG C, and the reaction time is 0.5~5h;
Preferably, in the polymerisation of the phenolic resin, the phenol monomer in terms of hydroxyl, the aldehyde monomer in terms of aldehyde radical and catalyst
Mol ratio be 1:(0.7~1):(0.005~0.05);
Preferably, the acidic catalyst preferably includes the group of any a kind or at least 2 kinds in hydrochloric acid, oxalic acid, acetic acid or sulfuric acid
Close.
6. the preparation method as described in one of Claims 1 to 5, it is characterised in that the phenolic compound include phenol and its
In derivative, preferably phenol, cresols, xylenol, naphthols, alkyl-substituted phenol, alkyl-substituted naphthols, bisphenol-A or Bisphenol F
Any a kind or at least 2 kinds of combination;
Preferably, the aldehyde compound includes formaldehyde and its derivative, any a kind or extremely preferably in formaldehyde, acetaldehyde or furfural
Few 2 kinds combination.
7. the preparation method as described in one of claim 1~6, it is characterised in that methods described comprises the following steps:
(a1 ') dispersed graphite alkenes material obtains graphite alkenes material dispersion liquid in solvent;Dispersed polymeres in solvent,
Obtain polymer dispersion liquid;
(a1) graphite alkenes material dispersion liquid and the polymer dispersion liquid mixing for obtaining step (a1 '), stirring obtain Graphene
The mixed liquor of class material and polymer;
(a2) to the mixed liquor for adding step (a1) to obtain in the polymerized monomer of phenolic resin in the way of being added dropwise, thermoplasticity is carried out
The polymerisation of phenolic resin obtains reaction solution, and modified phenolic resin is obtained after purification;
(a3) after the phenolic resin being obtained into phenolic fibre precursor through melt spinning, solidification crosslinking obtains modified phenolic resin
Fiber;Or, methods described comprises the following steps:
(b1 ') dispersed graphite alkenes material obtains graphite alkenes material dispersion liquid in solvent;Dispersed polymeres in solvent,
Obtain polymer dispersion liquid;
(b1) graphite alkenes material dispersion liquid and the polymer dispersion liquid mixing for obtaining step (b1 '), stirring obtain Graphene
The mixed liquor of class material and polymer;
(b2) it is mixed described in step (b1) to being added in reaction solution by phenolic compound and after aldehyde compound reaction a period of time
Liquid is closed, reaction obtains reaction solution, modified phenolic resin is obtained after purification;
(b3) after the phenolic resin being obtained into phenolic fibre precursor through melt spinning, solidification crosslinking obtains modified phenolic resin
Fiber;
Or, methods described comprises the following steps:
(c1 ') dispersed graphite alkenes material obtains graphite alkenes material dispersion liquid in solvent;Dispersed polymeres in solvent,
Obtain polymer dispersion liquid;
(c1) graphite alkenes material dispersion liquid and the polymer dispersion liquid mixing for obtaining step (c1 '), stirring obtain Graphene
The mixed liquor of class material and polymer;
(c2) mixed liquor described in step (c1) is added in phenolic resin, modified phenolic resin is obtained;
(c3) after the phenolic resin being obtained into phenolic fibre precursor through melt spinning, solidification crosslinking obtains modified phenolic resin
Fiber.
8. a kind of modified phenolic fiber, it is characterised in that the modified phenolic fiber by claim 1~
The preparation method of one of 7 described modified phenolic fibers is obtained.
9. a kind of purposes of phenolic fiber as claimed in claim 8 modified, it is characterised in that the modified phenolic aldehyde
Resin fibre is used as in reinforcing material, flame resistant heat insulation material, insulation material, padded coaming, phenolic aldehyde base carbon fibre, electrode material
Any a kind or at least 2 kinds of combination.
10. a kind of electrode composite material, it is characterized in that, by the obtained phenolic fiber of one of claim 1~9 through carbonizing
Arrive.
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